WO2009127722A1 - Novel microbiocides - Google Patents

Abstract

Compounds of 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, carboxamides. 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.

Fungicidally active N-(4-pyridin-2-ylbutyl)benzamide derivatives are described for example in WO 2008/003745 and WO 2007/141009. It has been found that novel carboxamides have microbiocidal activity.

The present invention accordingly relates to compounds of formula I

wherein

Ri is hydrogen or d-C₄alkyl; R₂ is hydrogen or Ci-C₄alkyl; or R₁ and R₂ together are C₂-C₅alkylene;

R₃ is hydrogen or C₃-C₇cycloalkyl;

B is the group B₁

wherein

R₄ is hydrogen, halogen or CrC₆alkyl;

R₅ is hydrogen or halogen;

R₆ is hydrogen, halogen, CrC₆alkyl, C₂-C₆alkenyl, C₃-C₆alkinyl, C₃-C₆cycloalkyl-C₃-C₆alkinyl, halophenoxy, halophenyl-C₃-C₆alkinyl, C(C₁-C₄alkyl)=NO-C₁-C₄alkyl, C_rC₆haloalkyl, C₁-

C₆haloalkoxy, C₂-C₆haloalkenyl, or C₂-C₆haloalkenyloxy; R₇ is hydrogen or halogen;

R₈ is hydrogen, halogen, d-C₆alkyl, d-C₆alkoxy,

G is selected from the group consisting of CH₂S, C(O)CH₂, C(=NOCH₃)CH₂ and (CH₂)₄;

A is the group A₁

^R10 /

^N-N NΛ^RH ¹¹ (A₁), wherein

R₉

R₉ is hydrogen or Ci-C₄alkyl;

R₁₀ is Ci-C₄alkyl, CrC₄haloalkyl or halogen;

R₁₁ is hydrogen or halogen; and agronomically acceptable salts/isomers/structural isomers/stereoisomers/diastereoisomers/enantio-mers/tautonners 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 te/f-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. Halophenyl is preferably phenyl substituted by 1 , 2 or 3 halogen atoms, for example 4- chloro-phenyl. Halophenoxy is preferably phenoxy substituted by 1 , 2 or 3 halogen atoms, for example 4-chloro-phenoxy.

In the groups which represent the substituent G, the right free valence is bonded to the substituent B.

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, wherein R₃ is hydrogen, may occur in different tautomeric forms. For example, compounds of formula I exist in the tautomeric forms Ii and Ni:

In a preferred group of compounds, A is the group A₁

^N-κ NΛ^Rn ¹¹ (A₁), wherein

R₉

R₉ is methyl; R₁₀ is CrC₄haloalkyl, preferably difluoromethyl or trifluoromethyl and R₁₁ is hydrogen.

Preferred compounds of formula I are represented by formula Ia

('a)

- A -

wherein R₃ is hydrogen and G, R-i, R₂, R₄, R5, Re, R7 and Rs are as defined for formula I. Preferred compounds of formula Ia wherein R₃ is hydrogen are listed in Table 1 below (compounds 1.001-1.156). Further preferred compounds of formula I are represented by formula Ia, wherein R₃ is cyclopropyl and the substituents G, Ri, R₂, R₄, R5, Re, R7 and R₈ are as defined as for each of the individual compounds 1.001-1.156 listed in Table 1. The individual compounds of formula Ia, wherein R₃ is cyclopropyl are therefore defined as compounds 2.001-2.156. Further preferred compounds of formula I are those, in which R₁₀ is trifluoromethyl. From this group of compounds, the compounds represented by formula Ic

wherein R₃ is hydrogen and G, Ri, R₂, R₄, R5, Re, R7 and R₈ are as defined under formula I are especially preferred. Individual compounds of this preferred group of compounds of formula Ic are described in Table 1 below, wherein R₃ is hydrogen and G, Ri, R₂, R₄, R₅, R₆, R7 and R₈ are as defined in Table 1. Said compounds are therefore described as compounds 3.001-3.156. Further individual compounds of this preferred group of compounds of formula Ic are described in Table 1 below, wherein R₃ is cyclopropyl and G, Ri, R₂, R₄, R₅, R₆, R7 and R₈ are as defined in Table 1. Said compounds are therefore described as compounds 4.001-4.156.

Ri is preferably hydrogen. R₂ is preferably hydrogen or methyl, or R₁ and R₂ together are ethylene. R₃ is preferably hydrogen. R₄ is preferably halogen or methyl, in particular chlorine. R₅ is hydrogen or halogen, in particular hydrogen or chlorine. R₆ is preferably hydrogen or halogen, in particular chlorine. R₇ is preferably hydrogen or halogen, preferably hydrogen. R₈ is halogen, methyl or methoxy, in particular chlorine, methyl or methoxy most preferred chlorine.

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

in which B, R₁, R₂, R3 and G are as defined under formula I; with a compound of formula III

A-C(=O)-R^* (III),

in which A is as defined under formula I, and R^* is halogen, hydroxy or d-6 alkoxy, preferably chloro.

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 -20⁰C and +120⁰C. In general, the reactions are slightly exothermic and, as a rule, they can be carried out at ambient 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.

Compounds of formula Ib

wherein A, B and Ri and R₂ are as defined under formula I above may be prepared as described in reaction scheme 1 :

Scheme 1 :

^Rκ V A ²

AA^{' ^} HHaalI

(IV) (NIb) (V) (Vl)

oxidation

(Ib) (VIII) (VII)

Compounds of formula V, in which A, R₁ and R₂ are as defined under formula Ib, may be prepared by reacting an amino alcohol of formula IV, in which R₁ and R₂ are as defined under formula Ib, with a compound of formula INb, in which A is as defined under formula Ib and Hal stands for halogen, 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 between O⁰ C and reflux, preferably 20 to 25 ⁰C. Cyclic sulfamidites of formula Vl, in which A, R₁ and R₂ are as defined under formula Ib, can then be prepared from the compounds of formula V by using SOCI₂. This cyclisation reaction may be performed in the presence of a base. A suitable base is pyridine. Suitable solvents include dichloromethane and nitriles such as acetonitrile and propionitrile. The reaction temperature typically lies in the range of -50⁰C to 20⁰C.

