RU2779183C2 - Triazole derivatives with microbiocidal activity - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: invention relates to a compound of the formula (I), where R¹ is fluorine; R² is hydrogen; R³ is halogen or C₁-C₄alkyl; R⁴ is hydrogen; R⁵ is C₁-C₆alkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkylC_1-2alkyl, C₂-C₆alkinyl, phenyl, heterocyclyl or heterocyclylC₁alkyl, where heterocyclyl is a 4- or 6-element nonaromatic monocyclic ring containing 1 oxygen atom, or a 5-9-element nonaromatic annulated or spirocyclic carbobicyclic ring system optionally containing 1 oxygen atom and optionally bound to the rest of a molecule by a methylene (-CH₂-) linker; where any of the specified C₁-C₆alkyl, C₃-C₆cycloalkyl and C₂-C₆alkinyl fragments are optionally substituted with 1-4 groups represented by R⁷, or 1 group represented by R⁸; where any of the specified phenyl or heterocyclyl fragments are optionally substituted with 1 or 2 groups represented by R⁹, or 1 group represented by R¹⁰, or optionally substituted with 1 or 2 groups represented by R⁹ and 1 group represented by R¹⁰; and where the annulated or spirocyclic carbobicyclic ring is optionally substituted with 1 or 2 groups represented by R⁷, or the annulated carbobicyclic ring system is optionally substituted with C₄-C₅cycloalkyl to form a spirocyclic fragment; R⁷ is independently selected from chlorine, bromine, fluorine, cyano, hydroxyl, methyl, trifluoromethyl, methoxy, butoxy, methoxymethyl, cyclopropyl, cyclohexyl, cyclooctyl, cyclopropyl methyl, acetyloxymethyl and ethoxycarbonyl; where cyclopropyl is unsubstituted or substituted with 2 groups of chlorine; R⁸ is phenyl, benzyl or isoxazole, unsubstituted or substituted with 1-3 groups represented by R⁹ or 1 group represented by R¹⁰; R⁹ is independently selected from halogen, cyano, hydroxyl and C₁-C₄alkyl; R¹⁰ is selected from phenyl, benzyl and C₆-C₈cycloalkoxy, each of which is unsubstituted or substituted with 1-3 groups represented by R¹¹; R¹¹ is independently selected from halogen and methyl; X is C-H or N; or its salts. The invention also relates to a fungicidal composition containing the fungicidal effective amount of a compound according to the invention and an agrochemical diluent or carrier. The compound according to the invention is used in a method for control or prevention of an infection of useful plants with phytopathogenic microorganisms.

EFFECT: thiazole derivatives with fungicidal activity.

12 cl, 2 tbl, 2 ex

Description

The present invention relates to thiazole derivatives having microbiocidal activity, such as active ingredients 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 agricultural or horticultural uses of the thiazole derivatives or compositions thereof for the control or prevention of infection in plants, harvested food crops. crops, seeds or non-living materials by phytopathogenic microorganisms, mainly fungi.

WO 2010/012793 describes aminothiazole derivatives as pesticides.

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

where

R ¹ is halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy, with C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy optionally substituted with 1-3 groups represented by R ⁶ ;

R ² and R ⁴ independently represent hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₃ -C ₆ cycloalkyl, while C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C ₃ - C ₆ cycloalkyl are optionally substituted with 1-3 groups represented by R ⁶ ;

R ³ is halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₃ -C ₆ cycloalkyl, with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C ₃ -C ₆ cycloalkyl optional substituted with 1-3 groups represented by R ⁶ ;

R ⁵ is C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₆ cycloalkenyl, C ₃ -C ₁₀ cycloalkylC ₁ -C ₂ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl , aryl, heteroaryl, wherein 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, wherein heterocyclyl is 4-, 5- or 6-membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms, individually selected from nitrogen, oxygen and sulfur, heterocyclylC ₁ -C ₂ alkyl or 5-10-membered non-aromatic annelated or spirocyclic carbobicylyl ring system, optionally containing 1, 2, 3, 4 or 5 heteroatoms individually selected from nitrogen, oxygen and sulfur, and optionally linked to the rest of the molecule via a C ₁ -C ₂ alkylene linker;

where any of the specified C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₂ -C ₁₀ alkenyl and C ₂ -C ₁₀ alkynyl fragments are optionally substituted with 1-4 groups represented by R ⁷ , or 1 group represented by R ⁸ ; or

where any of the specified aryl, heteroaryl and heterocyclyl fragments are optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ , or optionally substituted with 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ ; or

where an annelated or spirocyclic carbobicyclyl ring system is optionally substituted with 1-3 groups represented by R ⁷ , or an annelated carbobicyclyl ring system is optionally substituted with C ₃ -C ₆ cycloalkyl to form a spirocyclyl moiety;

R ⁶ is independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkoxy and C ₃ -C ₆ cycloalkyl;

R ⁷ is independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxyC ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl , C ₃ -C ₆ cycloalkylC ₁ -C ₂ alkyl, C ₂ -C ₆ acyl, C ₂ -C ₆ acyloxy, C ₂ -C ₆ acyloxyC ₁ -C ₆ alkyl and C ₁ -C ₄ alkoxycarbonyl;

wherein if R ⁷ is C ₃ -C ₆ cycloalkylC ₁ -C ₂ alkyl, then the C ₃ -C ₆ cycloalkyl moiety is optionally substituted with 1 or 2 groups independently selected from halogen and C ₁ -C ₆ alkyl;

R ⁸ is aryl, aryloxy, arylC ₁ -C ₆ alkyl, heteroaryl, wherein heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur, heteroaryloxy or heteroarylC ₁ -C ₆ alkyl, wherein aryl and heteroaryl are optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ ;

R ⁹ is independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkynyloxy,

while C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkynyloxy optionally substituted with 1-3 groups represented by R ¹¹ ;

R ¹⁰ is selected from C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkoxy, C ₃ -C ₆ cycloalkylthio, aryl, aryloxy, arylthio, arylC ₁ -C ₆ alkyl, heteroaryl, heteroaryl being 5- or 6- membered aromatic monocyclic ring containing 1, 2, 3 or 4 heteroatoms, individually selected from nitrogen, oxygen and sulfur, heteroaryloxy, heteroarylthio, heteroarylC ₁ -C ₆ alkyl, heterocyclyl, while heterocyclyl is 4-, 5- or 6 -membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms, individually selected from nitrogen, oxygen and sulfur, heterocyclyloxy, heterocyclylthio or heterocyclylC ₁ -C ₆ alkyl,

while C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkoxy, C ₃ -C ₆ cycloalkylthio, aryl, aryloxy, arylthio, arylC ₁ -C ₆ alkyl, heteroaryl, heteroaryloxy, heteroarylthio, heteroarylC ₁ -C ₆ alkyl, heterocyclyl , heterocyclyloxy, heterocyclylthio and heterocyclylC ₁ -C ₆ alkyl are optionally substituted with 1-3 groups represented by R ¹¹ ;

R ¹¹ is independently selected from halo and methyl;

X is C-H or N;

or its salt or N-oxide.

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

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

According to a third aspect of the present invention, there is provided a method for controlling or preventing the infestation of beneficial plants by phytopathogenic microorganisms, wherein a fungicidally 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 applied to their locus. .

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

When substituents are said to be "optionally substituted" this means that they may or may not carry one or more identical or different substituents, for example one, two or three R ⁹ substituents. For example, C ₁ -C ₆ alkyl substituted with 1, 2, or 3 halogens may include, but is not limited to -CH ₂ Cl, -CHCl ₂ , -CCl ₃ , -CH ₂ F, -CHF ₂ , -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, CH ₂ ClO-, CHCl ₂ O-, CCl ₃ O-, CH ₂ FO-, CHF ₂ O-, CF ₃ O-, CF ₃ CH ₂ O- or CH ₃ CF ₂ O-.

As used herein, the term "hydroxyl" or "hydroxy" refers to a -OH group.

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

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

As used herein, the term "C ₁ -C ₆ alkyl" refers to a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms, containing no unsaturations, having from one to six carbon atoms, and which is attached to the rest of the molecules with a single bond. The term "C ₁ -C ₁₀ alkyl" should be interpreted accordingly. Examples of C ₁ -C ₆ alkyl include, without limitation, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and their isomers, for example isopropyl, isobutyl, sec-butyl, t-butyl or isoamyl. The group "C ₁ -C ₆ alkylene" refers to the corresponding definition of C ₁ -C ₆ 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, without limitation, -CH ₂ -, -CH ₂ CH ₂ - and -(CH ₂ ) ₃ -.

As used herein, the term "C ₂ -C ₆ alkenyl" refers to a group that is a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms, containing at least one double bond, which may be located either in (E )-, or in the (Z)-configuration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond. The term "C ₂ -C ₁₀ alkenyl" should be interpreted accordingly. Examples of C ₂ -C ₆ alkenyl include, without limitation, ethenyl (vinyl), prop-1-enyl, prop-2-enyl (allyl), but-1-enyl.

As used herein, the term "C ₂ -C ₆ alkynyl" refers to a group that is a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms containing at least one triple bond having two to six carbon atoms. , and which is attached to the rest of the molecule by a single bond. The term "C ₂ -C ₁₀ alkynyl" should be interpreted accordingly. Examples of C ₂ -C ₆ alkynyl include, without limitation, ethynyl, prop-1-ynyl, but-1-ynyl.

As used herein, the term "C ₁ -C ₆ alkoxy" refers to a radical of the formula -OR _a , where R _a is a C ₁ -C ₆ alkyl radical as generally defined above. The term "C ₁ -C ₄ alkoxy" should be interpreted accordingly. Examples of C ₁ -C ₆ alkoxy include, without limitation, methoxy, ethoxy, 1-methylethoxy (isopropoxy), propoxy, butoxy, 1-methylpropoxy, and 2-methylpropoxy.

As used herein, the term "C ₁ -C ₆ alkoxyC ₁ -C ₆ alkyl" refers to a radical of the formula R _b -OR _a -, where R _b is a C ₁ -C ₆ alkyl radical as generally defined above, and R _a is a C ₁ -C ₆ alkylene radical as generally defined above. Examples of C ₁ -C ₆ alkoxyC ₁ -C ₆ alkyl include, without limitation, methoxymethyl.

As used herein, the term "C ₁ -C ₄ alkoxycarbonyl" refers to a radical of formula -C(O)OR _a , where R _a is a C ₁ -C ₄ alkyl radical as generally defined above. Examples of C ₁ -C ₄ alkoxycarbonyl include, without limitation, methoxycarbonyl, ethoxycarbonyl.

Used in this document, the term C ₁ -C ₆ alkylthio means the group-SR _a where R _a represents a C ₁ -C ₆ alkyl radical, as generally defined above.

As used herein, the term "C ₁ -C ₆ haloalkyl" refers to a C ₁ -C ₆ alkyl radical, as generally defined above, substituted with one or more of the same or different halogen atoms. The terms "C ₁ -C ₄ haloalkyl" and "C ₁ -C ₂ haloalkyl" are to be construed accordingly. Examples of C ₁ -C ₆ haloalkyl include, without limitation, trifluoromethyl.

The term "C ₃ -C ₆ cycloalkyl" as used herein refers to a radical which is a monocyclic saturated ring system and which contains 3-6 carbon atoms. The terms "C ₃ -C ₁₀ cycloalkyl" and "C ₃ -C ₈ cycloalkyl" should be interpreted accordingly and may include bridged structures (eg, norbornane). Examples of C ₃ -C ₁₀ cycloalkyl include, without limitation, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

The term "C ₃ -C ₁₀ cycloalkylC ₁ -C ₂ alkyl" as used herein refers to a cycloalkyl ring attached to the rest of the molecule via a C ₁ -C ₂ alkyl radical as defined above. The term "C ₃ -C ₆ cycloalkylC ₁ -C ₂ alkyl" should be interpreted accordingly. Examples of C ₃ -C ₁₀ cycloalkylC ₁ -C ₂ alkyl include, without limitation, cyclopropylmethyl, cyclobutyl methyl, and cyclopentylmethyl.

As used herein, the term "C ₃ -C ₁₀ cycloalkenyl" refers to a radical which is a monocyclic non-aromatic ring system consisting solely of carbon and hydrogen atoms and which contains 3-10 carbon atoms and 1 or 2 intra-ring double bonds. They may include bridged structures (eg, norbornene and 2,5-norbornadiene). Examples of C ₃ -C ₁₀ cycloalkenyl include, without limitation, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and cyclooctenyl.

As used herein, the term "C ₃ -C ₈ cycloalkoxy" refers to a radical of the formula -OR _a , where R _a is a C ₃ -C ₆ cycloalkyl radical as generally defined above. The term C ₃ -C ₆ cycloalkoxy should be interpreted accordingly. Examples of C ₃ -C ₈ cycloalkoxy include, without limitation, cyclopropyloxy, cyclopentyloxy, or cyclohexyloxy.

As used herein, the term "C ₃ -C ₆ cycloalkylthio" refers to a radical of the formula -SR _a , where R _a is a C ₃ -C ₆ cycloalkyl radical as generally defined above. Examples of C ₃ -C ₆ cycloalkylthio include, without limitation, cyclopropylthio, cyclopentylthio, or cyclohexylthio.

As used herein, the term "C ₂ -C ₆ alkenyloxy" refers to a radical of the formula -OR _a , where R _a is a C ₂ -C ₆ alkenyl radical as generally defined above. Examples of C ₂ -C ₆ alkenyloxy include, without limitation, allyloxy or butenyloxy.

As used herein, the term "C ₂ -C ₆ alkynyloxy" refers to a radical of the formula -OR _a , where R _a is a C ₂ -C ₆ alkynyl radical as generally defined above. Examples of C ₂ -C ₆ alkynyloxy include, without limitation, propargyloxy or butynyloxy.

Used in this document, the term "C ₂ -C ₆ acyl" refers to the radical R _a C(=O)-, where R _a represents a C ₁ -C ₅ alkyl radical or aryl radical, as generally defined above. Acyl groups include, without limitation, acetyl, propanoyl, and benzoyl.

The term "C ₂ -C ₆ acyloxy" as used herein refers to a radical of the formula -OR _b , where R _b is formyl or a C ₂ -C ₆ acyl radical, as generally defined above. C ₂ -C ₆ acyloxy groups include, without limitation, acetoxy.

As used herein, the term "C ₂ -C ₆ acyloxyC ₁ -C ₆ alkyl" refers to a radical of the formula R _a C(=O)OR _b -, where R _a is a C ₁ -C ₅ alkyl radical or an aryl radical which generally defined above, and where R _b represents a C ₁ -C ₆ alkylene radical, which is generally defined above.

As used herein, the term "heterocyclyl" or "heterocyclic" refers to a stable 4-, 5-, or 6-membered non-aromatic monocyclic ring that contains 1, 2, or 3 heteroatoms, the heteroatoms being individually selected from nitrogen, oxygen, and sulfur. The heterocyclyl radical may be linked to the rest of the molecule via a carbon atom or a heteroatom. Examples of heterocyclyl include, without limitation, azetidinyl, oxetanyl, thietanyl, tetrahydrofuryl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, piperidinyl, piperazinyl, morpholinyl, dioxolanyl, dithiolanyl, and thiazolidinyl.

As used herein, the term "heterocyclyloxy" refers to a radical of the formula -OR _a , where R _a is a heterocyclyl radical as generally defined above. Examples of heterocyclyloxy include, without limitation, tetrahydrofuranyloxy and morpholinyloxy.

