LT3956B - Fungicidal oxime esters, process for preparing thereof, fungicidal preparation, method of fungi control - Google Patents

Abstract

The invention includes new compounds, which have this generalised formula:<IMAGE>R1 means C1-4-alkyl and (Y-X) means CH2, C1-2-alkylthio-CH = or C1-2-alkyl-ON = and Z means the group of the intention of aldimine, the method of its production, also the fungicidal attributes of these compounds, as active particles. The compounds can be used for the protection against fungus diseases in agriculture, gardening and the protection of timber

Description

The present invention relates to oxime esters, processes for their preparation, fungicidal compositions comprising these oxime esters and their use in agriculture and horticulture.

Preparations used to combat phytopathogenic fungi are disclosed in DE2927480 and GB-2024824, which contain 3-cyano-4-phenylpyrrole derivatives as the active ingredient. This type of preparation, phenylcyclonyl, is described in EP-A236272. 1,2,4-Triazole derivatives having fungicidal properties are described in DE-3406993 and EP-0251775; related oxime structures are disclosed in EP-0254426 and DE-3827361.

The present invention describes oxime esters of general formula I:

in which

R j represents C 1-6 alkyl;

(Χ-Υ) represents CH 2 =, C 1 -C 2 -alkylthio-CH =, or C 1 -C 2 -alkyl-ON =; Z represents an aldimino- or ketimino-group, namely a group

N-,

Ri in which

R 2 represents H, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 cycloalkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-4 alkoxymethyl, C 1-2 alkylthiomethyl, C 1-4 alkylsulfonyl, C 1-3 alkyl; alkoxy, C 1-3 alkylthio or cyano; and

R 3 represents G 1-4 alkyl, aryl-C 1-4 alkyl, heteroaryl-C 1-4 alkyl, C 2-12 alkenyl, aryl-C 1-4 alkenyl, aryloxy-C 1-4 alkyl , heteroaryloxy-C 1-6 -alkyl, heteroaryl-C 1-6 -alkenyl, C 1-6 -cycloalkyl, aryl, heteroaryl;

or R 2 and R 3, taken together with the carbon atom to which they are attached, form a substituted 4- to 7-membered saturated or unsaturated ring which may contain oxygen, sulfur and / or nitrogen, which may further be bonded to replaced by a fused benzene ring.

The compounds of the present invention have fungicidal properties and are suitable as l'ungideic biologically active compounds for use in agriculture and horticulture.

The present invention further relates to a process for the preparation of the compounds of the present invention, a l'-union composition comprising these compounds as active ingredients, as well as the use of these compounds, and a fungicide in agriculture and horticulture.

More particularly, the present invention relates to oxime esters of formula I wherein

Denotes C 1-4 alkyl, (Υ-Χ) denotes CH 2 =, C 1-2 alkylthio-CH = or C 1-2 alkyl-ON =, and Z denotes an aldimino or ketimino group, namely a group wherein

R 2 denotes H, C 1-6 alkyl, C 1-6 haloalkyl, C 1-4 cycloalkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-2 alkoxymethyl, C 1-2 alkylthiomethyl, C 3-4 alkylsulfonyl, C 1-6 alkyl. -alkoxy, C 1-6 alkylthio or cyano, and

R 3 represents alkyl, aryl-C 1-6 -alkyl, heteroaryl-C 1-4 -alkyl, C 2-6 -alkenyl, aryl-C 2-4 -alkenyl, heteroaryl-C 1-6 -alkenyl, C 3-6 -cycloalkyl, aryl, heteroaryl, C 2-5 alkanoyl, aryl, heteroaryl, or R 2 and R 3 taken together with the carbon atom to which they are attached form a substituted four-membered to seven-membered saturated ring containing an optionally oxygen or sulfur atom, which may additionally have a substituted condensed benzene ring. In the above Formula I and further formulas, all alkyl and alkenyl groups, as such or as a fragment of a large group, are illustrated in FIG. heteroarylalkyl may be linear and branched depending on the number of carbon atoms. In addition, alkenyl groups may have one or more double bonds. Halogen as a substituent means chlorine, fluorine, bromine, or iodine, with fluorine, chlorine and bromine being more preferred. The haloalkyl group may have one or more identical or different halogen substituents. Aryl is called phenyl, naphthyl, phenanthryl or fluorenyl. A heteroaryl is a heterocyclic ring of aromatic properties with 1-3 heteroatoms--, Ο and / or S. Most preferred is a triazole or other five- or six-membered ring with 1-2 heteroatoms, which in turn may additionally contain one or two fused benzene rings.

Examples which do not limit the scope of the present invention and will hereinafter be referred to as Het groups include pyrrolyl, pyridyl, furyl, thienyl, isoxazolyl, pyrazinyl, pyridazinyl, imidazilyl, pyrimidinyl or triazolyl groups or these groups condensed with benzene, e.g. quinolinyl, quinoxalinyl, benzofuryl, benzothienyl or dibenzofuryl. By definition, this also applies to aryl or heteroaryl as a fragment of large groups, e.g. aralkyl or heteroarylalkyl groups. Aryl or heteroaryl groups may be substituted by one or more of the following, as appropriate:

halogen, C 1-4 alkyl, C 1-4 haloalkyl, aryl-C 1-6 alkyl, aryloxyC 1-6 alkyl, C 2-4 alkenyl, aryl C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, aryl, C 1-6 alkoxy, C 1-6 haloalkoxy, aryl C 1-6 alkoxy, C 1-6 alkylthio, aryloxy, cyano, nitro, C 2-4 haloalkenyl, C 2-4 alkenyloxy, C2-4haloalkenyloxy, C3-4alkynyloxy, C3-4haloalkynyloxy, cyclopropylmethoxy, cyclopropyl (in this case substituted with 1-3 halogens and / or methyl), cyanomethoxy (-OCH2CN), C1-4alkylmethyl, -alkylsulfinylmethyl, C 1-4 alkylsulfonylmethyl, arylthio, thiocyanato, C 1-4 alkoxyiminomethyl, C 1-4 alkanoyloxy, C 4,4 alkoxycarbonyl;

as well as a heteroaryl (radical), heteroaryl-C 1-4 -alkyl, heteroaryloxy-C 1-4 -alkyl, heteroaryl-C 2-4 -alkenyl, heteroaryl C 1-4 -alkoxy or heteroaryloxy; in addition, the heteroaryl mentioned herein is a representative of the aforementioned Het group.

Almost all of the above-mentioned aryl and heteroaryl substituents can be found once or twice, usually once except for € 4.4- alkyl which is substituted 4 times and halogen which can be 3 times and fluorine up to 5 times.

Most often the aryl group is phenyl, whether alone or as part of another substituent. Most often the aryl group is benzoyl, respectively.

