EA045799B1 - MICROBIOCIDAL THIAZOLE DERIVATIVES - Google Patents

Description

The present invention relates to microbiocidal thiazole derivatives, such as active ingredients, for example, which have microbiocidal activity, in particular fungicidal activity. The present invention also relates to the preparation of such thiazole derivatives, to agrochemical compositions that contain at least one of the thiazole derivatives, and to applications of thiazole derivatives or compositions based thereon in agriculture or horticulture for the control or prevention of infection of plants harvested from food crops. crops, seeds or non-living materials by phytopathogenic microorganisms, mainly fungi.

WO 2010/012793 and WO 2017/207362 describe thiazole derivatives as pesticides.

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

Fhn^

N where Y represents C-F, C-H or N;

R ¹ represents hydrogen, halogen, cyano, ^-^-alkyl, C ₁ -C 4 -alkoxy, C ₁ -C ₄ -haloalkyl or HC(O)NH-;

R ² represents C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy, C3-C8-cycloalkyl, C3-C8cycloalkyl-C1-C2-alkyl (where the cycloalkyl groups are optionally substituted by 1-3 groups represented by R ³ ), phenyl, phenyl-C1- _C2- alkyl (where the phenyl rings are optionally substituted with 1-3 groups represented by ^R3 ), heteroaryl, heteroaryl- _C1 - _C2 -alkyl, where heteroaryl is a 5- or 6- a membered aromatic monocyclic ring containing 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur, heterocyclyl, heterocyclyl-C ₁ -C ₂ -alkyl, where heterocyclyl is a 4-, 5- or 6-membered a non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, or a 5-12 membered non-aromatic spirocyclic carbobi- or carbothricyclyl ring system optionally containing 1, 2, 3, 4 or 5 heteroatoms, separately selected from nitrogen, oxygen and sulfur, and wherein each spirocyclic carbobi- or carbothricyclyl ring system is optionally linked to the rest of the molecule by a C ₁ -C ₂ -alkylene linker;

R ³ is halogen, C ₁ -C ₄ -alkyl _, C ₁ -C ₄ -alkoxy, C ₁ -C 4 -haloalkyl, C ₃ -C ₈ -cycloalkyl or C ₃ -C ₈ -cycloalkyl-C ₁ -C ₂ -alkyl;

X represents N or CH;

or a salt or N-oxide thereof.

Surprisingly, it has been found that the new compounds of formula (I) have, for practical purposes, a very effective level of biological activity for protecting plants from diseases that are caused by fungi.

Moreover, it has been discovered that the new compounds of formula (I) may exhibit improved solubility properties (particularly in non-polar solvents) and/or light stability properties compared to their corresponding free amines (i.e. where the nitrile group at the nitrogen atom is replaced hydrogen), which are known, for example, from WO 2017/207362.

In accordance with a second aspect of the present invention, there is provided an agrochemical composition containing a fungicidal effective amount of a compound of formula (I) in accordance with the present invention. Such a composition for agricultural use may further contain at least one additional active ingredient and/or an agrochemically acceptable diluent or carrier.

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

According to a fourth aspect of the present invention, there is provided the use of a compound of formula (I) as a fungicide. In accordance with this particular aspect of the present invention, use may or may not include methods of treating a human or animal body through surgery or therapy.

When substituents are stated to be optionally substituted, this means that they may or may not carry one or more identical or different substituents, e.g.

- 1 045799 one, two or three substituents R ³ . For example, C ₁ -C ₆ -alkyl substituted with 1, 2 or 3 halogen atoms may include, without limitation, the groups -CH ₂ Cl, -CHCl ₂ , -CCl ₃ , -CH2F, -CHF2, -CF ₃ , -CH ₂ CF ₃ or -CF ₂ CH ₃ .

As another example, C ₁ -C ₆ -alkoxy substituted with 1, 2 or 3 halogen atoms may include, without limitation, the groups CH ₂ ClO-, CHCl ₂ O-, CCl ₃ O-, CH2FO-, CHF2O-, CF ₃ O-, CF3CH2O- or CH3CF2O-.

As used herein, the term cyano refers to a -CN group.

As used herein, the term halogen means fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo).

As used herein, the term C ₁ -C ₈ -alkyl means a straight or branched hydrocarbon radical consisting solely of carbon and hydrogen atoms, free of unsaturation, containing from one to eight carbon atoms and which is attached to the rest of the molecule by single connection. The terms C ₁ -C ₆ alkyl, C ₁ -C4 alkyl and C1C ₃ alkyl should be construed accordingly. Examples of C ₁ -C ₈ -alkyl include, but are not limited to, methyl, ethyl, n-propyl and isomers thereof, eg isopropyl. A C ₁ -C ₆ alkylene group means the corresponding definition of a C ₁ -C6 alkyl, except that such a radical is attached to the rest of the molecule by two single bonds. The term C ₁ -C ₂ -alkylene should be interpreted accordingly. Examples of C ₁ -C ₆ -alkylene include, but are not limited to, -CH2-, -CH2CH2, and -( _CH2 ) _3- .

As used herein, the term C ₁ -C ₈ -haloalkyl means a C ₁ -C ₈ -alkyl radical as generally defined above, substituted by one or more of the same or different halogen atoms. Examples of C ₁ -C ₈ -haloalkyl include, but are not limited to, trifluoromethyl.

As used herein, the term C ₁ -C ₈ -alkoxy means a radical of the formula -OR _a where R _a is a C ₁ -C ₈ -alkyl radical as generally defined above. The terms C1-C6 alkoxy, C ₁ -C4 alkoxy and C ₁ -C ₃ alkoxy should be construed accordingly. Examples of C ₁ -C ₈ -alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (isopropoxy) and propoxy.

As used herein, the term C ₃ -C ₆ -cycloalkyl means a radical that is a monocyclic saturated ring system and that contains 3-6 carbon atoms. The term C ₃ -C ₄ -cycloalkyl should be interpreted accordingly. Examples of C ₃ -C ₆ -cycloalkyl include, but are not limited to, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 1,1-dimethylcyclobutyl, 2-methylcyclobutyl and 2,2-dimethylcyclobutyl.

As used herein, the term C ₃ -C ₆ -cycloalkyl-C ₁ -C ₂ -alkyl means a C ₃ -C ₆ cycloalkyl ring attached to the remainder of the molecule by a C ₁ -C ₂ -alkylene linker as defined above.

As used herein, the term phenyl-C ₁ -C ₂ -alkyl means a phenyl ring attached to the remainder of the molecule by a C ₁ -C ₂ -alkylene linker as defined above. Examples of phenyl-C ₁ -C ₂ -alkyl include, but are not limited to, benzyl and 1-phenylethyl.

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

As used herein, the term heteroaryl-C ₁ -C ₂ -alkyl means a heteroaryl ring attached to the remainder of the molecule by a C ₁ -C ₂ -alkylene linker as defined above.

As used herein, the term heterocyclyl means a stable 4-, 5-, or 6-membered non-aromatic monocyclic ring that contains 1, 2, or 3 heteroatoms, where the heteroatoms are individually selected from nitrogen, oxygen, and sulfur. The heterocyclyl radical may be linked to the rest of the molecule through a carbon atom or a heteroatom. Examples of heterocyclyl include, but are not limited to, aziridinyl, azetidinyl, oxetanyl, thietanyl, tetrahydrofuryl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, dioxolanyl, dithiolanyl, and thiazolidinyl.

As used herein, the term heterocyclyl-C ₁ -C ₂ -alkyl means a heterocyclyl ring attached to the remainder of the molecule by a C ₁ -C ₂ -alkylene linker as defined above.

As used herein, the expression spirocyclic carbobi- or carbothricyclyl ring is a non-aromatic bicyclic ring system containing two rings joined together by one carbon atom, i.e. having one common carbon atom. Examples of a spirocyclic carbobi- or carbothricyclyl ring system include, but are not limited to, spiro[3.3]heptanyl, spiro[3.4]octanyl, spiro[4.5]decanyl, spiro[cyclobutane-1,2'indanyl], or spiro[cyclopentane-1,2'-tetralinyl ].

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. Atropoisomers may also occur as a result of limited

- 2 045799 rotations around a single bond. 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 includes 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 in salt form, for example an agronomically useful 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 R ¹ , R ² , R ³ , X and Y with reference to compounds of formula (I). With respect to any of these substituents, any of the definitions given below can be combined with any of the definitions of any other substituent given below or elsewhere in this document.

Y is C-F, C-H, or N. In one embodiment, Y is C-F. In another embodiment, Y is C-H. In a further embodiment, Y is N.

R ¹ is hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl or HC(O)NH-. Preferably R ¹ is hydrogen, halogen, C 1 -C ₃ alkyl, C ₁ -C ₃ alkoxy, C ₁ -C ₂ haloalkyl or HC(O)NH-, more preferably halogen, C ₁ -C ₂ alkyl, C ₁ -C ₂ -alkoxy or HC(O)NH. Even more preferably, R ¹ is chlorine, bromine, methyl, methoxy or HC(O)NH-. Even more preferably, R ¹ is methyl or HC(O)NH-, and most preferably methyl.

R ² represents C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxy, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C2 alkyl (where the cycloalkyl groups are optionally substituted by 1-3 groups represented by R ³ ), phenyl, phenyl-C1- _C2- alkyl (where the phenyl rings are optionally substituted with 1-3 groups represented by ^R3 ), heteroaryl, heteroaryl- _C1 - _C2 -alkyl, where heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur, heterocyclyl, heterocyclyl-C ₁ -C ₂ -alkyl, where heterocyclyl is a 4-, 5- or 6-membered non-aromatic monocyclic a ring containing 1, 2 or 3 heteroatoms, individually selected from nitrogen, oxygen and sulfur, or a 5-12 membered non-aromatic spirocyclic carbobi- or carbothricyclyl ring system, optionally containing 1, 2, 3, 4 or 5 heteroatoms, individually selected from nitrogen, oxygen and sulfur, and wherein each spirocyclic carbobi- or carbothricyclyl ring system is optionally linked to the rest of the molecule by a C ₁ -C ₂ -alkylene linker.

Preferably R ² is C1-C6 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C2 alkyl (wherein the cycloalkyl groups are optionally substituted by 1-3 groups represented by R ³ ), phenyl, phenyl-C 1 -C ₂ -alkyl (where the phenyl rings are optionally substituted with 1-3 groups represented by R ³ ), heteroaryl, heteroaryl-C ₁ -C ₂ -alkyl, where heteroaryl is 5- or 6 -membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, heterocyclyl, heterocyclyl-C ₁ -C ₂ -alkyl, where heterocyclyl is a 4-, 5- or 6-membered non-aromatic a monocyclic ring containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, or a 5-12 membered non-aromatic spirocyclic carbobi- or carbothricyclyl ring system optionally containing 1, 2 or 3 heteroatoms individually selected from nitrogen , oxygen and sulfur, and wherein each spirocyclic carbobi- or carbothricyclyl ring system is optionally linked to the rest of the molecule by a C ₁ -C ₂ -alkylene linker.

More preferably, R ² is C1-C6 alkyl, C1-C3 alkoxy, C3-C6 cycloalkyl, C3C6 cycloalkyl-C1-C2 alkyl (where the cycloalkyl groups are optionally substituted with 1-3 groups represented by R ³ ), phenyl , phenyl-C1-C ₂ -alkyl (where the phenyl rings are optionally substituted with 1-3 groups represented by R ³ ), heteroaryl, where heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms, according to separately selected from nitrogen, oxygen and sulfur, heterocyclyl, where heterocyclyl is a 4-, 5- or 6-membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms selected separately from nitrogen, oxygen and sulfur, or 5-12 -membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system, optionally containing one heteroatom selected from nitrogen, oxygen and sulfur.

Even more preferably, R ² is C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C2 alkyl (where the cycloalkyl groups are optionally substituted with 1 or 2 groups represented by R ³ ), phenyl-C1-C ₂ -alkyl (where the phenyl rings are optionally substituted with 1 or 2 groups represented by R ³ ), or a 5-12 membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system.

