WO1995014015A1

WO1995014015A1 - Benzothiophene derivatives possessing a methoxyimino substituent as microbicides

Info

Publication number: WO1995014015A1
Application number: PCT/EP1994/003540
Authority: WO
Inventors: Stephan Trah
Original assignee: Ciba-Geigy Ag
Priority date: 1993-11-19
Filing date: 1994-10-27
Publication date: 1995-05-26
Also published as: IL111675A0; ZA949177B; AU7992594A

Abstract

Compounds of formula (I), wherein: W is oxygen or NR1; Z is OR2 or NHR3; R4 is aryl that is unsubstituted or is substituted by from 1 to 3 identical or different substituents selected from C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C1-C4alkoxy C1-C4alkyl, C1-C4haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO2, C1-C4alkoxycarbonyl, C1-C4alkanoyl, unsubstituted alkylenedioxy and alkylenedioxy substituted by from 1 to 4 halogen atoms; or heteroaryl to which a benzo group may have been fused, and wherein these heteroaryl and benzo groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C1-C4haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO2 and C1-C4alkoxycarbonyl; R1, R2, R3 each independently of the others is hydrogen or C1-C4alkyl; in free form or in the form of their salts, are suitable for the control and prevention of infestation of plants with microorganisms.

Description

BENZOTHIOPHENE DERIVATIVES POSSESSING A METHOXYIMINO SUBSTITUENT AS MICROBICIDES

The invention relates to microbicidally active compounds of formula I

wherein:

W is oxygen or NR_j.

Z is OR₂ or NHR₃;

R₄ is aryl that is unsubstituted or is substituted by from 1 to 3 identical or different substituents selected from C_rC₄alkyl, C₁-C₄alkoxy, C_rC₄haloalkyl, C_rC₄alkoxy-

C_rC₄alkyl, C_rC₄haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂, C_rC₄alkoxy- carbonyl, C_rC₄alkanoyl, unsubstituted alkylenedioxy and alkylenedioxy substituted by from 1 to 4 halogen atoms; or heteroaryl to which a benzo group may have been fused, and wherein these heteroaryl and benzo groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from Cj-Gjalkyl, C₁-C₄alkoxy, C_rC₄haloalkyl, C_rC₄haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂ and Cj-Qalkoxycarbonyl;

R_}, R₂, R₃ each independently of the others is hydrogen or C_rC₄alkyl; in free form or in the form of a salt thereof.

The compounds according to the invention have microbicidal properties and are suitable as fungicidal active ingredients, especially for use in agriculture and in horticulture.

The invention further relates to a process for the preparation of the compounds according to the invention, to microbicidal compositions comprising such compounds as active ingredients, and to the use of such compounds and compositions in the control of phytopathogenic fungi.

In the above formula I and in the following, alkyl, haloalkyl, haloalkoxy and alkoxy groups are straight-chain or branched, depending upon the number of carbon atoms. Alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

Halogen on its own or as part of an alkyl or alkoxy group is fluorine, chlorine, bromine or iodine.

Aryl is, for example, naphthyl or, especially, phenyl.

Heteroaryl is a 5- to 7-membered aromatic ring that comprises the hetero atoms N, O and/or S and to which an unsubstituted or substituted benzo group or a further heteroaryl group may have been fused. Examples of heteroaryl groups are: benzimidazolyl, benzo- coumarinyl, benzofuryl, benzothiadiazolyl, benzothiazolyl, benzothienyl, benzoxazolyl, benzodiazolyl, quinazolinyl, quinolyl, quinoxalinyl, carbazolyl, dihydrobenzofuryl, ethylenedioxyphenyl, furyl, imidazolyl, indazolyl, indolyl, isoquinolyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, naphthyridinyl, oxazolyl, phenanthridinyl, phthal- azinyl, pteridinyl, purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyrazolo[3,4-b]pyridyl, pyrid- ', pyrimidinyl, pyrrolyl, tetrazolyl, thiadiazolyl, thiazolyl, thienyl, triazinyl and triazoiyl.

Compounds of formula I that contain asymmetric carbon atoms will occur in optically active form. The compounds will in any case occur in the [E]- or the [Z]-form solely by virtue of the presence of the oxime double bond. Atropisomerism may also occur. Formula I is intended to include all of these possible isomeric forms and also mixtures thereof, e.g. racemic mixtures and any [E/Z]-mixtures.

Within the scope of this invention, the following standard configuration terms are applicable with regard to the oxime double bond:

CH₃0

The E-form is preferred.

The compounds of formula I may, if they have at least one basic centre, form acid addition salts. These salts are formed, for example, with mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with organic carboxylic acids, such as, for example, acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, with hydroxycarboxylic acids, e.g. ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with organic sulfonic acids, such as, e.g. methane- or p-toluene-sulfonic acid. Within the scope of this invention, agrochemically advantageous salts are preferred. The compounds of formula I are also to be understood as including such acid addition salts.

Important groups of formula I are:

(1) compounds wherein: W is oxygen or NCH₃; Z is OCH₃ or NHCH₃.

(2) Of the compounds mentioned in (1), those wherein:

R₄ is phenyl or naphthyl, wherein those groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from C_j- alkyl, C_j-C alkoxy, C_rC₄haloalkyl, C₁-C₄alkoxy-C₁-C alkyl, C_rC₄haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂, C_rC₄alkoxycarbonyl, C_rC₄alkanoyl, unsubstituted alkylenedioxy and alkylenedioxy substituted by from 1 to 4 halogen atoms; a 5- or 6-membered heteroaryl group that comprises from 1 to 3 hetero atoms selected from the group consisting of O, N and S and to which a benzo group may have been fused, wherein those heteroaryl and benzo groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from C_rC₄alkyl, C_rC₄alkoxy, C_rC₄haloalkyl, C_rC₄haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂ and C_rC₄alkoxycarbonyl.