C2-alkanoyl is acetyl. By haloalkyl is meant alkyl groups having up to 6 identical or different halofluorocarbons, chlorine, bromine and / or iodine. Examples of haloalkyl groups as stand-alone groups or as moieties of other substituents (as haloalkoxy) include CH ₂ Cl, CHCl ₂ CCl ₃ CHBr ₂ , CH ₂ CH ₂ Cl, CHCl 1 -CHCl ₂ CF ₂ Cl, CH ₂ J, CF ₃ , ClF. ^ CF ₂ -CF ₂ Chh CHF ₂ , CH ₂ F, CF ₂ CHFcF ₃

Preferred are trifluoromethylene, difluoromethoxy and trifluoromethoxy.

In addition, aryl groups (in addition to phenyl) may have one or two atoms of oxygen, a five-, six- or seven-membered saturated or unsaturated ring which may be substituted one or more times under these conditions with methyl, methoxy, phenyl or halogen. , cyano or oxo (C = O) alternately. Examples of such groups are 5-benzofuryl, 6-benzodioxanyl and 5- (1,3-benzodioxalyl).

In the case where R ₂ to R ₃ together with the carbon atom to which they are attached form an optionally substituted ring, as described in detail above, this refers, in the case of ring substitutions, partially to ,μθ-alkyl or allowed phenyl. The ubiquitous condensed benzene ring can also be replaced. The substituents on the phenyl group or on the benzene ring itself are the substituents mentioned above those bonded to the aryl group.

In the case where the compounds of formula I contain an asymmetric carbon atom, they are optically active compounds. Due to the aliphatic or imido-double bond X = C and the imido-double bond aldimino- or ketoamine group Z, the compounds are in each case in the form of / E / - or / Z / -. Further, atropoisomerism can still be found. The compounds of formula I include all possible isomeric forms and mixtures thereof, e.g. racemic mixtures and spontaneous / E / Z / - mixtures.

In the compound of formula I, R j is usually methyl, and (Y-Χ) independently methylene, methylthiomethylene (CH-SCH ₃ ) or methoxyimine (N-OCH ₃ ); of particular interest are compounds wherein R j represents methoxyimine.

The group (R ₂₎ (R 3) C = N-1 _<2 is usually hydrogen, Cj ^ - alkyl (typically methyl or ethyl), Cj ^ -haloalkyl (typically trifluoromethyl) or C ₃ θ-eikloalkilas (typically cyclopropyl) and In the most common conditions, R is substituted phenyl, naphthyl (usually β-naphthyl) or benzyl; in addition, all substituents are usually up to three identical or different halogen atoms (usually fluorine, chlorine and / or bromine), C 1-4 alkyl (usually methyl), C 1-4 haloalkyl (usually trifluoromethyl), C 1-4 haloalkoxy (usually trifluoromethoxy) and alkylenedioxy (partially 3,4-methylenedioxy) or heteroaryl, usually in the given conditions, substituted with two methyl groups, furyl, in the given conditions chloro- or methyl-substituted thienyl, pyridyl or benzofuryl.

In the case where R3 represents heteroaryl, R2 is usually methyl.

Other representatives of formula I may be:

those compounds of formula I wherein R j represents methyl, (Y-Χ) represents CH ₂ ,

Z represents the group / R2 // R3 / C = N-,

R ₂ represents methyl and

R 3 represents 3-trifluoromethylbenzyl, 4-chloro-3-trifluoromethylbenzyl, 1,4,4,8-trimethyl-nona-1,3,7-trienyl, phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-bromophenyl, 3,4- dichlorophenyl, 3,5-dichlorophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-fluoro-5-methyl-phenyl, 4-methoxyphenyl, 3,4,5-trimethoxyphenyl, 3-trifluoromethoxyphenyl, 3,5-di- (trifluoromethyl) phenyl , β-naphthyl, 2-furyl, 2-thienyl, 2-pyridyl, 2-benzofuryl or 5-chloro-2-thienyl;

those compounds of the formula I in which R 1 represents methyl, (Y-Χ) represents CH ₂ ,

Z represents a group / R ₂ / R / 3 / C = N-,

R3 represents phenyl and

R 2 represents ethyl, propyl or isopropyl;

those compounds of formula I wherein R j represents methyl, (Y-Χ) represents CH ₂ ,

Z represents a group / R ₂ / R / 3 / C = N,

R 2 represents trifluoromethyl and

R 3 represents 2- (3-naphthyl) ethylene, phenyl, 3-chlorophenyl, 4-chlorophenyl, ptoluyl, α, α, α-trifluoro-m-toluyl, β-naphthyl or 2-pyridyl;

those compounds of formula I wherein R j represents methyl, (Y-Χ) represents CH ₂ ,

Z represents a group / R ₂ / R / 3 / O = N-,

R 2 represents cyclopropyl and

R 3 represents phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-bromophenyl, α, α, α-trifluoro-m-toluyl, 4-phenoxyphenyl or β-naphthyl;

those compounds of formula I wherein R a represents methyl, (Υ-Χ) represents methylthiomethylene (= CH-SCH 3),

Z represents the group / R2 / / R3 / C = N-,

R2 represents methyl and

R 3 represents 3-trifluoromethylbenzyl, 4-chloro-3-trifluoromethylbenzyl, 1,4,8-trimethyl-nona-1,3,7-trienyl, phenyl, 4-fluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-bromophenyl, 3, 5-dichlorophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-fluoro-5-methylphenyl, 4-methoxyphenyl, 3,4,5-trimethoxyphenyl, 3-trifluoromethoxyphenyl, 3,5-di (trifluoromethyl) phenyl, 2-furyl, 2-benzofuryl or 5-chloro-2-trienyl;

those compounds of formula I wherein Rj represents methyl, (Υ-Χ) represents methylthiomethylene,

Z represents the group / R2 // R3 / C = N-,

R2 represents trifluoromethyl and

R 3 represents 2- (p-naphthyl) ethylene, phenyl, 3-chlorophenyl, 4-chlorophenyl, p toluyl, α, α, α-trifluoro- m-toluyl, β-naphthyl or 2-pyridyl;

those compounds of formula I wherein Rj represents methyl, (Υ-Χ) represents methylthiomethylene,

Z represents the group / R2 / / R3 / C = N-,

R2 represents cyclopropyl,

R 3 represents phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-bromophenyl, α, α, α trifluoro-m-toluyl, 4-phenoxyphenyl or β-naphthyl;

those compounds of formula I wherein R j represents methyl, (Υ-Χ) represents methoxyimino / = N-OCH 3 /,

Z represents the group / R2 / / R3 / C = N-,

R2 represents methyl and

R 3 represents 4-chloro-3-trifluoromethylbenzyl, phenyl, 3-chlorophenyl, 3,5-dichlorophenyl, 2-fluoro-5-methylphenyl, 3-trifluoromethoxyphenyl or 5-fluoro-2 thienyl;

those compounds of formula I wherein R j represents methyl, (Υ-Χ) represents methoxyimino,

Z represents the group / R2 / / R3 / C = N-,

R2 represents trifluoromethyl and

R 3 represents 2- (p-naphthyl) ethenyl, phenyl, 3-chlorophenyl, 4-chlorophenyl, p toluyl, α, α, α-trifluoro-m-toluyl, β-naphthyl or 2-pyridyl;

those compounds of formula I wherein R j represents methyl, (Y-Χ) represents methoxyimino,

Z represents the group / R ^ / / R3 / C = N-,

R 2 denotes eicopropyl and denotes 3-eblorophenyl, 4-echlorophenyl, 3-bromophenyl, α, α, α-trifluoromethyl, 4-phenoxyphenyl or -naltyl.

