[go: up one dir, main page]

WO2021249800A1 - Substituted [1,2,4]triazole compounds as fungicides - Google Patents

Substituted [1,2,4]triazole compounds as fungicides Download PDF

Info

Publication number
WO2021249800A1
WO2021249800A1 PCT/EP2021/064484 EP2021064484W WO2021249800A1 WO 2021249800 A1 WO2021249800 A1 WO 2021249800A1 EP 2021064484 W EP2021064484 W EP 2021064484W WO 2021249800 A1 WO2021249800 A1 WO 2021249800A1
Authority
WO
WIPO (PCT)
Prior art keywords
compounds
combination
line
corresponds
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2021/064484
Other languages
French (fr)
Inventor
Jan Klaas Lohmann
Ian Robert CRAIG
Tim Alexander STOESSER
Martin Semar
Marcus Fehr
Bernd Mueller
Wassilios Grammenos
Thomas Grote
Michael Seet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2021249800A1 publication Critical patent/WO2021249800A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the present invention relates to substituted [1 ,2,4]triazole compounds and the N-oxides and the salts thereof, to the use of said compounds and methods for combating phytopathogenic fungi and to seeds coated with at least one such compound.
  • the invention also relates to processes for preparing these compounds and to compositions comprising at least one compound I.
  • the fungicidal activity of known fungicidal compounds is unsatisfactory. Based on this, it was an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic harmful fungi.
  • R 1 is selected from hydrogen, OH, CrC 4 -halogenalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -halogenalkenyl, C 2 -C 4 -alkynyl, C 2 -C 4 -halogenalkynyl;
  • R a is independently of one another selected from hydrogen or halogen
  • R 2 is hydrogen
  • R 3 is selected from halogen or CrC 4 -halogenalkyl
  • R 4 , R 4 ’, and R 4 ” are independently of one another selected from hydrogen, halogen, CrC 4 -alkyl, CrC 4 -halogenalkyl;
  • R 5 and R 5 ’ are independently of one another selected from hydrogen or halogen; or
  • the compounds of formula I can be prepared as described in WO 2015/185708.
  • the compounds of formula I can be prepared as follows.
  • Compounds II, wherein R 3 is as defined for compounds I and Halo 1 is a halogen, preferably Br, are reacted with (R 4 R 4 ’R 4 ”C)-LG, wherein R 4 , R 4 ’ and R 4 ” are as defined for compounds I and LG represents a nucleophilically replaceable leaving group, such as halogen, alkylsulfonyl, alkylsulfonyloxy and arylsulfonyloxy, preferably Cl, Br or I, preferably in the presence of a base, such as, e.g., NaH, K 2 CO 3 , Na 2 C0 3 or the like, in a suitable solvent such as THF, DMF or the like.
  • a base such as, e.g., NaH, K 2 CO 3 , Na 2 C0 3 or the like, in a suitable solvent
  • ketones V are transformed into Grignard reagents by the reaction with transmetallation reagents, such as isopropylmagnesium halides, and subsequently reacted with compounds IV, preferably under anhydrous conditions, to obtain ketones V.
  • a catalyst such as CuCI, CuCh, AlCb or LiCI, can be optionally added.
  • the ketones V are reacted with trimethylsulf(ox)onium halides, preferably iodide, preferably in the presence of a base such as sodium hydroxide, leading to the epoxides VI which after a reaction with 1 H-1 , 2, 4-triazole, preferably in the presence of a base, such as potassium carbonate, give the final compounds 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.
  • CrC4-alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2- methylpropyl and 1 ,1-dimethylethyl.
  • a preferred embodiment of a CrC4-alkyl is a C2-C4-alkyl.
  • 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).
  • CrC4-haloalkyl or "Ci-C4-halogenalkyl” refers to an alkyl group having 1 or 4 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above.
  • a preferred embodiment of a CrC4-haloalkyl is a Ci-C2-haloalkyl.
  • Representative CrC2-haloalkyl groups include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 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-tri chloroethyl or pentafluoroethyl.
  • C2-C4-alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and at least one double bond in any position, 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-C4-haloalkenyl or "C2-C4-halogenalkenyl” refers to an alkenyl group having 2 or 4 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above.
  • a preferred embodiment of a C2-C4-haloalke- nyl is a C2-C3-haloalkenyl.
  • C2-C4-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and containing at least one triple bond, such as ethynyl, prop-1-ynyl (-CoC-CH3), prop-2-ynyl (propargyl), but-1-ynyl, but-2-ynyl, but-3-ynyl, 1-methyl-prop-2-ynyl.
  • C2-C4-haloalkynyl or "C 2 -C4-halogenalkynyl” refers to an alkynyl group having 2 or 4 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above.
  • a preferred embodiment of a C2-C4-halo- alkynyl is a C2-C3-haloalkynyl.
  • Representative C2-C3-haloalkynyl groups include F-ethynyl, Cl- ethynyl, Br-ethynyl, Br-prop-2-ynyl (-CH2-CoC-Br) and CI-prop-2-ynyl (-CH2-CoC-CI).
  • aliphatic or “aliphatic group” is to be understood to refer to a non-cyclic compound, substituent or residue composed of hydrogen and carbon atoms only, and it may be saturated or unsaturated, as well as linear or branched. An aliphatic compound, substituent or residue may be optionally substituted where indicated. Examples of an aliphatic compound, substituent or residue comprise alkyl, alkenyl, and alkynyl, all with a variable number of carbon atoms.
  • any of the variables is optionally substituted, it is understood that this applies to moieties containing carbon-hydrogen bonds, wherein the hydrogen atom is substituted by the corresponding substituent, however, not to moieties such as hydrogen, halogen, CN or the like.
  • a hydroxymethyl group is generated.
  • Agriculturally acceptable salts of the inventive compounds 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 said compounds.
  • 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 carry one to four CrC4-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 sulfoxonium ions
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of CrC4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting such inventive compound with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the inventive compounds can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
  • the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or diastereomers and their mixtures are subject matter of the present invention.
  • R 1 is selected from hydrogen, OH, CrC 4 -halogenalkyl, C 2 -C 4 -alk- enyl, C 2 -C 4 -halogenalkenyl, C 2 -C 4 -alkynyl, C 2 -C 4 -halogenalkynyl; preferably from hydrogen, CrC 4 -halogenalkyl, C 2 -C 4 -halogenalkenyl, C 2 -C 4 -halogenalkynyl; more preferably from CrC 4 -halogenalkyl, C 2 -C 4 -halogenalkenyl, C 2 -C 4 -halogenalkynyl, provided that if m is 0 and three or four R a are hydrogens, then R 1 is not hydrogen.
  • R 1 is hydrogen, provided that if m is 0, then one or two R a are not hydrogens.
  • R 1 is OH.
  • R 1 is CrC 4 -halogenalkyl, such as CF 3 , CHF 2 , CF 2 CH 3 , CH 2 CF 3 , CHFCH 3 or CF 2 CF 3 ; preferably CrC 2 -halogenalkyl, most preferably preferably Cr halogenalkyl.
  • R 1 is C2-C4-alkynyl, such as CoCH, CoCCH 3 , CH 2 -CoC-H or CH 2 -CoC-CH 3 .
  • R 1 is C2-C4-halogenalkynyl, such as CoCCI, CoCBr, CoC-I, CH 2 CoCCI, CH 2 CoCBr.
  • R 1 Particularly preferred R 1 according to the invention are listed in Table P1 below, wherein each line of lines P1-1 to P1-35 corresponds to one specific embodiment of the invention.
  • R a according to the invention is independently selected from hydrogen or halogen; preferably from halogen.
  • R a is hydrogen
  • R a is halogen, preferably F or Cl.
  • each R a is made independently of one another, and all R a may be identical or different.
  • R 2 according to the invention is hydrogen.
  • R 3 according to the present invention is selected from halogen or Ci-C4-halogenalkyl. According one embodiment R 3 is halogen, preferably F, Cl or Br.
  • R 3 is CrC4-halogenalkyl, preferably CrC2-halogenalkyl, such as CFs, CHF 2 , CH 2 F, CCI 3 , CHCI 2 or CH 2 CI.
  • R 3 Accordingly preferred R 3 according to the invention are listed in Table P3 below, wherein each line of lines P3-1 to P3-9 corresponds to one specific embodiment of the invention:
  • R 4 , R 4 ’, and R 4 ” are independently of one another selected from hydrogen, halogen, CrC4-alkyl, CrC4-halogenalkyl; preferably from hydrogen, F, Cl, CrC2-alkyl and CrC2-halogenalkyl.
  • each of the three variables R 4 , R 4 ’, and R 4 is made independently of one another, and R 4 , R 4 ’, and R 4 ” may be identical or different. According to one embodiment, at least one of R 4 , R 4 ’, and R 4 ” is not hydrogen.
  • only one of R 4 , R 4 ’, and R 4 ” is hydrogen.
  • R 4 , R 4 ’, and R 4 ” are independently selected from hydrogen or halogen. According to another embodiment, at least one of R 4 , R 4 ’, and R 4 ” is halogen, preferably F or Cl. According to another embodiment, at least two of R 4 , R 4 ’, and R 4 ” are halogens, preferably F or Cl. According to another embodiment, each of R 4 , R 4 ’, and R 4 ” is halogen, preferably F or Cl.
  • R 4 , R 4 ’, and R 4 ” are independently selected from hydrogen, halogen, such as F, Cl or Br, CrC4-alkyl, such as CF , C2H5, C 3 H7, CH(CH 3 )2, C(CH 3 )3, CH 2 C(CH 3 )3 and CH 2 CH(CH 3 )2; and CrC4-halogenalkyl, such as CF 3 , CF 2 Br, CHF 2 ,
  • R 4 , R 4 ’, and R 4 are listed in Table P4 below, wherein each line of lines P4-1 to P4-20 corresponds to one particular embodiment of the invention, wherein P4-1 to P4- 20 are also in any combination a preferred embodiment of the present invention.
  • CR 4 R 4 ’R 4 ” is CrC 4 -alkyl, such as CH 3 , C 2 H 5 , C 3 H 7 , CH(CH 3 )2, CH 2 CH(CH 3 )2 or C(CH 3 ) 3 ; preferably CrC 3 -alkyl, such as CH 3 , C 2 H 5 , C 3 H 7 , or CH(CH 3 ) 2 ; more preferably, CrC 2 -alkyl, such as CH 3 , C 2 H 5 .
  • CR 4 R 4 ’R 4 ” is CrC 4 -halogenalkyl, preferably C 1 -C 3 - halogenalkyl, such as CF 3 , CHF 2 , CH 2 F, CBrF 2 , CHFCI, CHFCF 3 , CF 2 CH 3 , CF 2 CHF 2 , CH 2 CF 3 , CF 2 CF 3 or CH 2 CF 2 CHF 2 , more preferably CrC 2 -halogenalkyl, such as such as CF 3 , CHF 2 , CH 2 F, CBrF 2 , CHFCI, CHFCFs, CF 2 CH 3 , CF 2 CHF 2 , CH 2 CF 3 or CF 2 CF 3 .
  • R 5 according to the present invention is hydrogen or halogen, such as F, Cl or Br; preferably F or Cl. According to one embodiment, R 5 is H. According to another embodiment, R 5 is Cl. According to another embodiment, R 5 is F.
  • R 5 ’ according to the present invention is selected from hydrogen or halogen, such as F, Cl or Br. According to one embodiment, R 5 ’ is hydrogen. According to another embodiment,
  • R 5 ’ is Cl. According to another embodiment, R 5 ’ is F.
  • R 5 and R 5 ’ are hydrogens, then at least one R a is not hydrogen.
  • R 6 is independent from one another is selected from hydrogen, halogen or CrC4-alkyl.
  • CR 5 R 5 ’ may be CH2, provided that at least one R a is not hydrogen.
  • R 6 is independently of one another selected from halogen or CrC4-alkyl.
  • m according to the present invention is 0 or 1. According to one embodiment, m is 0. According to another embodiment, m is 1.
  • Table T2 One specific embodiment or the invention relates to compounds of formula I, wherein m is 0 and all R a are H (compounds I. A). Another specific embodiment to compounds of formula I, wherein m is 1 and all R a are H (compounds I.B): Another specific embodiment or the invention relates to compounds of formula I, wherein m is 0; two geminal R a are H and two other two geminal R a are F (compounds I.C). Another specific embodiment to compounds of formula I, wherein m is 1 two geminal R a are H and two other two geminal R a are F (compounds I.D): Particular preference is given to the compounds of the formula I.A compiled in the Tables
  • 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), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (syn. Fungi imperfecti). 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 phytopathogenic 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, pears,
  • 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.
  • 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,
  • 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, 19-51 a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN 10224, MON 1445, 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.105, 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, BN LA-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). Further information on specific events and methods to detect them can be found for canola events MS1, MS8, RF3, GT73, MON88302, KK179 in W001/031042, W001/041558, W001/041558, W002/036831,
  • GHB614, T304-40 GHB119, MON88701, 81910 in WO02/034946, W002/100163, W002/100163, WO03/013224, WO04/072235, WO04/039986, WO05/103266, WO05/103266, WO06/128573, W007/017186, W008/122406, W008/151780, WO12/134808, W013/112527; 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, W
  • 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. porn), 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. triticina) ⁇ , Aphanomyces spp.
  • 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.
  • Botrytis cinerea teleomorph: Botryotinia fuckeliana grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages); B. squamosa
  • miyabeanus anamorph: H. oryzae
  • Colletotrichum teleomorph: Glomerella
  • spp. anthracnose
  • cotton e. g. C. gossypii
  • corn e. g. C. graminicola: Anthracnose stalk rot
  • soft fruits 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
  • Corynespora cassiicola leaf spots
  • Cycloconium spp. e. g. C. oleaginum on olive trees
  • G. sabinae rust on pears
  • Helminthosporium spp. syn. Drechslera, teleomorph: Cochliobolus
  • Hemileia spp. e. g. H. vastatrix (coffee leaf rust) on coffee
  • Isariopsis clavispora syn. Cladosporium vitis
  • Macrophomina phaseolina syn. phaseoli
  • root and stem rot on soybeans and cotton
  • Microdochium syn. Fusarium
  • nivale pink snow mold
  • Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (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 ⁇ .
  • meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata : 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.
  • soybeans e. g. P. viticoia ⁇ can and leaf spot
  • soybeans e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum
  • Physoderma maydis brown spots
  • Phytophthora spp. wilt, root, leaf, fruit and stem root
  • paprika and cucurbits e. g. P. capsici
  • soybeans e. g. P. megasperma, syn. P. sojae
  • potatoes and tomatoes e. g. P. infestans. late blight
  • broad-leaved trees e. g. P. ramorunr.
  • Plasmodiophora brassicae club root
  • 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; Pseudopezicula tracheiphila (red fire disease or .rotbrenner’, anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P.
  • rusts rusts
  • hordei dwarf rust
  • P. graminis stem or black rust
  • P. recondita brown or leaf rust
  • cereals such as e. g. wheat, barley or rye
  • P. kuehnii range rust
  • 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: Mycosphaerella areola ) on cotton and R.
  • 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. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and R. sescalis and
  • 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.
  • 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.
  • T. deformans leaf curl disease
  • T. pruni plum pocket
  • Thielaviopsis spp. black root rot
  • tobacco, pome fruits, vegetables, soybeans and cotton e. g. T. basicola (syn. Chalara elegans ); Tilletia spp.
  • 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.
  • 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. Botryt
  • 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.
  • 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 invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I.
  • 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.
  • 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.
  • 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
  • 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.
  • 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, tetrahydronaphtha- lene, 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.
  • N- methyl pyrrolidone N- 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 ethoxy lated 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 alkylisothiazolinones 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.
  • composition types and their preparation are: i) Water-soluble concentrates (SL, LS)
  • a compound I and 5-15 wt% wetting agent e. g. alcohol alkoxylates
  • a water-soluble solvent e. g. alcohols
  • the active substance dissolves upon dilution with water.
  • Emulsifiable concentrates 15-70 wt% of a compound I and 5-10 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e. g. aromatic hydrocarbon) ad 100 wt%. Dilution with water gives an emulsion.
  • Emulsions EW, EO, ES)
  • emulsifiers e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e. g. aromatic hydrocarbon
  • a compound I In an agitated ball mill, 20-60 wt% of a compound I are comminuted with addition of 2-10 wt% dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt% thickener (e. g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition, up to 40 wt% binder (e. g. polyvinyl alcohol) is added.
  • WG, SG Water-dispersible granules and water-soluble granules
  • a compound I 50-80 wt% of a compound I are ground finely with addition of dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e. g. sodium lignosulfonate and alcohol ethoxylate
  • wt% of a compound I are ground in a rotor-stator mill with addition of 1-5 wt% dispersants (e. g. sodium lignosulfonate), 1-3 wt% wetting agents (e. g. alcohol ethoxylate) and solid carrier (e. g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e. g. sodium lignosulfonate
  • wetting agents e. g. alcohol ethoxylate
  • solid carrier e. g. silica gel
  • Microemulsion (ME) 5-20 wt% of a compound I are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethyl amide and cyclohexanone), 10-25 wt% surfactant blend (e. g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
  • CS Microcapsules
  • An oil phase comprising 5-50 wt% of a compound I, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e. g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). Radical polymerization results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), and an isocyanate monomer (e. g.
  • diphenylmethene-4,4’-diisocyanatae are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol).
  • a protective colloid e. g. polyvinyl alcohol.
  • the addition of a polyamine results in the formation of polyurea microcapsules.
  • the monomers amount to 1-10 wt%.
  • the wt% relate to the total CS composition.
  • a compound I is ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%.
  • solid carrier e. g. silicate
  • Granulation is achieved by extrusion, spray-drying or fluidized bed.
  • organic solvent e. g. aromatic hydrocarbon
  • compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% colorants.
  • auxiliaries such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% colorants.
  • 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.
  • Inhibitors of complex III at Q 0 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), mandestrobin (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-methoxyi
  • C14 demethylase inhibitors triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromu- conazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (B.1.20), penconazole (B.1.21), propiconazole (B.1.2
  • 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
  • MAP / 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);
  • 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
  • Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. amyloliquefaciens ssp. plantarum (also referred to as B. velezensis), B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, B.
  • catenulate also named Gliocladium catenulatum
  • Gliocladium roseum Lysobacter antibioticus
  • L enzymogenes Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea
  • Muscodor albus Paenibacillus alvei, Paenibacillus epiphyticus, P. polymyxa
  • Gliocladium catenulatum also named Gliocladium catenulatum
  • Gliocladium roseum Lysobacter antibioticus
  • L enzymogenes Metschnikowia fructicola
  • Microdochium dimerum Microdochium dimerum
  • Microsphaeropsis ochracea Muscodor albus
  • Paenibacillus alvei Paenibacillus epiphyticus
  • P. polymyxa P. polymyxa
  • Pantoea vagans Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes myco- parasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Tricho- derma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, 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. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B.
  • brongniartii brongniartii, Burkholderia spp., Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV),
  • Flavobacterium spp. Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhedrovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopliae, M. anisopliae var. anisopliae, M. anisopliae var.
  • 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 leguminosarum bv. phaseoli, R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium melilotr,
  • Acetylcholine esterase (AChE) inhibitors aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, 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,
  • 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, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fen
  • Nicotinic acetylcholine receptor (nAChR) agonists acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; 4,5-dihydro-/V-nitro- 1-(2-oxiranylmethyl)-1/-/-imidazol-2-amine, (2£)-1-[(6-chloropyridin-3-yl)methyl]-/ ⁇ /-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, (3R)-3-(2-chlorothiazol-5-yl)-8
  • Nicotinic acetylcholine receptor allosteric activators spinosad, spinetoram;
  • Chloride channel activators abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin;
  • 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;
  • Mite growth inhibitors clofentezine, hexythiazox, diflovidazin; etoxazole;
  • Bacillus thuringiensis Bacillus sphaericus and the insecticdal proteins they produce: Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, the Bt crop proteins: CrylAb, CrylAc, CrylFa,
  • 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, flucycloxuron, 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;
  • Mitochondrial complex I electron transport inhibitors fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone;
  • Mitochondrial complex IV electron transport inhibitors aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide;
  • Mitochondrial complex II electron transport inhibitors cyenopyrafen, cyflumetofen
  • insecticidal compounds of unknown or uncertain mode of action afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, broflanilide, bromopropylate, chino- methionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, tioxazafen, 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-11-en- 10-one, 3-(4’-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1
  • 2-carboxamide A/-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; 1-[(6-chlo- ro-3-pyridinyl)methyl]-1,2,3,5,6,7-hexahydro-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;
  • 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.
  • the compounds described by lUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968;
  • 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.
  • 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 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 3) 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.
  • the application rates generally range from 1 x 10 6 to 1 x 10 12 (or more) CFU/seed, preferably from 1 x 10 6 to 1 x 10 9 CFU/seed. Furthermore, the application rates with respect to seed treatment generally range from 1 x 10 7 to 1 x 10 14 (or more) CFU per 100 kg of seed, preferably from 1 x 10 9 to 1 x 10 12 CFU per 100 kg of seed.
  • mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Q 0 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 Q, site in group A), more preferably selected from compounds (A.2.1), (A.2.3) and (A.2.4); particularly selected from (A.2.3) and (A.2.4).
  • 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.3.28), (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.3.31)
  • mixtures comprising as component 2) at least one active substance selected from other respiration nhibitors 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) and (B.1.46); 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.138), (B.1.43) and (B.1.46).
  • mixtures comprising as component 2) at least one active substance selected from Deltal 4-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 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 F), more preferably selected from compounds (F.1.2), (F.1.4) and (F.1.5).
  • 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).
  • 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).
  • 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) and (K.1.47); particularly selected from (K.1.41), (K.1.44) and (K.1.47).
  • the biopesticides from group L1) and/or L2) may also have insecticidal, acaricidal, molluscidal, 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.
  • 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;
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 amylolique- faciens AP-188 (L.1.2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B. amyloliquefaciens 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), B. pumilus GHA 180 (L.1.10), B. pumilus INR-7 (L.1.11), B. 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), Trichoderma asperelloides JM41R (L.1.23), T. harzianum T-22 (L.1.24);
  • 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);
  • 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),
  • 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),
  • 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: For- mulation of Micobial Biopesticides, Springer, 1998; WO 2008/002371, US 6,955,912, US 5,422,107).
  • the present invention furthermore relates to compositions comprising one compound I (component 1) and one pesticide II (component 2), which pesticide II is selected from the column "Co. 2" of the lines C-1 to C-353 of Table C.
  • a further embodiment relates to the compositions C-1 to C-353 listed in Table C, where a row of Table C corresponds in each case to a fungicidal composition comprising as active components one of the in the present specification individualized compounds of formula I (component 1) and the respective pesticide II from groups A) to O) (component 2) stated in the row in question.
  • the compositions described comprise the active components in synergistically effective amounts.
  • Table C Compositions comprising as active components one individualized compound I (I) (in Column Co. 1) and as component 2) (in Column Co. 2) one pesticide from groups A) to O) [which is coded e. g. as (A.1.1) for azoxystrobin as defined above].
  • Step a Synthesis of compound 2 Alternative 1.
  • K 2 CO 3 700 g, 5 mol
  • the solution was stirred for 30 min.
  • a solution of 2,2,2- trifluoroethyl-p-toluenesulfonate 720 g, 2.5 mol
  • the resulting reaction solution was heated to 135°C and stirred overnight. Thereafter, reaction was extracted with water/methyl-tert-butyl ether and the resulting oil was purified by silica gel flash column chromatography (EtOAc/hexane) to provide the compound 2 in 80% yield.
  • the compound I.A/T1-24/T2-21 was prepared according to the following scheme:
  • Step d Preparation of a Grignard solution i-PrMgCI (2 M, 4.03 L) was added dropwise to the solution of compound 7 (2.00 kg, 6.20 mol) in THF (10.0 L) under nitrogen at -40°C. The resulting mixture was stirred for 1h.
  • Step e Synthesis of compound 10
  • a solution of compound 9 (834 g, 2.33 mol) in AcOH (4.20 L) was added AgOAc (584 g, 3.50 mol) under nitrogen.
  • the mixture was heated to 120 °C for 4 h, then concentrated and the residue was dissolved in methyl-tert-butyl ether (5.00 L).
  • the solution was washed with aq. NaHCC>3 (5.00 L) and brine (5.00 L), the organic layer was dried over Na2SC>4 and concentrated.
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to the compound to give a total of 5 ml. Water was then added to the total volume of 100 ml. This stock solution was diluted with a solvent-emulsifier-water mixture to the given concentration.
  • Leaves of pot-grown soy bean seedlings were inoculated with spores of Phakopsora pachyrhizi. To ensure the success of the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and 20 to 24°C for 24 h. The next day the plants were cultivated for 3 days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80 %. Then the plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. Then the trial plants were cultivated for 14 days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • Leaves of pot-grown soy bean seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below.
  • the plants were allowed to air-dry.
  • the trial plants were cultivated for 6 days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80%.
  • the plants were inoculated with spores of Phakopsora pachyrhizi.
  • the plants were transferred to a humid chamber with a relative humidity of about 95 % and 20 to 24°C for 24 h.
  • the trial plants were cultivated for fourteen days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80%.
  • the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • Leaves of pot-grown soy bean seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below.
  • the plants were allowed to air-dry.
  • the trial plants were cultivated for 10 days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80 %.
  • the plants were inoculated with spores of Phakopsora pachyrhizi.
  • the plants were transferred to a humid chamber with a relative humidity of about 95 % and 20 to 24°C for 24 h.
  • the trial plants were cultivated for fourteen days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80%.
  • the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • the first two developed leaves of pot-grown wheat seedling were dusted with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99 % and 20 to 24°C for 24 h. The next day the plants were cultivated for 3 days in a greenhouse chamber at 20-24°C and a relative humidity between 65 and 70%. Then the plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants could air-dry. Then the trial plants were cultivated for 8 days in a greenhouse chamber at 20-24°C and a relative humidity between 65 and 70%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to substituted [1,2,4]triazole compounds of formula I and the N-oxides and the salts thereof, to the use of said compounds and methods for combating phytopathogenic fungi and to seeds coated with at least one such compound. The invention also relates to processes for preparing these compounds and to compositions comprising at least one compound I.

