WO2016016118A1 - Microbiocidal imidazole derivatives - Google Patents

Abstract

Compounds of theformula (I), wherein X and Y are independently O, S or NR⁵, R¹, R² and R⁴ are independently hydrogen, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆haloalkoxy, R⁵ is halogen, cyano, C₁-C₆alkyl or C₁- C₆haloalkyl and R³ is aryl, aryl substituted by one or more further substituents, heteroaryl or heteroaryl substituted by one or more further substituents are useful as a pesticides especially fungicide.

Description

Microbiocidal Imidazole Derivatives

The present invention relates to microbiocidal imidazole derivatives usefull as active ingredients which have microbiocidal activity, in particular fungicidal activity. The invention also relates to preparation of these imidazole derivatives, to imidazole derivatives used as intermediates in the preparation of these imidazole derivatives which have microbiocidal activity, to preparation of these intermediates, to agrochemical compositions which comprise at least one of the imidazole derivatives, to preparation of these compositions and to use of the imidazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.

The present invention provides a compound of formula (I):

wherein,

X and Y are independently O, S or NR⁶;

R , R² and R⁴ are independently hydrogen, halogen, CrC₆alkyl, Ci-C₆haloalkyl, d-C₆alkoxy or d- C₆haloalkoxy;

R³ is aryl, aryl substituted by one or more substituents R⁷, heteroaryl or heteroaryl substituted by one or more substituents R⁷;

R⁵ is halogen, cyano, Ci-C₆alkyl or Ci-C₆haloalkyl;

R⁶ is hydrogen, Ci-C₆alkyl, d-C₆alkoxy or C₃-C₆cycloalkyl;

R⁷ is halogen, nitro, cyano, hydroxyl, amino, Ci-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkenyloxy, Ci-C₆alkyloxy, C₂-C₆alkynyl, C₂-C₆alkynyloxy, Ci-C₆haloalkyl, d-C₆alkoxy, d-C₆haloalkoxy, d-C₆cycloalkyl, C₃- dhalocycloalkyl, d-C₆cycloalkyloxy, aryl, aryloxy, heteroaryl, or heteroaryloxy and wherein the aryl and heteroaryl moieties can be further independently substituted by one or more substituents selected from halogen, nitro, cyano, hydroxyl, amino, d-C₆alkyl, d-C₆haloalkyl, d-C₆alkoxy or d- dhaloalkoxy and wherein the alkyl, alkenyl, alkynyl moieties can be further independently substituted by one or more substituents selected from nitro, cyano, hydroxyl or amino;

and wherein aryl is a mono- or bi-cyclic five- to ten-membered ring system and heteroaryl is a mono- or bi-cyclic five- to ten-membered ring system and the heteroaryl group contains 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms;

or a salt or a N-oxide thereof.

Where substituents are indicated as being optionally substituted, this means that they may or may not carry one or more identical or different substituents, e.g. one to three substituents. Normally not more than three such optional substituents are present at the same time. Where a group is indicated as being substituted, e.g. alkyl, this includes those groups that are part of other groups, e.g. the alkyl in alkoxy or phenyl in phenyloxy. „

2

The number of substituents does not exceed the number of available C-H and N-H bonds, for example in the aryl group substituted by one or more R⁷ has only one to five substituents if phenyl is meant.

The term "halogen" refers to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

Alkyl substituents can be straight-chained or branched. Alkyl on its own or as part of another substituent is, depending upon the number of carbon atoms mentioned, for example, methyl, ethyl, n- propyl, n-butyl, n-pentyl, n-hexyl and the isomers thereof, for example, iso-propyl, iso-butyl, sec-butyl, tert-butyl or iso-amyl.

Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Alkenyl substituents can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-configu ration. Examples are vinyl and allyl. The alkenyl groups are preferably C₂-C₆, more preferably C₂-C₄ and most preferably C₂-C₃ alkenyl groups.

Alkynyl substituents can be in the form of straight or branched chains. Examples are ethynyl and propargyl. The alkynyl groups are preferably C₂-C₆, more preferably C₂-C₄ and most preferably C₂- C₃ alkynyl groups.

Haloalkyl groups may contain one or more identical or different halogen atoms and, for example, may stand for CH₂CI, CHCI₂, CCI₃, CH₂F, CHF₂, CF₃, CF₃CH₂, CH₃CF₂, CF₃CF₂ or CCI₃CCI₂.

Haloalkenyl groups are alkenyl groups, respectively, which are substituted with one or more of the same or different halogen atoms and are, for example, 2,2-difluorovinyl or 1 ,2-dichloro-2-fluoro- vinyl.

Alkoxy means a radical -OR, where R is alkyl, e.g. as defined above. Alkoxy groups include, but are not limited to, methoxy, ethoxy, 1 -methylethoxy, propoxy, butoxy, 1 -methylpropoxy and 2- methylpropoxy.

Haloalkoxy means a radical -OR, where R is haloalkyl, e.g . is described above. Haloalkloxy groups include, but are not limited to, CH₂CIO, CHCI₂0, CCI₃0, CH₂FO, CHF₂0-, CF₃0-, CF₃CH₂0-, CH₃CF₂0 or CCI₃CCI₂0-.

Cyano means a -CN group.

Amino means an -NH₂ group.

Hydroxyl or hydroxy stands for a -OH group.

Aryl means a ring system which can be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.

Preferred optional substituents for aryl are halogen, cyano, hydroxyl, amino, nitro, Ci-C₆alkyl, d- C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆halocycloalkyl, d-C₆alkoxy, Ci-C₆haloalkoxy, C₃-C₆cycloalkoxy, d- C₆alkylthio, Ci-C₆haloalkylthio, C₃-C₆cycloalkylthio, Ci-C₆alkylsulfinyl, Ci-C₆haloalkylsulfinyl, C₃- C₆cycloalkylsulfinyl, Ci-C₆alkylsulfonyl, Ci-C₆haloalkylsulfonyl, C₃-C₆cycloalkylsulfonyl, d- dalkylcarbonyl, d-C₆alkenyl, C₂-dhaloalkenyl, C₂-dalkenyloxy, C₂-dalkenylthio, C₂- dhaloalkenyloxy, d-C₆alkynyl, C₃-dcycloalkylC₂-dalkynyl, C₂-dalkynyloxy, C₂-dalkynyloxy, aryl, arylalkyl, aryloxy, arylthio, heteroaryl, heteroarylalkyl, heteroaryloxy and heteroarylthio, in which the aryl and heteroaryl groups are optionally substituted by one or more R⁵. Heteroaryl stands for aromatic heterocyclic ring systems, which can be mono-, bi- or tricyclic and wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member, which can be accompanied by other oxygen, nitrogen, sulphur atoms as ring members. Monocyclic and bicyclic aromatic ring systems are preferred. For example, monocyclic heteroaryl can be a 5- or 6-membered ring containing one to three heteroatoms selected from oxygen, nitrogen and sulfur, more preferably selected from nitrogen and sulfur. Bicyclic heteroaryl can be a 9- or 10-membered bicyclic ring containing one to five heteroatoms, preferably one to three heteroatoms, selected from oxygen, nitrogen and sulfur. Examples of heteroaryl are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl. Heteroaryl rings do not contain adjacent oxygen ring atoms, adjacent sulfur ring atoms or adjacent oxygen and sulfur ring atoms. Preferred optional substituents for heteroaryl are halogen, cyano, hydroxyl, amino, nitro, Ci-C₆alkyl, d- C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆halocycloalkyl, d-C₆alkoxy, Ci-C₆haloalkoxy, C₃-C₆cycloalkoxy, d- C₆alkylthio, Ci-C₆haloalkylthio, C₃-C₆cycloalkylthio, Ci-C₆alkylsulfinyl, Ci-C₆haloalkylsulfinyl, C₃- C₆cycloalkylsulfinyl, Ci-C₆alkylsulfonyl, Ci-C₆haloalkylsulfonyl, C₃-C₆cycloalkylsulfonyl, d- dalkylcarbonyl, C₂-dalkenyl, d-C₆haloalkenyl, d-C₆alkenyloxy, d-C₆alkenylthio, C₂- dhaloalkenyloxy, d-C₆alkynyl, d-C₆cycloalkyld-C₆alkynyl, d-C₆alkynyloxy, d-C₆alkynyloxy, aryl, arylalkyl, aryloxy, arylthio, heteroaryl, heteroarylalkyl, heteroaryloxy and heteroarylthio, in which the aryl and heteroaryl groups are optionally substituted by one or more R⁵.

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

In each case, the compounds of formula I according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.

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

The term "fungicide" as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term "fungicidally effective amount" means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi.

Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.

The term "herbicide" as used herein means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means the quantity of such a compound or combination of such compounds that is capable of producing a controlling or modifying effect on the growth of plants. Controlling or modifying effects include all deviation from natural development, for example killing, retardation, leaf burn, albinism, dwarfing and the like.

The term "insecticide" as used herein means a compound that controls or modifies the growth of insects. The term "insecticidally effective amount" means the quantity of such a compound or combination of such compounds that is capable of killing, controlling, or infecting insects, retarding the growth or reproduction of insects, reducing an insect population, and/or reducing damage to plants caused by insects.