(3) Of the compounds mentioned in (2), those wherein:

R₄ is a 5- or 6-membered heteroaryl group that comprises from 1 to 3 hetero atoms selected from the group consisting of O, N and S and to which a benzo group may have been fused, wherein those heteroaryl and benzo groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from C_rC₄alkyl, C_rC₄alkoxy, C_rC₄haloalkyl, C_rC₄haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂ and C_rC₄- alkoxycarbonyl.

(4) Of the compounds mentioned in (3), those wherein:

R₄ is a 5- or 6-membered heteroaryl group that comprises from 1 to 3 N-atoms and to which a benzo group may have been fused, wherein those heteroaryl and benzo groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from C_rC₃alkyl, C_rC₃alkoxy, C_j- haloalkyl, Cj-C₃haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂ and C_rC₃alkoxycarbonyl.

(5) Of the compounds mentioned in (4), those wherein:

R is isoxazolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, indolyl, quinolyl, quinazolinyl and quinoxalinyl.

(6) Of the compounds mentioned in (2), those wherein:

R₄ is phenyl or naphthyl each unsubstituted or substituted by from 1 to 3 identical or different substituents selected from C_rC₃alkyl, C_rC₃alkoxy, C_rC₃haloalkyl, C_rC₃halo- alkoxy, halogen, hydroxy, cyano, thiocyano, NO₂, C₁-C₂alkoxycarbonyl, C_rC₄alkanoyl, methylenedioxy, difluoromethylenedioxy, unsubstituted ethylenedioxy and ethylenedioxy substituted by from 1 to 4 halogen atoms.

(7) Of the compounds mentioned in (6), those wherein:

R₄ is phenyl that is unsubstituted or substituted by 1 or 2 identical or different substituents selected from fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and trifluoromethoxy.

(8) Of the compounds mentioned in (2), those wherein:

R₄ is phenyl or naphthyl, wherein those groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, formyl, acetyl, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylenedioxy and difluoromethylenedioxy; a 5- or 6-membered heteroaryl group that comprises from 1 to 3 hetero atoms selected from the group consisting of O, N and S and to which a benzo group may have been fused, wherein those heteroaryl and benzo groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy and 2,2,2-trifluoro¬ ethoxy. (9) Of the compounds mentioned in (2), also those wherein:

R₄ is a 5- or 6-membered heteroaryl group that comprises from 1 to 3 hetero atoms selected from the group consisting of O and N and that is unsubstituted or is substituted by from 1 to 3 identical or different substituents selected from C_rC₃alkyl, C_rC₃alkoxy, C_rC₃haloalkyl, Cj-Gjhaloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂ and C_rC₃- alkoxycarbonyl.

(10) Of the compounds mentioned in (9), those wherein:

R₄ is a 5- or 6-membered heteroaryl group that comprises 1 or 2 hetero atoms selected from the group consisting of O and N and that is unsubstituted or is substituted by from 1 to 3 identical or different substituents selected from fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and trifluoromethoxy.

(11) Also preferred are compounds wherein:

Ri, R₂ and R₃ each independently of the others is methyl or ethyl; and, among them, especially those groups wherein:

W is NCH₃;

Z is OCH₃ or NHCH₃; or

W is oxygen or NCH₃; Z is OCH₃; or

W is oxygen or NCH₃; Z is NHCH₃; or

W is oxygen; Z is OCH₃.

The esters of the general formula II, wherein R₂ is alkyl and R is as defined above, can be prepared from the intermediates XV, wherein R₂ is alkyl, by reaction with an alcohol R₄OH in the presence of a base, such as, for example, potassium carbonate, sodium hydride or sodium methanolate, in a suitable organic solvent, such as, for example, dimethylformamide, acetone or tetrahydrofuran, at temperatures of from 0°C to 100°C.

(XV) (ll)

The amides of the general formula HI, wherein R₃ and R₄ are as defined above, can be prepared, for example, in accordance with the following scheme:

(II) (III)

The esters π are reacted with an amine H NR₃ in a suitable solvent, such as, for example, ethanol, dimethylformamide or toluene, at a temperature of from -20°C to +60°C.

Imino ethers of the general formula IV, wherein R₂ is alkyl and R₁ and R₄ are as defined above, can be prepared from the amides III.

(Ill)

For that purpose, the amides III are reacted with a trialkyloxonium tetrafluoroborate at a temperature of from 0°C to 50°C in a suitable solvent, such as, for example, dichloromethane, chloroform or toluene.

Amidines of the general formula V, wherein R R₃ and R are as defined above, can be prepared from the imino ethers IV by reaction with an amine H₂NR₃ in a suitable solvent, such as, for example, dioxane, dimethylformamide or toluene, at a temperature of from -20°C to +60°C.

In a further form of the process, imino ethers and amidines of the general formula VII, wherein Z, R_t and R₄ are as defined above, can be obtained starting from chlorides of the general formula VI, wherein R_j and R₄ are as defined above, by reaction with alcoholates and with alcohols, respectively, in the presence of a base or with amines in a suitable organic solvent, such as, for example, diethyl ether, dimethylformamide or toluene, at a temperature of from -20°C to +80°C.

The chlorides of the general formula VI are obtainable from the corresponding amides III, for example by reaction with thionyl chloride, phosphorus oxychloride or triphenyl- phosphine/carbon tetrachloride. See in this connection C. Fern, "Reaktionen der organischen Synthese", p. 564, 6. Thieme Verlag, Stuttgart 1978.

The isolation and purification of the compounds of formula I prepared in that manner may be carried out by methods that are known per se. Any isomeric mixtures obtained, for example mixtures of E/Z isomers, can be separated into the pure isomers likewise by methods that are known per se, for example by chromatography or fractional crystal¬ lisation.

The intermediates of the general formula XV, wherein R₂ is alkyl, can be prepared by analogy with known methods, in accordance with Synthesis Scheme 1. For the conversion VIII-→IX→X see, for example, K. Deuchert et al. , Synthesis 1973, 777.

