WO1998021174A1

WO1998021174A1 - Strobilurine analogue compounds with fungicidal activity

Info

Publication number: WO1998021174A1
Application number: PCT/EP1997/006400
Authority: WO
Inventors: Paolo Piccardi; Isabella Venturini; Ernesto Signorini; Lucio Filippini
Original assignee: Isagro Ricerca S.R.L.
Priority date: 1996-11-14
Filing date: 1997-11-13
Publication date: 1998-05-22
Also published as: ITMI962366A0; EP0944576A1; ITMI962366A1; IT1287161B1; JP2001504112A

Abstract

Strobilurine analogue compounds of general formula (I). Said compounds possess high fungicidal activity.

Description

STROBILURINE ANALOGUE COMPOUNDS WITH FUNGICIDAL ACTIVITY

This invention relates to strobilurin analogue compounds.

More particularly the invention relates to strobilurin analogue compounds with high fungicidal activity, their preparation process and their use in agriculture for controlling phytopathogenic fungi .

Strobil urines are secondary metabolites isolated from certain

Basidomycetes strains, which are characterised by the presence of a 1-methoxycarbonyl-2-methoxyethen-1-yl group and are able to inhibit itochondrial respiration. The compounds of the present invention are synthetic analogues of said strobilurins.

Consequently the present invention provides strobilurin analogue compounds of general formula (I): R2

Tox in which: - Ri represents a linear or branched Ci-Cε fluoroalkyl group; or a linear or branched Ci-C^ alkyl group;

R₂ represents a hydrogen atom; a linear or branched Ci-Cε al kyl or hal oal kyl group ; a l i near or branched C, -C , al koxy or hal oal koxy

I 0 group; a linear or branched C -C carboalkoxy group; a nitrile group. Tox represents a group of general formula (Ila) or (lib):

0

/ \

R3 (Ha)

R4

in which:

W represents an =N- azo group; or a =C(Rs)- group;

Y represents an oxygen atom; or a -N(R6)- group;

R' and R", which can be equal or different, represent a hydrogen atom; or a linear or branched C-i-Cβ alkyl group;

R3 and R₄, which can be equal or different, represent a linear or branched Ci-Cβ alkyl or haloalkyl group;

Rs and Re, which can be equal or different, represent a hydrogen atom; or a linear or branched Ci-Cβ alkyl or haloalkyl group;

K represents a chain of general formula (Ilia):

-(Gl)m-(C2nH2n+2)-(G2)p- (Ilia); and, if Ri represents a linear or branched Ci-Cβ fluoroalkyl group, K also representing a chain of general formula (Illb): -(G3)C=C(G₄)- (Illb); in which: m and p, which can be equal or different, can be 0 or 1; - n represents a whole number between 0 and 10, end values included;

Gi and G2, which can be equal or different, represent an oxygen atom or a sulphur atom; or represent one of the following groups of formula (Va), (Vb), (Vc) and (Vd): -N=C(Rτ)- (Va)

-C(Rτ)=N- (Vb)

-C(Rτ)=N-0- (Vc)

-0-N=C(R₇)- (Vd) in which R7 represents a linear or branched Ci-Cβ alkyl or haloalkyl group; a linear or branched Ci-Ce alkoxy or haloalkoxy group; a linear or branched C1-C6 thioalkyl or halothioalkyl group; a C3-C9 cycloalkyl group; a cyano group; a linear or branched C2-C10 carboalkoxy group; G3 and G4, which can be equal or different, represent a hydrogen atom; a halogen atom chosen from fluorine, chlorine and bromine; a linear or branched Ci-Cβ alkyl or haloalkyl group; X represents a phenyl group; a naphthyl group; a penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a benzocondensed penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; said phenyl, naphthyl , penta- or hexa-atomic aromatic heterocyclic, or benzocondensed penta- or hexa-atomic aromatic heterocyclic groups being optionally substituted with one or more equal or different Ra groups; - Ra represents a linear or branched Ci-Cs alkyl or haloalkyl group; a linear or branched Ci-Ca alkoxy or haloalkoxy group; a linear or branched C1-C6 thioalkyl or halothioalkyl group; a C3-C3 cycloalkyl group; a phenyl group; a naphthyl group; a phenoxy group; a naphthoxy group; a penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a benzocondensed penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a penta- or hexa-atomic aromatic heterocycloxy group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a benzocondensed penta- or hexa-atomic aromatic heterocycloxy group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; said C3-C9 cycloalkyl, phenyl, naphthyl, phenoxy, naphthoxy, penta- or hexa-atomic aromatic heterocyclic, benzocondensed penta- or hexa-atomic aromatic heterocyclic, penta- or hexa-atomic aromatic heterocycloxy, or benzocondensed penta- or hexa-atomic aromatic heterocycloxy groups being optionally substituted with one or more equal or different halogen atoms chosen from fluorine, chlorine and bromine, or with one or more equal or different groups chosen from linear or branched Ci-Ce alkyl or haloalkyl groups, linear or branched Ci-Cε alkoxy or haloalkoxy groups, or cyano groups. The compounds of general formula (I) can present geometrical isomerisms. The first isomerism relates to the double bond explicitly represented in formula (I). The second isomerism relates to the double bond present in the Tox group when said group is represented by the aforesaid general formula (Ha). It is therefore within the spirit of the present invention to consider both isomerically pure compounds of general formula (I) and mixtures thereof in any proportion. Generally, the preferred compounds of general formula (I) are those in which the Ri group is in the trans position to the -K-X group relative to the double bond -C=C-. More preferred are those compounds of general formula (I) in which in the Tox group, represented by general formula (Ila), the -0-R3 group is trans to the -C0-Y-R4 group relative to the double bond -C=W-. Examples of linear or branched Ci-Cβ fluoroalkyl groups are: fluoromethyl , difluoromethyl , trifluoro ethyl , 2,2,2- trifluoroethyl , 2,2,3,3-tetrafluoropropyl , 2,2,3,3,3- pentafluoropropyl , etc. Examples of linear or branched Ci-Cβ alkyl or haloalkyl groups are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl , s-pentyl , neo-pentyl , fluoromethyl , difluoromethyl , trifluoromethyl , 2,2,2-trifluoroethyl , 1,1 ,2,2-tetrafluoroethyl , trichloromethyl , 2,2,2-trichloroethyl , 2, 2, 3, 3-tetrafluoropropyl , 2,2,3,3,3-pentafluoropropyl , 2,2,2-trichloro-1 , 1-difluoroethyl , etc.