As used herein, the term "heterocyclylthio" refers to a radical of the formula -SR _a , where R _a is a heterocyclyl radical as generally defined above. Examples of heterocyclylthio include, without limitation, tetrahydrofuranylthio and morpholinylthio.

As used herein, the term "heterocyclylC ₁ -C ₆ alkyl" refers to a heterocyclyl ring attached to the rest of the molecule via a C ₁ -C ₆ alkyl radical as defined above. The term heterocyclylC ₁ -C ₂ alkyl should be interpreted accordingly. Examples of heterocyclylC ₁ -C ₆ alkyl include, without limitation, tetrahydrofuranylmethyl or morpholinylmethyl.

As used herein, the term "aryl" refers to an aromatic ring system consisting solely of carbon and hydrogen atoms, which may be mono-, bi-, or tricyclic. Examples of such ring systems include phenyl, naphthalene, anthracenyl, indenyl or phenanthrenyl.

As used herein, the term "aryloxy" refers to a radical of the formula -OR _a , where R _a is an aryl radical, as generally defined above. Examples of aryloxy include, without limitation, phenoxy and naphthyloxy.

As used herein, the term "arylthio" refers to a radical of the formula -SR _a , where R _a is an aryl radical, as generally defined above. Examples of arylthio include, without limitation, phenylthio and naphthylthio.

As used herein, the term "arylC ₁ -C ₆ alkyl" refers to an aryl ring attached to the rest of the molecule via a C ₁ -C ₆ alkylene radical as defined above. Examples of arylC ₁ -C ₆ alkyl include, without limitation, benzyl or 2-phenylethyl.

As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring radical that contains 1, 2, 3, or 4 heteroatoms individually selected from nitrogen, oxygen, and sulfur. Examples of heteroaryl include, without limitation, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, or pyridyl.

As used herein, the term "heteroaryloxy" refers to a radical of the formula -OR _a , where R _a is a heteroaryl radical as generally defined above. Examples of heteroaryloxy include, without limitation, pyridyloxy and thienyloxy.

As used herein, the term "heteroarylthio" refers to a radical of the formula -SR _a , where R _a is a heteroaryl radical as generally defined above. Examples of heteroarylthio include, without limitation, pyridylthio and thienylthio.

As used herein, the term "heteroarylC ₁ -C ₆ alkyl" refers to a heteroaryl ring attached to the rest of the molecule via a C ₁ -C ₆ alkyl radical as defined above. The term "heteroarylC ₁ -C ₂ alkyl" should be interpreted accordingly.

As used herein, the term C ₁ -C ₆ alkylsulfonyl means the group -S(O) ₂ R _a , where R _a is a C ₁ -C ₆ alkyl radical as generally defined above.

Used in this document, the term C ₁ -C ₆ alkylcarbonyloxy means the group -OC(=O)R _a where R _a represents a C ₁ -C ₆ alkyl radical, as generally defined above.

Used in this document, the designation =O means oxo group, which, for example, is in the carbonyl group (-C(=O)-).

As used herein, the term "annelated carbobicyclyl ring" is a non-aromatic bicyclic ring system containing two rings fused together, i.e. that share two carbon atoms.

As used herein, the term "spirocyclic carbobicyclyl ring" is a non-aromatic bicyclic ring system containing two rings linked together via a single carbon atom, i.e. that share one carbon atom.

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. Atropisomers may also occur as a result of limited rotation 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. Similarly, 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 in the form of an agronomically applicable 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, of the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ and X with reference to compounds of formula (I). With respect to any of these substituents, any of the definitions below may be combined with any definition of any other substituent below or elsewhere herein.

R ¹ is halogen, cyano, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy, with C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy optionally substituted with 1-3 groups represented by R ⁶ . R ¹ may be halogen, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, with C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy optionally substituted with 1-3 groups represented by R ⁶ . Preferably R ¹ is halogen, cyano, methyl, trifluoromethyl, methoxy or trifluoromethoxy. More preferably R ¹ is halogen or cyano, even more preferably halogen and even more preferably fluorine.

R ² is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₃ -C ₆ cycloalkyl, with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C ₃ -C ₆ cycloalkyl optional substituted with 1-3 groups represented by R ⁶ . Preferably R ² is hydrogen or C ₁ -C ₆ alkoxy (including C ₁ -C ₄ alkoxy), more preferably hydrogen or methoxy, and even more preferably hydrogen.

R ³ is halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₃ -C ₆ cycloalkyl, with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C ₃ -C ₆ cycloalkyl optional substituted with 1-3 groups represented by R ⁶ . Preferably R ³ is halogen or C ₁ -C ₆ alkyl (including C ₁ -C ₄ alkyl), more preferably halogen (particularly chlorine or bromine) or methyl, even more preferably bromine or methyl and even more preferably methyl .

R ⁴ is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or C ₃ -C ₆ cycloalkyl, with C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and C ₃ -C ₆ cycloalkyl optional substituted with 1-3 groups represented by R ⁶ . Preferably R ⁴ is hydrogen or C ₁ -C ₆ alkoxy (including C ₁ -C ₄ alkoxy); more preferably hydrogen or methoxy, and even more preferably hydrogen.

R ⁵ is C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkylC ₁ -C ₂ alkyl, C ₃ -C ₁₀ cycloalkenyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl , aryl, heteroaryl, wherein 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, wherein heterocyclyl is 4-, 5- or 6-membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms, individually selected from nitrogen, oxygen and sulfur, heterocyclylC ₁ -C ₂ alkyl or 5-10-membered (preferably 7-10-membered) non-aromatic annelated or a spirocyclic carbobicyclyl ring system optionally containing 1, 2, 3, 4 or 5 heteroatoms individually selected from nitrogen, oxygen and sulfur, and optionally linked to the rest of the molecule via a C ₁ -C ₂ alkylene linker;

where any of the specified C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₂ -C ₁₀ alkenyl and C ₂ -C ₁₀ alkynyl fragments are optionally substituted with 1-4 groups represented by R ⁷ , or 1 group represented by R ⁸ ; or

where any of the specified aryl, heteroaryl and heterocyclyl fragments are optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ , or optionally substituted with 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ ; or

wherein the annelated or spirocyclic carbobicylyl ring is optionally substituted with 1-3 groups represented by R ⁷ , or the annelated carbobicylyl ring system is optionally substituted with C ₃ -C ₆ cycloalkyl to form a spirocyclyl moiety.

Preferably R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkylC ₁ -C ₂ alkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, phenyl, heteroaryl, wherein 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, wherein heterocyclyl is 4- , 5- or 6-membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms, individually selected from nitrogen, oxygen and sulfur, heterocyclylC ₁ -C ₂ alkyl or 5-10-membered non-aromatic annelated or spirocyclic carbobicylyl ring system, optional containing 1, 2 or 3 heteroatoms, individually selected from nitrogen, oxygen and sulfur, and optionally associated with the rest of the molecule through a C ₁ -C ₂ alkylene linker;

where any of the specified C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl and C ₂ -C ₆ alkynyl fragments are optionally substituted with 1-4 groups represented by R ⁷ , or 1 group represented by R ⁸ ; or

where any of the specified phenyl, heteroaryl and heterocyclyl fragments are optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ , or optionally substituted with 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ ; or

wherein the annelated or spirocyclic carbobicylyl ring is optionally substituted with 1-3 groups represented by R ⁷ , or the annelated carbobicylyl ring system is optionally substituted with C ₃ -C ₆ cycloalkyl to form a spirocyclyl moiety.

More preferably R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₅ cycloalkylC _1-2 alkyl, C ₂ -C ₆ alkynyl, phenyl, heterocyclyl, wherein heterocyclyl is 4- or 6-membered non-aromatic monocyclic ring containing 1 oxygen atom, heterocyclyl C ₁ alkyl, or 5-9-membered non-aromatic annelated or spirocyclic carbobicyclyl ring system, optionally containing 1 oxygen atom and optionally linked to the rest of the molecule via methylene (-CH ₂ -) linker;

where any of these C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl and C ₂ -C ₆ alkynyl moieties are optionally substituted with 1-4 groups represented by R ⁷ or 1 group represented by R ⁸ ;

where any of these phenyl or heterocyclyl moieties are optionally substituted with 1 or 2 groups represented by R ⁹ or 1 group represented by R ¹⁰ , or optionally substituted with 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ ; and

wherein the annelated or spirocyclic carbobicylyl ring is optionally substituted with 1 or 2 groups represented by R ⁷ , or the annelated carbobicylyl ring system is optionally substituted with C ₄ -C ₅ cycloalkyl to form a spirocyclyl moiety.

Even more preferably R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkylC ₁ -C ₂ alkyl or C ₂ -C ₆ alkynyl, any of C ₁ -C ₆ alkyl , C ₂ -C ₆ alkynyl and C ₃ -C ₆ cycloalkyl moieties are optionally substituted with 1-4 groups represented by R ⁷ or 1 group represented by R ⁸ , wherein

R ⁷ is independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxyC ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl , C ₃ -C ₆ cycloalkylC _1-2 alkyl and C ₁ -C ₃ alkoxycarbonyl, wherein R ⁸ is phenyl, benzyl or isoxazole optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ , and wherein

R ⁹ is halogen and R ¹⁰ is phenyl optionally substituted with 1-3 groups represented by R ¹¹ which are halogen.

Even more preferably R ⁵ is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ cycloalkylC ₁ -C ₂ alkyl, optionally substituted with 1 group represented by R ⁷ , when this R ⁷ represents methyl, hydroxyl, cyano, trifluoromethyl, methoxymethyl, C ₃ -C ₆ cycloalkyl, ethoxycarbonyl, acetyloxymethyl or 2,2-dichlorocyclopropyl; or 2 groups represented by R ⁷ , with each R ⁷ independently representing methyl, cyano or cyclopropyl; or 3 groups represented by R ⁷ , with each R ⁷ independently representing methyl, bromine, chlorine, fluoro or butoxy; or 4 groups represented by R ⁷ , each R ⁷ is methyl, or 1 group represented by R ⁸ , where R ⁸ is phenyl, benzyl or isoxazole, optionally substituted with 1-3 groups represented by R ⁹ , or 1 a group represented by R ¹⁰ , and at the same time

R ⁹ is halogen and R ¹⁰ is phenyl optionally substituted with 1-3 groups represented by R ¹¹ which are halogen;

or

R ⁵ is phenyl, pyridylmethyl (including 2-pyridylmethyl, 3-pyridylmethyl and 4-pyridylmethyl), oxetanyl (including oxetan-2-yl, oxetan-3-yl), tetrahydrofuranyl (tetrahydrofuran-2-yl, tetrahydrofuran-3-yl) or tetrahydropyranyl (tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl), each of which is optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ , or 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ , wherein

R ⁹ is independently selected from halogen and C ₁ -C ₄ alkyl, and R ¹⁰ is selected from phenyl, benzyl, or C ₆ -C ₈ cycloalkoxy, each of which is optionally substituted with 1-3 groups represented by R ¹¹ , which are independently selected from halogen or methyl;

or

R ⁵ is an fused or spirocyclic ring system selected from:

each of which is optionally substituted with 1-3 groups represented by R ⁷ independently selected from C ₁ -C ₄ alkyl and C ₂ -C ₄ acyloxyC ₁ -C ₄ alkyl.

Even more preferably R ⁵ is C ₁ -C ₄ alkyl optionally substituted with 1 group represented by R ⁷ selected from C ₃ -C ₆ cycloalkyl; or

R ⁵ is an fused or spirocyclic ring system selected from:

each of which is optionally substituted with 1-3 groups represented by R ⁷ independently selected from C ₁ -C ₄ alkyl, in particular methyl.

In particularly preferred embodiments of the present invention, R ⁵ is (3,4-difluorophenyl)methyl, (2,4,5-trifluorophenyl)methyl, (2-chloro-4,5-difluorophenyl)methyl, (2-bromo-4 ,5-difluorophenyl)methyl, 1-cyclohexylethyl, 1-phenylethyl, 1-(3-phenylisoxazol-5-yl)ethyl, 1-[3-(2-iodophenyl)isoxazol-5-yl]ethyl, [2-methyl -1-(trifluoromethyl)propyl], [1-(hydroxymethyl)-2,2-dimethyl-propyl], (1-benzyl-2,2-dimethyl-propyl), (1-isopropyl-2-methyl-but- 3-ynyl), [1-(1-cyanoethyl)-2-methyl-propyl], [3-methyl-1-(1-methyl-2-phenyl-ethyl)butyl], (1-cyclohexylcyclopropyl), (3 -isobutoxy-2,2-dimethyl-cyclobutyl), spiro[3.3]heptan-7-yl], [(7R)-spiro[3.3]heptan-7-yl], spiro[3.4]octan-3-yl, spiro [3.4]octan-2-yl, [3-(acetoxymethyl)-8-oxaspiro[3.4]octan-1-yl], spiro[3.5]nonan-2-yl, [(1R,5S,6R)-6- bicyclo[3.2.0]heptanyl], [(1S,5R,7R)-5-methyl-7-bicyclo[3.2.0]heptanyl], 6,6-dimethyl-7-bicyclo[3.2.0]heptanyl], [(1S,5R,7S)-6,6-dimethyl-7-bicyclo[3.2.0]heptanyl], [(1S,5S)-6,6-dimethyl-7-bicyclo[3.2.0]hept-3 -enyl], (6,6-dimethyl -4-oxabicyclo[3.2.0]heptan-7-yl), spiro[4-oxabicyclo[3.2.0]heptan-6,1'-cyclobutan]-7-yl, spiro[4-oxabicyclo[3.2.0] heptan-6,1'-cyclopentan]-7-yl, [(1S,6R,8R)-6-methyl-8-bicyclo[4.2.0]octanyl], (7,7-dimethyl-5-oxabicyclo[4.2 .0]octan-8-yl), (1-benzylcyclohexyl), (3,3,5,5-tetramethylcyclotexyl), (6-methyl-2-bicyclo[4.2.0]octanyl), [(3S)-2 -(2,4-dichlorophenyl)oxetan-3-yl], (4-benzyl-2,6-dimethyl-tetrahydropyran-4-yl), [4-(4,4-dimethylcyclohexoxy)-2-fluoro-phenyl] , [4-(cyclooctoxy)-2-fluoro-phenyl], [4-(4-chlorophenoxy)phenyl], 2,2-dimethylpropyl, (1-methylcyclopropyl)methyl, (1-methylcyclopentyl)methyl, (4-methyltetrahydropyran -4-yl)methyl, (3-methoxy-2,2-dimethyl-propyl), (1-methylcyclobutyl)methyl, (1-cyclopropylcyclopropyl), (1-cyano-1-cyclopropyl-ethyl), (1-ethoxycarbonylcyclopropyl) )methyl, [1-(cyclopropylmethyl)cyclopropyl]methyl, (3-methyloxetan-3-yl)methyl, (1-methoxycyclopentyl)methyl, 1-(2-pyridyl)ethyl, spiro[2.2]pentan-5-yl, [1-(methoxymethyl)cyclopropyl]methyl, 6-oxaspiro[2.5]octan-2-ylmethyl, [1-(trifluoro methyl)cyclopropyl]methyl; and [1-(methoxymethyl)cyclopentyl]methyl.

