WO2017186616A1 - Microbiocidal imidazole derivatives - Google Patents

Abstract

Compounds of the formula (I) wherein the substituents are as defined in claim 1, are useful as a pesticides especially fungicide.

Description

MICROBICIDAL IMIDAZOLE DERIVATIVES

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

wherein,

R¹, R², R³, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are independently hydrogen, halogen, cyano, Ci-C₆alkyl, Ci-C6haloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy, C3-C_cycIoalkyl, aryl, aryloxy, heteraryl or heteroaryloxy, wherein aryl, aryloxy, heteroaryl and heteroaryloxy are optionally substituted with 1 to 3 groups represented by R¹², and under the condition that not both of R³ and R¹¹ are hydrogen at the same time;

X is CR¹¹ or N;

R⁴ and R⁵ are independently hydrogen, Ci-C6alkyl or Ci-C6haloalkyl;

R¹² is independently selected from halogen, cyano, hydroxyl, Ci-C6alkyl, Ci-C6haloalkyl, Ci- Ceaikoxy, Ci-C6haloalkoxy, Ci-C6alkylthio, Ci-Cehaloalkylthio, C3-C8cycloalkyl, C3-Cecycloalkoxy or C3- Cshalocycloalkyl;

or a salt or an N-oxide thereof.

As used herein, the term "halogen" refers to fluorine, chlorine, bromine or iodine.

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

As used herein, the term "hydroxyl" or "hydroxy" stands for a -OH group.

As used herein, the term "Ci-C6alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of Ci- CealkyI include, but are not limited to, 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.

As used herein, the term "Ci-C6haloalkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon, hydrogen and halogen atoms, containing no unsaturation, having from one to six carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of Ci-Cehaloalkyl include, but are not limited to, CH₂CI, CHC , CC , CH2F, CHF2, CF₃, CF3CH2, CH3CF2, CF3CF2 or CCI3CCI2. As used herein, the term "d-Cealkoxy" refers to a radical of the formula -OR_a where R_a is a Ci- Cealkyl radical as generally defined above. Examples of C-i-Ce alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (iso-propoxy), propoxy, butoxy, 1-methylpropoxy and 2- methylpropoxy.

As used herein, the term "Ci-C6haloalkoxy" refers to a radical of the formula -OR_a where R_a is a

C1-C6 haloalkyl radical as generally defined above. Examples of C1-C6 alkoxy include, but are not limited to, CHaCIO, CHCI2O, CC O, CH2FO, CHF2O-, CF3O-, CF3CH2O-, CH3CF2O, CF3CF2O- or CCI3CCI2O-

As used herein, the term "Ci-Cealkylthio" refers to a radical of the formula -SR_a where R_a is a Ci- CealkyI radical as generally defined above. Examples of Ci-C6alkylthio include, but are not limited to, methylthio, ethylthio, propylthio or butylthio.

As used herein, the term "Ci-C6haloalkylthio" refers to a radical of the formula -SR_a where R_a is a C1-C6 haloalkyl radical as generally defined above. Examples of Ci-Cehaloalkyithio include, but are not limited to, CH2CIS, CHCI2S, CC S, CH2FS, CHF2S-, CF3S-, CF3CH2S-, CH3CF2S, CF3CF2S- or

As used herein, the term "Cs-Cecycloalkyl" refers to a radical which is a mono- or bicyclic saturated ring system and which contains 3 to 8 carbon atoms. Examples of C3-Cgcycloalkyl include, but are not limited to, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, cycloheptyl, cyclooctyl or norbornyl.

As used herein, the term "Cs-Cscycloalkoxy" refers to a radical of the formula -OR_a where R_a is a

C3-Cgcycloalkyl radical as generally defined above. Examples of C3-Ci>cycloalkoxy include, but are not limited to, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy or cycloheptyloxy.

As used herein, the term "Cs-Cehalocycloalkyl" refers to a radical which is a mono- or bicyclic saturated ring system and which contains 3 to 8 carbon atoms. Examples of C3-C9cycloalkyl include, but are not limited to, 2-cfilorocyclopropyl, 2,2-dichlorocyclopropyl, 2-fluorocyclopropyl, 2- chlorocyclobutyl or 2,2-dichlorocyclobutyl.

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

As used herein, the term "aryloxy" refers to a radical of the formula -OR_a where R_a is an aryl radical as generally defined above. Aryloxy groups include, but are not limited to, phenoxy.

As used herein, the term "heteroaryl" refers to an aromatic heterocyclic ring system, 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 may 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 may 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, cinnoiinyl and naphthyridinyl. Heteroaryl rings do not contain adjacent oxygen ring atoms, adjacent sulfur ring atoms or adjacent oxygen and sulfur ring atoms.

As used herein, the term "heteroaryloxy" refers to a radical of the formula -OR_a where R_a is a heteroaryl radical as generally defined above.