Cyclic sulfamidates of formula VII, in which A, R₁ and R₂ are as defined under formula Ib, may be prepared by oxidation of the cyclic sulfamidites of formula Vl. Suitable oxidation reagents are RuO₄ and RuCls 3H₂O in combination with NaIO₄. Suitable solvents include mixtures of nitriles and water; as nitrile can be used, for example, acetonitrile or propionitrile. The reaction temperature typically lies in the range of 0⁰C to 30⁰C. For a review of preparation methods for cyclic sulfates and sulfamidates, see Lohray, B. B. in /Advances in Heterocyclic Chemistry; Katritzky, A.R., Ed.; Academic Press: San Diego, 1997; Vol. 68, pp 89-180; and Posakony J. J., J. Org. Chem., 2002, 67, 5164-5169. The cyclic sulfamidates of formula VII may then react with compounds of formula VIII, in which B is as defined under formula Ib, to form compounds of formula Ib. This ring-opening by using sulfur nucleophiles may be performed in the presence of a base. Suitable bases include carbonates, such as lithium hydroxide, cesium carbonate, potassium carbonate, or metal hydrides, such as sodium hydride and lithium hydride. Suitable solvents include N, N- dimethylformamide, dimethylacetamide and DMSO. The reaction temperature can vary within wide limits, but typically is from ambient temperature to 100⁰C. Compounds of formula I, wherein R₃ is C₃-C₇cycloalkyl can be prepared analogously.

The compounds of the formula IV and VIII, wherein the substituents as described above, are known and commercially available or can be prepared according to the above- mentioned references or according to methods known in the art.

The compounds of the formula INb, 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 93/1 1 1 17 and Arch. Pharm. Res. 2000, 23(4), 315-323.

Compounds of formula Ib1

in which A, B and Ri and R₂ are as defined under formula I above may be prepared as described in reaction scheme 2: Scheme 2:

Compounds of formula X, in which A, R₁ and R₂ are as defined under formula Ib, may be prepared by reacting an amino acid ester of formula IX, in which R₁ and R₂ are as defined under formula Ib, with a compound of formula INb, in which A is as defined under formula Ib and Hal is halogen, 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 between O⁰ C and reflux, preferably 20 to 25 ⁰C. Compounds of formula Xl, in which A, R₁ and R₂ are as defined under formula Ib, can then be prepared by hydrolysis of compounds of formula X. This hydrolysis reaction may be performed in the presence of a base. Suitable bases include hydroxydes, such as lithium hydroxide, cesium hydroxide and potassium hydroxide. Suitable solvents include THF, water, methanol, ethanol and mixtures thereof. The reaction temperature can vary within wide limits, but typically is from ambient temperature to 50⁰C.

Acid compounds of formula Xl can be converted to the corresponding acylchloride and this acylchloride can then in situ be reacted with N,O-dimethylhydroxylamine to afford a Weinreb amide of formula XIII. Alternatively, acid compounds of formula Xl may cyclised to an compound of formula XII, that further may be transformed into the Weinreb amide XIII by ring opening reaction with N,O-dimethylhydroxylamine. A subsequent reaction with a Grignard reagent of the formula XV, prepared from a compound of formula XIV, wherein B is as defined under formula Ib, yields the ketone compound of formula 1 b2. Compounds of formula 1 b1 , wherein the substituents are described above, can be prepared by the reaction of compounds of formula 1 b2 and O-alkyl-hydroxylamine hydrochloride. Compounds of formula I, wherein R₃ is C₃-C₇cycloalkyl, can be prepared analogously.

The intermediates of formula XIIIa

(XIIIa)

wherein A, R₁, R₂ and R₃ are as defined under formula I above are novel and are developed specifically for the preparation of the compounds of the formula Ib. Accordingly, these intermediates of the formula XIIIa also form part of the subject-matter of the present invention.

The intermediates of formula Ib2a

wherein A, B, R₁, R₂ and R₃ are as defined under formula I above are novel and are developed specifically for the preparation of the compounds of the formula Ib. Accordingly, these intermediates of the formula Ib2a also form part of the subject-matter of the present invention.

Compounds of formula Ib3

(Ib3),

in which A, B and R-i, R₂ and R3 are as defined under formula I may be prepared as described in reaction scheme 3. Scheme 3

The acid of the formula XVII, prepared from the aldehyde of formula XVI and Meldrum's acid wherein B is as defined under formula Ib, can be converted to the corresponding acylchloride and this acylchloride can then in situ be reacted with N, O- dimethylhydroxylamine to afford a Weinreb amide of formula XVIII, wherein B is as defined under formula Ib. Partial reduction of the Weinrebamide XVIII with LiAIH₄, yields the aldehyde of formula XIX. α,β-unsaturated ketones of formula XX may be prepared by a Wittig reaction of the aldehydes of formula XIX and a Wittig reagent of formula XXIV. Ketones of formula XXI may be prepared by catalytic reduction of the α,β-unsaturated ketones of formula XX. Amines of formula Nb3 wherein R₁, R₃, and B are as defined under formula Ib may be prepared according to a process which comprises the reaction of a compound of general formula XXI with an amine or an salt thereof of formula XXIII to provide an imine derivative of general formula XXII. A second step comprises the reduction of the imine derivative of general formula XXII by hydrogenation or by an hydride donor, in the same or a different pot to provide an amine of general formula Nb3 or one of its salt. Preferably, the hydride donor is chosen as being metal or metal hydride such as LiAIH₄, NaBH₄, NaBH₃CN, NaBH(OAc)₃, KBH₄, B₂H₆.

The intermediates of formula Nb3

T (Nb3),

R₃-^NH wherein B, R₁ and R₃ are as defined under formula I above are novel and are developed specifically for the preparation of the compounds of the formula Ib. Accordingly, these intermediates of the formula Nb3 also form part of the subject-matter of the present invention.

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 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.

Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bi ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bi ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); Nature- Gard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.