Description

SUBSTITUTED [1 ,2,4]TRIAZOLE COMPOUNDS AS FUNGICIDES
The present invention relates to substituted [1 ,2,4]triazole compounds and the N-oxides and the salts thereof, to the use of said compounds and methods for combating phytopathogenic fungi and to seeds coated with at least one such compound. The invention also relates to processes for preparing these compounds and to compositions comprising at least one compound I.
In many cases, in particular at low application rates, the fungicidal activity of known fungicidal compounds is unsatisfactory. Based on this, it was an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic harmful fungi.
Surprisingly, this object is achieved by the use of the inventive substituted [1,2,4]triazol compounds of formula I having favorable fungicidal activity against phytopathogenic fungi.
Compounds of the formula I
Figure imgf000002_0001
wherein
R1 is selected from hydrogen, OH, CrC4-halogenalkyl, C2-C4-alkenyl, C2-C4-halogenalkenyl, C2-C4-alkynyl, C2-C4-halogenalkynyl;
Ra is independently of one another selected from hydrogen or halogen;
R2 is hydrogen;
R3 is selected from halogen or CrC4-halogenalkyl;
R4, R4’, and R4” are independently of one another selected from hydrogen, halogen, CrC4-alkyl, CrC4-halogenalkyl;
R5 and R5’ are independently of one another selected from hydrogen or halogen; or
R5 and R5’ together are =C(R6)2, wherein R6 is independently of one another selected from halogen or CrC4-alkyl; m is O or l; provided that if m is 0 and three or four Ra are hydrogens, then R1 is not hydrogen; and provided that if m is 1 and CR5R5’ is CH2, then at least one Ra is not hydrogen, and the N-oxides and the agriculturally acceptable salts thereof.
The compounds of formula I can be prepared as described in WO 2015/185708. Alternatively, the compounds of formula I can be prepared as follows.
Figure imgf000003_0001
Compounds II, wherein R3 is as defined for compounds I and Halo1 is a halogen, preferably Br, are reacted with (R4R4’R4”C)-LG, wherein R4, R4’ and R4” are as defined for compounds I and LG represents a nucleophilically replaceable leaving group, such as halogen, alkylsulfonyl, alkylsulfonyloxy and arylsulfonyloxy, preferably Cl, Br or I, preferably in the presence of a base, such as, e.g., NaH, K2CO3, Na2C03 or the like, in a suitable solvent such as THF, DMF or the like.
Compounds II and (R4R4’R4”C)-LG are commercially available or can be prepared according to the methods known in the art.
Thereafter, the resulting compounds III are transformed into Grignard reagents by the reaction with transmetallation reagents, such as isopropylmagnesium halides, and subsequently reacted with compounds IV, preferably under anhydrous conditions, to obtain ketones V. A catalyst, such as CuCI, CuCh, AlCb or LiCI, can be optionally added. The ketones V are reacted with trimethylsulf(ox)onium halides, preferably iodide, preferably in the presence of a base such as sodium hydroxide, leading to the epoxides VI which after a reaction with 1 H-1 , 2, 4-triazole, preferably in the presence of a base, such as potassium carbonate, give the final compounds I.
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 "CrC4-alkyl" refers to a straight-chained or branched saturated hydrocarbon group having 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2- methylpropyl and 1 ,1-dimethylethyl. A preferred embodiment of a CrC4-alkyl is a C2-C4-alkyl. 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 "CrC4-haloalkyl" or "Ci-C4-halogenalkyl" refers to an alkyl group having 1 or 4 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above. A preferred embodiment of a CrC4-haloalkyl is a Ci-C2-haloalkyl. Representative CrC2-haloalkyl groups include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 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-tri chloroethyl or pentafluoroethyl.
The term "C2-C4-alkenyl" refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and at least one double bond in any position, 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-C4-haloalkenyl" or "C2-C4-halogenalkenyl" refers to an alkenyl group having 2 or 4 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above. A preferred embodiment of a C2-C4-haloalke- nyl is a C2-C3-haloalkenyl. Representative C2-C3-haloalkenyl groups include 1-F-ethenyl, 1-CI- ethenyl, 2,2-di-F-ethenyl, 2,2-di-CI-ethenyl, 3,3-di-F-prop-2-en-1-yl and 3,3-di-CI-prop-2-en-1-yl, 2-CI-allyl (-CH2-CCI=CH2), 2-Br-allyl (-CH2-CBr=CH2), 2-(CF3)-allyl (-CH2-C(CF3)=CH2), 3-CI- allyl (-CH2-CH=CCIH), 3-Br-allyl (-CH2-CH=CBrH), 3-(CF3)-allyl (-CH2-CH=C(CF3)H). The term "C2-C4-alkynyl" refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and containing at least one triple bond, such as ethynyl, prop-1-ynyl (-CºC-CH3), prop-2-ynyl (propargyl), but-1-ynyl, but-2-ynyl, but-3-ynyl, 1-methyl-prop-2-ynyl.
The term "C2-C4-haloalkynyl" or "C2-C4-halogenalkynyl" refers to an alkynyl group having 2 or 4 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above. A preferred embodiment of a C2-C4-halo- alkynyl is a C2-C3-haloalkynyl. Representative C2-C3-haloalkynyl groups include F-ethynyl, Cl- ethynyl, Br-ethynyl, Br-prop-2-ynyl (-CH2-CºC-Br) and CI-prop-2-ynyl (-CH2-CºC-CI).
The term “aliphatic” or “aliphatic group” is to be understood to refer to a non-cyclic compound, substituent or residue composed of hydrogen and carbon atoms only, and it may be saturated or unsaturated, as well as linear or branched. An aliphatic compound, substituent or residue may be optionally substituted where indicated. Examples of an aliphatic compound, substituent or residue comprise alkyl, alkenyl, and alkynyl, all with a variable number of carbon atoms.
If any of the variables is optionally substituted, it is understood that this applies to moieties containing carbon-hydrogen bonds, wherein the hydrogen atom is substituted by the corresponding substituent, however, not to moieties such as hydrogen, halogen, CN or the like. As an exemplary embodiment, if methyl is substituted by OH, a hydroxymethyl group is generated.
Agriculturally acceptable salts of the inventive compounds 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 said compounds. 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 carry one to four CrC4-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 sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of CrC4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting such inventive compound with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid. The inventive compounds can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
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. All different types of isomers are comprised by the compounds of formula I, in particular enantiomers, diasteriomers or geometric isomers, and they all form part of the subject matter of the present invention.
Depending on the substitution pattern, the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or diastereomers and their mixtures are subject matter of the present invention.
In the following, particular embodiments of the inventive compounds are described. Therein, specific meanings of the respective substituents are further detailed, 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 of formula I also apply to the intermediates.
A skilled person will readily understand that the preferences for the substituents (also those in the tables below) 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 with each other the meanings as defined herein.
R1 according to the invention is selected from hydrogen, OH, CrC4-halogenalkyl, C2-C4-alk- enyl, C2-C4-halogenalkenyl, C2-C4-alkynyl, C2-C4-halogenalkynyl; preferably from hydrogen, CrC4-halogenalkyl, C2-C4-halogenalkenyl, C2-C4-halogenalkynyl; more preferably from CrC4-halogenalkyl, C2-C4-halogenalkenyl, C2-C4-halogenalkynyl, provided that if m is 0 and three or four Ra are hydrogens, then R1 is not hydrogen.
According to one embodiment R1 is hydrogen, provided that if m is 0, then one or two Ra are not hydrogens.
According to another embodiment R1 is OH. According to another embodiment R1 is CrC4-halogenalkyl, such as CF3, CHF2, CF2CH3, CH2CF3, CHFCH3 or CF2CF3; preferably CrC2-halogenalkyl, most preferably preferably Cr halogenalkyl.
According to another embodiment R1 is C2-C4-alkenyl, such as CH=CH2, CH2CH=CH2, CH=CHCH3 or C(CH3)=CH2.
According to another embodiment R1 is C2-C4-halogenalkenyl, such as CH=CHF, CH=CF2, CF=CH2, CF=CHF, CF=CF2, CH=CHCI, CH=CCI2, CCI=CH2, CCI=CHCI, CCI=CCI2.
According to another embodiment R1 is C2-C4-alkynyl, such as CºCH, CºCCH3, CH2-CºC-H or CH2-CºC-CH3. According to another embodiment R1 is C2-C4-halogenalkynyl, such as CºCCI, CºCBr, CºC-I, CH2CºCCI, CH2CºCBr.
Particularly preferred R1 according to the invention are listed in Table P1 below, wherein each line of lines P1-1 to P1-35 corresponds to one specific embodiment of the invention.
Table P1 :
Figure imgf000007_0001
Figure imgf000007_0002
Figure imgf000008_0001
Figure imgf000008_0002
Ra according to the invention is independently selected from hydrogen or halogen; preferably from halogen.
According to one embodiment Ra is hydrogen.
According to another embodiment Ra is halogen, preferably F or Cl.
It should be noted that the selection of each Ra is made independently of one another, and all Ra may be identical or different.
R2 according to the invention is hydrogen. R3 according to the present invention is selected from halogen or Ci-C4-halogenalkyl. According one embodiment R3 is halogen, preferably F, Cl or Br.
According to another embodiment R3 is CrC4-halogenalkyl, preferably CrC2-halogenalkyl, such as CFs, CHF2, CH2F, CCI3, CHCI2 or CH2CI.
Particularly preferred R3 according to the invention are listed in Table P3 below, wherein each line of lines P3-1 to P3-9 corresponds to one specific embodiment of the invention:
Table P3:
Figure imgf000008_0003
Figure imgf000008_0004
Figure imgf000008_0005
R4, R4’, and R4” according to the present invention are independently of one another selected from hydrogen, halogen, CrC4-alkyl, CrC4-halogenalkyl; preferably from hydrogen, F, Cl, CrC2-alkyl and CrC2-halogenalkyl.
It should be noted that the selection of each of the three variables R4, R4’, and R4” is made independently of one another, and R4, R4’, and R4” may be identical or different. According to one embodiment, at least one of R4, R4’, and R4” is not hydrogen.
According to another embodiment, only one of R4, R4’, and R4” is hydrogen.
According to another embodiment, R4, R4’, and R4” are independently selected from hydrogen or halogen. According to another embodiment, at least one of R4, R4’, and R4” is halogen, preferably F or Cl. According to another embodiment, at least two of R4, R4’, and R4” are halogens, preferably F or Cl. According to another embodiment, each of R4, R4’, and R4” is halogen, preferably F or Cl.
According to one preferred embodiment, R4, R4’, and R4” are independently selected from hydrogen, halogen, such as F, Cl or Br, CrC4-alkyl, such as CF , C2H5, C3H7, CH(CH3)2, C(CH3)3, CH2C(CH3)3 and CH2CH(CH3)2; and CrC4-halogenalkyl, such as CF3, CF2Br, CHF2,
CHFCI, CHFCFs, CF2CH3, CF2CHF2, CH2CF3 or CF2CF3.
Particularly preferred R4, R4’, and R4” are listed in Table P4 below, wherein each line of lines P4-1 to P4-20 corresponds to one particular embodiment of the invention, wherein P4-1 to P4- 20 are also in any combination a preferred embodiment of the present invention. Table P4:
Figure imgf000009_0003
Figure imgf000009_0001
Figure imgf000009_0002
According to a specific embodiment, CR4R4’R4” is CrC4-alkyl, such as CH3, C2H5, C3H7, CH(CH3)2, CH2CH(CH3)2 or C(CH3)3; preferably CrC3-alkyl, such as CH3, C2H5, C3H7, or CH(CH3)2; more preferably, CrC2-alkyl, such as CH3, C2H5. According to another specific embodiment, CR4R4’R4” is CrC4-halogenalkyl, preferably C1-C3- halogenalkyl, such as CF3, CHF2, CH2F, CBrF2, CHFCI, CHFCF3, CF2CH3, CF2CHF2, CH2CF3, CF2CF3 or CH2CF2CHF2, more preferably CrC2-halogenalkyl, such as such as CF3, CHF2, CH2F, CBrF2, CHFCI, CHFCFs, CF2CH3, CF2CHF2, CH2CF3 or CF2CF3. R5 according to the present invention is hydrogen or halogen, such as F, Cl or Br; preferably F or Cl. According to one embodiment, R5 is H. According to another embodiment, R5 is Cl. According to another embodiment, R5 is F.
R5’ according to the present invention is selected from hydrogen or halogen, such as F, Cl or Br. According to one embodiment, R5’ is hydrogen. According to another embodiment,
R5’ is Cl. According to another embodiment, R5’ is F.
If both R5 and R5’are hydrogens, then at least one Ra is not hydrogen.
R5 and R5’ together can form =C(R6)2; wherein R6 is independent from one another is selected from hydrogen, halogen or CrC4-alkyl. Specifically, CR5R5’ may be selected from CHF, CHCI, CF2, CCI2 or C=CH2, preferably from CHF, CHCI, CF2 or CCI2. Alternatively, CR5R5’ may be CH2, provided that at least one Ra is not hydrogen.
R6 is independently of one another selected from halogen or CrC4-alkyl. m according to the present invention is 0 or 1. According to one embodiment, m is 0. According to another embodiment, m is 1.
Particular preference is further given to compounds I having R4, R4’ and R4” in combinations defined in the Table T1.
Table T1:
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000011_0001
Figure imgf000011_0002
Further, particular preference is given to compounds I having R1 and R3 in combinations as defined in the Table T2. Table T2:
Figure imgf000011_0003
Figure imgf000011_0004
Figure imgf000012_0001
Figure imgf000012_0002
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000015_0001
Figure imgf000015_0002
Figure imgf000016_0002
Figure imgf000016_0001
One specific embodiment or the invention relates to compounds of formula I, wherein m is 0 and all Ra are H (compounds I. A). Another specific embodiment to compounds of formula I, wherein m is 1 and all Ra are H (compounds I.B):
Figure imgf000017_0001
Another specific embodiment or the invention relates to compounds of formula I, wherein m is 0; two geminal Ra are H and two other two geminal Ra are F (compounds I.C). Another specific embodiment to compounds of formula I, wherein m is 1 two geminal Ra are H and two other two geminal Ra are F (compounds I.D):
Figure imgf000017_0002
Particular preference is given to the compounds of the formula I.A compiled in the Tables
1.1. A to 40. I.A.
Table 1.1. A
Compounds of the formula I.A in which the combination of R4, R4’ and R4” corresponds to line T1-1 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-1/T2-1 to I.A/T1-1/T2-306).
Table 2.I.A
Compounds of the formula I.A in which the combination of R4, R4’ and R4” corresponds to line T1-2 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-2/T2-1 to I.A/T1-2/T2-306). Table 3.1. A
Compounds of the formula I.A in which the combination of R4, R4’ and R4” corresponds to line T1-3 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-3/T2-1 to I.A/T1-3/T2-306).
Table 4.1. A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-4 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-4/T2-1 to I.A/T1-4/T2-306).
Table 5.1. A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-5 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-5/T2-1 to I.A/T1-5/T2-306).
Table 6.1. A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-6 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-6/T2-1 to I.A/T1-6/T2-306).
Table 7.1. A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-7 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-7/T2-1 to I.A/T1-7/T2-306).
Table 8.1. A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-8 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-1/T2-8 to I.A/T1-8/T2-306).
Table 9.1. A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-9 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-9/T2-1 to I.A/T1-9/T2-306).
Table 10.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-10 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-10/T2-1 to I.A/T1-10/T2-306).
Table 11.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-11 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-11/T2-1 to I.A/T1-11/T2-306). Table 12.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-12 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-12/T2-1 to I.A/T1-12/T2-306).
Table 13.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-13 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-13/T2-1 to I.A/T1-13/T2-306).
Table 14.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-14 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-14/T2-1 to I.A/T1-14/T2-306).
Table 15.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-15 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-15/T2-1 to I.A/T1-15/T2-306).
Table 16.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-16 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-16/T2-1 to I.A/T1-16/T2-306).
Table 17.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-17 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-17/T2-1 to I.A/T1-17/T2-306).
Table 18.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-18 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-18/T2-1 to I.A/T1-18/T2-306).
Table 19.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-19 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-19/T2-1 to I.A/T1-19/T2-306).
Table 20.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line in each case to one line of Table T2 (compounds I.A/T1-20/T2-1 to I.A/T1-20/T2-306).
Table 21.1.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-21 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-21/T2-1 to I.A/T1-21/T2-306).
Table 22.1.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-22 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-22/T2-1 to I.A/T1-22/T2-306).
Table 23.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-23 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-23/T2-1 to I.A/T1-23/T2-306).
Table 24.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-24 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-24/T2-1 to I.A/T1-24/T2-306).
Table 25.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-25 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-25/T2-1 to I.A/T1-25/T2-306).
Table 26.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-26 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-26/T2-1 to I.A/T1-26/T2-306).
Table 27.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-27 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-27/T2-1 to I.A/T1-27/T2-306).
Table 28.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-28 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-28/T2-1 to I.A/T1-28/T2-306). Table 29.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-29 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-29/T2-1 to I.A/T1-29/T2-306).
Table 30.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-30 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-30/T2-1 to I.A/T1-30/T2-306).
Table 31.1.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-31 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T 1-31/T2-1 to I.A/T1-31/T2-306).
Table 32.1.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-32 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-32/T2-1 to I.A/T1-32/T2-306).
Table 33.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-33 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-33/T2-1 to I.A/T1-33/T2-306).
Table 34.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-34 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-34/T2-1 to I.A/T1-34/T2-306).
Table 35.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-35 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-35/T2-1 to I.A/T1-35/T2-306).
Table 36.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-36 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-36/T2-1 to I.A/T1-36/T2-306).
Table 37.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-37 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-37/T2-1 to I.A/T1-37/T2-306).
Table 38.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-38 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-38/T2-1 to I.A/T1-38/T2-306).
Table 39.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-39 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-39/T2-1 to I.A/T1-39/T2-306).
Table 40.I.A
Compounds of the formula I. A in which the combination of R4, R4’ and R4” corresponds to line T1-40 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.A/T1-40/T2-1 to I.A/T1-40/T2-306).
Further, preference is given to the compounds of the formula I.B compiled in the Tables
1.1. B- 1 to 40.I.B-2.