The term "locus" as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.

The term "metabolism" as used herein means the conversion or breakdown of a substance from one form to another by a living organism.

The term "nematicide" as used herein means a compound that controls or modifies the growth of nematodes. The term "nematicidally effective amount" means the quantity of such a compound or combination of such compounds that is capable of killing, controlling, or infecting nematodes, retarding the growth or reproduction of nematodes, reducing a nematode population, and/or reducing damage to plants caused by nematodes.

A nematicidally effective amount" as used herein refers to an amount of nematicide capable of killing, controlling, or infecting nematodes, retarding the growth or reproduction of nematodes, reducing a nematode population, and/or reducing damage to plants caused by nematodes

The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.

The following list provides definitions, including preferred definitions, for substituents R , R², R³, R⁴, R⁵, R⁶, R⁷ X and Y with reference to compounds of formula I. For any one of these substituents, any of the definitions given below can be combined with any definition of any other substituent given below or elsewhere in this document.

Preferably X and Y are independently O or S, more preferably X and Y are both S.

Preferably R , R² and R⁴ are independently hydrogen, halogen, Ci-C₆alkyl or Ci-C₆haloalkyl; more preferably hydrogen or Ci-C₆alkyl; even more preferably hydrogen or methyl, most preferably each of R , R² and R⁴ are hydrogen.

Preferably R³ is aryl or aryl substituted by one or more substituents R⁷, more preferably R³ is phenyl or phenyl substituted by one or more substituents R⁷, even more preferably R³ is phenyl or phenyl independently substituted by one or more halogen, cyano, Ci-C₆alkyl, cyano-Ci-C₆alkyloxy, C₂- C₆alkynyloxy, Ci-C₆haloalkoxy , Ci-C₆haloalkyl, pyrazolyl, phenyloxy substituted by halogen, pyrimidinyloxy or pyrimidinyloxy substituted by halogen, even more preferably R³ is phenyl substituted by halogen, cyano, Ci-C₄alkyl, cyano-Ci-C₄alkyl, Ci-C₄alkynyloxy, Ci-C₄haloalkoxy , Ci-C₄haloalkyl.

Preferably R⁵ is Ci-C₆alkyl or Ci-C₆haloalkyl, more preferably methyl or difluoromethyl, even more preferably methyl.

Preferably R⁶ is hydrogen or Ci-C₆alkyl, more preferably hydrogen or methyl, even more preferably hydrogen. Preferably R⁷ is halogen, cyano, Ci-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, Ci-C₆haloalkyl, d- C₆alkoxy, Ci-C₆haloalkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, and wherein the aryl and heteroaryl moieties can be further independently substituted by one or more substituents selected from halogen, nitro, cyano, hydroxyl, amino, Ci-C₆alkyl, Ci-C₆haloalkyl, d-C₆alkoxy or d- C₆haloalkoxy and wherein the alkyl, alkenyl and alkynyl moieties can be further independently substituted by one or more substituents selected from nitro, cyano, hydroxyl or amino;

more preferably R⁷ is halogen, cyano, Ci-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₂-C₆alkynyloxy, d- C₆haloalkyl, d-C₆alkoxy, d-C₆haloalkoxy, phenyl, phenyloxy,pyrazolyl, pyrimidinyloxy, wherein the aryl and heteroaryl moieties can be further independently substituted by one or more substituents selected from halogen, nitro, cyano, hydroxyl, amino, d-C₆alkyl, d-C₆haloalkyl, d-C₆alkoxy or d- dhaloalkoxy and wherein the alkyl, alkenyl and alkynyl moieties can be further independently substituted by one or more substituents selected from nitro, cyano, hydroxyl or amino;

Even more preferably R⁷ is halogen, cyano, d-C₆alkyl, cyano-d-C₆alkyl, C₂-dalkynyloxy, d- dhaloalkoxy , d-C₆haloalkyl, pyrazolyl, phenyloxy substituted by halogen, pyrimidinyloxy or pyrimidinyloxy substituted by halogen.

Most preferably R⁷ is halogen, cyano, d-dalkyl, cyano-d-dalkyloxy, C₂-C₄alkynyloxy, d- dhaloalkoxy , d-dhaloalkyl.

A preferred compound according to the invention is a compound of formula (I) wherein X and Y are both S;

R , R² and R⁴ are independently hydrogen, halogen, d-C₆alkyl, d-C₆haloalkyl, d-C₆alkoxy or d- dhaloalkoxy;

R³ is aryl, aryl substituted by one or more substituents R⁷, heteroaryl or heteroaryl substituted by one or more substituents R⁷;

R⁵ is halogen, cyano, d-C₆alkyl or d-C₆haloalkyl;

R⁷ is halogen, nitro, cyano, hydroxyl, amino, d-C₆alkyl, d-C₆alkenyl, d-C₆alkenyloxy, d-C₆alkyloxy, d-C₆alkynyl, d-C₆alkynyloxy, d-C₆haloalkyl, d-C₆alkoxy, d-C₆haloalkoxy, d-dcycloalkyl, d- dhalocycloalkyl, d-dcycloalkyloxy, aryl, aryloxy, heteroaryl, or heteroaryloxy and wherein the aryl and heteroaryl moieties can be further independently substituted by one or more substituents selected from halogen, nitro, cyano, hydroxyl, amino, d-dalkyl, d-C₆haloalkyl, d-dalkoxy or d- dhaloalkoxy and wherein the alkyl, alkenyl, alkynyl moieties can be further independently substituted by one or more substituents selected from nitro, cyano, hydroxyl or amino;

and wherein aryl is a mono- or bi-cyclic five- to ten-membered ring system and heteroaryl is a mono- or bi-cyclic five- to ten-membered ring system and the heteroaryl group contains 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms.

A further preferred compound according to the invention is a compound of formula (I) wherein X and Y are both S;

R , R² and R⁴ are independently hydrogen, halogen, d-dalkyl, d-C₆haloalkyl, d-dalkoxy or d- dhaloalkoxy;

R³ is aryl or aryl substituted by one or more substituents R⁷;

R⁵ is halogen, cyano, d-dalkyl or d-dhaloalkyl; R⁷ is halogen, cyano, Ci-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₂-C₆alkynyloxy, Ci-C₆haloalkyl, d- C₆alkoxy, Ci-C₆haloalkoxy, phenyl, phenyloxy, pyrazolyl, pyrimidinyloxy, wherein the aryl and heteroaryl moieties can be further independently substituted by one or more substituents selected from halogen, nitro, cyano, hydroxyl, amino, Ci-C₆alkyl, Ci-C₆haloalkyl, d-C₆alkoxy or d- C₆haloalkoxy and wherein the alkyl, alkenyl and alkynyl moieties can be further independently substituted by one or more substituents selected from nitro, cyano, hydroxyl or amino.

A further preferred compound according to the invention is a compound of formula (I) wherein X and Y are both S;

R , R² and R⁴ are independently hydrogen, Ci-C₆alkyl;

R³ is phenyl or phenyl substituted by one or more substituents R⁷;

R⁵ is halogen, Ci-C₄alkyl or Ci-C₄haloalkyl;

R⁷ is halogen, cyano, Ci-C₆alkyl, cyano-C₂-C₆alkyloxy, C₂-C₆alkynyloxy, Ci-C₆haloalkoxy , d- C₆haloalkyl, pyrazolyl, phenyloxy substituted by halogen, pyrimidinyloxy or pyrimidinyloxy substituted by halogen.

A further preferred compound according to the invention is a compound of formula (I) wherein

X and Y are both S;

R , R² and R⁴ are independently hydrogen or methyl;

R³ is phenyl or phenyl independently substituted by one or more halogen, cyano, Ci-C₆alkyl, cyano-

C₂-C₆alkyloxy, C₂-C₆alkynyloxy, Ci-C₆haloalkoxy , Ci-C₆haloalkyl, pyrazolyl, phenyloxy substituted by halogen, pyrimidinyloxy or pyrimidinyloxy substituted by halogen;

R⁵ is Ci-C₆alkyl or Ci-C₆haloalkyl;

A further preferred compound according to the invention is a compound of formula (I) wherein

X and Y are both S;

R , R² and R⁴ are each hydrogen;

R³ is phenyl substituted by halogen, cyano, Ci-C₄alkyl, cyano-C₂-C₄alkyloxy,C₂-C₄alkynyloxy, d- dhaloalkoxy , d-dhaloalkyl, pyrazolyl, phenyloxy substituted by halogen, pyrimidinyloxy or pyrimidinyloxy substituted by halogen

R⁵ is d-C₆alkyl or d-C₆haloalkyl;

A more preferred compound according to the invention is a compound of formula (I) wherein X and Y are both S;

R , R² and R⁴ are each hydrogen;

R³ is phenyl or phenyl independently substituted by one or more substituents selected from phenyl substituted by halogen, cyano, d-dalkyl, cyano-d-C₄alkloxy,C₂-C₄alkynyloxy, d-dhaloalkoxy , d- dhaloalkyl, pyrazolyl, phenyloxy substituted by halogen, pyrimidinyloxy or pyrimidinyloxy substituted by halogen;

R⁵ is halogen, methyl or difluoromethyl.