According to the present invention, the process for the preparation of the compounds of formula I differs in that the oxime Z-OH, namely the oxime of the general formula

Ri

C = N-OH,

II

R.2 and Rj have the meanings given above, reacting with benzyl alcohol derivatives of general formula III

III wherein R i and Y-Χ have the meanings given above.

This reaction refers to the nucleophilic substitution that occurs under normal conditions for this reaction. The benzyl substituent group V in formula III is understood to mean chlorine, bromine, iodine, mesyloxy, benzenesulfonyloxy or tosyloxy. The reaction is carried out in an inert organic solvent, tetrahydrofuran or, e.g., a cyclic ether such as diosane, acetone, dimethylformamide or dimethylsulfoxide in the presence of a base such as sodium hydroxide, sodium or potassium carbonate, a tertiary amine such as trialkylamine, partially diazobicyclone or , or silver oxide at temperatures between -20 ° C and 80 ° C, preferably between 0 ° C and 20 ° C.

Alternatively, the reaction may be carried out in a catalytic phase transfer, in an organic solvent such as methylene chloride, in the presence of an aqueous alkaline solution such as sodium hydroxide, and in the presence of a phase transfer catalyst such as tetrabutylammonium dibrosulfate, at room temperature. (see eg WE

Keller Phasen-Transfer Reactions, Huka Compendium. Vok I, II, Georg Thieme Verlag, Sluttgart, 1936, 1937, and Chemistry Letters, 1930, p.869370).

The isolation and purification of the compounds of formula I thus obtained can be carried out by known methods. Mixtures of isomers may also be isolated in known ways, e.g., the mixture of E / Z-isomers may be divided into pure isomers, e.g. by chromatography or fractional crystallization.

In the process of this invention, the oximes Z-OH are used as starting materials, e.g. of Formula II are either known or obtained by known methods, for example by reacting the corresponding carbonyl compound 1 ^ 2 ^ 3 ^ = O with hydroxylamino-hydrochloride in the presence of a base such as sodium or potassium hydroxide or pyridine. Other methods can be found in Houben-Weil's "Methoder der Organische Chemie", Rd.4, S.3-303, 1968.

The starting compounds also include compounds of formula III, i.e., α- (2-VCH 2 -phenyl) acrylic acid alkyl esters of formula IIIa, α- (2-VCH 2 phenyl) -p- (C 1 -C 2 alkylthio) acrylic acid alkyl ester of formula IIIb, and as well as the alkyster of O (C 1 -C 2 -alkyl) oxime of formula IIIc 2 (2-VCH 2 -phenyl) glyoxylic acid

which are either known or obtainable by known means. For example, EP 348766 describes a process for the preparation of methyl ester of α- (2-bromomethylphenyl) acrylic acid, EP 310954 and Angew. Chemie, 71, 349-365 (1959), Method for the preparation of a (2-bromomethylphenyl) -? - methylthioacrylic acid methyl ester, and EP 363818 and Angew. Chemie, 71, 349-365 (1959) A process for the preparation of 2- (2-bromomethylphenyl) glyoxylic acid-methyl ester-O-methyloxime. The present invention relates to a process for the preparation of compounds of formula IIIa, IIIb, IIIc.

The preparation of C 1-6 alkyl esters of α- (2-bromomethylphenyl) -p-methylthioacrylic acid can be utilized in a manner different from that described in EP 310954, which in the first step activates the corresponding 3- (4-bromobenzenesulfonyloxy) -2 (O-loluyl) acrylic acid. Bromination of the C 1-6 alkyl ester with N-bromosuccinimide to form 3- (4-bromobenzenesulfonyloxy) -2- (2-bromomethylphenyl) acrylic acid

C 1-6 alkyl ester and the compound obtained in the second step reacts with sodium methiolate to give the desired bond. The starting compound 3- (4-Bromobenzenesulfonyloxy) -2- (O-toluyl) acrylic acid methyl ester is described, for example, in EP 310954.

The compounds of the present invention exhibit fungicidal activity and may find applications to stop or prevent fungal diseases in agriculture, horticulture, and wood protection. In part, they are suitable for stopping growth or destroying phytopathogenic fungi on parts of plants, such as leaves, stems, roots, roots, fruits or flowers, or seeds, which are found in the soil.

Further, the compounds of the invention can be used to control wood pests that damage or discolour it. The compounds of the invention are active in killing fungi of the following classes: Deuteromycetes, Ascomycetes, Basidiomycetes and Phycomycetes.

The compounds of the present invention are particularly suitable for controlling the following pests: mildew fungi (e.g., Erysiphe graminis, Erysiphe cichoracearum,

Podosphaera leucotricha, Uncinula necator, Sphaerotheca spp.F, rust fungi (e.g., Puccinia tritici, Puccinia recondita,

Pucciniahordei, Puccinia coronata, Puccinia striiformis, Pucciniaarachidis,

Hemileia vastatrix, Uromyces fabaep, shotgun fungi (e.g. Vert. Inacgualis)

Cercospora spp. (e.g., Cercospora arachidicola, Cercosporabeticola) Mycosphacrella spp. (e.g. Mycosphacrella phylogeny}

Altemaria spp. (e.g. Altemaria brassicae, Altemaria mali}

Septoria spp. (e.g. Septoria nodorum)

Hclminthosporium spp. (e.g. Helminthosporium teres, Helminthosporium oryzea)

Plasmopara spp. (e.g. Plasmopara viticola)

Pscudopcronospora spp .., (e.g. Pscudoperonosporacubcnsis)

Phytophthora spp. (e.g. Phytophthorainfestans)

Pscudocercosporella spp. (e.g. Pseudocercosporella herpotrichoidcs) Piricularia spp. (e.g. Piriculariaoryzae)

Further, the compounds act, for example, against fungi of the following genera:

Tilletia, Ustilago, Rhizoctonia, Verticillium, Fusarium, Pythium,

Gaeumannomyces, Sclerotinia, Monilia, Botrytis, Peronospora, Bremia,

Gloeosporium, Cercosporidium, Penicillium, Ceratocystis, Rhynchosporium,

Pyrenophora, Diaporthe, Ramuiaris, Leptosphaeria.

The known agent of the compounds of the present invention also has activity against wood fungi such as fungi of the following genera:

Coniophora, Cloeophyllum, Poria, Merulius, Trametes, Aureobasidium,

Sclerophoma and Trichoderma.

The compounds of the formula I according to the invention have a prophylactic and curative effect and, in particular, exhibit systemic effects.