The presence of an acyclic C-N double bond in the compounds of formula I means that they may occur as E-isomer, as Z-isomer or as mixture of E and Z isomers. Also enantiomers may occur as a result of the presence of a possible asymmetric carbon atom. Furthermore 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, enantiomers, diastereomers and atropisomers, and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof 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 following list provides definitions, including preferred definitions, for substituents R , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R ⁰, R¹ , R¹² and X with reference to compounds of formula I. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.

Preferably R¹, R², R³, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, halogen, Ci-C₆alkyl or Ci- Cehaloalkyl; more preferably hydrogen, halogen or Ci-C6haloalkyl; even more preferably hydrogen or halogen.

Preferably X is C-H, C-F, C-CI, C-CFs or N; more preferably C-H, C-CI or N; even more preferably C- Cl or N. In a further preferred embodiment X is C-F, C-CI, C-CF3 or N; more preferably X is C-F, C-CI,

Preferably R⁴ and R⁵ are independently hydrogen or Ci-C6alkyl; more preferably hydrogen or methyl; even more preferably hydrogen.

Preferably R¹² is halogen, cyano, Ci-Csalkyl, Ci-Cehaloalkyl, Ci-Cealkoxy, Ci-Cehaloalkoxy, Ci-

Cealkylthio or Cs-Cecycloalkyl; more preferably halogen, Ci-C6alkyl, Ci-C6haloalkyl, Ci-C6alkoxy or C3- Cecycloalkyl; even more preferably halogen, Ci-Cehaloalkyl or Ci-C6alkoxy; even more preferably R ² is halogen. Preferably R¹, R², R³, R⁶, R⁷, R⁸, R⁹and R ⁰ are independently hydrogen, halogen, Ci-C₆alkyl or Ci- Cehaloalkyl;

X is C-H, C-F, C-CI, C-CF3 or N; and

R⁴ and R⁵ are independently hydrogen or Ci-Cealkyl. More preferably R¹, R², R³, R⁶, R⁷, R⁸, R⁹and R¹⁰ are independently hydrogen, halogen, Ci-C6alkyl or Ci-C6haloalkyl, Ci-Cealkoxy; X is C-H, C-F, C-CI, C-CFs or N; and

R⁴ and R⁵ are independently hydrogen or Ci-C6alkyl.

Even ore preferably R¹, R², R³, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, halogen or Ci- C6haloalkyl;

X is C-H, C-CI or N; and

R⁴ and R⁵ are independently hydrogen or methyl.

Further more preferably R¹, R², R³, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen or halogen; X is C-CI or N;

R⁴ and R⁵ are independently hydrogen.

In one embodiment X is C-H, C-F, C-CI, C-CF₃; preferably X is C-F, C-CI, C-CF₃. In an other embodiment X is N.

In one preferred embodiment R¹, R², R³, R⁶, R⁷, R⁸, R⁹and R ⁰ are independently hydrogen, halogen, Ci-Cealkyl or Ci-Cehaloalkyl; X is C-F, C-CI, C-CF3; and R⁴ and R⁵ are independently hydrogen or Ci- Cealkyl.

In a further preferred embodiment R¹, R², R³, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, halogen or Ci-C6haloalkyl; X is C-H, C-CI; and R⁴ and R⁵ are independently hydrogen or methyl. In a further preferred embodiment R¹, R², R³, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen or halogen; X is C-CI; and R⁴ and R⁵ are independently hydrogen. In one preferred embodiment X is C- R¹¹ or N; R¹ and R² are both H; R³ is H, halogen, Ci-C4alkyl or Ci-C₄haloalkyl; R⁴ is H or Ci-C₄alkyl; R⁵ is H or Ci-C₄alkyl; R⁶, R⁷, R⁹and R¹⁰ are independently H, halogen, Ci-C₄alkyl, Ci-C haloalkyl or Ci-C₄alkoxy; and R¹¹ is H, halogen, Ci-C4alkyl or Ci-C₄haloalkyl.

In another preferred embodiment X is C-F, C-CI, C-Br, C-CH3, C-CF3, C-H or N; R¹ and R² are both H; R³ is H, F, CI, Br, Ci-C₄alkyl or Ci-C₄haloalkyl; R⁴ is H or Ci-C₄alkyl; R⁵ is H or Ci-C₄alkyl; and R⁶, R⁷, R⁹and R ⁰ are independently H, F, CI, Ci-C₄alkyl, Ci-C₄haloalkyl or Ci-C₄alkoxy.

In another preferred embodiment X is C-F, C-CI, C-Br, C-CHa, C-CF3, C-H or N; R¹ and R² are both H; R³ is H, F, CI, Br, Ci-C₄alkyl or Ci-C4haloalkyl; R⁴ is H or Ci-C₄alkyl; R⁵ is H or Ci-C4alkyl; R⁶ and R⁷ are both H; R⁸ is H, F, CI, Ci-C4alkyl, Ci-C₄haloalkyl or Ci-C4alkoxy, R⁹ is H,or CI; and R ⁰ is F, CI, Ci- C alkyl, Ci-C₄haloalkyl or Ci-C4alkoxy.

