GB2276380A - Fungicidal and insecticidal compounds containing a phenylsulphurpentafluoride group - Google Patents

Abstract

Compounds having the general formula (I): <IMAGE> and stereoisomers thereof, wherein W is CH3O.CH=C.CO2CH3, CH3O.CH=C.CONR'R", CH3O.N=C.CO2CH3 or CH3O.N=C.CONR'R" wherein R' and R" are independently H or C1-4 alkyl and either (i) X is H, Y is SF5, and R<1> and R<2> are independently H, halo or cyano or (ii) X is SF5, Y is H and R<1> and R<2> are both H, are useful as fungicides and insecticides.

Description

FUNGICIDAL AND INSECTICIDAL COMPOUNDS CONTAINING A PHENYLSULPHURPENTAFLUORIDE GROUP The present invention relates to novel oximes, to processes for their preparation, to compositions containing them and to methods of using them to combat fungi, especially fungal infections of plants, and insect pests.

Pesticidal oximes of the type to which the present invention relates are described in, for example, EP-A-0370629, EP-A-0463488 and EP-A-0414153.

The invention compounds are distinguished by the presence of a phenylsulphurpentafluoride group connected to the oxime moiety. They show fungicidal and insecticidal activity.

According to the present invention there is provided a compound of the general formula (I) or a stereoisomer thereof, wherein W is CH30.CH=C.C02CH3, CH3O.CH=C.CONR' R", CH30.N=C.C02CH3 or CH30.N=C.CONR'R" wherein R' and R" are independently H or C14 alkyl, and either (i) X is H, Y is are and R and R are independently H, halo or cyano or (ii) X is SF5, Y is H and R1 and R2 are both H. When Y is SF5, one or both of R1 and R2 are suitably H.

Because the carbon-carbon or carbon-nitrogen double bond of the W group is unsymmetrically substituted the compounds of the invention may be obtained in the form of mixtures of (E)- and (L)-geometric isomers.

However, these mixtures can be separated into individual isomers, and this invention embraces such isomers and mixtures thereof in all proportions.

The (E)-isomers with respect to the W group are usually the more fungicidally active and form a preferred embodiment of the invention.

Halo includes chloro and bromo.

The C14 alkyl group which R' and R" can be is an alkyl group containing from 1 to 4 carbon atoms in the form of a straight or branched chain. Examples are ethyl, iso-propyl, tert-butyl and preferably methyl.

It is preferred that R' is H and R" is methyl.

In one aspect, the invention provides a compound of the general formula (I) or a stereoisomer thereof, wherein R1 and R2 are both H, one of X and Y is H and the other is SF5 and W is as defined above. Of especial interest is the (E)-isomer of the compounds where W is CH30.CH=C.C02CH3.

In another aspect, the invention provides a compound of the general formula (I) wherein Y, R1 and R2 are H, X is SF5 and W is CH30.CH=C.CONR'R", CH3O.N=C.CO2CH31 CH30.N=C.CO-NR'R" or, preferably, the (E)-isomer of CH30.CH=C.C02CH3, wherein R' and R" are as defined above.

The present invention is illustrated by compounds of the general formula (I) listed in Tables 1 to 4. Throughout the Tables the W group has the (E)-configuration. In the compounds of Table 1, W is CH30.CH=C.C02CH3.

TABLE 1 Compound R1 R2 X Y No 1 H H SF5 H 2 H H H SF5 3 Cl H H SF5 4 Br H H SF5 5 Cl Cl H SF5 6 Br Br H SF5 7 CN H H SF5 TABLE 2 Table 2 comprises 7 compounds of general formula (I) wherein W is CH30.CH=C.CONHCH3 and R11 R21 X and Y are as shown for the correspondingly numbered compound in Table 1.

TABLE 3 Table 3 comprises 7 compounds of general formula (I) wherein W is CH30.N=C.C02CH3 and R1, R2, X and Y are as shown for the correspondingly numbered compound in Table 1.

TABLE 4 Table 4 comprises 7 compounds of general formula (I) wherein W is CH3O.N=C.CONHCH3 and R11 R2, X and Y are as shown for the correspondingly numbered compound in Table 1.