They are active against phytopathogenic fungi in greenhouse conditions at concentrations ranging from 0.5 mg to 500 mg per liter of culture broth already in the presence of the biologically active substance. Fields typically use doses of 20g to 1g of active ingredient of formula I per 1 hectare. Doses used for seed fungicide treatment or soil treatment are usually from 0.001 g to 1.0 g of the active ingredient of formula I, pgg seeds.

The compounds of the invention may be formulated in various forms, e.g., solutions, suspensions, emulsions, emulsifiable concentrates, and powder formulations. The fungicidal compositions according to the invention are characterized in that they contain an active amount of at least one compound of the general formula I as well as a formulation of excipients. When formulating a recipe, it is most appropriate to include at least one of the following excipients:

solid carriers, solvents or dispersants, surfactants (wetting and emulsifying agents), dispersing agents (non-surfactant), and stabilizers.

Solid carriers may include natural minerals such as kaolin, bentonite, clay, kieselguhr, talc, chalk such as precipitated lime, limestone, quartz, dolomite, atapulgite, montmorillonite and infuser earth, as well as synthetic minerals, such as high dispersion silica, alumina and silicates; and organic materials such as cellulose, starch, urea, and synthetic resins; and mineral fertilizers such as phosphates and nitrates; in addition, such carriers may be in the form of granules or powders.

The following materials may be used as solvents or dispersants: aromatic hydrocarbons such as toluene, xylene, benzene and ii-alkylnaphthalenes; chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons such as echlorobenzenes, chloroethylenes and methylene chloride; aliphatic hydrocarbons such as cyclohexane and paraffins such as petroleum fractions; alcohols such as butanol or glycol as well as ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and highly polar solvents or dispersants, such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, and wherein such solvents or dispersants are characterized by a flash point of at least 30 ° C and a boiling point of greater than 50 ° C; and also water.

Solvents or dispersants may also be so-called liquefied gaseous diluents or carriers, which are products which are gaseous at room temperature and under normal pressure. Examples of such products include, in part, working aerosol gases such as (halohydrocarbons).

When using solvent water, it is possible to use e.g. and organic solvents as auxiliaries.

Surfactants (wetting agents and emulsifiers) may be used to form compounds such as condensation products of saturated acids, saturated alcohols or ethylene oxide; ethers or esters of saturated acids and sugars or polyhydric alcohols; products obtained from sugars or polyhydric alcohols by condensation with ethylene oxide; block copolymers of ethylene oxide and propylene oxide; or alkyldimethylamine oxides.

Surfactants may also include anionic substances such as soaps, sulfuric esters of saturated acids such as sodium dodecyl sulfate, sodium octadecyl sulfate and sodium cetyl sulfate; alkylsulfonates, arylsulfonates and saturated aromatic sulfonates such as alkylbenzenesulfonate, such as calcium dodecylbenzenesulfonate, and butylnaphthalenesulfonate; and complex sulfonates of saturated acids, such as the amide condensation product of oleic acid with N-methylurine and sodium sulfonate.

Finally, cationic compounds such as methylbenzylammonium chloride, dialkyldimethylammonium chloride, alkyltrimethylammonium chloride and ethoxylated quaternary ammonium chloride may also be present as surfactants.

Dispersants (without surfactant effect) may be used lignin, sodium and ammonium salts of lignin sulfonic acid, sodium salts of di-isobutylenic copolymer of maleic anhydride, sulfonates of sodium and ammonium salts of polycondensation products of naphthalene and formaldehyde, and processed sulfite alkalis.

Suitable dispersants which are particularly suitable as thickeners or pre-precipitation agents are, for example, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.

Examples of suitable stabilizers include acidic constituents such as epichlorohydrin, phenylglycid ester and other epoxides; antioxidants such as gallic acid and butylhydroxytoluene ester; an ultraviolet sensitizer such as substituted benzophenone, diphenylacrylonitrile ester and cinnamic acid ester; and deactivators, such as ethylenediaminetetraacetic acid salts and polyglycols.

The fungicidal compositions may contain, together with the active compound of the formula I, other active additives, such as other fungicides, insecticides, acaricides, bactericides, plant growth regulators and mineral fertilizers. Such combinations are required for broadening the spectrum of action of the formulations or for specific effects on plant growth.

Depending on the species, the inventive compositions contain between 0.0001 and 85% by weight of the active ingredients of the invention. They are in a form suitable for storage and transport. In this form, e.g., as emulsifying concentrates, the concentration of active substance is higher than the above range. Such forms may be diluted, with the aid of the same or different excipients, to the concentration of the active substance in a formulation required for use in practice, and such concentrations will generally fall within the lower limit of the stated concentration range. Emulsifying concentrates generally contain from 5 to 85% by weight, usually from 25 to 75% by weight, of the compounds of the invention. The formulations used include solutions, emulsions and suspensions suitable for, for example, spraying. The concentration of such a composition may be between 0.0001 and 20% by weight. Ultra-low volume formulations may formulate the active ingredient in an amount of preferably from 0.5 to 20% by weight, while in low volume and high volume formulations, the concentration of active ingredient in the spray formulation is preferably from 0.02 to 1.0 or 0.002 to 0.1% by weight.

The fungicidal compositions of the invention may be prepared by mixing at least one compound of the invention with an excipient to form a formulation.

The formulation is prepared in a known manner, for example, by mixing the active ingredient with a solid carrier or by reconstitution or suspension in a suitable solvent or dispersant, depending on the conditions, using surfactants, wetting agents or emulsifiers or dispersants, and diluting ready-to-use emulsifiers. solvents or dispersants, and the like.

In powder formulations, the active ingredient may be mixed with a solid carrier, for example by grinding; or it is possible to impregnate the solid carrier with a solution or suspension of the active ingredient and then remove the solvent or dispersant by elongation, heating or suction under reduced pressure. The addition of a surfactant or dispersant makes it possible to form a powder which is readily wettable with water and can be easily suspended in water suitable for subsequent application, such as spraying.

The switches of the present invention may be mixed with a surfactant and a solid carrier to form a wettable powder which is dispersible in water or may be mixed with a pre-granulated solid carrier to form a granular preparation.

If desired, the compounds of the invention may be dissolved in a solvent immiscible with water, such as an acyclic ketone in which an emulsifier is dissolved, which makes the solution emulsifiable upon addition of water. Alternatively, the active ingredient may be mixed with an emulsifier and then diluted with water to the desired concentration. In addition, the active ingredient may be dissolved in the solvent and then mixed with the emulsifier. Such a mixture may also be diluted with water to the desired concentration. This results in bulking concentrates or ready-to-use emulsions.

The inventive preparations are used in crop protection or in conventional agriculture. The method of controlling the fungi according to the present invention is characterized in that the desired site or material, such as plants, parts of plants or seeds, is treated with an effective amount of the compound of the present invention or with the agent of the invention.

The following examples illustrate the invention.

A process for the preparation of an active compound of formula I.

