AU719443B2

AU719443B2 - Fungicides containing hydroximic and hydrazonic groups

Info

Publication number: AU719443B2
Application number: AU45608/97A
Authority: AU
Inventors: Philippe Desbordes; Joseph Perez; Christine Veyrat; Jean-Pierre Vors
Original assignee: Rhone Poulenc Agro SA
Current assignee: Bayer CropScience SA
Priority date: 1996-10-09
Filing date: 1997-10-06
Publication date: 2000-05-11
Anticipated expiration: 2017-10-06
Also published as: HUP0000194A3; BR9712223A; TR199900768T2; WO1998015512A2; WO1998015512A3; EP1021399A2; IL129331A0; FR2754254A1; CA2268021A1; AU4560897A; PL333183A1; EA199900346A1; FR2754254B1; JP2001501943A; KR20000049024A; SK45699A3; HUP0000194A2; CZ121499A3

Description

P:\OPER\PDB\45608-97.SPE 29/2/00 1 Fungicides containing hydroximic and hydrazonic groups The present invention relates to novel compounds containing a hydroximic or hydrazonic function, to their use as fungicides, in particular in the form of a fungicidal composition, and to a process for controlling phytopathogenic fungi of crops using these compounds or these compositions.

The derivatives containing a hydroximic function which are used for controlling phytopathogenic fungi of crops are known, in particular, from patents EP 463,488 and EP 370,629.

6 *e P:\OPER\PDB\45608 97.SPE 2912/00 2 General definition of the invention: The invention relates to compounds containing the hydroximic or hydrazonic function, of general formula in which G is chosen from groups G1 to G9: RS

OI-

C 'C

C

S

C. C C

C

i.e C

C

i

B

C

C.

q c.

'C C CC Rs S, I 4 4I (cH)n (Cf-)n Y R7 2 a2 G4 G5 G6 R 4 Rio l Rio 0-- 02 G7 G8 G9 in which: n 0 or 1 Q1 is a nitrogen atom or a CH group, Q2 is an oxygen or sulphur atom, Q3 is an oxygen or sulphur atom, Q4 is a nitrogen atom or a group CR 1 is an oxygen or sulphur atom or a group NR12, Y is an oxygen or sulphur atom or an amino (NH) or oxyamino (ONH) group W1 is an oxygen or sulphur atom or a sulphinyl (SO) or sulphonyl group, W2 is an oxygen atom or a group NR,,, p 1 when W2 is an oxygen atom, p 0 or 1 when W2 is a group NR 13

X

1

X

2 and X 3 are, independently of each other, a hydrogen atom, a halogen atom; or a hydroxyl, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosuiphonyl group; a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsuiphinyl, haloalkylsulphinyl, alkylsuiphonyl, haloalkylsulphonyl or alkoxysulphonyl group; or a lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio group; or an amino, N-alkylamino, N,N-dialkylamino, acylamino, aminoalkyl, N-alkylaminoalkyl, N,Ndialkylaminoalkyl or acylaminoalkyl group; or a carboxyl, carbamoyl, N-alkylcarbamoyl, N,Ndialkylcarbamoyl or lower alkoxycarbonyl group; or an acyl group; X4 is a hydrogen atom, a halogen atom; or a lower alkyl, lower haloalkyl, alkoxy or haloalkoxy group; or cyano or nitro radicals, R, and R 2 are, independently of each other, a L7 44) 4/ %riyQo hydrogen atom, a lower alkyl or lower haloalkyl group, a lower cycloalkyl or lower halocycloalkyl group, an alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl or cyanoalkyl group; or a cyano, acyl, carboxyl, carbamoyl, N-alkylcarbamoyl or N,N-dialkylcarbamoyl group, a lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or alkylthiothiocarbonyl group; or an aminoalkyl, N-alkylaminoalkyl, N,Ndialkylaminoalkyl or acylaminoalkyl group, Ri and R 2 together can form a divalent radical such as an alkylene group, optionally substituted with one or more halogen atoms, or optionally substituted with one or more lower alkyl groups,

R

3 is a hydrogen atom, a lower alkyl or lower haloalkyl group, a lower cycloalkyl or lower halocycloalkyl group, an alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl or cyanoalkyl group; or a nitro, cyano, acyl, carboxyl, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or S alkylthiothiocarbonyl group; or an alkenyl, alkynyl, N,N-dialkylamino or N,Ndialkylaminoalkyl group; or an optionally substituted phenyl or benzyl group, R, is a lower alkyl or lower haloalkyl group, a lower cycloalkyl, lower halocycloalkyl or alkoxyalkyl group; or an alkoxy, haloalkoxy, alkylthio, alkylamino or dialkylamino group, R. or R 6 is, independently of each other, a lower alkyl or lower haloalkyl group, R 8 is a lower alkyl, lower haloalkyl, a:alkoxyalkyl, haloalkoxyalkyl, alkenylo alkynyl group, haloa R 8 is alowerpaokya lower halalyloawkyr hlcclyalkoxyalkyl, haloalkoxyalkyl, alkenyl, lyyfry ackyl group, R1.i aoe tm alwraklo oe ~hlo y g ;rousap yroe ao, a lower cylalkyl or lower halocycloalkyl group or an alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl or haloalkylsulphonyl group, R, and R 12 are, independently of .each other, a hydrogen atom, a lower alkyl or lower haloalkyl group or a lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl group,

R

13 is a hydrogen atom, a lower alkyl or lower haloalkyl group, a lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl or haloalkylthioalkyl group, an optionally substituted ally group, an.optionally.

substituted propargyl group or an-optionally 15 substituted benzyl group; or an acyl, N-alkylcarbamoyl, N,Ndialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or 20 alkylthiothiocarbonyl group; or an alkylsulphonyl, haloalkylsulphonyl or o. ptionally substituted arylsulphonyl group, a.

with the restrictions that: when W1 represents a sulphur atom and W2 represents a nitrogen atom, then R3 cannot represent P:\OPER\PDB\45608-97.SPE 2912100 8 alkylthio; when W2 and Q2 are an oxygen atom and when G represents the group Gl, then R 5 is other than an alkyl group, and R 4 is other than an alkoxy, alkylamino or dialkylamino group, and R 3 is other than a hydrogen atom, an alkyl or haloalkyl group, a cycloalkyl or halocycloalkyl group, an alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, cyanoalkyl, alkenyl, alkynyl or dialkylaminoalkyl group, or an optionally substituted phenyl or benzyl group, as well as the salts and the metal and metalloid complexes of the compounds of formula as have just been defined.

Advantageously the present invention may provide a novel family of fungicidally useful compounds containing the hydroximic or hydrazonic function.

In a preferred form the present invention may provide a novel family of compounds containing the hydroximic or hydrazonic function which have a broad spectrum of action on the phytopathogenic fungi of crops.

In another preferred form the present invention may provide a novel family of compounds containing the hydroximic or hydrazonic function which have a broad spectrum of action on the phytopathogenic fungi of crops, allowing the specific problems encountered to be overcome.

25 In still another form, the present invention may provide a novel family of compounds containing the hydroximic or hydrazonic function which have an improved spectrum of action on the phytopathogenic fungi of crops.

Advantageously the present invention may provide a novel family of compounds containing the hydroximic or hydrazonic function which have an improved spectrum of action on the Sphytopathogenic fungi of crops such as rice, cereals, fruit rees, grapevine and beetroot.

S U) In the text of the present invention, the term P:\OPER\PDB\45608-97.SPE 29/2/00 "hydroximic group" includes both. the "hydroximic group" per se (with the O-C=N-O sequence) and the "thiohydroximic group" (with the S-C=N-O sequence). Similarly, the term "hydrazonic group" includes both the "hydrazonic group". per se (with the O-C=N-N sequence) and the "thiohydrazonic group" (with the S- C=N-N sequence).

Moreover, the following generic terms are used with the following meanings: halogen atom means a fluorine, chlorine, bromine or iodine atom, the adjective "lower" qualifying an organic radical means that this radical contains from 1 to 6

C

*o*

S

C

carbon atoms, except for the cycloalkyl radical in which the adjective "lower" means from 3 to 6 carbon atoms, the alkyl radicals can be linear or branched, the haloalkyl radicals can contain one or more identical or different halogen atoms, acyl radical means alkylcarbonyl or cycloalkylcarbonyl, the adjective "lower" qualifying the acyl term applies to the alkyl or cycloalkyl part of this radical, alkylene radical denotes the radical

-(CH

2 where m 2 to when the amino radical is disubstituted, the two substituents can constitute a saturated or unsaturated nitrogenous heterocycle of 5 or 6 atoms, when the carbamoyl radical is disubstituted, the two substituents can constitute a saturated or unsaturated nitrogenous heterocycle of or 6 atoms.

Preferred embodiments of the invention are those in which the products of formula also have one and/or other of the following characteristics, taken separately or in combination: n 0 or 1 p 1 Q2 is an oxygen atom, and/or Q3 is an oxygen atom, and/or Q4 is a nitrogen atom, and/or Q5 is an oxygen atom; W1 is an oxygen or sulphur atom W2 is an oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino or allylamino group, Y is an oxygen atom,

X

1

X

2

X

3 and X 4 are, independently of each other, a hydrogen atom, a lower alkyl group, a halogen atom or cyano, trifluoromethyl or methoxy radicals, RI and R 2 are, independently of each other, a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyl, N-alkylaminoalkyl, N,N-dialkylaminoalkyl, acylaminoalkyl, lower alkoxycarbonyl, N-alkylcarbamoyl or N,N-dialkylcarbamoyl group,

R

3 is a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl or alkoxyalkyl group, preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl or methoxymethyl radical,

R

4 is a lower alkyl, alkoxy, alkylamino or dialkylamino group, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino or ethylamino radical, Rs, R 6

R

8 and R 9 are, independently of each other, a lower alkyl or lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl or propyl radical, A .441j

J

11 R, is a lower alkyl or lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl or propyl radical, or an allyl or propargyl group,

R

10 is a chlorine atom, a lower alkyl or lower haloalkyl group, preferably methyl, or an alkoxy or alkylthio group, preferably methoxy or methylthio, R, and R 12 are, independently of each other, a lower alkyl, lower haloalkyl, alkoxyalkyl, allyl or propargyl group,

R

13 is a hydrogen atom or a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl or benzyl group.

Among the above variants, those which will be chosen more particularly are the following variants, taken separately or in combination: W1 is an oxygen atom, RI is a hydrogen atom or a methyl radical,

R

2 is a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N,N-dialkylaminoalkyl, lower alkoxycarbonyl or lower N,N-dialkylcarbamoyl group.

Compounds which are even more particularly preferred are those in which the substituents W1 and W2 are in a trans position (see below) relative to the double bond -C(R 3 12 The compounds of general formula and the compounds which can optionally be used as intermediates in the preparation processes, and which will be defined in the description of these processes, can exist in one or more forms of geometrical isomers depending on the number of double bonds in the compound. The compounds of general formula in which G is a group GI, G2 or G3 can contain four different stereoisomers, noted as or depending on the configuration of the two double bonds. The notation E and Z can be replaced, respectively, by the terms syn and anti, or cis and trans. Reference will be made in particular to the book by E. Eliel and S. Wilen "Stereochemistry of Organic Compounds" published by Wiley (1994) for the description and use of these notations.

By convention, in the case of the present invention, the terms and (Z,Z) denote by the first letter the configuration of the double bond of the group Gl, G2 or G3, and by the second letter the configuration of the hydroximic or hydrazonic group.

The compounds of general formula in which G is a group G4 to G9 can contain two different stereoisomers noted as or depending on the configuration of the hydroximic or hydrazonic group.

The compounds of general formula and the Scompounds which can optionally be used as intermediates in the preparation processes, and which will be defined in the description of these processes, can exist in one or more optical or chiral isomer forms depending on the number of asymmetric centres in the compound. The invention thus relates equally to all the optical isomers and to their racemic mixtures and to the corresponding diastereoisomers as a mixture or separated. The diastereoisomers and/or the optical isomers can be separated according to the methods which are known per se Eliel, ibid.).

Preparation processes: The compounds of the present invention of general formula and the compounds which can optionally be used as intermediates in the preparation processes, can be prepared by at least one of the general preparation methods described below: methods A to L.

The preparation of the reagents used in one or other of the general preparation methods is usually known per se and is usually described specifically in the prior art or in a manner such that a person skilled in the art can adapt it to the desired aim. The prior art which can be used by a person skilled in the art to establish the conditions for preparing the reagents can be found in many general chemistry books, such as "Advanced Organic Chemistry" by J. March, published by Wiley (1992), "Methoden der organischen Chemie" (Houben-Weyl), published by Georg Thieme Verlag, or "Chemical Abstracts" published by the American Chemical Society, as well as in the publicly accessible computer databases.

Method A: The compounds of general formula for which G is one of the groups G1 to G9, the other substituents having the definition already indicated, can be obtained by a process consisting in placing a compound of formula (II)A:

G

(II)A

in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definitions as those given for formula X 4 having the same definition as that given for formula V, is a halogen atom (preferably chlorine or bromine), an alkylsulphonate or haloalkylsulphonate (preferably methylsulphonate or trifluoromethylsulphonate), or an arylsulphonate (preferably 4-methylphenylsulphonate) group, in contact with a compound of the formula

(III)A:

H RI _X, X2

R

3

(II)A

W1, W2, Ri, R 2

R

3

R

13

X

1

X

2

X

3 and p having the same definition as that given for formula in the presence of an organic or inorganic base, in the absence or presence of a solvent. The reaction is generally carried out at a temperature of between -80 0 C and 180 0 C (preferably between 0°C and 150 0 C) or at the boiling point of the solvent used. The appropriate solvent for this reaction can be an aliphatic hydrocarbon such as pentane, hexane, heptane 10 or octane; .an aromatic hydrocarbon such as benzene, toluene, xylenes or halobenzenes; an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane or dimethoxyethane; a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane

S

or 1,1,1-trichloroethane; an ester such as methyl acetate or ethyl acetate, a nitrile such as ""acetonitrile, propionitrile or benzonitrile; a dipolar aprotic solvent such as dimethylformamide, 4 dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or dimethyl sulphoxide; or water.

