WO2009024342A2

WO2009024342A2 - Novel microbiocides

Info

Publication number: WO2009024342A2
Application number: PCT/EP2008/006869
Authority: WO
Inventors: Daniel Stierli; Harald Walter; Hans Tobler
Original assignee: Syngenta Participations AG
Current assignee: Syngenta Participations AG
Priority date: 2007-08-23
Filing date: 2008-08-21
Publication date: 2009-02-26
Anticipated expiration: 2010-02-23
Also published as: WO2009024342A3

Abstract

Compounds of the formula I in which the substituents are as defined in claim 1, are suitable for use as microbiocides.

Description

Novel Microbiocides

The present invention relates to novel microbiocidally active, in particular fungicidally active, pyrazole-4-carboxylic acid amides, which are at least di-substituted at the methylene group. It further relates to intermediates used in the preparation of these compounds, to compositions which comprise these compounds and to their use in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

Herbicidally active carboxamides which are substituted at the nitrogen atom by a benzyl group and at the carbonyl group by a pyridyl, pyrazolyl or thiazolyl group are described in WO 2005/070889. N-cycloalkyl-benzyl-amide derivatives are disclosed in WO 2007/087906.

It has been found that novel pyrazole-4-carboxylic acid amides have microbiocidal activity.

The present invention accordingly relates to compounds of formula I

wherein

Ri is C₁-C₄SIkYl;

R₂ is CrC₄haloalkyl;

R₃ is d-Cβalkyl, C_rC₆haloalkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-

C₆alkynyl or C₂-C₆haloalkynyl;

R₄ is hydrogen, CτC₆alkyl, Ci-C₆haloalkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,

C₂-C₆alkynyl or C₂-C₆ haloalkynyl; or R₃ and R₄ together are a C₂-C₅alkylene group, which is can be mono- or polysubstituted by Ci-C₆alkyl;

B is phenyl, naphthyl or a 5 to 10-membered monocyclic- or fused bicyclic heteroaromatic ring system containing one to three heteroatoms, each heteroatom is independently selected from oxygen, nitrogen and sulphur, wherein the phenyl group is mono- or polysubstituted by substituents selected from R₅; and wherein the naphthyl or 5 to 10-membered monocyclic- or fused bicyclic heteroaromatic ring system can be mono- or polysubstituted by substituents selected from R₅; it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; each substituent R₅ independently of each other, is halogen, d-Cehaloalkoxy, C₁-

C₆haloalkylthio, cyano, nitro or -C(R^a)=N(OR^b); or is

CrC₆alkyl, which can be mono- or polysubstituted by R₆;

C₃-C₆cycloalkyl, which can be mono- or polysubstituted by R₆;

C₆-C₁₄bicycloalkyl, which can be mono- or polysubstituted by R₆;

C₂-C₆alkenyl, which can be mono- or polysubstituted by R₆;

C₂-C₆alkynyl, which can be mono- or polysubstituted by R₆; phenyl, which can be mono- or polysubstituted by R₆; or phenoxy, which can be mono- or polysubstituted by R₆; each R₆ independently of each other, is halogen, nitro, C₃-C₆cycloalkyl, CrC₆alkoxy, C₁-

C₆haloalkoxy, CrC₆alkylthio, CrCehaloalkylthio, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, phenyl, halophenyl or -C(R^c)=N(OR^d); each R^a and R^c independently of each other, is hydrogen or CrC₆alkyl; and each R^b and R^d independently of each other, is CrC₆alkyl;

R₁₅ is hydrogen or C₃-C₇cycloalkyl; with the proviso that B is different from phenyl if R₁₅ is C₃-

C₇cycloalkyl; and agronomically acceptable salts/isomers/structural isomers/stereoisomers/diastereoisomers/enantio-mers/tautomers and N-oxides of those compounds.

The alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, /so-propyl, n-butyl, sec-butyl, /so-butyl or tert-butyl. Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned. The alkenyl and alkynyl groups can be mono- or di- unsaturated.

The cycloalkyl groups occuring in the definitions of the substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine. This also applies, correspondingly, to halogen in combination with other meanings, such as halogenalkyl or halogenalkoxy.

Haloalkyl groups preferably have a chain length of from 1 to 4 carbon atoms. Halonalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1-difluoro- 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy. Halogenalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1 ,1 ,2,2- tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2- trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxy methyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

Halophenyl is preferably phenyl substituted by 1 , 2 or 3 halogen atoms, for example 4- chloro-phenyl.

In the context of the present invention "mono- to polysubstituted" in the definition of the substituents, means typically, depending on the chemical structure of the substituents, monosubstituted to seven-times substituted, preferably monosubstituted to five-times substituted, more preferably mono-, double- or triple-substituted.