Synthesis Scheme 1:

gent

TMS = trimethylsilyl LDA = lithium diisopropylamide NBS = N-bromosuccinimide AIBN = azobisisobutyronitrile

The aldehyde VIII is first converted into the silylated cyanohydrin IX which is reacted with lithium diisopropylamide and then with a chloroformic acid alkyl ester to form the α-keto ester X. The latter is condensed with O-methylhydroxylamine hydrochloride to form XIV. Bromination of the latter then gives the intermediate XV.

Alternatively, the intermediates XV may be prepared from the carboxylic acid XL The latter is esterified to form XII and then reacted with an alkyl nitrite, e.g. isopentyl nitrite, in the presence of a base, e.g. sodium methanolate. The oxime XIII so obtained is then reacted with a methylating agent, e.g. dimethyl sulfate, in the presence of a base, e.g. potassium carbonate, to form XIV.

Similarly by analogy with known methods, the intermediates XV, wherein R₂ is alkyl, can be prepared in accordance with the following Synthesis Scheme 2

Synthesis Scheme 2:

(XIX)

3-Methylbenzo[b]thiophene XVI is reacted at a temperature of from -20°C to +20°C with n-butyllithium and then with carbon dioxide to form the carboxylic acid XVII. After conversion into the acid chloride XVIII, there is obtained by reaction with a cyanide, such as, for example, cupric cyanide, the cyanoketone XIX which is converted by hydrolysis in the presence of an alcohol R₂OH into the α-keto ester X. The invention likewise relates to the intermediates of formula XV.

Methoximinoacetic acid derivatives having a microbicidal action are known, for example, from EP-A-398 692; EP-A-400 417 and EP-A-528 681.

It has now been found that compounds of formula I, which differ structurally in a characteristic manner from methoximinoacetic acid derivatives in the literature, have for practical purposes a very advantageous microbicidal spectrum for the control of phytopathogenic microorganisms, especially fungi. They possess very advantageous curative, preventive and, especially, systemic properties and can be used for the protection of numerous crop plants. With the compounds of formula I it is possible to inhibit or destroy pests occurring on various crops of useful plants or on parts of such plants (fruit, blossom, leaves, stems, tubers, roots), while parts of the plants which grow later also remain protected against phytopathogenic microorganisms.

The compounds of formula I can also be used as dressings for protecting seed (fruit, tubers, grains) and plant cuttings from fungal infections and against phytopathogenic fungi that occur in the soil.

Compounds of formula I are effective, for example, against phytopathogenic fungi belonging to the following classes: Fungi imperfecti (especially Botrytis, and also Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, Cercosporella and Alternaria); Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). They are furthermore effective against the class of the Ascomycetes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula), but especially also against that of the Oomycetes (e.g. Phyto- phthora, Peronospora, Bremia, Pythium, Plasmopara).

Target crops to be protected within the scope of this invention comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, triticale, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, gooseberries, raspberries and blackberries); leguminous plants (beans, lentils, peas and soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts); cucumber plants (marrows, cucumbers and melons); fibre plants (cotton, flax, hemp and jute); citrus fruit (oranges, lemons, grapefruit and mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika); lauraceae (avocados, cinnamon and camphor) and plants such as tobacco, nuts, coffee, sugar cane, tea, pepper and other aromatic plants, vines, hops, aubergines, bananas and natural rubber plants, and also ornamentals.

The compounds of formula I are normally applied in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with further active ingredients. These further active ingredients may be fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides, and insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology.

Suitable carriers and adjuvants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binding agents or fertilisers.

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite.

Especially advantageous application-promoting adjuvants which are able to reduce substantially the rate of application are also natural (animal or vegetable) or synthetic phospholipids of the series of the cephalins and lecithins, which can be obtained, for example, from soybeans. Depending upon the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂). e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.

Suitable non-ionic surfactants are polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said deriva¬ tives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Representative examples of non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy- polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C₈-C₂₂alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.

The anionic, non-ionic or cationic surfactants customarily employed in formulation technology are known to one skilled in the art or can be found in the relevant specialist literature:

- "Mc Cutcheon's Detergents and Emulsifiers Annual", Mc Publishing Corp., Glen Rock, New Jersey, 1988.

- M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981. - Dr. Helmut Stache "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna 1981.

The agrochemical compositions usually comprise 0.1 to 99 %, preferably OJ to 95 %, of a compound of formula 1, 99.9 to 1 %, preferably 99.9 to 5 %, of a solid or liquid adjuvant, and 0 to 25 %, preferably OJ to 25 %, of a surfactant.

Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further auxiliaries, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.

The formulations, i.e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with an extender, e.g. with a solvent (mixture), a solid carrier and, where appropriate, surface-active compounds (surfactants).

A preferred method of applying an active ingredient of formula I, or an agrochemical composition comprising at least one of those active ingredients, is application to the foliage of the plants (foliar application), the frequency and the rate of application depending upon the risk of infestation by the pathogen in question. However, the active ingredients of formula I can also penetrate the plants through the roots via the soil (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredients are incorporated into the soil in solid form, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field. The compounds of formula I may also, however, be applied to seeds (coating), either by treating the seeds with a liquid or powder foπnulation of the active ingredient (seed dressing) or by coating them with a solid formulation. It is possible, in principle, to protect any kind of plant propagation material with compounds of formula I, e.g. seed, roots or stems.

The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for that purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in e.g. polymer substances. As with the nature 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. Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare, preferably from 25 g to 800 g a.i./ha, most preferably from 50 g to 400 g a.i./ha. When used as seed dressings, rates of from 0.001 g to 1.0 g of active ingredient per kg of seed are advantageously used.