- 3 045799

Even more preferably, R ² is C1-C6 alkyl, C3-C5 cycloalkyl, C3-C5 cycloalkyl-C1-C2 alkyl (where the cycloalkyl groups are optionally substituted with 1 or 2 groups represented by R ³ ), phenyl-C1-C ₂ -alkyl (where the phenyl rings are optionally substituted with 1 or 2 groups represented by R ³ ), or a 5-12 membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system.

Even more preferably, R ² is n-butyl, isobutyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, 1-(cyclopropylmethyl)cyclopropylmethyl, cyclobutyl, 2,2-dimethylcyclobutyl, 1-methylcyclopentyl, benzyl , 1-phenylethyl, 3,5-bis-(trifluoromethyl)phenylmethyl, spiro[3.3]heptanyl, spiro[3.4]octanyl or spiro[cyclobutan-1,2'-indanyl], and most preferably 1(cyclopropylmethyl)cyclopropylmethyl, cyclobutyl , 2,2-dimethylcyclobutyl, spiro[3.3]heptan-3-yl, spiro[3.4]octan-3-yl or spiro[cyclobutan-1,2'-indan]-1-yl.

In one set of embodiments, R ² is C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxy, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C2 alkyl (wherein the cycloalkyl groups are optionally substituted 1-3 groups represented by R ³ ), phenyl, phenyl-C1-C ₂ -alkyl, heteroaryl, heteroaryl-C ₁ -C ₂ -alkyl, where heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur, heterocyclyl, heterocyclyl-C ₁ -C ₂ -alkyl, where heterocyclyl is a 4-, 5- or 6-membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms, individually selected from nitrogen, oxygen and sulfur, or a 5-12 membered non-aromatic spirocyclic carbobi- or carbothricyclyl ring system, optionally containing 1, 2, 3, 4 or 5 heteroatoms, individually selected from nitrogen, oxygen and sulfur, and wherein each spirocyclic carbobi- or carbothricyclyl ring system is optionally linked to the rest of the molecule by a C1C ₂ -alkylene linker.

Preferably R ² is C1-C6-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C3-C6cycloalkyl, C3-C6-cycloalkyl-C1-C2-alkyl (wherein the cycloalkyl groups are optionally substituted by 1-3 groups represented by R ³ ), phenyl, heteroaryl, heteroaryl-C1-C ₂ -alkyl, where heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, heterocyclyl , heterocyclyl-C ₁ -C ₂ -alkyl, where heterocyclyl is a 4-, 5- or 6-membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, or 5-12 -membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system, optionally containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, and wherein each spirocyclic carbobi- or carbotricyclyl ring system is optionally linked to the rest of the molecule by a C ₁ - C ₂ -alkylene linker.

More preferably, R ² is C ₁ -C 4 -alkyl, C ₁ -C ₃ -alkoxy, C ₃ -C ₆ -cycloalkyl, C _{3 -C 6} -cycloalkyl-C ₁ -C ₂ -alkyl (wherein the cycloalkyl groups are optionally substituted with 1 -3 groups represented by R ³ ), phenyl, heteroaryl, where heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, heterocyclyl, where heterocyclyl is a 4-, 5-, or 6-membered non-aromatic monocyclic ring containing 1, 2, or 3 heteroatoms individually selected from nitrogen, oxygen, and sulfur, or a 5-12-membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system, optionally containing one a heteroatom selected from nitrogen, oxygen and sulfur.

Even more preferably, R ² is C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₂ alkyl (where the cycloalkyl groups are optionally substituted with 1 or 2 groups represented by R ³ ), or 5-12- membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system.

Even more preferably, R ² is C ₃ -C4 cycloalkyl, C ₃ -C4 cycloalkyl-C ₁ -C ₂ alkyl (where the cycloalkyl groups are optionally substituted with 1 or 2 groups represented by R ³ ), or a 5-12 membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system.

Even more preferably, R ² is 1-(cyclopropylmethyl)cyclopropylmethyl, cyclobutyl, 2,2-dimethylcyclobutyl, spiro[3.3]heptanyl, spiro[3.4]octanyl or spiro[cyclobutane-1,2'indanyl], and most preferably 1 -(cyclopropylmethyl)cyclopropylmethyl, cyclobutyl, 2,2dimethylcyclobutyl, spiro[3.3]heptan-3-yl, spiro[3.4]octan-3-yl or spiro[cyclobutan-1,2'-indan]-1yl.

R ³ represents halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl-C1-C2 alkyl. Preferably R ³ is halogen, C 1 -C ₃ alkyl, C 1 -C 3 alkoxy, C ₁ -C ₂ haloalkyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkyl-C ₁ -C ₂ alkyl, more preferably halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, C ₁ -C ₃ -haloalkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₂ -alkyl. Even more preferably, R ³ is C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl or C ₃ -C ₆ cycloalkyl, _{C 1} -C ₂ alkyl. Even more preferably, R ³ is methyl, ethyl, isopropyl, trifluoromethyl,

- 4 045799 cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl or cyclobutylethyl, and most preferably R ³ is methyl, trifluoromethyl or cyclopropylmethyl.

In one set of embodiments, R ³ is C ₁ -C ₃ alkyl or C ₃ -C ₆ cycloalkyl-Cl-C ₂ alkyl. Preferably ^R3 is methyl, ethyl, isopropyl, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl or cyclobutylethyl, and more preferably ^R3 is methyl or cyclopropylmethyl.

X represents N or C-H. In one embodiment, X is N. In another embodiment, X is C-H.

In the compound of formula (I) according to the present invention, it is preferable

R ¹ represents hydrogen, halogen, C ₁ -C ₃ -alkyl, Cl-C ₃ -alkoxy, C ₁ -C ₂ -haloalkyl or HC(O)NH-;

R ² represents C1-C6 alkyl, C1-C3 alkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C2 alkyl (where the cycloalkyl groups are optionally substituted with 1-3 groups represented by R ³ ), phenyl, phenyl -C1-C2 _- alkyl (where the phenyl rings are optionally substituted with 1-3 groups represented by ^R3 ), heteroaryl, where heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms, individually selected of nitrogen, oxygen and sulfur, heterocyclyl, where heterocyclyl is a 4-, 5- or 6-membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, or a 5-12 membered a non-aromatic spirocyclic carbobi- or carbotricyclyl ring system, optionally containing one heteroatom selected from nitrogen, oxygen and sulfur; R ³ is C ₁ -C ₃ -alkyl, C ₁ -C ₃ -haloalkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₂ -alkyl;

X represents N or C-H; and Y is C-F, C-H or N.

More preferable

R ¹ represents methyl or HC(O)NH-;

R ² represents C1-C6 alkyl, C3-C5 cycloalkyl, C3-C5 cycloalkyl-C1-C2 alkyl (where the cycloalkyl groups are optionally substituted by 1 or 2 groups represented by R ³ ), phenyl-C1-C ₂ - alkyl, where the phenyl rings are optionally substituted with 1 or 2 groups represented by R ³ , or a 5-12 membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system;

R ³ is C ₁ -C ₃ -alkyl, C ₁ -C ₃ -haloalkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₂ -alkyl;

X represents N or C-H; And

Y represents C-F, C-H or N.

Even more preferable

R ¹ represents methyl or HC(O)NH-;

R ² represents n-butyl, isobutyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, 1(cyclopropylmethyl)cyclopropylmethyl, cyclobutyl, 2,2-dimethylcyclobutyl, 1-methylcyclopentyl, benzyl, 1-phenylethyl, 3,5-bis(trifluoromethyl)phenylmethyl, spiro[3.3]heptanyl, spiro[3.4]octanyl or spiro[cyclobutan-1,2'-indanyl];

X represents N or C-H; And

Y represents C-F, C-H or N.

In another group of preferred embodiments, in the compound of formula (I) of the present invention, it is preferable

R ¹ represents hydrogen, halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, C ₁ -C ₂ -haloalkyl or HC(O)NH-;

R ² is C ₁ -C 4 alkyl, C ₁ -C ₃ alkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl-C ₁ -C ₂ alkyl (where the cycloalkyl groups are optionally substituted 1-3 groups represented by R ³ ), phenyl, heteroaryl, where heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, heterocyclyl, where heterocyclyl is 4 -, 5- or 6-membered non-aromatic monocyclic ring system containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, or a 5-12 membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system, optionally containing one heteroatom, selected from nitrogen, oxygen and sulfur;

R ³ represents C ₁ -C ₃ -alkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₂ -alkyl;

X represents N or C-H; And

Y represents C-F, C-H or N.

More preferable

R ¹ represents halogen, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -alkoxy or HC(O)NH-;

R ² is C ₁ -C 4 alkyl, C ₁ -C ₃ alkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl-C ₁ -C ₂ alkyl (where the cycloalkyl groups are optionally substituted 1-3 groups represented by R ³ ), phenyl, heteroaryl, where heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, heterocyclyl, where heterocyclyl is 4 -, 5- or 6-membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms selected separately from nitrogen, oxygen and sulfur, or

- 5 045799

a 5-12 membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system, optionally containing one heteroatom selected from nitrogen, oxygen and sulfur;

R ³ represents C ₁ -C3-alkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₂ -alkyl;

X represents N; And

Y represents C-F.

Even more preferable

R ¹ represents methyl or HC(O)NH-;

R ² is C ₃ -C ₄ -cycloalkyl, C ₃ -C ₄ -cycloalkyl-C ₁ -C ₂ -alkyl (where the cycloalkyl groups are optionally substituted by 1 or 2 groups represented by R ³ ), or a 5-12 membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system;

R ³ represents methyl or cyclopropylmethyl;

X represents N; And

Y represents C-F.

In a particularly preferred embodiment, the compound of formula (I) is

In an even more preferred embodiment, the compound of formula (I) is 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-formamidothiazole-4-carboxamide ( 1.b.25), 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-N-[[1-(cyclopropylmethyl)cyclopropyl]methyl]5-methylthiazol-4-carboxamide (1.f .23), 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.3]heptan-3-ylthiazol-4-carboxamide (1.e.23), 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[cyclo- 6 045799 butane-2,2'-indan]-1-ylthiazol-4-carboxamide (1 .d.23) or 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-I-(2,2dimethylcyclobutyl)-5-methylthiazol-4-carboxamide (1.b.23).

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

The compounds of formula (I) of the present invention wherein R ¹ , R ² , X and Y are defined for formula (I) can be prepared by converting a compound of formula (II) wherein R ¹ , R ² , X and Y are defined for formula ( I), using a compound of formula (III) wherein R ¹¹ is a halogen, preferably bromine, either by thermal heating or by a base, preferably sodium hydride or lithium base. This is shown in Diagram 1 below.

Scheme 1

Compounds of formula (II), wherein R ¹ , R ² , X and Y are defined for formula (I), can be prepared by converting a compound of formula (IV), wherein X and Y are defined for formula (I), using a compound of formula (V ), wherein R ¹ and R ² are as defined for formula (I), and R ¹² is a halogen, preferably bromine, either by thermal heating, a base, or under Buchwald-Hartwig transition metal catalyzed amination conditions. This is shown in Diagram 2 below.

Scheme 2

Compounds of formula (V), wherein R ¹ and R ² are defined for formula (I), and R ¹² is halogen, preferably bromine, can be prepared by converting a compound of formula (VI), wherein R ¹ is defined for formula (I), and R ¹² is a halogen, preferably bromine, and a compound of formula (VII), where R ² is defined for formula (I), either through the use of an acid chloride intermediate or directly using a peptide bond forming agent. This is shown in diagram 3 below.

Scheme 3

(VI) (V)

Compounds of formula (VI), wherein R ¹ is defined for formula (I), and R ¹² is halogen, preferably bromine, can be prepared by converting a compound of formula (VIII), wherein R ¹ is defined for formula (I), R ¹² is halogen, preferably bromine, and R ¹³ represents C ₁ -C ₆ -alkyl, and bases. This is shown in diagram 4.

Scheme 4

(VIII) (VI)

Alternatively, compounds of formula (II), wherein R ¹ , R ² , X and Y are defined for formula (I),

- 7 045799 can be prepared by converting a compound of formula (IX), where R ¹ , X and Y are defined for formula (I), using a compound of formula (VII), where R ² is defined for formula (I), or by using an intermediate , which is an acid chloride, or directly using a peptide bond forming agent. This is shown in diagram 5.

