EA048372B1 - MICROBIOCIDAL BENZOTHIAZINE DERIVATIVES OF QUINOLINE/QUINOXALINE - Google Patents

Description

The invention relates to microbiocidal benzothiazine derivatives of quinoline/quinoxaline, for example as active ingredients, which have microbiocidal activity, in particular fungicidal activity. The present invention also relates to the production of such benzothiazine derivatives of quinoline/quinoxaline, to intermediates useful in the production of such benzothiazine derivatives of quinoline/quinoxaline, to the production of such intermediates, to agrochemical compositions that contain at least one of the benzothiazine derivatives of quinoline/quinoxaline, to the production of such compositions and to the use of benzothiazine derivatives of quinoline/quinoxaline or compositions in agriculture or horticulture for controlling or preventing the infection of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.

Wheat is a cereal crop grown for its seed, the cereal grain, which is a staple food throughout the world. The many species of wheat together make up the genus Triticum; the most widely grown is common wheat (T: aestivuni). However, there are many problems with wheat cultivation. Septoria tritici spot is caused by the ascomycete fungus Mycosphaerella graminicola (asexual stage: Septoria tritici) and is one of the most important diseases of wheat - it is one of the most economically important diseases of this crop (currently the most economically important disease in Europe).

Therefore, there is, in particular, a constant need to develop new methods for controlling or preventing infection of cereal crops by fungal phytopathogens, for example, Mycosphaerella graminicola of cereals, in particular wheat, especially while maintaining fungicidal activity against other fungal pathogens, i.e. a broad spectrum of activity.

Certain fungicidal quinoline compounds are described in WO 2009/119089.

According to the present invention, there is provided a compound of formula (I)

5

where R ¹ is fluorine, chlorine, cyano or methyl;

R ² represents hydrogen or fluorine;

R ³ represents hydrogen, difluoromethyl or methyl;

R ⁴ is C1-C ₆ alkyl, C1-C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₂ - _{C 6} haloalkenyl, C ₃ - _{C 6} cycloalkyl, C ₃ - _{C 6} cycloalkylC1-C ₂ alkyl or heteroarylC1-C ₂ alkyl; wherein the heteroaryl group is a 5- or 6-membered monocyclic aromatic ring containing 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and is optionally substituted with 1, 2 or 3 substituents individually selected from halogen, C1-C ₃ alkyl, C1-C ₃ alkoxy or cyano; and

R ⁵ is hydrogen or C1-C ₄ alkyl or

R ⁴ and R ⁵ together with the linking carbon atom form a cyclobutyl, cyclopentyl or cyclohexyl ring, wherein the ring structure is optionally substituted with 1, 2, 3 or 4 substituents independently selected from fluoro, cyano, methyl, methoxy;

R ⁶ is chlorine, bromine, iodine, C1-C ₄ alkyl, C1-C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ haloalkenyl, C ₂ -C ₄ alkynyl, C1-C ₄ alkoxy, C1-C ₄ alkylthio, C ₃ - _{C 5} cycloalkoxy, C1-C ₄ haloalkoxy, cyano, C ₃ - _{C 5} cycloalkyl or CR ¹⁰ (=NOR ⁸ ); and

R ⁷ is hydrogen, halogen, C1-C ₄ alkyl, C1-C ₄ haloalkyl or cyano; or

R ⁶ represents fluorine, and R ⁷ represents halogen or C1-C ₄ alkyl;

R ⁸ is C1-C ₄ alkyl, C1-C ₄ haloalkyl, C ₃ - _{C 5} alkenyl, C ₃ - _{C 5} haloalkenyl or C3-C 5 alkynyl;

A represents N or CR ⁹ ;

R ⁹ is hydrogen, difluoromethyl or methyl; and

R ¹⁰ is C1-C ₄ alkyl; or an agronomically acceptable salt, enantiomer, S-oxide or N-oxide thereof. It has been unexpectedly found that the novel compounds of formula (I) have, for practical reasons, a very effective level of biological activity for protecting plants from diseases caused by fungi. In particular, such an effect is observed with respect to a number of fungal pathogens, including Mycosphaerella graminicola (Septoria tritici).

According to a second aspect of the present invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I). Such a composition,

- 1 048372 intended for use in agriculture, may additionally contain at least one additional active ingredient and/or an agrochemically acceptable diluent or carrier.

According to a third aspect of the present invention, a method is provided for controlling or preventing infection of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) or a composition containing this compound as an active ingredient is applied to plants, their parts or their place of growth.

According to a fourth aspect of the present invention, there is provided herein the use of a compound of formula (I) as a fungicide. According to this particular aspect of the present invention, the use may exclude methods of treating the human or animal body by means of surgical intervention or therapy.

Where substituents are indicated as optionally substituted, this means that they may or may not bear one or more identical or different substituents, for example from one to four substituents. Generally, no more than three such optional substituents are present at any one time. Preferably, no more than two such optional substituents are present at any one time (i.e., a group may be optionally substituted by one or two substituents indicated as optional). Where the group of an optional substituent is a larger group such as cycloalkyl or phenyl, it is most preferred that only one such optional substituent is present. Where a group is indicated as substituted, for example alkyl, this includes those groups which are part of other groups, for example alkyl in alkylthio.

As used herein, the term halogen or halo refers to fluorine (fluorine), chlorine (chlorine), bromine (bromine) or iodine (iodine), preferably fluorine, chlorine or bromine.

As used in this document, the term cyano refers to the -CN group.

As used herein, the term _C1 - _C6 alkyl refers to a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, containing from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond. C1- _C4 alkyl shall be construed accordingly. Examples of _C1 - _C6 alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1,1-dimethylethyl (tert-butyl).

As used herein, the term _C1 - _C6 haloalkyl refers to a _C1 - _C6 alkyl radical, as generally defined above, substituted by one or more, same or different, halogen atoms. C1- _C4 haloalkyl shall be construed accordingly. Examples of C1- _C6 haloalkyl include, but are not limited to, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl and 2,2,2-trifluoroethyl.

As used herein, the term _C2 - _C6 alkenyl refers to a group which is a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms, containing at least one double bond which may be in either the (E)- or (E)-configuration, containing from two to six carbon atoms, which is attached to the remainder of the molecule by a single bond. C3- _C56 alkenyl shall be construed accordingly. Examples of _C2 - _C6 alkenyl include, but are not limited to, vinyl (ethenyl), prop-1-enyl, allyl (prop-2-enyl), and but-1-enyl.

As used herein, the term _C2 - _C6 haloalkenyl refers to a _C2 - _C6 alkenyl radical, as generally defined above, substituted by one or more, same or different, halogen atoms.

As used herein, the term C2-C6 alkynyl refers to a group which is a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms, containing at least one triple bond containing from two to six carbon atoms and which is attached to the remainder of the molecule by a single bond. The term _C3 -C5 alkynyl shall be construed accordingly. Examples of C2-C5 alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.

As used herein, the term _C3 - _C6 cycloalkyl refers to a stable monocyclic ring radical that is saturated and contains from 3 to 6 carbon atoms. C3-C4 cycloalkyl shall be construed accordingly. Examples of _C3 - _C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

As used herein, the term C3-C6cycloalkylC1-C2alkyl refers to a C3C6cycloalkyl group as defined above, bonded to the remainder of the molecule through a C1C2alkylene group.

As used herein, the term C1- _C4 alkoxy refers to a radical of the formula R _a O-, wherein R a is a C1- _C4 alkyl radical as generally defined above. Examples of _C1C4 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy.

As used herein, the term C ₁ -C ₄ haloalkoxy refers to a C ₁ -C ₄ alkoxy group,

- 2 048372 as defined above, substituted by one or more, same or different, halogen atoms. Examples of C1- _C4 haloalkoxy include, but are not limited to, fluoromethoxy, difluoromethoxy, fluoroethoxy, trifluoromethoxy and trifluoroethoxy.

As used herein, the term _C1 - _C4 alkylthio refers to a radical of the formula RaS-, where Ra is a C1- _C4 alkyl radical as generally defined above. Examples of _C1C4 alkylthio include methylsulfanyl.

As used herein, the term heteroaryl refers to a 5- or 6-membered monocyclic aromatic ring radical that contains 1, 2, 3, or 4 heteroatoms individually selected from nitrogen, oxygen, and sulfur. The heteroaryl radical may be bonded to the rest of the molecule via a carbon atom or a heteroatom. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, and pyridyl.

As used herein, the term heteroarylC ₁ -C ₂ alkyl refers to a heteroaryl group as defined above, bonded to the rest of the molecule through a N-N alkylene group.

The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) means that the compounds may occur in optically isomeric forms, i.e. enantiomeric or diastereomeric forms. Also, as a result of limited rotation about a single bond, atropisomers may occur. Formula (I) is intended to include all such possible isomeric forms and mixtures thereof. The present invention includes all such possible isomeric forms of the compound of formula (I) and mixtures thereof. Likewise, formula (I) is intended to include all possible tautomers. The present invention provides all possible tautomeric forms of the compound of formula (I).

In each case, the compounds of formula (I) according to the present invention are in free form, in oxidized form as an N-oxide or S-oxide, in covalently hydrated form or in salt form, for example in the form of an agronomically acceptable or agrochemically acceptable salt.

N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described, for example, in the book Heterocyclic N-oxides, A. Albini and S. Pietra, CrC Press, Boca Raton 1991.

The following list provides definitions, including preferred definitions, for the substituents ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , A, ^R8 , ^R9 and ^R10 with reference to the compounds of formula (I) according to the present invention. For any of these substituents, any of the definitions below may be combined with any definition of any other substituent given below or elsewhere in this document.

R ¹ is fluorine, chlorine, cyano or methyl. Preferably, R ¹ is fluorine.

R ² represents hydrogen or fluorine.

Preferably, if R ¹ is fluorine, R ² is hydrogen or fluorine.

R ³ is hydrogen, difluoromethyl or methyl. Preferably, R ³ is hydrogen or methyl. More preferably, R ³ is hydrogen.

R ⁴ is C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 haloalkenyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C2 alkyl or heteroarylC1-C2 alkyl; wherein the heteroaryl group is a 5- or 6-membered monocyclic aromatic ring containing 1, 2, 3 or 4 heteroatoms individually selected from N, O and S and optionally substituted with 1, 2 or 3 substituents individually selected from halogen, C1-C3 alkyl, C1-C3 alkoxy or cyano. Preferably, R ⁴ is C1-C4 alkyl, C1- _C4 haloalkyl, _C2 - _C4 alkenyl, _C2 - _C4 alkynyl, _C2 - _C4 haloalkenyl, _C3 - _C6 cycloalkyl, _C3 - _C6 cycloalkylC1- _C2 alkyl or heteroarylC1- _C2 alkyl, wherein the heteroaryl group is a 5- or 6-membered monocyclic aromatic ring containing 1, 2, 3 or 4 heteroatoms individually selected from N, O and S and optionally substituted with 1 or 2 substituents individually selected from halogen, methyl, ethyl, methoxy, ethoxy or cyano. More preferably, R ⁴ is C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl or heteroarylC1-C2 alkyl, wherein heteroaryl is pyridinyl (pyridin-2yl, pyridin-3-yl, pyridin-4-yl) optionally substituted with 1, 2 or 3 substituents independently selected from fluorine and chlorine. Even more preferably, R ⁴ is C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl or (6-chloropyridin-3-yl)methyl. Most preferably, R ⁴ is methyl, ethyl, difluoromethyl, trifluoromethyl, C4-C5 cycloalkyl or (6-chloropyridin-3yl)methyl.

R ⁵ is hydrogen or C1-C4 alkyl. Preferably R ⁵ is hydrogen or methyl, and more preferably R ⁵ is methyl.

In other cases, R ⁴ and R ⁵ together with the linking carbon atom form a cyclobutyl, cyclopentyl or cyclohexyl ring, wherein the ring structure is optionally substituted with 1, 2, 3 or 4 substituents independently selected from fluoro, cyano, methyl, methoxy. Preferably, R ⁴ and R ⁵

- 3 048372 together with the linking carbon atom form a cyclopentyl ring, wherein the ring structure is optionally substituted with 1 or 2 substituents independently selected from fluoro, cyano, methyl, methoxy.

In some embodiments of the present invention (if R ⁶ is not fluoro):

R ⁶ is chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C1-C4 alkylthio, C3-C5 cycloalkoxy, C1-C4 alkoxy, cyano, C3-C6 cycloalkyl or CR ¹⁰ (=NOR ⁸ ); and R ⁷ is hydrogen, halogen, C1-C4 alkyl, C ₁ - _C4 haloalkyl or cyano.

In such embodiments (if R ⁶ is not fluoro), preferably R ⁶ is chloro, bromo, iodino, C1-C ₄ alkyl, C1-C ₄ alkylthio, cyano, C1-C ₄ haloalkyl, C1-C ₄ alkoxy, C ₁ -C ₄ alkoxy or C ₃ -C ₅ cycloalkyl, more preferably R ⁶ is chloro, bromo, iodino, methyl, ethyl, methylsulfanyl, cyano, difluoromethyl, trifluoromethyl, methoxy, ethoxy, cyclopropyl, cyclobutyl and most preferably R ⁶ is chloro, methyl, cyano, methylsulfanyl (e.g. chlorine); and preferably R ⁷ is hydrogen, chlorine or methyl.

In other embodiments of the present invention (if R ⁶ is fluoro):

R ⁶ is fluorine and R ⁷ is halogen or C1-C ₄ alkyl. Preferably, R ⁶ is fluorine and R ⁷ is chlorine, methyl or ethyl. More preferably, R ⁶ is fluorine and R ⁷ is methyl.

R ⁸ is C1-C4 alkyl, C1-C4 haloalkyl, C3-C5 alkenyl, C3-C5 haloalkenyl or C3C5 alkynyl. Preferably, R ⁸ is C1-C4 alkyl, C1- _C4 fluoroalkyl. More preferably, R ⁸ is methyl or ethyl.

A is N or CR ⁹ . In some embodiments of the present invention, A is N. In other embodiments of the present invention, A is CR ⁹ , wherein R ⁹ is hydrogen, difluoromethyl or methyl, and preferably hydrogen.

R ¹⁰ is C1-C ₄ alkyl, and preferably methyl or ethyl.

In preferred embodiments of the present invention, R ¹ and R ² are fluorine, or R ¹ is fluorine and R ² is hydrogen.

In preferred embodiments of the present invention, R ⁴ and R ⁵ are methyl.

In some embodiments of the present invention, the compound of formula (I) may be selected from one of

F F (ΙΑ) (IB)

In embodiments (IA) and (IB), R ⁶ may be chloro or methyl and R ⁷ may be hydrogen or methyl, or R ⁶ is fluoro and R ⁷ is methyl.

Preferably, the compound of formula (I) is a compound selected from one of E.01 to E.25 in Table E (below).

According to the present invention, there is provided a method for controlling or preventing infection of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound according to the present invention or a composition containing this compound as an active ingredient is applied to plants, their parts or their place of growth. Preferably, the phytopathogenic microorganism is: (i) Mycosphaerella graminicola, (ii) Monographella nivalis (Microdochium nivale) or (iii) Gibberella zeae (anamorph: Fusarium grammearum). Preferably, the useful plant is cereals, in particular wheat.

Specific examples of compounds of formula (I) are illustrated in Tables A1 - A5 below.

- 4 048372

Table A1 presents 105 compounds of formula (I) in

where R ¹ is -F, R ² and R ³ are -H, and A is -CH; and where the values of R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined in Table Z below.

Table Z

R ⁴ R ⁵ R ⁶ R' Z.01 -CH ₃ -CH ₃ -C1 -H Z.02 -CH ₃ -CH ₃ -Vg -H Z.03 -CH ₃ -CH ₃ -I -H Z.04 -CH ₃ -CH ₃ -CH ₃ -H Z.05 -CH ₃ -CH ₃ -CN -H Z.06 -CH ₃ -CH ₃ -chf ₂ -H Z.07 -CH ₃ -CH ₃ -OSNz -H Z.08 -CH ₃ -CH ₃ -ochf ₂ -H Z.09 -CH ₃ -CH ₃ -CH ₂ CH ₃ -H Z.10 -CH ₃ -CH ₃ -cyclopropyl -H Z.11 -CH ₃ -CH ₃ -CF ₃ -H Z.12 -CH ₃ -CH ₃ -Cl -CH ₃ Z.13 -CH ₃ -CH ₃ -Br -CH ₃ Z.14 -CH ₃ -CH ₃ -I -CH ₃ Z.15 -CH ₃ -CH ₃ -CH ₃ -CH ₃ Z.16 -CH ₃ -CH ₃ -CN -CH ₃ Z.17 -CH ₃ -CH ₃ -chf ₂ -CH ₃ Z.18 -CH ₃ -CH ₃ -OSNz -CH ₃ Z.19 -CH ₃ -CH ₃ -ochf ₂ -CH ₃ Z.20 -CH ₃ -CH _{3 -CH2CH3 ​} -CH ₃ Z.21 -CH ₃ -CH ₃ -cyclopropyl -CH ₃ Z.22 -CH ₃ -CH ₃ -CF ₃ -CH ₃ Z.23 -CH ₃ -CH ₃ -F -CH ₃ Z.24 -CH ₃ -CH ₃ -Cl -Cl Z.25 -CH ₃ -CH ₃ -Br -Cl Z.26 -CH ₃ -CH ₃ -I -Cl Z.27 -CH ₃ -CH ₃ -CH ₃ -Cl Z.28 -CH ₃ -CH ₃ -CN -Cl Z.29 -CH ₃ -CH ₃ -chf ₂ -Cl Z.30 -CH ₃ -CH ₃ -OSNz -Cl Z.31 -CH ₃ -CH ₃ -ochf ₂ -Cl Z.32 -CH ₃ -CH _{3 -CH2CH3 ​} -Cl Z.33 -CH ₃ -CH ₃ -cyclopropyl -Cl