In even more preferred embodiments, R ⁵ is (3,4-difluorophenyl)methyl, (2,4,5-trifluorophenyl)methyl, (2-chloro-4,5-difluorophenyl)methyl, (2-bromo-4, 5-difluorophenyl)methyl, 1-cyclohexylethyl, 1-phenylethyl, 1-(3-phenylisoxazol-5-yl)ethyl, 1-[3-(2-iodophenyl)isoxazol-5-yl]ethyl, [2-methyl- 1-(trifluoromethyl)propyl], [1-(hydroxymethyl)-2,2-dimethyl-propyl], (1-benzyl-2,2-dimethyl-propyl), (1-isopropyl-2-methyl-but-3 -ynyl), [1-(1-cyanoethyl)-2-methyl-propyl], [3-methyl-1-(1-methyl-2-phenyl-ethyl)butyl], (1-cyclohexylcyclopropyl), (3- isobutoxy-2,2-dimethyl-cyclobutyl), spiro[3.3]heptan-7-yl], [(7R)-spiro[3.3]heptan-7-yl], spiro[3.4]octan-3-yl, spiro[ 3.4]octan-2-yl, [3-(acetoxymethyl)-8-oxaspiro[3.4]octan-1-yl], spiro[3.5]nonan-2-yl, [(1R,5S,6R)-6-bicyclo [3.2.0]heptanyl], [(1S,5R,7R)-5-methyl-7-bicyclo[3.2.0]heptanyl], 6,6-dimethyl-7-bicyclo[3.2.0]heptanyl], [ (1S,5R,7S)-6,6-dimethyl-7-bicyclo[3.2.0]heptanyl], [(1S,5S)-6,6-dimethyl-7-bicyclo[3.2.0]hept-3- enyl], (6,6-dimethyl-4-oxabicyclo[3.2.0]g eptan-7-yl), spiro[4-oxabicyclo[3.2.0]heptan-6,1'-cyclobutan]-7-yl, spiro[4-oxabicyclo[3.2.0]heptan-6,1'-cyclopentane] -7-yl, [(1S,6R,8R)-6-methyl-8-bicyclo[4.2.0]octanyl], (7,7-dimethyl-5-oxabicyclo[4.2.0]octan-8-yl) , (1-benzylcyclohexyl), (3,3,5,5-tetramethylcyclohexyl), (6-methyl-2-bicyclo[4.2.0]octanyl), [(3S)-2-(2,4-dichlorophenyl)oxetane -3-yl], (4-benzyl-2,6-dimethyl-tetrahydropyran-4-yl), [4-(4,4-dimethylcyclohexoxy)-2-fluoro-phenyl], [4-(cyclooctoxy)-2 -fluorophenyl], [4-(4-chlorophenoxy)phenyl], 2,2-dimethylpropyl, (1-methylcyclopropyl)methyl, (1-methylcyclopentyl)methyl, (4-methyltetrahydropyran-4-yl)methyl, (3 -methoxy-2,2-dimethyl-propyl), (1-methylcyclobutyl)methyl, (1-cyclopropylcyclopropyl), (1-cyano-1-cyclopropyl-ethyl), (1-ethoxycarbonylcyclopropyl)methyl, [1-(cyclopropylmethyl) cyclopropyl]methyl, (3-methyloxetan-3-yl)methyl, 1-(2-pyridyl)ethyl, spiro[2.2]pentan-5-yl, [1-(trifluoromethyl)cyclopropyl]methyl and [1-(methoxymethyl) cyclopentyl]methyl.

In even more preferred embodiments, R ⁵ is 1-cyclohexylethyl, 1-phenylethyl, 1-(3-phenylisoxazol-5-yl)ethyl, spiro[3.3]heptan-7-yl], spiro[3.4]octane-3- yl, spiro[3.4]octan-2-yl, spiro[3.5]nonan-2-yl, [3-(acetoxymethyl)-8-oxaspiro[3.4]octan-1-yl], 6,6-dimethyl-7- bicyclo[3.2.0]heptanyl], (6,6-dimethyl-4-oxabicyclo[3.2.0]heptan-7-yl), spiro[4-oxabicyclo[3.2.0]heptan-6,1'-cyclobutane] -7-yl, spiro[4-oxabicyclo[3.2.0]heptan-6,1'-cyclopentan]-7-yl, (6-methyl-2-bicyclo[4.2.0]octanyl) and spiro[2.2]pentane -5-yl.

R ⁶ is independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkoxy and C ₃ -C ₆ cycloalkyl. Preferably R ⁶ is independently selected from halogen, cyano, hydroxyl, C ₁ -C ₄ alkoxy and C ₃ -C ₆ cycloalkyl.

R ⁷ is independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxyC ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl , C ₃ -C ₆ cycloalkylC _1-2 alkyl, C ₂ -C ₆ acyl, C ₂ -C ₆ acyloxy, C ₂ -C ₆ acyloxyC ₁ -C ₆ alkyl and C ₁ -C ₄ alkoxycarbonyl.

Preferably R ⁷ is independently selected from halogen, cyano, hydroxyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxyC ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkylC _1-2 alkyl and C ₁ -C ₄ alkoxycarbonyl; wherein the C ₃ -C ₆ cycloalkyl moiety is optionally substituted with 1 or 2 groups selected from halo and C ₁ -C ₆ alkyl.

More preferably R ⁷ is independently selected from chlorine, bromine, fluorine, cyano, hydroxyl, methyl, trifluoromethyl, methoxy, butoxy, methoxymethyl, cyclopropyl, cyclohexyl, cyclooctyl, cyclopropylmethyl, acetyloxymethyl and ethoxycarbonyl; wherein the cyclopropyl is optionally substituted with 2 chlorine-containing groups.

R ⁸ is aryl, aryloxy, arylC ₁ -C ₆ alkyl, heteroaryl, wherein heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur, heteroaryloxy or heteroarylC ₁ -C ₆ alkyl, wherein aryl and heteroaryl are optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ .

Preferably R ⁸ is phenyl, benzyl or isoxazole optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ . More preferably R ⁸ is phenyl, benzyl or isoxazole, where isoxazole is optionally substituted with 1 group represented by R ¹⁰ .

R ⁹ is independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkynyloxy, while C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₂ - C ₆ alkynyl, C ₂ -C ₆ alkynyloxy are optionally substituted with 1-3 groups represented by R ¹¹ . Preferably R ⁹ is independently selected from halogen, cyano, hydroxyl and C ₁ -C ₄ alkyl. More preferably R ⁹ is independently selected from chlorine, bromine, fluorine and methyl.

R ¹⁰ is selected from C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkoxy (preferably C ₃ -C ₆ cycloalkoxy), C ₃ -C ₆ cycloalkylthio, aryl, aryloxy, arylthio, arylC ₁ -C ₆ alkyl, heteroaryl, with this heteroaryl is a 5 - or 6-membered aromatic monocyclic ring containing 1, 2, 3 or 4 heteroatoms, individually selected from nitrogen, oxygen and sulfur, heteroaryloxy, heteroarylthio, heteroarylC ₁ -C ₆ alkyl, heterocyclyl, when in this 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, heterocyclyloxy, heterocyclylthio and heterocyclylC ₁ -C ₆ alkyl,

where C ₃ -C ₆ cycloalkyl, C ₃ -C ₈ cycloalkoxy, C ₃ -C ₆ cycloalkylthio, aryl, aryloxy, arylthio, arylC ₁ -C ₆ alkyl, heteroaryl, heteroaryloxy, heteroarylthio, heteroarylC ₁ -C ₆ alkyl, heterocyclyl, heterocyclyloxy, heterocyclylthio and heterocyclylC ₁ -C ₆ alkyl are optionally substituted with 1-3 groups represented by R ¹¹ .

Preferably R ¹⁰ is selected from phenyl, benzyl and C ₆ -C ₈ cycloalkoxy, each of which is optionally substituted with 1-3 groups represented by R ¹¹ . More preferably R ¹⁰ is phenyl optionally substituted with 1 R ¹¹ .

R ¹¹ is independently selected from halo and methyl.

X is CH or N. In one embodiment of the present invention, X is CH. In another embodiment of the present invention, X is N.

Preferably according to the present invention:

R ¹ is halogen or cyano;

R ² is hydrogen or C ₁ -C ₄ alkoxy;

R ³ is halogen or C ₁ -C ₆ alkyl;

R ⁴ is hydrogen;

R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkylC ₁ -C ₂ alkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl , phenyl, heteroaryl, while 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, while heterocyclyl is 4-, 5- or 6-membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms, individually selected from nitrogen, oxygen and sulfur, heterocyclylC ₁ -C ₂ alkyl or 5-10-membered non-aromatic annelated or spirocyclic carbobicylyl ring system, optionally containing 1, 2, or 3 heteroatoms, individually selected from nitrogen, oxygen, and sulfur, and optionally linked to the rest of the molecule via a C ₁ -C ₂ alkylene linker;

where any of the specified C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl and C ₂ -C ₆ alkynyl fragments are optionally substituted with 1-4 groups represented by R ⁷ , or 1 group represented by R ⁸ ; or

where any of the specified phenyl, heteroaryl and heterocyclyl fragments are optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ , or optionally substituted with 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ , and

where an annelated or spirocyclic carbobicylyl ring system is optionally substituted with 1-3 groups represented by R ⁷ , or an annelated carbobicylyl ring system is optionally substituted with C ₃ -C ₆ cycloalkyl to form a spirocyclic moiety; and

R ⁷ is independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxyC ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl , C ₃ -C ₆ cycloalkylC ₁ -C ₂ alkyl, C ₂ -C ₄ acyloxyC ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxycarbonyl, while C ₃ -C ₆ cycloalkyl fragment C ₃ -C ₆ cycloalkylC _1-2 alkyl is optionally substituted with 1 or 2 groups selected from halo and C ₁ -C ₆ alkyl;

R ⁸ is phenyl, benzyl or isoxazole optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ ;

R ⁹ is independently selected from halo and C ₁ -C ₄ alkyl;

R ¹⁰ is phenyl, benzyl or C ₆ -C ₈ cycloalkoxy optionally substituted with 1-3 groups represented by R ¹¹ ;

R ¹¹ is halogen; and

X is CH.

More preferably R ¹ is halogen;

R ² is hydrogen or methoxy;

R ³ is bromine or methyl;

R ⁴ is hydrogen;

R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkylC ₁ -C ₂ alkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl , phenyl, heteroaryl, while heteroaryl is a 5- or 6-membered aromatic monocyclic ring containing 1, 2 or 3 heteroatoms, individually selected from nitrogen, oxygen and sulfur, heterocyclyl, while heterocyclyl is 4-, 5- or a 6-membered non-aromatic monocyclic ring containing 1, 2 or 3 heteroatoms, individually selected from nitrogen, oxygen and sulfur, heterocyclyl C ₁ -C ₂ alkyl or a 5-10 membered non-aromatic annelated or spirocyclic carbobicyclyl ring system, optionally containing 1, 2 or 3 heteroatoms individually selected from nitrogen, oxygen and sulfur, and optionally linked to the rest of the molecule via a C ₁ -C ₂ alkylene linker;

where any of the specified C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkenyl, C ₂ -C ₆ alkenyl and C ₂ -C ₆ alkynyl fragments are optionally substituted with 1-4 groups represented by R ⁷ , or 1 group represented by R ⁸ ;

where any of the specified phenyl, heteroaryl and heterocyclyl fragments are optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ or optionally substituted with 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ , and

where the annelated or spirocyclic carbobicylyl ring is optionally substituted with 1-3 groups represented by R ⁷ , or the annelated carbobicylyl ring system is optionally substituted with C ₃ -C ₆ cycloalkyl to form a spirocyclic moiety; and

R ⁷ is independently selected from halogen, cyano, hydroxyl, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxyC ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl , C ₃ -C ₆ cycloalkylC ₁ -C ₂ alkyl, C ₂ -C ₄ acyloxyC ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxycarbonyl, while C ₃ -C ₆ cycloalkyl fragment C ₃ -C ₆ cycloalkylC _1-2 alkyl is optionally substituted with 1 or 2 groups selected from halo and C ₁ -C ₆ alkyl;

R ⁸ is phenyl, benzyl or isoxazole optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ ;

R ⁹ is independently selected from halo and C ₁ -C ₄ alkyl;

R ¹⁰ is phenyl, benzyl or C ₆ -C ₈ cycloalkoxy optionally substituted with 1-3 groups represented by R ¹¹ ;

R ¹¹ is halogen; and

X is CH.

Even more preferably R ¹ is fluorine;

R ² is hydrogen;

R ³ is bromine or methyl;

R ⁴ is hydrogen;

R ⁵ is C ₁ -C ₆ alkyl optionally substituted with 1 group represented by R ⁷ selected from C ₃ -C ₆ cycloalkyl, or an fused or spirocyclic ring system selected from:

each of which is optionally substituted with 1-3 groups represented by R ⁷ independently selected from C ₁ -C ₄ alkyl.

Even more preferably R ¹ is fluorine;

R ² is hydrogen;

R ³ is bromine or methyl;

R ⁴ is hydrogen;

R ⁵ is C _1-4 alkyl optionally substituted with 1 group represented by R ⁷ selected from cyclopropyl, cyclopentyl or cyclohexyl, or

annulated or spirocyclic ring system selected from:

each of which is optionally substituted with 1-3 groups,

represented by R ⁷ independently selected from methyl.

In a further preferred embodiment:

R ¹ is fluorine;

R ² is hydrogen;

R ³ is bromine or methyl;

R ⁴ is hydrogen;

R ⁵ is C ₁ -C ₄ alkyl optionally substituted with 1 cyclohexyl group; or

annulated or spirocyclic ring system selected from:

each of which is optionally substituted with 1 or 2 groups represented by R ⁷ where R ⁷ is methyl.

Preferably the compound according to formula (I) is selected from:

5-bromo-N-(1-cyclohexylethyl)-2-(3,5-difluoroanilino)thiazole-4-carboxamide;

N-(1-cyclohexylethyl)-2-(3,5-difluoroanilino)-5-methyl-thiazole-4-carboxamide;

5-bromo-2-(3,5-difluoroanilino)-N-spiro[3.3]heptan-7-yl-thiazole-4-carboxamide;

2-(3,5-difluoroanilino)-5-methyl-N-spiro[3.3]heptan-7-yl-thiazole-4-carboxamide;

5-bromo-2-(3,5-difluoroanilino)-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide;

2-(3,5-difluoroanilino)-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide;

5-bromo-2-(3,5-difluoroanilino)-N-(6,6-dimethyl-7-bicyclo[3.2.0]heptanyl)thiazole-4-carboxamide;

2-(3,5-difluoroanilino)-N-(6,6-dimethyl-7-bicyclo[3.2.0]heptanyl)-5-methyl-thiazole-4-carboxamide;

5-bromo-2-(3,5-difluoroanilino)-N-(6-methyl-2-bicyclo[4.2.0]octanyl)thiazole-4-carboxamide;

2-(3,5-difluoroanilino)-5-methyl-N-(6-methyl-2-bicyclo[4.2.0]octanyl)thiazole-4-carboxamide;

2-[(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide;

5-bromo-2-[(2,6-difluoro-4-pyridyl)amino]-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide;

5-chloro-2-[(2,6-difluoro-4-pyridyl)amino]-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide;

2-[(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[2.2]pentan-2-yl-thiazole-4-carboxamide;

2-(3,5-difluoroanilino)-5-methyl-N-spiro[2.2]pentan-2-yl-thiazol-4-carboxamide and

5-chloro-2-[(2,6-difluoro-4-pyridyl)amino]-N-spiro[2.2]pentan-2-yl-thiazole-4-carboxamide.