Scheme 5

(IX)

Compounds of formula (IX) wherein R ¹ , X and Y are defined for formula (I) can be prepared by converting a compound of formula (X) wherein R ¹ , X and Y are defined for formula (I) and R ¹³ is C ₁ -C ₆ -alkyl, using a base. This is shown in diagram 6.

Scheme 6

(X) (IX)

Compounds of formula (X) wherein R ¹ , X, and Y are defined for formula (I) and R ¹³ is C1C6 alkyl can be prepared by converting a compound of formula (IV) wherein X and Y are defined for formula (I) , using a compound of formula (VII), where R ¹ is defined for formula (I), R ¹² is halogen, preferably bromine, and R ¹³ is C1-C ₆ -alkyl, either by thermal heating or by using a base, or under transition metal-catalyzed Buchwald-Hartwig amination conditions. This is shown in diagram 7.

Scheme 7

n (iv) (vii) oo

Alternatively, compounds of formula (X), wherein R ¹ , X and Y are defined for formula (I), and R ¹³ is C1-C6 alkyl, can be prepared by converting a compound of formula (XI), where X and Y are defined for formula (I), and R ¹² represents a halogen, preferably bromine or iodo, using a compound of formula (XII), where R ¹ is defined for formula (I), and R ¹³ represents C1-C ₆ -alkyl, under the conditions Transition metal-catalyzed amination according to Buchwald-Hartwig. This is shown in diagram 8.

Scheme 8

Alternatively, compounds of formula (II), wherein R ¹ , R ² , X and Y are defined for formula (I), can be prepared by converting a compound of formula (XI), wherein X and Y are defined for formula (I), and R ¹² is a halogen, preferably bromine or iodine, using a compound of formula (XIII), where R ¹ and R ² are defined for formula (I), either by thermal heating, or by a base, or under the conditions of a transition metal catalyzed Buchwald amination -Hartwig. This is shown in diagram 9.

- 8 045799

Scheme 9

Alternatively, compounds of formula (I) of the present invention, wherein R ¹ , R ² , X and Y are defined for formula (I), can be prepared by converting a compound of formula (V), wherein R ¹ and R ² are defined for formula ( I), and R ¹² is a halogen, preferably bromine, using a compound of formula (XIV), where X and Y are defined for formula (I), either by thermal heating, or with a base, or under transition metal catalyzed amination conditions according to Buchwald-Hartwig. This is shown in diagram 10.

Scheme 10

Compounds of formula (XIV), wherein X and Y are defined for formula (I), can be prepared by converting a compound of formula (XV), wherein X and Y are defined for formula (I), with a compound of formula (III), wherein R ¹¹ is is a halogen, preferably bromine, either by thermal heating or by a base. This is shown in diagram 11.

Scheme 11

Surprisingly, it has been found in this work that the new compounds of formula (I) have, for practical purposes, a very effective level of biological activity for protecting plants from diseases that are caused by fungi.

The compounds of formula (I) can be used in agriculture and related applications, 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 harmful to humans. The new compounds have excellent activity at low application rates, are well tolerated by plants and are safe for the environment. They are characterized by very useful therapeutic, 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) of various crops that are beneficial plants, while at the same time protecting those plant parts which develop later, for example, from phytopathogenic microorganisms.

The present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating the plants or plant propagation material and/or harvested food crop, wherein an effective amount of a compound of formula (I) is applied to plants, parts thereof or where they grow.

Also, the compounds of formula (I) can be used as a fungicide. As used herein, the term fungicide means a compound that controls, modifies or prevents the growth of fungi. The term fungicidal effective amount means an amount of such a compound or combination of such compounds that is capable of having 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 the plant to prevent fungal infection.

Also, the compounds of formula (I) can be used as dressing agents for the purpose of treating plant propagation material, for example seeds, for example fruits, tubers or grains, or plant shoots (for example, rice), to protect against fungal infections, as well as against phytopathogenic fungi found in soil. The propagation material can be treated with a composition containing a compound of formula (I) before planting: the seed, for example, can be treated before sowing.

The active ingredients of the present invention can also be applied to grains (coating), either by impregnating the seeds in a liquid composition or by coating them with a solid composition. The composition can also be applied to a planting site during planting of 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 plant propagation material processed in this manner.

Moreover, the compounds in accordance with the present invention can be used for the control of fungi in related fields, for example, in the field of protection of technical materials, including wood and wood-related technical products, in the field of food storage, in the field of sanitary processing.

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) can, for example, be effective against fungi and fungal disease vectors, as well as against phytopathogenic bacteria and viruses. These fungi and fungal disease vectors, as well as phytopathogenic bacteria and viruses, are, for example: Absidia corymbifera, Alternaria 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., in including B. cinerea, Candida spp., including C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp., including C. albicans, C. glabrata, C. krusei, 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. oxysporum, 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 H. capsulatum, Laetisaria fuciformis, Lept graphium 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., 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.

Within the scope of the present invention, the target crops and/or beneficial plants to be protected generally include perennial and annual crops such as berry plants, for example, varieties of blackberries, blueberries, cranberries, raspberries and strawberries; grains, such as barley, maize (corn), millet, varieties of oats, rice, rye, sorghum, triticale and wheat; fibrous plants such as cotton, flax, hemp, jute and sisal; field crops such as sugar beet, fodder beet, coffee tree, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea bush and tobacco; fruit trees such as apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses, such as Bermuda grass, bluegrass, bentgrass, Eremochloa serpentine, fescue, ryegrass, Augustine grass and Japanese zoysia; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes, such as varieties of beans, lentils, peas and soybeans; nuts such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachio and walnuts; palm trees, such as oil palm; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa tree, coconut tree, olive tree and rubber tree; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumber, garlic, lettuce, zucchini, melon, okra, onions, peppers, potatoes, pumpkin, rhubarb, spinach and tomato; as well as grape varieties, for example, varieties of grapes.

The term beneficial plants should be understood to also include beneficial plants that have been made tolerant to herbicides such as bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example, primisulfuron, prosulfuron and trifloxysulfuron, EPSPS inhibitors (5- enol-pyrovyl-shikimate-3-phosphate synthase), GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) as a result of traditional breeding methods or genetic engineering. An example of a crop that has been made tolerant of imidazolinones, such as imazamox, through traditional breeding techniques (mutagenesis) is Clearfield® rapeseed (canola). Examples of crops that have been made tolerant of herbicides or classes of herbicides through genetic engineering techniques include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, HerculexI® and LibertyLink®.

The term beneficial plants should be understood to also include beneficial plants that have been transformed by the use of recombinant DNA techniques such that they are capable of synthesizing one or more selective toxins such as those known, for example, from toxin-producing bacteria, especially bacteria of the genus Bacillus.

Examples of such plants are: YieldGard® (a maize variety expressing the CryIA(b) toxin); YieldGard Rootworm® (maize variety expressing CryIIIB(b1) toxin); YieldGard Plus® (maize variety expressing CryIA(b) toxin and CryIIIB(b1) toxin); Starlink® (a maize variety expressing the Cry9(c) toxin); Herculex I® (a maize variety expressing the CryIF(a2) toxin and the enzyme phosphinothricin-Nacetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety expressing CryIA(c) toxin); Bollgard I® (cotton variety expressing CryIA(c) toxin); Bollgard II® (cotton variety expressing CryIA(c) toxin and CryIIA(b) toxin); VIPCOT® (cotton variety expressing VIP toxin); NewLeaf® (potato variety expressing CryIIIA toxin); NatureGard® Agrisure® GT Advantage (GA21 with glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 with corn borer (CB) resistance trait), Agrisure® RW (with Western corn rootworm resistance trait) and Protecta®.

The term crops should be understood to also include crop plants that have been transformed by recombinant DNA techniques 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, especially bacteria of the genus Bacillus.

Toxins that may be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 5-endotoxins, for example, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example, Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins from bacteria colonizing nematodes, such as 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 inhibitors, cystatin inhibitors, papain inhibitors; ribosome inactivating proteins (RIPs), such as ricin, maize RIP, abrin, luffin, saporin or bryodin; steroid metabolic enzymes such as 3hydroxysteroid oxidase, ecdysteroid UDP glycosyl transferase, 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.

In the context of the present invention, 5-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, should definitely also be understood as hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly using a new combination of different domains of these proteins (see, for example, WO 02/15701). Known

- 11 045799 truncated toxins, for example truncated CrylAb. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are substituted. With such amino acid substitutions, sequences recognized by proteases that are not present in the natural toxin are preferably introduced into the toxin, for example, in the case of Cry3A055, a sequence recognized by cathepsin G is introduced into the Cry3A toxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0374753, WO 93/07278, WO 95/34656, EP-A-0427529, EP-A-451878 and WO 03/052073.

Methods for producing such transgenic plants are generally known to one skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0367474, EP-A-0401979 and WO 90/13651.

The toxin contained in transgenic plants gives the plants tolerance 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, and some of them are commercially available. Examples of such plants are: YieldGard® (a maize variety expressing the Cry1Ab toxin); YieldGard Rootworm® (a maize variety expressing the Cry3Bb1 toxin); YieldGard Plus ® (maize variety expressing Cry1Ab toxin and Cry3Bb1 toxin); 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® (cotton variety expressing Cry1Ac toxin); Bollgard I® (cotton variety expressing the Cry1Ac toxin); Bollgard II® (cotton variety expressing Cry1Ac toxin and Cry2Ab toxin); VipCot® (cotton variety expressing Vip3A toxin and Cry1Ab toxin); NewLeaf® (potato variety expressing the Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 with glyphosate tolerance), Agrisure® CB Advantage (Bt11 with corn borer (CB) resistance) and Protecta®.

Additional examples of such transgenic crops are the following.

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

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

3. Maize MIR604 from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 Saint-Sauveur, France, registration number C/FR/96/05/10. Maize that has been rendered resistant to insects 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 is resistant to some insects of the order Coleoptera.

5. Cotton plant 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. Genetically modified maize to express the Cry1F protein to provide resistance to certain Lepidoptera insects and the PAT protein to provide 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. It consists of hybrid varieties of maize, bred by the traditional method of crossing genetically modified varieties NK603 and MON 810. Maize NK603 x M0N 810 transgenically expresses the CP4 EPSPS protein obtained from the strain Agrobacterium sp. CP4, which confers tolerance to the herbicide Roundup® (contains glyphosate), as well as the toxin Cry1Ab, derived from Bacillus thuringiensis subsp. kurstaki, which provides tolerance to some members of the order Lepidoptera, including the corn borer.

- 12 045799

The term growing site as used herein 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 soil, seeds and seedlings, and existing green plants.

The term plant refers to all the 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 a plant, such as seeds that can be used for propagation of the plant, and vegetative material, such as shoots or tubers, for example, potatoes. Mention may be made here of, for example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and plant parts. We can also mention sprouted plants and young plants that should be replanted after germination or after emerging from the soil. These young plants can be protected until transplanting by full or partial dipping treatment. Preferably, plant propagation material should be understood to mean seeds.

The pesticides referred to herein 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 auxiliary substances conventionally used in the field of formulation. Therefore, for convenience, they can be formulated by a known method into emulsifiable concentrates, applied as paste coatings, directly sprayed or diluted solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dust preparations, granulates, as well as encapsulated forms, e.g. in polymeric substances. As with the type of compositions, methods of application, such as atomization, fine mist, dusting, diffusing, coating or watering, are selected in accordance with the intended purposes and prevailing conditions. The compositions may also contain additional auxiliary substances such as stabilizers, antifoams, viscosity regulators, binders or tackifiers, as well as fertilizers, micronutrient donors or other compositions to obtain special effects.

Suitable carriers and auxiliaries, for example for agricultural use, may be solid or liquid and are substances useful in formulation technology, for example natural or regenerated minerals, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are, for example, described in WO 97/33890.

The compounds of formula (I) are usually 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 may be, for example, fertilizers, or micronutrient donors, or other drugs that affect plant growth. They may also be selective herbicides or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if necessary together with additional carriers, surfactants or application aids commonly used in the field. compilation.