TABLE 5 Table 5 shows melting points where measurable and selected proton NMR data obtained at 270MHz for certain compounds described in Tables 1 to 4.

Chemical shifts are measured at 200C in ppm from tetramethylsilane and deuterochloroform was used as solvent, unless otherwise stated. The following abbreviations are used: s = singlet m = multiplet ppm = parts per million Compound Melting Point Proton NMR Data (8) No. (Table) "C ppm 1 (1) Oil 2.25(3H,s); 3.69(3H,s); 3.82(3H,s); 5.18(2H,s); 7.13-7.21(1H,m); 7.28-7.55(4H,m); 7.60(1H,s); 7.68-7.80(2H,m); 8.04(1H,s) Compounds of formula (I) can be prepared by reacting an acetophenone of formula (II) with a compound of formula (III) in the presence of a base (such as tri ethyl amine or pyridine) in a convenient solvent (such as methanol or water) at a temperature of 20-50"C.

Alternatively compounds of formula (I) can be prepared by reacting oximes of formula (IV) with compounds of formula (V), in the presence of a base (such as sodium hydride, potassium carbonate or triethylamine), in a convenient solvent (such as N,N-dimethylformamide, acetone or tetrahydrofuran) at a temperature of 10-110 C.

The Z substituent in formula (V) is a leaving group such as halogen (chlorine, bromine or iodine), CH3S02 or CH3S020.

The oximes of formula (IV) can be prepared from the corresponding ketones of formula (II) in known manner, for example by treatment with hydroxyl amine.

The ketones of formula (II) can be prepared from the corresponding bromo compound (VI) by known methods, for example by reaction with (1-ethoxyvinyl)-tri-n-butyltin in the presence of bis (triphenylphosphine)palladium (II) chloride to form the ethoxyethylene derivative (VII) which is then transformed to the ketone (II) on acidification.

The bromo compound (VI) can be prepared from the corresponding amino compound (VIII) by, for example, treatment with copper (II) bromide in t-butyl nitrite.

The preparation of both the bromo compound (VI) and the amino precursor (VIII) is described in the Journal of the American Chemical Society, 84, 2064 (1962).

Where Y is SF5 and X is H, the amino compound (VIII) can be halogenated, for example, by treatment with concentrated hydrochloric acid and hydrogen peroxide or with pl-chlorosuccinimide to form the compound where R1 and R2 are both chloro, by treatment with bromine in glacial acetic acid to form the compound where R1 and R2 are both bromo or by treatment with fi-bromo- or -chlorosuccinimide to form the compound where R1 is bromo or chloro and R2 is H. The monobrominated compound can be transformed into the corresponding nitrile by treatment with copper(I) cyanide.

The compounds of formula (V) may be prepared as described in EP-A-0203606 (where W is CH30.CH=C.C02CH3) or EP-A-0254426 (where W is CH30.N=C.C02CH3), and the corresponding amides (where W is CH30.CH=C.CONR'R" or CH30N=C.CONR'R") formed by standard procedures.

The compounds of formula (III) can be prepared by treatment with hydrazine hydrate of the compounds of formula (IX), obtained as described in EP-A-0463488.

The invention also provides processes for preparing the compounds of the invention as herein described and the intermediate compounds of formulae (X) and (XI).

The compounds of formula (I) are active fungicides and may be used to control one or more of the following pathogens: Pyricularia orvzae on rice and wheat and other Pvricularia spp. on other hosts; Puccini a recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g. turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants; Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts such as Sphaerotheca macularis on hops, Sphaerotheca fuliainea on cucurbits (e.g. cucumber), Podosphaera leucotricha on apple and Uncinula necator on vines; Cochliobolus spp., Helminthosporium spp., Drechslera spp. (Pvrenophora spp.), Rhvnchosporium spp., Septoria spp. (including Mvcosphaerella araminicola and Leptosphaeria nodorum), Pseudocercosporella herpotrichoides and Gaeumannomvces araminis on cereals (e.g. wheat, barley, rye), turf and other hosts; Cercospora arachidicola and Cercosporidium personatum on peanuts and other Cercospora species on other hosts, for example, sugar beet, bananas, soya beans and rice; Botrvtis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrvtis spp. on other hosts; Alternaria spp. on vegetables (e.g. cucumber), oil-seed rape, apples, tomatoes, cereals (e.g. wheat) and other hosts;Venturia spp. (including Venturia inaegualis (scab)) on apples, pears, stone fruit, tree nuts and other hosts; Cladosporium spp. on a range of hosts including cereals (e.g.

