EP1021399A2 - Fungicides with hydroximic and hydrazonic groups - Google Patents

Abstract

The invention concerns fungicidal compounds, and compositions containing them, of general formula (I) in which G is selected from the groups G1 to G9: (a) in which the different symbols represent various organic groups. The invention also concerns a method for treating plants using these compounds.

Description

 Hydroximic and hydrazonic fungicides

The present invention relates to new compounds comprising a hydroximic or hydrazonic function, their use as fungicides, in particular in the form of a fungicidal composition, a process for controlling phytopathogenic fungi in crops using these compounds or compositions. The derivatives comprising a hydroximic function used for the control of phytopathogenic fungi in cultures are known in particular from patents EP 463 488 and EP 370 629.

An object of the present invention is therefore to propose a new family of compounds comprising the hydroximic or hydrazonic function useful as fungicides.

Another object of the present invention is to provide a new family of compounds comprising the hydroximic or hydrazonic function having a broad spectrum of action on phytopathogenic fungi in crops. Another object of the present invention is to provide a new family of compounds comprising the hydroximic or hydrazonic function having a broad spectrum of action on phytopathogenic fungi of cultures making it possible to solve the specific problems encountered.

Another object of the present invention is to provide a new family of compounds comprising the hydroximic or hydrazonic function having a broad spectrum of action improved on phytopathogenic fungi of cultures.

Another object of the present invention is to provide a new family of compounds comprising the hydroximic or hydrazonic function having a broad spectrum of action improved on phytopathogenic fungi of crops such as rice, cereals, fruit trees, vines and beet.

It has been found that these objects can be achieved, in whole or in part, by the compounds described in the present invention. General definition of the invention:

The invention relates to compounds comprising the hydroximic or hydrazonic function of general formula (I):

in which G is chosen from the groups Gl to G9

Gl G2 G3

G4 G5 G6

G7 G8 G9

where n = 0 or 1

Ql is the nitrogen atom or the CH group, Q2 is the oxygen or sulfur atom, Q3 is the oxygen or sulfur atom, Q4 is the nitrogen atom or the group CR] \. Q5 is the oxygen or sulfur atom or the group NR] 2,

Y is the oxygen or sulfur atom or the amino (NH) or oxyamino (ONH) group

Wl is the oxygen or sulfur atom or the sulfinyl (SO) or sulfonyl (SO2) groups,

W2 is the oxygen atom or the NR13 group,

p = 1 when W2 is the oxygen atom, p = 0 or 1 when W2 is the group NR13.

X], X2, X3 are, independently of each other, a hydrogen atom, a halogen atom; or a hydroxy, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl group; a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyle, alkylthioalkyle, haloalkylthioalkyle, cyanoalkyle, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl; or a lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio group; or an amino, N-alkylamino, N, N-dialkylamino, acylamino, aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl group; or a carboxy, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl group; or, an acyl group;

X4 is a hydrogen atom, a halogen atom; or a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy group; or the cyano, nitro, R-, R2 are, independently of each other, a hydrogen atom, a lower alkyl group, lower haloalkyl, a lower cycloalkyl group, lower halocycloalkyl, an alkoxyalkyl group, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; or a cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl group, a lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthio-thiocarbonyl group; or an aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl group

R] and R2 may together form a radical which is equal to an alkylene group, optionally substituted by one or more halogen atoms, optionally substituted by one or more lower alkyl groups,

R3 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkvle, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; or a nitro, cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N.N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxy-carbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl group; or an alkenyl, alkynyl, N, N-dialkylamino, N, N-dialkylaminoalkyl group; or an optionally substituted phenyl or benzyl group,

R4 is lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl; or an alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino group,

R5, R is independently of each other a lower alkyl, lower haloalkyl group, R7 is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxvalkyle, alkenyl, alkynyl group,

Rg is a lower alkyl, lower haloalkyl, alkoxyalkyl group. haloalkoxyalkyle, alkenyl, alkynyle, formyle, acyle,

R9 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,

RjO ^{is a} halogen atom, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl. haloalkylsulfonyl,

R-, R] _2 ^are independently of each other hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,

R] _3 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, optionally substituted allyl group, optionally substituted propargyl group, benzyl group optionally substituted; or an acyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl group; or an optionally substituted alkylsulfonyl, haloalkylsulfonyl, arylsulfonyl group,

provided that: when W2 and Q2 are the oxygen atom and G represents the group Gl, then R5 is other than an alkyl group, and R4 is other than an alkoxy group, alkylamino, dialkylamino, and R3 is other than hydrogen, alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, cyanoalkyl, alkenyl, alkynyl, dialkylaminoalkyl, or phenyl or benzyl possibly substituted.

as well as the salts, the metallic and metalloid complexes of the compounds of formula (I) as just defined.

In the text of the present invention, the designation "hydroximic group" includes both the strict "hydroximic group" (with the O-C = N-O sequence) and the "thiohydroximic group" (with the S-C = N-O sequence). Likewise, the designation "hydrazonic group" includes both the strict "hydrazonic group" (with the O-C = N-N sequence) and the "thiohydrazonic group" (with the S-C = N-N sequence).

In addition, the following generic terms are used with the following meanings:

- the halogen atom means the fluorine, chlorine, bromine or iodine atom,

- the adjective "lower" qualifying an organic radical, means that this radical has from 1 to 6 carbon atoms, with the exception of the cycloalkyl radical where the adjective "lower" means from 3 to 6 carbon atoms,

- the alkyl radicals may be linear or branched, - the halogenated alkyl radicals may contain one or more identical or different halogen atoms,

the acyl radical signifies alkylcarbonyl, or cycloalkylcarbonyl,

- the lower adjective qualifying the term acyl applies to the alkyl or cycloalkyl part of this radical, - the alkylene radical denotes the radical - (CH2) _m - where m = 2 to 5,

- when the amino radical is disubstituted, the two substituents can constitute a saturated or unsaturated nitrogen heterocycle, of 5 or 6 atoms,

- When the carbamoyl radical is disubstituted, the two substituents can constitute a saturated or unsaturated nitrogen heterocycle, of 5 or 6 atoms. Preferred embodiments of the invention are those in which the products of formula (I) also have one and / or the other of the following characteristics, taken individually or in combination:

n = 0 or 1 p ^≈ l

Q2 is the oxygen atom, and / or Q3 is the oxygen atom, and / or Q4 is the nitrogen atom, and / or Q5 is the oxygen atom; Wl is the oxygen or sulfur atom

W2 is the oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino, allylamino group, Y is the oxygen atom,

X], X2. X3 and X4 are independently of each other a hydrogen atom, a lower alkyl group, a halogen atom, or the cyano, trifluoromethyl, methoxy,

R} and R2 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, N, N- dialkylcarbamoyle,

R3 is a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl group, preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl, methoxymethyl radical, R4 is a lower alkyl, alkoxy, alkylamino, dialkylamino group, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino radical. ethylamino,

R5, Rg, Rg and R9 are, independently of each other, a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl, radical.