In the context of the present invention a "5 to 10-membered monocyclic- or fused bicyclic heterocyclic ring system containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur" is, depending of the number of ring members, for example, selected from the group consisting of pyrrolyl, pyridyl, pyrazolyl, pyrimidyl, pyrazinyl, imidazolyl, thiadiazolyl, quinazolinyl, furyl, oxadiazolyl, indolizinyl, pyranyl, isobenzofuranyl, thienyl, naphthyridinyl, (1-methyl-1 H-pyrazol-3-yl)-, (1-ethyl-1 H-pyrazol-3- yl)-, (1-propyl-1 H-pyrazol-3-yl)-, (1 H-pyrazol-3-yl)-, (1 ,5-dimethyl-1 H-pyrazol-3-yl)-, (4-chloro- 1 -methyl-1 H-pyrazol-3-yl)-, (1H-pyrazol-1-yl)-, (3-methyl-1H-pyrazol-1-yl)-, (3,5-dimethyl-1H- pyrazol-1-yl)-, (3-isoxazolyl)-, (5-methyl-3-isoxazolyl)-, (3-methyl-5-isoxazolyl)-, (5-isox- azolyl)-, (I H-pyrrol-2-yl)-, (1 -methyl-1 H-pyrrol-2-yl)-, (1 H-pyrrol-1-yl)-, ( 1 -methyl- 1 H-pyrrol-3- yl)-, (2-furanyl)-, (5-methyl-2-furanyl)-, (3-furanyl)-, (5-methyl-2-thienyl)-, (2-thienyl)-, (3- thienyl)-, (1 -methyl-1 H-imidazol-2-yl)-, (IH-imidazol-2-yl)-, (1 -methyl-1 H- imidazol-4-yl)-, (1- methyl-1 H-imidazol-5-yl)-, (4-methyl-2-oxazolyl)-, (5-methyl-2-oxazolyl)-, (2-oxazolyl)-, (2- methyl-5-oxazolyl)-, (2-methyl-4-oxazolyl)-, (4-methyl-2-thiazolyl)-, (5-methyl-2-thiazolyl)-, (2- thiazolyl)-, (2-methyl-5-thiazolyl)-, (2-methyl-4-thiazolyl)-, (3-methyl-4-isothiazolyl)-, (3- methyl-5-isothiazolyl)-, (5-methyl-3-isothiazolyl)-, (1 -methyl-1 H-1 , 2, 3-triazol-4-yl)-, (2-methyl- 2H-1 ,2,3-triazol-4-yl)-, (4-methyl-2H-1 ,2,3-triazol-2-yl)-, (1 -methyl-1 H-1 ,2,4-triazol-3-yl)-, (1 ,5- dimethyl-1 H-1 ,2,4-triazol-3-yl)-, (3-methyl-1 H-1 ,2,4-triazol-i-yl)-, (5-methyl-1 H-1 ,2,4-triazol- 1-yl)-, (4,5-dimethyl-4H-1 ,2,4-triazol-3-yl)-, (4-methyl-4H-1 ,2,4-triazol-3-yl)-, (4H-1 ,2,4-triazol- 4-yl)-, (5-methyl-1 ,2,3-oxadiazol-4-yl)-, (1 ,2,3-oxadiazol-4-yl)-, (3-methyl-1 ,2,4-oxadiazol-5- yl)-, (5-methyl-1 ,2,4-oxadiazol-3-yl)-, (4-methyl-3-furazanyl)-, (3-furazanyl)-, (5-methyl-1 ,2,4- oxadiazol-2-yl)-, (5-methyl-1 ,2,3-thiadiazol-4-yl)-, (1 ,2,3-thiadiazol-4-yl)-, (3-methyl-1 ,2,4- thiadiazol-5-yl)-, (5-methyl-1 ,2,4-thiadiazol-3-yl)-, (4-methyl-1 ,2,5-thiadiazol-3-yl)-, (5-methyl- 1 ,3,4-thiadiazol-2-yl)-, (1 -methyl-1 H-tetrazol-5-yl)-, (1 H-tetrazol-5-yl)-, (5-methyl-1 H-tetrazol- 1 -yl)-, (2-methyl-2H-tetrazol-5-yl)-, (2-ethyl-2H-tetrazol-5-yl)-, (5-methyl-2H-tetrazol-2-yl)-, (2H-tetrazol-2-yl)-, (2-pyridyl)-, (6-methyl-2-pyridyl)-, (4-pyridyl)-, (3-pyridyl)-, (6-methyl-3- pyridazinyl)-, (5-methyl-3-pyridazinyl)-, (3-pyridazinyl)-, (4,6-dimethyl-2-pyrimidinyl)-, (4- methyl-2-pyrimidinyl)-, (2-pyrimidinyl)-, (2-methyl-4-pyrimidinyl)-, (2-chloro-4-pyrimidinyl)-, (2,6-dimethyl-4-pyrimidinyl)-, (4-pyrimidinyl)-, (2-methyl-5-pyrimidinyl)-, (6-methyl-2-pyr- azinyl)-, (2-pyrazinyl)-, (4,6-dimethyl-1 ,3,5-triazin-2-yl)-, (4,6-dichloro-1 ,3,5-triazin-2-yl)-, (1 ,3,5-triazin-2-yl)-, (4-methyl-1 ,3,5-triazin-2-yl)-, (3-methyl-1 ,2,4-triazin-5-yl)-, (3-methyl- 1 ,2,4-triazin-6-yl)-, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, cinnolinyl and phthalazinyl, in particular selected from pyrazolyl (especially pyrazol-4-yl), thiazolyl (especially thiazol-5-yl), pyrrolyl (especially pyrrol-3-yl), 1 ,2,3 triazolyl, oxazolyl (especially oxazol-5-yl), pyridyl (especially pyrid-3-yl) and 2,3 dihydro-[1 ,4]oxathiinyl (especially 2,3 dihydro-[1 ,4]oxathiin-5-yl).