- 5 048372

R ⁴ R ⁵ R ⁶ R' Z.34 -CH ₃ -CH ₃ -CF ₃ -Cl Z.35 -CH ₃ -CH ₃ -F -Cl Z.36 -CH ₂ CH ₃ -CH ₃ -Cl -H Z.37 -CH ₂ CH ₃ -CH ₃ -Br -H Z.38 -CH ₂ CH ₃ -CH ₃ -I -H Z.39 -CH ₂ CH ₃ -CH ₃ -SNz -H Z.40 -CH ₂ CH ₃ -SNz -CN -H Z.41 -CH ₂ CH ₃ -CH ₃ -chf ₂ -H Z.42 -CH ₂ CH ₃ -SNz -OCH3 -H Z.43 -CH ₂ CH ₃ -SNz -ochf ₂ -H Z.44 -CH ₂ CH ₃ -SNz _{-CH2CH3 ​} -H Z.45 -CH ₂ CH ₃ -SNz -cyclopropyl -H Z.46 -CH ₂ CH ₃ -SNz -CF ₃ -H Z.47 -CH ₂ CH ₃ -SNz -Cl -CH ₃ Z.48 -CH ₂ CH ₃ -SNz -Br -CH ₃ Z.49 -CH ₂ CH ₃ -CH ₃ -I -CH ₃ Z.50 -CH ₂ CH ₃ -CH ₃ -CH ₃ -CH ₃ Z.51 -CH ₂ CH ₃ -CH ₃ -CN -CH ₃ Z.52 -CH ₂ CH ₃ -CH ₃ -chf ₂ -CH ₃ Z.53 -CH ₂ CH ₃ -CH ₃ -OCH3 -CH ₃ Z.54 -CH ₂ CH ₃ -CH ₃ -ochf ₂ -CH ₃ Z.55 -CH ₂ CH ₃ -CH _{3 -CH2CH3 ​} -CH ₃ Z.56 -CH ₂ CH ₃ -CH ₃ -cyclopropyl -CH ₃ Z.57 -CH ₂ CH ₃ -CH ₃ -CF ₃ -CH ₃ Z.58 -CH ₂ CH ₃ -CH ₃ -F -CH ₃ Z.59 -CH ₂ CH ₃ -CH ₃ -Cl -Cl Z.60 -CH ₂ CH ₃ -SNz -Br -Cl Z.61 -CH ₂ CH ₃ -SNz -I -Cl Z.62 -CH ₂ CH ₃ -SNz -CH ₃ -Cl Z.63 -CH ₂ CH ₃ -SNz -CN -Cl Z.64 -CH ₂ CH ₃ -SNz -chf ₂ -Cl Z.65 -CH ₂ CH ₃ -SNz -OCH3 -Cl Z.66 -CH ₂ CH ₃ -SNz -ochf ₂ -Cl Z.67 -CH ₂ CH ₃ -SNz _{-CH2CH3 ​} -Cl Z.68 -CH ₂ CH ₃ -SNz -cyclopropyl -Cl Z.69 -CH ₂ CH ₃ -SNz -CF ₃ -Cl Z.70 -CH ₂ CH ₃ -SNz -F -Cl Z.71 -CH ₂ (CH ₂ ) ₂ CH ₂ - -Cl -H

- 6 048372

R ⁴ R ⁵ R ⁶ R' Z.72 -CH ₂ (CH ₂ ) ₂ CH ₂ - -Vg -H Z.73 -CH ₂ (CH ₂ ) ₂ CH ₂ - -I -H Z.74 -CH ₂ (CH ₂ ) ₂ CH ₂ - -CH ₃ -H Z.75 -CH ₂ (CH ₂ ) ₂ CH ₂ - -CN -H Z.76 -CH ₂ (CH ₂ ) ₂ CH ₂ - -chf ₂ -H Z.77 -CH ₂ (CH ₂ ) ₂ CH ₂ - -OSNz -H Z.78 -CH ₂ (CH ₂ ) ₂ CH ₂ - -ochf ₂ -H Z.79 -CH ₂ (CH ₂ ) ₂ CH ₂ - -CH ₂ CH ₃ -H Z.80 -CH ₂ (CH ₂ ) ₂ CH ₂ - -cyclopropyl -H Z.81 -CH ₂ (CH ₂ ) ₂ CH ₂ - -CF ₃ -H Z.82 -CH ₂ (CH ₂ ) ₂ CH ₂ - -Cl -CH ₃ Z.83 -CH ₂ (CH ₂ ) ₂ CH ₂ - -Br -CH ₃ Z.84 -CH ₂ (CH ₂ ) ₂ CH ₂ - -I -CH ₃ Z.85 -CH ₂ (CH ₂ ) ₂ CH ₂ - -SNz -CH ₃ Z.86 -CH ₂ (CH ₂ ) ₂ CH ₂ - -CN -CH ₃ Z.87 -CH ₂ (CH ₂ ) ₂ CH ₂ - -chf ₂ -CH ₃ Z.88 -CH ₂ (CH ₂ ) ₂ CH ₂ - -OSNz -CH ₃ Z.89 -CH ₂ (CH ₂ ) ₂ CH ₂ - -ochf ₂ -CH ₃ Z.90 -CH ₂ (CH ₂ ) ₂ CH ₂ - _{-CH2CH3 ​} -CH ₃ Z.91 -CH ₂ (CH ₂ ) ₂ CH ₂ - -cyclopropyl -CH ₃ Z.92 -CH ₂ (CH ₂ ) ₂ CH ₂ - -CF ₃ -CH ₃ Z.93 -CH ₂ (CH ₂ ) ₂ CH ₂ - -F -CH ₃ Z.94 -CH ₂ (CH ₂ ) ₂ CH ₂ - -Cl -Cl Z.95 -CH ₂ (CH ₂ ) ₂ CH ₂ - -Br -Cl Z.96 -CH ₂ (CH ₂ ) ₂ CH ₂ - -I -Cl Z.97 -CH ₂ (CH ₂ ) ₂ CH ₂ - -CH ₃ -Cl Z.98 -CH ₂ (CH ₂ ) ₂ CH ₂ - -CN -Cl Z.99 -CH ₂ (CH ₂ ) ₂ CH ₂ - -chf ₂ -Cl Z.100 -CH ₂ (CH ₂ ) ₂ CH ₂ - -OSNz -Cl Z.101 -CH ₂ (CH ₂ ) ₂ CH ₂ - -ochf ₂ -Cl Z.102 -CH ₂ (CH ₂ ) ₂ CH ₂ - _{-CH2CH3 ​} -Cl Z.103 -CH ₂ (CH ₂ ) ₂ CH ₂ - -cyclopropyl -Cl Z.104 -CH ₂ (CH ₂ ) ₂ CH ₂ - -CF ₃ -Cl Z.105 -CH ₂ (CH ₂ ) ₂ CH ₂ - -F -Cl

Table A2 presents 105 compounds of formula (I) wherein R ¹ is -F, R ² is -F, R ³ is -H, A is -CH; and wherein the meanings of R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined in Table Z above.

Table A3 presents 105 compounds of formula (I) wherein R ¹ is -F, R ² is -H, R ³ is -CH3, A is -CH; and wherein the meanings of R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined in Table Z above.

Table A4 presents 105 compounds of formula (I) wherein R ¹ is -F, R ² is -H, R ³ is -H, A is -N; and wherein the meanings of R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined in Table Z above.

Table A5 presents 105 compounds of formula (I) wherein R ¹ is -F, R ² is -F, R ³ is -H, A is -N; and wherein the meanings of R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined in Table Z above.

The compounds of the present invention can be prepared as shown in the following Schemes 1-5, in which, unless otherwise indicated, the definition of each variable is as defined above for the compound of formula (I).

- 7 048372

Compounds of formula (I) can be prepared, for example, according to scheme 1.

Scheme 1

Carbonyl compounds of formula (IV) can be prepared by treating heterocycles of formula (II), wherein X is bromine, chlorine or iodine, and an aldehyde of formula (III), as described in European Journal of Organic Chemistry 2017, pp. 5080-5093. Thiophenol compounds of formula (VI) can be prepared by subjecting carbonyl compounds of formula (IV) to a Newman-Quart rearrangement followed by hydrolysis. Typical conditions for individual steps involving the formation, rearrangement and hydrolysis of the thiocarbamate have been reviewed and described in Synthesis 2008, pp. 661689, Org. Lett. 2018, pp. 7483-7487, and WO 2002/092076.

Compounds of formula (I) can be prepared from thiophenols of formula (VI) by treatment with a source of ammonia such as gaseous ammonia or bis(trimethylsilyl)amine in the presence of a dehydrating agent such as zinc chloride or titanium ethoxide as described in ACIEE 2018, pp. 5350-5354 to give imines of formula (VII). Such imines can be condensed with carbonyl compounds of formula (VIII-a) or substitutes thereof such as acetals of formula (VIII-b) wherein R ²¹ is C1- _C4 alkyl in the presence of an acid catalyst such as n-toluenesulfonic acid, a dehydrating agent such as molecular sieves, and optionally a nucleophilic amine catalyst such as pyrrolidine. Closely related processes are described in Tetrahedron 2001, p. 7501-7506.

Heterocycles of formula (II) are readily available from inexpensive starting materials, as described in WO 2018/172133 or Tetrahedron 2017, pp. 1618-1632. Aldehydes of general formula (III) are readily prepared from commercially available materials by methods well known to those skilled in the art.

Alternatively, thiophenols of formula (VI) can be prepared by rearrangement of thioesters of formula (XI) by treatment with a Lewis acid such as aluminum chloride in a solvent such as nitrobenzene at temperatures from 100°C to 210°C, as described in Bioorganic & Medicinal Chemistry 2007, pp. 3505-3514. This is shown in Scheme 2.

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Scheme 2

Thioesters of formula (XI) can be prepared by reacting carboxylic acid derivatives of formula (IX), wherein R ²² is OH, chlorine, bromine or iodine, with thiophenols of formula (X). The conditions for such transformations are well known to those skilled in the art and are described in Bioorganic & Medicinal Chemistry Letters 2015, pp. 1509-1514.

Carboxylic acids of the general formula (IX) can be obtained from heterocyclic compounds of the formula (II) by interconversions of functional groups well known to those skilled in the art. Thiophenols of the formula (X) can be obtained by interconversions of functional groups from the corresponding disulfides, anilines, phenols or aryl halides using methods well known to those skilled in the art.

Alternatively, imines of formula (VII) can be prepared from nitriles of formula (XII) by treatment with thiophenols of formula (X) in the presence of a strong base such as n-butyl lithium, as described in J. Heterocyclic Chem., 1995, p. 1683. Similarly, imines of formula (VII) can be prepared from heterocyclic compounds of formula (II), where X is bromine or iodine, and nitriles of formula (XIII) in the presence of organometallic reagents capable of halogen-metal exchange reactions, such as isopropyl magnesium chloride-lithium chloride complex (turbo-Grignard), in a solvent such as tetrahydrofuran. This is shown in Scheme 3.

Scheme 3

(ii) (Xi)

Compounds of formula (I) can also be prepared from heterocyclic compounds of formula (XVIII) wherein ^R23 is -B(OH) ₂ , -Bpin, _-SO2Na , _SO2CH2CH = _CH2 , -ZnBr or -Zn( _O2CC ( _CH3 ) ₃ , and imines of formula (XVII) wherein ^R24 is chlorine, bromine, iodine or -OSO2CF3, in the presence of a Ni or Pd catalyst with suitable phosphine ligands such as 1,1'- _bis- (di-tert-butylphosphino)ferrocene and an optional base such as K3PO4, in an inert solvent such as THF or DMF.

Imines of formula (XVII), wherein R ²⁴ is chlorine, bromine, iodine or -OSO2CF3, are prepared from compounds of formula (XVI) in the presence of a suitable activating agent such as a Vilsmeier salt or triflate anhydride and an optional base such as 2,6-lutidine in an inert solvent such as DCM or toluene. Compounds of formula (XVI) are prepared from thiophenols of formula (XV) and carbonyl compounds of formula (VIII-a) or substitutes thereof such as acetals of formula

- 9 048372 (VIII-b), where R ²¹ is C1-C ₄ alkyl, in the presence of an acid catalyst such as ptoluenesulfonic acid, a dehydrating agent such as molecular sieves, and optionally a nucleophilic amine catalyst such as pyrrolidine. This is shown in Scheme 4.

Scheme 4

Thiophenols of formula (XV) can be prepared by various methods, with a non-limiting description of the more preferred methods shown in Scheme 5.

I. Thiophenols of formula (XV) can be prepared from benzoic acids of formula (XVI-a) by treatment with a strong base such as lithium diisopropylamide or sec-butyl lithium and a disulfide of formula (XVII-a), where R ²⁵ is C1-C4 alkyl, phenylC1-C2 alkyl or -CHCHSi(CH3)3, to form thioethers of formula (XVI-b). By interconversion of functional groups (from acid to amide) using methods well known to those skilled in the art and removal of the R ²⁵ group using nucleophiles such as C1-C14 alkylthiols in combination with a strong base such as sodium tert-butoxide or with a fluoride source such as tetrabutylammonium fluoride when R ²⁵ is -CHCHSi(CH ₃ ) ₃ , acids of formula (XVI-b) are converted to thiophenols of formula (XV).

II. Thiophenols of formula (XV) can be prepared from anthranilic acid derivatives of formula (XVI-d), wherein R ²⁷ is H or C1-C4 alkyl, by treatment with nitrosating agents such as sodium nitrite/HCl or isoamyl nitrite, followed by sulfur-containing reagents such as Na2S2 or sodium xanthate, to give sulfides of formula (XVI-e), wherein R ²⁶ is H or -C(S) _OCH2CH3 . This has been described in JP 2002053580 and US 2004/0116734. By interconversion of functional groups (from acid/ester to amide) using methods well known to those skilled in the art, followed by an optional cleavage step if R ²⁷ is -C(S)OCH ₂ CH ₃ , by treatment with aq. the base solution ensures the conversion of sulfides of formula (XVI-e) into thiophenols of formula (XV).

III. Thiophenols of formula (XV) can be prepared from ortho-halobenzamides of formula (XVI-f), where X is fluorine or chlorine, by treatment with a sulfide source such as sodium sulfide in an inert solvent such as X-methyl-2-pyrrolidone.

IV. Thiophenols of formula (XV) can be prepared from ortho-halobenzamides of formula (XVI-f), wherein X is bromine or iodine, by treatment with a sulfide source such as sulfur, sodium sulfide, thiourea, or sodium thiosulfate in the presence of a suitable catalyst such as Cu, Ni, or Pd salts stabilized with amine or phosphine supporting ligands. Examples are described in Tetrahedron Letters 2011, pp. 205-208; Org. Lett., 2009, pp. 5250-5253, and JP 2017-095415.

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Scheme 5

(XVI-d) (XVI-e)

Methods for obtaining benzoic acids of formula (XVI-a), anthranilic acid derivatives of formula (XVI-d) and benzamides of formula (XVI-f) from readily available starting materials are well known to those skilled in the art.

Alternatively, compounds of formula (I) can be prepared by converting another closely related compound of formula (I) (or an analogue thereof) using standard synthetic procedures known to those skilled in the art. Non-limiting examples include oxidation reactions, oxygenation reactions, reduction reactions, hydrogenation reactions, hydrolysis reactions, coupling reactions, aromatic nucleophilic or electrophilic substitution reactions, nucleophilic substitution reactions, deoxyfluorination reactions, alkylation reactions, radical addition reactions, nucleophilic addition reactions, condensation reactions, and halogenation reactions.

Certain intermediate compounds described in the above schemes are novel and in themselves form a further aspect of the present invention.

The compounds of formula (I) can be used in the agricultural sector and related fields of application, for example as active ingredients for the control of plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially dangerous to humans. The new compounds are characterized by excellent activity at low application rates, while being well tolerated by plants and safe for the environment. They are characterized by very useful curative, preventive and systemic properties and can be used to protect numerous cultivated plants. The compounds of formula (I) can be used to suppress or destroy pests that occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) or various agricultural crops of useful plants, while also protecting those parts of the plants that develop later, for example from phytopathogenic microorganisms.

Also, the compounds of formula (I) can be used as a fungicide. The term fungicide as used herein means a compound that controls, modifies or prevents the growth of fungi. The term fungicidally effective amount means the amount of such a compound or combination of such compounds that is capable of exerting an effect on the growth of fungi. Controlling or modifying effects include all deviations from natural development, such as killing, inhibition of development, etc., and prevention includes a barrier or other protective formation in or on a plant to prevent infection caused by fungi.

The compounds of formula (I) can also be used as dressing agents for treating plant propagation material, such as seeds, such as fruits, tubers or grains, or plant sprouts (e.g. rice), to protect against fungal infections and also against phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition containing a compound of formula (I) before planting: the seed can, for example, be dressed before sowing. The compounds of formula (I) can also be applied to grains (coating), either by impregnating the seeds with a liquid composition or by coating them with a solid composition. The composition can also be applied to the planting site when planting the propagation material, for example to a seed furrow during sowing. The present invention also relates to such methods for treating plant propagation material and to the plant propagation material thus treated.

In addition, the compounds according to the present invention can be used to control fungi in related fields, for example, in the protection of technical materials, including wood and wood-related technical products, in the storage of food products, and in the organization of sanitization.

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In addition, the present invention can be used to protect non-living materials from fungal attack, such as lumber, siding, and paint.

The compounds of formula (I) and fungicidal compositions containing them can be used to control plant diseases caused by a wide range of fungal plant pathogens. They are effective in providing control of a wide range of plant diseases, such as foliar pathogens of ornamental, lawn, vegetable, field, grain and fruit agricultural crops.

These fungi and disease vectors related to fungi, as well as phytopathogenic bacteria and viruses that can be controlled are, for example, Absidia corymbifera, Altemaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp., including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terms, Aureobasidium spp., including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp., including B. dothidea, B. obtusa, Botrytis spp., including B. cinerea, Candida spp., including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp., Cercospora spp., including C. arachidicola, Cercosporidium personatum, Cladosporium spp, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., Colletotrichum spp., including C. musae, Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp, Elsinoe spp, Epidermophyton spp, Erwinia amylovora, Erysiphe spp., including E. cichoracearum, Eutypa lata, Fusarium spp., including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxyspomm F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp., including N. capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp., including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp., including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp., including P. maydis, P. philippinensis and P. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsis viticola, Phytophthora spp., including P. infestans, Plasmopara spp., including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp., including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp., Pseudoperonospora spp., including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia Spp., including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp., in including P. oryzae, Pythium spp., including P. ultimum, Ramularia spp, Rhizoctonia spp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp, Scedosporium spp., including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp, Septoria spp, including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp,. Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp., including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturia spp., including V. inaequalis, Verticillium spp and Xanthomonas spp.