R7 is a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl, an allyl, propargyl group, Rj O is a chlorine atom, a lower alkyl group, lower haloalkyl, preferably methyl, an alkoxy, alkylthio group, preferably methoxy, methylthio,

R] i and R] 2 are, independently of one another, a lower alkyl, lower haloalkyl, alkoxyalkyl, allyl, propargyl,

R 3 is hydrogen, lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl, benzyl.

Among the preceding variants, the following variants will be chosen more particularly taken in isolation:

Wl is the oxygen atom,

R is the hydrogen atom or the methyl radical,

R2 is a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N.N-dialkyl-carbamoyl group,

Even more particularly preferred compounds are those where the substituents W1 and W2 are in the trans position (see below) relative to the double bond -C (R3) = N-.

The compounds of general formula (I) and the compounds which may be used as intermediates in the preparation processes, and which will be defined when describing these processes, may exist in one or more forms of geometric isomers depending on the number of double bonds of the compound. The compounds of general formula (I) where G is the group G1, G2 or G3 may contain four different stereoisomers denoted (E, E), (E, Z), (Z, E), (Z, Z) 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. We will refer in particular to the work of E.Eliel and S. Wilen "Stereochemistry of Organic Compounds" Ed. Wiley (1994) for the description and the use of these notations.

By convention, in the case of the present invention, the designations (E, E), (E, Z), (Z, E) 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 (I) where G is the group G4 to G9 can comprise two different stereoisomers denoted (E) or (Z) depending on the configuration of the hydroximic or hydrazonic group.

The compounds of general formula (I) and the compounds which may be used as intermediates in the preparation processes, and which will be defined when describing these processes, may exist in one or more forms of optical isomers or chiral depending on the number of asymmetric centers of the compound. The invention therefore relates to all the optical isomers as well as their racemic mixtures and the corresponding diastereoisomers as a mixture or as separate. The separation of diastereoisomers and / or optical isomers can be carried out according to methods known per se (E.Eliel ibid.).

Preparation processes:

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

The preparation of the reagents used in either of the general preparation methods is usually known per se and is usually described specifically in the prior art or in such a manner that one skilled in the art can '' adapt to the desired goal. The prior art which can be used by those skilled in the art to establish the conditions for the preparation of the reagents, can be found in numerous general works of chemistry such as "Advanced Organic Chemistry" by J. March, Ed. Wiley (1992), "Methoden der organischen Chemie" (Houben- Weyl), Ed. Georg Thieme Verlag or the "Chemical Abstracts" Ed. American Chemical Society as well as in computer databases accessible to the public. Method A:

The compounds of general formula (I) 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 bringing a compound of formula (IDA:

in which G is one of the groups Gl to G9, the groups Gl to G9 having the same definition as those indicated for the formula (I), X4 having the same definition as that indicated for the formula (I),

Vi is a halogen atom (preferably chlorine or bromine), an alkylsulfonate or haloalkylsulfonate group (preferably methylsulfonate or trifluoromethylsulfonate), arylsulfonate (preferably 4-methylphenylsulfonate),

with a compound of formula (III) A:

(III) A

W1, W2, R], R2, R3, R13, X], X2, X3 and p having the same definition as that indicated for formula (I), in the presence of an organic or inorganic base, in the absence or in the presence of a solvent. The reaction is generally carried out at a temperature between - 80 ° C and 180 ° C (preferably between 0 ° C and 150 ° C) or at the boiling point of the solvent used. The suitable solvent for this reaction can be an aliphatic hydrocarbon such as pentane, hexane, heptane, octane; an aromatic hydrocarbon such as benzene, toluene, xylenes, halobenzenes; an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane; a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane; an ester such as methyl acetate, ethyl acetate, a nitrile such as acetonitrile, propionitrile, benzonitrile; a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolyleneurea, dimethylsulfoxide; or water. Mixtures of these different solvents can also be used.

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

As organic or inorganic base suitable for this reaction, mention may be made of alkali and alkaline earth metal hydroxides such as sodium, potassium, cesium or calcium hydroxide; alkali and alkaline earth alcoholates such as potassium ter-butoxide, alkali and alkaline earth hydrides, such as sodium, potassium or cesium hydride; alkali and alkaline earth metal carbonates and bicarbonates such as sodium, potassium, calcium carbonate or sodium, potassium or calcium bicarbonate; organic bases, preferably nitrogen, such as pyridine, alkylpyridines, alkylamines such as trimethylamine, triethylamine or diisopropylethylamine, aza derivatives such as 1.5-diazabicyclo [4.3.0] non-5-ene or l, 8 -diazabicyclo [5.4.0] undec-7-ene.

There is no strict limitation for the relative proportions of the compounds of formula (II) A and of formula (III) A. It is however advantageous to choose a molar ratio (III) A / (II) A of between 0.1 and 10, preferably 0.5 to 2.

According to the conditions used, the compounds of general formula (I) are obtained in the form of a variable mixture of isomers (E) and (Z) or of a single isomer (E) or of a single isomer (Z) depending on the configuration of the hydroximic or hydrazonic group. If necessary, the compounds of general formula (I) and of configuration (E) or (Z) depending on the configuration of the hydroximic or hydrazonic group, can be isolated and purified according to methods known per se such as for example extraction, crystallization or chromatography. The hydroxamic or thiohydroxamic acids of formula (III) A where W2 is the oxygen atom and p = 1 or the hydrazonic or thiohydrazonic acids of formula (III) A where W2 is the group NR13 and p = 0 or 1, Wl , R], R2, R3, Ri 3, Xj, X2, X3 having the same definition as that indicated for formula (I), can be obtained by a process consisting in bringing a compound of formula (IV) into contact:

(IV)

W2. R], R2, R13, Xl, X2 _> X3 and p having the same definition as that indicated for formula (I), with a compound of formula (V):

W _t -U,

(V)

Wl, R3 having the same definition as that indicated for formula (I), Ul is a halogen atom (preferably chlorine or bromine), or a hydroxy, lower alkoxy or benzyloxy, lower alkylthio, amino, or the group - 0 (C = 0) R _a . R _a having the same definition as that of R3 indicated for formula (I) and being identical to R3 or different, preferably a halogen atom, the compound of formula (V) then being an acid halide.

