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WO2024104815A1 - Substituted benzodiazepines as fungicides - Google Patents

Substituted benzodiazepines as fungicides Download PDF

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Publication number
WO2024104815A1
WO2024104815A1 PCT/EP2023/080910 EP2023080910W WO2024104815A1 WO 2024104815 A1 WO2024104815 A1 WO 2024104815A1 EP 2023080910 W EP2023080910 W EP 2023080910W WO 2024104815 A1 WO2024104815 A1 WO 2024104815A1
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Prior art keywords
alkyl
phenyl
halogen
alkynyl
methyl
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PCT/EP2023/080910
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French (fr)
Inventor
Philipp Georg Werner SEEBERGER
Wassilios Grammenos
Bernd Mueller
Benjamin Juergen MERGET
Aymane SELMANI
Ronan Le Vezouet
Annette SCHUSTER
Christian Winter
Andreas Koch
Dorothee Sophia ZIEGLER
Jochen Dietz
Jan Klaas Lohmann
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BASF SE
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BASF SE
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Priority to CN202380079348.1A priority Critical patent/CN120202195A/en
Priority to EP23801449.2A priority patent/EP4619392A1/en
Publication of WO2024104815A1 publication Critical patent/WO2024104815A1/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to new benzodiazepine compounds and the N-oxides and the salts thereof as fungicides as well as to their use.
  • the invention also relates to the composition comprising at least one compound I, to the method for combating phytopathogenic fungi and to the seed coated with at least one compound of the formula I.
  • WO 2011037128 discloses some benzodiazepine compounds. However, in many cases, in particular at low application rates, the fungicidal activity of known compounds is unsatisfactory. Based on this, it was an objective of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic fungi. Another object of the present invention is to provide fungicides with improved toxicological properties or with improved environmental fate properties.
  • Y is N, CR 1 ;
  • R 1 is in each case independently selected from H, halogen, CN, Ci-C4-alkyl, Ci-C4-halogen- alkyl;
  • R 2 is in each case independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-halogenalkyl, C2-Ce-alkenyl, C2-C6-halogenalkenyl, C2-Ce-alkynyl, C2-Ce-halogenalkynyl, O-Ci-Ce-alkyl, O-C2-Ce-alkenyl, O-C2-Ce-alkynyl, Cs-Ce-cycloalkyl, S-Ci-Ce-alkyl, S-C2-Ce-alkenyl, S-C2- Ce-alkynyl;
  • R 3 is in each case independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-halogenalkyl, C2-Ce-alkenyl, C2-C6-halogenalkenyl, C2-Ce-alkynyl, C2-Ce-halogenalkynyl, O-C
  • R 4 is in each case independently selected from H, halogen, CN, Ci-C4-alkyl, Ci-C4-halogen- alkyl;
  • R 5 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R 5a ; where each R 5a is independently halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Ci-Ce-alkyl;
  • R 6 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R 6a ; where each R 6a is independently halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Ci-Ce-alkyl; or
  • R 5 and R 6 together with the carbon atom to which they are bound, form a 3-, 4-, 5- or 6-mem- bered saturated carbocyclic ring or a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O and S as ring members; where the carbocyclic or heterocyclic ring is unsubstituted or carries 1 , 2 or 3 substituents R 56 ; where each R 56 is independently halogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl; R 7 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or
  • R 8 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R 8a ; where each R 8a is independently halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Ci-Ce-alkyl; or
  • R 7 and R 8 together with the carbon atom to which they are bound, form a 3-, 4-, 5- or 6-mem- bered saturated carbocyclic ring or a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O and S as ring members;
  • R 9a is Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl or benzyl, where the phenyl ring in the two last-mentioned radicals is unsubstituted or carries 1 , 2 or 3 substituents each independently selected from the group consisting of halogen, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-C6-haloalkenyl, C2-Ce-alkynyl and C2-Ce-haloalkynyl;
  • X is in each case independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Cs-Ce-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy, phenyl, benzyl, phenoxy, benzoxy, Ci-Ce-thioalkyl; n is 0, 1 , 2 or 3; or the N-oxides, tautomers, stereoisomers or agriculturally acceptable salts thereof.
  • the N-oxides may be prepared from the inventive compounds according to conventional oxidation methods, e. g. by treating compounds I with an organic peracid such as metachloroperbenzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(11), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-8, 1981) or ox- one (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001).
  • the oxidation may lead to pure mono- N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.
  • Agriculturally acceptable salts of the compounds of the formula I encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I.
  • Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may be substituted with one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and
  • Anions of acceptable acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Stereoisomers of the formula I can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers arising from restricted rotation about a single bond of asymmetric groups and geometric isomers. They also form part of the subject matter of the present invention.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the compounds of the invention may be present as a mixture of stereoisomers, e.g. a racemate, individual stereoisomers, or as an optically active form.
  • the embodiments of the intermediates obtained during preparation of compounds I correspond to the embodiments of the compounds of formula I.
  • the term “compounds I” refers to compounds of the formula I.
  • C n -C m indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • Ci-Ce-alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1 -methylpropyl, 2- methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methyl butyl, 2,2-dime- thylpropyl, 1-ethylpropyl, 1 , 1-dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethyl- butyl, 2,2-dimethylbutyl, 2,3-dimethylbut
  • C2-C4-alkyl refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1-methylethyl (iso-propoyl), butyl, 1 -methylpropyl (sec.- butyl), 2-methylpropyl (iso-butyl), 1 ,1 -dimethylethyl (tert.-butyl).
  • Ci-Ce-halogenalkyl refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • Examples are "Ci-C2-halogenalkyl” groups such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoro- ethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro- 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-t
  • C2-C6-alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position.
  • Examples are “C2-C4-alkenyl” groups, such as ethenyl, 1-propenyl, 2-propenyl (allyl), 1 -methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1 -propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl.
  • C2-C6-halogenalkenyl refers to an alkyl group having 2 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • C2-C6-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond.
  • Examples are "C2-C4-al- kynyl” groups, such as ethynyl, prop-1-ynyl, prop-2-ynyl (propargyl), but-1-ynyl, but-2-ynyl, but- 3-ynyl, 1-methyl-prop-2-ynyl.
  • C2-C6-halogenalkynyl refers to an alkyl group having 2 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • Cs-Ce-cycloalkyl refers to monocyclic saturated hydrocarbon radicals having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. Accordingly, a saturated three-, four-, five-, six-, seven-, eight-, nine or ten-membered carbocyclyl or carbocycle is a "Cs-Cio-cycloalkyl".
  • C3-C8-cycloalkyl-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), where at least one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical having 3 to 8 carbon atoms (as defined above).
  • saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine or ten- membered heterocyclyl or heterocycle, wherein the heterocyclyl or heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from N, O and S is to be understood as meaning both saturated and partially unsaturated heterocycles, wherein the ring member atoms of the heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms independently selected from the group of O, N and S.
  • a 3- or 4-membered saturated heterocycle which contains 1 or 2 heteroatoms from the group consisting of O, N and S as ring members such as oxirane, aziridine, thiirane, oxetane, azetidine, thiethane, [1 ,2]dioxetane, [1 ,2]dithietane, [1 ,2]diazetidine; and a 5- or 6-membered saturated or partially unsaturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of O, N and S as ring members such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isox- azolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiothi
  • substituted refers to substitued with 1 , 2, 3 or up to the maximum possible number of substituents.
  • 5-or 6-membered heteroaryl or “5-or 6-membered heteroaromatic” refers to aromatic ring systems incuding besides carbon atoms, 1 , 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, for example, a 5-membered heteroaryl such as pyrrol-1 -yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan- 2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxa
  • R 1 is in each case independently selected from H, halogen, CN, Ci-C4-alkyl, Ci-C4-halogenalkyl, preferred R 1 is in each case independently selected from H, Ci-C4-alkyl, Ci-C4-halogenalkyl, more preferred R 1 is in each case independently selected from H, Ci-C4-alkyl, most preferred R 1 is in each case H.
  • R 2 is selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-halogenalkyl, C2-Ce-alkenyl, C2-C6-halogenalkenyl, C2-Ce-alkynyl, C2-Ce-halo- genalkynyl, O-Ci-Ce-alkyl, O-C2-Ce-alkenyl, O-C2-Ce-alkynyl, Cs-Ce-cycloalkyl, S-Ci-Ce-alkyl, S- C2-Ce-alkenyl, S-C2-Ce-alkynyl.
  • R 2 is in each case independently selected from Ci-C4-alkyl and Ci-C4-halogenalkyl, preferred R 2 is in each case independently selected from H, Ci-C4-alkyl, Ci-C4-halogenalkyl, more preferred R 2 is in each case independently selected from CH3 and CF2H, most preferred R 2 is in each case CH3.
  • R 2 is halogen, in particular F, Cl, Br or I, more specifically F, Cl or Br, in particular F or Cl.
  • R 2 is F.
  • R 2 is Cl
  • R 2 is Br
  • R 2 is CN
  • R 2 is Ci-Ce-alkyl, in particular Ci-C4-alkyl, such as CH 3 or C2H5, in particular CH 3 or CH 2 CH 3 .
  • R 2 is Ci-Ce-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF3.
  • R 2 is C2-Ce-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as CHCH, CH2CHCH, CHCCI, CH2CHCCI, or CCI2CHCCI.
  • R 2 is O-Ci-Ce-alkyl, in particular C1-C4- alkyl, more specifically Ci-C2-alkoxy.
  • R 2 is such as OCH3 or OCH2CH3.
  • R 2 is O-Ci-Ce-alkyl
  • R 2 is O-C2-Ce-alkenyl in particular C2- C4-alkenyl, more specifically C2-C3-alkenyl.
  • R 2 is O-C2-Ce-alkynyl, in particular C2- Ce-alkynyl, in particular C2-C4-alkynyl, more specifically C2-C3-alkynyl.
  • R 2 is such as O-CH 2 - CHCH.
  • R 2 is Cs-Ce-cycloalkyl, in particular cyclopropyl or cyclobutyl.
  • R 2 is S-Ci-Ce-alkyl, in particular C1-C4- alkyl, more specifically Ci-C2-alkoxy.
  • R 2 is such as SCH3 or SCH2CH3.
  • R 2 is S-Ci-Ce-alkyl,
  • R 2 is S-C2-Ce-alkenyl in particular C2- C4-alkenyl, more specifically C2-C3-alkenyl.
  • R 2 is S-C2-Ce-alkynyl, in particular C2- Ce-alkynyl, in particular C2-C4-alkynyl, more specifically C2-C3-alkynyl.
  • R 2 is such as S-CH2- CHCH.
  • R 2 Particularly preferred embodiments of R 2 according to the invention are in Table P2 below, wherein each line of lines P2-1 to P2-21 corresponds to one particular embodiment of the invention, wherein P2-1 to P2-21 are also in any combination with one another a preferred embodi- ment of the present invention.
  • the connection point to the carbon atom, to which R 2 is bound is marked with “#” in the drawings.
  • R 3 is selected from the group consisting of Ci-Ce- alkyl, Ci-Ce-halogenalkyl, Cs-Ce-cycloalkyl, in particular CH3, C2H5, CF3, CH2F, CHF2, cyclopropyl, cyclobutyl, more specifically CH3, CH2F, CF2H, CF3, cyclopropyl, cyclobutyl most preferred CH 3 , CF 2 H.
  • R 3 is Ci-Ce-alkyl, in particular Ci-C4-alkyl, such as CH 3 or C2H5, in particular CH 3 or CH2CH 3 .
  • R 3 is Ci-Ce-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF 3 , FCH2, F2CH, CF 3 CH2.
  • R 3 is C2-Ce-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as CHCH, CH 2 CHCH, CHCCI, CH2CHCCI, or CChCHCCI.
  • R 3 is O-Ci-Ce-alkyl, in particular C1-C4- alkyl, more specifically Ci-C2-alkoxy.
  • R 3 is such as OCH 3 or OCH2CH 3 .
  • R 3 is O-C2-Ce-alkenyl in particular C 2 - C4-alkenyl, more specifically C2-C 3 -alkenyl.
  • R 3 is O-C2-Ce-alkynyl, in particular C 2 - Ce-alkynyl, in particular C2-C4-alkynyl, more specifically C2-C 3 -alkynyl.
  • R 3 is such as O-CH2- CHCH.
  • R 3 is O-Ci-Ce-halogenalkyl, in particular OCF 3 , OCCI 3 , OFCH2, OCICH2, OF2CH, OChCH, OCF 3 CH 2 , OCCI 3 CH 2 or OCF 2 CHF 2 , more specifically OCF 3 , OF2CH, OFCH2.
  • R 3 is C 3 -C6-cycloalkyl, in particular cyclopropyl, cyclobutyl.
  • R 3 is S-Ci-Ce-alkyl, in particular C1-C4- alkyl, more specifically Ci-C2-alkoxy.
  • R 2 is such as SCH 3 or SCH2CH 3 .
  • R 3 is S-Ci-Ce-alkyl
  • R 3 is S-C2-Ce-alkenyl in particular C2-C4- alkenyl, more specifically C2-C 3 -alkenyl.
  • R 3 is S-C2-Ce-alkynyl, in particular C 2 - Ce-alkynyl, in particular C2-C4-alkynyl, more specifically C2-C 3 -alkynyl.
  • R 2 is such as S-CH2- CHCH.
  • R 3 Particularly preferred embodiments of R 3 according to the invention are in Table P3 below, wherein each line of lines P3-1 to P3-17 corresponds to one particular embodiment of the inven- tion, wherein P3-1 to P3-17 are also in any combination with one another a preferred embodiment of the present invention.
  • the connection point to the carbon atom, to which R 3 is bound is marked with “#” in the drawings.
  • R 4 is in each case independently selected from H, halogen, CN, Ci-C4-alkyl, Ci-C4-halogenalkyl, preferred R 4 is in each case independently selected from H, Ci-C4-alkyl, Ci-C4-halogenalkyl, more preferred R 4 is in each case independently selected from H, Ci-C4-alkyl, most preferred R 4 is in each case H.
  • R 5 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-haloal- kenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH 2 heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R 5a ; where each R 5a is independently halogen, CN, Ci-Ce-alkyl, Ci- Ce-haloalkyl or O-Ci-Ce-alkyl.
  • R 5 is in each case independently selected from Ci-Ce-alkyl (embodiment 5.1), Ci-Ce-halogenalkyl (embodiment 5.2), Ci-Ce-alkyl- O-Ci-Ce-alkyl (embodiment 5.3), phenyl, CH2-phenyl (embodiment 5.4), wherein phenyl and CH2-phenyl is unsubstituted or substituted by one or two halogen.
  • R 5 is CH 3 or CF 3 .
  • R 5 is CH 3 .
  • R 5 is CH 2 CH 3 , CH(CH 3 ) 2 ,
  • R 5 is phenyl, 2-F-phenyl, 4- F-phenyl, 2,4-F 2 -phenyl, 2-CI-phenyl, 4-CI-phenyl, CH 2 -phenyl, CH 2 -2-F-phenyl, CH 2 -4-F-phe- nyl.
  • R 6 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C 2 -C6-alkenyl, C 2 -C6-haloal- kenyl, C 2 -C6-alkynyl, C 2 -C6-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH 2 heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R 6a ; where each R 6a is independently halogen, CN, Ci-Ce-alkyl, Ci- Ce-haloalkyl or O-Ci-Ce-alkyl.
  • R 6 is in each case independently selected from Ci-Ce-alkyl (embodiment 6.1), Ci-Ce-alkyl-O-phenyl (embodiment 6.2), Ci-Ce-al- kyl-O-Ci-Ce-alkyl (embodiment 6.3).
  • R 5 and R 6 form together with the C atoms to which they are bound a C 3 -C6-cycloalkyl or a a 3 - to 6-membered saturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of O and S, wherein the cycloalkyl or heterocycle can be unsubsituted or substitued by halogene, Ci-Ce- alkyl, Ci-Ce-halogenalkyl.
  • R 5 and R 6 form C 3 -Ce-cy- cloalkyl (embodiment 6.4).
  • R 5 , R 6 are in Table P5 below, wherein each line of lines P5-1 to P5-19 corresponds to one particular embodiment of the invention, wherein P5-1 to P5-19 are also in any combination with one another a preferred embodiment of the present invention.
  • the connection point to the carbon atom, to which R 5 and R 6 is bound is marked with “#” in the drawings.
  • R 7 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-haloal- kenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH 2 heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R 7a ; where each R 7a is independently halogen, CN, Ci-Ce-alkyl, Ci- Ce-haloalkyl or O-Ci-Ce-alkyl.
  • R 7 is in each case independently selected from Ci-Ce-alkyl (embodiment 7.1), Ci-Ce-halogenalkyl (embodiment 7.2), Ci-Ce-alkyl- O-Ci-Ce-alkyl (embodiment 7.3), phenyl, CH2-phenyl (embodiment 7.4), wherein phenyl and CF phenyl is unsubstituted or substituted by one or two halogen.
  • R 7 is CH 3 or CF 3 .
  • R 7 is CH 3 .
  • R 7 is phenyl, 2-F-phenyl, 4- F-phenyl, 2,4-F2-phenyl, 2-CI-phenyl, 4-CI-phenyl, CH2-phenyl, CH2-2-F-phenyl, CH2-4-F-phe- nyl.
  • R 8 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-haloal- kenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CF ⁇ heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R 8a ; where each R 8a is independently halogen, CN, Ci-Ce-alkyl, Ci- Ce-haloalkyl or O-Ci-Ce-alkyl.
  • R 8 is in each case independently selected from Ci-Ce-alkyl (embodiment 8.1), Ci-Ce-alkyl-O-phenyl (embodiment 8.2), Ci-Ce-al- kyl-O-Ci-Ce-alkyl (embodiment 8.3).
  • R 7 and R 8 form together with the C atoms to which they are bound a C 3 -C6-cycloalkyl or a a 3 - to 6-membered saturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of O and S, wherein the cycloalkyl or heterocycle can be unsubsituted or substitued by halogene, Ci-Ce- alkyl, Ci-Ce-halogenalkyl.
  • R 7 and R 8 form C 3 -Ce-cy- cloalkyl (embodiment 8.4). According to one further embodiment of the compound of formula I, R 7 and R 8 form 3- to 6- membered saturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of O and S.
  • R 7 , R 8 are in Table P78 below, wherein each line of lines P7-1 to P7-19 corresponds to one particular embodiment of the invention, wherein P7-1 to P7-19 are also in any combination with one another a preferred embodiment of the present invention.
  • the connection point to the carbon atom, to which R 7 and R 8 is bound is marked with “#” in the drawings.
  • R 9a is Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl or benzyl, where the phenyl ring in the two last-mentioned radicals is unsubstituted or carries 1 , 2 or 3 substituents each independently selected from the group consisting of halogen, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl and C2-Ce-haloalkynyl.
  • R 9 is Cl, F.
  • R 9 is CN, CH2CN or CH(CH3)CN.
  • R 9 is OCH3 or OCH2CH3.
  • R 9 is Ci-Ce-alkyl, such as CH 3 , C2H5, n-pro- pyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
  • R 9 is Ci-Ce-alkyl, in particular Ci-C4-alkyl, such as CH 3 , C2H5, n-propyl, i-propyl.
  • R 9 is Ci-Ce-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF 3 , CCI 3 , FCH 2 , CICH 2 , F 2 CH, CI 2 CH, CF3CH2, CCI3CH2 or CF 2 CHF 2 .
  • R 9 is Cs-Ce-cycloalkyl, in particular cyclopropyl.
  • R 9 is Cs-Ce-halogencycloalkyl.
  • R 9b is fully or partially halogenated cyclopropyl, such as 1-F-cyclopropyl, 1-CI- cyclopropyl, 1 ,1-F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl .
  • R 9 is C2-Ce-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as CHCH, CH 2 CHCH.
  • R 9 is aryl, in particular phenyl, wherein the aryl or phenyl moiety in each case is unsubstituted or substituted by identical or different groups R 9b which independently of one another are selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl and Ci-C2-halogenalkoxy, in particular F, Cl, Br, CH3, OCH3, CF3 and OCF3. According to one embodiment, R 9 is unsubstituted phenyl.
  • R 9 is phenyl, that is substituted by one, two or three, in particular one, halogen, in particular selected from F, Cl and Br, more specifically selected from F and Cl.
  • R 9 is a 5-membered heteroaryl such as pyr- rol-1-yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1-yl, pyrazol- 3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2- yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxxazol-3-yl, isox
  • R 9 is a 6-membered heteroaryl such as pyri- din-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, py- rimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
  • R 9 is in each case independently selected from H, halogen, OH, CN, Ci-Ce-alkyl, Ci-Ce-halogenalkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce- alkoxy, Ci-Ce-halogenalkoxy, C 3 -Ce-alkenyloxy, C 3 -Ce-alkynyloxy and Cs-Ce-cycloalkyl wherein the acyclic moieties of R 9 are unsubstituted or substituted with identical or different groups R 9a as defined and preferably defined herein, and wherein the carbocyclic, phenyl and heteroaryl moieties of R 9 are unsubstituted or substituted with identical or different groups R 9b as defined and preferably defined herein.
  • R 9 Particularly preferred embodiments of R 9 according to the invention are in Table P9 below, wherein each line of lines P9-1 to P9-31 corresponds to one particular embodiment of the invention, wherein P9-1 to P9-31 are also in any combination with one another a preferred embodiment of the present invention.
  • the connection point to the carbon atom, to which R 9 is bound is marked with “#” in the drawings.
  • X is in each case independently selected from halogen (embodiment X.1), CN, Ci-Ce-alkyl (embodiment X.2), Ci-Ce-halogen- alkyl (embodiment X.3), O-Ci-Ce-alkyl (embodiment X.4), O-Ci-Ce-halogenalkyl (embodiment X.5).
  • X is in each case independently selected from halogen, O-Ci-Ce-alkyl.
  • X is in each case independently selected from F or Cl.
  • X is Cs-Ce-cycloalkyl.
  • n 0.
  • n 1
  • n is 2.
  • Xn is as defined below: and X is F.
  • n 0.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, which represent preferred combinations of embodiments that are defined above for each of the variables R 2 , R 3 and X (represented by embodiments X.1 to X.6), n in compounds of formula I as defined below.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table
  • R 5 is represented by embodiment 5.1 and R 6 is represented by embodiment 6.1.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.2 and R 6 is represented by embodiment 6.1. In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.3 and R 6 is represented by embodiment 6.1.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.4 and R 6 is represented by embodiment 6.1.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.1 and R 6 is represented by embodiment 6.2. In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.2 and R 6 is represented by embodiment 6.2.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.3 and R 6 is represented by embodiment 6.2.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.4 and R 6 is represented by embodiment 6.2.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.1 and R 6 is represented by embodiment 6.3.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.2 and R 6 is represented by embodiment 6.3.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.3 and R 6 is represented by embodiment 6.3.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 is represented by embodiment 5.4 and R 6 is represented by embodiment 6.3.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 and R 6 arerepresented by embodiment 6.4.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 5 and R 6 arerepresented by embodiment 6.5.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.1 and R 8 is represented by embodiment 8.1.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.2 and R 8 is represented by embodiment 8.1.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.3 and R 8 is represented by embodiment 8.1.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.4 and R 8 is represented by embodiment 8.1.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.1 and R 8 is represented by embodiment 8.2.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.2 and R 8 is represented by embodiment 8.2.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.3 and R 8 is represented by embodiment 8.2.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.4 and R 8 is represented by embodiment 8.2.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.1 and R 8 is represented by embodiment 8.3.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.2 and R 8 is represented by embodiment 8.3.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.3 and R 8 is represented by embodiment 8.3.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 is represented by embodiment 7.4 and R 8 is represented by embodiment 8.3. In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 and R 8 arerepresented by embodiment 8.4.
  • the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R 7 and R 8 arerepresented by embodiment 8.7.
  • preference is given to the compounds of the compounds LA-1 , I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8; that are compiled in the Tables 1a to 12a.
  • Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
  • Table 1a Compounds of the formula LA-1, LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, I.A-8 in which R 9 is CH 3 and the meaning for the combination of X 1 , X 2 , R 5 , R 6 R 7 and R 8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.1a.B-1 to I.A- 1.1a.B-784, I.A-2.1a.B-1 to LA-2.1 a. B-784, I.A-3.1a.B-1 to LA-3.1a. B-784, I.A-4.1a.B-1 to I.A-
  • R 9 is CH2CH3 and the meaning for the combination of X 1 , X 2 , R 5 , R 6 R 7 and R 8 for each individ- ual compound corresponds in each case to one line of Table B (compounds I.A-1.2a.B-1 to I.A-
  • Table 3a Compounds of the formula LA-1, LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, I.A-8 in which R 9 is CH2CH2CH3 and the meaning for the combination of X 1 , X 2 , R 5 , R 6 R 7 and R 8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.3a.B-1 to I.A-1.3a.B-784, I.A-2.3a.B-1 to I.A-2.3a.B-784, I.A-3.3a.B-1 to I.A-3.3a.B-784, I.A-4.3a.B-1 to I.A-4.3a.B-784, I.A-5.3a.B-1 to I.A-5.3a.B-784, I.A-6.3a.B-1 to I.A-6.3a.B-784, I.A-7.3a.B-1 to I.A-7.3a.B-784, I.A-8.3a.B-1 to I.A-8
  • Table 4a Compounds of the formula LA-1, LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R 9 is CN and the meaning for the combination of X 1 , X 2 , R 5 , R 6 R 7 and R 8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.4a.B-1 to I.A- 1.4a.B-784, I.A-2.4a.B-1 to I.A-2.4a.B-784, I.A-3.4a.B-1 to I.A-3.4a.B-784, I.A-4.4a.B-1 to I.A- 4.4a.B-784, I.A-5.4a.B-1 to I.A-5.4a.B-784, I.A-6.4a.B-1 to I.A-6.4a.B-784, I.A-7.4a.B-1 to I.A- 7.4a.B-784, I.A-8.4a.B-1 to I.A-8.4
  • Table 5a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R 9 is CH2CN and the meaning for the combination of X 1 , X 2 , R 5 , R 6 R 7 and R 8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.5a.B-1 to I.A- 1.5a.B-784, I.A-2.5a.B-1 to I.A-2.5a.B-784, I.A-3.5a.B-1 to I.A-3.5a.B-784, I.A-4.5a.B-1 to I.A- 4.5a.B-784, I.A-5.5a.B-1 to I.A-5.5a.B-784, I.A-6.5a.B-1 to I.A-6.5a.B-784, I.A-7.1a.B-1 to I.A- 7.5a.B-784, I.A-8.5a.B-1 to I.A-8.5a.
  • Table 6a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R 9 is CHO and the meaning for the combination of X 1 , X 2 , R 5 , R 6 R 7 and R 8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.6a.B-1 to I.A- 1.6a.B-784, I.A-2.6a.B-1 to I.A-2.6a.B-784, I.A-3.6a.B-1 to I.A-3.6a.B-784, I.A-4.6a.B-1 to I.A- 4.6a.B-784, I.A-5.6a.B-1 to I.A-5.6a.B-784, I.A-6.6a.B-1 to I.A-6.6a.B-784, I.A-7.6a.B-1 to I.A- 7.6a.B-784, LA-8.1 '6a.B-1 to I.A-8.
  • Table 7a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R 9 is C(CH 3 ) 3 and the meaning for the combination of X 1 , X 2 , R 5 , R 6 R 7 and R 8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.7a.B-1 to I.A- 1.7a.B-784, I.A-2.7a.B-1 to I.A-2.7a.B-784, I.A-3.7a.B-1 to I.A-3.7a.B-784, I.A-4.7a.B-1 to I.A- 5.7a.B-784, I.A-5.7a.B-1 to I.A-5.7a.B-784, I.A-6.7a.B-1 to I.A-6.7a.B-784, I.A-7.7a.B-1 to I.A- 7.7a.B-784, I.A-8.7a.B-1 to
  • Table 8a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R 9 is COCH 3 and the meaning for the combination of X 1 , X 2 , R 5 , R 6 R 7 and R 8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.8a.B-1 to I.A- 1.8a.B-784, I.A-2.8a.B-1 to I.A-2.8a.B-784, I.A-3.8a.B-1 to I.A-3.8a.B-784, I.A-4.8a.B-1 to LA- 5.8a.
  • B-784 I.A-5.8a.B-1 to I.A-5.8a.B-784, I.A-6.8a.B-1 to I.A-6.8a.B-784, I.A-7.8a.B-1 to I.A- 7.8a. B-784, I.A-8.8a.B-1 to I.A-8.8a.B-784)
  • Table 9a Compounds of the formula LA-1, LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, I.A-8 in which R 9 is CH 2 C(CH 3 ) 3 and the meaning for the combination of X 1 , X 2 , R 5 , R 6 R 7 and R 8 for each individual compound corresponds in each case to one line of Table B (compounds LA-1.9a. B-1 to LA-1.9a. B-784, I.A-2.9a.B-1 to I.A-2.9a.B-784, I.A-3.9a.B-1 to I.A-3.9a.B-784, I.A-4.9a.B-1 to LA-5.9a.
  • B-784 I.A-5.9a.B-1 to I.A-5.9a.B-784, I.A-6.9a.B-1 to I.A-6.9a.B-784, I.A-7.9a.B-1 to LA-7.9a. B-784, I.A-8.9a.B-1 to I.A-8.9a.B-784)
  • B-784 LA-6.10a.B-1 to I.A-6.10a.B- 784, LA-7.10a.B-1 to LA-7.10a. B-784, LA-8.10a.B-1 to LA-8.10a. B-784)
  • Table 11a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R 9 is CH 2 CCH and the meaning for the combination of X 1 , X 2 , R 5 , R 6 R 7 and R 8 for each individual compound corresponds in each case to one line of Table B (compounds LA-1.11a. B-1 to LA-1.11 a. B-784, LA-2.11a.B-1 to LA-2.11a.B-784, LA-3.11a.B-1 to LA-3.11a.B-784, LA- 4.11a.B-1 to LA-5.11a. B-784, LA-5.11a.B-1 to LA-5.11a. B-784, LA-6.11a.B-1 to LA-6.11a.B- 784, LA-7.11a.B-1 to LA-7.11a. B-784, LA-8.11a.B-1 to LA-8.11a. B-784)
  • Table 12a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R 9 is CH 2 CeH5 and the meaning for the combination of X 1 , X 2 , R 5 , R 6 R 7 and R 8 for each individual compound corresponds in each case to one line of Table B (compounds LA-1.12a. B-1 to LA-1.12a. B-784, LA-2.12a.B-1 to LA-2.12a. B-784, LA-3.12a.B-1 to LA-3.12a. B-784, I.A-
  • compounds I can be prepared via alkylation or acylation of benzodiazepines represented by the formula (2) with a range of alkyl halides and acyl chlorides, which can be ef- fected by deprotonation of the benzodiazepines (2) with a range of organic or inorganic bases, such as potassium tert-butoxide or sodium hydride.
  • the reaction is preferentially performed at 0 °C to room temperature, with in some cases sluggish reactions being carried out at temperatures up to 60 °C, and using 1-5 equivalents of base and 1-3 equivalents of alkylating/acylating reagent, as described in Chem. Eur. J. (2016), 22, 10607-10613, CN114349714 A, W02008/118141 A2, or US2012/184732 A1.
  • the benzodiazepine compounds represented by the formula (2) can be prepared by reacting a range of diamines (or HCI salts thereof) represented by the formula (4) with pyridyl/pyrazidyl aryl ketones (3) substituted with at least 1 halogen (represented by X 1 , preferentially F) in the presence of a base.
  • the reaction is preferentially performed from rt to 120 °C, with 1-6 equivalents of base and 1 to 1.5 equivalents of diamine, analogous to a method described in
  • Aryl ketones (3) are either commercially available, or can be prepared by scheme by oxidation of the aryl alcohol 5, using for example manganese dioxide, as described in Inorganica Chimica Acta (2012), 382, 72- 78, WO 2000/038618, CN 107879989 A, or Chinese Science Bulletin 2010, 55(25), 2817-2819.
  • Aryl alcohols (5) can be prepared by by isopropyl magnesium chloride-mediated bromine/io- dine-magnesium exchange of 7, and subsequent addition to commercially available aldehydes represented by the general formula (6).
  • the reaction is preferentially carried out at 0 °C, with an equimolar ratio of iPrMgCI and aryl halides (7), the intermediate of which is employed in a ratio of 1.2-1.3:1 with respect to aldehydes (6), as described in WO2021/71821 A1 , J. Med. Chem., (2013), 56, 10158-10170, WO2014/102233 A1 , or US2016/83401 A1.
  • the scaffold represented by formula (2) may also be accessed by reacting aryl ketones (3) with partially protected diamines (8) in the presence of organic or inorganic bases at temperatures up to 200 °C under microwave irradiation, as described in US2006/178386 A1 , Bioorganic & Medicinal Chemistry Letters (2021), 35,127813, Chem. Sci. (2021), 12, 4519- 4525, or J. Org. Chem. (2005), 70, 8924-8931.
  • the resulting product 9 may then be further reacted at 0 °C in a 1.5:7 mixture of TFA:DCM to lead to the condensated product represented by formula 2, as described in US2006/3995, J. Bioorg. Med. Chem. Lett. (2007), 17, 2527-2530, W02022/99011 A1, Org Lett. (2012), 14, 5916-5919, or J. Med. Chem. (2016), 59, 10661-
  • the compounds I and the compositions thereof, respectively, are suitable as fungicides effective against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, in particular from the classes of Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridi- omycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (syn. Fungi im- perfecti). They can be used in crop protection as foliar fungicides, fungicides for seed dressing, and soil fungicides.
  • the compounds I and the compositions thereof are preferably useful in the control of phytopath- ogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats, or rice; beet, e. g. sugar beet or fodder beet; fruits, e. g. pomes (apples, pears, etc.), stone fruits (e.g. plums, peaches, almonds, cherries), or soft fruits, also called berries (strawberries, raspberries, blackberries, gooseberries, etc.); leguminous plants, e. g. lentils, peas, alfalfa, or soybeans; oil plants, e. g.
  • cereals e. g. wheat, rye, barley, triticale, oats, or rice
  • beet e. g. sugar beet or fodder beet
  • fruits e. g. pomes (apples,
  • oilseed rape mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts, or soybeans; cucurbits, e. g. squashes, cucumber, or melons; fiber plants, e. g. cotton, flax, hemp, or jute; citrus fruits, e. g. oranges, lemons, grapefruits, or mandarins; vegetables, e. g. spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits, or paprika; lauraceous plants, e. g. avocados, cinnamon, or camphor; energy and raw material plants, e. g.
  • corn, soybean, oilseed rape, sugar cane, or oil palm corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants; or ornamental and forestry plants, e. g. flowers, shrubs, broad-leaved trees, or evergreens (conifers, eucalypts, etc.); on the plant propagation material, such as seeds; and on the crop material of these plants.
  • compounds I and compositions thereof, respectively are used for controlling fungi on field crops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, oilseed rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • field crops such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, oilseed rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant, such as seeds; and vegetative plant materials, such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants; including seedlings and young plants to be transplanted after germination or after emergence from soil.
  • treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • all of the above cultivated plants are understood to comprise all species, subspecies, variants, varieties and/or hybrids which belong to the respective cultivated plants, including but not limited to winter and spring varieties, in particular in cereals such as wheat and barley, as well as oilseed rape, e.g. winter wheat, spring wheat, winter barley etc.
  • Corn is also known as Indian corn or maize (Zea mays) which comprises all kinds of corn such as field corn and sweet corn.
  • all maize or corn subspecies and/or varieties are comprised, in particular flour corn (Zea mays var. amylacea), popcorn (Zea mays var. evert a), dent corn (Zea mays var. indentata), flint corn (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy corn (Zea mays var. ceratina), amylomaize (high amylose Zea mays varieties), pod corn or wild maize (Zea mays var. t unicat a) and striped maize (Zea mays var. japonica).
  • soybean cultivars are classifiable into indeterminate and determinate growth habit, whereas Glycine soja, the wild progenitor of soybean, is indeterminate (PNAS 2010, 107 (19) 8563-856).
  • the indeterminate growth habit (Maturity Group, MG 00 to MG 4.9) is characterized by a continuation of vegetative growth after flowering begins whereas determinate soybean varieties (MG 5 to MG 8) characteristically have finished most of their vegetative growth when flowering begins.
  • all soybean cultivars or varieties are comprised, in particular indeterminate and determinate cultivars or varieties.
  • cultivagenesis includes random mutagenesis using X-rays or mutagenic chemicals, but also targeted mutagenesis to create mutations at a specific locus of a plant genome.
  • Targeted mutagenesis frequently uses oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases.
  • Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination.
  • one or more genes are integrated into the genome of a plant to add a trait or improve or modify a trait. These integrated genes are also referred to as transgenes, while plant comprising such transgenes are referred to as transgenic plants.
  • the process of plant transformation usually produces several transformation events, wich differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
  • Herbicide tolerance has been created by using mutagenesis and genetic engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by mutagenesis and breeding are e.g. available under the name Clearfield®. Herbicide tolerance to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitors and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione, has been created via the use of transgenes.