In particular, the compounds of formula (I) and fungicidal compositions containing them can be used to control plant diseases caused by a wide range of fungal plant pathogens in the classes Basidiomycete, Ascomycete, Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and/or Mucoromycete.

Such pathogens may include Oomycetes, including those that cause Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora, and Phytophthora erythroseptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare, and Pythium ultimum; diseases caused by Peronosporales such as those caused by Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo Candida, Sclerophthora macrospora and Bremia lactucae; and others such as Aphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghi and Sclerospora graminicola; Ascomycetes, including those causing spot, blotch, blast or burn varieties and/or rots such as those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis, Alternaria alternata, Alternaria brassicicola, Alternaria solani and Alternaria tomatophila, Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and Cercosporella herpotrichoides, Cladosporium carpophilum, Cladosporium effusum, Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerella gramini

- 12 048372 cola, Mycovellosiella koepkeii, Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramularia beticola, Ramularia collo-cygni, Magnaporthales, such as Gaeumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae, Diaporthales such as Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsa ceratosperma, and others such as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp., Capnodium ramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioides spp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata, Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta, Griphospaeria corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssonina graminicola, Microdochium nivale, Monilinia fructicola, Monographella albescens, Monosporascus cannonballus, Naemacyclus spp., Ophiostoma novo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum, Pestalotia rhododendri, Petriellidium spp., Pezicula spp., Phialophora gregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor; Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; pathogens that cause powdery mildew species, such as diseases caused by Erysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaera macularis Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossypii, Phyllactinia guttata and Oidium arachidis; those that lead to mould species such as those caused by Botryosphaeriales such as Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta cucurbitacearum; those which lead to anthracnose diseases, such as those caused by Glommerelales such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata, and Colletotrichum graminicola; and those that cause wilt or blight species, such as those caused by Hypocreales such as Acremonium strictum, Claviceps purpurea, Fusarium culmorum, Fusarium graminearum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladium spp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae; Basidiomycetes, including those that cause smut species, such as those caused by Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rust species, such as those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis, Pucciniastrum coryli, or Uredinales, such as Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and those that lead to other types of rot and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia caries; Blastocladiomycetes such as Physoderma maydis; Mucoromycetes such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus; as well as those that lead to diseases caused by pathogens of other species and genera closely related to those listed above.

Any reference to Mycosphaerella graminicola or Septoria tritici above or below in the text is understood to be a reference to Zymoseptoria tritici (the correct taxonomic name).

Monographella nivalis (Microdochium nivale) is a fungal plant pathogen that attacks cereal crops at all stages of development, causing a variety of diseases such as seedling white rot, snow mold, root rot and head rot, among others.

Gibberella zeae (anamorph: Fusarium graminearum) is a fungal plant pathogen that causes Fusarium head blight, a devastating disease of wheat and barley. However, Fusarium culmorum is also a fungal plant pathogen and the causal agent of seedling white rot, root rot, head rot, stem rot, common root rot and other diseases of cereal crops, and is the causal agent of Fusarium head blight. Fusarium head blight (FHB), also known as scab, is a fungal disease of small grain cereals including wheat, barley, oats, rye, maize, triticale, canaryseed and some forage grasses.

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In addition to fungicidal activity, the compounds and compositions containing them may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Streptomyces scabies, and other related species, as well as certain protozoa.

Within the scope of the present invention, target crops and/or useful plants to be protected typically include perennial and annual crops such as berry plants, for example, varieties of blackberry, blueberry, cranberry, raspberry and strawberry; cereals, for example, barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, for example, cotton, flax, hemp, jute and sisal; field crops, for example, sugar and fodder beet, coffee tree, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea bush and tobacco; fruit trees, for example, apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; Grasses such as Bermuda grass, bluegrass, bent grass, Eremochloa serpentina, fescue, ryegrass, St. Augustine's grass, and zoysia japonica; Herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage, and thyme; Legumes such as beans, lentils, peas, and soybeans; Nuts such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios, and walnuts; Palms such as oil palm; Ornamentals such as flowers, shrubs, and trees; Other trees such as cocoa, coconut, olive, and rubber trees; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumber, garlic, lettuce, squash, melon, okra, onions, peppers, potatoes, pumpkin, rhubarb, spinach, and tomatoes; and vine crops such as grape varieties.

Useful plants and/or target crops according to the present invention include conventional as well as genetically improved or engineered varieties, such as, for example, insect-resistant (e.g., Bt and VIP varieties), as well as disease-resistant, herbicide-tolerant (e.g., glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode-tolerant varieties. For example, suitable genetically improved or engineered varieties of crops include the cotton varieties Stoneville 5599BR and Stoneville 4892BR.

The expression useful plants and/or target crops shall be understood as also including useful plants which have been rendered tolerant to herbicides such as bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enolpyrovylshikimate-3-phosphate synthase) inhibitors, GS (glutamine synthase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) as a result of conventional breeding methods or genetic engineering. An example of an agricultural crop which has been rendered tolerant to imidazolinones such as imazamox by means of conventional breeding methods (mutagenesis) is Clearfield® rape (canola). Examples of crops that have been genetically engineered to be tolerant to herbicides or classes of herbicides include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

The term useful plants and/or target crops shall be understood to include those that are inherently resistant or have been rendered resistant to harmful insects. It includes plants transformed by recombinant DNA technology, for example, in such a way that they are capable of synthesizing one or more selective toxins, such as those known, for example, from toxin-producing bacteria. Examples of toxins that can be expressed include 5-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonizing nematodes, and toxins produced by scorpions, arachnids, wasps and fungi. An example of a crop that has been modified to express a Bacillus thuringiensis toxin is KnockOut® Bt maize (Syngenta Seeds). An example of a crop that contains more than one gene encoding insect resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Crops or their seed material can also be resistant to several types of pests (so-called stacked gene transgenic objects if they are obtained by genetic modification). For example, a plant can be characterized by the ability to express an insecticidal protein while being tolerant to herbicides, such as Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

The expression useful plants and/or target crops shall be understood as also including useful plants which have been modified by the application of recombinant DNA technologies in such a way that they are capable of synthesizing antipathogenic substances,

- 14 048 372 having a selective effect, such as, for example, the so-called pathogenesis-related proteins (PRPs, see, for example, EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.

Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins of Bacillus cereus or Bacillus popilliae; or insecticidal proteins of Bacillus thuringiensis, such as 5-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or 0'13'90. or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIPs), such as ricin, maize RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UOD-glycosyltransferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA reductase, ion channel blockers such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, dibenzyl synthase, chitinases and glucanases.

Furthermore, in the context of the present invention, 5-endotoxins, such as CrylAb, CrylAc, CrylF, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), such as Vipl, Vip2, Vip3 or Vip3A, are expressly also to be understood as hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by means of a new combination of different domains of these proteins (see, for example, WO 02/15701). Truncated toxins are known, such as truncated CrylAb. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid substitutions, sequences recognized by proteases that are not found in the natural toxin are preferably introduced into the toxin, as, for example, in the case of Cry3A055, a sequence recognized by cathepsin G is introduced into the Cry3A toxin (see WO 03/018810).

More examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. Deoxyribonucleic acids of the Ov1 type and their production are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in transgenic plants makes the plants tolerant to harmful insects. Such insects can belong to any taxonomic group of insects, but are especially common among beetles (Coleoptera), dipterans (Diptera) and butterflies (Lepidoptera).

Transgenic plants containing one or more genes that encode insect resistance and express one or more toxins are known, some of which are commercially available. Examples of such plants include: YieldGard® (a maize variety expressing the Cry1Ab toxin); YieldGard Rootworm® (a maize variety expressing the Cry3Bb1 toxin); YieldGard Plus ® (a maize variety expressing both Cry1Ab and Cry3Bb1 toxins); Starlink® (a maize variety expressing the Cry9C toxin); Herculex I® (a maize variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing the Cry1Ac toxin); Bollgard I® (cotton variety expressing the Cry1Ac toxin); Bollgard II® (cotton variety expressing the Cry1Ac and Cry2Ab toxins); VipCot® (cotton variety expressing the Vip3A and Cry1Ab toxins); NewLeaf® (potato variety expressing the Cry3A toxin); NatureGard® Agrisure® GT Advantage (GA21 with glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 with European corn borer (CB) resistance trait) and Protecta®.

Additional examples of such transgenic crops include the following.

1. Bt11 maize from Syngenta Seeds SAS, Chemin de 1'Hobit 27, F-31 790 Saint-Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays rendered resistant to European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Btll maize also transgenically expresses the PAT enzyme to achieve tolerance to the herbicide glufosinate ammonium.

- 15 048372

2. Maize Bt176 from Syngenta Seeds SAS, Chemin de 1'Hobit 27, F-31 790 Saint-Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays rendered resistant to European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of the Cry1Ab toxin. Maize Bt176 also transgenically expresses the PAT enzyme, conferring tolerance to the herbicide glufosinate ammonium.

3. Maize MIR604 from Syngenta Seeds SAS, Chemin de 1'Hobit 27, F-31 790 Saint-Sauveur, France, registration number C/FR/96/05/10. Maize rendered insect resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a sequence recognized by the protease cathepsin G. The production of such transgenic maize plants is described in WO 03/018810.

4. Maize MON 863 from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses the Cry3Bb1 toxin and has resistance to certain insects of the order Coleoptera.

5. Cotton IPC 531 from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. Maize 1507 from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Maize genetically modified to express the Cry1F protein to achieve resistance to certain insects of the order Lepidoptera and the PAT protein to achieve tolerance to the herbicide glufosinate ammonium.

7. Maize NK603 x MON 810 from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of hybrid maize varieties conventionally bred by crossing the genetically modified varieties NK603 and M0N 810. Maize NK603 x M0N 810 transgenically expresses the CP4 EPSPS protein obtained from Agrobacterium sp., strain CP4, which confers tolerance to the herbicide Roundup® (containing glyphosate), and the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki, which confers tolerance to certain representatives of the order Lepidoptera, including the European corn borer.

As used in this document, the term growing place means the fields in or on which plants are grown or where the seeds of cultivated plants are sown or where the seeds will be placed in the soil. It includes the soil, the seeds and seedlings, and the established vegetation.

The term plant means all physical parts of a plant, including seeds, seedlings, shoots, roots, tubers, stems, petioles, leaves, and fruits.

The term plant propagation material is understood to mean the generative organs of the plant, such as seeds, which can be used for propagation of the latter, and vegetative material, such as sprouts or tubers, for example, of potatoes. In this case, for example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants can be mentioned. Germinated plants and young plants can also be mentioned, which are to be transplanted after germination or after emerging from the soil. These young plants can be protected before transplantation by a complete or partial immersion treatment. Preferably, seeds are understood as plant propagation material.

Pesticide products referred to in this document by their common names are known, for example, from The Pesticide Manual, 15th Ed., British Crop Protection Council 2009.

The compounds of formula (I) can be used in unmodified form or, preferably, together with auxiliaries conventionally used in the field of formulation. In this connection, for the sake of convenience, they can be formulated by known methods into emulsifiable concentrates, pastes applied as coatings, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulated forms, for example in polymeric substances. As with the type of composition, the application methods, such as spraying, fine spraying, dusting, scattering, coating or pouring, are selected in accordance with the intended purposes and the prevailing conditions. The compositions may also contain additional auxiliary substances such as stabilizers, antifoams, viscosity regulators, binders or tackifiers, as well as fertilizers, microelement donors or other compounds to obtain special effects.

Suitable carriers and auxiliary substances, for example for use in agriculture, can be solid or liquid and are substances suitable for formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers are described, for example, in WO 97/33890.

Suspension concentrates are aqueous compositions in which finely divided solid particles of the active compound are suspended. Such compositions include anti-settling agents and dispersing agents and may additionally include a wetting agent to enhance

- 16 048372 activity, as well as an antifoaming agent and a crystal growth inhibitor. When used, these concentrates are diluted with water and are usually applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

Wettable powders are in the form of finely divided particles that disperse readily in water or other liquid vehicles. The particles contain the active ingredient held in a solid matrix. Typical solid matrices include fuller's earth, kaolin clays, silica varieties, and other readily wettable organic or inorganic solids. Wettable powders typically contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing, or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or another liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent or may also contain a liquid carrier such as xylene, heavy naphthas containing aromatic compounds, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or another liquid and are typically applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

Granular formulations include both extrudates and relatively large particles and are generally applied undiluted to the area to be treated. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, sandstone, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, ground corn cob, ground peanut hulls, sugars, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesium oxide, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate and other organic or inorganic materials which absorb the active compound or which may be coated with it. Granular formulations typically contain from 5% to 25% active ingredients, which may include surface-active agents such as aromatic-containing heavy naphthas, kerosene and other petroleum fractions or vegetable oils, and/or adhesives such as dextrins, glue or synthetic resins.

Dusts are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clays, fine powders and other organic and inorganic solids which act as dispersing agents and carriers.

Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell that allows the enclosed materials to be released into the environment at controlled rates. The diameter of the encapsulated droplets is typically 1 to 50 microns. The enclosed liquid typically constitutes 50 to 95% of the capsule weight and may include a solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the openings of the pores of the granules, trapping the active substances in liquid form within the pores of the granules. The diameter of the granules is typically in the range of 1 mm to 1 cm, and preferably 1 to 2 mm. The granules are formed by extrusion, agglomeration or granulation, or they are natural. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and granulated carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other suitable formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the required concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprayers may also be used, where the active ingredient is dispersed in finely divided form by evaporation of the low-boiling dispersant carrier solvent.

Suitable agriculturally useful adjuvants and carriers that are useful in formulating the compositions of the present invention into the above-described types of formulations are well known to those skilled in the art.

Liquid carriers that can be used include, for example, water, toluene, xylene, ligroin, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates , diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, KH-dimethylformamide. dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol

- 17 048372 kohl, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidinone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, dlimonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerin, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, noctylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG 400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol and high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerin and N-methyl-2-pyrrolidinone. In general, the best carrier for diluting concentrates is water.

Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.

A wide range of surface-active agents have been employed successfully in both the liquid and solid compositions mentioned, particularly in those intended to be diluted with a carrier prior to use. Such agents, when employed, typically constitute from 0.1% to 15% by weight of the composition. They may be anionic, cationic, nonionic or polymeric in nature and may be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface-active agents include alkyl sulfate salts such as diethanolammonium lauryl sulfate; alkyl aryl sulfonate salts such as calcium dodecylbenzenesulfonate; alkyl phenol alkylene oxide addition products such as nonylphenol C18 ethoxylate; alcohol alkylene oxide addition products such as tridecyl alcohol C16 ethoxylate; soaps such as sodium stearate; alkyl naphthalene sulfonate salts such as sodium dibutyl naphthalene sulfonate; dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryl trimethyl ammonium chloride, polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide and salts of mono- and dialkyl phosphate esters.

Other excipients commonly used in agricultural formulations include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, light blocking agents, compatibilizers, defoamers, complexing agents, neutralizing agents and buffers, corrosion inhibitors, dyes, fragrances, spreading agents, penetration enhancers, trace elements, softening agents, lubricants, and adhesion promoters.

In addition, other biocidally active ingredients or compositions can also be combined with the compositions of the present invention and used in the methods of the present invention, and used simultaneously or sequentially with the compositions of the present invention. When used simultaneously, these additional active ingredients can be formulated together with the compositions of the present invention or mixed, for example, in a spray tank. These additional biologically active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.

In addition, the compositions of the present invention can also be used with one or more inducers of systemic acquired resistance (SAR inducer). SAR inducers are known and described, for example, in US Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-N-methyl.

The compounds of formula (I) are generally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or sequentially with additional compounds. Such additional compounds can be, for example, fertilizers or microelement donors or other preparations that affect plant growth. They can also be selective herbicides or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several such preparations, if necessary, together with additional carriers, surfactants or application aids commonly used in the field of formulation.

The compounds of formula (I) can be used in the form of (fungicidal) compositions for the implementation of

- 18 048372 control or protection against phytopathogenic microorganisms, containing as an active ingredient at least one compound of formula (I) or at least one preferred individual compound defined above, in free form or in the form of an agrochemically applicable salt and at least one of the above auxiliary substances.

Therefore, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I), an agriculturally acceptable carrier and optionally an adjuvant. The agriculturally acceptable carrier is, for example, a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, said composition may comprise at least one or more pesticidally active compounds, for example an additional fungicidally active ingredient in addition to the compound of formula (I).

The compound of formula (I) may be the sole active ingredient of the composition or, if desired, it may be mixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator. The additional active ingredient may, in some cases, lead to unexpected synergistic activities.