Condensation between the compound of formula (IV) and compound of formula (V) is carried out in the presence of an organic or inorganic base, or of a dehydration reagent such as anhydrides of carboxylic acids, preferably acetic anhydride or propionic anhydride, in the absence or in the presence of a solvent. The general conditions of condensation between the compound of formula (IV) and compound of formula (V) are similar or identical to the conditions of condensation between the compound of formula (II) A and 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 where W2 is the oxygen atom and p = 1 or the hydrazonic acids of formula (III) A where W2 is the group NR13 and p = 1, Wl, R], R2, R3, R13, X], X2, X3 having the same definition as that indicated for formula (I), can also be obtained by a process consisting in bringing a compound of formula (VI) into contact:

R], R2, X], X2, X3 having the same definition as that indicated for formula (I), and U2 is a halogen atom (preferably chlorine or bromine), an alkylsulfonate group (preferably methylsulfonate or trifluoromethylsulfonate ), with a hydroxamic acid derivative where W2 is the oxygen atom or a hydrazonic acid derivative where W2 is the group NR13, R3 and R13 having the same definition as that indicated for formula (I), of formula (VII):

H

IW ₂ -H

Ra

(SEEN)

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 absence or in the presence of a solvent.

The general conditions of condensation between the compound of formula (VI) and compound of formula (VII) are similar or identical to the conditions of condensation between the compound of formula (II) A and compound of formula (III) A and are known per se according to "Houben-Weyl" volume E5, pages 1148-1149. The compounds of formula (IV), formula (V), formula (VI) and formula (VII), Wl, W2. Rj, R2, R3, Ri 3, X], X2. 3 and p having the same definition as that indicated for formula (I), Uj and U2 having the same definition as that indicated in method A can be prepared according to methods known per se.

The compounds of formula (II) A in which G is one of the groups Gl to G9, the groups Gl to G9 having the same definition as that indicated for formula (I), X4 having the same definition as that indicated for the formula (I) and V] is a halogen atom (preferably chlorine or bromine), an alkylsulfonate group (preferably methylsulfonate or trifluoromethyl-sulfonate), arylsulfonate (preferably 4-methylphenylsulfonate), will be by convention, for the following of the description of the preparation methods, designated by the generic term "benzyles halide derivatives".

The benzyl halide derivatives of formula (II) A where Vj is a halogen atom (preferably chlorine or bromine) can be obtained by halogenation of a compound of formula (VIII):

in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definition as that indicated for the formula (I), X4 having the same definition as that indicated for the formula (I).

The halogenation of the compound of formula (VIII) can be carried out by radical, thermal or photochemical route, the various processes not being mutually exclusive, with an N-haloacetamide such as N-bromosuccinimide, N-chlorosuccinimide , N-bromoacetamide, in an inert solvent such as benzene or carbon tetrachloride or in the absence of a solvent with or without a free radical initiator at a temperature of 20 ° C to 170 ° C, preferably 80 ° C at 100 ° C according to J. March ibid. pages 689-697. The benzyl halide derivatives of formula (II) A where V \ is a halogen atom (preferably chlorine or bromine) can also be obtained by halogenation of 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 indicated for formula (I) and R4 is the group alkylamino, dialkylamino, the groups G8 and G9 having the same definition as that indicated for formula (I), X4 having the same definition as that indicated for formula (I), Wj is the oxygen atom, with a halogenating agent such as thionyl chloride, phosphorus oxytrichloride , 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 where Vj is a halogen atom (preferably chlorine or bromine) can also be obtained by cleavage of a compound of formula (II) C:

in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that indicated for formula (I) and R4 is the group alkylamino, dialkylamino, the groups G8 and G9 having the same definition as that indicated for formula (I), X4 having the same definition as that indicated for formula (I), W] is the oxygen atom, and P is a protecting group for the alcohol function as an ester preferably acetic or benzoic, or an ether preferably methyl, methoxymethyl, phenyl, benzyl, (we will refer advantageously to the work "Protective Groups in Organic Synthesis" by W. Greene and P.Wuts, Ed. Wiley (1991) for the choice and preparation of said protective groups), with a Lewis acid such as boron tribromide, or anhydrous hydracids such as hydrogen chloride. This cleavage reaction is known in particular according to patent EP 525516

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 known per se. These different methods or the related prior art will be explained in methods J, K and L.

Method B:

The compounds of general formula (I) for which G is one of the groups

Gl to G9, the groups Gl to G7 having the same definition as that indicated for formula (I) and R4 is the group or radical amino, alkylamino, dialkylamino. the groups G8 and G9 having the same definition as that indicated for the formula (I), X4 having the same definition as that indicated for the formula (I), can be obtained by a process consisting in bringing 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 indicated for formula (I) and R4 is the group or radical amino, alkylamino, dialkylamino, the groups G8 and G9 having the same definition as that indicated for formula (I), X4 having the same definition as that indicated for formula (I), and Wi is the oxygen or sulfur atom,

with a compound of formula (III) B:

(III) B W2, Ri, R2, R3, R] 3, X}, X2, X3 t P having the same definition as that indicated for formula (I), U3 being a halogen atom preferably an atom of chlorine, the double bond U3-C (R3) = N-W2- can be of stereochemistry (E) or (Z).

This reaction is carried out in the presence of an organic or inorganic base, in the absence or in the presence of a solvent. The reaction is generally carried out at a temperature between - 80 ° C and 180 ° C (preferably between 0 ° C and 150 ° C) or at the boiling point of the solvent used. The solvent suitable for this reaction can be an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, a nitrile such as acetonitrile, propionitrile, benzonitrile, a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimé hylprolylène urea, or dimethylsulfoxide. Mixtures of these different solvents can also be used.