A even more preferred compound according to the invention is a compound of formula (I) wherein

X and Y are both S;

R , R² and R⁴ are each hydrogen; R³ is phenyl or phenyl independently substituted by one or more halogen, cyano, Ci-C₆alkyl, cyano- Ci-C₆alkyl, C₂-C₆alkynyloxy, Ci-C₆haloalkoxy , Ci-C₆haloalkyl;

R⁵ is halogen, methyl or difluoromethyl.

The most preferred compound according to the invention is a compound of formula (I) wherein X and Y are both S;

R , R² and R⁴ are each hydrogen;

R³ is phenyl substituted by halogen, cyano, Ci-C₄alkyl, cyano- Ci-C₄alkyl, cyano-Ci-C₄alkynyloxy,Ci- C₄alkynyloxy, Ci-C₄haloalkoxy , Ci-C₄haloalkyl, pyrazolyl, phenyloxy substituted by halogen, pyrimidinyloxy or pyrimidinyloxy substituted by halogen;

R⁵ is halogen, methyl or difluoromethyl.

The invention also relates to compounds of formula (1-1 ):

in which R , R², R³, R⁴ and R⁵ have the definitions as described for formula I. Preferred definitions of R , R², R³, R⁴ and R⁵ are as defined for formula I.

The invention also relates to compounds of formula (I-2):

wherein R³ and R⁵ have the definition as described for formula I. Preferred definitions of R³ and R⁵ are as defined for formula I.

The invention also relates to compounds of formula (I-3):

wherein R⁷ and R⁵ have the definition as described for formula I and n is selected from 0, 1 , 2, 3 and 4 and each R⁷ is independent from each other. Preferred definitions of R⁷ and R⁵ are as defined for formula I and n is selected from 0, 1 , 2, 3 and 4 and each R⁷ is independent from each other.

Further preferred embodiments of the present invention are the embodiments E-I.a to E-I.bp, which are defined as compounds of formula I which are represented by one formula selected from the group consisting of the formula (I. a) to (I. bp) as described below, wherein in formulae (I. a) to (I. bp) the meanings of the substituents X, Y, R , R², R⁴ and R⁵ have the meanings as mentioned above or one of the meanings 1 to 140 given in the corresponding Table 1.

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

and the substituents X, Y, R , R², R⁴ and R⁵ have the meanings as defined above or one of the meanings 1 to 140 given in the Table 1.

Embodiments E-I.b to E-I.bp are defined accordingly and the substituents X, Y, R , R², R⁴ and

R⁵ have the meanings as defined above or one of the meanings 1 to 140 given in the corresponding Table 1.

In a preferred embodiment the compounds of the present invention are selected from the formula (l.a), (l.b), (l.c), (l.d), (l.e), (l.f), (l.g), (l.h), (l.i), (l.j), (l.k), (l.m), (l.n), (l.o), (l.p), (l.q), (l.r), (l.s), (l.t), (l.u), (l.v), (l.w), (l.x), (l.y), (l.z), (l.aa), (l.ab), (l.ac), (l.ad), (l.ae), (l.af), (Lag), (l.ah), (l.ai), (l.aj), (l.ak), (l.am), (l.an), (l.ao), (l.aq), (l.ar), (l.as), (l.at), (l.au), (l.av), (Law), (Lax), (Lay), (l.az), (l.ba), (l.bb), (I. be), (l.bd), (I. be), (l.bf), (l.bg), (l.bh), (l.bi), (l.bj), (l.bk), (l.bm), (l.bn), (I. bo) and (I. bp) and X and Y are both S and R , R² and R⁴ are each hydrogen and R⁵ is as defined above.

In a more preferred embodiment the compounds of the present invention are selected from the formula l.p.123, l.p.121 , l.p.125, l.v.123, l.x.123, l.z.123, l.ad.123, l.af.123, l.bi.123, l.bj.123, l.bk.123, l.bm.123, l.bn.123, I. bo.123 and l.bp.123 and X and Y are both S and R , R² and R⁴ are each hydrogen and R⁵ is as defined above.

The invention further relates to a process for the preparation of a compound of formula (I) and to compounds obtainable by this process

(I)

comprising reacting 2-(5-R⁵- imidazol-1-yl-acetonitrile

with acorn pound of formula (III)

and a compound of formula (IV)

X=C=Y (IV)

In the presence of a base, wherein X, Y, R , R², R³, R⁴ and R⁵ are as defined as above and Hal is halogen. Preferably the base is sodium hydroxide or potassium hydroxide. Preferably the reaction is carried out at room temperature (= ambient temperature) which denotes a temperature between 10°C and 30 °C, more preferable at 20°C to 25°C. Preferably the reaction is carried out in a polar aprotic solvent, preferably in dimethylformamide (DMF), acetonitrile (MeCN), or dimethyl sulfoxide (DMSO), most preferably in dimethyl sulfoxide (DMSO).

The invention further relates to a process for the preparation of a compound of formula (I) and to compounds obtainable by this process

comprising reacting 2-(5-R⁵- imidazol-1-yl-acetonitrile

with a compound of formula (XI)

and a compound of formula (IV)

X=C=Y (IV)

In the presence of a base, wherein X, Y, R , R², R³, R⁴ and R⁵ are as defined as above, R⁸ is a R⁸ is a sulfonyl group, preferably Ci-C₄alkylsulfonyl or phenylsulphonyl which can be substituted by d- C₄alkyl, more preferably methylsulfonyl or p-tosylsulfonyl, and Hal is halogen. Preferably the base is sodium hydroxide or potassium hydroxide. Preferably R⁸ is sodium hydroxide or potassium hydroxide. Preferably the reaction is carried out at room temperature (= ambient temperature) which denotes a temperature between 10°C and 30 °C, more preferable at 20°C to 25°C. Preferably the reaction is carried out in a polar aprotic solvent, preferably in dimethylformamide (DMF), acetonitrile (MeCN), or dimethyl sulfoxide (DMSO), most preferably in dimethyl sulfoxide (DMSO).

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

The compounds of formula I, wherein X, Y, R , R², R³, R⁴ and R⁵ are as defined for formula I, can be obtained by transformation of a compound of formula II, wherein R⁵ is as defined for formula I, a compound of formula III, wherein R , R², R³ and R⁴ are as defined for formula I and Hal is halogen, and a compound of formula IV, wherein X and Y are as defined for formula I, with a base, such as sodium hydroxide or potassium hydroxide. This is shown in Scheme 1.

Scheme 1

(I)

The compounds of formula III, wherein R , R², R³ and R⁴ are as defined for formula I and Hal is halogen, can be obtained by transformation of a compound of formula V, wherein R , R², R³ and R⁴ are as defined for formula I and Hal is halogen, with a halogenation reagent, such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide. This is shown in Scheme 2.

Scheme 2

R P(=0)Hal₃ or R

R R

S(=0)Hal₂

Hal (V)

OH Hal

Alternatively, the compounds of formula III, wherein R , R², R³ and R⁴ are as defined for formula I and Hal is halogen, can be obtained by transformation of a compound of formula VI, wherein R , R², _ _

11

R³ and R⁴ are as defined for formula I, with a halogenation reagent, such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide. This is shown in Scheme 3.

Scheme 3

The compounds of formula V wherein R , R² and R³ are as defined for formula I, R⁴ is hydrogen and Hal is halogen, can be obtained by transformation of a compound of formula VII, wherein R , R² and R³ are as defined for formula I and Hal is halogen, with a reducing agent, such as sodium borohydride. This is shown in Scheme 4.

Scheme 4

The compounds of formula VII, wherein R , R² and R³ are as defined for formula I and Hal is halogen, can be obtained by transformation of a compound of formula VIII, wherein R , R² and R³ are as defined for formula I, with a halogenation reagent, such as chlorine or bromine. This is shown in Scheme 5.

Scheme 5

Alternatively, the compounds of formula V, wherein R , R² and R³ are as defined for formula I, R⁴ is hydrogen and Hal is halogen, can be obtained by transformation of a compound of formula IX, wherein R³ is as defined for formula I, with a compound of formula X, wherein R and R² are as defined for formula I and Hal is halogen, preferably chloro or bromo, and a base. This is shown in Scheme 6.

Scheme 6

Alternatively, the compounds of formula I, wherein X, Y, R , R², R³, R⁴ and R⁵ are as defined for formula I, can be obtained by transformation of a compound of formula II, wherein R⁵ is as defined for formula I, a compound of formula XI, wherein R , R², R³ and R⁴ are as defined for formula I, R⁶ is a sulfonyl group, such as m ethyls ulfony I or p-tolylsulfonyl, and Hal is halogen, and a compound of formula IV, wherein X and Y are as defined for formula I, with a base, such as sodium hydroxide or potassium hydroxide. This is shown in Scheme 7.

Scheme 7

The compounds of formula XI, wherein R , R², R³ and R⁴ are as defined for formula I, R⁸ is a sulfonyl group, such as m ethyls ulfony I or p-tosylsulfonyl, and Hal is halogen, can be obtained by transformation of a compound of formula V, wherein R , R², R³ and R⁴ are as defined for formula I and Hal is halogen, with a sulfonyl halide, such as mesyl chloride or tosyl chloride. This is shown in Scheme 8.