Exampl es of l i near or branched Ci-Cβ al koxy or haloal koxy groups are : methoxy , ethoxy , t ri f l uoromethoxy , 1 , 1 , 2 , 2-tet raf l uoroethoxy , 2,2,2-trifluoroethoxy, 3,3,3,2,2-pentaf1 uoropropyloxy , 2,2,2- trichloro-1 , 1-di fluoroethoxy , etc.

Examples of linear or branched Ci-Cβ thioalkyl or halothioalkyl groups are: thiomethyl, thioethyl, trifluorothiomethoxy, 1,1,2,2- tetrafluorothioethoxy, etc.

Examples of C3-C9 cycloalkyl groups are: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , etc.

Examples of linear or branched C2-C10 carboalkoxy groups are: carboxymethyl, carboxyethyl , carboxyisopropyl , etc. Examples of penta- or hexa-atomic aromatic heterocyclic groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur, and benzocondensed penta- or hexa-atomic aromatic heterocyclic groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur are: pyrrole, imidazole, pyrazole, triazole, tetrazole, isoxazole, benzoisoxazole, oxazole, thiazole, isothiazole, benzothiazole, pyridine, pyrazine, pyrimidine, pyridazine, furan, benzofuran, thiophene, benzothiophene, benzoxazole, indole, etc. Examples of penta- or hexa-atomic aromatic heterocycloxy groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur, and benzocondensed penta- or hexa-atomic aromatic heterocycloxy groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur are: pyridoxy, pyrimidoxy, benzoxazolyloxy, benzothiazolyloxy, etc. Compounds of general formula (I) not illustrated in the examples but equally interesting for their fungicidal activity are:

E,E,E-5-phenyl-3-methyl-2-(1-methoxycarbonyl-2-methoxyethen-1- yl )-1 , 1 , 1-trif luoropenta-2,4-diene;

Ξ,E,E-4-phenyl-1-(1-methoxycarbonyl-2-methoxyethen-1-yl )-1- bromobuta-1 ,3-diene;

E, E-2-(4-chlorophenyl )-1-( 1-methoxycarbonyl-2-methoxyethen-1- yl )-1-chloroethene;

E,E-2-(3-phenoxyphenyl )-1-(1-methoxycarbonyl-2-methoxyethen-1- yl )-1-chloroethene;

E,E-4-(4-phenoxyphenoxy)-2-(1-methoxycarbony -2-methoxyethen- 1—yl )-1 , 1 , 1-trifluorobut-2-ene; - E,E-4-(4-phenoxyphenoxy)-3-trifluoromethyl-2-(1- methoxycarbonyl-2-methoxyethen-1-yl )-but-2-ene;

E,E-4-(3-phenoxyphenoxy)-2-(1-methoxycarbonyl-2-methoxyethen- 1—yl )-1 , 1 , 1-trifluorobut-2-ene;

E,E-4-(3-phenoxyphenoxy)-3-methyl-2-(1-methoxycarbonyl-2- methoxyethen-1-yl )-1 , 1 , 1-trifluorobut-2-ene;

E,E,E-6-aza-5-oxa-7-phenyl-2-(1-methoxycarbonyl-2- methoxyethen-1-yl )-1 , 1 , 1 ,8,8,8-hexafluoroocta-2,6-diene;

E,E,E-6-aza-5-oxa-7-phenyl-3-trifluoromethyl -2-(1- methoxycarbonyl -2-methoxyethen-1-yl )-8 , 8 , 8-t ri f1 uoroocta-2 , 6- diene.

The compounds of general formula (I) of the present invention can be prepared by various synthetic paths, some of which are illustrated in the ensuing Schemes A-H in which, if not otherwise stated, the symbols used assume the meanings defined heretofore for the compounds of general formula (I). For greater clarity, all the preparation methods for said compounds are illustrated by the synthesis of particular cases of the compounds of general formula (I), the described method being however generally applicable to all compounds of general formula (I), with only those exceptions stated appropriately in the description.

The compounds of general formula (I) can be conveniently obtained, for example, by condensation between an organic zinc of general formula (a2) or (a3) and a suitable compound of general formula

(a1) or (a4) respectively, operating in the presence of a palladium catalyst, in accordance with the procedure illustrated in the following schemes A and B: SCHEME A

(a4) (I) in which Qi represents a halogen atom chosen from chlorine, bromine and iodine, or a sulphonic ester such as tnfluoromethanesulphonic ester or paratoluenesul phonic ester, and

Q2 represents a halogen atom chosen from chlorine, bromine and iodine.

The organic zinc of general formula (a2) can be conveniently prepared starting from a compound of general formula (a4) as described, for example, in "Journal Organic Chemistry" (1996), vol . 61 , pp. 3200-3204.

The compounds of general formula (a1) can be prepared, for example, as described in "Synlett" (1995), pp. 32-33. The organic zinc of general formula (a3) can be prepared by reacting a compound of general formula (a1) with a Zn/Ag mixture, prepared as described for example in "Tetrahedron Letters" (1981), vol. 22, pp. 649-652, in the presence of a chelating agent such as N,N,N' ,N'-tetramethyl-1 ,2-diaminoethane, in a dipolar aprotic solvent such as dimethyl formamide (DMF) or n-methyl-pyrrol idone (NMP), or an ether solvent such as tetrahydrofuran (THF). As stated, the organic zinc compounds of general formula (a2) and (a3) are reacted with the compounds of general formula (a1) and (a4) respectively, in the presence of a palladium catalyst or a precursor thereof, known in the literature.