An example

To a suspension of 0.24 g of sodium hydrate (55-60% in oil) in 20 ml of dimethylformamide under argon is added dropwise 0.637 g

Of 2- (2-bromomethylphenyl) acrylic acid methyl ester, as well as 0.5 g of 3-trifluoromethylacetophenone oxime in 2 ml of dimethylformamide. The reaction mixture was then stirred for another 30 minutes. After completion of the reaction, the solution is poured into water and the aqueous portion is extracted 3 times with ethyl acetate. The organic layer was washed twice with water, dried over sodium sulfate and evaporated in vacuo. The remaining oil was purified by chromatography on silica gel using solvent-n-hexane / methylene chloride (1: 1).

This gives the methyl ester of 2- (α) / (E / Z) -methyl-3-trifluoromethylbenzyl (imino) (oxy) -o-toluyl / -acrylic acid as a colorless oil / MS: 377 (4); 115 /.

Example 1.27g of 2- (2-bromomethylphenyl) acrylic acid methyl ester and 0.94g of phenylcyclohexanone oxime are added to a biphasic mixture of 30ml of methylene chloride and 30ml of 2.2N NaOH containing 4.38g of tetrabutylammonium hydrosulfate as a phase transfer catalyst. The mixture was then stirred vigorously for 30 minutes. At the end of the reaction, the organic phase is separated off and dried over sodium sulfate, after which the organic solvent is evaporated. The remaining mass was purified by chromatography on silica gel using solvent-ethyl acetate / n-hexane (1: 9).

There is thus obtained 2- (α) / (4-phenylcyclohexylidene (amino) (oxy) -otoluoyl / acrylic acid methyl ester in the form of a yellowish oil / MS: 363 (5); 115 /.

Example 1g a- (2-Bromomethylphenyl) -P-methylthioacrylic acid methyl ester and 0.67g

3-Trifluoromethylacetophenone oxime is added to a two-phase mixture consisting of 3 ml of methylene chloride and 3 ml of a 2.2 N NaOH solution containing 1.5 g of tetrabutylammonium hydrosulphate as a phase transfer catalyst. The reaction mixture was stirred vigorously at room temperature for about 15 minutes. The same volumes of methylene chloride, 2.2 N NaOH solution and tetrabutylammonium hydrosulfate are then added and stirred for 15 minutes. After completion of the reaction, the reaction contents are neutralized with a saturated sodium bicarbonate solution, the organic layer is separated, washed three times with water and dried. sodium sulfate. After evaporation of the organic solvent, the remaining oil is purified by silica gel chromatography using diethyl ether / n-hexene (1: 1) as the solvent.

The methyl ester of 2- (α) / (α-methyl-3-trifluoromethylbenzyl) (imino) (oxy) -o-toluyl / -3-methylthioacrylic acid is thus obtained in the form of a yellowish oil / MS: 376 (30); 161 /.

An example

To a suspension of 0.78 g of sodium hydrate (80% in oil) in 20 ml of dimethylformamide under argon are added 5 g of 2- (2-bromomethylphenyl) -glyoxylic acid-methyl ester-o-methyloxime and 3.2 g of β-acetonone-onoxime in 80 ° C. of dimethylformamide and the reaction mixture was stirred at 0 ° C for 4 h. At the end of the reaction, the contents are hydrolysed with saturated ammonium chloride solution and extracted three times with diethyl ether. The organic layer was dried over anhydrous sodium sulfate and then the solvent was evaporated. The remaining oil is purified by chromatography on silica gel using diethyl ether / n-hexene (1: 1) as solvent and the product crystallized from methylene chloride / diethyl ether / n-hexene.

This gives 2- (a) - [1- (p-naphthyl) (ethyl) (imino) (oxy) -o-toluyl / glyoxylic acid methyl ester-O-methyloxime as white crystals, m.p. 97-98 ° C / MS: 390 (4); 116 /.

5-41 Examples

By analogy to the methods described in Example 1 (Method 1), Example 2 (Method 2), Example 3 (Method 3) or Example 4 (Method 4) from the corresponding O-substituted benzoyl bromide of formula III (V = Br) and the corresponding oxime of formula II, the compounds of formula I 5-11 in the tables below are prepared in the form of an oil.

They, like the compounds of Examples 1-4, are characterized by their mass spectra. The first value represents the maximum absorption, the second the major peak. Brackets indicate the peak intensity as a percentage of the base peak (= 100%).

Υ-Χ .COOCH ₃ V

Table 1

An example

Υ-Χ r ₂ r ₃ Physical data Methods

5 ch ₂ H 4-Chlorophenyl 329 (1); 115 1 6th ch ₂ H phenyl 295 (2); 115 2 7th ch ₂ 4-Tet. butylcyclohexyl den 343 (6); 115 2 7a ch ₂ CH3 3,4-methylenedioxyphenyl 353 (6); 115 1 8th CH3S-CH CH3 3,4-Dichlorophenyl las 424 (2); 161 3 9th CH3S-CH CH3 β-naltyl 405 (1); 161 3 10th CH3S-CH CH3 2-thienyl 314 (29); 161 3 11th CH3S-CH CH3 2-pyridyl 356 (0.5); 161 3

In an analogous manner, generally according to Method 4, the following methoxyiminoglyoxylic acid derivatives, as crystals or oils, which are characterized in melting point and / or mass spectra (MS), can be obtained.

CH ₃ ON = C-COOCH'C = NO-CH

Table 2

An example r ₂ ^ 3 Physical data 1 2 3 4 12th CH3 α, α, α-trifluoro-n- -toll oil 408 (0.5); 186 13th CH3 3,4-dichlorlenyl m.p. 1.103-105 ° C 14th CH3 2-thienyl oil 346 (2); 116 15th CH3 2-pyridyl melt t. 82-84 ° C

16th 17th 1,2,3,4-Tetrahydro-a-naphtha 366 (1); 116 accounts cryst. 343 (2); 116 ch ₃ 4-Chlorophenyl 18th n-propyl phenyl cryst. 368 (0.5); 116 19th ch ₃ 4-methoxyphenyl cryst. 370 (10); 116 20th ch ₃ 3,4,5-trifluoromethyl- oxyphenyl oil 430 (49); 116 21st ch ₃ 2-furyl melt t. 95-97 OC 22nd ch ₃ 3-Bromophenyl cryst. 389 (0.5); 116 23rd ch ₃ 1,4,8-trimethylnone-1,3,7-trienyl oil 426 (2); 116 24th ch ₃ 3-trifluoromethylbenzyl oil 422 (4); 116 25th ch ₃ 4-nitrophenyl cryst. 354 (1); 116 26th ch ₃ 3-nitrophenyl cryst. 354 (0.5); 116 27th cf ₃ phenyl cryst. 222 (4); 116 28th ch ₃ ch ₂ phenyl oil 323 (2); 116 29th isopropyl phenyl oil 368 (1); 116 30th cf ₃ 3-Bromophenyl oil 252 (2); 116 31st cf ₃ 4-tolyl cryst. 222 (6); 116 32 ch ₃ 2-benzofuryl melts 110-112 ° C 33 ch ₃ 3,5-di (trifluoromethyl) - -phenyl melt t. 76-78 ° C 34 ch ₃ 4-fluorophenyl melts 89-90 ° C 35 ch ₃ o-ch ₂ - β-naphthyl oil 420 (4); 45 36 cyclopropyl phenyl oil 355 (3); 116 37 ch ₃ 1-phenoxyethyl cryst. 291 (63); 116 38 ch ₃ 3,4-methylenedioxy phenyl oil 384 (12); 116 39 cf ₃ 3-trifluoromethylphenyl oil 240 (3); 116 40 ch ₃ 3-fluorophenyl 41 cyclopropyl 3,4-methylenedioxyphenyl 42 isopropyl 3,4-methylenedioxyphenyl 43 ch ₃ 6- / 1,4-Benzodioxanyl 44 cyclopropyl 6- / 1,4-Benzodioxanyl