The present invention also relates to compounds of formula I-1,

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the definitions described for formula I. Preferred definitions of R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined for formula (I) .

The present invention also relates to compounds of formula I-2,

where R ² , R ³ , R ⁴ , R ⁵ and X have the definition described for formula I. Preferred definitions of R ² , R ³ , R ⁴ , R ⁵ and X are as defined for formula (I).

The present invention also relates to compounds of formula I-3,

where R ¹ , R ³ , R ⁴ , R ⁵ and X have the definition described for formula (I). Preferred definitions of R ¹ , R ³ , R ⁴ , R ⁵ and X are as defined for formula (I).

The present invention also relates to compounds of formula I-4,

where R ¹ , R ² , R ⁴ , R ⁵ and X have the definition described for formula (I). Preferred definitions of R ¹ , R ² , R ⁴ , R ⁵ and X are as defined for formula (I).

The present invention also relates to compounds of formula I-5,

where R ¹ , R ² , R ³ , R ⁵ and X have the definition described for formula (I). Preferred definitions of R ¹ , R ² , R ³ , R ⁵ and X are as defined for formula (I).

Further preferred embodiments of the present invention are embodiments of EI.aEI.bk which are defined as compounds of formula (I) which are represented by a single formula selected from the group consisting of formulas (Ia)-(I.bk) described below. , where in the formulas (Ia)-(I.bk) the values of the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X have the preferred meanings indicated above, or one of the values 1-80 given in the corresponding table one.

For example, embodiment E-I.a is represented by compounds of formula (I.a),

and substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are as defined above or one of the values 1-80 shown in Table 1.

Embodiments EI.bEI.bk are defined as appropriate, and substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are as defined above or one of the values 1-80 given in the corresponding Table 1.

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

Compounds of formula (I) in accordance with the present invention, where R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are as defined for formula (I), can be obtained by converting the compounds of formula (II), where R ¹ , R ² and X are as defined for formula (I) using a compound of formula (III) wherein R ³ , R ⁴ and R ⁵ are as defined for formula (I) and R ¹² is is a halogen, preferably bromine, either by thermal heating, or by means of a base, or under the conditions of a Buchwald-Hartwig-catalyzed transition metal amination. This is shown in diagram 1 below.

Scheme 1

Compounds of formula (III) where R ³ , R ⁴ and R ⁵ are as defined for formula (I) and R ¹² is halogen, preferably bromine, can be obtained by converting a compound of formula (IV) where R ³ is as defined for formula (I) and R ⁹ is halogen, preferably bromine, and compounds of formula (V) wherein R ⁴ and R ⁵ are as defined for formula (I), either by using an acid chloride intermediate, or directly with the peptide agent involved in the coupling reaction. This is shown in diagram 2 below.

Scheme 2

Compounds of formula (IV) wherein R ³ is as defined for formula (I) and R ¹² is halogen, preferably bromine, can be prepared by converting a compound of formula (VI) where R ³ is as defined for formula (I) R ¹² is halogen, preferably bromine, and R ¹³ is C ₁ -C ₆ alkyl, with a base. This is shown in diagram 3 below.

Scheme 3

Alternatively, compounds of formula (I) where R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are as defined for formula (I) can be obtained by converting a compound of formula (VII) where R ¹ , R ² , R ³ and X are as defined for formula (I), using a compound of formula (V), where R ⁴ and R ⁵ are as defined for formula (I), or by using an acid chloride intermediate , or directly using the peptide agent involved in the coupling reaction. This is shown in diagram 4 below.

Scheme 4

Compounds of formula (VII) where R ¹ , R ² , R ³ and X are as defined for formula (I) can be obtained by converting a compound of formula (VIII) where R ¹ , R ² , R ³ and X are such as defined for formula (I), and R ¹³ represents C ₁ -C ₆ alkyl, with the help of a base. This is shown in diagram 5 below.

Scheme 5

Compounds of formula (VIII) wherein R ¹ , R ² , R ³ and X are as defined for formula (I) and R ¹³ is C ₁ -C ₆ alkyl can be prepared by converting a compound of formula (II) where R ¹ , R ² and X are as defined for formula (I), using a compound of formula (VI), where R ³ is as defined for formula (I), R ¹² is halogen, preferably bromine, and R ¹³ is C ₁ -C ₆ alkyl, either by thermal heating, or by means of a base, or under Buchwald-Hartwig transition metal catalyzed amination conditions. This is shown in diagram 6 below.

Scheme 6

Alternatively, compounds of formula (VIII) wherein R ¹ , R ² , R ³ and X are as defined for formula (I) and R ¹³ is C ₁ -C ₆ alkyl can be prepared by converting a compound of formula (IX) where R ¹ and X are as defined for formula (I) and R ¹² is halogen, preferably bromine or iodine, with a compound of formula (X) where R ² and R ³ are as defined for formula (I), and R ¹³ represents C ₁ -C ₆ alkyl, under conditions catalyzed by the transition metal amination according to Buchwald-Hartwig. This is shown in diagram 7 below.

Scheme 7

Alternatively, compounds of formula (I) in accordance with the present invention, where R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are as defined for formula (I), can be obtained by converting the compounds of formula ( IX) where R ¹ and X are as defined for formula (I) and R ¹² is halogen, preferably bromine or iodine, with a compound of formula (XI) where R ² , R ³ , R ⁴ and R ⁵ are as defined for formula (I) under the conditions of Buchwald-Hartwig catalyzed transition metal amination. This is shown in diagram 8 below.

Scheme 8

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

The compounds of formula (I) can be used in agriculture and related applications, for example, as active ingredients to control plant pests or on inanimate materials to control spoilage microorganisms or organisms potentially harmful to humans. The new compounds have excellent activity at low application levels, are well tolerated by plants and are environmentally friendly. They are characterized by very useful curative, preventive and systemic properties and can be used to protect numerous cultivated plants. The compounds of formula (I) can be used to control or kill pests that occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of various crops of useful plants, while protecting at the same time those parts of plants that 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 attack by microorganisms by treating the plants or plant propagation material and/or harvested food crops, wherein an effective amount of a compound of formula (I) is applied to the plants, their parts, or applied to their place of growth.

Also the compounds of formula (I) can be used as a fungicide. Used in this document, the term "fungicide" means a compound with which control, modify or prevent the growth of fungi. The term "fungicidally effective amount" means an amount of such a compound, or combination of such compounds, that is capable of providing an effect on the growth of fungi. Controlling or modifying effects include all deviations from natural development such as killing, developmental inhibition, and the like, and prevention includes a barrier or other protective formation in or on the plant to prevent fungal infection.

The compounds of formula (I) can also be used as dressing agents for treating plant propagation material, for example seeds, for example fruits, tubers or grains, or cuttings of a plant (for example rice), to protect against infections caused by fungi, and also from phytopathogenic fungi found in the soil. The propagation material may be treated with a composition containing a compound of formula (I) prior to planting: the seed may, for example, be dressed prior to sowing.

The active ingredients of the present invention can also be applied to seeds (coating), either by soaking the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to a planting site at the time of planting the propagation material, for example, in a seed furrow during sowing. The present invention also relates to such methods for treating plant propagation material and to such treated plant propagation material.

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

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

The compounds of formula (I) may, for example, be effective against fungi and disease vectors related to fungi, as well as against phytopathogenic bacteria and viruses. These fungi and disease vectors related to fungi, 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., including B. cinerea, Candida spp., including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp, Cercospora spp. ., including C.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 including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. prolifera tum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cing, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp., including H. capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp., including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides Penillium 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 useful plants to be protected generally include perennial and annual crops such as berry plants, for example, blackberry, blueberry, cranberry, raspberry and strawberry varieties; cereals such as barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fibrous plants such as cotton, flax, hemp, jute and sisal; field crops such as sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees such as apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses such as bermuda grass, bluegrass, bent grass, serpentine eremochloa, fescue, tares, augustin grass, and Japanese zoisia; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage, and thyme; legumes, such as beans, lentils, peas and soybeans; nuts, such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios, and walnuts; palm trees, eg 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, squash, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach, and tomato; and vine crops, such as varieties of grapes.

The term "useful plants" should be understood to also include useful plants that have been made tolerant to herbicides such as bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS inhibitors (5 -enol-pyrovyl-shikimate-3-phosphate synthase), GS (glutamine synthase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) as a result of conventional breeding or genetic engineering methods. An example of a crop that has been made tolerant to imidazolinones, eg imazamox, by conventional breeding methods (mutagenesis) is Clearfield® rape (canola). Examples of crops that have been rendered tolerant to herbicides or herbicide classes by genetic engineering include glyphosate and glufosinate resistant maize varieties commercially available under the tradenames RoundupReady®, Herculex I® and LibertyLink®.

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

Examples of such plants are: YieldGard® (maize variety expressing CryIA(b) toxin); YieldGard Rootworm® (maize variety expressing CryIIIB(b1) toxin); YieldGard Plus® (maize variety expressing CryIA(b) toxin and CryIIIB(b1) toxin); Starlink® (maize variety expressing Cry9(c) toxin); Herculex I® (maize cultivar expressing CryIF(a2) toxin and phosphinothricin-N-acetyltransferase (PAT) enzyme tolerant to the herbicide ammonium glufosinate); NuCOTN 33B® (cotton variety expressing CryIA(c) toxin); Bollgard I® (cotton cultivar 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), Agrisure® CB Advantage (Bt11 with corn borer (CB) resistance), Agrisure® RW (with Western corn bug resistance), and Protecta®.

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

Toxins that can 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 δ-endotoxins, eg Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3b1 or Cry9C, or vegetative insecticidal proteins (Vip), eg Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of nematode colonizing bacteria, eg Photorhabdus spp. or Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus; animal-produced toxins such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycetes toxins, plant lectins such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIPs) such as ricin, maize RIP, abrin, luffin, saporin, or bryodin; steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyltransferase, cholesterol oxidase, 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, under δ-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 with a novel combination of different domains of these proteins (see, for example, WO 02/15701). Truncated toxins are known, such as truncated Cry1Ab. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are substituted. With such amino acid substitutions, sequences not found in the natural toxin and recognized by proteases 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 obtaining such transgenic plants are generally known to the person 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 the transgenic plants makes the plants tolerant to harmful insects. Such insects can belong to any taxonomic group of insects, but are especially common among beetles (Coleoptera), diptera (Diptera) and butterflies (Lepidoptera).

Transgenic plants are known that contain one or more genes that encode for insect resistance and express one or more toxins, some of which are commercially available. Examples of such plants are: YieldGard® (maize variety expressing Cry1Ab toxin); YieldGard Rootworm® (maize variety expressing Cry3Bb1 toxin); YieldGard Plus® (maize variety expressing Cry1Ab toxin and Cry3Bb1 toxin); Starlink® (maize variety expressing Cry9C toxin); Herculex I® (maize cultivar expressing Cry1Fa2 toxin and phosphinothricin-N-acetyltransferase (PAT) enzyme tolerant to the herbicide ammonium glufosinate); NuCOTN 33B® (cotton variety expressing Cry1Ac toxin); Bollgard I® (cotton cultivar expressing Cry1Ac toxin); Bollgard II® (cotton cultivar expressing Cry1Ac toxin and Cry2Ab toxin); VipCot® (cotton variety expressing Vip3A toxin and Cry1Ab toxin); NewLeaf® (potato variety expressing 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 as follows.

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

2. Maize Bt176 from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 Saint Sauveur, France, registration number C/FR/96/05/10. A genetically modified Zea mays that has been rendered resistant to attack by the corn borer (Osthnia nubilalis and Sesamia nonaghoides) by transgenic expression of the Cry1Ab toxin. Maize Bt176 also transgenic expresses the PAT enzyme to achieve tolerance to the herbicide ammonium glufosinate.

3. Maize MIR604 from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 Saint Sauveur, France, registration number C/FR/96/05/10. Maize that has been rendered insect resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by inserting a sequence recognized by the cathepsin G protease. 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 from the order Coleoptera.

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

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

7. Maize NK603 × MON 810 from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of hybrid maize varieties traditionally bred by crossing genetically modified varieties NK603 and MON 810. Maize NK603 × MON 810 transgenic expresses the CP4 EPSPS protein derived from Agrobactehum sp, a CP4 strain that confers tolerance to the Roundup® herbicide (contains glyphosate) and also the Cry1Ab toxin, derived from Bacillus thuhngiensis subspecies kurstaki, which provides tolerance to certain members of the order Lepidoptera, including the corn borer.

As used herein, the term "place of growth" means fields in which 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, as well as available green plants.

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

The term "plant propagation material" is understood to mean the generative organs of a plant, such as seeds, which can be used to propagate the latter, and vegetative material, such as cuttings or tubers, such as potatoes. Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants can also be mentioned, which should be transplanted after germination or after emerging from the soil. These young plants can be protected prior to transplantation by full or partial dip treatment. Preferably, "plant propagation material" should be understood to mean seeds.

Pesticides referred to in this document using their traditional name 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 excipients conventionally used in the field of formulation. To this end, they can traditionally be formulated in a known manner into emulsifiable concentrates, coating pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, powdered preparations, granulates, as well as encapsulated forms, for example, in polymeric substances. As with the type of compositions, methods of application, such as spraying, misting, dusting, spreading, coating or watering, are selected in accordance with the intended purposes and the prevailing conditions. The compositions may also contain additional adjuvants such as stabilizers, defoamers, viscosity regulators, binders or tackifiers, as well as fertilizers, trace element donors or other formulations to obtain special effects.

Suitable carriers and adjuvants, e.g. for agricultural use, may be solid or liquid and are substances useful in formulating technology, e.g. 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 they can be applied to the area under cultivation or the plant to be treated, simultaneously or sequentially with additional compounds. Such additional compounds may be, for example, fertilizers or micronutrient donors or other preparations which affect plant growth. They may also be selective herbicides or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematocides, molluscicides, or mixtures of several such preparations, if necessary, together with additional carriers, surfactants or facilitating the application of auxiliary substances commonly used in the field of drafting.

The compounds of formula (I) can be used in the form of a (fungicidal) composition for the control or protection against phytopathogenic microorganisms, containing as active ingredient at least one compound of formula (I) or at least one preferred single compound, as defined above, in free form or in the form of an agrochemically applicable salt; and at least one of the excipients listed above.

The present invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I), an agriculturally acceptable carrier, and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art. Preferably said composition may contain at least one or more pesticidally 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 in the composition, or it may be mixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator, if desired. The additional active ingredient may, in some cases, lead to unexpected synergistic activities.