Examples of suitable additional active ingredients include the following: 1,2,4-thiadiazoles, 2,6-dinitroanilines, acylalanines, aliphatic nitrogen compounds, amidines, aminopyrimidinols, anilides, aniline pyrimidines, anthraquinones, antibiotics, arylphenyl ketones, benzamides, benzenesulfonamides, benzimidazoles, benzothiazoles, benzothiodiazoles, benzothiophenes, benzoylpyridines, benzthiadiazoles, benzylcarbamates, butylamines, carbamates, carboxamides, carpropamides, chloronitriles, cinnamic acid amides, copper-containing compounds, cyanoacetamidoximes, cyanoacrylates, cyanoimidazoles, cyanomethylene thiazolidines, dicarbonitriles, dicarboxamides, dicarboximides, dimethyl sulfamates, dinitrophenol carbonates, dinitrophenyls, dinitrophenyl crotonates, diphenyl phosphates, dithiin compounds, dithiocarbamates, dithioethers, dithiolanes, ethylaminothiazole carboxamides, ethyl phosphonates, furan carboxamides, glucopyranosyls, glucopyranoxyls, glutaronitriles, guanidines, herbicides/plant growth regulators, hexapyranosyl antibiotics, hydroxy-(2-amino)pyrimidines, hydroxyanilides, hydroxyisoxazoles, imidazoles, imidazolinones, insecticides/plant growth regulators, isobenzofuranones, isoxazolidinylpyridines, isoxazolines, maleimides, mandelic acid amides, mectin derivatives, morpholines, norpholines, n-phenylcarbamates, organotin compounds, oxathiine carboxamides, oxazoles, oxazolidinediones, phenols, phenoxyquinolines, phenylacetamides, phenylamides, phenylbenzamides, phenyloxoethylthiophene amides, phenylpyrroles, phenylureas, phosphothiolates, phosphoric acids, phthalamic acids, phthalimides, picolinamides, piperazines, piperidines, plant extracts, polyoxins, propionamides, phthalimides, pyrazole-4-carboxamides, pyrazolinones, pyridazinones, pyridines, pyridinecarboxamides, pyridinylethylbenzamides, pyrimidineamines, pyrimidines, pyrimidineamines, pyrimidine hydrazone, pyrrolidines, pyrrolequinolinones, quinazolinones, quinolines, derivatives of quinoline, quinoline-7-carboxylic acids, quinoxalines, spiroketalamines, strobilurins, sulfamoyltriazoles, sulfamides, tetrazolyloximes, thiadiazines, thiadiazolecarboxamides, thiazolecarboxamides, thiocyanates, thiophenecarboxamides, toluamides, triazines, triazobenthiazoles, triazoles, triazolethiones, triazolopyrimidylamine, valinamide carbamates, ammonium methylphosphonates, arsenic-containing compounds, benzimidazole carbamates, carbonitriles, carboxanilides, carboximidamides, carboxyl phenylamides, diphenylpyridines, furanilides, hydrazine carboxamides, imidazoline acetates, isophthalates, isoxazolones, mercury salts, organomercury compounds, organophosphorus compounds, oxazolidinediones, pentylsulfonylbenzenes, phenylbenzamides, phosphonothionates, phosphorothioates, pyridylcarboxamides, pyridylfurfuryl ethers, pyridyl methyl ethers, SDHI, thiadiazine anthiones, thiazolidines.

Examples of suitable additional active ingredients also include the following: a compound selected from the group of substances consisting of petroleum oils, 1,1-bis-(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenylsulfone, acetoprole, aldoxycarb, amidithione, amidothioate, amiton, amiton hydroxalate, amitraz, aramit, arsenic oxide, azobenzene, azotoate, benomyl, benoxafos, benzyl benzoate, bixafen, brophenvalerate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbonolate, carbophenothione, cimiazole, quinomethionate, chlorbenzide, chlordimeform, chlordimeform hydrochloride, chlorphenethol, chlorfensone, chlorphensulfide, chlorobenzilate, chloromebuform, chloromethiuron, chlorpropylate, chlorthiophos, cinerin I, cinerin II, cinerins, closantel, coumaphos, crotamiton, crotoxyfos, cufraneb, cyantoate, DCPM, DDT, demefion, demefion-O, demefion-S, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-^-methylsulfone, dichlorfluanid, dichlorvos, dicliphos, dienochlor, dimefox, dinex, dinex-diclexin, dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfone, dinoterbone, dioxathione, diphenylsulfone, disulfiram, DNOC, dofenapine, doramectin, endothion, eprinomectin, ethoate-methyl, etrimfos, fenazaflor, fenbutatin oxide, fenothiocarb, fenpyrad, fenpyroximate, fenpyrazamine,

- 19 048372 fenzone, fentrifanil, flubenzymine, flucycloxuron, fluenethyl, fluorbenzide, FMC 1137, formethanate, formethanate hydrochloride, formparanate, gamma-NSN, glyodine, galfenprox, hexadecylcyclopropanecarboxylate, isocarbophos, jasmoline I, jasmoline II, iodofenphos, lindane, malonoben, mecarbam, mephospholane, mesulfene, metacryphos, methyl bromide, metolcarb, mexacarbate, milbemycin oxime, mipafox, monocrotophos, morphothione, moxidectin, naled, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6iodo-3-pyridyl)methoxy]pyridazin-3-one, nifluridide, nikkomycins, nitrilecarb, nitrilecarb-zinc chloride complex 1:1, omethoate , oxydeprophos, oxydisulfoton, pp'-DDT, parathion, permethrin, phencapton, fosalone, phospholane, phosphamidon, polychlorterpenes, polynactins, proclonol, promacil, propoxur, protidation, protoate, pyrethrin I, pyrethrin II, pyrethrins, pyridafenthion, pyrimitate, quinalphos, quinthiophos, R-1492, phosglycine, rotenone, shradan, sebuphos, selamectin, sofamide, SSI-121, sulfiram, sulfluramide, sulfotep, seru, difluvidazine, tau-fluvalinate, TERR, terbam, tetradifon, tetrasul, tiafenox, thiocarboxim, thiofanox, thiomethon, thioquinox, thuringiensin, triamiphos, triaraten, triazophos, triazuron, trifenophos, trinactin, vamidothione, vaniliprole, betoxazine, copper dioctanoate, copper sulfate, cybutryne, dichlone, dichlorophen, endothal, fentin, slaked lime, nabam, quinoclamine, quinonamide, simazine, triphenyltin acetate, triphenyltin hydroxide, crufomate, piperazine, thiophanate, chloralose, fenthion, pyridine -4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, dodicin, fenaminosulf, formaldehyde, hydrargaphene, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate, probenazole, streptomycin, streptomycin sesquisulfate, tecloftalam, thiomersal, Adoxophyes orana GV, Agrobacterium radiobacter, Amblyseius spp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and N. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Orius spp., Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii, afolate, bisazir, busulfan, dimatif, hemel, hempu, metepu, methiotepu, methylafolat, morside, penfluron, tepu, thiochempu, thiotepu, tretamine, uredepu, (E)-dec-5-en-1-ylacetate with (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-ylacetate, (E)-6methylhept-2- en-4-ol, (E^)-tetradeca-4,10-dien-1-ylacetate, (L)-dodec-7-en-1-ylacetate. (X)-hexadec-11enal, ^)-hexadec-11-en-1-yl acetate, ^)-hexadec-13-en-11-yn-1-yl acetate, ^)-icos-13-en-10-one , (Z)tetradec-7-en-1-al, (L)-tetradec-9-en-1-ol, (L)-tetradec-9-ene-1-yl acetate, (7E^)-dodeca-7,9-dien-1-yl acetate, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate, (9Z, 12E)-tetradeca-9,12-dien-1-ylacetate, 14-methyloctadec-1-ene, 4-methylnonan-5-ol s 4-methylnonan-5-one, alpha-multistriatin, brevicomine, codlelur, codlemon, quelur, disparlur, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodeca-8,10-diene- 1-yl acetate, dominicalur, ethyl-4-methyloctanoate, eugenol, frontalin, grandlur, grandlur I, grandlur II, grandlur III, grandlur IV, hexalur, ipsdienol, ipsenol, japonilur, lineatin, litlur, luplur, medlur, megatomoic acid, methyleugenol, muscalur , octadeca-2,13-dien-1-yl acetate, octadeca-3,13-dien-1-yl acetate, orfralur, oryctalur, ostramon, siglur, sordidin, sulcatol, tetradec-11-en-1-yl acetate, trimedlur, trimedlur A, trimedlur B1, trimedlur B ₂ , trimedlur C, trunc-call, 2-(octylthio)ethanol, butopyronoxyl, butoxy (polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyltoluamide, dimethyl carbate, dimethyl phthalate, ethylhexanediol, hexamide, methoquin-butyl, methylneodecanamide, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-bis-(4-ethylphenyl )ethane, 1,2-dichloropropane with 1,3-dichloropropene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl-2-ethylsulfinylethyl methyl phosphate, 2-(1,3- dithiolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate, 2-(4-chloro-3,5xylyloxy)ethanol, 2 -chlorovinyl diethyl phosphate, 2-imidazolidone, 2-isovalerylindane-1,3-dione, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate, 2-thiocyanatoethyl laurate, 3 -bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate, 5,5-dimethyl-3-oxocyclohex-1 -enylmethylcarbamate, acetone, acrylonitrile, aldrin, allosamidine, allixicarb, alpha-ecdysone, aluminum phosphide, aminocarb, anabasine, atidathion, azamethiphos, Bacillus thuringiensis deltaendotoxins, barium hexafluorosilicate, barium polysulfide, bartrin, Bayer 22/190, Bayer 22408, beta- cyfluthrin, beta-cypermethrin, bioethanomethrin, biopermethrin, bis-(2-chloroethyl) ether, borax, bromfenvinphos, brom-DDT, bufencarb, butacarb, butathiophos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, tetrachlormethane, carta hydrochloride, cevadin, chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin, chlorphoxim, chlorprazophos, cis-resmethrin, cismethrin, clocitrin , copper acetoarsenite, copper arsenate, copper oleate, cumitoate, cryolite, CS 708, cyanofenphos, cyanophos, cicletrin, cythioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidefos, dicapton, dichlorfenthion, dicresyl, dicyclanil, dieldrin, diethyl-5-methylpyrazol-3-ylphosphate, dilor, dimefluthrin, dimethane,

- 20 048372 dimethrine, dimethylvinphos, dimethylan, dinoprop, dinosam, dinoseb, diofenolan, dioxabenzophos, diticrophos, DSP, ecdysterone, EI 1642, EMPC, EPBP, 2, ethiofencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenchlorvos, fenethacarb, fenitrothion, fenoxacrim, fenpyritrin, fensulfothion, fenthion-ethyl, flucofuron, fosmethylan, fospirate, fosthiethane, furathiocarb, furethrin, guazatine, guazatine acetates, sodium tetrathiocarbonate, halfenprox, HCH, HEOD, heptachlor, heterophos, HHDN, hydrogen cyanide, Hiquincarb, IPSP, Isazophos, Isobenzan, Isodrin, Isofenphos, Isolan, Isoprothiolane, Isoxathione, Juvenile Hormone I, Juvenile Hormone II, Juvenile Hormone III, Kelevan, Kinoprene, Lead Arsenate, Leptophos, Lirimfos, Lithidathion, M-Cumenyl Methylcarbamate, Magnesium Phosphide, Mazidox, Mecarfone, Menazon, Mercuric Chloride, Mesulfenfos, Metam, Metam Potassium, Metam Sodium, Methanesulfonyl Fluoride, Methocrotophos, Methoprene, Methotrin, Methoxychlor, Methyl Isothiocyanate, Methyl Chloroform, Methylene Chloride, Methoxadiazone, Mirex, Naphthalofos, Naphthalene, NC-170, Nicotine, Nicotine Sulfate, Nitiazine, Nornicotine, O-5-dichloro-4-iodophenyl-O-ethyl ethyl phosphonothioate, O,O-diethyl-O-4-methyl2-oxo-2H-chromen-7-yl phosphorothioate, O,O-diethyl-O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate, O,O,O',O'-tetrapropyl dithiopyrophosphate, oleic acid, para-dichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, PH 60-38, fenkapton, phosnichlor, phosphine, phoxim-methyl, pyrimetaphos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocen I, precocen II, precocen III, primidophos, profluthrin, promecarb, prothiophos, pyrazophos, pyresmethrin, quassia, quinalfos-methyl, quinothion, rafoxanide, resmethrin, rotenone, cadetrin, ryania, ryanodine, sabadilla), shradan, sebufos, SI-0009, tiapronil, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenoxide, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron sodium, sulfuryl fluoride, sulprofos, tar oils, tazimcarb, TDE, tebupirimfos, temephos, terallethrin, tetrachloroethane, thicrophos, thiocyclam, thiocyclam hydrooxalate, thionazine, thiosultap, thiosultap sodium, tralomethrin, transpermethrin, triazamate, trichlormetaphos-3, trichloronate, trimethacaryl, tolprocarb, triclopyricarb, triprene, veratridine, veratrine, CMC, zetamethrin, zinc phosphide, zolaprofos and meperfluthrin, tetramethylfluthrin, bis-(tributyltin oxide), bromoacetamide, ferrous phosphate, niclosamide-olamine, tributyltin oxide, pyrimorph, triphenmorph, 1,2-dibromo-3-chloropropane, 1,3-dichloropropene, 3,4-dichlorotetrahydrothiophene-1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, 2-Fluoro-N-(3-methoxyphenyl)-9H-purine-6-amine, benclothiase, cytokinins, DCIP, furfural, isamidophos, kinetin, Myrothecium verrucaria composition, tetrachlorothiophene, xylenols, zeatin, potassium ethyl xanthate, acibenzolar, acibenzolar-^-methyl, Reynoutria sachalinensis extract, alpha-chlorohydrin, anthu, barium carbonate, bisthiosemycin, brodifacoum, bromadiolone, bromethalin, chlorophacinone, chloroinconazide, cholecalciferol, coumachlor, coumafuril, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropadine, hydrochloride flupropadine, norbormide, fosacetim, phosphorus, pindone, pyrinuron, scilliroside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethyl piperonylate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, verbutin, MGK 264, piperonyl butoxide, piperothal, propyl isomer, S421, sesamex, sesamolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate, ziram, imaninin, ribavirin, mercuric oxide, thiophanate-methyl, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furamethpyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazol, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrizoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, ancymidol, fenarimol, nuarimol, bupirimate, dimethyrimol, ethirimol, dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole, chlozolinate, dichlozolin, myclozolin, procymidone, vinclozolin, boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin, dimoxystrobin, enestroburine, phenaminestrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluorimide, folpet, tolylfluanid, Bordeaux mixture, cupric oxide, mancopper, copper oxine, nitrothal-isopropyl, edifenfos, iprobenfos, fosdifen, tolclofos-methyl, anilazine, benthiavalicarb, blasticidin-S, chloroneb, chlorothalonil, cyflufenamide, cymoxanil, cyclobutrifluram, diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, fluopicolide, flusulfamide, fluxapyroxad, fenhexamide, fosetyl aluminum, himexazole, iprovalicarb, cyazofamid, metasulfocarb, metrafenone, pencycuron, phthalide, polyoxins, propamocarb, pyribencarb, proquinazid, pyroquilone, pyriophenone, quinoxyfen, quintozene, tiadinil, triazoxide, tricyclazole, triforine, validamycin, valiphenalate, zoxamide, mandipropamide, flubeneteram, isopyrazam, sedaxan, benzovindiflupyr, pidiflumetofen, (3',4',5'-trifluorobiphenyl-2-yl)amide 3-difluoromethyl-1-methyl-1Hpyrazole-4-carboxylic acid, isoflucipram, isothianil, dipimethitrone, 6-ethyl-5,7-dioxo- 21 048372 pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine-3-carbonitrile, (R)-3(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethylpyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, cumethoxystrobin (jiaxiangjunzhi), lubenmixianan, dichlobenthiazox, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiproline, tert-butyl-N-[6-[[[(1-methyltetrazol-5-yl)-phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate, pyraziflumide, inpirfluxam, trolprocarb, mefentrifluconazole, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1dimethylindan-4-yl]pyridin-3-carboxamide, N-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-Nmethylformamidine, N-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine, [2-[3-[2-[1-[2-[3,5-Bis-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chlorophenyl]methanesulfonate, but-3-ynyl-M-[6-[[^)-[(1-methyl1'etrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate, methyl-M-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2methylphenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridachloromethyl, 3-(difluoromethyl)-1-methyl-K-[1,1,3-trimethylindan-4-yl]pyrazol-4-carboxamide, 1-[2-[[1-(4chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methylphenyl] -4-methyltetrazol-5-one, 1-methyl-4-[3 -methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one, aminopyrifen, amethoctradine, amisulbrom, penflufen, (N,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpent-3-enamide, florylpicoxamide, fenpicoxamide, tebufloquine, ipflufenoquine, quinofumelin, isofetamide, N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide, benzothiostrobin, fenamacryl, zinc salt of 5-amino-1,3,4-thiadiazole-2-thiol (2:1), fluopyram, flutianil, fluopimamide, pyrapropone, picarbutrazox, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylindan-4yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, methyltetrapropyl, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, α(1,1-dimethylethyl)-a-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol, fluoxapiproline, enoxastrobin, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, 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, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, trinexapac, kumoxystrobin, zhongshengmycin, copper thiodiazole, zinc thiazole, amectotractin, iprodione, N-οκτήλ-N'-|2(octylamino)ethyl]ethane-1,2-diamine, N-[5-bromo-2-methyl-6-[(N)-1-methyl-2-propoxyethoxy]-3-pyridyl]N-ethyl-N-methylformamidine, N'-[5-bromo-2-methyl-6-[(N)-1-methyl-2-propoxyethoxy] -3-pyridyl]-N-ethyl-N-methylformamidine, N-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-isopropyl-N-methylformamidine (such compounds can be prepared using the methods described in WO 2015/155075); N'-[5-bromo-2-methyl-6-(2-propoxypropyl)-3-pyridyl]-N-ethyl-N-methylformamidine (such a compound can be prepared using the methods described in IPCOM000249876D); N-isopropylN'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methylformamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxyethyl)-5-methoxy-2-methylphenyl]-N-isopropyl-N-methylformamidine (such compounds can be prepared using the methods described in WO 2018/228896); ^ethyl-N'[5-methoxy-2-methyl-4-[2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methylformamidine, N-ethyl-N'-[5methoxy-2-methyl-4-[2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methylformamidine (such compounds can be prepared using the methods described in WO 2019/110427); N-[(1R)-1-benzyl-3-chloro-1-methylbut-3-enyl]-8-fluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methylbut-3-enyl]-8-fluoroquinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methylpropyl]-8-fluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methylpropyl]-8-fluoroquinoline-3-carboxamide, N-[(1R)-1benzyl-1,3-dimethyl-butyl]-7,8-difluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethylbutyl]-7,8-difluoroquinoline-3-carboxamide -carboxamide, 8-fluoro-N-[(III)-1-[(3-fluorophenyl)methyl]-1,3-dimethylbutyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethylbutyl]quinoline-3-carboxamide, N[(III)-1-benzyl-1,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methylbut-3-enyl)-8-fluoroquinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1-methylbut-3-enyl)-8-fluoroquinoline-3-carboxamide (these compounds can be prepared using the methods described in WO 2017/153380); 1-(6,7-dimethylpyrazolo[1,5a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)4,4,6-trifluoro-3,3-dimethylisoquinoline, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1 -(6-chloro7-methylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethylisoquinoline (these compounds can be synthesized by 22 048372 using the methods described in WO 2017/025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4methylbenzimidazol-1-yl)-3,3-dimethylisoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds can be prepared using the methods described in WO 2016/156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N-2-dimethoxy-N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, H-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3yl]phenyl]methyl]pyrazole-4-carboxylate, ethyl dimethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared using the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared using the methods described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared using the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared using the methods described in WO 2016/156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared using the methods described in WO 2016/156290); (4-phenoxyphenyl)methyl 2-amino-6-methylpyridine-3-carboxylate (this compound can be prepared using the methods described in WO 2014/006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone (this compound can be prepared using the methods described in WO 2011/138281) N-methyl-4-[5-(trifluoromethyl)1,2,4-oxadiazol-3-yl]benzenecarbothioamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpent-3enamide (this compound can be prepared using the methods described in WO 2018/153707); N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine; N-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylformamidine (this compound can be prepared using the methods described in WO 2016/202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethylindan-4-yl]pyrimidine-3-carboxamide (this compound can be prepared using the methods described in WO 2014/095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds can be prepared using the methods described in WO 2017/220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound can be prepared using the methods described in WO 2018/065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound can be prepared using the methods described in WO 2018/158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, N-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-methoxyiminomethyl]-4-[5(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[N-methoxy-C-methylcarbonimidoyl]-4-[5(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared using the methods described in WO 2018/202428).