45 ch ₃ 3,4- (difluoromethylenedioxy) phenyl 46th ch ₃ 3,4- (difluoromethylenedioxy) benzyl 47 ch ₃ 3,4- (ethylenedioxy) benzyl 48 ch ₃ 2,5- (difluoromethylenedioxy) phenyl 49 ch ₃ 4-Methoxy-3- (methylthiomethyl)

C _s H ₃ (m-CF ₃ , p-Cl)

54 ch ₃ 3,4- (methylenedioxy) benzyl 55 ch ₃ 6-nitro-3,4- (methylenglyloxy) - phenyl 56 H 3,4- (difluoromethylenedioxy) phenyl 57 ch ₃ 2- (3,4-methylenedioxy) ethenyl 58 ch ₃ 2- (3,4-methylenedioxyphenyl) ethyl

CH ₃ ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ ch ₃

4-Meloxy-3- (methylsulfinylmethyl) phenyl

4-Meloxy-3- (methylsulfonylmethyl) phenyl

X) '

OCH,

3,4-methylenedioxybenzoyl

ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ ch ₄

H ch ₃ ch ₃

3-Allyloxyphenyl

3-Propargyloxyphenyl

3-Cyclopropylmethoxyphenyl

3- (2,2-Dichloro-vinyloxy) -phenyl

3-cyanophenyl

3-Thiocyanaphthylphenyl

4- (2,2-Dichloro-vinyl) -phenyl

5- (2-Cyanobenzofuryl

4-Dilluoromethoxyphenyl

3-aethoxyphenyl

CH3 4-methoxy-3-nitro phenyl

CH 3 4-methoxy-3- (methoxymethyl) phenyl

CH3 3-Allyloxy-4-methoxyphenyl

CH3 3-Ethoxy-4-methoxyphenyl

CH3 ch ₃

CH3 cyclopropyl

CH3

H

CH3

CH3

CH ₃ ch ₃ ch = ch

CN

CH3SO2

CH3CH2

CH3CH2CH2 isopropyl cyclopropyl

CH3OCH2

CH3

H

CHa

I oil

3- (2,5-Dimethylthienyl)

2- (5-methylthienyl)

4-fluorophenyl

4-Fluoro-3-trifluoromethylenephenyl

3-nitrophenyl

3-cyanomethoxyphenyl

4-Fluoro-3-phenoxyphenyl

4-Thiocyanato-3-trifluoromethylphenyl

3,4-methylenedioxyphenyl

3,4-methylenedioxyphenyl

3.4- Methylenedioxyphenyl

3.4- (Difluoromethylenedioxy) phenyl

3.4- (Difluoromethylenedioxy) phenyl

3.4- (Dilluoromethylenedioxy) phenyl

3.4- (Difluoromethylenedioxy) phenyl

3,4- (Difluoromethylenedioxy) phenyl 1- (3,4-methylenedioxyphenyl) ethyl 1-methyl-1- (3,4-methylenedioxyphenyl) ethyl

H 2-lienoyl ch ₃ 4- (pentallorethoxy) phenyl ch ₃ 4- (2,2,2-trityloxyethoxy) phenyl ch ₃ 4- (1,1,2,3,3-Hexafluoropropoxy) - phenyl CH ₃ SCH ₂ 3,4-methylenedioxyphenyl ch ₃ ch ₂ 2-thienyl CH ₃ CH ₂ CH ₂ 4-tolyl ch ₃ 4-chloro-2-methoxyphenyl ch ₃ ch = ch 3-trifluoromethylphenyl f " ³ H ch ₃ 'CXi

ch ₃ 6-methoxy-p-naphthyl ch ₃ ch ₂ β-naphthyl ch ₃ ch ₂ ch ₂ β-naphthyl isopropyl β-naphthyl tert.butyl β-naphthyl CH ₃ S. phenyl CH ₃ s 4-Echlorophenyl CH ₃ s 3-trifluoromethylphenyl ch ₃ o 4-Echlorophenyl

oil oil

1 2 3 4

128 ch ₃ 4-fluorobenzoyl 129 ch ₃ 3-Bromobenzoyl 130 ch ₃ 3-nitrobenzoyl 131 ch ₃ 3-trifluoromethylbenzoyl 132 ch ₃ 2-toluyl 133 ch ₃ 4-chloro-3-trifluoromethylbenzoyl 134 ch ₃ phenyl 135 ch ₃ 3-chlorophenyl 136 ch ₃ 3,5-dichlorophenyl 137 ch ₃ 6-fluoro-3-tolyl 138 ch ₃ 3-trifluoromethoxy-phenyl 139 ch ₃ 2- (5-chlorothienyl) 140 cf ₃ 2- (p-naphthyl) ethenyl 141 cf ₃ 3-chlorophenyl 142 cf ₃ 4-Chlorophenyl 143 cf ₃ β-naphthyl 144 cf ₃ 2-pyridyl 145 cyclopropyl 3-Chlorophenyl 146 cyclopropyl 4-Chlorophenyl 147 cyclopropyl 3-Bromophenyl 148 cyclopropyl 3-trifluoromethylphenyl 149 cyclopropyl 4-phenoxyphenyl 150 cyclopropyl β-naphthyl

Examples 151-157

In analogy to the procedure described in Example 1 (Method 1), the corresponding o-substituted benzoibromide of formula III (V = Br) and the corresponding oxime of formula II gives the compounds of formula I in Table 3 in the form of an oil:

YX = C-COOH ₂ CH ₃

C = NO-CH ₂ \> ^

Table 3

An example

Υ-Χ r ₂ R3 Physical data

151 ch ₂ ch ₃ 4-fluorophenyl 341 (3); 115 152 * ch ₂ ch ₃ 2-thienyl 329 (4); 115 153 * ch ₂ ch ₃ 2-thienyl 329 (6); 115 154 ch ₂ ch ₃ 3,4-Dichlorophenyl 391 (2); 115 155 ch ₂ CF ₃ phenyl 205 (0.5); 115 156 ch ₂ ch ₃ 4-nitrophenyl 368 (2); 115 157 ch ₂ ch ₃ β-naphthyl 373 (7); 115

* Compounds 152 and 153-E / Z-isomers.