Scheme 8

Surprisingly, it has now been found that the novel compounds of formula I have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.

The compounds of formula (I) of this invention are useful as plant disease control agents. The present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound.

Compounds of formula (I) and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete,

Ascomycete, Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and/or Mucoromycete classes.

They are effective in controlling a broad spectrum of plant diseases, such as foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.

These pathogens may include:

Oomycetes, including Phytophthora diseases such as those caused by Phytophthora capsici,

Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola,

Plasmopara halstedii, Pseudoperonospora cubensis, Albugo Candida, Sclerophthora macrospora and Bremia lactucae; and others such as Aphanomyces cochlioides, Labyrinthula zosterae,

Peronosclerospora sorghi and Sclerospora graminicola. Ascomycetes, including blotch, spot, blast or blight diseases and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva,

Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola,

Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium

oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis, Alternaria alternata, Alternaria brassicicola, Alternaria solani and Alternaria tomatophila, Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and Cercosporella herpotrichoides, Cladosporium carpophilum, Cladosporium effusum, Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum , Isariopsis clavispora,

Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeii, Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramularia beticola, Ramularia collo-cygni, Magnaporthales such as Gaeumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae, Diaporthales such as Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp. , Valsa ceratosperma, and others such as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp. , Capnodium ramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioides spp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata, Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta, Griphospaeria corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssonina graminicola, Microdochium nivale, Monilinia fructicola, Monographella albescens, Monosporascus cannonballus, Naemacyclus spp., Ophiostoma novo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum, Pestalotia rhododendri, Petriellidium spp., Pezicula spp.,

Phialophora gregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor,

Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; powdery mildew diseases for example those caused by Erysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaera macularis Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossypii,

Phyllactinia guttata and Oidium arachidis; molds for example those caused by Botryosphaeriales such as Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, _

14

Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola,

Macrophomina phaseolina, Phyllosticta cucurbitacearum; anthracnoses for example those caused by Glommerelales such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata, and Colletotrichum graminicola; and wilts or blights for example those caused by Hypocreales such as Acremonium strictum, Claviceps purpurea, Fusarium culmorum, Fusarium graminearum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae,

Gliocladium spp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae.

Basidiomycetes, including smuts for example those caused by Ustilaginales such as

Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis,

Pucciniastrum coryli, or Uredinales such as Cronartium ribicola, Gymnosporangium juniperi- viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia caries.

Blastocladiomycetes, such as Physoderma maydis.

Mucoromycetes, such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus, As well as diseases caused by other species and genera closely related to those listed above. In addition to their fungicidal activity, the compounds and compositions comprising them may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.

Compounds of formula (I) may be mixed with one or more of compounds selected from those in the following chemical or functional classes:- 1 ,2,4-thiadiazoles, 2,6-dinitroanilines, acylalanines, aliphatic nitrogenous compounds, amidines, aminopyrimidinols, anilides, anilino-pyrimidines, anthraquinones, antibiotics, aryl-phenylketones, benzamides, benzene-sulfonamides, benzimidazoles, benzothiazoles, benzothiodiazoles, benzothiophenes, benzoylpyridines, benzthiadiazoles, benzylcarbamates, butylamines, carbamates, carboxamides, carpropamids, chloronitriles, cinnamic acid amides, copper containing compounds, cyanoacetamideoximes, cyanoacrylates,

cyanoimidazoles, cyanomethylene-thiazolidines, dicarbonitriles, dicarboxamides, dicarboximides, dimethylsulphamates, dinitrophenol carbonates, dinitrophenysl, dinitrophenyl crotonates, diphenyl phosphates, dithiino compounds, dithiocarbamates, dithioethers, dithiolanes, ethyl-amino-thiazole carboxamides, ethyl-phosphonates, furan carboxamides, glucopyranosyls, glucopyranoxyls, glutaronitriles, guanidines, herbicides/plant growth regulatosr, hexopyranosyl antibiotics, hydroxy(2- amino)pyrimidines, hydroxyanilides, hydroxyisoxazoles, imidazoles, imidazolinones, insecticides/plant growth regulators, isobenzofuranones, isoxazolidinyl-pyridines, isoxazolines, maleimides, mandelic acid amides, mectin derivatives, morpholines, norpholines, n-phenyl carbamates, organotin compounds, oxathiin carboxamides, oxazoles, oxazolidine-diones, phenols, phenoxy quinolines, phenyl-acetamides, phenylamides, phenylbenzamides, phenyl-oxo-ethyl-thiophenes amides, phenylpyrroles, phenylureas, phosphorothiolates, phosphorus acids, phthalamic acids, phthalimides, picolinamides, piperazines, piperidines, plant extracts, polyoxins, propionamides, pthalimides, pyrazole-4-carboxamides, pyrazolinones, pyridazinones, pyridines, pyridine carboxamides, pyridinyl- ethyl benzamides, pyrimdinamines, pyrimidines, pyrimidine-amines, pyrimidione-hydrazone, pyrrolidines, pyrrolquinoliones, quinazolinones, quinolines, quinoline derivatives, quinoline-7- carboxylic acids, quinoxalines, spiroketalamines, strobilurins, sulfamoyl triazoles, sulphamides, tetrazolyloximes, thiadiazines, thiadiazole carboxamides, thiazole carboxanides, thiocyanates, thiophene carboxamides, toluamides, triazines, triazobenthiazoles, triazoles, triazole-thiones, triazolo- pyrimidylamine, valinamide carbamates, ammonium methyl phosphonates, arsenic-containing compounds, benyimidazolylcarbamat.es, carbonitriles, carboxanilides, carboximidamides, carboxylic phenylamides, diphenyl pyridines, furanilides, hydrazine carboxamides, imidazoline acetates, isophthalates, isoxazolones, mercury salts, organomercury compounds, organophosphates, oxazolidinediones, pentylsulfonyl benzenes, phenyl benzamides, phosphonothionates,

phosphorothioates, pyridyl carboxamides, pyridyl furfuryl ethers, pyridyl methyl ethers, SDHIs, thiadiazinanethiones, thiazolidines.

Particularly preferred fungicidal combinations include the following where "I" designates compounds of formula (I): I + (.+/-.)-cis-1-(4-chlorophenyl)-2-(1 H-1 ,2,4-triazol-1-yl)-cycloheptanol (huanjunzuo), I + (2RS)-2-bromo-2-(bromomethyl)glutaronitrile (bromothalonil), I + (E)-N-methyl-2- [2- (2, 5-dimethylphenoxymethyl) phenyl]-2-methoxy-iminoacetamide, (mandestrobin), I + 1 -(5-bromo- 2-pyridyl)-2-(2,4-difluorophenyl)-1 ,1-difluoro-3-(1 ,2,4-triazol-1-yl)propan-2-ol, I + 1- methylcyclopropene, I + 2-methyl-, [[4-methoxy-2-[[[(3SJR,8R,9S)-9-methyl-8-(2-methyl-1- oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1 ,5-dioxonan-3-yl]amino]carbonyl]-3-pyridinyl]oxy]propanoic acid methyl ester, I + 2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1 ,2,4-triazol-1-yl)-propan-2-ol (TCDP), I + 2,4-D, I + 2,4-DB, I + 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, I + 2,6-dimethyl- [1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone, I + 2-[[(1 R,5S)-5-[(4-fluorophenyl)methyl]- 1-hydroxy-2,2-dimethyl-cyclopentyl]methyl]-4H-1 ,2,4-triazole-3-thione I + 2-[[3-(2-chlorophenyl)-2-(2,4- difluorophenyl)oxiran-2-yl]methyl]-4H-1 ,2,4-triazole-3-thione I + ametoctradin (imidium), I + 2-[2-[(7,8- difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol I + 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol I + cyflufenamid, I + 2-benzyl-4-chlorophenol (Chlorophene), I + 3- (difluoromethyl)-N-(7-fluoro-1 ,1 ,3,3-tetramethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide I + diclocymet, I + 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6- trichlorophenyl)ethyl]pyrazole-4-carboxamide, I + 3'-chloro-2-methoxy-N-[(3RS)-tetrahydro-2- oxofuran-3-yl]acet-2',6'-xylidide (clozylacon), I + 3-iodo-2-propinyl n-butylcarbamate (IPBC), I + 4,4,5- trifluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline I + 4,4-difluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline I + 5-fluoro-3,3,4,4-tetramethyl-1-(3-quinolyl)isoquinoline I + 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1 ,4- benzoxazepine I + tebufloquin, I + 4-CPA, I + 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine I + ferimzone, I + acibenzolar, I + acibenzolar-S-methyl, I + allyl alcohol, I + ametoctradin, I + amisulbrom, I + anilazine, I + aureofungin, I + azaconazole, I + azafenidin, I + azithiram, I + azoxystrobin, I + benalaxyl, I + benalaxyl-M, I + benalaxyl-M (kiralaxyl), I + benomyl, I + benthiavalicarb, I + benthiazole (TCMTB), I + benzalkonium chloride, I + benzamorf, I +

