WO2001012615A2

WO2001012615A2 - Fungicidal heteroaryl hepta-2,6-dienoic acid derivatives

Info

Publication number: WO2001012615A2
Application number: PCT/US2000/021536
Authority: WO
Inventors: Werner Simon; Paul Carter; Gerhard Hoefle; Udo Soeker
Original assignee: Gesellschaft Fur Biotechnologische Forschung Mbh
Priority date: 1999-08-12
Filing date: 2000-08-07
Publication date: 2001-02-22
Also published as: WO2001012615A3; AU6624300A

Abstract

Compounds of formula (I) show excellent fungicidal activity and systemicity; wherein A represents an organic radical which is bonded directly or via an oxy, iminoxy, mercapto, amino, carbamoyl, thiocarbamoyl, imidoyl or thioimidoyl group; R2 represents a hydrogen atom or an alkyl group; R3 represents an alkoxy group; R?4 and R5¿ each independently represent a hydrogen atom or an alkyl group; R6 represents an alkyl group, and R7 represents a group of formula -COOR8 or -CONR8R9, in which R?8 and R9¿ each independently represent a hydrogen atom or an alkyl group; X and Y each independently represent S, O, N, NR?10, CL1, CL1¿-N, N-CL?1 or CL1-CL2¿, in which R10 represents a hydrogen atom or an alkyl group, and L?1 and L2¿ each independently represent a hydrogen or halogen atom or an alkyl group; with the proviso that one of X and Y represents S, O, N or NR10; W represents S, N or CL1, with the proviso that X represents CL1, when W represents S; and wherein the zigzag lines indicate that the connected groups may have the (E)- or (Z)-configuration.

Description

FUNGICIDAL HETEROARYL HEPTA-2.6-DIENOIC ACID DERIVATIVES

BACKGROUND OF THE INVENTION

This invention relates to heteroaryl substituted hepa-2,6-dienoic acid derivatives, a novel process for their preparation, compositions containing such compounds, a method for combating a fungus at a locus comprising treating the locus with such compounds and their use as fungicides.

Food production relies upon a variety of agricultural technologies to ensure the growing population's dietary needs remain affordable, nutritious and readily available on grocery store shelves. Crops and food are constantly threatened by a variety of fungal organisms, which, if left uncontrolled, can cause ruined crops and devastated harvests. Fungicides are thus an important agricultural technology which can be used to protect crops and foods from fungus and fungal diseases. The preparation of melithiazole C by reductive cleavage of myxothiazol A with subsequent transformation of the resulting melithiazole C amide into the corresponding methyl ester has been described by a poster of B. Bόhlendorf et al. presented at the Dechema Naturstofftagung in Irsee, Germany in 1996. Melithiazole C disclosed on this poster shows weak in vitro activity against Bortrytis cinera.

The International Patent Application WO 98/46583 discloses certain derivatives of Melithiazole C which show high activity against a broad range of phytopathogenic fungi. However, these derivatives are produced in very small amounts from natural Melithiazole C. Up to now there is no way to produce these derivatives on a commercial scale. The underlying problem of the present invention was to find similar derivatives having high in vivo activity against a broad range of phytopathogenic fungi, which are producible on an economic scale.

SUMMARY OF THE INVENTION

The present invention provides compounds of formula

wherein

A represents an organic radical which is bonded directly or via an oxy, iminoxy, mercapto, amino, carbamoyl, thiocarbamoyl, imidoyl or thioimidoyl group; preferably an oximether group of formula

wherein

R¹ represents a hydrogen atom or an optionally substituted alkyl, alkenyl, or aryl group;

R² represents a hydrogen atom or an alkyl group; and wherein the zigzag line -*'^*' indicates that the connected groups may have the (E)- or (Z)-configuration.

R³ represents an alkoxy group; R⁴ and R⁵ each independently represent a hydrogen atom or an alkyl group;

R⁶ represents an alkyl group, and

R⁷ represents a group of formula -COOR⁸ or -CONR⁸R⁹, in which R⁸ and R⁹ each independently represent a hydrogen atom or an alkyl group; X and Y each independently represent S, O, N, NR™, CL¹ , CL¹-N, N-CL¹ or CL¹-CL², in which R¹⁰ represents a hydrogen atom or an alkyl group, and L¹ and L² each independently represent a hydrogen or halogen atom or an alkyl group, with the proviso that one of X and Y represents S, O, N, NR¹⁰, CL¹-N or N-CL¹ ;

W represents S, N or CL¹ , with the proviso that X represents CH, when W represents S; and wherein the zigzag line -^^** indicates that the connected groups may have the (E)- or (Z)-configu ration. The new compounds are easily produced and combine excellent fungicidal activities against a broad range of phytopathogenic fungi in various crops with comparably high systemicities.

Further, the present invention relates to a process for the preparation of the novel oximethers, to the novel intermediate compounds of formula IIA

in which R¹ , R², W, X and Y are as hereinbefore defined for formula I and L³ represents a halogen atom, and to the novel intermediate compounds of formula III

in which R³ _' R⁴, R⁵, R⁶, and R⁷ are as hereinbefore defined and

R^{1 1} and R¹² each independently represent a hydrogen atom or an alkyl group, or R^{1 1} and R¹² taken together represent an alkylenediyl group.

It is thus an object of the invention to provide methods for controlling an undesired fungus by contacting said plants with a fungicidally effective amount of the new compounds.

It is another object of the invention to provide fungicidal compositions containing the new compounds as active ingredients.

These and other objects and features of the invention will be more apparent from the detailed description set forth hereinbelow, and from the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

It has surprisingly been found that oximether derivatives of the general formula I

wherein

A, R³, R⁴, R⁵, R⁶, R⁷, W, X and Y are as hereinbefore defined possess excellent fungicidal activity against diseases caused by phytopathogenic fungi at low dose rates with high bioavailability due to their high systemicity.