Composition examples

Fl:

The emulsifying concentrate contains, for example, the following composition:

&

Active substance from Tables 1-3 100.0

Nonylphenol- (10) ethoxylate (nonionic 50.0 emulsifier)

Calcium dodecylbenzene sulphonate (anionic 25,0 emulsifier

N-Methyl-2-pyrrolidone (dissolving agent) 200.0

Alkylbenzene mixture 1 liter

The active ingredient and emulsifiers are dissolved in the solvent and the dissolving agent. By emulsifying this concentrate in water, a ready-to-use spray solution can be prepared.

F2

The spray powder may have, for example, the following composition:

% by weight

Active substance from Tables 1-3 25.0

Silicic acid (hydrated; carrier) 20,0

Sodium lauryl sulphate (wetting agent) 2,0

Lignosulfonate sodium (dispersant) 4,0

Kaolin (carrier) 49.0

The components are mixed with each other and ground in the appropriate mill. The mixture is dispersed in water to form a suspension suitable for use as a spray formulation.

Biological tests

JV Example: Puocinia coronata (treatment).

30-40 barley seedling Seimas (housed in 7 cm diameter 2 cups) are sprayed with an aqueous spore suspension (about 150,000 uredospores / ml) and infected with puocinia coronata. The test seedlings are then incubated for 24 hours. 20-24 ° C at dew point conditions. The barley seedlings are then thoroughly pollinated on all sides by the preparation of the active ingredient (160 mg / ml / l). The cultivation is continued in a climatic chamber at 19 ° C for 14 hours. for photoperiod. The test results are evaluated 9-10 days after infection in percentage of leaves of Puocinia coronata on infected plants but untreated for control.

At a dose of 160 mg, more than 75% of the effect was shown, for example, by the following compounds: 3, 8, 9,11,12,17, 78, 90,107,128,131,133,138,148.

Untreated but infected control plants show 100% damage to the fungus Puccinia coronata.

Example B2: Effect against Ceriospora orachidicola on peanuts (treatment).

Two specimens of peanuts of Tamnut species at leaf stage 4 are sprayed with a conidial suspension of Cercospora arachidicola (about 20,000 conidia / ml) and then incubated at 25 to 26 ° C under dew point. After 2 days, the plants are thoroughly sprayed on all sides with a powder-based formulation (160 ppm of active ingredient). The affected plants are incubated in a climatic chamber under the following conditions: 25-27 ° C, 80% humidity day, 20 ° C and dew point conditions - frost; the photoperiod is 16 hours, respectively. After 12 days of treatment, experimental evaluation is performed by determining the percentage of injured leaf surface relative to the infected plants in the control group.

When compared to untreated but infected control plants (stain number and size = 100%), peanut samples treated with active compounds from the tables show a significant reduction in the effect of the fungus Coreospora arachidicola.

At a dose of 160 md, more than 75% of the effect was demonstrated by, for example, the following compounds: 3, 8, 9, 10.11, 12,13,14,17, 19, 22, 24, 25, 26, 30, 32, 33, 34, 36, 38, 40, 41, 44, 49, 52, 66, 68, 71, 83, 90, 101, 129, 130, 133, 138,145, 148.

Example B3: Erysiphe graminis (protective effect).

30-40 wheat sprouts Lita (placed in 7 cm diameter 2 cups) are sprayed thoroughly with a preparation of the powdered active ingredient (160 m.p.) in leaf stage 1 and immediately cultivated in a greenhouse. After a day, the plants are pollinated with the conidia Erysiphe graminis. The test results are evaluated 7 days after infection by measuring the percentage of leaf surface overgrowth in Erysiphe graminis compared to only infected control plants.

At a dose of 160 md, more than 75% of the effect was demonstrated by, for example, the following compounds: 1, 3, 4, 5, 7 A, 8, 9, 10, 11, 13, 15, 16, 18, 23, 24, 25 , 27, 29, 31, 33, 34, 37, 39, 40, 52, 53, 70, 86, 89, 105, 119, 120, 126, 127, 128, 135, 137, 141, 149.

Untreated but infected control plants show 100% effect of Erysiphe graminis.

Example B4: Venturia inalgualis (therapeutic effect).

apple seedlings of Golden Delicions are sprayed with a suspension of conidia Venturia inalgualis and then incubated at 18 ° C dew point. After 24 or. the plants are sprayed thoroughly from all sides with a preparation of powder-like active ingredient (50 ppm). The treated seedlings are then cultivated in a greenhouse. 9 to 10 days after treatment, test results are evaluated by determining percentages of leaf overgrowth in Venturia inalgualis compared to infected control plants only.

At a dose of 50 md, more than 75% of the effect is shown by, for example, the following plants: 1, 3, 7 A, 8, 9, 10,12, 13, 14,15, 17, 19, 20, 22, 24, 28 , 29, 30, 31, 32, 33, 34, 36, 38, 44, 49, 54, 61, 64, 66, 78, 82, 83, 85, 105, 106, 117, 124, 131,134, 135,139,142,147,154,157.

Example Alternaria hrassicae (protective effect).

cabbage plants of Forbote species, planted in 2 cups, are sprayed thoroughly with leaf-based active ingredient (50 ppm) at leaf stage 6 and then cultivated in a climatic chamber at 19 ° C for 16 hours. daily. After 2 days, the plants are infected by pollination of the plants with a conidia suspension (about 3000 conidia / ml). The cabbage plants are then incubated at a dew point of 24-26 ° C for 16 hours. 2-5 days after infection, test results are evaluated by determining the percentage of damaged leaf surfaces in the fungal yl /iemflmz brassicae compared to the infected but untreated plants only.

At a dose of 50 md, more than 75% of the effect is demonstrated by, for example, the following compounds: 1, 3, 4, 8, 9, 12, 13, 14, 17, 20, 22, 23, 24, 25, 26, 28, 29, 30, 31, 32, 33, 34, 36, 38, 54, 55, 67, 92,105,124,130,136,138,143,150,157. Example B6: Effect against Phytophtora infestans on tomatoes

(a) Healing effects

Tomato sprout species The Red Gnome is sprayed with a suspension of fungal zoospores after 3 weeks of growth and incubated at 18-20 ° C and a saturated humidity chamber. The plant is watered every 24 or. After drying, the plants are sprayed with a solution containing 200 ppm of the active ingredient. After the sprayed plants have dried, they are returned to the chamber for 4 days. The number and size of the typical spots on the leaves is an indicator of the effect of the substance.

(b) Protective systemic effects

Prepared dusting powder containing 60 ppm of active substance. (relative to soil volume) are applied to the soil surface where 3-week-old Red Gnomes are grown. After 3 days, the lower half of the leaves is intensively sprayed with an emulsion of Phytophtora infestans zoospores. The plants are then kept in the chamber for 5 days under constant fine-spraying at 18 to 20 C. Typical spots on the leaves are formed, the number and size of which indicate the effective action of the test compound.