The compounds of formula I can occur in different isomeric forms; the invention covers all those isomers and mixtures thereof. The compounds of formula I may occur in different tautomeric forms. For example, compounds of formula I, wherein R₁₅ is hydrogen, exist in the tautomeric forms Ii and In:

The invention covers all those tautomeric forms and mixtures thereof.

Preferably, Ri₅ is hydrogen.

In preferred groups of compounds, a) R₁ is methyl; and/or b) R₂ is difluoromethyl; and/or c) R₃ is methyl; and/or d) R₄ is hydrogen.

In a preferred group of compounds of formula I, B is selected from the following groups B₁ to B₂^

^Ri2 R₁T-(N Λ"

wherein

Rio is in particular hydrogen, CrC₄alkyl, C_rC₄haloalkyl, halogen, C₂-C₆alkinyl, C₁-

C₄alkylamino, C_rC₄alkylcarbonyl, C_rC₄alkoxy or cyano, preferably chloro, trifluromethyl or methyl;

Rn is in particular hydrogen, C_rC₄alkyl, C_rC₄haloalkyl, halogen, C₂-C₆alkinyl, or phenyl substituted by halogen, preferably hydrogen, methyl or chloro;

R₁₂ is in particular hydrogen, -CHO, C_rC₄alkyl, C₂-C₄alkenyloxy, C₂-C₄haloalkenyloxy, C₁-

C₄alkylcarbonyl, C_rC₄haloalkyl, halogen, C₂-C₆alkinyl which may be mono- or disubstituted by substituents selected from CrC₄alkoxy and phenyl which phenyl group in turn may be substituted by halogen, or is phenyl substituted by halogen, or is phenoxy substituted by halogen or C_rC₄haloalkyl, or is pyridyloxy which may be mono- or di substituted by substituents selected from halogen and CrC₄haloalkyl, C₃-C₆cycloalkyl and C₂-

Cehaloalkenyloxy, or R₁₂ is a group -C(R^a)=N(OR^b), wherein R^a is C_rC₄alkyl and R^b is C₁-

C₄alkyl;

R₁₃ is in particular hydrogen, CrC₄alkyl, or halogen, preferably hydrogen; and Ri₄ is in particular hydrogen, CrC₄alkyl, or halogen, preferably hydrogen.

In especially preferred compound of formula I, B is B₁.

Compounds of formula I may be prepared by reacting a compound of formula Il

wherein B, R₃ , R₄ and R₁₅ are as defined under formula I, with a compound of formula III

in which R₁ and R₂ are defined under formula I, and R^* is halogen, hydroxy or C_1-6 alkoxy, preferably chloro, in the presence of a base, such as triethylamine, Hunig base, sodium bicarbonate, sodium carbonate, potassium carbonate, pyridine or quinoline, but preferably triethylamine, and in a solvent, such as diethylether, TBME, THF, dichloromethane, chloroform, DMF or NMP, for between 10 minutes and 48 hours, preferably 12 to 24 hours, and at temperatures between O⁰ C and reflux, preferably 20 to 25 ⁰C.

When R* is hydroxy, a coupling agent, such as benzotriazol-i-yloxytris(dimethylamino) phosphoniumhexafluorophosphate, bis-(2-oxo-3-oxazolidinyl)-phosphinic acid chloride (BOP- Cl), N.N'-dicyclohexylcarbodiimide (DCC) or 1 ,1 '-carbonyl-diimidazole (CDI), may be used.

Intermediates of the formula II, in which B, R₃ , R₄ and R₁₅ are as defined under formula I; may be prepared according to the following reaction schemes (schemes 1 to 4) or in analogy to those reaction schemes (shown for R₁₅ is hydrogen, compounds wherein R₁₅ is C₃- C₇cyclopropyl can be prepared analogously, see also Tetrahedron 57, (2001), 4507-4522).

Intermediates of formula Mb

R,

H₂N X (Hb), in which B and R₃ are as defined under formula commercially available or are readily prepared by numerous well known methods, several of which are described in schemes 1 to 3.

As shown in scheme 1 , compounds of formula Nb can be prepared from aldehyds by the method of Hart et al as described in J. Org. Chem. 1983, 48(3), 289-298. Lithium bis(trimethylsilyl)amide V, which can be prepared by treatment of 1 ,1 , 1 ,3,3,3- hexamethyldisilizane with a strong base such as lithium diisopropylamide or n-butyllithium, is reacted with an aldehyde of formula IV in a suitable solvent such as tetrahydrofuran or diethylether at temperatures ranging from -78°C to room temperature. The addition of a Grignard reagent of formula Vl then provides an amine of formula lib.

Scheme 1 :

As shown in scheme 2, amines of formula Nc or lid having a chiral center denoted by the asterisk (*) in formula Mc and Md can be prepared enantiomerically enriched with the depicted configuration by the reduction of chiral imines of formula VII using methods analogues to those described U.S. Patent Application Publication 2002/103400 or Organic Letters 2003, 5(7), 1007-1010.

Scheme 2:

Chiral

The chiral imine of formula VII comprises a chiral auxiliary group, which transfers chirality to the new chiral center created during reduction. The chiral auxiliary is chosen to provide the new center with the absolute configuration depicted for formula Mc. Examples of reducing agents useful for reducing the imine include sodium borohydride and lithium aluminium hydride. The chiral auxiliary is removed after the imine is reduced, either by reduction or hydrolysis depending on the choice of chiral auxiliary.