Table 1.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-1 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-1/T2-1 to I.B- 1/T1-1/T2-315).
Table 2.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-2 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-2/T2-1 to I.B- 1/T1-2/T2-315).
Table 3.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-3 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-3/T2-1 to I.B- 1/T1-3/T2-315).
Table 4.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-4 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-4/T2-1 to I.B- 1/T1-4/T2-315).
Table 5.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-5 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-5/T2-1 to I.B- 1/T1-5/T2-315).
Table 6.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-6 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-6/T2-1 to I.B- 1/T1-6/T2-315).
Table 7.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-7 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-7/T2-1 to I.B- 1/T1-7/T2-315).
Table 8.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-8 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-1/T2-8 to I.B- 1/T1-8/T2-315).
Table 9.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-9 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-9/T2-1 to I.B- 1/T1-9/T2-315).
Table 10.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-10 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-10/T2-1 to I . B- 1 /T 1-10/T2-315) . Table 11.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-11 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-11/T2-1 to I.B-1/T1-11/T2-315).
Table 12.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-12 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-12/T2-1 to I . B- 1 /T 1-1 /T2-315) .
Table 13.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-13 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-13/T2-1 to I . B- 1 /T 1-13/T2-315) .
Table 14.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-14 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-14/T2-1 to I . B- 1 /T 1-14/T2-315) .
Table 15.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-15 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-15/T2-1 to I . B- 1 /T 1-15/T2-315) .
Table 16.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-16 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-16/T2-1 to I . B- 1 /T 1-16/T2-315) .
Table 17.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-17 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-17/T2-1 to I . B-1/T 1 -17/T2-315).
Table 18.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-18 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-18/T2-1 to I . B- 1 /T 1-18/T2-315) .
Table 19.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-19 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-19/T2-1 to I . B- 1 /T 1-19/T2-315) .
Table 20.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-20 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B- 1 /T 1 -20/T2- 1 to I . B- 1 /T 1 -20/T2-315) .
Table 21.1. B- 1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-21 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T1-21/T2-1 to I.B-1/T1-21/T2-315).
Table 22.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-22 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B- 1 /T 1 -22/T2- 1 to I . B- 1 /T 1 -22/T2-315) .
Table 23.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-23 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B- 1 /T 1 -23/T2- 1 to I . B- 1 /T 1 -23/T2-315) .
Table 24.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-24 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B- 1 /T 1 -24/T2- 1 to I . B- 1 /T 1 -24/T2-315) .
Table 25.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-25 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B- 1 /T 1 -25/T2- 1 to I . B- 1 /T 1 -25/T2-315) .
Table 26.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-26 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B- 1 /T 1 -26/T2- 1 to I . B- 1 /T 1 -26/T2-315) .
Table 27.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-27 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B- 1 /T 1 -27/T2- 1 to I.B-1/T1-27/T2-315).
Table 28.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-28 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B- 1 /T 1 -28/T2- 1 to I . B- 1 /T 1 -28/T2-315) .
Table 29.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-29 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B- 1 /T 1 -29/T2- 1 to I . B- 1 /T 1 -29/T2-315) .
Table 30.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-30 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-30/T2-1 to I . B- 1 /T 1 -30/T2-315) . Table 31.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-31 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-31/T2-1 to I . B-1/T 1 -31 /T2-315).
Table 32.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-32 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-32/T2-1 to I . B- 1 /T 1 -32/T2-315) .
Table 33.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-33 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-33/T2-1 to I . B- 1 /T 1 -33/T2-315) .
Table 34.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-34 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-34/T2-1 to I . B- 1 /T 1 -34/T2-315) .
Table 35.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-35 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-35/T2-1 to I . B- 1 /T 1 -35/T2-315) .
Table 36.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-36 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-36/T2-1 to I . B- 1 /T 1 -36/T2-315) .
Table 37.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-37 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-37/T2-1 to I.B-1/T1-37/T2-315).
Table 38.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-38 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-38/T2-1 to I . B- 1 /T 1 -38/T2-315) .
Table 39.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-39 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-1/T 1-39/T2-1 to I . B- 1 /T 1 -39/T2-315) .
Table 40.I.B-1
Compounds of the formula I.B in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-40 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B- 1 /T 1 -40/T2- 1 to I . B- 1 /T 1 -40/T2-315) .
Table 1.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-1 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-1/T2-1 to I.B- 2/T1-1/T2-315).
Table 2.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-2 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-2/T2-1 to I.B- 2/T1-2/T2-315).
Table 3.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-3 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-3/T2-1 to I.B- 2/T1-3/T2-315). Table 4.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-4 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-4/T2-1 to I.B- 2/T1-4/T2-315).
Table 5.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-5 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-5/T2-1 to I.B- 2/T1-5/T2-315).
Table 6.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-6 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-6/T2-1 to I.B- 2/T1-6/T2-315).
Table 7.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-7 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-7/T2-1 to I.B- 2/T1-7/T2-315).
Table 8.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-8 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-1/T2-8 to I.B- 2/T1-8/T2-315).
Table 9.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-9 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-9/T2-1 to I.B- 2/T1-9/T2-315).
Table 10.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-10 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B-2/T 1-10/T2- 1 to I . B-2/T 1-10/T2-315) .
Table 11.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-11 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B-2/T 1-11 /T2- 1 to I.B-2/T1-11/T2-315).
Table 12.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-12 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B-2/T 1-12/T2- 1 to I . B-2/T 1-12/T2-315) .
Table 13.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-13 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B-2/T 1-13/T2- 1 to I . B-2/T 1-13/T2-315) .
Table 14.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-14 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B-2/T 1-14/T2- 1 to I . B-2/T 1-14/T2-315) .
Table 15.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-15 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B-2/T 1-15/T2- 1 to I . B-2/T 1-15/T2-315) .
Table 16.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-16 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B-2/T 1-16/T2- 1 to I . B-2/T 1-16/T2-315) .
Table 17.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-17 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B-2/T 1-17/T2- 1 to I . B-2/T1 -17/T2-315).
Table 18.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-18 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B-2/T 1-18/T2- 1 to I . B-2/T 1-18/T2-315) .
Table 19.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-19 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B-2/T 1-19/T2- 1 to I . B-2/T 1-19/T2-315) .
Table 20.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-20 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-20/T2-1 to I . B-2/T 1 -20/T2-315) .
Table 21.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-21 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . B-2/T 1-21 /T2- 1 to I . B-2/T 1-21/T2-315).
Table 22.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-22 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-22/T2-1 to I . B-2/T 1 -22/T2-315) .
Table 23.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-23 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-23/T2-1 to I . B-2/T 1 -23/T2-315) . Table 24.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-24 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-24/T2-1 to I . B-2/T 1 -24/T2-315) .
Table 25.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-25 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-25/T2-1 to I . B-2/T 1 -25/T2-315) .
Table 26.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-26 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-26/T2-1 to I . B-2/T 1 -26/T2-315) .
Table 27.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-27 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-27/T2-1 to I.B-2/T1-27/T2-315).
Table 28.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-28 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-28/T2-1 to I . B-2/T 1 -28/T2-315) .
Table 29.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-29 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-29/T2-1 to I . B-2/T 1 -29/T2-315) .
Table 30.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-30 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-30/T2-1 to I . B-2/T 1 -30/T2-315) .
Table 31.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-31 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T 1-31/T2-1 to I.B-2/T1-31/T2-315).
Table 32.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-32 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-32/T2-1 to I . B-2/T 1 -32/T2-315) .
Table 33.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-33 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-33/T2-1 to I . B-2/T 1 -33/T2-315) .
Table 34.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-34 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-34/T2-1 to I . B-2/T 1 -34/T2-315) .
Table 35.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-35 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-35/T2-1 to I . B-2/T 1 -35/T2-315) .
Table 36.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-36 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-36/T2-1 to I . B-2/T 1 -36/T2-315) .
Table 37.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-37 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-37/T2-1 to I.B-2/T1-37/T2-315).
Table 38.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-38 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-38/T2-1 to I . B-2/T 1 -38/T2-315) .
Table 39.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-39 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-39/T2-1 to I . B-2/T 1 -39/T2-315) .
Table 40.I.B-2
Compounds of the formula I.B in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-40 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.B-2/T1-40/T2-1 to I . B-2/T 1 -40/T2-315) .
Further, preference is given to the compounds of the formula I.B compiled in the Tables 1.I.C to 40.I.C.
Table 1.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-1 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T 1-1/T2-1 to I.C/T1-1/T2-315).
Table 2.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-2 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-2/T2-1 to I.C/T1-2/T2-315).
Table 3.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-3 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-3/T2-1 to I.C/T1-3/T2-315). Table 4.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-4 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-4/T2-1 to I.C/T1-4/T2-315).
Table 5.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-5 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-5/T2-1 to I.C/T1-5/T2-315).
Table 6.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-6 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-6/T2-1 to I.C/T1-6/T2-315).
Table 7.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-7 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-7/T2-1 to I.C/T1-7/T2-315).
Table 8.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-8 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-1/T2-8 to I.C/T1-8/T2-315).
Table 9.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-9 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-9/T2-1 to I.C/T1-9/T2-315).
Table 10.1. C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-10 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . C/T 1-10/T2- 1 to I.C/T1-10/T2-315).
Table 11. I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-11 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T 1-11/T2-1 to I . C/T 1-11/T2-315).
Table 12. I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-12 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . C/T 1-12/T2- 1 to I.C/T1-12/T2-315).
Table 13.1. C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-13 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . C/T 1-13/T2- 1 to I.C/T1-13/T2-315).
Table 14.1. C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-14 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . C/T 1-14/T2- 1 to I.C/T1-14/T2-315).
Table 15.1. C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-15 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . C/T 1-15/T2- 1 to I.C/T1-15/T2-315).
Table 16.1. C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-16 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . C/T 1-16/T2- 1 to I.C/T1-16/T2-315).
Table 17.1. C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-17 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . C/T 1-17/T2- 1 to I.C/T1-17/T2-315).
Table 18.1. C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-18 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . C/T 1-18/T2- 1 to I.C/T1-18/T2-315).
Table 19.1. C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-19 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . C/T 1-19/T2- 1 to I.C/T1-19/T2-315).
Table 20.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-20 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-20/T2-1 to I.C/T1-20/T2-315). Table 21.1. C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-21 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-21/T2-1 to I.C/T1-21/T2-315).
Table 22. I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-22 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-22/T2-1 to I.C/T1-22/T2-315).
Table 23.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-23 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-23/T2-1 to I.C/T1-23/T2-315).
Table 24.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-24 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-24/T2-1 to I.C/T1-24/T2-315).
Table 25.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-25 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-25/T2-1 to I.C/T1-25/T2-315).
Table 26.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-26 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-26/T2-1 to I.C/T1-26/T2-315).
Table 27.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-27 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-27/T2-1 to I.C/T1-27/T2-315).
Table 28.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-28 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-28/T2-1 to I.C/T1-28/T2-315).
Table 29.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-29 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-29/T2-1 to I.C/T1-29/T2-315).
Table 30.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-30 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-30/T2-1 to I.C/T1-30/T2-315).
Table 31. I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-31 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T 1-31/T2-1 to I.C/T1-31/T2-315).
Table 32. I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-32 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-32/T2-1 to I.C/T1-32/T2-315).
Table 33.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-33 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-33/T2-1 to I.C/T1-33/T2-315).
Table 34.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-34 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-34/T2-1 to I.C/T1-34/T2-315).
Table 35.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-35 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-35/T2-1 to I.C/T1-35/T2-315).
Table 36.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-36 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-36/T2-1 to I.C/T1-36/T2-315).
Table 37.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-37 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-37/T2-1 to I.C/T1-37/T2-315). Table 38.1. C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-38 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-38/T2-1 to I.C/T1-38/T2-315).
Table 39.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-39 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-39/T2-1 to I.C/T1-39/T2-315).
Table 40.I.C
Compounds of the formula I.C in which the combination of R4, R4’ and R4” corresponds to line T1-40 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.C/T1-40/T2-1 to I.C/T1-40/T2-315).
Further, preference is given to the compounds of the formula I.B compiled in the Tables 1.1. D- 1 to 40.I.D-3.
Table 1.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-1 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-1/T2-1 to I.D- 1/T 1-1/T2-315).
Table 2.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-2 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-2/T2-1 to I.D- 1/T1-2/T2-315).
Table 3.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-3 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-3/T2-1 to I.D- 1/T1-3/T2-315).
Table 4.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-4 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-4/T2-1 to I.D- 1/T1-4/T2-315).
Table 5.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-5 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-5/T2-1 to I.D- 1/T1-5/T2-315).
Table 6.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-6 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-6/T2-1 to I.D- 1/T1-6/T2-315).
Table 7.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-7 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-7/T2-1 to I.D- 1/T1-7/T2-315).
Table 8.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-8 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-1/T2-8 to I.D- 1/T1-8/T2-315).
Table 9.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-9 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-9/T2-1 to I.D- 1/T1-9/T2-315).
Table 10.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-10 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-10/T2-1 to I.D-1/T 1-10/T2-315).
Table 11.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-11 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-11/T2-1 to I.D-1/T1-11/T2-315).