  • HPPD 4-hydroxyphenylpyruvate dioxygenase
  • Transgenes to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601 , gat4621 , goxv247; for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 , aad-12; for tolerance to dicamba: dmo; for tolerance to oxynil herbicies: bxn; for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA; for tolerance to ALS inhibitors: csr1-2; and for tolerance to HPPD inhibitors: hppdPF, W336, avhppd-03.
  • Transgenic corn events comprising herbicide tolerance genes include, but are not limited to, DAS40278, MON801 , MON802, MON809, MON810, MON832, MON87411 , MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHGOJG, HCEM485, VCO-01981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.
  • Transgenic soybean events comprising herbicide tolerance genes include, but are not limited to, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127.
  • Transgenic cotton events comprising herbicide tolerance genes include, but are not limited to, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.
  • Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1 , MS8, PHY14, PHY23, PHY35, PHY36, RF1 , RF2 and RF3.
  • Transgenes to provide insect resistance preferably are toxin genes of Bacillus spp. and synthetic variants thereof, like cry1A, crylAb, cry1Ab-Ac, crylAc, cry1A.1O5, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1 , cry34Ab1 , cry35Ab1 , cry9C, vip3A(a), vip3Aa20.
  • transgenes of plant origin such as genes coding for protease inhibitors, like CpTI and pinll, can be used.
  • a further approach uses transgenes such as dvsnf7 to produce double-stranded RNA in plants.
  • Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA include, but are not limited to, Bt10, Bt11 , Bt176, MON801 , MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351 , MIR162, DBT418 and MZIR098.
  • Transgenic soybean events comprising genes for insecticidal proteins include, but are not limited to, MON87701 , MON87751 and DAS-81419.
  • Transgenic cotton events comprising genes for insecticidal proteins include, but are not limited to, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Eventl, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281- 24-236, 3006-210-23, GHB119 and SGK321.
  • Cultivated plants with increased yield have been created by using the transgene athb17 (e.g. corn event MON87403), or bbx32 (e.g. soybean event MON87712).
  • athb17 e.g. corn event MON87403
  • bbx32 e.g. soybean event MON87712
  • Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A (e.g. soybean events 260-05, MON87705 and MON87769).
  • Preferred combinations of traits are combinations of herbicide tolerance traits to different groups of herbicides, combinations of insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, combinations of herbicide tolerance with one or several types of insect resistance, combinations of herbicide tolerance with increased yield as well as combinations of herbicide tolerance and tolerance to abiotic conditions.
  • Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art.
  • detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations “International Service for the Acquisition of Agri-biotech Applications (ISAAA)” (http://www.isaaa.org/gmapprovaldatabase) and the “Center for Environmental Risk Assessment (CERA)” (http://cera-gmc.org/GMCropDatabase).
  • effects which are specific to a cultivated plant comprising a certain transgene or event may result in effects which are specific to a cultivated plant comprising a certain transgene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigour, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
  • the compounds I and compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases:
  • Albugo spp. white rust on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis Alternaria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauci or A. porri), oilseed rape (A. brassicicola or brassicae), sugar beets (A. tenuis), fruits (e.g. A. grandis), rice, soybeans, potatoes and tomatoes (e. g. A. solani, A. grandis or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat (e.g. A. triticinay Aphanomyces spp.
  • vegetables e. g. A. Candida
  • sunflowers e. g. A. tragopogonis Alternaria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauci or A. porri), oilseed rape
  • Ascochyta spp. on cereals and vegetables e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Aureobasidium zeae (syn. Kapatiella zeae) on corn; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (8. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. 8.
  • Corticium spp. e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans, cotton and ornamentals; Cy- cloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C.
  • lirio- dendri teleomorph: Neonectria liriodendrr. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyr- enophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis’.
  • barley e. g. D. teres, net blotch
  • wheat e. g. D. tritici-repentis’.
  • ampelina anthracnose
  • Entyloma oryzae leaf smut
  • Epicoccum spp. black mold
  • Ery- siphe spp. pepperdery mildew
  • sugar beets E. betae
  • vegetables e. g. E. pisi
  • cucurbits e. g. E. cichoracearum
  • cabbages oilseed rape (e. g. E. cruciferarum)'
  • Eutypa lata Eu- typa canker or dieback
  • anamorph Cytosporina lata, syn.
  • Microsphaera diffusa prowdery mildew
  • Monilinia spp. e. g. M. laxa, M. fructicola and M. fructi- gena (syn. Monilia spp.: bloom and twig blight, brown rot) on stone fruits and other rosaceous plants
  • Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Zymoseptoria tritici formerly Septoria tritici: Septoria blotch) on wheat or M. fijiensis (syn.
  • meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. g reg ata'. stem rot); Phoma lingam (syn. Leptosphaeria biglobosa and L. maculans'. root and stem rot) on oilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off) on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn; Phomopsis spp.
  • soybeans e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorumy Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans’. late blight) and broad-leaved trees (e. g. P. ramorunr.
  • stem rot P. phaseoli, teleomorph: Diaporthe phaseolorumy Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew
  • P. leucotricha on apples curcurbits
  • P. xanthiiy Polymyxa spp. e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P.
  • Pseudocercosporella herpotrichoides (syn. Oculimacula yallundae, O. acuformis'. eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudo- pezicula tracheiphila (red fire disease or .rotbrenner’, anamorph: Phialophora) on vines; Puc- cinia spp.
  • rusts on various plants e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenopeziza spp., e.g. P.
  • oligandrum on mushrooms
  • Ramularia spp. e. g. P. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley, P. areola (teleomorph: Myco- sphaerella areola) on cotton and P. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants, e. g. P. solani (root and stem rot) on soybeans, P. solani (sheath blight) on rice or P.
  • Athelia rolfsii on soybeans, peanut, vegetables, corn, cereals and ornamentals; Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (syn. Zymoseptoria tritici, Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Se- tosphaeria spp. (leaf blight) on corn (e.
  • S. turcicum syn. Helminthosporium turcicum
  • turf Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana, syn. Ustilago reiliana’. head smut), sorghum und sugar cane; Sphaerotheca fuliginea (syn. Podosphaera xanthir. powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleo- morph: Leptosphaeria [syn. Phaeosphaeria] nodorum, syn. Septoria nodorum) on wheat;
  • Synchytrium endobioticum on potatoes potato wart disease
  • Taphrina spp. e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums
  • Thielaviopsis spp. black root rot
  • tobacco, pome fruits, vegetables, soybeans and cotton e. g. T. basicola (syn.
  • Chalara elegans Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Trichoderma harzianum on mushrooms’, Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appen- diculatus, syn. U. phaseoli), sugar beets (e.
  • U. betae or U. beticola and on pulses (e.g. U. vignae, U. pisi, U. viciae-fabae and U. fabae)', Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis'. corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. . inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. . longisporum on oilseed rape, . dahliae on strawberries, oilseed rape, potatoes and tomatoes, and . fungicola on mushrooms; Zymoseptoria tritici on cereals.
  • the compounds I and compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases: rusts on soybean and cereals (e.g.
  • powdery mildews on specialty crops and cereals e.g. Uncinula necatoron vines, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals
  • leaf spots on cereals, soybean and corn e.g. Septoria tritici and S. nodorum on cereals, S. glycines on soybean, Cercospora spp. on corn and soybean.
  • compounds I.A-1.1a.B-1 to I.A-1.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-2.1a.B-1 to I.A-2.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-3.1a.B-1 to I.A-3.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-4.1a.B-1 to I.A-4.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-5.1a.B-1 to I.A-5.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-6.1a.B-1 to I.A-6.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-1.2a.B-1 to I.A-1.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-2.2a.B-1 to I.A-2.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-3.2a.B-1 to I.A-3.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-4.2a.B-1 to I.A-4.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-5.2a.B-1 to I.A-5.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-6.2a.B-1 to I.A-6.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-1.3a.B-1 to I.A-1.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-2.3a.B-1 to I.A-2.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-3.3a.B-1 to I.A-3.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-4.3a.B-1 to I.A-4.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-5.3a.B-1 to I.A-5.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-6.3a.B-1 to I.A-6.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-1.4a.B-1 to I.A-1.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-2.4a.B-1 to I.A-2.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-3.4a.B-1 to I.A-3.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-4.4a.B-1 to I.A-4.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-5.4a.B-1 to I.A-5.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-6.4a.B-1 to I.A-6.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-1.5a.B-1 to I.A-1.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-2.5a.B-1 to I.A-2.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-3.5a.B-1 to I.A-3.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-4.5a.B-1 to I.A-4.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-5.5a.B-1 to I.A-5.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-6.5a.B-1 to I.A-6.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-1.6a.B-1 to I.A-1.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-2.6a.B-1 to I.A-2.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-3.6a.B-1 to I.A-3.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-4.6a.B-1 to I.A-4.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-5.6a.B-1 to I.A-5.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-6.6a.B-1 to I.A-6.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-1.7a.B-1 to I.A-1.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-2.7a.B-1 to I.A-2.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-3.7a.B-1 to I.A-3.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-4.7a.B-1 to I.A-4.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-5.7a.B-1 to I.A-5.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds I.A-6.7a.B-1 to I.A-6.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • compounds Ex-1 to Ex-92 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
  • Albugo spp. white rust on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis Alternaria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauci or A. porri), oilseed rape (A. brassicicola or brassicae), sugar beets (A. tenuis), fruits (e.g. A. grandis), rice, soybeans, potatoes and tomatoes (e. g. A. solani, A. grandis or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat (e.g. A. triticinay Aphanomyces spp.
  • vegetables e. g. A. Candida
  • sunflowers e. g. A. tragopogonis Alternaria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauci or A. porri), oilseed rape
  • Ascochyta spp. on cereals and vegetables e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Aureobasidium zeae (syn. Kapatiella zeae) on corn; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. 8.
  • Colletotrichum teleomorph: Glomerella spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes'. black dot), beans (e. g. C. lindemuthianum), soybeans (e. g. C. truncatum or C. gloeosporioides), vegetables (e.g. C. lagenarium or C. capsici), fruits (e.g. C. acutatum), coffee (e.g. C. C.
  • Corticium spp. e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans, cotton and ornamentals; Cy- cloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C.
  • lirio- dendri teleomorph: Neonectria liriodendrr. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyr- enophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis'.
  • barley e. g. D. teres, net blotch
  • wheat e. g. D. tritici-repentis'.
  • ampelina anthracnose
  • Entyloma oryzae leaf smut
  • Epicoccum spp. black mold
  • Ery- siphe spp. potowdery mildew
  • sugar beets E. betae
  • vegetables e. g. E. pisi
  • cucurbits e. g. E. cichoracearum
  • cabbages oilseed rape (e. g. E. cruciferarum)-
  • Eutypa lata Eu- typa canker or dieback
  • anamorph Cytosporina lata, syn.
  • Microsphaera diffusa prowdery mildew
  • Monilinia spp. e. g. M. laxa, M. fructicola and M. fructi- gena (syn. Monilia spp.: bloom and twig blight, brown rot) on stone fruits and other rosaceous plants
  • Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Zymoseptoria tritici formerly Septoria triticr'. Septoria blotch) on wheat or M. fijiensis (syn.
  • meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. g reg ata'. stem rot); Phoma lingam (syn. Leptosphaeria biglobosa and L. maculans’. root and stem rot) on oilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off) on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn; Phomopsis spp.
  • soybeans e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans'. late blight) and broad-leaved trees (e. g. P. ramorunr.
  • stem rot P. phaseoli, teleomorph: Diaporthe phaseolorum Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew
  • P. leucotricha on apples curcurbits
  • P. xanthii Polymyxa spp. e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P.
  • Pseudocercosporella herpotrichoides (syn. Oculimacula yallundae, O. acuformis'. eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudo- pezicula tracheiphila (red fire disease or .rotbrenner’, anamorph: Phialophora) on vines; Puc- cinia spp.
  • rusts on various plants e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenopeziza spp., e.g. P.
  • oligandrum on mushrooms
  • Ramularia spp. e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley, R. areola (teleomorph: Myco- sphaerella areola) on cotton and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R.
  • Athelia rolfsii on soybeans, peanut, vegetables, corn, cereals and ornamentals; Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (syn. Zymoseptoria tritici, Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Se- tosphaeria spp. (leaf blight) on corn (e.
  • S. turcicum syn. Helminthosporium turcicum
  • turf Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana, syn. Ustilago reiliana'. head smut), sorghum und sugar cane; Sphaerotheca fuliginea (syn. Podosphaera xanthir. powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum, syn. Septoria nodorum) on wheat;
  • Synchytrium endobioticum on potatoes potato wart disease
  • Taphrina spp. e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums
  • Thielaviopsis spp. black root rot
  • tobacco, pome fruits, vegetables, soybeans and cotton e. g. T. basicola (syn.
  • Chalara elegans Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Trichoderma harzianum on mushrooms’, Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appen- diculatus, syn. U. phaseoli), sugar beets (e.
  • U. betae or U. beticola and on pulses (e.g. U. vignae, U. pisi, U. viciae-fabae and U. fabae)', Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis'. corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. . inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. .
  • the compounds I and compositions thereof, respectively, are also suitable for controlling harmful microorganisms in the protection of stored products or harvest, and in the protection of materials.
  • stored products or harvest is understood to denote natural substances of plant or animal origin and their processed forms for which long-term protection is desired.
  • Stored products of plant origin for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment.
  • timber whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.
  • Stored products of animal origin are hides, leather, furs, hairs and alike.
  • stored products is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms, where application of compounds I and compositions thereof can also prevent disadvantageous effects such as decay, discoloration or mold.
  • protection of materials is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper, paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber, or fabrics against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • the compounds I and compositions thereof, respectively, may be used for improving the health of a plant.
  • the invention also relates to a method for improving plant health by treating a plant, its propagation material, and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other, such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves (“greening effect”)), quality (e. g. improved content or composition of certain ingredients), and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e. g. improved plant growth and/or greener leaves (“greening effect”)
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e. g. improved content or composition of certain ingredients
  • the compounds I are employed as such or in form of compositions by treating the fungi, the plants, plant propagation materials, such as seeds; soil, surfaces, materials, or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds; soil, surfaces, materials or rooms by the fungi.
  • An agrochemical composition comprises a fungicidally effective amount of a compound I.
  • fungicidally effective amount denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of stored products or harvest or of materials and which does not result in a substantial damage to the treated plants, the treated stored products or harvest, or to the treated materials.
  • Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant, stored product, harvest or material, the climatic conditions and the specific compound I used.
  • Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance of generally from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kg of plant propagation material (preferably seeds) are required.
  • the user applies the agrochemical composition usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready- to-use spray liquor are applied per hectare of agricultural useful area.
  • compositions e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types see also “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International) are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g.
  • CS, ZC pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecticidal articles (e. g. LN), as well as gel formulations for the treatment of plant propagation materials, such as seeds (e. g. GF).
  • WP wettable powders or dusts
  • pressings e. g. BR, TB, DT
  • granules e. g. WG, SG, GR, FG, GG, MG
  • insecticidal articles e. g. LN
  • gel formulations for the treatment of plant propagation materials such as seeds (e. g. GF).
  • compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or by Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers, and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e. g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, and alkylated naphthalenes; alcohols, e. g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol, glycols; DMSO; ketones, e. g. cyclohexanone; esters, e. g.
  • mineral oil fractions of medium to high boiling point e. g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalene,
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e. g. /V-methyl pyrrolidone, fatty acid dimethyl amides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e. g. cellulose, star
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and of alkyl naphthalenes, sulfosuccinates, or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids, of oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, /V-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • Examples of /V-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters, or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters, or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinyl pyrrolidone, vinyl alcohols, or vinyl acetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide, and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.
  • Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e. g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives, such as alkylisothiazoli- nones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water-soluble dyes.
  • examples are inorganic colorants (e. g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e. g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • the agrochemical compositions generally comprise between 0.01 and 95 %, preferably between 0.1 and 90 %, more preferably between 1 and 70 %, and in particular between 10 and 60 %, by weight of active substances (e.g. at least one compound I).
  • the agrochemical compositions generally comprise between 5 and 99.9 %, preferably between 10 and 99.9 %, more preferably between 30 and 99 %, and in particular between 40 and 90 %, by weight of at least one auxiliary.
  • the active substances (e.g. compounds I) are employed in a purity of from 90 % to 100 %, preferably from 95-% to 100 % (according to NMR spectrum).
  • compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60 % by weight, preferably from 0.1 to 40 %, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying compound I and compositions thereof, respectively, onto plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking, as well as in-furrow application methods.
  • compound I or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating, and dusting.
  • oils, wetters, adjuvants, fertilizers, or micronutrients, and further pesticides may be added to the compounds I or the compositions thereof as premix, or, not until immediately prior to use (tank mix).
  • pesticides e. g. fungicides, growth regulators, herbicides, insecticides, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 : 100 to 100: 1 , preferably 1 : 10 to 10: 1.
  • a pesticide is generally a chemical or biological agent (such as pestidal active ingredient, compound, composition, virus, bacterium, antimicrobial, or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests.
  • Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease.
  • pesticide includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
  • Biopesticides have been defined as a form of pesticides based on microorganisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, microbial and biochemical pesticides:
  • Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classified as microbial pesticides, even though they are multi-cellular.
  • Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mammals.
  • azoxystrobin (A.1.1), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), man- destrobin (A.1.10), metominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin
  • respiration inhibitors diflumetorim (A.4.1); nitrophenyl derivates: binapacryl (A.4.2), di- nobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone
  • organometal compounds organometal compounds: fentin salts, e.g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.11); silthiofam (A.4.12);
  • - C14 demethylase inhibitors triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromucona- zole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), dinicona- zole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusi- lazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipcona- zole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobu- trazole (B.1.20), penconazole (
  • benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);
  • nucleic acid synthesis inhibitors hymexazole (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-
  • tubulin inhibitors benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (D1.3), thiabendazole (D.1.4), thiophanate-methyl (D.1.5), pyridachlometyl (D.1.6), / ⁇ /-ethyl-2-[(3-ethynyl-8-methyl- 6-quinolyl)oxy]butanamide (D.1.8), / ⁇ /-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methyl- sulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/ ⁇ /-(2-fluoroethyl)butan- amide (D.1.10), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/ ⁇ /-(2-fluoroethyl)-2-methoxy-ace
  • diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7), phenamac- ril (D.2.8);
  • cyprodinil E.1.1
  • mepanipyrim E.1.2
  • pyrimethanil E.1.3
  • blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydro- chloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6);
  • fluoroimid F.1.1
  • iprodione F.1.2
  • procymidone F.1.3
  • vinclozolin F.1.4
  • fludioxonil F.1.5
  • quinoxyfen F.2.1
  • edifenphos G.1.1
  • iprobenfos G.1.2
  • pyrazophos G.1.3
  • isoprothiolane G.1.4
  • dicloran G.2.1
  • quintozene G.2.2
  • tecnazene G.2.3
  • tolclofos-methyl G.2.4
  • biphenyl G.2.5
  • chloroneb G.2.6
  • etridiazole G.2.7
  • zinc thiazole G.2.8
  • dimethomorph G.3.1
  • flumorph G.3.2
  • mandipropamid G.3.3
  • pyrimorph G.3.4
  • benthiavalicarb G.3.5
  • iprovalicarb G.3.6
  • valifenalate G.3.7
  • propamocarb (G.4.1);
  • oxathiapiprolin G.5.1
  • fluoxapiprolin G.5.3
  • 4-[1-[2-[3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]-/ ⁇ /-tetralin-1-yl-pyridine- 2-carboxamide G.5.4
  • 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]-A/-te- tralin-1-yl-pyridine-2-carboxamide G.5.5
  • 4-[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyra- zol-1-yl]acetyl]-4-piperidyl]-/ ⁇ /-tetralin-1-yl-pyridine-2-carboxamide G.5.6
  • ferbam H.2.1
  • mancozeb H.2.2
  • maneb H.2.3
  • metam H.2.4
  • metiram H.2.5
  • propineb H.2.6
  • thiram H.2.7
  • zineb H.2.8
  • ziram H.2.9
  • organochlorine compounds anilazine (H.3.1), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.11);
  • guanidine H.4.1
  • dodine H.4.2
  • dodine free base H.4.3
  • guazatine H.4.4
  • guazatine-acetate H.4.5
  • iminoctadine H.4.6
  • iminoctadine-triacetate H.4.7
  • iminoctadine-tris(albesilate) H.4.8
  • dithianon H.4.9
  • 2,6-dimethyl-1/7,5/7-[1 ,4]di- thiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2/7,6/-/)-tetraone H.4.10
  • H.4.10 2,6-dimethyl-1/7,5/7-[1 ,4]di- thiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2/7,6/-/)-tetraone
  • - melanin synthesis inhibitors pyroquilon (1.2.1), tricyclazole (1.2.2), carpropamid (1.2.3), dicyclomet (1.2.4), fenoxanil (1.2.5);
  • violaceusniger Tala- romyces flavus, Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula pha- corrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
  • Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity harpin protein, Reynoutria sachalinensis extract;
  • Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. ai- zawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B.
  • Agrobacterium radiobacter Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. ai- zawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp
  • brongniartii Burkholderia spp., Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobac- terium spp., Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucle- opolyhedrovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L.
  • HearNPV Helicoverpa armigera nucleopolyhedrovirus
  • HzNPV Helicoverpa zea nucle- opolyhedrovirus
  • HzSNPV Helicoverpa zea single capsi
  • Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium legumi- nosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium melilotr,
  • Acetylcholine esterase (AChE) inhibitors aldicarb, alanycarb, bendiocarb, benfuracarb, bu- tocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, aza- methiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanopho
  • GABA-gated chloride channel antagonists endosulfan, chlordane; ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole;
  • Sodium channel modulators acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cyclo- prothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cy- permethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, f
  • Nicotinic acetylcholine receptor (nAChR) agonists acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; 4,5-dihydro-/V-nitro-
  • 2-pentylidenehydrazinecarboximidamide 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 5-propoxy-1 ,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine; nicotine; sulfoxaflor, flupyradifurone, triflumezopyrim, fenmezoditiaz, flupyrimin;
  • Nicotinic acetylcholine receptor allosteric activators spinosad, spinetoram;
  • Chloride channel activators abamectin, emamectin benzoate, ivermectin, lepimectin, milbe- mectin;
  • Juvenile hormone mimics hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen;
  • miscellaneous non-specific (multi-site) inhibitors methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;
  • Mite growth inhibitors clofentezine, hexythiazox, diflovidazin; etoxazole;
  • Microbial disruptors of insect midgut membranes Bacillus thuringiensis, B. sphaericus and the insecticdal proteins they produce: Bacillus thuringiensis subsp. israelensis, B. sphaericus, B. thuringiensis subsp. aizawai, B. thuringiensis subsp. kurstaki, B. thuringiensis subsp. tenebrionis, the Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Ab1 ;
  • Inhibitors of mitochondrial ATP synthase diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon;
  • Nicotinic acetylcholine receptor (nAChR) channel blockers bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium;
  • Inhibitors of the chitin biosynthesis type 0 bistrifluron, chlorfluazuron, diflubenzuron, flu- cycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;
  • Ecdyson receptor agonists methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide;
  • Octopamin receptor agonists amitraz
  • Mitochondrial complex III electron transport inhibitors hydramethylnon, acequinocyl, fluacrypyrim, bifenazate; 1 Mitochondrial complex I electron transport inhibitors: fenazaquin, fenpyroximate, pyrim- idifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone; 2 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone, 2-[2-(4-cyano- phenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-/ ⁇ /-[4-(difluoromethoxy)phenyl]-hydrazinecar- boxamide, /V-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)-[4-[methyl(methylsulfonyl)- amino]phenyl]methylene
  • O.IIN Insecticidal compounds of unknown or uncertain mode of action: afoxolaner, azadirachtin, amidoflumet, ben-zoximate, bromopropylate, chino _, methionat, cryolite, cyproflanilid, dicloro- mezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopy- ram, fluralaner, metaldehyde, metoxadiazone, piperonyl butoxide, pyridalyl, tioxazafen, triflu- enfuronate, umifoxolaner, 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-aza- dispiro[4.2.4.2]-tetradec-11-en-10-one, 3-(4’
  • component 2 The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available.
  • IIIPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968;
  • the solid material (dry matter) of the biopesticides (with the exception of oils such as Neem oil) are considered as active components (e. g. to be obtained after drying or evaporation of the extraction or suspension medium in case of liquid formulations of the microbial pesticides).
  • the weight ratios and percentages used for a biological extract such as Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).
  • the total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including dormant forms can be determined using the amount of CFU of the respective microorganism to calculate the total weight of the respective active component with the following equation that 1 x 10 10 CFU equals one gram of total weight of the respective active component.
  • Colony forming unit is measure of viable microbial cells.
  • CFU may also be understood as the number of (juvenile) individual nematodes in case of nematode biopesticides, such as Steinernema feltiae.
  • the weight ratio of the component 1) and the component 2) generally depends from the properties of the components used, usually it is in the range of from 1 :10,000 to 10,000:1 , often from 1 :100 to 100:1 , regularly from 1 :50 to 50:1 , preferably from 1 :20 to 20:1 , more preferably from 1 : 10 to 10:1 , even more preferably from 1 :4 to 4: 1 and in particular from 1 :2 to 2:1.
  • the weight ratio of the component 1) and the component 2) usually is in the range of from 1000:1 to 1 :1 , often from 100: 1 to 1 :1 , regularly from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , more preferably from 10:1 to 1 :1 , even more preferably from 4: 1 to 1 : 1 and in particular from 2: 1 to 1 : 1 .
  • the weight ratio of the component 1) and the component 2) usually is in the range of from 20,000:1 to 1 :10, often from 10,000:1 to 1 :1 , regularly from 5,000:1 to 5:1 , preferably from 5,000:1 to 10:1 , more preferably from 2,000:1 to 30:1 , even more preferably from 2,000:1 to 100:1 and in particular from 1 ,000:1 to 100:1.
  • the weight ratio of the component 1) and the component 2) usually is in the range of from 1 :1 to 1 :1000, often from 1 :1 to 1 :100, regularly from 1 :1 to 1 :50, preferably from 1 :1 to 1 :20, more preferably from 1 :1 to 1 :10, even more preferably from 1 :1 to 1 :4 and in particular from 1 :1 to 1 :2.
  • the weight ratio of the component 1) and the component 2) usually is in the range of from 10:1 to 1 :20,000, often from 1 :1 to 1 :10,000, regularly from 1 :5 to 1 :5,000, preferably from 1 :10 to 1 :5,000, more preferably from 1 :30 to 1 :2,000, even more preferably from 1 :100 to 1 :2,000 to and in particular from 1 :100 to 1 :1 ,000.
  • the ternary mixtures i.e.
  • compositions comprising the component 1) and component 2) and a compound III (component 3), the weight ratio of component 1) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100: 1 , regularly from 1 :50 to 50: 1 , preferably from 1 :20 to 20: 1 , more preferably from 1 : 10 to 10:1 and in particular from 1 :4 to 4:1 , and the weight ratio of component 1) and component s) usually it is in the range of from 1 :100 to 100:1 , regularly from 1 :50 to 50:1 , preferably from 1 :20 to 20: 1 , more preferably from 1 : 10 to 10: 1 and in particular from 1 :4 to 4: 1 .
  • Any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the component 1). These ratios are also suitable for mixtures applied by seed treatment.
  • the application rates range from 1 x 10 6 to 5 x 10 16 (or more) CFU/ha, preferably from 1 x 10 8 to 1 x 10 13 CFU/ha, and even more preferably from 1 x 10 9 to 5 x 10 15 CFU/ha and in particular from 1 x 10 12 to 5 x 10 14 CFU/ha.
  • the application rates regularly range from 1 x 10 5 to 1 x 10 12 (or more), preferably from 1 x 10 8 to 1 x 10 11 , more preferably from 5 x 10 8 to 1 x 10 10 individuals (e. g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha.
  • mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Q o site in group A), more preferably selected from compounds (A.1.1), (A.1.4), (A.1.8), (A.1.9), (A.1.10), (A.1.12), (A.1.13), (A.1.14), (A.1.17), (A.1.21), (A.1.25), (A.1.34) and (A.1.35); particularly selected from (A.1.1), (A.1.4), (A.1.8), (A.1.9), (A.1.13), (A.1.14), (A.1.17), (A.1.25), (A.1.34) and (A.1.35).
  • mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Qi site in group A), more preferably selected from compounds (A.2.1), (A.2.3), (A.2.4) and (A.2.6); particularly selected from (A.2.3), (A.2.4) and (A.2.6).
  • mixtures comprising as component 2) at least one active substance selected from inhibitors of complex II in group A), more preferably selected from compounds (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.11), (A.3.12), (A.3.15), (A.3.16), (A.3.17), (A.3.18), (A.3.19), (A.3.20), (A.3.21), (A.3.22), (A.3.23), (A.3.24), (A.3.28), (A.3.31), (A.3.32), (A.3.33), (A.3.34), (A.3.35), (A.3.36), (A.3.37), (A.3.38) and (A.3.39); particularly selected from (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.12), (A.3.15), (A.3.17), (A.3.19), (A.3.22), (A.3.23)
  • mixtures comprising as component 2) at least one active substance selected from other respiration inhibitors in group A), more preferably selected from compounds (A.4.5) and (A.4.11); in particular (A.4.11).
  • mixtures comprising as component 2) at least one active substance selected from C14 demethylase inhibitors in group B), more preferably selected from compounds (B.1.4), (B.1.5), (B.1.8), (B.1.10), (B.1.11), (B.1.12), (B.1.13), (B.1.17), (B.1.18), (B.1.21), (B.1.22), (B.1.23), (B.1.25), (B.1.26), (B.1.29), (B.1.34), (B.1.37), (B.1.38), (B.1.43), (B.1.46), (B.1.53), (B.1.54) and (B.1.55); particularly selected from (B.1.5), (B.1.8), (B.1.10), (B.1.17), (B.1.22), (B.1.23), (B.1.25), (B.1.33), (B.1.34), (B.1.37), (B.1.38), (B.1.43) and (B.1.46).
  • mixtures comprising as component 2) at least one active substance selected from Delta 14-reductase inhibitors in group B), more preferably selected from compounds (B.2.4), (B.2.5), (B.2.6) and (B.2.8); in particular (B.2.4).
  • mixtures comprising as component 2) at least one active substance selected from phenylamides and acyl amino acid fungicides in group C), more preferably selected from compounds (C.1.1), (C.1.2), (C.1.4) and (C.1.5); particularly selected from (C.1.1) and (C.1.4).
  • mixtures comprising as component 2) at least one active substance selected from other nucleic acid synthesis inhibitors in group C), more preferably selected from compounds (C.2.6), (C.2.7) and (C.2.8).
  • mixtures comprising as component 2) at least one active substance selected from group D), more preferably selected from compounds (D.1.1), (D.1.2), (D.1.5), (D.2.4) and (D.2.6); particularly selected from (D.1.2), (D.1.5) and (D.2.6).
  • mixtures comprising as component 2) at least one active substance selected from group E), more preferably selected from compounds (E.1.1), (E.1.3), (E.2.2) and (E.2.3); in particular (E.1.3).
  • mixtures comprising as component 2) at least one active substance selected from group H), more preferably selected from compounds (H.2.2), (H.2.3), (H.2.5), (H.2.7), (H.2.8), (H.3.2), (H.3.4), (H.3.5), (H.4.9) and (H.4.10); particularly selected from (H.2.2), (H.2.5), (H.3.2), (H.4.9) and (H.4.10).
  • mixtures comprising as component 2) at least one active substance selected from group I), more preferably selected from compounds (1.2.2) and (1.2.5).
  • mixtures comprising as component 2) at least one active substance selected from group J), more preferably selected from compounds (J.1.2), (J.1.5), (J.1.8), (J.1.11) and (J.1.12); in particular (J.1.5).
  • mixtures comprising as component 2) at least one active substance selected from group K), more preferably selected from compounds (K.1.41), (K.1.42), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59); particularly selected from (K.1.41), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59).
  • the biopesticides from group L1) and/or L2) may also have insecticidal, acaricidal, mollus- cidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity.
  • the biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity.
  • the biopesticides from group L5) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
  • the microbial pesticides in particular those from groups L1), L3) and L5), embrace not only the isolated, pure cultures of the respective microorganism as defined herein, but also its cell- free extract, its suspension in a whole broth culture and a metabolite-containing culture medium or a purified metabolite obtained from a whole broth culture of the microorganism.
  • velezensis FZB42 isolated from soil in Brandenburg, Germany (DSM 23117; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. RhizoVital® 42 from AbiTEP GmbH, Germany), B. a. ssp. plantarum or B. velezensis MBI600 isolated from faba bean in Sutton Bonington, Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRL B-50595; US 2012/0149571 A1 ; e. g. Integral® from BASF Corp., USA), B. a. ssp. plantarum or B.
  • velezensis QST-713 isolated from peach orchard in 1995 in California, U.S.A. (NRRL B-21661 ; e. g. Serenade® MAX from Bayer Crop Science LP, USA), B. a. ssp. plantarum or B. velezensis TJ1000 isolated in 1992 in South Dakoda, U.S.A, (also called 1 BE; ATCC BAA-390; CA 2471555 A1 ; e. g. QuickRootsTM from TJ Technologies, Watertown, SD, USA); B.
  • CNCM 1-1582 a variant of parental strain EIP- N1 (CNCM 1-1556) isolated from soil of central plain area of Israel (WO 2009/126473, US 6,406,690; e. g. Votivo® from Bayer CropScience LP, USA), B. pumilus GHA 180 isolated from apple tree rhizosphere in Mexico (IDAC 260707-01 ; e. g. PRO-MIX® BX from Premier Horticulture, Quebec, Canada), B. pumilus INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tracheiphila (NRRL B-50185, NRRL B- 50153; US 8,445,255), B.
  • pumilus KFP9F isolated from the rhizosphere of grasses in South Africa at least before 2008 (NRRL B-50754; WO 2014/029697; e. g. BAC-UP or FUSION-P from BASF Agricultural Specialities (Pty) Ltd., South Africa), B. pumilus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL B-30087; e. g. Sonata® or Ballad® Plus from Bayer Crop Science LP, USA), B. simplex ABU 288 (NRRL B- 50304; US 8,445,255), B.
  • subtilis FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA-11857; System. Appl. Microbiol. 27, 372-379, 2004; US 2010/0260735; WO 2011/109395); B. thuringiensis ssp. aizawai ABTS-1857 isolated from soil taken from a lawn in Ephraim, Wisconsin, U.S.A., in 1987 (also called ABG-6346; ATCC SD- 1372; e. g. XenTari® from BioFa AG, Munsingen, Germany), B. t. ssp.
  • israeltaki ABTS-351 identical to HD-1 isolated in 1967 from diseased Pink Bollworm black larvae in Brownsville, Texas, U.S.A. (ATCC SD-1275; e. g. Dipel® DF from Valent BioSciences, IL, USA), B. t. ssp. kurstaki SB4 isolated from E. saccharina larval cadavers (NRRL B-50753; e. g. Beta Pro® from BASF Agricultural Specialities (Pty) Ltd., South Africa), B. t. ssp.
  • tenebrionis NB-176-1 a mutant of strain NB-125, a wild type strain isolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM 5480; EP 585215 B1; e. g. Novodor® from Valent BioSciences, Switzerland), Beauveria bassiana GHA (ATCC 74250; e. g. BotaniGard® 22WGP from Laverlam Int. Corp., USA), B. bassiana JW-1 (ATCC 74040; e. g. Naturalis® from CBC (Europe) S.r.l., Italy), B.
  • DSM 5480 Tenebrio molitor
  • EP 585215 B1 e. g. Novodor® from Valent BioSciences, Switzerland
  • Beauveria bassiana GHA ATCC 74250; e. g. BotaniGard® 22WGP from Laverlam Int. Corp., USA
  • B. bassiana JW-1
  • bassiana PPRI 5339 isolated from the larva of the tortoise beetle Conchyloctenia punctata (NRRL 50757; e. g. BroadBand® from BASF Agricultural Specialities (Pty) Ltd., South Africa), Bradyrhi- zobium elkanii strains SEMIA 5019 (also called 29W) isolated in Rio de Janeiro, Brazil and SEMIA 587 isolated in 1967 in the State of Rio Grande do Sul, from an area previously inoculated with a North American isolate, and used in commercial inoculants since 1968 (Appl. Environ. Microbiol. 73(8), 2635, 2007; e. g. GELFIX 5 from BASF Agricultural Specialties Ltd., Brazil), B.
  • japonicum 532c isolated from Wisconsin field in U.S.A. (Nitragin 61A152; Can. J. Plant. Sci. 70, 661-666, 1990; e. g. in Rhizoflo®, Histick®, Hicoat® Super from BASF Agricultural Specialties Ltd., Canada), B. japonicum E-109 variant of strain USDA 138 (INTA E109, SEMIA 5085; Eur. J. Soil Biol. 45, 28-35, 2009; Biol. Fertil. Soils 47, 81-89, 2011); B. japonicum strains deposited at SEMIA known from Appl. Environ. Microbiol.