Alternatively as shown in scheme 3, a chiral enriched amine of formula Nc or Nd can be prepared by reducing an imine of formula VIII with one of the many chiral reducing agents known in the art. Such chiral reducing agents include enzymes (see, for example PCT Patent Application Publication WO 03/048151) and chiral complexes (see, for example J. Chem. Soc, Perkin Trans. 1, 1990, 7, 1859-1863 and X. Zhang et al. J. Org. Chem. 2003, 68, 4120-4122.

Scheme 3:

wherein R₂o is H, or groups such as OH, CrC₃ alkoxy, C(O)CH₃, SiMe₃ or optionally substituted phenyl.

Chiral amines of formula Mc can also be prepared by additional methods taught by L. Storace et al. in Organic Process Research & Development 2002, 54-63. Methods are well known in the art for separating pure enantiomers of chiral amines from enantiomerically enriched or even racemic mixtures. These methods include liquid chromatography on columns comprising a chiral support and recrystallization of salts of amines of formula Mb with chiral carboxylic acids such as tartaric acid.

Intermediates of formula Ne

H₂N^B <^lle) in which B is as defined under formula I may be prepared as described in reaction scheme 4.

Scheme 4: CH₃CH₂MgHaI

(IX)

(He)

Nitriles of formula IX can undergo a Ti-(I l)-mediated coupling with a Grignard-reagent of formula XXI, in which Hal stands for halogen, to afford the desired compounds of formula Nd. Reaction conditions for this reaction are described, for example, by P. Bertus and J. Szymoniak (J. Org. Chem., 2002, 67, 3965-3968) and in EP-1 -595-873.

The compounds of the formula III, wherein the substituents as described above, are known and partially commercially available. They can be prepared analogously as described, for example, in WO 00/09482 , WO 02/38542, WO 04/018438, EP-0-589-301 , WO 93/11117 and Arch. Pharm. Res. 2000, 23(4), 315-323.

For preparing all further compounds of formula I functionalized according to the definitions of B₁ R₁, R₂, R₃ , R₄, and R₁₅, there are a large number of suitable known standard methods, such as alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction. The choice of the preparation methods which are suitable are depending on the properties (reactivity) of the substituents in the intermediates.

The reactions to give compounds of formula I are advantageously carried out in aprotic inert organic solvents. Such solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as N,N-dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are advantageously between -2O⁰C and +120⁰C. In general, the reactions are slightly exothermic and, as a rule, they can be carried out at room temperature. To shorten the reaction time, or else to start the reaction, the mixture may be heated briefly to the boiling point of the reaction mixture. The reaction times can also be shortened by adding a few drops of base as reaction catalyst. Suitable bases are, in particular, tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5-diazabicyclo- [5.4.0]undec-7-ene. However, inorganic bases such as hydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g. sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, or hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate may also be used as bases. The bases can be used as such or else with catalytic amounts of a phase-transfer catalyst, for example a crown ether, in particular 18-crown-6, or a tetraalkylammonium salt.

The compounds of formula I can be isolated in the customary manner by concentrating and/or by evaporating the solvent and purified by recrystallization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.

The compounds I and, where appropriate, the tautomers thereof, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.

The compounds I and, where appropriate, the tautomers thereof, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.

It has now been found that the compounds of formula I according to the invention have, for practical purposes, a very advantageous spectrum of activities for protecting useful plants against diseases that are caused by phytopathogenic microorganisams, such as fungi, bacteria or viruses.

The invention relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula I is applied as acitve ingredient to the plants, to parts thereof or the locus thereof. The term "preventing infestation" as used herein means reducing the probability that a disease, infestation, or growth of a fungus, will be established in a plant. The compounds of formula I according to the invention are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous useful plants. The compounds of formula I can be used to inhibit or destroy the diseases that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.

It is also possible to use compounds of formula I as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.

Furthermore the compounds of formula I according to the invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage or in hygiene management.

The compounds of formula I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). Outstanding activity has been observed against powdery mildew (Erysiphe spp.). Furthermore, the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus). Good activity has been observed against Asian soybean rust (Phakopsora pachyrhizi).

Within the scope of the invention, useful plants to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

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

The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

The term "useful plants" is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-O 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-O 392 225, WO 95/33818, and EP-A-O 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. The term "locus" of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil. An example for such a locus is a field, on which crop plants are growing.

The term "plant propagation material" is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material" is understood to denote seeds.

The compounds of formula I can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation.

Therefore the invention also relates to compositions for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula I and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula I as acitve ingredient and an inert carrier, is applied to the plants, to parts thereof or the locus thereof.

To this end compounds of formula I and inert carriers are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects. Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.

The compounds of formula I or compositions, comprising a compound of formula I as acitve ingredient and an inert carrier, can be applied to the locus of the plant or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.

A preferred method of applying a compound of formula I, or a composition, comprising a compound of formula I as acitve ingredient and an inert carrier, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.

A formulation, i.e. a composition comprising the compound of formula I and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface-active compounds (surfactants).

The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1 % by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant. Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.

Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 1Og to 1 kg a.i./ha, most preferably from 2Og to 60Og a.i./ha. When used as seed drenching agent, convenient rates of application are from 10mg to 1g of active substance per kg of seeds. The rate of application for the desired action can be determined by experiments. It depends for example on the type of action, the developmental stage of the useful plant, and on the the application (location, timing, application method) and can, owing to these parameters, vary within wide limits.