benzovindiflupyr (solatenol), I + bethoxazin, I + biphenyl, I + bitertanol (biloxazol), I + bixafen, 1 + BLAD, I + blasticidin-S, I + Bordeaux mixture, I + boscalid, I + bromuconazole, I + bupirimate, I + but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate I + dazomet, I + butylamine, I + calcium polysulfide, I + captafol, I + captan, I + carbaryl, I + carbendazim, I + carbendazim chlorhydrate, I + carboxin, I + CAS 517875-34-2 (DAS777), l + chinomethionate, I + chinomethionate (oxythioquinox, quinoxymethionate), I + chitosan, I + chlobenthiazone, I + chlorfenazole, I + chlormequat, I + chloroneb, I + chloropicrin, l +

chlorothalonil, I + chlozolinate, I + climbazole, I + clofencet, I + copper acetate, I + copper carbonate, I + copper hydroxide, I + copper naphthenate, I + copper oleate, I + copper oxychloride, I + copper oxyquinolate, I + copper silicate, I + copper sulphate, I + copper tallate, I +

coumoxystrobin, I + cresol, I + cuprous oxide, I + cyazofamid, I + cyclafuramid, I + cymoxanil, I + cyproconazole, I + cyprodinil, I + daracide, I + dichlofluanid, I + dichlorophen (dichlorophene), l + dichlorprop, I + diclomezine, I + dicloran, I + diethofencarb, I + difenoconazole, I + difenzoquat, I + diflumetorim, I + dimetachlone (dimethaclone), I + dimetconazole, I + dimethipin, I + dimethirimol, I + dimethomorph, I + dimoxystrobin, I + dingjunezuo (Jun Si Qi), I + diniconazole, I + diniconazole- M, I + , I + dinobuton, I + dinocap, I + dinocton, I + dinopenton, I + diphenylamine, I + dipyrithione, I + ditalimfos, I + dithianon, I + dithioether, I + dodemorph, I + dodicin, I + dodine, I + doguadine, I + drazoxolon, I + edifenphos, I + endothal, I + enestroburin, enoxastrobin I + fenamistrobin, I + epoxiconazole, I + etaconazole, I + etem, I + ethaboxam, I + ethephon, I + ethoxyquin, I + famoxadone, I + fenamidone, I + fenarimol, I + fenbuconazole, I + fenfuram, I + fenhexamid, I + fenoxanil, I + fenpiclonil, I + fenpropidin, I + fenpropimorph, I + fenpyrazamine, I + fentin acetate, I + fentin hydroxide, I + ferbam, I + fluazinam, I + fludioxonil, I + flufenoxystrobin, I + flumetralin, I + flumorph, I + fluopicolide, I + fluopicolide (flupicolide), I + fluopyram, I + fluoroimide, l +

fluoxastrobin, I + fluquinconazole, I + flusilazole, I + flusulfamide, l + flutianil, I + flutolanil, l + flutriafol, I + fluxapyroxad, l + folpet, I + forchlorfenuron, I + fosetyl, I + fuberidazole, l + furalaxyl, I + furametpyr, I + gibberellic acid, I + gibberellins, I + guazatine, I + hexachlorobenzene, I + hexaconazole, I + hymexazol, I + hymexazole, hydroxyisoxazole I + imazalil, I + I + etridiazole, I + imazalil, I + imazalil sulphate, I + imibenconazole, I + iminoctadine, I + iminoctadine triacetate, I + iodocarb (isopropanyl butylcarbamate), I + ipconazole, I + iprobenfos, I + iprodione, I + iprovalicarb, I + isofetamid, I + isopropanyl butylcarbamate (iodocarb), I + isoprothiolane, I + isopyrazam, l + isotianil, I + kasugamycin, I + kresoxim-methyl, I + KSF-1002, I + maleic hydrazide, I + mancozeb, I + mandestrobin, I + mandipropamid, I + maneb, I + mepanipyrim, I + mepiquat, I + mepronil, I + meptyldinocap, I + metalaxyl, I + metalaxyl-M (mefenoxam), I + metam, I + metaminostrobin, I + metconazole, I + methyl bromide, I + methyl iodide, I + methyl isothiocyanate, I + metiram

(polyram), I + metiram-zinc, I + metominostrobin, I + metrafenone, I + m-phenylphenol, I + myclobutanil, I + N'-(2,5-Dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, I + N'-[4-(4,5- Dichloro-thiazol-2-yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, I + N'-[4-[[3-[(4- chlorophenyl)methyl]-1 ,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, I + ethirimol, I + N-(2-p-chlorobenzoylethyl)-hexaminium chloride, I + N-[(5-chloro-2-isopropyl- phenyl)methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazole-4-carboxamide I + N- cyclopropyl-3-(difluoromethyl)-5-fluoro-N-[(2-isopropylphenyl)methyl]-1-methyl-pyrazole-4- carboxamide I + carpropamid, I + nabam, I + naphthalene acetamide, l + NNF-0721 , I + octhilinone, I + ofurace, I + orysastrobin, I + osthol, I + oxadixyl, I + oxasulfuron, I + oxathiapiprolin, I + oxine- copper, I + oxolinic acid, I + oxpoconazole, I + oxycarboxin, I + paclobutrazol, I + pefurazoate, I + penconazole, I + pencycuron, I + penflufen, I + penthiopyrad, I + phenamacril, I + phosdiphen, I + phosetyl-AI, I + phosetyl-AI (fosetyl-al), I + phosphorus acids, I + phthalide (fthalide), I +

picarbutrazox, I + picoxystrobin, I + piperalin, I + polycarbamate, I + polyoxin D (polyoxrim), I + p- phenylphenol, I + probenazole, I + prochloraz, I + procymidone, I + prohexadione, I +

prohexadione-calcium, I + propamidine, I + propamocarb, I + propiconazole, I + propineb, I + propionic acid, I + proquinazid, I + prothioconazole, I + pyraclostrobin, I + pyrametostrobin, l + pyraoxystrobin, I + pyrazophos, I + pyribencarb (KIF-7767), I + pyrifenox, I + pyrimethanil, I + pyriofenone (IKF-309), I + pyroquilon, I + quinoxyfen, I + quintozene, I + sedaxane, I + silthiofam, I + simeconazole, I + spiroxamine, I + streptomycin, I + sulphur, I + tebuconazole, I + tebufloquin, I + tecloftalam, I + tecnazene, (TCNB), I + tetraconazole, I + thiabendazole, I + thicyofen, I + thidiazuron, I + thifluzamide, I + thiophanate-methyl, I + thiram, I + tiadinil, I + tioxymid, I + tolclofos-methyl, I + tolprocarb, I + tolylfluanid, I + triadimefon, I + triadimenol, I + triazoxide, I + tribromophenol (TBP), I + tribufos (tributyl phosphorotrithioate), I + triclopyricarb , I + tricyclazole, I + tridemorph, I + trifloxystrobin, I + triflumizole, I + triforine, I + trinexapac, I + triticonazole, I + uniconazole, I + validamycin, I + valifenalate, I + vapam, I + vapam (metam sodium), I + vinclozolin, I + zineb, I + ziram, I + zoxamide, I + onaphthalene acetic acid.

Compounds of this invention can also be mixed with one or more further pesticides including insecticides, nematocides, bactericides, acaricides, growth regulators, chemosterilants,

semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.

Examples of such agricultural protectants with which compounds of this invention can be formulated are:

Insecticides such as abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap,

chlorantraniliprole (DPX-E2Y45), chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate, tau-fluvalinate, flufenerim (UR-50701 ), flufenoxuron, fonophos, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde,

methamidophos, methidathion, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, _„

18

profluthrin, pymetrozine, pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid,

thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, trichlorfon and triflumuron;

Bactericides such as streptomycin;

Acaricides such as amitraz, chinomethionat, chlorobenzilate, cyenopyrafen, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and

Biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.

Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compounds may also be applied to seeds to protect the seeds and seedlings developing from the seeds. The compounds may also be applied through irrigation water to treat plants.

The present invention envisages application of the compounds of the invention to plant propagation material prior to, during, or after planting, or any combination of these.

Although active ingredients can be applied to plant propagation material in any physiological state, a common approach is to use seeds in a sufficiently durable state to incurr no damage during the treatment process. Typically, seed would have been harvested from the field; removed from the plant; and separated from any cob, stalk, outer husk, and surrounding pulp or other non-seed plant material. Seed would preferably also be biologically stable to the extent that treatment would not cause biological damage to the seed. It is believed that treatment can be applied to seed at any time between seed harvest and sowing of seed including during the sowing process.

Methods for applying or treating active ingredients on to plant propagation material or to the locus of planting are known in the art and include dressing, coating, pelleting and soaking as well as nursery tray application, in furrow application, soil drenching, soil injection, drip irrigation, application through sprinklers or central pivot, or incorporation into soil (broad cast or in band).

Alternatively or in addition active ingredients may be applied on a suitable substrate sown together with the plant propagation material.

Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than about 1 g/ha to about 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from about 0.1 to about 10g per kilogram of seed.

Crops of useful plants in which the composition according to the invention can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.

Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

Crops are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO- inhibitors. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer canola. Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include δ-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.