The compounds of the present invention may also be used in combination with anthelmintics. Such anthelmintics include compounds selected from the class of macrocyclic lactone compounds such as the ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives described in EP-357460, EP-444964 and EP-594291. Additional anthelmintics include semi-synthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5,015,630, WO-9415944 and WO-9522552. Additional anthelmintics include benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of this class. Additional anthelmintics include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel, or morantel. Additional anthelmintics include flukicides such as triclabendazole and clorsulon, and cestocides such as praziquantel and epsiprantel.

The compounds of the present invention can be used in combination with derivatives and analogues of anthelmintic agents of the paraherquamide/marcfortine class, as well as with antiparasitic oxazolines such as those disclosed in US-5478855, US-4639771 and DE-19520936.

The compounds of the present invention can be used in combination with derivatives and analogs

- 23 048 372 g of the general class of dioxomorpholine antiparasitic agents described in WO 96/15121, as well as with anthelmintic active cyclic depsipeptides such as those described in WO 96/11945, WO 93/19053, WO 93/25543, EP 0626375, EP 0382173, WO 94/19334, EP 0382173 and EP 0503538.

The compounds of the present invention can be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide, etc.; neonicotinoids such as imidacloprid, etc.

The compounds of the present invention can be used in combination with terpene alkaloids, such as those described in International Patent Application Publication Nos. WO 95/19363 or WO 04/72086, in particular the compounds disclosed therein.

Other examples of such biologically active compounds in combination with which the compounds of the present invention can be used include, but are not limited to, the following.

Organophosphorus compounds: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methylsulfone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprofos, etrimfos, famfur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazophos, fonophos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, methacryphos, methamidophos, methidathion, methyl parathion, mevinphos, monocrotophos, naled, omethoate, oxydemetonmethyl, paraoxon, parathion, parathion-methyl, phentoate, fosalone, phospholane, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimifos, pirimiphos-methyl, profenofos, propafos, proethamphos, prothiophos, pyraclofos, pyridapention, quinalphos, sulprofos, temefos, terbufos, tebupirimphos, tetrachlorvinphos, timeton, tiazofos, trichlorfon, vamidothion.

Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloetocarb, ethiofencarb, fenoxycarb, fentiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiophanox, triazamate, UC-51717.

Pyrethroids: Acrinathrin, Allethrin, Alphamethrin, 5-Benzyl-3-furylmethyl-(E)-(1H)-cis-2.2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, Bifenthrin, Beta-Cyfluthrin, Cyfluthrin, Alpha-Cypermethrin, Beta-Cypermethrin, Bioallethrin, Bioallethrin ((^)-Cyclopentyl-isomer), Bioresmethrin, Bifenthrin, NCI-85193, Cycloprotrin, Cyhalothrin, Citrin, Cyphenothrin, Deltamethrin, Empenthrin, Esfenvalerate, Etofenprox, Fenfluthrin, Fenpropathrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate (D-isomer), Imiprothrin, Cyhalothrin, Lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, tau-fluvalinate, tefluthrin, tralomethrin, zeta-cypermethrin.

Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorphentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.

Other antiparasitic agents: acequinocil, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorbenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidin, cyromazine, diacloden, diafenthiuron, DBI-3204, dynactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, etofenprox, fenazaquin, flumit, MTI-800, fenpyroximate, fluacrypyrim, flubenzimin, flubrocitrinate, flufenzin, flufenprox, fluproxyfen, halofenprox, hydramethylnon, IKI-220, canemit, NC-196, neem gard, nidinorterfuran, nitenpyram, SD-35651, WL-108477, pyridaryl, propargite, protrifenbut, pymetrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, silomadin, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, verbutin, verthalek, YI-5301.

Biological agents: Bacillus thuringiensis ssp. aizawai, kurstaki, Bacillus thuringiensis delta-endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi.

Bactericides: chlortetracycline, oxytetracycline, streptomycin.

Other biological agents: enrofloxacin, febantel, penetamate, moloxicam, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiofur, carprofen, metaflumizone, praziquarantel, triclabendazole, flumethylsulforim, fluoxythioconazole, flufenoxadiazam, metarilpicoxamide.

Preferred are the following mixtures of compounds of formula (I) with active ingredients. The abbreviation TX means one compound selected from the group consisting of the compounds presented in Tables A1 to A5 or Table E (below), i.e. one of the compounds E.01 to E.25: a compound selected from the group of substances consisting of petroleum oils + TX, 1,1-bis-(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chloro

- 24 048372 phenylphenylsulfone + TX, acetoprol + TX, aldoxycarb + TX, amidithione + TX, amidothioate + TX, amiton + TX, amitone hydroxalate + TX, amitraz + TX, aramit + TX, arsenic oxide + TX, azobenzene + TX, nitrogen + TX, benomyl + TX, benoxaphos + TX, benzyl benzoate + TX, bixafen + TX, brofenvalerate + TX, bromocyclen + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridabene + TX, calcium polysulfide + TX, camphechlor + TC, carbanolate + TC, carbophenothione + TX, cimiazole + TX, quinomethionate + TX, chlorobenzide + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorphenethol + TX, chlorphenson + TX, chlorphensulfide + TX, chlorobenzilate + TX, chloromebuform + TX, chloromethiuron + TX, chloropropylate + TX, chlorothiophos + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxyphos + TX, kufraneb + TX, cyanoate + TX, DCPM + TX, DDT + TX, demefion + TX, demefion-O + TX, demethion-S + TX, demeton-methyl + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton^-methyl + TX, demeton^-methylsulfone + TX, dichlofluanid + TX, dichlorvos + TX, diclifos + TX, dienochlor + TX, dimefox + TX, dinex + TX, dinex-diclexin + TX, dinocap-4 + TX, dinocap-6 + TX, dinoctone + TX, dinopentone + TX, dinosulfone + TX, dinoterbon + TX, dioxathion + TX, diphenylsulfone + TX, disulfiram + TX, DNOC + TX, dophenapine + TX, doramectin + TX, endothion + TX, eprinomectin + TX, ethoate-methyl + TX, etrimphos + TX, phenazaflor + TX, fenbutatin oxide + TX, phenothiocarb + TX, fenpyrad + TX, fenpyroximate + TX, fenpyrazamine + TX, fenzone + TX, fentrifanil + TX, flubenzymine + TX, flucycloxuron + TX , fluenethyl + TX, fluorbenzide + TX, FMC 1137 + TX, formethanate + TX, formethanate hydrochloride + TX, formparanate + TX, gamma-CHN + TX, glyodine + TX, galfenprox + TX, hexadecyl-cyclopropanecarboxylate + TX, isocarbophos + TX, jasmoline I + TX , jasmoline II + TX, iodofenphos + TX, lindane + TX, malonoben + TX, mecarbam + TX, mephospholan + TX, mesulfen + TX, metacryphos + TX, methyl bromide + TX, metolcarb + TX, mexacarbate + TX, milbemycin oxime + TX, mipafox + TX, monocrotophos + TX, morphothion + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, nifluridide + TX, nikkomycins + TX, nitrilecarb + TX, complex of nitrilecarb and zinc chloride 1:1 + TC, omethoate + TC, oxydeprofos + TC, oxydisulfoton + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, phencapton + TX, fosalone + TX, phospholane + TX, phosphamidon + TX, polychlorterpenes + TX, polynactins + TX, proclonol + TX, promacil + TX, propoxur + TX , protidation + TX, protoate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrins + TX, pyridafenthione + TX, pyrimitate + TX, quinalphos + TX, quinthiophos + TX, R-1492 + TX, phosglycine + TX, rotenone + TX, shradan + TX, sebuphos + TX, selamectin + TX, sofamid + TX, SSI-121 + TX, sulfiram + TX, sulfluramide + TX, sulfotep + TX, sulfur + TX, difluvidazine + TX, tau-fluvalinate + TX, TERR + TX, terbam + TX, tetradifon + TX, tetrasul + TX, thiafenox + TX, thiocarboxim + TX, thiophanox + TX, thiometon + TX, thioquinox + TX, thuringiensin + TX, triamiphos + TX, triarathene + TX, triazophos + TX, triazuron + TX, triphenofos + TX, trinactin + TX, vamidothion + TX, vaniliprole + TX, betoxazine + TX, copper dioctanoate + TX, copper sulfate + TX, cibutrin + TX, dichlon + TX, dichlorophen + TX, endothal + TX, fentin + TC, slaked lime + TC, nabam + TC, quinoclamine + TC, quinonamide + TC, simazine + TC, triphenyltin acetate + TC, triphenyltin hydroxide + TC, crufomate + TC, piperazine + TC, thiophanate + TC, chloralose + TC, fenthion + TX, pyridin-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxalin-2ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodicine + TX, fenaminosulf + TX, formaldehyde + TX, hydrargafen + TX, kasugamycin + TH, kasugamycin hydrochloride hydrate + TH, nickel bis(dimethyldithiocarbamate) + TH, nitrapyrin + TH, octhilinone + TH, oxolinic acid + TH, oxytetracycline + TH, potassium hydroxyquinoline sulfate + TH, probenazole + TH, streptomycin + TH, sesquisulfate streptomycin + TX, tecloftalam + TX, thiomersal + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, Amblyseius spp. + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX , Cryptolaemus montrouzieri + TX, Cydia pomonella GV + TX, Dacnusa sibirica + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Eretmocerus eremicus + TX, Heterorhabditis bacteriophora and N. megidis + TX, Hippodamia convergens + TX, Leptomastix dactylopii + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp. + TX, Typhlodromus occidentalis + TX, Verticillium lecanii + TX, afolate + TX, bisazir + TX, busulfan + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiothepa + TX, methylafolate + TX, morzide + TX, penfluron + TX, tepa + TX, thiochempa + TX, thiotepa + TX, tretamine + TX, uredepa + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E )-tridec-4-en1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E^)-tetradeca-4,10-dien-1-ylacetate + TX, (X)-dodec7-en-1-yl acetate + TX, ^)-hexadec-11-enal + TX, ^)-hexadec-11 -ene-1-ylacetate + TX, (X)-hexadec-13ene-11-yne-1-yl acetate + TH, (U)-eicos-13-en-10-one + TH, ^)-tetradec-7-en-1-al + TH, (X)-tetradec-9-ene

- 25 048372

1-ol + TX, ^)-tetradec-9-en-1-yl acetate + TX, (7E,92)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)tetradeca-9, 11-dien-1-yl acetate + TX, (9Z, 12E)-tetradeca-9,12-dien-1-ylacetate + TX, 14-methyloctadec-1ene + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, alpha-multistriatin + TX, brevicomin + TX, codelur + TX, codelemon + TX, kuelur + TX, disparlur + TX, dodec-8-ene-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodeca-8 + TX, 10-dien-1-yl acetate + TX, dominicalur + TX, ethyl-4-methyloctanoate + TX, eugenol + TX, frontalin + TX, grandlur + TX, Grandlur I + TX, Grandlur II + TX, Grandlur III + TX, grandlur IV + TX, hexalur + TX, ipsdienol + TX, ipsenol + TX, japonilur + TX, lineatin + TX, litlur + TX, luplur + TX, medlur + TX, megatomoic acid + TX, methyleugenol + TX, muscalur + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-diene-1-yl acetate + TX, orfralur + TX, oryctalur + TX, ostramon + TX, siglur + TX, sordidin + TX, sulcatol + TX, tetradec-11-en-1-yl acetate + TX, trimedlur + TX, trimedlur A + TX, trimedlur Bi + TX, trimedlur Br + TX, trimedlur C + TX, trunc-call + TX, 2(octylthio)ethanol + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diethyltoluamide + TX , dimethylcarbate + TX, dimethyl phthalate + TC, ethylhexanediol + TC, hexamide + TC, methoquin-butyl + TC, methylneodecanamide + TC, oxamate + TC, picaridin + TC, 1-dichloro-1-nitroethane + TC, 1,1-dichloro-2,2-bis-(4-ethylphenyl )ethane + TX, 1,2-dichloropropane with 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl-2-ethylsulfinylethyl methylphosphate + TX, 2-(1,3dithiolane- 2-yl)phenyldimethylcarbamate + TX, 2-(2-butoxyethoxy)ethylthiocyanate + TX, 2-(4,5-dimethyl1,3-dioxolan-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX, 2- isovaleryl lindane-1,3-dione + TX, 2-methyl(prop2-ynyl)aminophenylmethylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate + TX, 4-methyl( prop-2-ynyl)amino-3,5xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate + TX, acethione + TH, acrylonitrile + TH, aldrin + TH, allosamidine + TH, allixicarb + TH, alpha-ecdysone + TH, aluminum phosphide + TH, aminocarb + TH, anabasine + TH, atidathion + TH, azamethiphos + TH, Bacillus thuringiensis delta-endotoxins + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, bartrin + TX, Bayer 22/190 + TX, Bayer 22408 + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bioethanomethrin + TX, biopermethrin + TX, bis -(2-chloroethyl) ether + TX, borax + TX, bromfenvinphos + TX, brom-DDT + TX, bufencarb + TC, butacarb + TC, butathiophos + TC, butonate + TC, calcium arsenate + TC, calcium cyanide + TC, carbon disulfide + TC, carbon tetrachloride + TC, cartap hydrochloride + TC, cevadin + TC, chlorobicyclene + TC, chlordane + TC, chlordecone + TC, chloroform + TC, chloropicrin + TC, chlorphoxime + TC, chlorprazophos + TC, cis-resmethrin + TC, cismethrin + TC, clocitrin + TC, copper acetoarsenite + TC, copper arsenate + TC, copper oleate + TC, cumitoate + TC, cryolite + TC, CS 708 + TH, cyanophenphos + TH, cyanophos + TX, cycletrin + TX, cythioate + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, decarbofuran + TX, diamidaphos + TX, dicaptone + TX, dichlorofenthione + TX, dicresyl + TX, dicyclanil + TX, dieldrin + TX, diethyl-5- methylpyrazol-3-ylphosphate + TX, dilor + TX, dimefluthrin + TX, dimethane + TX, dimetrin + TX, dimethylvinphos + TX, dimethylane + TX, dinoprop + TX, dinosam + TX, dinoseb + TX, diophenolan + TX, dioxabenzophos + TX, dithikrofos + TX, DSP + TX, ecdysterone + TX, EI 1642 + TX, EMRS + TX, ERVR + TX, etafos + TX, etiophencarb + TX, ethyl formate + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, EXD + TX, fenchlorvos + TX, fenetacarb + TX, fenitrothion + TX, fenoxacrim + TX, fenpyritrin + TX, fensulfothione + TX, fenthion- ethyl + TX, flucofuron + TX, fosmethylane + TX, fospirat + TX, fostiethane + TX, furathiocarb + TX, furethrin + TX, guazatin + TX, guazatin acetates + TX, sodium tetrathiocarbonate + TX, galfenprox + TX, NCH + TX, HEOD + TX, heptachlor + TX, heterophos + TX, HHDN + TX, hydrogen cyanide + TX, hiquincarb + TX, IPSP + TX, isazophos + TX, isobenzan + TX, isodrin + TX, isofenphos + TX, isolan + TX, isoprothiolane + TX, isoxathione + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, Kelevan + TX, kinoprene + TX, arsenate lead + TX, leptophos + TX, lyrimphos + TX, lithidathion + TX, mcumenylmethylcarbamate + TX, magnesium phosphide + TX, mazidox + TX, mekarfon + TX, menazone + TX, mercuric chloride + TX, mesulfenphos + TX, metam + TX, metam-potassium + TC, metam-sodium + TX, methanesulfonyl fluoride + TX, metocrotophos + TX, methoprene + TX, methotrin + TX, methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, methylene chloride + TX, methoxadiazone + TX, mirex + TX, naphthalophos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, nornicotine + TX, O-5-dichloro-4-iodophenyl-O-ethylethylphosphonothioate + TX, O,O-diethyl-O-4-methyl-2-oxo-2Hchromen-7-ylphosphorothioate + TX, O,O-diethyl-O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate + TX, Ο,Ο,Ο',Ο'-tetrapropyldithiopyrophosphate + TX, oleic acid + TX, para-dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, pH 60-38 + TX, phencapton + TX, phosnichlor + TX, phosphine + TX, phoxim-methyl + TX, pyrimethafos + TX, polychlorodicyclopentadiene isomers + TX, potassium arsenite + TX, potassium thiocyanate + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, profluthrin + TX, promecarb + TX, prothiophos + TX, pyrazophos + TX, pyresmethrin + TX, quassia + TX, quinalphos-methyl + TX, quinothione + TX, rafoxanide + TX, resmethrin + TX, rotenone + TX, cadetrin + TX, ryanium + TX, ryanodine + TX, sabadilla) + TX, shradan + TX, sebuphos + TX, SI-0009 + TX, tiapronil + TX, sodium arsenite + TC, sodium cyanide + TC, sodium fluoride + TC,