wheat); Monilinia spp. on stone fruit, tree nuts and other hosts; Didymella spp. on tomatoes, turf, wheat and other hosts Phoma spp. on oil-seed rape, turf, rice, potatoes, wheat and other hosts; Asperoillus spp. and Aureobasidium spp. on wheat, lumber and other hosts; Ascochvta spp. on peas, wheat, barley and other hosts; Plasmopara viticola on vines; other downy mildews such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits;Pvthium spp. (including Pvthium ultimum) on turf and other hosts; Phvtophthora infestans on potatoes and tomatoes and other Phvtophthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and other hosts; Thanatephorus cucumeris on rice and turf and other Rhizoctonia species on various hosts such as wheat and barley, vegetables, cotton and turf; Sclerotinia spp. on turf, peanuts, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts and other hosts; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fuciformis on turf; Mvcosphaerella spp. on banana, peanut, citrus, pecan, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pear, lupin and other hosts; Elsinoe spp. on citrus, vines, olives, pecans, roses and other hosts;Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp., Tvphula spp., Microdochium nivale, Ustilago spp., Urocvstis spp., Tilletia spp., and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp. on sugar beet and other hosts; post-harvest diseases particularly of fruit (e.g.Pencillium dioitatum and P. italicum and Trichoderma viride on oranges, Colletotrichum musae and Gloeosporium musarum on bananas and Botrvtis cinerea on grapes); other pathogens on vines, notably Eutvpa lata Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopezicula tracheiphila and Stereum hirsutum; other pathogens on lumber, notably Cephaloascus fragrans, Ceratocvstis spp., Ophiostoma piceae, Penicillium spp., Trichoderma pseudokoninaii, Trichoderma viride Trichoderma harzianum, Aspergillus niaer, Leptooraphium lindberoi and Aureobasidium pullulans; and fungal vectors of viral diseases e.g. Polvmvxa graminis on cereals as the vector of barley yellow mosaic virus (BYMV).

Some of the compositions show a broad range of activities against fungi in vitro.

Further, some of the compositions may be active as seed dressings against pathogens including Fusarium spp., Septoria spp., Tilletia spp., (e.g. bunt, a seed-borne disease of wheat) Ustilago spp. and Helminthosporium spp. on cereals, Rhizoctonia solani on cotton and Pvricularia orvzae on rice. In particular, some of the compounds show particularly good activity against Puccini a recondita, Septoria nodorum and Ervsiphe graminis tritici.

The compounds may move acropetally/locally in plant tissue. Moreover, the compounds may be volatile enough to be active in the vapour phase against fungi on the plant.

The invention therefore provides a method of combating fungi which comprises applying to a plant, to a seed of a plant or to the locus of the plant or seed a fungicidally effective amount of a compound as hereinbefore defined, or a composition containing the same.

The compounds also exhibit insecticidal and acaricidal activity, including activity against mites, aphids and houseflies, and, at appropriate rates of application, may be used to combat a range of insect pests.

Therefore in another aspect of the invention there is provided a method of combating insect or acarine pests which comprises applying to the locus of the pest an insecticidally or acaricidally effective amount of a compound as hereinbefore defined or a composition containing the same.

The compounds may be used directly for agricultural purposes but are more conveniently formulated into compositions using a carrier or diluent.

The invention thus provides fungicidal compositions comprising a compound as hereinbefore defined and an acceptable carrier or diluent therefor. It is preferred that all compositions, both solid and liquid formulations, comprise 0.0001 to 95%, more preferably 1 to 85%, for example 1 to 25% or 25 to 60%, of a compound as hereinbefore defined.

When applied the foliage of plants, the compounds of the invention are applied at rates of 0.19 to 10kg, preferably lg to 8kg, more preferably 109 to 4kg, of active ingredient (invention compound) per hectare.