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 10g 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 1 g 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 recondita, 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 I, 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. krυsei 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 arrhizus. 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 [2- (2,6-dichloro-phenylsulfanyl)-1-methyl-ethyl1-amide (compound 1.002):

To a solution of 2,6-dichloro-benzenethiol (0.448g; 2.5mmol) in dimethylformamide (10ml) sodium hydride 50% in oil (0.12g; 2.5mmol) is added portion wise. The reaction mixture is stirred for 20 minutes at ambient temperature followed by the addition of 3-difluoromethyl- 1 -methyl-1 H-pyrazol-4-yl)-4-methyl-2,2-dioxo-2-λ-^*6^*-[1 ,2,3]oxathiazolidin-3-yl)-methanone (0.80Og; 2.7mmol), which is prepared as described in example P8c, in dimethylformamide (6ml). The reaction mixture is stirred for 5 hours at ambient temperature then poured onto 1 M HCI (50ml) and extracted with ethyl acetate (2x50ml). The combined ethyl acetate layers are washed with water (40ml) and then dried over Na₂SO₄. After removal of the solvent the residue (1.5g oil) is purified by flash chromatography over silica gel (eluent: cyclo hexane/ethyl acetate 2:8). 0.88g (88% of theory) of 3-difluoromethyl-1 -methyl-1 H-pyrazole- 4-carboxylic acid [2-(2,6-dichloro-phenylsulfanyl)-1-methyl-ethyl]-amide (compound 1.002) is obtained in form of a solid (m.p.103-106⁰C).

¹H NMR (400MHz, CDCI₃): δ 1.32(d,3H,CH₃),3.1 1-3.23(m,2H,CH₂),3.92(s,3H,CH₃), 4.18-4.30(m,1 H,CH), 6.37(m_broad,1 H,NH), 6.73-6.96(t,1 H₁CHF₂), 7.10-7.17(dxd,1 H₁Ar-H), 7.32-7.37(d,2H,2H-Ar),7.80(s,1 H,Pyrazol-H). MS [M+H]⁺ 394/396/398. Example P2: Preparation of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid f(S)-3- (2,4-dichloro-phenyl)-1-methyl-2-oxo-propyl1-amide (compound 1.067):

To a suspension of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid [(S)-I- (methoxy-methyl-carbamoyl)-ethyl]-amide (compound prepared as described in example P9c) (600mg, 2.06mmol) in water free THF (12ml) at -15°C is added under argon atmosphere 2,4-dichlorbenzylmagnesium chloride (12.4 mmol in 1 1 ml water free Et₂O ) in three portions. Between the three additions the cooling bath is removed and reaction mixture is stirred at r.t for 30 min. After the final addition of grignard reagent the reaction mixture is stirred for 1 hour at ambient temperature. Then the reaction is quenched with 10% solution of citric acid (35 ml), extracted with ethyl acetate (50 ml) and dried with anhydrous Na₂SO₄. After concentration under reduced pressure the crude product is purified by flash chromatography over silicagel (eluent: n-hexane/ethylacetate 1 :2). 410mg (51.0% of theory) of 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid [(S)-3-(2,4- dichloro-phenyl)-1-methyl-2-oxo-propyl]-amide (compound 1.067) is obtained in form of a solid (m.p.123-125°C). 1H NMR: (CDCI₃, 300MHz):

1.51 and 1.53(2xs, 3H, CH₃); 3,93(s, 3H, CH₃-N-Har); 3.97 and 4.00(2xs, 2H, CH₂-Ar); 4.80-4.90(m, 1H, CH); 6.87(t, 1H, J= 54Hz, CHF₂); 6.99(br-s, 1 H, NH); 7.18-7.25(m, 2H, 2xH-Ar); 7.40-7.42(m, 1H, H-Ar); 7.90(s, 1H, H-Har). MS [M+H]⁺ 388/390/392.

Example P3: Preparation of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid [3- (2,4-dichloro-phenyl)-1 ,1-dimethyl-2-oxo-propyl1-amide (compound 1.075):

To suspension of 3-amino-1-(2,4-dichloro-phenyl)-3-methyl-butan-2-one hydrochloride (compound Z1.075, prepared as described in example P1 1 e) (300 mg; 1.06 mmol) in CH₂C^ (5 ml) is added triethylamine (0.15 ml; 1.06 mmol) at ambient temperature under argon atmosphere. This reaction mixture is cooled to 0⁰C and 3-difluoromethyl-1-methyl-1 H- pyrazole-4-carbonyl chloride (0.41 g; 2.12 mmol) and then triethylamine (0.30 ml; 2.12 mmol) is added. The reaction mixture is stirred at 0-2⁰C during 2 hours and then the cooling bath is removed and stirred at ambient temperature for 15 hours. Saturated solution of NaHCC>3 (35 ml) and CH₂CI₂ (20 ml) is added and layers are separated. The organic phase is extracted with water (1x40 ml), 2N HCI (2x25 ml), finally with water (40 ml) and dried with anhydrous Na₂SO₄. After concentration under reduced pressure the crude product is purified by column chromatography (eluent: hexane/ethyl acetate 1 :2). 150mg (35.0% of theory) of 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid [3-(2,4-dichloro-phenyl)- 1 ,1-dimethyl-2-oxo-propyl]-amide (compound 1.075) is obtained in form of a solid (mp. 1 15- 1 18°C).

¹H NMR: (CDCI₃, 300MHz):

1.60(s, 6H, 2xCH₃); 3,93(s, 3H, CH₃-N-Har); 4.03(s, 2H, CH₂-Ar); 6.85(t, 1 H, J= 54Hz, CHF₂); 6.91 (br-s, 1 H, NH); 7.18-7.20(m, 2H, H-Ar); 7.38(s, 1 H, H-Ar); 7.93(s, 1 H, H-Har). MS [M+H]⁺ 402/404/406.

Example P4: Preparation of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid {1-[2-

(2,4-dichloro-phenyl)-acetvH-cvclopropyl)-amide (compound 1.085):

To a suspension of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid [1-(methoxy- methyl-carbamoyl)-cyclopropyl]-amide, prepared as described in example P10c (300mg, 0.992mmol) in water free THF (1 OmI) at -15°C is added under argon atmosphere 2,4- dichlorbenzylmagnesium chloride (5.95 mmol in 5 ml water free Et₂O ) in three portions. Between the three additions the cooling bath is removed and reaction mixture is stirred at ambient temperature for 30 min. After the final addition of grignard reagent the reaction mixture is stirred for 1 hour at ambient temperature. Then the reaction is quenched with 10% solution of citric acid (25 ml), extracted with ethyl acetate (1x40 ml) and dried with anhydrous Na₂SO₄. After concentration under reduced pressure the crude product is purified by flash chromatography over silicagel (eluent: ethylacetate). 250mg (62.0% of theory) of 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid {1-[2-(2,4-dichloro- phenyl)-acetyl]-cyclopropyl}-amide (compound 1.085) is obtained in form of a resin.