Preparation Examples

Example P-l: Preparation of

1.5 g of [E]-methyl-2-{3-bromomethylbenzo[b]thien-2-yl}-2-methoximinoacetate and 0.52 g of 2-fluorophenol in 10 ml of dimethylformamide are stirred with 1.21 g of potassium carbonate at room temperature for 2 hours. The reaction mixture is diluted with water and extracted twice with 50 ml of ethyl acetate each time. The organic phases are washed with 100 ml of sodium chloride solution, dried over anhydrous sodium sulfate and concentrated in vacuo. The residue is purified by chromatography on silica gel using hexane/diethyl ether (4:1) as eluant. [E]-methyl-2-{3-[2-fluorophenoxymethyl]benzo- [b]thien-2-yl}-2-methoximinoacetate crystallises from diethyl ether/hexane in the form of colourless crystals, m.p. 90-92°C (Comp. No. 16, Tab. 1). Example P-2: Preparation of

1.6 g of [E]-methyl-2-{3-[2-fluorophenoxymethyl]benzo[b]thien-2-yl}-2-methoximino- acetate from Example P-1 are stirred with 1.6 ml of 33 % methylaminc. solution in ethanol for 8 hours at room temperature. The product, which crystallises out, _;_ filtered off with suction and then washed with ethanol:

[E]-N-methyl-2-{3-[2-fluorophenoxymethyl]benzo[b]thien-2-yl}-2-methoximinoacet- amide, m.p. 135-137°C [Comp. No. 53, Tab. 1).

Example P-3: Preparation of

A solution of 1.25 g of [E]-N-methyl-2-{3-[2-fluorophenoxymethyl]benzo[b]thien-2-yl}- 2-methoximinoacetamide from Example P-2 in 5 ml of dichloromethane is added at room temperature, with stirring, to 0.52 g of trimethyloxonium tetrafluoroborate in 5 ml of dichloromethane. The reaction mixture is stirred for 48 hours, washed in succession with sodium hydrogen carbonate solution and sodium chloride solution and dried over anhydrous sodium sulfate. After concentration in vacuo, the residue is chromatographed on silica gel using hexane/diethyl ether (9:1) as eluant, to yield N,O-dimethyl-2-{3-[2- fluorophenoxymethyl]benzo[b]thien-2-yl}-2-methoximinoacetimidate in the form of a yellow oil, MS: M⁺ 386 (19), 275 (100) (Comp. No. 67, Tab. 1).

Example P-4: Preparation of

1.0 g of N,O-dimethyl-2-{3-[2-fluorophenoxymethyl]benzo[b]thien-2-yl}-2-methoximino- acetimidate from Example P-3 is stirred with 1 ml of 33 % methylamine solution in ethanol for 24 hours at room temperature. After concentration in vacuo, the residue is chromatographed on silica gel using ethyl acetate as eluant, to yield N,N'-dimethyl-2-{3- [2-fluorophenoxymethyl]benzo[b]thien-2-yl}-2-methoxyiminoacetamidine in the form of a yellow oil, MS: M⁺ 385 (11), 260 (100) (Comp. No. 83, Table 1).

In that manner or in accordance with one of the methods indicated hereinbefore, it is possible to prepare the following compounds:

(Abbreviations: Me = methyl; Et = ethyl; E/Z: configuration of the oxime double bond.)

Table 1

Comp. W z R₄ Isomer Phys. Data

No.

1 O OMe phenyl E oil Z oil

2 O OMe 2-methylphenyl E m.p. 76-78°C Z m.p. 87-89°C

3 O OMe 3-methylphenyl E m.p. 60-62°C Z m.p. 76-78°C

4 O OMe 4-methylphenyl

5 O OMe 2-ethylphenyl E oil

6 O OMe 3-ethylphenyl

7 O OMe 4-ethylphenyl

8 O OMe 2-methoxyphenyl E oil

Z m.p. 86°C

O OMe 3-methoxyphenyl E oil Z oil

10 O OMe 4-methoxyphenyl

11 O OMe 2-ethoxyphenyl

12 O OMe 4-ethoxyphenyl

13 O OMe 2-trifluoromethylphenyl E oil

14 O OMe 3-trifluoromethylphenyl E m.p. 81°C Z oil

15 O OMe 3-trifluoromethoxyphenyl

16 O OMe 2-fluorophenyl E m.p. 90-92°C Comp. W R, Isomer Phys. Data

No.

Z m.p. 94-96°C

17 O OMe 3-fluorophenyl

18 O OMe 4-fluorophenyl E m.p. 115-117°C

Z m.p. 100-102°C

19 O OMe 2-chlorophenyl E m.p. 97-99°C

Z m.p. 99-101°C

20 O OMe 3-chlorophenyl

21 O OMe 4-chlorophenyl E m.p. 125-127°C

Z m.p. 94-96°C

22 O OMe 2-bromophenyl E m.p. 91-93°C

Z m.p. 92-94°C

23 O OMe 3-bromophenyl

24 O OMe 4-bromophenyl

25 O OMe 3-iodophenyl

26 O OMe 4-iodophenyl

27 O OMe 2-cyanophenyl E m.p. 132-134°C

Z m.p. 141-143°C

28 O OMe 3-cyanophenyl

29 O OMe 4-cyanophenyl

30 O OMe 2-nitrophenyl E m.p. 109-111 °C

Z m.p. 134-136°C

31 O OMe 3-nitrophenyl

32 O OMe 4-nitrophenyl

33 O OMe 2-methoxycarbonylphenyl E m.p. 76-78°C

Z m.p. 127-129°C

34 O OMe 3,4-methylenedioxyphenyl E m.p. 92-94°C

Z m.p. 107-109°C

35 O OMe 2,3-difluorophenyl

36 O OMe 2,4-difluorophenyl

37 O OMe 2,5-difluorophenyl E m.p. 84-86°C

Z m.p. 94-96°C

38 O OMe 2,6-difluorophenyl Comp. W z R₄ Isomer Phys. Data

No.