Table 12.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-12 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-12/T2-1 to I.D-1/T 1-12/T2-315).
Table 13.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-13 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-13/T2-1 to I.D-1/T 1-13/T2-315).
Table 14.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-14 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-14/T2-1 to I.D-1/T 1-14/T2-315).
Table 15.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-15 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-15/T2-1 to I.D-1/T 1-15/T2-315).
Table 16.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-16 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-16/T2-1 to I.D-1/T 1-16/T2-315).
Table 17.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-17 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-17/T2-1 to I.D-1/T 1-17/T2-315). Table 18.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-18 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-18/T2-1 to I.D-1/T 1-18/T2-315).
Table 19.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-19 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-19/T2-1 to I.D-1/T 1-19/T2-315).
Table 20.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-20 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-20/T2-1 to I.D-1/T1-20/T2-315).
Table 21.1. D- 1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-21 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-21/T2-1 to I.D-1/T 1-21/T2-315).
Table 22.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-22 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D- 1 /T 1 -22/T2- 1 to I.D-1/T1-22/T2-315).
Table 23.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-23 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T 1-23/T2-1 to I.D-1/T1-23/T2-315).
Table 24.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-24 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-24/T2-1 to I.D-1/T1-24/T2-315).
Table 25.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-25 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T 1-25/T2-1 to I.D-1/T1-25/T2-315).
Table 26.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-26 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-26/T2-1 to I.D-1/T1-26/T2-315).
Table 27.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-27 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-27/T2-1 to I.D-1/T1-27/T2-315).
Table 28.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-28 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T 1-28/T2-1 to I.D-1/T1-28/T2-315).
Table 29.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-29 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T 1-29/T2-1 to I.D-1/T1-29/T2-315).
Table 30.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-30 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-30/T2-1 to I.D-1/T1-30/T2-315).
Table 31.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-31 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-31/T2-1 to I.D-1/T 1-31/T2-315).
Table 32.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-32 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D- 1 /T 1 -32/T2- 1 to I.D-1/T1-32/T2-315).
Table 33.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-33 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D- 1 /T 1 -33/T2- 1 to I.D-1/T1-33/T2-315).
Table 34.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-34 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-34/T2-1 to I.D-1/T1-34/T2-315).
Table 35.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-35 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D- 1 /T 1 -35/T2- 1 to I.D-1/T1-35/T2-315).
Table 36.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-36 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-36/T2-1 to I.D-1/T1-36/T2-315).
Table 37.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-37 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D- 1 /T 1 -37/T2- 1 to I.D-1/T1-37/T2-315). Table 38.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-38 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D- 1 /T 1 -38/T2- 1 to I.D-1/T1-38/T2-315).
Table 39.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-39 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D- 1 /T 1 -39/T2- 1 to I.D-1/T1-39/T2-315).
Table 40.I.D-1
Compounds of the formula I.D in which CR5R5’ is CHF, the combination of R4, R4’ and R4” corresponds to line T1-40 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-1/T1-40/T2-1 to I.D-1/T1-40/T2-315).
Table 1.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-1 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-1/T2-1 to I.D- 2/T1-1/T2-315).
Table 2.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-2 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-2/T2-1 to I.D- 2/T1-2/T2-315).
Table 3.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-3 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-3/T2-1 to I.D- 2/T1-3/T2-315).
Table 4.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-4 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-4/T2-1 to I.D- 2/T1-4/T2-315).
Table 5.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-5 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-5/T2-1 to l.D- 2/T1-5/T2-315).
Table 6.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-6 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-6/T2-1 to I.D- 2/T1-6/T2-315).
Table 7.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-7 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-7/T2-1 to l.D- 2/T1-7/T2-315).
Table 8.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-8 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-1/T2-8 to I.D- 2/T1-8/T2-315).
Table 9.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-9 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-9/T2-1 to l.D- 2/T1-9/T2-315).
Table 10.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-10 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-10/T2-1 to I.D-2/T1-10/T2-315).
Table 11.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-11 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-2/T 1-11 /T2- 1 to I.D-2/T1-11/T2-315).
Table 12.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-12 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-2/T 1-12/T2- 1 to I.D-2/T1-12/T2-315).
Table 13.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-13 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-2/T 1-13/T2- 1 to I.D-2/T1-13/T2-315).
Table 14.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-14 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-14/T2-1 to I.D-2/T1-14/T2-315).
Table 15.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-15 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-2/T 1-15/T2- 1 to I.D-2/T1-15/T2-315).
Table 16.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-16 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-16/T2-1 to I.D-2/T1-16/T2-315).
Table 17.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-17 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-2/T 1-17/T2- 1 to I.D-2/T1-17/T2-315). Table 18.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-18 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-2/T 1-18/T2- 1 to I.D-2/T1-18/T2-315).
Table 19.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-19 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-2/T 1-19/T2- 1 to I . D-2/T1 -19/T2-315) .
Table 20.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-20 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-20/T2-1 to I.D-2/T1-20/T2-315).
Table 21.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-21 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-2/T 1-21 /T2- 1 to I.D-2/T1-21/T2-315).
Table 22.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-22 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-22/T2-1 to I.D-2/T1-22/T2-315).
Table 23.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-23 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-23/T2-1 to I.D-2/T1-23/T2-315).
Table 24.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-24 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-24/T2-1 to I.D-2/T1-24/T2-315).
Table 25.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-25 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-25/T2-1 to I.D-2/T1-25/T2-315).
Table 26.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-26 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-26/T2-1 to I.D-2/T1-26/T2-315).
Table 27.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-27 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-27/T2-1 to I.D-2/T1-27/T2-315).
Table 28.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-28 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-28/T2-1 to I.D-2/T1-28/T2-315).
Table 29.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-29 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-29/T2-1 to I.D-2/T1-29/T2-315).
Table 30.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-30 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-30/T2-1 to I.D-2/T1-30/T2-315).
Table 31.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-31 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-2/T 1-31 /T2- 1 to I . D-2/T1 -31/T2-315).
Table 32.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-32 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-32/T2-1 to I.D-2/T1-32/T2-315).
Table 33.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-33 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-33/T2-1 to I.D-2/T1-33/T2-315).
Table 34.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-34 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-34/T2-1 to I.D-2/T1-34/T2-315).
Table 35.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-35 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-35/T2-1 to I.D-2/T1-35/T2-315).
Table 36.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-36 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-36/T2-1 to I.D-2/T1-36/T2-315).
Table 37.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-37 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-37/T2-1 to I.D-2/T1-37/T2-315). Table 38.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-38 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-38/T2-1 to I.D-2/T1-38/T2-315).
Table 39.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-39 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-39/T2-1 to I.D-2/T1-39/T2-315).
Table 40.I.D-2
Compounds of the formula I.D in which CR5R5’ is CF2, the combination of R4, R4’ and R4” corresponds to line T1-40 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-2/T1-40/T2-1 to I.D-2/T1-40/T2-315).
Table 1.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-1 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-1/T2-1 to I.D- 3/T1-1/T2-315).
Table 2.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-2 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-2/T2-1 to I.D- 3/T1-2/T2-315).
Table 3.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-3 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-3/T2-1 to I.D- 3/T1-3/T2-315).
Table 4.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-4 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-4/T2-1 to I.D- 3/T1-4/T2-315).
Table 5.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-5 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-5/T2-1 to l.D- 3/T1-5/T2-315).
Table 6.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-6 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-6/T2-1 to I.D- 3/T1-6/T2-315).
Table 7.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-7 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-7/T2-1 to l.D- 3/T1-7/T2-315).
Table 8.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-8 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-1/T2-8 to I.D- 3/T1-8/T2-315).
Table 9.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-9 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-9/T2-1 to l.D- 3/T1-9/T2-315).
Table 10.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-10 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-10/T2-1 to I.D-3/T1-10/T2-315).
Table 11.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-11 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-3/T 1-11 /T2- 1 to I.D-3/T1-11/T2-315).
Table 12.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-12 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-3/T 1-12/T2- 1 to I.D-3/T1-12/T2-315).
Table 13.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-13 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-3/T 1-13/T2- 1 to I.D-3/T1-13/T2-315).
Table 14.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-14 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-14/T2-1 to I.D-3/T1-14/T2-315).
Table 15.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-15 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-3/T 1-15/T2- 1 to I.D-3/T1-15/T2-315).
Table 16.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-16 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-16/T2-1 to I.D-3/T1-16/T2-315).
Table 17.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-17 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-3/T 1-17/T2- 1 to I.D-3/T1-17/T2-315). Table 18.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-18 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-3/T 1-18/T2- 1 to I.D-3/T1-18/T2-315).
Table 19.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-19 of Table T1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-3/T 1-19/T2- 1 to I . D-3/T1 -19/T2-315) .
Table 20.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-20 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-20/T2-1 to I.D-3/T1-20/T2-315).
Table 21.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-21 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-3/T 1-21 /T2- 1 to I.D-3/T1-21/T2-315).
Table 22.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-22 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-22/T2-1 to I.D-3/T1-22/T2-315).
Table 23.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-23 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-23/T2-1 to I.D-3/T1-23/T2-315).
Table 24.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-24 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-24/T2-1 to I.D-3/T1-24/T2-315).
Table 25.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-25 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-25/T2-1 to I.D-3/T1-25/T2-315).
Table 26.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-26 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-26/T2-1 to I.D-3/T1-26/T2-315).
Table 27.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-27 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-27/T2-1 to I.D-3/T1-27/T2-315).
Table 28.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-28 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-28/T2-1 to I.D-3/T1-28/T2-315).
Table 29.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-29 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-29/T2-1 to I.D-3/T1-29/T2-315).
Table 30.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-30 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-30/T2-1 to I.D-3/T1-30/T2-315).
Table 31.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-31 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I . D-3/T 1-31 /T2- 1 to I.D-3/T1-31/T2-315).
Table 32.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-32 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-32/T2-1 to I.D-3/T1-32/T2-315).
Table 33.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-33 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-33/T2-1 to I.D-3/T1-33/T2-315).
Table 34.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-34 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-34/T2-1 to I.D-3/T1-34/T2-315).
Table 35.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-35 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-35/T2-1 to I.D-3/T1-35/T2-315).
Table 36.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-36 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-36/T2-1 to I.D-3/T1-36/T2-315).
Table 37.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-37 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-37/T2-1 to I.D-3/T1-37/T2-315). Table 38.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-38 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-38/T2-1 to I.D-3/T1-38/T2-315).
Table 39.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-39 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-39/T2-1 to I.D-3/T1-39/T2-315).
Table 40.I.D-3
Compounds of the formula I.D in which CR5R5’ is CH2, the combination of R4, R4’ and R4” corresponds to line T1-40 of Table T 1 and the combination of R1 and R3 for each individual compound corresponds in each case to one line of Table T2 (compounds I.D-3/T1-40/T2-1 to I.D-3/T1-40/T2-315).
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), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (syn. Fungi imperfecti). 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 phytopathogenic 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.
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, 19-51 a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN 10224, MON 1445, 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.105, 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, BN LA-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 W001/031042, W001/041558, W001/041558, W002/036831,
W01 1/153186, W013/003558; for cotton events MON 1445, MON 15985, MON531 (MON 15985), LLCotton25, MON88913, COT102, 281-24-236, 3006-210-23, COT67B,
GHB614, T304-40, GHB119, MON88701, 81910 in WO02/034946, W002/100163, W002/100163, WO03/013224, WO04/072235, WO04/039986, WO05/103266, WO05/103266, WO06/128573, W007/017186, W008/122406, W008/151780, WO12/134808, W013/112527; 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, WO09/103049, WO09/111263, W010/077816, W011/084621, W011/062904, W01 1/022469, W013/169923, W014/116854, WO15/053998, W015/142571; for potato events E12, F10, J3, J55, V11, X17, Y9 in WO14/178910, W014/178913, W014/178941,
W01 4/179276, W016/183445, W017/062831 , W017/062825; 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, W008/002872, WO09/064652, WO09/102873, W0 10/080829, W010/037016, W011/066384, W011/034704, WO12/051199, WO12/082548, W0 13/016527, 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. porn), 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. triticina)·, 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.
B. 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); B. squamosa or B. 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. fulvum 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. oryzae)\ 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; Cycloconium 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. liriodendri, 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: Pyrenophora ) 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 Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (formerly Phaeoacremonium chiamydosporum) , 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; Erysiphe 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 (Eutypa 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. turcicum)·, Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as E. graminearum or E. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), E. oxysporum on tomatoes, E. solani (f. sp. glycines now syn. E. virguliforme ) and E. tucumaniae and E. brasiliense each causing sudden death syndrome on soybeans, and E. verticillioides 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; Grain- staining 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; Microdochium (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. fructigena (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. gregata : 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. viticoia\ 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; Pseudopezicula tracheiphila (red fire disease or .rotbrenner’, anamorph: Phialophora) on vines; Puccinia 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: Mycosphaerella 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; Setosphaeria 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. appendiculatus, 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. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. longisporum on oilseed rape, V. dahliae on strawberries, oilseed rape, potatoes and tomatoes, and V. 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. Peronospora parasitica on vines, Phytophthora infestans on potatoes); powdery mildews on specialty crops and cereals (e.g. Uncinula necator on 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).