The reaction time depends on the conditions used and is generally between 0.1 to 48 h. As organic or inorganic base suitable for this reaction, mention may be made of hydrides of alkali and alkaline earth metals, such as sodium, potassium or cesium hydride, alcoholates of alkali and alkaline earth metals, such as tert-butoxide of potassium.

There is no strict limitation for the relative proportions of the compounds of formula (II) B and of formula (III) B. It is however advantageous to choose a molar ratio (III) B / (II) B of between 0.1 and 10, preferably 0.5 to 2.

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

The compounds of general formula (III) B are prepared according to methods known per se, 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 where Wl is the sulfur atom and W2 is the oxygen atom or the thiohydrazonic acids of formula (III) A where Wl is the sulfur atom and W2 is the group NR13 , Ri, R2, R3, R13, X \, X2, X3 and p having the same definition as that indicated for formula (I), are also the object of the present invention.

They can be obtained by thionation of the hydroxamic acids of formula (III) A where Wl is the oxygen atom and W2 is the oxygen atom or the hydrazonic acids of formula (III) A where Wl is the atom d oxygen and W2 is the group NR13, Ri, R2, R3, R13, X], X2, X3 and p having the same definition as that indicated for formula (I), with thionating agents such as phosphorus pentasulfide or the Lawesson reagent in a manner identical or similar to the methods described in "Houben-Weyl" volume E5, pages 1279-1280 and Synthesis (1984), 829.

Method D:

The compounds of general formula (I) for which G is the group G3, Q2 being the oxygen atom, R4 being the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for the formula (I ) and R _fj is a lower alkyl or lower haloalkyl group, can be obtained by a process consisting in bringing a compound of formula (IX) into contact:

(IX)

in which R4 is the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for formula (I), with a Wittig-Horner reagent of formula (X) A:

R ₆ -CH ₂ -P (= O) (OR _b ) ₂ (X) A

Rβ being a lower alkyl or lower haloalkyl group, R ^ being a lower alkyl, phenyl or benzyl group,

or with a Wittig reagent of formula (X) B:

R ₆ -CH ₂ -P (R _d ) 3 ⁺ ; Hal "(X) B

Rβ being a lower alkyl or lower haloalkyl group, R ^ 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 or alkaline earth alcoholates, preferably sodium ethylate, sodium methylate or potassium tert-butoxide, hydrides of alkali and alkaline earth metals, preferably sodium or potassium hydride, of an organometallic derivative such as alkyllithians, preferably butyllithium, alkylmagnesium halides or lithium diisopropylamide in an aprotic solvent such as ethers, preferably diethyl ether or tetrahydrofuran at a temperature of - 78 ° C to 50 ° C preferably - 70 ° C to 20 ° C according to J.March ibid, pages 956-963 or patent WO 9529896.

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

Method E

The compounds of general formula (I) for which G is the Gl or G2 group, Ql being the nitrogen atom or the CH group, Q2 being the oxygen atom, R4 being the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for formula (I) and R5 is a lower haloalkyl group, can be obtained by a process consisting in bringing a compound of formula (XI) into contact:

(XI)

in which T is the oxygen atom and M is an alkaline or alkaline earth ion, Ql being the nitrogen atom or the CH group, R4 being the alkoxy, alkylamino, dialkylamino, Wl, W2, Rj, R, R3 group , R13, Xj, X2, X3, X4 and p having the same definition as that indicated for formula (I), with a halogen compound of formula CHq (Hal) 4_q where q = 1 or 2 and Hal denotes the atoms of halogens identical or different to each other and one of which at least is the chlorine or bromine atom, in a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dime hylprolylene urea, or well dimethyl sulfoxide in the presence or not of a catalytic amount of iodide ion, at a temperature between - 20 ° C and 250 ° C preferably 25 ° C to 150 ° C or at reflux of the solvent. This reaction is described in particular in patents DE 4424788 and WO 9606072.

The compounds of formula (XI) in which T is the oxygen atom and M an alkaline or alkaline-earth ion, Ql being the nitrogen atom, R4 being the alkoxy, alkylamino, dialkylamino, Wl, W2 group, R, R, R3, R13, X \. X2, X3, X4 and p having the same definition as that indicated for formula (I), can be easily obtained from the compounds of formula (IX), in which R4 is the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for formula (I), by the action of hydroxylamine and of a base according to J. March ibid. pages 906-907.

The compounds of formula (XI) in which T is the oxygen atom and M an alkaline or alkaline-earth ion, Ql being the group CH, R4 being the group alkoxy, alkylamino, dialkylamino, Wl, W2, R \, R, R3, R 3, X \, X2, X3, X4 and p having the same definition as that indicated for formula (I) can in particular be prepared in a manner similar to patent EP 176826. Method F:

The compounds of general formula (I) for which G is the group G4 in which n = 1, Q2 being the oxygen atom, R4 being the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for formula (I), can be obtained by reaction between a compound of formula (XII) A:

(XII) A

wherein R4 is the alkoxy group. alkylamino, dialkylamino, the other substituents having the same definition as that indicated for formula (I), with a reagent of formula (XIII):

V, ORs

(XIII)

in which W \ is a halogen atom (preferably chlorine or bromine), R5 having the same definition as that indicated for formula (I), by the action of one or more base equivalents such as the hydroxides of alkali metals or alkaline earth, alkali or alkaline earth alcoholates, alkali and alkaline earth hydrides, carbonates and bicarbonates of alkali or alkaline earth metals, optionally in the presence of a phase transfer catalyst such as quaternary ammonium, in a solvent aprotic such as ethers preferably diethyl ether or tetrahydrofuran at a temperature of -78 ° C to 40 ° C preferably between -20 and 25 ° C.

The compounds of general formula (XII) A, in which R4 is the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition than that indicated for formula (I), can be obtained by reaction of a compound of general formula (XII) B

in which R4 is the alkoxy, alkylamino, dialkylamino, X4 group having the same definition as that indicated for formula (I),

V1 is a halogen atom (preferably chlorine or bromine), an alkylsulfonate group (preferably methylsulfonate or trifluoromethylsulfonate), arylsulfonate (preferably 4-methylphenylsulfonate),

with a compound of formula (III) A, Wl, W2, Rj, R2, R3, R 3, X], Xi, X3, and p having the same definition as that indicated for formula (I).

The general conditions of condensation between the compound of formula (XII) B and the compound of formula (III) A are similar or identical to the conditions of 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 reference EP 498396.