The compounds of formula (I) can be used in the form of (fungicidal) compositions for the control or protection against phytopathogenic microorganisms containing as active ingredient at least one compound of formula (I) or at least one preferred individual compound as defined above in free form or in the form of an agrochemically usable salt and at least one of the above auxiliary substances.

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 excipient. An agriculturally acceptable carrier is, for example, a carrier that is suitable for agricultural use. Agricultural media are well known in the art. Preferably, said composition may contain at least one or more pesticidal active compounds, for example, an additional fungicidal 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, result in unexpected synergistic activities.

Examples of suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenic fungicides, aryl phenyl ketone fungicides, benzamide fungicides , benzanilide group fungicides, benzimidazole group fungicides, benzothiazole group fungicides, plant fungicides, bridging biphenyl group fungicides, carbamate group fungicides, carbanilate group fungicides, conazole group fungicides, copper-containing fungicides, dicarboximide group fungicides, dinitrophenol group fungicides, di group fungicides thiocarbamates, fungicides of the dithiolane group , fungicides of the furamide group, fungicides of the furanilide group, fungicides of the hydrazides group, fungicides of the imidazoles group, mercury-containing fungicides, fungicides of the morpholine group, fungicides of the organophosphorus group, fungicides of the organotin group, fungicides of the oxatiin group, fungicides of the oxazole group, fungicides of the phenylsulfonamide group, fungicides of the group polysulfides, fungicides of the pyrazole group, fungicides of the pyridine group, fungicides of the pyrimidine group, fungicides of the pyrrole group, fungicides of the quaternary ammonium compounds group, fungicides of the quinoline group, fungicides of the quinone group, fungicides of the quinoxaline group, fungicides of the strobilurin group, fungicides of the sulfonanilide group, fungicides of the thiadiazole group, fungicides of the thiazole group, thiazolidine group fungicides, thiocarbamate group fungicides, thiophene group fungicides, triazine group fungicides, triazole group fungicides, triazolopyrimidine group fungicides, urea group fungicides, valinamide group fungicides and zinc-containing fungicides.

Examples of suitable additional active ingredients also include the following: petroleum oils, 1,1-bis-(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methylN-1-naphthylacetamide, 4-chlorophenylphenylsulfone, acetoprol, aldoxycarb, amidition, amidothioate, amiton, amitone hydrogenoxalate, amitraz, aramit, arsenic oxide, azobenzene, azotoate, benomyl, benoxaphos, benzyl benzoate, bixafen, brofenvalerate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, bu tilpyridaben, calcium polysulfide , camphechlor, carbanolate, carbophenothione, cimiazole, quinomethionate, chlorobenzide, chlordimeform, chlordimeform hydrochloride, chlorphenetol, chlorphenson, chlorphensulfide, chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate, chlorothiophos, cinerin I, cinerin II, cinerins, closantel, coumaphos, moles tone, crotoxiphos, kufraneb, cyanoate, DCPM, DDT, demefion, demefion-O, demefion-S, demeton-methyl, demeton-O, demeton-Omethyl, demeton-S, demeton-S-methyl, demeton-S-methylsulfone, dichlorfluanid, dichlorvos, diclifos, dienochlor, dimefox, dinex, dinex-dichlorexin, dinocap-4, dinocap-6, dinoctone, dinopentone, dinosulfone, dinoterbon, dioxathion, diphenylsulfone, disulfiram, DNOC, dofenapine, doramectin, endothione, eprinomectin, ethoate-methyl, etrimphos, phenazaflor, phenbutatin oxide, phenothiocarb, fenpyrad, fenpiroximate, fenpyrazamine, fenzone, fentrifanil, flubenzymine, flucycloxuron, fluenethyl, fluorbenzide, FMC 1137, formatenate, formatenate hydrochloride, formparanate, gamma-HCN, glyodine, galfenprox, hexadecylcyclopropane carboxylate, isocarbophos, jasmoline I, jasmoline II, iodofenphos, lindane, malonobene, mecarbam, mephospholane, mesulfene, metacryphos, methyl bromide, metolcarb, mexacarbate, milbemycin-oxime, mipafox, monocrotophos, morphothione, moxidectin, naled, 4-chloro-2-(2-chloro-2methylpropyl) -5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, nifluridide, nikkomycins, nitrilecarb, nitrilecarb-zinc chloride 1:1 complex, omethoate, oxydeprophos, oxydisulfoton, pp'-DDT, parathion, permethrin , phencapton, fosalone, phospholane, phosphamidon, polychlorterpenes, polynactins, proclonol, promacil, propoxur, protidathion, protoate, pyrethrin I, pyrethrin II, pyrethrins, pyridafenthion, pyrimitate, quinalphos, hinthiophos, R-1492, phosglycine, rotenone, shradan, sebuphos , selamectin, sofamide, SSI-121, sulfiram, sulfluramide, sulfotep, sulfur, difluvidazine, tau-fluvalinate, TERP, terbam, tetradifon, tetrasul, thiafenox, thiocarboxim, thiophanox, thiometon, thioquinox, thuringiensin, triamiphos, triarathene, triazophos, tri azuron , triphenofos, trinactin, vamidothione, vaniliprole, betoxazine, copper dioctanoate, copper sulfate, cybutrin, dichlon, dichlorophen, endothal, fentin, slaked lime, nabam, quinoclamine, quinonamide, simazine, triphenyltine acetate, triphenyltine hydroxide, crufomate, piperazine, ti ofanate, chloralose, fenthion, pyridin-4-amine, strychnine, 1-hydroxy-III-pyridine-2-thione, 4(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, dodicine, fenaminosulf , formaldehyde, hydrargafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis-(dimethyldithiocarbamate), nitrapyrin, octylinone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate, probenazole, streptomycin, streptomycin sesquisulfate, teclophthalam, thiomersal, Adoxophy es 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., Trichogram ma spp., Typhlodromus occidentalis, Verticillium lecanii, afolate, bisazir, busulfan, dimatif, hemel, hempu, metepu, metiotepu, methylafolate, morzide, penfluron, tepu, tiohempu, thiotepu, treta

- 14 045799 min, uredepu, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-yl acetate, ( E)-6methylhept-2-en-4-ol, (E,Z)-tetradeca-4,10-dien-1-ylacetate, (Z)-dodec-7-en-1-ylacetate, (Z)-hexadec -11enal, (Z)-hexadec-11-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-eicos-13-en-10-one, ( Z)tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodeca-7, 9-diene-1 yl acetate, (9Z,11E)-tetradeca-9,11-dien-1-ylacetate, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate, 14methyloctadec-1-ene, 4 -methylnonan-5-ol with 4-methylnonan-5-one, alpha-multistriatin, brevicomin, codelur, codemon, quelur, disparlur, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodeca -8,10-dien-1yl acetate, dominicalur, ethyl-4-methyloctanoate, eugenol, frontalin, granlur, granlur I, granlur II, granlur III, granlur IV, hexalur, ipsdienol, ipsenol, japonilur, lineatin, litlur, luplur, medlur , megatomic acid, methyl eugenol, muscalur, octadeca-2,13-dien-1-ylacetate, octadeca-3,13-dien-1-yl acetate, orfralur, oryctalur, ostramon, siglur, sordidine, sulcatol, tetradec-11-ene-1- yl acetate, trimedlur, trimedlur A, trimedlur B1, trimedlur B ₂ , trimedlur C, trunk call, 2-(octylthio)ethanol, butopyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyltoluamide, dimethyl carbate, dimethyl phthalate, ethylhexanediol , hexamide , metochine-butyl, methylneodecanamide, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-bis-(4-ethylphenyl)ethane, 1,2dichloropropane with 1,3-dichloropropene, 1- bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl-2-ethylsulfinylethyl methylphosphate, 2-(1,3-dithiolan-2-yl)phenyldimethylcarbamate, 2-(2butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate, 2-(4-chloro-3,5xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidone, 2 -isovalerylindane-1,3-dione, 2-methyl(prop-2-ynyl)aminophenylmethylcarbamate, 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-enyldimethylcarbamate, acethione, acrylonitrile, aldrin, allosamidine, allixicarb, alpha-ecdysone, aluminum phosphide, aminocarb, anabasine, atidation , azametifos, 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, bromo- DDT, bufencarb, butacarb, butathiophos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, cevadin, chlorobicyclene, chlordane, chlordecone, chloroform, chloropicrin, chlorfoxime, chlorprazophos, cis-resmethrin, cismethrin, clocitrin, copper acetoarsenite, Copper arsenate, copper oleate, cumitoate, cryolite, CS 708, cyanophenphos, cyanophos, cycletrin, cythioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidaphos, dicaptone, dichlorofenthione, dicresyl, dicyclanil, dieldrin, diethyl-5-methylpyrazole-3 -ylphosphate, dilor, dimefluthrin, dimethane, dimethrin, dimethylvinphos, dimethylane, dinoprop, dinosam, dinoseb, diophenolan, dioxabenzophos, dithicrofos, DSP, ecdysterone, EI 1642, EMPC, ERBP, ethaphos, etiophencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenchlorvos, fenetacarb, fenitrothion, fenoxacrim, fenpyritrin, fensulfothion, fenthion-ethyl, flucofuron, fosmethylane, fospirat, fostiethane, furatiocarb, furethrin, guazatin, guazatin acetates, sodium tetrathiocarbonate, galfenprox, NCH, HEOD, heptachlor, heterophos, HHDN, hydrocyanic acid, hiquincarb, IPSP, isazophos, isobenzan, isodrine, isofenphos, isolan, isoprothiolane, isoxathione, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lead arsenate, leptophos, lyrimphos, lithidathione, m-cumenyl methylcarbamate , magnesium phosphide, mazidox, mecarfon, menazone, mercuric chloride, mesulfenphos, metham, metam-potassium, metam-sodium, methanesulfonyl fluoride, metocrotophos, methoprene, methotrin, methoxychlor, methyl isothiocyanate, methyl chloroform, methylene chloride, methoxadiazone, mirex, naphthalofos, naphtha alin , NC-170, nicotine, nicotine sulfate, nithiazine, nornicotine, O-5-dichloro-4-iodophenyl-O-ethylethylphosphonothioate, O,O-diethyl-O-4-methyl2-oxo-2H-chromen-7-ylphosphorothioate, O,O-diethyl-O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate, O,O,O',O'-tetrapropyldithiopyrophosphate, oleic acid, para-dichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, pH 60- 38, phencapton, phosnichlor, phosphine, phoxim-methyl, pyrimethafos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocene I, precocene II, precocene III, primidophos, profluthrin, promecarb, prothiophos, pyrazophos, pyresmethrin, cassia, quinalphos-methyl, quinothione, rafoxanide, resmethrin, rotenone, cadetrin, ryanium, ryanodine, sabadilla), shradan, sebuphos, 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, tebupyrimphos, temephos, terallethrin, tetrachloroethane, ticrofos, thiocyclam, thiocyclam hydrogenoxalate, thionazine, thiosultap, thiosultapodium, tralomethrin, transpermethrin, triazamate, tri chlormetaphos-3, trichloronate, trimetacarb, tolprocarb, trichloropyricarb, triprene, veratridine, veratrine, CMS, zetamethrin, zinc phosphide, zolaprophos and meperfluthrin, tetramethylfluthrin, bis-(tributyltin)oxide, bromoacetamide, ferric phosphate, niclosamide-olamine, tributyltin oxide, pyrimorph, triphenmorph, 1,2 -dibromo-3-chloropropane, 1,3dichloropropene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6thioxo-1,3,5-thiadiazinan-3- ilacetic acid, 6-isopentenylaminopurine, benclothiaz, cytokinins, DCIP, furfural, isamidophos, kinetin, composition based on Myrothecium verrucaria, tetrachlorothiophene, xylenols, zeatin, potassium ethyl xanthate, acibenzolar, acibenzolar-D-methyl, Reynoutria sachalinensis extract, alpha-chlorohydrin , antu, barium carbonate, bistiosemi, brodifacoum, bromadiolone, bromethalin, chlo