Mixtures of these various solvents can also be used.

The reaction time depends on the conditions II v used and is generally between 0.1 and 48 h.

As organic or inorganic base which is suitable for this reaction, mention may be made of alkali metal and alkaline-earth metal hydroxides, such as sodium, potassium, caesium or calcium hydroxide; alkali metal and alkaline-earth metal alkoxides, such as potassium tert-butoxide, alkali metal and alkalineearth metal hydrides, such as sodium, potassium or caesium hydride; alkali metal and alkaline-earth metal carbonates and bicarbonates such as sodium, potassium or calcium carbonate or sodium, potassium or calcium bicarbonate; organic bases, which are preferably nitrogenous, such as pyridine, alkylpyridines, alkylamines such as trimethylamine, triethylamine or diisopropylethylamine, aza derivatives such as 15 diazabicyclo[4.3.0]non-5-ene or 1-,8-diazabicyclo- 5 5.4 .0]undec-7-ene There is no strict limitation as regards the relative proportions of the compounds of formula (II)A and of formula (III)A. However, it is advantageous to 20 choose a (III)A/(II)A molar ratio of between 0.1 and 10, preferably 0.5 to 2.

The compounds of formula (III)A are new and "in this respect also form part of the invention.

Depending on the conditions used, the compounds of general formula are obtained in the form of a variable mixture of and isomers or in the form of a single isomer or a single isomer (Z) 17 depending on the configuration of the hydroximic or hydrazonic group. If necessary, the compounds of general formula and of or configuration, depending on the configuration of the hydroximic or hydrazonic group, can be isolated and purified according to methods which are known per se, such as, for example, extraction, crystallization or chromatography.

The hydroxamic or thiohydroxamic acids of formula (III)A in which W2 is an oxygen atom and p 1, or the hydrazonic or thiohydrazonic acids of formula (III)A in which W2 is a group NR 13 and p 0 or 1, Wl,

R

I

R

2

R

3

R

1 3

X

1

X

2 and X 3 having the same definition as that given for formula can be obtained by a process consisting in placing a compound of the formula

W

3 W2, R i

R

2 R1,3, X. and p having the 15 same definition as that given for formula in contact with a compound of formula w* given for formula U1 is a halogen atom (preferably chlorine or bromine), or a hydroxyl, lower alkoxy or rI

I

II II 18 benzyloxy, lower alkylthio or amino radical, or a group O(C=O)Ra, Ra having the same definition as that of R 3 given for formula and being identical to or different from R 3 preferably a halogen atom, the compound of formula then being an acid halide.

The condensation between the compound of formula (IV) and the compound of formula is carried out in the presence of an organic or inorganic base, or a dehydrating reagent such as carboxylic acid anhydrides, preferably acetic anhydride or propionic anhydride, in the absence or presence of a solvent. The general conditions for condensation between the compound of formula (IV) and the compound of formula are similar or identical to the conditions for condensation between the compound of formula (II)A and the compound of formula (III)A and are known per se according to "Houben-Weyl" ibid. volume E5, pages 1144- 1149.

The hydroxamic acids of formula (III)A in which W2 is an oxygen atom and p 1, or the hydrazonic acids of formula (III)A in which W2 is a group NR 13 and p 1, W1, R 1

R

2

R

3

R

13

X

1

X

2 and X 3 having the same definition as that given for formula can also be obtained by a process consisting in placing a compound of formula (VI): 1 19 R2 2

X

2 X3

(VI)

RI, R 2

X

1

X

2 and X 3 having the same definition as that given for formula and U 2 is a halogen atom (preferably chlorine or bromine) or an alkylsulphonate group (preferably methylsulphonate or trifluoromethylsulphonate), in contact with a hydroxamic acid derivative in which W2 is an oxygen atom, or a hydrazonic acid derivative in which W2 is a group NR, R 3 and R 1 3 having the same definition as that given for formula of formula (VII):

H

W

2

-H

R3

(VII)

The condensation between the compound of formula (VI) and the compound of formula (VII) is carried out in the presence of an organic or inorganic base, in the presence or absence of a solvent.

The general conditions for condensation between the compound of formula (VI) and the compound of formula (VII) are similar or identical to the conditions for condensation between the compound of formula (II)A and the compound of formula (III)A and 7O are known per se according to "Houben-Weyl" volume 1 I k| pages 1148-1149.

The compounds of formula formula formula (VI) and formula (VII), Wl, W2, R 1

R

2

R

3

R

13

X

1

X

3 and p having the same definition as that given for formula U 1 and U 2 having the same definition as that given in method A, can be prepared according to processes which are known per se.

The compounds of formula (II)A in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definition as that given for formula X 4 having the same definition as that given for formula and V, is a halogen atom (preferably chlorine or bromine), an alkylsulphonate group (preferably methylsulphonate or trifluoromethylsulphonate) or an arylsulphonate group (preferably 4-methylphenylsulphonate), will by convention, for the remainder of the description of the preparation methods, be denoted by the generic term "benzyl halide derivatives".

The benzyl halide derivatives of formula (II)A in which Vi is a halogen atom (preferably chlorine or bromine) can be obtained by halogenation of a compound of formula (VIII): X4^ CH3

G

(VIII)

in which G is one of the groups G1 to G9, the I II *II 21 groups G1 to G9 having the same definition as that given for formula X 4 having the same definition as that given for formula Halogenation of the compound of formula (VIII) can be carried out via a radical, thermal or photochemical route, the various processes not excluding each other, by an N-haloacetamide such as N-bromosuccinimide, N-chlorosuccinimide or N-bromoacetamide, in an inert solvent such as benzene or carbon tetrachloride, or in the absence of solvent, with or without a free-radical initiator, at a temperature of from 20 0 C to 170 0 C, preferably from 80 0

C

to 100 0 C, according to J. March ibid. pages 689-697.

The benzyl halide derivatives of formula (II)A in which Vi is a halogen atom (preferably chlorine or bromine) can also be obtained by halogenating a compound of formula (II)B: xfW,- H G

(II)B

in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that given for formula and R 4 is an alkylamino or dialkylamino group, the groups G8 and G9 having the same definition as that given for formula X 4 having the same definition as that given for formula and W, is an oxygen atom, 22 with a halogenating agent such as thionyl chloride, phosphorus oxytrichloride or phosphorus tribromide according to J. March ibid. pages 431-433 or with the lithium halide/mesyl halide/collidine reagent according to J. Org. Chem. (1971), 36, 3044.

The benzyl halide derivatives of formula (II)A in which V I is a halogen atom (preferably chlorine or bromine) can also be obtained by cleaving a compound of formula (II)C: xe wi-p G (1)C in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that given for formula and R 4 is an alkylamino or dialkylamino group, the groups G8 and G9 having the same definition as that given for formula X 4 having the same definition as that given for formula W, is an oxygen atom and P is a protecting group for the alcohol function, such as an ester, preferably acetic or benzoic, or an ether, preferably methyl, methoxymethyl, phenyl or benzyl (reference will be made advantageously to the book "Protective groups in Organic Synthesis" by W. Greene and P. Wuts, published by Wiley (1991) for the choice and preparation of the said protecting groups),

I)

(I

23 with a Lewis acid such as boron tribromide, or anhydrous hydracids such as hydrogen chloride. This cleavage reaction is known in particular from patent EP 525,516.

The benzyl halide derivatives of formula (II)A and the compounds of formula (VIII), (II)B and (II)C can be prepared according to methods which are known per se. These various methods or the prior art relating thereto will be outlined in methods J, K and

L.

Method B The compounds of general formula for which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that given for formula and R 4 is an amino, alkylamino or dialkylamino group or radical, the groups G8 and G9 having the same definition as that given for formula X 4 having the same definition as that given for formula can be obtained by a process consisting in placing a compound of formula (II)B, in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that given for formula and R 4 is an amino, alkylamino or dialkylamino group or radical, the groups G8 and G9 having the same definition as that given for formula X 4 having the same definition as that given for formula and W 1 is an oxygen or sulphur atom, in contact with a compound of formula (III)B: i I

I

r I L 24

()B

W2, R 1

R

2 R3, R 13 Xi, X 2

X

3 and p having the same definition as that given for formula U 3 being a halogen atom, preferably a chlorine atom, it being possible for the double bond U 3

-C(R

3

N-W

2 to be of or stereochemistry.

This reaction is carried out in the presence of an organic or inorganic base, in the absence or presence of a solvent. The reaction is generally carried out at a temperature of between -80 0 C and 180 0

C

(preferably between 0°C and 150 0 C) or at the boiling point of the solvent used. The appropriate solvent for this reaction can be an ether, such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane or dimethoxyethane, a nitrile, such as acetonitrile, propionitrile or benzonitrile, a dipolar aprotic solvent, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or dimethylprolyleneurea, or dimethyl sulphoxide. Mixtures of these various solvents can also be used.

The reaction time depends on the conditions used and is generally between 0.1 and 48 h.

As organic or inorganic base which is suitable for this reaction, mention may be made of alkali metal and alkaline-earth metal hydrides, such as

(I

sodium hydride, potassium hydride or caesium hydride, and alkali metal and alkaline-earth metal alkoxides, such as potassium tert-butoxide.

There is no strict limitation for the relative proportions of the compounds of formula (II)B and of formula (III)B. However, it is advantageous to choose a (III)B/(II)B molar ratio of between 0.1 and preferably 0.5 to 2.

Depending on the conditions used, the compounds of general formula are obtained in the form of a variable mixture of and isomers or a single isomer or a single isomer depending on the configuration of the hydroximic or hydrazonic group. If necessary, the compounds of general formula and of or configuration, depending on the configuration of the hydroximic or hydrazonic group, can be isolated and purified according to methods which are known per se, such as, for example, extraction, crystallization or chromatography.

The compounds of general formula (III)B are prepared according to methods which are known per se, such as, for example, J. Org. Chem. (1985), 50, 993, J.

Org. Chem. (1971), 36, 234, and Chem. Abstracts (1970), 73, 34750s.

Method C: The thiohydroxamic acids of formula (III)A in which W1 is a sulphur atom and W2 is an oxygen atom, or the thiohydrazonic acids of formula (III)A in which W1 26 is a sulphur atom and W2 is a group NR 13

R

I

R

2

R

3

R

13

X

1

X

2

X

3 and p having the same definition as that given for formula are also a subject of the present invention.

They can be obtained by thionation of the hydroxamic acids of formula (III)A in which W1 is an oxygen atom and W2 is an oxygen atom, or the hydrazonic acids of formula (III)A in which W1 is an oxygen atom and W2 is a group NR 13 Ri, R 2

R

3

R

13 XI, X 2

X

3 and p having the same definition as that given for formula with thionating agents such as phosphorus pentasulphide or Lawesson's reagent, in an identical or similar manner to that of the processes described in "Houben-Weyl" volume E5, pages 1279-1280 and Synthesis (1984), 829.

Method D: The compounds of general formula for which G is the group G3, Q2 being an oxygen atom, R 4 being an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given for formula and R 6 is a lower alkyl or lower haloalkyl group, can be obtained by a process consisting in placing a compound of formula (IX): 'I g I 27

X,

x 4 R

R

x2 0

(IX)

in which R 4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given for formula in contact with a Wittig-Horner reagent of formula (X)A:

R

6

-CH

2 (ORb) 2

(X)A

R

6 being a lower alkyl or lower haloalkyl group, Rb being a lower alkyl, phenyl or benzyl group, or alternatively with a Wittig reagent of formula (X)B:

R

6

-CH

2 -P(Rd) 3 ;Hal- (X)B R, being a lower alkyl or lower haloalkyl group, Rd being an optionally substituted phenyl group, Hal- being a halide ion, by the action of one or more equivalents of a base such as alkali metal or alkaline-earth metal alkoxides, preferably sodium ethoxide, sodium methoxide or potassium tert-butoxide, or alkali metal and i I, I n 28 alkaline-earth metal hydrides, preferably sodium hydride or potassium hydride, or by the action of an organometallic derivative, such as alkyllithiums, preferably butyllithium, alkylmagnesium halides or lithium diisopropylamide in an aprotic solvent such as ethers, preferably diethyl ether or tetrahydrofuran, at a temperature of from -780C to 50 0 C, preferably -70 0

C

to 20 0 C, according to J. March, ibid. pages 956-963 or patent WO 95/29896.

The Wittig-Horner reagents of formula (X)A and the Wittig reagents of formula (X)B can be obtained according to processes which are known per se.