39 O OMe 2,3-dichlorophenyl

40 O OMe 2,5-dichlorophenyl E m.p. 128-130°C Z m.p. 106-108°C

41 O OMe 2,3-dimethylphenyl

42 O OMe 2,5-dimethylphenyl E m.p. 90-93°C Z m.p. 88-90°C

43 O OMe 2,3-dimethoxyphenyl

44 O OMe 3_.5-dimethoxyphenyl E oil Z m.p. 90-92°C

45 O OMe 4-chloro-2-methylphenyl E m.p. 92-94°C Z m.p. 69-71°C

46 O OMe 2-chloro-5-methylphenyl E m.p. 136-138°C Z m.p. 80-82°C

47 O OMe 2-fluoro-5-trifluoromethylphenyl

48 O OMe 2-pyridyl E foam Z m.p. 135-137°C

49 O OMe 2-quinolyl

50 O OMe 2-quinoxalinyl E m.p. 164-166°C Z m.p. 109-111°C

51 O OMe 2-naphthyl E foam Z foam

52 O NHMe 2-methylphenyl E m.p. 105-107°C

Z m.p. 126-128°C

53 O NHMe 2-fluorophenyl E m.p. 135-137°C

Z m.p. 140-142°C

54 O NHMe 2-chlorophenyl E m.p. 102-104°C

Z m.p. 143-145°C

55 O NHMe 2-bromophenyl E m.p. 145-147°C

Z m.p. 141-142°C

56 O NHMe 2-cyanophenyl E m.p. 141-144°C

Z m.p. 178-180°C

57 O NHMe 2-nitrophenyl E m.p. 115-117°C Comp. W Z R₄ Isomer Phys Data

No.

Z m.p. 155-157°C

58 O NHMe 2-ethylphenyl E m.p. 129-131°C

59 O NHMe 2-chloro-5-methylphenyl E m.p. 152-154°C

Z m.p. 155-157°C

60 O NHMe 2,5-dimethylphenyl E m.p. 120-122°C

Z m.p. 150-153°C

61 O NHMe 2,5-dichlorophenyl E m.p. 135-138°C

Z m.p. 177-179°C

62 O NHMe 2,5-difluorophenyl E m.p. 154-156°C

Z m.p. 176-178°C

63 O NHMe 2-fluoro-5-trifluoromethylphenyl

64 O NHMe 3,4-methylenedioxyphenyl E m.p. 131-133°C

Z m.p. 146-148°C

65 O NHMe 2-pyridyl

66 NMe OMe 2-methylphenyl

67 NMe OMe 2-fluorophenyl oil

68 NMe OMe 2-chloroρhenyl

69 NMe OMe 2-bromophenyl

70 NMe OMe 2-chloro-5-methylphenyl

71 NMe OMe 2,5-dimethylphenyl

72 NMe OMe 2,5-dichlorophenyl

73 NMe OMe 2-pyridyl

74 NMe OEt 2-methylphenyl

75 NMe OEt 2-fluorophenyl

76 NMe OEt 2-chlorophenyl

77 NMe OEt 2-bromophenyl

78 NMe OEt 2-chloro-5-methylphenyl

79 NMe OEt 2,5-dimethylphenyl

80 NMe OEt 2,5-dichlorophenyl

81 NMe OEt 2-pyridyl

82 NMe NHMe 2-methylphenyl

83 NMe NHMe 2-fluorophenyl oil Comp. W R_ Isomer Phys. Data No.

84 NMe NHMe 2-chlorophenyl

85 NMe NHMe 2-bromophenyl

86 NMe NHMe 2-chloro-5-methylphenyl

87 NMe NHMe 2,5-dimethylphenyl

88 NMe NHMe 2,5-dichlorophenyl

89 NMe NHMe 2-pyridyl

90 O OMe 2-formylpheny; E m.p.97-99°C

Z m.p.130-132°C

91 O OMe 2-acetylphenyl E m.p.120-123°C

Z m.p.108-110°C

2. Formulation Examples for compounds of formula I (throughout, percentages are by weight

2.1. Wettable powders a) b) c) a compound of Table 1 25% 50% 75% sodium lignosulfonate 5% 5% - sodium lauryl sulfate 3% - 5% sodium diisobutylnaphthalenesulfonate - 6% 10% octylphenol polyethylene glycol ether - 2% - (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% kaolin 62% 27% _

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

2.2. Emulsifiable concentrate a compound of Table 1 10% octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3% cyclohexanone 34% xylene mixture 50%

Emulsions of any required dilution can be obtained from this concentrate by dilution with water.

2.3. Dusts a) b) a compound of Table 1 5% 8% talcum 95% _ kaolin 92%

Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. 2.4. Extruder granules a compound of Table 1 10 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % kaolin 87 %

The active ingredient is mixed and ground with the adjuvants, and the mixture is moist¬ ened with water. The mixture is extruded and then dried in a stream of air.

2.5. Coated granules a compound of Table 1 3 % polyethylene glycol (mol. wt. 200) 3 % kaolin 94 %

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

2.6. Suspension concentrate a compound of Table 1 40 % ethylene glycol 10 % nonylphenol polyethylene glycol ether 6 % (15 mol of ethylene oxide) sodium lignosulfonate 10 % carboxymethylcellulose 1 %

37 % aqueous formaldehyde solution 0.2 % silicone oil in the form of a 75 % aqueous emulsion 0.8 % water 32 %

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. 3. Biological Examples

Compounds according to the invention exhibit a marked action against fungal infestation by the following pathogens.

Example B-l: Action against Phytophthora infestans on tomato plants a) Curative action

After a cultivation period of 3 weeks, tomato plants of the variety "Red Gnome" are sprayed with a zoospore suspension of the fungus and incubated in a humidity chamber at 18 to 20° and saturated humidity. Humidifying is interrupted after 24 hours. When the plants have dried off, they are sprayed with a mixture prepared from a wettable powder formulation of the test compound at a concentration of 200 ppm. After the spray coating has dried, the plants are again placed in the humidity chamber for 4 days. The number and size of the typical leaf specks that have appeared after that time serve as a measure for evaluating the effectiveness of the tested compounds.

b) Preventive-systemic action

A wettable powder formulation of the test compound is poured at a concentration of 60 ppm (based on the volume of the soil) onto the surface of the soil in which three-week-old tomato plants of the variety "Red Gnome" have been potted. After a waiting period of three days, the undersides of the leaves of the plants are sprayed with a zoospore suspension of Phytophthora infestans. The treated plants are then placed in a spray cabin for 5 days at 18 to 20°C and saturated humidity. After that period, typical leaf specks appear, the number and size of which are used to evaluate the effectiveness of the test compounds.