The compounds of general formula (a4) can be prepared by the procedures illustrated in the following Schemes C1 and C2, the compounds of general formula (c3) and (c5) obtained leading to structures of type (a4). SCHEME C1

(C3) SCHEME C2

(C5) The reactions indicated in Schemes C1 and C2 are conducted by reacting the haloalkane of general formula (d) with a suitable nucleophilic of general formula (c2) or (c4), in the presence of an inorganic base such as sodium or potassium carbonate, or in the presence of an organic base such as triethylamine, and in the presence of a dipolar aprotic solvent such as dimethyl formamide (DMF) or dimethylsulphoxide (DMSO), or an ether solvent such as tetrahydrofuran (THF), or an aromatic solvent such as toluene or xylene. Said reactions are conducted at a temperature of between ambient temperature and the boiling point of the solvent used. The process illustrated in Schemes C1 and C2 is new and therefore falls within the spirit of the present invention. The nucleophil ics of general formula (c2) and (c4) are commercially available, and can also be easily prepared by processes described in the known art.

The haloalkane of general formula (d) can be prepared for example by the procedure illustrated in the following Scheme D.

SCHEME D

The haloalkane 1 , 1 , 1-tribromo-2,2,2-trifluoroethane of formula (d1) is added, for radical reaction, to an alkene of formula (d2), in the presence of copper salts or of a radical inhibitor such as dibenzoylperoxide or azoisobutyronitrile (AIBN), to obtain the adduct of formula (d) in the case in which R₂, in general formula (d), represents a hydrogen atom. The haloalkane of formula (d1) and the alkene of formula (d2) are commercially available products, and can also be easily prepared by the processes described in the known art.

Compounds of general formula (a4), where K represents a group of general formula (Illb), can be prepared for example by the procedure illustrated in the following Scheme E. SCHEME E

The haloalkane 1 , 1 , 1-trichloro-2,2,2-trif luoroethane of formula (e1) is reacted with zinc (Zn) in anhydrous dimethyl formamide (DMF), after which the suitable cinnamaldehyde of general formula (e2) and acetic anhydride are added, operating at a temperature of between 20°C and 100°C. The zinc used could be activated by adding a catalytic quantity of silver salts as described for example in "Journal Organic Chemistry" (1996), vol. 61, pp. 3200- 3204. The haloalkane of formula (e1) and the cinnamaldehyde of general formula (e2) are commercially available products, and can also be easily prepared by the processes described in the known art. The compounds of general formula (I) of the present invention can also be prepared by the procedure illustrated in the following Scheme F. SCHEME F

(f2)

The compound of general formula (f1), obtainable as described for example in "Journal of American Chemical Society" (1951), vol. 73, pp. 3648-3686 and in "Synthesis" (1985), pp. 850-855, is reacted with the phosphorus ilide of general formula (f3), in which Ph represents the phenyl group and J represents the -K-χ- group, if compatible with the reaction conditions. If not, then the compound of general formula (f1) is reacted with a precursor ilide of the phosphorus ilide of general formula (f3). The phosphorus ilide of general formula (f3) is a commercially available product, and can also be easily prepared by the processes described in the known art.

The compounds of general formula (f2) can also be obtained by the procedure illustrated in the following Scheme G.

SCHEME G

The phosphorus ilide of general formula (g1), obtainable as described for example in Houben-Weil (1982), Band E1 , p. 616, in which R_P represents a linear or branched Ci-Cβ alkyl group, is reacted with a compound of general formula (g2) in which J represents a -K-X- group.

The product of general formula (g2) is a commercially available product, and can also be easily prepared by the processes described in the known art.

Compounds of general formula (I), where said formula corresponds to the general formula (h4) given below, can be obtained by the procedure illustrated in the following Scheme H.

SCHEME H

(h3) (h4) The compound of general formula (f1) is reacted with an organometal compound of general formula (hi) in which Met represents lithium chloride, magnesium chloride or magnesium bromide, in the presence of an ether solvent such as tetrahydrofuran (THF) at a temperature of between -60°C and 50°C, to obtain the allyl alcohol of general formula (h2). Said allyl alcohol (h2) is then reacted, for example, with mesyl chloride in the presence of an organic base, for example pyridine, to obtain the esylate of general formula (h3) in which Ms represents the mesyl group. The mesylate (h3) is then reacted, for example, with a group of general formula H-G2-X in which G2 represents an oxygen or sulphur atom, or a previously described group of general formula (Vd), in presence of an inorganic base, as for example potassium carbonate, in the presence of a dipolar aprotic solvent such as dimethyl formamide (DMF), or an ether solvent such as tetrahydrofuran (THF) The organometal compound of formula (hi) and the group of general formula H-G2-X are commercially available products, and can also be easily prepared by the processes described in the known art. The compounds of general formula (I) possess particularly high fungicidal activity against those phytopathogenic fungi which attack vines, sugar beet, cereals, Cucurbitaceae and fruit trees. The following are examples of plant diseases which can be combated using the compounds of general formula (I) according to the present invention:

Helminthosporium teres on cereals; Erysphe graminis on cereals; Puccinia spp. on cereals; - Plasmopara viticola on vines; Phytium on vegetables; Phytophthora spp. on vegetables; Septoria spp. on cereals;

Sphaerotheca fuliginea on Cucurbitaceae (eg. cucumber); - Rhynchosporiu on cereals;

Podosphaera leucotricha on apple trees; Unicinula necator on vines; Venturia spp. on fruit-bearing plants; Pyricularia oryzae on rice; Botrytis cinerea; Fusarium spp. on cereals; etc. The compounds of general formula (I) are able to provide a fungicidal action of both curative and preventive character, and in addition they demonstrate little or no phytotoxicity. Per practical uses in agriculture it is often useful to form fungicidal compositions containing one or more compounds of general formula (I), possibly as a mixture of isomers, as the active substance.