  • SEMIA 5079 isolated from soil in Cerrados region, Brazil by Embrapa-Cerrados used in commercial inoculants since 1992 (CPAC 15; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum SEMIA 5080 obtained under lab condtions by Embrapa- Cerrados in Brazil and used in commercial inoculants since 1992, being a natural variant of SEMIA 586 (CB1809) originally isolated in U.S.A. (CPAC 7; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil); Burkholderia sp.
  • CPAC 15 e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil
  • B. japonicum SEMIA 5080 obtained under lab condtions by Embrapa- Cerrados in Brazil and used in commercial inoculants since 1992, being a natural variant of SEMI
  • HSSNPV single capsid nucleopolyhedrovirus
  • ABA-NPV-U e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia
  • Heterorhabditis bacteriophora e. g.
  • Met52® Novozymes Biologicals BioAg Group, Canada Metschnikowia fructicola 277 isolated from grapes in the central part of Israel (US 6,994,849; NRRL Y-30752; e. g. formerly Shemer® from Agrogreen, Israel), Paecilomyces ilacinus 251 isolated from infected nematode eggs in the Philippines (AGAL 89/030550; W01991/02051 ; Crop Protection 27, 352-361 , 2008; e. g.
  • Paenibacillus alvei NAS6G6 isolated from the rhizosphere of grasses in South Africa at least before 2008 (WO 2014/029697; NRRL B-50755; e.g. BAC-UP from BASF Agricultural Specialities (Pty) Ltd., South Africa), Paenibacillus strains isolated from soil samples from a variety of European locations including Germany: P. epiphyticus Lu17015 (WO 2016/020371 ; DSM 26971), P. polymyxa ssp. plantarum Lu16774 (WO 2016/020371 ; DSM 26969), P. p. ssp.
  • WO 1995/017806 e. g. Jump Start®, Provide® from Novozymes Biologicals BioAg Group, Canada
  • Reynoutria sachalinensis extract EP 0307510 B1 ; e. g. Regalia® SC from Marrone BioInnovations, Davis, CA, USA or Milsana® from BioFa AG, Germany
  • Steinernema carpocapsae e. g. Millenium® from BASF Agricultural Specialities Limited, UK
  • S. feltiae e. g.
  • the at least one pesticide II is selected from the groups L1) to L5):
  • Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Aureobasidium pullulans DSM 14940 and DSM 14941 (L1.1), Bacillus amyloliquefa- ciens AP-188 (L.1.2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B. amyloliquefa- ciens ssp. plantarum FZB24 (L.1.4), B. amyloliquefaciens ssp. plantarum FZB42 (L.1.5), B. amyloliquefaciens ssp.
  • subtilis FB17 (L.1.15), Coniothyrium minitans CON/M/91-08 (L.1.16), Metschnikowia fructicola NRRL Y-30752 (L.1.17), Paenibacillus alvei NAS6G6 (L.1.18), P. epiphyticus Lu17015 (L.1.25), P. polymyxa ssp. plantarum Lu16774 (L.1.26), P. p. ssp. plantarum strain Lu17007 (L.1.27), Penicillium bilaiae ATCC 22348 (L.1.19), P.
  • Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity Bacillus firmus 1-1582 (L.3.1); B. thuringiensis ssp. aizawai ABTS-1857 (L.3.2), B. t. ssp. kurstaki ABTS-351 (L.3.3), B. t. ssp. kurstaki SB4 (L.3.4), B. t. ssp. tenebrionis NB-176-1 (L.3.5), Beauveria bassiana GHA (L.3.6), B. bassiana JW-1 (L.3.7), B.
  • bassiana PPRI 5339 (L.3.8), Burkholderia sp. A396 (L.3.9), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (L.3.10), Helicoverpa zea nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.11), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (L.3.12), Heterohabditis bacteriophora (L.3.13), Isaria fumosorosea Apopka-97 (L.3.14), Metarhizium anisopliae var.
  • HearNPV Helicoverpa armigera nucleopolyhedrovirus
  • HzNPV Helicoverpa zea nucleopolyhedrovirus
  • HzSNPV Helicoverpa zea single capsid nucleopolyhedrovirus
  • anisopliae F52 (L.3.15), Paecilomyces lilacinus 251 (L.3.16), Pasteuria nishizawae Pn1 (L.3.17), Steinernema carpocapsae (L.3.18), S. feltiae (L.3.19);
  • Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity Azospirillum brasilense Ab-V5 and Ab-V6 (L.5.1), A. bra- silense Sp245 (L.5.2), Bradyrhizobium elkanii SEMIA 587 (L.5.3), B. elkanii SEMIA 5019 (L.5.4), B. japonicum 532c (L.5.5), B. japonicum E-109 (L.5.6), B. japonicum SEMIA 5079 (L.5.7), B. japonicum SEMIA 5080 (L.5.8).
  • the present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1) and at least one biopesticide selected from the group L) (component 2), in particular at least one biopesticide selected from the groups L1) and L2), as described above, and if desired at least one suitable auxiliary.
  • the present invention furthermore relates to agrochemical compositions comprising a mixture of of at least one compound I (component 1) and at least one biopesticide selected from the group L) (component 2), in particular at least one biopesticide selected from the groups L3) and L4), as described above, and if desired at least one suitable auxiliary.
  • mixtures comprising as pesticide II (component 2) a biopesticide selected from the groups L1), L3) and L5), preferably selected from strains denoted above as (L.1.2), (L.1.3), (L.1.4), (L.1.5), (L.1.6), (L.1.7), (L.1.8), (L.1.10), (L.1.11), (L.1.12), (L.1.13), (L.1.14), (L.1.15), (L.1.17), (L.1.18), (L.1.19), (L.1.20), (L.1.21), (L.1.25), (L.1.26), (L.1.27), (L.3.1); (L.3.9), (L.3.16), (L.3.17), (L.5.1), (L.5.2), (L.5.3), (L.5.4), (L.5.5), (L.5.6), (L.5.7), (L.5.8); (L.4.2), and (L.4.1); even more preferably selected from (L.1.2), (L.1.3), (L.
  • mixtures comprising as pesticide II (component 2) a biopesticide selected from the groups L1), L3) and L5), preferably selected from strains denoted above as (L1.1), (L.1.2), (L.1.3), (L.1.6), (L.1.7), (L.1.9), (L.1.11), (L.1.12), (L.1.13), (L.1.14), (L.1.15), (L.1.17), (L.1.18), (L.1.22), (L.1.23), (L.1.24), (L.1.25), (L.1.26), (L.1.27), (L.2.2); (L.3.2), (L.3.3), (L.3.4), (L.3.5), (L.3.6), (L.3.7), (L.3.8), (L.3.10), (L.3.11), (L.3.12), (L.3.13), (L.3.14), (L.3.15), (L.3.18), (L.3.19); (L.4.2), even more preferably selected from (L1.1), (L
  • compositions comprising mixtures of active ingredients can be prepared by usual means, e. g. by the means given for the compositions of compounds I.
  • compositions When living microorganisms, such as pesticides II from groups L1), L3) and L5), form part of the compositions, such compositions can be prepared by usual means (e. g. H.D. Burges: Formulation of Microbial Biopesticides, Springer, 1998; WO 2008/002371 , US 6,955,912, US 5,422,107).
  • Step 1 Preparation of (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanol
  • 1 ,2-difluoro-3-iodobenzene (16.8 g, 0.07 mol) in THF (150 mL) was added /- PrMgCI (2M) (36 mL, 0.073 mol) at 0 °C under N2 and the mixture was stirred at 0 °C for 30 min.
  • Step 3 Preparation of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1 ,2-dihydro- spiro[benzo[e][1 ,4]diazepine-3, 1 -cyclopropane]
  • Step 4 Preparation of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1-methyl-1 ,2-dihydro- spiro[benzo[e][1 ,4]diazepine-3, 1 -cyclopropane]
  • Step 1 Preparation of tert- butyl (2-((2-(6-(difluoromethyl)-5-methylnicotinoyl)-6-fluoro- phenyl)amino)-2-methylpropyl)carbamate
  • Step 2 Preparation of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-2,2-dimethyl-2,3-dihy- dro-1 H-benzo[e][1 ,4]diazepine
  • tert-butyl (2-((2-(6-(difluoromethyl)-5-methylnicotinoyl)-6-fluorophenyl)amino)- 2-methylpropyl)carbamate (0.14 g, 0.31 mmol) in DCM (7 mL), was added TFA (1.4 mL) at 0°C and stirred at 0°C for 4 h.
  • Step 3 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1 ,2,2-trimethyl-2,3-dihydro-1 H- benzo[e][1 ,4]diazepine
  • R t retention time in minutes.
  • the compound was dissolved in a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a ratio (volume) solventemulsifier of 99 to 1 to give a total volume of 5 ml. Subsequently, water was added to total volume of 100 ml.
  • Wettol which is based on ethoxylated alkylphenoles
  • This stock solution was then diluted with the described solvent-emulsifier-water mixture to the final concentration given in the table below.
  • Example 1 Preventative fungicidal control of Botrytis cinerea on leaves of green pepper
  • Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or mixture mentioned in the table below. The next day the plants were inoculated with an aqueous biomalt or DOB solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24°C and a saturated relative humidity, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • Example 3 Preventative fungicidal control of white mold on soybeans caused by Sclerotinia sclerotiorum
  • Example 4 Preventative fungicidal control of white mold on oilseed rape caused by Sclerotinia sclerotiorum
  • Oilseed rapes were grown in pots to the 13 to 14 leaf stage. These plants were sprayed to runoff with previously described spray solution, containing the concentration of active ingredient or their mixture mentioned in the table below. The plants could air-dry. The next day the applicated rape petals were fixed wit 25pl of 2.5% methylcellulose on leaf 1 and 2. 25 pl of a spore suspension of Sclerotinia sclerotiorum was pipetted on each fixed rape petal. After 14 days at 20°C and a relative humidity of 60 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • Example 5 Preventative fungicidal control of white mold on cabagge caused by Sclerotinia sclerotiorum
  • Cabagges were grown in pots to the 13 to 14 leaf stage. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or their mixture mentioned in the table below. The plants could air-dry. The next day the cabbage leaves were inoculated with 50 pl of a mixture of ground petals, methylcellulose, water, and yeast-bacto- peptone media (inkludes spores of Sclerotinia sclerotiorum). After 8 days at 21 °C and a relative humidity of 60 % the extent of fungal attack on the leaves were visually assessed as % diseased leaf area.
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added.
  • the plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of the Cercospora sojina in an aqueous biomalt or yeast-bactopeptone-sodi- umacetate solution was then added.
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Fusarium culmorum in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
  • Example 10 Activity against the leaf blotch on wheat caused by Septoria tritici in the microtiterplate test
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Septorion tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
  • Example 11 Activity against the leaf blotch on wheat caused by Alternaria solani in the microtiterplate test
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Alternaria solani in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
  • Example 12 Activity against the leaf blotch on wheat caused by Cercospora beticula in the microtiterplate test
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Cercospora beticula in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
  • Example 13 Activity against the leaf blotch on wheat caused by Cercospora zeae maydis in the microtiterplate test
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Cercospora zeae maydis in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
  • Example 14 Activity against the leaf blotch on wheat caused by Pyricularia oryzae in the microtiterplate test
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
  • the measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.

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Abstract

The present invention relates to the compounds of formula (I) wherein the variables are defined as given in the description and claims. The invention further relates to their use and composition.

Description

SUBSTITUTED BENZODIAZEPINES AS FUNGICIDES
The present invention relates to new benzodiazepine compounds and the N-oxides and the salts thereof as fungicides as well as to their use. The invention also relates to the composition comprising at least one compound I, to the method for combating phytopathogenic fungi and to the seed coated with at least one compound of the formula I.
WO 2011037128 discloses some benzodiazepine compounds. However, in many cases, in particular at low application rates, the fungicidal activity of known compounds is unsatisfactory. Based on this, it was an objective of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic fungi. Another object of the present invention is to provide fungicides with improved toxicological properties or with improved environmental fate properties.
These and further objects are achieved by the benzodiazepine compounds of formula (I), as defined below, and by their agriculturally suitable.
Accordingly, the present invention relates to the compounds of formula I
Figure imgf000002_0001
Y is N, CR1;
R1 is in each case independently selected from H, halogen, CN, Ci-C4-alkyl, Ci-C4-halogen- alkyl;
R2 is in each case independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-halogenalkyl, C2-Ce-alkenyl, C2-C6-halogenalkenyl, C2-Ce-alkynyl, C2-Ce-halogenalkynyl, O-Ci-Ce-alkyl, O-C2-Ce-alkenyl, O-C2-Ce-alkynyl, Cs-Ce-cycloalkyl, S-Ci-Ce-alkyl, S-C2-Ce-alkenyl, S-C2- Ce-alkynyl; R3 is in each case independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-halogenalkyl, C2-Ce-alkenyl, C2-C6-halogenalkenyl, C2-Ce-alkynyl, C2-Ce-halogenalkynyl, O-Ci-Ce-alkyl, O-C2-Ce-alkenyl, O-C2-Ce-alkynyl, Cs-Ce-cycloalkyl, S-Ci-Ce-alkyl, S-C2-Ce-alkenyl, S-C2- Ce-alkynyl;
R4 is in each case independently selected from H, halogen, CN, Ci-C4-alkyl, Ci-C4-halogen- alkyl;
R5 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R5a; where each R5a is independently halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Ci-Ce-alkyl;
R6 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R6a; where each R6a is independently halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Ci-Ce-alkyl; or
R5 and R6 form together an oxo group (=0); or a thioxo group (=S); or
R5 and R6 together with the carbon atom to which they are bound, form a 3-, 4-, 5- or 6-mem- bered saturated carbocyclic ring or a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O and S as ring members; where the carbocyclic or heterocyclic ring is unsubstituted or carries 1 , 2 or 3 substituents R56; where each R56 is independently halogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl; R7 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R7a; where each R7a is independently halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Ci-Ce-alkyl;;
R8 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R8a; where each R8a is independently halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Ci-Ce-alkyl; or
R7 and R8 form together an oxo group (=0) or a thioxo group (=S); or
R7 and R8 together with the carbon atom to which they are bound, form a 3-, 4-, 5- or 6-mem- bered saturated carbocyclic ring or a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O and S as ring members;
R9 is in each case independently selected from CN, CH2CN, CH(CH3)CN, CH(=O), -C(=O)Ci- C6-alkyl, -C(=O)C2-C6-alkenyl, -C(=O)C2-C6-alkynyl, -C(=O)C3-C6-cycloalkyl, -C(=O)- N(H)Ci-C4-alkyl, -C(=O)-N(Ci-C4-alkyl)2, Ci-Ce-alkyl, Ci-Ce-alkoxy, Ci-C4-haloalkyl, C3- Ce- cycloalkyl, Cs-Ce-halocycloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2- Ce-haloalkynyl, -S(=O)2-R9a, five- or six-membered heteroaryl, aryl or benzyl; wherein heteroaryl contains 1 , 2 or 3 heteroatoms selected from N, O and S as ring members; wherein aryl and the phenyl ring in benzyl are unsubstituted or carry 1 , 2, 3, 4 or 5 substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, C1- C4-alkoxy and Ci-C4-haloalkoxy; wherein
R9a is Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl or benzyl, where the phenyl ring in the two last-mentioned radicals is unsubstituted or carries 1 , 2 or 3 substituents each independently selected from the group consisting of halogen, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-C6-haloalkenyl, C2-Ce-alkynyl and C2-Ce-haloalkynyl;
X is in each case independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Cs-Ce-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy, phenyl, benzyl, phenoxy, benzoxy, Ci-Ce-thioalkyl; n is 0, 1 , 2 or 3; or the N-oxides, tautomers, stereoisomers or agriculturally acceptable salts thereof.
The N-oxides may be prepared from the inventive compounds according to conventional oxidation methods, e. g. by treating compounds I with an organic peracid such as metachloroperbenzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(11), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-8, 1981) or ox- one (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001). The oxidation may lead to pure mono- N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.
Agriculturally acceptable salts of the compounds of the formula I encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may be substituted with one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxo- nium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
Anions of acceptable acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
Compounds of the formula I can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers arising from restricted rotation about a single bond of asymmetric groups and geometric isomers. They also form part of the subject matter of the present invention. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, e.g. a racemate, individual stereoisomers, or as an optically active form.
Compounds of the formula I can be present in different crystal modifications whose biological activity may differ. They also form part of the subject matter of the present invention.
In respect of the variables, the embodiments of the intermediates obtained during preparation of compounds I correspond to the embodiments of the compounds of formula I. The term “compounds I” refers to compounds of the formula I.
In the following, the intermediate compounds are further described. A skilled person will readily understand that the preferences for the substituents, also in particular the ones given in the tables below for the respective substituents, given herein in connection with compounds I apply for the intermediates accordingly. Thereby, the substituents in each case have independently of each other or more preferably in combination the meanings as defined herein.
If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.
In the definitions of the variables given above, collective terms are used which are generally representative for the substituents in question. The term "Cn-Cm" indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
The term "halogen" refers to fluorine, chlorine, bromine and iodine.
The term "Ci-Ce-alkyl" refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1 -methylpropyl, 2- methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methyl butyl, 2,2-dime- thylpropyl, 1-ethylpropyl, 1 , 1-dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethyl- butyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-tri- methylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl. Likewise, the term "C2-C4-alkyl" refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1-methylethyl (iso-propoyl), butyl, 1 -methylpropyl (sec.- butyl), 2-methylpropyl (iso-butyl), 1 ,1 -dimethylethyl (tert.-butyl).
The term "Ci-Ce-halogenalkyl" refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above. Examples are "Ci-C2-halogenalkyl" groups such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoro- ethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro- 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl.
The term "C2-C6-alkenyl" refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position. Examples are "C2-C4-alkenyl" groups, such as ethenyl, 1-propenyl, 2-propenyl (allyl), 1 -methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1 -propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl.
The term "C2-C6-halogenalkenyl" refers to an alkyl group having 2 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
The term "C2-C6-alkynyl" refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond. Examples are "C2-C4-al- kynyl" groups, such as ethynyl, prop-1-ynyl, prop-2-ynyl (propargyl), but-1-ynyl, but-2-ynyl, but- 3-ynyl, 1-methyl-prop-2-ynyl.
The term "C2-C6-halogenalkynyl" refers to an alkyl group having 2 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
The term "Cs-Ce-cycloalkyl" refers to monocyclic saturated hydrocarbon radicals having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. Accordingly, a saturated three-, four-, five-, six-, seven-, eight-, nine or ten-membered carbocyclyl or carbocycle is a "Cs-Cio-cycloalkyl".
The term "C3-C8-cycloalkyl-Ci-C4-alkyl" refers to alkyl having 1 to 4 carbon atoms (as defined above), where at least one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical having 3 to 8 carbon atoms (as defined above).
The term “saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine or ten- membered heterocyclyl or heterocycle, wherein the heterocyclyl or heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from N, O and S” is to be understood as meaning both saturated and partially unsaturated heterocycles, wherein the ring member atoms of the heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms independently selected from the group of O, N and S. For example: a 3- or 4-membered saturated heterocycle which contains 1 or 2 heteroatoms from the group consisting of O, N and S as ring members such as oxirane, aziridine, thiirane, oxetane, azetidine, thiethane, [1 ,2]dioxetane, [1 ,2]dithietane, [1 ,2]diazetidine; and a 5- or 6-membered saturated or partially unsaturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of O, N and S as ring members such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isox- azolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazoli- dinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazoli- dinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl,
1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4-oxadiazolidin-5-yl, 1 ,2 ,4-thiadiazolidin-3-yl , 1 ,2,4-thiadiazol idi n-5- yl, 1 ,2,4-triazolidin-3-yl, 1 ,3,4-oxadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-2-yl, 1 ,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-
2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-
3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxa- zolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5- yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4- yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyra- zol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropy- razol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydro- pyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihy- dropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihy- drooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihy- drooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidi- nyl, 3-piperidinyl, 4-piperidinyl, 1 ,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tet- rahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hex- ahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1 ,3,5-hexahydrotriazin-2-yl and 1 ,2,4- hexahydrotriazin-3-yl and also the corresponding -ylidene radicals; and a 7-membered saturated or partially unsaturated heterocycle such as tetra- and hexahydroaze- pinyl, such as 2,3,4,5-tetrahydro[1 H]azepin-1-,-2-,-3-,-4-,-5-,-6- or-7-yl, 3,4,5,6-tetrahy- dro[2H]azepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1-,-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,6,7-tetrahydro[1 H]azepin-1-,-2-,-3-,-4-,-5-,-6- or-7-yl, hexahydroazepin- 1-, -2-, -3- or-4-yl, tetra- and hexahydrooxepinyl such as 2,3,4,5-tetrahydro[1 H]oxepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2 , 3,4, 7-tetrahydro[1 H]oxepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,6,7-tetrahydro[1 H]oxepin-2-, -3-,-4-,-5- ,-6- or-7-yl, hexahydroazepin-1-,-2-,-3- or-4-yl, tetra- and hexahydro-1 , 3-diazepinyl, tetra- and hexahydro-1 , 4-diazepinyl, tetra- and hexahydro-1 , 3-oxazepinyl, tetra- and hexahydro-1 , 4-oxa- zepinyl, tetra- and hexahydro-1 , 3-dioxepinyl, tetra- and hexahydro-1 , 4-dioxepinyl and the corresponding -ylidene radicals.
The term “substituted” refers to substitued with 1 , 2, 3 or up to the maximum possible number of substituents.
The term “5-or 6-membered heteroaryl” or “5-or 6-membered heteroaromatic” refers to aromatic ring systems incuding besides carbon atoms, 1 , 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, for example, a 5-membered heteroaryl such as pyrrol-1 -yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan- 2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl,
1 .2.4-triazolyl-1 -yl, 1 ,2,4-triazol-3-yl 1 ,2,4-triazol-5-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl and 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-thiadiazol-5-yl; or a 6-membered heteroaryl, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyri- dazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and
1 .2.4-triazin-3-yl.
In the following, particular embodiments of the inventive compounds are described. Therein, specific meanings of the respective substituents are further detained, wherein the meanings are in each case on their own but also in any combination with one another, particular embodiments of the present invention.
Furthermore, in respect of the variables, generally, the embodiments of the compounds I also apply to the intermediates.
According to one embodiment of the compound of formula I, R1 is in each case independently selected from H, halogen, CN, Ci-C4-alkyl, Ci-C4-halogenalkyl, preferred R1 is in each case independently selected from H, Ci-C4-alkyl, Ci-C4-halogenalkyl, more preferred R1 is in each case independently selected from H, Ci-C4-alkyl, most preferred R1 is in each case H.
According to one embodiment of the compound of formula I, R2 is selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-halogenalkyl, C2-Ce-alkenyl, C2-C6-halogenalkenyl, C2-Ce-alkynyl, C2-Ce-halo- genalkynyl, O-Ci-Ce-alkyl, O-C2-Ce-alkenyl, O-C2-Ce-alkynyl, Cs-Ce-cycloalkyl, S-Ci-Ce-alkyl, S- C2-Ce-alkenyl, S-C2-Ce-alkynyl.
According to one embodiment of the compound of formula I, R2 is in each case independently selected from Ci-C4-alkyl and Ci-C4-halogenalkyl, preferred R2 is in each case independently selected from H, Ci-C4-alkyl, Ci-C4-halogenalkyl, more preferred R2 is in each case independently selected from CH3 and CF2H, most preferred R2 is in each case CH3.
According to still another embodiment of formula I, R2 is halogen, in particular F, Cl, Br or I, more specifically F, Cl or Br, in particular F or Cl.
According to still another embodiment of formula I, R2 is F.
According to still another embodiment of formula I, R2 is Cl.
According to still another embodiment of formula I, R2 is Br.
According to still another embodiment of formula I, R2 is CN.
According to still another embodiment of formula I, R2 is Ci-Ce-alkyl, in particular Ci-C4-alkyl, such as CH3 or C2H5, in particular CH3 or CH2CH3.
According to still another embodiment of formula I, R2 is Ci-Ce-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF3.
According to still a further embodiment of formula I, R2 is C2-Ce-alkenyl, in particular C2-C4-alk- enyl, such as CH=CH2, C(CH3)=CH2, CH2CH=CH2.
According to a further specific embodiment of formula I, R2 is C2-Ce-halogenalkenyl, in particular C2-C4-halogenalkenyl, more specifically C2-C3-halogenalkenyl such as CH=CHF, CH=CHCI, CH=CF2, CH=CCI2, CH2CH=CHF, CH2CH=CHCI, CH2CH=CF2, CH2CH=CCI2, CF2CH=CF2, CCI2CH=CCI2, CF2CF=CF2, CCI2CCI=CCI2.
According to still a further embodiment of formula I, R2 is C2-Ce-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as CHCH, CH2CHCH, CHCCI, CH2CHCCI, or CCI2CHCCI.
According to a further specific embodiment of formula I, R2 is O-Ci-Ce-alkyl, in particular C1-C4- alkyl, more specifically Ci-C2-alkoxy. R2 is such as OCH3 or OCH2CH3.
According to a further specific embodiment of formula I, R2 is O-Ci-Ce-alkyl,
According to a further specific embodiment of formula I, R2 is O-C2-Ce-alkenyl in particular C2- C4-alkenyl, more specifically C2-C3-alkenyl. R2 is such as OCH=CH2, OCH2CH=CH2.
According to a further specific embodiment of formula I, R2 is O-C2-Ce-alkynyl, in particular C2- Ce-alkynyl, in particular C2-C4-alkynyl, more specifically C2-C3-alkynyl. R2 is such as O-CH2- CHCH.
According to still another embodiment of formula I, R2 is Cs-Ce-cycloalkyl, in particular cyclopropyl or cyclobutyl.
According to a further specific embodiment of formula I, R2 is S-Ci-Ce-alkyl, in particular C1-C4- alkyl, more specifically Ci-C2-alkoxy. R2 is such as SCH3 or SCH2CH3. According to a further specific embodiment of formula I, R2 is S-Ci-Ce-alkyl,
According to a further specific embodiment of formula I, R2 is S-C2-Ce-alkenyl in particular C2- C4-alkenyl, more specifically C2-C3-alkenyl. R2 is such as SCH=CH2, SCH2CH=CH2.
According to a further specific embodiment of formula I, R2 is S-C2-Ce-alkynyl, in particular C2- Ce-alkynyl, in particular C2-C4-alkynyl, more specifically C2-C3-alkynyl. R2 is such as S-CH2- CHCH.
Particularly preferred embodiments of R2 according to the invention are in Table P2 below, wherein each line of lines P2-1 to P2-21 corresponds to one particular embodiment of the invention, wherein P2-1 to P2-21 are also in any combination with one another a preferred embodi- ment of the present invention. The connection point to the carbon atom, to which R2 is bound is marked with “#” in the drawings.
Table P2:
Figure imgf000011_0002
Figure imgf000011_0001
According to one embodiment of formula I, R3 is selected from the group consisting of Ci-Ce- alkyl, Ci-Ce-halogenalkyl, Cs-Ce-cycloalkyl, in particular CH3, C2H5, CF3, CH2F, CHF2, cyclopropyl, cyclobutyl, more specifically CH3, CH2F, CF2H, CF3, cyclopropyl, cyclobutyl most preferred CH3, CF2H.
According to still another embodiment of formula I, R3 is Ci-Ce-alkyl, in particular Ci-C4-alkyl, such as CH3 or C2H5, in particular CH3 or CH2CH3.
According to still another embodiment of formula I, R3 is Ci-Ce-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF3, FCH2, F2CH, CF3CH2.
According to still a further embodiment of formula I, R3 is C2-Ce-alkenyl, in particular C2-C4-alk- enyl, such as CH=CH2, C(CH3)=CH2, CH2CH=CH2.
According to still a further embodiment of formula I, R3 is C2-Ce-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as CHCH, CH2CHCH, CHCCI, CH2CHCCI, or CChCHCCI.
According to a further specific embodiment of formula I, R3 is O-Ci-Ce-alkyl, in particular C1-C4- alkyl, more specifically Ci-C2-alkoxy. R3 is such as OCH3 or OCH2CH3.
According to a further specific embodiment of formula I, R3 is O-C2-Ce-alkenyl in particular C2- C4-alkenyl, more specifically C2-C3-alkenyl. R3 is such as OCH=CH2, OCH2CH=CH2.
According to a further specific embodiment of formula I, R3 is O-C2-Ce-alkynyl, in particular C2- Ce-alkynyl, in particular C2-C4-alkynyl, more specifically C2-C3-alkynyl. R3 is such as O-CH2- CHCH.
According to a further specific embodiment of formula I, R3 is O-Ci-Ce-halogenalkyl, in particular OCF3, OCCI3, OFCH2, OCICH2, OF2CH, OChCH, OCF3CH2, OCCI3CH2 or OCF2CHF2, more specifically OCF3, OF2CH, OFCH2.
According to still another embodiment of formula I, R3 is C3-C6-cycloalkyl, in particular cyclopropyl, cyclobutyl.
According to a further specific embodiment of formula I, R3 is S-Ci-Ce-alkyl, in particular C1-C4- alkyl, more specifically Ci-C2-alkoxy. R2 is such as SCH3 or SCH2CH3.
According to a further specific embodiment of formula I, R3 is S-Ci-Ce-alkyl,
According to a further specific embodiment of formula I, R3 is S-C2-Ce-alkenyl in particular C2-C4- alkenyl, more specifically C2-C3-alkenyl. R2 is such as SCH=CH2, SCH2CH=CH2.
According to a further specific embodiment of formula I, R3 is S-C2-Ce-alkynyl, in particular C2- Ce-alkynyl, in particular C2-C4-alkynyl, more specifically C2-C3-alkynyl. R2 is such as S-CH2- CHCH.
Particularly preferred embodiments of R3 according to the invention are in Table P3 below, wherein each line of lines P3-1 to P3-17 corresponds to one particular embodiment of the inven- tion, wherein P3-1 to P3-17 are also in any combination with one another a preferred embodiment of the present invention. The connection point to the carbon atom, to which R3 is bound is marked with “#” in the drawings.
Table P3:
Figure imgf000013_0003
Figure imgf000013_0002
Figure imgf000013_0001
According to one embodiment of the compound of formula I, R4 is in each case independently selected from H, halogen, CN, Ci-C4-alkyl, Ci-C4-halogenalkyl, preferred R4 is in each case independently selected from H, Ci-C4-alkyl, Ci-C4-halogenalkyl, more preferred R4 is in each case independently selected from H, Ci-C4-alkyl, most preferred R4 is in each case H.
According to one embodiment of the compound of formula I, R5 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-haloal- kenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R5a; where each R5a is independently halogen, CN, Ci-Ce-alkyl, Ci- Ce-haloalkyl or O-Ci-Ce-alkyl.
According to one embodiment of the compound of formula I, R5 is in each case independently selected from Ci-Ce-alkyl (embodiment 5.1), Ci-Ce-halogenalkyl (embodiment 5.2), Ci-Ce-alkyl- O-Ci-Ce-alkyl (embodiment 5.3), phenyl, CH2-phenyl (embodiment 5.4), wherein phenyl and CH2-phenyl is unsubstituted or substituted by one or two halogen. According to one further embodiment of the compound of formula I, R5 is CH3 or CF3.
According to one further embodiment of the compound of formula I, R5 is CH3.
According to one further embodiment of the compound of formula I, R5 is CH2CH3, CH(CH3)2,
CH(CH3)CH2CH3, C(CH3)3, CH2-CH(CH3)2, CH2-C(CH3)3, CH2-O-CH3.
According to one further embodiment of the compound of formula I, R5 is CH=CH2, CH2CH=CH2.
According to one further embodiment of the compound of formula I, R5 is phenyl, 2-F-phenyl, 4- F-phenyl, 2,4-F2-phenyl, 2-CI-phenyl, 4-CI-phenyl, CH2-phenyl, CH2-2-F-phenyl, CH2-4-F-phe- nyl.
According to one embodiment of the compound of formula I, R6 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-C6-alkenyl, C2-C6-haloal- kenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R6a; where each R6a is independently halogen, CN, Ci-Ce-alkyl, Ci- Ce-haloalkyl or O-Ci-Ce-alkyl.
According to one embodiment of the compound of formula I, R6 is in each case independently selected from Ci-Ce-alkyl (embodiment 6.1), Ci-Ce-alkyl-O-phenyl (embodiment 6.2), Ci-Ce-al- kyl-O-Ci-Ce-alkyl (embodiment 6.3).
According to one further embodiment of the compound of formula I, R6 is CH2CH3, CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, CH2-CH(CH3)2, CH2-C(CH3)3, CH2-CH(CH3)-C(CH3)3, CH2-CH2- C(CH3)3, CH2-O-CH3, CH2-O-(CH3)3, CH2-O-phenyl, is CH=CH2, CH2CH=CH2, CH2-phenyl.
According to one further embodiment of the compound of formula I, R5 and R6 form together with the C atoms to which they are bound a C3-C6-cycloalkyl or a a 3 - to 6-membered saturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of O and S, wherein the cycloalkyl or heterocycle can be unsubsituted or substitued by halogene, Ci-Ce- alkyl, Ci-Ce-halogenalkyl.
According to one further embodiment of the compound of formula I, R5 and R6 form C3-Ce-cy- cloalkyl (embodiment 6.4).
According to one further embodiment of the compound of formula I, R5 and R6 form 3- to 6- membered saturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of O and S. According to one further embodiment of the compound of formula I, R5 and R6 form together a (=0) group (embodiment 6.5).
Prefferred embodiments of R5, R6 according to the invention are in Table P5 below, wherein each line of lines P5-1 to P5-19 corresponds to one particular embodiment of the invention, wherein P5-1 to P5-19 are also in any combination with one another a preferred embodiment of the present invention. The connection point to the carbon atom, to which R5 and R6 is bound is marked with “#” in the drawings.
Table P5,6:
Figure imgf000016_0001
Figure imgf000016_0002
According to one embodiment of the compound of formula I, R7 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-haloal- kenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R7a; where each R7a is independently halogen, CN, Ci-Ce-alkyl, Ci- Ce-haloalkyl or O-Ci-Ce-alkyl.
According to one embodiment of the compound of formula I, R7 is in each case independently selected from Ci-Ce-alkyl (embodiment 7.1), Ci-Ce-halogenalkyl (embodiment 7.2), Ci-Ce-alkyl- O-Ci-Ce-alkyl (embodiment 7.3), phenyl, CH2-phenyl (embodiment 7.4), wherein phenyl and CF phenyl is unsubstituted or substituted by one or two halogen.
According to one further embodiment of the compound of formula I, R7 is CH3 or CF3.
According to one further embodiment of the compound of formula I, R7 is CH3.
According to one further embodiment of the compound of formula I, R7 is CH2CH3, CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, CH2-CH(CH3)2, CH2-C(CH3)3, CH2-O-CH3, CH=CH2, CH2CH=CH2.
According to one further embodiment of the compound of formula I, R7 is phenyl, 2-F-phenyl, 4- F-phenyl, 2,4-F2-phenyl, 2-CI-phenyl, 4-CI-phenyl, CH2-phenyl, CH2-2-F-phenyl, CH2-4-F-phe- nyl.
According to one embodiment of the compound of formula I, R8 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-haloal- kenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CF^heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R8a; where each R8a is independently halogen, CN, Ci-Ce-alkyl, Ci- Ce-haloalkyl or O-Ci-Ce-alkyl.
According to one embodiment of the compound of formula I, R8 is in each case independently selected from Ci-Ce-alkyl (embodiment 8.1), Ci-Ce-alkyl-O-phenyl (embodiment 8.2), Ci-Ce-al- kyl-O-Ci-Ce-alkyl (embodiment 8.3).
According to one further embodiment of the compound of formula I, R8 is CH2CH3, CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, CH2-CH(CH3)2, CH2-C(CH3)3, CH2-CH(CH3)-C(CH3)3, CH2-CH2- C(CH3)3, CH2-O-CH3, CH2-O-(CH3)3, CH2-O-phenyl CH=CH2, CH2CH=CH2, CH2-phenyl.
According to one further embodiment of the compound of formula I, R7 and R8 form together with the C atoms to which they are bound a C3-C6-cycloalkyl or a a 3 - to 6-membered saturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of O and S, wherein the cycloalkyl or heterocycle can be unsubsituted or substitued by halogene, Ci-Ce- alkyl, Ci-Ce-halogenalkyl.
According to one further embodiment of the compound of formula I, R7 and R8 form C3-Ce-cy- cloalkyl (embodiment 8.4). According to one further embodiment of the compound of formula I, R7 and R8 form 3- to 6- membered saturated heterocycle which contains 1 , 2 or 3 heteroatoms from the group consisting of O and S.
According to one further embodiment of the compound of formula I, R7 and R8 form together a (=0) group (embodiment 8.5).