Whereas infestation in untreated and infected control plants is 100 %, with the compounds of the formula I the infestation is reduced to 20 % or less in both tests.

Example B-2: Action against Plasmopara viticola (Bert, et Curt.) (Berl. et DeToni) on vines a) Residual-preventive action

Vine cuttings of the variety "Chasselas" are cultivated in a greenhouse. At the 10-leaf stage, 3 plants are sprayed with a mixture comprising the active ingredient in a concentration of 200 ppm. After the spray coating has dried, the plants are uniformly infected on the undersides of the leaves with a spore suspension of the fungus. The plants are then kept in a humidity chamber for 8 days. After that time, distinct disease symptoms appear in the control plants. The number and size of the infection sites on the treated plants serve as a measure for evaluating the effectiveness of the test compounds.

b) Curative action

Vine cuttings of the variety "Chasselas" are cultivated in a greenhouse and are infected at the 10-leaf stage, on the undersides of the leaves, with a spore suspension of Plasmopara viticola. After being kept in a humidity chamber for 24 hours, the plants are sprayed with a mixture comprising the active ingredient in a concentration of 200 ppm. The plants are then kept in the humidity chamber for a further 7 days. After that time, the disease symptoms appear on the control plants. The number and size of the infection sites on the treated plants serve as a measure for evaluating the effectiveness of the test compounds.

In comparison with the control plants, the plants treated with compounds of formula I exhibit an infestation of 20 % or less.

Example B-3: Action against Pythium debarvanum on sugar beet (Beta vulgaris) a) Action after soil application

The fungus is cultivated on sterile oat grains and added to a soil/sand mixture. The infected soil is placed in flower pots and sown with sugar beet seeds. Immediately after sowing, a wettable powder formulation of the test compounds in the form of an aqueous suspension is poured over the soil (20 ppm active ingredient based on the volume of the soil). The pots are then placed in a greenhouse for 2-3 weeks at 20-24°C. The soil is constantly kept uniformly moist by lightly spraying with water. In evaluating the test, the emergence of the sugar beet plants and also the proportion of healthy and diseased plants is determined.

b) Action after application by dressing

The fungus is cultivated on sterile oat grains and added to a soil/sand mixture. The infected soil is placed in flower pots and sown with sugar beet seeds that have been dressed with the test compounds formulated as a dressing powder (1000 ppm active ingredient based on the weight of the seeds). The sown pots are placed in a greenhouse for 2-3 weeks at 20-24 °C, the soil being kept uniformly moist by lightly spraying with water.

In evaluating the test, the emergence of the sugar beet plants and the proportion of healthy and diseased plants is determined. After treatment with compounds of formula I, over 80 % of the plants emerge and have a healthy appearance. In the control pots, only isolated emergence of plants, which have a sickly appearance, is observed.

Example B-4: Residual-protective action against Cercospora arachidicola on groundnut plants

Groundnut plants 10-15 cm in height are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), and infected 48 hours later with a conidia suspension of the fungus. The infected plants are incubated for 72 hours at 21° and high humidity and then placed in a greenhouse until the typical leaf specks appear. Evaluation of the action of the active ingredient is made 12 days after infection and is based on the number and size of the leaf specks.

Compounds of formula I bring about a reduction in the leaf specks to less than about 10 % of the leaf surface area. In some cases, the disease is completely suppressed (0-5 % infestation).

Example B-5: Action against Puccinia graminis on wheat a) Residual-protective action

6 days after sowing, wheat plants are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), and infected 24 hours later with a uredospore suspension of the fungus. After an incubation period of 48 hours (conditions: 95 to 100 % relative humidity at 20°), the plants are placed in a greenhouse at 22°. Evaluation of rust pustule development is made 12 days after infection.

b) Systemic action

Wheat plants are watered 5 days after sowing with an aqueous spray mixture (0.006 % active ingredient, based on the volume of the soil). Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. The treated plants are infected 48 hours later with a uredospore suspension of the fungus. After an incuba¬ tion period of 48 hours (conditions: 95 to 100 % relative humidity at 20°), the plants are placed in a greenhouse at 22°. Evaluation of rust pustule development is made 12 days after infection.

Compounds of formula I bring about a distinct reduction in the fungus infestation, in some cases to 10-0 %.

Example B-6: Action against Pyricularia oryzae on rice plants a) Residual-protective action

After a cultivation period of 2 weeks, rice plants are sprayed to drip point with an aqueous spray mixture (0.02 % active ingredient), and infected 48 hours later with a conidia suspension of the fungus. Evaluation of fungus infestation is made 5 days after infection, during which time 95 to 100 % relative humidity and a temperature of 22° are maintained.

b) Systemic action

2-week-old rice plants are watered with an aqueous spray mixture (0.006 % active ingredient, based on the volume of the soil). Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. The pots are then filled with water so that the lowermost parts of the stalks of the rice plants stand in water. After 96 hours, the plants are infected with a conidia suspension of the fungus and are kept for 5 days at 95 to 100 % relative humidity and a temperature of 24°C.

Compounds of formula I largely prevent the outbreak of the disease on the infected plants.

Example B-7: Residual-protective action against Venturia inaequalis on apples Apple cuttings with 10-20 cm long fresh shoots are sprayed to drip point with a spray mixture (0.02 % active ingredient), and infected 24 hours later with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90-100 % relative humidity and placed in a greenhouse for a further 10 days at 20-24°C. Scab infestation is evaluated 15 days after infection.

Compounds of formula I have predominantly a lasting action against scab diseases.