These compositions can be applied to any part of the plant, for example on leaves, stems, branches and roots, or on the seeds themselves before sewing, or even on the soil in which the plant grows .

The compositions used can be in the form of dry powder, wettable powder, emulsifiable concentrates, icroemulsions, paste, granulates, solutions, suspensions etc. The choice of the type of composition depends on the specific use. The compositions are prepared in known manner, for example by diluting or dissolving the active substance with a solvent medium and/or a solid diluent, possible with surfactants present. The following can be used as solid diluents or supports: silica, kaolin, bentonite, talc, kieselguhr, dolomite, calcium carbonate, magnesia, chalk, clays, synthetic silicates, attapulgite, sepiol ite. In addition to water, suitable liquid diluents include various solvents, for example aromatic solvents (xylenes or alkyl-benzene mixtures), chloroaro atic solvents (chlorobenzene) , paraffins (petroleum fractions), alcohols (methanol, propanol , butanol , octanol , glycerin), amines, amides (N,,N-dimethyl formamide, N- methylpyrrol idone) , ketones (cyclohexanone, acetone, acetophenone, isophorone, ethylamylketone) , esters (isobutyl acetate). Usable surfactants include sodium, calcium, triethanolamine or triethyla ine salts, alkyl sulphonates, alkylarylsulphonates, polyethoxylated alkylphenols, fatty alcohols condensed with ethylene oxide, polyoxyethylated fatty acids, polyoxyethylated sorbitol esters, 1 igninsulphonates.

The compositions can also contain special additives for particular purposes, for example adhesive-forming additives such as gum arabic, polyvinyl alcohol, polyvinylpyrrol idone. If desired, other compatible active principles can be added to the compositions of the present invention, such as fungicides, phytoregulators, antibiotics, herbicides, insecticides, fertil izers. Examples of fungicides which can beincluded in the composition of the invention are alanicarb, ampropylfos, anilazine, azaconazole, azoxyst robin, BAS 490 F, BAY KTU 3616 benalaxyl, benomyl , bilosazol, binapacryl , bitertanol, blasticidin S, bromoconazole, bupirimate, butenaclor, buthiobate, captafol , captan, carbendazim, carbox, chinoethionat , chlorobenzothiazone, chloroneb, chlorothalonil , clozolinate, clozylacon, copper salts, cyclohexyl imide, cymoxanil, cyproconazole, cyprofurane, cyprodinyl, CGA 245 704, diclofluanid, dichlone, diclobutrazole, diclomezine, dicloran, didecyl or dimethyl-ammonium chloride, diethofencarb, difeconazole, dimefluazole, dimethconazole, dimetomorph, dimethi rimol , diniconazole, dinocap, dipyri thione, ditali fos, dithianon, dode orph, dodine, doguadine, ediphenphos, epoxyconazole, etaconazole, ethirymol, ethoxyquin, etridazole, fa oxadone, fena inosulf , fenapanyl , fenarimol, fenbuconazole, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, ferbam, ferimzone, fluazinam, fludioxonyl, fluoroimide, fluotrimazole, flutolanyl, flutriafol, fluzilazole, folpet, fuberidazole, furalaxyl, cis-furconazole, guazatine, ICI A 5504, hydroxyisoxazole, i esazole, i azalil, imibenconazole, ipconazole, ipbrobenphos, iprodione, isoprothiolane, kasugamycin, kresoximethyl , mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, methconazole, methfuroxam, methiram, metsulfovax, myclobutanyl , neoasozin, nuarimol , ofurace, oxadixil, oxycarboxin, perfurazoate, penconazole, pencycuron, phenazine oxide, phosethyl-Al, phosphoric acids, phthalide, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, prothiocarb, pyracarbol id, pyrazophos, pyrimethanyl , pyriphenox, pyroquilon, pyroxyfur, pyrrolnitrin, compounds containing quaternary ammonium, quinconazole, quinomethionate, quintozene, rabenazole, sodium pentachlorophenate, SSF 126, SSF 129, spiroxamine, streptomycin, sulphur, tebuconazole, teclophthalam, tecnazene, thiabendazole, thicarbanyl, thicyophen, thifluzamide, 2-(thiocyanomethylthio)-benzothiazole, thiophanate methyl , timibenconazole, methyl ticlophos, tolylfluanid, triacetate salt of 1 , 1 '-imino-di (octa-methylene)diguanidine, triadimefon, triadi enol, triazabutyl, triazaoxide, tricycloazole, tridemorph, triforine, trif1 umizole, tri ticonazole, validamycin A, vapam, vinclozolin, zineb and ziram.

The active substance concentration in said compositions can vary within a wide range, depending on the active compound, the crop, the pathogen, the environmental conditions and the type of formulation used.

In general the active substance concentration varies between 0.1% and 95%, preferably between 0.5% and 90%. The ensuing examples are given as non-limiting illustration of the present invention.

Analytical data for the compounds obtained as described in the following examples are given in Table 1.

EXAMPLE 1 Preparation of E,E,E-5-phenyl-2-(1-methoxycarbonyl-2-methoxyethen-

1—yl )—1 ,1 , 1-trifluoropenta-2,4-diene (Compound No. 1).

0.185 cm³ of chlorotrimethylsilane are added in a nitrogen atmosphere to a suspension of 2.45 g of Zn/Ag (prepared by the procedure described in "Tetrahedron Letters" (1981), vol. 22, pp. 649-652) in 12 cm³ of anhydrous tetrahydrofuran.

After 10 minutes at ambient temperature, a mixture of 3.63 g of methyl 3-methoxy-2-iodopropenoate (prepared by the procedure described in "Synlett" (1995), pp. 32-33) and 2.26 cm³ of

N,N,N' ,N'-tetramethyl-1 ,2-diaminoethane in 5 cm³ of tetrahydrofuran is added.