In another preferred embodiment X is C-F, C-CI, C-Br, C-CH₃, C-CF₃, C-H or N; R¹ and R² are both H; R³ is H, F, CI, Br, CH₃ or CF₃; R⁴ is H or CH₃; R⁵ is H or CH₃; R⁶ and R⁷ are both H; R⁸ is H, F, CI, CH_3> CF₃ or OCH3, R⁹ is H,or CI; and R¹⁰ is F, CI, CH₃, CF₃ or OCH₃.

In another preferred embodiment X is C-F, C-CI, C-Br, C-CH₃, C-CF₃, C-H or N; R¹ and R² are both H; R³ is H, F, CI, Br, CH₃ or CF₃; R⁴ is H or CH₃; R⁵ is H or CH₃; R⁶ is H; R⁷ is H; R⁸ is H, F, CI, CH₃, CF₃ or OCHs, R⁹ is H,or CI; and R¹⁰ is F, CI, CH₃, CF₃ or OCH₃. Preferred individual compounds are:

N (5-chloro-3-fluoro-2-pyridyl)methoxy]-1-(2,4-difluorophenyl)-2-imidazol-1-yl-ethanimine;

N-[(3,5-dichloro-2-pyridyl)methoxy]-1-(2^-difluorophenyl)-2-imidazol-1-yl-ethanimine; 1-(4-chloro-2-fluoro-phenyl)-N-[(5-chloro-3-fluoro 1 -(2-chloro-4-fluoro-phenyl)-N-[(5-chloro-3-fluoro-2-pyridyl)methoxy]-2-imidazol-1 -yl-ethanimine; 1-(2-chloro-4-fluoro-phenyl)-N-[(3,5-dichloro-2-pyridyl)methoxy]-2-imidazol-1-yl-ethanimine; 1-(4-chloro-2-fluoro-phenyl)-N-[(3,5-dichloro-2-pyridyl)methoxy]-2-imidazol-1 -yl-ethanimine;

N-[(5-chloro-3-fluoro-2-pyridyl)methoxy]-1 -(2, 4-dichlorophenyl)-2-imidazol-1 -yl-ethanimine; 1-(2,4-dichlorophenyl)-N-[(3,5-dichloro-2-pyridyl)methoxy]-2-imidazol-1-yl-ethanimine. The invention also relates to compounds of formula 1-1 :

in which R¹, R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ have the definitions as described for formula I. Preferred definitions of R¹, R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are as defined for formula I.

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

wherein R , R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ have the definition as described for formula I.

Preferred definitions of R\ R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are as defined for formula I.

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

wherein R¹, R², R³, R⁶, R⁷, R⁸, R⁹, R¹⁰ and X have the definition as described for formula I. Preferred definitions of R¹, R², R³, R⁶, R⁷, R⁸, R⁹, R¹⁰ and X are as defined for formula I.

The invention also relates to com ounds of formula I-4:

wherein R¹, R², R³, R⁴, R⁵, R⁷, R⁹, R¹⁰ and X have the definition as described for formula I. Preferred definitions of R¹, R², R³, R⁴, R⁵, R⁷, R⁹, R ⁰ and X are as defined for formula I.

Further preferred embodiments of the present invention are the embodiments E-I.a to E-I.ac, 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 (l.ac) as described below, wherein in formulae (I. a) to (l.ac) the meanings of the substituents X, R¹, R², R³, R⁴ and R⁵ have the preferred meanings as mentioned above or one of the meanings 1 to 120 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, R¹, R³, R², R⁴ and R⁵ have the meanings as defined above or one of the meanings 1 to 120 given in the Table 1.

Embodiments E-I.b to E-I.ac are defined accordingly and the substituents X, R¹, R², R³, R⁴ and R⁵ have the meanings as definded above or one of the meanings 1 to 120 given in the corresponding Table 1.

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 R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and X are as defined for formula I, can be obtained by transformation of a compound of formula II, wherein R¹ , R², R³, R⁴, R⁵ and X are as defined for formula I and R¹³ is halogen, such as chlorine or bromine, or a sulfonate, such as a mesylate, and a compound of formula III, wherein R⁶, R⁷, R⁸, R⁹ and R¹⁰ are as defined for formula I, with a base, such as sodium hydroxide, sodium hydride, or potassium carbonate. This is shown in Scheme 1.

The compounds of formula II, wherein R¹, R², R³, R⁴, R⁵ and X are as defined for formula I and

R¹³ is halogen, such as chlorine or bromine, or a sulfonate, such as a mesylate, can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴, R⁵ and X are as defined for formula I, with a halogenation reagent, such as phosphorus oxychloride, phosphorus oxybromide, thionyl chloride or thionyl bromide, or a sulfonyl chloride, such as methanesulfonylchloride. This is shown in Scheme 2.