An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds). An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

The compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water- dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil- in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water- miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the „„

20

Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.

The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the

microcapsules are not themselves encapsulated.

The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, A/,A/-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 , 1- trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene,

perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as _

21

amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, A/-methyl-2-pyrrolidone and the like.

Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.

A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di- alkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981 ).

Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.

The compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C₈-C₂2 fatty acids, especially the methyl derivatives of Ci₂-Ci₈ fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10^th Edition, Southern Illinois University, 2010.

The inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations. The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.

Preferred formulations can have the following compositions (weight %):

Emulsifiable concentrates:

active ingredient: 1 to 95 %, preferably 60 to 90 %

surface-active agent 1 to 30 %, preferably 5 to 20 %

liquid carrier: 1 to 80 %, preferably 1 to 35 %

Dusts:

active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %

solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates

active ingredient: 5 to 75 %, preferably 10 to 50 %

water: 94 to 24 %, preferably 88 to 30 %

surface-active agent: 1 to 40 %, preferably 2 to 30 %

Wettable powders:

active ingredient: 0.5 to 90 %, preferably 1 to 80 %

surface-active agent: 0.5 to 20 %, preferably 1 to 15 %

solid carrier: 5 to 95 %, preferably 15 to 90 %

Granules:

active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %

solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The following Examples further illustrate, but do not limit, the invention.

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

Powders for drv seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % -

Kaolin 65 % 40 % -

Talcum - 20

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

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

The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Suspension concentrate

active ingredients 40 %

propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %

Sodium lignosulfonate 10 %

carboxymethylcellulose 1 %

silicone oil (in the form of a 75 % emulsion in water) 1 %

Water 32 %

The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Flowable concentrate for seed treatment

The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Slow Release Capsule Suspension

28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

The Examples which follow serve to illustrate the invention. The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm or 0.8 ppm.

Example 1 : This example illustrates the preparation of (2E)-2-[4-(2-chlorophenyl)-1 ,3-dithiolan-2- ylidene]-2-(5-methylimidazol-1-yl)acetonitrile (compound I. p.123)

a) Preparation of [2-bromo-1-(2-chlorophenyl)ethyl] methanesulfonate A 50 mL round bottom flask is successively charged with 2-bromo-1-(2-chlorophenyl)ethanol (4.47 g, 19 mmol), ethyl acetate (20 mL), triethyl amine (3 mL, 20.9 mmol) and is cooled at 0^°C with an ice bath. Then methanesulfonyl chloride (1.49 mL, 19 mmol) is added dropwise. After 15 minutes stirring at 0^°C, the resulting white suspension is filtered and the mother liquor is neutralized with a 5 saturated aqueous solution of sodium hydrogen carbonate (15 mL) and water (10 mL). The aqueous phase is extracted with ethyl acetate (2 ^χ 20 mL).The combined organic phases are washed with brine (20 mL), dried with sodium sulphate, filtered and evaporated to give [2-bromo-1-(2-chlorophenyl)ethyl] methanesulfonate as a light yellow oil. H-NMR (400 MHz, CDCI₃): δ = 7.58 (dd, J = 2.2, 7.3 Hz, 1 H), 7.45-7.32 (m, 4H), 6.13 (dd, J = 3.8, 8.1 Hz, 1 H), 3.75 (dd, J = 3.8, 1 1 .4 Hz, 1 H), 3.64 (dd, J = 8.1 ,

10 1 1 .4 Hz, 1 H), 3.06 (s, 3H).

b) Preparation of 2-(5-methylimidazol-1-yl)acetonitrile

A 250 mL flask was charged with 4(5)-methylimidazole (10 g, 1 19.4 mmol), acetonitrile (100 mL), potassium carbonate (20 g, 143.2 mmol) and 2-bromoacetonitrile (1 19.4 mmol, 8.66 mL). The reaction flask was fitted with a condenser and the white suspension was stirred at 80^°C for 3 hours.

15 The resulting suspension was filtered, the white precipitate was washed with acetonitrile (2 x 10 mL) and the mother liquor was evaporated to give a crude dark brown oil. Purification by chromatography on silica gel (dichloromethane/methanol, 1 :0→20:1→10: 1 ) afford a (70:30) mixture of 2-(4- methylimidazol-1-yl)acetonitrile and 2-(5-methylimidazol-1-yl)acetonitrile which was used as such in the next step. GC-MS (CI): m/z = 122 (M+1 ).

20 c) Preparation of (2E)-2-[4-(2-chlorophenyl)-1 ,3-dithiolan-2-ylidene]-2-(5-methylimidazol-1- yl)acetonitrile (compound I. p.123)

A 50 mL flask was charged with powdered potassium hydroxide (1.5 g, 23 mmol), dimethylsulfoxide (10 mL), purged with argon and was cooled at 10^°C with a water bath. A solution of 2-(5-methylimidazol-1-yl)acetonitrile (1.39 g, 1 1.5 mmol) and carbon disulfide (1.44 mL, 23.9 mmol) in

25 dimethylsulfoxide (2 mL) was then added slowly to give an orange mixture. The cooling bath was

removed and the reaction was stirred at room temperature for 30 minutes. A solution of [2-bromo-1-(2- chlorophenyl)ethyl] methanesulfonate (3 g, 9.6 mmol) in dimethylsulfoxide (5 mL) was then added dropwise. After 2 hours, the reaction mixture is poured into H₂0 (50 mL). The aqueous phase was extracted with dichloromethane (3 * 50 mL), the combined organic phases are washed with brine,

30 dried with sodium sulphate, filtered and evaporated to give a crude orange gum. Purification by

chromatography on silica gel (heptanes/ethyl acetate, 1 :0→20: 1→1 :1→1 :2) afford (2E)-2-[4-(2- chlorophenyl)-1 ,3-dithiolan-2-ylidene]-2-(5-methylimidazol-1-yl)acetonitrile (compound I. p.123) as a yellow solid. H-NMR (400 MHz, CDCI₃): δ = 7.70-7.64 (m, 1 H), 7.50-7.43 (m, 2H), 7.39-7.32 (m, 2H), 6.87 (s, 1 H), 5.78 (dd, J = 5.2, 7.7 Hz, 1 H), 3.87 (dd, J = 5.2, 1 1 .9 Hz, 1 H), 3.67 (dd, J = 7.7, 12.1 Hz,

35 1 H), 2.24 (s, 3H). MS (ESI): m/z = 334, 336 (M+1 ).

Table 1 below illustrates examples of individual compounds of formula I according to the invention.

Table 1 : individual compounds of formula I according to the invention Comp.

X Y R¹ R² R⁴ R⁵ No.