Method E: The compounds of general formula for which G is the group G1 or G2, Q1 being a nitrogen atom or a CH group, Q2 being an oxygen atom, R 4 being an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given for formula and R 5 is a lower haloalkyl group, can be obtained by a process consisting in placing a compound of formula (XI): X4 W2 X M x -X wx 0

(XI)

in which T is an oxygen atom and M is an alkali metal or alkaline-earth metal ion, Ql being a nitrogen atom or a CH group, R 4 being an alkoxy, alkylamino or dialkylamino group, W1, W2, R 1

R

2

R

3

R

13

X

1

X

2

X

3

X

4 and p having the same definition as that given for formula in contact with a halogenated compound of formula CHq(Hal) 4 q where q 1 or 2 and Hal denotes halogen atoms which may be identical to or different from each other and at least one of which is a chlorine or bromine atom, in a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolyleneurea or dimethyl sulphoxide, in the presence or absence of a catalytic amount of an iodide ion, at a temperature of between 0 C and 250 0 C, preferably 25 0 C to 150 0 C or at the reflux point of the solvent. This reaction is described in particular in patents DE 4,424,788 and WO 96/06072.

The compounds of formula in which T is an oxygen atom and M is an alkali metal or alkalineearth metal ion, Q1 being a nitrogen atom, R 4 being an alkoxy, alkylamino or dialkylamino group, Wl, W2, R,,

R

2

R

3

R

13

X

1

X

2

X

3

X

4 and p having the same definition as that given for formula can be readily obtained from the compounds of formula (IX) in which R 4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given for formula by the action of hydroxylamine and a base, according to J. March, ibid.

pages 906-907.

The compounds of formula in which T is an oxygen atom and M is an alkali metal or alkalineearth metal ion, Q1 being a CH group, R 4 being an alkoxy, alkylamino or dialkylamino group, and W1, W2,

R

I

R

2

R

3

R

13

X

1

X

3

X

4 and p having the same definition as that given for formula can be prepared in particular in a similar manner to that of patent EP 176,826.

Method F: The compounds of general formula for which G is the group G4 in which n 1, Q2 being an oxygen atom, R4 being an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given for formula can be obtained by reaction between a compound of formula

(XII)A:

JT R, X2 HN .R 4

R

3 2

(XII)A

in which R 4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given for formula with a reagent of formula (XIII): 31 VI ORI O

(XIII)

in which V, is a halogen atom (preferably chlorine or bromine), R 5 having the same definition as that given for formula by the action of one or more equivalents of base, such as alkali metal or alkaline-earth metal hydroxides, alkali metal or alkaline-earth metal alkoxides, alkali metal or alkaline-earth metal hydrides, alkali metal or alkaline-earth metal carbonates and bicarbonates, optionally in the presence of a phase-transfer catalyst such as a quaternary ammonium, in an aprotic solvent such as ethers, preferably diethyl ether or tetrahydrofuran, at a temperature of from -780C to 400C, preferably between and 25 0

C.

The compounds of general formula (XII)A, in which R 4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given for formula can be obtained by reaction of a compound of general formula (XII)B: o H V

(XII)B

in which R 4 is an alkoxy, alkylamino or «1 32 dialkylamino group, X 4 having the same definition as that given for formula V, is a halogen atom (preferably chlorine or bromine) or an alkylsulphonate (preferably methylsulphonate or trifluoromethylsulphonate) or arylsulphonate (preferably 4-methylphenylsulphonate) group, with a compound of formula (III)A, W1, W2, R 1 R2, R3, R13, Xi, X 2 X3 and p having the same definition as that given for formula The general conditions for condensation between the compound of formula (XII)B and compound of formula (III)A are similar or identical to the conditions for condensation between the compound of formula (II)A and compound of formula (III)A described in Method A.

The compounds of general formula (XII)B can be obtained according to the reference EP 498,396.

Method G: The compounds of general formula for which G is the group G1 to G7 and R 4 is an alkylamino or dialkylamino group, the other-substituents having the same definition as that given for formula can be obtained by a process which consists in placing a compound of general formula for which G is a group G1 to G7 and R 4 is an alkoxy or alkylthio group, the other substituents having the same definition as that Sgiven for formula in contact with an alkylamine or dialkylamine, preferably methylamine, in an alcoholic solvent, such as methanol, ethanol, propanol or isopropanol, at a temperature of from -50 0 C to 100 0 C or at the boiling point of the solvent chosen. It is generally advantageous to use an excess of from 1 to equivalents, preferably 1.1 to 2 equivalents, of alkylor dialkylamine relative to the compound of general formula for which G is a group G1 to G7 and R 4 is an alkoxy or alkylthio group, the other substituents having the same definition as that given for formula Method H: The compounds of general formula for which W1 is a sulphoxide (SO) or sulphone (SO 2 group, G being one of the groups Gl, G3, G4 and G6 to G9, Q2 and Q3 being an oxygen atom, the other substituents having the same definition as that given for formula can be obtained by oxidation of the compounds of general formula for which W1 is a sulphur atom, G being one of the groups Gl, G3, G4 and G6 to G9, Q2 and Q3 being an oxygen atom, the other substituents having the same definition as that given for formula using one or more equivalents of an oxidizing agent such as organic peroxides, preferably peracetic acid or 3chloroperbenzoic acid, inorganic peroxides, hydroperoxides such as hydrogen peroxide, inorganic S oxychlorides or oxygen, in the presence or absence of a catalyst, in an inert solvent, according to J. March, ibid. pages 1201-1203.

Method I: The compounds of general formula prepared according to Method A or Method B can be obtained with the atoms or groups W1 and W2, W1 and W2 having the same meaning as for formula in a cis position (see above) relative to the double bond -C(R 3 (hydroximic or hydrazonic group).

The isomers of general formula with the atoms or group W1 and W2 in a trans position relative to the double bond -C(R 3 (hydroximic or hydrazonic group) can be prepared from the cis isomers by heating in a solvent, preferably under ultraviolet irradiation, with or without a catalyst, in particular an acid catalyst. The reaction time is chosen so as to obtain a total conversion of the cis isomer into the trans isomer. The reaction is generally carried out at a temperature of between 0°C and the boiling point of the solvent. The appropriate solvent for this reaction can be an aliphatic hydrocarbon such as pentane, hexane, heptane or octane; an aromatic hydrocarbon such as benzene, toluene or xylenes, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane or dimethoxyethane; a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane or 1,1,1-trichloroethane; an ester such as methyl acetate or ethyl acetate; a nitrile such as acetonitrile, propionitrile or benzonitrile; an alcohol such as methanol, ethanol, propanol or isopropanol; a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolyleneurea or dimethyl sulphoxide; or water.

Mixtures of these various solvents can also be used.

The solvent will preferably be an aromatic solvent such as toluene or xylenes or an ether such as diisopropyl ether. The catalyst, preferably an acid catalyst, will be chosen from anhydrous hydracids such as hydrogenchloride, carboxylic acids such as acetic acid, propionic acid or trifluoroacetic acid, sulphonic acids such as methanesulphonic acid, trifluoromethanesulphonic acid or 4-methylphenylsulphonic acid, or sulphuric acid.

Method J: (Benzyl halide derivatives of formula (II)A and the like) The benzyl halide derivatives of formula (II)A and the compounds of formula (VIII), (II)B and (II)C can be prepared according to a great many methods which are known per se.

Mention will be made, as non-limiting and non-exhausting examples, of various patents describing the processes for preparing the benzyl halide derivatives of formula (II)A or compounds of formula (VIII) or compounds of formula (II)B or compounds of Sformula (II)C: The benzyl halide derivatives of formula (II)A and the like, in which G is a group G1 or G2 of or stereochemistry, can be prepared according to that which is described in patents EP 426,460, EP 398,692, EP 617,014, EP 585,751, EP 487,409, EP 535,928 and DE 4,305,502.

The benzyl halide derivatives of formula (II)A and the like, in which G is a group G3 of or stereochemistry, are known according to patent WO 96/16943.

The benzyl halide derivatives of formula (II)A and the like, in which G is a group G4, G5 or G6, are known according to patents EP 498,396, EP 619,301 and WO 93/15046.

The benzyl halide derivatives of formula (II)A and the like, in which G is a group G7, are known according to patents WO 95/27693 and WO 96/07633.

The benzyl halide derivatives of formula (II)A and the like, in which G is a group G8 or G9, are known according to patent WO 95/14009.

Method K: The compounds of general formula in which the groups W1, W2, R 1

R

2

R

3

X

1

X

2

X

3

X

4 and p have the same meaning as in formula and G is a group G7, can also be prepared using the following process, which is also a subject of the present invention.

This process consists in placing the I) II I:

II

37 intermediates of general formula (III)A, in which the groups W1, W2, R 1

R

2

R

3

R

1 3

X

1

X

2

X

3 and p have the same meaning as in formula in contact with a compound of general formula (II)A for which G is a group G7, X 4 having the same definition as that given for formula and V, is a halogen atom, preferably chlorine or bromine, according to the process described in Method A.

The compounds of general formula (II)A, for which G is a group G7, X 4 having the same definition as that given for formula and V, is a halogen atom, preferably chlorine or bromine, can be obtained by a cleavage reaction of the compounds of formula (XIV)A: O OCORc 02

(XIV)A

in which Y, X 4 Q2, R 4 and R, have the same meaning as for formula and Rc is a hydrogen atom or a lower alkyl group optionally substituted with one or more halogens or an alkoxy group, an optionally substituted benzyl or an optionally substituted aryl, by reaction with a halogenating agent.

This reaction can be carried out at a temperature of between -30 0 C and 50 0 C in an inert solvent. The term "inert solvent" means an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or petroleum ether; or else an aromatic compound such as toluene or xylenes; or else chlorinated compounds such as methylene chloride, chloroform, 1,1,1trichloroethane and chlorobenzene; or else ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole or tetrahydrofuran; or else a nitrile such as acetonitrile or propionitrile, or an alcohol such as methanol, ethanol, n-propanol, isopropanol, butanol and tert-butanol; or dimethyl sulphoxide, or dimethylformamide, or a mixture of these solvents.

Halogenating agents which can be used, for example, are Lewis acids such as aluminium chloride or boron trichloride, or a halogenated hydracid such as hydrogen chloride or hydrogen bromide. The halogenating agent will be in equimolar amount or in excess.

The compounds of formula (XIV)A, in which Y,

X

4 Q2, R 4 and R 8 have the same meaning as for formula and Rc is a hydrogen atom or a lower alkyl group optionally substituted with one or more halogens or an alkoxy group, an optionally substituted benzyl or an optionally substituted aryl, can be obtained by alkylating the compounds of formula (XIV)B: -u i \tf, B OFF* f 39 X4 O CORc 02

(XIV)B

in which Y, X 4 Q2 and R 4 have the same meaning as for formula and Rc is a hydrogen atom or a lower alkyl group optionally substituted with one or more halogens or an alkoxy group, an optionally substituted benzyl or an optionally substituted aryl.

The alkylating agent which will be used is an alkyl or acyl halide or sulphonate of formula (XV): RS-VI (XV) in which R 8 is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, formyl or acyl group and V, is a halogen atom (preferably bromine or iodine) or an alkylsulphonate (preferably trifluoromethylsulphonate) or arylsulphonate group, in the presence of silver derivatives such as silver salts or oxides, according to J. Chem. Soc.

(1969), 2372 and Bull. Chem. Soc. Jpn. (1978), 51, 866.

The reaction is carried out in a dipolar aprotic solvent, for instance amides such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone at a temperature of between -700C and 180 0 C, preferably between -300C and 800C.

The compounds of formula (XIV)B, in which Y, I) II

X

4 Q2 and R 4 have the same meaning as for formula (I) and Rc has the same meaning as for compound (XIV)A, can be obtained by reducing the compounds of formula (XIV)C: 02 OCQRc

(XIV)C

in which Y, X 4 Q2 and R 4 have the same meaning as for formula and Rc has the same meaning as for compound (XIV)A, using a reducing agent such as an alkali metal or alkaline-earth metal hydride, preferably sodium borohydride, in an alcohol such as methanol, ethanol, propanol, isopropanol, butanol or tert-butanol, according to J. March ibid. page 910.

The compounds of formula (XIV)C, in which Y,

X

4 Q2 and R 4 have the same meaning as for formula (I) and Rc has the same meaning as for compound (XIV)A, can be obtained by a process consisting in placing a compound of formula (XIV)D: 0JV,

(XIV)D

ll 41 in which Y, X 4 Q2 and R 4 have the same meaning as for formula and V, is a halogen atom, preferably chlorine or bromine, in contact with an inorganic carboxylate such as a formate, an acetate or a propionate, or another inorganic salt of a lower alkylcarboxylic acid, in which the alkyl group can be optionally substituted with one or more halogens or an alkoxy group or an optionally substituted phenyl group, or alternatively a salt of optionally substituted benzoic acid, according to J. March ibid. p. 398.

The reaction is preferably carried out in a dipolar aprotic solvent such as amides, preferably formamide, acetamide, dimethylacetamide or N-methylpyrrolidine, at a temperature ranging from 00 to the refluxing point of the solvent.

The compounds (XIV)D are obtained according to methods which are known per se, as described in patent EP 374,811.

Method L: The compounds of general formula in which the groups Wl, W2, R

I

R

2

R

3

X

1

X

2

X

3

X

4 and p have the same meaning as for formula and G is a group G3, and R 6 is a trifluoromethyl radical, can also be prepared using the following process, which is also a subject of the present invention.

This process consists in placing the intermediates of general formula (III)A, in which the groups Wl, W2, R

I

R

2

R

3

R

13 Xi, X 2

X

3 and p have the same meaning as for formula in contact with a compound of general formula (II)A for which G is a group G3, R 6 is a trifluoromethyl radical, X 4

R

4 and Q2 having the same definition as that given for formula and V, is a halogen atom, preferably chlorine or bromine, according to the process described in Method A.