When used as seed dressings, the compounds of the invention are used at rates of 0.0001g (for example 0.001g or 0.059) to 10g, preferably 0.005g to 8g, more preferably 0.005g to 49, of active ingredient (invention compound) per kilogram of seed.

The compounds can be applied in a number of ways. For example, they can be applied, formulated or unformulated, directly to the foliage of a plant, to seeds or to other medium in which plants are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or they can be applied as a vapour or as slow release granules.

Application can be to any part of the plant including the foliage, stems, branches or roots, or to soil surrounding the roots, or to the seed before it is planted, or to the soil generally, to paddy water or to hydroponic culture systems. The invention compounds may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.

The term "plant" as used herein includes seedlings, bushes and trees.

Furthermore, the fungicidal method of the invention includes preventative, protectant, prophylactic, systemic and eradicant treatments.

The compounds are preferably used for agricultural and horticultural purposes in the form of a composition. The type of composition used in any instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granules comprising the active ingredient (invention compound) and a solid diluent or carrier, for example, fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, gypsum, diatomaceous earth and china clay. Such granules can be preformed granules suitable for application to the soil without further treatment.

These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler. Compositions for dressing seed may include an agent (for example, a mineral oil) for assisting the adhesion of the composition to the seed; alternatively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example, N-methylpyrrolidone, propylene glycol or N,N-dimethylformamide). The compositions may also be in the form of water dispersible powders or water dispersible granules comprising wetting or dispersing agents to facilitate the dispersion in liquids. The powders and granules may also contain fillers and suspending agents.

The compositions may also be in the form of soluble powders or granules, or in the form of solutions in polar solvents.

Soluble powders may be prepared by mixing the active ingredient with a water-soluble salt such as sodium bicarbonate, sodium carbonate1 magnesium sulphate or a polysaccharide, and a wetting or dispersing agent to improve water dispersibility/solubility. The mixture may then be ground to a fine powder. Similar compositions may also be granulated to form water-soluble granules. Solutions may be prepared by dissolving the active ingredient in polar solvents such as ketones, alcohols and glycol ethers. These solutions may contain surface active agents to improve water dilution and prevent crystallisation in a spray tank.

Emulsifiable concentrates or emulsions may be prepared by dissolving the active ingredient in an organic solvent optionally containing a wetting or emulsifying agent and then adding the mixture to water which may also contain a wetting or emulsifying agent. Suitable organic solvents are aromatic solvents such as alkylbenzenes and alkylnaphthalenes, ketones such as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbons such as chlorobenzene and trichlorethane, and alcohols such as benzyl alcohol, furfuryl alcohol, butanol and glycol ethers.

Aqueous suspension concentrates of largely insoluble solids may be prepared by ball or bead milling with a dispersing agent with a suspending agent included to stop the solid settling.

Compositions to be used as sprays may be in the form of aerosols wherein the formulation is held in a container under pressure of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.

The invention compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating in enclosed spaces a smoke containing the compounds.

Alternatively, the compounds may be used in micro-encapsulated form.

They may also be formulated in biodegradable polymeric formulations to obtain a slow, controlled release of the active substance.

By including suitable additives1 for example additives for improving the uptake, distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities. Other additives may be included to improve the biological efficacy of the various formulations. Such additives can be surface active materials to improve the wetting and retention on surfaces treated with the formulation and also the uptake and mobility of the active material, or additionally can include oil based spray additives, for example, certain mineral oil and natural plant oil (such as soya bean and rape seed oil) additives, or blends of them with other adjuvants.

The invention compounds can be used as mixtures with fertilisers (e.g.

nitrogen-, potassium- or phosphorus-containing fertilisers). Compositions comprising only granules of fertiliser incorporating, for example coated with, a compound of formula (I) are preferred. Such granules suitably contain up to 25% by weight of the compound. The invention therefore also provides a fertiliser composition comprising a fertiliser and the compound of general formula (I) or a salt or metal complex thereof.

Water dispersible powders, emulsifiable concentrates and suspension concentrates will normally contain surfactants, e.g. a wetting agent, dispersing agent, emulsifying agent or suspending agent. These agents can be cationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, for example, cetyltrimethylammonium bromide. Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example, sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example, sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropylnaphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, alkyl glucosides, polysaccharides and the lecithins and the condensation products of the said partial esters with ethylene oxide.