Surprisingly, it has now been found that the compounds of formula I can also be used in methods of protecting crops of useful plants against attack by phytopathogenic organisms as well as the treatment of crops of useful plants infested by phytopathogenic organisms comprising administering a combination of glyphosate and at least one compound of formula I to the plant or locus thereof, wherein the plant is resistant or sensitive to glyphosate.

Said methods may provide unexpectedly improved control of diseases compared to using the compounds of formula I in the absence of glyphosate. Said methods may be effective at enhancing the control of disease by compounds of formula I. While the mixture of glyphosate and at least one compound of formula I may increase the disease spectrum controlled, at least in part, by the compound of formula I, an increase in the activity of the compound of formula I on disease species already known to be controlled to some degree by the compound of formula I can also be the effect observed.

Said methods are particularly effective against the phytopathogenic organisms of the kingdom Fungi, phylum Basidiomycot, class Uredinomycetes, subclass Urediniomycetidae and the order Uredinales (commonly referred to as rusts). Species of rusts having a particularly large impact on agriculture include those of the family Phakopsoraceae, particularly those of the genus Phakopsora, for example Phakopsora pachyrhizi, which is also referred to as Asian soybean rust, and those of the family Pucciniaceae, particularly those of the genus Puccinia such as Puccinia graminis, also known as stem rust or black rust, which is a problem disease in cereal crops and Puccinia recondite, also known as brown rust.

An embodiment of said method is a method of protecting crops of useful plants against attack by a phytopathogenic organism and/or the treatment of crops of useful plants infested by a phytopathogenic organism, said method comprising simultaneously applying glyphosate, including salts or esters thereof, and at least one compound of formula I₁ which has activity against the phytopathogenic organism to at least one member selected from the group consisting of the plant, a part of the plant and the locus of the plant.

The compounds of formula (I), or a pharmaceutical salt thereof, described above may also have an advantageous spectrum of activity for the treatment and/or prevention of microbial infection in an animal.

"Animal" can be any animal, for example, insect, mammal, reptile, fish, amphibian, preferably mammal, most preferably human. "Treatment" means the use on an animal which has microbial infection in order to reduce or slow or stop the increase or spread of the infection, or to reduce the infection or to cure the infection. "Prevention" means the use on an animal which has no apparent signs of microbial infection in order to prevent any future infection, or to reduce or slow the increase or spread of any future infection. According to the present invention there is provided the use of a compound of formula (I) in the manufacture of a medicament for use in the treatment and/or prevention of microbial infection in an animal. There is also provided the use of a compound of formula (I) as a pharmaceutical agent. There is also provided the use of a compound of formula (I) as an antimicrobial agent in the treatment of an animal. According to the present invention there is also provided a pharmaceutical composition comprising as an active ingredient a compound of formula (I), or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable diluent or carrier. This composition can be used for the treatment and/or prevention of antimicrobial infection in an animal. This pharmaceutical composition can be in a form suitable for oral administration, such as tablet, lozenges, hard capsules, aqueous suspensions, oily suspensions, emulsions dispersible powders, dispersible granules, syrups and elixirs. Alternatively this pharmaceutical composition can be in a form suitable for topical application, such as a spray, a cream or lotion. Alternatively this pharmaceutical composition can be in a form suitable for parenteral administration, for example injection. Alternatively this pharmaceutical composition can be in inhalable form, such as an aerosol spray. The compounds of formula (I) may be effective against various microbial species able to cause a microbial infection in an animal. Examples of such microbial species are those causing Aspergillosis such as Aspergillus fumigatus, A. flavus, A. terms, A. nidulans and A. niger, those causing Blastomycosis such as Blastomyces dermatitidis; those causing Candidiasis such as Candida albicans, C. glabrata, C. tropicalis, C. parapsilosis, C. krusei and C. lusitaniae; those causing Coccidioidomycosis such as Coccidioides immitis; those causing Cryptococcosis such as Cryptococcus neoformans; those causing Histoplasmosis such as Histoplasma capsulatum and those causing Zygomycosis such as Absidia corymbifera, Rhizomucor pusillus and Rhizopus arrhizυs. Further examples are Fusarium Spp such as Fusarium oxysporum and Fusarium solani and Scedosporium Spp such as Scedosporium apiospermum and Scedosporium prolificans. Still further examples are Microsporum Spp, Trichophyton Spp, Epidermophyton Spp, Mucor Spp, Sporothorix Spp, Phialophora Spp, Cladosporium Spp, Petriellidium spp, Paracoccidioides Spp and Histoplasma Spp.

The following non-limiting Examples illustrate the above-described invention in greater detail without limiting it.

Preparation examples:

Example P1 : Preparation of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid (1-[4- (3-chloro-5-trifluoromethyl-pyridin-2-yloxy)-phenyl1-ethyl)-amide (compound No. 1.040):