Compounds of Tables 1-3 inhibit harmful effects on the plant by up to 20%. Example B7: Plasmopara viticola (protective effect).

grape seedlings of Risling and Silvaner species are sprayed on all sides with a preparation of the powdered active compound (160 d.) on a 4-5 leaf stage and then placed in a climate chamber at 170 ° C and a relative humidity of 70-80%. The illuminated period is 16 hours. After 6 days, infection is carried out by spraying the lower half of the leaf with zoosporanhienes of the fungus Plasmopara viticola suspended in distilled water (about 30,000 sporanichen / ml). The grape seedlings are then incubated in the following order: 1 day in the dark at 22 ° C dew point and then 4 days in the greenhouse.

In order to incubate the growth of Plasmopara vitikola, the grape seedlings were kept in an infection chamber at dew point for 22 days after infection.

At 6 days post-infection, the test results are evaluated by observing the percentage of leaves affected by Plaspopara viticola compared to the infected but untreated control plants.

At a dose of 160 ppm, more than 75% of the effect is exemplified by the following compounds; 3, 4, 8, 9, 11, 12, 17, 22, 24, 28, 29, 30, 31, 32, 36, 38, 41, 43, 45, 53, 61, 62, 82, 102, 107, 120, 125, 129, 135, 138, 147, 150.

Claims (13)

DEFINITION OF INVENTION I. Oxime esters having the general formula in which R 1 represents C 1-4 alkyl, (Υ-Χ) represents CH ₂ =, Ομ ₂ -alkylthio-CH = or C _1-2 alkyl-ON =, and Z represents an aldimino- or ketimino-group having fungicidal activity. 2. Oxime esters according to claim 1, wherein Z represents a group ^R 2 ^R 3 C = N- in which R ₂ represents hydrogen, Cj_4 alkyl, haloalkyl or C3.5 Cj.4 cycloakyl, R 3 represents a Cj.g alkyl, aryl-C | _4 alkyl, heteroaryl-Cj.ą _alkyl, C2 _6 alkenyl _aryl-C2 _4 alkenyl, _{heteroaryl-C2} _4 alkenyl, CA. ^ - cycloalkyl, aryl, heteroaryl, C ₂ _4 alkanoyl, aroyl or beteroaroilą or R ₂ and R 3 together with the carbon atom to which they bonded, if necessary, to form a substituted, optionally oxygen or sulfur atom, four-membered or seven-membered ring which may additionally have a substituted fused benzene ring. Compounds according to claim 1, characterized in that R 1 represents methyl. Compounds according to one of claims 1 to 3, characterized in that (YX) represents melylene, methylthiomethylene or methoxyimine. Compounds according to claim 1, characterized in that Z represents a group R ₂ C = N- in which R 2 denotes hydrogen, C 1-6 alkyl, (C 4-6 haloalkyl, C 3-6 cycloalkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-4 alkoxymethyl, C 1-4 alkylthiomethyl, C 1-6 alkylsulfonyl, C 1-6 alkoxy , C 1-3 alkylthio or cyano; and R 3 represents C 1-4 alkyl, aryl-C 1-4 alkyl, heteroaryl-C 1-4 alkyl, C 242 alkenyl, aryl-C 2-4 alkenyl, aryloxy-C 4-4 alkyl, heteroaryloxy-C 1-4 alkyl, heteroaryl -C 2-4 alkenyl, C 3-6 cycloalkyl, aryl, heteroaryl, C 2-5 alkanoyl, aroyl or heteroaryl; or R 2 to _R 3 together with the carbon atom to which they are attached form, under the given conditions, an substituted oxygen atom, a sulfur atom and / or a nitrogen atom, a ketumar-seven-membered ring which may additionally have a substituted fused benzene ring. Compounds according to claim 5, characterized in that R 1 represents methyl and (Υ-Χ) represents methoxyimine. Compounds according to one of claims 2 to 4, characterized in that in the group R 2 R 3 C = N- the substituent R 2 represents hydrogen, C 1-6 alkyl, (4.4 haloalkyl or C 3-6 cycloalkyl) and the R 3 substituent represents a phenyl or heteroaryl substituted under the given conditions. 8. Compounds according to claim 1, characterized in that they are selected from: 2- (a) - / (a-Methyl-3-trifluoromethylbenzylimino) -oxy-o-toluyl / -3-methylthio-acrylic acid methyl ester, 3-methylthio-2- (a) - / (1- (p- naphthyl) -ethyl (imino) -oxy-toluyl / acrylic acid methyl ester, 2- (a) - / (α-methyl-2-thienyl (imino) (oxy) -o-toluyl / -3-methylthioacrylic acid methyl ester, 2- (a) - / (a-methyl-3,4-dichlorobenzyl (imino) (oxy) -o-toluyl / -3-methylthioacrylic acid methyl ester, 2- (a) - / 1- (a-naphthyl) -ethyl (imino) (oxy) -o-toluyl / glyoxylic acid-methyl ester-O-methyloxime, 2- (a) - / (α-methyl-3-trifluoromethylbenzyl (imino) (oxy) -o-toluoyl / -glyoxylic acid-methyl ester-O-methyloxime, 2- (a) - / (a-methyl) (2-thienyl) (imino) (oxy) -o-toluoyl / glyoxylic acid-methyl ester-O-methyloxime, and 2- (a) - / (a-Methyl) (3-trifluoromethylbenzyl) (imino) (oxy) -o-toluyl / acrylic acid methyl ester. 9. Compounds according to claim 5, characterized in that they are selected from: 2- (a) - / (a-methyl-3-bromobenzyl (imino) (oxy) -o-toluyl / -glyoxylic acid methyl ester-O-methyloxime, 2- (a) - / (a-methyl) -m-trifluoromethyl (phenethyl) (imino) (oxy) -o-toluyl / -glyoxylic acid methyl ester-O-methyloxime, 2- (a) - [1- (2-Benzofylethyl (imino) (oxy) -o-toluoyl] -glyoxylic acid methyl ester-O-methyloxime, 2- (a) 7 (α-Methyl-3,5-bis-trifluoromethylbenzyl (imino) (oxy) -o-toluoyl / glyoxylic acid-methyl ester-O-methyloxime, and 2- (a) - / (a-methyl-3,4-methylenedioxybenzyl (imino) (oxy) -o-toluoyl / -glyoxylic acid-methyl ester-O-methyloxime. Compounds of the general formula wherein Rj stands for C 1-4 alkyl, (Y-Χ) CH 2 =, C 1-2 alkylthio-CH = or C 1-2 alkyl-N = and Z represents an aldimino or ketimino group, characterized in that the oxime Z-OH, where Z represents an aldimino or ketimino group, acts on benzyl alcohol derivatives of the general formula wherein Rj and (Y-Χ) have the above meanings and V represents a leaving group. 11. A process according to claim 10 wherein the leaving group V is chloro, bromo, iodo, mesyloxy, benzenesulfonyloxy or tosyloxy. 12. A fungicide containing the active ingredient and common additives, wherein the active ingredient is oxime esters of the formula I in an amount of 0.0001-85% and the remainder are the necessary additives. Compounds of the formula I according to claims 1-9 for the eradication or control of fungal diseases in agriculture and horticulture or for the protection of wood.