After about 2 hours, the supernatant solution is added to a solution of 2.7 g of 5-phenyl-2-chloro-1 , 1 , l-trifluoropenta-2,4- diene (prepared by the procedure described in "Tetrahedron

Letters" (1986), vol. 27, pp. 3655-3658) and 0.360 g of (PhsP)4Pd in 7 cm³ of tetrahydrofuran. After 48 hours at 60°C, the reaction mixture is poured into brine and ethyl acetate. The organic phase is separated and dried over sodium sulphate, and is then evaporated under reduced pressure.

The crude product obtained in this manner is purified by silica gel chromatography, eluting with 9/1 hexane/ethyl acetate. 0.4 g of Compound No. 1 are obtained (yield 11.2%). EXAMPLE 2

Operating in a like manner to that described in Example 1, the following compounds are prepared:

E , E , E-5-(2-methyl phenyl )-2-( 1-methoxycarbonyl -2-methoxyethen-

1-yl )-1 , 1 , 1-trifluoropenta-2,4-diene (Compound No. 2); - E,E,E-5-(4-trifluoromethylphenyl )-2-(1-methoxycarbonyl-2- methoxyethen-1-yl )-1 ,1 , 1-trifluoropenta-2,4-diene (Compound No.

3);

E,E,E-5-(2-cyanophenyl)-2-(1-methoxycarbonyl-2-methoxyethen-1- yl )-1 , 1 , 1-trifluoropenta-2,4-diene (Compound No. 4); - E,E,E-5-(2,4-limethylpyrimidin-5-yl )-2-(l-methoxycarbonyl-2- methoxyethen-1-yl )-1 , 1 , 1-trifluoropenta-2,4-diene (Compound No.

5);

E,E-3-phenyl-2-(1-methoxycarbonyl-2-methoxyethen-1-yl )-1 , 1 , 1- trifluoroprop-2-ene (Compound No. 6); - E,E-3-(4-chlorophenyl )-2-( 1-methoxycarbonyl-2-methoxyethen-1- yl )-1 , 1 , 1-trifluoroprop-2-ene (Compound No. 7).

EXAMPLE 3 Operating in a like manner to that described in Example 1, but starting from a 1 , 1-dihaloethene (prepared by the procedure described in "Synthesis" (1993), pp. 43-46), the following compounds are prepared: - E,E-2-(4-chlorophenyl )-1-(1-methoxycarbonyl-2-methoxyethen- - yl )-1-bromoethene (Compound No. 8);

E,E-2-(3-phenoxyphenyl )-1-(1-methoxycarbonyl-2-methoxyethen-l- yl )-1-bromoethene (Compound No. 9).

EXAMPLE 4 Preparation of E,E-4-(4-phenoxyphenoxy)-2-(1-methoxycarbonyl-2- methoxyethen-1-yl)-1 ,1 , 1-trifluorobut-2-ene (Compound No. 10).

15 g of 1 , 1 , 1-trifluoro-2,2,4-tribromobutane are slowly added to a suspension of 4 g of 4-phenoxyphenol and 5.9 g of potassium carbonate in 60 cm³ of anhydrous dimethyl formamide. After 8 hours at 50°C, the mixture is poured into water, which is then extracted with ethyl acetate.

The organic phase obtained in this manner is washed with saturated sodium chloride, dried over sodium sulphate and evaporated under reduced pressure. The crude product obtained in this manner is purified by silica gel chromatography, eluting with 8/1 hexane/ethyl acetate. 5.3 g of E-4-(4-phenoxyphenoxy)-2-bromo-1 , 1 , 1-trifluoro-but-2-ene are obtained.

0.124 cm³ of trichloro—methylsilane are added to a suspension of 1.6 g of Zn/Ag in 8 cm³ of anhydrous tetrahydrofuran. After 10 minutes at ambient temperature, a mixture of 2.3 g of methyl 3- methoxy-2-iodopropenoate and 1.5 cm³ of N,N,N' ,N'-tetramethyl-1 ,2- diaminoethane in 4 cm³ of tetrahydrofuran is added. After about 2 hours, the supernatant solution is added to a solution of 2.8 g of E-4-(4-phenoxyphenoxy)-2-bromo-1 , 1 , 1- trifluoro-but-2-ene and 0.570 g of ( h3P)4Pd in 7 cm³ of tetrahydrofuran. After 24 hours at 60°C, the reaction mixture is poured into water which is then extracted with ethyl acetate. The organic phase is separated and dried over sodium sulphate, and is then evaporated under reduced pressure. The crude product obtained in this manner is purified by silica gel chromatography, eluting with 9/1 hexane/ethyl acetate. 0.85 g of Compound No. 10 are obtained (yield 28%). EXAMPLE 5

Operating in a like manner to that described in Example 4, the following compounds are prepared from the intermediates indicated in parentheses, in substitution of phenoxyphenol :

E,E-4-(3-phenoxyphenoxy)-2-(1-methoxycarbonyl-2-methoxyethen- 1-yl)-1 , 1 , 1-trifluorobut-2-ene (Compound No. 11) (from 3- phenoxyphenol ) ;

E , E , E-6-aza-5-oxa-7-pheny1-2-( 1-methoxycarbony1-2- methoxyethen-1-yl )-1 , 1 , 1-trifluorohepta-2,6-diene (Compound No.

12) (from hydroxyimino-4-chloroacetophenone); E,E,E-6-aza-5-oxa-7-(4-methyl phenyl )-2-(1-methoxycarbonyl-2- methoxyethen-1-yl)-1 , 1 , 1-trifluorohepta-2,6-diene (Compound No.

13) (from hydroxyimi no-4-methyl acetophenone) . EXAMPLE 6

Determination of preventive fungicidal activity against cucumber oidium (Sphaeroteca fuliginea). Leaves of cultigen Marketer cucumber plants grown in pots in a conditioned environment (20±1°C, 70% relative humidity) are treated by spraying both sides of the leaves with Compounds 1-13 in a 20 vol% acetone/water solution. After remaining for 24 hours in the conditioned environment, the plants were sprayed on both leaf sides with an aqueous suspension of Sphaeroteca fuliginea conidia (200000 conidia per cm³).