Method G:

The compounds of general formula (I) for which G is the group G 1 to G7 and R4 is the alkylamino or dialkylamino group, the other substituents having the same definition as that indicated for formula (I), can be obtained by a process consisting in bringing into contact a compound of general formula (I) for which G is the group G1 to G7 and R4 is the alkoxy or alkylthio group, the other substituents having the same definition as that indicated for formula (I), with an alkylamine or dialkylamine, preferably methylamine, in an alcoholic solvent such as methanol, ethanol, propanol or isopropanol, at a temperature of - 50 ° C to 100 ° C or at the boiling point of the chosen solvent . It is generally advantageous to use an excess of 1 to 5 equivalents, preferably 1.1 to 2 equivalents of alkyl or dialkylamine relative to the compound of general formula (I) for which G is the group G1 to G7 and R4 is the alkoxy or alkylthio group, the other substituents having the same definition as that indicated for formula (I). Method H:

The compounds of general formula (I) for which W1 is the sulfoxide (SO) or sulfone (SO2) group and G being one of the groups Gl, G3. G4, G6 to G9, Q2 and Q3 being the oxygen atom, the other substituents having the same definition as that indicated for formula (I), can be obtained by oxidation of the compounds of general formula (I) for which Wl is the sulfur atom, G being one of the groups Gl, G3, G4, G6 to G9, Q2 and Q3 being the oxygen atom, the other substituents having the same definition as that indicated for the formula (I ), using one or more equivalent of an oxidizing agent such as organic peroxides, preferably peracetic acid, 3-chloroperbenzoic acid, mineral peroxides, hydroperoxides such as hydrogen peroxide, oxychlorides minerals or oxygen, in the presence or absence of a catalyst in an inert solvent according to J. Mardi ibid. pages 1201-1203. Method I:

The compounds of general formula (I) prepared according to method A or method B can be obtained with the atoms or groups Wl and W2, Wl and W2 having the same meaning as for formula (I), in the cis position (see more top) with respect to the double bond -C (R3) = N- (hydroximic or hydrazonic group).

The isomers of general formula (I) with the atoms or group Wl and W2 in the trans position with respect to the double bond -C (R3) = N- (hydroximic or hydrazonic group) can be prepared from the cis isomers by heating in a solvent preferably under ultraviolet irradiation, with or in the absence of 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 between 0 ° C and the boiling point of the solvent. The suitable solvent for this reaction can be an aliphatic hydrocarbon such as pentane, hexane, heptane, octane; an aromatic hydrocarbon such as benzene, toluene, xylenes, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane; a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane; an ester such as methyl acetate, ethyl acetate; a nitrile such as acetonitrile, propionitrile, benzonitrile; an alcohol such as methanol, ethanol, propanol, isopropanol; a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolylene urea, dime hylsulfoxide; or water. Mixtures of these different 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 hydrogen chloride, carboxylic acids such as acetic acid, propionic acid, trifluoroacetic acid, sulfonic acids such as methanesulfonic acid, trifiuorométhanesulfonique, 4-methylphenylsulphonique or sulfuric 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 very numerous methods known per se.

Mention will be made, by way of non-limiting and non-exhaustive examples, of various patents describing the processes for the preparation of benzyl halide derivatives of formula (II) A or of the compounds of formula (VIII) or of the compounds of formula (II) B or compounds of formula (II) C:

The benzyl halide derivatives of formula (II) A and the like where G is the group G1 or G2 of stereochemistry (E) or (Z), can be prepared according to this which is described in patents EP 426460, EP 398692, EP 617014, EP 585751, EP 487409, EP 535928, DE 4305502,

The benzyl halide derivatives of formula (II) A and analogues where G is the group G3 of stereochemistry (E) or (Z), are known according to patent WO 9616943,

The benzyl halide derivatives of formula (II) A and analogues where G is the group G4, G5 or G6, are known according to patents EP 498396, EP 619301, WO 9315046,

The benzyl halide derivatives of formula (II) A and analogues where G is the group G7, are known according to patents WO 9527693, WO 9607633,

The benzyl halide derivatives of formula (II) A and the like where G is the group G8 or G9, are known according to patent WO 9514009.

Method K:

The compounds of general formula (I) in which the groups W1, W2,

R], R2, R3, X], X2, X3 _> X4 and p having the same meaning as for the formula

(I) and G is the group G7 can also be prepared from the following process which is also the subject of the present invention. This process consists in bringing into contact the intermediaries of general formula (III) A in which the groups W1, W2, R \, R, R3, R13, X \, X2, 3, and p have the same meaning as for the formula (I), with a compound of general formula (II) A for which G is the group G7,

X4 having the same definition as that indicated for formula (I) and V 1 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 the group G7, X4 having the same definition as that indicated for formula (I) and V 1 is a halogen atom preferably chlorine or bromine can be obtained by reaction for cleavage of the compounds of formula (XIV) A:

in which Y, X4, Q2, R4 and Rg have the same meaning as for formula (I) and Rc is a hydrogen atom or a lower alkyl group optionally substituted by one or more halogens or an alkoxy group, a benzyl optionally substituted, optionally substituted aryl, by reaction with a halogenating agent.

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

As halogenating agent, it is possible to use, for example, a Lewis acid such as Aluminum chloride, 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, X4, Q2, R4 and Rg have the same meaning as for formula (I) and Rc is a hydrogen atom or a lower alkyl group optionally substituted by one or more halogens or an alkoxy group, an optionally substituted benzyl, an optionally substituted aryl, can be obtained by alkylation of the compounds of formula (XIV) B:

in which Y, X4, Q2 and R4 have the same meaning as for formula (I) and Rc is a hydrogen atom or a lower alkyl group optionally substituted by one or more halogens or an alkoxy group, an optionally substituted benzyl, an optionally substituted aryl.

As alkylating agent, an alkyl or acyl halide or sulfonate of formula (XV) will be used:

Rg-Vi (XV)

in which Rg is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, formyl or acyl group, and Vj is a halogen atom (preferably bromine or iodine), an alkylsulfonate group (preferably trifluoromethylsulfonate), arylsulfonate,

in the presence of silver derivatives such as salts or oxides according to J. Chem Soc. (1969), 2372 and Bull. Chem. Soc. Jpn. (1978), 5J_, 866. The reaction is carried out in a dipolar aprotic solvent such as amides such as dimethylformamide, dimethylacetamide, N-methylpyrolidone at a temperature between - 70 ° C and 180 ° C, preferably between - 30 ° C and 80 ° C.