Optionally substituted moieties in the compounds of formula I may be unsubstituted or have from one up to the maximal possible number of substituents. Typically, 0 to 2 substituents are present. Each optionally substituted group is independently substituted by one or more halogen atoms, or nitro, cyano, cycloalkyl, preferably C₃.₆ cycloalkyl, cycloalkenyl, preferably C₃.₆ cycloalkenyl, haloalkyl, preferably C-|_₆ haloalkyl, halocycloalkyl, preferably C_3-6 halocycioalkyl, alkoxy, preferably C^ alkoxy, haloalkoxy, preferably C_{1 -6} haloalkoxy, phenyl, mono- di- or trihalo-phenyl or pyridyl groups. In general terms, unless otherwise stated, the term "halogen atom" as used herein denotes a bromine, iodine, chlorine or fluorine atom, and is preferably a bromine, chlorine or fluorine atom.

A preferably represents a group of formula B-Z-, wherein Z represents -O-, -CR¹³=N-O-, -S-, - CH₂O-, - CH₂S-, -CO-NR¹³-, -CS-NR¹³-, -C(OR¹³)=N-, -C(SR¹³)=N- or a single bond, in which R¹³ represents preferably a hydrogen atom or an optionally substituted alkyl group, and B preferably represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoximinoalkyl or aryl group or an optionally substituted 5- or- 6-membered heteroaryl group. X preferably represents S, N or CH, in particular N. Y preferably represents, O, N or CH-N, in particular S; or CH or CH-CH, when W represents S or N respectively. W represents preferably CH, S or N, in particular CH. Accordingly, the group of formula

is preferably selected from the group consisting of

In general terms, unless otherwise stated herein, the terms alkyl, alkenyl, alkynyl and alkoxy as used herein with respect to a radical or moiety refer to a straight or branched chain radical or moiety. As a rule, such radicals have up to 10, in particular up to 6, carbon atoms. Preferably, an alkyl or alkoxy moiety has from 1 to 6 carbon atoms, and most preferably, from 1 to 5 carbon atoms. A preferred alkyl moiety is the methyl, ethyl, n-propyl, isopropyl or n-butyl group.

An aryl group as substituent or part of other substituents is suitably an optionally substituted phenyl or naphthyl group. An heteroaryl group as substituent or part of other substituents is suitably an optionally substituted 5- or 6-membered heterocyclus containing one or more heteroatoms selected from nitrogen, oxygen and sulfur, at least 1 oxygen, 1 sulfur atom or 1 to 3 nitrogen atoms being preferred. Examples of such groups are thienyl, furanyl, pyrazolyl, imidazolyl, tnazolyl, tetrazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, and triazinyi groups. 5- or 6-membered heterocycles may be fused with a benzene ring.

"Aryl" and "heteroaryl" preferably represent a phenyl, pyridyl, thienyl or pyrazolyl group being substituted by one or more of the same or different substituents selected from halogen atoms, alkyl groups, alkoxy groups, cyano groups, haloalkyl groups, haloalkoxy groups, alkylthio groups and haloalkylthio groups.

Also included in the invention are the stereo and optical isomers of the compounds of formula I and mixtures of these isomers in ail proportions. The compounds of formula I, wherein the vinyl group attached to the heterocyclyl group exists in the (E)-configuration and/or the carbon atom attached to R³ exists in the (S)-configu ration, are particularly preferred.

The invention particularly relates to compounds of the general formula I in which any alkyl part of the groups A, R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R^{1 1} , R¹², L¹ and L², which may be straight chained or branched, contains 1 to 10 carbon atoms, preferably 1 to 9 carbon atoms, more preferably 1 to 6 carbon atoms, and in which each optionally substituted group may be independently substituted by one or more halogen atoms or nitro, cyano, cycloalkyl, preferably C₃^ cycloalkyl, cycloalkenyl, preferably C3-6 cycloalkenyl, haloalkyl, preferably C_{1 -6} haloalkyl, halocycloalkyl, preferably C3.6 halocycloalkyl, alkoxy, preferably C^ alkoxy, haloalkoxy, preferably Ci_e haloalkoxy, phenyl, or pyridyl groups, in which the phenyl moiety is optionally substituted by one to three substituents selected from halogen atoms, cyano, C-|_6 alkyl and Cι_-6 alkoxy groups. The invention especially relates to compounds of the general formula I in which R¹ represents a straight-chained or branched C_{1 - 0} alkyl, in particular a straight-chained Cι_-6 alkyl group, in which the alkyl moiety may be unsubstituted or substituted by 1 to 3 substituents selected from the group consisting of halogen atoms, aryl, alkoxy, haloalkyl and haloalkoxy groups, most preferably being a methyl, ethyl, propyl or benzyl group.

L¹ and L² each independently preferably represent a hydrogen, fluorine or chlorine atom or a C→_₄ alkyl group, in particular a hydrogen atom or an methyl group. Most preferably both L¹ and L² represent a hydrogen atom.

Preferred compounds of the general formula I are those in which A represents an oxim ether group of formula

^R\

O

c

2/

R² wherein

R² represents a hydrogen atom or an alkyl group; and wherein the zigzag line -"^*"' indicates that the connected groups may have the (E)- or (Z)-configuration.

Particularly preferred compounds of the general formula I are those in which R² represents a C₁_₁₀ alkyl group, preferably a Cι_4 alkyl, and most preferably a methyl group. Especially preferred compounds of the general formula I are those in which R³ represents a C_{1 -10} alkoxy group, preferably a C_{1 -} alkoxy, in particular, a methoxy group.

Also preferred are the compounds of the general formula I wherin R⁴ and R⁵ each independently represent a hydrogen atom or a C_{1 -10} alkyl group, preferably a C_{1 -} alkyl, in particular, a methyl group. Most preferred are those compounds of formula I in which R⁴ represents a C1.4 alkyl, in particular a methyl group and R⁵ represents a hydrogen atom. Most preferred are those compounds of formula I, in which R⁵ represents a hydrogen atom and the carbon atom attached to R⁴ exist in the (R)- configuration.

Other preferred compounds of the general formula I are those in which R⁶ represents a C→.-₀ alkyl group, preferably a C→^ alkyl, and most preferably, a methyl group.