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.
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 invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I.
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.
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.
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.
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, tetrahydronaphtha- lene, 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.
N- 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 ethoxy lated 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 alkylisothiazolinones 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.
Examples for composition types and their preparation are: i) Water-soluble concentrates (SL, LS)
10-60 wt% of a compound I and 5-15 wt% wetting agent (e. g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e. g. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water. ii) Dispersible concentrates (DC)
5-25 wt% of a compound I and 1-10 wt% dispersant (e. g. polyvinyl pyrrolidone) are dissolved in organic solvent (e. g. cyclohexanone) ad 100 wt%. Dilution with water gives a dispersion. iii) Emulsifiable concentrates (EC) 15-70 wt% of a compound I and 5-10 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e. g. aromatic hydrocarbon) ad 100 wt%. Dilution with water gives an emulsion. iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound I and 1-10 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e. g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt% by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion. v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound I are comminuted with addition of 2-10 wt% dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt% thickener (e. g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition, up to 40 wt% binder (e. g. polyvinyl alcohol) is added. vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound I are ground finely with addition of dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound I are ground in a rotor-stator mill with addition of 1-5 wt% dispersants (e. g. sodium lignosulfonate), 1-3 wt% wetting agents (e. g. alcohol ethoxylate) and solid carrier (e. g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance. viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound I are comminuted with addition of 3-10 wt% dispersants (e. g. sodium lignosulfonate), 1-5 wt% thickener (e. g. carboxymethyl cellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance. ix) Microemulsion (ME) 5-20 wt% of a compound I are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethyl amide and cyclohexanone), 10-25 wt% surfactant blend (e. g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion. x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound I, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e. g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). Radical polymerization results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), and an isocyanate monomer (e. g. diphenylmethene-4,4’-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). The addition of a polyamine (e. g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1-10 wt%. The wt% relate to the total CS composition. xi) Dustable powders (DP, DS)
1-10 wt% of a compound I are ground finely and mixed intimately with solid carrier (e. g. finely divided kaolin) ad 100 wt%. xii) Granules (GR, FG)
0.5-30 wt% of a compound I is ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or fluidized bed. xiii) Ultra-low volume liquids (UL)
1-50 wt% of a compound I are dissolved in organic solvent (e. g. aromatic hydrocarbon) ad 100 wt%.
The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% colorants.
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) 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), mandestrobin (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-methoxyimino-/\/-methyl-acetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb/chlorodincarb (A.1.20), famoxadone (A.1.21), fenamidone (A.1.21), methyl-/\/-[2-[(1 ,4-dimethyl-5-phenyl- pyrazol-3-yl)oxylmethyl]phenyl]-/\/-methoxy-carbamate (A.1.22), metyltetraprole (A.1.25), (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-/\/,3-dimethyl-pent-3-enamide (A.1.34), (Z,2£)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-/\/,3-dimethyl-pent-3- enamide (A.1.35), pyriminostrobin (A.1.36), bifujunzhi (A.1.37), 2-(ortho-((2,5-dimethylphenyl- oxymethylen)phenyl)-3-methoxy-acrylic acid methylester (A.1.38); inhibitors of complex III at Q, 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-dioxo- 1,5-dioxonan-7-yl] 2-methylpropanoate (A.2.3), fenpicoxamid (A.2.4), florylpicoxamid (A.2.5); 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), pyraziflumid (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-(trifluoro- methyl)phenoxy]phenyl]-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazole-4-carboxamide (A.3.29), methyl (£)-2-[2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3-methoxy-prop-2-enoate (A.3.30), isoflucypram (A.3.31), 2-(difluoromethyl)-/\/-(1,1,3-trimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.32), 2-(difluoromethyl)-/\/-[(3R)-1,1,3-trimethylindan-4-yl]pyridine-3-carboxamide (A.3.33), 2-(difluoromethyl)-/\/-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.34), 2- (difluoromethyl)-/\/-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (A.3.35), 2- (difluoro ethyl)-/\/-(1,1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide (A.3.36), 2- (difluoromethyl)-/\/-[(3R)-1 ,1-dimethyl-3-propyl-indan-4-yl]pyridine-3-carboxamide (A.3.37), 2- (difluoro ethyl)-/\/-(3-isobutyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.38), 2- (difluoromethyl)-/\/-[(3R)-3-isobutyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (A.3.39); other respiration inhibitors: diflumetorim (A.4.1); nitrophenyl derivates: binapacryl (A.4.2), dinobuton (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), bromu- conazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (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), 4-[[6-[2-(2,4-difluorophenyl)-1,1- difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (B.1.33), ipfentrifluconazole (B.1.37), mefentrifluconazole (B.1.38), 2-(chloromethyl)-2-methyl-5-(p- tolylmethyl)-1-(1,2,4-triazol-1-ylmethyl)cyclopentanol (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); Deltal 4-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), spiroxa ine (B.2.8);
Inhibitors of 3-keto reductase: fenhexa id (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), A/-ethyl-2-[(3- ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1.8), A/-ethyl-2-[(3-ethynyl-8-methyl- 6-quinolyl)oxy]-2-methylsulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/\/-(2- fluoroethyl)butanamide (D.1.10), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/\/-(2-fluoroethyl)-2- methoxy-acetamide (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- methyl-6-quinolyl)oxy]-/\/-(2-fluoroethyl)-2-methylsulfanyl-acetamide (D.1.15), 4-(2-bromo-4- fluoro-phenyl)-/\/-(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), phenamacril (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 hydrochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6);
F) Signal transduction inhibitors MAP / 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]-/\/-tetralin-1- yl-pyridine-2-carboxamide (G.5.5), 4-[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyrazol-1- yl]acetyl]-4-piperidyl]-/\/-tetralin-1-yl-pyridine-2-carboxamide (G.5.6), 4-[1-[2-[5-cyclopropyl-3- (difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-/\/-tetralin-1-yl-pyridine-2-carboxamide (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(trifluoromethyl)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]-/\/-tetralin-1-yl-pyridine-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-1H,5H-[1 ,4]di- thiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-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), prohexadione-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-/\/-(2,4-dimethoxy- phenyl)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), difenzoquat-methylsulfate (K.1.10), diphenylamin (K.1.11), fenitropan (K.1.12), fenpyrazamine (K.1.13), flumetover (K.1.14), flusulfamide (K.1.15), flutianil (K.1.16), harpin (K.1.17), metha- sulfocarb (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), tebufloquin (K.1.24), tecloftalam (K.1.25), triazoxide (K.1.26), L/ -(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-/\/-ethyl-/\/-methyl formamidine (K.1.27), N -(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-/\/-ethyl-/\/- methyl formamidine (K.1.28), L/ -[4-[[3-[(4-chlorophenyl)methyl]-1 ,2,4-thiadiazol-5-yl]oxy]-2,5- dimethyl-phenyl]-/\/-ethyl-/\/-methyl-formamidine (K.1.29), L/ -(5-bromo-6-indan-2-yloxy-2-methyl- 3-pyridyl)-/V-ethyl-/\/-methyl-formamidine (K.1.30), A/-[5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]- 2-methyl-3-pyridyl]-/\/-ethyl-/\/-methyl-formamidine (K.1.31), A/-[5-bromo-6-(4- isopropylcyclohexoxy)-2-methyl-3-pyridyl]-/\/-ethyl-/\/-methyl-formamidine (K.1.32), N’-[ 5-bromo- 2-methyl-6-(1-phenylethoxy)-3-pyridyl]-/\/-ethyl-/\/-methyl-formamidine (K.1.33), /\/’-(2-methyl-5- trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-/\/-ethyl-/\/-methyl formamidine (K.1.34), N’- (5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-/\/-ethyl-/\/-methyl formamidine (K.1.35), 2-(4-chloro-phenyl)-/\/-[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 (pyrisoxazole) (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/-/-benzoimidazole (K.1.39), ethyl (Z)-3-amino-2-cyano-3- phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41), pentyl A/-[6-[[(Z)-[(1-methyltetrazol-5-yl)- phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.42), but-3-ynyl L/-[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), A/-(2,5-dimethyl-4-phenoxy-phenyl)-/\/- ethyl-/\/-methyl-formamidine (K.1.53), pyrifenamine (K.1.54), fluopimomide (K.1.55), N'-[ 5- bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.56);
L) Biopesticides
L1) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. amyloliquefaciens ssp. plantarum (also referred to as B. velezensis), 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, Microsphaeropsis 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 myco- parasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Tricho- derma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, 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. aizawai, 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),
Flavobacterium spp., Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhedrovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, 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 fluorescens, Spodoptera littoralis nucleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces gal bus, S. microflavus
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (£,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, ( E,Z )- 2,4-ethyl decadienoate (pear ester), (Z,Z,£)-7,11,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1 -butanol, methyl eugenol, methyl jasmonate, (£,Z)-2,13-octadecadien-1-ol, (£,Z)-2,13-octadecadien-1-ol acetate, (E,Z)- 3,13- octadecadien-1-ol, (R)-1-octen-3-ol, pentatermanone, (£,Z,Z)-3,8,11-tetradecatrienyl acetate, (Z,£)-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 leguminosarum 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, butocarboxim, 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, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, 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, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluthrin, 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/-/-imidazol-2-amine, (2£)-1-[(6-chloropyridin-3-yl)methyl]-/\/-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, (3R)-3-(2-chlorothiazol-5-yl)-8-methyl-5-oxo-6-phenyl-2,3-dihydrothiazolo[3,2- a]pyrimidin-8-ium-7-olate, (3S)-3-(6-chloro-3-pyridyl)-8-methyl-5-oxo-6-phenyl-2,3-di- hydrothiazolo[3,2-a]pyrimidin-8-ium-7-olate, (3S)-8-methyl-5-oxo-6-phenyl-3-pyrimidin-5-yl-2,3- dihydrothiazolo[3,2-a]pyrimidin-8-ium-7-olate, (3R)-3-(2-chlorothiazol-5-yl)-8-methyl-5-oxo-6-[3- (trifluoromethyl)phenyl]-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-7-olate; (3R)-3-(2- chlorothiazol-5-yl)-6-(3,5-dichlorophenyl)-8-methyl-5-oxo-2,3-dihydrothiazolo[3,2-a]pyrimidin-8- ium-7-olate, (3R)-3-(2-chlorothiazol-5-yl)-8-ethyl-5-oxo-6-phenyl-2,3-dihydrothiazolo[3,2- a]pyrimidin-8-ium-7-olate;
0.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, spinetoram;
0.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin;
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: pymetrozine, pyrifluquinazon;
0.10 Mite growth inhibitors: clofentezine, hexythiazox, diflovidazin; etoxazole;
0.11 Microbial disruptors of insect midgut membranes: Bacillus thuringiensis, Bacillus sphaericus and the insecticdal proteins they produce: Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus 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, flucycloxuron, 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;
0.21 Mitochondrial complex I electron transport inhibitors: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad; rotenone;
0.22 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone, 2-[2-(4-cyano- phenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-/\/-[4-(difluoromethoxy)phenyl]-hydrazine- carboxamide, A/-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)-[4-[methyl(methylsulfonyl)- amino]phenyl]methylene]-hydrazinecarboxamide; 0.23 Inhibitors of the of acetyl CoA carboxylase: spirodiclofen, spiromesifen, spirotetramat, spiropidion;
0.24 Mitochondrial complex IV electron transport inhibitors: aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide;
0.25 Mitochondrial complex II electron transport inhibitors: cyenopyrafen, cyflumetofen;
0.26 Ryanodine receptor-modulators: flubendiamide, chlorantraniliprole, cyantraniliprole, cycla- niliprole, tetraniliprole; (R)-3-chloro-/\/1-{2-methyl-4-[1 ,2,2,2 -tetrafluoro-l-(trifluoromethyl)- ethyl]phenyl}-/\/2-(1-methyl-2-methylsulfonylethyl)phthalamide, (S)-3-chloro-/\/1-{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/-/-pyrazol-5-yl]- carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate; A/-[4,6-dichloro-2-[(diethyl-lambda- 4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; A/-[4-chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3- chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; A/-[4-chloro-2-[(di-2-propyl-lambda- 4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; A/-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3- chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; A/-[4,6-dibromo-2-[(diethyl-lambda-
4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; A/-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3- chloro-2-pyridinyl)-1/-/-pyrazole- 5-carboxamide; 3-chloro-1-(3-chloro-2-pyridinyl)-/\/-[2,4-dichloro- 6-[[(1-cyano-1-methylethyl)amino]carbonyl]phenyl]-1/-/-pyrazole-5-carboxamide; tetrachlorantraniliprole; A/-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3- chloro-2-pyridinyl)-3-(fluoromethoxy)-1/-/-pyrazole- 5-carboxamide; cyhalodiamide;
0.27: Chordotonal organ modulators - undefined target site: flonicamid;
0.28. insecticidal compounds of unknown or uncertain mode of action: afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, broflanilide, bromopropylate, chino- methionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, tioxazafen, 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro[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, 1-[2-fluoro-4-methyl-5-[(2, 2, 2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1 /-/-1,2,4-triazole-
5-amine, Bacillus firmus 1-1582; flupyrimin; fluazaindolizine; 4-[5-(3,5-dichlorophenyl)-5-(tri- fluoromethyl)-4/-/-isoxazol-3-yl]-2-methyl-/\/-(1-oxothietan-3-yl)benzamide; fluxametamide; 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1/-/-pyrazole; 4-cyano-/\/-[2-cyano- 5-[[2,6-dibromo-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]-2- methyl-benzamide; 4-cyano-3-[(4-cyano-2-methyl-benzoyl)amino]-/\/-[2,6-dichloro-4-[1,2,2,3,3,3- hexafluoro-1-(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide; A/-[5-[[2-chloro-6-cyano- 4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano- 2-methyl-benzamide; A/-[5-[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)- ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; A/-[5-[[2-bromo-6-chlo- ro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-
4-cyano-2-methyl-benzamide; 4-cyano-/\/-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-
1-(trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; 4-cyano-/\/-[2-cyano-
5-[[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl- benzamide; A/-[5-[[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carba- moyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; 2-(1,3-dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thi- azolyl]-pyridine; 2-[6-[2-(5-fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; 2-[6-[2-(3-pyridi- nyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; A/-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-
2-carboxamide; A/-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; 1-[(6-chlo- ro-3-pyridinyl)methyl]-1,2,3,5,6,7-hexahydro-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;
1-isopropyl-/\/,5-dimethyl-/\/-pyridazin-4-yl-pyrazole-4-carboxamide; 1-(1,2-dimethylpropyl)- A/-ethyl-5-methyl-/\/-pyridazin-4-yl-pyrazole-4-carboxamide; /\/,5-dimethyl-/\/-pyridazin-4-yl-1- (2,2,2-trifluoro-1-methyl-ethyl)pyrazole-4-carboxamide; 1-[1-(1-cyanocyclopropyl)ethyl]-/\/-ethyl- 5-methyl-/\/-pyridazin-4-yl-pyrazole-4-carboxamide; A/-ethyl-1-(2-fluoro-1-methyl-propyl)-
5-meth-yl-/\/-pyridazin-4-yl-pyrazole-4-carboxamide; 1-(1,2-dimethylpropyl)-/\/,5-dimethyl- A/-pyridazin-4-yl-pyrazole-4-carboxamide; 1-[1-(1-cyanocyclopropyl)ethyl]-/\/,5-dimethyl-/\/-pyri- dazin-4-yl-pyrazole-4-carboxamide; /\/-methyl-1-(2-fluoro-1-methyl-propyl]-5-methyl-/\/-pyridazin- 4-yl-pyrazole-4-carboxamide; 1-(4,4-difluorocyclohexyl)-/\/-ethyl-5-methyl-/\/-pyridazin-4-yl-pyr- azole-4-carboxamide; 1-(4,4-difluorocyclohexyl)-/\/,5-dimethyl-/\/-pyridazin-4-yl-pyrazole-4-car- boxamide, L/-(1 -methylethyl)-2-(3-pyridinyl)-2/-/-indazole-4-carboxamide; /V-cyclopropyl-
2-(3-pyridinyl)-2/-/-indazole-4-carboxamide; A/-cyclohexyl-2-(3-pyridinyl)-2/-/-indazole-4-carbox- amide; 2-(3-pyridinyl)-/V-(2,2,2-trifluoroethyl)-2/-/-indazole-4-carboxamide; 2-(3-pyridinyl)- A/-[(tetrahydro-2-furanyl)methyl]-2/-/-indazole- 5-carboxamide; methyl 2-[[2-(3-pyridinyl)-2/-/- indazol-5-yl]carbonyl]hydrazinecarboxylate; A/-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)- 2/-/-indazole-5-carboxamide; A/-(2,2-difluoropropyl)-2-(3-pyridinyl)-2/-/-indazole-5-carboxamide; 2-(3-pyridinyl )-/V-(2-pyrimidinylmethyl )-2/-/-indazole- 5-carboxamide; A/-[(5-methyl-2-pyrazinyl)- methyl]-2-(3-pyridinyl)-2/-/-indazole-5-carboxamide, tyclopyrazoflor; sarolaner, lotilaner, A/-[4-chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)- 4-(trifluoromethyl)-1/-/-pyrazole-5-carboxamide; 2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6- (trifluoromethyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-
6-(trifluoromethyl)imidazo[4,5-b]pyridine, isocycloseram, A/-[4-chloro-3- (cyclopropylcarbamoyl)phenyl]-2-methyl-5-(1 , 1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)- pyrazole-3-carboxamide, A/-[4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl- 5-(1 , 1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide; acynonapyr; benzpyrimoxan; tigolaner; chloro-/\/-(1-cyanocyclopropyl)-5-[1-[2-methyl-
5-(1 , 1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide, oxazosulf- yl, [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl]-/\/-[4-[1-[4-(tri- fluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate, [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-