¹H NMR: (CDCI₃, 300MHz):

1.24-1.28(m, 2H, CH₂); 1.72-1.76(m, 2H, CH₂); 3.95(s, 3H, CH₃-N-Har); 4.12(s, 2H, CH₂-Ar); 6.82(t,

1H, J= 54, CHF₂);7.02(br-s, 1 H, NH); 7.10-7.37(m, 3H, 3xH-Ar); 7.99(s, 1H, H-Har).

MS [M+H]⁺ 400/402/404.

Example P5: Preparation of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid {(S)-3- (2,4-dichloro-phenyl)-2-[(E or Z)-methoxyimino1-1-methyl-propyl)-amide (compound 1.093):

A mixture of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid [(S)-3-(2,4-dichloro- phenyl)-1-methyl-2-oxo-propyl]-amide (compound 1.067, prepared as described in example P2) (370 mg; 0.95 mmol), O-methyl hydroxylamine hydrochloride (100 mg; 1.18 mmol) and pyridine (0.1 ml; 1.18 mmol) in methanol (6 ml) is stirred overnight (18h) at ambient temperature. Water (15 ml) is added and the mixture is extracted with ethyl acetate (4x25 ml). The combined organic phases are washed with 2N HCI (1x45 ml), water (1x45 ml) and dried with anhydrous Na₂SC>₄. After concentration under reduced pressure the crude product is purified by column chromatography over silicagel (eluent: ethylacetate). 185mg (46.0% of theory) of 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid {(S)-3-(2,4- dichloro-phenyl)-2-[(E or Z)-methoxyimino]-1-methyl-propyl}-amide (compound 1.093) is obtained in form of a yellow viscous oil. 1H NMR: (CDCI₃, 300MHz):

1.27 and 1.29 + 1.34 and 1.36(4xs, 3H, CH₃); 3.87-3.94(m, 8H, CH₃-O, CH₃-N-Har, CH₂-Ar); 4.61-4.70 and 4.96-5.01 (2xm, 1 H, CH); 6.77 and 6.84(2xt, 1 H, J= 54Hz, CHF₂); 7.10- 7.36(m, 4H, 3xH-Ar, NH); 7.82 and 7.84(2xs, 1 H, H-Har). MS [M+H]⁺ 417/419/421.

Example P6: Preparation of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid {3- (2,4-dichloro-phenyl)-2-[(E or Z)-methoxyimino1-1 ,1-dimethyl-propyl)-amide (compound 1.101 ):

A mixture of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid [3-(2,4-dichloro- phenyl)-1 ,1-dimethyl-2-oxo-propyl]-amide (compound 1.075, prepared as described in example P3) (150 mg; 0.37 mmol), O-methyl hydroxylamine hydrochloride (62 mg; 0.74 mmol) and pyridine (0.09 ml; 1.1 1 mmol) in methanol (2 ml) is refluxed during 48 hours. Water (10 ml) is added after cooling to ambient temperature and is extracted with ethyl acetate (4x15 ml). The combined organic phases are extracted with 2N HCI (1x25 ml), water (1x20 ml) and dried with anhydrous Na₂SC>₄. After concentration under reduced pressure the crude product is purified by column chromatography over silicagel (eluent: ethylacetate). 108mg (67.0% of theory) of 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid {3-(2,4- dichloro-phenyl)-2-[(E or Z)-methoxyimino]-1 ,1-dimethyl-propyl}-amide (compound 1.101 ) is obtained in form of a yellow viscous oil. 1H NMR: (CDCI₃, 300MHz):

1.57(s, 6H, 2xCH₃); 3.76(s, 2H, CH₂-Ar); 3.89(s, 3H, CH₃-O); 3,92(s, 3H, CH₃-N-Har); 6.84(t, 1 H, J= 54Hz, CHF₂); 7.05(s, 1 H, H-Ar); 7.15(dd, 1 H, J= 8.1 Hz and J= 2.1 Hz, H-Ar); 7.25(br-s, 1 H, NH); 7.32(d, 1 H, J= 2.1 Hz, H-Ar); 7.78(s, 1 H, H-Har). MS [M+H]⁺ 433/435/437.

Example P7: Preparation of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid(1-{2- (2,4-dichloro-phenyl)-1-[(E or Z)-methoxyimino1-ethyl)-cvclopropyl)-amide (compound

A mixture of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid {1-[2-(2,4-dichloro- phenyl)-acetyl]-cyclopropyl}-amide (compound 1.085, prepared as described in example P4) (130 mg; 0.323 mmol), O-methyl hydroxylamine hydrochloride (108 mg; 1.29 mmol) and pyridine (0.16 ml; 1.93 mmol) in methanol (2 ml) is refluxed during 5 hours. Water (15 ml) is added after cooling to ambient temperature and is extracted with ethyl acetate (4x20 ml). The combined organic phases are extracted with 2N HCI (1x35 ml), water (1x35 ml) and dried with anhydrous Na₂SO₄. After concentration under reduced pressure the crude product is purified by column chromatography over silicagel (eluent: ethylacetate). 88mg (63.0% of theory) of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid(1-{2-(2,4- dichloro-phenyl)-1-[(E or Z)-methoxyimino]-ethyl}-cyclopropyl)-amide (compound 1.1 1 1 ) is obtained in form of a yellow viscous oil. 1H NMR: (CDCI₃, 300MHz):

1.57(s, 6H, 2xCH₃); 3.76(s, 2H, CH₂-Ar); 3.89(s, 3H, CH₃-O); 3,92(s, 3H, CH₃-N-Har); 6.84(t, 1 H, J= 54Hz, CHF₂); 7.05(s, 1 H, H-Ar); 7.15(dd, 1 H, J= 8.1 Hz and J= 2.1 Hz, H-Ar); 7.25(br-s, 1 H, NH); 7.32(d, 1 H, J= 2.1 Hz, H-Ar); 7.78(s, 1 H, H-Har). MS [M+H]⁺ 431/433/435.