The compounds of general formula (II)A, for which G is a group G3, R 6 is a trifluoromethyl radical,

X

4

R

4 and Q2 having the same definition as that given for formula and V, is a halogen atom, preferably chlorine or bromine, can be obtained by halogenating compounds of general formula (VIII) for which G is a group G3, R 6 is a trifluoromethyl radical, X 4

R

4 and Q2 having the same definition as that given for formula according to the process described in Method A.

The compounds of general formula (VIII), for which G is a group G3, R 6 is a trifluoromethyl radical,

X

4

R

4 and Q2 having the same definition as that given for formula can be obtained by dehydrating the compounds of formula (XVI):

(XVI)

in which X 4

R

4 and Q2 have the same meaning as for formula using a dehydrating agent such as anhydrous hydracids (preferably sulphuric acid), their alkali metal or alkaline-earth metal salts (preferably potassium hydrogen sulphate) or anhydrides such as phosphorus pentoxide, according to J. March, ibid.

pages 1011 et seq. or Chem. Ber. (1986), 119, 2233, or phosphorus oxytrichloride, alkylsulphonate (preferably methylsulphonate or trifluoromethylsulphonate) chlorides, or arylsulphonate (preferably 4-methylphenylsulphonate) chlorides, in the presence of a nitrogenous base such as pyridine, alkylpyridines or alkylamines such as trimethylamine, triethylamine or diisoprylethylamine Tetrahedron: Asymmetry (1990), 1, 521, or dialkyl diazodicarboxylates (preferably diethyl diazodicarboxylate), in the presence of a triarylphosphine such as diphenylphosphine, according to J. Org. Chem. (1984), 49, 1430.

This reaction is carried out in the absence or in the presence of a solvent. The reaction is generally carried out at a temperature of between -80 0

C

and 180 0 C (preferably between 0°C and 1500C) or at the boiling point of the solvent used. The appropriate solvent for this reaction can be a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2dichloroethane or l,l,l-trichloroethane, an ether such Sas diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane or dimethoxyethane, a nitrile such as acetonitrile, propionitrile or benzonitrile, a nitrogenous base such as pyridine or alkylpyridines, a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolyleneurea or dimethyl sulphoxide. Mixtures of these various solvents can also be used.

The compounds of general formula (XVI), in which X 4

R

4 and Q2 have the same meaning as that given for formula can be obtained by an aldol condensation reaction of the compounds of formula

(XVII):

X4CH 3 (XVII) (xvn) in which X 4

R

4 and Q2 have the same meaning as for formula with gaseous trifluoroacetaldehyde, by the action of one or more equivalents of a base such as alkali metal and alkaline-earth metal hydrides, preferably sodium hydride or potassium hydride, alkali metal and alkaline-earth metal alkoxides, an organometallic derivative such as alkyllithiums, preferably butyllithium, alkylmagnesium halides or alkali metal and alkaline-earth metal amides such as lithium diisopropylamide or lithium hexamethyldisilazane amide, in an aprotic solvent such as ethers, preferably diethyl ether or tetrahydrofuran, at a temperature of from -780C to 500C, preferably -700C to 200C.

The invention also relates to fungicidal compositions containing an effective amount of at least one active material of formula (I) The fungicidal compositions according to the invention comprise, besides the active material of formula agriculturally acceptable solid or liquid supports and/or surfactants which are also agriculturally acceptable. In particular, common inert supports and common surfactants can be used. These compositions include not only compositions which are ready to be applied to the plant or seed to be treated by means of a suitable device, such as a spraying or dusting device, but also concentrated commercial compositions which must be diluted before they are applied to the crop.

These fungicidal compositions according to the invention can also contain other ingredients of any kind, such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestering agents, etc. More Sgenerally, the active materials can be combined with

,Q

r 46 any solid or liquid additive which complies with the usual formulation techniques.

In general, the compositions according to the invention usually contain from 0.05 to 95% (by weight) of active material, one or more solid or liquid supports and, optionally, one or more surfactants.

In the present specification, the term "support" denotes a natural or synthetic, organic or inorganic material with which the active material is combined to make it easier to apply to the parts of the plant. This support is thus generally inert and should be agriculturally acceptable. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, in particular butanol, etc.).

The surfactant can be an emulsifier, a dispersing agent or a wetting agent of ionic or nonionic type or a mixture of such surfactants. Mention may be made, for example, of polyacrylic acid salts, lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the above compounds containing sulphate, sulphonate and phosphate functions. The presence of at least one surfactant is generally essential when the active material and/or the inert support are water-insoluble and when the vector agent for the application is water.

Thus, the compositions for agricultural use according to the invention can contain the active material in a very wide range, from 0.05% to 95% (by weight). Their surfactant content is advantageously between 5% and 40% by weight. Except where otherwise indicated, the percentages given in this description are weight percentages.

These compositions according to the invention are themselves in quite diverse, solid or liquid forms.

As solid composition forms, mention may be made of powders for dusting (with an active material content which can be up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support or by granulation from a powder (the active material content in these granules being between 0.5 and 80% for the latter cases).

The fungicidal compositions according to the invention can also be used in the form of powders for dusting; compositions comprising 50 g of active material and 950 g of talc can also be used; compositions comprising 20 g of active material, 10 g Q of finely divided silica and 970 g of talc can also be 48 used; these constituents are mixed together and ground and the mixture is applied by dusting.

As liquid composition forms or forms intended to constitute liquid compositions when applied, mention may be made of solutions, in particular water-soluble concentrates, emulsions, concentrated suspensions and wettable powders (or powders for spraying) The concentrated suspensions, which can be applied by spraying, are prepared so as to obtain a stable fluid product which does not become deposited, and they usually contain from 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0.1 to of thixotropic agents, from 0 to 10% of suitable additives, such as antifoaming agents, corrosion inhibitors, stabilizers, penetration agents and adhesives, and, as support, water or an organic liquid in which the active material is insoluble or only sparingly soluble: certain organic solid materials or inorganic salts can be dissolved in the support to help prevent sedimentation or as antifreezes for the water.

By way of example, there follows a composition of a concentrated suspension: Example CS1: Active material 500 g Polyethoxylated tristyrylphenol phosphate 50 g Polyethoxylated alkylphenol 50 g Polysodium carboxylate 20 g 1IC 49 Ethylene glycol 50 g Polyorganosiloxane oil (antifoaming agent) 1 g Polysaccharide 1.5 g Water 316.5 g The wettable powders (or powders for spraying) are usually prepared such that they contain to 95% of active material, and they usually contain, in addition to the solid support, from 0 to 30% of a wetting agent, from 3 to 20% of a dispersant and, when necessary, from 0.1 to 10% of one or more stabilizers and/or other additives, such as penetration agents, adhesives, anticaking agents, dyes, etc.

In order to obtain the powders for spraying or wettable powders, the active materials are intimately mixed with the additional substances in suitable mixers and are ground with mills or other suitable blenders. Powders for spraying with advantageous wettability and suspension formation are thus obtained; they can be placed in suspension with water at any desired concentration and these suspensions can be used very advantageously, in particular for application, for example, to plant leaves or to seeds.

By way of example, there follow various wettable powder compositions (or powders for spraying): Example WP1 Active material Ethoxylated fatty alcohol (wetting agent) Ethoxylated phenylethylphenol (dispersant) Chalk (inert support) 42.5% Example WP2: Active material Synthetic C13 oxo alcohol of branched type, ethoxylated with 8 to 10 ethylene oxide (wetting agent) 0.75% Neutral calcium lignosulphonate (dispersant) 12% Calcium carbonate (inert filler) qs 100% Example WP3: This wettable powder contains the same ingredients as in the above example, in the following proportions: Active material Wetting agent 1.50% Dispersant 8% Calcium carbonate (inert filler) qs 100% Example WP4: Active material Ethoxylated fatty alcohol (wetting agent) 4% Ethoxylated phenylethylphenol (dispersant) 6% Example Active material

I,

51 Mixture of anionic and nonionic surfactants (wetting agent) Sodium lignosulphonate (dispersant) Kaolinic clay (inert support) 42.5% The aqueous dispersions and emulsions, for example the compositions obtained by diluting a wettable powder according to the invention with water, are included within the general scope of the present invention. The emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency, such as that of a "mayonnaise".

The fungicidal compositions according to the invention can be formulated in the form of waterdispersible granules, which are also included within the scope of the invention.

These dispersible granules, with an apparent density generally of between about 0.3 and about 0.6, have a particle size generally of between about 150 and about 2000 and preferably between 300 and 1500 microns.

The active material content of these granules is generally between about 1% and about 95% and preferably between 25% and The rest of the granule is essentially composed of a solid support and optionally of surfactant adjuvants which give the granule waterdispersibility properties. These granules can be essentially of two different types depending on whether the support selected is soluble or insoluble in water.

I II 52 When the support is water-soluble, it can be inorganic or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble support, it is preferably inorganic, for example such as kaolin or bentonite. It is then advantageously accompanied by surfactants (in a proportion of from 2 to 20% by weight of the granule) more than half of which consists, for example, of at least one dispersant, which is essentially anionic, such as an alkali metal or alkaline-earth metal polynaphthalene sulphonate or an alkali metal or alkaline-earth metal lignosulphonate, the remainder consisting of nonionic or anionic wetting agents such as an alkali metal or alkaline-earth metal alkylnaphthalene sulphonate.

Moreover, although this is not essential, other adjuvants can be added, such as antifoaming agents.

The granule according to the invention can be prepared by mixing together the required ingredients, followed by granulation according to several techniques which are known per se (granulator, fluid bed, sprayer, extrusion, etc.). The process generally ends by a crushing operation, followed by an operation of screening to the particle size chosen within the limits mentioned above. Granules obtained as above and then impregnated with a composition containing the active material can also be used.

Preferably, it is obtained by extrusion, by 11 1 h I 53 performing the process as indicated in the examples below.

Example DG1: Dispersible granules by weight of active material and 10% of urea pellets are mixed together in a mixer. The mixture is then ground in a toothed roll crusher. A powder is obtained, which is moistened with about 8% by weight of water. The wet powder is extruded in a perforatedroller extruder. A granulate is obtained, which is dried and then crushed and screened, so as to retain, respectively, only the granules between 150 and 2000 microns in size.

Example DG2: Dispersible granules The constituents below are mixed together in a mixer: Active material Wetting agent (sodium alkylnaphthalene sulphonate) 2% Dispersant (polysodium naphthalene sulphonate) 8% Water-insoluble inert filler (kaolin) This mixture is granulated in a fluid bed, in the presence of water, and then dried, crushed and screened so as to obtain granules between 0.15 and 0.80 mm in size.

These granules can be used alone, or as a solution or dispersion in water so as to obtain the Sdesired dose. They can also be used to prepare combinations with other active materials, in particular fungicides, these being in the form of wettable powders, granules or aqueous suspensions.

The compounds of the invention can also be mixed with one or more insecticides, fungicides, bactericides, attractant acaricides or pheromones or other compounds with biological activity. The mixtures thus obtained have a broadened spectrum of activity.

Mixtures with other fungicides are particularly advantageous, in particular mixtures with carbendazim, thiuram, dodin, maneb, mancozeb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, captafol, folpet, folpel, thiophanate, thiabendazole, phosetyl-Al, chlorothalonil, dichloran, metalaxyl, iprodione, oxadixyl, vinchlozoline, tebuconazole, difenconazole, diniconazole, metconazole, penconazole, propiconazole, prochloraz, fenarimol, triadimenol, furalaxyl, copper derivatives such as the copper hydroxide or copper oxychloride, and probenazole.

The compositions according to the invention are useful for treating the seeds of cereals (wheat, rye, triticale and barley in particular), potato, cotton, pea, rapeseed, corn or flax, or alternatively the seeds of forest trees (in particular resiniferous trees).

It will be noted in this respect that, in the terminology of the person skilled in the art, the term ,'A"treatment of seeds" in fact relates to the treatment of the grains. The application techniques are well known to those skilled in the art and they can be used without any drawback in the context of the present invention. Mention may be made, for example, of filmcladding or coating.

Another subject of the invention is a process for curatively or preventively combating the phytopathogenic fungi of crops, characterized in that an effective (agronomically effective) and nonphytotoxic amount of an active material of formula preferably in the form of a fungicidal composition according to the invention, is applied to the plant seeds or to the plant leaves or to the soil in which the plants are growing or in which it is desired to grow them.

The expression "effective and non-phytotoxic amount" means an amount of composition according to the invention which is sufficient to control or destroy the fungi present or liable to appear on the crops, and which does not entail any appreciable symptom of phytotoxicity for the said crops. Such an amount can vary within a wide range depending on the fungus to be combated, the type of crop, the climatic conditions and the compounds included in the fungicidal composition according to the invention. This amount can be determined by systematic field trials, which are within the capabilities of a person skilled in the art.

Lastly, the invention relates to a process .4 56 for preventively or curatively protecting plant multiplication products, as well as the plants resulting therefrom, against fungal diseases, characterized in that the said products are coated with an effective and non-phytotoxic dose of a composition according to the invention.

Among the plant multiplication products concerned, mention may be made in particular of seeds or grains, and tubers.

It is preferred to use the method according to the invention in the case of seeds.

As has been indicated above, the methods for coating the plant multiplication products, in particular seeds, are well known in the art and in particular involve film-cladding or coating techniques.

The products and compositions according to the invention can also be applied to the leaves of the plant crops.