- 15 045799 rofacinone, cholecalciferol, coumachlor, coumafuril, coumatetralyl, crimidin, difenacoum, difethialone, diphacinone, ergocalciferol, flocumafen, fluoroacetamide, flupropadine, flupropadine hydrochloride, norbormide, fosacetim, phosphorus, pindon, pirinuron, skilliroside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethylpiperonilate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, verbutin, MGK 264, piperonyl butoxide, piprotal, propyl isomer, S421 , sesamex, sesasmolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate, ziram, imanin, ribavirin, mercuric oxide, thiophanate-methyl, aconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole , fluquinconazole, flusilazole, flutriafol, furamethpyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazol, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pirizoxazole, simeconazole, tebuconazole, tetracona zol, 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, ofuras, oxadixil, carbenda zim, debacarb , fuberidazole, thiabendazole, chlozolinate, dichlozolin, myclozolin, procymidone, vinclozolin, boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, tifluzamide, dodine, iminoctadin, azoxystrobin, dimoxystrobin, enestroburin, phenaminestrobin, fl uphenoxystrobin, fluoxastrobin, kresoxim-methyl , metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide, folpet, tolylfluanide, Bordeaux mixture, copper oxide, mancopper, oxine copper, nitrotal - isopropyl, edifenfos, iprobenfos, phosdifen, toclofos-methyl, anilazine, benthiavalicarb, blasticidin-S, chloroneb, chlorothalonil, cyflufenamide, cymoxanil, diclocimet, diclomesin, dicloran, dietofencarb, dimethomorph, flumorph, dithianone, ethaboxam, etridiazole, famoxa don, fenamidon, fenoxanil, ferimzone, fluazinam, fluopicolide, flusulfamide, fluxapyroxad, fenhexamide, fosetyl-aluminum, gimexazole, iprovalicarb, cyazofamide, metasulfocarb, metrafenone, pencycuron, phthalide, polyoxins, propamocarb, pyribencarb, proquinazide, pyroquilone, pyriophenone, x inoxifen, quintozene, tiadinil, triazoxide, tricyclazole, triforin, validamycin, valifenalate, zoxamide, mandipropamide, isopyrazam, sedaxane, benzovindiflupyr, pidiflumetofen, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluorobiphenyl- 2-yl)amide, isoflucipram, isothianyl, dipimethytrone, 6-ethyl-5,7-dioxopyrrolo[4,5][1,4]dithiino[1,2-c]isothiazol-3carbonitrile, 2-(difluoromyl)-N -[3-ethyl-1,1-dimethylundan-4-ul]nurudin-3-kαrboxamide, 4-(2,6difluorophenyl)-6-methyl-5-phenylpyridazin-3-carbonitrile, (R)-3-(difluoromethyl )-1-methyl-N-[1,1,3trimethylindan-4-yl]pyrazol-4-carboxamide, 4-(2-bromo-4-fluorophenyl)-K-(2-chloro-6-fluorophenyl)-2 ,5dimethylpyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-C-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, coumethoxysrobin (jiaxiangjunzhi ), lvbenmixianan, dichlorobenthiazox, mandestrobin, 3 -(4,4-difluoro-3,4-dihydro-3,3-dimethyl-isoquinolin-1 -yl)quinolone, 2-[2-fluoro-6-[(8- fluoro-2-methyl-3 quinolyl)oxy]phenyl]propan-2-ol, oxathiapiproline, tert-butyl-K-[6-[[[(1-methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2 -pyridyl]carbamate, pyraziflumide, inpirfluxam, trolprocarb, mefentrifluconazole, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylindan-4-yl]pyridin-3carboxamide, K'-( 2,5-dimethyl-4-phenoxyphenyl)-C-ethyl-M-methylformamidine, K'-[4-(4,5-dichlorothiazol-2yl)oxy-2,5-dimethylphenyl]-C-ethyl-C-methylformamidine , [2-[3-[2-[1-[2-[3,5-bis-(difluoromethyl)pyrazol1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydro- isoxazol-5-yl]-3-chlorophenyl]methanesulfonate, but3-ynyl-N-[6-[[(Z)-[(1-methyltetrazol-5-yl)phenylmethylene] amino]oxymethyl]-2-pyridyl]carbamate , methyl K-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methylphenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4(2,4, 6-trifluorophenyl)pyridazine, pyridachloromethyl, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4yl]pyrazole-4-carboxamide, 1-[2-[[1-(4-chlorophenyl )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)phenoxyyl]phenyl]tetrazol-5one, aminopyrifen, amethoctradine, amisulbrom, penflufen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3yl]oxy-2-methoxyimino-K ,3-dimethylpent-3-enamide, florylpicoxamide, fenpicoxamide, tebufloquine, ipflufenoquine, quinofumeline, isofetamide, K-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1methylpyrazole-4-carboxamide, K- [2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1methylpyrazole-4-carboxamide, benzothiostrobin, phenamacryl, zinc salt of 5-amino-1,3,4-thiadiazol-2thiol ( 2:1), fluopyram, flutianil, fluopimomide, pyrapropone, picarbutrazox, 2-(difluoromethyl)-K-(3ethyl-1,1-dimethylindan-4-yl)pyridin-3-carboxamide, 2-(difluoromethyl)-N- ((3R)-1,1,3-trimethylindan-4yl)pyridin-3-carboxamide, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3- (1,2,4-triazol-1yl)propyl]-3-pyridyl]oxy]benzonitrile, methyltetraprole, 2-(difluoromethyl)-K-((3R)-1,1,3-trimethylindan-4-yl) pyridine-3-carboxamide, α-(1,1-dimethylethyl)-a-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5pyrimidinemethanol, fluoxapiproline, enoxastrobin, 4-[[6 -[2-(2,4-difluorophenyl)-1,1-difluoro-2hydroxy-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-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1 -yl)propyl ]-3-pyridyl]oxy]benzonitrile, trinexapac, cumoxystrobin, zhongshenmitsin, copper thiodiazole, zinc thiazole, amectotrac

- 16 045799 tin, iprodione, 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-3methyl-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, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole -3yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxad iazol-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-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1, 2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine, which can be prepared by 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-1yl)propan-2-ol (this compound may be prepared by 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 by the methods described in WO 2017/029179), 3-[2-(1chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this the compound can be prepared by 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 by the methods described in WO 2016/156290), (4-phenoxyphenyl)methyl-2-amino-6methylpyridine-3-carboxylate (this compound can be prepared by the methods described in WO 2014/006945), 2,6- dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dinyrrole-1,3,5,7(2H,6H)-tetron (this compound can be prepared by methods described in WO 2011/138281), Nmethyl-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,3dimethylpent-3-enamide (this compound can be prepared by the methods described in WO 2018/153707), N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine, N-[2-chloro-4-(2fluorophenoxy )-5-methylphenyl]-N-ethyl-N-methylformamidine (this compound can be prepared by the methods described in WO 2016/202742), 2-(difluoromethyl)-N-[(3S)-3-ethyl-1, 1dimethylindan-4-yl]pyridin-3-carboxamide (this compound can be prepared by the methods described in wO 2014/095675).

The compounds of the present invention can also be used in combination with anthelmintics. Such anthelmintics include compounds selected from the class of macrocyclic lactone compounds, such as the derivatives of ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin, described in EP-357460, EP-444964 and EP-594291. Additional anthelmintics include semisynthetic and biosynthetic derivatives of avermectin/milbemycin, such as those described in US-5015630, WO-9415944 and WO-9522552. Additional anthelmintics include benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxybendazole, 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 flucides such as triclabendazole and clorsulon, and cestodocides such as praziquantel and epsiprantel.

The compounds of the present invention can be used in combination with derivatives and analogues of the paraherquamide/marcfortine class of anthelmintics, as well as 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 of the general class of dioxomorpholine antiparasitics described in WO-9615121, as well as with anthelmintic active cyclic depsipeptides such as those described in WO9611945, WO-9319053, WO-9325543, EP-626375, EP-382173, WO-9419334, EP-382173 and EP-503538.

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

The compounds of the present invention can be used in combination with terpene alkaloids described, for example, in WO 95/19363 or WO 04/72086, in particular the compounds disclosed in these documents.

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

Organophosphorus compounds: acephate, azametifos, azinphos-ethyl, azinphos-methyl, bromphos, bromphos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demetonD-methyl, demeton-O-methylsulfone, dialifos, diazinon, dichlorvos, dicrotophos , dimethoate, disulfo

- 17 045799 tone, ethion, ethoprofos, etrimphos, famfour, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazophos, fonofos, formotion, fosthiazate, heptenophos, isazofos, isothioate, isoxathion, malathion, metacryphos, methamidophos, methidathion, methyl parathion, m evinphos , monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phentoate, fosalone, phospholane, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos-methyl, profenofos, propafos, proethamphos, prothiophos, pyraclofos , pyridapention, quinalphos, sulprofos, temephos, terbufos, tebupirimphos, tetrachlorvinphos, timeton, thiazophos, trichlorfon, vamidothion.

Carbamates: alanicarb, aldicarb, 2-sec-butylphenylmethylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloetocarb, etiophencarb, fenoxycarb, fentiocarb, furatiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenyl butyryl( methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiophanox, triazamate, UC-51717.

Pyrethroids: acrinathrine, allethrin, alphamethrin, 5-benzyl-3-furylmethyl-(E)-(1R)-cis-2,2dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin , alpha-cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cytitrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucitrinate, 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: benzoylurea compounds: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diophenolan, hexythiazox, etoxazole, chlorophentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.

Other antiparasitics: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, biphenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidin , cyromazine, diaclodene, diafenthiuron, DBI-3204, dynactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, etofenprox, phenazaquin, flumite, MTI-800, fenpiroximate, fluacripyrim, flubenzimine, flubrocitrinate, flufenzine, flufenprox, fluproxifen , halofenprox, hydramethylnon , IKI-220, kanemite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651, WL-108477, pyridaril, propargite, protrifenbut, pymetrozine, pyridaben, pyrimidifene, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, silomadine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosin, trinactin, verbutin, vertalek, YI-5301.

Biological agents: delta-endotoxin Bacillus thuringiensis ssp. aizawai, kurstaki, Bacillus thuringiensis, 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, cefquinom, florfenicol, buserelin, cefovecin, tulathromycin, ceftiofur, carprofen, metaflumizone, praziquaran tel., triclabendazole.

Another aspect of the present invention relates to the use of a compound of formula (I) or a preferred individual compound as defined above, a composition containing at least one compound of formula (I) or at least one preferred individual compound as defined above, or a fungicidal or insecticidal mixture, containing at least one compound of formula (I) or at least one preferred single compound as defined above, in mixture with other fungicides or insecticides described above, for the control or prevention of infestation of plants, for example beneficial plants such as crops, material for their propagation, eg seeds, harvested crops, eg harvested food crops, or non-living materials by insects or plant pathogens, preferably fungal organisms.

A further aspect of the present invention relates to a method for controlling or preventing the infestation of plants, for example beneficial plants such as crops, their propagation material such as seeds, harvested crops such as harvested food crops, or non-living materials by insects or phytopathogenic or spoilage microorganisms, or organisms potentially harmful to humans, especially fungal organisms, which involves the use of a compound of formula (I) or a preferred individual compound as defined above as an active ingredient in relation to plants, parts of plants or their place of growth, in relation to the material for their reproduction or in relation to any part of non-living materials.

Control or prevention means reducing the degree of infestation by insects, or phytopathogenic or spoilage microorganisms, or organisms potentially harmful to humans, especially fungal organisms, to such a level that improvement is visible.

A preferred method of controlling or preventing infection of crops by phytopathogenic microorganisms, especially fungal or insect organisms, which involves the use of a compound of formula (I) or an agrochemical composition containing at least one of these compounds is foliar application. The frequency of application and rate of application will depend on the risk of infection by the relevant pathogen or insect. However, the compounds of formula (I) can also enter the plant from the soil through the roots (systemic action) by irrigating the plant site 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 water rice crops, such granules can be applied to a flooded rice field. The compounds of formula (I) can also be applied to seeds (coating) by impregnating the seeds or tubers with either a liquid fungicide composition or by coating them with a solid composition.

A composition, for example a composition containing a compound of formula (I) and, if necessary, solid or liquid excipients 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 surfactants (surfactants).