Example B-8: Action against Erysiphe graminis on barley a) Residual-protective action

Barley plants about 8 cm in height are sprayed to drip point with an aqueous spray mixture

(0.02 % active ingredient) and dusted 3 to 4 hours later with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. The fungus infestation is evaluated

10 days after infection. b) Systemic action

Barley plants about 8 cm in height are watered with an aqueous spray mixture (0.002 % active ingredient, based on the volume of the soil). Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. The treated plants are dusted 48 hours later with conidia of the fungus. The infected plants are placed in a greenhouse at 22°. The fungus infestation is evaluated 10 days after infection.

Compounds of formula I in general are able to suppress infestation with the disease to less than 20 % and, in some cases, to suppress it completely.

Example B-9: Action against Podosphaera leucotricha on apple shoots Residual-protective action

Apple cuttings with approximately 15 cm long fresh shoots are sprayed with a spray mixture (0.06 % active ingredient). The treated plants are infected 24 hours later with a conidia suspension of the fungus and are placed in a climatic chamber at 70 % relative humidity and 20°C. The fungus infestation is evaluated 12 days after infection.

After treatment with compounds of formula I, infestation with the disease is less than 20 %. Infestation in control plants is 100 %.

Example B-10: Action against Botrytis cinerea on apple fruit

Residual- protective action

Artificially damaged apples are treated by applying drops of a spray mixture (0.02 % active ingredient) to the damage sites. The treated fruits are then inoculated with a spore suspension of the fungus and incubated for one week at high humidity and about 20°C.

The fungicidal action of the test compound is derived from the number of damage sites that have begun to rot.

Compounds of formula I are able to prevent the spread of the rot in some cases completely.

Example B-l 1: Action against Helminthosporium gramineum

Wheat grains are contaminated with a spore suspension of the fungus and left to dry. The contaminated grains are dressed with a suspension of the test compound (600 ppm of active ingredient based on the weight of the seeds). After two days, the grains are set out on suitable agar dishes and, four days later, the development of the fungus colonies around the grains is assessed. The number and size of the fungus colonies are used to evaluate the test compound. Compounds of formula I exhibit in some cases a good action, i.e. inhibition of the fungus colonies.

Example B-12: Action against Colletotrichum lagenarium on cucumbers After a cultivation period of 2 weeks, cucumber plants are sprayed with a spray mixture (concentration 0.002 %). Two days later, the plants are infected with a spore suspension (1.5xl0⁵ spores/ml) of the fungus and incubated for 36 hours at 23°C and high humidity. Incubation is then continued at normal atmospheric humidity and about 22-23 °C. The fungal infestation that has occurred is evaluated 8 days after infection. Fungal infestation in untreated and infected control plants is 100 %. Compounds of formula I cause in some cases an almost complete inhibition of disease infestation.

Example B-13: Action against Fusarium nivale on rye

Rye of the variety Tetrahell naturally infected with Fusarium nivale is dressed in a roller mixer with the fungicide to be tested, the following concentrations being used: 20 or 6 ppm (based on the weight of the seed).

The infected and treated rye is sown in the open in October in plots of 3 m length and 6 seed rows using a sowing machine. 3 replicates are made for each concentration.

Until evaluation of the infestation, the test crop is cultivated under normal field conditions (preferably in a region having unbroken snow cover during the winter months).

In order to evaluate the phytoxicity, the emergence of the plants is assessed in the autumn and the crop density/number of plants per unit area is assessed in the spring.

In order to determine the activity of the compounds, in spring, immediately after the snow has melted, the percentage proportion of plants infested with Fusarium is calculated. The number of infested plants is, in the present case, less than 5 %. The emerged plants have a healthy appearance.

Example B-14: Action against Septoria nodorum on wheat

Wheat plants are sprayed at the 3-leaf stage with a spray mixture (60 ppm a.i.) prepared from a wettable powder formulation of the test compounds. 24 hours later, the treated plants are infected with a conidia suspension of the fungus. The plants are then incubated for 2 days at 90-100 % relative humidity and placed in a greenhouse at 20-24 °C for a further 10 days. Fungal infestation is evaluated 13 days after infection. Less than 1 % of the wheat plants show infestation.

Example B-15: Action against Rhizoctonia solani on rice Protective local soil application

10-day-old rice plants are watered with a suspension (spray mixture) prepared from a formulation of the test compound, without contaminating the parts of the plants above the soil. Infection is carried out three days later by placing between the rice plants in each pot a blade of barley straw infected with Rhizoctonia solani. Fungal infestation is evaluated after 6 days' incubation in a climatic chamber at 29°C day temperature and 26°C night temperature and 95 % relative humidity. Less than 5 % of the rice plants show infestation. The plants have a healthy appearance.

Protective local foliar application

12-day-old rice plants are sprayed with a suspension prepared from a formulation of the test compound. Infection is carried out one day later by placing between the rice plants in each pot a blade of barley straw infected with Rhizoctonia solani. Evaluation is made after 6 days' incubation in a climatic chamber at 29°C day temperature and 26°C night temperature and 95 % relative humidity. Fungal infestation on untreated and infected control plants is 100 %. Compounds of formula I cause in some cases an almost complete inhibition of the fungal infestation.

Claims

What is claimed is:

1. A compound of formula I

wherein:

W is oxygen or NR_j;

Z is OR₂ or NHR₃;

C₁-C₄alkyl, C₁-C₄haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂, C₁-C₄alkoxy- carbonyl, C_rC₄alkanoyl, unsubstituted alkylenedioxy and alkylenedioxy substituted by from 1 to 4 halogen atoms; or heteroaryl to which a benzo group may have been fused, and wherein these heteroaryl and benzo groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from C_rC₄alkyl, Cj-C₄alkoxy, C_rC₄haloalkyl, C_rC₄haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂ and C_rC alkoxycarbonyl;

Rj, R₂, R₃ each independently of the others is hydrogen or C_rC₄alkyl; in free form or in the form of a salt thereof.