Suitable suspending agents are hydrophilic colloids (for example, polyvinylpyrrolidone and sodium carboxymethylcellulose), and swelling clays such as bentonite or attapulgite.

Compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being diluted with water before use.

These concentrates should preferably be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain up to 95%, suitably 1-85%, for example 1-25% or 25-60%, by weight of the active ingredient.

After dilution to form aqueous preparations, such preparations may contain varying amounts of the active ingredient depending upon the intended purpose, but an aqueous preparation containing 0.0001 to 10%, for example 0.005 to 10%, by weight of active ingredient may be used.

The compositions of this invention may contain other compounds having biological activity, e.g. compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal or insecticidal activity.

By including another fungicide, the resulting composition can have a broader spectrum of activity or a greater level of intrinsic activity than the compound of general formula (I) alone. Further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of general formula (I). Examples of fungicidal compounds which may be included in the composition of the invention are (RS)-1-aminopropyl- phosphonic acid, (RS)-4-(4-chlorophenyl)-2-phenyl-2-(lH-1,2,4-triazol-1-yl- methyl)butyronitrile, (Z)-N-but-2-enyloxymethyl-2-chloro-2',6'-diethylacetanilide, 1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea, 4-(2,2-difluoro -1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile, 4-bromo-2-cyano-N,N-dimethyl- -6-trifluoromethylbenzimidazole-1-sulphonamide, 5-ethyl-5,8-dihydro-8 -oxo(1,3)-dioxol-(4,5-g)quinoline-7-carboxylic acid, a-[E-(3-chloro-2,6- -xylyl)-2-methoxyacetamido]-g-butyrolactone, fi-(2-methoxy-5-pyridyl)-cyclo- propane carboxamide, alanycarb, aldimorph, ampropylfos, anilazine, azaconazole, BAS 490F, benalaxyl, benomyl, biloxazol, binapacryl, bitertanol, blasticidin S, bromuconazole, bupirimate, butenachlor, buthiobate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, chinomethionate, chlorbenzthiazone, chloroneb, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate, and Bordeaux mixture, cycloheximide, cymoxanil, cyproconazole, cyprofuram, debacarb, di-2-pyridyl disulphide 1,1'-dioxide, dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran, didecyl dimethyl ammonium chloride, diethofencarb, difenoconazole, Q,Q-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, etaconazole, ethirimol, ethoxyquin, ethyl (Z)-N-benzyl-N-([methyl(methyl-thioethylideneamino-oxycarbonyl)amino]thio)- -p-alaninate, etridiazole, fenaminosulph, fenapanil, fenarimol, fenbuconazole, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, ICIA5504, imazalil, imibenconazole, ipconazole, iprobenfos, iprodione, isopropanyl butyl carbamate, isoprothiolane, kasugamycin, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methfuroxam, metiram, metiram-zinc, metsulfovax, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxolinic acid, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al, phosphorus acids, phthalide, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, propionic acid, prothiocarb, pyracarbolid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinconazole, quinomethionate, quintozene, rabenazole, sodium pentachlorophenate, streptomycin, sulphur, tebuconazole, techlofthalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thifluzamide, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triacetate salt of l,1'-iminodi(octamethylene)diguanidine, triadimefon, triadimenol, triaz butyl, triazoxide, tricyclazole, tridemorph, triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, XRD-563, zineb and ziram.

The compounds of general formula (I) can be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.

The following Examples illustrate the invention. Throughout the Examples, the term 'ether' refers to dimethyl ether, anhydrous magnesium sulphate was used to dry solutions except where otherwise indicated, and solutions were concentrated under reduced pressure. All reactions were performed under an atmosphere of nitrogen and solvents were dried before use, where appropriate. Unless otherwise stated, chromatography was performed on a column of silica gel as the stationary phase.

EXAMPLE 1 This Example illustrates the preparation of (r),(r)-methyl 3-methoxy -2-[2-(3-pentafluorothiophenylacetoxyiminomethyl)phenyl]propenoate (Compound No 1 of Table 1).