Prefferred embodiments of R7, R8 according to the invention are in Table P78 below, wherein each line of lines P7-1 to P7-19 corresponds to one particular embodiment of the invention, wherein P7-1 to P7-19 are also in any combination with one another a preferred embodiment of the present invention. The connection point to the carbon atom, to which R7 and R8 is bound is marked with “#” in the drawings.
Table P7,8:
Figure imgf000018_0001
Figure imgf000018_0002
Figure imgf000019_0001
According to one further embodiment of the compound of formula I,
R9 is in each case independently selected from CN, CH2CN, CH(CH3)CN, CH(=O), -C(=O)Ci- Ce-alkyl, -C(=O)C2-C6-alkenyl, -C(=O)C2-C6-alkynyl, -C(=O)C3-C6-cycloalkyl, -C(=O)- N(H)Ci-C4-alkyl, -C(=O)-N(Ci-C4-alkyl)2, Ci-Ce-alkyl, Ci-Ce-alkoxy, Ci-C4-haloalkyl, C3- Ce- cycloalkyl, Cs-Ce-halocycloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2- Ce-haloalkynyl, -S(=O)2-R9a, five- or six-membered heteroaryl, aryl or benzyl; wherein heteroaryl contains 1 , 2 or 3 heteroatoms selected from N, O and S as ring members; wherein aryl and the phenyl ring in benzyl are unsubstituted or carry 1 , 2, 3, 4 or 5 substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, C1- C4-alkoxy and Ci-C4-haloalkoxy; wherein the phenyl ring in benzyl is unsubstituted or carries 1 , 2 or 3 substituents selected from the group consisting of CN and halogen; wherein
R9a is Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl or benzyl, where the phenyl ring in the two last-mentioned radicals is unsubstituted or carries 1 , 2 or 3 substituents each independently selected from the group consisting of halogen, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl and C2-Ce-haloalkynyl.
According to still another embodiment of formula I, R9 is Cl, F.
According to still another embodiment of formula I, R9 is CN, CH2CN or CH(CH3)CN.
According to a further specific embodiment of formula I, R9 is CH(=O).
According to a further specific embodiment of formula I, R9 is OCH3 or OCH2CH3.
According to a further specific embodiment of formula I, R9 is C(=O)Ci-Ce-alkyl, wherein alkyl is CH3, C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
According to a further specific embodiment of formula I, R9 is C(=O)C2-Ce-alkenyl, wherein alkenyl is CH=CH2, CH2CH=CH2. According to a further specific embodiment of formula I, R9 is C(=O)C2-C6-alkynyl, wherein al- kynyl is CHCH, CH2CHCH.
According to a further specific embodiment of formula I, R9 is C(=O)C3-C6-cycloalkyl, wherein cycloalkyl is cyclopropyl (C3H7) or cyclobutyl (C4H9).
According to a further specific embodiment of formula I, R9 is C(=O)NH-Ci-C4-alkyl or C(=O)N- (Ci-C4-alkyl)2, wherein alkyl is CH3, C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl,
According to still another embodiment of formula I, R9 is Ci-Ce-alkyl, such as CH3, C2H5, n-pro- pyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
According to still another embodiment of formula I, R9 is Ci-Ce-alkyl, in particular Ci-C4-alkyl, such as CH3, C2H5, n-propyl, i-propyl.
According to still another embodiment of formula I, R9 is Ci-Ce-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF3, CCI3, FCH2, CICH2, F2CH, CI2CH, CF3CH2, CCI3CH2 or CF2CHF2.
According to still another embodiment of formula I R9 is Cs-Ce-cycloalkyl, in particular cyclopropyl.
According to still another embodiment of formula I, R9 is Cs-Ce-halogencycloalkyl. In a special embodiment R9b is fully or partially halogenated cyclopropyl, such as 1-F-cyclopropyl, 1-CI- cyclopropyl, 1 ,1-F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl .
According to still a further embodiment of formula I, R9 is C2-Ce-alkenyl, in particular C2-C4-alk- enyl, such as CH=CH2, C(CH3)=CH2, CH2CH=CH2.
According to a further specific embodiment of formula I, R9 is C2-C6-halogenalkenyl, in particular C2-C4-halogenalkenyl, more specifically C2-C3-halogenalkenyl such as CH=CHF, CH=CHCI, CH=CF2, CH=CCI2, CH2CH=CHF, CH2CH=CHCI, CH2CH=CF2, CH2CH=CCI2, CF2CH=CF2, CCI2CH=CCI2, CF2CF=CF2, CCI2CCI=CCI2.
According to still a further embodiment of formula I, R9 is C2-Ce-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as CHCH, CH2CHCH.
According to still a further embodiment of formula I, R9 is -S(=O)2-R9a, wherein R9a is preferably Ci-Ce-alkyl, in particular Ci-C4-alkyl, such as CH3, C2H5, n-propyl, i-propyl.
According to still another embodiment of formula I, R9 is aryl, in particular phenyl, wherein the aryl or phenyl moiety in each case is unsubstituted or substituted by identical or different groups R9b which independently of one another are selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl and Ci-C2-halogenalkoxy, in particular F, Cl, Br, CH3, OCH3, CF3 and OCF3. According to one embodiment, R9 is unsubstituted phenyl. According to another embodiment, R9 is phenyl, that is substituted by one, two or three, in particular one, halogen, in particular selected from F, Cl and Br, more specifically selected from F and Cl. According to still another embodiment of formula I, R9 is a 5-membered heteroaryl such as pyr- rol-1-yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1-yl, pyrazol- 3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2- yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1 ,2,4-triazolyl-1-yl, 1 ,2,4-triazol-3-yl 1 ,2,4-triazol-5-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl and 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-thia- diazol-5-yl.
According to still another embodiment of formula I, R9 is a 6-membered heteroaryl such as pyri- din-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, py- rimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
According to still another embodiment of formula I, R9 is in each case independently selected from H, halogen, OH, CN, Ci-Ce-alkyl, Ci-Ce-halogenalkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce- alkoxy, Ci-Ce-halogenalkoxy, C3-Ce-alkenyloxy, C3-Ce-alkynyloxy and Cs-Ce-cycloalkyl wherein the acyclic moieties of R9 are unsubstituted or substituted with identical or different groups R9a as defined and preferably defined herein, and wherein the carbocyclic, phenyl and heteroaryl moieties of R9 are unsubstituted or substituted with identical or different groups R9b as defined and preferably defined herein.
Particularly preferred embodiments of R9 according to the invention are in Table P9 below, wherein each line of lines P9-1 to P9-31 corresponds to one particular embodiment of the invention, wherein P9-1 to P9-31 are also in any combination with one another a preferred embodiment of the present invention. The connection point to the carbon atom, to which R9 is bound is marked with “#” in the drawings.
Table P9:
Figure imgf000021_0001
Figure imgf000021_0002
Figure imgf000022_0001
According to one embodiment of the compound of formula I, X is in each case independently selected from halogen (embodiment X.1), CN, Ci-Ce-alkyl (embodiment X.2), Ci-Ce-halogen- alkyl (embodiment X.3), O-Ci-Ce-alkyl (embodiment X.4), O-Ci-Ce-halogenalkyl (embodiment X.5).
According to one embodiment of the compound of formula I, X is in each case independently selected from halogen, O-Ci-Ce-alkyl.
According to one embodiment of the compound of formula I, X is in each case independently selected from F or Cl.
According to one embodiment of the compound of formula I, X is Cs-Ce-cycloalkyl.
According to one embodiment of the compound of formula I, n is 0.
According to one embodiment of the compound of formula I, n is 1.
According to one embodiment of the compound of formula I, n is 2.
According to one embodiment Xn is as defined below:
Figure imgf000023_0001
and X is selected from F, Cl, I, CH3, cyclopropyl, CH=CH2, C-CH, OCH3, OCHF2, CF3, CHF2, CH2CH3, CN.
According to one embodiment Xn is as defined below:
Figure imgf000023_0002
According to one embodiment Xn is as defined below:
Figure imgf000024_0001
and X is selected from F, Cl, I, CH3, cyclopropyl, CH=CH2, C-CH, OCH3, OCHF2, CF3, CHF2, CH2CH3, CN.
According to one embodiment Xn is as defined below:
Figure imgf000024_0002
and X is F.
According to one embodiment n is 0.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, which represent preferred combinations of embodiments that are defined above for each of the variables R2, R3 and X (represented by embodiments X.1 to X.6), n in compounds of formula I as defined below.
Figure imgf000024_0003
Table E:
Figure imgf000024_0004
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table
E, wherein R5 is represented by embodiment 5.1 and R6 is represented by embodiment 6.1.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 is represented by embodiment 5.2 and R6 is represented by embodiment 6.1. In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 is represented by embodiment 5.3 and R6 is represented by embodiment 6.1.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 is represented by embodiment 5.4 and R6 is represented by embodiment 6.1.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 is represented by embodiment 5.1 and R6 is represented by embodiment 6.2. In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 is represented by embodiment 5.2 and R6 is represented by embodiment 6.2.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 is represented by embodiment 5.3 and R6 is represented by embodiment 6.2.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 is represented by embodiment 5.4 and R6 is represented by embodiment 6.2.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 is represented by embodiment 5.1 and R6 is represented by embodiment 6.3.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 is represented by embodiment 5.2 and R6 is represented by embodiment 6.3.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 is represented by embodiment 5.3 and R6 is represented by embodiment 6.3.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 is represented by embodiment 5.4 and R6 is represented by embodiment 6.3.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 and R6 arerepresented by embodiment 6.4.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R5 and R6 arerepresented by embodiment 6.5.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.1 and R8 is represented by embodiment 8.1.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.2 and R8 is represented by embodiment 8.1.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.3 and R8 is represented by embodiment 8.1.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.4 and R8 is represented by embodiment 8.1.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.1 and R8 is represented by embodiment 8.2.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.2 and R8 is represented by embodiment 8.2.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.3 and R8 is represented by embodiment 8.2.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.4 and R8 is represented by embodiment 8.2.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.1 and R8 is represented by embodiment 8.3.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.2 and R8 is represented by embodiment 8.3.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.3 and R8 is represented by embodiment 8.3.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 is represented by embodiment 7.4 and R8 is represented by embodiment 8.3. In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 and R8 arerepresented by embodiment 8.4.
In further aspects the present invention relates to the embodiments E.1 to E.275 listed in Table E, wherein R7 and R8 arerepresented by embodiment 8.7. In particular with a view to their use, according to one embodiment, preference is given to the compounds of the compounds LA-1 , I.A-2, I.A-3, I.A-4, I.A-5, I.A-6, I.A-7, I.A-8; that are compiled in the Tables 1a to 12a. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
Figure imgf000035_0001
Table 1a Compounds of the formula LA-1, LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, I.A-8 in which R9 is CH3 and the meaning for the combination of X1 , X2, R5, R6 R7 and R8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.1a.B-1 to I.A- 1.1a.B-784, I.A-2.1a.B-1 to LA-2.1 a. B-784, I.A-3.1a.B-1 to LA-3.1a. B-784, I.A-4.1a.B-1 to I.A-
4.1a. B-784, I.A-5.1a.B-1 to LA-5.1a. B-784, I.A-6.1a.B-1 to LA-6.1a. B-784, I.A-7.1a.B-1 to I.A- 7.1a. B-784, I.A-8.1a.B-1 to LA-8.1a. B-784).
Table 2a Compounds of the formula LA-1, LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which
R9 is CH2CH3 and the meaning for the combination of X1 , X2, R5, R6 R7 and R8 for each individ- ual compound corresponds in each case to one line of Table B (compounds I.A-1.2a.B-1 to I.A-
1.2a. B-784, I.A-2.2a.B-1 to I.A-2.2a.B-784, I.A-3.2a.B-1 to I.A-3.2a.B-784, I.A-4.2a.B-1 to LA- 4.2a.B-784, I.A-5.2a.B-1 to I.A-5.2a.B-784, I.A-6.2a.B-1 to I.A-6.2a.B-784, I.A-7.2a.B-1 to I.A- 7.2a.B-784, I.A-8.2a.B-1 to I.A-8.2a.B-784).
Table 3a Compounds of the formula LA-1, LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, I.A-8 in which R9 is CH2CH2CH3 and the meaning for the combination of X1, X2, R5, R6 R7 and R8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.3a.B-1 to I.A-1.3a.B-784, I.A-2.3a.B-1 to I.A-2.3a.B-784, I.A-3.3a.B-1 to I.A-3.3a.B-784, I.A-4.3a.B-1 to I.A-4.3a.B-784, I.A-5.3a.B-1 to I.A-5.3a.B-784, I.A-6.3a.B-1 to I.A-6.3a.B-784, I.A-7.3a.B-1 to I.A-7.3a.B-784, I.A-8.3a.B-1 to I.A-8.3a.B-784)
Table 4a Compounds of the formula LA-1, LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R9 is CN and the meaning for the combination of X1, X2, R5, R6 R7 and R8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.4a.B-1 to I.A- 1.4a.B-784, I.A-2.4a.B-1 to I.A-2.4a.B-784, I.A-3.4a.B-1 to I.A-3.4a.B-784, I.A-4.4a.B-1 to I.A- 4.4a.B-784, I.A-5.4a.B-1 to I.A-5.4a.B-784, I.A-6.4a.B-1 to I.A-6.4a.B-784, I.A-7.4a.B-1 to I.A- 7.4a.B-784, I.A-8.4a.B-1 to I.A-8.4a.B-784).
Table 5a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R9 is CH2CN and the meaning for the combination of X1 , X2, R5, R6 R7 and R8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.5a.B-1 to I.A- 1.5a.B-784, I.A-2.5a.B-1 to I.A-2.5a.B-784, I.A-3.5a.B-1 to I.A-3.5a.B-784, I.A-4.5a.B-1 to I.A- 4.5a.B-784, I.A-5.5a.B-1 to I.A-5.5a.B-784, I.A-6.5a.B-1 to I.A-6.5a.B-784, I.A-7.1a.B-1 to I.A- 7.5a.B-784, I.A-8.5a.B-1 to I.A-8.5a.B-784)
Table 6a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R9 is CHO and the meaning for the combination of X1 , X2, R5, R6 R7 and R8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.6a.B-1 to I.A- 1.6a.B-784, I.A-2.6a.B-1 to I.A-2.6a.B-784, I.A-3.6a.B-1 to I.A-3.6a.B-784, I.A-4.6a.B-1 to I.A- 4.6a.B-784, I.A-5.6a.B-1 to I.A-5.6a.B-784, I.A-6.6a.B-1 to I.A-6.6a.B-784, I.A-7.6a.B-1 to I.A- 7.6a.B-784, LA-8.1 '6a.B-1 to I.A-8.6a.B-784)
Table 7a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R9 is C(CH3)3 and the meaning for the combination of X1, X2, R5, R6 R7 and R8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.7a.B-1 to I.A- 1.7a.B-784, I.A-2.7a.B-1 to I.A-2.7a.B-784, I.A-3.7a.B-1 to I.A-3.7a.B-784, I.A-4.7a.B-1 to I.A- 5.7a.B-784, I.A-5.7a.B-1 to I.A-5.7a.B-784, I.A-6.7a.B-1 to I.A-6.7a.B-784, I.A-7.7a.B-1 to I.A- 7.7a.B-784, I.A-8.7a.B-1 to I.A-8.7a.B-784)
Table 8a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R9 is COCH3 and the meaning for the combination of X1 , X2, R5, R6 R7 and R8 for each individual compound corresponds in each case to one line of Table B (compounds I.A-1.8a.B-1 to I.A- 1.8a.B-784, I.A-2.8a.B-1 to I.A-2.8a.B-784, I.A-3.8a.B-1 to I.A-3.8a.B-784, I.A-4.8a.B-1 to LA- 5.8a. B-784, I.A-5.8a.B-1 to I.A-5.8a.B-784, I.A-6.8a.B-1 to I.A-6.8a.B-784, I.A-7.8a.B-1 to I.A- 7.8a. B-784, I.A-8.8a.B-1 to I.A-8.8a.B-784)
Table 9a Compounds of the formula LA-1, LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, I.A-8 in which R9 is CH2C(CH3)3 and the meaning for the combination of X1 , X2, R5, R6 R7 and R8 for each individual compound corresponds in each case to one line of Table B (compounds LA-1.9a. B-1 to LA-1.9a. B-784, I.A-2.9a.B-1 to I.A-2.9a.B-784, I.A-3.9a.B-1 to I.A-3.9a.B-784, I.A-4.9a.B-1 to LA-5.9a. B-784, I.A-5.9a.B-1 to I.A-5.9a.B-784, I.A-6.9a.B-1 to I.A-6.9a.B-784, I.A-7.9a.B-1 to LA-7.9a. B-784, I.A-8.9a.B-1 to I.A-8.9a.B-784)
Table 10a Compounds of the formula LA-1, LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R9 is CH2CH=CH2 and the meaning for the combination of X1, X2, R5, R6 R7 and R8 for each individual compound corresponds in each case to one line of Table B (compounds LA-1.10a. B-1 to LA-1.10a. B-784, LA-2.10a.B-1 to I.A-2.10a.B-784, LA-3.10a.B-1 to I.A-3.10a.B-784, I.A- 4.10a. B-1 to LA-5.10a. B-784, LA-5.10a.B-1 to LA-5.10a. B-784, LA-6.10a.B-1 to I.A-6.10a.B- 784, LA-7.10a.B-1 to LA-7.10a. B-784, LA-8.10a.B-1 to LA-8.10a. B-784)
Table 11a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R9 is CH2CCH and the meaning for the combination of X1, X2, R5, R6 R7 and R8 for each individual compound corresponds in each case to one line of Table B (compounds LA-1.11a. B-1 to LA-1.11 a. B-784, LA-2.11a.B-1 to LA-2.11a.B-784, LA-3.11a.B-1 to LA-3.11a.B-784, LA- 4.11a.B-1 to LA-5.11a. B-784, LA-5.11a.B-1 to LA-5.11a. B-784, LA-6.11a.B-1 to LA-6.11a.B- 784, LA-7.11a.B-1 to LA-7.11a. B-784, LA-8.11a.B-1 to LA-8.11a. B-784)
Table 12a Compounds of the formula LA-1 , LA-2, LA-3, LA-4, LA-5, LA-6, LA-7, LA-8 in which R9 is CH2CeH5 and the meaning for the combination of X1 , X2, R5, R6 R7 and R8 for each individual compound corresponds in each case to one line of Table B (compounds LA-1.12a. B-1 to LA-1.12a. B-784, LA-2.12a.B-1 to LA-2.12a. B-784, LA-3.12a.B-1 to LA-3.12a. B-784, I.A-
4.12a. B-1 to LA-5.12a. B-784, LA-5.12a.B-1 to LA-5.12a. B-784, LA-6.12a.B-1 to I.A-6.12a.B- 784, LA-7.1a. B-1 to LA-7.12a. B-784, LA-8.12a.B-1 to LA-8.12a. B-7842)
Table B
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Compounds of the present invention can be made as shown in the following schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula I. The compounds of the formula I can be prepared according to methods or in analogy to methods that are described in the prior art. The synthesis takes advantage of starting materials that are commercially available or may be prepared according to conventional procedures starting from readily available compounds.
For example, compounds I can be prepared via alkylation or acylation of benzodiazepines represented by the formula (2) with a range of alkyl halides and acyl chlorides, which can be ef- fected by deprotonation of the benzodiazepines (2) with a range of organic or inorganic bases, such as potassium tert-butoxide or sodium hydride. The reaction is preferentially performed at 0 °C to room temperature, with in some cases sluggish reactions being carried out at temperatures up to 60 °C, and using 1-5 equivalents of base and 1-3 equivalents of alkylating/acylating reagent, as described in Chem. Eur. J. (2016), 22, 10607-10613, CN114349714 A, W02008/118141 A2, or US2012/184732 A1.
Figure imgf000068_0001
The benzodiazepine compounds represented by the formula (2) can be prepared by reacting a range of diamines (or HCI salts thereof) represented by the formula (4) with pyridyl/pyrazidyl aryl ketones (3) substituted with at least 1 halogen (represented by X1, preferentially F) in the presence of a base. The reaction is preferentially performed from rt to 120 °C, with 1-6 equivalents of base and 1 to 1.5 equivalents of diamine, analogous to a method described in
WO2016/87370 A1, Org. Biomol. Chem. (2014), 12, 6895-6900, WO2006/44753 A2 or Heterocycles (1994), 38, 125-134.
Figure imgf000068_0002
Aryl ketones (3) are either commercially available, or can be prepared by scheme by oxidation of the aryl alcohol 5, using for example manganese dioxide, as described in Inorganica Chimica Acta (2012), 382, 72- 78, WO 2000/038618, CN 107879989 A, or Chinese Science Bulletin 2010, 55(25), 2817-2819.
Figure imgf000068_0003
Aryl alcohols (5) can be prepared by by isopropyl magnesium chloride-mediated bromine/io- dine-magnesium exchange of 7, and subsequent addition to commercially available aldehydes represented by the general formula (6). The reaction is preferentially carried out at 0 °C, with an equimolar ratio of iPrMgCI and aryl halides (7), the intermediate of which is employed in a ratio of 1.2-1.3:1 with respect to aldehydes (6), as described in WO2021/71821 A1 , J. Med. Chem., (2013), 56, 10158-10170, WO2014/102233 A1 , or US2016/83401 A1.
Figure imgf000069_0001
Alternatively, the scaffold represented by formula (2) may also be accessed by reacting aryl ketones (3) with partially protected diamines (8) in the presence of organic or inorganic bases at temperatures up to 200 °C under microwave irradiation, as described in US2006/178386 A1 , Bioorganic & Medicinal Chemistry Letters (2021), 35,127813, Chem. Sci. (2021), 12, 4519- 4525, or J. Org. Chem. (2005), 70, 8924-8931. The resulting product 9 may then be further reacted at 0 °C in a 1.5:7 mixture of TFA:DCM to lead to the condensated product represented by formula 2, as described in US2006/3995, J. Bioorg. Med. Chem. Lett. (2007), 17, 2527-2530, W02022/99011 A1, Org Lett. (2012), 14, 5916-5919, or J. Med. Chem. (2016), 59, 10661-
10675. Alkylation/acylation as to obtain the compounds I can then be carried out as described above.
Figure imgf000069_0002
The compounds I and the compositions thereof, respectively, are suitable as fungicides effective against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, in particular from the classes of Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridi- omycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (syn. Fungi im- perfecti). They can be used in crop protection as foliar fungicides, fungicides for seed dressing, and soil fungicides.
The compounds I and the compositions thereof are preferably useful in the control of phytopath- ogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats, or rice; beet, e. g. sugar beet or fodder beet; fruits, e. g. pomes (apples, pears, etc.), stone fruits (e.g. plums, peaches, almonds, cherries), or soft fruits, also called berries (strawberries, raspberries, blackberries, gooseberries, etc.); leguminous plants, e. g. lentils, peas, alfalfa, or soybeans; oil plants, e. g. oilseed rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts, or soybeans; cucurbits, e. g. squashes, cucumber, or melons; fiber plants, e. g. cotton, flax, hemp, or jute; citrus fruits, e. g. oranges, lemons, grapefruits, or mandarins; vegetables, e. g. spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits, or paprika; lauraceous plants, e. g. avocados, cinnamon, or camphor; energy and raw material plants, e. g. corn, soybean, oilseed rape, sugar cane, or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants; or ornamental and forestry plants, e. g. flowers, shrubs, broad-leaved trees, or evergreens (conifers, eucalypts, etc.); on the plant propagation material, such as seeds; and on the crop material of these plants.
More preferably, compounds I and compositions thereof, respectively are used for controlling fungi on field crops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, oilseed rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant, such as seeds; and vegetative plant materials, such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants; including seedlings and young plants to be transplanted after germination or after emergence from soil.
Preferably, treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
According to the invention all of the above cultivated plants are understood to comprise all species, subspecies, variants, varieties and/or hybrids which belong to the respective cultivated plants, including but not limited to winter and spring varieties, in particular in cereals such as wheat and barley, as well as oilseed rape, e.g. winter wheat, spring wheat, winter barley etc.
Corn is also known as Indian corn or maize (Zea mays) which comprises all kinds of corn such as field corn and sweet corn. According to the invention all maize or corn subspecies and/or varieties are comprised, in particular flour corn (Zea mays var. amylacea), popcorn (Zea mays var. evert a), dent corn (Zea mays var. indentata), flint corn (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy corn (Zea mays var. ceratina), amylomaize (high amylose Zea mays varieties), pod corn or wild maize (Zea mays var. t unicat a) and striped maize (Zea mays var. japonica).
Most soybean cultivars are classifiable into indeterminate and determinate growth habit, whereas Glycine soja, the wild progenitor of soybean, is indeterminate (PNAS 2010, 107 (19) 8563-856). The indeterminate growth habit (Maturity Group, MG 00 to MG 4.9) is characterized by a continuation of vegetative growth after flowering begins whereas determinate soybean varieties (MG 5 to MG 8) characteristically have finished most of their vegetative growth when flowering begins. According to the invention all soybean cultivars or varieties are comprised, in particular indeterminate and determinate cultivars or varieties.
The term "cultivated plants" is to be understood as including plants which have been modified by mutagenesis or genetic engineering to provide a new trait to a plant or to modify an already present trait. Mutagenesis includes random mutagenesis using X-rays or mutagenic chemicals, but also targeted mutagenesis to create mutations at a specific locus of a plant genome. Targeted mutagenesis frequently uses oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases. Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant to add a trait or improve or modify a trait. These integrated genes are also referred to as transgenes, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, wich differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
Herbicide tolerance has been created by using mutagenesis and genetic engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by mutagenesis and breeding are e.g. available under the name Clearfield®. Herbicide tolerance to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitors and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione, has been created via the use of transgenes.
Transgenes to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601 , gat4621 , goxv247; for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 , aad-12; for tolerance to dicamba: dmo; for tolerance to oxynil herbicies: bxn; for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA; for tolerance to ALS inhibitors: csr1-2; and for tolerance to HPPD inhibitors: hppdPF, W336, avhppd-03.
Transgenic corn events comprising herbicide tolerance genes include, but are not limited to, DAS40278, MON801 , MON802, MON809, MON810, MON832, MON87411 , MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHGOJG, HCEM485, VCO-01981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275. Transgenic soybean events comprising herbicide tolerance genes include, but are not limited to, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127. Transgenic cotton events comprising herbicide tolerance genes include, but are not limited to, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40. Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1 , MS8, PHY14, PHY23, PHY35, PHY36, RF1 , RF2 and RF3.
Transgenes to provide insect resistance preferably are toxin genes of Bacillus spp. and synthetic variants thereof, like cry1A, crylAb, cry1Ab-Ac, crylAc, cry1A.1O5, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1 , cry34Ab1 , cry35Ab1 , cry9C, vip3A(a), vip3Aa20. In addition, transgenes of plant origin, such as genes coding for protease inhibitors, like CpTI and pinll, can be used. A further approach uses transgenes such as dvsnf7 to produce double-stranded RNA in plants.
Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA include, but are not limited to, Bt10, Bt11 , Bt176, MON801 , MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351 , MIR162, DBT418 and MZIR098. Transgenic soybean events comprising genes for insecticidal proteins include, but are not limited to, MON87701 , MON87751 and DAS-81419. Transgenic cotton events comprising genes for insecticidal proteins include, but are not limited to, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Eventl, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281- 24-236, 3006-210-23, GHB119 and SGK321.
Cultivated plants with increased yield have been created by using the transgene athb17 (e.g. corn event MON87403), or bbx32 (e.g. soybean event MON87712).
Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A (e.g. soybean events 260-05, MON87705 and MON87769).
Tolerance to abiotic conditions, such as drought, has been created by using the transgene cspB (corn event MON87460) and Hahb-4 (soybean event IND-00410-5).
Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process resulting in a cultivated plant with stacked traits. Preferred combinations of traits are combinations of herbicide tolerance traits to different groups of herbicides, combinations of insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, combinations of herbicide tolerance with one or several types of insect resistance, combinations of herbicide tolerance with increased yield as well as combinations of herbicide tolerance and tolerance to abiotic conditions.
Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art. For example, detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations “International Service for the Acquisition of Agri-biotech Applications (ISAAA)” (http://www.isaaa.org/gmapprovaldatabase) and the “Center for Environmental Risk Assessment (CERA)” (http://cera-gmc.org/GMCropDatabase). Further information on specific events and methods to detect them can be found for canola events MS1 , MS8, RF3, GT73, MON88302, KK179 in WG01/031042, WG01/041558, WG01/041558, WG02/036831 , WO1 1/153186, WO13/003558; for cotton events MON 1445, MON 15985, MON531 (MON15985), LLCotton25, MON88913, COT102, 281-24-236, 3006-210-23, COT67B, GHB614, T304-40, GHB119, MON88701 , 81910 in WO02/034946, W002/100163, W002/100163, W003/013224, WO04/072235, WO04/039986, WO05/103266, WO05/103266, WO06/128573, W007/017186, W008/122406, W008/151780, WO12/134808, WO13/112527; for corn events GA21 , MON810, DLL25, TC1507, MON863, MIR604, LY038, MON88017, 3272, 59122, NK603, MIR162, MON89034, 98140, 32138, MON87460, 5307, 4114, MON87427, DAS40278, MON87411 , 33121 , MON87403, MON87419 in W098/044140, US02/102582, US03/126634, WO04/099447, W004/011601 , W005/103301 , W005/061720, W005/059103, WO06/098952, WO06/039376, US2007/292854, WO07/142840, WO07/140256,
WO08/112019, W009/103049, WO09/111263, W010/077816, WO11/084621 , WO11/062904, WO11/022469, WO13/169923, WO14/116854, WO15/053998, WO15/142571 ; for potato events E12, F10, J3, J55, V11 , X17, Y9 in WO14/178910, WO14/178913, WO14/178941 , WO1 4/179276, WO16/183445, WO17/062831 , WO17/062825; for rice events LLRICE06, LLRICE601 , LLRICE62 in WO00/026345, WO00/026356, WO00/026345; and for soybean events H7-1 , MON89788, A2704-12, A5547-127, DP305423, DP356043, MON87701 , MON87769, CV127, MON87705, DAS68416-4, MON87708, MON87712, SYHT0H2, DAS81419, DAS81419 X DAS44406-6, MON87751 in WO04/074492, W006/130436, WO06/108674, WO06/108675, WO08/054747, WG08/002872, WO09/064652, WO09/102873, WG10/080829, WG10/037016, WO11/066384, WO11/034704, WO12/051199, WO12/082548, WO13/016527, WO13/016516, WO14/201235.
The use of compounds I and compositions thereof, respectively, on cultivated plants may result in effects which are specific to a cultivated plant comprising a certain transgene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigour, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases:
Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis Alternaria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauci or A. porri), oilseed rape (A. brassicicola or brassicae), sugar beets (A. tenuis), fruits (e.g. A. grandis), rice, soybeans, potatoes and tomatoes (e. g. A. solani, A. grandis or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat (e.g. A. triticinay Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Aureobasidium zeae (syn. Kapatiella zeae) on corn; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (8. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. 8. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana'. grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages); 8. squamosa or 8. allii on onion family), oilseed rape, ornamentals (e.g. B eliptica), vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladobotryum (syn. Dactylium) spp. (e.g. C. mycophilum
(formerly Dactylium dendroides, teleomorph: Nectria albertinii, Nectria rosella syn. Hypomyces rosellus) on mushrooms; Cladosporium spp. on tomatoes (e. g. C. fulvunr. leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. ory- zae Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes'. black dot), beans (e. g. C. lindemuthianum), soybeans (e. g. C. truncatum or C. gloeosporioides), vegetables (e.g. C. lagenarium or C. capsici), fruits (e.g. C. acutatum), coffee (e.g. C. coffeanum or C. kahawae) and C. gloeosporioides on various crops; Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans, cotton and ornamentals; Cy- cloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. lirio- dendri, teleomorph: Neonectria liriodendrr. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyr- enophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis’. tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formiti- poria (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (formerly Phae- oacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa', Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta'. anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Ery- siphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, oilseed rape (e. g. E. cruciferarum)', Eutypa lata (Eu- typa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium') spp. on corn (e. g. E. turci- cum) Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguliforme ) and F. tucu- maniae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticil- lioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuror. Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals, potatoes and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdo- chium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructi- gena (syn. Monilia spp.: bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Zymoseptoria tritici formerly Septoria tritici: Septoria blotch) on wheat or M. fijiensis (syn. Pseudocercospora fijiensis’. black Sigatoka disease) and M. musicola on bananas, M. arachidicola (syn. M. arachidis or Cercospora arachidis), M. berkeleyi on peanuts, M. pisi on peas and M. brassiciola on brassicas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), oilseed rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica)-, Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. g reg ata'. stem rot); Phoma lingam (syn. Leptosphaeria biglobosa and L. maculans'. root and stem rot) on oilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off) on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn; Phomopsis spp. on sunflowers, vines (e. g. P. viticola'. can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorumy Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans’. late blight) and broad-leaved trees (e. g. P. ramorunr. sudden oak death); Plasmodiophora brassicae (club root) on cabbage, oilseed rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits (e. g. P. leucotricha on apples) and curcurbits (P. xanthiiy Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (syn. Oculimacula yallundae, O. acuformis'. eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudo- pezicula tracheiphila (red fire disease or .rotbrenner’, anamorph: Phialophora) on vines; Puc- cinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenopeziza spp., e.g. P. brassicae on oilseed rape; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea'. rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, oilseed rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum) and P. oligandrum on mushrooms; Ramularia spp., e. g. P. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley, P. areola (teleomorph: Myco- sphaerella areola) on cotton and P. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants, e. g. P. solani (root and stem rot) on soybeans, P. solani (sheath blight) on rice or P. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis and P. commune (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables (S. minor and S. sclerotiorum) and field crops, such as oilseed rape, sunflowers (e. g. S. sclerotiorum) and soybeans, S. rolfsii (syn. Athelia rolfsii) on soybeans, peanut, vegetables, corn, cereals and ornamentals; Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (syn. Zymoseptoria tritici, Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Se- tosphaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana, syn. Ustilago reiliana’. head smut), sorghum und sugar cane; Sphaerotheca fuliginea (syn. Podosphaera xanthir. powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleo- morph: Leptosphaeria [syn. Phaeosphaeria] nodorum, syn. Septoria nodorum) on wheat;
Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn.
Chalara elegans Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Trichoderma harzianum on mushrooms’, Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appen- diculatus, syn. U. phaseoli), sugar beets (e. g. U. betae or U. beticola) and on pulses (e.g. U. vignae, U. pisi, U. viciae-fabae and U. fabae)', Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis'. corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. . inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. . longisporum on oilseed rape, . dahliae on strawberries, oilseed rape, potatoes and tomatoes, and . fungicola on mushrooms; Zymoseptoria tritici on cereals.
The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases: rusts on soybean and cereals (e.g.
Phakopsora pachyrhizi and P. meibomiae on soy; Puccinia tritici and P. striiformis on wheat); molds on specialty crops, soybean, oil seed rape and sunflowers (e.g. Botrytis cinerea on strawberries and vines, Sclerotinia sclerotiorum, S. minor and S. rolfsii on oil seed rape, sunflowers and soybean); Fusarium diseases on cereals (e.g. Fusarium culmorum and F. graminearum on wheat); downy mildews on specialty crops (e.g. Plasmopara viticola on vines, Phytophthora in- festans on potatoes); powdery mildews on specialty crops and cereals (e.g. Uncinula necatoron vines, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals); and leaf spots on cereals, soybean and corn (e.g. Septoria tritici and S. nodorum on cereals, S. glycines on soybean, Cercospora spp. on corn and soybean).
According to one embodiment compounds I.A-1.1a.B-1 to I.A-1.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.1a.B-1 to I.A-2.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.1a.B-1 to I.A-3.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z. According to one embodiment compounds I.A-4.1a.B-1 to I.A-4.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.1a.B-1 to I.A-5.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.1a.B-1 to I.A-6.1a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.2a.B-1 to I.A-1.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.2a.B-1 to I.A-2.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.2a.B-1 to I.A-3.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.2a.B-1 to I.A-4.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.2a.B-1 to I.A-5.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.2a.B-1 to I.A-6.2a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.3a.B-1 to I.A-1.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.3a.B-1 to I.A-2.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.3a.B-1 to I.A-3.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.3a.B-1 to I.A-4.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.3a.B-1 to I.A-5.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.3a.B-1 to I.A-6.3a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.4a.B-1 to I.A-1.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z. According to one embodiment compounds I.A-2.4a.B-1 to I.A-2.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.4a.B-1 to I.A-3.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.4a.B-1 to I.A-4.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.4a.B-1 to I.A-5.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.4a.B-1 to I.A-6.4a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.5a.B-1 to I.A-1.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.5a.B-1 to I.A-2.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.5a.B-1 to I.A-3.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.5a.B-1 to I.A-4.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.5a.B-1 to I.A-5.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.5a.B-1 to I.A-6.5a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.6a.B-1 to I.A-1.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.6a.B-1 to I.A-2.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.6a.B-1 to I.A-3.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.6a.B-1 to I.A-4.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.6a.B-1 to I.A-5.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z. According to one embodiment compounds I.A-6.6a.B-1 to I.A-6.6a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-1.7a.B-1 to I.A-1.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-2.7a.B-1 to I.A-2.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-3.7a.B-1 to I.A-3.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-4.7a.B-1 to I.A-4.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-5.7a.B-1 to I.A-5.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds I.A-6.7a.B-1 to I.A-6.7a.B-180 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
According to one embodiment compounds Ex-1 to Ex-92 are particularly suitable for controlling the causal agents of plant diseases according to the list Z.