The compounds of formula (XIV) B in which Y, X4, Q2 and R4 have the same meaning as for formula (I) and Rc has the same meaning as for compound (XIV) A, can be obtained by reduction of the compounds of formula (XIV) C:

in which Y, X4, Q2 and R4 have the same meaning as for formula (I) and Rc has the same meaning as for compound (XIV) A, using a reducing agent such as an alkali or alkaline hydride preferably earth sodium borohydride in an alcohol such as methanol, ethanol, propanol, isopropanol. butanol, tertiobutanol according to J. March ibid. page 910.

The compounds of formula (XIV) C in which Y, X4, Q2 and R4 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 bringing a compound of formula (XIV) D into contact:

in which Y, X4, Q2 and R4 have the same meaning as for formula (I) and V is a halogen atom preferably chlorine or bromine, with a mineral carboxylate such as a formate, an acetate, a propionate or other salt mineral of lower alkylcarboxylic acid, the alkyl group of which may be optionally substituted by one or more halogens or an alkoxy group or an optionally substituted phenyl, or else a benzoic acid salt optionally substituted according to J.March ibid.p398.

The reaction is preferably carried out in a dipolar aprotic solvent such as the amides, preferably formamide, acetamide, dimethylacetamide, N-methylpyrrolidine, at a temperature ranging from 0 ° to reflux of the solvent.

The compounds (XIV) D are obtained according to methods known per se as described in patent EP 37481 1.

Method L:

The compounds of general formula (I) in which the groups W1, W2, Rj, R2, R3, Xj, X2, X3, X4 and p having the same meaning as for formula (I) and G is the group G3, and Rg and the trifluoromethyl radical can also be prepared from the following process which is also the subject of the present invention.

This process consists in bringing into contact the intermediaries of general formula (III) A in which the groups W1, W2, R \, R2, R3, R13, X \, Xi, X3, and p have the same meaning as for the formula (I), with a compound of general formula (II) A for which G is the group G3, Rg is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I) and Vi 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 the group G3, Rg is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I) and V] is a halogen atom preferably chlorine or bromine can be obtained by halogenation of the compounds of general formula (VIII) for which G is the group G3, Rg is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I) , according to the method described in method A.

The compounds of general formula (VIII) for which G is the group G3,

Rg is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I), can be obtained by dehydration of the compounds of formula (XVI):

in which X4, R4 and Q2 have the same meaning as for the formula

(I), using a dehydrating agent such as anhydrous hydracids (preferably sulfuric acid), their alkali or alkaline earth salts (preferably potassium hydrogen sulfate) or anhydrides such as phosphoric anhydride according to J.March ibid. pages 101 1 et seq. or Chem.Ber. (1986) ,! 19, 2233, or phosphorus oxytrichloride, alkylsulfonate chlorides (preferably methylsulfonate or trifluoromethylsulfonate), arylsulfonate chlorides (preferably 4-methylphenylsulfonate) in the presence of a nitrogenous base such as pyridine, alkylpyridines, alkylamines such as trimethylamine, triethylamine or diisoprylethylamine TetrahedromAsymmetry (1990),!, 521, or dialkyldiazodicarboxylates (preferably diethyldiazodicarboxylate) in the presence of a triarylphosphine such as diphenylphophine 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 between - 80 ° C and 180 ° C (preferably between 0 ° C and 150 ° C) or at the boiling point of the solvent used. The solvent suitable for this reaction can be a halogenated hydrocarbon such as dichloromethane, chloroform, 1, 2-dichloroethane, 1,1,1, -trichloroethane, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, a nitrile such as acetonitrile, propionitrile, benzonitrile, a nitrogenous base such as pyridine, alkylpyridines, a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolylene urea, or dimethylsulfoxide . Mixtures of these different solvents can also be used.

The reaction time depends on the conditions used and is generally between 0.1 to 48 h. The compounds of general formula (XVI) in which X4, R4 and Q2 have the same meaning as that indicated for formula (I), can be obtained by aldolic condensation reaction of the compounds of formula (XVII):

in which X4, R4 and Q2 have the same meaning as for the formula (D.

with the gaseous trifluoroacetaldehyde,

by the action of one or more equivalents of a base such as alkali and alkaline earth hydrides, preferably sodium or potassium hydride, alkali and alkaline earth alcoholates, of an organometallic derivative such as the alkylllithians, preferably the butyllithium, alkyl magnesium halides or amides of alkali and alkaline earth metals such as lithium diisopropylamide or lithium amide of hexamethyldisilazane, in an aprotic solvent such as ethers preferably diethyl ether or tetrahydrofuran at a temperature from - 78 ° C to 50 ° C preferably - 70 ° C to 20 ° C

The invention also relates to fungicidal compositions comprising an effective amount of at least one active material of formula (I).

The fungicidal compositions according to the invention comprise, in addition to the active material of formula (I), solid or liquid carriers, acceptable in agriculture and / or surfactants also acceptable in agriculture. In particular, the supports can be used inert and usual and the usual surfactants. These compositions cover not only the compositions 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 the concentrated commercial compositions which must be diluted before application to Culture.

These fungicidal compositions according to the invention can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, sequestrants, etc. More generally, the active ingredients can be combined with any solid or liquid additive corresponding to the usual techniques of formulation.

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.

By the term "support", in the present description, is meant an organic or mineral, natural or synthetic material, with which the active material is combined to facilitate its application on the parts of the plant. This support is therefore generally inert and it must be acceptable in agriculture. 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 emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surfactants. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic or naphthalene sulfonic acids, polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines , substituted phenols (in particular alkylphenols or arylphenols), ester salts of sulfosuccinic acids, taurine derivatives (in particular alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols, esters of acids fatty acids and polyols, sulfate, sulfonate and phosphate derivatives of the above compounds. The presence of at least one surfactant is generally essential when the active material and / or the inert support are not soluble in water and the vector agent for the application is water.

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

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

As forms of solid compositions, mention may be made of powders for dusting (with an active material content of up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, 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; one can also use compositions comprising 50 g of active material and 950 g of talc; one can also use compositions comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by dusting.