At O⁰C, a solution of S-difluoromethyM-methyl-I H-pyrazole^-carbonyl chloride (97mg; 0.5 mmol) in dichloromethane (2ml) was added dropwise to a stirred solution of 158mg (0.5 mmol) of a 1-[4-(3-chloro-5-trifluoromethyl-pyridin-2-yloxy)-phenyl]-ethylamine, and triethylamine (0.1g; LOmmol) in dichloromethane (4ml). After stirring the mixture for 2 hours at ambient temperature, it was purified by column chromatography (using 60-120mesh-silica gel in hexane; eluent: ethyl acetate) to yield 70mg 3-difluoromethyl-1-methyl-1 H-pyrazole-4- carboxylic acid {1 -[4-(3-chloro-5-trifluoromethyl-pyridin-2-yloxy)-phenyl]-ethyl}-amide (29.5% of theory) as a yellow waxy solid. ¹H NMR (400 MHz, CDCI3): δ 1.47- 1.49(d,3H,CH₃),3.78(s,3H,CH₃),5.16-5.23(m,1 H,CH), 6.67(s,1 H,NH),6.63-6.90(t,1 H,CHF₂), 6.98(d,1 H), 7.09(s,1 H), 7.19(d,1 H), 7.32(t,1 H), 7.78(s,1 H), 7.89(s,1 H), 8.16(s,1 H,pyrazole-H). LC-MS [M+H]⁺: 475 / 477

The invention is further illustrated by the preferred individual compounds of formula (Ia)

listed in Table 1 below, wherein B is one of the preferred groups Bi to B₂β:

Characterising data is given in Table 2. In Table 1 below "Me" stands for methyl, "Et" stands for ethyl, "n-Pr" stands for n-propyl, "i-Pr" stands for isopropyl "c-Pr" stands for cyclopropyl, "n-Bu" stands for n- butyl, "c-Bu" stands for cyclobutyl, "t-Bu" stands for tertiary butyl and "c- Hex" stands for cyclohexyl.

Table 1 : preferred compounds of formula Ia:

Table 2 lists selected melting point and selected NMR data for compounds described in Table 1. CDCI₃ was used as the solvent for NMR measurements, unless otherwise stated. If a mixture of solvents was present, this is indicated as, for example: CDCI₃Zd₆-DMSO).

In Table 2 and throughout the description that follows, temperatures are given in degrees Celsius; "NMR" means nuclear magnetic resonance spectrum; MS stands for mass spectrum; "%" is percent by weight, unless corresponding concentrations are indicated in other units. LCMS-data for physico-chemical characterization were obtained on an analytical Waters LC-MS instrument (W2790, ZMD-2000). Column was an Atlantis dC18, 3um 3.0mm x 20mm. Solvents were: A = 0.1% formic acid in water, B = 0.1% formic acid in acetonitrile. Gradient was 10% to 90% B in 2.9 min; flow rate was 1.7 ml/min. Physicochemical data are reported in the following format: retention time (min); M found in positive ionisation mode (m/z⁺). The following abbreviations are used throughout this description:

m.p. = melting point b.p.= boiling point.

S = singlet br = broad d = doublet dd = doublet of doublets t = triplet q = quartet m = multiplet ppm = parts per million

Table 2: Characterising data:

The invention is further illustrated by the preferred individual compounds of formula (Ib)

listed in Table 1a below, wherein B is one of the preferred groups Bi to B₂₈:

In Table 1a below "Me" stands for methyl, "Et" stands for ethyl, "n-Pr" stands for n-propyl, "i Pr" stands for isopropyl "c-Pr" stands for cyclopropyl, "n-Bu" stands for n- butyl, "c-Bu" stands for cyclobutyl, "t-Bu" stands for tertiary butyl and "c-Hex" stands for cyclohexyl

Table 1a: preferred compounds of formula Ib:

FORMULATION EXAMPLES FOR COMPOUNDS OF FORMULA I: Example F-1.1 to F-1.2: Emulsifiable concentrates

Components F-1.1 F-1.2

compound of Table 1or 1a 25% 50% calcium dodecylbenzenesulfonate 5% 6% castor oil polyethylene glycol ether (36 mol ethylenoxy units) 5% tributylphenolpolyethylene glycol ether (30 mol ethylenoxy units) 4% cyclohexanone 20% xylene mixture 65% 20%

Emulsions of any desired concentration can be prepared by diluting such concentrates with water. Example F-2: Emulsifiable concentrate

Components F-2

compound of Table 1 or 1a 10% octylphenolpolyethylene glycol ether

(4 to 5 mol ethylenoxy units) 3% calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether

(36 mol ethylenoxy units) 4% cyclohexanone 30% xylene mixture 50%

Emulsions of any desired concentration can be prepared by diluting such concentrates with water.

Examples F-3.1 to F-3,4: Solutions

Components F-3.1 F-3.2 F-3.3 F-3.4

compound of Table 1 or 1a 8800%% 1100%% 55%% 95% propylene glycol monomethyl ether 20% - - polyethylene glycol (relative molecular mass: 400 atomic mass units) 70%

N-methylpyrrolid-2-one - 20% - epoxidised coconut oil -- -- 11%% 5% benzin (boiling range: 160-190°) 94%

The solutions are suitable for use in the form of microdrops.

Examples F-4.1 to F-4.4: Granulates

Components F-4.1 F-4.2 F-4.3 F-4.4 compound of Table 1 or 1a 5% 10% 8% 21% kaolin 94% 79% 54% highly dispersed silicic acid 1% 13% 7% attapulgite 90% 18%

The novel compound is dissolved in dichloromethane, the solution is sprayed onto the carrier and the solvent is then removed by distillation under vacuum.

Examples F-5.1 and F-5.2: Dusts

Components F-5.1 F-5.2

compound of Table 1 or 1a 2% 5% highly dispersed silicic acid 1% 5% talcum 97% - kaolin - 90%

Ready for use dusts are obtained by intimately mixing all components.