Also preferred are compounds of the general formula I in which R⁷ represents group of formula -COOR⁸, wherein R⁸ represents a Cj.-io alkyl group, preferably a C_{1 -} alkyl, in particular, a methyl group. The compounds of formula I are oils, gums, or crystalline solid materials and possess valuable fungicidal properties when used as a fungicide for control of diseases in agronomic crops, additionally, the compound may be used as a biocide for the control of insect pests and nematodes, as a biocide of human/animal diseases/pests, and as a protectant or preservative for wood, leather or tissue. As a fungicide in agronomic crops, the compounds of the present invention can curatively and protectively be used against a broad spectrum of diseases in plant and fruit production such as grain producing crops (wheat, barley, rice, rye, triticale, oat, maize, sorghum and others), grape vine plants and fruits, solanaceous crops (potato, tomato, tobacco, pepper and others) top fruit, stone fruits, soft fruits and fruit crops (apples, pears, citrus, mango, bananas, coffee, cocoa and others), oil producing crops (soybeans, sunflowers, groundnuts, rape, olives, palms and others), vegetables (like beans, lettuce, cucumbers, pumpkins, brassicas and others), horticultural plants, hops, sugarbeets, ornamentals, flowers, forestry trees and crops and others. Protection for all parts of the plant including roots, stems, leaves, flowers and fruits can be provided by the compounds of formula I. A broad spectrum of diseases belonging to the Oomycetes, Ascomycetes, Basidiomycetes, Hymenomycetes and Fungi Imperfecti are controlled. Examples (but not excluding others) of such diseases are powdery mildews, downy mildews and late blights, anthracnoses, septorioses, blasts and blights, scabs and spots, blotches, rots on fruits, stems, leaves and roots, rusts, altemarioses, cercosporoses, sclerotinioses, moulds, wilts, smuts and bunts and others. The compounds of formula I possess a high fungicidal activity over a wide concentration range. Moreover, the compounds according to the invention show enhanced curative and residual control of fungi and fungal diseases such as cereal, grape, apple and solanaceous crops diseases, and improved foliar systemicity compared with conventional fungicides. Good results in terms of control of diseases caused by phythopathogenic fungi are obtained with the compounds of formula I wherein R¹ represents a C→.₆ alkyl or benzyl group, the phenyl moiety of which may be unsubstituted or substituted by one or two substituents selected from the group consisiting of halogen atoms, Cι_₄ alkyl, C1.4 alkoxy, cyano and nitro groups, R² represents a Cι_₄ alkyl group, R³ represents a methoxy group, R⁴ represents a methyl group, R⁵ represents a hydrogen atom.

Particularly preferred are the compounds of formula I wherein Y represents S. Most preferred are the compounds of formula IA

in which W, X and Y are as hereinbefore defined for formula I.

Especially good results in terms of control of phytopathogenic fungi are obtained by using compounds of formulae IA1 , IA2 and IA3

The compounds of the present invention are prepared via a process which comprises treating a compound of formula II,

in which A, W, X and Y are as hereinbefore defined and L³ represents a suitable leaving group, with a boronic acid or derivative thereof of formula

in which R³, R⁴, R⁵, R⁶ and R⁷ are as hereinbefore, and R^{1 1} and R¹² each independently represent a hydrogen atom or an alkyl group, or R^{1 1} and R¹² taken together represent an alkylenediyl, preferably, an ethylene-1 ,2-diyl or a 1 ,1 ,2,2-tetramethylethylene-1 ,2-diyl group, in the presence of a transition metal or a transition metal complex and optionally, a base.

The compounds of formula II, in which L represents a halogen atom; and A represents an oximether group of formula

R

\

O

\ c

wherein R¹ and R² are defined as hereinbefore are novel intermediates thus comprise a part of the present invention.

In addition, the compounds of formula III are novel intermediates and thus comprise a part of the present invention.

The known intermediates may themselves be prepared according to established methods or routine adaptations thereof. Substituents which are not compatible with the selected reaction conditions may be introduced afterwards. They may be generated by known methods such as subsequent dehvatization or substitution of a suitable group or by cleaving off a suitable protecting group. The compounds of formula II, wherein A represents an alkoximinoalkyl group can be prepared by reaction of known alkanoyl substituted heteroaromatic compounds of formula IV

wherein L³, W, X and Y are defined as hereinbefore, and R' represents a hydrogen atom or an alkyl group with an O-alkyl-hydroxylamine derivative of formula V,

R -O-NH₂ V in which R¹ has the meaning given. The compounds of formula II, wherein A represents an alkenyl group can be prepared by reaction of known alkanoyl substituted heteroaromatic compounds of formula IV with an ylid of formula VI,

_R14_R15_C=P(0)_n(R^,,)₃ VI wherein R¹⁴ and R¹⁵ represent each independently a hydrogen atom or an alkyl group, and R" represents an alkyl, aryl or alkoxy group, and n is 0 or 1.

The compounds of formula II, wherein A represents an alkyl group can be prepared by hydrogenation of the corresponding alkenyl compounds. The novel intermediates of formula II and III can be prepared according to the following reaction schemes 1 and 2

Scheme 1

Preparation the novel intermediates of formula II, wherein L³ represents a halogen atom, X represents N, W represents CH and Y represents O or S

wherein R¹, R² are as herinbefore defined and Y is O or S; Hal is halogen and L³ is Cl, Br or I

Step (a): the halogenation is preferably carried out with chlorine, bromine or iodine in an inert diluent and at a temperature from -40 to +100 °C Step (b): the reaction with urea or thiourea is preferably carried out in an inert diluent and at a temperature from -40 to +100 °C to yield the corresponding hydrohalide, which is subsequently treated with an aqueous base to obtain the free amino compound. Step (c) the amine is preferably converted in-situ to a diazonium salt with nitric acid at a temperature from -40 to +10 °C; the diazonium salt is consequently treated with the hydrohalide, prefarably in the presence of catalytic amounts of copper in an inert diluent at a temperature from -40 to +10 °C. Scheme 2

Preparation of formula III, wherein R^{1 1} and R¹² are each a hydrogen or together represent a ethylene-1 ,2-diyl group

(A) (B)

(C) ("I) wherein R³, R⁴, R⁵, R⁶ and R⁷ are as hereinbefore defined. This reaction is preferably carried out analogously to the process described by D. Schummer and G. Hofle, Tetrahedron, Vol 51 , No 41 , pp. 11219-11222, 1995.