2. A compound according to claim 1 , wherein W is oxygen or NCH₃; Z is OCH₃ or NHCH₃.

3. A compound according to claim 2, wherein

R₄ is phenyl or naphthyl, wherein those groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from C_rC₄alkyl, C_rC₄alkoxy, C_rC haloalkyl, C_rC₄alkoxy-Cj-C₄alkyl, C_rC haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂, C_rC₄alkoxycarbonyl, C_rC alkanoyl, unsubstituted alkylenedioxy and alkylenedioxy substituted by from 1 to 4 halogen atoms; a 5- or 6-membered heteroaryl group that comprises from 1 to 3 hetero atoms selected from the group consisting of O, N and S and to which a benzo group may have been fused, wherein these heteroaryl and benzo groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from C_rC alkyl, Cj-C₄alkoxy, C_rC₄haloalkyl, ^haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂ and C₁-C₄alkoxycarbonyl.

4. A compound according to claim 3, wherein:

R₄ is a 5- or 6-membered heteroaryl group that comprises from 1 to 3 hetero atoms selected from the group consisting of O, N and S and to which a benzo group may have been fused, wherein these heteroaryl and benzo groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from C_rC alkyl, C_rC alkoxy, C_rC₄haloalkyl, C C₄haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂ and C_!-C₄- alkoxycarbonyl.

5. A compound according to claim 4, wherein:

R₄ is a 5- or 6-membered heteroaryl group that comprises from 1 to 3 N-atoms and to which a benzo group may have been fused, wherein these heteroaryl and benzo groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from C_rC₃alkyl, C_!-C₃alkoxy,

C_rC₃haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂ and Cj-Csalkoxycarbonyl.

6. A compound according to claim 5, wherein:

R₄ is isoxazolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, indolyl, quinolyl, quinazolinyl and quinoxalinyl.

7. A compound according to claim 3, wherein:

R₄ is phenyl or naphthyl each unsubstituted or substituted by from 1 to 3 identical or different substituents selected from C_rC₃alkyl, C_rC₃alkoxy, C_rC₃haloalkyl, C_rC₃halo- alkoxy, halogen, hydroxy, cyano, thiocyano, NO₂, C_rC₂alkoxycarbonyl, C_rC₄alkanoyl, methylenedioxy, difluoromethylenedioxy, unsubstituted ethylenedioxy and ethylenedioxy substituted by from 1 to 4 halogen atoms.

8. A compound according to claim 7, wherein:

9. A compound according to claim 3, wherein:

R₄ is phenyl or naphthyl, wherein those groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, formyl, acetyl, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylenedioxy and difluoromethylenedioxy; a 5- or 6-membered heteroaryl group that comprises from 1 to 3 hetero atoms selected from the group consisting of O, N and S and to which a benzo group may have been fused, wherein these heteroaryl and benzo groups are unsubstituted or are substituted by from 1 to 3 identical or different substituents selected from fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy and 2,2,2-trifluoro¬ ethoxy.

10. A compound according to claim 3, wherein:

R₄ is a 5- or 6-membered heteroaryl group that comprises from 1 to 3 hetero atoms selected from the group consisting of O and N and that is unsubstituted or is substituted by from 1 to 3 identical or different substituents selected from C_rC₃alkyl, C_rC₃alkoxy, C_rC₃haloalkyl, Cj- haloalkoxy, halogen, hydroxy, cyano, thiocyano, NO₂ and C_rC₃- alkoxycarbonyl.

11. A compound according to claim 10, wherein:

12. A compound according to claim 1, wherein:

R_j, R₂ and R₃ each independently of the others is methyl or ethyl.

13. A compound according to claim 9, wherein: W is NCH₃;

Z is OCH₃ or NHCH₃.

14. A compound according to claim 9, wherein: W is oxygen or NCH₃; Z is OCH₃.

15. A compound according to claim 9, wherein: W is oxygen or NCH₃;

Z is NHCH₃.

16. A compound according to claim 9, wherein: W is oxygen;

Z is OCH₃.

17. A compound according to any one of claims 1 to 16, wherein the compound has the E-form at the oxime double bond.

18. A process for the preparation of a compound of formula I according to claim 1, wherein:

(1) for the preparation of a compound of formula II

(XV) (II)

a compound of formula XV is reacted with an alcohol R OH in the presence of a suitable base in a suitable organic solvent at from 0°C to 100°C, wherein R₂ is C_rC₄alkyl and R₄ is as defined for formula I;

(2) for the preparation of a compound of formula III

(II) (III) a compound of formula II is reacted with an amine H₂NR₃ in a suitable solvent at from -20°C to +60°C, wherein R₂ is C_rC₄alkyl and R₃ and R₄ are as defined for formula I;

(3) for the preparation of a compound of formula IV

a compound of formula III is reacted with a trialkyloxonium tetrafluoroborate in a suitable solvent at from 0 to 50°C, wherein R_lt R , R₃ and R₄ are as defined for formula I;

(4) for the preparation of a compound of formula V

(IV) (V) a compound of formula IV is reacted with an amine H₂NR₃ in a suitable solvent at from -20°C to +60°C, wherein R₂ is C_rC₄alkyl and R_{1 ?} R₃ and R₄ are as defined for formula I;

(5) for the preparation of a compound of formula VII

(VI) (VII) a compound of formula VI is reacted with a compound of formula HZ in a suitable organic solvent, where appropriate in the presence of a base, at from -20°C to +80°C, wherein Z, Ri and R₄ are as defined for formula I.

19. A microbicidal composition comprising as active ingredient at least one compound of formula I according to claim 1, together with a suitable carrier and, where appropriate, a surface-active adjuvant.

20. A composition according to claim 19, comprising as active ingredient at least one compound according to any one of claims 2 to 17.

21. A process for the preparation of a composition according to claim 19 by homogeneously mixing and/or grinding the active ingredient with a carrier and, where appropriate, a surface-active adjuvant.

22. The use of a compound of formula I according to claim 1 as a microbicide.

23. A method of controlling plant diseases and preventing infestation with microorganisms by applying to the plant, parts thereof or the locus thereof a compound of formula I according to claim 1.

24. A compound of formula XV,

wherein R₂ is as defined in claim 1.