Preferred application rates are typically 5 g to 2 kg active ingredient (a.i.) per hectare (ha), preferably 10 g to 1 kg-a.i./ha, most preferably 20 g to 600 g-a. .i./ha. When used as a seed drench, suitable dosages range from 10 mg to 1 g of active substance per 1 kg of seeds.

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

The compositions of the present invention can be used in any conventional form, for example, in the form of a twin pack, dry seed treatment powder (DS), seed treatment emulsion (ES), flowable seed treatment concentrate (FS), seed treatment solution (LS ), water-dispersible seed treatment powder (WS), seed treatment capsule suspension (CF), seed treatment gel (GF), emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension ( CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsion (EO), oil-in-water emulsion (EW), microemulsion (ME), oil dispersion (OD), oil miscible fluid Substance (OF), Oil Miscible Liquid (OL), Soluble Concentrate (SL), Ultra Low Volume Suspension (SU), Ultra Low Volume Liquid (UL), Technical Concentrate (TK), Dispersible Concentrate (DC), Wettable Powder (WP) or any commercially 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, excipients and optionally other formulation ingredients such as surfactants, biocides, antifreeze additives, tackifiers, thickeners and compounds , which provide auxiliary effects). If long-term action is required, traditional slow-release formulations can also be used. In particular, spray formulations such as water-dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders and granules may contain surfactants , such as wetting and dispersing agents and other compounds that provide auxiliary effects, for example, formaldehyde naphthalene sulfonate condensate, alkylaryl sulfonate, lignin sulfonate, fatty acid alkyl sulfate and ethoxylated alkyl phenol, and ethoxylated fatty alcohol.

The seed treatment 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 treatment composition, for example, an aqueous suspension or a dry powder form having good adhesion to the seeds. Such seed dressing compositions are known in the art. Seed dressing compositions may contain individual active ingredients or a combination of active ingredients in encapsulated form, such as capsules or slow release microcapsules.

Typically, the formulations contain from 0.01 to 90% by weight active agent, from 0 to 20% agriculturally acceptable surfactant, and from 10 to 99.99% solid or liquid inert formulation components and auxiliary(s). ) substance(s), wherein the active agent consists of at least a compound of formula (I) together with component (B) and

- 19 045799 (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 active agent. The formulation forms used may, for example, contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight, of active agent. Since commercial products will preferably be formulated as concentrates, the end user will typically use diluted formulations.

In table 1 below illustrates examples of individual compounds of formula (I) in accordance with the present invention.

Table 1

Individual compounds of formula (I) according to the present invention______

Connection no. X Y R ¹ Connection no. X Y R ¹ 01 CH CH C1 16 N CH C1 02 CH CH Vg 17 N CH Vg 03 CH CH CH ₃ 18 N CH СНз 04 CH CH -OSNZ 19 N CH -OSNZ 05 CH CH -NHCHO 20 N CH -NHCHO 06 CH CF C1 21 N CF C1 07 CH CF Vg 22 N CF Vg 08 CH CF СНз 23 N CF СНз 09 CH CF -OSNZ 24 N CF -OSNZ 10 CH CF -NHCHO 25 N CF -NHCHO eleven CH N C1 26 N N C1 12 CH N Vg 27 N N Vg 13 CH N CH ₃ 28 N N CH ₃ 14 CH N -OSNZ 29 N N -OSNZ 15 CH N -NHCHO thirty N N -NHCHO

Where:

a) 30 compounds of formula (I.a):

where R ¹ , X and Y are defined in table. 1; b) 30 compounds of formula (Ib):

where R ¹ , X and Y are defined in table. 1; c) 30 compounds of formula (Ic):

- 20 045799 where R ¹ , X and Y are defined in table. 1; d) 30 compounds of formula (Id):

where R ¹ , X and Y are defined in table. 1; e) 30 compounds of formula (Ie):

where R ¹ , X and Y are defined in table. 1; f) 30 compounds of formula (If):

where R ¹ , X and Y are defined in table. 1; g) 30 compounds of formula (Ig):

where R ¹ , X and Y are defined in table. 1; h) 30 compounds of formula (Ih):

-21 045799

where R ¹ , X and Y are defined in table. 1;

i) 30 compounds of formula (I.i):

where R ¹ , X and Y are defined in table. 1. j) 30 compounds of formula (Ij):

where R ¹ , X and Y are defined in table. 1; k) 30 compounds of formula (Ik):

where R ¹ , X and Y are defined in table. 1;

l) 30 compounds of formula (I.l):

where R ¹ , X and Y are defined in table. 1; m) 30 compounds of formula (Im):

- 22 045799

where R ¹ , X and Y are defined in table. 1; n) 30 compounds of formula (In):

where R ¹ , X and Y are defined in table. 1; o) 30 compounds of formula (Io):

where R ¹ , X and Y are defined in table. 1; p) 30 compounds of formula (Ip):

where R ¹ , X and Y are defined in table. 1. Examples of compositions.

- 23 045799

Wettable powders A) b) With) active ingredient [compound of formula (I)] 25% 50% 75% sodium lignosulfonate 5% 5% - sodium lauryl sulfate 3% - 5% sodium diisobutylnaphthalene sulfonate - 6% 10% polyethylene glycol phenolic 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.

Powders for dry seed treatment A) b) With) 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 thoroughly ground in a suitable mill to obtain powders that can be used directly for seed treatment. Emulsifiable concentrate active ingredient [compound of formula (I)] 10% polyethylene glycol octylphenol ether 3% (4-5 mol ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether 4% (3 5 mol ethylene oxide) cyclohexanone 30% xylene mixture 50%

From this concentrate, by diluting with water, one can 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 powdered preparations are prepared by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry seed dressing options. Extruded granules active ingredient [compound 15% of formula (I)] sodium lignosulfonate 2% carboxymethylcellulose 1% kaolin 82%

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The active ingredient is mixed and crushed 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 [compound 8% of formula (I)] polyethylene glycol (MW 200) 3% kaolin 89%

The finely ground active ingredient is evenly applied to the kaolin moistened with polyethylene glycol in a mixing device. In this way, non-dust-like, coated granules are obtained.

Suspension concentrate active ingredient [compound of formula (I)] 40% propylene glycol 10% polyethylene glycol nonylphenol ether (15 mol 6% ethylene oxide) sodium lignosulfonate 10% carboxymethylcellulose 1% silicone oil (as a 75% emulsion in water) 1% water 32%

The finely divided active ingredient is thoroughly mixed with the excipients to obtain a suspension concentrate from which suspensions of any desired degree of dilution can be prepared by dilution with water. With the help of such diluted solutions, living plants, as well as plant propagation material, can be treated and protected from contamination by microorganisms by spraying, watering or immersing.

Flowable seed treatment concentrate active ingredient [compound of formula (I)] 40% propylene glycol 5% butanol-PO/EO copolymer 2% tristyrene phenol with 10-20 moles EO 2%

1,2-benzisothiazolin-3-one (as a 20% solution in water) 0.5% calcium salt of monoazopigment 5% silicone oil (as a 75% emulsion in water) 0.2% water 45.3%

The finely divided active ingredient is thoroughly mixed with the excipients to obtain a suspension concentrate from which suspensions of any desired degree of dilution can be prepared by dilution with water. With the help of such diluted solutions, living plants, as well as plant propagation material, can be treated and protected from contamination by microorganisms by spraying, watering or immersing. Slow-release capsule suspension

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

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

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

Examples

The following examples serve to illustrate the present invention. The compounds of the present invention may differ from known compounds due to higher effectiveness at low rates of application, which can be verified by one skilled in the art using

- 25 045799 experimental procedures outlined in the Examples section, using lower application rates if necessary, for example 50, 12.5, 6, 3, 1.5, 0.8 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 against diseases caused by fungi, or superior properties for use as agrochemically active ingredients (e.g., higher biological activity, preferential spectrum of activity, improved safety profile (including improved crop tolerance), improved physicochemical properties or increased biodegradability).

List of Abbreviations bs = wide singlet;

°C = degrees Celsius;

CDCl ₃ = chloroform-d;

d = doublet;

Pd ₂ (dba) ₃ = tris-(dibenzylideneacetone)dipalladium(0);

DIPEA = N,N-diisopropylethylamine;

DMF = dimethylformamide;

h = hours;

HATU = 1-[bis-(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium-3-oxidehexafluorophosphate;

m = multiplet;

MHz = megahertz;

m.p. = melting point;

n. = normal;

ppm = parts per million;

s = singlet;

THF = tetrahydrofuran;

Xantphos = 4,5-bis-(diphenylphosphino)-9,9-dimethylxanthene.

Example 1 This example illustrates the preparation of 2-[cyano-(2,6-difluoro-4pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methylthiazol-4-carboxamide (compound I.b.23)

a) Preparation of methyl 2-[(2,6-difluoro-4-pyridyl)amino]-5-methylthiazole-4-carboxylate

n

Under argon, Xantphos (0.2 eq), Pd ₂ (dba) ₃ (0.1 eq), and cesium carbonate (2 eq) were added to the degassed, stirred mixture of methyl 2-bromo-5-methylthiazol-4 -carboxylate (4.6 g, 18.5 mmol, 1 eq.) and 2,6-difluoropyridin-4-amine (1 eq.) in 1,4-dioxane (660 ml). The reaction mixture was heated to reflux temperature and stirred for 4 hours, after which the temperature was allowed to drop to room temperature. The mixture was diluted with ethyl acetate and filtered through celite, and the resulting filtrate was concentrated using a rotary evaporator. Purification by silica gel column chromatography (cyclohexane/ethyl acetate eluting mixture) provided the desired methyl 2-[(2,6-difluoro-4-pyridyl)amino]-5-methylthiazol-4-carboxylate (1.8 g , 6.31 mmol).

^1H NMR (400 MHz, CDCb): δ = 2.73 (s, 3H), 3.94 (s, 3H), 6.75 (s, 1H).

b) Preparation of 2-[(2,6-difluoro-4-pyridyl)amino]-5-methyl-thiazole-4-carboxylic acid

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Add lithium hydroxide monohydrate (4 eq.) to a solution of 2-[(2,6-difluoro-4-pyridyl)amino]-5methylthiazole-4-carboxylic acid (1.8 g, 6.31 mmol) in a mixture of tetrahydrofuran (35 ml) and water (12 ml). The reaction mixture was stirred for 16 h at room temperature, then the solvents were removed in vacuo. The residue was diluted with ethyl acetate and water, then 2 N was added slowly. hydrochloric acid solution until pH 3-4 is achieved. The resulting precipitate was isolated by filtration and washed twice with water to give the desired product as 2-[(2,6-difluoro-4pyridyl)amino]-5-methylthiazole-4-carboxylic acid (1.55 g, 5.71 mmol) . Ή NMR (400 MHz, (CD ₃ ) ₂ SO): δ = 2.69 (s, 3H), 7.30 (s, 2H), 11.35 (bs, 1H), 12.90 (bs, 1H ).

c) Preparation of 2-[(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methylthiazol-4carboxamide

n

(2,2-Dimethylcyclobutyl)ammonium chloride (1.1 eq.), HATU (1.1 eq.) and DIPEA (2.6 eq.) were added sequentially to a solution of 2-[(2,6-difluoro-4- pyridyl)amino]-5-methylthiazole-4-carboxylic acid (250 mg, 0.92 mmol, 1 eq.) in DMF (9.2 ml). The resulting solution was stirred at room temperature for 1 hour until the starting material was consumed (monitored by LCMS). Then a saturated NaHCO ₃ solution was added to the mixture and the solution was extracted three times with ethyl acetate. The organic phases were combined, dried over sodium sulfate and volatiles were removed using a rotary evaporator. Purification by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate) gave the desired product as 2-[(2,6-difluoro-4pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5- methylthiazole-4-carboxamide (280 mg, 86% yield). ¹ NMR (400 MHz, CDC13): δ = 1.17 (s, 3H), 1.20 (s, 3H), 1.50-1.75 (m, 2H), 1.86-1.92 ( m, 1H), 2.29-2.36 (m, 1H), 2.79 (s, 3H), 4.25-4.31 (m, 1H), 6.87 (s, 2H), 7 .32 (d 1H), 7.67 (s, 1H).

d) 2-[Cyano-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methylthiazol-4-carboxamide (compound I.b.23)

Add butyllithium (2.5 M solution in hexane, 1.25 eq.) at -78°C to a stirred solution of 2[(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl) -5-methylthiazole-4-carboxamide (300 mg, 0.85 mmol, 1 eq.) in THF (4.3 ml). After 30 minutes, cyanogen bromide was added to the solution, the reaction mixture was allowed to reach room temperature, and it was stirred for 2 hours. The reaction mixture was then quenched with a saturated aqueous NaHCO ₃ solution and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were dried over sodium sulfate and volatiles were removed using a rotary evaporator. Purification by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate mixtures) gave the desired product as 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl )-5-methylthiazole-4-carboxamide (190 mg, 0.50 mmol, 59% yield). 1H NMR (400 MHz, CDC13): δ = 1.10 (s, 3H), 1.21 (s, 3H), 1.55-1.69 (m, 2H), 1.80-1.93 ( m, 1H), 2.25-2.35 (m, 1H), 2.90 (s, 3H), 4.25-4.31 (m, 1H), 6.92 (s, 2H), 7 .12(d, 1H).