6-methyl-tetrahydropyran-2-yl] N-[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]- A/-[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]-/\/-[4-[1-[4-(1,1,2,2,2-penta- fluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate, (2Z)-3-(2-isopropylphenyl)- 2-[(E)-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylenehydra- zono]thiazolidin-4-one; 2-(6-chloro-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-3-methyl-6- (trifluoromethyl)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-[3-ethylsulfonyl-6- (trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2- (7-chloro-3-ethylsulfonyl-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]pyridine, 3-ethylsulfonyl-6-iodo-2-[3-methyl-6- (trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]imidazo[1,2-a]pyridine-8-carbonitrile, 2-[3- ethylsulfonyl-8-fluoro-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoro- methyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3- methyl-6-(trifluoromethylsulfinyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-7-(trifluorometh- yl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine, 2-(6-bromo-3- ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine.
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 lUPAC 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 226917; EP-A 243970; EP-A 256503; EP-A 428941; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122244,
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 3) 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 Q0 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 Q, site in group A), more preferably selected from compounds (A.2.1), (A.2.3) and (A.2.4); particularly selected from (A.2.3) and (A.2.4).
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.3.28), (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.3.31), (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 nhibitors 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) and (B.1.46); 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.138), (B.1.43) and (B.1.46).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from Deltal 4-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) and (K.1.47); particularly selected from (K.1.41), (K.1.44) and (K.1.47).
The biopesticides from group L1) and/or L2) may also have insecticidal, acaricidal, molluscidal, 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/bv acronym/), are referred to in literature, registered and/or are commercially available: mixtures of Aureobasidium pullulans 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 AzoMax from Novozymes BioAg Produtos papra Agricultura Ltda., Quattro 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 (Int. 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. Rhizo Vital® 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. thurin- giensis 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), Bradyrhizobium 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), Coniothyrium 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 Koppert, 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. anisopliae 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. bilaii) 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), Streptomyces microflavus NRRL B-50550 (WO 2014/124369; Bayer CropScience, Germany), Trichoderma asperelloides JM41R 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 amylolique- faciens AP-188 (L.1.2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B. amyloliquefaciens 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), B. pumilus GHA 180 (L.1.10), B. pumilus INR-7 (L.1.11), B. 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), Trichoderma asperelloides JM41R (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. brasilense Sp245 (L.5.2), Bradyrhizobium elkanii SEMI A 587 (L.5.3), B. elkanii SEMI A 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: For- mulation of Micobial Biopesticides, Springer, 1998; WO 2008/002371, US 6,955,912, US 5,422,107).
Accordingly, the present invention furthermore relates to compositions comprising one compound I (component 1) and one pesticide II (component 2), which pesticide II is selected from the column "Co. 2" of the lines C-1 to C-353 of Table C. A further embodiment relates to the compositions C-1 to C-353 listed in Table C, where a row of Table C corresponds in each case to a fungicidal composition comprising as active components one of the in the present specification individualized compounds of formula I (component 1) and the respective pesticide II from groups A) to O) (component 2) stated in the row in question. Preferably, the compositions described comprise the active components in synergistically effective amounts.
Table C: Compositions comprising as active components one individualized compound I (I) (in Column Co. 1) and as component 2) (in Column Co. 2) one pesticide from groups A) to O) [which is coded e. g. as (A.1.1) for azoxystrobin as defined above].
Figure imgf000094_0001
Figure imgf000094_0002
Figure imgf000094_0003
Figure imgf000095_0001
Figure imgf000095_0002
Figure imgf000095_0003
Figure imgf000096_0001
Figure imgf000096_0002
Figure imgf000096_0003
Figure imgf000097_0001
Figure imgf000097_0002
Figure imgf000097_0003
Figure imgf000098_0002
Figure imgf000098_0003
Figure imgf000098_0004
Experimental part I. Synthesis
1.1 Synthesis of reagents
Example R1. Synthesis of 1-(t fluoromethyl)-cyclopropanecarbonyl chloride r-1
Figure imgf000098_0001
To a solution of 1-(trifluoromethyl)-cyclopropanecarboxylic acid (25.0 g, 162.3 mmol) in anhydrous dichloromethane (250 ml), under nitrogen, was added dropwise N,N- dimethylformamide (15 drops), followed by further dropwise addition of oxalyl chloride (21.2 ml, 243.5 mmol). The reaction mixture was then stirred overnight, under nitrogen, at room temperature before concentrating in vacuo to give the compound r-1 (28.0 g) as an oil which was then purified by distillation at 119-121°C.
Example R2. Synthesis of cyclobutanecarbonyl chloride r-2
Figure imgf000099_0001
The cyclobutanecarboxylic acid (950 g, 9.49 mol, 905 ml_) was cooled to 0°C, and then SOCI2 (2.00 L) was added dropwise with stirring. Thereafter, the mixture was stirred at 90°C for 1.5 h. The reaction mixture was distilled in vacuum (80°C, 20 mmHg) to give compound r-2 (1.10 kg, 48.9% yield) as a colorless liquid.
1.2 Synthesis of azol compounds
Example 1. Synthesis of compound A.T1-8.T2-2 The compound I.A.T1-8.T2-2 was prepared according to the following scheme:
Figure imgf000099_0002
I.AT1-8.T2-2 4
Step a. Synthesis of compound 2 Alternative 1. To a solution of 4-bromo-3-chlorophenol 1 (500 g, 2.4 mol) in DMF (1 L) was added K2CO3 (700 g, 5 mol). The solution was stirred for 30 min. Then a solution of 2,2,2- trifluoroethyl-p-toluenesulfonate (720 g, 2.5 mol) in DMF (1L) was added dropwise. The resulting reaction solution was heated to 135°C and stirred overnight. Thereafter, reaction was extracted with water/methyl-tert-butyl ether and the resulting oil was purified by silica gel flash column chromatography (EtOAc/hexane) to provide the compound 2 in 80% yield.
Alternative 2. To a solution of 4-bromo-3-chlorophenol 1 (498 g, 2.4 mol) in DMF (1 L) was added K2CO3 (870 g, 6.3 mol). The solution was stirred for 30 min. Then, 1,1,1 -trifl uoro-2- iodoethane (720 g, 4.3 mol) was quickly added. The reaction mixture was stirred at 70°C for two hours. Thereafter, DMSO (300 ml_) and 1.5 mol of 1,1,1-trifluor-2-iodoethane were added and the reaction mixture was stirred at 95°C until full conversion. The reaction mixture was poured onto 4L ice and HCI were added (2L of 10% solution). The resulting solution was extracted with methyl-tert-butyl ether and the combined organic phases were washed 3x with 10% HCI solution followed by brine and dried over Na2SC>4. The compound 2 was obtained in 93% yield.
Step b. Synthesis of compound 3
Step b1. Preparation of a Grignard solution
To a solution of compound 2 (120g, 0.4mol) in THF (50 ml_) at 0-5°C was dropwise added turbo-Grignard (500 ml_ 1.3 M, 0.7 mol). The resulting solution was stirred at 0°C for 30 min.
Step b2. Grignard reaction
To a solution of compound r-1 (81 g, 1.2) in THF (50ml_) at 0°C was added catalytic CuCI and LiCI. The reaction mixture was stirred for 30 min at 0°C. The Grignard solution from Step b1 was then added dropwise and the reaction was warmed up to room temperature and stirred for 2h. Then the reaction mixture was poured into ice-cooled ammonium chloride solution and extracted with methyl-tert-butyl ether. The combined organic extracts were washed with an ammonia solution followed by brine and then dried over Na2S04. The crude product 3 (80% yield) was used in the next step.
Step c. Synthesis of the epoxide compound 4
To a solution of sodium hydride (21 g, 0.9 mol) in THF (700ml_) at 0°C was dropwise added a solution of trimethylsulfoniumiodide (181 g, 0.9mol) in DMSO (500ml_). A solution of compound 3 (137g,0.4mol) in THF (300ml_) was added after 15 minutes. Then the reaction mixture was warmed up to room temperature and stirred for 3 hours. The reaction solution was poured into ice water and extracted with methyl-tert-butyl ether. The combined organic layers were washed with brine and dried over Na2S04. The crude compound 4 (90% yield) was used in the next step. Step d. Synthesis of the azole compound I.A.T1-8.T2-2
To a solution of epoxide 4 (142g, 0.4mol) in NMP (1.5L) were added 1,2,4-triazole (136g, 2mol) and sodium hydroxide (47g, 1.2 mol). The reaction was stirred at 50°C overnight, then poured into a concentrated ammonium chloride solution and extracted with methyl-tert-butyl ether. The combined organic layers were dried over Na2SC>4. After flash silica gel column chromatography (10L heptane followed by 70% ethyl acetate), the target azole I.A.T1 -8. T2-2 was isolated in 53% yield.
The following compounds of the formula I.A and compounds of formula I.C were prepared as described in Example 1.
Figure imgf000101_0001
Figure imgf000102_0001
The following compounds of the formula I.B and compounds of formula I.D were prepared as described above.
Figure imgf000103_0001
The following compounds of the formula I without specific numbers were prepared as described above.
Figure imgf000104_0001
Example 28. Synthesis of compound (I.AP1-24/T2-21)
The compound I.A/T1-24/T2-21 was prepared according to the following scheme:
Figure imgf000105_0001
Step a. Synthesis of compound 6
To a solution of compound 5 (1.00 kg, 5.65 mol, 763 ml_) in MeCN (3.00 L) was added thiocyanate (829 g, 6.21 mol). The mixture was stirred at 40°C for 24 h under N2, then concentrated and diluted with water (7.00 L). Thereafter, it was extracted with methyl-tert-butyl ether (2.00 L x 3). The organic layer was washed with brine (1.00 L), dried over Na2SC>4, filtered and concentrated. The crude product was triturated with HCI/EtOAc (6.00 L) at 20°C for 4 h to give compound 6 (2.60 kg, 92.8% yield, HCI) as a purple solid. 1H NMR (400 MHz MeOD): d 7.64-7.62 (m, 2H), 7.45-7.42 (m, 1H).
Step b. Synthesis of compound 7
To a mixture of compound 6 (2.25 kg, 10.6 mol) in 3M HCI (22.5 L) was added the solution of NaNC>2 (807 g, 11.7 mol) in H2O (1.12 L) at 0°C and the mixture was stirred for 3 h. Then the solution of Kl (2.30 kg, 13.8 mol) in H2O (2.80 L) was added, the reaction mixture was warmed up to 20°C and stirred for 16 hrs. Thereafter, the reaction mixture was extracted with EtOAc (2.00 L x 5). The combined organic layers were washed with saturated Na2S2C>3 solution (1.00 L), saturated NaHCC>3 solution (1.00 L) and with brine (1.00 L), dried over Na2SC>4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography (S1O2, petroleum ether/ethyl acetate = 50/1 to 5/1) to give compound 7 (2.90 kg, 74.2% yield) as a purple liquid.
1H NMR (400 MHz CDCIs): d 7.88 (d, J = 8.8 Hz, 1H), 7.36-7.35 (m, 1 H), 6.90-6.87 (m 1 H).
Step c. Synthesis of compound 8
Step d . Preparation of a Grignard solution i-PrMgCI (2 M, 4.03 L) was added dropwise to the solution of compound 7 (2.00 kg, 6.20 mol) in THF (10.0 L) under nitrogen at -40°C. The resulting mixture was stirred for 1h.
Step c2. Grignard reaction
To the solution of compound r-2 (1.10 kg, 9.30 mol, 1.06 L) in THF (5.50 L) under nitrogen were added CuCI (92.1 g, 930 mmol, 22.3 ml_) and LiCI (78.9 g, 1.86 mol, 38.1 ml_) and the mixture was stirred for 30 min. The Grignard solution from Step d was then added quickly under nitrogen at -20 °C. Then the reaction was warmed up to 20°C and stirred for 1h. The reaction mixture was quenched with aq. NH4CI (5.00 L) and extracted with methyl-tert-butyl ether (5.00 L x 2), the organic layer was washed with aq. NaHCOs (5.00 L) and brine (5.00 L), dried over Na2S04 and concentrated. The residue was purified by column chromatography (S1O2, petroleum ether/ethyl acetate = 1/0) to give compound 8 (2.20 kg, 79.7% yield) as a yellow oil.
1H NMR (400 MHz CDCIs): 6 7.51 (d, J = 8.4 Hz, 1H), 7.29-7.28 (m, 1 H), 7.19-7.17 (m, 1H), 3.98-3.90 (m, 1H), 2.39-2.34 (m, 2H), 2.27-2.24 (m, 2H), 2.05-1.92 (m, 2H).
Figure imgf000106_0001
To a solution of compound 8 (500 g, 1.79 mol) in CH2CI2 (3.50 L) was added Br2 (313 g, 1.96 mol, 101 ml_) at 0°C under nitrogen and the mixture was stirred at 20 °C for 4 h. The reaction mixture was quenched with aq. NaHCOs (5.00 L) and extracted with CH2CI2 (4.00 L x 3). The organic layer was washed with aq. Na2S203 (5.00 L), dried over Na2S04 and concentrated to give compound 9 (2.50 kg, crude) as a yellow oil, which was used in the next step without further purification.
1H NMR (400 MHz CDCIs): 6 7.85 (d, J = 8.4 Hz, 1H), 7.35 (s, 1H), 7.17 (d, J = 8.4 Hz, 1 H), 3.11-3.05 (m, 2H), 2.69-2.64 (m, 2H), 2.41-2.38 (m, 1H), 1.97-1.93 (m, 1H).
Step e. Synthesis of compound 10 To a solution of compound 9 (834 g, 2.33 mol) in AcOH (4.20 L) was added AgOAc (584 g, 3.50 mol) under nitrogen. The mixture was heated to 120 °C for 4 h, then concentrated and the residue was dissolved in methyl-tert-butyl ether (5.00 L). The solution was washed with aq. NaHCC>3 (5.00 L) and brine (5.00 L), the organic layer was dried over Na2SC>4 and concentrated. The residue was purified by column chromatography (S1O2, petroleum ether/ethyl acetate = 50/1 to 3/1) to give compound 10 (2.28 kg, crude) as a yellow oil.
1H NMR (400 MHz CDCI3): d 7.31-7.29 (m, 2H), 7.19-7.17 (m, 1H), 4.22 (s, 2H), 1.97 (s, 3H), 1.54-1.51 (m, 2H), 1.21-1.18 (m, 2H).
Step f. Synthesis of compound 11
To the solution of trimethylsulfonium iodide (1.31 kg, 5.94 mol) in DMSO (17.0 L) was added t- BuOK (667 g, 5.94 mol) under nitrogen. The mixture was stirred for 1 h. Then compound 10 (667 g, 1.98 mol) in DMSO (1.30 L) was added and the resulting mixture was stirred for 12 h at 15°C. Thereafter, it was diluted with water (18.0 L) and extracted with EtOAc (5.00 L x 3). The organic layer was washed with water (5.00 L x 2), brine (3.00 L), dried over Na2S04 and concentrated to give compound 11 (480 g, crude) as a yellow oil, which was used in the next step without further purification.
1H NMR (400 MHz CDCIs): d 7.55 (d, J = 8.4 Hz, 1H), 7.25-7.14 (m, 2H), 3.56-3.53 (m, 1H), 3.38-3.37 (m, 1 H), 3.35-3.26 (m, 1 H), 2.93-2.92 (m, 1 H), 0.79-0.56 (m, 4 H).
Step Q. Synthesis of compound 12
To the solution of compound 11 (480 g, 1.37 mol) in MeOH (2.80 L) was added K2CO3 (284 g, 2.05 mol) at 20 °C and the mixture was stirred for 1 h at 20°C. Then, the reaction mixture was filtered and the pH of the filtrate was adjusted to 7 with citric acid. The filtrate was concentrated and the residue was dissolved in EtOAc (2.00 L) and washed with brine (1.00 L), dried over Na2S04 and concentrated to give compound 12 (468 g, crude) as a yellow oil, which was used in the next step without further purification.
1H NMR (400 MHz CDCIs): d ppm 7.55 (d, J = 8.4 Hz, 1H), 7.27-7.25 (m, 1 H), 7.17-7.14 (m,
1 H), 3.56-3.53 (m, 1H), 3.37-3.27 (m, 2H), 2.93-2.92 (m, 1H), 0.79-0.55 (m, 4H).
Step h. Synthesis of compound 13
To compound 12 (156 g, 505 mmol) in CH2CI2 (3.00 L) was added Dess-Martin periodinane (279 g, 657 mmol). The resulting mixture was stirred at 30 °C for 1 h and then quenched with aq. NaHCCh (4.00 L) and extracted with CH2CI2 (2.00 L x 2). The organic layer was washed with brine (1.00 L), dried over Na2SC>4 and concentrated. The residue was purified by column chromatography (S1O2, petroleum ether/ethyl acetate = 100/1 to 3/1) to give compound 13 (207 g, 66.8% yield) as a yellow oil.
1H NMR (400 MHz CDCIs): d 9.28 (s, 1 H), 7.66 (d, J = 8.4 Hz, 1H), 7.26-7.14 (m, 2H), 3.24 (d, J = 4.8 Hz, 1 H), 3.03 (d, J = 4.8 Hz, 1 H), 1.35-1.22 (m, 4H).
Step /'. Synthesis of compound 14
To compound 13 (55.0 g, 179 mmol) in THF (550 ml_) was added CF2Br2 (150 g, 538 mmol) and hexamethylphoshoric acid triamide (87.8 g, 538 mmol, 97.8 ml_) at -78 °C under nitrogen and the mixture was stirred for 0.5 h at 25°C. Zn (35.2 g, 538 mmol) and HMPT (87.8 g, 538 mmol, 97.8 ml_) were added at 25 °C and the mixture was stirred for 30 min. The reaction mixture was quenched with aq. NH4CI (1.00 L), filtered and extracted with methyl-tert-butyl ether (300 ml_). The organic layer was dried over Na2SC>4 and concentrated to give compound 14 (99.0 g,
81.0% yield) as a yellow oil.
1H NMR (400 MHz CDCIs): d 7.47 (d, J = 8.4 Hz, 1H), 7.24-7.23 (m, 1 H), 7.16-7.14 (m, 1 H), 4.39-4.33 (m, 1H), 3.13-3.11 (m, 1 H), 2.91-2.90 (m, 1H), 0.94-0.63 (m, 4H).
Step /'. Synthesis of compound LA/T1-24/T2-21
To compound 14 (99.0 g, 291 mmol) in i-PrOH (1.50 L) were added DBU (133 g, 872 mmol, 131 ml_) and 1 ,2,4-triazole (60.2 g, 872 mmol). The resulting mixture was heated to 100°C for 10 h, then diluted with H2O (4.00 L) and extracted with EtOAc (1.00 L x 6). The combined organic layers were washed with brine (2.00 L), dried over Na2SC>4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography (S1O2, petroleum ether/ethyl acetate = 50/1 to 0/1) to give compound I.A/T1-24/T2-21 (51.0 g, 42.8% yield) as a white solid.
1H NMR (400 MHz CDCI3): d 8.12 (s, 1 H), 7.80-7.77 (m, 2H), 7.14 (s, 1H), 7.06-7.04 (m, 1 H), 5.67-5.63 (m, 1H), 5.24 (s, 1H), 4.48-4.41 (m, 2H), 1.05-1.02 (m, 2H), 0.80-0.71 (m, 2H).
The following compound I.A/T1-24/T2-26 of the formula I.B and compounds of formula I.D were prepared as described above.
Figure imgf000108_0001
Figure imgf000109_0001
II. Biological examples
Microtest
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
Green House Test
A mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to the compound to give a total of 5 ml. Water was then added to the total volume of 100 ml. This stock solution was diluted with a solvent-emulsifier-water mixture to the given concentration.
1. Curative control of soy bean rust on soy beans caused by Phakopsora pachyrhizi (Phakpa K4)
Leaves of pot-grown soy bean seedlings were inoculated with spores of Phakopsora pachyrhizi. To ensure the success of the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and 20 to 24°C for 24 h. The next day the plants were cultivated for 3 days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80 %. Then the plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. Then the trial plants were cultivated for 14 days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
2. Protective control of soy bean rust on soy beans caused by Phakopsora pachyrhizi (Phakpa P6)
Leaves of pot-grown soy bean seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The trial plants were cultivated for 6 days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80%. Then the plants were inoculated with spores of Phakopsora pachyrhizi. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95 % and 20 to 24°C for 24 h. The trial plants were cultivated for fourteen days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
3. Protective control of soy bean rust on soy beans caused by Phakopsora pachyrhizi (Phakpa P10)
Leaves of pot-grown soy bean seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The trial plants were cultivated for 10 days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80 %. Then the plants were inoculated with spores of Phakopsora pachyrhizi. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95 % and 20 to 24°C for 24 h. The trial plants were cultivated for fourteen days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
4. Curative control of brown rust on wheat caused by Puccinia recondita (Puccrt K4)
The first two developed leaves of pot-grown wheat seedling were dusted with spores of Puccinia recondita. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber without light and a relative humidity of 95 to 99 % and 20 to 24°C for 24 h. The next day the plants were cultivated for 3 days in a greenhouse chamber at 20-24°C and a relative humidity between 65 and 70%. Then the plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. The plants could air-dry. Then the trial plants were cultivated for 8 days in a greenhouse chamber at 20-24°C and a relative humidity between 65 and 70%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
Table Z. Biological activity
Figure imgf000110_0001
Figure imgf000111_0001