Among the plants targeted by the method according to the invention, mention may be made of: wheat, as regards controlling the following seed diseases: fusaria (Microdochium nivale and Fusarium roseum), stinking smut (Tilletia caries, Tilletia controversa or Tilletia indica) and septoria disease (Septoria nodorum); wheat, as regards controlling the following diseases of the aerial parts of the plant: cereal eyespot (Pseudocercosporella herpotrichoides), take-all I I. I' 57 (Gaeumannomyces graminis), foot blight culmorum, F. graminearum), black speck (Rhizoctonia cerealis), powdery mildew (Erysiphe graminis forma specie tritici), rusts (Puccinia striiformis and Puccinia recondita) and septoria diseases (Septoria tritici and Septoria nodorum); wheat and barley, as regards controlling bacterial and viral diseases, for example barley yellow mosaic; barley, as regards controlling the following seed diseases: net blotch (Pyrenophora graminea, Pyrenophora teres and Cochliobolus sativus), loose smut (Ustilago nuda) and fusaria (Microdochium nivale and Fusarium roseum); barley, as regards controlling the following diseases of the aerial parts of the plant: cereal eyespot (Pseudocercosporella herpotrichoides), net blotch (Pyrenophora teres and Cochliobolus sativus), powdery mildew (Erysiphe graminis forma specie hordei), dwarf leaf rust (Puccinia hordei) and leaf blotch (Rhynchosporium secalis); potato, as regards controlling tuber diseases (in particular Helminthosporium solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani) and certain viruses (virus Y); cotton, as regards controlling the following diseases of young plants grown from seeds: Sdamping-off and collar rot (Rhizoctonia solani, I I 58 Fusarium oxysporum) and black root rot (Thielaviopsis basicola); pea, as regards controlling the following seed diseases: anthracnose (Ascochyta pisi, Mycosphaerella pinodes), fusaria (Fusarium oxysporum) and grey mould (Botrytis cinerea); rapeseed, as regards controlling the following seed diseases: Phoma lingam and Alternaria brassicae; corn, as regards controlling seed diseases: (Rhizopus sp., Penicillium sp., Trichoderma sp., Aspergillus sp., and Gibberella fujikuroi); flax, as regards controlling the seed disease: Alternaria linicola; forest trees, as regards controlling damping-off (Fusarium oxysporum, Rhizoctonia solani).

Wheat and barley are the preferred plants for carrying out the method according to the invention.

The dose of composition applied is, generally, advantageously such that the dose of active material is between 2 and 200 g of active material per 100 kg of seed, preferably between 3 and 150 g per 100 kg in the case of seed treatments.

In the case of plant treatments, doses of from 10 to 800 g/ha, preferably 50 to 300 g/ha, are generally applied as a foliar treatment.

The examples which follow illustrate the S present invention: Example 1: Preparation of (Z)-N-methoxy-Nmethoxycarbonyl-2-[l-(1- (phenyl)ethyloxyimino)ethyloxymethyl]aniline 1.47 g of N-(l-(phenyl)ethyloxy)acetamide are dissolved in 30 ml of anhydrous acetonitrile. 2.26 g of 2-bromomethyl-N-methoxy-N-methoxycarbonylaniline and 2.67 g of caesium carbonate are successively added and the reaction medium is refluxed for 2 hours. After cooling, salts are filtered off and washed with acetonitrile, which gives an organic solution which is concentrated, and 3.2 g of a red oil are thus obtained.

This oil is taken up in water and re-extracted three times with ethyl acetate to give, after drying and evaporation, 2.63 g of a dark yellow oil.

Chromatography on silica makes it possible to isolate 0.6 g of the expected compound, of stereochemistry, in the form of a yellow oil. nD 1.5270 (230C) (these terms refer to the refractive index at 23 0 C using the sodium D-line as light).

Example 2: Preparation of (E)-N-methoxy-Nmethoxycarbonyl-2-[- (1- (phenyl)ethyloxyimino)ethyloxymethyl]aniline 0.4 g of (Z)-N-methoxy-N-methoxycarbonyl-2- [l-(l-(phenyl)ethyloxyimino)ethyloxymethyl]aniline is dissolved in 25 ml of anhydrous toluene. After adding a few drops of acetic acid, the reaction medium is refluxed for 2 hours. The medium is poured into 50 ml of water and the toluene phase is separated out after settling has taken place, washed until neutral and dried, which gives 0.4 g of a yellow oil.

Chromatography on silica makes it possible to isolate 0.33 g of the expected compound, of (E) stereochemistry, in the form of a pale yellow oil which gradually crystallizes. m.p. 700C (this term refers to the melting point).

Example 3: Preparation of (Z)-2,4-dihydro-5-methoxy-2methyl-4-[2-[1-(1- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-3H-1,2,4triazol-3-one 3.58 g of N-(l-(phenyl)ethyloxy)acetamide are dissolved in 40 ml of anhydrous acetonitrile. 5.96 g of 4-[2-(bromomethyl)phenyl]-2,4-dihydro-5-methoxy-2methyl-3H-l,2,4-triazol-3-one and 7.82 g of caesium carbonate are successively added and the reaction medium is refluxed for 4 hours. After cooling, the salts are filtered off and washed with acetonitrile and the organic fractions are then concentrated to give g of an orange-coloured oil. After chromatography on silica, 0.82 g of the expected compound, of (Z) stereochemistry, is isolated in the form of a yellow oil. Rf 0.24 (1/3 heptane/ethyl acetate). (This refers to the coefficient of retention on a chromatography plate on a thin layer of silica) I I 61 Example 4: Preparation of (E)-2,4-dihydro-5-methoxy-2methyl-4-[2-[1-(1- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-3H-1,2,4triazol-3-one 0.4 g of (Z)-2,4-dihydro-5-methoxy-2-methyl- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-3H-1,2,4triazol-3-one are dissolved in 20 ml of anhydrous toluene. The reaction medium is refluxed for 13 hours under ultraviolet irradiation. The medium is concentrated to give 0.4 g of a yellow oil.

Chromatography on silica makes it possible to isolate 0.18 g of the expected compound, of (E) stereochemistry, in the form of a pale yellow oil.

nD 1.5310 (21 0

C).

Example Preparation of methyl (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-2methoxyacetate Step 1: Preparation of methyl 2-(2acetoxymethylphenyl)-2-oxoacetate A mixture of 25 g of methyl 2-(2bromomethylphenyl)-2-oxoacetate, 9.57 g of potassium acetate and 0.5 g of potassium iodide is refluxed for 3 hours in 150 ml of dimethylformamide. After cooling and diluting with water, the reaction mixture is 0I' 62 re-extracted with ether. After purification by chromatography on silica, 11 g of the expected product are obtained. nD: 1.5292 (25 0

C).

Step 2: Preparation of methyl 2-(2-acetoxymethylphenyl)-2-hydroxyacetate 11 g of the above compound are loaded into 150 ml of methanol. After cooling on an ice bath, 0.4 g of sodium borohydride is added and the mixture is stirred for 30 min at 0°C. 5 ml of acetic acid are then added, after which the methanolic phase is concentrated. After re-extraction, washing with aqueous sodium bicarbonate solution and drying, 10.5 g of the expected product are isolated in the form of a yellow oil. NMR (CDC1 3 2.10 s, 3H; 3.72, s 3H; 5.28, AB, 1H; 5.42, s. 1H; 7.25-7.45, m, 4H).

Step 3: Preparation of methyl 2-(2-acetoxymethylphenyl)-2-methoxyacetate 1.5 g of silver oxide are added over 1 hour to 10 g of the above compound and 11.36 g of methyl iodide dissolved in 200 ml of N-methylpyrrolidone.

After heating at 40 0 C for 2 hours, the reaction mixture is filtered, diluted with water and re-extracted with ether. After purification by chromatography on silica, g of the expected compound are obtained in the form of a yellow oil.

Step 4: Preparation of methyl 2-(2-bromomethylphenyl)-2-methoxyacetate Hydrogen bromide gas is bubbled, at a temperature of between 0 and 5 0 C, into a solution of g of the above compound in 10 ml of dichloromethane. After concentration and purification by chromatography on silica, 0.25 g of a yellow liquid is obtained. NMR (CDC1 3 3.42 s, 3H; 3.75, s 3H; 4.55, d, 1H; 4.82, d, 1H; 5.20, s, 1H; 7.25-7.55, m 4H.

Step Preparation of methyl (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-2methoxyacetate A mixture of 0.125 g of N-(1- (phenyl)ethyloxy)acetamide, 0.2 g of methyl 2-(2bromomethylphenyl)-2-methoxyacetate and 0.234 g of caesium carbonate in 15 ml of acetonitrile is refluxed for 4 hours. After purification by chromatography on silica, 0.1 g of the expected compound, of (E) stereochemistry, is obtained in the form of a 50/50 mixture of two diastereoisomers. nD: 1.5330 (25 0

C).

Example 6: Preparation of methyl 2 benzyl-N 2 -methylhydrazono) ethyloxymethyl phenyl] -3methoxyacrylate Step 1: Preparation of N 2 -benzyl-N 2 0^F methylacethydrazide 5.4 ml of acetyl chloride are poured dropwise onto a vigorously stirred mixture, at room temperature, of 9.4 g of l-methyl-l-benzylhydrazine, prepared according to Synth. Comm. (1990), 20, 185, dissolved in ml of ether and 2.76 g of sodium hydroxide dissolved in 25 ml of water. After reaction for 2 hours, the phases in the reaction mixture, are separated by settling and the organic phase is worked up in the usual manner. After purification by chromatography on silica, 8.36 g of expected product are obtained in the form of a yellow oil. NMR (CDC1 3 2.5, s, 3H; 2.95, bs, 2H; 3.62, s, 2H; 7.25-7.45, m, Step 2: Preparation of methyl 2 benzyl-N 2 -methylhydrazono)ethyloxymethyl]phenyl]-3methoxyacrylate 3 g of methyl (E)-2-(2-bromomethylphenyl)-3methoxyacrylate dissolved in 90 ml of dry dimethylformamide are gradually added, at 200C, to a mixture of 2.06 g of N 2 -benzyl-N 2 -methylacethydrazide obtained as above and 1.3 g of potassium tert-butoxide in 60 ml of dry dimethylformamide. After reaction for hours, the mixture is poured into 300 ml of water and re-extracted several times with ethyl acetate. After purification by chromatography on silica, 70 mg of the expected product, of stereochemistry, are obtained in the form of a syrup. NMR (CDC1 3 1.88, s, 3H; 2.42, s, 3H; 3.66, s, 3H; 3.68, s, 2H; 3.72, s, 3H; 4.93, s, 2H; 7.10-7.50, m, 9H; 7.47, s, 1H.

Example 7: Preparation of methyl (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-4,4,4trifluorobut-2-enoate Step 1: Preparation of methyl 3-hydroxy-2-[2- (methyl)phenyl]-4,4,4-trifluorobutanoate 28.75 g (0.15 mol) of methyl 2-[2- (methyl)phenyl]acetate dissolved in 100 ml of dry tetrahydrofuran are added dropwise to 200 ml of lithium diisopropylamide (1M in dry tetrahydrofuran) and cooled to -700C. Dry trifluoroacetaldehyde, prepared according to J. Chem. Educ. (1975), 52, 131, is bubbled into the reaction medium for 1 h. After stirring for 3 hours at -700C, the medium is poured into 500 ml of water and 200 ml of 1M hydrochloric acid, re-extracted with ethyl acetate and dried. Evaporation of the solvents leaves 37 g of a yellow oil which is distilled under reduced pressure 115-1200C at 4 mmHg; these expressions refer to the boiling point at a pressure expressed in mm of mercury) to give 35.60 g of a colourless oil.

After purification by chromatography on silica, 21.26 g of a syn:anti mixture in a 70:30 ratio of the expected compound are obtained. The major diastereoisomer, of syn configuration, can be isolated pure and crystallized: I 66 4 JHH 5 Hz; m.p. 580C.

Step 2: Preparation of methyl (methyl)phenyl]-4,4,4-trifluorobut-2-enoate 9.34 g of triphenylphosphine are added to 9.34 g of the syn:anti mixture of methyl 3-hydroxy-2- [2-(methyl)phenyl]-4,4,4-trifluorobutanoate obtained as above, dissolved in 40 ml of diethyl ether. The medium is cooled to 0°C and 6.19 g of diethyl azodicarboxylate are added dropwise. The medium is stirred for 15 hours at 200C and the triphenylphosphine oxide is then filtered off. The filtrate is distilled in a bulb oven to given 7 g of the expected compound, of (E) stereochemistry, in the form a colourless liquid. nD: 1.4722 (20 0

C).

Step 3: Preparation of methyl (bromomethyl)phenyl]-4,4,4-trifluorobut-2-enoate 5.34 g of N-bromosuccinimide and 0.1 g of benzoyl peroxide are added to 7 g of methyl (methyl)phenyl]-4,4,4-trifluorobut-2-enoate obtained as above, dissolved in 100 ml of carbon tetrachloride, and the medium is refluxed for 2 hours. After cooling, the succinimide is filtered off and the organic phase is washed with water and dried. Evaporation of the solvent leaves 8.63 g of the expected compound, of (E) stereochemistry, contaminated with about 15% of the Sstarting compound.