Examples F-6.1 to F-6.3: Wettable powders

Components F-6.1 F-6.2 F-6.3

compound of Table 1 or 1a 25% 50% 75% sodium lignin sulfonate 5% 5% - sodium lauryl sulfate 3% - 5% sodium diisobutylnaphthalene sulfonate - 6% 10% octylphenolpolyethylene glycol ether

(7 to 8 mol ethylenoxy units) - 2% - highly dispersed silicic acid 5% 10% 10% kaolin 62% 27% - AII components are mixed and the mixture is thoroughly ground in a suitable mill to give wettable powders which can be diluted with water to suspensions of any desired concentration.

Example F7: Flowable concentrate for seed treatment compound of Table 1 or 1a 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 0. 5 % water) monoazo-pigment calcium salt 5 %

Silicone oil (in the form of a 75 % emulsion in water) 0. 2 %

Water 45. 3 %

The finely ground active ingredient 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.

BIOLOGICAL EXAMPLES: FUNGICIDAL ACTIONS

Example B-1 : Action against Erysiphe graminis f.sp. tritici (wheat powdery mildew) Wheat leaf segments were placed on agar in multiwell plates (24-well format) and sprayed with test solutions (0.02% active ingredient). After drying, the leaf disks were inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound was assessed 7 days after inoculation as preventive fungicidal activity. Compounds 1.194, 1.015, 1.481 , 1.004, 1.043, 1.005, 1.016, 1.021 , 1.037, 1.042, 1.045, 1.003, 1.014, 1.040, 1.009 and 1.098 showed good activity in this test (at least 50% inhibition).

Example B-2: Action against Pyrenophora teres (net blotch) on barley

Barley leaf segments were placed on agar in multiwell plates (24-well format) and sprayed with test solutions (0.02% active ingredient). After drying, the leaf disks were inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound was assessed 4 days after inoculation as preventive fungicidal activity. Compounds 1.194, 1.029, 1.264, 1.193, 1.015, 1.481 , 1.004, 1.043, 1.005, 1.016, 1.021 , 1.037, 1.042, 1.045, 1.003, 1.271 , 1.018, 1.081 , 1.014, 1.301 , 1.198, 1.040, 1.009, 1.048, 1.201 , 1.037, 1.039 and 1.742 showed good activity in this test (at least 50% inhibition).

Example B-3: Action against Botrvtis cinerea - fungal growth assay Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds (0.02% active ingredient) into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24⁰C and the inhibition of growth is measured photometrically after 3-4 days. The activity of a compound is expressed as fungal growth inhibition. 1.029, 1.481 , 1.043, 1.037, 1.042, 1.045, 1.081 , 1.014, 1.198, 1.040, 1.009, 1.048, 1.201 , 1.037 and 1.039 showed good activity in this test (at least 50% inhibition).

Example B-4: Action against Mvcosphaerella arachidis (early leaf spot of groundnut; Cercospora arachidicola fanamorphP- fungal growth assay

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds (0.02% active ingredient) 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 is measured photometrically after 6-7 days. The activity of a compound was expressed as fungal growth inhibition. Compounds 1.194, 1.029, 1.193, 1.015, 1.481 , 1.004, 1.043, 1.005, 1.016, 1.021 , 1.037, 1.042, 1.045, 1.003, 1.271 , 1.018, 1.081 , 1.331 , 1.081 , 1.014, 1.198, 1.040, 1.009, 1.048, 1.201 , 1.037, 1.039, 1.055 and 1.742 showed good activity in this test (at least 50% inhibition).

Example B-5: Action against Septoria tritici - fungal growth assay Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds (0.02% active ingredient) into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24⁰C and the inhibition of growth was determined photometrically after 72 hrs. The activity of a compound is expressed as fungal growth inhibition. Compounds 1.194, 1.029, 1.193, 1.015, 1.481 , 1.004, 1.043, 1.005, 1.016, 1.021 , 1.037, 1.042, 1.045, 1.003, 1.271 , 1.018, 1.081 , 1.331 , 1.081 , 1.301 , 1.014, 1.198, 1.040, 1.009, 1.048, 1.201 , 1.037, 1.039, 1.055 and 1.578 showed good activity in this test (at least 50% inhibition).

Example B-6: Action against Monographella nivalis (anamorph: Fusarium nivale, Microdochium nivale; Snow mould) - fungal growth assay

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a DMSO-solution of the test compounds (0.02% active ingredient) into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24⁰C and the inhibition of growth was measured photometrically after 72 hrs. Compounds 1.029, 1.015, 1.481, 1.043, 1.005, 1.021 , 1.037, 1.042, 1.045, 1.003, 1.018, 1.014, 1.198, 1.040, 1.009, 1.048, 1.201 , 1.037, 1.039, 1.055, 1.578 and 1.742 showed good activity in this test (at least 50% inhibition).

Example B-7: Curative action against Puccinia recondita (brown rust) on wheat

Wheat leaf segments were placed on agar in multiwell plates (24-well format) and inoculated with a spore suspension of the fungus. One day after inoculation the leaf segments were sprayed with test solutions (0.02% active ingredient). After appropriate incubation the activity of a compound was assessed 8 days after inoculation as curative fungicidal activity.

Compounds 1.481 , 1.048 and 1.201 showed good activity in this test (at least 50% inhibition).

Example B-8: Action against Tapesia vallundae - fungal growth assay Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds (0.02% active ingredient) 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 after 6-7 days. The activity of a compound was expressed as fungal growth inhibition. Compounds 1.045, 1.003, 1.271 , 1.018, 1.081 , 1.014, 1.301 , 1.198, 1.040, 1.009, 1.048, 1.201 , 1.037, 1.039, 1.055, 1.578 and 1.742 showed good activity in this test (at least 50% inhibition).