1 NH NH H H H CI

2 NH NH H H H CN

3 NH NH H H H CH₃

4 NH NH H H H CF₃

5 NH NH H H H CF₂H

6 NH NH CH₃ H H CI

7 NH NH CH₃ H H CN

8 NH NH CH₃ H H CH₃

9 NH NH CH₃ H H CF₃

10 NH NH CH₃ H H CF₂H

11 NH NH CH₃ CH₃ H CI

12 NH NH CH₃ CH₃ H CN

13 NH NH CH₃ CH₃ H CH₃

14 NH NH CH₃ CH₃ H CF₃

15 NH NH CH₃ CH₃ H CF₂H

16 NH NH H H CH₃ CI

17 NH NH H H CH₃ CN

18 NH NH H H CH₃ CH₃

19 NH NH H H CH₃ CF₃

20 NH NH H H CH₃ CF₂H

21 NH 0 H H H CI

22 NH 0 H H H CN

23 NH 0 H H H CH₃

24 NH 0 H H H CF₃

25 NH 0 H H H CF₂H

26 NH 0 CH₃ H H CI

27 NH 0 CH₃ H H CN

28 NH 0 CH₃ H H CH₃

29 NH 0 CH₃ H H CF₃

30 NH 0 CH₃ H H CF₂H

31 NH 0 CH₃ CH₃ H CI

32 NH 0 CH₃ CH₃ H CN

33 NH 0 CH₃ CH₃ H CH₃

34 NH 0 CH₃ CH₃ H CF₃

35 NH 0 CH₃ CH₃ H CF₂H

36 NH 0 H H CH₃ CI

37 NH 0 H H CH₃ CN NH 0 H H CH₃ CH₃

NH 0 H H CH₃ CF₃

NH 0 H H CH₃ CF₂H

NH S H H H CI

NH S H H H CN

NH S H H H CH₃

NH S H H H CF₃

NH S H H H CF₂H

NH S CH₃ H H CI

NH S CH₃ H H CN

NH s CH₃ H H CH₃

NH s CH₃ H H CF₃

NH s CH₃ H H CF₂H

NH s CH₃ CH₃ H CI

NH s CH₃ CH₃ H CN

NH s CH₃ CH₃ H CH₃

NH s CH₃ CH₃ H CF₃

NH s CH₃ CH₃ H CF₂H

NH s H H CH₃ CI

NH s H H CH₃ CN

NH s H H CH₃ CH₃

NH s H H CH₃ CF₃

NH s H H CH₃ CF₂H

0 NH H H H CI

0 NH H H H CN

0 NH H H H CH₃

0 NH H H H CF₃

0 NH H H H CF₂H

0 NH CH₃ H H CI

0 NH CH₃ H H CN

0 NH CH₃ H H CH₃

0 NH CH₃ H H CF₃

0 NH CH₃ H H CF₂H

0 NH CH₃ CH₃ H CI

0 NH CH₃ CH₃ H CN

0 NH CH₃ CH₃ H CH₃

0 NH CH₃ CH₃ H CF₃

0 NH CH₃ CH₃ H CF₂H

0 NH H H CH₃ CI

0 NH H H CH₃ CN 78 0 NH H H CH₃ CH₃

79 0 NH H H CH₃ CF₃

80 0 NH H H CH₃ CF₂H

81 0 0 H H H CI

82 0 0 H H H CN

83 0 0 H H H CH₃

84 0 0 H H H CF₃

85 0 0 H H H CF₂H

86 0 0 CH₃ H H CI

87 0 0 CH₃ H H CN

88 0 0 CH₃ H H CH₃

89 0 0 CH₃ H H CF₃

90 0 0 CH₃ H H CF₂H

91 0 0 CH₃ CH₃ H CI

92 0 0 CH₃ CH₃ H CN

93 0 0 CH₃ CH₃ H CH₃

94 0 0 CH₃ CH₃ H CF₃

95 0 0 CH₃ CH₃ H CF₂H

96 0 0 H H CH₃ CI

97 0 0 H H CH₃ CN

98 0 0 H H CH₃ CH₃

99 0 0 H H CH₃ CF₃

100 0 0 H H CH₃ CF₂H

101 s NH H H H CI

102 s NH H H H CN

103 s NH H H H CH₃

104 s NH H H H CF₃

105 s NH H H H CF₂H

106 s NH CH₃ H H CI

107 s NH CH₃ H H CN

108 s NH CH₃ H H CH₃

109 s NH CH₃ H H CF₃

110 s NH CH₃ H H CF₂H

111 s NH CH₃ CH₃ H CI

112 s NH CH₃ CH₃ H CN

113 s NH CH₃ CH₃ H CH₃

114 s NH CH₃ CH₃ H CF₃

115 s NH CH₃ CH₃ H CF₂H

116 s NH H H CH₃ CI

117 s NH H H CH₃ CN 118 S NH H H CH₃ CH₃

119 S NH H H CH₃ CF₃

120 S NH H H CH₃ CF₂H

121 S S H H H CI

122 S S H H H CN

123 S S H H H CH₃

124 S S H H H CF₃

125 S S H H H CF₂H

126 S S CH₃ H H CI

127 S S CH₃ H H CN

128 S S CH₃ H H CH₃

129 S S CH₃ H H CF₃

130 S S CH₃ H H CF₂H

131 S S CH₃ CH₃ H CI

132 S S CH₃ CH₃ H CN

133 S S CH₃ CH₃ H CH₃

134 S S CH₃ CH₃ H CF₃

135 S S CH₃ CH₃ H CF₂H

136 S S H H CH₃ CI

137 S S H H CH₃ CN

138 S S H H CH₃ CH₃

139 S S H H CH₃ CF₃

140 s s H H CH₃ CF₂H where

a) 140 specific compounds of formula (I. a):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1.

b) 140 specific compounds of formula (l.b):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. c) 140 specific compounds of formula (l.c):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. d) 140 specific compounds of formula (l.d):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in a row of Table 1. e) 140 specific compounds of formula (l.e):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. f) 140 specific compounds of formula (l.f):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. g) 140 specific compounds of formula (l.g):

(i g)

Wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in a row of Table 1. h) 140 specific compounds of formula (l.h):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in a row of Table 1. i) 140 specific compounds of formula (l.i):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. j) 140 specific compounds of formula (l.j):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. k) 140 specific compounds of formula (l.k):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in a row of Table 1. m) 140 specific compounds of formula (l.m):

(l.m)

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. n) 140 specific compounds of formula (l.n):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in a row of Table 1. o) 140 specific compounds of formula (l.o):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in a row of Table 1. p) 140 specific compounds of formula (l.p):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. q) 140 specific compounds of formula (l.q):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in a row of Table . r) 140 specific compounds of formula (l.r):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. 00 s) 140 specific compounds of formula (l.s):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. t) 140 specific compounds of formula (l.t):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. u) 140 specific compounds of formula (l.u):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. v) 140 specific compounds of formula (l.v):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. w) 140 specific compounds of formula (l.w):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. x) 140 specific compounds of formula (l.x):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. y) 140 specific compounds of formula (l.y):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. z) 140 specific compounds of formula (l.z):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. aa) 140 specific compounds of formula (l.aa):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. ab) 140 specific compounds of formula (l.ab):

wherein X, Y, R , R², R⁴ and R° are as defined in a row of Table 1. ac) 140 specific compounds of formula (l.ac):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. ad) 140 specific compounds of formula (I. ad):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. ae) 140 specific compounds of formula (l.ae):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. af) 140 specific compounds of formula (l.af):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. ag) 140 specific compounds of formula (Lag):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. ah) 140 specific compounds of formula (I. ah):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. ai) 140 specific compounds of formula (l.ai):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. aj) 140 specific compounds of formula (l.aj):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. ak) 140 specific compounds of formula (l.ak):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. am) 140 specific compounds of formula (l.am):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. an) 140 specific compounds of formula (I. an):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. ao) 140 specific compounds of formula (l.ao):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. ap) 140 specific compounds of formula (Lap):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. aq) 140 specific compounds of formula (l.aq):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. ar) 140 specific compounds of formula (l.ar):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. as) 140 specific compounds of formula (I. as):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. at) 140 specific compounds of formula (I. at):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. au) 140 specific compounds of formula (l.au):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. av) 140 specific compounds of formula (l.av):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1 aw) 140 specific compounds of formula (Law):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. ax) 140 specific compounds of formula (Lax):

wherein X, Y, R , R , R and R are as defined in a row of Table 1. ay) 140 specific compounds of formula (Lay):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. az) 140 specific compounds of formula (l.az):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. ba) 140 specific compounds of formula (l.ba):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. bb) 140 specific compounds of formula (l.bb):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. be) 140 specific compounds of formula (I. be):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. bd) 140 specific compounds of formula (l.bd):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. be) 140 specific compounds of formula (I. be):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in a row of Table 1. bf) 140 specific compounds of formula (l.bf):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. bg) 140 specific compounds of formula (l.bg):

wherein X, Y, R , R², R⁴ and R° are as defined in a row of Table 1. bh) 140 specific compounds of formula (l.bh):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. bi) 140 specific compounds of formula (I.bi):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in a row of Table 1. bj) 140 specific compounds of formula (l.bj):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. bk) 140 specific compounds of formula (l.bk):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1. bm) 140 specific compounds of formula (l.bm):

wherein X, Y, R , R , R and R are as defined in a row of Table 1.

bn) 140 specific compounds of formula (l.bn):

wherein X, Y, R , R , R and R are as defined in a row of Table 1.

bo) 140 specific compounds of formula (I. bo):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1.

bp) 140 specific compounds of formula (I. bp):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in a row of Table 1.

Throughout this description, temperatures are given in degrees Celsius and "m.p." means melting point. LC/MS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the method is: (ACQUITY UPLC from Waters, Phenomenex Gemini C18, 3 Dm particle size, 1 10 Angstrom, 30 x 3 mm column, 1 .7mL/min., 60 °C, H₂0 + 0.05% HCOOH (95%) /

CH₃CN/MeOH 4: 1 + 0.04% HCOOH (5%) - 2 min. - CH₃CN/MeOH 4: 1 + 0.04% HCOOH (5%) - 0.8 min., ACQUITY SQD Mass Spectrometer from Waters, ionization method: electrospray (ESI), Polarity: positive ions, Capillary (kV) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700)).

Table 2: Melting point and LC/MS data for compounds of Table 1

5 Biological examples

Alternaria solani I tomato / leaf disc (early blight)

Tomato leaf disks cv. Baby were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf disks were incubated at 10 23 °C / 21°C (day/night) and 80% rh under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application).

Compounds I. p.123, l.v.123, l.x.123, l.ad.123, l.af.123, l.bm.123 and l.bn.123 at 200 ppm 15 gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Blumeria graminis f. sp. tritici (Erysiphe graminis f. sp. tritici) I wheat / leaf disc preventative (Powdery mildew on wheat)

Wheat leaf segments cv. Kanzler were placed on agar in a multiwell plate (24-well format) and 20 sprayed with the formulated test compound diluted in water. The leaf disks were inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks were incubated at 20°C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h „_.

45

darkness in a climate chamber and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application).

Compounds l.p.123, l.p.125, l.v.123, l.x.123, l.af.123 and l.bm.123 at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Botryotinia fuckeliana (Botrytis cinerea) I liquid culture (Gray mould)

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application.

Compounds I. p.123, I . b j .123 and l.bm.123 at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Fusarium culmorum I liquid culture (Head blight)

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96- well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24oC and the inhibition of growth was determined photometrically 3-4 days after application.