Throughout this description, temperatures are given in degrees Celsius (°C) and m.p. means melting point. LC/MS means liquid chromatography - mass spectrometry, and the description of the device and method is as follows.

Method A: ACQUITY UPLC from Waters, Waters UPLC HSS T3, 1.8 µm particle size, column

30x2.1 mm, 0.85 ml/min, 60°C, H ₂ O/MeOH 95:5 + 0.05% HCOOH (90%)/CH ₃ CN + 0.05% HCOOH (10%) 1, 2 min - CH3CN + 0.05% HCOOH (100%) - 0.30 min, ACQUITY SQD mass spectrometer from Waters, ionization method: electrospray (ESI), polarity: positive ions, capillary voltage (kV) 3.00 , cone voltage (V) 30.00, extractor voltage (V) 2.00, initial temperature (°C) 150, desolvation temperature (°C) 350, gas flow in cone (l/h) 0, gas flow desolvation (l/hour) 650).

Method B: ACQUITY UPLC from Waters, Waters UPLC HSS T3, 1.8 µm particle size, 30x2.1 mm column, 0.85 ml/min, 60°C, H ₂ O/MeOH 95:5 + 0.05% HCOOH (90%)/CH ₃ CN + 0.05% HCOOH (10%) - 27 045799

2.7 min - CH3CN + 0.05% HCOOH (100%) - 0.30 min, ACQUITY SQD mass spectrometer from Waters, ionization method: electrospray (ESI), polarity: positive ions, capillary voltage (kV)

3.00, cone voltage (V) 30.00, extractor voltage (V) 2.00, initial temperature (°C)

150, desolvation temperature (°C) 350, gas flow in the cone (l/hour) 0, desolvation gas flow (l/hour) 650)).

Method C: MS: Waters ZQ mass spectrometer (single quadrupole mass spectrometer) Instrument parameters: ionization method: electrospray, polarity: positive (negative) ions, capillary voltage (kV) 3.00, cone voltage (V) 30 .00, extractor voltage (V) 2.00, gas temperature (°C) 350, drying gas flow (ml/min) 9.8, nozzle pressure 45 psi. inch, mass range: 90 Da to 1000 Da.

HPLC: Agilent HP 1100 HPLC: Solvent degasser, ZCQ/ZDQ pump, heated column space, and diode array detector. Column: porpshell 120 C18, particle size 2.7 µm, 120 angstrom, 4.6x50 mm, temperature: 30°C. DAD wavelength range (nm): 190-400, solvent gradient: A = water + 0.1% HCOOH. B = acetonitrile + 0.08% HCOOH.

Time (min.) A% IN% Flow (ml/min.) 0.00 85.0 15.0 0.6 4.00 5.00 95.00 0.6 10.00 5.00 95.00 0.6

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table 2

Melting point and LC/MS data (Rt = retention time) for selected compounds from the table. 1 „ Name Connection No.

1.a.18 2-[Cyano-(5-fluoro-3pyridyl)amino]-Ncyclobutyl-5methylhyazol-4carboxamide

I.b.18 2-[Cyano-(5-fluoro-3pyridyl)amino]-N-(2,2dimethylcyclobutyl)-5 methylhyazol-4carboxamide

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- 30 045799

- 31 045799

- 32 045799

Surprisingly, it has been discovered that the new compounds of formula (I) can exhibit improved solubility properties (particularly in non-polar solvents) and/or light stability properties compared to their corresponding free amines (i.e. where the nitrile group at the nitrogen atom is replaced by hydrogen) , which are known, for example, from WO 2017/207362.

Throughout the following description, LogP means the logarithm of the distribution coefficient, ppm means parts per million, and _T50 represents the half-life of the compound under irradiation conditions.

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The methods used to carry out these measurements are presented below.

Distribution coefficient.

Octanol-water partition coefficients (represented as LogP) were measured by HPLC using octanol-coated reverse phase minicolumns. The distribution coefficient P is directly proportional to the HPLC retention factor. The general principles of this method have been described, for example, in J. Pharm. Sci., 67 (1978) 1364-7.

A Waters HPLC system (model 1525 binary pump; 2707 autosampler with thermostat and 2298 photodiode array detector) was used with Hichrom minicolumns and an aqueous mobile phase containing 20 mM phosphate buffers adjusted to pH 7, saturated with 1-octanol ( Aldrich, HPLC purity). The minicolumns used were HiRPB stationary phase, either 4.6 mm i.d. x 4 mm long or 2 mm i.d. x 10 mm long. Anisole (Aldrich, 99%+ purity, LogP 2.11) was used as the primary standard for system calibration.

Light stability.

Light stability testing was carried out by irradiating thin film deposits of the compounds and formulations on a glass surface using a xenon filter lamp system (Atlas Suntest) that replicated the spectrum and intensity of sunlight. Suntest's spectral output power was set to 750 W/ ^m2 , which represents a typical daytime maximum irradiance at midday (UK, midsummer).

Test compounds were typically dissolved in HPLC grade methanol to produce 1 g/L stock solutions. Alternatively, the formulated compounds were suspended in water at the same concentration. 2 μL drops of test solutions were applied to microscopy coverslips in a 3D printed stand, allowed to dry, then irradiated under Suntest for various periods of time. The coverslips were then removed from the Suntest and placed into 4-dram vials; 1 ml of wash solvent (usually a mixture of 30:70 acetonitrile:0.2% aqueous formic acid) was added and the vials were shaken to extract the compounds into the solution. Solutions were analyzed by reverse phase HPLC, typically using a Waters UPLC system with a photodiode array (PDA) and Waters columns (BEN C18, 100x2.1 mmx1.7 µm) using a mixed mobile phase of water:acetonitrile, acidified using 0.2% formic acid. Peaks were recorded at the optimal wavelength for each candidate compound, and PDA peak areas were used for quantification. Graphs of % loss versus time were used to estimate _T50 values using the time of loss of the first 50% of the test compound.

Solubility.

Saturated solutions of the test compounds were prepared either in aqueous buffer solutions (10 mM mixed phosphate, pH 7.20) or in heptane. Typically, 1 mg of test compound in a 2 dram vial with 1 ml of buffer or heptane is left overnight (20 hours) on a roller shaker after first being placed in an ultrasonic bath for a period of 20 minutes. The saturated samples were then filtered through 0.45 μm Millex-HV syringe filters (aqueous or non-aqueous version depending on the solvent). Aqueous samples were then analyzed by direct injection into the LCMS, and peak areas obtained using PDA detection were compared to standards of known concentration; samples in heptane were first dried and redissolved in an LC-compatible solvent, typically a 30:70 mixture of acetonitrile:0.2% formic acid solution. Protocol variations included pre-saturation of filters for compounds expected to have extremely low solubility and centrifugation of saturated samples in the case of oils.

In table 3 below illustrates unexpected physicochemical properties (partition coefficient LogP, solubility in heptane and/or light stability) relative to earlier compounds known in the art from WO 2017/207362.

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Table 3

Connection name

Structure

LogP

Solubility in water (ppm)

Solubility in heptane (ppm)

2-[Cyano-(2,6difluoro-4pyridyl)amino]-N(2,2dimethylcyclobutyl)5-methylthiazol-4 carboxamide

2-[(2,6-Difluoro-4pyridyl)amino]-N(2,2dimethylcyclobutyl)5-methylthiazol-4 carboxamide

Light stability

Biological examples.

Example Bl. Alternaria solani/tomato/leaf disk (alternaria).

Baby tomato leaf disks were placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compound diluted in water. Leaf discs were inoculated with a suspension of fungal spores 2 days after application. The inoculated leaf disks were incubated at 23°C/21°C (day/night) and 80% relative humidity under a 12/12 hour light/dark regime in a climate chamber and the activity of the compound was assessed as a percentage of disease control. , compared with untreated material when the corresponding degree of damage due to disease appears on untreated leaf disks, which represent control disks (5-7 days after application). The following compounds provided at least 80% control of Alternaria solani at 200 ppm compared to the untreated control, which showed extensive disease development under the same conditions: I.a.23, I.b.08, I.b.23.1.c.23, I.g.23.1. i.23,1.k. 18.1.m.18.

Example B2. Botryotiniafuckeliana (Botrytis cerea)/liquid culture (grey mold).

Fungal conidia from cryogenic storage were directly mixed with nutrient broth (Vogel broth). After adding the solution (DMSO) of the test compound, nutrient broth containing fungal spores was added to a microtiter plate (96-well format). The test compound plates were incubated at 24°C and growth inhibition was determined photometrically 3-4 days after application. The following compounds provided at least 80% control of Botryotinia fuckeliana at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions: I.b.23,1.c.23,1.h.23,1.k.23 ,1.0.23.

Example B3. 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, nutrient broth containing fungal spores was added to a microtiter plate (96-well format). The test compound plates were incubated at 24°C and growth inhibition was measured photometrically 3-4 days after application.

The following compounds provided at least 80% control of Glomerella lagenarium at 20 ppm compared to the untreated control, which under the same conditions showed extensive disease development: I.a.18, I.b.08, I.b.18, I.b.23, I.b.25, I.c.23, I.d.23 , I.e.23, I.f.23, I.g.08, I.g.23, Lh.18, Lh.23,1.i.23,1.j.23,1.k.18,1.k.23,1.1.18,1.1 .23, Lm.18, Lo.23,1.p.23.

Example B4. Blumeria graminis f. sp. tritici (Erysiphe graminis f. sp. thys1)/wheat/prevention of leaf disc infection (powdery mildew of wheat).

Wheat leaf segments of the cultivar Kanzler were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. Leaf discs were inoculated by shaking powdery mildew-infected plants over test plates 1 day after application. The inoculated leaf disks were incubated at 20°C and 60% relative humidity under a light regime of 24 hours dark followed by 12 hours light/12 hours dark in a climate chamber and the activity of the compound was assessed as a percentage of disease control compared to untreated material at manifestation of the corresponding degree of damage due to the disease on untreated control leaf segments (6-8 days after application).

The following compounds provided at least 80% control of Blumeria graminis f. sp. tritici

-35 045799 at 200 ppm compared to the untreated control, which under the same conditions showed extensive disease development: I.a.23, I.b.08, I.b.18, I.b.23, I.c.23, I.d.23, I.e.23, I.f.23, I.g.08, I.g. 23, I.h.23,

I.i.23, I.j.23, I.k.18, I.k.23, I.l.23, I.m.18, I.o.23, I.p.23.

Example B5. Fusarium culmorum/wheat/prevention of spikelet infection (fusarium).

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

The following compounds provided at least 80% control of Fusarium culmorum at 200 ppm compared to the untreated control, which showed extensive disease development under the same conditions: I.b.23.

Example B6. Phaeosphaeria nodorum (Septoria nodorum)/wheat/prevention of leaf disc infection (septoria glume blight).