Examples of suitable additional active ingredients include the following: acycloamino acid group fungicides, aliphatic nitrogen compound group fungicides, amide group fungicides, anilide group fungicides, antibiotic group fungicides, aromatic group fungicides, arsenic-containing fungicides, arylphenyl ketone group fungicides, benzamide group fungicides, benzanilide group fungicides, benzimidazole group fungicides, benzothiazole group fungicides, vegetable fungicides, bridging diphenyl group fungicides, carbamate group fungicides, carbanylate group fungicides, conazole group fungicides, copper-containing fungicides, dicarboximide group fungicides, dinitrophenol group fungicides, dithiocarbamate group fungicides, dithiolane group fungicides , fungicides of the furanilide group, fungicides of the hydrazide group, fungicides of the imidazole group, mercury-containing fungicides, fungicides of the morpholine group, fungicides of the organophosphorus group compounds, organotin group fungicides, oxathiine group fungicides, oxazole group fungicides, phenylsulfamide group fungicides, poly and sulfide group fungicides, pyrazole group fungicides, pyridine group fungicides, pyrimidine group fungicides, pyrrole group fungicides, quaternary ammonium group fungicides, quinoline group fungicides , quinone group fungicides, quinone group fungicides, strobilurin group fungicides, sulfonanilide group fungicides, thiadiazole group fungicides, thiazole group fungicides, thiazolidine group fungicides, thiocarbamate group fungicides, thiophene group fungicides, triazine group fungicides, triazol pyrimidine group fungicides, triazolopyrimidine group fungicides urea groups, valinamide group fungicides and zinc-containing fungicides.

Examples of suitable additional active ingredients also include the following: 3-difluoromethyl-1-methyl-1H-pyrazol- 4-carboxylic acid, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide, (2-dichloromethylene- 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid 3-ethyl-1-methyl-indan-4-yl)-amide (1072957-71-1), (4'-methylsulfanyl-biphenyl-2- yl)-amide of 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid, [2-(2,4-dichloro-phenyl)-2-methoxy-1-methyl-ethyl]-amide 1-methyl- 3-difluoromethyl-4H-pyrazole-4-carboxylic acid, (5-chloro-2,4-dimethyl-pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, ( 5-bromo-4-chloro-2-methoxy-pyridin-3-yl)-(2,3,4-trimethoxy-6-methyl-phenyl)-methanone, 2-{2-[(E)-3-( 2,6-dichloro-phenyl)-1-methyl-prop-2-en-(E)-ylideneaminooxymethyl]-phenyl}-2-[(Z)-methoxyimino]-N-methylacetamide, 3-[5- (4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, (E)-N-methyl-2-[2-(2,5-dimethylphenol) xymethyl)phenyl]-2-methoxy-iminoacetamide, 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulfonamide, a-[N-(3-chloro-2,6-xylyl)- 2-methoxyacetamido]-y-butyrolactone, 4-chloro-2-cyano-N, -dimethyl-5-p-tolylimidazole-1-sulfonamide, N-allyl-4,5-dimethyl-2-trimethylsilylthiophene-3-carboxamide, N-(I-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide, N-(2-methoxy-5-pyridyl)-cyclopropanecarboxamide, (.+-.)-cis-1- (4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol, 2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2 ,4-triazol-1-yl)-propan-2-ol, 2',6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazol-5-carboxanilide, 1-imidazolyl -1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one, methyl-(E)-2-[2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl]3-methoxyacrylate , methyl-(E)-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl-(E)-2-[2-[6-(2- fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl-(E)-2-[2-[6-(2,6-difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl -(E)- 2-[2-[3-(pyrimidin-2-yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl-(E)-2-[2-[3-(5-methylpyrimidin-2-yloxy)-phenoxy] phenyl]-3-methoxyacrylate, methyl-(E)-2-[2-[3-(phenyl-sulfonyloxy)phenoxy]phenyl-3-methoxyacrylate, methyl-(E)-2-[2-[3-(4 -nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl-(E)-2-[2-phenoxyphenyl]-3-methoxyacrylate, methyl-(E)-2-[2-(3,5-dimethyl-benzoyl) pyrrol-1-yl]-3-methoxyacrylate, methyl-(E)-2-[2-(3-methoxyphenoxy)phenyl]-3-methoxyacrylate, methyl-(E)-2[2-(2-phenylethene-1 -yl)-phenyl]-3-methoxyacrylate, methyl-(E)-2-[2-(3,5-dichlorophenoxy)pyridin-3-yl]-3-methoxyacrylate, methyl-(E)-2-(2 -(3-(1,1,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate, methyl-(E)-2-(2-[3-(alpha-hydroxybenzyl)phenoxy]phenyl)-3- methoxyacrylate, methyl-(E)-2-(2-(4-phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate, methyl-(E)-2-[2-(3-n-propyloxy-phenoxy)phenyl ]3-methoxyacrylate, methyl-(E)-2-[2-(3-isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl-(E)-2-[2-[3-(2-fluorophenoxy)phenoxy]phenyl ]-3-methoxyacrylate, methyl-(E)-2-[2-(3 -ethoxyphenoxy)phenyl]-3-methoxyacrylate, methyl-(E)-2-[2-(4-tert-butyl-pyridin-2-yloxy)phenyl]-3-methoxyacrylate, methyl-(E)-2-[ 2-[3-(3-cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl-(E)-2-[2-[(3-methyl-pyridin-2-yloxymethyl)phenyl]-3-methoxyacrylate, methyl -(E)-2-[2-[6-(2-methyl-phenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl-(E)-2-[2-(5-bromo-pyridine -2-yloxymethyl)phenyl]-3-methoxyacrylate, methyl-(E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxyacrylate, methyl-(E)- 2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate, methyl-(E), (E)-2-[2-(5,6- dimethylpyrazin-2-ylmethyloxyminomethyl)phenyl]-3-methoxyacrylate, methyl-(E)-2-{2-[6-(6-methylpyridin-2-yloxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, methyl -(E), (E)-2-{2-(3-methoxyphenyl)methyloxyminomethyl]-phenyl}-3-methoxyacrylate, methyl-(E)-2-{2-(6-(2-azidophenoxy)-pyrimidine -4-yloxy]phenyl}-3-methoxyacrylate, methyl-(E), (E)-2-{2-[6-phenylpyrimidin-4-yl)-methyloxyminomethyl]phenyl}-3-methoxyacrylate, methyl-(E ), (E)-2-{ 2-[(4-chlorophenyl)-methyloxyminomethyl]-phenyl}-3-methoxyacrylate, methyl-(E)-2-{2-[6-(2-n-propylphenoxy)-1,3,5-triazine-4 -yloxy]phenyl}-3-methoxyacrylate, methyl-(E), (E)-2-{2-[(3-nitrophenyl)methyloxyminomethyl]phenyl}-3-methoxyacrylate, 3-chloro-7-(2-aza -2,7,7-trimethyl-oct-3-en-5-in), 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, 3-iodine-2-propynyl alcohol, 4-chlorophenyl-3 -iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodine-2-propynyl-n -butylcarbamate, 3-iodine-2-propynyl-n-hexylcarbamate, 3-iodine-2-propynyl-cyclohexylcarbamate, 3-iodine-2-propynyl-phenylcarbamate; phenolic derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol , 5-hydroxy-2(5H)-furanone; 4,5-dichlorodithiazolinone, 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone, 4,5-dichloro-(3H)-1,2-dithiol-3-one, 3,5-dimethyl-tetrahydro-1,3, 5-thiadiazine-2-thione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, acibenzolar, acipetax, alanicarb, albendazole, aldimorph, allicin, allyl alcohol, amethoctradin, amisulbrom, amobam, ampropylphos, anilazine, asomat, aureofungin, Azonazol, Azafendin, Azitiram, Azoxystrobin, Barium Polysulfide, Benalaxyl, Benalaxyl-M, Benodanil, Benomyl, Benquinox, Bentaluron, Benthiavalicarb, Benthiazole, Benzalkonium Chloride, Benzamacryl, Benzamorph, Benzohydroxamic Acid, Benzovindiflupyr, Berberine, Biloxolpakazine , bitertanol, bitionol, bixaphene, blasticidin-S, boscalid, bromothalonil, bromuconazole, bupirimate, butiobate, butylamine, calcium polysulfide, captafol, captan, carbamorph, carbendazim, carbendazim hydrochloride, carboxine, carpropamide, carvone, CGA41396, CGA41397, quinomethionate, chitosan , chlobentiazone, chloraniformmethane, chloranil, chlorphenazo l, chloroneb, chlorpicrin, chlorothalonil, chlorozolinate, chlosolinate, climbazole, clotrimazole, closilacone copper-containing compounds such as copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper oxyquinolate, copper silicate, copper sulfate , copper tallate, copper and zinc chromate and Bordeaux mixture, cresol, kufraneb, cuprobam, copper (I) oxide, cyazofamide, cyclafuramide, cycloheximide, cyfluphenamide, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, debacarb, decafentine, dehydroacetic acid, di -2-pyridyl-disulfide-1,1'-dioxide, dichlorofluanid, diclomesin, dichlon, dicloran, dichlorophene, dichlozolin, diclobutrazol, diclocimet, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O-di-isopropyl-S-benzylthiophosphate, dimefluazole, dimethaclone, dimethconazole, dimethomorph, dimethirimol, diniconazole, diniconazole-M, dinobuton, dinocap, dinoctone, dinopentone, dinosulfone, dinoterbone, diphenylamine, dipyrithione, disulfiram, dithalymphos, dithianone, dithioether, dodecyldimethylammo nium chloride, dodemorph, dodicin, dodin, doguadin, drazoxolone, edifenfos, enestroburin, epoxiconazole, ethaconazole, etem, ethaboxam, etirimol, ethoxykin, ethylicine, ethyl-(Z)-N-benzyl-N-([methyl-(methyl- thioethylideneamino-oxycarbonyl)amino]thio)-β-alaninate, etridiazol, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamide, fenitropan, fenoxanil, fenpiclonil, fenpicoxamide, fenpropidine, fenpropimorph, fenpyrazamine, phenol hydroxide, , ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, flupicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, fluzilazole, flusulfamide, flutanil, flutolanil, flutriafol, fluxapiroxad, folpet, formaldehyde, furabanylcaridazole, furabanylcaridazole, , furconazole, furfural, furmecyclox, furofanate, gliodine, griseofulvin, guazatin, galacrinate, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiophos, hydrarhafen, hydroxyisoxazole, chemexaz ol, imazalil, imazalyl sulfate, imibenconazole, imoctadine, imoctadine triacetate, inezin, iodocarb, ipconazole, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butylcarbamate, isoprothiolane, isopyrazam, isotianil, isovaledione, isopamphos, kasugamycin, kresoxim LY248908, mancozeb, mandipropamide, maneb, mebenil, mecarbinzide, mefenoxam, mefentrifluconazole, mepanipyrim, mepronil, mercuric chloride, mercuric chloride, meptyldinocap, metalaxyl, metal axyl-M, metam, metazoxolone, metconazole, metasulfocarb, methylisobromide metfuroxam , metiram, metiram-zinc, methominostrobin, metrafenone, metsulfovax, milneb, moroxidine, myclobutanil, myclozolin, nabam, natamycin, neoasosin, nickel dimethyldithiocarbamate, nitrostyrene, nitrotal-isopropyl, nuarimol, octilinone, ofuras, organomercury, orysastrobin, osthole, oxadixyl , oxasulfuron, oxathiapiproline, oxinic copper, oxolinic acid, oxpoconazole, oxycarboxin, pa rinol, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, penthiopyrad, fenamacryl, phenazine oxide, fosdifen, fosetyl-Al, phosphoric acids, phthalide, picoxystrobin, piperalin, polycarbamate, polyoxin D, polyoxorim, polyram, probenazole, prochloraz, procymidone, propamidine , propamocarb, propiconazole, propineb, propionic acid, proquinazid, prothiocarb, prothioconazole, pidiflumethofen, pyracarbolide, pyraclostrobin, pyrametostrobin, pyroxystrobin, pyrazophos, pyribencarb, pyridinitrile, pyrifenox, pyrimethanil, pyrophenone, pyroquilon, pyroxychlor, pyroammonium, pyrrolic pyrolyxfur compounds quinacetol, quinazamide, quinconazole, quinomethionate, quinoxyfen, quintozene, rabenzazole, santonin, sedaxan, silthiopham, simeconazole, sipconazole, sodium pentachlorophenolate, spiroxamine, streptomycin, sulfur, sultropene, tebuconazole, tebufloquin, tecloftalam, teknazen, tecoram, tetraconazole, thiabendazole , thicyophene, thifluzamide, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thioquinox, thiram, thiadinil, thymibenconazole, thioximide, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triamifos, triarimol, triazbutyl, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumazol, triforin, triflumizole, triticonazole, uniconazole, urbacid, valifenamycin, vapam, vinclozolin, zarilamide, cineb, cyram and zoxamide.

The compounds of the present invention may also be used in combination with anthelmintic agents. Such anthelmintics include compounds selected from the class of macrocyclic lactone compounds such as the ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives described in EP-357460, EP-444964 and EP-594291. Additional anthelmintics include semi-synthetic and biosynthetic avermectin/milbemycin derivatives such as those described in US-5015630, WO-9415944 and WO-9522552. Additional anthelmintic agents include benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole and other members of this class. Additional anthelmintics include imidazothiazoles and tetrahydropyrimidines such as tetramizole, levamisole, pyrantel pamoate, oxanthel or morantel. Additional anthelmintic agents include flukicides such as triclabendazole and clorsulon as well as cestodocides such as praziquantel and epsiprantel.

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

The compounds of the present invention can be used in combination with derivatives and analogs of the general class of dioxomorpholine antiparasitic agents described in WO-9615121, as well as with anthelmintic active cyclic depsipeptides such as those described in WO-9611945, 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; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenoside and the like; neonicotinoids such as imidacloprid and the like.

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

Other examples of such biologically active compounds in combination with which the compounds of the present invention may be used include, without limitation, the following.

Organophosphates: acephate, azamethifos, azinphos-ethyl, azinphos-methyl, bromphos, bromphos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorphenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulfone, dialyphos, diazinon, dichlorvos , dicrotophos, dimethoate, disulfotone, ethion, etoprofos, etrymphos, famfur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazophos, phonophos, formotion, fostiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, methacryphos, methamidophos, metidathione, methyl parathion , mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, fentoate, phosalone, phospholane, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pyrimiphos, pyrimiphos-methyl, profenofos, propafos, proetamphos, prothiophos , pyraclophos, pyridapentione, quinalphos, sulprofos, temephos, terbufos, tebupyrimphos, tetrachlorvinphos, timeton, thiazophos, trichlorfon, vamidothion.

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

Pyrethroids: acrinatin, allethrin, alphamethrin, 5-benzyl-3-furylmethyl-(E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin , cyfluthrin, alpha-cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cytitrin, cyfenotrin, deltamethrin, empentrin, esfenvalerate, etofenprox, fenfluthrin, fenpropatrin, fenvalerate, flucitrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, pralletrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, tau-fluvalinate, tefluthrin, tralometrin, zeta-cypermethrin.

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

Other antiparasitics: acequinocil, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, biphenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorbenzilate, chlordimeform, chlorfenapyr, chromafenoside, clothianidin , cyromazine, diacloden, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, etofenprox, fenazaquin, flumit, MTI-800, fenpyroximate, fluacripyrim, flubenzimine, flubrocitrinate, flufenzine, flufenprox, flufenproxifen, hydramethylproxifen , IKI-220, Kanemite, NC-196, Neem Guard, Nidinorterfuran, Nitenpyram, SD-35651, WL-108477, Pyridaryl, Propargite, Protrifenbut, Pymetrozine, Pyridabene, Pyrimidifen, NC-1111, R-195, RH-0345, RH-2485 RYI-210 S-1283 S-1833 SI-8601 YI-5301.