Compounds l.p.123, l.v.123, l.x.123, l.z.123, Lad.123, l.af.123, l.bm.123, l.bn.123 and

I. bo.123 at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Gaeumannomyces graminis I liquid culture (Take-all of cereals)

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

Compounds l.p.123, l.v.123, l.x.123, l.z.123, l.ad.123, l.bn.123 and l.bp.123 at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Glomerella lagenarium (Colletotrichum lagenarium) / liquid culture (Anthracnose)

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

Compounds l.p.123, l.v.123, l.x.123, l.z.123, l.ad.123, l.af.123, l.bm.123 and l.bn.123 at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Magnaporthe grisea (Pyricularia oryzae) I rice / leaf disc preventative (Rice Blast) „„

46

Rice leaf segments cv. Ballila were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The 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% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application).

Compounds l.p.121 , l.v.123, l.x.123, l.ad.123 and l.bn.123 at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Monographella nivalis (Microdochium nivale) / liquid culture (foot rot cereals)

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

Compounds l.p.123, l.p.125, l.v.123, l.x.123, l.ad.123, l.af.123, l.bj.123, l.bm.123 and l.bn.123 at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Mycosphaerella arachidis (Cercospora arachidicola) I liquid culture (early leaf spot)

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

Compounds l.p.123, l.v.123, l.x.123, l.z.123, l.ad.123, l.af.123, l.bm.123, l.bn.123 and I. bo.123 at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Mycosphaerella graminicola (Septoria tritici) I liquid culture (Septoria blotch)

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

Compounds l.p.123, l.p.125, l.v.123, l.x.123, l.ad.123, l.af.123, l.bm.123, l.bn.123 and I. bp.123 at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Pyrenophora teres I barley / leaf disc preventative (Net blotch)

Barley leaf segments cv. Hasso were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segmens were inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments were incubated at 20°C and 65% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound was assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application). Compounds l.p.121 , I. p.123, l.v.123, l.x.123, l.ad.123, l.af.123, l.bk.123, l.bm.123 and l.bn.123 at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Thanatephorus cucumeris (Rhizoctonia solani) I liquid culture (foot rot, dampinq-off)

Mycelia fragments of a newly grown liquid culture of the fungus were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format), the nutrient broth containing the fungal material is added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application.

Compounds l.p.123, l.v.123, l.x.123, l.ad.123, l.af.123, l.bm.123 and l.bn.123 at 200 ppm gave at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which showed extensive disease development.

Gaeumannomyces graminis / wheat (Take-all on wheat)

A defined amount of mycelium of G. graminis is mixed with water. The formulated test compounds were added to the mycelium suspension. The mixture is applied into a pouch which was previously equipped with a filter paper. After the application wheat seeds cv. Arina were sown into the upper fault of the filter paper. The prepared pouches were then incubated for 14 days at 18° C / 16°C (day/night) and a rel. humidity of 80% with a photo period of 14h. The evaluation was made by assessing the degree of root browning.

Claims

Claims:

1. A compound of formula (I):

wherein,

X and Y are independently O, S or NR⁶;

R , R² and R⁴ are independently hydrogen, halogen, CrC₆alkyl, Ci-C₆haloalkyl, d-C₆alkoxy or d- C₆haloalkoxy;

R³ is aryl, aryl substituted by one or more substituents R⁷, heteroaryl or heteroaryl substituted by one or more substituents R⁷;

R⁵ is halogen, cyano, Ci-C₆alkyl or Ci-C₆haloalkyl;

R⁶ is hydrogen, Ci-C₆alkyl, d-C₆alkoxy or C₃-C₆cycloalkyl;

R⁷ is halogen, nitro, cyano, hydroxyl, amino, Ci-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkenyloxy, Ci-C₆alkyloxy, C₂-C₆alkynyl, C₂-C₆alkynyloxy, Ci-C₆haloalkyl, d-C₆alkoxy, d-C₆haloalkoxy, d-C₆cycloalkyl, C₃- dhalocycloalkyl, d-C₆cycloalkyloxy, aryl, aryloxy, heteroaryl, or heteroaryloxy and wherein the aryl and heteroaryl moieties can be further independently substituted by one or more substituents selected from halogen, nitro, cyano, hydroxyl, amino, d-C₆alkyl, d-C₆haloalkyl, d-C₆alkoxy or d- dhaloalkoxy and wherein the alkyl, alkenyl, alkynyl moieties can be further independently substituted by one or more substituents selected from nitro, cyano, hydroxyl or amino;

and wherein aryl is a mono- or bi-cyclic five- to ten-membered ring system and heteroaryl is a mono- or bi-cyclic five- to ten-membered ring system and the heteroaryl group contains 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms;

or a salt or a N-oxide thereof.

2. A compound of formula (I) according to claim 1 wherein

X and Y are both S.

3. A compound of formula (I) according to claim 1 or 2 wherein

R , R² and R⁴ are independently hydrogen, halogen, d-C₆alkyl or d-C₆haloalkyl.

4. A compound of formula (I) according to anyone of the claims 1 to 3 wherein

R³ is aryl or aryl substituted by one or more substituents R⁷.

5. A compound of formula (I) according to anyone of the claims 1 to 4 wherein R⁷ is halogen, cyano, Ci-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, Ci-C₆haloalkyl, d-C₆alkoxy, d- C₆haloalkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, and wherein the aryl and heteroaryl moieties can be further independently substituted by one or more substituents selected from halogen, nitro, cyano, hydroxyl, amino, Ci-C₆alkyl, Ci-C₆haloalkyl, d-C₆alkoxy or Ci-C₆haloalkoxy and wherein the alkyl, alkenyl and alkynyl moieties can be further independently substituted by one or more substituents selected from nitro, cyano, hydroxyl or amino.

6. A compound of formula (I) according to anyone of the claims 1 to 5 wherein

R , R² and R⁴ are each hydrogen;

7. A compound of formula (I) according to anyone of the claims 1 to 6 wherein

R⁵ is halogen, methyl or difluoromethyl.

8. A compound of formula (I) according to anyone of the claims 1 to 7 wherein

X and Y are both S;

R , R² and R⁴ are independently hydrogen, halogen, CrC₆alkyl, Ci-C₆haloalkyl, d-C₆alkoxy or d- dhaloalkoxy;

R³ is aryl or aryl substituted by one or more substituents R⁷;

R⁵ is halogen, cyano, d-C₆alkyl or d-C₆haloalkyl;

R⁷ is halogen, cyano, d-C₆alkyl, C₂-dalkenyl, C₂-dalkynyl, C₂-dalkynyloxy, d-C₆haloalkyl, d- dalkoxy, d-C₆haloalkoxy, phenyl, phenyloxy, pyrazolyl, pyrimidinyloxy, wherein the aryl and heteroaryl moieties can be further independently substituted by one or more substituents selected from halogen, nitro, cyano, hydroxyl, amino, d-C₆alkyl, d-C₆haloalkyl, d-C₆alkoxy or d- dhaloalkoxy and wherein the alkyl, alkenyl and alkynyl moieties can be further independently substituted by one or more substituents selected from nitro, cyano, hydroxyl or amino.

9. A compound of formula (I) according to anyone of the claims 1 to 8 wherein

X and Y are both S;

R , R² and R⁴ are independently hydrogen, d-C₆alkyl;

R³ is phenyl or phenyl substituted by one or more substituents R⁷;

R⁵ is halogen, d-dalkyl or d-dhaloalkyl;

R⁷ is halogen, cyano, d-C₆alkyl, cyano-C₂-dalkyloxy, C₂-dalkynyloxy, d-C₆haloalkoxy , d- dhaloalkyl, pyrazolyl, phenyloxy substituted by halogen, pyrimidinyloxy or pyrimidinyloxy substituted by halogen.

10. A method for controlling or preventing infestation of a plant or plant propagation material and/or harvested crop susceptible to microbial attack, characterized in that an effective amount a compound of formula (I) as defined in any of the claims 1 to 9 is applied to the plant or plant propagation material and/or harvested crop, or to parts thereof or the locus thereof.

1 1. A method of controlling phytopathogenic diseases on a plant or plant propagation material and/or harvested crop susceptible to microbial attack, characterized in that an effective amount a compound of formula (I) as defined in anyone of the claims 1 to 9 is applied to the plant or plant propagation material and/or harvested crop, or to parts thereof or the locus thereof.

12. A composition comprising a fungicidally effective amount of a compound of formula (I) as defined in anyone of the claims 1 to 9.

13. A process for the preparation of a compound of formula (I)

prising reacting 2-(5-R⁵- imidazol-1-yl-acetonitrile

with a compound of formula (III)

and a compound of formula (IV)

X=C=Y (IV)

in the presence of a base, wherein X, Y, R , R², R³ and R⁴ are as defined as in any of the claims 1 to 9 and Hal is halogen.

14. A process for the preparation of a compound of formula (I)

(I)

comprising reacting 2-(5-R - imidazol-1-yl-acetonitrile

with a compound of formula (XI)

and a compound of formula (IV)

X=C=Y (IV)

in the presence of a base, wherein X, Y, R , R², R³ and R⁴ are as defined as in any of the claims 1 to 9 and Hal is halogen and R⁸ is a sulfonyl group.