A solution of 3-nitrophenylsulphur pentafluoride (3.0g, 9.3 mmol) (prepared as described in JACS, 84, 3064 (1962)) in isopropanol (50ml) was added to a mixture of reduced iron powder (4.51g, 80.5 mmol), water (20ml) and concentrated hydrochloric acid (0.3ml). The mixture was stirred at 80"C for 2 hours, cooled to room temperature, filtered through Hyflo supercel filter aid and washed with ethyl acetate. The filtrate was washed with water (2 x 30ml) and dried. Removal of the solvent gave a brown oil which was purified by column chromatography (silica gel eluted with ethyl acetate: n-hexane 1:4) to give 3-aminophenylsulphur pentafluoride (0.7g, 33%) as a light brown liquid.

A solution of 3-aminophenylsulphur pentafluoride (1.5g, 6.85 mmol) in acetonitrile (10ml) was added dropwise to a suspension of copper(II) bromide (1.539, 6.85 mmol) in t-butylnitrite (1.76g, 17.12 mmol) and acetonitrile (1Oml) at OOC. After complete addition, the reaction mixture was stirred at room temperature for 4 hours, poured into water (15ml), acidified with 2N hydrochloric acid and extracted with ethyl acetate. The ethyl acetate extracts were washed, dried and the solvent removed to give 3-bromophenylsulphur pentafluoride (1.59, 79%) as a pale yellow oil which was used in the next stage without further purification.

A solution of 3-bromophenylsulphur pentafluoride (1.30g, 4.47 mmol), (1-ethoxyvinyl)-tri-n-butyltin (1.699, 4.7 mmol) and bis (triphenylphosphine)palladium (II) chloride (150mg) in fi,fi-dimethyl- formamide (35ml) was heated at 800C for 3 hours. The reaction mixture was cooled to room temperature and potassium fluoride (50ml of a 10% aqueous solution) was added. The resulting mixture was stirred for 1 hour then filtered through Hyflo supercel filter aid which was rinsed through with ether. The filtrate was washed with brine, dried and concentrated to give a brown oil. This was purified by column chromatography (silica gel eluted with n-hexane) to give 1-ethoxy-1-(3-pentafluorothiophenyl)ethylene (0.71g, 58%) as a colourless oil.

A solution of 1-ethoxy-1-(3-pentafluorothiophenyl)ethylene (0.49g, 1.79 mmol) in acetone (25ml) was treated with 2N hydrochloric acid (2 drops). The reaction mixture was allowed to stand at room temperature for 3 hours diluted with water (15ml) and neutralised with sodium bicarbonate.

The aqueous phase was extracted with ethyl acetate (2x30ml), and the combined extracts washed with brine, dried and concentrated to give 3-pentafluorothioacetophenone (0.5g, 94%) as a pink oil which was used in the next stage without further purification.

(E)-methyl-2[2-(phthalimidooxymethyl)phenyl]-3-methoxypropenoate (0.759, 2.03 mmol) (prepared as described in Recipe 4 (page 11) of EP-A-0463488) was suspended in methanol (20ml) at room temperature, hydrazine hydrate (0.1g, 2.03mmol) was added and the resulting solution stirred for 3 hours. The white precipitate which formed was filtered off and the solvent removed to give a white semi solid. This was diluted with ether, the white solid filtered off and the filtrate evaporated to give (E)-methyl 2-[2-(aminomethyl)phenyl]-3-methoxypropenoate (93%) as a yellow oil which was used immediately in the next stage without further purification.

A mixture of (E)-methyl-2-[2-(aminoxymethyl)phenyl]-3-methoxy- propenoate (0.539), 3-pentafluorothioacetophenone (0.5g, 2.03 mmol) and pyridine (O.lml) in methanol (1Oml) and water (1.5ml) was stirred at room temperature for 24 hours. The solution was evaporated to dryness to give a solid residue which was purified by flash column chromatography (silica eluted with ethyl acetate:n-hexane:acetic acid 1:4:0.025) to give the title compound (0.34g, 36%) as a colourless oil. Analysis by 1H NMR (see Table I) showed this to be a single isomer.