Step 4: Preparation of methyl (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-4,4,4trifluorobut-2-enoate 0.8 g of N-(1-(phenyl)ethyloxy)acetamide is dissolved in 20 ml of anhydrous acetonitrile. 1.45 g of methyl (E)-2-[2-(bromomethyl)phenyl]-4,4, 4 trifluorobut-2-enoate, obtained as above, and 1.76 g of caesium carbonate are successively added and the reaction medium is refluxed for 2 hours. After cooling, the medium is poured into 100 ml of water, re-extracted with ethyl acetate, dried and then concentrated to give 1.7 g of a yellow oil. Chromatography on silica makes it possible to isolate 0.4 g of the expected compound, of stereochemistry, in the form of a yellow oil.

nD 1.5251 (200C).

Example 8: Preparation of methyl (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-4,4,4trifluorobut-2-enoate In a similar manner to that of the process described in Example 2, 130 mg of methyl (1-(phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-4,4,4trifluorobut-2-enoate are isomerized in refluxing toluene in the presence of acetic acid. Chromatography on silica makes it possible to isolate 70 mg of the expected compound, of stereochemistry, in the Sform of a yellow oil. nD 1.5107 (26 0

C)

Example 9: Preparation of (E,E)-2-methoxyimino-N-methyl- 2-[2-[l-(l-(N-methylcarbamoyl)-l- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]acetamide Step 1: Preparation of methyl 2-bromo-2phenylpropanoate 10.7 g of N-bromosuccinimide and 0.1 g of benzoyl peroxide are added to 9.58 g of methyl 2-phenylpropanoate dissolved in 120 ml of carbon tetrachloride, and the medium is refluxed for 4 hours.

After cooling, the succinimide is filtered off and the organic phase is washed with 0.1N sodium thiosulphate, with water and dried. Evaporation of the solvent leaves 13.5 g of an orange-coloured oil which is distilled in a bulb oven 175 0 C at 5 mmHg) to give 12.5 g of the expected compound in the form of a colourless liquid. nD 1.5478 (19 0

C)

Step 2: Preparation of N-[1-(methoxycarbonyl)-1- (phenyl)ethyloxy]acetamide 2.43 g of sodium methoxide are added portionwise to a solution of 12.16 g of methyl 2-bromo- 2-phenylpropanoate, obtained as above, and 3.75 g of acetohydroxamic acid in 60 ml of anhydrous methanol heated to 40 0 C. The medium is heated at 40 0 C for 8 h.

After evaporation of the methanol, the residue is taken S up in 50 ml of water, re-extracted with ethyl acetate and dried. Evaporation of the solvents leaves 12 g of a colourless oil which gradually crystallizes. The solid is recrystallized from 100 ml of a 4/1 mixture of pentane/chloroform to give 8.7 g of the expected compound in the form of a white solid. m.p. 940C.

Step .3: Preparation of methyl (E,Z)-2-methoxyimino-2- [2-[1-(1-(methoxycarbonyl)-1- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]acetate 5.7 g of N-[l-(methoxycarbonyl)-1- (phenyl)ethyloxy]acetamide, obtained as above, are dissolved in 50 ml of anhydrous acetonitrile. 6.87 g of methyl (E)-2-methoxyimino-2-[2- (bromomethyl)phenyl]acetate and 9.38 g of caesium carbonate are successively added and the reaction medium is refluxed for 4 hours. After cooling, the caesium salts are filtered off and the filtrate is concentrated to give 12 g of a brown oil. Chromatography on silica makes it possible to isolate 4.5 g of the expected compound, of stereochemistry, in the form of a white solid. m.p. 1080C.

Step 4: Preparation of methyl (E,E)-2-methoxyimino-2- [2-[1-(1-(methoxycarbonyl)-1- (phenyl)ethyloxyimino)ethyloxymethyl]phenyllacetate In a similar manner to that of the process described in Example 2, 3.5 g of methyl methoxyimino-2-[2-[1-(1-methoxycarbonyl)-1-

II

(phenyl)ethyloxyimino)ethyloxymethyl]phenyl]acetate are isomerized in refluxing toluene in the presence of acetic acid. Recrystallization of the crude solid in diisopropyl ether makes it possible to isolate 3.2 g of the expected compound, of stereochemistry, in the form of a white solid. m.p. 117 0

C.

Step Preparation of (E,E)-2-methoxyimino-N-methyl- 2-[2-[1-(1-(methoxycarbonyl)-1- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]acetamide 14 ml of 40% by weight methylamine in water are added to 3.2 g of methyl (E,E)-2-methoxyimino-2-[2- [1-(l-(methoxycarbonyl)-1- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]acetate, obtained as above, dissolved in 70 ml of methanol, and the mixture is stirred vigorously at 20 0 C for 4 hours.

The methanol is evaporated off and the residue, taken up in 50 ml of ethyl acetate, is washed with water and dried. Evaporation of the solvents leaves 3.33 g of expected compound, of stereochemistry, in the form of a colourless oil. nD 1.5390 (19 0

C).

Step 6: Preparation of (E,E)-2-methoxyimino-N-methyl- 2-[2-[1-(1-(N-methylcarbamoyl)-l- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]acetamide 0.16 g of 60% sodium hydride is added to 0.88 g of (E,E)-2-methoxyimino-N-methyl-2-[2-[1-(1- (methoxycarbonyl)-1-(phenyl)ethyloxyimino)ethyloxy- 71 methyl]phenyl]acetamide, obtained as above, dissolved in 20 ml of anhydrous N-methylpyrrolidone. The medium is cooled to 0 C and gaseous methylamine is introduced by bubbling for 30 min. The reaction medium is stirred at 0°C for 3 hours and then poured into 100 ml of water. The pH is brought to 6 by addition of 1N hydrochloric acid and the aqueous phase is re-extracted with ethyl acetate, washed with water and dried.

Evaporation of the solvents leaves 1.0 g of a colourless oil. After purification by chromatography on silica, 0.15 g of the expected compound, of (E,E) stereochemistry, is obtained in the form of a colourless oil which gradually crystallizes, m.p. 152 0

C.

Example Preparation of methyl (methoxycarbonyl)-1-(phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-4,4,4-trifluorobut-2-enoate 1.54 g of N-[l-(methoxycarbonyl)-1- (phenyl)ethyloxy]acetamide, obtained according to step 2 of Example 9, are dissolved in 20 ml of anhydrous acetonitrile. 2.1 g of methyl (bromomethyl)phenyl]-4,4,4-trifluorobut-2-enoate, obtained according to step 3 of Example 7, and 2.33 g of caesium carbonate are successively added and the reaction medium is maintained at 50 0 C for 7 hours.

After cooling, the caesium salts are filtered off and Sthe medium is concentrated to give 3.2 g of a yellow oil. Chromatography on silica makes it possible to isolate 1.5 g of the expected compound, of (E,Z) stereochemistry, in the form of a yellow oil. Rf 0.19 (3/1 heptane/ethyl acetate).

Example 11: Preparation of methyl (methoxycarbonyl)-1- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-4,4,4trifluorobut-2-enoate In a similar manner to that of the process described in Example 2, 1.15 g of methyl (1-(methoxycarbonyl)-1- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-4,4,4trifluorobut-2-enoate are isomerized in refluxing toluene in the presence of acetic acid. Recrystallization of the crude solid in diisopropyl ether makes it possible to isolate 0.85 g of the expected compound, of stereochemistry, in the form of a white solid.

m.p. 82 0

C.

Example 12: Preparation of (Z)-2,4-dihydro-5-methoxy-2methyl-4-[2-[l-(1-(methoxycarbonyl)-1- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-3H-1,2,4triazol-3-one 1.9 g of N-[1-(methoxycarbonyl)-1- (phenyl)ethyloxy]acetamide, obtained according to step 2 of Example 9, are dissolved in 20 ml of anhydrous Sacetonitrile. 2.39 g of 4-[2-(bromomethyl)phenyl]- 2 4 dihydro-5-methoxy-2-methyl-3H-l,2,4-triazol-3-one and 3.13 g of caesium carbonate are successively added and the reaction medium is refluxed for 2 hours. After cooling, the salts are filtered off and washed with acetonitrile and the organic fractions are then concentrated to give 4.4 g of a yellow oil. By chromatography on silica, 2.21 g of the expected compound, of stereochemistry, are isolated in the form of a yellow oil which gradually crystallizes. m.p.

110 0

C.

Example 13: Preparation of (E)-2,4-dihydro-5-methoxy-2methyl-4-[2-[1-(1-(methoxycarbonyl)-1- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-3H-1,2,4triazol-3-one 2.07 g of (Z)-2,4-dihydro-5-methoxy-2-methyl- 4-[2-[l-(l-(methoxycarbonyl)-l- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-3H-1,2,4triazol-3-one are dissolved in 10 ml of anhydrous toluene. 0.5 ml of acetic acid is added and the reaction medium is refluxed for 52 hours under ultraviolet irradiation. The medium is diluted with ml of toluene, washed with water, dried and concentrated to give 2 g of a yellow oil.

Chromatography on silica makes it possible to isolate 0.17 g of the expected compound, of (E) stereochemistry, in the form of a pale yellow oil which gradually crystallizes. m.p. 110 0

C.

Example 14: Preparation of (E)-N-methoxycarbonyl-Nmethoxymethyl-2-[1-(1- (phenyl)ethyloxyimino)ethyloxymethyl]aniline Step 1: Preparation of (E)-N-methoxycarbonyl-2-[1-(1- (phenyl)ethyloxyimino)ethyloxymethyl]aniline g of N-(l-(phenyl)ethyloxy)acetamide are dissolved in 150 ml of anhydrous acetonitrile. 8.8 g of methyl N-(2-(bromomethyl)phenyl)carbamate and 14.1 g of caesium carbonate are successively added and the reaction medium is refluxed for 2 hours. After cooling, the salts are filtered off and washed with acetonitrile, and the filtrate is concentrated to give 10 g of an orange-coloured oil. Chromatography on silica makes it possible to isolate 1.0 g of the expected compound, of stereochemistry, in the form of a yellow oil. nD 1.5571 (220C) Step 2: Preparation of (E)-N-methoxycarbonyl-Nmethoxymethyl-2-[1-(1- (phenyl)ethyloxyimino)ethyloxymethyl]aniline 0.33 g of potassium tert-butoxide is added to g of (E)-N-methoxycarbonyl-2-[1-(1- (phenyl)ethyloxyimino)ethyloxymethyl]aniline, obtained as above, dissolved in 20 ml of anhydrous tetrahydrofuran. After stirring for 15 min at 200C, 0.32 ml of bromomethyl methyl ether is added and the 0.32 ml of bromomethyl methyl ether is added and the mixture is stirred for 30 min at 20 0 C. The reaction medium is poured into 100 ml of brine, re-extracted with ethyl acetate, washed with water and dried.

Evaporation of the solvents gives 1.2 g of a yellow oil. Chromatography on silica makes it possible to isolate 1.0 g of the expected compound, of (E) stereochemistry, in the form of a yellow oil. nD 1.5402 (120C).

Example Preparation of (E,E)-2-methoxyimino-N-methyl- 2-[2-[l-(l-(carboxyl)-1- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]acetamide 0.27 g of sodium amide is added to 0.88 g of (E,E)-2-methoxyimino-N-methyl-2-[2-[1-(1- (methoxycarbonyl)-l- (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]acetamide, obtained as described in step 5 of Example 9, dissolved in 20 ml of anhydrous N-methylpyrrolidone. The reaction medium is heated at 55 0 C for 3 hours and then poured into 100 ml of water. The pH is brought to 7 by addition of 1N hydrochloric acid and the aqueous phase is re-extracted with ethyl acetate, washed with water and dried over magnesium sulphate. Evaporation of the solvents leaves 0.6 g of a yellow oil. Trituration with the minimum amount of diisopropyl ether gives 0.31 g of the expected compound in the form of a white solid.

m.p. 144 0

C.

Example 16: Preparation of methyl (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]-but-2enoate Step 1: Preparation of methyl (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]but-2enoate 1.1 g of N-(1-(phenyl)ethyloxy)acetamide are dissolved in 50 ml of anhydrous acetonitrile. 1.6 g of methyl (E)-2-[2-(bromomethyl)phenyl]but-2-enoate, prepared according to US 5,416,068, and 2.11 g of caesium carbonate are successively added and the reaction medium is refluxed for 4 hours. After cooling, the medium is filtered through Celite and the Celite is washed with acetonitrile. After concentration, chromatography on silica of the residual oil gives g of the expected compound, of (E,Z) stereochemistry, in the form of a yellow oil. Rf 0.67 (1/1 heptane/ethyl acetate).

Step 2: Preparation of methyl (phenyl)ethyloxyimino)ethyloxymethyl]phenyl]but-2enoate In a similar manner to that of the process described in Example 2, 1.0 g of methyl (1-(phenyl)ethyloxyimino)ethyloxymethyl]phenyl]but-2enoate is isomerized in refluxing toluene in the 77 presence of acetic acid. Evaporation of the solvent leaves 1.0 g of the expected compound, of (E,E) stereochemistry, in the form of a pale yellow syrup.

nD 1.5460 (24 0

C).

Example Bl: in vivo test on Plasmopara viticola (vine mildew): An aqueous suspension of the active material to be tested, having the composition below, is prepared by fine grinding: active material: 60 mg surfactant Tween 80 (polyoxyethylenated derivative of sorbitan oleate) diluted to 10% in water: 0.3 ml acetone: 5 ml completion to 60 ml with water.

This aqueous suspension is then diluted with water so as to obtain the desired concentration in ppm (parts per million).

Cuttings of vine (Vitis vinifera), Chardonnay variety, are cultivated in plant pots. When these plants are 2 months old to 10-leaf stage, 10 to cm in height), they are treated by spraying with the above aqueous suspension.