- 26 048372 sodium hexafluorosilicate + TX, sodium pentachlorophenoxide + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfuryl fluoride + TX, sulprophos + TX, tar oils + TX, tazimcarb + TX, TDE+ TX, tebupirimphos + TX, temephos + TX, teralletrin + TX, tetrachloroethane + TX, ticrofos + TX, thiocyclam + TX, thiocyclam hydroxalate + TX, thionazine + TX, thiosultap + TX, thiosultap-sodium + TX, tralomethrin + TX, transpermethrin + TX, triazamate + TX, trichlorometaphos-3 + TC, trichloronate + TC, trimetacarb + TC, tolprocarb + TC, trichloropyricarb + TC, triprene + TC, veratridine + TC, veratrin + TC, CMS + TC, zetamethrin + TC, zinc phosphide + TC, zolaprophos + TC and meperfluthrin + TC , tetramethylfluthrin + TX, bis-(tributyltin) oxide + TX, bromoacetamide + TX, ferrous phosphate + TX, niclosamide-olamine + TX, tributyltin oxide + TX, pyrimorph + TX, triphenmorph + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropene + TX, 3,4dichlorotetrahydrothiophene-1,1-dioxide + TC, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 2-fluoro-N-(3methoxyphenyl) -9H-purin-6-amine + TX, benclothiasis + TX, cytokinins + TX, DCIP + TX, furfural + TX, isamidophos + TX, kinetin + TX, composition based on Myrothecium verrucaria + TX, tetrachlorothiophene + TX, xylenols + TX, zeatin + TX, potassium ethyl xanthate + TX, acibenzolar + TX, acibenzolar^- methyl + TX, Reynoutria extract sachalinensis + TX, alpha-chlorohydrin + TX, antu + TX, barium carbonate + TX, bisthiosemie + TX, brodifacoum + TX, bromadiolone + TX, bromethalin + TX, chlorophacinone + TX, cholecalciferol + TX, coumachlor + TX, coumafuryl + TX, coumatetralyl + TX, crimidin + TX, difenacoum + TX, difethialon + TX, diphacinone + TX, ergocalciferol + TX, flocumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, norbormide + TX, fosacetim + TX, phosphorus + TX, pindon + TX, pyrinuron + TX, scylliroside + TX, fluoroacetate sodium + thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethylpiperonilate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2enone + TX, farnesol with nerolidol + TX, verbutin + TX, MGK 264 + TX, piperonyl butoxide + TX, piprotal + TX, propyl isomer + TX, S421 + TX, sesamex + TX, sesasmolin + TX, sulfoxide + TX, anthraquinone + TX, copper naphthenate + TX, copper oxychloride + TX, dicyclopentadiene + TX, thiram + TX, zinc naphthenate + TX, ziram + TX, imanin + TX , ribavirin + TX, mercuric oxide + TX, thiophanate-methyl + TX, azaconazole + TX, bitertanol + TX, bromuconazole + TX, cyproconazole + TX, difenoconazole + TX, diniconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furamethpyr + TX, hexaconazole + TX, imazalil + TX, imibenconazole + TX, ipconazole + TX, metconazole + TX, myclobutanil + TX, paclobutrazol + TX, pefurazoate + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyrizoxazole + TX, simeconazole + TX, tebuconazole + TX, tetraconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triticonazole + TX, ancymidol + TX, fenarimol + TX, nuarimol + TX, bupirimate + TX, dimethyrimol + TX, ethirimol + TX, dodemorph + TX, fenpropidine + TX, fenpropimorph + TX, spiroxamine + TX, tridemorph + TX, cyprodinil + TX, mepanipyrim + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl -+ TX, R-metalaxyl + TX, ofuras + TX , oxadixil + TX, carbendazim + TX, debacarb + TX, fuberidazole + TX, thiabendazole + TX, chlozolinate + TX, dichlozolin + TX, myclozolin + TX, procymidone + TX, vinclozolin + TX, boscalid + TX, carboxin + TX, fenfuram + TX, flutolanil + TX, mepronil + TX, oxycarboxin + TX, pentiopyrad + TX, tifluzamide + TX, dodine + TX, iminoctadine + TX, azoxystrobin + TX, dimoxystrobin + TX, enestroburin + TX, phenaminstrobin + TX, flufenoxystrobin + TX, fluoxastrobin + TX, kresoxim-methyl + TX, metominostrobin + TX, trifloxystrobin + TX, orysastrobin + TX, picoxystrobin + TX, pyraclostrobin + TX, pyramethostrobin + TX, pyraoxystrobin + TX, ferbam + TX, mancozeb + TX, maneb + TX, metiram + TX, propineb + TX, zineb + TX, captafol + TX, captan + TX, fluorimide + TX , folpet + TX, tolylfluanid + TC, Bordeaux mixture + TC, copper oxide + TC, mancopper + TC, copper oxine + TC, nitrotal-isopropyl + TC, edifenphos + TC, iprobenphos + TC, phosdifene + TC, tolclofosmethyl + TC, anilazine + TC, benthiavalicarb + TC , blasticidin-S + TX, chloroneb + TX, chlorothalonil + TX, cyflufenamide + TX, cymoxanil + TX, cyclobutrifluram + TX, diclocimet + TX, diclomesin + TX, dicloran + TX, dietofencarb + TX, dimethomorph + TX, flumorph + TX, dithianon + TX, ethaboxam + TX, etridiazole + TX, famoxadone + TX, fenamidone + TX, fenoxanil + TX, ferimzone + TX, fluazinam + TX, fluopicolide + TX, flusulfamide + TX, fluxapyroxad + TX, fenhexamide + TX, fosetylaluminum + TX, himexazole + TX, iprovalicarb + TX, cyazofamide + TX, metasulfocarb + TX , metrafenone + TX, pencikuron + TX, phthalide + TX, polyoxins + TX, propamocarb + TX, pyribencarb + TX, proquinazide + TX, pyroquilone + TX, pyriophenone + TX, quinoxifene + TX, quintozene + TX, tiadinyl + TX, triazoxide + TX, tricyclazole + TX, triforin + TX, validamycin + TX, valifenalate + TX, zoxamide + TX, mandipropamide + TX, flubeneteram + TX, isopyrazam + TX, sedaxane + TX, benzovindiflupyr + TX, pidiflumetofen + TX, (3',4',5'-trifluorobiphenyl-2-yl)amide 3-difluoromethyl-1-methyl-1Hpyrazole-4-carboxylic acid + TX, isoflucipram + TX, isothianyl + TX, dipimethytrone + TX, 6-ethyl5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazol-3-carbonitrile + TX, 2-(difluoromethyl)-N-[ 3-ethyl1,1-dimethylindan-4-yl]pyridin-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine3-carbonitrile + TX,^)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl] pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethylpyrazol-3-amine + TX, 4-(2-bromo-4

- 27 048372 fluorophenyl)-Ы-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX, fluindapyr + TX, cumethoxystrobin (jiaxiangjunzhi) + TX, luibenmisianan + TX, dichlobenthiazox + TX, mandestrobin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, oxathiapiproline + TX, tert-butyl-H-[6-[[[(1methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumide + TX, inpirfluxam + TX, trolprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole + TX, 2(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylindan-4-yl]pyridin-3-carboxamide + TX, I-(2.5-dimethyl-4phenoxyphenyl)-N-ethyl-N-methylformamidine + TX, N-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5dimethylphenyl]-N-ethyl-N-methylformamidine + TX, [2-[3-[2-[1-[2-[3,5-bis-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chlorophenyl]methanesulfonate + TX, but-3-ynyl H-[6-[[(2)-[(1-methyltetrazol-5-yl)phenylmethylene|amino]oxymethyl]-2-pyridyl]carbamate + TX, methyl H-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methylphenyl]methyl]carbamate + TX, 3-chloro-6methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridachloromethyl + TX, 3-(difluoromethyl)-1methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl|oxymethyl|-3-methylphenyl|-4-methyltetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy|methyl|phenyl|tetrazol-5-one + TX, aminopyrifen + TX, amethoctradine + TX, amisulbrom + TX, penflufen + TX, (2,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyiminoK3-dimethylpent-3-enamide + TX, florylpicoxamide + TX, fenpicoxamide + TX, tebufloquin + TX, ipflufenoquin + TX, quinofumelin + TX, isofetamide + TX, N[2-[2,4-dichlorophenoxy]phenyl]-3(difluoromethyl)-1-methylpyrazole-4-carboxamide + TX, №[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3(difluoromethyl)-1-methylpyrazole-4-carboxamide + TX, benzothiostrobin + TX, fenamacryl + TX, zinc salt 5-amino-1,3,4-thiadiazol-2-thiol (2:1) + TX, fluopyram + TX, flutianil + TX, fluopimomide + TX, pyrapropone + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylindan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, methyltetrapropyl + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, a-(1,1-dimethylethyl)-a-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluoxapiproline + TX, enoxastrobin + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 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 + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1 yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac + TX, cumoxystrobin + TX, zhongshengmi qing + TX, copper thiodiazole + TX, zinc thiazole + TX, amectotractin + TX, iprodione + TX, Na-octyl-N'-[2 (octylamino)ethyl]ethane-1,2-diamine + TX; N-[5-bromo-2-methyl-6-[(N)-1-methyl-2-propoxyethoxy]-3 pyridyl]-N-ethyl-N-methylformamidine + TX, I-[5-bromo-2-methyl-6-[(1K)-1-methyl-2-propoxyethoxy|-3pyridyl]-N-ethyl-N-methylformamidine + TX, pyridyl]-N-ethyl-N-methylformamidine + TX, pyridyl]-N-ethyl-N-methylformamidine + TX, pyridyl]-H-isopropyl-N-methylformamidine + TX N-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3N-[5-chloro-2-methyl-6-(1-methyl-2-propoxyethoxy)-3N-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3(these compounds can be prepared using the methods described in WO 2015/155075); N-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-Nmethylformamidine + TX (this compound can be prepared using the methods described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methylformamidine + TX, N-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxyethyl)-5methoxy-2-methylphenyl]-N-isopropyl-N-methylformamidine + TX (these compounds can be prepared using the methods described in WO 2018/228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methylformamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methylformamidine + TX (these compounds can be prepared using the methods described in WO 2019/110427); N-[(1R)-1-benzyl-3-chloro-1-methylbut-3-enyl]-8-fluoroquinoline-3-carboxamide + TX, N-[(^)-1-benzyl-3-chloro-1-methylbut-3-enyl]-8-fluoroquinoline-3-carboxamide + TX, N-[(t)-1-benzyl-3,3,3-trifluoro-1-methylpropyl]-8-fluoroquinoline-3-carboxamide + TX, N-[(^)-1-benzyl-3,3,3-trifluoro-1-methylpropyl]-8-fluoroquinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethylbutyl]-7,8-difluoroquinoline-3-carboxamide + TX, N[(^)-1-benzyl-1,3-dimethylbutyl]-7,8-difluoroquinoline-3-carboxamide + TX, 8-fluoro-N-[(t)-1-[(3-fluorophenyl)methyl]-1,3-dimethylbutyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(^)-1-[(3-fluorophenyl)methyl]-1,3-dimethylbutyl]quinoline-3-carboxamide + TX, N[(t)-1-benzyl-1,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide + TX, N[(^)-1-benzyl-1,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methylbut-3-enyl)-8-fluoroquinoline-3-carboxamide + TX, N-((^)-1-benzyl-3-chloro-1-methylbut-3-enyl)-8-fluoroquinoline-3-carboxamide + TX (these compounds can be prepared using the methods described in WO 2017/153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a|pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethylisoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a|pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a|pyridin-3-yl)isoquinoline + TX, 1-(6-chloro-7- 28 048372 methylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethylisoquinoline + TX (these compounds can be prepared using the methods described in WO 2017/025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methylbenzimidazol-1-yl)-3,3-dimethylisoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared using the methods described in WO 2016/156085); Nmethoxy-N[[4-[5-(trifluoromethyl)-1,2,4oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, K2-dimethoxy^-[[4-[5-(trifluoromethyl)1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, No. ethyl-2-methyl-No. 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3yl]phenyl]methyl]urea + TX, No. [[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3yl](enyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(tri(fluoromethyl)-1,2,4-oxadiazol-3-yl](enyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(tri(fluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph can be prepared using the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689; 2[6-(4-chlorophenoxy)-2-(1-fluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared using the methods described in WO 2017/029179); 2-[6-(4-bromo(enoxy)-2(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared using the methods described in WO 2017/029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared using the methods described in WO 2016/156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared using the methods described in WO 2016/156290); (4-(enoxy(enyl)methyl 2-amino-6-methylpyridine-3-carboxylate + TX (this compound can be prepared using the methods described in WO 2014/006945); 2,6-dimethyl-1H,5H[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone + TX (this compound can be prepared using the methods described in WO 2011/138281); N-methyl 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide + TX; N-methyl 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (2,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpent-3-enamide + TX (this compound can be prepared using the methods described in WO 2018/153707); N-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine + TX; N-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylformamidine + TX (this compound can be prepared using the methods described in WO 2016/202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared using the methods described in WO 2014/095675); (5-methyl-2-pyridyl)[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (3-methylisoxazol-5-yl)-[4-[5(tri(fluoromethyl)-1,2,4-oxadiazol-3-yl](enyl]methanone + TX (these compounds can be prepared using the methods described in WO 2017/220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl](enyl]acetamide + TX (this compound can be prepared using the methods described in WO 2018/065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (this compound can be prepared using the methods described in WO 2018/158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-methoxy-C-methylcarbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds can be prepared using the methods described in WO 2018/202428), chloroinconazide + TX, (lumethylsul(orimin + TX, (luoxythioconazole + TX, (lu(enoxadiazam + TX, metarylpicoxamide + TX.

References in square brackets following active ingredients, e.g. [3878-19-1], refer to the Chemical Abstracts Service registry number. The above-described ingredients for compounding are known. When active ingredients are included in The Pesticide Manual [The Pesticide Manual - A World Compendium; thirteenth edition; edited by: C. D. S. TomLin; British Crop Protection Council], they are described therein under the entry number given in parentheses above in this document for the specific compound; for example, the compound abamectin is described under registry number (1). When [CCN] is added to a specific compound above in this document, the compound in question is included in the Compendium of Pesticide Common Names, which is available on the Internet [A. Wood, Compendium of Pesticide Common Names, Copyright © 1995-2004], for example, the compound acetoprole is described on the Internet at http://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are listed in this document above under the so-called common name, which corresponds to the common name according to ISO or another common name that is used in individual cases. If the designation

- 29 048372 the name is not the common name, for the specific compound the nature of the designation used instead is given in parentheses; in this case the IUPAC name, the IUPAC/Chemical Abstracts Service name, the chemical name, the traditional name, the compound name or the designation code shall apply or, if none of these designations nor the common name are used, the alternative name shall be used. CAS registry number means the Chemical Abstracts Service registry number.

A mixture of active ingredients in the form of compounds of formula (I), selected from one of the compounds presented in Tables A1 - A5 or Table E (below) is preferably in a mixing ratio of from 100:1 to 1:6000, in particular from 50:1 to 1:50, more in particular in a ratio of from 20:1 to 1:20, even more in particular from 10:1 to 1:10, especially from 5:1 to 1:5, with particular preference given to a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 is similarly preferred, in particular the ratio is 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. These ratios of the mixture components are indicated by weight.

The above-described mixtures can be used in a method for controlling pests, which includes applying a composition containing the above-described mixture to pests or their habitat, with the exception of a method for treating a human or animal body by surgical intervention or therapy and diagnostic methods used in practice with respect to a human or animal body.

Mixtures containing a compound as set forth in Tables A1 to A5 or Table E (below) and one or more active ingredients as described above may be used, for example, in the form of a separate ready-mix, in a combined spray mixture consisting of separate formulations of the individual components constituting the active ingredients, such as a tank mix, and when using the individual active ingredients together, when applied in a sequential manner, i.e. one after the other over an appropriately short period, such as several hours or days. The order of application of the compound as set forth in Tables A1 to A5 or Table E (below) and the active ingredient(s), as described above, is not essential to the practice of the present invention.

The compositions according to the present invention may also contain additional solid or liquid auxiliary substances, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients to provide specific effects, for example bactericides, fungicides, nematicides, plant growth activators, molluscicides or herbicides.

The compositions according to the present invention are prepared by a method known per se, in the absence of auxiliary agents, for example by grinding, sifting and/or pressing the solid active ingredient, and in the presence of at least one auxiliary agent, for example by thoroughly mixing and/or grinding the active ingredient with the auxiliary agent(s). Such methods for preparing the compositions and the use of the compounds (I) for preparing such compositions are also an object of the present invention.

Another aspect of the present invention relates to the use of a compound of formula (I) or a preferred single compound as defined herein, a composition comprising at least one compound of formula (I) or at least one preferred single compound as defined above, or a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred single compound as defined above, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, for example useful plants such as agricultural plants, their propagation material such as seeds, harvested crops such as harvested food crops, or non-living materials by insects or phytopathogenic microorganisms, preferably organisms that are fungi.

A further aspect of the present invention relates to a method for controlling or preventing the infestation of plants, for example useful plants such as agricultural crops, their propagation material, for example seeds, harvested crops, for example harvested food crops, or non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to humans, especially organisms that are fungi, which comprises using a compound of formula (I) or a preferred single compound as defined above as an active ingredient in relation to plants, parts of plants or their locus of growth, their propagation material, or any part of the non-living materials.

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Control or prevention means reducing the level of infestation by insects or phytopathogenic or spoilage microorganisms or organisms potentially harmful to humans, especially fungi, to a level where improvement occurs.

A preferred method for controlling or preventing infection of agricultural crops by phytopathogenic microorganisms, especially fungal or insect organisms, which comprises the use of a compound of formula (I) or an agrochemical composition containing at least one of said compounds, is foliar application.

The frequency of application and the application rate will depend on the risk of infection by the pathogen or insect in question. However, the compounds of formula (I) can also be absorbed into the plant from the soil via the roots (systemic action) by irrigating the growing site of the plant with a liquid formulation or by applying the compounds in solid form to the soil, for example in granular form (soil application). In the case of crops such as water rice, these granules can be applied to the flooded rice field. The compounds of formula (I) can also be applied to the seed (coating) either by impregnating the seed or the tubers with a liquid formulation of the fungicide or by coating them with a solid formulation.

A composition, for example a formulation, comprising a compound of formula (I) and, if appropriate, a solid or liquid excipient or monomers for encapsulating the compound of formula (I) can be prepared in a known manner, typically by thoroughly mixing and/or grinding the compound with excipients, for example solvents, solid carriers and optionally surface-active compounds (surfactants).