Scheme 2

The compounds of formula III, wherein R⁶, R⁷, R⁸, R⁹ and R¹⁰ are as defined for formula I, can be obtained by transformation of a compound of formula V, wherein R⁶, R⁷, R⁸, R⁹ and R¹⁰ are as defined for formula I, with hydroxylamine hydrochloride. This is shown in Scheme 3.

The compounds of formula V wherein R⁶, R⁷, R⁸, R⁹ and R¹⁰ are as defined for formula I, can be obtained by transformation of a compound of formula VI, wherein R⁶, R⁷, R⁸, R⁹ and R¹⁰ are as defined for formula I and R¹³ is halogen, such as chlorine or bromine, or a sulfonate, such as a mesylate, with imidazole. This is shown in Scheme 4.

Alternatively, the compounds of formula I, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and X are as defined for formula I, can be obtained by transformation of a compound of formula VII, wherein R¹, R², R³, R⁴, R⁵ and X are as defined for formula I, and a compound of formula V, wherein R⁶, R⁷, R⁸, R⁹ and R¹⁰ are as defined for formula I, with an acid or a base. This is shown in Scheme 5.

Scheme 5

The compounds of formula VII, wherein R¹, R², R³, R⁴, R⁵ and X are as defined for formula I, can be obtained by transformation of a compound of formula VIII, wherein R¹, R², R³, R⁴, R⁵ and X are as defined for formula I, with a hydrazine derivative. This is shown in Scheme 6.

The compounds of formula VIII, wherein R¹, R², R³, R⁴, R⁵ and X are as defined for formula I, can be obtained by transformation of a compound of formula IV, wherein R¹, R², R³, R⁴, R⁵ and X are as defined for formula I, with phthalimide and an organophosphine, such as triphenylphosphine or tributylphosphine. This is shown in Scheme 7.

Scheme 7

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, Diaporthaies 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 yaap/7, 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, 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 VerticiHium 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, pyrazolones, 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 Ί" 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-met oxy-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, 1 + 1- methylcyclopropene, I + 2-methyl-[[4-methoxy-2-[[[(3S,7f?,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- difIuorophenyl)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-methyt-pyrazole-4-carboxamide I + diclocymet, l + 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, I + 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, I +

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), I + 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 + fiuazinam, I + fiudioxonii, I + flufenoxystrobin, I + flumetraiin, I + flumorph, I + fluopicolide, I + fluopicolide (flupicolide), I + fluopyram, I + fluoroimide, I +

fluoxastrobin, I + fluquinconazole, I + flusilazole, I + flusulfamide, I + flutianil, I + flutolanil, I + flutriafol, I + fluxapyroxad, I + folpet, I + forchlorfenuron, I + fosetyl, I + fuberidazole, I + 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, I + 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, I + pyraoxystrobin, I + pyrazophos, I + pyribencarb (KIF-7767), I + pyrifenox, I + pyrimethanil, I + pyriofenone (I F-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 + tiadinii, 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 + a-naphthalene 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, 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 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, cyciohexanol, 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, W,W-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, /7-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 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 C12-C18 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.

a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

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. Dusts a) b) c)

Active ingredients 5 % 6 % 4 %

Talcum 95 % - -

Kaolin - 94 % - mineral filler - - 96 %

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

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

active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 %

Tristyrenephenole with 10-20 moles EO 2 %

1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 %

Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 %

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.

5 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

10 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.

15 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, 0.4 ppm, 0.2 ppm, 0.1 ppm or even at lower concentrations (e.g. 0.04 and 0.008

20 ppm or even lower) and any concentration in between the mentioned concentrations.

Example 1 : This example illustrates the preparation of N-[(5-bromo-2-pyridyl)methoxy]-1-(2,4- dichlorophenyl)-2-imidazol-1-yl-ethanimine (compound I.0.3)

25

a) Preparation of 1-(2,4-dichlorophenyl)-2-imidazol-1-yl-ethanone oxime

A solution of hydroxylamine hydrochloride (3.8 g, 54 mmol) in 4 ml of 35 % aqueous sodium hydroxide was added at room temperature to a mixture of 1-(2,4-dichlorophenyl)-2-imidazol-1-yl- ethanone (9.1 g, 36 mmol, known from Chapman and Bauer, J. Heterocycl. Chem. 1990, 27, 2053) in 30 86 ml of ethanol. The reaction mixture was heated to reflux for 4 h. Subsequently the solvent was removed in vacuo and the remainder taken up in water. The soild which formed was filtered, washed with a small amount of ethanol and dried in high vacuum to deliver 1-(2,4-dichlorophenyl)-2-imidazol- 1-yl-ethanone oxime (4.7 g, 17 mmol) as a white solid. ¹H-N R (400 MHz, CDCb): δ = 5.29 (s, 2H), 6.71 (s, 1 H), 6.95 (s, 1 H), 7.30 (d, 1 H), 7.37 (d, 1 H), 7.50 (s, 1 H), 7.59 (s, 1 H), 12.11 (s, 1 H).