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

Bactericides: chlortetracycline, oxytetracycline, streptomycin. Other biological agents: enrofloxacin, febantel, penetamate, moloxicam, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprol, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiur, carprofen, metaflumizone, praziquarantel, triclabendazol.

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

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

Control or prevention means reducing an infestation by insects, or phytopathogenic or spoilage microorganisms, or organisms potentially harmful to humans, especially organisms that are fungi, to such a level that improvement is noticeable.

A preferred method for controlling or preventing infestation of crops by phytopathogenic microorganisms, especially fungal organisms or insects, which includes the application of a compound of formula (I) or an agrochemical composition that contains at least one of these compounds, is foliar application. Application frequency and application rate will depend on the risk of infestation by the relevant pathogen or insect. However, the compounds of formula (I) can also enter the plant through the roots from the soil (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 granulates can be applied to a flooded paddy field. The compounds of formula (I) can also be applied to seeds (coating) by impregnating the seeds or tubers with either a liquid fungicide formulation or by coating them with a solid formulation.

A formulation, for example a formulation containing a compound of formula (I) and, if appropriate, solid or liquid excipient or monomers for encapsulating a compound of formula (I), can be prepared in a known manner, generally by thoroughly mixing and/or grinding the compound with excipients. , for example solvents, solid carriers and optionally surface-active compounds (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 from 20 g to 600 g and. i. / ha. When used as a seed impregnation agent, conventional doses are from 10 mg to 1 g of active substance per kg of seed.

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

The compositions of the present invention may be used in any conventional form, e.g., double 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 emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersion (OD), miscible with oil fluid formulation (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 technically feasible composition in combination with agriculturally acceptable excipients.

Such compositions may be prepared in the conventional manner, for example by mixing the active ingredients with the appropriate inert formulation components (diluents, solvents, excipients and optionally other formulation ingredients such as surfactants, biocides, antifreezes, adhesives, thickeners and compounds, which provide ancillary effects). If long-term action is desired, conventional slow release formulations may 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, the condensation product of formaldehyde with naphthalenesulfonate, alkylarylsulfonate, ligninsulfonate, fatty acid alkyl sulfate and ethoxylated alkylphenol, and ethoxylated fatty alcohol.

The seed dressing composition is applied in a manner known per se to seeds using a combination of the present invention and a diluent in a suitable form of the seed dressing composition, e.g. as an aqueous suspension or in the form of a dry powder having good adhesion to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain single active ingredients or a combination of active ingredients in encapsulated form, such as slow release capsules or microcapsules.

Typically, formulations contain 0.01 to 90% by weight of active agent, 0 to 20% of an agriculturally acceptable surfactant, and 10 to 99.99% of the 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 (C) and optionally other active agents, in particular microbiocides or preservatives or the like. Concentrated form compositions typically contain from about 2% to 80%, preferably from about 5% to 70%, by weight of the active agent. Formulation forms used may, for example, contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of the active agent. Since commercial products will preferably be formulated as concentrates, the final consumer will in most cases use dilute formulations.

Examples

The following examples serve to illustrate the present invention. Compounds of the present invention may differ from known compounds due to higher efficiency at low application rates, which can be verified by a person skilled in the art using the experimental procedures set forth in the examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

The compounds of formula (I) may have a number of advantages including, inter alia, advantageous levels of biological activity for plant protection against fungal diseases or excellent properties for use as agrochemically active ingredients (e.g., higher biological activity, advantageous spectrum of activity, improved safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

Example 1 This example illustrates the preparation of N-(1-cyano-1,2-dimethyl-propyl)-2-(3,5-difluoroanilino)-5-methyl-thiazole-4-carboxamide (compound 1.n.3 )

a) Preparation of methyl 2-(3,5-difluoroanilino)-5-methyl-thiazole-4-carboxylate

A mixture of methyl 2-bromo-5-methyl-thiazole-4-carboxylate (5.0 g, 20 mmol) and 3,5-difluoroaniline (13.3 g, 101 mmol) was heated to 130°C for 1 h. while stirring. The reaction mixture was cooled to room temperature and diluted with ethyl acetate and water. The phases were separated, the aqueous phase was extracted with ethyl acetate, the combined organic layer was washed with water and brine, dried over magnesium sulfate and evaporated under reduced pressure. The residue was purified by silica gel chromatography using ethyl acetate and heptane as eluents to give methyl 2-(3,5-difluoroanilino)-5-methyl-thiazole-4-carboxylate (4.9 g, 17 mmol). ¹ H-NMR (400 MHz, CDCl ₃ ): δ=2.73 (s, 3H), 3.94 (s, 3H), 6.52 (t, 1H), 6.86 (d, 2H), 7.43 (bs, 1H).

b) Preparation of 2-(3,5-difluoroanilino)-5-methyl-thiazole-4-carboxylic acid

Lithium hydroxide monohydrate (1.7 d, 69 mmol). The reaction mixture was stirred for 16 hours at room temperature, then the solvents were removed in vacuo. The residue was diluted with ethyl acetate and water, then slowly added 2N. hydrochloric acid until a pH of 3-4 is reached. The insoluble solid was removed from the biphasic mixture by filtration and the first crop of the desired product was isolated. The various phases of the filtrate were separated, the aqueous phase was extracted with ethyl acetate, the combined organic layer was washed with water and brine, dried over magnesium sulfate and evaporated under reduced pressure to isolate the second part of the desired product. Both portions of the solid were combined and dried under high vacuum to give 2-(3,5-difluoroanilino)-5-methyl-thiazole-4-carboxylic acid (4.6 g, 16 mmol). ¹ H-NMR (400 MHz, MeOD): δ=2.69 (s, 3H), 6.51 (t, 1H), 7.30 (d, 2H).

c) Preparation of N-(1-cyano-1,2-dimethyl-propyl)-2-(3,5-difluoroanilino)-5-methyl-thiazole-4-carboxamide (compound I.n.3)

Triethylamine (0.22 g, 2.22 mmol ) and propanephosphonic acid anhydride (TZR, 0.94 g, 1.48 mmol). The reaction mixture was stirred for 30 minutes. at room temperature, then 2-amino-2,3-dimethylbutyronitrile (0.1 g, 0.89 mmol) was added. Stirring at room temperature was continued for 16 hours, then the reaction mixture was diluted with ethyl acetate, washed with water, dried over magnesium sulfate and evaporated under reduced pressure. The residue was purified by silica gel chromatography using ethyl acetate and heptane as eluents to give N-(1-cyano-1,2-dimethyl-propyl)-2-(3,5-difluoroanilino)-5-methyl-thiazole-4- carboxamide (In3 compounds, 0.14 g, 0.36 mmol). ¹ H-NMR (400 MHz, CDCl ₃ ): δ=1.19 (d, 3H), 1.25 (d, 3H), 1.78 (s, 3H), 2.39 (hep., 1H) , 2.78 (s, 3H), 6.54 (t, 1H), 6.96-7.02 (m, 2H), 7.40 (bs, 1H).

Example 2 This example illustrates the preparation of 5-bromo-N-(1-cyclohexylethyl)-2-(3,5-difluoroanilino)thiazole-4-carboxamide (compound 1.e.2)

a) Preparation of ethyl 2-(3,5-difluoroanilino)thiazole-4-carboxylate

Potassium phosphate (1.9 g, 8.7 mmol), tris( dibenzylideneacetone) dipalladium (0.27 g, 0.29 mmol), Xantphos (0.17 g, 0.29 mmol) and 3,5-difluoroiodobenzene (1.5 g, 6.4 mmol). The mixture was purged with argon for 20 minutes, then heated in a microwave oven to 140° C. for 1 hour. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate and water, dried over magnesium sulfate, and evaporated under reduced pressure. The residue was purified by silica gel chromatography using ethyl acetate and cyclohexane as eluents to give ethyl 2-(3,5-difluoroanilino)thiazole-4-carboxylate (0.16 g, 0.56 mmol). ¹ H-NMR (400 MHz, CDCl ₃ ): δ=1.41 (t, 3H), 4.40 (q, 2H), 6.54 (t, 1H), 6.95 (d, 2H), 7.63 (s, 1H).

b) Preparation of 2-(3,5-difluoroanilino)thiazole-4-carboxylic acid

Lithium hydroxide monohydrate (54 mg, 2.2 mmol). The reaction mixture was stirred for 16 hours at room temperature, then the solvents were removed in vacuo. The residue was diluted with water, then slowly added 2N. hydrochloric acid until a pH of 3-4 is reached. The mixture was extracted with ethyl acetate, the organic layer was washed with water and brine, dried over magnesium sulfate and evaporated under reduced pressure to give 2-(3,5-difluoroanilino)thiazole-4-carboxylic acid (98 mg, 0.38 mmol). ¹ H-NMR (400 MHz, MeOD): δ=6.52 (t, 1H), 7.33 (d, 2H), 7.72 (s, 1H).

c) Preparation of N-(1-cyclohexylethyl)-2-(3,5-difluoroanilino)thiazole-4-carboxamide

Triethylamine (49 mg, 0.48 mmol) and propanephosphonic acid anhydride (TZP, 0 .2 g, 0.32 mmol). The reaction mixture was stirred for 30 minutes. at room temperature, then 1-cyclohexylethylamine (24 mg, 0.19 mmol) was added. Stirring at room temperature was continued for 16 hours, then the reaction mixture was diluted with ethyl acetate, washed with water, dried over magnesium sulfate and evaporated under reduced pressure. The residue was purified by silica gel chromatography using ethyl acetate and cyclohexane as eluents to give N-(1-cyclohexylethyl)-2-(3,5-difluoroanilino)thiazole-4-carboxamide (29 mg, 0.08 mmol). ¹ H-NMR (400 MHz, CDCl ₃ ): δ=1.02-1.13 (m, 4H), 1.20 (d, 3H), 1.48 (q, 1H), 1.65-1 .82 (m, 6H), 4.03 (q, 1H), 6.55 (t, 1H), 7.03 (d, 2H), 7.55 (s, 1H).

d) Preparation of 5-bromo-N-(1-cyclohexylethyl)-2-(3,5-difluoroanilino)thiazole-4-carboxamide (compound 1.e.2)

N-bromosuccinimide (12 mg, 0 .07 mmol). The reaction mixture was stirred for 1 hour at room temperature, then diluted with ethyl acetate and washed with water. The organic layer was dried over magnesium sulfate and evaporated under reduced pressure. The residue was purified by silica gel chromatography using ethyl acetate and cyclohexane as eluents to give 5-bromo-N-(1-cyclohexylethyl)-2-(3,5-difluoroanilino)thiazole-4-carboxamide (compounds Ie2, 18 mg, 0 .04 mmol). ¹ H-NMR (400 MHz, CDCl ₃ ): δ=1.01-1.18 (m, 4H), 1.21 (d, 3H), 1.48 (q, 1H), 1.67-1 .83 (m, 6H), 3.99 (q, 1H), 6.54 (t, 1H), 7.06 (d, 2H).

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

where

a) 80 compounds of formula (I.a),

where R ¹ , R ² , R ³ and X are as defined in table 1.

b) 80 compounds of formula (I.b),

where R ¹ , R ² , R ³ and X are as defined in table 1.

c) 80 compounds of formula (I.c),

where R ¹ , R ² , R ³ and X are as defined in table 1.

d) 80 compounds of formula (I.d),

where R ¹ , R ² , R ³ and X are as defined in table 1.

e) 80 compounds of formula (I.e),

where R ¹ , R ² , R ³ and X are as defined in table 1.

f) 80 compounds of formula (I.f),

where R ¹ , R ² , R ³ and X are as defined in table 1.

g) 80 compounds of formula (I.g),

where R ¹ , R ² , R ³ and X are as defined in table 1.

h) 80 compounds of formula (I.h),

where R ¹ , R ² , R ³ and X are as defined in table 1.

i) 80 compounds of formula (I.i),

where R ¹ , R ² , R ³ and X are as defined in table 1.

j) 80 compounds of formula (I.j),

where R ¹ , R ² , R ³ and X are as defined in table 1.

k) 80 compounds of formula (I.k),

where R ¹ , R ² , R ³ and X are as defined in table 1.

m) 80 compounds of formula (I.m),

where R ¹ , R ² , R ³ and X are as defined in table 1.

n) 80 compounds of formula (I.n),

where R ¹ , R ² , R ³ and X are as defined in table 1.

o) 80 compounds of formula (I.o),

where R ¹ , R ² , R ³ and X are as defined in table 1.

p) 80 compounds of formula (I.p),

where R ¹ , R ² , R ³ and X are as defined in table 1.

q) 80 compounds of formula (I.q),

where R ¹ , R ² , R ³ and X are as defined in table 1.

r) 80 compounds of formula (I.r),

where R ¹ , R ² , R ³ and X are as defined in table 1.

s) 80 compounds of formula (I.s),

where R ¹ , R ² , R ³ and X are as defined in table 1.

t) 80 compounds of formula (I.t),

where R ¹ , R ² , R ³ and X are as defined in table 1.

u) 80 compounds of formula (I.u),

where R ¹ , R ² , R ³ and X are as defined in table 1.

v) 80 compounds of formula (I.v),

where R ¹ , R ² , R ³ and X are as defined in table 1.

w) 80 compounds of formula (I.w),

where R ¹ , R ² , R ³ and X are as defined in table 1.

x) 80 compounds of formula (I.x),

where R ¹ , R ² , R ³ and X are as defined in table 1.

y) 80 compounds of formula (I.y),

where R ¹ , R ² , R ³ and X are as defined in table 1.

z) 80 compounds of formula (I.z),

where R ¹ , R ² , R ³ and X are as defined in table 1.

aa) 80 compounds of formula (I.aa),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ab) 80 compounds of formula (I.ab),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ac) 80 compounds of formula (I.ac),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ad) 80 compounds of formula (I.ad),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ae) 80 compounds of formula (I.ae),

where R ¹ , R ² , R ³ and X are as defined in table 1.

af) 80 compounds of formula (I.af),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ag) 80 compounds of formula (I.ag),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ah) 80 compounds of formula (I.ah),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ai) 80 compounds of formula (I.ai),

where R ¹ , R ² , R ³ and X are as defined in table 1.

aj) 80 compounds of formula (I.aj),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ak) 80 compounds of formula (I.ak),

where R ¹ , R ² , R ³ and X are as defined in table 1.

am) 80 compounds of formula (I.am),

where R ¹ , R ² , R ³ and X are as defined in table 1.

an) 80 compounds of formula (I.an),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ao) 80 compounds of formula (I.ao),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ap) 80 compounds of formula (I.ap),

where R ¹ , R ² , R ³ and X are as defined in table 1.

aq) 80 compounds of formula (I.aq),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ar) 80 compounds of formula (I.ar),

where R ¹ , R ² , R ³ and X are as defined in table 1.

as) 80 compounds of formula (I.as),

where R ¹ , R ² , R ³ and X are as defined in table 1.

at) 80 compounds of formula (I.at),

where R ¹ , R ² , R ³ and X are as defined in table 1.

au) 80 compounds of formula (I.au),

where R ¹ , R ² , R ³ and X are as defined in table 1.

av) 80 compounds of formula (I.av),

where R ¹ , R ² , R ³ and X are as defined in table 1.

aw) 80 compounds of formula (I.aw),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ax) 80 compounds of formula (I.ax),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ay) 80 compounds of formula (I.ay),

where R ¹ , R ² , R ³ and X are as defined in table 1.

az) 80 compounds of formula (I.az),

where R ¹ , R ² , R ³ and X are as defined in table 1.

ba) 80 compounds of formula (I.ba),

where R ¹ , R ² , R ³ and X are as defined in table 1.

bb) 80 compounds of formula (I.bb),

where R ¹ , R ² , R ³ and X are as defined in table 1.

bc) 80 compounds of formula (I.bc),

where R ¹ , R ² , R ³ and X are as defined in table 1.

bd) 80 compounds of formula (I.bd),

where R ¹ , R ² , R ³ and X are as defined in table 1.

be) 80 compounds of formula (I.be),

where R ¹ , R ² , R ³ and X are as defined in table 1.

bf) 80 compounds of formula (I.bf),

where R ¹ , R ² , R ³ and X are as defined in table 1.

bg) 80 compounds of formula (I.bg),

where R ¹ , R ² , R ³ and X are as defined in table 1.

bh) 80 compounds of formula (I.bh),

where R ¹ , R ² , R ³ and X are as defined in table 1.

bi) 80 compounds of formula (I.bi),

where R ¹ , R ² , R ³ and X are as defined in table 1.

bj) 80 compounds of formula (I.bj),

where R ¹ , R ² , R ³ and X are as defined in table 1.

bk) 80 compounds of formula (I.bk),

where R ¹ , R ² , R ³ and X are as defined in table 1.