The reactions mentioned hereinabove and hereinbelow are conveniently carried out in an organic solvent. Generally, any inert organic solvent is suitable, preferably aliphatic, cycloaliphatic or aromatic hydrocarbons, which may be halogenated such as hexane, ligroine, petrol ethers, cyclohexane, benzene, toluene, xylene, di-, tri- or tetrachloromethane, ethylenechloride, trichloroethylene and chlorobenzene; ethers such as diethylether, methylethylether, methyl-tert- butylether, diisopropylether, dibutylether, tetrahydrofuran and dioxane; ketones such as acetone and butan-2-one; nitrites, such as acetonitrile and propionitrile, carboxylic esters, such as ethyl acetate and amyl acetate; carboxylic amides, such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfoxides, such as dimethylsulfoxide; sulfones, such as sulfoiane.

Suitable bases are inorganic and organic bases such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, sodium ethylate, sodium methylate, potassium tert-butylate, thethylamine, dimethylaminopyridine, pyridine, sodium hydride, sodium amide, butyllithium and lithium diisopropyiamide.

Suitable transition metals are palladium and nickel, in particular palladium which is complexed by phosphine ligands such as thphenylphosphine, tricyclohexylphosphine or tri-isopropylphosphine, most preferred is tetrakis-(triphenylphosphine)-palladium.

The prepared compounds of formula I may be isolated and purified using conventional methods and techniques. The starting compounds for the preparation of compounds of this invention are either known or can be prepared according to known methods.

The molar ratio between the compounds of formula II and formula III is as a rule in the range of 0.3 to 1.9, preferably 0.8 to 1.2, in particular 0.9 to 1.1 , most preferably the compounds of formulae II and III are used in about equimolar ratios. The reaction is preferably carried out at a temperature between 0 and 150 °C, and preferably, at ambient temperature.

The reactants of formula (B) are also known compounds which can be prepared by oxidative cleavage of Myxothiazol A or 7-phenyl-3,5- dimetoxy-4-methyl-hepta-2,6-dienoates with osmium tetroxide, as described for example by Martin er a/., Tetrahedron Letters, 34, No. 32, pp. 5151-5154, 1993.

Due to their biological activity, the compounds of formula I may be used in cultivation of all plants where infection by phytopathogenic fungi is not desired, e.g. cereals, solanaceous crops, vegetables, legumes, apples, and vines.

The compounds of general formula I have been found to have fungicidal activity. Accordingly, the invention further provides a fungicidal composition which comprises an active ingredient, which is at least one compound of formula I as defined above, and one or more carriers. A method of making such a composition is also provided which comprises bringing a compound of formula I as defined above into association with the carrier(s). Such a composition may contain a single active ingredient or a mixture of several active ingredients of the present invention. It is also envisaged that different isomers or mixtures of isomers may have different levels or spectra of activity and thus compositions may comprise individual isomers or mixtures of isomers.

A composition according to the invention preferably contains from 0.5% to 95% by weight (w/w) of active ingredient.

A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may be, for example, a plant, seed, soil, or water in which a plant grows, or to facilitate storage, transport or handling. A carrier may be a solid or a liquid, including material which is normally a gas but which has been compressed to form a liquid.

The compositions of the present invention may be manufactured into suitable agricultural formulations, e.g. emulsion concentrates, solutions, oil in water emulsions, wettable powders, soluble powders, suspension concentrates, dusts, granules, water dispersible granules, micro-capsules, gels, tablets and other formulation types by well-established procedures. These procedures include intensive mixing and/or milling of the active ingredients with other substances, such as fillers, solvents, solid carriers, surface active compounds (surfactants), and optionally solid and/or liquid auxiliaries and/or adjuvants. The form of application such as spraying, atomizing, dispersing or pouring may be chosen like the compositions according to the desired objectives and the given circumstances.

Typical solvents are those such as aromatic hydrocarbons, e.g. Solvesso^® 200, substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, e.g. cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters, e.g. ethanol, ethyleneglycol mono- and dimethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, or γ-butyrolactone, higher alkyl pyrrolidones, e.g. n-octylpyrrolidone or cydohexylpyrrolidone, epoxidized plant oil esters, e.g. methylated coconut or soybean oil ester and water. Mixtures of different liquids are often suitable.

Solid carriers, which may be used for dusts, wettable powders, water dispersible granules, or granules, may be mineral fillers, such as calcite, talc, kaolin, montmorillonite or attapulgite. The physical properties may be improved by addition of highly dispersed silica gel or polymers. Carriers for granules may be porous material, e.g. pumice, kaolin, sepiolite, bentonite; non-sorptive carriers may be calcite or sand. Additionally, a multitude of pre- granulated inorganic or organic materials may be used, such as dolomite or crushed plant residues.

Pesticidal compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of a carrier which is a surfactant facilitates this process of dilution. Thus, preferably at least one carrier in a composition according to the invention is a surfactant. For example, the composition may contain at two or more carriers, at least one of which is a surfactant.

Surfactants may be nonionic, anionic, cationic or zwitterionic substances with good dispersing, emulsifying and wetting properties depending on the nature of the compound according to general formula I to be formulated. Surfactants may also mean mixtures of individual surfactants.

The compositions of the invention may, for example, be formulated in a variety of forms such as wettable powders, water dispersible granules, dusts, granules, tablets, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders usually contain 5 to 90% w/w of active ingredient and usually contain in addition to solid inert carrier, 3 to10% w/w of dispersing and wetting agents and, where necessary, 0 to 10% w/w of stabilizer(s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and may be diluted in the field with further solid carrier to give a composition usually containing 0.5 to 10% w/w of active ingredient. Water dispersible granules and granules are usually prepared to have a size between 0.15 mm and 2.0 mm and may be manufactured by a variety of techniques. Generally, these types of granules will contain 0.5 to 90% w/w active ingredient and 0 to 20% w/w of additives such as stabilizer, surfactants, slow release modifiers and binding agents. The so-called "dry flowables" consist of relatively small granules having a relatively high concentration of active ingredient. Emulsifiable concentrates usually contain, in addition to a solvent or a mixture of solvents, 1 to 80% w/v active ingredient, 2 to 20% w/v emulsifiers and 0 to 20% w/v of other additives such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are usually milled so as to obtain a stable, non-sedimenting flowable product and usually contain 5 to 75% w/v active ingredient, 0.5 to 15% w/v of dispersing agents, 0.1 to 10% w/v of suspending agents such as protective colloids and thixotropic agents, 0 to 10% w/v of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation and crystaiization or as antifreeze agents for water.