35

b) Preparation of N-[(5-bromo-2-pyridyl)methoxy]-1 -(2,4-dichlorophenyl)-2-imidazol-1 -yl-ethanimine (compound I.0.3)

1 ml of a 30 % aqueous sodium hydroxide solution, tetrabutylammonium bromide (60 mg, 0.18 mmol) and then 5-bromo-2-(chloromethyl)pyridine (0.5 g, 2.4 mmol, commercially available from 40 Aldrich)) were added sequentially at room temperature to a solution of 1-(2,4-dichlorophenyl)-2- imidazol-1-yl-ethanone oxime (0.5 g, 1.8 mmol) in 4 ml of dichloromethane. The reaction mixture was stirred for 2 h at 40 °C, then diluted with water and extracted with dichloromethane. The combined organic layer was washed with water, dried over sodium sulfate and evaporated, the residue purified by chromatography on silica gel (ethyl acetate/cyclohexane) to obtain N-[(5-bromo-2-pyridyl)methoxy]- 1-(2,4-dichlorophenyl)-2-imidazol-1-yl-ethanimine (compound 1.0.3, 0.45 g, 1.0 mmol) as yellow oil. ¹H- N R (400 MHz, CDC ): δ = 4.90 (s, 2H), 5.19 (s, 2H), 6.63 (d, 1 H), 6.81 (s, 1 H), 7.04 (s, 1 H), 7.14 - 7.21 (m, 2H), 7.31 (s, 1 H), 7.43 (s, 1 H), 7.80 (d, 1 H), 8.62 (s, 1 H).

Example 2: This example illustrates the preparation of N-[(3,5-dichloro-2-pyridyl)methoxy]-1-(2,4- difluorophenyl)-2-imidazol-1-yl-ethanimine (compound l.c.22) a) Preparation of 1-(2,4-difluorophenyl)-2-imidazol-1-yl-ethanone oxime

A solution of hydroxylamine hydrochloride (2.2 g, 31 mmol) in 2.5 ml of 35 % aqueous sodium hydroxide was added at room temperature to a mixture of 1-(2,4-difluorophenyl)-2-imidazol-1-yl- ethanone (4.6 g, 21 mmol, known from Chapman and Bauer, J. Heterocycl. Chem. 1990, 27, 2053) in 50 ml of ethanol. The reaction mixture was heated to reflux for 4 h. Subsequently the solvent was removed in vacuo and the remainder taken up in water. The soild which formed was filtered, washed with a small amount of ethanol and dried in high vacuum to deliver 1-(2,4-difluorophenyl)-2-imidazol-1- yl-ethanone oxime (4.1 g, 17 mmol) as a white solid. ¹H-NMR (400 MHz, CDCb): δ = 5.28 (s, 2H), 6.76 (s, 1H), 6.99 (s, 1 H), 7.05 - 7.22 (m, 2H), 7.44 - 7.53 (m, 2H), 12.22 (s, 1 H). b) Preparation of N-[(3,5-dichloro-2-pyridyl)methoxy]-1-(2,4-difluorophenyl)-2-imidazol-1-yl-ethanimine (compound l.c.22)

1 ml of a 30 % aqueous sodium hydroxide solution, tetrabutylammonium bromide (68 mg, 0.21 mmol) and then 3,5-dichloro-2-(chloromethyl)pyridine (0.45 g, 2.3 mmol, commercially available from Aldrich)) were added sequentially at room temperature to a solution of 1-(2,4-difluorophenyl)-2- imidazol-1-yl-ethanone oxime (0.5 g, 2.1 mmol) in 5 ml of dichloromethane. The reaction mixture was stirred for 2 h at 40 °C, then diluted with water and extracted with dichloromethane. The combined organic layer was washed with water, dried over sodium sulfate and evaporated, the residue purified by chromatography on silica gel (ethyl acetate/cyclohexane) to obtain N-[(3,5-dichloro-2- pyridyl)methoxy]-1-(2,4-difluorophenyl)-2-imidazol-1-yl-ethanimine (compound l.c.22, 0.41 g, 1.0 mmol) as yellow oil. ¹H-NMR (400 MHz, CDCb): δ = 5.28 (s, 2H), 5.51 (s, 2H), 6.77 - 6.86 (m, 3H), 6.92 (s, 1H), 7.23 - 7.28 (m, 1 H), 7.45 (s, 1 H), 7.80 (s, 1 H), 8.52 (s, 1 H). 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 R¹ R² R³ R⁴ R⁵ No.