List Z:
Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis Alternaria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauci or A. porri), oilseed rape (A. brassicicola or brassicae), sugar beets (A. tenuis), fruits (e.g. A. grandis), rice, soybeans, potatoes and tomatoes (e. g. A. solani, A. grandis or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat (e.g. A. triticinay Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Aureobasidium zeae (syn. Kapatiella zeae) on corn; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. 8. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana'. grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages); 8. squamosa or 8. allii on onion family), oilseed rape, ornamentals (e.g. B eliptica), vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladobotryum (syn. Dactylium) spp. (e.g. C. mycophilum
(formerly Dactylium dendroides, teleomorph: Nectria albertinii, Nectria rosella syn. Hypomyces rosellus) on mushrooms; Cladosporium spp. on tomatoes (e. g. C. fulvunr. leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobo- lus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. ory- zae) Colletotrichum (teleomorph: Glomerella spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes'. black dot), beans (e. g. C. lindemuthianum), soybeans (e. g. C. truncatum or C. gloeosporioides), vegetables (e.g. C. lagenarium or C. capsici), fruits (e.g. C. acutatum), coffee (e.g. C. coffeanum or C. kahawae) and C. gloeosporioides on various crops; Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans, cotton and ornamentals; Cy- cloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. lirio- dendri, teleomorph: Neonectria liriodendrr. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyr- enophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis'. tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formiti- poria (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (formerly Phae- oacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa, Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta. anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Ery- siphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, oilseed rape (e. g. E. cruciferarum)-, Eutypa lata (Eu- typa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turci- cum) Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguliforme ) and F. tucu- maniae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticil- lioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuror. Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals, potatoes and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdo- chium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructi- gena (syn. Monilia spp.: bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Zymoseptoria tritici formerly Septoria triticr'. Septoria blotch) on wheat or M. fijiensis (syn. Pseudocercospora fijiensis'. black Sigatoka disease) and M. musicola on bananas, M. arachidicola (syn. M. arachidis or Cercospora arachidis), M. berkeleyi on peanuts, M. pisi on peas and M. brassiciola on brassicas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), oilseed rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. g reg ata'. stem rot); Phoma lingam (syn. Leptosphaeria biglobosa and L. maculans’. root and stem rot) on oilseed rape and cabbage, P. betae (root rot, leaf spot and damping-off) on sugar beets and P. zeae-maydis (syn. Phyllostica zeae) on corn; Phomopsis spp. on sunflowers, vines (e. g. P. viticola'. can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans'. late blight) and broad-leaved trees (e. g. P. ramorunr. sudden oak death); Plasmodiophora brassicae (club root) on cabbage, oilseed rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits (e. g. P. leucotricha on apples) and curcurbits (P. xanthii Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (syn. Oculimacula yallundae, O. acuformis'. eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudo- pezicula tracheiphila (red fire disease or .rotbrenner’, anamorph: Phialophora) on vines; Puc- cinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenopeziza spp., e.g. P. brassicae on oilseed rape; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea'. rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, oilseed rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum) and P. oligandrum on mushrooms; Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley, R. areola (teleomorph: Myco- sphaerella areola) on cotton and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis and R. commune (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables (S. minor and S. sclerotiorum) and field crops, such as oilseed rape, sunflowers (e. g. S. sclerotiorum) and soybeans, S. rolfsii (syn. Athelia rolfsii) on soybeans, peanut, vegetables, corn, cereals and ornamentals; Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (syn. Zymoseptoria tritici, Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Se- tosphaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana, syn. Ustilago reiliana'. head smut), sorghum und sugar cane; Sphaerotheca fuliginea (syn. Podosphaera xanthir. powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum, syn. Septoria nodorum) on wheat;
Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn.
Chalara elegans), Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Trichoderma harzianum on mushrooms’, Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appen- diculatus, syn. U. phaseoli), sugar beets (e. g. U. betae or U. beticola) and on pulses (e.g. U. vignae, U. pisi, U. viciae-fabae and U. fabae)', Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis'. corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. . inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. . longisporum on oilseed rape, . dahliae on strawberries, oilseed rape, potatoes and tomatoes, and . fungicola on mushrooms; Zymoseptoria tritici on cereals. The compounds I and compositions thereof, respectively, are also suitable for controlling harmful microorganisms in the protection of stored products or harvest, and in the protection of materials.
The term "stored products or harvest" is understood to denote natural substances of plant or animal origin and their processed forms for which long-term protection is desired. Stored products of plant origin, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment. Also falling under the definition of stored products is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood. Stored products of animal origin are hides, leather, furs, hairs and alike. Preferably, "stored products" is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms, where application of compounds I and compositions thereof can also prevent disadvantageous effects such as decay, discoloration or mold.
The term "protection of materials" is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper, paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber, or fabrics against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
The compounds I and compositions thereof, respectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material, and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other, such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves (“greening effect”)), quality (e. g. improved content or composition of certain ingredients), and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
The compounds I are employed as such or in form of compositions by treating the fungi, the plants, plant propagation materials, such as seeds; soil, surfaces, materials, or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds; soil, surfaces, materials or rooms by the fungi.
An agrochemical composition comprises a fungicidally effective amount of a compound I. The term "fungicidally effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of stored products or harvest or of materials and which does not result in a substantial damage to the treated plants, the treated stored products or harvest, or to the treated materials. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant, stored product, harvest or material, the climatic conditions and the specific compound I used.
Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials, such as seeds, e. g. by dusting, coating, or drenching, amounts of active substance of generally from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kg of plant propagation material (preferably seeds) are required.
The user applies the agrochemical composition usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready- to-use spray liquor are applied per hectare of agricultural useful area.
The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types (see also “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International) are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecticidal articles (e. g. LN), as well as gel formulations for the treatment of plant propagation materials, such as seeds (e. g. GF). The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or by Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers, and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e. g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, and alkylated naphthalenes; alcohols, e. g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol, glycols; DMSO; ketones, e. g. cyclohexanone; esters, e. g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e. g. /V-methyl pyrrolidone, fatty acid dimethyl amides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and of alkyl naphthalenes, sulfosuccinates, or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids, of oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, /V-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of /V-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters, or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters, or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinyl pyrrolidone, vinyl alcohols, or vinyl acetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide, and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.
Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e. g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives, such as alkylisothiazoli- nones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e. g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e. g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e. g. alizarin-, azo- and phthalocyanine colorants). Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
The agrochemical compositions generally comprise between 0.01 and 95 %, preferably between 0.1 and 90 %, more preferably between 1 and 70 %, and in particular between 10 and 60 %, by weight of active substances (e.g. at least one compound I). The agrochemical compositions generally comprise between 5 and 99.9 %, preferably between 10 and 99.9 %, more preferably between 30 and 99 %, and in particular between 40 and 90 %, by weight of at least one auxiliary. The active substances (e.g. compounds I) are employed in a purity of from 90 % to 100 %, preferably from 95-% to 100 % (according to NMR spectrum).
For the purposes of treatment of plant propagation materials, particularly seeds, solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60 % by weight, preferably from 0.1 to 40 %, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying compound I and compositions thereof, respectively, onto plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, soaking, as well as in-furrow application methods. Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating, and dusting.
Various types of oils, wetters, adjuvants, fertilizers, or micronutrients, and further pesticides (e. g. fungicides, growth regulators, herbicides, insecticides, safeners) may be added to the compounds I or the compositions thereof as premix, or, not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 : 100 to 100: 1 , preferably 1 : 10 to 10: 1.
A pesticide is generally a chemical or biological agent (such as pestidal active ingredient, compound, composition, virus, bacterium, antimicrobial, or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term “pesticide” includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
Biopesticides have been defined as a form of pesticides based on microorganisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, microbial and biochemical pesticides:
(1) Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classified as microbial pesticides, even though they are multi-cellular.
(2) Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mammals.
Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained (synergistic mixtures).
The following list of pesticides II, in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:
A) A) Respiration inhibitors
- Inhibitors of complex III at Q0 site: azoxystrobin (A.1.1), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), man- destrobin (A.1.10), metominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin
(A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methox- yimino-/V-methyl-acetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb/chlorodincarb (A.1.20), famoxadone (A.1.21), fenamidone (A.1.21), methyl-/V-[2-[(1 ,4-dimethyl-5-phenyl- pyrazol-3-yl)oxylmethyl]phenyl]-/V-methoxy-carbamate (A.1.22), metyltetraprole (A.1.25), (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-/V,3-dimethyl-pent-3-en- amide (A.1 .34), (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-/V,3-dimethyl- pent-3-enamide (A.1.35), pyriminostrobin (A.1.36), bifujunzhi (A.1.37), 2-(ortho-((2,5-dimeth- ylphenyl-oxymethylen)phenyl)-3-methoxy-acrylic acid methylester (A.1.38);
- inhibitors of complex III at Qi site: cyazofamid (A.2.1), amisulbrom (A.2.2), [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-di- oxo-1 , 5-dioxonan-7-yl] 2-methylpropanoate (A.2.3), fenpicoxamid (A.2.4), florylpicoxamid (A.2.5), metarylpicoxamid (A.2.6);
- inhibitors of complex II: benodanil (A.3.1), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.11), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.15), penthiopyrad (A.3.16), pydiflumetofen (A.3.17), pyra- ziflumid (A.3.18), sedaxane (A.3.19), tecloftalam (A.3.20), thifluzamide (A.3.21), inpyrfluxam (A.3.22), pyrapropoyne (A.3.23), fluindapyr (A.3.28), N-[2-[2-chloro-4-(trifluoromethyl)phe- noxy]phenyl]-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazole-4-carboxamide (A.3.29), methyl (E)-2-[2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3-methoxy-prop-2-enoate (A.3.30), isoflucypram (A.3.31 ), 2-(difluoromethyl)-/V-(1 , 1 ,3-trimethyl-indan-4-yl)pyridine-3-carbox- amide (A.3.32), 2-(difluoromethyl)-/V-[(3R)-1 , 1 ,3-trimethylindan-4-yl]pyridine-3-carboxamide (A.3.33), 2-(difluoromethyl)-/V-(3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide
(A.3.34), 2-(difluoromethyl)-/V-[(3R)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (A.3.35), 2-(difluoromethyl)-/V-(1 ,1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide (A.3.36), 2-(difluoromethyl)-/V-[(3R)-1 ,1-dimethyl-3-propyl-indan-4-yl]pyridine-3-carboxamide (A.3.37), 2-(difluoromethyl)-/V-(3-isobutyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.38), 2-(difluoromethyl)-/V-[(3R)-3-isobutyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carbox- amide (A.3.39) cyclobutrifluram (A.3.24);
- other respiration inhibitors: diflumetorim (A.4.1); nitrophenyl derivates: binapacryl (A.4.2), di- nobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone
(A.4.7); organometal compounds: fentin salts, e.g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.11); silthiofam (A.4.12);
B) Sterol biosynthesis inhibitors (SBI fungicides)
- C14 demethylase inhibitors: triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromucona- zole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), dinicona- zole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusi- lazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipcona- zole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobu- trazole (B.1.20), penconazole (B.1.21), propiconazole (B.1.22), prothioconazole (B.1.23), simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1.28), triticonazole (B.1.29), uniconazole (B.1.30), 2-(2,4-difluorophenyl)-1 ,1- difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-2-pyridyl]propan-2-ol (B.1 .31), 2-(2,4-difluorophenyl)-1 ,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(trifluoromethoxy)phenyl]-2- pyridyl]propan-2-ol (B.1.32), fluoxytioconazole (B.1.33), ipfentrifluconazole (B.1.37), mefen- trifluconazole (B.1 .38), (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1 ,2,4-tria- zol-1-yl)propan-2-ol, (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1 ,2,4-triazol-1- yl)propan-2-ol, 2-(chloromethyl)-2-methyl-5-(p-tolylmethyl)-1-(1 ,2,4-triazol-1-ylmethyl)cyclo- pentanol (B.1.43); imidazoles: imazalil (B.1.44), pefurazoate (B.1.45), prochloraz (B.1.46), triflumizol (B.1.47); pyrimidines, pyridines, piperazines: fenarimol (B.1.49), pyrifenox (B.1.50), triforine (B.1 .51), [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]- (3-pyridyl)methanol (B.1.52), 4-[[6-[2-(2,4-difluorophenyl)-1 , 1-difluoro-2-hydroxy-3-(1 ,2,4-tria- zol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (B.1.53), 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-
3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (B.1.54), 2-[6-(4-chlorophenoxy)-2-(trifluorome- thyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (B.1.55), methyl 2-[2-chloro-4-(4-chlorophe- noxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate (B.1.56), methyl 2-[2-chloro-4-(4- chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propanoic acid (B.1.57);
- Delta14-reductase inhibitors: aldimorph (B.2.1), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spi- roxamine (B.2.8);
- Inhibitors of 3-keto reductase: fenhexamid (B.3.1);
- Other Sterol biosynthesis inhibitors: chlorphenomizole (B.4.1);
C) Nucleic acid synthesis inhibitors
- phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);
- other nucleic acid synthesis inhibitors: hymexazole (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-
4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-fluoro- 2-(4-chlorophenylmethoxy)pyrimidin-4 amine (C.2.8);
D) Inhibitors of cell division and cytoskeleton
- tubulin inhibitors: benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (D1.3), thiabendazole (D.1.4), thiophanate-methyl (D.1.5), pyridachlometyl (D.1.6), /\/-ethyl-2-[(3-ethynyl-8-methyl- 6-quinolyl)oxy]butanamide (D.1.8), /\/-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methyl- sulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/\/-(2-fluoroethyl)butan- amide (D.1.10), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/\/-(2-fluoroethyl)-2-methoxy-acetam- ide (D.1.11), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/\/-propyl-butanamide (D.1.12), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methoxy-/\/-propyl-acetamide (D.1 .13), 2-[(3-ethynyl- 8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-/\/-propyl-acetamide (D.1.14), 2-[(3-ethynyl-8-meth- yl-6-quinolyl)oxy]-/V-(2-fluoroethyl)-2-methylsulfanyl-acetamide (D.1.15), 4-(2-bromo-4-fluoro- phenyl)-/V-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine (D.1.16);
- other cell division inhibitors: diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7), phenamac- ril (D.2.8);
E) Inhibitors of amino acid and protein synthesis
- methionine synthesis inhibitors: cyprodinil (E.1.1), mepanipyrim (E.1.2), pyrimethanil (E.1.3);
- protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydro- chloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6);
F) Signal transduction inhibitors
- MAP I histidine kinase inhibitors: fluoroimid (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fludioxonil (F.1.5);
- G protein inhibitors: quinoxyfen (F.2.1);
G) Lipid and membrane synthesis inhibitors
- Phospholipid biosynthesis inhibitors: edifenphos (G.1.1), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4);
- lipid peroxidation: dicloran (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7), zinc thiazole (G.2.8);
- phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7);
- compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1);
- inhibitors of oxysterol binding protein: oxathiapiprolin (G.5.1), fluoxapiprolin (G.5.3), 4-[1-[2-[3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]-/\/-tetralin-1-yl-pyridine- 2-carboxamide (G.5.4), 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]-A/-te- tralin-1-yl-pyridine-2-carboxamide (G.5.5), 4-[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyra- zol-1-yl]acetyl]-4-piperidyl]-/\/-tetralin-1-yl-pyridine-2-carboxamide (G.5.6), 4-[1-[2-[5-cyclo- propyl-3-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-/\/-tetralin-1-yl-pyridine-2-carbox- amide (G.5.7), 4-[1-[2-[5-methyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-/\/-tetralin- 1-yl-pyridine-2-carboxamide (G.5.8), 4-[1-[2-[5-(difluoromethyl)-3-(trifluoromethyl)pyrazol- 1-yl]acetyl]-4-piperidyl]-/\/-tetralin-1-yl-pyridine-2-carboxamide (G.5.9), 4-[1-[2-[3,5-bis(trifluo- romethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-/\/-tetralin-1-yl-pyridine-2-carboxamide (G.5.10), (4-[1 -[2-[5-cyclopropyl-3-(trifluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]-A/-tetralin-1 -yl-pyri- dine-2-carboxamide (G.5.11); H) Inhibitors with Multi Site Action
- inorganic active substances: Bordeaux mixture (H.1.1), copper (H.1.2), copper acetate (H.1.3), copper hydroxide (H.1.4), copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sulfur (H.1.7);
- thio- and dithiocarbamates: ferbam (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);
- organochlorine compounds: anilazine (H.3.1), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.11);
- guanidines and others: guanidine (H.4.1), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1/7,5/7-[1 ,4]di- thiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2/7,6/-/)-tetraone (H.4.10);
I) Cell wall synthesis inhibitors
- inhibitors of glucan synthesis: validamycin (1.1.1), polyoxin B (1.1.2);
- melanin synthesis inhibitors: pyroquilon (1.2.1), tricyclazole (1.2.2), carpropamid (1.2.3), dicyclomet (1.2.4), fenoxanil (1.2.5);
J) Plant defence inducers
- acibenzolar-S-methyl (J.1.1), probenazole (J.1.2), isotianil (J.1.3), tiadinil (J.1.4), prohexadi- one-calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), calcium phosphonate (J.1.11), potassium phosphonate (J.1.12), potassium or sodium bicarbonate (J.1.9), 4-cyclopropyl-/V-(2,4-dimethoxyphenyl)thiadiazole- 5-carboxamide (J.1.10);
K) Unknown mode of action
- bronopol (K.1.1), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclocymet (K.1.7), diclomezine (K.1.8), difenzoquat (K.1.9), difen- zoquat-methylsulfate (K.1.10), diphenylamin (K.1.11), fenitropan (K.1.12), fenpyrazamine (K.1.13), flumetover (K.1.14), flumetylsulforim (K.1.60), flusulfamide (K.1.15), flutianil
(K.1.16), harpin (K.1.17), methasulfocarb (K.1 .18), nitrapyrin (K.1.19), nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21), oxin-copper (K.1.22), proquinazid (K.1.23), seboctylamine (K.1.61), tebufloquin (K.1.24), tecloftalam (K.1.25), triazoxide (K.1.26), /\/-(4-(4-chloro-3-tri- fluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-/\/-ethyl-/\/-methyl formamidine (K.1.27), /\/-(4-(4- fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-/\/-ethyl-/\/-methyl formamidine (K.1.28), /V -[4-[[3-[(4-chlorophenyl)methyl]-1 ,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-/\/- ethyl-/V-methyl-formamidine (K.1 .29), /V’-(5-bromo-6-indan-2-yloxy-2-methyl-3-pyridyl)-/\/- ethyl-/V-methyl-formamidine (K.1 .30), /V’-[5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methyl-
3-pyridyl]-/V-ethyl-/V-methyl-formamidine (K.1.31), /V-[5-bromo-6-(4-isopropylcyclohexoxy)-2- methyl-3-pyridyl]-/V-ethyl-/V-methyl-formamidine (K.1 .32), /V’-[5-bromo-2-methyl-6-(1-phe- nylethoxy)-3-pyridyl]-/V-ethyl-/V-methyl-formamidine (K.1.33), /V -(2-methyl-5-trifluoromethyl-
4-(3-trimethylsilanyl-propoxy)-phenyl)-/V-ethyl-/V-methyl formamidine (K.1.34), /\/-(5-difluoro- methyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-/\/-ethyl-/\/-methyl formamidine
(K.1.35), 2-(4-chloro-phenyl)-/V-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy- acetamide (K.1.36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxa- zole) (K.1.37), 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (K.1.38), 5- chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1/7-benzoimidazole (K.1.39), ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41), pentyl /\/-[6- [[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.42), but-3-ynyl /V-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2- pyridyl]carbamate (K.1.43), ipflufenoquin (K.1.44), quinofumelin (K.1.47), benziothiazolinone (K.1.48), bromothalonil (K.1.49), 2-(6-benzyl-2-pyridyl)quinazoline (K.1.50), 2-[6-(3-fluoro- 4-methoxy-phenyl)-5-methyl-2-pyridyl]quinazoline (K.1.51), dichlobentiazox (K.1.52), /\/’-(2,5- dimethyl-4-phenoxy-phenyl)-/V-ethyl-/V-methyl-formamidine (K.1.53), aminopyrifen (K.1.54), fluopimomide (K.1.55), /V'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-/\/- ethyl-/V-methyl-formamidine (K.1 .56), /V-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phe- nyl]-/V-ethyl-/V-methyl-formamidine (K.1.57), flufenoxadiazam (K.1.58), /V-methyl-4-[5-(trifluo- romethyl)-1 ,2,4-oxadiazol-3-yl]benzenecarbothioamide (K.1 .59), /V-methoxy-/V-[[4-[5-(trifluo- romethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (K.1.60;
WO2018/177894, WO 2020/212513), /V-((4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phe- nyl)methyl)propanamide (K.1.62), 3,3,3-trifluoro-/V-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]propanamide (K.1.63), 3,3,3-trifluoro-/V-[[2-fluoro-4-[5-(trifluoro- methyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (K.1.64), A/-[2,3-difluoro-4-[5-(tri- fluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzyl]butanamide (K.1.65), /\/-[[2,3-difluoro-4-[5-(trifluoro- methyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3,3-trifluoro-propanamide (K.1.66), 1-methoxy- 1-methyl-3-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea (K.1.67), 1 ,1-di- ethyl-3-[[4-[5-[trifluoromethyl]-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea (K.1.68), A/, 2-d i- methoxy-/V-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (K.1.69), /V-ethyl-2-methyl-/V-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (K.1.70), 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]me- thyl]urea (K.1 .71), 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2- one (K.1.72), 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one (K.1.73), 4-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]morpholin-3-one (K.1.74), 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazoli- din-3-one (K.1.75), 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin- 3-one (K.1.76), 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]- isoxazolidin-3-one (K.1 .77), 3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phen- yl]methyl]piperidin-2-one (K.1 .78), 2-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]meth- yl]oxazinan-3-one (K.1.79), 1-[[3-fluoro-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]me- thyl]azepan-2-one (K.1.80), 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phe- nyl]methyl]pyrrolidin-2-one (K.1.81), 5-methyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]phenyl]methyl]pyrrolidin-2-one (K.1.82), ethyl 1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-
3-yl]phenyl]methyl]pyrazole-4-carboxylate (K.1.83), /V-methyl-1-[[4-[5-(trifluoromethyl)-
1 .2.4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (K.1 .84), /V,/V-dimethyl- 1-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzyl]-1 H-1 ,2,4-triazol-3-amine (K.1.85), /V-methoxy-/V-methyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-
4-carboxamide (K.1.86), propyl-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]- pyrazole-4-carboxamide (K.1.87), /V-methoxy-1-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]phenyl]methyl]pyrazole-4-carboxamide (K.1.88), /V-al lyl-/V-[[4-[5- (trifl uoromethyl)-
1.2.4-oxadiazol-3-yl]phenyl]methyl]propanamide (K.1.89), 3-ethyl-1-methoxy-1-[[4-[5-(trifluo- romethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea (K.1.90), 1 ,3-dimethoxy-1-[[4-[5-(trifluoro- methyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]urea (K.1.91), A/-allyl-A/-[[4-[5-(trifluoromethyl)-
1 .2.4-oxadiazol-3-yl]phenyl]methyl]acetamide (K.1.92), /V-[4-[5-(trifluoromethyl)-1 ,2,4-oxadia- zol-3-yl]benzyl]cyclopropanecarboxamide (K.1.93), 1-methyl-3-[[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]methyl]urea (K.1.94), /V '-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phe- nyl]-/V-ethyl-/V-methyl-formamidine (K.1 .95), /V'-[2-chloro-4-[(4-methoxy-phenyl)methyl]-5- methyl-phenyl]-/V-ethyl-/V-methyl-formamidine (K.1.96), /V '-[2-chloro-4-[(4-cyano-phenyl)me- thyl]-5-methyl-phenyl]-/V-ethyl-/V-methyl-formamidine (K.1.97), /V '-[2,5-dimethyl-4-(o-tolylme- thyl)phenyl]-/V-ethyl-N-methyl-formamidine (K.1.98), 6-chloro-3-(3-cyclopropyl-2-fluoro-phe- noxy)-/V-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide
(K.1.99), 3-(3-bromo-2-fluoro-phenoxy)-6-chloro-/V-[2-(2-chloro-4-methyl-phenyl)-2,2- difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (K.1 .100), 6-chloro-/V-[2-(2-chloro-4-me- thyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-car- boxamide (K.1.101), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-/\/-[2-(3,4-dimethylphenyl)- 2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (K.1 .102), 6-chloro-3-(3-chloro-2- fluoro-phenoxy)-/V-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carbox- amide (K.1 .103), /V-[2-(2-bromo-4-methyl-phenyl)-2,2-difluoro-ethyl]-6-chloro-3-(3-cyclopro- pyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (K.1.104);
L) Biopesticides L1)Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudi- nis, B. amyloliquefaciens, B. amyloliquefaciens ssp. plantarum (also referred to as B. vele- zensis), B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, B. velezensis, Candida oleophila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Micro- sphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus epiphyticus, P. polymyxa, Pantoea vagans, Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Tala- romyces flavus, Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula pha- corrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract;
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. ai- zawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B. brongniartii, Burkholderia spp., Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobac- terium spp., Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucle- opolyhedrovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. musca- rium, Metarhizium anisopliae, M. anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluo- rescens, Spodoptera littoralis nucleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces galbus, S. microflavus',
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2,4- ethyl decadienoate (pear ester), (Z,Z,E)-7,11 ,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1 -butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadien-1-ol acetate, (E,Z)-3,13- octadecadien-1-ol, (R)-1-octen-3-ol, pentatermanone, (E,Z,Z)-3, 8, 11 -tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1-yl acetate, (Z)-7-tetradecen-2-one, (Z)-9-tetradecen-1-yl acetate, (Z)-11-tetradecenal, (Z)-11-tetradecen-1-ol, extract of Chenopodium ambrosiodes, Neem oil, Quillay extract;
L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium legumi- nosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium melilotr,
O) Insecticides from classes 0.1 to 0.29
0.1 Acetylcholine esterase (AChE) inhibitors: aldicarb, alanycarb, bendiocarb, benfuracarb, bu- tocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, aza- methiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosa- lone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, pro- thiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion;
0.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole;
0.3 Sodium channel modulators: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cyclo- prothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cy- permethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, me- perfluthrin, metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluth- rin, tetramethylfluthrin, tetramethrin, tralomethrin, transfluthrin; DDT, methoxychlor;
0.4 Nicotinic acetylcholine receptor (nAChR) agonists: acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; 4,5-dihydro-/V-nitro-
1-(2-oxiranylmethyl)-1/7-imidazol-2-amine, (2E)-1-[(6-chloropyridin-3-yl)methyl]-/V’-nitro-
2-pentylidenehydrazinecarboximidamide; 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 5-propoxy-1 ,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine; nicotine; sulfoxaflor, flupyradifurone, triflumezopyrim, fenmezoditiaz, flupyrimin;
0.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, spinetoram;
0.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, lepimectin, milbe- mectin;
0.7 Juvenile hormone mimics: hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen;
0.8 miscellaneous non-specific (multi-site) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;
0.9 Chordotonal organ TRPV channel modulators: afidopyropen, pymetrozine, pyrifluquinazon;
0.10 Mite growth inhibitors: clofentezine, hexythiazox, diflovidazin; etoxazole;
0.11 Microbial disruptors of insect midgut membranes: Bacillus thuringiensis, B. sphaericus and the insecticdal proteins they produce: Bacillus thuringiensis subsp. israelensis, B. sphaericus, B. thuringiensis subsp. aizawai, B. thuringiensis subsp. kurstaki, B. thuringiensis subsp. tenebrionis, the Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Ab1 ;
0.12 Inhibitors of mitochondrial ATP synthase: diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon;
0.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient: chlorfenapyr, DNOC, sulfluramid;
0.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium;
0.15 Inhibitors of the chitin biosynthesis type 0: bistrifluron, chlorfluazuron, diflubenzuron, flu- cycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;
0.16 Inhibitors of the chitin biosynthesis type 1: buprofezin;
0.17 Moulting disruptors: cyromazine;
0.18 Ecdyson receptor agonists: methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide;
0.19 Octopamin receptor agonists: amitraz;
0.20 Mitochondrial complex III electron transport inhibitors: hydramethylnon, acequinocyl, fluacrypyrim, bifenazate; 1 Mitochondrial complex I electron transport inhibitors: fenazaquin, fenpyroximate, pyrim- idifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone; 2 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone, 2-[2-(4-cyano- phenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-/\/-[4-(difluoromethoxy)phenyl]-hydrazinecar- boxamide, /V-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)-[4-[methyl(methylsulfonyl)- amino]phenyl]methylene]-hydrazinecarboxamide, /\/-[4-chloro-2-[[(1 ,1-dimethylethyl)ami- no]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1/7-pyrazole-5-car- boxamide, 2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-/\/-[4-(difluorometh- oxy)phenyl]-hydrazinecarboxamide; 3 Inhibitors of the of acetyl CoA carboxylase: spirodiclofen, spiromesifen, spirotetramat, spi- ropidion, spirobudifen, 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-aza- dispiro[4.2.4.2]tetradec-11-en-10-one, spidoxamat; 4 Mitochondrial complex IV electron transport inhibitors: aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide; 5 Mitochondrial complex II electron transport inhibitors: cyenopyrafen, cyflumetofen, cy- etpyrafen, pyflubumide; 8 Ryanodine receptor-modulators: chlorantraniliprole, cyantraniliprole, cyclaniliprole, fluben- diamide, fluchlodiniliprole, (R)-3-chloro-/V1-{2-methyl-4-[1 ,2,2,2 -tetrafluoro- 1-(trifluorometh- yl)ethyl]phenyl}-/\/2-(1-methyl-2-methylsulfonylethyl)phthalamide, (S)-3-chloro-/V1-{2-methyl- 4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-/\/2-(1-methyl-2-methylsulfonylethyl)- phthalamide, methyl-2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1/7-pyrazol-5-yl]- carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate; /\/-[4,6-dichloro-2-[(diethyl- lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole- 3-carboxamide; /V-[4-chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; /V-[2-(5-amino-1 ,3,4-thiadi- azol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1/7-pyrazole-5-carbox- amide; 3-chloro-1-(3-chloro-2-pyridinyl)-/V-[2,4-dichloro-6-[[(1-cyano-1-meth- ylethyl)amino]carbonyl]phenyl]-1/7-pyrazole-5-carboxamide; tetrachlorantraniliprole; tetraniliprole; tiorantraniliprole; /V-[4-chloro-2-[[(1 ,1-dimethylethyl)amino]carbonyl]-6-meth- ylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1/7-pyrazole-5-carboxamide; cyhalodi- amide; /V-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2- pyridinyl)-1/7-pyrazole-5-carboxamide; .29 Chordotonal organ modulators: flonicamid; 0.30 GABA-gated chloride channel allosteric modulators: broflanilide, fluxametamide, isocyclo- seram;
0.33 Calcium-activated potassium channel modulators: acynonapyr;
0.34 Mitochondrial complex III electron transport inhibitors at Qi site: flometoquin;
O.IIN Insecticidal compounds of unknown or uncertain mode of action: afoxolaner, azadirachtin, amidoflumet, ben-zoximate, bromopropylate, chino_,methionat, cryolite, cyproflanilid, dicloro- mezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopy- ram, fluralaner, metaldehyde, metoxadiazone, piperonyl butoxide, pyridalyl, tioxazafen, triflu- enfuronate, umifoxolaner, 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-aza- dispiro[4.2.4.2]-tetradec-11-en-10-one, 3-(4’-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8- oxa-1-azaspiro[4.5]dec-3-en-2-one, 4-cyano-/V-[2-cyano-5-[[[2,6-dibromo-4-[1 ,2,2,3,3,3-hex- afluoro-1-(trifluoromethyl)propyl]phenyl]amino]carbonyl]phenyl]-2-methyl-benzamide, 4-cy- ano-3-[(4-cyano-2-methyl-benzoyl)amino]-/\/-[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluo- romethyl)propyl]phenyl]-2-fluoro-benzamide, /\/-[5-[[[2-chloro-6-cyano-4-[1 ,2,2,3,3,3-hex- afluoro-1-(trifluoromethyl)propyl]phenyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl- benzamide, /V-[5-[[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]phe- nyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide, /V-[5-[[[2-bromo-6-chloro- 4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]amino]carbonyl]-2-cyano-phenyl]-
4-cyano-2-methyl-benzamide, 4-cyano-/V-[2-cyano-5-[[[2,6-dichloro-4-[1 ,2,2,3,3,3-hex- afluoro-1-(trifluoromethyl)propyl]phenyl]amino]carbonyl]phenyl]-2-methyl-benzamide, 1-[2- fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1 H-1 ,2,4-triazole-5- amine, /V-[5-[[[2-bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phe- nyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide, 4-cyano-/V-[2-cyano-5- [[[2,6-dichloro-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]amino]carbonyl]phenyl]-2- methyl-benzamide, actives on basis of Bacillus firmus (Votivo, 1-1582); fluazaindolizine;
5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1/7-pyrazole; /V-[5-[[2-bromo-6- chloro-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)-propyl]phenyl]carbamoyl]-2-cyano-phe- nyl]-4-cyano-2-methyl-benzamide; 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,3,3,3-hex- afluoro-1-(trifluoromethyl)-propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; 4-cyano- /V-[2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carba- moyl]-'phenyl]-2-methyl-benzamide; /V-[5-[[2-bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1-(trifluo- romethyl)ethyl]phenyl]carba-,moyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; 2-(1 ,3- dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine; 2-[6-[2-(5-fluoro-3-pyridinyl)-5-thiazo_,lyl]- 2-pyridinyl]-pyrimidine; 2-[6-[2-(3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; /V-methyl- suhfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; /V-methylsulfonyl-6-[2-(3- pyridyl)thiazol-5-yl]pyridine-2-carboxamide; 1-[(6-chloro-3-pyridinyl)methyl]-1 ,2,3,5,6,7-hexa- hydro-5-methoxy-7-methyl-8-nitro-imidazo[1 ,2-a]pyridine; 1 -[(6-chloropyridin-3-yl)methyl]-7- methyl-8-nitro- 1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-5-ol ; /\/-(3-chloro-2-methylphenyl)- 2-[(4-chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarbox- amide; 1-[(6-chloro-3-pyridinyl)methyl]-1 ,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro- imidazo[1 ,2-a]pyridine; 2-(3-pyridinyl)-/V-(2-pyrimidinylmethyl)-2H-indazole-5-carboxamide; tyclopyrazoflor; sarolaner, lotilaner; /V-[4-chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1- methyl-3-(1 , 1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)-1 H-pyrazole-5-carboxamide; N-[4- chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1-methyl-3-(1 , 1 ,2,2, 2-pentafluoroethyl)-4- (trifluoromethyl)-1/7-pyrazole-5-carboxamide; 2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(tri-flu- oromethyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-6- (trifluoromethyl)imidazo[4,5-b]pyridine; /V-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-me- thy I-5- ( 1 , 1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide, /\/-[4-chloro-3- [(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-5-(1 , 1 ,2,2, 2-pentafluoroethyl)-4-(trifluoro- methyl)pyrazole-3-carboxamide; benzpyrimoxan; tigolaner; oxazosulfyl; [(2S,3R,4R,5S,6S)- 3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl]-/V-[4-[1-[4-(trifluoromethoxy)phenyl]-
1.2.4-triazol-3-yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahy- dropyran-2-yl]-/V-[4-[1-[4-(trifluoromethoxy)phenyl]-1 ,2,4-triazol-3-yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl]-/\/-[4-[1-[4- (1 ,1 ,2,2,2-pentafluoroethoxy)phenyl]-1 ,2,4-triazol-3-yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-
3.4.5-trimethoxy-6-methyl-tetrahydropyran-2-yl]-/V-[4-[1-[4-(1 ,1 ,2,2,2-pentafluoroethoxy)phe- nyl]-1 ,2,4-triazol-3-yl]phenyl]carbamate; (2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[1-[4-(trifluoro- methoxy)phenyl]-1 ,2,4-triazol-3-yl]phenyl]methylenehydrazono]thiazolidin-4-one, (2Z)-3-(2- isopropylphenyl)-2-[(E)-[4-[1-[4-(1 ,1 ,2,2,2-pentafluoroethoxy)phenyl]-1 ,2,4-triazol-3-yl]phe- nyl]methylenehydrazono]thiazolidin-4-one, (2Z)-3-(2-isopro-,pyhphenyl)-2-[(E)-[4-[1-[4- (1 ,1 ,2,2,2-pentafluoroethoxy)phenyl]-1 ,2,4-triazol-3-yl]phenyl]methylenehydrazono]thiazoli- din-4-one; 2-(6-chloro-3-ethylsulfonyl-imidazo[1 ,2-a]pyridin-2-yl)-3-methyl-6-(trifluorome- thyl)imidazo[4,5-b]pyridine, 2-(6-bromo-3-ethylsulfonyl-imidazo[1 ,2-a]pyridin-2-yl)-3-methyl- 6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(3-ethylsulfonyl-6-iodo-imidazo[1 ,2-a]pyridin-2- yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(7-chloro-3-ethylsulfonyl-imid- azo[1 ,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(7-chloro-3-ethyl- sulfonyl-imidazo[1 ,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(3- ethylsulfonyl-7-iodo-imidazo[1 ,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyri- dine, 3-ethylsulfonyl-6-iodo-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]imid- azo[1 ,2-a]pyridine-8-carbonitrile, 2-[3-ethylsulfonyl-8-fluoro-6-(trifluoromethyl)imidazo[1 ,2- a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-7-(trifluo- romethyl)imidazo[1 ,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethylsulfinyl)imidazo[4,5-b]pyri- dine, 2-[3-ethylsulfonyl-7-(trifluoromethyl)imidazo[1 ,2-a]pyridin-2-yl]-3-methyl-6-(trifluorome- thyl)imidazo[4,5-c]pyridine, 2-(6-bromo-3-ethylsulfonyl-imidazo[1 ,2-a]pyridin-2-yl)-6-(trifluoro- methyl)pyrazolo[4,3-c]pyridine; /\/-[[2-fluoro-4-[(2S,3S)-2-hydroxy-3-(3,4,5-trichlorophenyl)-3- (trifluoromethyl)pyrrolidin-1-yl]phenyl]methyl]cyclopropanecarboxamide; 2-[2-fluoro-4-methyl- 5-(2,2,2-trifluoroethylsulfinyl)phenyl]imino-3-(2,2,2-trifluoroethyl)thiazolidin-4-one; flupenti- ofenox, /V-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-2-methylsulfonyl-propanamide, cyclobutriflu- ram; /V-[4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-4-methylsulfonyl-5- (1 ,1 ,2,2,2-pentafluoroethyl)pyrazole-3-carboxamide, cyproflanilide, nicofluprole; 1 ,4-dime- thyl-2-[2-(pyridin-3-yl)-2/7-indazol-5-yl]-1 , 2, 4-triazolidine-3, 5-dione, 2-[2-fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfanyl)phenyl]imino-3-(2,2,2-trifluoroethyl)thiazolidin-4-one, indazapy- roxamet, /V-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-/V-ethyl-3-methylsulfonyl-propanamide, /V-cy- clopropyl-5-[(5S)-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4/7-isoxazol-3-yl]isoquin- oline-8-carboxamide, 5-[(5S)-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4/7-isoxazol- 3-yl]-/V-(pyrimidin-2-ylmethyl)isoquinoline-8-carboxamide, /\/-[1-(2,6-difluorophenyl)pyrazol-3- yl]-2-(trifluoromethyl)benzamide, 5-((1R,3R)-3-(3,5-bis(trifluoromethyl)phenyl)-2,2-dichlorocy- clopropane-1-carboxamido)-2-chloro-/\/-(3-(2,2-difluoroacetamido)-2,4-difluorophenyl)ben- zamide, 1-[6-(2,2-difluoro-7-methyl-[1 ,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3- pyridyl]cyclopropanecarbonitrile, 6-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro- 7-methyl-[1 ,3]dioxolo[4,5-f]benzimidazole.