As forms of liquid compositions or intended to constitute liquid compositions during application, mention may be made of solutions, in particular water-soluble concentrates, emulsions, concentrated suspensions, wettable powders (or spray powder) .

The concentrated suspensions, applicable in spraying, are prepared so as to obtain a stable fluid product which does not deposit and they usually contain from 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents. from 0 to 10% of suitable additives, such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as support, water or an organic liquid in which the active ingredient is poorly or not soluble: some organic solids or mineral salts may be dissolved in the carrier to help prevent sedimentation or as antifreeze for water.

As an example, here is a concentrated suspension composition:

Example SC 1:

- active ingredient 500 g - polyethoxylated tristyrylphenol phosphate 50 g

- polyethoxylated alkylphenol 50 g

- sodium polycarboxylate 20 g

- ethylene glycol 50 g

- organopolysiloxane oil (antifoam) 1 g - polysaccharide 1.5 g

- water 316.5 g

Wettable powders (or spray powder) are usually prepared so that they contain 20 to 95% of active ingredient, and they usually contain, in addition to the solid support, 0 to 30% of a wetting agent, 3 20% of a dispersing agent, and, when necessary, 0.1 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, dyes, etc. To obtain the spraying powders or wettable powders, the active materials are intimately mixed in the appropriate mixers with the additional substances and ground with mills or other suitable grinders. This gives sprayable powders whose wettability and suspension are advantageous; we can suspend them with water at any desired concentration and these suspensions can be used very advantageously in particular for application for example on the leaves of plants or on seeds. As an example, here are various compositions of wettable powders (or spraying powders):

Example PM 1

- active ingredient 50% - ethoxylated fatty alcohol (wetting agent) 2.5%

- ethoxylated phenylethylphenol (dispersing agent) 5%

- chalk (inert support) 42.5%

Example PM 2: - active ingredient 10%

- branched type oxo synthetic alcohol, C13 ethoxylated with 8 to 10 ethylene oxide (wetting agent) 0.75%

- neutral calcium lignosulfonate (dispersing agent) 12% - calcium carbonate (inert filler) q.s.p. 100%

Example PM 3:

This wettable powder contains the same ingredients as in the previous example, in the following proportions: - active material 75%

- wetting agent 1.50%

- dispersing agent 8%

- calcium carbonate (inert filler) q.s.p. 100%

Example PM 4:

- active ingredient 90%

- ethoxylated fatty alcohol (wetting agent) 4%

- ethoxylated phenylethylphenol (dispersing agent) 6% Example PM 5:

- active ingredient 50%

- mixture of anionic and nonionic surfactants (wetting agent) 2.5%

- sodium lignosulfonate (dispersing agent) 5%

- kaolin 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 in 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 like that of a "mayonnaise". The fungicidal compositions according to the invention can be formulated in the form of water-dispersible granules also included within the scope of the invention.

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

The active material content of these granules is generally between approximately 1% and 95%, and preferably between 25% and 90%. The rest of the granule is essentially composed of a solid filler and optionally surfactant additives giving the granule properties of dispersibility in water. These granules can be essentially of two distinct types depending on whether the selected filler is soluble or not in water. When the filler is water-soluble, it can be mineral or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble filler, it is preferably mineral, such as for example kaolin or bentonite. It is then advantageously accompanied by surfactants (at a rate of 2 to 20% by weight of the granule) of which more than half is, by example, consisting of at least one dispersing agent, essentially anionic, such as an alkaline or alkaline earth polynaphthalene sulfonate or an alkaline or alkaline earth lignosulfonate, the remainder consisting of nonionic or anionic wetting agents such as an alkyl naphthalene sulfonate alkaline or alkaline earth.

Furthermore, although this is not essential, other adjuvants can be added such as anti-foaming agents.

The granule according to the invention can be prepared by mixing the necessary ingredients and then granulation according to several techniques known per se (bezel, fluid bed, atomizer, extrusion, etc.). It generally ends with a crushing followed by sieving to the particle size chosen within the limits mentioned above. It is also possible to use granules obtained as above and then impregnated with a composition containing the active material. Preferably, it is obtained by extrusion, operating as indicated in the examples below.

Example GDI: Dispersible granules

In a mixer, 90% by weight of active material and 10% urea pearls are mixed. The mixture is then ground in a pin mill. A powder is obtained which is moistened with approximately 8% by weight of water. The wet powder is extruded in a perforated roller extruder. A granule is obtained which is dried, then crushed and sieved, so as to keep respectively only the granules of a size between 150 and 2000 microns.

Example GD2: Dispersible granules

In a mixer, the following constituents are mixed:

- active ingredient 75% - wetting agent (sodium alkylnaphthalene sulfonate) 2%

- dispersing agent (sodium polynaphthalene sulfonate) 8%>

- inert filler insoluble in water (kaolin) 15% This mixture is granulated in a fluid bed, in the presence of water, then dried, crushed and sieved so as to obtain granules of size between 0.15 and 0.80 mm.

These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active materials, in particular fungicides, the latter being in the form of wettable powders, or aqueous granules or 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 broad spectrum activity. Mixtures with other fungicides are particularly advantageous, in particular mixtures with carbendazim, thiuram, dodine, maneb, mancozeb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, captafol . folpet, folpel, thiophanate, thiabendazole, phosetyl-Al, chlorothalonil, dichloran, metalaxyl, iprodione, oxadixyl, vinchlozoline, letebuconazole, difenconazole, diniconazole, lemetconazole , propiconazole, prochloraz, fenarimol, triadimenol, furalaxyl, copper derivatives like hydroxide and oxychloride, probenazole.

The compositions according to the invention are useful for treating cereal seeds (wheat, rye, triticale and barley in particular), potato, cotton, peas, rapeseed, corn, flax or even seeds of forest trees (especially conifers).

It will be noted in this connection that in the jargon of a person skilled in the art, the term seed treatment actually refers to the treatment of seeds. The application techniques are well known to those skilled in the art and they can be used without disadvantage in the context of the present invention. Mention may be made, for example, of film-coating or coating. Another subject of the invention is a method for combating, for curative or preventive purposes, phytopathogenic fungi in crops, characterized in that one applies to the seeds of plants or to the leaves of plants or to soils where 'We make or where we want to grow plants, an effective (agronomically effective) and non-phytotoxic amount of an active material of formula (I), preferably in the form of a fungicidal composition according to the invention.