1 C-F H H H H H

2 C-CI H H H H H

3 C-Br H H H H H

4 C-Chh H H H H H

5 C-CFa H H H H H

6 CH H H F H H

7 CH H H CI H H

8 CH H H Br H H

9 CH H H CH₃ H H

10 CH H H CF₃ H H

11 N H H F H H

12 N H H CI H H

13 N H H Br H H

14 N H H CH₃ H H

15 N H H CF₃ H H

16 C-F H H F H H

17 C-F H H CI H H

18 C-F H H Br H H

19 C-F H H CH₃ H H

20 C-F H H CF₃ H H

21 C-CI H H F H H

22 C-CI H H CI H H

23 C-CI H H Br H H

24 C-CI H H CH₃ H H

25 C-Ci H H CF₃ H H

26 C-Br H H F H H

27 C-Br H H CI H H

28 C-Br H H Br H H

29 C-Br H H CH₃ H H

30 C-Br H H CF₃ H H

31 C-CHs H H F H H

32 C-CHa H H CI H H

33 C-CHs H H Br H H

34 C-CH₃ H H CH₃ H H

35 C-CHs H H CF₃ H H

36 C-CFs H H F H H

37 C-CFs H H CI H H C-CFs H H Br H H

C-CFs H H CHs H H

C-CFs H H CFs H H

C-F H H H CHs H

C-CI H H H CHs H

C-Br H H H CHs H

C-CHs H H H CHs H

C-CFs H H H CHs H

CH H H F CHs H

CH H H CI CHs H

CH H H Br CHs H

CH H H CHs CHs H

CH H H CFs CHs H

N H H F CHs H

N H H CI CHs H

N H H Br CHs H

N H H CHs CHs H

N H H CFs CHs H

C-F H H F CHs H

C-F H H CI CHs H

C-F H H Br CHs H

C-F H H CHs CHs H

C-F H H CFs CHs H

C-CI H H F CHs H

C-CI H H CI CHs H

C-CI H H Br CHs H

C-CI H H CHs CHs H

C-CI H H CFs CHs H

C-Br H H F CHs H

C-Br H H CI CHs H

C-Br H H Br CHs H

C-Br H H CHs CHs H

C-Br H H CFs CHs H

C-CHs H H F CHs H

C-CHs H H CI CHs H

C-CHs H H Br CHs H

C-CHs H H CHs CHs H

C-CHs H H CFs CHs H

C-CFs H H F CHs H

C-CFs H H CI CHs H C-CFs H H Br CHs H

C-CFs H H CHs CHs H

C-CFs H H CFs CHs H

C-F H H H CHs CHs

C-CI H H H CHs CHs

C-Br H H H CHs CHs

C-CHs H H H CHs CHs

C-CFs H H H CHs CHs

CH H H F CHs CHs

CH H H CI CHs CHs

CH H H Br CHs CHs

CH H H CHs CHs CHs

CH H H CFs CHs CHs

N H H F CHs CHs

N H H CI CHs CHs

N H H Br CHs CHs

N H H CHs CHs CHs

N H H CFs CHs CHs

C-F H H F CHs CHs

C-F H H CI CHs CHs

C-F H H Br CHs CHs

C-F H H CHs CHs CHs

C-F H H CFs CHs CHs

C-CI H H F CHs CHs

C-CI H H CI CHs CHs

C-CI H H Br CHs CHs

C-CI H H CHs CHs CHs

C-CI H H CFs CHs CHs

C-Br H H F CHs CHs

C-Br H H CI CHs CHs

C-Br H H Br CHs CHs

C-Br H H CHs CHs CHs

C-Br H H CFs CHs CHs

C-CHs H H F CHs CHs

C-CHs H H CI CHs CHs

C-CHs H H Br CHs CHs

C-CHs H H CHs CHs CHs

C-CHs H H CFs CHs CHs

C-CFs H H F CHs CHs

C-CFs H H CI CHs CHs 118 C-CFs H H Br CH₃ CH₃

119 C-CFa H H CH₃ CH₃ CH₃

120 C-CFs H H CF₃ CH₃ CH₃ where

a 120 compounds of formula (I. a):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. b) 120 compounds of formula (l.b):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. c) 120 compounds of formula (l.c):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. d) 120 compounds of formula (l.d):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. e) 120 compounds of formula (l.e):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. f) 120 compounds of formula (l.f):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. g) 120 com ounds of formula (l.g):

Wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1 h) 120 compounds of formula (l.h):

wherein X, Y, R\ R², R⁴ and R⁵ are as defined in Table 1. i) 120 compounds of formula (l.i):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. j) 120 compounds of formula (l.j):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. k 120 compounds of formula (l.k):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. m 120 compounds of formula (l.m):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. n) 120 compounds of formula (l.n):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. o 120 compounds of formula (l.o):

(l.o)

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. p) 120 compounds of formula (l.p):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. q 120 compounds of formula (l.q):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. r 120 compounds of formula (l.r):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. s) 120 compounds of formula (l.s):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. t) 120 compounds of formula (l.t):

wherein X, Y, R , R², R⁴ and R⁵ are as defined in Table 1. u) 120 compounds of formula (l.u):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. v 120 compounds of formula (l.v):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. w 120 compounds of formula (l.w):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. x) 120 compounds of formula (l.x):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. y 120 compounds of formula (l.y):

wherein X, Y, R¹, R², R⁴ and R⁵ are as defined in Table 1. z 120 compounds of formula (l.z):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in Table 1. aa 120 compounds of formula (l.aa):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in Table 1.