The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by IIIPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968;
EP-A 141 317; EP-A 152 031 ; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272;
US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404;
WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ;
WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388;
WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689;
WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325;
WO 06/87343; WO 07/82098; WO 07/90624, WO 10/139271 , WO 11/028657, WO 12/168188, WO 07/006670, WO 11/77514; WO 13/047749, WO 10/069882, WO 13/047441 , WO 03/16303, WO 09/90181 , WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/24010, WO 13/047441 , WO 13/162072, WO 13/092224, WO 11/135833, CN 1907024, CN 1456054, CN 103387541 , CN 1309897, WO 12/84812, CN 1907024, WO 09094442, WO 14/60177, WO 13/116251 , WO 08/013622, WO 15/65922, WO 94/01546, EP 2865265, WO 07/129454, WO 12/165511 , WO 11/081174, WO 13/47441 , WO 16/156241 , WO 16/162265). Some compounds are identified by their CAS Registry Number which is separated by hyphens into three parts, the first consisting from two up to seven digits, the second consisting of two digits, and the third consisting of a single digit.
According to the invention, the solid material (dry matter) of the biopesticides (with the exception of oils such as Neem oil) are considered as active components (e. g. to be obtained after drying or evaporation of the extraction or suspension medium in case of liquid formulations of the microbial pesticides). The weight ratios and percentages used for a biological extract such as Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).
The total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including dormant forms, can be determined using the amount of CFU of the respective microorganism to calculate the total weight of the respective active component with the following equation that 1 x 1010 CFU equals one gram of total weight of the respective active component. Colony forming unit is measure of viable microbial cells. In addition, CFU may also be understood as the number of (juvenile) individual nematodes in case of nematode biopesticides, such as Steinernema feltiae.
In the binary mixtures the weight ratio of the component 1) and the component 2) generally depends from the properties of the components used, usually it is in the range of from 1 :10,000 to 10,000:1 , often from 1 :100 to 100:1 , regularly from 1 :50 to 50:1 , preferably from 1 :20 to 20:1 , more preferably from 1 : 10 to 10:1 , even more preferably from 1 :4 to 4: 1 and in particular from 1 :2 to 2:1. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 1000:1 to 1 :1 , often from 100: 1 to 1 :1 , regularly from 50:1 to 1 :1 , preferably from 20:1 to 1 :1 , more preferably from 10:1 to 1 :1 , even more preferably from 4: 1 to 1 : 1 and in particular from 2: 1 to 1 : 1 . According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 20,000:1 to 1 :10, often from 10,000:1 to 1 :1 , regularly from 5,000:1 to 5:1 , preferably from 5,000:1 to 10:1 , more preferably from 2,000:1 to 30:1 , even more preferably from 2,000:1 to 100:1 and in particular from 1 ,000:1 to 100:1. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 1 :1 to 1 :1000, often from 1 :1 to 1 :100, regularly from 1 :1 to 1 :50, preferably from 1 :1 to 1 :20, more preferably from 1 :1 to 1 :10, even more preferably from 1 :1 to 1 :4 and in particular from 1 :1 to 1 :2. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 10:1 to 1 :20,000, often from 1 :1 to 1 :10,000, regularly from 1 :5 to 1 :5,000, preferably from 1 :10 to 1 :5,000, more preferably from 1 :30 to 1 :2,000, even more preferably from 1 :100 to 1 :2,000 to and in particular from 1 :100 to 1 :1 ,000. In the ternary mixtures, i.e. compositions comprising the component 1) and component 2) and a compound III (component 3), the weight ratio of component 1) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100: 1 , regularly from 1 :50 to 50: 1 , preferably from 1 :20 to 20: 1 , more preferably from 1 : 10 to 10:1 and in particular from 1 :4 to 4:1 , and the weight ratio of component 1) and component s) usually it is in the range of from 1 :100 to 100:1 , regularly from 1 :50 to 50:1 , preferably from 1 :20 to 20: 1 , more preferably from 1 : 10 to 10: 1 and in particular from 1 :4 to 4: 1 . Any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the component 1). These ratios are also suitable for mixtures applied by seed treatment.
When mixtures comprising microbial pesticides are employed in crop protection, the application rates range from 1 x 106 to 5 x 1016 (or more) CFU/ha, preferably from 1 x 108 to 1 x 1013 CFU/ha, and even more preferably from 1 x 109 to 5 x 1015 CFU/ha and in particular from 1 x 1012 to 5 x 1014 CFU/ha. In the case of nematodes as microbial pesticides (e. g. Steinernema feltiae), the application rates regularly range from 1 x 105 to 1 x 1012 (or more), preferably from 1 x 108 to 1 x 1011, more preferably from 5 x 108 to 1 x 1010 individuals (e. g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha.
When mixtures comprising microbial pesticides are employed in seed treatment, the application rates generally range from 1 x 106 to 1 x 1012 (or more) CFU/seed, preferably from 1 x 106 to 1 x 109 CFU/seed. Furthermore, the application rates with respect to seed treatment generally range from 1 x 107 to 1 x 1014 (or more) CFU per 100 kg of seed, preferably from 1 x 109 to 1 x 1012 CFU per 100 kg of seed.
Preference is given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Qo site in group A), more preferably selected from compounds (A.1.1), (A.1.4), (A.1.8), (A.1.9), (A.1.10), (A.1.12), (A.1.13), (A.1.14), (A.1.17), (A.1.21), (A.1.25), (A.1.34) and (A.1.35); particularly selected from (A.1.1), (A.1.4), (A.1.8), (A.1.9), (A.1.13), (A.1.14), (A.1.17), (A.1.25), (A.1.34) and (A.1.35).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Qi site in group A), more preferably selected from compounds (A.2.1), (A.2.3), (A.2.4) and (A.2.6); particularly selected from (A.2.3), (A.2.4) and (A.2.6).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex II in group A), more preferably selected from compounds (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.11), (A.3.12), (A.3.15), (A.3.16), (A.3.17), (A.3.18), (A.3.19), (A.3.20), (A.3.21), (A.3.22), (A.3.23), (A.3.24), (A.3.28), (A.3.31), (A.3.32), (A.3.33), (A.3.34), (A.3.35), (A.3.36), (A.3.37), (A.3.38) and (A.3.39); particularly selected from (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.12), (A.3.15), (A.3.17), (A.3.19), (A.3.22), (A.3.23), (A.3.24), (A.3.31), (A.3.32), (A.3.33), (A.3.34), (A.3.35), (A.3.36), (A.3.37), (A.3.38) and (A.3.39).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from other respiration inhibitors in group A), more preferably selected from compounds (A.4.5) and (A.4.11); in particular (A.4.11).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from C14 demethylase inhibitors in group B), more preferably selected from compounds (B.1.4), (B.1.5), (B.1.8), (B.1.10), (B.1.11), (B.1.12), (B.1.13), (B.1.17), (B.1.18), (B.1.21), (B.1.22), (B.1.23), (B.1.25), (B.1.26), (B.1.29), (B.1.34), (B.1.37), (B.1.38), (B.1.43), (B.1.46), (B.1.53), (B.1.54) and (B.1.55); particularly selected from (B.1.5), (B.1.8), (B.1.10), (B.1.17), (B.1.22), (B.1.23), (B.1.25), (B.1.33), (B.1.34), (B.1.37), (B.1.38), (B.1.43) and (B.1.46).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from Delta 14-reductase inhibitors in group B), more preferably selected from compounds (B.2.4), (B.2.5), (B.2.6) and (B.2.8); in particular (B.2.4).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from phenylamides and acyl amino acid fungicides in group C), more preferably selected from compounds (C.1.1), (C.1.2), (C.1.4) and (C.1.5); particularly selected from (C.1.1) and (C.1.4).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from other nucleic acid synthesis inhibitors in group C), more preferably selected from compounds (C.2.6), (C.2.7) and (C.2.8).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group D), more preferably selected from compounds (D.1.1), (D.1.2), (D.1.5), (D.2.4) and (D.2.6); particularly selected from (D.1.2), (D.1.5) and (D.2.6).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group E), more preferably selected from compounds (E.1.1), (E.1.3), (E.2.2) and (E.2.3); in particular (E.1.3).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group F), more preferably selected from compounds (F.1.2), (F.1.4) and (F.1.5). Preference is also given to mixtures comprising as component 2) at least one active substance selected from group G), more preferably selected from compounds (G.3.1), (G.3.3), (G.3.6), (G.5.1), (G.5.3), (G.5.4), (G.5.5), G.5.6), G.5.7), (G.5.8), (G.5.9), (G.5.10) and (G.5.11); particularly selected from (G.3.1), (G.5.1) and (G.5.3).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group H), more preferably selected from compounds (H.2.2), (H.2.3), (H.2.5), (H.2.7), (H.2.8), (H.3.2), (H.3.4), (H.3.5), (H.4.9) and (H.4.10); particularly selected from (H.2.2), (H.2.5), (H.3.2), (H.4.9) and (H.4.10).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group I), more preferably selected from compounds (1.2.2) and (1.2.5).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group J), more preferably selected from compounds (J.1.2), (J.1.5), (J.1.8), (J.1.11) and (J.1.12); in particular (J.1.5).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group K), more preferably selected from compounds (K.1.41), (K.1.42), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59); particularly selected from (K.1.41), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59).
The biopesticides from group L1) and/or L2) may also have insecticidal, acaricidal, mollus- cidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L5) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
The microbial pesticides, in particular those from groups L1), L3) and L5), embrace not only the isolated, pure cultures of the respective microorganism as defined herein, but also its cell- free extract, its suspension in a whole broth culture and a metabolite-containing culture medium or a purified metabolite obtained from a whole broth culture of the microorganism.
Many of these biopesticides have been deposited under deposition numbers mentioned herein (the prefices such as ATCC or DSM refer to the acronym of the respective culture collection, for details see e. g. here: http://www. wfcc.info/ccinfo/collection/by acronym/), are referred to in literature, registered and/or are commercially available: mixtures of Aureobasidium pullu- lans DSM 14940 and DSM 14941 isolated in 1989 in Konstanz, Germany (e. g. blastospores in Blossom Protect® from bio-ferm GmbH, Austria), Azospirillum brasilense Sp245 originally isolated in wheat reagion of South Brazil (Passo Fundo) at least prior to 1980 (BR 11005; e. g. GELFIX® Gramineas from BASF Agricultural Specialties Ltd., Brazil), A. brasilense strains Ab- V5 and Ab-V6 (e. g. in Azo Max from Novozymes BioAg Produtos papra Agricultura Ltda., Quat- tro Barras, Brazil or Simbiose-Maiz® from Simbiose-Agro, Brazil; Plant Soil 331 , 413-425, 2010), Bacillus amyloliquefaciens strain AP-188 (NRRL B-50615 and B-50331 ; US 8,445,255); B. amyloliquefaciens ssp. plantarum strains formerly also sometimes referred to as B. subtilis, recently together with B. methylotrophicus, and B. velezensis classified as B. velezensis (I nt. J. Syst. Evol. Microbiol. 66, 1212-1217, 2016): B. a. ssp. plantarum or B. velezensis D747 isolated from air in Kikugawa-shi, Japan (US 20130236522 A1 ; FERM BP-8234; e. g. Double Nickel™ 55 WDG from Certis LLC, USA), B. a. ssp. plantarum or B. velezensis FZB24 isolated from soil in Brandenburg, Germany (also called SB3615; DSM 96-2; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. Taegro® from Novozyme Biologicals, Inc., USA), B. a. ssp. plantarum or B. velezensis FZB42 isolated from soil in Brandenburg, Germany (DSM 23117; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. RhizoVital® 42 from AbiTEP GmbH, Germany), B. a. ssp. plantarum or B. velezensis MBI600 isolated from faba bean in Sutton Bonington, Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRL B-50595; US 2012/0149571 A1 ; e. g. Integral® from BASF Corp., USA), B. a. ssp. plantarum or B. velezensis QST-713 isolated from peach orchard in 1995 in California, U.S.A. (NRRL B-21661 ; e. g. Serenade® MAX from Bayer Crop Science LP, USA), B. a. ssp. plantarum or B. velezensis TJ1000 isolated in 1992 in South Dakoda, U.S.A, (also called 1 BE; ATCC BAA-390; CA 2471555 A1 ; e. g. QuickRoots™ from TJ Technologies, Watertown, SD, USA); B. firmus CNCM 1-1582, a variant of parental strain EIP- N1 (CNCM 1-1556) isolated from soil of central plain area of Israel (WO 2009/126473, US 6,406,690; e. g. Votivo® from Bayer CropScience LP, USA), B. pumilus GHA 180 isolated from apple tree rhizosphere in Mexico (IDAC 260707-01 ; e. g. PRO-MIX® BX from Premier Horticulture, Quebec, Canada), B. pumilus INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tracheiphila (NRRL B-50185, NRRL B- 50153; US 8,445,255), B. pumilus KFP9F isolated from the rhizosphere of grasses in South Africa at least before 2008 (NRRL B-50754; WO 2014/029697; e. g. BAC-UP or FUSION-P from BASF Agricultural Specialities (Pty) Ltd., South Africa), B. pumilus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL B-30087; e. g. Sonata® or Ballad® Plus from Bayer Crop Science LP, USA), B. simplex ABU 288 (NRRL B- 50304; US 8,445,255), B. subtilis FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA-11857; System. Appl. Microbiol. 27, 372-379, 2004; US 2010/0260735; WO 2011/109395); B. thuringiensis ssp. aizawai ABTS-1857 isolated from soil taken from a lawn in Ephraim, Wisconsin, U.S.A., in 1987 (also called ABG-6346; ATCC SD- 1372; e. g. XenTari® from BioFa AG, Munsingen, Germany), B. t. ssp. kurstaki ABTS-351 identical to HD-1 isolated in 1967 from diseased Pink Bollworm black larvae in Brownsville, Texas, U.S.A. (ATCC SD-1275; e. g. Dipel® DF from Valent BioSciences, IL, USA), B. t. ssp. kurstaki SB4 isolated from E. saccharina larval cadavers (NRRL B-50753; e. g. Beta Pro® from BASF Agricultural Specialities (Pty) Ltd., South Africa), B. t. ssp. tenebrionis NB-176-1 , a mutant of strain NB-125, a wild type strain isolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM 5480; EP 585215 B1; e. g. Novodor® from Valent BioSciences, Switzerland), Beauveria bassiana GHA (ATCC 74250; e. g. BotaniGard® 22WGP from Laverlam Int. Corp., USA), B. bassiana JW-1 (ATCC 74040; e. g. Naturalis® from CBC (Europe) S.r.l., Italy), B. bassiana PPRI 5339 isolated from the larva of the tortoise beetle Conchyloctenia punctata (NRRL 50757; e. g. BroadBand® from BASF Agricultural Specialities (Pty) Ltd., South Africa), Bradyrhi- zobium elkanii strains SEMIA 5019 (also called 29W) isolated in Rio de Janeiro, Brazil and SEMIA 587 isolated in 1967 in the State of Rio Grande do Sul, from an area previously inoculated with a North American isolate, and used in commercial inoculants since 1968 (Appl. Environ. Microbiol. 73(8), 2635, 2007; e. g. GELFIX 5 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum 532c isolated from Wisconsin field in U.S.A. (Nitragin 61A152; Can. J. Plant. Sci. 70, 661-666, 1990; e. g. in Rhizoflo®, Histick®, Hicoat® Super from BASF Agricultural Specialties Ltd., Canada), B. japonicum E-109 variant of strain USDA 138 (INTA E109, SEMIA 5085; Eur. J. Soil Biol. 45, 28-35, 2009; Biol. Fertil. Soils 47, 81-89, 2011); B. japonicum strains deposited at SEMIA known from Appl. Environ. Microbiol. 73(8), 2635, 2007: SEMIA 5079 isolated from soil in Cerrados region, Brazil by Embrapa-Cerrados used in commercial inoculants since 1992 (CPAC 15; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum SEMIA 5080 obtained under lab condtions by Embrapa- Cerrados in Brazil and used in commercial inoculants since 1992, being a natural variant of SEMIA 586 (CB1809) originally isolated in U.S.A. (CPAC 7; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil); Burkholderia sp. A396 isolated from soil in Nikko, Japan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc., USA), Coni- othyrium minitans CON/M/91-08 isolated from oilseed rape (WO 1996/021358; DSM 9660; e. g. Contans® WG, Intercept® WG from Bayer CropScience AG, Germany), harpin (alpha-beta) protein (Science 257, 85-88, 1992; e. g. Messenger™ or HARP-N-Tek from Plant Health Care pic, U.K.), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol. 107, 112-126, 2011; e. g. Helicovex® from Adermatt Biocontrol, Switzerland; Diplomata® from Kop- pert, Brazil; Vivus® Max from AgBiTech Pty Ltd., Queensland, Australia), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (e. g. Gemstar® from Certis LLC, USA), Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditis bacteriophora (e. g. Nemasys® G from BASF Agricultural Specialities Limited, UK), Isaria fumosorosea Apopka-97 isolated from mealy bug on gynura in Apopka, Florida, U.S.A. (ATCC 20874; Biocontrol Science Technol. 22(7), 747-761 , 2012; e. g. PFR-97™ or PreFeRal® from Certis LLC, USA), Metarhizium anisopliae var. an- isopliae F52 also called 275 or V275 isolated from codling moth in Austria (DSM 3884, ATCC 90448; e. g. Met52® Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicola 277 isolated from grapes in the central part of Israel (US 6,994,849; NRRL Y-30752; e. g. formerly Shemer® from Agrogreen, Israel), Paecilomyces ilacinus 251 isolated from infected nematode eggs in the Philippines (AGAL 89/030550; W01991/02051 ; Crop Protection 27, 352-361 , 2008; e. g. BioAct®from Bayer CropScience AG, Germany and MeloCon® from Certis, USA), Paenibacillus alvei NAS6G6 isolated from the rhizosphere of grasses in South Africa at least before 2008 (WO 2014/029697; NRRL B-50755; e.g. BAC-UP from BASF Agricultural Specialities (Pty) Ltd., South Africa), Paenibacillus strains isolated from soil samples from a variety of European locations including Germany: P. epiphyticus Lu17015 (WO 2016/020371 ; DSM 26971), P. polymyxa ssp. plantarum Lu16774 (WO 2016/020371 ; DSM 26969), P. p. ssp. plantarum strain Lu17007 (WO 2016/020371 ; DSM 26970); Pasteuria nishizawae Pn1 isolated from a soybean field in the mid-2000s in Illinois, U.S.A. (ATCC SD-5833; Federal Register 76(22), 5808, February 2, 2011 ; e.g. Clariva™ PN from Syngenta Crop Protection, LLC, USA), Penicillium bilaiae (also called P. bilaif) strains ATCC 18309 (= ATCC 74319), ATCC 20851 and/or ATCC 22348 (= ATCC 74318) originally isolated from soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can. J. Plant Sci. 78(1), 91-102, 1998; US 5,026,417,
WO 1995/017806; e. g. Jump Start®, Provide® from Novozymes Biologicals BioAg Group, Canada), Reynoutria sachalinensis extract (EP 0307510 B1 ; e. g. Regalia® SC from Marrone BioInnovations, Davis, CA, USA or Milsana® from BioFa AG, Germany), Steinernema carpocapsae (e. g. Millenium® from BASF Agricultural Specialities Limited, UK), S. feltiae (e. g. Nemashield® from BioWorks, Inc., USA; Nemasys® from BASF Agricultural Specialities Limited, UK), Strepto- myces microflavus NRRL B-50550 (WO 2014/124369; Bayer CropScience, Germany), Tricho- derma asperelloides JM41 R isolated in South Africa (NRRL 50759; also referred to as T. fertile’, e. g. Trichoplus® from BASF Agricultural Specialities (Pty) Ltd., South Africa), T. harzianum T- 22 also called KRL-AG2 (ATCC 20847; BioControl 57, 687-696, 2012; e. g. Plantshield® from BioWorks Inc., USA or SabrEx™ from Advanced Biological Marketing Inc., Van Wert, OH, USA).
According to another embodiment of the mixtures, the at least one pesticide II is selected from the groups L1) to L5):
L1) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Aureobasidium pullulans DSM 14940 and DSM 14941 (L1.1), Bacillus amyloliquefa- ciens AP-188 (L.1.2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B. amyloliquefa- ciens ssp. plantarum FZB24 (L.1.4), B. amyloliquefaciens ssp. plantarum FZB42 (L.1.5), B. amyloliquefaciens ssp. plantarum MBI600 (L.1.6), B. amyloliquefaciens ssp. plantarum QST-713 (L.1.7), B. amyloliquefaciens ssp. plantarum TJ1000 (L.1.8), B. pumilus GB34 (L.1.9), 8. pumilus GHA 180 (L.1.10), 8. pumilus INR-7 (L.1.11), 8. pumilus KFP9F (L.1.12), B. pumilus QST 2808 (L.1.13), B. simplex ABU 288 (L.1.14), B. subtilis FB17 (L.1.15), Coniothyrium minitans CON/M/91-08 (L.1.16), Metschnikowia fructicola NRRL Y-30752 (L.1.17), Paenibacillus alvei NAS6G6 (L.1.18), P. epiphyticus Lu17015 (L.1.25), P. polymyxa ssp. plantarum Lu16774 (L.1.26), P. p. ssp. plantarum strain Lu17007 (L.1.27), Penicillium bilaiae ATCC 22348 (L.1.19), P. bilaiae ATCC 20851 (L.1.20), Penicillium bilaiae ATCC 18309 (L.1.21), Streptomyces microflavus NRRL B-50550 (L.1.22), Tricho- derma asperelloides JM41 R (L.1.23), T. harzianum T-22 (L.1.24);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: harpin protein (L.2.1), Reynoutria sachalinensis extract (L.2.2);
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Bacillus firmus 1-1582 (L.3.1); B. thuringiensis ssp. aizawai ABTS-1857 (L.3.2), B. t. ssp. kurstaki ABTS-351 (L.3.3), B. t. ssp. kurstaki SB4 (L.3.4), B. t. ssp. tenebrionis NB-176-1 (L.3.5), Beauveria bassiana GHA (L.3.6), B. bassiana JW-1 (L.3.7), B. bassiana PPRI 5339 (L.3.8), Burkholderia sp. A396 (L.3.9), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (L.3.10), Helicoverpa zea nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.11), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (L.3.12), Heterohabditis bacteriophora (L.3.13), Isaria fumosorosea Apopka-97 (L.3.14), Metarhizium anisopliae var. anisopliae F52 (L.3.15), Paecilomyces lilacinus 251 (L.3.16), Pasteuria nishizawae Pn1 (L.3.17), Steinernema carpocapsae (L.3.18), S. feltiae (L.3.19);
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: cis-jasmone (L.4.1), methyl jasmonate (L.4.2), Quillay extract (L.4.3);
L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity: Azospirillum brasilense Ab-V5 and Ab-V6 (L.5.1), A. bra- silense Sp245 (L.5.2), Bradyrhizobium elkanii SEMIA 587 (L.5.3), B. elkanii SEMIA 5019 (L.5.4), B. japonicum 532c (L.5.5), B. japonicum E-109 (L.5.6), B. japonicum SEMIA 5079 (L.5.7), B. japonicum SEMIA 5080 (L.5.8).
The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1) and at least one biopesticide selected from the group L) (component 2), in particular at least one biopesticide selected from the groups L1) and L2), as described above, and if desired at least one suitable auxiliary.
The present invention furthermore relates to agrochemical compositions comprising a mixture of of at least one compound I (component 1) and at least one biopesticide selected from the group L) (component 2), in particular at least one biopesticide selected from the groups L3) and L4), as described above, and if desired at least one suitable auxiliary. Preference is also given to mixtures comprising as pesticide II (component 2) a biopesticide selected from the groups L1), L3) and L5), preferably selected from strains denoted above as (L.1.2), (L.1.3), (L.1.4), (L.1.5), (L.1.6), (L.1.7), (L.1.8), (L.1.10), (L.1.11), (L.1.12), (L.1.13), (L.1.14), (L.1.15), (L.1.17), (L.1.18), (L.1.19), (L.1.20), (L.1.21), (L.1.25), (L.1.26), (L.1.27), (L.3.1); (L.3.9), (L.3.16), (L.3.17), (L.5.1), (L.5.2), (L.5.3), (L.5.4), (L.5.5), (L.5.6), (L.5.7), (L.5.8); (L.4.2), and (L.4.1); even more preferably selected from (L.1.2), (L.1.6), (L.1.7), (L.1.8), (L.1.11), (L.1.12), (L.1.13), (L.1.14), (L.1.15), (L.1.18), (L.1.19), (L.1.20), (L.1.21), (L.3.1); (L.3.9), (L.3.16), (L.3.17), (L.5.1), (L.5.2), (L.5.5), (L.5.6); (L.4.2), and (L.4.1). These mixtures are particularly suitable for treatment of propagation materials, i. e. seed treatment purposes and likewise for soil treatment. These seed treatment mixtures are particularly suitable for crops such as cereals, corn and leguminous plants such as soybean.
Preference is also given to mixtures comprising as pesticide II (component 2) a biopesticide selected from the groups L1), L3) and L5), preferably selected from strains denoted above as (L1.1), (L.1.2), (L.1.3), (L.1.6), (L.1.7), (L.1.9), (L.1.11), (L.1.12), (L.1.13), (L.1.14), (L.1.15), (L.1.17), (L.1.18), (L.1.22), (L.1.23), (L.1.24), (L.1.25), (L.1.26), (L.1.27), (L.2.2); (L.3.2), (L.3.3), (L.3.4), (L.3.5), (L.3.6), (L.3.7), (L.3.8), (L.3.10), (L.3.11), (L.3.12), (L.3.13), (L.3.14), (L.3.15), (L.3.18), (L.3.19); (L.4.2), even more preferably selected from (L.1.2), (L.1.7), (L.1.11), (L.1.13), (L.1.14), (L.1.15), (L.1.18), (L.1.23), (L.3.3), (L.3.4), (L.3.6), (L.3.7), (L.3.8), (L.3.10), (L.3.11), (L.3.12), (L.3.15), and (L.4.2). These mixtures are particularly suitable for foliar treatment of cultivated plants, preferably of vegetables, fruits, vines, cereals, corn, and leguminous crops such as soybeans.
The compositions comprising mixtures of active ingredients can be prepared by usual means, e. g. by the means given for the compositions of compounds I.
When living microorganisms, such as pesticides II from groups L1), L3) and L5), form part of the compositions, such compositions can be prepared by usual means (e. g. H.D. Burges: Formulation of Microbial Biopesticides, Springer, 1998; WO 2008/002371 , US 6,955,912, US 5,422,107).
I. Synthesis examples in-3-yl)-9-fluoro-1-methyl-1 ,2-dihy-
Figure imgf000111_0001
Step 1 : Preparation of (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanol The solution of 1 ,2-difluoro-3-iodobenzene (16.8 g, 0.07 mol) in THF (150 mL) was added /- PrMgCI (2M) (36 mL, 0.073 mol) at 0 °C under N2 and the mixture was stirred at 0 °C for 30 min. Then 6-(difluoromethyl)-5-methylnicotinaldehyde (10 g, 0.058 mol) in THF was added at 0 °C and the mixture was stirred for 4 h at 0~20 °C under N2. TLC (PE:EtOAc=3:1) showed the reaction complete. The reaction mixture was quenched with NH4CI aq. (200 mL), extracted with EtOAc (150 mL) and washed with brine (200 mL). The organic layer was dried over Na2SO4 and concentrated to give (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanol (16.7 g, crude) as yellow solid. The title compound was used directly without further purification.
1H NMR (400 MHz, CDCI3) 6 [ppm] = 8.38 (s, 1 H) 7.54 (s, 1 H) 7.20 - 7.25 (m, 1 H) 7.02 - 7.09 (m, 2 H) 6.45 - 6.75 (m, 1 H) 6.14 (s, 1 H) 2.40 - 2.44 (m, 3 H).
Step 2: Preparation of (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanone
The solution of (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanol (16.7 g, 0.059 mol) in THF (200 mL) was added MnC>2 (51 g, 0.59 mol) and the mixture was stirred at 80 °C for 16 h. TLC (PE: EtOAc=3:1) showed the reaction complete. The reaction mixture was filtered and the filtrate was concentrated, purified by column (PE: EtOAc=7: 1) to give Preparation of (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanone (12.5 g, 75%) as yellow oil. The title compound was used directly without further purification.
1H NMR (400 MHz, CDCI3) 6 [ppm] = 8.69 (s, 1 H) 7.95 (s, 1 H) 7.27 - 7.41 (m, 2 H) 7.19 - 7.24 (m, 1 H) 6.49 - 6.84 (m, 1 H) 2.53 (s, 3 H).
Step 3: Preparation of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1 ,2-dihydro- spiro[benzo[e][1 ,4]diazepine-3, 1 -cyclopropane]
To a solution of (6-(difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanone (1.63 g, 5.8 mmol) in nBuOH (40 mL) was added Na2CC>3 (2.2 g, 20.8 mmol) and 1-(aminomethyl)cyclo- propan-1 -amine dihydrochloride (1.1 g, 6.9 mmol) at 25 °C and stirred at 120 °C for 16 hrs under N2. TLC (PE: EtOAc= 1 :1) showed the reaction was completed. The mixture was quenched with H2O (50 mL) and extracted with EtOAc (30 mL x 3). The organic layer was washed with brine (20 mL x 2), dried over Na2SO4 and concentrated. The residue was purified by column (PE: EtOAc=3: 1 to 1 : 1) to give the title compound (1.1 g) as yellow oil.
1H NMR (400 MHz, CDCI3) 6 [ppm] = 8.47 (s, 1 H) 7.72 (s, 1 H) 7.05 (ddd, =11.19, 7.94, 1.25 Hz, 1 H) 6.51 - 6.87 (m, 4 H) 4.85 (br s, 1 H) 3.60 (d, J=4.13 Hz, 2 H) 2.53 (s, 3 H) 1.09 - 1.14 (m, 2 H) 0.97 - 1.02 (m, 2 H). Step 4: Preparation of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1-methyl-1 ,2-dihydro- spiro[benzo[e][1 ,4]diazepine-3, 1 -cyclopropane]
To a solution of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1 ,2-dihydro- spiro[benzo[e][1 ,4]diazepine-3,1'-cyclopropane] (2.2 g, 6.6 mmol) in DMF (20 mL) was added NaH (-60%) (398 mg, 10 mmol) at 0 °C and stirred at 0 °C for 15 min under N2. Then Mel (2.3 g, 16.6 mmol) was added at 0 °C and stirred at 0 °C - 25 °C for 16 hrs under N2. TLC (PE: EtOAc = 3 :1) showed -65% the desired product and -30% starting material in reaction. The mixture was quenched with NH4CI aq. (30 mL), extracted with EtOAc (15 mL x 3). The organic layer was washed with brine (15 x 2 mL), dried over Na2SO4 and concentrated. The residue was purified by column (PE: EtOAc = 3: 1 to 1 : 1) to give 5-(6-(difluoromethyl)-5-methylpyridin- 3-yl)-9-fluoro-1-methyl-1 ,2-dihydrospiro[benzo[e][1 ,4]diazepine-3,1'-cyclopropane] (1.7 g, 74.6%) as yellow oil.
1H NMR (400 MHz, CDCI3) 6 [ppm] = 8.52 (s, 1 H) 7.91 (br s, 1 H) 7.12 (br dd, =11 .38, 7.25 Hz, 1 H) 6.93 (td, J=7.88, 4.75 Hz, 1 H) 6.56 - 6.86 (m, 2 H) 3.55 (s, 2 H) 2.99 (d, J=6.38 Hz, 3 H) 2.53 (s, 3 H) 0.77 (br s, 4 H).
Example 2: 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1 ,2,2-trimethyl-2,3-dihydro-1 H- benzo[e][1 ,4]diazepine
Step 1 : Preparation of tert- butyl (2-((2-(6-(difluoromethyl)-5-methylnicotinoyl)-6-fluoro- phenyl)amino)-2-methylpropyl)carbamate
To the solution of tert-butyl (2-amino-2-methylpropyl)carbamate (1.66 g, 8.83 mmol) and (6- (difluoromethyl)-5-methylpyridin-3-yl)(2,3-difluorophenyl)methanone (0.5 g, 1.77 mmol) in DMA (15 mL) was added DIEA (0.68 g, 5.30 mmol) and the mixture was stirred at 200°C for 4 h under Microwave. TLC (PE: EtOAc=5:1) showed the reaction was completed. The reaction mixture was quenched with brine (20 mL). The mixture was extracted with EtOAC (20 mL x 3) and the organic layer was washed with brine (50 mL), dried over Na2SC>4 and concentrated. The residue was purified by column (PE: EtOAc=85:15) and concentrated to give the title compound (0.12 g, yield: 15.0%) as yellow oil.
1H NMR (400 MHz, CDCI3) 6 [ppm] = 8.65 (s, 1 H), 7.90 (s, 1 H), 7.18 - 7.27 (m, 3 H), 6.62 - 6.90 (m, 2 H), 4.97 (br d, J=3.25 Hz, 1 H), 3.32 (br d, J=5.88 Hz, 2 H), 2.60 (s, 3 H), 1.44 (s, 9 H), 1.26 (s, 6 H).