Plants, used as controls, are treated with an aqueous solution which does not contain the active material.

After drying for 24 hours, each plant is contaminated by spraying with an aqueous suspension of spores of Plasmopara viticola obtained from a 4-5 day old culture, and then placed in suspension at a rate of 100,000 units per cm 3 The contaminated plants are then incubated for two days at about 18 0 C, in an atmosphere of saturated humidity and then for five days at about 22 0 C under 90-100% relative humidity.

Reading is carried out seven days after contamination, by comparison with the control plants.

Under these conditions, good (at least or total protection is observed, at a dose of 5 ppm, with the following compounds: 1, 4, 5 and 9.

Example B2: in vivo test on Puccinia recondita (wheat rust): An aqueous suspension of the active material to be tested, having the composition below, is prepared by fine grinding: active material: 60 mg surfactant Tween 80 (polyoxyethylenated derivative of sorbitan oleate) diluted to 10% in water: 0.3 ml acetone: 5 ml completion to 60 ml with water.

Wheat (Scipion variety) in plant pots, sown Son a 50/50 pozzolana earth peat substrate and maintained at 12 0 C, is treated at the 1-leaf stage (height of 10 cm) by spraying with the above aqueous suspension.

After 24 hours, each plant is contaminated by spraying with an aqueous suspension of spores (150,000 spores per cm 3 of Puccinia recondita. This suspension is obtained from contaminated plants.

The contaminated wheat plants are then incubated for 24 hours at about 201C, in an atmosphere of saturated humidity and then for seven to fourteen days at 60% relative humidity.

Reading is carried out between the 8th and the 15th day after the contamination, by comparison with the control plants.

Under these conditions, good (at least or total protection is observed, at a dose of 40 ppm, with the following compounds: i, 2, 3, 4, 5, 6, 9, 14, and 16.

Example B3: in vivo test on Septoria tritici (septoria disease in wheat): An aqueous suspension of the active material to be tested, having the composition below, is prepared by fine grinding: active material: 60 mg I. .1 surfactant Tween 80 (polyoxyethylenated derivative of sorbitan oleate) diluted to 10% in water: 0.3 ml acetone: 5 ml completion to 60 ml with water.

Wheat (Scipion variety) in plant pots, sown on a 50/50 pozzolana earth peat substrate and maintained at 12 0 C, is treated at the 1-leaf stage (height of 10 cm) by spraying with the above aqueous suspension.

After 24 hours, each plant is contaminated by spraying with an aqueous suspension of spores (500,000 spores per cm 3 of Septoria tritici. The spores are harvested from a seven-day-old culture.

The contaminated wheat plants are incubated for 72 hours at about 20 0 C, in a humid atmosphere and then for twenty days at 90% relative humidity.

Reading is carried out twenty-one days after the contamination, by comparison with the control plants.

Under these conditions, good (at least Sor total protection is observed, at a dose of 40 ppm, with the following compounds: 1, 2, 3, 4, 5, 6, 9, 14 and 16.

Example B4: in vivo test on Septoria nodorum (septoria disease in wheat): An aqueous suspension of the active material to be tested, having the composition below, is prepared by fine grinding: active material: 60 mg surfactant Tween 80 (polyoxyethylenated derivative of sorbitan oleate) diluted to 10% in water: 0.3 ml acetone: 5 ml completion to 60 ml with water.

Wheat (Scipion variety) in plant pots, sown on a 50/50 pozzolana earth peat substrate and maintained at 120C, is treated at the 1-leaf stage (height of 10 cm) by spraying with the above aqueous suspension.

After 24 hours, each plant is contaminated by spraying with an aqueous suspension of spores (500,000 spores per cm 3 of Septoria nodorum. The spores are harvested from a seven-day-old culture.

The contaminated wheat plants are incubated for 72 hours at about 20 0 C, in a humid atmosphere and then for fourteen days at 90% relative humidity.

Reading is carried out fifteen days after the contamination, by comparison with the control plants.

Under these conditions, good (at least or total protection is observed, at a dose of 40 ppm, with the following compounds: 1, 2, 3, 4, 5, 6, 9, 14 and 16.

Example B5: in vivo test on Erisyphe graminis fsp tritici (powdery mildew in wheat): An aqueous suspension of the active material to be tested, having the composition below, is prepared by fine grinding: active material: 60 mg surfactant Tween 80 (polyoxyethylenated derivative of sorbitan oleate) diluted to 10% in water: 0.3 ml acetone: 5 ml completion to 60 ml with water.

Wheat (Audace variety) in plant pots, sown on a 50/50 pozzolana earth peat substrate and maintained at 120C, is treated at the 1-leaf stage (height of cm) by spraying with the above aqueous suspension.

After 24 hours, the wheat plants are sprinkled with spores of Erisyphe graminis, the sprinkling being carried out using diseased plants.

Reading is carried out seven to fourteen days after the contamination, by comparison with the control plants.

Under these conditions, good (at least or total protection is observed, at a dose of 40 ppm, with the following compounds: 1, 2, 3, 4, 5, 9, 11, 14 and 16.

Example B6: in vivo test on Erisyphe graminis fsp hordei (powdery mildew in barley): An aqueous suspension of the active material to be tested, having the composition below, is prepared by fine grinding: active material: 60 mg surfactant Tween 80 (polyoxyethylenated derivative of sorbitan oleate) diluted to 10% in water: 0.3 ml acetone: 5 ml completion to 60 ml with water.

Barley (Express variety) in plant pots, sown Son a 50/50 pozzolana earth peat substrate and II i," 84 maintained at 12°C, is treated at the 1-leaf stage (height of 10 cm) by spraying with the above aqueous suspension.

After 24 hours, the barley plants are sprinkled with spores of Erisyphe graminis, the sprinkling being carried out using diseased plants.

Under these conditions, good (at least or total protection is observed, at a dose of 40 ppm, with the following compounds: 1, 2, 4, 5, 14 and 16.

Example B7: in vivo test on Pyrenophora teres (net blotch in barley): An aqueous suspension of the active material to be tested, having the composition below, is prepared by fine grinding: active material: 60 mg surfactant Tween 80 (polyoxyethylenated derivative of sorbitan oleate) diluted to 10% in water: 0.3 ml acetone: 5 ml completion to 60 ml with water.

This aqueous suspension is then diluted with PAOPER\PDB\45608-97.SPE 29/2/00 water so as to obtain the desired concentration in ppm (parts per million).

Barley (Express variety) in plant pots, sown on a 50/50 pozzolana earth peat substrate and maintained at 120C, is treated at the 1-leaf stage (height of 10 cm) by spraying with the above aqueous suspension.

After 24 hours, each plant is contaminated by spraying with an aqueous suspension of spores (12,000 spores per cm 3 of Pyrenophora teres. This suspension is obtained from contaminated plants.

The contaminated barley plants are then incubated for 24 hours at about 200C, in an atmosphere of saturated humidity and then for seven to fourteen days at 80% relative humidity.

Under these conditions, good (at least 75%) or total 20 protection is observed, at a dose of 40 ppm, with the following compounds: 1, 2, 4, 5, 6, 7, 9, 10, 11, 14, 15 and 16.

Throughout this specification and the claims which 25 follow, unless the context requires otherwise, the word ""omprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

Claims

1. Compounds containing the hydroximic or hydrazonic function, of geneiral formula in which G is chosen from groups G1 to G9: R 5 R4 0a y G1 G2 G3 a a a a a a *aa. a a a a a R 5 0, 4 RSS, ,I R (cN 2 "Y 0hr Rs ~y 92 9 RK N~R 4 G4 G7 G8 in which: n 0 or 1 Q1 is a nitrogen atom or a CH group, Q2 is an oxygen or sulphur atom, Q3 is an oxygen or sulphur atom, Q4 is a nitrogen atom or a group CR,, is an oxygen or sulphur atom or a group NR12, Y is an oxygen or sulphur atom or an amino (NH) or oxyamino (ONH) group; W1 is an oxygen or sulphur atom or a sulphinyl (SO) or sulphonyl (SO 2 group, W2 is an oxygen atom or a group NR 13 p 1 when W2 is an oxygen atom, p 0 or 1 when W2 is a group NR 13 Xi, X 2 and X 3 are, independently of each other, a hydrogen atom, a halogen atom; or a hydroxyl, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulphonyl group; a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl

4- 88 or alkoxysuiphonyl group; or a lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio group; or an amino, N-alkylamino, N,N-dialkylamino, acylamino, aminoalkyl, N-alkylaminoalkyl, N,N- dialkylaminoalkyl or acylaminoalkyl group; or a carboxyl, carbamoyl, N-alkylcarbamoyl, N,N- dialkylcarbamoyl or lower alkoxycarbonyl group; or an acyl group; X4 is a hydrogen atom, a halogen atom; or a lower alkyl, lower haloalkyl, alkoxy or haloalkoxy group; or cyano or nitro radicals, R, and R 2 are, independently of each other, a hydrogen atom, a lower alkyl or lower haloalkyl group, a lower cycloalkyl or lower halocycloalkyl group, an alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl or cyanoalkyl group; or a cyano, acyl, carboxyl, carbamoyl, N-alkylcarbamoyl or N,N-dialkylcarbaroyl group, a lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or alkylthiothiocarbonyl group; or an aminoalkyl, N-alkylaminoalkyl, N,N- K, dia lkylaminoalkyl or acylaminoalkyl group, 89 R, and R 2 together can form a divalent radical, optionally substituted with one or more halogen atoms, or optionally substituted with one or more lower alkyl groups, R 3 is a hydrogen atom, a lower alkyl or lower haloalkyl group, a lower cycloalkyl or lower, halocycloalkyl group, an alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl. or cyanoalkyl group; or a nitro, cyano, acyl, carboxyl, carbarnoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower_ alkoxycarbonyl, ,alkyithiocarbpnyl,. haloalkoxycarbonyl,, alkoxythiocarbonyl, haloalkoxythiocarbonyl or alkyithiothiocarbonyl group; or an alkenyl, alkynyl, N,N-dialkylanino -or N,N- dialkylaxninoalkyl group; or *an optionally substituted phenyl or benzyl group, 20 R 4 is a lower alkyl or lower haloalkyl group, Pa lower cycloalkyl, lower halocycloalkyl or alkoxyalkyl group; or an alkoxy, haloalkoxy, alkylthio, alkylamino ~.or dialkylamino group, R 5 or R 6 is, independently of each other, a a' lower alkyl or lower haloalkyl group, R 7 is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl group, R 8 is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, formyl or acyl group, R 9 is a hydrogen atom, a lower alkyl or lower haloalkyl group or a lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl group, R, is a halogen atom, a lower alkyl' o-r:lower haloalkyl group, a lower cycloalkyl or lower halocycloalkyl group or an alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsuiphinyl, haloalkylsulphinyl, alkylsuiphonyl or haloalkylsulphonyl grouj, Rj and R, 2 are, independently of each other, a hydrogen atom, a lower alkyl or lower haloalkyl group or a lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl group, 3i~L~9R,, is a hydrogen atom, a lower alkyl or lower z\haloalkyl group, a lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl or haloalkylthioalkyl group, an optionally substituted allyl group, an optionally substituted propargyl group or an optionally substituted benzyl group; or an acyl, N-alkylcarbanoyl, N,N- dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or alkylthiothiocarbonyl group; or an alkylsulphonyl, haloalkylsulphobnyl or optionally substituted arylsulphonyl group,- with the restrictions that: when W1 represents a'sulphur' at'oma-,nd W2 represents-a nitrogen atom, then,,R3 -cannorepresent ,alkylthio; when W2 and Q2 are an oxygen atom:. an d' whenri G represents the group G1, then R 5 is other than an* alkyl group, and R' is other than an alkoxy, alkylanino or dialkylamino group, and R 3 is other than a hy drogen, atom, an alkyl or haloalkyij group, a cycldalkyl, or .9 halocycloalkyl group, an alkoxyAlkyl,:-haloalkoxyalkyl, alkylthioalkyl, cyanoalkyl, alkenyl, alkynyl or dialkylaminoalkyl group, or an optionally substituted phenyl or benzyl group, the term "lower alkyl" denoting radicals containing from 1 to 6 carbon atoms, 9999 z=- P:\OPER\PDB\45608-97.SPE 9/3/00 92 as well as the salts, the metal and metalloid complexes and the optical and geometrical isomers of the compounds of formula as have just been defined. 2. Compounds according to claim 1, in which n=O or 1, p 1 and W1 is an oxygen or sulphur atom, W2 is an oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino or allylamino group, Y is an oxygen atom. 3. Compounds according to claim 1 or 2 in which Q2 is an oxygen atom and W1 is an oxygen or sulphur atom, W2 is an oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino or allylamino group, Y is an oxygen atom. o" 4. Compounds according to any one of claim 1 to 3 in which Q3 is an oxygen atom and W1 is an oxygen or sulphur atom, W2 is an oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino or allylamino group, Y is an oxygen atom.

5. Compounds according to any one of claims 1 to 4 in which Q4 is a nitrogen atom and W1 is an oxygen or sulphur atom, W2 is an oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino or allylamino group, Y is an oxygen atom.

6. Compounds according to any one of claims 1 to 5 in which Q5 is an oxygen atom and W1 is an oxygen or sulphur atom, W2 is an oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino or allylamino group, T_ Y is an oxygen atom. 7 ST 7. Compounds according to any one of the preceding P:\OPER\PDB\45608-97.SPE 29/2/00 93 claims, in which Xi, X 2 X 3 and X 4 are, independently of each other, a hydrogen atom, a lower alkyl group, a halogen atom or cyano, trifluoromethyl or methoxy radicals.