120 compounds of formula (l.ab):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in Table 1. ac) 120 compounds of formula (l.ac):

wherein X, Y, R¹ , R², R⁴ and R⁵ are as defined in 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 pm particle 5 size, 110 Angstrom, 30 x 3 mm column, 1.7mL/min., 60 °C, H₂0 + 0.05% HCOOH (95%) /

CHsCN/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) 10 700)).

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

Compound No. Melting point (°C) LC/MS

I.a.37 Rt = 1.16 min; MS: m/z = 413 (M+1)

l.b.37 Rt = 1.17 min; MS: m/z = 413 (M+1)

I.C.22 Rt = 1.07 min; MS: m/z = 397 (M+1 )

l.c.37 Rt = 0.79 min; MS: m/z = 431 (M+1)

l.d.3 Rt = 1.07 min; MS: m/z = 423 (M+1)

l.d.21 Rt = 1.11 min; MS: m/z = 397 (M+1)

l.d.22 Rt = 1.16 min; MS: m/z = 413 (M+1)

l.d.37 Rt = 1.31 min; MS: m/z = 447 (M+1)

l.h.3 Rt = 0.73 min; MS: m/z = 423 (M+1)

l.h.21 90 - 100

l.h.22 Rt = 0.76 min; MS: m/z = 413 (M+1)

l.h.37 Rt = 0.81 min; MS: m/z = 447 (M+1)

l.j.3 Rt = 1.13 min; MS: m/z = 457 (M+1 )

l.j.21 Rt = 1.14 min; MS: m/z = 431 (M+1)

l.j.22 Rt = 1.22 min; MS: m/z = 447 (M+1 )

l.j.37 Rt = 1.23 min; MS: m/z = 481 (M+1 )

l.m.22 Rt = 1.13 min; MS: m/z = 395 (M+1)

l.m.37 Rt = 0.77 min; MS: m/z = 429 (M+1)

l.n.22 Rt = 1.09 min; MS: m/z = 395 (M+1 )

l.n.37 Rt = 1.32 min; MS: m/z = 429 (M+1 )

I.0.3 Rt = 1.18 min; MS: m/z = 439 (M+1)

1.0.21 Rt = 1.09 min; MS: m/z = 413 (M+1 ) Compound No. Melting point (°C) LC/MS

1.0.22 Rt = 1.23 min; MS: m/z = 429 (M+1 )

1.0.37 Rt = 1.33 min; MS: m/z = 463 (M+1 )

l.q.3 Rt = 1.16 min; MS: m/z = 473 (M+1 )

l.q.21 Rt = 1.22 min; MS: m/z = 447 (M+1 )

l.q.22 Rt = 1.24 min; MS: m/z = 463 (M+1 )

l.aa.21 Rt = 1.1 1 min; MS: m/z = 373 (M+1)

l.aa.22 Rt = 1.17 min; MS: m/z = 389 (M+1 )

l.ab.21 98 - 99

l.ab.22 Rt = 0.91 min; MS: m/z = 429 (M+1)

l.ac.22 Rt = 0.80 min; MS: m/z = 395 (M+1 )

l.ac.37 Rt = 0.88 min; MS: m/z = 429 (M+1 )

Biological examples

Alternaria solani I tomato / leaf disc (early blight)

Tomato leaf disks cv. Baby are placed on agar in multiweil plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf disks are incubated at 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 is 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 l.c.22, l.d.21 , l.h.22 and 1.0.21 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development. Blumeria praminis f. sp. tritici (Ervsiphe araminis f. sp. tritici) I wheat / leaf disc preventative (Powdery mildew on wheat)

Wheat leaf segments cv. Kanzler are placed on agar in a multiweil plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks are incubated at 20°C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is 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.c.22, l.d.3, l.d.21 , l.d.22, l.h.22, l.m.22, l.n.22, 1.0.3, 1.0.21 , 1.0.22, l.ab.22 and l.ac.22 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development. Botryotinia fuckeliana (Botrytis cinerea) I liquid culture (Gray mould)

Conidia of the fungus from cryogenic storage are 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 are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application.

Compounds l.c.22, l.d.3, l.d.21 , l.d.22, l.h.22, l.m.22, l.n.22, I.0.3, 1.0.21 , I.0.22, l.ab.22 and l.ac.37 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development. Fusarium culmorum I liquid culture (Head blight)

Conidia of the fungus from cryogenic storage are 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 are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application.

Compounds l.c.22, l.d.22, l.h.22, l.m.22, 1.0.21 and I.0.22 at 200 ppm gives at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

Gaeumannomyces praminis 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 are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.