Example P8: Preparation of 3-difluoromethyl-1-methyl-1 H-pyrazol-4-yl)-4-methyl-2,2-dioxo- 2-λ-^*6^*-π ,2.31oxathiazolidin-3-yl)-methanone a) Preparation of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid (2-hvdroxy-1- methyl-ethvD-amide:

At 0⁰C, a solution of 38.9g 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carbonyl chloride (0.2mol) in 100ml dichloromethane is added dropwise to a stirred solution of 15g alaninol (0.2mol) and 25g triethylamine (0.25mol) in 400ml dichloromethane. The reaction mixture is stirred for 1 h at ambient temperature and then allowed to stand for 3h at ambient temperature. After removal of the solvent the residue is purified by flash chromatography over silica gel 40Og (eluent: ethyl acetate/methanol 19:1 ). 42g (90% of theory) of 3- difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid (2-hydroxy-1-methyl-ethyl)-amide is obtained in form of a solid (mp. 81-87°C).

¹H NMR (400MHz, CDCI₃): δ 1.23-1.26(d,3H), 2.97(s,1 H,OH), 3.57-3.73(ddd,2H), 3.94(s,3H), 4.17-4.23(m,1 H), 6.57(s,1 H), 6.75-7.02(t,1 H), 7.90(s,1 H). MS [M+H]⁺ 234. b) Preparation of 3-difluoromethyl-1-methyl-1 H-pyrazol-4-yl)-4-methyl-2-oxo-2-λ-^*4^*- [1 ,2,31oxathiazolidin-3-yl)-methanone:

A solution of 14.6ml SOCI₂ (200mmol) in 98ml water free acetonitrile under nitrogen atmosphere is cooled to -40⁰C and 18.6g 3-difluoromethyl-1-methyl-1 H-pyrazole-4- carboxylic acid (2-hydroxy-1-methyl-ethyl)-amide (80mmol) in 70ml acetonitrile is added dropwise. 32.2ml water free pyridine is added slowly. The mixture is then allowed to warm to ambient temperature and stirred for 1.5h. The solvent volume is reduced to 100ml, 200ml ethylacetate is added and the resulting precipate is filtered off. The filtrate is concentrated to an oil residue. Purification is achieved by filtration over 4Og silica gel with 400ml ethylacetate to obtain 10.5g (47% of theory) of 3-difluoromethyl-1-methyl-1 H-pyrazol-4-yl)-4- methyl-2-oxo-2-λ-^*4^*-[1 ,2,3]oxathiazolidin-3-yl)-methanone in form of a resin. MS [M+H]⁺ 280. c) Preparation of 3-difluoromethyl-1-methyl-1 H-pyrazol-4-yl)-4-methyl-2,2-dioxo-2-λ-^*6^*- [1 ,2,31oxathiazolidin-3-yl)-methanone:

To a solution of 0.73g 3-difluoromethyl-1-methyl-1 H-pyrazol-4-yl)-4-methyl-2-oxo-2-λ-^*4^*- [1 ,2,3]oxathiazolidin-3-yl)-methanone (2.6mmol) in 3.8ml acetonotrile is added 0.85mg ruthenium(lll)chloride hydrate and 820mg sodium(meta)periodate (3.8mmol) at 0⁰C. 3.8ml water is added dropwise. The reaction became exothermic up to 8°C while cooling. The resulting dark suspension is allowed to warm to ambient temperature and stirred for 2h, poured onto 40ml water and extracted with ethylacetate (2x30ml). The organic layer is dried over anhydrous sodium sulphate, filtered over 5g silica gel and the solvent is removed to obtain 0.63g (82% of theory) of 3-difluoromethyl-1-methyl-1 H-pyrazol-4-yl)-4-methyl-2,2- dioxo-2-λ-^*6^*-[1 ,2,3]oxathiazolidin-3-yl)-methanone in form of a resin.

¹H NMR (400MHz, CDCI₃): δ 1.51-1.53(d,3H), 3.98(s,3H), 4.30-4.34+4.77-4.81 (01,2H), 4.91-

4.99(m,1 H), 6.85-7.12(t,1 H), 8.18(s,1 H). MS [M+H]⁺ 296.

Example P9: S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid [(S)-I -(methoxy- methyl-carbamovD-ethyli-amide: a) Preparation of (S^-fS-difluoromethyl-i-methyl-I H-pyrazole^-carbonyli-aminoi-propionic acid methyl ester:

A stirred suspension of (S)-alanine methyl ester hydrochloride (1.5g; 11.9 mmol) in CH₂CI₂ (80 ml) is cooled to 0⁰C under argon atmosphere. 3-difluoromethyl-1-methyl-1 H-pyrazole-4- carbonyl chloride (2.32g; 1 1.9 mmol) in CH₂CI₂ (20 ml) and then triethylamine (5 ml; 35.8 mmol) is added. The reaction mixture is stirred at 0-2⁰C during 2 hours and then the cooling bath is removed and stirred at ambient temperature for next 2 hours. The reaction mixture is diluted with CH₂CI₂ (60 ml) and extracted with saturated solution of K₂CO₃ (1x120 ml), 10% HCI (1x120 ml), water (1x150 ml) and dried with anhydrous Na₂SO₄. After concentration under reduced pressure the crude product is purified by column chromatography over silica gel (eluent: hexane/ethyl acetate 1 :2). 2.29g (73.0% of theory) of (S)-2-[3-difluoromethyl-1- methyl-1 H-pyrazole-4-carbonyl]-amino]-propionic acid methyl ester is obtained in form of a yellow viscous oil. 1H NMR: (CDCI₃, 300MHz):

1.48 and 1.50(2xs, 3H, CH₃); 3.78(s, 3H, CH₃-O); 3,93(s, 3H, CH₃-N-Har); 4.70-4.77(m, 1 H, CH); 6.86(br-s, 1 H, NH); 6.88(t, 1 H, J= 54Hz, CHF₂); 7.91 (s, 1 H, H-Har).