Step 2: Preparation of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-2,2-dimethyl-2,3-dihy- dro-1 H-benzo[e][1 ,4]diazepine To the solution of tert-butyl (2-((2-(6-(difluoromethyl)-5-methylnicotinoyl)-6-fluorophenyl)amino)- 2-methylpropyl)carbamate (0.14 g, 0.31 mmol) in DCM (7 mL), was added TFA (1.4 mL) at 0°C and stirred at 0°C for 4 h. TLC (PE: EtOAc=1 :1) showed the reaction was completed. The reaction mixture was quenched by NaHCCh aq. (20 mL), extracted with DCM (10 mL x 2) and the organic layer was washed with brine (20 mL), dried over Na2SO4 and concentrated under reduced pressure. The residue was purified by column chromatography (PE: EtOAc=85: 15) and concentrated under reduced pressure to give 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9- fluoro-2,2-dimethyl-2,3-dihydro-1 H-benzo[e][1 ,4]diazepine (50 mg, 49.0%) as yellow oil.
1H NMR (400 MHz, MeOD) 5 [ppm] = 8.47 (s, 1 H), 7.82 (s, 1 H), 7.18 - 7.25 (m, 1 H), 6.73 - 7.00 (m, 3 H), 3.63 (s, 2 H), 2.52 (s, 3 H), 1.38 (s, 6 H)
Step 3: 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1 ,2,2-trimethyl-2,3-dihydro-1 H- benzo[e][1 ,4]diazepine
To a mixture of 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-2,2-dimethyl-2,3-dihydro-1 H- benzo[e][1 ,4]diazepine (70 mg, 0.21 mmol) in DMF (1 mL) was added NaH (60%) (13 mg, 0.31 mmol) at 0 °C under N2 and the mixture was stirred for 20 min at 0 °C. Then Mel (45 mg, 0.31 mmol) in DMF (0.5 mL) was added and the mixture was stirred at 0°C for 3 h under N2. LCMS showed the reaction was completed. The reaction mixture was quenched with NH4CI aq. (10 mL) and extracted with EtOAc (10 x 2 mL). The organic layer was washed with brine (10 mL), dried over Na2SO4 and concentrated. The residue was purified by Prep-HPLC (NH4HCO3) to give the 5-(6-(difluoromethyl)-5-methylpyridin-3-yl)-9-fluoro-1 ,2,2-trimethyl-2,3-dihydro-1 H- benzo[e][1 ,4]diazepine (40 mg, 54.9%) as yellow solid.
1H NMR (400 MHz, MeOD) 5 [ppm] = 8.54 (d, >1.13 Hz, 1 H), 7.89 (s, 1 H), 7.26 (ddd, >12.51 , 8.25, 1.38 Hz, 1 H), 7.13 (td, >7.94, 4.75 Hz, 1 H), 6.73 - 7.00 (m, 2 H), 3.36 - 3.72 (m, 2 H), 2.87 (d, >6.00 Hz, 3 H), 2.52 (s, 3 H), 1.35 (br s, 6 H).
The compounds listed in Table I were prepared in an analogous manner.
Table I: Compounds Ex-1 to Ex-124 of formula I, wherein the meaning of R2, R3 R5, R6, R7, R8, R9 and Xn are as defined in each line.
*LCMS: Liquid chromatography-mass spectrometry; Shimadzu Nexera LC-30 LCMS-2020
(ESI+) using HPLC-column Kinetex XB C18 1 ,7pm (50 x 2.1 mm); eluent: acetonitrile / water + 0.1% trifluoroacetic acid (gradient from 5:95 to 100 : 0 in 1.5 min at 60°C, flow gradient from 0.8 to 1.0 ml/min in 1.5 min);
**LCMS: Liquid chromatography-mass spectrometry; Shimadzu Nexera LC-30 LCMS-2020 (ESI+) using HPLC-column LUX Cellulose-1 5 pm (150 x 4.6 mm); eluent: acetonitrile I water + 0.1% formic acid (gradient from 50:50 to 100 : 0 in 10 min at 40°C, flow fate 0.6 ml/min in);
Rt: retention time in minutes.
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000130_0001
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000133_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_0001
II. Biological Examples
Green House
The compound was dissolved in a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a ratio (volume) solventemulsifier of 99 to 1 to give a total volume of 5 ml. Subsequently, water was added to total volume of 100 ml.
This stock solution was then diluted with the described solvent-emulsifier-water mixture to the final concentration given in the table below.
Example 1 - Preventative fungicidal control of Botrytis cinerea on leaves of green pepper
Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or mixture mentioned in the table below. The next day the plants were inoculated with an aqueous biomalt or DOB solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24°C and a saturated relative humidity, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the samples which had been treated with 250 ppm of the active substance from examples from Ex-5, Ex-6, Ex-7, Ex-8, Ex-29, Ex-30, Ex-32 and Ex-33 respectively, showed up to at most 13 % growth of the pathogen whereas the untreated plants were 90% infected.
In this test, the samples which had been treated with 125 ppm of the active substance from examples from Ex-43, Ex-45, Ex-47, Ex-48, Ex- 52, Ex-53, Ex- 54, Ex-55, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61 , Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70, Ex-71 , Ex-75, Ex-76, Ex-77, Ex-78, Ex-85, Ex-88, Ex-89, Ex-90, Ex-91 , Ex-92, Ex-93, Ex-95, Ex-96, Ex-97, Ex-102, Ex-110 respectively, showed up to at most 22 % growth of the pathogen whereas the untreated plants were 90% infected.
Example 2 - Long lasting control of Botrytis cinerea on leaves of green pepper
Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or mixture mentioned in the table below. The plants were then cultivated in the greenhouse for 7 days and then inoculated with an aqueous biomalt or DOB solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24°C and a saturated relative humidity, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, the samples which had been treated with 63 ppm of the active substance from examples from Ex-5, Ex-6, Ex-7 and Ex-8 respectively, showed up to at most 17 % growth of the pathogen whereas the untreated plants were 90% infected.
Example 3 - Preventative fungicidal control of white mold on soybeans caused by Sclerotinia sclerotiorum
Young seedlings of soybeans were grown in pots. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or mixture mentioned in the table below. The next day the treated plants were inoculated with a biomalt suspension, containing the mycelium of Sclerotinia sclerotiorum. Then the trial plants were cultivated for 6 days in a greenhouse chamber at 23°C and a relative humidity between 80 and 85%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the samples which had been treated with 250 ppm of the active substance from examples from Ex-29, Ex-30, Ex-32 and Ex-33 respectively, showed up to at most 14 % growth of the pathogen whereas the untreated plants were 100% infected.
Example 4 - Preventative fungicidal control of white mold on oilseed rape caused by Sclerotinia sclerotiorum
Oilseed rapes were grown in pots to the 13 to 14 leaf stage. These plants were sprayed to runoff with previously described spray solution, containing the concentration of active ingredient or their mixture mentioned in the table below. The plants could air-dry. The next day the applicated rape petals were fixed wit 25pl of 2.5% methylcellulose on leaf 1 and 2. 25 pl of a spore suspension of Sclerotinia sclerotiorum was pipetted on each fixed rape petal. After 14 days at 20°C and a relative humidity of 60 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, the samples which had been treated with 100 g/ha of the active substance from examples from Ex-18, Ex-29, Ex-32 and Ex-33 respectively, showed up to at most 2 % growth of the pathogen whereas the untreated plants were 100% infected.
Example 5 - Preventative fungicidal control of white mold on cabagge caused by Sclerotinia sclerotiorum
Cabagges were grown in pots to the 13 to 14 leaf stage. These plants were sprayed to run-off with previously described spray solution, containing the concentration of active ingredient or their mixture mentioned in the table below. The plants could air-dry. The next day the cabbage leaves were inoculated with 50 pl of a mixture of ground petals, methylcellulose, water, and yeast-bacto- peptone media (inkludes spores of Sclerotinia sclerotiorum). After 8 days at 21 °C and a relative humidity of 60 % the extent of fungal attack on the leaves were visually assessed as % diseased leaf area.
In this test, the samples which had been treated with 125 ppm of the active substance from examples Ex-45, Ex-52, Ex-53, Ex-55, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61 , Ex-71 , Ex-75, Ex-78, Ex-91 , Ex-93, Ex-95 respectively, showed up to at most 20 % growth of the pathogen whereas the untreated plants were 80 % infected.
Microtest
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
Example 6 - Activity against the grey mold Botrytis cinerea in the microtiterplate test
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-1 , Ex-3, Ex-4, Ex-5, Ex-5, Ex-6, Ex-7, Ex-8, Ex-11 , Ex-12, Ex-15, Ex-16, Ex-18, Ex-19, Ex-20, Ex-22, Ex-23, Ex-24, Ex-28, Ex-29, Ex-30, Ex-31 , Ex-32, Ex-33, Ex-34, Ex-35,
Ex-36, Ex-37, Ex-38, Ex-48, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60,
Ex-61 , Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70, Ex-71 , Ex-72, Ex-73,
Ex-74, Ex-75, Ex-76, Ex-77, Ex-78, Ex-79, Ex-80, Ex-81 , Ex-82, Ex-85, Ex-86, Ex-87, Ex-88,
Ex-89, Ex-90, Ex-91 , Ex-92, Ex-93, Ex-94, Ex-95, Ex-96, Ex-97, Ex-98, Ex-99, Ex-100, Ex-101 , Ex-102, Ex-103, Ex-104, Ex-105, Ex-106, Ex-107, Ex-108, Ex-109, Ex-110, Ex-111 , Ex-113, Ex- 115, Ex-116, Ex-117, Ex-118 respectively, showed 14 % growth of the pathogen.
Example 7 - Activity against Cercospora sojina in the microtiterplate test
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Cercospora sojina in an aqueous biomalt or yeast-bactopeptone-sodi- umacetate solution was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-29, Ex-32, Ex-33, Ex-47, Ex-48, Ex-57, E-59, Ex-60, Ex-61 , Ex-72, Ex-75, Ex-76, Ex- 78, Ex-88, Ex-89, Ex-90, Ex-91 , Ex-92, Ex-95, Ex-97 respectively, showed 20 % growth of the pathogen.
Example 8 - Activity against Corynespora cassiicola (CORYCA-G) G413A mutant in the microtiterplate test
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the Corynespora cassiicola (CORYCA-G) G413A mutant isolates in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-29, Ex-32, Ex-33, Ex-43, Ex-45, Ex-47, Ex-48, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61 , Ex-62, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70, Ex-71 , Ex-72, Ex-85, Ex-86, Ex-89, Ex-90 respectively, showed 21 % growth of the pathogen.
Example 9 - Activity against Fusarium culmorum in the microtiterplate test
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Fusarium culmorum in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-2, Ex-3, Ex-5, Ex-5, Ex-6, Ex-8, Ex-26, Ex-28, Ex-29, Ex-30, Ex-32, Ex-33, Ex-35, Ex-36, Ex-37, Ex-38, Ex-48, Ex-52, Ex-54, Ex-57, Ex-63, Ex-64, Ex-65, Ex-66, Ex-67, Ex-69, Ex-70, Ex-71 , Ex-72, Ex-75, Ex-76, Ex-77, Ex-78, Ex-85, Ex-86, Ex-87, Ex-95, Ex-98, Ex-99, Ex-103, Ex-110, Ex-113, Ex-117, Ex-118 respectively, showed 21 % growth of the pathogen.
Example 10 - Activity against the leaf blotch on wheat caused by Septoria tritici in the microtiterplate test The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septorion tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-6, Ex-8, Ex-29, Ex-32, Ex-52, Ex-62, Ex-69, Ex-70, Ex-72, Ex-75, Ex-76, Ex-77, Ex- 78, Ex-81 , Ex-85, Ex-88, Ex-89, Ex-90, Ex-93 respectively, showed 22 % growth of the pathogen.
Example 11 - Activity against the leaf blotch on wheat caused by Alternaria solani in the microtiterplate test
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Alternaria solani in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-43, Ex-45, Ex-47, Ex-48, Ex-52, Ex-53, Ex-54, Ex-55, Ex-57, Ex-58, Ex-60, Ex-62, Ex-64, Ex-66, Ex-67, Ex-69, Ex-70, Ex-71, Ex-72, Ex-76, Ex-85, Ex-86 respectively, showed up to 21 % growth of the pathogen.
Example 12 - Activity against the leaf blotch on wheat caused by Cercospora beticula in the microtiterplate test
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Cercospora beticula in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-48, Ex-53, Ex-72, Ex-75, Ex-76, Ex-85, Ex-88, Ex-89, Ex-90, Ex-92, Ex-95 respectively, showed up to 18% growth of the pathogen.
Example 13 - Activity against the leaf blotch on wheat caused by Cercospora zeae maydis in the microtiterplate test The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Cercospora zeae maydis in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-48, Ex-57, Ex-69, Ex-75, Ex-76, Ex-78, Ex-85, Ex-86, Ex-89, Ex-91 , Ex-92, Ex-95 respectively, showed up to 17% growth of the pathogen.
Example 14 - Activity against the leaf blotch on wheat caused by Pyricularia oryzae in the microtiterplate test
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.
In this test, the samples which had been treated with 31 ppm of the active substance from examples Ex-43, Ex-45, Ex-47, Ex-52, Ex-53, Ex-54, Ex-55, Ex-56, Ex-57, Ex-58, Ex-59, Ex-60, Ex-61 , Ex-62, Ex-63, Ex-64, Ex-66, Ex-67, Ex-68, Ex-69, Ex-70, Ex-71 , Ex-76, Ex-89 respectively, showed up to 22 % growth of the pathogen.
The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.

Claims

Claims
1. Compounds of formula I
Figure imgf000144_0001
Y is N, CR1;
R1 is in each case independently selected from H, halogen, CN, Ci-C4-alkyl, Ci-C4-halogen- alkyl;
R2 is in each case independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-halogenalkyl, C2-Ce-alkenyl, C2-Ce-halogenalkenyl, C2-Ce-alkynyl, C2-Ce-halogenalkynyl, O-Ci-Ce-alkyl, O-C2-Ce-alkenyl, O-C2-Ce-alkynyl, Cs-Ce-cycloalkyl, S-Ci-Ce-alkyl, S-C2-Ce-alkenyl, S-C2- Ce-alkynyl;
R3 is in each case independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-halogenalkyl, C2-Ce-alkenyl, C2-Ce-halogenalkenyl, C2-Ce-alkynyl, C2-Ce-halogenalkynyl, O-Ci-Ce-alkyl, O-C2-Ce-alkenyl, O-C2-Ce-alkynyl, Cs-Ce-cycloalkyl, S-Ci-Ce-alkyl, S-C2-Ce-alkenyl, S-C2- Ce-alkynyl;
R4 is in each case independently selected from H, halogen, CN, Ci-C4-alkyl, Ci-C4-halogen- alkyl;
R5 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R5a; where each R5a is independently halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Ci-Ce-alkyl;
R6 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-C6-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R6a; where each R6a is independently halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Ci-Ce-alkyl; or
R5 and R6 form together an oxo group (=0); or a thioxo group (=S); or
R5 and R6 together with the carbon atom to which they are bound, form a 3-, 4-, 5- or 6-mem- bered saturated carbocyclic ring or a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O and S as ring members; where the carbocyclic or heterocyclic ring is unsubstituted or carries 1 , 2 or 3 substituents R56; where each R56 is independently halogen, Ci-Ce-alkyl or Ci-Ce-haloalkyl;
R7 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R7a; where each R7a is independently halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Ci-Ce-alkyl;;
R8 is in each case independently selected from hydrogen, halogen, CN, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl, benzyl, five- or six-membered heteroaryl or five- or six-membered CH2heteroaryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the aliphatic or aromatic radicals are unsubstituted or carry 1 , 2 or 3 substituents R8a; where each R8a is independently halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl or O-Ci-Ce-alkyl; or
R7 and R8 form together an oxo group (=0) or a thioxo group (=S); or
R7 and R8 together with the carbon atom to which they are bound, form a 3-, 4-, 5- or 6-mem- bered saturated carbocyclic ring or a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O and S as ring members;
R9 is in each case independently selected from CN, CH2CN, CH(CH3)CN, CH(=O), -C(=O)Ci- Ce-alkyl, -C(=O)C2-C6-alkenyl, -C(=O)C2-C6-alkynyl, -C(=O)C3-C6-cycloalkyl, -C(=O)- N(H)Ci-C4-alkyl, -C(=O)-N(Ci-C4-alkyl)2, Ci-Ce-alkyl, Ci-Ce-alkoxy, Ci-C4-haloalkyl, C3- Ce- cycloalkyl, Cs-Ce-halocycloalkyl, C2-Ce-alkenyl, C2-C6-haloalkenyl, C2-Ce-alkynyl, C2- Ce-haloalkynyl, -S(=O)2-R9a, five- or six-membered heteroaryl, aryl or benzyl; wherein heteroaryl contains 1 , 2 or 3 heteroatoms selected from N, O and S as ring members; wherein aryl and the phenyl ring in benzyl are unsubstituted or carry 1 , 2, 3, 4 or 5 substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-haloalkyl, C1- C4-alkoxy and Ci-C4-haloalkoxy; wherein the phenyl ring in benzyl is unsubstituted or carries 1 , 2 or 3 substituents selected from the group consisting of CN and halogen; wherein
R9a is Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl, C2-Ce-haloalkynyl, phenyl or benzyl, where the phenyl ring in the two last-mentioned radicals is unsubstituted or carries 1 , 2 or 3 substituents each independently selected from the group consisting of halogen, Ci-Ce-alkyl, Ci-Ce- haloalkyl, C2-Ce-alkenyl, C2-Ce-haloalkenyl, C2-Ce-alkynyl and C2-Ce-haloalkynyl;
X is in each case independently selected from halogen, CN, Ci-Ce-alkyl, Ci-Ce-haloalkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, Cs-Ce-cycloalkyl, Ci-Ce-alkoxy or Ci-Ce-haloalkoxy, phenyl, benzyl, phenoxy, benzoxy, Ci-Ce-thioalkyl;
N is 0, 1 , 2 or 3; or the N-oxides, tautomers, stereoisomers or agriculturally acceptable salts thereof.
2. Compound of claim 1 , wherein Y is CR1 and R1 is H.
3. Compound of any one of claims 1 to 2, wherein R2 is Ci-Ce-alkyl.
4. Compound of any one of claims 1 to 3, wherein R2 is CH3.
5. Compound of any one of claims 1 to 4, wherein R3 is selected from Ci-Ce-alkyl, Ci-Ce-hal- ogenalkyl.
6. Compound of any one of claims 1 to 5, wherein R3 is CH3 or CHF2.
7. Compound of any one of claims 1 to 6, wherein R4 is H.
8. Compound of any one of claims 1 to 7, wherein R5 and R6 are H or Ci-Ce-alkyl.
9. Compound of any one of claims 1 to 8, wherein R5 and R6 form together with the C atoms to which they are bound a Cs-Ce-cycloalkyl or a (=0) group.
10. Compound of any one of claims 1 to 9, wherein R7 and R8 are H or Ci-Ce-alkyl.
11. Compound of any one of claims 1 to 10, wherein R6 and R7 form together with the C atoms to which they are bound a (=0) group.
12. Compound of any one of claims 1 to 11 , wherein X is selected from halogen, Ci-Ce-alkyl, O-Ci-Ce-alkyl, O-Ci-Ce-halogenalkyl.
13. A composition, comprising one compound of formula I, as defined in any of the claims 1 to 12, an N-oxide or an agriculturally acceptable salt thereof.
14. A method for combating phytopathogenic fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I, as defined in any of the claims 1 to 12 or with a composition, as defined in any of the claim 13.
15. Seed, coated with at least one compound of the formula I, as defined in any of the claims 1 to 12 or an agriculturally acceptable salt thereof or with a composition, as defined in any of the claim 13, in an amount of from 0.1 to 10 kg per 100 kg of seed.
PCT/EP2023/080910 2022-11-16 2023-11-07 Substituted benzodiazepines as fungicides Ceased WO2024104815A1 (en)

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Citations (161)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0141317A2 (en) 1983-10-21 1985-05-15 BASF Aktiengesellschaft 7-Amino-azolo[1,5-a]pyrimidines and fungicides containing them
EP0152031A2 (en) 1984-02-03 1985-08-21 Shionogi & Co., Ltd. Azolyl cycloalkanol derivatives and agricultural fungicides
EP0226917A1 (en) 1985-12-20 1987-07-01 BASF Aktiengesellschaft Acrylic acid esters and fungicides containing these compounds
EP0243970A1 (en) 1986-05-02 1987-11-04 Stauffer Chemical Company Fungicidal pyridyl imidates
EP0256503A2 (en) 1986-08-12 1988-02-24 Mitsubishi Kasei Corporation Pyridinecarboxamide derivatives and their use as fungicide
EP0307510B1 (en) 1987-09-17 1991-02-06 BASF Aktiengesellschaft Process for combating fungicides
WO1991002051A1 (en) 1989-08-03 1991-02-21 The Australian Technological Innovation Corporation Myconematicide
EP0428941A1 (en) 1989-11-10 1991-05-29 Agro-Kanesho Co., Ltd. Hexahydrotriazine compounds and insecticides
US5026417A (en) 1987-03-17 1991-06-25 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Agriculture Methods and compositions for increasing the amounts of phosphorus and/or micronutrients available for plant uptake from soils
EP0532022A1 (en) 1991-09-13 1993-03-17 Ube Industries, Ltd. Acrylate compound, preparation process thereof and fungicide using the same
WO1994001546A1 (en) 1992-07-01 1994-01-20 Cornell Research Foundation, Inc. Elicitor of the hypersensitive response in plants
US5422107A (en) 1992-12-25 1995-06-06 Hokkaido Green Kosan, Incorporated Trichoderma harzianum SK-55 fungus, fungicide containing it, and method of manufacture of the same and its use
WO1995017806A1 (en) 1993-12-29 1995-07-06 Philom Bios Inc. Methods and compositions for increasing the benefits of rhizobium inoculation to legume crop productivity
WO1996021358A1 (en) 1995-01-14 1996-07-18 Prophyta Biologischer Pflanzenschutz Gmbh Fungus isolate, preparation for combatting plant-pathogenic fungi, process for producing it and its use
WO1998044140A1 (en) 1997-04-03 1998-10-08 Dekalb Genetics Corporation Glyphosate resistant maize lines
EP0585215B1 (en) 1989-11-17 1999-09-15 Abbott Laboratories Mutants or variants of bacillus thuringiensis producing high yields of delta endotoxin
WO2000026356A1 (en) 1998-11-03 2000-05-11 Aventis Cropscience N. V. Glufosinate tolerant rice
WO2000026345A1 (en) 1998-11-03 2000-05-11 Aventis Cropscience N.V. Glufosinate tolerant rice
WO2000038618A2 (en) 1998-12-24 2000-07-06 Du Pont Pharmaceuticals Company SUCCINOYLAMINO BENZODIAZEPINES AS INHIBITORS OF Aβ PROTEIN PRODUCTION
EP1028125A1 (en) 1998-11-30 2000-08-16 Isagro Ricerca S.r.l. Dipeptide compounds having fungicidal activity and their agronomic use
EP1035122A1 (en) 1999-03-11 2000-09-13 Rohm And Haas Company Heterocyclic subsituted isoxazolidines and their use as fungicides
WO2001031042A2 (en) 1999-10-29 2001-05-03 Aventis Cropscience N.V. Male-sterile brassica plants and methods for producing same
WO2001041558A1 (en) 1999-12-08 2001-06-14 Aventis Cropscience N.V. Hybrid winter oilseed rape and methods for producing same
EP1122244A1 (en) 2000-02-04 2001-08-08 Sumitomo Chemical Company, Limited Uracil compounds and their use
CN1309897A (en) 2000-02-24 2001-08-29 沈阳化工研究院 Unsaturated oximino ether bactericide
EP1201648A1 (en) 1999-08-05 2002-05-02 Kumiai Chemical Industry Co., Ltd. Carbamate derivatives and agricultural/horticultural bactericides
WO2002034946A2 (en) 2000-10-25 2002-05-02 Monsanto Technology Llc Cotton event pv-ghgt07(1445) and compositions and methods for detection thereof
WO2002036831A2 (en) 2000-10-30 2002-05-10 Monsanto Technology Llc Canola event pv-bngt04(rt73) and compositions and methods for detection thereof
US6406690B1 (en) 1995-04-17 2002-06-18 Minrav Industries Ltd. Bacillus firmus CNCM I-1582 or Bacillus cereus CNCM I-1562 for controlling nematodes
US20020102582A1 (en) 2000-09-13 2002-08-01 Levine Elaine B. Corn event MON810 and compositions and methods for detection thereof
WO2002100163A2 (en) 2001-06-11 2002-12-19 Monsanto Technology Llc Cotton event moni5985 and compositions and methods for detection
WO2003013224A2 (en) 2001-08-06 2003-02-20 Bayer Bioscience N.V. Herbicide tolerant cotton plants and methods for producing and identifying same
WO2003016303A1 (en) 2001-08-20 2003-02-27 Dainippon Ink And Chemicals, Inc. Tetrazoyl oxime derivative and agricultural chemical containing the same as active ingredient
US20030126634A1 (en) 1990-08-09 2003-07-03 Dekalb Genetics Corporation Methods and compositions for the increase of yield in plants
WO2003064572A1 (en) 2002-01-31 2003-08-07 Exxonmobil Research And Engineering Company Lubricating oil compositions with improved friction properties
WO2003066609A1 (en) 2002-02-04 2003-08-14 Bayer Cropscience Aktiengesellschaft Disubstituted thiazolyl carboxanilides and their use as microbicides
WO2003074491A1 (en) 2002-03-05 2003-09-12 Syngenta Participations Ag O-cyclopropyl-carboxanilides and their use as fungicides
CN1456054A (en) 2003-03-25 2003-11-19 浙江省化工研究院 Methoxy methyl acrylate compounds as bactericidal agent
WO2004011601A2 (en) 2002-07-29 2004-02-05 Monsanto Technology, Llc Corn event pv-zmir13 (mon863) plants and compositions and methods for detection thereof
WO2004039986A1 (en) 2002-10-29 2004-05-13 Syngenta Participations Ag Cot102 insecticidal cotton
WO2004049804A2 (en) 2002-11-29 2004-06-17 Syngenta Participations Ag Fungicidal combinations for crop potection
WO2004072235A2 (en) 2003-02-12 2004-08-26 Monsanto Technology Llc Cotton event mon 88913 and compositions and methods for detection thereof
WO2004074492A1 (en) 2003-02-20 2004-09-02 Kws Saat Ag Glyphosate tolerant sugar beet
WO2004083193A1 (en) 2003-03-17 2004-09-30 Sumitomo Chemical Company, Limited Amide compound and bactericide composition containing the same
WO2004099447A2 (en) 2003-05-02 2004-11-18 Dow Agrosciences Llc Corn event tc1507 and methods for detection thereof
WO2005059103A2 (en) 2003-12-15 2005-06-30 Monsanto Technology Llc Corn plant mon88017 and compositions and methods for detection thereof
WO2005061720A2 (en) 2003-12-11 2005-07-07 Monsanto Technology Llc High lysine maize compositions and methods for detection thereof
WO2005063721A1 (en) 2003-12-19 2005-07-14 E.I. Dupont De Nemours And Company Herbicidal pyrimidines
WO2005087772A1 (en) 2004-03-10 2005-09-22 Basf Aktiengesellschaft 5,6-dialkyl-7-amino-triazolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said compounds
WO2005087773A1 (en) 2004-03-10 2005-09-22 Basf Aktiengesellschaft 5,6-dialkyl-7-amino-triazolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said compounds
US6955912B2 (en) 2000-03-31 2005-10-18 Yasuharu Sasaki Process for producing Trichoderma harzianum ferm BP-4346
WO2005103301A2 (en) 2004-03-25 2005-11-03 Syngenta Participations Ag Corn event mir604
WO2005103266A1 (en) 2004-03-26 2005-11-03 Dow Agrosciences Llc Cry1f and cry1ac transgenic cotton lines and event-specific identification thereof
CA2471555A1 (en) 2004-06-18 2005-12-18 Thomas D. Johnson Controlling plant pathogens with fungal/bacterial antagonist combinations comprising trichoderma virens and bacillus amyloliquefaciens
WO2005120234A2 (en) 2004-06-03 2005-12-22 E.I. Dupont De Nemours And Company Fungicidal mixtures of amidinylphenyl compounds
WO2005123689A1 (en) 2004-06-18 2005-12-29 Basf Aktiengesellschaft 1-methyl-3-trifluoromethyl-pyrazole-4-carboxylic acid (ortho-phenyl)-anilides and to use thereof as fungicide
WO2005123690A1 (en) 2004-06-18 2005-12-29 Basf Aktiengesellschaft 1-methyl-3-difluoromethyl-pyrazol-4-carbonic acid-(ortho-phenyl)-anilides, and use thereof as a fungicide
US20060003995A1 (en) 2004-06-30 2006-01-05 Wisys Technology Foundation, Inc. Stereospecific anxiolytic and anticonvulsant agents with reduced muscle-relaxant, sedative-hypnotic and ataxic effects
US6994849B2 (en) 2001-03-14 2006-02-07 State Of Israel, Ministry Of Agriculture, Agricultural Research Organization Yeast Metschnikowia fructicola NRRL Y-30752 for inhibiting deleterious microorganisms on plants
WO2006015866A1 (en) 2004-08-12 2006-02-16 Syngenta Participations Ag Method for protecting useful plants or plant propagation material
WO2006039376A2 (en) 2004-09-29 2006-04-13 Pioneer Hi-Bred International, Inc. Corn event das-59122-7 and methods for detection thereof
WO2006044753A2 (en) 2004-10-19 2006-04-27 Smithkline Beecham Corporation Chemical compounds
US20060178386A1 (en) 2005-02-10 2006-08-10 Saleem Ahmad Dihydroquinazolinones as 5HT modulators
WO2006087325A1 (en) 2005-02-16 2006-08-24 Basf Aktiengesellschaft 5-alkoxyalkyl-6-alkyl-7-amino-azolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said substances
WO2006087343A1 (en) 2005-02-16 2006-08-24 Basf Aktiengesellschaft Pyrazole carboxylic acid anilides, method for the production thereof and agents containing them for controlling pathogenic fungi
WO2006098952A2 (en) 2005-03-16 2006-09-21 Syngenta Participations Ag Corn event 3272 and methods of detection thereof
WO2006108675A2 (en) 2005-04-11 2006-10-19 Bayer Bioscience N.V. Elite event a5547-127 and methods and kits for identifying such event in biological samples
WO2006108674A2 (en) 2005-04-08 2006-10-19 Bayer Bioscience N.V. Elite event a2704-12 and methods and kits for identifying such event in biological samples
WO2006130436A2 (en) 2005-05-27 2006-12-07 Monsanto Technology Llc Soybean event mon89788 and methods for detection thereof
WO2006128573A2 (en) 2005-06-02 2006-12-07 Syngenta Participations Ag Ce43- 67b, insecticidal transgenic cotton expressing cry1ab
WO2007006670A1 (en) 2005-07-07 2007-01-18 Basf Aktiengesellschaft N-thio-anthranilamid compounds and their use as pesticides
CN1907024A (en) 2005-08-03 2007-02-07 浙江化工科技集团有限公司 Methoxyl group displacement methyl acrylate compound bactericidal agent
WO2007017186A1 (en) 2005-08-08 2007-02-15 Bayer Bioscience N.V. Herbicide tolerant cotton plants and methods for identifying same
WO2007082098A2 (en) 2006-01-13 2007-07-19 Dow Agrosciences Llc 6-(poly-substituted aryl)-4-aminopicolinates and their use as herbicides
WO2007090624A2 (en) 2006-02-09 2007-08-16 Syngenta Participations Ag A method of protecting a plant propagation material, a plant, and/or plant organs
WO2007129454A1 (en) 2006-05-08 2007-11-15 Kumiai Chemical Industry Co., Ltd. 1,2-benzisothiazole derivative, and agricultural or horticultural plant disease-controlling agent
WO2007140256A1 (en) 2006-05-26 2007-12-06 Monsanto Technology, Llc Corn plant and seed corresponding to transgenic event mon89034 and methods for detection and use thereof
WO2007142840A2 (en) 2006-06-03 2007-12-13 Syngenta Participations Ag Corn event mir162
US20070292854A1 (en) 2000-06-22 2007-12-20 Behr Carl F Corn event PV-ZMGT32(nk603) and compositions and methods for detection thereof
WO2008002371A1 (en) 2006-06-23 2008-01-03 Becker Underwood Inc. Improved shelf life and on seed stabilization of liquid bacterium inoculants
WO2008002872A2 (en) 2006-06-28 2008-01-03 Pioneer Hi-Bred International, Inc. Soybean event 3560.4.3.5 and compositions and methods for the identification and/or detection thereof
WO2008013622A2 (en) 2006-07-27 2008-01-31 E. I. Du Pont De Nemours And Company Fungicidal azocyclic amides
WO2008054747A2 (en) 2006-10-31 2008-05-08 E. I. Du Pont De Nemours And Company Soybean event dp-305423-1 and compositions and methods for the identification and/or detection thereof
WO2008112019A2 (en) 2006-10-30 2008-09-18 Pioneer Hi-Bred International, Inc. Maize event dp-098140-6 and compositions and methods for the identification and/or detection thereof
WO2008118141A2 (en) 2006-10-17 2008-10-02 Acadia Pharmaceuticals Inc. Use of cannabinoid modulating compounds in combination with other therapeutic compounds for adjunctive therapy
WO2008122406A1 (en) 2007-04-05 2008-10-16 Bayer Bioscience N.V. Insect resistant cotton plants and methods for identifying same
WO2008151780A1 (en) 2007-06-11 2008-12-18 Bayer Bioscience N.V. Insect resistant cotton plants comprising elite event ee-gh6 and methods for identifying same
WO2009064652A1 (en) 2007-11-15 2009-05-22 Monsanto Technology Llc Soybean plant and seed corresponding to transgenic event mon87701 and methods for detection thereof
WO2009090181A2 (en) 2008-01-15 2009-07-23 Bayer Cropscience Sa Pesticide composition comprising a tetrazolyloxime derivative and a fungicide or an insecticide active substance
WO2009094442A2 (en) 2008-01-22 2009-07-30 Dow Agrosciences Llc 5-fluoro pyrimidine derivatives
WO2009103049A2 (en) 2008-02-14 2009-08-20 Pioneer Hi-Bred International, Inc. Plant genomic dna flanking spt event and methods for identifying spt event
WO2009102873A1 (en) 2008-02-15 2009-08-20 Monsanto Technology Llc Soybean plant and seed corresponding to transgenic event mon87769 and methods for detection thereof
WO2009111263A1 (en) 2008-02-29 2009-09-11 Monsanto Technology Llc Corn plant event mon87460 and compositions and methods for detection thereof
WO2009126473A1 (en) 2008-04-07 2009-10-15 Bayer Cropscience Lp Stable aqueous spore-containing formulation
WO2010037016A1 (en) 2008-09-29 2010-04-01 Monsanto Technology Llc Soybean transgenic event mon87705 and methods for detection thereof
WO2010069882A1 (en) 2008-12-17 2010-06-24 Syngenta Participations Ag Isoxazole derivatives for use as fungicides
WO2010077816A1 (en) 2008-12-16 2010-07-08 Syngenta Participations Ag Corn event 5307
WO2010080829A1 (en) 2009-01-07 2010-07-15 Basf Agrochemical Products B.V. Soybean event 127 and methods related thereto
US20100260735A1 (en) 2009-04-13 2010-10-14 University of Delawre Methods for promoting plant health
WO2010139271A1 (en) 2009-06-05 2010-12-09 中国中化股份有限公司 E-type phenyl acrylic ester compounds containing substituted anilino pyrimidine group and uses thereof