Compounds l.c.22, l.d.21 , l.d.22, l.h.22, l.m.22, I.0.3, 1.0.21 and I.0.22 at 200 ppm gives at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

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

Conidia of the fungus from cryogenic storage are 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 are incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.

Compounds l.c.22, l.d.21 , l.d.22, l.h.22, l.m.22, l.n.22, 1.0.21 and 1.0.22 at 200 ppm gives at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

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

Rice leaf segments cv. Ballila are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are 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 is 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).

Compound l.d.22 at 200 ppm gives at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

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

Conidia of the fungus from cryogenic storage are 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 are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.

Compounds l.c.22, l.d.21 , l.d.22, l.h.22, l.m.22, 1.0.21 , Lo.22, l.ab.22 and l.ac.22 at 200 ppm gives at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

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

Conidia of the fungus from cryogenic storage are 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 are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.

Compounds l.c.22, l.d.3, l.d.21 , l.d.22, l.h.22, l.m.22, l.n.22, 1.0.3, 1.0.21 , Lo.22, l.ac.22 and l.ac.37 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development. Mycosphaerella graminicola (Septoria tritici) I liquid culture (Septoria blotch)

Conidia of the fungus from cryogenic storage are 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 are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.

Compounds l.c.22, l.d.3, l.d.21 , l.d.22, l.h.22, l.m.22, l.n.22, I.0.3, 1.0.21 , 1.0.22, l.ab.21 and l.ac.22 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

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

Barley leaf segments cv. Hasso are placed on agar in a muitiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segmens are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are 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 is 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.c.22, l.d.3, l.d.21 , l.d.22, l.h.22, l.m.22, l.n.22, 1.0.21 , I.0.22, l.ab.22, l.ac.22 and l.ac.37 at 200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show 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 are 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 are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application.

Compounds l.c.22, l.d.3, l.d.21 , l.d.22, l.h.22, l.m.22, l.n.22, I.0.3, 1.0.21 , I.0.22 and l.ac.22 at

200 ppm give at least 80% disease control in this test when compared to untreated control leaf disks under the same conditions, which show extensive disease development.

Claims

Claims:

1. A compound of formula (I):

R¹, R², R³, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are independently hydrogen, halogen, cyano, Ci-Cealkyl, Ci-C6haloalkyl, C3-Cgcycloalkyl, Ci-C6alkoxy, Ci-C6haloalkoxy, aryl, aryloxy, heteraryl or heteroaryloxy, wherein aryl, aryloxy, heteroaryl and heteroaryloxy are optionally substituted with 1 to 3 groups represented by R¹², and under the condition that not both of R³ and R¹¹ are hydrogen at the same time;

X is CR¹ or N;

R⁴ and R⁵ are independently hydrogen, Ci-Cealkyl or Ci-C6haloalkyl;

R ² is independently selected from halogen, cyano, hydroxyl, Ci-C6alkyl, Ci-C6haloalkyl, Ci- C6alkoxy, Ci-C6haloalkoxy, Ci-Cealkylthio, Ci-Cehaloalkylthio, C3-Cgcycloalkyl, C3-Cgcycloalkoxy or C3- C9cycloalkylthio;

or a salt or an N-oxide thereof.

2. A compound of formula (I) according to claim 1 wherein R¹, R², R³, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are independently hydrogen, halogen, Ci-C6alkyl or Ci-C6haloalkyl.

3. The compound according to claim 1 , wherein X is C-H, C-F, C-CI, C-CF3.

4. The compound according to claim 1 , wherein X is N

5. The compound according to any one of claims 1 to 4, wherein R⁴ and R⁵ are independently hydrogen or Ci-C6alkyl.

6. The compound according to any one of claims 1 to 5, wherein R⁴ and R⁵ are both hydrogen.

7. The compound according to any one of claims 1 to 6, wherein X is C-F, C-CI, C-CF3.

8. The compound according to any one of claims 1 to 7, wherein

R¹, R², R³, R⁶, R⁷, R⁸, R⁹and R¹⁰ are independently hydrogen, halogen, Ci-Cealkyl or Ci-Cehaloalkyl; X is C-F, C-CI, C-CF₃; and

R⁴ and R⁵ are independently hydrogen or Ci-C6alkyl

9. The compound according to any one of claims 1 to 7, wherein

R¹, R², R³, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen, halogen or Ci-Cehaloalkyl;

X is C-H, C-CI; and

R⁴ and R⁵ are independently hydrogen or methyl.

10. The compound according to any one of claims 1 to 7, wherein

R¹, R², R³, R⁶, R⁷, R⁸, R⁹ and R ⁰ are independently hydrogen or halogen;

X is C-CI; and

R⁴ and R⁵ are independently hydrogen.

11. An agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to any one of claims 1 to 10.

12. The composition according to claim 11 , further comprising at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.

13. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) according to any of claims 1 to 10, or a composition comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.

14. Use of a compound of formula (I) according to any one of claims 1 to 10 or a composition according to claim 12 or claim 13, as a fungicide.