b) Preparation of (S^-fS-difluoromethyl-i-methyl-I H-pyrazole^-carbonyli-aminoi-propionic acid:

To stirred solution of (S)-2-[3-difluoromethyl-1-methyl-1 H-pyrazole-4-carbonyl]-amino]- propionic acid methyl ester (2.25g; 8.6 mmol) in mixture of THF/H₂O (3:1 ; 32 ml) is added lithium hydroxide monohydrate (0.54g; 12.9 mmol) and reaction mixture is stirred for 15 hours (18 hours). Water (30 ml) is added and reaction mixture is acidified with 2N HCI (pH~3) and extracted with ethyl acetate (3x40 ml). The combined organic layers are dried with anhydrous Na₂SO₄ and concentrated under reduced pressure. 0.97g (45.0% of theory) of (S)-2-[3-difluoromethyl-1-methyl-1 H-pyrazole-4-carbonyl]-amino]-propionic acid is obtained in form of a yellow viscous oil. 1H NMR: (CDCI₃, 300MHz):

1.53 and 1.55(2xs, 3H, CH₃); 3,93(s, 3H, CH₃-N-Har); 4.69-4.75(m, 1 H, CH); 6.88(t, 1 H, J= 54Hz, CHF₂); 6.95(br-s, 1 H, NH); 7.98(s, 1 H, H-Har); 8.40-8.80(br-s, 1 H, OH).

c) Preparation of 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid [(S)-I -(methoxy- methyl-carbamovD-ethyli-amide:

To stirred suspension of N,O-dimethyl hydroxylamine hydrochloride (700mg; 7.2 mmol) in CH₂CI₂ (10 ml) is added triethylamine (1 ml; 7.2 mmol) and is vigorously stirred at ambient temperature for 30 minutes. The precipitate is filtered off and to filtrate is added (S)-2-[3- difluoromethyl-1-methyl-1 H-pyrazole-4-carbonyl]-amino]-propionic acid (890mg; 3.60 mmol) in CH₂CI₂ (12 ml). This reaction mixture is cooled to 5°C under argon atmosphere and DCC (0.81 g; 3.96 mmol) is added in one portion. The cooling bath is removed and reaction mixture is stirred during 5 hours. The precipitate is filtered off and filtrate is concentrated under reduced pressure. Crude product is purified by column chromatography over silica gel (eluent: ethyl acetate). The solvent is evaporated under reduced pressure. 0.6Og (59.0% of theory) of 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid [(S)-I -(methoxy-methyl- carbamoyl)-ethyl]-amide is obtained in form of a white solid (mp. 123-125°C).

¹H NMR: (CDCI₃, 300MHz):

1.42 and 1.44(2xs, 3H, CH₃); 3.24(s, 3H, CH₃-O); 3.80(s, 3H, CH₃-N); 3,93(s, 3H, CH₃-N-

Har); 5.05-5.10(m, 1 H, CH); 6.97(t, 1 H, J= 54Hz, CHF₂); 7.08(br-s, 1 H, NH); 7.86(s, 1 H, H-

Har).

Example P10: S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid [1-(methoxy-methyl- carbamovD-cyclopropyll-amide:

a) Preparation of 1-amino-cyclopropane carboxylic acid methylester hydrochloride:

1-Aminocyclopropane-i -carboxylic acid (2 g; 19.78 mmol) is suspended in water free methanol (50 ml) and cooled to 0⁰C. Thionyl chloride (1.58 ml; 21.66 mmol) is added dropwise to the solution. After the complete addition of tionyl chloride the cooling bath is removed and reaction mixture is stirred for 15 hours (20 hours). The reaction mixture is concentrated under reduced pressure and white solid residue is dried on oil pump for 30 min. 1.32g (88.0% of theory) of 1-amino-cyclopropane carboxylic acid methylester hydrochloride is obtained in form of a white solid. 1H NMR: (CD₃OD, 300MHz): 1.36-1.57(m, 4H, 2xCH₂); 3.82(s, 3H, CH₃-O).

b) Preparation of 5-(3-(difluoromethyl)-1-methyl-1 H-pyrazol-4-yl)-6-oxa-4-aza- spiro[2.41)hept-4-en-7-one:

A suspension of 1-amino-cyclopropane carboxylic acid methylester hydrochloride (1.Og; 6.59 mmol) in CH₂CI₂ (80 ml) is cooled to 5°C under argon atmosphere. 3-difluoromethyl-1- methyl-1 H-pyrazole-4-carbonyl chloride (2.56g; 13.19 mmol) in CH₂CI₂ (20 ml) and then triethylamine (2.75 ml; 19.79 mmol) is added. The reaction mixture is stirred at 5-10⁰C during 2 hours and then the cooling bath is removed and stirred at ambient temperature for 15 hours. The reaction mixture is diluted with CH₂CI₂ (40 ml) and extracted with saturated solution of K₂CO₃ (1x120 ml), 10% HCI (1x120 ml), water (1x150 ml) and dried with anhydrous Na₂SO₄. After concentration under reduced pressure the crude product is purified by column chromatography over silica gel (eluent: ethyl acetate). 0.36g (22.0% of theory) of 5-(3-(difluoromethyl)-1-methyl-1 H-pyrazol-4-yl)-6-oxa-4-aza-spiro[2.4])hept-4-en- 7-one is obtained in form of a white solid (m.p. 125-127°C). 1H NMR: (CDCI₃, 300MHz):

1.73-1.79(m, 2H, CH₂); 1.82-1.88(m, 2H, CH₂); 4.01 (s, 3H, CH₃-N-Har); 7.12(t, 1 H, J= 53.7Hz, CHF₂); 7.88(s, 1 H, H-Har).

c) Preparation of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid [1-(methoxy- methyl-carbamovD-cvclopropyli-amide:

To stirred solution of 5-(3-(difluoromethyl)-1-methyl-1 H-pyrazol-4-yl)-6-oxa-4-aza- spiro[2.4])hept-4-en-7-one (0.28g; 1.16 mmol) in water free CH₂CI₂ (8 ml) under argon atmosphere is added N,O-dimethyl hydroxylamine hydrochloride (0.226g; 2.32 mmol) and pyridine (0.28ml; 3.48 mmol) at ambient temperature. The reaction mixture is stirred during 18 hours. Then the solvent is evaporated under reduced pressure and crude product is purified by column chromatography over silica gel (eluent: ethyl acetate). 0.28g (80.0% of theory) of S-difluoromethyl-i-methyl-I H-pyrazole^-carboxylic acid [1-(methoxy-methyl- carbamoyl)-cyclopropyl]-amide is obtained in form of a white solid (m.p. 185-187°C). 1H NMR: (CDCI₃, 300MHz): 1.09-1.13(m, 2H, CH₂); 1.54-1.59(m, 2H, CH₂); 3.18(s, 3H, CH₃-O); 3.66(s, 3H, CH₃-N); 3.92(s, 3H, CH₃-N-Har); 6.82(t, 1 H, J= 53.7Hz, CHF₂); 7.08(br-s, 1 H, NH); 7.97(s, 1 H, H- Har).