The methods of applying the compositions, i.e. the methods of controlling the pests of the above-mentioned type, such as spraying, atomizing, dusting, brushing, coating, scattering or watering, which should be selected to meet the intended objectives in view of the given circumstances, and the use of the compositions for controlling the pests of the above-mentioned type are other objects of the present invention. Typical rates of concentration of the active ingredient are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm. The application rate per hectare is preferably from 1 g to 2000 g of active ingredient per hectare, more preferably from 10 to 1000 g/ha, most preferably from 10 to 600 g/ha. In the case of application as a seed dressing, suitable dosages are from 10 mg to 1 g of active substance per kg of seed.

When the combinations according to the present invention are used for seed treatment, rates of from 0.001 to 50 g of compound of formula (I) per kg of seed, preferably from 0.01 to 10 g per kg of seed, are generally sufficient.

Accordingly, the composition containing the compound of formula (I) according to the present invention is used either for the purpose of prevention, which means use before the development of the disease, or for the purpose of treatment, which means use after the development of the disease.

The compositions of the present invention can be used in any conventional form, for example in the form of a twin pack, a dry seed treatment powder (DS), a seed treatment emulsion (ES), a flowable seed treatment concentrate (FS), a seed treatment solution (LS), a water-dispersible seed treatment powder (WS), a capsule suspension for seed treatment (CF), a seed treatment gel (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspoemulsion (SE), a capsule suspension (CS), water-dispersible granules (WG), emulsifiable granules (EG), a water-in-oil emulsion (EO), an oil-in-water emulsion (EW), a microemulsion (ME), an oil dispersion (OD), an oil-miscible fluid (OF), an oil-miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable excipients.

Such compositions can be prepared in a conventional manner, for example by mixing the active ingredients with appropriate inert formulation components (diluents, solvents, fillers and optionally other formulation ingredients such as surfactants, biocides, antifreeze additives, adhesives, thickeners and compounds that provide auxiliary properties). If a long-term effect is intended, conventional slow-release formulations can also be used. In particular, formulations used in spray form, such as water-dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders and granules, can contain surfactants such as wetting and dispersing agents and other compounds that provide auxiliary properties, such as a condensation product of formaldehyde with naphthalene sulfonate, alkyl aryl sulfonate, lignin sulfonate, alkyl fatty acid sulfate, and ethoxyls

- 31 048372 alkylphenol and ethoxylated fatty alcohol.

The seed dressing composition is applied in a manner known per se for seeds, using the combination of the present invention and a diluent in a suitable form of the seed dressing composition, for example in the form of an aqueous suspension or in the form of a dry powder, characterized by good adhesion to the seeds. Such seed dressing compositions are known from the state of the art. The seed dressing compositions may contain individual active ingredients or a combination of active ingredients in an encapsulated form, for example in the form of capsules or slow-release microcapsules.

Typically, the formulations contain from 0.01 to 90% by weight of the active agent, from 0 to 20% of an agriculturally acceptable surfactant and from 10 to 99.99% of solid or liquid inert formulation components and auxiliary substance(s), the active agent consisting of at least a compound of formula (I) together with component (B) and (C) and optionally other active agents, in particular microbiocides or preservatives or the like. Concentrated forms of the compositions typically contain from about 2 to 80%, preferably from about 5 to 70% by weight of the active agent. Usable forms of the formulation may, for example, contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of the active agent. Since the commercial products will preferably be formulated as concentrates, the end user will in most cases use diluted formulations.

Since commercial products are preferably formulated as concentrates, the end user will in most cases use diluted formulations.

Examples

The following examples serve to illustrate the present invention.

Certain compounds of the present invention may differ from known compounds in that they are more effective at low application rates, as can be verified by one skilled in the art using the experimental procedures set forth in the examples, using lower application rates if necessary, such as 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

The compounds of formula (I) may have a number of advantages, including, inter alia, advantageous levels of biological activity for protecting plants from diseases caused by fungi, or superior properties for use as agrochemical active ingredients (e.g. higher biological activity, advantageous spectrum of activity, improved safety profile (including improved crop tolerance), improved physicochemical properties or improved biodegradability).

Throughout this description, temperatures are in degrees Celsius, and mp means melting point. LC/MS means liquid chromatography with mass spectrometry, and the apparatus and methods are described below.

Examples of compositions.

Wettable powders A) b) With) Active ingredient [compound of formula (I)] 25% 50% 75% Sodium lignosulfonate 5% 5% - Sodium Lauryl Sulfate 3% - 5% Sodium diisobutylnaphthalenesulfonate - 6% 10% Polyethylene glycol phenol ether - 2% - (7-8 mol ethylene oxide) Highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27% -

The active ingredient is thoroughly mixed with the excipients and the mixture is thoroughly ground in a suitable mill to obtain wettable powders which can be diluted with water to obtain suspensions of the required concentration.

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Powders for dry seed treatment a) b) c)

Active ingredient [compound of formula (I)] 25% 50% 75%

Light mineral oil 5% 5%5%

Highly dispersed silicic acid 5% 5% Kaolin 65% 40% Talc -20

The active ingredient is thoroughly mixed with the excipients and the mixture is finely ground in a suitable mill to obtain powders that can be directly applied to seed treatment.

Emulsifiable concentrate

Active ingredient [compound of formula (I)] 10%

Octylphenol ether of polyethylene glycol 3% (4-5 mol ethylene oxide)

Calcium dodecylbenzenesulfonate 3%

Polyglycol ether of castor oil (3.5 mol 4% ethylene oxide)

Cyclohexanone 30%

Xylene mixture 50%

From this concentrate, by diluting with water, it is possible to obtain emulsions of any required degree of dilution, which can be used to protect plants.

Dust preparations a) b) c)

Active ingredient [compound of formula (I)] 5% 6% 4%

Talc 95% - Kaolin - 94% Mineral filler - - 96%

Ready-to-use dust preparations are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry seed dressing.

Extruded granules

Active ingredient [compound 15% of formula (I)]

Sodium lignosulfonate 2%

Carboxymethylcellulose 1%

Kaolin 82%

The active ingredient is mixed and ground with the excipients, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Coated granules

Active ingredient [8% compound of formula (I)]

Polyethylene glycol (molecular weight 3%)

200)

Kaolin 89%

The finely ground active ingredient is uniformly applied to polyethyleneglycol-moistened kaolin in a mixing device. In this way, non-dusting coated granules are obtained.

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Suspension concentrate

Active ingredient [compound of formula (I)] 40%

Propylene glycol 10%

Polyethyleneglycol ether of nonylphenol (15 mol 6% ethylene oxide)

Sodium lignosulfonate 10%

Carboxymethylcellulose 1%

Silicone oil (as 75% emulsion in water) 1%

Water 32%

The finely ground active ingredient is thoroughly mixed with the excipients to form a suspension concentrate, from which suspensions of any desired dilution can be obtained by diluting with water. Using such diluted solutions, living plants and plant propagation material can be treated and protected from contamination by microorganisms by spraying, watering or immersion.

Flowable concentrate for seed treatment

Active ingredient [compound of formula (I)] 40%

Propylene glycol 5%

Copolymer of butanol and PO/EO 2%

Tristyrenephenol with 10-20 mol EO 2%

1,2-Benzisothiazolin-3-one (as a 20% solution in water) 0.5%

Calcium salt of monoazo pigment 5%

Silicone oil (as 75% emulsion in water) 0.2%

Water 45.3%

The finely ground active ingredient is thoroughly mixed with excipients to obtain a suspension concentrate, from which suspensions of any desired degree of dilution can be obtained by diluting with water. Using such diluted solutions, living plants and plant propagation material can be treated and protected from contamination by microorganisms by spraying, watering or immersion. Slow-release capsule suspension

28 parts of a combination of compound of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a mixture of toluene diisocyanate/polymethylene polyphenylisocyanate (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoaming agent and 51.6 parts of water until the particles of the required size are obtained. To this emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is shaken until the polymerization reaction is complete.

The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The composition of the capsule suspension contains 28% of active ingredients. The average diameter of the capsules is 8-15 µm.

The resulting composition is applied to seeds in the form of an aqueous suspension in a device suitable for this purpose.

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List of abbreviations.

Aq = water Ag = argon br s = wide singlet _CaSO4 = calcium sulfate

CataCXium A Pd G3 = mesylate[(di(1-adamantyl)-n-butylphosphine)-2-(2'-amino-1,G-

CDC1 ₃ biphenyl)] palladium(P) = chloroform-d °C = degrees Celsius DCM = dichloromethane dd = doublet of doublets DMF = dimethylformamide d = doublet EtOAc = ethyl acetate equiv. = equivalent h. = hour(hours) NS1 = hydrochloric acid M = molar T = multiplet _MgSO4 = magnesium sulfate min = minutes MHz = megahertz t. pl. = melting point _NaHCO3 = sodium bicarbonate NaOH = sodium hydroxide _NH4C1 = ammonium chloride _PdCl2 (dtbpf) = [1,1'-bis(d-/77/?s/77-butylphosphino)ferrocene] dichloropalladium(II) PPm = parts per million k.t. = room temperature Rt = retention time 5 = singlet t = triplet TBME = /77/7C/77-BUTYL METHYL ether THF = tetrahydrofuran LC/MS = liquid chromatography with mass spectrometry (description of the device and methods used for LC/MS analysis are given above)

Examples of receipt.

Example A1. 7,8-Dichloro-4-(8-fluoro-3-quinolyl)-2,2-dimethyl-1,3-benzothiazine (compound E.05).

Stage 1.

A solution of 2-trimethylsilylethanethiol (0.50 g, 3.72 mmol) in THF (35 mL) was treated with triethylamine (0.38 g, 3.72 mmol) and n-toluenesulfonyl chloride (0.36 g, 1.86 mmol) at 0-5 °C. The resulting mixture was stirred for 45 min at 0-5 °C, diluted with DCM and washed with aq.

- 35 048372

HCl (1 M). The organic layer was washed with aq. NaHCO ₃ and brine, dried over MgSO ₄ , filtered and concentrated in vacuo. The residual oil was filtered through a short pad of silica gel (eluent: cyclohexane) to give trimethyl-[2-(2-trimethylsilylethyldisulfanyl)ethyl]silane as a colorless liquid.

1H NMR (400 MHz, CDC13) δ ppm: 2.68 - 2.83 (m, 4 H) 0.86 - 1.07 (m, 4 H) 0.05 (s, 18 H).

Stage 2.

To a solution of 3,4-dichlorobenzoic acid (0.14 g, 0.73 mmol) in tetrahydrofuran (4 mL) cooled at -70 °C was added n-butyl lithium (2.5 mol/L in hexane, 0.88 mL, 2.20 mmol) dropwise under argon. The solution was stirred for 2 h at -70 °C before adding trimethyl-[2-(2-trimethylsilylethyldisulfanyl)ethyl]silane (0.39 g, 1.47 mmol) in THF (5 mL). The reaction mixture was gradually warmed to rt over 4 h, diluted with TBME and extracted with H ₂ O. The aq. layer was acidified with HCl (2 M) to pH 1 and extracted with TBME. The organic layer was washed with water, dried over _MgSO4 , filtered and concentrated under reduced pressure. The residual solid was suspended in DCM, the undissolved solids were removed by filtration and the filtrate was concentrated under reduced pressure to give 3,4-dichloro-2-(2-trimethylsilylethylsulfanyl)benzoic acid as a white solid.

LC-MS (Method G), Rt = 1.18 min, (M-H) = 321.

^1H NMR (400 MHz, CDCl ₃ ) δ ppm: 8.06 (d, 1H), 7.63 (br d, 1H), 3.00-3.08 (m, 2H), 0.85-0 .94 (m, 2H), 0.03 (s, 9H).

Stage 3.

To a solution of 3,4-dichloro-2-(2-trimethylsilylethylsulfanyl)benzoic acid (0.18 g, 0.56 mmol) in toluene (1 mL) was added a drop of DMF and thionyl chloride (0.09 mL, 1.22 mmol) at rt. The reaction mixture was heated to 70 °C and maintained at this temperature for 2 h. All volatiles were then removed under reduced pressure, the residue was taken up in dioxane (0.6 mL) and ammonia (25% in water) (0.52 mL, 7.23 mmol) was slowly added at rt. The reaction mixture was stirred at rt for 45 min, diluted with water and extracted with EtOAc. The organic phase was washed with brine, dried over MgSO4, filtered and concentrated. The residue was purified by flash chromatography (silica gel, cyclohexane:EtOAc) to give 3,4-dichloro-2-(2-trimethylsilylethylsulfanyl)benzamide as a beige solid.

LC-MS (Method G), R _t = 1.10 min.

1H NMR (400 MHz, CDCl ₃ ) δ ppm: 7.67 (d, 1H), 7.53 (d, 1H), 7.10 (br s, 1H), 5.89 (br s, 1H), 2.91-3.09 (m, 2H), 0.82-0.92 (m, 2H), 0.02(s,9H).

Stage 4.

To a solution of 3,4-dichloro-2-(2-trimethylsilylethylsulfanyl)benzamide (0.08 g, 0.25 mmol) in THF (1 mL) was added tetrabutylammonium fluoride (1 M in THF, 0.74 mL, 0.74 mmol) at rt. The solution was stirred for 20 min at rt and then diluted with aq. HCl (1 M). The mixture was extracted with EtOAc, the organic phase was washed with brine, dried over _MgSO4 , filtered and concentrated. The residue was purified by flash chromatography (silica gel, cyclohexane:EtOAc) to afford 3,4-dichloro-2-sulfanylbenzamide as an orange solid.

LC-MS (Method G), Rt = 0.82 min, (M+H) = 222.

1H NMR (400 MHz, CDCl ₃ ) δ ppm = 7.41 (d, 1H), 7.31 (d, 1H), 6.22 (s, 1H), 5.72 (br s, 2H).

Stage 5.

A suspension of 3,4-dichloro-2-sulfanylbenzamide (0.03 g, 0.14 mmol), 2,2-dimethoxypropane (0.03 mL, 0.27 mmol), n-toluenesulfonic acid (1 small crystal), and 4 A molecular sieves in toluene (0.5 mL) was stirred for 18 h at 80 °C. The reaction mixture was cooled to rt, diluted with EtOAc, and the solids were removed by filtration. The filtrate was washed with water and brine, dried over MgSO ₄ , filtered, and concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, cyclohexane:EtOAc) to give 7,8-dichloro-2,2-dimethyl-3H-1,3-benzothiazin-4-one as an orange gum.

LC-MS (Method G), Rt = 0.99 min, (M+H) = 262.

1H NMR (400 MHz, CDCl ₃ ) δ ppm = 8.06 (d, 1H), 7.39 (d, 1H), 6.17 (br s, 1H), 1.77 (s, 6H).

Stage 6.

A solution of DMF (0.02 mL, 0.23 mmol) in DCM (0.2 mL) at 0 °C was treated with oxalyl chloride (0.014 mL, 0.15 mmol) and the resulting white suspension was stirred at 0 °C for 1 h. Then a solution of 7,8-dichloro-2,2-dimethyl-3H-1,3-benzothiazin-4-one (0.02 g, 0.076 mmol) in DCM (0.2 mL) was added to the suspension and the reaction mixture was allowed to warm to rt. After 40 min, LC-MS indicated complete conversion. The reaction mixture was diluted with DCM and poured onto a mixture of ice and aq. NaHCO ₃ . The mixture was extracted with DCM and the organic phase was dried over _MgSO4 , filtered and concentrated under reduced pressure to give 4,7,8-trichloro-2,2-dimethyl-1,3-benzothiazine (LC-MS (method G), Rt = 1.25 min, (M+H) = 282), which was used as received for the coupling reaction.

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To a degassed solution of 8-fluoro-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinoline (0.027 g, 0.09 mmol, 1.1 equiv.) and 4,7,8-trichloro-2,2-dimethyl-1,3-benzothiazine (0.02 g, 0.089 mmol) in DMF (0.4 mL) were added K ₃ PO ₄ (0.06 g, 0.27 mmol) and CataCXiumA Pd G3 (0.007 g, 0.009 mmol). The resulting mixture was heated to 60 °C and stirred for 20 min at this temperature. The reaction mixture was cooled to rt, diluted with EtOAc and washed with aq. NH4Cl. The organic phase was washed with brine, dried over _MgSO4 , filtered and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, cyclohexane:EtOAc) to give 7,8-dichloro-4-(8-fluoro-3-quinolyl)-2,2-dimethyl-1,3-benzothiazine as an orange solid.

LC-MS (Method G), Rt = 1.25 min, (M+H) =391.

¹ H NMR (400 MHz, CDC13) δ ppm: ¹ H NMR (1-CDCl ₃ ) δ: 9.07 (d, 1H), 8.33 (t, 1H), 7.69 (d, 1H), 7.407.61 (m, 2H), 7.27 (d, 1H), 7.16 (d, 1H), 1.75 (s, 6H).

¹⁹ F NMR (1-CDC13) δ: -124.91 (s).

Example A2. 8-Chloro-4-(8-fluoro-3-quinolyl)-2,2-dimethyl-1,3-benzothiazine (compound E.02).

Stage 1.

To _an ice-cooled solution of 2,3-dichlorobenzonitrile (3.0 g, 17.44 mmol) in DMSO (15 mL) were added K2CO3 (0.49 g, 3.49 mmol) and _H2O2 (30% in _H2O , 2.7 mL, 26.16 mmol). The reaction mixture was gradually warmed to rt and stirred for 2 h at this temperature. Ice water was then added and the precipitate was collected by filtration. Drying under reduced pressure gave 2,3-dichlorobenzamide.

LC-MS (Method Gl), Rt = 0.84 min, (M+H) = 190.

1H NMR (400 MHz, DMSO) δ ppm = 7.98 (br s, 1H), 7.70-7.76 (m, 1H), 7.61-7.69 (m, 1H), 7.36 -7.43 (m, 2H).

Stage 2.