Throughout this specification, temperatures are given in degrees Celsius (°C) and "mp" refers to the melting point. LC/MS stands for liquid chromatography-mass spectrometry, and the device and method description is as follows: (ACQUITY UPLC from Waters, Phenomenex Gemini C18, particle size 3 µm, 110 angstroms, column 30×3 mm, 1.7 ml/min., 60°C, H ₂ O + 0.05% HCOOH (95%) / CH ₃ CN/MeOH 4:1 + 0.04% HCOOH (5%) - 2 min -CH ₃ CN/MeOH 4:1 + 0.04% HCOOH (5%) - 0.8 min, Waters ACQUITY SQD mass spectrometer, ionization method: electrospray (ESI), polarity: positive ions, capillary voltage (kV) 3.00, cone voltage (V) 20.00, extractor voltage (V) 3.00, initial temperature (°C) 150, desolvation temperature (°C) 400, cone gas flow (l/h) 60, desolvation gas flow (l/ hour) 700)).

Composition examples

The active ingredient is intimately mixed with the excipients and the mixture is finely ground in a suitable mill to give wettable powders which can be diluted with water to give suspensions of the desired concentration.

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

Emulsifiable concentrate

From this concentrate, by dilution with water, emulsions of any desired dilution can be obtained, which can be used to protect the plant.

Ready-to-use pulverulent preparations are obtained 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.

Extruded granules

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

Coated granules

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

Suspension concentrate

The finely divided active ingredient is mixed directly with the excipients to form a suspension concentrate, from which suspensions of any desired dilution can be obtained by dilution with water. By using such dilutions, live plants as well as plant propagation material can be treated and protected from microorganism contamination by spraying, watering or dipping.

Flowable concentrate for seed treatment

Active ingredient [compound of formula (I)] 40% propylene glycol 5% Copolymer of butanol and PO/EO 2% Tristyrenephenol with 10-20 mol EO 2% 1,2-Benzisothiazolin-3-one (as 20% solution in water) 0.5% Calcium salt of monoazopigment 5% Silicone oil (as 75% emulsion in water) 0.2% Water 45.3%

The finely divided active ingredient is mixed directly with the excipients to form a suspension concentrate, from which suspensions of any desired dilution can be obtained by dilution with water. By using such dilutions, live plants as well as plant propagation material can be treated and protected from microorganism contamination by spraying, watering or dipping.

Slow release capsule suspension

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

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

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

Biological examples

Leaf disc treatment / Tomato / Alternaria solani (Alternaria)

Tomato cv. Baby leaf discs were plated on agar in multi-well plates (24-well format) and sprayed with test compound formulated with DMSO and Tween 20 and diluted in water. Leaf disks were inoculated with a suspension of fungal spores 2 days after application. Inoculated leaf disks were incubated at 23°C/21°C (day/night) and 80% relative humidity under a 12/12 hour (light/dark) light cycle in a climate chamber and compound activity was evaluated as an indicator of disease control, expressed as a percentage , compared with the untreated material when showing the appropriate degree of damage due to the disease on the untreated leaf disks, which are control disks (5-7 days after application).

Compounds I.a.3, I.e.3, I.r.3, I.s.3, I.y.1, I.y.3, I.ac.3, I.s.43, I.ao.3, I.au.3, I.at.3, I.bb. 3, I.bb.43 at 200 ppm in the formulation resulted in at least 80% disease control in this test compared to untreated controls, which under the same conditions showed extensive mycelial growth.

Treatment to prevent leaf disc infection / wheat / Blumeria graminis f. sp. thtici (Erysiphe graminis f. sp. tritici) / (wheat powdery mildew)

Wheat leaf segments cv. Kanzler were plated on agar in a multi-well plate (24-well format) and sprayed with test compound formulated with DMSO and Tween 20 and diluted in water. Leaf discs were inoculated by shaking powdery mildew infected plants over test plates 1 day after application. Inoculated leaf disks were incubated at 20° C. and 60% relative humidity under a 24 h dark light regimen followed by 12 h light/12 h dark in a climate chamber, and compound activity was evaluated as an indicator of disease control, expressed as a percentage, compared to untreated material when an appropriate degree of disease damage is observed on untreated control leaf segments (6-8 days after application).

Compounds I.e.2, I.e.3, I.f.3, I.i.3, I.m.3, I.n.3, I.q.3, I.r.2, I.r.3, I.s.3, I.w.2, I.w.3, I.y.1, I.y.2, I.y.3, I.aa. 3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, I.ah.2, I.e.43, I.s.43, I.z.43, I.aa.43, I.ao .3, I.ao.43, I.ap.3, I.ap.43, I.aq.3, I.aq.43, I.ar.3, I.ar.43, I.as.43 , I.at.3, I.at.43, I.au.3, I.au.43, I.av.43, I.ax.43, I.ay.3, I.bb.3, I .bb.43, I.be.3 at 200 ppm formulation resulted in at least 80% disease control in this test compared to untreated controls, which under the same conditions showed extensive mycelial growth.

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

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

Compounds I.e.2, I.f.3, I.n.3, I.r.2, I.r.3, I.v.3, I.w.2, I.w.3, I.y.1, I.y.2, I.aa.3, I.ac.3, I.ag.3, I .ah.2, I.ah.3, I.s.43, I.aa.43, I.au.3, I.ax.3, I.ax.43, I.ay.3 at 200 ppm resulted in at least 80% disease control in this test compared to untreated controls, which under the same conditions showed extensive mycelial growth.

Liquid culture treatment / Gaeumannomyces graminis (grass dampening)

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

Compounds I.a.3, I.b.3, I.c.3, I.d.3, I.e.2, I.e.3, I.f.3, I.g.3, I.h.3, I.i.3, I.j.3, I.k.3, I.m.3, I.n.3, I.o.3, I.p.3, I.q. 3, I.r.2, I.r.3, I.s.3, I.t.3, I.u.3, I.v.3, I.w.2, I.w.3, I.x.3, I.y.1, I.y.2, I.y.3, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, I.af.3, I.ag.3, I.ah.2, I.ah.3, I.ai.3, I. aj.3, I.ak.3, I.am.3, and I.an.3 at 200 ppm formulation resulted in at least 80% disease control in this test compared to untreated control leaf discs, which at under the same conditions demonstrated extensive spread of the disease. Liquid culture processing / Glomerella lagenarium (Colletotrichum lapenarium) / (anthracnose)

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

Compounds I.a.3, I.b.3, I.c.3, I.e.2, I.e.3, I.f.3, I.h.3, I.i.3, I.k.3, I.m.3, I.n.3, I.p.3, I.q.3, I.r.2, I.r.3, I.s.3, I.t. 3, I.u.3, I.v.3, I.w.2, I.w.3, I.x.3, I.y.1, I.y.2, I.y.3, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, I.ag.3, I.ah.2, I.ah.3, I.e.43, I.s.43, I.z.43, I.aa.43, I.ao.3, I.ao.43 , I.ap.3, I.ap.43, I.aq.3, I.aq.43, I.at.3, I.at.43, I.au.3, I.au.43, I .av.43, I.aw.3, I.ax.3, I.ax.43, I.ay.3, I.bb.3, I.bb.43, I.be.3, I.bf .3 at 200 ppm in the formulation resulted in at least 80% disease control in this test compared to untreated controls, which under the same conditions showed extensive mycelial growth.

Treatment to prevent leaf disc infection / rice / Magnaporthe grisea (Pyricularia oryzae) / (rice blast)

Leaf segments of rice cv. Ballila were plated on agar in a multi-well plate (24-well format) and sprayed with test compound formulated with DMSO and Tween 20 and diluted in water. Leaf segments were inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments were incubated at 22° C. and 80% relative humidity under a 24 h dark light regimen followed by 12 h light/12 h dark in a climate chamber, and compound activity was evaluated as an indicator of disease control, expressed as a percentage, compared to untreated material when an appropriate degree of disease damage is observed on untreated control leaf segments (5-7 days after application).

Compounds I.a.3, I.b.3, I.e.3, I.f.3, I.k.3, I.m.3, I.n.3, I.p.3, I.r.2, I.r.3, I.s.3, I.t.3, I.y.2, I.y.3, I.aa.3, I .ab.3, I.ac.3, I.ah.2, I.s.43, I.ao.3, I.ao.43, I.ap.3, I.ap.43, I.aq.3, I.ar.43, I.at.3, I.at.43, I.au.3, I.au.43, I.av.43, I.aw.3, I.ax.3, I. ax.43, I.ay.3, I.bb.3, I.bb.43 at 200 ppm formulation resulted in at least 80% disease control in this test compared to untreated controls, which at those same conditions showed extensive growth of mycelium.

Liquid culture treatment / Monographella nivalis (Microdochium nivale) / (cereal root rot)

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

Compounds I.a.3, I.b.3, I.c.3, I.d.3, I.e.2, I.e.3, I.f.3, I.i.3, I.g.3, I.h.3, I.k.3, I.m.3, I.n.3, I.p.3, I.q.3, I.r.2, I.r. 3, I.s.3, I.t.3, I.u.3, I.v.3, I.w.2, I.w.3, I.x.3, I.y.1, I.y.2, I.y.3, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, I.ag.3, I.ah.2, I.ah.3, I.ai.3, I.aj.3, I.e.43, I.s.43, I.z.43 , I.aa.43, I.ao.3, I.ao.43, I.ap.3, I.aq.3, I.at.3, I.au.3, I.au.43, I .av.43, I.aw.3, I.ax.3, I.ax.43, I.ay.3, I.bb.3, I.bb.43, I.bf.3 at 200 ppm formulation resulted in at least 80% disease control in this test compared to untreated controls, which under the same conditions showed extensive mycelial growth.

Liquid culture treatment / Mycosphaerella arachidis (Cercospora arachidicola) / (Early Leaf Cercospora)

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

Compounds I.b.3, I.e.2, I.e.3, I.f.3, I.m.3, I.n.3, I.p.3, I.q.3, I.r.2, I.r.3, I.s.3, I.v.3, I.w.2, I.w.3, I.x.3, I.y.2, I.y. 3, I.aa.3, I.ab.3, I.ac.3, I.ae.3, I.ah.3, I.s.43, I.z.43, I.ao.3, I.ao.43, I.ap.3, I.ap.43, I.aq.3, I.at.3, I.at.43, I.au.3, I.ax.3, I.ax.43, I. bb.3, I.bb.43 at 200 ppm formulation resulted in at least 80% disease control in this test compared to untreated controls, which under the same conditions showed extensive mycelial growth.

Liquid culture treatment / Mycosphaerella graminicola (Septoria thtici) / (Septoria)

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

Compounds I.a.3, I.b.3, I.c.3, I.e.2, I.e.3, I.f.3, I.h.3, I.k.3, I.m.3, I.n.3, I.p.3, I.q.3, I.r.2, I.r.3, I.s.3, I.t.3, I.u. 3, I.v.3, I.w.2, I.w.3, I.x.3, I.y.1, I.y.2, I.y.3, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae .3, I.ag.3, I.ah.2, I.ah.3, I.ak.3, I.e.43, I.s.43, I.z.43, I.aa.43, I.ao.3, I. ao.43, I.ap.3, I.ap.43, I.aq.3, I.aq.43, I.ar.43, I.as.43, I.at.3, I.at. 43, I.au.3, I.au.43, I.av.43, I.aw.3, I.ax.3, I.ax.43, I.bb.3, I.bb.43, I.be.3 at 200 ppm in the formulation resulted in at least 80% disease control in this test compared to untreated controls, which under the same conditions showed extensive mycelial growth.

Treatment to prevent leaf disc infection / wheat / Puccinia recondita f. sp. tritici / (brown rust)

Wheat leaf segments cv. Kanzler were plated on agar in multi-well plates (24-well format) and sprayed with the test compound preparation diluted in water. Leaf discs were inoculated with a suspension of fungal spores 1 day after application. The inoculated leaf segments were incubated at 19° C. and 75% relative humidity under a 12 h light/12 h dark light regimen in a climate chamber, and compound activity was assessed as an indicator of disease control, expressed as a percentage, compared to untreated material when exhibiting the appropriate degree disease damage on untreated control leaf segments (7-9 days after application).

Compounds I.a.3, I.b.3, I.c.3, I.e.2, I.e.3, I.f.3, I.i.3, I.m.3, I.n.3, I.p.3, I.r.2, I.r.3, I.s.3, I.t.3, I.w.2, I.w.3, I.y. 1, I.y.2, I.y.3, I.aa.3, I.ab.3, I.ac.3, I.ad.3, I.ae.3, I.ah.2, I.e.43, I.s.43, I.z.43, I.aa.43, I.ao.3, I.ao.43, I.ap.3, I.ap.43, I.aq.3, I.aq.43, I.ar.43 , I.as.43, I.at.3, I.at.43, I.au.3, I.au.43, I.av.43, I.aw.3, I.ax.3, I .ax.43, I.ba.43, I.bb.3, I.bb.43, I.bf.3 at 200 ppm formulation resulted in at least 80% disease control in this test compared to untreated control samples, which under the same conditions showed extensive growth of mycelium.

Treatment to prevent leaf disc infection / barley / Pyrenophora teres (net spot)

Leaf segments of barley cv. Hasso were plated on agar in a multi-well plate (24-well format) and sprayed with test compound formulated with DMSO and Tween 20 and diluted in water. Leaf segments were inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments were incubated at 20° C. and 65% relative humidity under a 12 h light/12 h dark light regimen in a climate chamber and the activity of the compound was assessed as an indicator of disease control compared to the untreated material when an appropriate degree of disease damage was observed on the untreated control leaf segments (5-7 days after application).

Compounds I.b.3, I.e.2, I.e.3, I.h.3, I.r.2, I.r.3, I.s.3, I.t.3, I.w.2, I.w.3, I.y.1, I.y.2, I.aa.3, I.ab.3, I .ac.3, I.ad.3, I.ae.3, I.s.43, I.z.43, I.ao.3, I.ao.43, I.ap.3, I.aq.3, I.at .3, I.au.3, I.ay.3, I.bb.43 and I.be.3 at 200 ppm formulation resulted in at least 80% disease control in this test compared to untreated controls samples that, under the same conditions, showed extensive growth of mycelium.