Example P11 : 3-Amino-1-(2,4-dichloro-phenyl)-3-methyl-butan-2-one hydrochloride:

a) Preparation of 2-benzoylamino-2-methyl-propionic acid:

2-Amino-2-methyl-propionic acid (10.31g; l OOmmol) is dissolved in NaOH 2M (60ml) and cooled in an ice bath (O⁰C). Benzoyl chloride (14.06g; 100 mmol) and NaOH 2M (60 ml) are added simultaneously in ten portions every three minutes. The solution is stirred for an additional 45 min. at ambient temperature, then is cooled and treated with concentrated HCI. After 2 h the suspension is filtered and the solid is washed with acetone, before being dried (MgSO4). Acetone is removed by evaporation under reduced pressure to dryness. Then the crude product is washed three times with toluene on frit to remove benzoic acid. 8.33g (40.0% of theory) of 2-benzoylamino-2-methyl-propionic acid is obtained in form of a white powder (m.p. 204-206⁰C). 1H NMR: (DMSO, 300MHz):

1.45(s, 6H, 2xCH₃); 7.43-7.56(m, 3H, 3xH-Ar); 7.83-7.87(m, 2H, 2xH-Ar); 8.45(br-s, 1 H, NH); 12.18(br-s, 1 H₁ OH).

b) Preparation of 4,4-dimethyl-2-phenyl-4H-oxazol-5-one:

2-Benzoylamino-2-methyl-propionic acid (2g; 9.6 mmol) is dissolved in water free CH₂CI₂ (100 ml) and DCC (2.19g; 10.6 mmol) is added in one portion at ambient temperature under argon atmosphere. The reaction mixture is stirred for 30 min. The precipitate is filtered off, washed with CH₂CI₂ (25 ml) and evaporated to dryness. Semicrystaline crude product is washed with hexane several times and filtrate is concentrated to dryness. 1.89g (99.0% of theory) of 4,4-dimethyl-2-phenyl-4H-oxazol-5-one is obtained in form of a yellow oil.

c) Preparation of N-[1-(methoxy-methyl-carbamoyl)-1-methyl-ethyl1-benzamide:

To stirred solution of 4,4-dimethyl-2-phenyl-4H-oxazol-5-one (9.7g; 51 mmol) in water free CH₂CI₂ (150ml) under argon atmosphere is added N,O-dimethyl hydroxylamine hydrochloride (10.Og; 102mmol) and pyridine (12.5ml; 153 mmol) at ambient temperature. The reaction mixture is stirred during 17 hours. Then CH₂CI₂ (500 ml) is added and extracted with water (1x350ml) then with 2N HCI (350ml) and finally with water (350ml). The organic phase is dried with anhydrous Na₂SO₄ , filtrated through a short column over silica gel (h=10 cm; d= 5 cm) and washed out with CH₂CI₂. The solvent is evaporated under reduced pressure. 9.91 g (77.0% of theory) of N-[1-(methoxy-methyl-carbamoyl)-1-methyl- ethyl]-benzamide is obtained in form of a white solid (m.p. 201-203⁰C). 1H NMR: (CDCI₃, 300MHz):

1.80(s, 6H, 2xCH₃); 3.28(s, 3H, CH₃-O); 3,69(s, 3H, CH₃-N); 7.40-7.49(m, 3H, 3xH-Ar); 7.60(br-s, 1 H, NH); 7.80-7.83(m, 2H, 2xH-Ar).

d) Preparation of N-[3-(2,4-dichloro-phenyl)-1 ,1-dimethyl-2-oxo-propyl1-benzamide:

To a suspension of N-[1-(methoxy-methyl-carbamoyl)-1-methyl-ethyl]-benzamide (4.Og, 15.9mmol) in water free THF (80ml) at -20⁰C is added under argon atmosphere 2,4- dichlorbenzylmagnesium chloride (9.58 mmol in 70 ml water free Et₂O ) in three portions. Between the three additions the cooling bath is removed and reaction mixture is stirred at ambient temperature for 30 min. After the final addition of grignard reagent the reaction mixture is stirred for 1 hour at ambient temperature Then the reaction is quenched with 10% solution of citric acid (250 ml), extracted with ethyl acetate (1x300 ml) and dried with anhydrous Na₂SO₄. After concentration under reduced pressure the crude product is purified by flash column chromatography (eluted with hexane/ethyl acetate 1 :1 ). The solvent is evaporated under reduced pressure. 4.93g (88.0% of theory) of N-[3-(2,4-dichloro- phenyl)-1 ,1-dimethyl-2-oxo-propyl]-benzamide is obtained in form of a white solid (m.p. 147-

149°C).

¹H NMR: (CDCI₃, 300MHz):

1.70(s, 6H, 2xCH₃); 4.10(s, 2H, CH₂-Ar); 6.90(br-s, 1 H, NH); 7.22(s, 2H, 2xH-Ar); 7.38-

7.56(m, 4H, 4xH-Ar); 7.79-7.82(m, 2H, 2xH-Ar).

e) Preparation of 3-amino-1-(2,4-dichloro-phenyl)-3-methyl-butan-2-one hydrochloride:

N-[3-(2,4-dichloro-phenyl)-1 ,1-dimethyl-2-oxo-propyl]-benzamide (2.Og; 5.7mmol) is refluxed in 6N HCI/MeOH (3:1 ) (800 ml) during 24 hours. After cooling to ambient temperature the reaction mixture is extracted with ethyl acetate (2x200 ml). The water phase is concentrated under reduced pressure and dried with toluene (azeotropicaly). 0.3Og (18.0% of theory) of 3-amino-1-(2,4-dichloro-phenyl)-3-methyl-butan-2-one hydrochloride is obtained in form of a pale brown solid (210-235⁰C decomposition). 1H NMR: (CD₃OD, 300MHz):

1.72(s, 6H, 2xCH₃); 4.20(s, 2H, CH₂-Ar); 7.30-7.32(m, 2H, H-Ar); 7.48(d, 1 H, J=1.8Hz, H- Ar).