A solution of sodium sulfide (2.49 g, 31.6 mmol) in 1-methyl-2-pyrrolidine (150 mL) was heated for 2 h at 190 °C under a gentle stream of nitrogen. The resulting solution was cooled to 130 °C, 3-chloro-2-sulfanylbenzamide (5.0 g, 26.3 mmol) was added, and the mixture was heated to 175 °C and maintained at this temperature for 4 h. The mixture was then cooled to 70 °C and MgSO ₄ (3.23 g, 26.3 mmol), n-toluenesulfonic acid (5.50 g, 28.9 mmol), and 2,2-dimethoxypropane (17 mL, 131 mmol) were added. The resulting suspension was heated to 100 °C and stirred for 16 h at this temperature. The reaction mixture was cooled to rt, water was added and the mixture was acidified with aq. HCl (2 M). The resulting emulsion was extracted with EtOAc, the organic phase was washed with brine, dried over _MgSO4 , filtered and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, cyclohexane:EtOAc) to afford 8-chloro-2,2-dimethyl-3H-1,3-benzothiazin4-one as a yellow solid.

LC-MS (method G1), Rt = 1.02 min, (M+H) = 228.

1H NMR (400 MHz, CDCl ₃ ) δ ppm: 8.1 (dd, 1H), 7.51 (dd, 1H), 7.22 (t, 1H), 6.91 (br s, 1H), 1 .75 (s, 6H).

Stage 3.

A solution of DMF (0.06 mL, 0.79 mmol) in DCM (1.5 mL) at 0 °C was treated with oxalyl chloride (0.07 mL, 0.79 mmol). The resulting white suspension was stirred at 0 °C for 1 h. Then a solution of 8-chloro-2,2-dimethyl-3H-1,3-benzothiazin-4-one (0.100 g, 0.44 mmol) in DCM (1 mL) was added to the suspension at 0 °C and the mixture was gradually warmed to rt. After 2 h, LC-MS indicated complete conversion. The reaction mixture was diluted with DCM and poured onto a mixture of ice and aq. NaHCO3. The mixture was extracted with DCM and the organic phase was dried over _MgSO4 , filtered and concentrated under reduced pressure to give 4,8-dichloro-2,2-dimethyl-1,3-benzothiazine (LC-MS (method Gl), _Rt = 1.26 min, (M+H) = 246), which was used as received for the coupling reaction.

To a degassed solution of (8-fluoro-3-quinolyl)boronic acid (0.10 g, 0.53 mmol) and 4,8-dichloro-2,2-dimethyl-1,3-benzothiazine (0.118 g, 0.44 mmol) in DMF (2 mL) were added K3PO4 (0.31 g, 1.44 mmol) and _PdCl2 (dtbpf) (0.016 g, 0.024 mmol). The resulting mixture was heated to 60 °C and stirred for 1 h at this temperature. The reaction mixture was cooled to rt and partitioned between ice water and EtOAc. The organic phase was washed with brine, dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (silica gel, cyclohexane:EtOAc) to give 8-chloro-4-(8-fluoro-3-quinolyl)-2,2-dimethyl-1,3-benzothiazine as a beige solid.

LC-MS (method G1), R _t = 1.27 min, (M+H) = 357.

1H NMR (400 MHz, CDCl ₃ ) δ ppm: 9.07 (d, 1 H), 8.35 (t, 1 H), 7.69 (d, 1 H), 7.48 -7.60 ( m, 3 N), 7.20 (dd, 1 N), 7.11 (t, 1 N), 1.75 (s, 6 N).

¹⁹ F NMR (i-CDC1 ₃ ) δ: -125.08 (s).

Analytical methods.

Method G.

Spectra were recorded on a Waters mass spectrometer (single quadrupole mass spectrometer)

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SQD, SQDII) equipped with an electrospray source (polarity: positive and negative ions), capillary voltage: 3.00 kV, cone voltage range: 30 V, extractor voltage: 2.00 V, source temperature: 150 °C, desolvation temperature: 350 °C, cone gas flow rate: 50 L/h, desolvation gas flow rate: 650 L/h, mass range: from 100 to 900 Da), and Waters Acquity UPLC: binary pump, heated column compartment, diode array detector, and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30x2.1 mm, temp.: 60 °C, DAD wavelength range (nm): from 210 to 500; solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH: gradient: 10-100% B in 1.2 min; flow rate (ml/min) 0.85.

Method G1.

The spectra were recorded on a Waters mass spectrometer (SQD single quadrupole mass spectrometer, SQDII) equipped with an electrospray source (polarity: positive and negative ions), capillary voltage: 0.8 kV, cone voltage range: 25 V, source temperature: 120 °C, desolvation temperature: 600 °C, cone gas flow rate: 50 L/h, desolvation gas flow rate: 1000 L/h, mass range: from 110 to 850 Da), and an Acquity UPLC from Waters: a pump for two-component mixtures, a heated column compartment, a diode array detector, and an ELSD detector. Column: Waters UPLC HSS T3 C18, 1.8 µm, 30x2.1 mm, temp.: 40°C, wavelength range DAD (nm): from 230 to 400, solvent gradient: A = water + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH, gradient: 10-100% B in 1.6 min; flow rate (ml/min) 0.60.

Method H1.

Spectra were recorded on a Waters Acquity UPC2/QDa SFC system with detection on a Waters Acquity UPC ² PDA detector. Column: Daicel SFC CHIRALPAK® IE, 3 mm, 0.3 cm x 0 cm, 40°C, mobile phase: A: CO ₂ , B: 2-propanol, isocratic mode: 15% B over 4.8 min, ABPR: 1800 psi, flow rate: 2.0 mL/min, detection: at 240 nm; sample concentration: 1 mg/mL in methanol/2-propanol, injection volume: 2 µL.

Table E

Melting point (mp) and/or LC/MS data (retention time (Rt)) for compounds of formula (I)

Element Name according to the SHRAS list

RT [M+H] Method mp.

(min) (measured) (°C)

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E.06

E.07

E.08

E.09

E.10

E.ll

E.12

E.13

4-(8-fluoro-3-quinolyl)2,2,7,8-tetramethyl1,3-benzothiazine

4-(8-fluoro-3-quinolyl)2,2,7-trimethyl-1,3benzothiazine-8carbonitrile

8-fluoro-4-(8-fluoro-3quinolyl)-2,2,7-trimethyl-1,3-benzothiazine

8-chloro-4-(8-fluoro-3-quinolyl)-2,2,7-trimethyl-1,3-benzothiazine

8-chloro-4-(8-fluoro-3-quinolyl)-2,2-dimethyl-1,3-benzothiazine (27?)-2(difluoromethyl)-4-(8-fluoro-3-quinolyl)-2,8-dimethyl-1,3-benzothiazine (27?)-2(difluoromethyl)-4-(8-fluoro-3-quinolyl)-2,8-dimethyl-1,3-benzothiazine

8-chloro-2(difluoromethyl)-4-(8-fluoro-3-quinolyl)-2methyl-1,3-benzothiazine

.52 .18 .17 .09 .21 .19 .23 '.85

355

393

362

351

357

371

Hl

Hl

159

161

158

160

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Mycosphaerella graminicola (Septoria tritici) on wheat/warning.

Two-week-old Riband wheat plants were sprayed in a spray chamber with a mixture of

4-(7,8-difluoro-3-quinolyl)-2,2,8-trimethyl-1,3-enzothiazine-7-carbonitrile

7-chloro-4-(7,8-difluoro3-quinolyl)-2,2,8grimethyl-1,3oenzothiazine

7-chloro-4-(8-fluoro-3quinolyl)-8-methoxy2,2-dimethyl-1,3oenzothiazine

7-chloro-4-(8-fluoro-3-quinolyl)-2,2,8-trimethyl-1,3-enzothiazine

4-(7,8-difluoro-3quinolyl)-8-fluoro2,2,7-trimethyl-1,3oenzothiazine

8-chloro-2-|(6-chloro-3pyridyl)methyl I -4(7,8-difluoro-Zquinolyl)-2-methyl-1,3oenzothiazine

8-chloro-2-|(6-chloro-3pyridyl)methyl I -4-(8fluoro-3-quinolyl)-2methyl-1,3oenzothiazine

8-chloro-4-(8-fluoro-2methyl-3-quinolyl)-2,2-dimethyl-1,3-enzothiazine

4-(8-fluoro-3-quinolyl)2,2,8-trimethyl-1,3oenzothiazine

2-(difluoromethyl)-4-(8fluoro-3-quinolyl)-2,8dimethyl-1,3oenzothiazine

4-(8-fluoro-3-quinolyl)2,2,8-trimethyl oenzothiazine-7carbonitrile

8-chloro-4-(5fluoroquinoxalin-2yl)-2,2-dimethyl-1,3oenzothiazine

- 40 048372 test compound diluted in water. Test plants were inoculated by spraying with the spore suspension one day after spray application and then maintained at 22°C/21°C (day/night) in a greenhouse. Disease damage was assessed directly when the corresponding disease level occurred on untreated control plants and efficacy was calculated in comparison with untreated controls (16-19 days after the specified application).

The following compounds listed in Table E (above) provided at least 80% control of Mycosphaerella graminicola at 60 ppm compared to the untreated control under the same conditions, which showed extensive disease development:

E.01, E.02, E.03, E.05, E.08, E.11, E.12, E.13, E.14, E.16, E.25.

Fusarium culmorum/liquid culture (fusarium).

Fungal conidia from cryogenic storage were directly mixed with nutrient broth (potato dextrose broth, PDB). After adding the solution (DMSO) of the test compound to the microtiter plate (96-well format), nutrient broth containing fungal spores was added. The plates with the test compounds were incubated at 24°C and growth inhibition was determined photometrically 3-4 days after the specified application.

The following compounds in Table E (above) resulted in at least 80% control of Fusarium culmorum at 20 ppm compared to the untreated control under the same conditions, which showed widespread disease:

E.03, E.04, E.05, E.06, E.07, E.08, E.09, E.10, E.11, E.12, E.13, E.14, E. 15, E.16, E.17, E.19, E.21, E.23, E.24, E.25.

Fusarium culmorum/wheat/prevention of ear infection (fusarium).

Spikelets of Monsun wheat cultivars were plated on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. Spikelets were inoculated with the fungal spore suspension 1 day after the specified application. The inoculated spikelets were incubated at 20°C and 60% relative humidity under a light/darkness regime of 72 h/dark followed by 12 h/light/12 h/dark in a climate chamber and compound activity was assessed as a percentage of disease control compared to untreated material when the corresponding degree of disease damage was demonstrated on untreated control spikelets (6-8 days after the specified application).

The following compounds in Table E (above) resulted in at least 80% control of Fusarium culmorum at 200 ppm compared to the untreated control under the same conditions, which showed widespread disease:

E.05, E.06, E.08, E.14, E.15, E.19.

Monographella nivalis (Microdochium nivale)/liquid culture (root rot of cereals).

Fungal conidia from cryogenic storage were directly mixed with nutrient broth (potato dextrose broth, PDB). After adding the solution (DMSO) of the test compound to the microtiter plate (96-well format), nutrient broth containing fungal spores was added. The plates with the test compounds were incubated at 24°C and growth inhibition was determined photometrically 4-5 days after the specified application.

The following compounds in Table E (above) resulted in at least 80% control of Monographella nivalis at 20 ppm compared to the untreated control under the same conditions, which showed widespread disease:

E.03, E.04, E.05, E.06, E.07, E.08, E.09, E.11, E.12, E.13, E.14, E.15, E. 16, E.17, E.18, E.19, E.20, E.21, E.23, E.24.

Botryotinia fuckeliana (Botrytis cinerea)/liquid culture (gray rot).

Fungal conidia from cryogenic storage were directly mixed with nutrient broth (Vogel broth). After adding the solution (DMSO) of the test compound to the microtiter plate (96-well format), nutrient broth containing fungal spores was added. The plates with the test compound were incubated at 24°C and growth inhibition was determined photometrically 3-4 days after the specified application.

The following compounds provided at least 80% control of Botryotinia fuckeliana at 20 ppm compared to the untreated control under the same conditions, which showed extensive disease development:

E.01, E.02, E.03, E.04, E.05, E.06, E.07, E.08, E.09, E.10, E.11, E.12, E. 13, E.14, E.15, E.16, E.17, E.18, E.19, E.20, E.21, E.22, E.23, E.24, E.25.

Glomerella lagenarium (Colletotrichum lagenarium)/liquid culture (anthracnose).

Fungal conidia from cryogenic storage were directly mixed with nutrient broth (potato dextrose broth, PDB). After adding the solution (DMSO) of the test compound to the microtiter plate (96-well format), nutrient broth containing fungal spores was added. The test plates were incubated at 24°C and growth inhibition was measured photometrically 3-4 days after the specified application.

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The following compounds provided at least 80% control of Glomerella lagenarium at 20 ppm compared to the untreated control under the same conditions, which showed extensive disease development:

E.01, E.02, E.03, E.04, E.05, E.06, E.07, E.08, E.09, E.11, E.12, E.13, E. 14, E.15, E.17, E.18, E.19, E.20, E.25.

Comparative examples.

Mycosphaerella graminicola (Septoria tritici) on wheat/warning.

Two-week-old Riband wheat plants were sprayed in a spray chamber with a test compound formulated as an emulsifiable concentrate diluted in water. Test plants were inoculated by spraying with the spore suspension one day after the specified application and then maintained at 22°C/21°C (day/night) in a greenhouse. Disease damage was assessed directly when the corresponding disease level appeared on untreated control plants and efficacy was calculated relative to untreated controls (16-19 days after the specified application).

Connection Norm of application (RRt) Efficiency (control, %) Comparative compound A (compound 1b-69 according to WO 2009/119089) rUU F 60 11 Compound E.12 (according to the present invention) 60 92 Compound E.13 (according to the present invention) 60 96 Compound E.01 (according to the present invention) 60 72 Compound E.02 (according to the present invention) 60 99 Compound E.08 (according to the present invention) 60 89 Compound E.14 (according to the present invention) 60 83

Botrytis cinerea/tomato/warning (Botrytis on tomato).

Four-week-old tomato plants were treated by spraying in a spray chamber with a test compound formulated as an emulsifiable concentrate diluted in water. Test plants were inoculated by spraying with a spore suspension two days after the specified application. Inoculated test plants were incubated at 20°C and 95% relative humidity in a greenhouse and the percentage of leaf area covered by disease was assessed when the corresponding level of disease was observed on untreated control plants (5-6 days after the specified application).

Connection Norm of application (RRt) Efficiency (control, %) Comparative compound A (compound 1b-69 according to WO 2009/119089) F 200 95

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Connection by invention) E.12 (V in accordance With presently 200 95 Connection by invention) E.01 (V in accordance With presently 200 97 Connection by invention) E.02 (V in accordance With presently 200 95 Connection by invention) E.08 (V in accordance With presently 200 97 Connection by invention) E.14 (V in accordance With presently 200 93

Venturia inaequalis/apple tree/warning (apple scab).

Three-week-old apple seedlings were sprayed in a spray chamber with the test compound formulated as an emulsifiable concentrate diluted in water. The test plants were inoculated by spraying with the spore suspension 1 day after the specified application. After an incubation period of 2 days at 20°C and 95% relative humidity, the inoculated test plants were placed in a greenhouse at 20°C/19°C (day/night) and 60% relative humidity. The leaf area covered by the disease, expressed as a percentage, was assessed when the corresponding disease level appeared on the untreated control plants (11-13 days after the specified application).

Connection Application rate (ppm) Efficiency (control, %) Comparative compound A (compound 1b-69 according to WO 2009/119089) N'^'S F 200 100 Compound E.12 (according to the present invention) 200 100 Compound E.01 (according to the present invention) 200 97 Compound E.02 (according to the present invention) 200 97 Compound E.08 (according to the present invention) 200 80 Compound E.14 (according to the present invention) 200 100

Colletotrichum lagenarium/cucumber/warning (anthracnose).

One-week-old plants of cucumber cultivar Wisconsin were sprayed in a spray chamber with the test compound formulated as an emulsifiable concentrate diluted in water. The test plants were inoculated by spraying them with the spore suspension one day after the specified application. After an incubation period of 30 h in the dark at 23°C and 100% relative humidity, the inoculated test plants were maintained in a greenhouse at 23°C/21°C (day/night) and 70% relative humidity. The leaf area covered by the disease, expressed as a percentage, was assessed when the corresponding level of disease appeared on untreated control plants (6-8 days after the specified application).

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Connection Norm of application (RRt) Efficiency (control, %) Comparative compound A (compound 1b-69 according to WO 2009/119089) F 200 80 Compound E.12 (according to the present invention) 200 100 Compound E.01 (according to the present invention) 200 97 Compound E.02 (according to the present invention) 200 97 Compound E.14 (according to the present invention) 200 97

In the above comparative experimental examples for selected compounds according to the present invention, it is shown that their control on Mycosphaerella graminicola (Septoria tritici) is significantly superior to the control achieved using compounds from the prior art (WO 2009/119089).

Additionally, the above comparative examples demonstrate that the compounds of the present invention exhibit excellent control of Mycosphaerella graminicola (Septoria tritici) without adversely affecting the control of a number of other diseases by prior art compounds.

Claims (7)

1. Compound of formula (I) where R ¹ is fluorine; R ² represents hydrogen or fluorine; R ³ represents hydrogen or methyl; R ⁴ is C1-C ₄ alkyl, C1-C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl or (6-chloropyridin-3yl)methyl and R ⁵ represents hydrogen or methyl; R ⁶ represents chlorine, bromine, iodine, methyl, ethyl, methylsulfanyl, cyano, difluoromethyl, trifluoromethyl, methoxy, ethoxy, cyclopropyl, cyclobutyl and R ⁷ represents hydrogen, chlorine, methyl or R ⁶ is fluorine, and R ⁷ is halogen or C1-C ₄ alkyl and A represents N or CH. 2. The compound according to claim 1, wherein R ⁶ is fluorine and R ⁷ is methyl. 3. An agrochemical composition containing a fungicidally effective amount of a compound according to claim 1 or 2. 4. The composition according to claim 3, further comprising at least one additional active ingredient and an agrochemically acceptable diluent or carrier. 5. A method for monitoring or preventing infection of useful plants with phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound according to claim 1 or 2 or a composition containing this compound as an active ingredient is applied to plants, their parts or their place of growth. - 44 048372 6. The method according to claim 5, wherein the phytopathogenic microorganism is Mycosphaerella graminicola, and the beneficial plant is cereals, in particular wheat. 7. Use of a compound according to claim 1 or 2 as a fungicide.