Example B-9: Action against Leptosphaeria nodorum (Septoria nodorum; glume blotch) on wheat Wheat leaf segments were placed on agar in multiwell plates (24-well format) and sprayed with test solutions (0.02% active ingredient). After drying, the leaf disks were inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound was assessed 4 days after inoculation as preventive fungicidal activity. Compounds 1.029, 1.481 , 1.043, 1.037, 1.042, 1.081 , 1.198, 1.009, 1.048 and 1.037 showed good activity in this test (at least 50% inhibition).

Claims

WHAT IS CLAIMED IS:

1. A compound of formula I

wherein

R₁ is C_rC₄alkyl;

R₂ is CrC₄haloalkyl;

R₃ is CrCealkyl, C_rC₆haloalkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-

C₆alkynyl or C₂-C₆haloalkynyl;

R₄ is hydrogen, C_rC₆alkyl, C_rC₆haloalkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,

C₂-C₆alkynyl or C₂-C₆ haloalkynyl; or R₃ and R₄ together are a C₂-C₅alkylene group, which is can be mono- or polysubstituted by C_rC₆alkyl;

B is phenyl, naphthyl or a 5 to 10-membered monocyclic- or fused bicyclic heteroaromatic ring system containing one to three heteroatoms, each heteroatom is independently selected from oxygen, nitrogen and sulphur, wherein the phenyl group is mono- or polysubstituted by substituents selected from R₅; and wherein the naphthyl or 5- to 10-membered monocyclic- or fused bicyclic heteroaromatic ring system can be mono- or polysubstituted by substituents selected from R₅; it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms; each substituent R₅ independently of each other, is halogen, C_rC₆haloalkoxy, C₁-

C₆haloalkylthio, cyano, nitro or -C(R^a)=N(OR^b); or is

C_rC₆alkyl, which can be mono- or polysubstituted by R₆;

C₃-C₆cycloalkyl, which can be mono- or polysubstituted by R₆;

C₆-C₁₄bicycloalkyl, which can be mono- or polysubstituted by R₆;

C₂-C₆alkenyl, which can be mono- or polysubstituted by R₆;

C₂-C₆alkynyl, which can be mono- or polysubstituted by R₆; phenyl, which can be mono- or polysubstituted by R₆; or phenoxy, which can be mono- or polysubstituted by R₆; each R₆ independently of each other, is halogen, nitro, C₃-C₆cycloalkyl, C_rC₆alkoxy, C₁-

C₆haloalkoxy, C_rC₆alkylthio, C_rC₆haloalkylthio, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, phenyl, halophenyl or -C(R^c)=N(OR^d); each R^a and R^c independently of each other, is hydrogen or CτC₆alkyl;

R₁₅ is hydrogen or C₃-C₇cycloalkyl; with the proviso that B is different from phenyl if Ri₅ is C₃-C₇cycloalkyl; and each R^b and R^d independently of each other, is d-Cealkyl; and agronomically acceptable salts/isomers/structural isomers/stereoisomers/diastereoisomers/enantio-mers/tautomers and N-oxides of those compounds.

2. A compound according to claim 1 , wherein R₁₅ is hydrogen.

3. A compound according to claim 1 , wherein B is selected from the following groups B₁ to

B. B. B₁₂

wherein

R₁₀ is hydrogen, Ci-C₄alkyl, Ci-C₄haloalkyl, halogen, C₂-C₆alkinyl, CrC₄alkylamino, C₁-

C₄alkylcarbonyl, C_rC₄alkoxy or cyano; R₁₁ is hydrogen, Ci-C₄alkyl, CrC₄haloalkyl, halogen, C₂-C₆alkinyl, or phenyl substituted by halogen;

R₁₂ is hydrogen, -CHO, C_rC₄alkyl, C₂-C₄alkenyloxy, C₂-C₄haloalkenyloxy, C₁-

C₄alkylcarbonyl, d-dhaloalkyl, halogen, C₂-C₆alkinyl which may be mono- or disubstituted by substituents selected from C_rC₄alkoxy and phenyl which phenyl group in turn may be substituted by halogen, or is phenyl substituted by halogen, or is phenoxy substituted by halogen or C_rC₄haloalkyl, or is pyridyloxy which may be mono- or di substituted by substituents selected from halogen and CrC₄haloalkyl, C₃-C₆cycloalkyl and C₂-

C₆haloalkenyloxy, or R₁₂ is a group -C(R^a)=N(OR^b), wherein R^a is C_rC₄alkyl and R^b is C₁-

C₄alkyl;

R₁₃ is hydrogen, C_rC₄alkyl, or halogen; and

R₁₄ is hydrogen, Ci-C₄alkyl, or halogen.

4. A compound according to claim 3, wherein B is B₁.

5. A compound according to claim 1 , wherein R₁ is methyl.

6. A compound according to claim 1 , wherein R₂ is difluoromethyl.

7. A compound according to claim 1 , wherein R₃ is methyl.

8. A compound according to claim 1 , wherein R₄ is hydrogen.

9. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula I according to claim 1 or a composition, comprising this compound as active ingredient, is applied to the plants, to parts thereof or the locus thereof.

10. A composition for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula I according to claim 1.