The plants are maintained in a moisture-saturated environment at

21 °C for the fungus incubation period. At the end of this period (8 days) the fungicidal activity is evaluated on a percentage evaluation scale ranging from 100

(healthy plant) to 0 (plant completely infected.

All the synthesized compounds demonstrated a control level exceeding 90 at a concentration of 2000 ppm. EXAMPLE 7

Determination of preventive fungicidal activity against barley helminthosporia (Helminthosporium teres).

Leaves of cultigen Arna barley plants grown in pots in a conditioned environment (20±1°C, 70% relative humidity) are treated by spraying both sides of the leaves with Compounds 1-13 in a 20 vol% acetone/water solution.

After remaining for 24 hours in the conditioned environment, the plants were sprayed on both leaf sides with an aqueous suspension of Helminthosporium teres conidia (250000 conidia per cm³). The plants are maintained in a moisture-saturated environment at

21°C for the fungus incubation period.

At the end of this period (12 days) the fungicidal activity is evaluated on a percentage evaluation scale ranging from 100

(healthy plant) to 0 (plant completely infected.)

All the synthesized compounds demonstrated a control level exceeding 90 at a concentration of 2000 ppm. EXAMPLE 8

Determination of preventive fungicidal activity against vine mildew (Plasmopara viticola).

Leaves of cultigen Dolcetto vines grown in pots in a conditioned environment (20±1°C, 70% relative humidity) are treated by spraying both sides of the leaves with Compounds 1-13 in a 20 vol% acetone/water solution.

After remaining for 24 hours in the conditioned environment, the plants were sprayed on both leaf sides with an aqueous suspension of Plasmopara viticola conidia (200000 conidia per cm³). The plants are maintained in a moisture-saturated environment at

21 °C for the fungus incubation period.

At the end of this period (7 days) the fungicidal activity is evaluated on a percentage evaluation scale ranging from 100

(healthy plant) to 0 (plant completely infected.J All the synthesized compounds demonstrated a control level exceeding 90 at a concentration of 2000 ppm.

TABLE 1

COMPOUND %C (calc) %H (calc) %N (calc) %F (calc)

1 61.59 (61.54) 4.89 (4.84) - 18.30 (18.25)

2 62.50 (62.57) 5.29 (5.25) - 17.41 (17.47) 3 53.72 (53.69) 3.70 (3.71) - 29.99 (29.97)

4 60.47 (60.54) 4.23 (4.18) 4.23 (4.15) 16.84 (16.90)

5 56.14 (56.14) 4.99 (5.01) 8.10 (8.18) 16.66 (16.65)

6 58.63 (58.74) 4.56 (4.58) - 19.97 (19.91)

7 52.46 (52.43) 3.78 (3.77) - 17.79 (17.77)

8 47.12 (47.09) 3.62 (3.65)

9 58.59 (58.63) 4.41 (4.40)

10 61.72 (61.76) 4.69 (4.69) - 14.00 (13.96)

11 61.83 (61.76) 4.71 (4.69) - 14.02 (13.96)

12 52.11 (52.12) 4.31 (4.36) 3.60 (3.58) 14.49 (14.55)

13 58.26 (58.22) 5.47 (5.43) 3.80 (3.77) 15.34 (15.35)

(calc): the calculated value is given in parentheses.

Claims

CLAIMS 1. Strobilurineanalogue compounds of general formula (I)

in which:

Ri represents a linear or branched Ci-Ce fluoroalkyl group; or a linear or branched Cι-C₆ alkyl group; - R2 represents a hydrogen atom; a linear or branched Ci-Cβ alkyl or haloalkyl group; a linear or branched C -(Aalkoxy or haloalkoxy

I b group;a linear or branched C -C,_ncarboalkoxy group; a nitrile group. Tox represents a group of general formula (Ila) or (lib):

Ri

in which:

W represents an =N- azo group; or a =C(Rs)- group; Y represents an oxygen atom; or a -N(Rβ)- group; R' and R", which can be equal or different, represent a hydrogen atom; or a linear or branched Ci-Ca alkyl group;

R3 and R₄, which can be equal or different, represent a linear or branched Ci-Ce alkyl or haloalkyl group; - Rs and Re, which can be equal or different, represent a hydrogen atom; or a linear or branched Ci-Cβ alkyl or haloalkyl group;

K represents a chain of general formula (Ilia): -(Gι)m-(C2nH2n+2)-(G2)p- (Ilia); and, if Ri represents a linear or branched Ci-Cβ fluoroalkyl group, K also representing a chain of general formula (Illb): -(G₃)C=C(G4)- (Illb); in which: m and p, which can be equal or different, can be 0 or 1; - n represents a whole number between 0 and 10, end values included;

Gi and G2, which can be equal or different, represent an oxygen atom or a sulphur atom; or represent one of the following groups of formula (Va) , (Vb), (Vc) and (Vd): -N=C(Ry)- (Va);

-C(R₇)=N- (Vb);

-C(R₇)=N-0- (Vc);

-0-N=C(R₇)- (Vd); in which R₇ represents a linear or branched Ci-Cβ alkyl or haloalkyl group; a linear or branched Ci-Cβ alkoxy or haloalkoxy group; a linear or branched Ci-Cβ thioalkyl or halothioalkyl group; a C3-C3 cycloalkyl group; a cyano group; a linear or branched C2-C10 carboalkoxy group; G3 and G4, which can be equal or different, represent a hydrogen atom; a halogen atom chosen from fluorine, chlorine and bromine; a linear or branched Ci-Cβ alkyl or haloalkyl group;