8. Compounds according to any one of the preceding claims, in which R, and R 2 are, independently of each other, a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyl, N-alkylaminoalkyl, N,N-dialkylaminoalkyl, acylaminoalkyl, lower alkoxycarbonyl, N-alkylcarbamoyl group, R 3 is a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl or alkoxyalkyl group, R 5 R 6 R, and R 9 are, independently of each other, a lower alkyl or lower haloalkyl group, R 7 is a lower alkyl or lower haloalkyl group, or an allyl or propargyl group, R 1 -is a chlorine atom, a lower alkyl or lower haloalkyl group, or an alkoxy or alkylthio group, R 1 and R 12 are, independently of each other, a lower alkyl, lower haloalkyl, alkoxyalkyl, allyl or propargyl group, R 13 is a hydrogen atom or a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl or benzyl group.

9. Compounds according to one of the preceding claims, in which W1 is an oxygen atom, R is a hydrogen atom or a methyl radical, R 2 is a hydrogen atom or a lower alkyl, cyano, S cyanoalkyl, alkoxyalkyl, N,N-dialkylaminoalkyl, lower alkoxycarbonyl or lower N,N-dialkylcarbamoyl group. S10. Compounds according to any one of the preceding S .claims, in which the substituents W1 and W2 are in a trans position relative to the double bond -C(R 3

11. Fungicidal compositions containing an effective ount of at least one active material according to any one of I: ^f\ P:\OPER\PDB\45608-97.SPE 29/2/00 94 the preceding claims.

12. Fungicidal compositions according to claim 11, comprising, besides the active material of formula agriculturally acceptable solid or liquid supports and/or surfactants which are also agriculturally acceptable.

13. Fungicidal compositions according to either of claims 11 or 12, comprising from 0.05 to 95% by weight of active material.

14. Process for preventively or curatively combating the phytopathogenic fungi of crops, characterized in that an agronomically effective and non-phytotoxic amount of at least one active material or of a fungicidal composition containing an active material of formula as defined in claim 1 is applied to the plant seeds or to the plant leaves or to the soil in which the plants are growing or in'which it is desired to grow them. Process for preventively.or curatively treating plant multiplication products,- as well as the plants resulting therefrom, against fungal diseases, characterized in that the said products are coated with an effective and non-phytotoxic dose of a compound or composition according to any one of the preceding claims.

16. Process according to claim 15, in which rice, cereals, fruit trees, grapevine or beetroot is treated.

17. Process according to either of claims 15 or 16, in *which wheat or barley is treated.

18. Process according to claim 15, in which the seeds of cereals, of potato, of cotton, of pea, of rapeseed, of corn or of flax or the seeds of forest trees are treated. 0

19. Process according to any one of claims 14 to 18, in *0 which the dose of active material applied is between 20 and 200 g of active material per 100 kg of seed, in the case of '4se ed treatments. l20. Process according to any one of claims 14 to 18, in P:\OPER\PDB\45608-97.SPE 29/2/00 which the dose of active material applied is between 10 and 800 g of active material per hectare, in the case of foliar treatments.

21. Process for preparing the compounds according to any one of claims 1 to 10, which comprises placing a-.compound of formula (II)A: X V, G (II)A in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definition as those given in one of claims 1 to 10, X 4 having the same definition as -that given in one of claims 1 to V, is a halogen atom, an alkylsulphonate o:,,or haloalkylsulphonate or an .arylsulphonate group, in contact with a compound of formula H R, X, W3p X P X3 (Il)A W1, W2, Ri, R 2 R 3 R 1 3 X 2 X 3 and p having the-same definition as that given in one of claims 1 to. the benzyl halide derivative of formula (II)A in which Vi is a halogen atom being obtained: by halogenating a compound of formula (II)B: oIoo W,-H (I)B P:\OPER\PDB\45608-97.SPE 29/2/00 96 in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that given in claims 1 to and R 4 is an alkylamino or dialkylamino group, the groups G8 and G9 having the same definition as that given in claims 1 to 10, X 4 having the same definition as that given in claims 1 to 10, and Wi is an oxygen atom, with a halogenating agent or with the lithium halide/mesyl halide/collidine reagent; or by cleaving a compound of formula (II)C: WrP G Mc (II)C in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition, as that given for claims 1 to and R 4 is an alkylamino or dialkylamino group, the groups G8 and G9 having the same definition as that given in claims 1 to 10, X 4 having the same definition as that given in claims 1 to 10, W, is an oxygen atom and p is a protecting group for the alcohol function, with a Lewis acid or anhydrous hydracids.

22. Compounds of formula (III)A: H RI a t R3 R2 ffl )A in which W1, W2, Ri, R2, R3, Xl, X2, X3 and p have the same definition as that given in one of claims 1 to 10, with the exception of compounds in which W2 represent -NR13 and S. compounds in which R3 represents phenyl, benzyl, alkoxy or '\alkylthio. P:OPER\PD\45608-97SPE 29/2/00 97

23. Process for preparing compounds according to one of claims 1 to 10, for which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that given in one of claims 1 to 10 and R 4 is an amino, alkylamino or dialkylamino group or radical, the groups G8 and G9 having the same definition as that given in one of claims 1 to 10, and X 4 having the same definition as that given in one of claims 1 to which comprises placing a compound of formula (II)B: O WT G (U)B in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that given in one of claims 1 to 10 and R 4 is an amino,. alkylamino or dialkylamino group or radical, the groups G8 and G9 having the same definition as that given :in one of c 2 dlaimis: 'o 10, X having the same definition as that given in one of claims 1 to and W1 is an oxygen or sulphur atom, in contact with a compound of formula (III)B: X1 W2, R1, R2, R3, R13, X1, X2, X 3 and p having the same definition as that given in one of claims 1 to 10, U3 being a :.::logen atom, it being possible for the double bond U3 C(R3)=N-W 2 to be of or. stereochemistry. RR I4 S24. Process for preparing compounds accord(II)B claims 1 to 10, for which G is a group G3, Q2 being an oxygen 2 atom, R 4 being an alkoxy, alkylamino or dialkylamino group, he other substituents having the same definition as that SW2, e other substituents, X, X, X and p ha ving the same defi P:OPER\PDB\45608-97SPE 2912/00 98 given in one of claims 1 to 10, and R 6 is a lower alkyl or lower haloalkyl group, which comprises placing a compound of formula (IX): X 1 X4 WWN X3. R 4 R 3 P- 0 (IX) in which R 4 is an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given in one of claims 1 to in contact with a Wittig-Horner reagent of formula (X)A: R 6 -CH 2 -P (ORb)2 (X)A R 6 being a lower alkyl or lower haloalkyl group, Rb being a lower alkyl, 'phenyl or benzyl group, or alternatively with a Wittig reagent of formula. (X)B: R 6 -CH 2 -P(Rd) 3; Hal- (X)B R 6 being a lower alkyl or lower haloalkyl group, Rd being an optionally substituted phenyl group, Hal- being a Shalide ion. A

25. Process for preparing compounds.according to one of claims 1 to 10, for which G is a group Gl or G2, Q1 being a nitrogen atom or a CH group, Q2 being an oxygen atom, R 4 being an alkoxy, alkylamino or dialkylamino group, the other substituents having the same definition as that given in one e of claims 1 to 10 and R 5 is a lower haloalkyl group, which c comprises placing a compound of formula (XI): S P:\OPER\PDB\45608-97.SPE 29/2/00 r in which T is an oxygen atom and M is an "alkali metal or alkaline-earth metal ion, Q1 being a nitrogen atom or a CH group, R 4 being an alkoxy, alkylamino or dialkylamino group and Wl, W2, Ri, R 2 R 3 R 1 3 X 2 X 3 .X 4 and p having the same definition as that given inone of claims 1 to in contact with a halogenated compound of formula CHq(Hal)4_q in which q=l or 2 and Hal denotes halogen atoms which may be identical to or different from each other and at least one of which is a chlorine or bromine atom.

26. Process for preparing compounds according to one of claims 1 to 10, for which G is a group G4 in whi jh Ir Q2 being an oxygen atom, R4 being :an ,kalkoxyi aiky;lam.ino,:o dialkylamino-group, the other substituets- having theK same definition as that given in one of claims 1 to: 10, which comprises reacting a compound of formula (XII)A: Hf y R2 o HN R. R 3 "r O o 0(XII)A in which R 4 is an alkoxy, alkylamino or dialkylamino 0. group, the other substituents having.the same definition as that given for formula with a reagent of formula (XIII): d finition as that given in one of claims 1 to 'i P:\OPER\PDB\45608-97.SPE 29/2/00 100

27. Process for preparing the compounds according to one of claims 1 to 10, for which G is a group G1 to G7 and R 4 is an alkylamino or dialkylamino group, the other substituents having the same definition as that given in one of claims 1 to which comprises placing a compound of general formula for which G is:a group G1 to G7 and R 4 is an alkoxy or alkylthio group, the other.substituents having the same definition as that given in one of claims 1 to in contact with an alkylamine or dialkylamine.

28. Process for preparing the compounds according to one of claims 1 to 10, for which W1 is a sulphoxide (SO) or sulphone (SO 2 group and G being one of the groups GI, G3, G4 and G6 to G9, Q2 and Q3 being an oxygen atom, the other substituents having the same definition as that given in one of claims 1 to which comprises oxidizing the compounds of general formula for which Wi is a sulphur .atom, G being one of the groups Gl, G3, G4 and G6 to G9, Q2 and Q3 being an oxygen atom, the other substituents having the same definition as that given in one of claims 1 to 10, using one or more equivalents of an oxidizing agent.

29. Process for preparing the compounds according to one of claims 1 to 10, in which the groups Wl, W2, Ri, R 2 R 3 Xi, X 2 X 3 X 4 and p have the 4ame meaning as in one of claims 1 to 10 and G is a group G7, which comprises placing the intermediates of formula (III)A: (II)A a.. P:\OPER\PDB\45608-97.SPE 29/2/00 101 in which the groups W1, W2, R 1 R 2 R 3 R 13 Xi, X 2 X 3 and p have the same meaning as in one of claims 1 to in contact with a compound of general formula-(II)A: ^OV, 0 G(II)A for which G is a group G7, X 4 having the same definition as that given in one of claims 1 to 10 and V 1 is a halogen atom. Process for preparing the compounds according to one of claims 1 to 10, in which the groups W1, W2, R 1 R 2 R 3 Xi, X 3 X 4 and p have the same meaning as in one of claims 1 to 10 and G is a group G3, and R .is a trifluoromethyl. radical, which comprises placing the compounds of formula (III) A:- (UII)A in which the groups Wi, W2, RI, R 2 R 3 R 13 Xi, X 2 X 3 and p have the same meaning as irnone of claims 1 to in contact with a compound of general formula (II)A: NX W G (II)A cfor which G is a group G3, R 6 is a trifluoromethyl radical, X 4 R 4 and Q2 having the same definition as that given in one of claims 1 to 10 and Vi is a halogen atom.

31. Process for preparing the compounds of formula S(I according to claim 22, in which W2 is an oxygen atom P:\OPER\PDB\45608-97.SPE 29/2/00 102 and p=l, Wi, Ri, R 2 R 3 R 13 X 1 X 2 and X 3 having the same definition as that given in one of claims 1 to 10, which comprises placing a compound of formula (IV): xl H 2 R, X (IV) W2, R 1 R 2 R 13 Xi, X 2 X 3 and p having the same definition as that given in one of claims 1 to in contact with a compound of formula R3 (v) W1 and R3 having the same definition as that given in -one of claims- 1 to 10, Ul i.s a halgoen^atom ;:ora hydroxyl, lower alkoxy or benzyloxy, lower alkylthio or amino radical, or a group -O(C=O)Ra, Ra having the same definition as that of R3 given in one of claims 1 to 10 and being identical to or different from R 3 the compound of formula. then being an acid halide.

32. Process for preparing the compounds of formula (III)A, according to claim 22, in which W2 is an oxygen atom and p=l, or the hydrazonic acids of formula (III)A in which W2 group NR,3 and p=l, Wl, Ri, R 2 R 3 R 13 X 1 X 2 and X 3 having the same definition as that given in one of claims 1 to which comprises placing a compound of formula (VI): X, 1 P:\OPFR\PDB\45608-97.SPE 2912/00 103 R 1 R 2 X 1 ,I X 2 and X 3 having the same definition as that given in one of claims 1 to 10, and U 2 is a halogen atom or an alkylsuiphonate group, in contact with a hydroxarnic acid derivative, in which W.2 is an oxygen atom, or a hydrazonic acid derivative 'in .which W2 is a group NR 13 R 3 and R 13 having the same definition as that given in one of claims 1 to 10, of formula (VI H OY W 2 -H (V11)

33. A compound according to claim 1 or 22;-substantially as hereinbefore described.

34. A composition according to claim 11 substantially as hereinbefore described.- A preventative or curativ possacording to any on'fc1is4 or 15 substantially '-ashe ei'bef'oe described.

36. A process for preparing compounds according tany one of claims 21, 23-32 substantially as hereinibefore described. DATED this 29th day of February 2000 Rhone-Poulenc Agro BI~its Patent Attorneys DAVIES COLLISON CAVE SSS S S S S. S *5 5*55 S S. 'IS S S 'S SS .5 S z -A 'p2' OE~