Claims (73)

1. Compound of formula (I),

where R ¹ is fluorine; R ² is hydrogen; R ³ is halogen or C ₁ -C ₄ alkyl; R ⁴ is hydrogen; R ⁵ is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkylC _1-2 alkyl, C ₂ -C ₆ alkynyl, phenyl, heterocyclyl or heterocyclylC ₁ alkyl, where heterocyclyl is 4- or a 6-membered non-aromatic monocyclic ring containing 1 oxygen atom, or a 5-9-membered non-aromatic annelated or spirocyclic carbobicylyl ring system, optionally containing 1 oxygen atom and optionally linked to the rest of the molecule via a methylene (-CH ₂ -) linker; where any of these C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl and C ₂ -C ₆ alkynyl moieties are optionally substituted with 1-4 groups represented by R ⁷ or 1 group represented by R ⁸ ; where any of these phenyl or heterocyclyl moieties are optionally substituted with 1 or 2 groups represented by R ⁹ or 1 group represented by R ¹⁰ , or optionally substituted with 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ ; and where the annelated or spirocyclic carbobicylyl ring is optionally substituted with 1 or 2 groups represented by R ⁷ , or the annelated carbobicylyl ring system is optionally substituted with C ₄ -C ₅ cycloalkyl to form a spirocyclyl moiety; R ⁷ is independently selected from chlorine, bromine, fluorine, cyano, hydroxyl, methyl, trifluoromethyl, methoxy, butoxy, methoxymethyl, cyclopropyl, cyclohexyl, cyclooctyl, cyclopropylmethyl, acetyloxymethyl, and ethoxycarbonyl; where cyclopropyl is unsubstituted or substituted with 2 chlorine groups; R ⁸ is phenyl, benzyl or isoxazole, unsubstituted or substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ ; R ⁹ is independently selected from halogen, cyano, hydroxyl and C ₁ -C ₄ alkyl; R ¹⁰ is selected from phenyl, benzyl and C ₆ -C ₈ cycloalkoxy, each of which is unsubstituted or substituted with 1-3 groups represented by R ¹¹ ; R ¹¹ is independently selected from halo and methyl; X is C-H or N; or its salt. 2. A compound according to claim 1 wherein X is CH. 3. Connection according to claim 1 or 2, where: R ⁵ represents C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkylC ₁ -C ₂ alkyl or C ₂ -C ₆ alkynyl, where any of C ₁ -C ₆ alkyl, C ₂ - C ₆ alkynyl and C ₃ -C ₆ cycloalkyl moieties are optionally substituted with 1-4 groups represented by R ⁷ or 1 group represented by R ⁸ where R ⁷ is independently selected from chlorine, bromine, fluorine, cyano, hydroxyl, methyl, trifluoromethyl, methoxy, butoxy, methoxymethyl, cyclopropyl, cyclohexyl, cyclooctyl, cyclopropylmethyl, acetyloxymethyl, and ethoxycarbonyl; where cyclopropyl is unsubstituted or substituted with 2 chlorine groups, and where R ⁹ is halogen and R ¹⁰ is phenyl optionally substituted with 1-3 groups represented by R ¹¹ which are halogen. 4. The connection according to any one of paragraphs. 1-3 where: R ⁵ is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, or C ₃ -C ₆ cycloalkyl-C ₁ -C ₂ alkyl, where any of C ₁ -C ₆ alkyl, C ₂ -C ₆ alkynyl and C ₃ -C ₆ cycloalkyl moieties are optionally substituted with 1-4 groups represented by R ⁷ or 1 group represented by R ⁸ where R ⁷ is independently selected from chlorine, bromine, fluorine, cyano, hydroxyl, methyl , trifluoromethyl, methoxy, butoxy, methoxymethyl, cyclopropyl, cyclohexyl, cyclooctyl, cyclopropylmethyl, acetyloxymethyl and ethoxycarbonyl, where cyclopropyl is unsubstituted or substituted with 2 chlorine groups, and R ⁸ is phenyl, benzyl or isoxazole, optionally substituted with 1-3 groups represented by R ⁹ or 1 group represented by R ¹⁰ and where R ⁹ is halogen and R ¹⁰ is phenyl optionally substituted with 1-3 groups represented by R ¹¹ which is halogen; or R ⁵ is phenyl, oxetanyl or tetrahydropyranyl, each of which is optionally substituted with 1 or 2 groups represented by R ⁹ , or 1 group represented by R ¹⁰ , or 1 or 2 groups represented by R ⁹ and 1 group represented by R ¹⁰ , where R ⁹ is independently selected from halogen and C ₁ -C ₄ alkyl, and R ¹⁰ is selected from phenyl, benzyl or C ₆ -C ₈ cycloalkoxy, each of which is optionally substituted with 1-3 groups represented by R ¹¹ ; or R ⁵ is an fused or spirocyclic ring system selected from:

each of which is optionally substituted with 1 or 2 groups represented by R ⁷ independently selected from methyl and acetyloxymethyl. 5. A compound according to claim 4, wherein if R ⁵ is an annelated or spirocyclic ring system, then R ⁷ is methyl. 6. The connection according to any one of paragraphs. 1-4, where R ⁵ is (3,4-difluorophenyl)methyl, (2,4,5-trifluorophenyl)methyl, (2-chloro-4,5-difluorophenyl)methyl, (2-bromo-4,5 -difluorophenyl)methyl, 1-cyclohexylethyl, 1-phenylethyl, 1-(3-phenylisoxazol-5-yl)ethyl, 1-[3-(2-iodophenyl)isoxazol-5-yl]ethyl, [2-methyl-1 -(trifluoromethyl)propyl], [1-(hydroxymethyl)-2,2-dimethyl-propyl], (1-benzyl-2,2-dimethylpropyl), (1-isopropyl-2-methylbut-3-ynyl), [ 1-(1-cyanoethyl)-2-methylpropyl], [3-methyl-1-(1-methyl-2-phenylethyl)butyl], (1-cyclohexylcyclopropyl), (3-isobutoxy-2,2-dimethylcyclobutyl), [spiro[3.3]heptan-7-yl], [(7R)-spiro[3.3]heptan-7-yl], spiro[3.4]octan-3-yl, spiro[3.4]octan-2-yl, [3 -(acetoxymethyl)-8-oxaspiro[3.4]octan-1-yl], spiro[3.5]nonan-2-yl, [(1R,5S,6R)-6-bicyclo[3.2.0]heptanyl], [( 1S,5R,7R)-5-methyl-7-bicyclo[3.2.0]heptanyl], 6,6-dimethyl-7-bicyclo[3.2.0]heptanyl], [(1S,5R,7S)-6, 6-dimethyl-7-bicyclo[3.2.0]heptanyl], (6,6-dimethyl-4-oxabicyclo[3.2.0]heptan-7-yl), spiro[4-oxabicyclo[3.2.0]heptan- 6,1'-cyclobutan]-7-yl, spiro[4-oxabicyclo[3.2.0]hep tan-6,1'-cyclopentan]-7-yl, [(1S,6R,8R)-6-methyl-8-bicyclo[4.2.0]octanyl], (7,7-dimethyl-5-oxabicyclo-[ 4.2.0]octan-8-yl), (1-benzylcyclohexyl), (3,3,5,5-tetramethylcyclohexyl), (6-methyl-2-bicyclo[4.2.0]octanyl), [(3S)- 2-(2,4-dichlorophenyl)oxetan-3-yl], (4-benzyl-2,6-dimethyltetrahydropyran-4-yl), [4-(4,4-dimethylcyclohexoxy)-2-fluorophenyl], [4 -(cyclooctoxy)-2-fluorophenyl], 2,2-dimethylpropyl, (1-methylcyclopropyl)methyl, (1-methylcyclopentyl)methyl, (4-methyltetrahydropyran-4-yl)methyl, (3-methoxy-2,2- dimethylpropyl), (1-methylcyclobutyl)methyl, (1-cyclopropylcyclopropyl), (1-cyano-1-cyclopropylethyl), (1-ethoxycarbonylcyclopropyl)methyl, [1-(cyclopropylmethyl)-cyclopropyl]methyl, (3-methyloxetane-3 -yl)methyl, (1-methoxycyclopentyl)methyl, spiro[2.2]pentan-5-yl, [1-(methoxymethyl)cyclopropyl]methyl, 6-oxaspiro[2.5]octan-2-ylmethyl, [1-(trifluoromethyl) cyclopropyl]methyl or [1-(methoxymethyl)cyclopentyl]methyl. 7. Connection according to any one of paragraphs. 1-4, where R ⁵ is (3,4-difluorophenyl)methyl, (2,4,5-trifluorophenyl)methyl, (2-chloro-4,5-difluorophenyl)methyl, (2-bromo-4,5 -difluorophenyl)methyl, 1-cyclohexylethyl, 1-phenylethyl, 1-(3-phenylisoxazol-5-yl)ethyl, 1-[3-(2-iodophenyl)isoxazol-5-yl]ethyl, [2-methyl-1 -(trifluoromethyl)propyl], [1-(hydroxymethyl)-2,2-dimethylpropyl], (1-benzyl-2,2-dimethylpropyl), (1-isopropyl-2-methylbut-3-ynyl), [1- (1-cyanoethyl)-2-methylpropyl], [3-methyl-1-(1-methyl-2-phenylethyl)butyl], (1-cyclohexylcyclopropyl), (3-isobutoxy-2,2-dimethylcyclobutyl), [spiro [3.3]heptan-7-yl], [(7R)-spiro[3.3]heptan-7-yl], spiro[3.4]octan-3-yl, spiro[3.4]octan-2-yl, [3-( acetoxymethyl)-8-oxaspiro[3.4]octan-1-yl], spiro[3.5]nonan-2-yl, [(1R,5S,6R)-6-bicyclo[3.2.0]heptanyl], [(1S, 5R,7R)-5-methyl-7-bicyclo[3.2.0]heptanyl], 6,6-dimethyl-7-bicyclo[3.2.0]heptanyl], [(1S,5R,7S)-6,6- dimethyl-7-bicyclo[3.2.0]heptanyl], (6,6-dimethyl-4-oxabicyclo[3.2.0]heptan-7-yl), spiro[4-oxabicyclo[3.2.0]heptan-6, 1'-cyclobutan]-7-yl, spiro[4-oxabicyclo[3.2.0]hept an-6,1'-cyclopentan]-7-yl, [(1S,6R,8R)-6-methyl-8-bicyclo[4.2.0]octanyl], (7,7-dimethyl-5-oxabicyclo-[ 4.2.0]octan-8-yl), (1-benzylcyclohexyl), (3,3,5,5-tetramethylcyclohexyl), (6-methyl-2-bicyclo[4.2.0]octanyl), [(3S)- 2-(2,4-dichlorophenyl)oxetan-3-yl], (4-benzyl-2,6-dimethyltetrahydropyran-4-yl), [4-(4,4-dimethylcyclohexoxy)-2-fluorophenyl], [4 -(cyclooctoxy)-2-fluorophenyl], 2,2-dimethylpropyl, (1-methylcyclopropyl)methyl, (1-methylcyclopentyl)methyl, (4-methyltetrahydropyran-4-yl)methyl, (3-methoxy-2,2- dimethylpropyl), (1-methylcyclobutyl)methyl, (1-cyclopropylcyclopropyl), (1-cyano-1-cyclopropylethyl), (1-ethoxycarbonylcyclopropyl)methyl, [1-(cyclopropylmethyl)-cyclopropyl]methyl, (3-methyloxetane-3 -yl)methyl, spiro[2.2]pentan-5-yl, [1-(trifluoromethyl)cyclopropyl]methyl or [1-(methoxymethyl)cyclopentyl]methyl. 8. Connection according to any one of paragraphs. 1-4, where R ⁵ is 1-cyclohexylethyl, 1-phenylethyl, 1-(3-phenylisoxazol-5-yl)ethyl, spiro[3.3]heptan-7-yl], spiro[3.4]octan-3-yl , spiro[3.4]octan-2-yl, spiro[3.5]nonan-2-yl, [3-(acetoxymethyl)-8-oxaspiro[3.4]octan-1-yl], 6,6-dimethyl-7-bicyclo [3.2.0]-heptanyl], (6,6-dimethyl-4-oxabicyclo[3.2.0]heptan-7-yl), spiro[4-oxabicyclo-[3.2.0]heptan-6,1'-cyclobutane ]-7-yl, spiro[4-oxabicyclo[3.2.0]heptan-6,1'-cyclopentan]-7-yl, (6-methyl-2-bicyclo[4.2.0]octanyl) or spiro[2.2] pentan-5-yl. 9. Connection according to any one of paragraphs. 1-4 selected from:

5-bromo-N-(1-cyclohexylethyl)-2-(3,5-difluoroanilino)thiazole-4-carboxamide;

N-(1-cyclohexylethyl)-2-(3,5-difluoroanilino)-5-methylthiazole-4-carboxamide;

5-bromo-2-(3,5-difluoroanilino)-N-spiro[3.3]heptan-7-yl-thiazole-4-carboxamide;

2-(3,5-difluoroanilino)-5-methyl-N-spiro[3.3]heptan-7-ylthiazole-4-carboxamide;

5-bromo-2-(3,5-difluoroanilino)-N-spiro[3.4]octan-3-ylthiazole-4-carboxamide;

2-(3,5-difluoroanilino)-5-methyl-N-spiro[3.4]octan-3-ylthiazole-4-carboxamide;

5-bromo-2-(3,5-difluoroanilino)-N-(6,6-dimethyl-7-bicyclo[3.2.0]heptanyl)thiazole-4-carboxamide;

2-(3,5-difluoroanilino)-N-(6,6-dimethyl-7-bicyclo[3.2.0]heptanyl)-5-methylthiazole-4-carboxamide;

5-bromo-2-(3,5-difluoroanilino)-N-(6-methyl-2-bicyclo[4.2.0]octanyl)thiazole-4-carboxamide;

2-(3,5-difluoroanilino)-5-methyl-N-(6-methyl-2-bicyclo[4.2.0]octanyl)thiazole-4-carboxamide;

2-[(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-ylthiazole-4-carboxamide;

5-bromo-2-[(2,6-difluoro-4-pyridyl)amino]-N-spiro[3.4]octan-3-ylthiazole-4-carboxamide;

5-chloro-2-[(2,6-difluoro-4-pyridyl)amino]-N-spiro[3.4]octan-3-ylthiazole-4-carboxamide;

2-[(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[2.2]pentan-2-ylthiazole-4-carboxamide;

2-(3,5-difluoroanilino)-5-methyl-N-spiro[2.2]pentan-2-ylthiazole-4-carboxamide; and

5-chloro-2-[(2,6-difluoro-4-pyridyl)amino]-N-spiro[2.2]pentan-2-ylthiazole-4-carboxamide. 10. A fungicidal composition containing a fungicidally effective amount of a compound of formula (I) according to any one of paragraphs. 1-9 and an agrochemically acceptable diluent or carrier. 11. A method for controlling or preventing infection of useful plants with phytopathogenic microorganisms, where a fungicidally effective amount of a compound of formula (I) according to any one of paragraphs. 1-9 or the compositions according to claim 10 are applied to plants, parts thereof or applied to their place of growth. 12. The use of compounds of formula (I) according to any one of paragraphs. 1-9 as a fungicide.