Of particular interest in enhancing the duration of the protective activity of the compounds of this invention is the use of a carrier which will provide slow release of the pesticidal compounds into the environment of a plant which is to be protected.

The biological activity of the active ingredient can also be increased by including an adjuvant in the spray dilution. An adjuvant is defined here as a substance which can increase the biological activity of an active ingredient but is not itself significantly biologically active. The adjuvant can either be included in the formulation as a coformulant or carrier, or can be added to the spray tank together with the formulation containing the active ingredient. As a commodity the compositions may preferably be in a concentrated form whereas the end user generally employs diluted compositions. The compositions may be diluted to a concentration down to 0.001 % of active ingredient to provide doses usually in the range of from 0.01 to 10 kg a.i./ha. Compositions obtained by diluting the formulated product according to the invention with water, such as aqueous dispersions and emulsions also lie within the scope of the invention.

Examples of formulations according to the invention are:

Emulsion Concentrate (EC) Active Ingredient 1 30 % (w/v)

Emulsifier(s) Atlox^Θ 4856 B / Atlox^® 4858 B ⁾ 5 % (w/v)

(mixture containing calcium alkyl aryl sulfonate, fatty alcohol ethoxylates and light aromatics / mixture containing calcium alkyl aryl sulfonate, fatty alcohol ethoxylates and light aromatics) Solvent Shellsol^® A ²⁾ to 1000 ml

(mixture of C₉ - C₁₀ aromatic hydrocarbons) Suspension Concentrate (SO Active Ingredient 1 50 % (w/v) Dispersing agent Soprophor^® FL ³⁾ 3 % (w/v)

(polyoxyethylene polyaryl phenyl ether phosphate amine salt) Antifoaming agent Rhodorsil^® 422 ³⁾ 0.2 % (w/v)

(nonionic aqueous emulsion of polydimethylsiloxanes) Structure agent Kelzan^® S ⁴⁾ 0.2 % (w/v)

(Xanthan gum) Antifreezing agent Propylene glycol 5 % (w/v) Biocidal agent Proxel^{® 5)} 0.1 % (w/v)

(aqueous dipropylene glycol solution containing 20% 1 ,2-benisothiazolin-3-one) Water to 1000 ml Wettable Powder (WP)

Active Ingredient 1 60 % (w/w) Wetting agent Atlox^® 4995 ¹⁾ 2 % (w/w)

(polyoxyethylene alkyl ether)

Dispersing agent Witcosperse^® D-60 ⁶⁾ 3 % (w/w)

(mixture of sodium salts of condensed naphthalene sulfonic acid and alkylarylpolyoxy acetates

Carrier / Filler Kaolin 35 % (w/w) 11

Water Dispersible Granules (WG Active Ingredient 1 50 % (w/w)

Dispersing / Witcosperse^® D-450 ⁶⁾ 8 % (w/w) Binding agent (mixture of sodium salts of condensed naphthalene sulfonic acid and alkyl sulfonates)

Wetting agent Morwet^® EFW ⁶⁾ 2 % (w/w)

(formaldehyde condensation product) Antifoaming agent Rhodorsil^® EP 6703 ³⁾ 1 % (w/w)

(encapsulated silicone) Disintegrant Agrimer^® ATF ⁷⁾ 2 % (w/w)

(cross-linked homopolymer of N-vinyl-2- pyrrolidone) Carrier / Filler Kaolin 35 % (w/w)

¹⁾ commercially available from ICI Surfactants

²¹ commercially available from Deutsche Shell AG

³⁾ commercially available from Rhόne-Poulenc ¹ commercially available from Kelco Co.

⁵⁾ commercially available from Zeneca

6) commercially available from Witco 7) commercially available from International Speciality Products The compositions of this invention can also comprise other compounds having biological activity, e.g. compounds having similar or complementary pesticidal activity or compounds having plant growth regulating, fungicidal or insecticidal activity. These mixtures of pesticides can have a broader spectrum of activity than the compound of general formula I alone. Furthermore, the other pesticides can have a synergistic effect on the pesticidal activity of the compound of general formula I.

The other fungicidal compounds can be, for example, one which is also capable of combating diseases of cereals (e.g., wheat) such as those caused by Erysiphe, Puccinia, Septoria, Gibberella and Helminthosporium spp., seed and soil borne diseases and downy and powdery mildews on vines, early and late blight on solanaceous crops, and powdery mildew and scab on apples etc. Examples of such fungicidal compounds are:

AC 382042, alanycarb, aldimorph, ampropylfos, andoprim, anilazine, azaconazole, azafenidin, azoxystrobin, benalaxyl, benodanil, benomyl, benzamacril, bialaphos, biloxazol, binapacryl, biphenyl, bitertanol, blasticidin S, Bordeaux mixture, bromuconazole, bupirimate, butenachlor, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chinomethionate, chlorbenzthiazon, chlorfenazol, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, copper-containing compounds such as copper oxychloride, and copper sulfate, cufraneb, cycloheximide, cymoxanil, cypofuram, cyproconazole, cyprodinil, cyprofuram, debacarb, dichlofluanid, dichlone, dichloran, dichlorophen, diclobutrazol, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, dimefluazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamin, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon, edifenphos, epoxiconazole, etaconazole, ethirimol, ethoxyquin, etridiazole, famoxadone, fenapanil, fenamidone, fenaminosulph, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, fluoromid, fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole-cis, furmecyclox, guazatine, hexachlorobenzol, hexaconazole, hydroxyisoxazole, hymexazole, IKF-916, imazalil, imibenconazole, iminoctadine, iodocarb, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isovaledione, kasugamycin, RH-7281 , kitazin P, kresoxim-methyl, mancozeb, maneb, mefenoxam, meferimzone, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metominostrobon, metsulfovax, MON 65500, myclobutanil, myclozolin, neoasozin, nickel dimethyldithiocarbamate, nitrothalisopropyl, nuarimol, ofurace, organo mercury compounds, oxadixyl, oxamocarb, oxasulfuron, oxycarboxin, paclobutrazol, pefurazoate, penconazole, pencycuron, phenazineoxide, phosdiphen, phthalide, pimaricin, piperalin, polyoxin D, polyram, probenazole, prochloraz, procymidione, propamocarb, propiconazole, propineb, prothiocarb, pyracarbolid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinconazole, quinomethionate, quinoxyfen, quintozene, rabenazole, spiroxamine, SSF-126, SSF-129, streptomycin, sulfur, tebuconazole, tecloftalame, tecnazene, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofosmethyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamid, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazol, validamycin A, vapam, vinclozolin, XRD-563, zarilamid, zineb, and ziram. In addition, the compositions according to the invention may contain at least one compound of formula I and any of the following classes of biological control agents such as viruses, bacteria, nematodes, fungi, and other microorganisms which are effective in the control of insects, weeds or plant diseases, or to induce host resistance in the plants. Examples of such biological control agents are: Bacillus thuringiensis, Verticillium lecanii, Autographica californica NPV, Beauvaria bassiana, Ampelomyces quisqualis, Bacilis subtilis, Pseudomonas cholororaphis, Pseudomonas fluorescens, Steptomyces griseoviridis and Trichoderma harzianum. Moreover, the co-formulations according to the invention may contain at least one compound of formula I and a chemical agent that induces the systemic acquired resistance in plants such as, for example, isonicotinic acid or derivatives thereof, 2,2-dichloro-3,3- dimethylcyclopropylcarboxylic acid or BION. The compounds of general formula I can be mixed with soil, peat or other rooting media for the protection of the plants against seed-borne, soil-borne or foliar fungal diseases.

The invention still further provides the use as a fungicide of a compound of the general formula I as defined above or a composition as defined above, and a method for combating fungus at a locus, which comprises treating the locus, which may be, for example, plants subject to or subjected to fungal attack, seeds of such plants or the medium in which such plants are growing or are to be grown, with such a compound or composition.

The present invention is of wide applicability in the protection of crop and ornamental plants against fungal attack. Typical crops which may be protected include vines, grain crops such as wheat and barley, rice, sugar beet, top fruit, peanuts, potatoes, vegetables and tomatoes. The duration of the protection is normally dependent on the individual compound selected, and also a variety of external factors, such as climate, whose impact is normally mitigated by the use of a suitable formulation.

The compounds according to the invention have curative, protective and residual activity and are systemic in plants. The compounds control diseases after foliar, soil, into water or seed application. They can be applied in different formulations. The compounds have better curative and systemic properties than the presently commercialised strobilurine derivatives.

Biological Investigation Test Procedure

Test Plants: Test plants were grown up in the greenhouse. Either seed, pregerminated seed or rooted vegetative plant material was planted in pots containing a fertilized soil/peat mixture. Test plants were used for treating them with the various fungicides when they were in the primary leaf stage (cereals) or in the 3-4 leaf stage (tomatoes). The number of leaves of vegetatively propagated plant material was cut back to 3-4 leaves per plant.

Application: Test plants were treated with the test compound either 1 day before (protective treatments = 1 d res) or 2 days after (curative treatments = 2 d cur) the inoculation with a pathogen. The test compounds were applied to the test plants using a had held airbrush at a pressure of 0.5 bar. 2-4 plants were used per treatment.

Compounds: Technical material of the compound according to the invention was dissolved in acetone with 0.5% Triton X155 at a concentration of 0.5%. For application to the test plants, the dissolved materials were further diluted with demineralized water to obtain final concentrations of 100, 20, 4 and 0.8 ppm ingredient. The test plants were sprayed and wetted 'just before run-off with the spray wash containing the desired compound concentration.

Inoculations and culture conditions: For the protective tests, treated plants were kept 1 day in the greenhouse and then inoculated with a pathogen. For inoculation an aqueous spore suspension was sprayed or spores were dusted onto the plants. Then the plants were kept in specific chambers for incubation if required, and then were moved to a greenhouse for disease development. For curative tests, plants were inoculated and, if required, incubated 2 day before the application of the compound, and then moved to a greenhouse after application of the compounds. The temperature in the greenhouse was between 18 and 25 degree C. The relative humidity was about 50-80% in the greenhouses and up to 100% in the incubation chambers. The plants were watered as required for good plant growth. In the greenhouse additional light was supplied to maintain a 14 hours day and 10 hours night cycle.

Assessment of diseases: The percentage of leaf area infected was assessed by visual estimation when untreated control plants were just completely diseased. Each plant was individually evaluated and then the mean infection rating was calculated for each treatment. The fungicidal activity was calculated using the following formula: infection in treated leaves

% activity = 100 - x 100 % infection in untreated leaves The diseases, dose rate and % activity is given in Table I, in which the following abbreviations have been used:

Abbreviation Disease Fungus

GDM grape downy mildew Plasmopara viticola

TLB tomato late blight Phytophthora infestans

WLR wheat leaf rust Puccinia recondita

WPM wheat powdery mildew Blumeria graminis f. sp. tritici

BNB barley net blotch Pyrenophora teres

Table I: Curative (2 d cur) and protective (1 d res) activities

The following examples further illustrate the present invention. It should be understood, however, that the invention is not limited solely to the particular examples given below. Example 1

Preparation of [Methyl 7-[3-(1-(E/Z)-methoxyimino)-ethyl]thiazol-2-yl]-3,5- dimethoxy-4-methylheptan-2,6-dienoate (IA1 )

IA Butane-2,3-dione mono-(O-methyl-oxime)

Dimethylsulfate (75.7 g, 0.6 mole) is added to a mixture of butane-2,3- dione mono-oxime (50.55 g, 0.5 mole) and sodium hydroxide (25 g in 225 ml of water) within 20 minutes at a temperature from 20 to 45 °C. The reaction mixture is stirred at 45 ° C for 20 minutes and heated at reflux for 5 minutes. After cooling to ambient temperature the phases are separated and the aqueous phase is extracted twice with diethylether. The combined organic phases are washed with water and dried and concentrated. The residue is purified by fractional distillation (boiling point: 125 - 127 °C) to yield the pure title product, 35.3 g (61 %).