Table 1 : compounds of formula Ia:

In formula Ia, R₃ represents hydrogen or cyclopropyl. In the compounds 1.001-1.156 of Table 1 , R₃ represents hydrogen. "Me" means the methyl group.

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

which are listed below in Table 2.

Table 2: Preferred compounds of formula V:

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

which are listed below in Table 3.

Table 3 Preferred compounds of formula VIB:

Table 4: Characterising data

Table 4 lists selected melting point and selected NMR data for compounds of Table 1. CDCI3 is used as the solvent for NMR measurements, unless otherwise stated. If a mixture of solvents is present, this is indicated as, for example: CDCI₃/d₆-DMSO). In Table 4 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. 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 4:

Formulation examples for coumpounds of formula I:

Example F-1.1 to F-1.2: Emulsifiable concentrates

Components F-1.1 F-1.2

compound of Table 1 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 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 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 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 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 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 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:

Example B-1 : Action against Ervsiphe graminis f.sp. tritici (wheat powdery mildew) Wheat leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions (0.02% active ingredient). After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 7 days after inoculation as preventive fungicidal activity. Compounds 1.002, 1.003, 1.041 , 1.075, 1.093(rac), 1.093 (S-enantiomere), 1.101 , 1.1 1 1 and 1.120 show good activity in this test (at least 50% inhibition).

Example B-2: Action against Pyrenophora teres (net blotch) on barley Barley leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions (0.02% active ingredient). After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 4 days after inoculation as preventive fungicidal activity. Compounds 1.002, 1.003, 1.041 , 1.045, 1.067(rac), 1.075, 1.093(rac), 1.093 (S-enantiomere), 1.101 , 1.1 11 and 1.120 show 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 are 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 is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically after 3-4 days. The activity of a compound is expressed as fungal growth inhibition. Compounds 1.002, 1.003, 1.041 , 1.045, 1.093(rac) and 1.101 show good activity in this test (at least 50% inhibition).

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

Conidia of the fungus from cryogenic storage are 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 is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically after 6-7 days. The activity of a compound is expressed as fungal growth inhibition. Compounds 1.002, 1.003, 1.041 , 1.045, 1.067(rac), 1.075, 1.093(rac), 1.101 and 1.120 show 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 are 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 is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically after 72 hrs. The activity of a compound is expressed as fungal growth inhibition. Compounds 1.002, 1.003, 1.041 , 1.045, 1.067(rac), 1.093(rac), 1.101 , and 1.120 show 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 are 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 is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically after 72 hours. Compounds 1.041 , 1.045, 1.075, 1.101 and 1.120 show good activity in this test (at least 50% inhibition).

Example B-7: Curative action against Puccinia recondita (brown rust) on wheat Wheat leaf segments are 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 are sprayed with test solutions (0.02% active ingredient). After appropriate incubation the activity of a compound is assessed 8 days after inoculation as curative fungicidal activity. Compounds 1.002, 1.041 , 1.045, 1.085, 1.093(rac), 1.093 (S-enantiomere), 1.101 , 1.1 1 1 and 1.120 show good activity in this test (at least 50% inhibition).

Example B-8: Action against Leptosphaeria nodorum (Septoria nodorum; glume blotch) on wheat

Wheat leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions (0.02% active ingredient). After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 4 days after inoculation as preventive fungicidal activity. Compounds 1.002, 1.041 , 1.093(rac), 1.101 , 1.1 1 1 and 1.120 show good activity in this test (at least 50% inhibition).

Claims

WHAT IS CLAIMED IS:

1. A compound of formula I

wherein

Ri is hydrogen or Ci-C₄alkyl;

R₂ is hydrogen or Ci-C₄alkyl; or Ri and R₂ together are C₂-C D₅alkylene

R₃ is hydrogen or C₃-C₇cycloalkyl;

B i is the group I Bi

wherein

R₄ is hydrogen, halogen or d-C₆alkyl;

R₅ is hydrogen or halogen;

R₆ is hydrogen, halogen, d-C₆alkyl, C₂-C₆alkenyl, C₃-C₆alkinyl, C₃-C₆cycloalkyl-C₃-C₆alkinyl, halophenoxy, halophenyl-C₃-C₆alkinyl, C(Ci-C₄alkyl)=NO-Ci-C₄alkyl, C_rC₆haloalkyl, C_r

C₆haloalkoxy, C₂-C₆haloalkenyl, or C₂-C₆haloalkenyloxy;

R₇ is hydrogen or halogen;

R₈ is hydrogen, halogen, d-C₆alkyl, Ci-C₆alkoxy,

G is selected from the group consisting of CH₂S, C(O)CH₂, C(=NOCH₃)CH₂ and (CH₂)₄;

A is the group A₁ ^R10 /

^N-N NΛ^RH ¹¹ (A₁), wherein

R₉

R₉ is hydrogen or d-C₄alkyl;

Rio is CrC₄alkyl, Ci-C₄haloalkyl or halogen;

Rn is hydrogen or halogen; 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 R₁₀ is difluoromethyl or trifluoromethyl.

3. A compound according to claim 1 , wherein R₁ is hydrogen.

4. A compound according to claim 1 , wherein R₂ is hydrogen or methyl.

5. A compound of formula XIIIa

(XIIIa)

wherein A, R₁ R₂ and R3 are as defined under formula I in claim 1.

6. A compound of formula Ib2a

wherein A, B, R₁, R₂ and R₃are as defined under formula I in claim 1.

7. A compound of formula Ilb3

wherein B, R₁ and R3 are as defined under formula I in claim 1.

8. 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.

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