X represents a phenyl group; a naphthyl group; a penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a benzocondensed penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; said phenyl, naphthyl, penta- or hexa-atomic aromatic heterocyclic, or benzocondensed penta- or hexa-atomic aromatic heterocyclic groups being optionally substituted with one or more equal or different R_a groups; - Ra represents a linear or branched Ci-Cβ alkyl or haloalkyl group; a linear or branched Ci-Cβ alkoxy or haloalkoxy group; a linear or branched Ci-Cβ thioalkyl or halothioalkyl group; a C3-C9 cycloalkyl group; a phenyl group; a naphthyl group; a phenoxy group; a naphthoxy group; a penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a benzocondensed penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a penta- or hexa-atomic aromatic heterocycloxy group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a benzocondensed penta- or hexa-atomic aromatic heterocycloxy group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; said C3-C9 cycloalkyl, phenyl, naphthyl, phenoxy, naphthoxy, penta- or hexa-atomic aromatic heterocyclic, benzocondensed penta- or hexa-atomic aromatic heterocyclic, penta- or hexa-atomic aromatic heterocycloxy, or benzocondensed penta- or hexa-atomic aromatic heterocycloxy groups being optionally substituted with one or more equal or different halogen atoms chosen from fluorine, chlorine and bromine, or with one or more equal or different groups chosen from linear or branched Ci-Cβ alkyl or haloalkyl groups, linear or branched Ci-Cβ alkoxy or haloalkoxy groups, or cyano groups.

2. Antifungal agents consisting of strobilurire analogue compounds of general formula (I):

R2

Ri

/

K (I)

Tox in which:

Ri represents a linear or branched Ci-Cβ fluoroalkyl group; or a linear or branched C1-C6 alkyl group; - R2 represents a hydrogen atom; a linear or branched Ci-Cβ alkyl or haloalkyl group; a linear or branched C -C\ alkoxy or haloalkoxv group; a linear or branched C₂-C_l0 carboalkoxy group; a nitrile group. Tox represents a group of general formula (Ila) or (lib):

i n whi ch:

W represents an azo =N- group; or a =C(Rs)- group; Y represents an oxygen atom; or a -N(Rβ)- group; R' and R", which can be equal or different, represent a hydrogen atom; or a linear or branched Ci-Cβ alkyl group;

R3 and R4, which can be equal or different, represent a linear or branched Ci-Cβ alkyl or haloalkyl group;

K represents a chain of general formula (Ilia): . -(Gι)_m-(C2nH2n₊2)-(G₂)p- (Ilia); and, if Ri represents a linear or branched Ci-Cε fluoroalkyl group, K also representing a chain of general formula (Illb): -(G3)C=C(G4)- (Illb); in which: and p, which can be equal or different, can be 0 or 1; n represents a whole number between 0 and 10, end values included;

Gi and G₂, which can be equal or different, represent an oxygen atom or a sulphur atom; or represent one of the following groups of formula (Va) , (Vb), (Vc) and (Vd):

-N=C(R₇)- (Va)

-C(R₇)=N- (Vb)

-C(R₇)=N-0- (Vc)

in which R₇ represents a linear or branched Ci-Cβ alkyl or haloalkyl group; a linear or branched Ci-Cβ alkoxy or haloalkoxy group; a linear or branched Ci-Cβ thioalkyl or halothioalkyl group; a C3-C9 cycloalkyl group; a cyano group; a linear or branched C2-C10 carboalkoxy group; - G3 and G4, which can be equal or different, represent a hydrogen atom; a halogen atom chosen from fluorine, chlorine and bromine; a linear or branched Ci-Cβ alkyl or haloalkyl group; X represents a phenyl group; a naphthyl group; a penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a benzocondensed penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; said phenyl, naphthyl, penta- or hexa-atomic aromatic heterocyclic, or benzocondensed penta- or hexa-atomic aromatic heterocyclic groups being optionally substituted with one or more equal or different R_a groups; Ra represents a linear or branched Cι-Cs alkyl or haloalkyl group; a linear or branched Ci-Cβ alkoxy or haloalkoxy group; a linear or branched Ci-Cβ thioalkyl or halothioalkyl group; a C3-C9 cycloalkyl group; a phenyl group; a naphthyl group; a phenoxy group; a naphthoxy group; a penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a benzocondensed penta- or hexa-atomic aromatic heterocyclic group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a penta- or hexa-atomic aromatic heterocycloxy group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; a benzocondensed penta- or hexa-atomic aromatic heterocycloxy group containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur; said C3-Cg cycloalkyl, phenyl, naphthyl, phenoxy, naphthoxy, penta- or hexa-atomic aromatic heterocyclic, benzocondensed penta- or hexa-atomic aromatic heterocyclic, penta- or hexa-atomic aromatic heterocycloxy, or benzocondensed penta- or hexa-atomic aromatic heterocycloxy groups being optionally substituted with one or more equal or different halogen atoms chosen from fluorine, chlorine and bromine, or with one or more equal or different groups chosen from linear or branched Ci-Cβ alkyl or haloalkyl groups, linear or branched Ci-Cβ alkoxy or haloalkoxy groups, or cyano groups. 3. Antifungal agents as claimed in claim 2, wherein the linear or branched Ci-Cβ fluoroalkyl groups are: fluoromethyl , difluoromethyl , trifluoromethyl , 2, 2, 2-trifluoroethyl , 2,2,3,3- tetrafluoropropyl , 2,2,3,3,

3-pentafluoropropyl .

4. Antifungal agents as claimed in claim 2, wherein the linear or branched Ci-Cβ alkyl or haloalkyl groups are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl , s- pentyl , neo-pentyl , fluoromethyl , difluoromethyl , trifluoromethyl , 2, 2, 2-trifluoroethyl , 1 , 1 ,2,2-tetrafluoroethyl , trichloromethyl, 2,2,2-trichloroethyl , 2, 2, 3, 3-tetrafluoropropyl , 2,2,3,3,3- pentafluoropropyl , 2,2,2-trichloro-1 , 1-difluoroethyl .

5. Antifungal agents as claimed in claim 2, wherein the linear or branched Ci-Cβ alkoxy or haloalkoxy groups are: methoxy, ethoxy, trifluoromethoxy, 1 , 1 ,2,2-tetrafluoroethoxy, 2,2,2- tri f1 uoroethoxy , 3,3,3,2, 2-pentaf1 uoropropyloxy , 2,2, 2-trichl oro- 1 , 1-difluoroethoxy.