I B 1-Bromo-butane-2,3-dione 3-(0-methyl-oxime) Bromine (48 g, 0.3 mole) is added to a mixture of IA (35 g, 0.3 mole) and methanol (40 ml) within 80 minutes at temperature from 10 to 15 °C. The reaction mixture is diluted with a mixture of water (200 ml) and diethylether (300 ml). The phases are separated and the organic phase is washed with water dried and concentrated to yield the title product, 54.8 g (93 %).

jC 5-[1 -(E/Z)-methoxyimino)-ethyl]-thiazol-2-ylamine A mixture of IB (54.8 g, 0.28 mole) and acetone (75 ml) is added to a stirred mixture of thiourea (23.1 g, 0.3 mole) and acetone (450 ml) within 20 minutes at ambient temperature. After 20 hours post reaction at room temperature, the precipitate is filtered off, washed with water and dried yielding the hydrobromide of 1C as a white solid, 63.3 g (89%) m.p. 180- 182 °C, which is diluted with water (1.81) at 40 °C. Subsequently an aqueous solution of sodium bicarbonate is added. The precipitate is filtered off and dried at 50 °C to afford the pure title product as a white solid, 32.6 g (67.4%) m.p. 173-176 °C.

I D 2-Bromo-5-[1 -(E/Z)-methoxyimino)-ethyl]-thiazole Nitric acid (17.5 ml, 65 %) is added to a mixture of 1C (9.9 g, 0.058 mole) and phosphoric acid (60 ml, 85 %) at -5 °C. Sodium nitrite (5.7 g in 9 ml of water) is added to the reaction mixture over a period of 75 minutes. The resulting mixture is added to a suspension of copper powder (6 g) in hydrobromic acid (116 ml HBr, 62 % in 34 ml of water) with vigorous stirring over a 15 minute period at a temperature from -5 to 0 °C. The reaction mixture is neutralized with aqueous sodium carbonate, the precipitate is filtered off, dried and diluted with diethylether. The crude product is purified by chromatography to yield the pure title product as an oil 1.4 g (10 %), which crystallizes slowly m.p. 30 - 30.5 °C.

1 E Methyl (E)-3,5-dimethoxy-6-oxo-4-methylhex-2-enoate

A solution of osmiumtetroxide (445 μl, 2.5wt.-%) in terf-butanol and water (1.3 ml) is added to a mixture of the methyl ester of Myxothiazol A (580 mg, 1.16 mmole; obtained according to DE 44 10 449), 4- methylmorpholine-4-oxide (470 mg, 4.64 mmol) and acetone (11.6 ml). The reaction mixture is stirred at room temperature for 20 hours and concentrated. The residue is diluted with ethyl acetate and water, the aqueous phase is extracted with ethyl acetate twice and the combined organic phases are dried with sodium sulfate. The mixture is concentrated in vacuo and the residue is diluted with tetrahydrofuran (15.5 ml). The mixture is treated with an aqueous solution of sodium periodate (1.13 g). The reaction mixture is stirred at room temperature for 40 minutes and concentrated in vacuo. The residue is diluted with ethyl acetate and water, the aqueous phase is extracted with ethyl acetate twice and the combined organic phases are dried with sodium sulfate. This mixture is then concentrated in vacuo. The residue is purified by column chromatography (Sephadex LH-20 as stationary phase; methanol as eluent) to yield 200 mg (80 %) of the desired title product. H-NMR (300 MHz, CDCI₃): δ [ppm] = 1.18 (d), 3.53 (dd), 3.41 (s), 3.62

(s), 3.66 (s), 4.45 (dq), 5.04 (s), 9.57 (d).

1F 1 -(ethylendioxyboryl)-(3,5-dimethoxy-6-methoxycarbonyl-4- methylhexa-1 ,5-diene

1G (3,5-dimethoxy-6-methoxycarbonyl-4-methylhexa-1 ,5-dien-1 -yl)- boronic acid and

A solution of n-buthyllithium in hexane (1.44 ml, 1.6 M) is added to a mixture of tris(ethylendioxyboryl)-methane (550 mg, 2.6 mmol), tetrahydrofuran (5 ml) and dichloromethane (5 ml) at -70 °C. The reaction mixture is stirred for two hours at the same temperature. Subsequently, a mixture of IE (160 mg, 0.74 mmol), tetrahydrofuran (1 ml) and dichloromethane (1 ml) is added. The reaction mixture is allowed to warm up to ambient temperature, stirred for about 20 hours and concentrated. The residue is diluted with ethyl acetate and water, the aqueous phase is extracted with ethyl acetate twice and the combined organic phases are dried with sodium sulfate. The mixture is concentrated in vacuo to obtain 220 mg of a crude product which contains 74 % IF (E/Z 9:1 ).

Η-NMR (300 MHz, CDCI₃): δ [ppm] = 1.14 (d), 3.26 (s), 3.57 (s), 3.65

(s), 3.69 (dd), 4.04 (m), 4.21 (s), 5.59, (d), 6.43 (dd). Crude IF (27 mg) is hydroiyzed and purified by preparative HPLC to obtain 8 mg 1_G (58 %, E/Z 9:1 ), which is characterized by the following selected physical data:

Η-NMR (300 MHz, CDCI₃). δ [ppm] = 6.26 (dd, 1 H, J, = 7 0, J₂ = 18 2), 5.63 (d, 1 H, J = 18.2).

1 H IA1

A mixture of crude 1_F (12 mg, 74%, 25 μmol, E/Z 9:1 ), potassium hydroxide (5.5 mg, 100 μmol), tetra-π- butylammonium chloride (3.9 mg, 12 μmol) , tetrakis-(trιphenylphosphιne)-palladιum (2 mg, 1.7 umol) and 1 D (18 mg, 77 μmol)) is heated for 30 minutes to about 105-110 °C The reaction mixture is cooled to ambient temperature, diluted with water, the organic phase is separated and the aqueous phase is extracted with ethyl acetate twice. The combined organic phases are dried with sodium sulfate. The mixture is concentrated in vacuo and the residue purified with PSC (diethylether / petrol ethers 50:50) to obtain 5.5 mg (60%) of IA1 {E/Z = 9:1 ).