WO2011022469A2 (en) 2009-08-19 2011-02-24 Dow Agrosciences Llc Aad-1 event das-40278-9, related transgenic corn lines, and event-specific identification thereof
WO2011028657A1 (en) 2009-09-01 2011-03-10 Dow Agrosciences Llc Synergistic fungicidal compositions containing a 5-fluoropyrimidine derivative for fungal control in cereals
WO2011034704A1 (en) 2009-09-17 2011-03-24 Monsanto Technology Llc Soybean transgenic event mon 87708 and methods of use thereof
WO2011037128A1 (en) 2009-09-28 2011-03-31 日本曹達株式会社 Nitrogen-containing heterocyclic compound and salt thereof, and bactericide for agricultural and horticultural use
WO2011062904A1 (en) 2009-11-23 2011-05-26 Monsanto Technology Llc Transgenic maize event mon 87427 and the relative development scale
WO2011066384A1 (en) 2009-11-24 2011-06-03 Dow Agrosciences Llc Aad-12 event 416, related transgenic soybean lines, and event-specific identification thereof
WO2011077514A1 (en) 2009-12-22 2011-06-30 三井化学アグロ株式会社 Plant disease control composition and method for controlling plant diseases by applying the composition
WO2011081174A1 (en) 2010-01-04 2011-07-07 日本曹達株式会社 Nitrogen-containing heterocyclic compound and agricultural/horticultural germicide
WO2011084621A1 (en) 2009-12-17 2011-07-14 Pioneer Hi-Bred International, Inc. Maize event dp-004114-3 and methods for detection thereof
WO2011109395A2 (en) 2010-03-01 2011-09-09 University Of Delaware Compositions and methods for increasing biomass, iron concentration, and tolerance to pathogens in plants
WO2011135833A1 (en) 2010-04-28 2011-11-03 Sumitomo Chemical Company, Limited Plant disease control composition and its use
WO2011153186A1 (en) 2010-06-04 2011-12-08 Monsanto Technology Llc Transgenic brassica event mon 88302 and methods of use thereof
WO2012051199A2 (en) 2010-10-12 2012-04-19 Monsanto Technology Llc Soybean plant and seed corresponding to transgenic event mon87712 and methods for detection thereof
US20120149571A1 (en) 2010-12-10 2012-06-14 Auburn University Inoculants Including Bacillus Bacteria for Inducing Production of Volatile Organic Compounds in Plants
WO2012082548A2 (en) 2010-12-15 2012-06-21 Syngenta Participations Ag Soybean event syht0h2 and compositions and methods for detection thereof
WO2012084812A1 (en) 2010-12-20 2012-06-28 Isagro Ricerca S.R.L. Aminoindanes amides having a high fungicidal activity and their phytosanitary compositions
WO2012134808A1 (en) 2011-03-30 2012-10-04 Monsanto Technology Llc Cotton transgenic event mon 88701 and methods of use thereof
WO2012165511A1 (en) 2011-05-31 2012-12-06 クミアイ化学工業株式会社 Method for controlling diseases in rice plant
WO2012168188A1 (en) 2011-06-07 2012-12-13 Bayer Intellectual Property Gmbh Active compound combinations
WO2013003558A1 (en) 2011-06-30 2013-01-03 Monsanto Technology Llc Alfalfa plant and seed corresponding to transgenic event kk 179-2 and methods for detection thereof
WO2013007767A1 (en) 2011-07-13 2013-01-17 Basf Se Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
WO2013010862A1 (en) 2011-07-15 2013-01-24 Basf Se Fungicidal alkyl-substituted 2-[2-chloro-4-(4-chloro-phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
WO2013016527A1 (en) 2011-07-26 2013-01-31 Dow Agrosciences Llc Insect resistant and herbicide tolerant soybean event 9582.814.19.1
WO2013024010A1 (en) 2011-08-12 2013-02-21 Basf Se N-thio-anthranilamide compounds and their use as pesticides
WO2013024009A1 (en) 2011-08-12 2013-02-21 Basf Se N-thio-anthranilamide compounds and their use as pesticides
WO2013032693A2 (en) 2011-08-27 2013-03-07 Marrone Bio Innovations, Inc. Isolated bacterial strain of the genus burkholderia and pesticidal metabolites therefrom-formulations and uses
WO2013047749A1 (en) 2011-09-29 2013-04-04 三井化学アグロ株式会社 Production method for 4, 4-difluoro-3,4-dihydroisoquinoline derivative
WO2013047441A1 (en) 2011-09-26 2013-04-04 日本曹達株式会社 Agricultural and horticultural bactericide composition
WO2013092224A1 (en) 2011-12-21 2013-06-27 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi resistant to qo inhibitors
WO2013112527A1 (en) 2012-01-23 2013-08-01 Dow Agrosciences Llc Herbicide tolerant cotton event pdab4468.19.10.3
WO2013116251A2 (en) 2012-02-01 2013-08-08 E. I. Du Pont De Nemours And Company Fungicidal pyrazole mixtures
WO2013127704A1 (en) 2012-02-27 2013-09-06 Bayer Intellectual Property Gmbh Active compound combinations containing a thiazoylisoxazoline and a fungicide
US20130236522A1 (en) 2010-11-10 2013-09-12 Kumiai Chemical Industry Co., Ltd. Microbial pesticidal composition
WO2013162072A1 (en) 2012-04-27 2013-10-31 Sumitomo Chemical Company, Limited Tetrazolinone compounds and its use as pesticides
CN103387541A (en) 2012-05-10 2013-11-13 中国中化股份有限公司 Preparation method of substituted pyrazolylether compound
WO2013169923A2 (en) 2012-05-08 2013-11-14 Monsanto Technology Llc Corn event mon 87411
WO2014029697A1 (en) 2012-08-22 2014-02-27 Basf Se Fungicidal ternary mixtures comprising fluazinam
WO2014060177A1 (en) 2012-10-16 2014-04-24 Syngenta Participations Ag Fungicidal compositions
WO2014102233A1 (en) 2012-12-27 2014-07-03 F. Hoffmann-La Roche Ag Comt inhibitors
WO2014116854A1 (en) 2013-01-25 2014-07-31 Pioneer Hi-Bred International, Inc. Maize event dp-033121-3 and methods for detection thereof
WO2014124369A1 (en) 2013-02-11 2014-08-14 Bayer Cropscience Lp Compositions comprising a streptomyces-based biological control agent and a fungicide
WO2014179276A1 (en) 2013-05-02 2014-11-06 J.R. Simplot Company Potato cultivar j55
WO2014201235A2 (en) 2013-06-14 2014-12-18 Monsanto Technology Llc Soybean transgenic event mon87751 and methods for detection and use thereof
WO2015053998A1 (en) 2013-10-09 2015-04-16 Monsanto Technology Llc Transgenic corn event mon87403 and methods for detection thereof
EP2865265A1 (en) 2014-02-13 2015-04-29 Bayer CropScience AG Active compound combinations comprising phenylamidine compounds and biological control agents
WO2015065922A1 (en) 2013-10-28 2015-05-07 Dexcom, Inc. Devices used in connection with continuous analyte monitoring that provide the user with one or more notifications, and related methods
WO2015142571A1 (en) 2014-03-20 2015-09-24 Monsanto Technology Llc Transgenic maize event mon 87419 and methods of use thereof
WO2016020371A1 (en) 2014-08-04 2016-02-11 Basf Se Antifungal paenibacillus strains, fusaricidin-type compounds, and their use
US20160083401A1 (en) 2013-05-11 2016-03-24 Merck Patent Gmbh Arylquinazolines
WO2016087370A1 (en) 2014-12-01 2016-06-09 Actelion Pharmaceuticals Ltd Cxcr7 receptor modulators
WO2016156241A1 (en) 2015-04-02 2016-10-06 Syngenta Participations Ag Herbicidal mixtures
WO2016162265A1 (en) 2015-04-07 2016-10-13 Syngenta Participations Ag Herbicidal mixtures
WO2016183445A1 (en) 2015-05-14 2016-11-17 J.R. Simplot Company Potato cultivar v11
WO2017062825A1 (en) 2015-10-08 2017-04-13 J.R. Simplot Company Potato cultivar y9
WO2017062831A1 (en) 2015-10-08 2017-04-13 J.R. Simplot Company Potato cultivar x17
CN107879989A (en) 2017-11-29 2018-04-06 河南龙湖生物技术有限公司 3,4,5 substitution ketone drug molecules of Benzodiazepine 2 with bioactivity and preparation method thereof
WO2018177894A1 (en) 2017-03-31 2018-10-04 Syngenta Participations Ag Fungicidal compositions
WO2020212513A1 (en) 2019-04-18 2020-10-22 Syngenta Crop Protection Ag Process for the preparation of microbiocidal oxadiazole derivatives
WO2021071821A1 (en) 2019-10-07 2021-04-15 D.E. Shaw Research, Llc Arylmethylene aromatic compounds as kv1.3 potassium shaker channel blockers
CN114349714A (en) 2021-12-23 2022-04-15 华中师范大学 Dibenzodiazepine derivative and preparation method and application thereof
WO2022099011A1 (en) 2020-11-06 2022-05-12 Cytokinetics, Inc. Bicyclic 1,4-diazepanones and therapeutic uses thereof

Patent Citations (168)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0141317A2 (en) 1983-10-21 1985-05-15 BASF Aktiengesellschaft 7-Amino-azolo[1,5-a]pyrimidines and fungicides containing them
EP0152031A2 (en) 1984-02-03 1985-08-21 Shionogi & Co., Ltd. Azolyl cycloalkanol derivatives and agricultural fungicides
EP0226917A1 (en) 1985-12-20 1987-07-01 BASF Aktiengesellschaft Acrylic acid esters and fungicides containing these compounds
EP0243970A1 (en) 1986-05-02 1987-11-04 Stauffer Chemical Company Fungicidal pyridyl imidates
EP0256503A2 (en) 1986-08-12 1988-02-24 Mitsubishi Kasei Corporation Pyridinecarboxamide derivatives and their use as fungicide
US5026417A (en) 1987-03-17 1991-06-25 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Agriculture Methods and compositions for increasing the amounts of phosphorus and/or micronutrients available for plant uptake from soils
EP0307510B1 (en) 1987-09-17 1991-02-06 BASF Aktiengesellschaft Process for combating fungicides
WO1991002051A1 (en) 1989-08-03 1991-02-21 The Australian Technological Innovation Corporation Myconematicide
EP0428941A1 (en) 1989-11-10 1991-05-29 Agro-Kanesho Co., Ltd. Hexahydrotriazine compounds and insecticides
EP0585215B1 (en) 1989-11-17 1999-09-15 Abbott Laboratories Mutants or variants of bacillus thuringiensis producing high yields of delta endotoxin
US20030126634A1 (en) 1990-08-09 2003-07-03 Dekalb Genetics Corporation Methods and compositions for the increase of yield in plants
EP0532022A1 (en) 1991-09-13 1993-03-17 Ube Industries, Ltd. Acrylate compound, preparation process thereof and fungicide using the same
WO1994001546A1 (en) 1992-07-01 1994-01-20 Cornell Research Foundation, Inc. Elicitor of the hypersensitive response in plants
US5422107A (en) 1992-12-25 1995-06-06 Hokkaido Green Kosan, Incorporated Trichoderma harzianum SK-55 fungus, fungicide containing it, and method of manufacture of the same and its use
WO1995017806A1 (en) 1993-12-29 1995-07-06 Philom Bios Inc. Methods and compositions for increasing the benefits of rhizobium inoculation to legume crop productivity
WO1996021358A1 (en) 1995-01-14 1996-07-18 Prophyta Biologischer Pflanzenschutz Gmbh Fungus isolate, preparation for combatting plant-pathogenic fungi, process for producing it and its use
US6406690B1 (en) 1995-04-17 2002-06-18 Minrav Industries Ltd. Bacillus firmus CNCM I-1582 or Bacillus cereus CNCM I-1562 for controlling nematodes
WO1998044140A1 (en) 1997-04-03 1998-10-08 Dekalb Genetics Corporation Glyphosate resistant maize lines
WO2000026356A1 (en) 1998-11-03 2000-05-11 Aventis Cropscience N. V. Glufosinate tolerant rice
WO2000026345A1 (en) 1998-11-03 2000-05-11 Aventis Cropscience N.V. Glufosinate tolerant rice
EP1028125A1 (en) 1998-11-30 2000-08-16 Isagro Ricerca S.r.l. Dipeptide compounds having fungicidal activity and their agronomic use
WO2000038618A2 (en) 1998-12-24 2000-07-06 Du Pont Pharmaceuticals Company SUCCINOYLAMINO BENZODIAZEPINES AS INHIBITORS OF Aβ PROTEIN PRODUCTION
EP1035122A1 (en) 1999-03-11 2000-09-13 Rohm And Haas Company Heterocyclic subsituted isoxazolidines and their use as fungicides
EP1201648A1 (en) 1999-08-05 2002-05-02 Kumiai Chemical Industry Co., Ltd. Carbamate derivatives and agricultural/horticultural bactericides
WO2001031042A2 (en) 1999-10-29 2001-05-03 Aventis Cropscience N.V. Male-sterile brassica plants and methods for producing same
WO2001041558A1 (en) 1999-12-08 2001-06-14 Aventis Cropscience N.V. Hybrid winter oilseed rape and methods for producing same
EP1122244A1 (en) 2000-02-04 2001-08-08 Sumitomo Chemical Company, Limited Uracil compounds and their use
CN1309897A (en) 2000-02-24 2001-08-29 沈阳化工研究院 Unsaturated oximino ether bactericide
US6955912B2 (en) 2000-03-31 2005-10-18 Yasuharu Sasaki Process for producing Trichoderma harzianum ferm BP-4346
US20070292854A1 (en) 2000-06-22 2007-12-20 Behr Carl F Corn event PV-ZMGT32(nk603) and compositions and methods for detection thereof
US20020102582A1 (en) 2000-09-13 2002-08-01 Levine Elaine B. Corn event MON810 and compositions and methods for detection thereof
WO2002034946A2 (en) 2000-10-25 2002-05-02 Monsanto Technology Llc Cotton event pv-ghgt07(1445) and compositions and methods for detection thereof
WO2002036831A2 (en) 2000-10-30 2002-05-10 Monsanto Technology Llc Canola event pv-bngt04(rt73) and compositions and methods for detection thereof
US6994849B2 (en) 2001-03-14 2006-02-07 State Of Israel, Ministry Of Agriculture, Agricultural Research Organization Yeast Metschnikowia fructicola NRRL Y-30752 for inhibiting deleterious microorganisms on plants
WO2002100163A2 (en) 2001-06-11 2002-12-19 Monsanto Technology Llc Cotton event moni5985 and compositions and methods for detection
WO2003013224A2 (en) 2001-08-06 2003-02-20 Bayer Bioscience N.V. Herbicide tolerant cotton plants and methods for producing and identifying same
WO2003016303A1 (en) 2001-08-20 2003-02-27 Dainippon Ink And Chemicals, Inc. Tetrazoyl oxime derivative and agricultural chemical containing the same as active ingredient
WO2003064572A1 (en) 2002-01-31 2003-08-07 Exxonmobil Research And Engineering Company Lubricating oil compositions with improved friction properties
WO2003066609A1 (en) 2002-02-04 2003-08-14 Bayer Cropscience Aktiengesellschaft Disubstituted thiazolyl carboxanilides and their use as microbicides
WO2003074491A1 (en) 2002-03-05 2003-09-12 Syngenta Participations Ag O-cyclopropyl-carboxanilides and their use as fungicides
WO2004011601A2 (en) 2002-07-29 2004-02-05 Monsanto Technology, Llc Corn event pv-zmir13 (mon863) plants and compositions and methods for detection thereof
WO2004039986A1 (en) 2002-10-29 2004-05-13 Syngenta Participations Ag Cot102 insecticidal cotton
WO2004049804A2 (en) 2002-11-29 2004-06-17 Syngenta Participations Ag Fungicidal combinations for crop potection
WO2004072235A2 (en) 2003-02-12 2004-08-26 Monsanto Technology Llc Cotton event mon 88913 and compositions and methods for detection thereof
WO2004074492A1 (en) 2003-02-20 2004-09-02 Kws Saat Ag Glyphosate tolerant sugar beet
WO2004083193A1 (en) 2003-03-17 2004-09-30 Sumitomo Chemical Company, Limited Amide compound and bactericide composition containing the same
CN1456054A (en) 2003-03-25 2003-11-19 浙江省化工研究院 Methoxy methyl acrylate compounds as bactericidal agent
WO2004099447A2 (en) 2003-05-02 2004-11-18 Dow Agrosciences Llc Corn event tc1507 and methods for detection thereof
WO2005061720A2 (en) 2003-12-11 2005-07-07 Monsanto Technology Llc High lysine maize compositions and methods for detection thereof
WO2005059103A2 (en) 2003-12-15 2005-06-30 Monsanto Technology Llc Corn plant mon88017 and compositions and methods for detection thereof
WO2005063721A1 (en) 2003-12-19 2005-07-14 E.I. Dupont De Nemours And Company Herbicidal pyrimidines
WO2005087772A1 (en) 2004-03-10 2005-09-22 Basf Aktiengesellschaft 5,6-dialkyl-7-amino-triazolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said compounds
WO2005087773A1 (en) 2004-03-10 2005-09-22 Basf Aktiengesellschaft 5,6-dialkyl-7-amino-triazolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said compounds
WO2005103301A2 (en) 2004-03-25 2005-11-03 Syngenta Participations Ag Corn event mir604
WO2005103266A1 (en) 2004-03-26 2005-11-03 Dow Agrosciences Llc Cry1f and cry1ac transgenic cotton lines and event-specific identification thereof
WO2005120234A2 (en) 2004-06-03 2005-12-22 E.I. Dupont De Nemours And Company Fungicidal mixtures of amidinylphenyl compounds
CA2471555A1 (en) 2004-06-18 2005-12-18 Thomas D. Johnson Controlling plant pathogens with fungal/bacterial antagonist combinations comprising trichoderma virens and bacillus amyloliquefaciens
WO2005123689A1 (en) 2004-06-18 2005-12-29 Basf Aktiengesellschaft 1-methyl-3-trifluoromethyl-pyrazole-4-carboxylic acid (ortho-phenyl)-anilides and to use thereof as fungicide
WO2005123690A1 (en) 2004-06-18 2005-12-29 Basf Aktiengesellschaft 1-methyl-3-difluoromethyl-pyrazol-4-carbonic acid-(ortho-phenyl)-anilides, and use thereof as a fungicide
US20060003995A1 (en) 2004-06-30 2006-01-05 Wisys Technology Foundation, Inc. Stereospecific anxiolytic and anticonvulsant agents with reduced muscle-relaxant, sedative-hypnotic and ataxic effects
WO2006015866A1 (en) 2004-08-12 2006-02-16 Syngenta Participations Ag Method for protecting useful plants or plant propagation material
WO2006039376A2 (en) 2004-09-29 2006-04-13 Pioneer Hi-Bred International, Inc. Corn event das-59122-7 and methods for detection thereof
WO2006044753A2 (en) 2004-10-19 2006-04-27 Smithkline Beecham Corporation Chemical compounds
US20060178386A1 (en) 2005-02-10 2006-08-10 Saleem Ahmad Dihydroquinazolinones as 5HT modulators
WO2006087325A1 (en) 2005-02-16 2006-08-24 Basf Aktiengesellschaft 5-alkoxyalkyl-6-alkyl-7-amino-azolopyrimidines, method for their production, their use for controlling pathogenic fungi and agents containing said substances
WO2006087343A1 (en) 2005-02-16 2006-08-24 Basf Aktiengesellschaft Pyrazole carboxylic acid anilides, method for the production thereof and agents containing them for controlling pathogenic fungi
WO2006098952A2 (en) 2005-03-16 2006-09-21 Syngenta Participations Ag Corn event 3272 and methods of detection thereof
WO2006108674A2 (en) 2005-04-08 2006-10-19 Bayer Bioscience N.V. Elite event a2704-12 and methods and kits for identifying such event in biological samples
WO2006108675A2 (en) 2005-04-11 2006-10-19 Bayer Bioscience N.V. Elite event a5547-127 and methods and kits for identifying such event in biological samples
WO2006130436A2 (en) 2005-05-27 2006-12-07 Monsanto Technology Llc Soybean event mon89788 and methods for detection thereof
WO2006128573A2 (en) 2005-06-02 2006-12-07 Syngenta Participations Ag Ce43- 67b, insecticidal transgenic cotton expressing cry1ab
WO2007006670A1 (en) 2005-07-07 2007-01-18 Basf Aktiengesellschaft N-thio-anthranilamid compounds and their use as pesticides
CN1907024A (en) 2005-08-03 2007-02-07 浙江化工科技集团有限公司 Methoxyl group displacement methyl acrylate compound bactericidal agent
WO2007017186A1 (en) 2005-08-08 2007-02-15 Bayer Bioscience N.V. Herbicide tolerant cotton plants and methods for identifying same
WO2007082098A2 (en) 2006-01-13 2007-07-19 Dow Agrosciences Llc 6-(poly-substituted aryl)-4-aminopicolinates and their use as herbicides
WO2007090624A2 (en) 2006-02-09 2007-08-16 Syngenta Participations Ag A method of protecting a plant propagation material, a plant, and/or plant organs
WO2007129454A1 (en) 2006-05-08 2007-11-15 Kumiai Chemical Industry Co., Ltd. 1,2-benzisothiazole derivative, and agricultural or horticultural plant disease-controlling agent
WO2007140256A1 (en) 2006-05-26 2007-12-06 Monsanto Technology, Llc Corn plant and seed corresponding to transgenic event mon89034 and methods for detection and use thereof
WO2007142840A2 (en) 2006-06-03 2007-12-13 Syngenta Participations Ag Corn event mir162
WO2008002371A1 (en) 2006-06-23 2008-01-03 Becker Underwood Inc. Improved shelf life and on seed stabilization of liquid bacterium inoculants
WO2008002872A2 (en) 2006-06-28 2008-01-03 Pioneer Hi-Bred International, Inc. Soybean event 3560.4.3.5 and compositions and methods for the identification and/or detection thereof
WO2008013622A2 (en) 2006-07-27 2008-01-31 E. I. Du Pont De Nemours And Company Fungicidal azocyclic amides
WO2008118141A2 (en) 2006-10-17 2008-10-02 Acadia Pharmaceuticals Inc. Use of cannabinoid modulating compounds in combination with other therapeutic compounds for adjunctive therapy
WO2008112019A2 (en) 2006-10-30 2008-09-18 Pioneer Hi-Bred International, Inc. Maize event dp-098140-6 and compositions and methods for the identification and/or detection thereof
WO2008054747A2 (en) 2006-10-31 2008-05-08 E. I. Du Pont De Nemours And Company Soybean event dp-305423-1 and compositions and methods for the identification and/or detection thereof
WO2008122406A1 (en) 2007-04-05 2008-10-16 Bayer Bioscience N.V. Insect resistant cotton plants and methods for identifying same
WO2008151780A1 (en) 2007-06-11 2008-12-18 Bayer Bioscience N.V. Insect resistant cotton plants comprising elite event ee-gh6 and methods for identifying same
WO2009064652A1 (en) 2007-11-15 2009-05-22 Monsanto Technology Llc Soybean plant and seed corresponding to transgenic event mon87701 and methods for detection thereof
WO2009090181A2 (en) 2008-01-15 2009-07-23 Bayer Cropscience Sa Pesticide composition comprising a tetrazolyloxime derivative and a fungicide or an insecticide active substance
WO2009094442A2 (en) 2008-01-22 2009-07-30 Dow Agrosciences Llc 5-fluoro pyrimidine derivatives
WO2009103049A2 (en) 2008-02-14 2009-08-20 Pioneer Hi-Bred International, Inc. Plant genomic dna flanking spt event and methods for identifying spt event
WO2009102873A1 (en) 2008-02-15 2009-08-20 Monsanto Technology Llc Soybean plant and seed corresponding to transgenic event mon87769 and methods for detection thereof
WO2009111263A1 (en) 2008-02-29 2009-09-11 Monsanto Technology Llc Corn plant event mon87460 and compositions and methods for detection thereof
WO2009126473A1 (en) 2008-04-07 2009-10-15 Bayer Cropscience Lp Stable aqueous spore-containing formulation
WO2010037016A1 (en) 2008-09-29 2010-04-01 Monsanto Technology Llc Soybean transgenic event mon87705 and methods for detection thereof
WO2010077816A1 (en) 2008-12-16 2010-07-08 Syngenta Participations Ag Corn event 5307
WO2010069882A1 (en) 2008-12-17 2010-06-24 Syngenta Participations Ag Isoxazole derivatives for use as fungicides
WO2010080829A1 (en) 2009-01-07 2010-07-15 Basf Agrochemical Products B.V. Soybean event 127 and methods related thereto
US20100260735A1 (en) 2009-04-13 2010-10-14 University of Delawre Methods for promoting plant health
WO2010139271A1 (en) 2009-06-05 2010-12-09 中国中化股份有限公司 E-type phenyl acrylic ester compounds containing substituted anilino pyrimidine group and uses thereof
WO2011022469A2 (en) 2009-08-19 2011-02-24 Dow Agrosciences Llc Aad-1 event das-40278-9, related transgenic corn lines, and event-specific identification thereof
WO2011028657A1 (en) 2009-09-01 2011-03-10 Dow Agrosciences Llc Synergistic fungicidal compositions containing a 5-fluoropyrimidine derivative for fungal control in cereals
WO2011034704A1 (en) 2009-09-17 2011-03-24 Monsanto Technology Llc Soybean transgenic event mon 87708 and methods of use thereof
EP2484672A1 (en) * 2009-09-28 2012-08-08 Nippon Soda Co., Ltd. Nitrogen-containing heterocyclic compound and salt thereof, and bactericide for agricultural and horticultural use
US20120184732A1 (en) 2009-09-28 2012-07-19 Nippon Soda Co., Ltd. Nitrogen-containing heterocyclic compound and salt thereof, and a fungicide for agricultural and horticultural use
WO2011037128A1 (en) 2009-09-28 2011-03-31 日本曹達株式会社 Nitrogen-containing heterocyclic compound and salt thereof, and bactericide for agricultural and horticultural use
WO2011062904A1 (en) 2009-11-23 2011-05-26 Monsanto Technology Llc Transgenic maize event mon 87427 and the relative development scale
WO2011066384A1 (en) 2009-11-24 2011-06-03 Dow Agrosciences Llc Aad-12 event 416, related transgenic soybean lines, and event-specific identification thereof
WO2011084621A1 (en) 2009-12-17 2011-07-14 Pioneer Hi-Bred International, Inc. Maize event dp-004114-3 and methods for detection thereof
WO2011077514A1 (en) 2009-12-22 2011-06-30 三井化学アグロ株式会社 Plant disease control composition and method for controlling plant diseases by applying the composition
WO2011081174A1 (en) 2010-01-04 2011-07-07 日本曹達株式会社 Nitrogen-containing heterocyclic compound and agricultural/horticultural germicide
WO2011109395A2 (en) 2010-03-01 2011-09-09 University Of Delaware Compositions and methods for increasing biomass, iron concentration, and tolerance to pathogens in plants
WO2011135833A1 (en) 2010-04-28 2011-11-03 Sumitomo Chemical Company, Limited Plant disease control composition and its use
WO2011153186A1 (en) 2010-06-04 2011-12-08 Monsanto Technology Llc Transgenic brassica event mon 88302 and methods of use thereof
WO2012051199A2 (en) 2010-10-12 2012-04-19 Monsanto Technology Llc Soybean plant and seed corresponding to transgenic event mon87712 and methods for detection thereof
US20130236522A1 (en) 2010-11-10 2013-09-12 Kumiai Chemical Industry Co., Ltd. Microbial pesticidal composition
US8445255B2 (en) 2010-12-10 2013-05-21 Auburn University Inoculants including Bacillus bacteria for inducing production of volatile organic compounds in plants
US20120149571A1 (en) 2010-12-10 2012-06-14 Auburn University Inoculants Including Bacillus Bacteria for Inducing Production of Volatile Organic Compounds in Plants
WO2012082548A2 (en) 2010-12-15 2012-06-21 Syngenta Participations Ag Soybean event syht0h2 and compositions and methods for detection thereof
WO2012084812A1 (en) 2010-12-20 2012-06-28 Isagro Ricerca S.R.L. Aminoindanes amides having a high fungicidal activity and their phytosanitary compositions
WO2012134808A1 (en) 2011-03-30 2012-10-04 Monsanto Technology Llc Cotton transgenic event mon 88701 and methods of use thereof
WO2012165511A1 (en) 2011-05-31 2012-12-06 クミアイ化学工業株式会社 Method for controlling diseases in rice plant
WO2012168188A1 (en) 2011-06-07 2012-12-13 Bayer Intellectual Property Gmbh Active compound combinations
WO2013003558A1 (en) 2011-06-30 2013-01-03 Monsanto Technology Llc Alfalfa plant and seed corresponding to transgenic event kk 179-2 and methods for detection thereof
WO2013007767A1 (en) 2011-07-13 2013-01-17 Basf Se Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
WO2013010862A1 (en) 2011-07-15 2013-01-24 Basf Se Fungicidal alkyl-substituted 2-[2-chloro-4-(4-chloro-phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds
WO2013016527A1 (en) 2011-07-26 2013-01-31 Dow Agrosciences Llc Insect resistant and herbicide tolerant soybean event 9582.814.19.1
WO2013016516A1 (en) 2011-07-26 2013-01-31 Dow Agrosciences Llc Insect resistant and herbicide tolerant breeding stack of soybean event pdab9582.814.19.1 and pdab4468.04.16.1
WO2013024010A1 (en) 2011-08-12 2013-02-21 Basf Se N-thio-anthranilamide compounds and their use as pesticides
WO2013024009A1 (en) 2011-08-12 2013-02-21 Basf Se N-thio-anthranilamide compounds and their use as pesticides
WO2013032693A2 (en) 2011-08-27 2013-03-07 Marrone Bio Innovations, Inc. Isolated bacterial strain of the genus burkholderia and pesticidal metabolites therefrom-formulations and uses
WO2013047441A1 (en) 2011-09-26 2013-04-04 日本曹達株式会社 Agricultural and horticultural bactericide composition
WO2013047749A1 (en) 2011-09-29 2013-04-04 三井化学アグロ株式会社 Production method for 4, 4-difluoro-3,4-dihydroisoquinoline derivative
WO2013092224A1 (en) 2011-12-21 2013-06-27 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi resistant to qo inhibitors
WO2013112527A1 (en) 2012-01-23 2013-08-01 Dow Agrosciences Llc Herbicide tolerant cotton event pdab4468.19.10.3
WO2013116251A2 (en) 2012-02-01 2013-08-08 E. I. Du Pont De Nemours And Company Fungicidal pyrazole mixtures
WO2013127704A1 (en) 2012-02-27 2013-09-06 Bayer Intellectual Property Gmbh Active compound combinations containing a thiazoylisoxazoline and a fungicide
WO2013162072A1 (en) 2012-04-27 2013-10-31 Sumitomo Chemical Company, Limited Tetrazolinone compounds and its use as pesticides
WO2013169923A2 (en) 2012-05-08 2013-11-14 Monsanto Technology Llc Corn event mon 87411
CN103387541A (en) 2012-05-10 2013-11-13 中国中化股份有限公司 Preparation method of substituted pyrazolylether compound
WO2014029697A1 (en) 2012-08-22 2014-02-27 Basf Se Fungicidal ternary mixtures comprising fluazinam
WO2014060177A1 (en) 2012-10-16 2014-04-24 Syngenta Participations Ag Fungicidal compositions
WO2014102233A1 (en) 2012-12-27 2014-07-03 F. Hoffmann-La Roche Ag Comt inhibitors
WO2014116854A1 (en) 2013-01-25 2014-07-31 Pioneer Hi-Bred International, Inc. Maize event dp-033121-3 and methods for detection thereof
WO2014124369A1 (en) 2013-02-11 2014-08-14 Bayer Cropscience Lp Compositions comprising a streptomyces-based biological control agent and a fungicide
WO2014178913A1 (en) 2013-05-02 2014-11-06 J.R. Simplot Company Potato cultivar f10
WO2014178941A1 (en) 2013-05-02 2014-11-06 J.R. Simplot Company Potato cultivar j3
WO2014179276A1 (en) 2013-05-02 2014-11-06 J.R. Simplot Company Potato cultivar j55
WO2014178910A1 (en) 2013-05-02 2014-11-06 J.R. Simplot Company Potato cultivar e12
US20160083401A1 (en) 2013-05-11 2016-03-24 Merck Patent Gmbh Arylquinazolines
WO2014201235A2 (en) 2013-06-14 2014-12-18 Monsanto Technology Llc Soybean transgenic event mon87751 and methods for detection and use thereof
WO2015053998A1 (en) 2013-10-09 2015-04-16 Monsanto Technology Llc Transgenic corn event mon87403 and methods for detection thereof
WO2015065922A1 (en) 2013-10-28 2015-05-07 Dexcom, Inc. Devices used in connection with continuous analyte monitoring that provide the user with one or more notifications, and related methods
EP2865265A1 (en) 2014-02-13 2015-04-29 Bayer CropScience AG Active compound combinations comprising phenylamidine compounds and biological control agents
WO2015142571A1 (en) 2014-03-20 2015-09-24 Monsanto Technology Llc Transgenic maize event mon 87419 and methods of use thereof
WO2016020371A1 (en) 2014-08-04 2016-02-11 Basf Se Antifungal paenibacillus strains, fusaricidin-type compounds, and their use
WO2016087370A1 (en) 2014-12-01 2016-06-09 Actelion Pharmaceuticals Ltd Cxcr7 receptor modulators
WO2016156241A1 (en) 2015-04-02 2016-10-06 Syngenta Participations Ag Herbicidal mixtures
WO2016162265A1 (en) 2015-04-07 2016-10-13 Syngenta Participations Ag Herbicidal mixtures
WO2016183445A1 (en) 2015-05-14 2016-11-17 J.R. Simplot Company Potato cultivar v11
WO2017062825A1 (en) 2015-10-08 2017-04-13 J.R. Simplot Company Potato cultivar y9
WO2017062831A1 (en) 2015-10-08 2017-04-13 J.R. Simplot Company Potato cultivar x17
WO2018177894A1 (en) 2017-03-31 2018-10-04 Syngenta Participations Ag Fungicidal compositions
CN107879989A (en) 2017-11-29 2018-04-06 河南龙湖生物技术有限公司 3,4,5 substitution ketone drug molecules of Benzodiazepine 2 with bioactivity and preparation method thereof
WO2020212513A1 (en) 2019-04-18 2020-10-22 Syngenta Crop Protection Ag Process for the preparation of microbiocidal oxadiazole derivatives
WO2021071821A1 (en) 2019-10-07 2021-04-15 D.E. Shaw Research, Llc Arylmethylene aromatic compounds as kv1.3 potassium shaker channel blockers
WO2022099011A1 (en) 2020-11-06 2022-05-12 Cytokinetics, Inc. Bicyclic 1,4-diazepanones and therapeutic uses thereof
CN114349714A (en) 2021-12-23 2022-04-15 华中师范大学 Dibenzodiazepine derivative and preparation method and application thereof

Non-Patent Citations (37)

* Cited by examiner, † Cited by third party
Title
"McCutcheon's", vol. 1, 2008, GLEN ROCK, article "Emulsifiers & Detergents, McCutcheon's Directories"
"Technical Monograph", May 2008, CROPLIFE INTERNATIONAL, article "Catalogue of pesticide formulation types and international coding system"
APPL. ENVIRON. MICROBIOL., vol. 73, no. 8, 2007, pages 2635
BIOCONTROL SCIENCE TECHNOL., vol. 22, no. 7, pages 747 - 761
BIOCONTROL, vol. 57, 2012, pages 687 - 696
BIOL. FERTIL. SOILS, vol. 47, 2011, pages 81 - 89
BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, vol. 35, 2021, pages 127813
CAN. J. PLANT SCI., vol. 48, no. 6, 1968, pages 587 - 94
CAN. J. PLANT SCI., vol. 78, no. 1, 1998, pages 91 - 102
CAN. J. PLANT. SCI., vol. 70, 1990, pages 661 - 666
CHEM. EUR. J., vol. 22, 2016, pages 10607 - 10613
CHEM. SCI., vol. 12, 2021, pages 4519 - 4525
CHINESE SCIENCE BULLETIN, vol. 55, no. 25, 2010, pages 2817 - 2819
CROP PROTECTION, vol. 27, 2008, pages 352 - 361
EUR. J. SOIL BIOL., vol. 45, 2009, pages 28 - 35
FEDERAL REGISTER, vol. 76, no. 22, 2 February 2011 (2011-02-02), pages 5808
FERTILIZER RES., vol. 39, 1994, pages 97 - 103
HETEROCYCLES, vol. 38, 1994, pages 125 - 134
INORGANICA CHIMICA ACTA, vol. 382, 2012, pages 72 - 78
INT. J. SYST. EVOL. MICROBIOL., vol. 66, 2016, pages 1212 - 1217
J. AM. CHEM. SOC., vol. 123, no. 25, 2001, pages 5962 - 5973
J. BIOORG. MED. CHEM. LETT., vol. 17, 2007, pages 2527 - 2530
J. HETEROCYC. CHEM., vol. 18, no. 7, 1981, pages 1305 - 8
J. INVERTEBRATE PATHOL., vol. 107, 2011, pages 112 - 126
J. MED. CHEM., vol. 38, no. 11, 1995, pages 1892 - 903
J. MED. CHEM., vol. 56, 2013, pages 10158 - 10170
J. MED. CHEM., vol. 59, 2016, pages 10661 - 10675
J. ORG. CHEM., vol. 70, 2005, pages 8924 - 8931
J. PLANT DIS. PROT., vol. 105, 1998, pages 181 - 197
KNOWLES: "New developments in crop protection product formulation, Agrow Reports DS243", 2005, T&F INFORMA
MOLLETGRUBEMANN: "Formulation technology", 2001, WILEY VCH
ORG LETT., vol. 14, 2012, pages 5916 - 5919
ORG. BIOMOL. CHEM., vol. 12, 2014, pages 6895 - 6900
PLANT SOIL, vol. 331, 2010, pages 413 - 425
PNAS, vol. 107, no. 19, 2010, pages 8563 - 856
SCIENCE, vol. 257, 1992, pages 85 - 88
SYSTEM. APPL. MICROBIOL., vol. 27, 2004, pages 372 - 379

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