EXAMPLE 2 The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cm diameter minipots. The test compounds were formulated either by bead milling with aqueous Dispersol T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use. The formulations (100 ppm active ingredient) were sprayed on to the foliage or applied to the roots of the plants in the soil. The sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i. in dry soil. Tween 20 was added to give a final concentration of 0.05% when the sprays were applied to cereals.

For most of the tests the compounds were applied to the soil (roots) or to the foliage (by spraying) one or two days before the plant was inoculated with the disease. An exception was the test on Ervsiphe araminis in which the plants were inoculated 24 hours before treatment.

Foliar pathogens were applied by spray as zoosporangial suspensions onto the leaves of test plants. After inoculation, the plants were put into an appropriate environment to allow infection to proceed and then incubated until the disease was ready for assessment. The period between inoculation and assessment varied from four to fourteen days according to the disease and environment.

The disease level present (i.e. leaf area covered by actively sporulating disease) on each of the treated plants was recorded using the following assessment scale: O = 0% disease present 20 = 10.1-20% disease present 1 = 0.1-1% disease present 30 = 20.1-30% disease present 3 = 1.1-3% disease present 60 = 30.1-60% disease present 5 = 3.1-5% disease present 90 = 60.1-100% disease present 10 = 5.1-10% disease present Each assessment was then expressed as a percentage of the level of disease present on the untreated control plants. This calculated value is referred to as a POCO (Percentage of Control) value.An example of a typical calculation is as follows: Disease level on untreated control = 90 Disease level on treated plant = 30 POCO = disease level on treated plant x 100 = ssQ x 100 = 33.3 disease level on untreated control 90 This calculated POCO value is then rounded to the nearest of the values in the 9-point assessment scale shown above. In this particular example, the POCO value would be rounded to 30. If the calculated POCO falls exactly mid-way between two of the points, it is rounded to the lower of the two values.

The results are shown in Table 6.

TABLE 6 Compound No per Egt Sn Lo AV Vi Lv eil of (Table No) 1(I) - O o 5a 0 0 0 0 Unless stated otherwise, data represent activity following application as a combined foliar spray and root drench treatment at 100 ppm.

a 10 ppm foliar application only - No result Kev to Diseases Pr Puccinia recondita Tc Thanetophorus cucumeris Egt Erysiphe araminis tritici Vi Venturia inaeoualis Sn Septoria nodorum Pv Plasmopara viticola Po Pvricularia orvzae Pil Phvtophthora infestans lvcopersici CHEMICAL FORMULAE (as in description)

CHEMICAL FORMULAE (as in description)

Claims (9)

1. CLAIMS 1. A compound having the general formula (I):

   or a stereoisomer thereof, wherein W is CH30.CH=C.C02CH3, CH30.CH=C.CONR'R", CH30.N=C.C02CH3 or CH30.N=C.CONRR" wherein R' and R" are independently H or C14 alkyl and either (i) X is H, Y is SF5, and R1 and R2 are independently H, halo or cyano or (ii) X is SF5, Y is H and R1 and R2 are both H.
2. 2. A compound according to claim 1 wherein R1 and R2 are both H and one of X and Y is H and the other is SF5.
3. 3. The (r)-isomer of a compound according to claim 1 or 2 wherein W is CH30.CH=C.C02CH3.
4. 4. A compound according to claim 1 wherein Y, R1 and R2 are H and X is SF5.
5. 5. The (E)-isomer of the compound according to claim 4 wherein W is CH30.CH=C.C02CH3.
6. 6. A fungicidal composition comprising a fungicidally effective amount of a compound according to claim 1 and a fungicidally acceptable carrier or diluent therefor.
7. 7. A method of combating fungi which comprises applying to plants, to the seeds of plants or to the locus of the plants or seeds, a compound according to claim 1 or a composition according to claim 6.
8. 8. An insecticidal or acaricidal composition comprising an insecticidally or acaricidally effective amount of a compound according to claim 1 and an insecticidally or acaricidally acceptable carrier or diluent therefor.
9. 9. A method of combating insect or acarine pests which comprises applying to the locus of the pest an insecticidally or acaricidally effective amount of a compound according to claim 1 or a composition according to claim 8.