6. Antifungal agents as claimed in claim 2, wherein the linear or branched Ci-Cβ thioalkyl or halothioalkyl groups are: thiomethyl , thioethyl , trifluorothio ethoxy, 1 ,1 ,2,2-tetrafluoro- thioethoxy.

7. Antifungal agents as claimed in claim 2, wherein the C3-C9 cycloalkyl groups are: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl .

8. Antifungal agents as claimed in claim 2, wherein the linear or branched C2-C10 carboalkoxy groups are: carboxymethyl, carboxyethyl , carboxyi sopropyl .

9. Antifungal agents as claimed in claim 2, wherein the penta- or hexa-atomic aromatic heterocyclic groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur, and benzocondensed penta- or hexa-atomic aromatic heterocyclic groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur are: pyrrole, imidazole, pyrazole, triazole, tetrazole, isoxazole, benzoisoxazole, oxazole, thiazole, isothiazole, benzothiazole, pyridine, pyrazine, pyrimidine, pyridazine, furan, benzofuran, thiophene, benzothiophene, benzoxazole, indole.

10. Antifungal agents as claimed in claim 2, wherein the penta- or hexa-atomic aromatic heterocycloxy groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur, and benzocondensed penta- or hexa-atomic aromatic heterocycloxy groups containing from one to four heteroatoms chosen from nitrogen, oxygen and sulphur are: pyridoxy, pyrimidoxy, benzoxazolyloxy , benzothiazolyloxy.

11. Antifungal agents as claimed in claim 2, consisting of E,E,E-5-phenyl-2-(1-methoxycarbonyl-2-methoxyethen-1-yl )-l , 1 , 1- trifluoropenta-2,4-diene.

12. Antifungal agents as claimed in claim 2, consisting of E,E,E-5-(2-methyl phenyl )-2-(1-methoxycarbony1-2-methoxyethen-1- yl)-1 , 1 , 1-trifluoropenta-2,4-diene.

13. Antifungal agents as claimed in claim 2, consisting of E,E,E-5-(4-trifluoromethyl phenyl )-2-(1-methoxycarbony1-2-methoxy- ethen-1-yl )-1 , 1 , 1-trifluoropenta-2,4-diene.

14. Antifungal agents as claimed in claim 2, consisting of E,E,E-5-(2-cyanoρhenyl )-2-(1-methoxycarbonyl-2-methoxyethen-1-yl )- 1,1, 1-trifluoropenta-2,4-diene.

15. Antifungal agents as claimed in claim 2, consisting of

E, E , E-5-(2 ,4- dimethyl pyrimi di n-5-yl ) -2- ( 1 -methoxycarbony1 -2-methoxy- ethen-1-yl )-1 , 1 , 1-trifluoropenta-2,4-diene.

16. Antifungal agents as claimed in claim 2, consisting of E,E-3-phenyl-2-(1-methoxycarbonyl-2-methoxyethen-1-yl )-1 , 1 , 1- trifluoroprop-2-ene.

17. Antifungal agents as claimed in claim 2, consisting of E,E-3-(4-chlorophenyl )-2-(1-methoxycarbonyl-2-methoxyethen-1-yl )- 1,1, 1-trifluoroprop-2-ene.

18. Antifungal agents as claimed in claim 2, consisting of

E, E-2-(4-chlorophenyl )-1-(1-methoxycarbonyl-2-methoxyethen-1-yl )- 1-bromoethene.

19. Antifungal agents as claimed in claim 2, consisting of

E,E-2-(3-phenoxyphenyl )-1-(1-methoxycarbonyl-2-ethoxyethen-1-yl )- 1-bromoethene.

20. Antifungal agents as claimed in claim 2, consisting of E,E-4-(4-phenoxyphenoxy)-2-(1-methoxycarbonyl-2-methoxyethen-1- yl)-1 ,1 , 1-trifluorobut-2-ene.

21. Antifungal agents as claimed in claim 2, consisting of E,E-4-(3-phenoxyphenoxy)-2-(1-methoxycarbonyl-2-methoxyethen-1- yl )-1 , 1 , 1-trifluorobut-2-ene.

22. Antifungal agents as claimed in claim 2, consisting of E,E,E-6-aza-5-oxa-7-phenyl-2-(1-methoxycarbonyl-2-methoxyethen-1- yl )-1 ,1 ,1-trifluorohepta-2,6-diene.

23. Antifungal agents as claimed in claim 2, consisting of E, E, E-6-aza-5-oxa-7-(4-methyl phenyl)-2-(1-methoxycarbony1-2- methoxyethen-1-yl )-1 , 1 , 1-trifluorohepta-2,6-diene.

24. A process for preparing compounds of general formula (a4): R₂

(a4) illustrated in the following Schemes C1 and C2:

SCHEME C1

(c1) (C2)

(c3) SCHEME C2

comprising reacting the haloalkane of general formula (d) with a suitable nucleophilic of general formula (c2) or (c4), in the presence of an inorganic base, or in the presence of an organic base, and in the presence of a dipolar aprotic solvent, or of an ether solvent, or of an aromatic solvent, at a temperature of between ambient temperature and the boiling point of the solvent used.

25. A process as claimed in claim 24, wherein the inorganic base is sodium or potass inn carbonate.

26. A process as claimed in claim 24, wherein the organic base is triethylamine.

27. A process as claimed in claim 24, wherein the dipolar aprotic solvent is dimethyl formamide or dimethylsulphoxide.

28. A process as claimed in claim 24, wherein the ether solvent is tetrahydrofuran or dioxane.

29. A process as claimed in claim 24, wherein the aromatic solvent is toluene or xylene.

30. Fungicidal compositions containing one or more compounds claimed in any one of claims 2 to 23, either alone or in the presence of solid supports, liquid diluents, surfactants, special additives or other active principles.

31. A method for combating fungine infections, consisting of applying fungicidal compositions claimed in claim 30 to plants, leaves, stems, branches and roots, or to seeds before sowing, or to the soil in which the plant grows.