Claims

Claims
1. Compounds of the formula I
Figure imgf000112_0001
R1 is selected from hydrogen, OH, CrC4-halogenalkyl, C2-C4-alkenyl, C2-C4- halogenalkenyl, C2-C4-alkynyl, C2-C4-halogenalkynyl;
Ra is independently of one another selected from hydrogen or halogen;
R2 is hydrogen;
R3 is selected from halogen or Ci-C4-halogenalkyl;
R4, R4’, and R4” are independently of one another selected from hydrogen, halogen, Cr C4-alkyl, Ci-C4-halogenalkyl;
R5 and R5’ are independently of one another selected from hydrogen or halogen; or
R5 and R5’ together are =C(R6)2, wherein R6 is halogen or Ci-C4-alkyl; m is O or l; provided that if m is 0 and three or four Ra are hydrogens, then R1 is not hydrogen; and provided that if m is 1 and CR5R5’ is CH2, then at least one Ra is not hydrogen, and the N-oxides and the agriculturally acceptable salts thereof.
2. The compounds of claim 1 , wherein m is 0.
3. The compounds of claim 1 , wherein m is 1.
4. The compounds of any one of claims 1 to 3, wherein R1 is selected from C1-C4- halogenalkyl, C2-C4-alkenyl, C2-C4-halogenalkenyl, C2-C4-alkynyl, C2-C4-halogenalkynyl.
5. The compounds of any one of claims 1 to 4, wherein R1 is selected from C1-C4- halogenalkyl, C2-C4-halogenalkenyl, C2-C4-halogenalkynyl.
6. The compounds of any one of claims 1 to 5, wherein two geminal Ra are halogens, and two remaining Ra are hydrogens.
7. The compounds of any one of claims 1 to 6, wherein R3 is halogen.
8. The compounds of any one of claims 1 to 7, wherein R3 is Ci-C4-halogenalkyl.
9. The compounds of any one of claims 1 to 8, wherein at least one of R4, R4’, and R4” is not hydrogen.
10. The compounds of any one of claims 1 to 9, wherein CR4R4’R4” is selected from CF3, CHF2, CH2F, CH2CF3 and CH2CF2CHF2.
11. The compounds of any one of claims 1 to 10, wherein CR4R4’R4” is selected from CF3 and CHF2.
12. A composition, comprising a compound of formula I, as defined in any of the claims 1 to 10, an N-oxide or an agriculturally acceptable salt thereof.
13. A use of a compound of the formula I, as defined in any of the claims 1 to 10, and/or of an agriculturally acceptable salt thereof or of the compositions, as defined in any of the claims 11 or 12, for combating phytopathogenic fungi.
14. A method for combating harmful 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 10, or with a composition, as defined in any of the claims 11 or 12.
15. Seed, coated with at least one compound of the formula I, as defined in any of the claims 1 to 10, and/or an agriculturally acceptable salt thereof or with a composition, as defined in any of the claims 11 or 12, in an amount of from 0.1 to 10 kg per 100 kg of seed.
PCT/EP2021/064484 2020-06-10 2021-05-31 Substituted [1,2,4]triazole compounds as fungicides Ceased WO2021249800A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20179149.8 2020-06-10
EP20179149 2020-06-10

Publications (1)

Publication Number Publication Date
WO2021249800A1 true WO2021249800A1 (en) 2021-12-16

Family

ID=71083478

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2021/064484 Ceased WO2021249800A1 (en) 2020-06-10 2021-05-31 Substituted [1,2,4]triazole compounds as fungicides

Country Status (1)

Country Link
WO (1) WO2021249800A1 (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024256433A1 (en) 2023-06-14 2024-12-19 Syngenta Crop Protection Ag Fungicidal compositions
WO2024256438A1 (en) 2023-06-14 2024-12-19 Syngenta Crop Protection Ag Fungicidal compositions
WO2025056767A1 (en) 2023-09-15 2025-03-20 Syngenta Crop Protection Ag Process for the preparation of enantiomerically enriched aliphatic amines
WO2025104152A1 (en) 2023-11-15 2025-05-22 Syngenta Crop Protection Ag Microbiocidal tetrahydroisoquinoline derivatives
WO2025114167A1 (en) 2023-11-28 2025-06-05 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2025120070A1 (en) 2023-12-08 2025-06-12 Syngenta Crop Protection Ag Polymorphs of a methoxyacrylate derivative
WO2025163143A1 (en) 2024-02-02 2025-08-07 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2025172374A1 (en) 2024-02-13 2025-08-21 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2025172368A1 (en) 2024-02-13 2025-08-21 Syngenta Crop Protection Ag (5-isoxazol-3-yl)-[4-(pyrazol-4-yl)-3,4-dihydro-1h-isoquinolin-2-yl]methanone derivatives for use as fungicides
WO2025191053A1 (en) 2024-03-14 2025-09-18 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2025202482A1 (en) 2024-03-28 2025-10-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2025202499A1 (en) 2024-03-28 2025-10-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2025210095A1 (en) 2024-04-03 2025-10-09 Syngenta Crop Protection Ag Microbiocidal tetrahydroisoquinoline compounds
WO2025210149A1 (en) 2024-04-04 2025-10-09 Syngenta Crop Protection Ag Fungicidal composition
WO2025210096A1 (en) 2024-04-03 2025-10-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2025233384A1 (en) 2024-05-08 2025-11-13 Syngenta Crop Protection Ag Microbiocidal pyrazole compounds
WO2025238048A1 (en) 2024-05-15 2025-11-20 Syngenta Crop Protection Ag Fungicidal compositions
WO2025257342A1 (en) 2024-06-12 2025-12-18 Syngenta Crop Protection Ag Microbiocidal bicyclic heterocyclic compounds
WO2026008511A1 (en) 2024-07-02 2026-01-08 Syngenta Crop Protection Ag Microbiocidal quinoline-amide compounds
WO2026022173A1 (en) 2024-07-26 2026-01-29 Syngenta Crop Protection Ag Microbiocidal pyrazole compounds
WO2026022188A1 (en) 2024-07-23 2026-01-29 Syngenta Crop Protection Ag Microbiocidal quinoline compounds