Η-NMR (300 MHz, CDCI₃): δ [ppm] = 1.18 (d), 2.26 (s), 3.30 (s), 3.57

(s), 3.65 (s), 3.77 (dd), 4.00 (s), 4.17 (dq), 4.95 (s), 6.36 (dd), 6.78, (d), 7.39 (s).

Examples 2-12

Using essentially the same procedures described hereinabove for Example 1 and the appropriate starting materials, and employing standard denvatization techniques where appropriate, the following compounds are prepared as shown in Table II: Table II

Example 13

Preparation of IA3

[Methyl 7-[2-(1-(E/Z)-methoxyimino)-ethyl]thien-5-yl]-3,5-dimethoxy-4- methylheptan-2,6-dienoate]

13A 5-Bromo-2-[1 -(E/Z)-methoxyimino)-ethyl]-thiophene Pyridine (7 ml) is added to a mixture of 2-acetyl-5-bromothiophene (25 mmol, prepared as described by M.W. Farrar et al., J Am. Chem. Soc. 1950, 72, 3695-3698), O-methylhydroxylamine hydrochloride (35 mmol) and 200 ml of methanol. The reaction mixture is stirred for 20 hours at room temperature The solvent is distilled off in vacuo and the residue acidified with 0 1 M hydrochloric acid and extracted with ether The combined organic phases are washed with a saturated sodium bicarbonate solution and dried with sodium sulfate The solvent is distilled off in vacuo 13A is obtained as a mixture of 60% (Z)- and 40% (E)- compound according to the ¹ H-NMR-data. The isomers can be separated by preparative HPLC (methanol/water 75:25).

13B Methyl 7-[2-(1-(E/Z)-methoxyιmιno)-ethyl]thιen-5-yl]-3,5-dιmethoxy- 4-methylheptan-2,6-dιenoate

A mixture of crude 1_F (25 μmol, E/Z 9:1 ), potassium hydroxide (5.5 mg, 100 μmol), tetra-n-butylammonium chloride (3.9 mg, 12 μmol) , tetrakis- (trιphenylphosphιne)-palladιum (1.7 μmol) and 13A (77 μmol)) is heated for 30 minutes to 105-110 °C. The reaction mixture is cooled to ambient temperature, diluted with water, the organic phase is separated and the aqueous phase is extracted with ethyl acetate twice The combined organic phases are dried with sodium sulfate. The mixture is concentrated in vacuo and the residue purified by chromatography (diethylether / petrol ethers 50:50) to obtain pure IA3 (E/Z = 9:1 ).

Examples 14-24

Using essentially the same procedures described hereinabove for Example 2 employing standard denvatization techniques where appropriate, the following compounds are prepared and shown in Table III Table III

Claims

What is claimed is:

1. A compound of the general formula I

wherein

A represents a represents an organic radical A represents an organic radical which is bonded directly or via an oxy, iminoxy, mercapto, amino, carbamoyl, thiocarbamoyl, imidoyl or thioimidoyl group;

R³ represents an alkoxy group;

R⁴ and R⁵ each independently represent a hydrogen atom or an alkyl group;

R⁶ represents an alkyl group, and

R⁷ represents a group of formula -COOR⁸ or -CONR⁸R⁹, in which R⁸ and

R⁹ each independently represent a hydrogen atom or an alkyl group;

X and Y each independently represent S, O, N, NR™, CL¹ , CL¹-N, N-CL¹ or CL¹-CL², in which R¹⁰ represents a hydrogen atom or an alkyl group, and L¹ and L² each independently represent a hydrogen or halogen atom or an alkyl group; with the proviso that one of X and Y represents S, 0, N or NR¹⁰;

W represents S, N or CL¹ , with the proviso that X represents CL¹ , when

W represents S; and wherein the zigzag lines -^" indicate that each connected group may have the (E)- or (Z)-confιguration.

2. A compound according to Claim 1 wherein A represents an oxim ether group of formula

^R\

O

C —

2/

R wherein

R² represents a hydrogen atom or an alkyl group; and wherein the zigzag line -*^{■ *}' indicates that the connected groups may have the (E)- or (Z)-configuration.

3. A compound according to Claim 2 wherein R¹ represents a C-|_6 alkyl or benzyl group, the phenyl moiety of which may be unsubstituted or substituted by one or three substituents selected from the group consisting of halogen atoms, C _-4 alkyl, Cι_₄ alkoxy, cyano and nitro groups, R² represents a C_{1 -} alkyl group, R³ represents a methoxy group, R⁴ represents a methyl group, R⁵ represents a hydrogen atom.

4. A compound according to Claim 1 wherein Y represents S.

5. A compound according to Claim 4 of formula IA

Pre-project 1232-P

6. A compound according to Claim 1 selected the group consisting of formulae IA1 , IA2 and IA3

7. A process for the preparation of a compound of formula I, which comprises treating a compound of formula II

in which A, W, X and Y are as defined in Claim 1 and L³ represents a suitable leaving group, with a boronic acid or derivative thereof of formula III

in which R³ through R⁷ are as defined in Claim 1 , and R^{1 1} and R¹² each independently represent a hydrogen atom or an alkyl group, or R^{1 1} and R¹² taken together represent an alkylenediyl group, in the presence of a transition metal or a transition metal complex.

8. A compound of formula IIA

in which R¹ , R², W, X and Y are as defined in claims 1 and 2 and L³ represents a halogen atom.

9. A compound of formula III

in which R³, R⁴, R⁵, R⁶ and R⁷ are as defined in Claim 1 , and

10. A fungicidal composition which comprises a carrier, and as active agent, at least one compound of formula I as defined in Claim 1.

11. A method of combating fungi or fungal plant diseases at a locus such as a plant which comprises treating the locus with a compound of formula I as defined in Claim 1.

12. The method according to Claim 11 wherein the disease is caused by a phytopathogenic fungus selected from the group comprising Oomycetes, Ascomycetes, Basidiomycetes and Fungi imperfecti.

13. A method of combating fungi or fungal plant diseases at a locus such as a plant which comprises treating the locus with a composition as defined in Claim 10.

14. The method according to claim 13 wherein the disease is caused by a phytopathogenic fungus selected from the group comprising Oomycetes, Ascomycetes, Basidiomycetes and Fungi imperfecti.