Leaf segments of the wheat variety Kanzler were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. Leaf discs were inoculated with a suspension of fungal spores 2 days after application. The inoculated test leaf disks were incubated at 20°C and 75% relative humidity under a 12-hour light/12-hour dark cycle in a climate chamber and the activity of the compound was assessed as a percentage of disease control compared to untreated material when exhibiting the appropriate degree of damage. due to disease on untreated control leaf disks (5-7 days after application).

The following compounds provided at least 80% control of Phaeosphaeria nodorum at 200 ppm compared to the untreated control, which under the same conditions showed extensive disease development: I.a.23, I.b.23, I.d.23, I.f.23, I.g.23, I.i.23, I.k.18 , I.k.23.

Example B7. Monographella nivalis (Microdochium nivale)/liquid culture (cereal root rot).

Fungal conidia from cryogenic storage were directly mixed with nutrient broth (potato dextrose broth, PDB). After adding a solution (DMSO) of the test compound, a nutrient broth containing fungal spores was added to a microtiter plate (96-well format). The test compound plates were incubated at 24°C and growth inhibition was determined photometrically 4-5 days after application. The following compounds provided at least 80% control of Monographella nivalis at 20 ppm compared to the untreated control, which under the same conditions showed extensive disease development: I.a.18, I.a.23, I.b.08, I.b.18, I.b.23, I.b.25, I.c.23 , I.d.23, I.e.23, I.f.23, I.g.08, I.g.23, I.h.18, I.h.23, I.i.23, I.j.23, I.k.18, I.k.23, I.l.18, I.l.23, I.m.18, I.o.23, I.p.23.

Example B8. Mycosphaerella arachidis (Cercospora arachidicola)/liquid culture (early cercospora leaf blight).

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

The following compounds provided at least 80% control of Mycosphaerella arachidis at 20 ppm compared to the untreated control, which under the same conditions showed extensive disease development: I.a.18, I.b.08, I.b. 18, I.b.23, I.c.23, I.d.23, I.e.23, I.f.23, I.g.08, I.g.23, I.h.18, I.h.23, I.i.23, I.k.18, I.k.23, I.l.18, I.l.23, I.m.18, I.o.23, I.p.23.

Example B9. Phakopsora pachyrhizi/soybean/warning (soybean rust).

Soybean leaf disks were placed on aqueous agar solution in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application, leaf discs were inoculated by spraying a spore suspension onto the lower surface of the leaf. After an incubation period of 24-36 hours in the climate chamber in the dark at 20°C and 75% relative humidity, the leaf disc was kept at 20°C with 12 hours of light/day and 75% relative humidity. Compound activity was assessed as a percentage of disease control compared to untreated material when the appropriate degree of disease damage was observed on untreated control leaf discs (12-14 days after application).

The following compounds provided at least 80% control of Phakopsora pachyrhizi at 200 ppm compared to the untreated control, which under the same conditions showed extensive disease development: I.b.23, I.f.23, I.g.23, I.h.23, I.i.23, I.l. 23, I.p.23.

Example B10. Plasmopara viticola/grape/prevention of leaf disc infection (late blight).

Cultivated grape leaf discs were placed on aqueous agar solution in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. Leaf discs were inoculated with a suspension of fungal spores 1 day after application. Inoculated leaf discs were incubated at 19°C and 80% relative humidity under a 12-hour light/12-hour dark climate chamber and the compound activity was assessed as a percentage of disease control compared to untreated material exhibiting the appropriate degree of damage due to diseases on untreated control leaf disks (6-8 days after application).

The following compounds provided at least 80% control of Plasmopara viticola at 200 ppm compared to the untreated control, which showed extensive disease development under the same conditions: I.g.08, I.l.18.

Example B11. Puccinia recondita f. sp. tritici/wheat/treatment of leaf disc infection (leaf rust).

Segments of wheat leaves of the Kanzler variety were placed on agar in multiwell plates (24-well format). Leaf segments were inoculated with a suspension of fungal spores. The plates were stored in the dark at 19°C and 75% relative humidity. The formulated test compound, diluted in water, was applied 1 day after inoculation. Leaf segments were incubated at 19°C and 75% relative humidity under a 12-hour light/12-hour dark cycle in a climate chamber and the activity of the compound was assessed as a percentage of disease control compared to untreated material when exhibiting the appropriate degree of disease damage. on untreated control leaf segments (6-8 days after application).

The following compounds provided at least 80% control of Puccinia recondita f. sp. tritici at 200 ppm compared to the untreated control, which under the same conditions showed extensive disease development: I.b.23, I.c.23, I.h.23, I.i.23, I.k.23, I.l.23, I.p.23.

Example B12. Puccinia recondita f. sp. tritici/wheat/prevention of leaf disc infection (leaf rust).

Wheat leaf segments of the cultivar Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. Leaf discs were inoculated with a suspension of fungal spores 1 day after application. Inoculated leaf segments were incubated at 19°C and 75% relative humidity under a 12-hour light/12-hour dark cycle in a climate chamber and compound activity was assessed as a percentage of disease control compared to untreated material exhibiting the appropriate degree of damage due to diseases on untreated control leaf segments (7-9 days after application).

The following compounds provided at least 80% control of Puccinia recondita f. sp. tritici at 200 ppm compared to the untreated control, which under the same conditions showed extensive disease development: I.a.18, I.a.23, I.b.08, I.b.18, I.b.23, I.c.23, I.d.23, I.e.23, I.f.23, I.g.08, I.g.23, I.h.18, I.h.23, I.i.23, I.j.23, I.k.23, I.l.18, I.l.23, I.m.18, I.o.23, I.p.23.

Example B13. Magnaporthe grisea (Pyricularia oryzae)/rice/prevention of leaf disk infection (rice blast).

Ballila rice leaf segments were placed on agar in a multi-well plate (24-well format) and sprayed with the formulated test compound diluted in water. Leaf segments were inoculated with a suspension of fungal spores 2 days after application. The inoculated leaf segments were incubated at 22°C and 80% relative humidity under a light regime of 24 hours dark followed by 12 hours light/12 hours dark in a climate chamber and the activity of the compound was assessed as a percentage of disease control compared to untreated material at manifestation of the corresponding degree of damage due to the disease on untreated control leaf segments (5-7 days after application).

The following compounds provided at least 80% control of Magnaporthe grisea at 200 ppm compared to the untreated control, which under the same conditions showed extensive disease development: I.a.18, I.a.23, I.b.08, I.b. 18, I.b.23, I.c.23, I.d.23, I.e.23, I.f.23, I.g.08, I.g.23, I.h.23, I.i.23, I.j.23, I.k.18, I.k.23, I.l.18, I.l.23, I.m.18, I.o.23, I.p.23.

Example B14. Pyrenophora teres/barley/prevention of leaf disc infection (net spot).

Hasso barley leaf segments were placed on agar in a multi-well plate (24-well format) and sprayed with the formulated test compound diluted in water. Leaf segments were inoculated with a suspension of fungal spores 2 days after application. The inoculated leaf segments were incubated at 20°C and 65% relative humidity under a 12-hour light/12-hour dark cycle in a climate chamber and the activity of the compound was assessed as a percentage of disease control compared to untreated material at development. appropriate degree of damage due to disease on untreated control leaf segments (5-7 days after application).

The following compounds provided at least 80% control of Pyrenophora teres at 200 ppm compared to the untreated control, which showed extensive disease development under the same conditions: I.a.23, I.b.18, I.b.23, I.c.23, I.d.23, I.g.23, I.i.23 , I.k.23, I.p.23.

Example B15. Sclerotinia sclerotiorum/liquid culture (white rot).

Mycelium fragments from a newly grown fungal culture in liquid medium were directly mixed with nutrient broth (PDB potato dextrose broth). After adding the solution (DMSO) of the test compound, nutrient broth containing fungal material was added to a microtiter plate (96-well format). The test compound plates were incubated at 24°C and growth inhibition was determined photometrically 3-4 days after application.

The following compounds provided at least 80% control of Sclerotinia sclerotiorum at 20 ppm compared to the untreated control, which under the same conditions showed extensive disease development: I.b.18, I.b.23, I.c.23, I.f.23, I.g.23, I.h.23, I.i.23 .

Example B16. Mycosphaerella graminicola (Septoria tritici)/liquid culture (septoria).

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

The following compounds provided at least 80% control of Mycosphaerella graminicola at 20 ppm compared to the untreated control, which under the same conditions showed extensive disease development: I.a.23, I.b.08, I.b.18, I.b.23, I.b.25, I.c.23, I.d.23 , I.e.23, I.f.23, I.g.23, I.h.18, I.h.23, I.i.23, I.j.23, I.k.18, I.k.23, I.l.18, I.l.23, I.m.18,1.o.23, I.p.23.

Claims (10)

1. Compound of formula (I) FHN^ N where Y represents C-F or C-H; R ¹ represents methyl or HC(O)NH-; R ² represents C1-C6 alkyl, C1-C3 alkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C2 alkyl, where the cycloalkyl groups are optionally substituted by 1-3 groups represented by R ³ , phenyl, phenyl- C1- _C2 alkyl, where the phenyl rings are optionally substituted with 1-3 groups represented by ^R3 , heteroaryl, where heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms, individually selected from nitrogen , oxygen and sulfur, heterocyclyl, where heterocyclyl is a 4-, 5- or 6-membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, or a 5-12 membered non-aromatic spirocyclic a carbobi or carbotricyclyl ring system, optionally containing one heteroatom selected from nitrogen, oxygen and sulfur; R ³ is C ₁ -C ₃ -alkyl, C ₁ -C ₃ -haloalkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₂ -alkyl and X represents N or C-H. 2. The compound according to claim 1, where R ¹ represents methyl. 3. A compound according to claim 1 or 2, wherein R ² represents C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C2 alkyl, wherein the cycloalkyl groups are optionally substituted by 1 or 2 groups represented by R ³ , phenyl-C1-C ₂ -alkyl, where the phenyl rings are optionally substituted with 1 or 2 groups represented by R ³ , or a 5-12 membered non-aromatic spirocyclic carbobi- or carbotricyclyl ring system. 4. A compound according to any one of claims 1 to 3, where R ² represents n-butyl, isobutyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, 1-(cyclopropylmethyl)cyclopropylmethyl, cyclobutyl, 2, 2-dimethylcyclobutyl, 1-methylcyclopentyl, benzyl, 1-phenylethyl, 3,5-bis-(trifluoromethyl)phenylmethyl, spiro[3.3]heptanyl, spiro[3.4]octanyl or spiro[cyclobutan-1,2'-indanyl]. 5. A compound according to any one of claims 1 to 4, where X represents N. 6. A compound according to any one of claims 1 to 5, where Y represents C-F. - 38 045799 7. A compound according to any one of claims 1 to 6, wherein the compound of formula (I) is 2-[cyano-(2,6difluoro-4-pyridyl)amino]-I-(2,2-dimethylcyclobutyl)-5-formamidothiazole -4-carboxamide (1.b.25), 2[cyano-(2,6-difluoro-4-pyridyl)amino]-K-[[1-(cyclopropylmethyl)cyclopropyl]methyl]-5-methylthiazol-4carboxamide ( l.f.23), 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-I-spiro[3.3]heptan-3-ylthiazol-4carboxamide (1.e.23), 2- [cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-I-spiro[3.4]octan-3-ylthiazol-4carboxamide (1.c.23), 2-[cyano-(2, 6-difluoro-4-pyridyl)amino]-5-methyl-I-spiro[cyclobutane-2,2'-indan]1-ylthiazol-4-carboxamide (l.d.23) or 2-[cyano-(2,6- difluoro-4-pyridyl)amino]-I-(2,2-dimethylcyclobutyl)-5-methylthiazol-4-carboxamide (1.b.23). 8. An agrochemical composition containing a fungicidal effective amount of a compound of formula (I) according to any one of claims 1 to 7. 9. A method for controlling or preventing infection of beneficial plants by phytopathogenic microorganisms, wherein a fungicidal effective amount of a compound of formula (I) according to any one of claims 1 to 7 or a composition containing this compound as an active ingredient is applied to plants, parts thereof or their place of growth. 10. Use of a compound of formula (I) according to any one of claims 1 to 7 as a fungicide, where said use excludes methods of treating humans or animals with surgery or therapy.