Citations (166)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3296272A (en) 1965-04-01 1967-01-03 Dow Chemical Co Sulfinyl- and sulfonylpyridines
US3325503A (en) 1965-02-18 1967-06-13 Diamond Alkali Co Polychloro derivatives of mono- and dicyano pyridines and a method for their preparation
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
DE19650197A1 (en) 1996-12-04 1998-06-10 Bayer Ag 3-thiocarbamoylpyrazole derivatives
WO1998044140A1 (en) 1997-04-03 1998-10-08 Dekalb Genetics Corporation Glyphosate resistant maize lines
WO1998046608A1 (en) 1997-04-14 1998-10-22 American Cyanamid Company Fungicidal trifluoromethylalkylamino-triazolopyrimidines
WO1999014187A1 (en) 1997-09-18 1999-03-25 Basf Aktiengesellschaft Benzamidoxim derivatives, intermediate products and methods for preparing and using them as fungicides
WO1999024413A2 (en) 1997-11-12 1999-05-20 Bayer Aktiengesellschaft Isothiazole carboxylic acid amides and the application thereof in order to protect plants
WO1999027783A1 (en) 1997-12-04 1999-06-10 Dow Agrosciences Llc Fungicidal compositions and methods, and compounds and methods for the preparation thereof
WO2000026345A1 (en) 1998-11-03 2000-05-11 Aventis Cropscience N.V. Glufosinate tolerant rice
WO2000029404A1 (en) 1998-11-17 2000-05-25 Kumiai Chemical Industry Co., Ltd. Pyrimidinylbenzimidazole and triazinylbenzimidazole derivatives and agricultura/horticultural bactericides
WO2000046148A1 (en) 1999-02-02 2000-08-10 Sintokogio, Ltd. Silica gel carrying titanium oxide photocatalyst in high concentration and method for preparation thereof
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
WO2000065913A1 (en) 1999-04-28 2000-11-09 Takeda Chemical Industries, Ltd. Sulfonamide derivatives
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
DE10021412A1 (en) 1999-12-13 2001-06-21 Bayer Ag Fungicidal active ingredient combinations
WO2001054501A2 (en) 2000-01-25 2001-08-02 Syngenta Participations Ag Herbicidal composition
EP1122244A1 (en) 2000-02-04 2001-08-08 Sumitomo Chemical Company, Limited Uracil compounds and their use
WO2001056358A2 (en) 2000-01-28 2001-08-09 Rohm And Haas Company Enhanced propertied pesticides
CN1309897A (en) 2000-02-24 2001-08-29 沈阳化工研究院 Unsaturated oximino ether bactericide
WO2002022583A2 (en) 2000-09-18 2002-03-21 E. I. Du Pont De Nemours And Company Pyridinyl amides and imides for use as fungicides
WO2002034946A2 (en) 2000-10-25 2002-05-02 Monsanto Technology Llc Cotton event pv-ghgt07(1445) and compositions and methods for detection thereof
EP1201648A1 (en) 1999-08-05 2002-05-02 Kumiai Chemical Industry Co., Ltd. Carbamate derivatives and agricultural/horticultural bactericides
WO2002036831A2 (en) 2000-10-30 2002-05-10 Monsanto Technology Llc Canola event pv-bngt04(rt73) and compositions and methods for detection thereof
WO2002040431A2 (en) 2000-11-17 2002-05-23 Dow Agrosciences Llc Compounds having fungicidal activity and processes to make and use same
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
JP2002316902A (en) 2001-04-20 2002-10-31 Sumitomo Chem Co Ltd Plant disease control agent composition
WO2002100163A2 (en) 2001-06-11 2002-12-19 Monsanto Technology Llc Cotton event moni5985 and compositions and methods for detection
WO2003010149A1 (en) 2001-07-25 2003-02-06 Bayer Cropscience Ag Pyrazolylcarboxanilides as fungicides
WO2003011853A1 (en) 2001-07-30 2003-02-13 Dow Agrosciences Llc 6-aryl-4-aminopicolinates and their use as herbicides
WO2003013224A2 (en) 2001-08-06 2003-02-20 Bayer Bioscience N.V. Herbicide tolerant cotton plants and methods for producing and identifying same
WO2003014103A1 (en) 2001-08-03 2003-02-20 Bayer Cropscience S.A. Iodobenzopyran-4-one derivatives having fungicidal activity
WO2003016286A1 (en) 2001-08-17 2003-02-27 Sankyo Agro Company, Limited 3-phenoxy-4-pyridazinol derivative and herbicide composition containing the 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
WO2003053145A1 (en) 2001-12-21 2003-07-03 Nissan Chemical Industries, Ltd. Bactericidal composition
WO2003061388A1 (en) 2002-01-18 2003-07-31 Sumitomo Chemical Takeda Agro Company, Limited Fused heterocyclic sulfonylurea compound, herbicide containing the same, and method of controlling weed with the same
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
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
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
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
DE102005009458A1 (en) 2005-03-02 2006-09-07 Bayer Cropscience Ag pyrazolylcarboxanilides
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
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
WO2008002371A1 (en) 2006-06-23 2008-01-03 Becker Underwood Inc. Improved shelf life and on seed stabilization of liquid bacterium inoculants
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
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
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
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
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
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
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
WO2013024009A1 (en) 2011-08-12 2013-02-21 Basf Se N-thio-anthranilamide compounds and their use as pesticides
WO2013024010A1 (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
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
WO2014178941A1 (en) 2013-05-02 2014-11-06 J.R. Simplot Company Potato cultivar j3
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
WO2015185708A1 (en) 2014-06-06 2015-12-10 Basf Se Substituted [1,2,4]triazole compounds
WO2016020371A1 (en) 2014-08-04 2016-02-11 Basf Se Antifungal paenibacillus strains, fusaricidin-type compounds, and their use
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

Patent Citations (171)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3325503A (en) 1965-02-18 1967-06-13 Diamond Alkali Co Polychloro derivatives of mono- and dicyano pyridines and a method for their preparation
US3296272A (en) 1965-04-01 1967-01-03 Dow Chemical Co Sulfinyl- and sulfonylpyridines
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
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
DE19650197A1 (en) 1996-12-04 1998-06-10 Bayer Ag 3-thiocarbamoylpyrazole derivatives
WO1998044140A1 (en) 1997-04-03 1998-10-08 Dekalb Genetics Corporation Glyphosate resistant maize lines
WO1998046608A1 (en) 1997-04-14 1998-10-22 American Cyanamid Company Fungicidal trifluoromethylalkylamino-triazolopyrimidines
WO1999014187A1 (en) 1997-09-18 1999-03-25 Basf Aktiengesellschaft Benzamidoxim derivatives, intermediate products and methods for preparing and using them as fungicides
WO1999024413A2 (en) 1997-11-12 1999-05-20 Bayer Aktiengesellschaft Isothiazole carboxylic acid amides and the application thereof in order to protect plants
WO1999027783A1 (en) 1997-12-04 1999-06-10 Dow Agrosciences Llc Fungicidal compositions and methods, and compounds and methods for the preparation thereof
WO2000026345A1 (en) 1998-11-03 2000-05-11 Aventis Cropscience N.V. Glufosinate tolerant rice
WO2000029404A1 (en) 1998-11-17 2000-05-25 Kumiai Chemical Industry Co., Ltd. Pyrimidinylbenzimidazole and triazinylbenzimidazole derivatives and agricultura/horticultural bactericides
EP1028125A1 (en) 1998-11-30 2000-08-16 Isagro Ricerca S.r.l. Dipeptide compounds having fungicidal activity and their agronomic use
WO2000046148A1 (en) 1999-02-02 2000-08-10 Sintokogio, Ltd. Silica gel carrying titanium oxide photocatalyst in high concentration and method for preparation thereof
EP1035122A1 (en) 1999-03-11 2000-09-13 Rohm And Haas Company Heterocyclic subsituted isoxazolidines and their use as fungicides
WO2000065913A1 (en) 1999-04-28 2000-11-09 Takeda Chemical Industries, Ltd. Sulfonamide derivatives
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
DE10021412A1 (en) 1999-12-13 2001-06-21 Bayer Ag Fungicidal active ingredient combinations
WO2001054501A2 (en) 2000-01-25 2001-08-02 Syngenta Participations Ag Herbicidal composition
WO2001056358A2 (en) 2000-01-28 2001-08-09 Rohm And Haas Company Enhanced propertied pesticides
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
WO2002022583A2 (en) 2000-09-18 2002-03-21 E. I. Du Pont De Nemours And Company Pyridinyl amides and imides for use as fungicides
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
WO2002040431A2 (en) 2000-11-17 2002-05-23 Dow Agrosciences Llc Compounds having fungicidal activity and processes to make and use same
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
JP2002316902A (en) 2001-04-20 2002-10-31 Sumitomo Chem Co Ltd Plant disease control agent composition
WO2002100163A2 (en) 2001-06-11 2002-12-19 Monsanto Technology Llc Cotton event moni5985 and compositions and methods for detection
WO2003010149A1 (en) 2001-07-25 2003-02-06 Bayer Cropscience Ag Pyrazolylcarboxanilides as fungicides
WO2003011853A1 (en) 2001-07-30 2003-02-13 Dow Agrosciences Llc 6-aryl-4-aminopicolinates and their use as herbicides
WO2003014103A1 (en) 2001-08-03 2003-02-20 Bayer Cropscience S.A. Iodobenzopyran-4-one derivatives having fungicidal activity
WO2003013224A2 (en) 2001-08-06 2003-02-20 Bayer Bioscience N.V. Herbicide tolerant cotton plants and methods for producing and identifying same
WO2003016286A1 (en) 2001-08-17 2003-02-27 Sankyo Agro Company, Limited 3-phenoxy-4-pyridazinol derivative and herbicide composition containing the 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
WO2003053145A1 (en) 2001-12-21 2003-07-03 Nissan Chemical Industries, Ltd. Bactericidal composition
WO2003061388A1 (en) 2002-01-18 2003-07-31 Sumitomo Chemical Takeda Agro Company, Limited Fused heterocyclic sulfonylurea compound, herbicide containing the same, and method of controlling weed with the same
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
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
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
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
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
DE102005009458A1 (en) 2005-03-02 2006-09-07 Bayer Cropscience Ag pyrazolylcarboxanilides
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
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
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
US20120149571A1 (en) 2010-12-10 2012-06-14 Auburn University Inoculants Including Bacillus Bacteria for Inducing Production of Volatile Organic Compounds in Plants
US8445255B2 (en) 2010-12-10 2013-05-21 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
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
WO2013016527A1 (en) 2011-07-26 2013-01-31 Dow Agrosciences Llc Insect resistant and herbicide tolerant soybean event 9582.814.19.1
WO2013024009A1 (en) 2011-08-12 2013-02-21 Basf Se N-thio-anthranilamide compounds and their use as pesticides
WO2013024010A1 (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
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
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
WO2014178913A1 (en) 2013-05-02 2014-11-06 J.R. Simplot Company Potato cultivar f10
WO2014178910A1 (en) 2013-05-02 2014-11-06 J.R. Simplot Company Potato cultivar e12
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
WO2015185708A1 (en) 2014-06-06 2015-12-10 Basf Se Substituted [1,2,4]triazole compounds
WO2016020371A1 (en) 2014-08-04 2016-02-11 Basf Se Antifungal paenibacillus strains, fusaricidin-type compounds, and their use
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

Non-Patent Citations (21)

* Cited by examiner, † Cited by third party
Title
"Technical Monograph", 2008, CROPLIFE INTERNATIONA, article "Catalogue of pesticide formulation types and international coding system"
APPL. ENVIRON. MICROBIOL, vol. 73, no. 8, 2007, pages 2635
APPL. ENVIRON. MICROBIOL., vol. 73, no. 8, 2007, pages 2635
BIOCONTROL SCIENCE TECHNOL., vol. 22, no. 7, 2012, pages 747 - 761
BIOCONTROL, vol. 57, 2012, pages 687 - 696
BIOL. FERTIL. SOILS, vol. 47, 2011, pages 81 - 89
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
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
INT. J. SYST. EVOL. MICROBIOL., vol. 66, 2016, pages 1212 - 1217
J. INVERTEBRATE PATHOL., vol. 107, 2011, pages 112 - 126
J. PLANT DIS. PROT., vol. 105, 1998, pages 181 - 197
KNOWLES: "Agrow Reports", 2005, article "New developments in crop protection product formulation"
MOLLETGRUBEMANN: "Formulation technology", 2001, WILEY VCH
SCIENCE, vol. 257, 1992, pages 85 - 88
SIMBIOSE-AGRO, BRAZIL, PLANT SOIL, vol. 331, 2010, pages 413 - 425
SYSTEM. APPL. MICROBIOL, vol. 27, 2004, pages 372 - 379

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024256433A1 (en) 2023-06-14 2024-12-19 Syngenta Crop Protection Ag Fungicidal compositions
WO2024256438A1 (en) 2023-06-14 2024-12-19 Syngenta Crop Protection Ag Fungicidal compositions
WO2025056767A1 (en) 2023-09-15 2025-03-20 Syngenta Crop Protection Ag Process for the preparation of enantiomerically enriched aliphatic amines
WO2025104152A1 (en) 2023-11-15 2025-05-22 Syngenta Crop Protection Ag Microbiocidal tetrahydroisoquinoline derivatives
WO2025114167A1 (en) 2023-11-28 2025-06-05 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2025120070A1 (en) 2023-12-08 2025-06-12 Syngenta Crop Protection Ag Polymorphs of a methoxyacrylate derivative
WO2025163143A1 (en) 2024-02-02 2025-08-07 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2025172374A1 (en) 2024-02-13 2025-08-21 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2025172368A1 (en) 2024-02-13 2025-08-21 Syngenta Crop Protection Ag (5-isoxazol-3-yl)-[4-(pyrazol-4-yl)-3,4-dihydro-1h-isoquinolin-2-yl]methanone derivatives for use as fungicides
WO2025191053A1 (en) 2024-03-14 2025-09-18 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives
WO2025202482A1 (en) 2024-03-28 2025-10-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2025202499A1 (en) 2024-03-28 2025-10-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2025210095A1 (en) 2024-04-03 2025-10-09 Syngenta Crop Protection Ag Microbiocidal tetrahydroisoquinoline compounds
WO2025210096A1 (en) 2024-04-03 2025-10-09 Syngenta Crop Protection Ag Fungicidal compositions
WO2025210149A1 (en) 2024-04-04 2025-10-09 Syngenta Crop Protection Ag Fungicidal composition
WO2025233384A1 (en) 2024-05-08 2025-11-13 Syngenta Crop Protection Ag Microbiocidal pyrazole compounds
WO2025238048A1 (en) 2024-05-15 2025-11-20 Syngenta Crop Protection Ag Fungicidal compositions
WO2025257342A1 (en) 2024-06-12 2025-12-18 Syngenta Crop Protection Ag Microbiocidal bicyclic heterocyclic compounds
WO2026008511A1 (en) 2024-07-02 2026-01-08 Syngenta Crop Protection Ag Microbiocidal quinoline-amide compounds
WO2026022188A1 (en) 2024-07-23 2026-01-29 Syngenta Crop Protection Ag Microbiocidal quinoline compounds
WO2026022173A1 (en) 2024-07-26 2026-01-29 Syngenta Crop Protection Ag Microbiocidal pyrazole compounds

Similar Documents

Publication Publication Date Title
WO2021249800A1 (en) Substituted [1,2,4]triazole compounds as fungicides
WO2022106304A1 (en) Compositions comprising mefentrifluconazole
WO2023072671A1 (en) Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors ix
EP4242198A1 (en) Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors xiv
WO2022017836A1 (en) Fungicidal compositions comprising (r)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1- (1,2,4-triazol-1-yl)propan-2-ol
AU2023369719A1 (en) Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors xv
EP3939961A1 (en) Strobilurin type compounds and their use for combating phytopathogenic fungi
EP4618761A1 (en) Fungicidal mixture comprising substituted pyridines
EP4018830A1 (en) Pesticidal mixtures
WO2023072670A1 (en) Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors x
WO2023072672A1 (en) Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors xi
EP4236691A1 (en) Compositions comprising mefentrifluconazole
EP3903583A1 (en) Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors iii
EP3903582A1 (en) Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors ii
EP3903581A1 (en) Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors i
EP3903584A1 (en) Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors iv
EP4618760A1 (en) Fungicidal mixture comprising substituted pyridines
WO2022243109A1 (en) New substituted quinolines as fungicides
WO2024165343A1 (en) New substituted quinoline compounds for combatitng phytopathogenic fungi
WO2022090069A1 (en) Compositions comprising mefenpyr-diethyl
WO2024223034A1 (en) Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors xvi
WO2025078183A1 (en) Fungicidal mixture comprising substituted quinazolyl quinolines
WO2025078181A1 (en) Fungicidal mixture comprising substituted pyridines
EP3960727A1 (en) Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors vi
EP4619393A1 (en) Substituted benzodiazepines as fungicides

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21729528

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21729528

Country of ref document: EP

Kind code of ref document: A1