By "effective and non-phytotoxic amount" means an amount of composition according to the invention sufficient to allow the control or destruction of the fungi present or likely to appear on the cultures, and not causing for said cultures any significant symptom of phytotoxicity. Such an amount is likely to vary within wide limits 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 quantity can be determined by systematic field tests, within the reach of those skilled in the art.

Finally, the invention relates to a method of protection, for preventive or curative purposes, of plant multiplication products, as well as of the plants resulting therefrom, against fungal diseases, characterized in that said products are covered with an effective dose and not phytotoxic of a composition according to the invention.

Among the multiplication products of the plants concerned, mention may in particular be made of seeds or seeds, and tubers. It is preferred to implement the method according to the invention in the case of seeds.

As indicated above, the procedures for recovering plant propagating products, in particular seeds, are well known in the art and call in particular on film-coating or coating techniques.

The products and compositions according to the invention can also be applied as a foliar application on plant crops.

Among the plants targeted by the method according to the invention, there may be mentioned: - wheat. with regard to the control of the following seed diseases: Fusarium wilt (Microdochium nivale and Fusarium roseum), caries (Tilletia caries. Tilletia controversa or Tilletia indica). septoria (Septoria nodorum); - wheat, with regard to the fight against the following diseases of the aerial parts of the plant: the foot rot (Pseudocercosporella herpotrichoïdes), the foot scald (Gaeumannomyces graminis), fusariosis of the foot {F. culmorum, F. gr amine arum), rhizoctonia (Rhizoctonia cerealis), powdery mildew (Erysiphe graminis forma specie tritici), rusts (Puccinia striiformis and Puccinia recondita) and septoria (Septoria tritici and Septoria nodorum);

- wheat and barley, as regards the fight against bacterial and viral diseases, for example the dwarfing jaundice of barley.

- barley, as regards the fight against the following seed diseases: helminthosporioses {Pyrenophora graminea,

Pyrenophora teres and Cochliobolus sativas), naked anthrax (Ustilago nuda) and fusarium wilt (Microdochium nivale and Fusarium roseum),

- barley, with regard to the fight against the following diseases of the aerial parts of the plant: the foot rot (Pseudocercosporella herpotrichoïdes), helminthosporioses (Pyrenophora teres and Cochliobolus sativus), powdery mildew (Erysiphe graminis forma specie hordeï ), dwarf rust (Puccinia hordei) and rhynchosporiosis (Rhynchosporium secalis);

- the potato, as regards the fight against tubercle diseases (in particular Helminthosporium solani, Phoma tuberosa,

Rhizoctonia solani, Fusarium solani) and certain viral infections (virus Y);

- cotton, with regard to the fight against the following diseases of young plants grown from seed: seedlings and necrosis of the crown (Rhizoctonia solani, Fusarium oxysporum), black root rot (Thielaviopsis basicola);

- pea, as regards the fight against the following seed diseases: anthracnose (Ascochyta pisi, Mycosphaerella pinodes), fusarium wilt (Fusarium oxysporum), gray rot (Botrytis cinerea); - rapeseed, as regards the fight against the following seed diseases: Phoma lingam and Alternaria bra sicae;

- maize, as regards the fight against seed diseases: {Rhizopus sp., Penicillium sp., Trichoderma sp., Aspergillus sp. and Gibberella fujikuroi);

- flax, as regards the fight against seed disease: Alternaria linicola;

- forest trees, with regard to the control of seedling huts (Fusarium oxysporum, Rhizoctonia solani). Wheat and barley are the preferred plants for the implementation of the method according to the invention.

The dose of composition applied is. in general, 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 10 to 800 g / ha, preferably 50 to 300 g / ha are generally applied as a foliar treatment.

The following examples illustrate the present invention:

Example 1:

Preparation of (Z) -N-methoxy-N-methoxycarbonyl-2- [1 - (1 - (phenyl) ethyl-oxyimino) ethyloxymethyl] aniline

1.47 g of N- (1- (phenyl) ethyloxy) acetamide are dissolved in 30 ml of anhydrous acetonitrile. 2.26 g of 2-bromo-methyl-N-methoxy-N-methoxycarbonylaniline and 2.67 g of cesium carbonate are successively added and the reaction medium is refluxed for 2 hours. After cooling, the salts are filtered, 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, reextracted three times with ethyl acetate to give, after drying and evaporation, 2.63 g of a dark yellow oil. Chromatography on silica isolates 0.6 g of the expected compound, of stereochemistry (Z), in the form of a yellow oil. n _D = 1.5270 (23 ° C) (these expressions denote the refractive index at 23 ° C using the D line of sodium as light).

Example 2:

Preparation of (E) -N-methoxy-N-methoxycarbonyl-2- [1 - (1 - (phenyl) ethyl-oxyimino) ethyloxymethyl] aniline

0.4 g of (Z) -N-methoxy-N-methoxycarbonyl-2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] aniline are dissolved in 25 ml of anhydrous toluene. After adding a few drops of acetic acid, the reaction medium is brought to reflux for 2 hours. The medium is poured into 50 ml of water, the toluene phase is decanted, washed until neutral and dried, which gives 0.4 g of a yellow oil. Chromatography on silica allows 0.33 g of the expected compound, of stereochemistry (E), to be isolated in the form of a light yellow oil which gradually crystallizes. F = 70 ° C (this expression denotes the melting point).

Example 3:

Preparation of (Z) -2,4-dihydro-5-methoxy-2-methyl-4- [2- [1- (1- (phenyl) ethyl-oxyimino) ethyloxymethyl] -phenyl] -3H- 1, 2, 4-triazol-3-one

3.58 g of N- (1- (phenyl) ethyloxy) acetamide are dissolved in 40 ml of anhydrous acetonitrile. 5.96 g of 4- [2- (bromomethyl) phenyl] -2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one and 7 are added successively. , 82 g of cesium carbonate and brings the reaction medium to boiling at reflux for 4 hours. After cooling, the salts are filtered, washed with acetonitrile then the organic fractions are concentrated to give 7.0 g of an orange oil. By chromatography on silica, 0.82 g of the expected compound, of stereochemistry (Z), is isolated, in the form of a yellow oil. Rf = 0.24 (heptane / ethyl acetate 1/3). (This is used to denote the retention coefficient on a silica thin layer chromatography plate). Example 4:

Preparation of (E) -2,4-dihydro-5-methoxy-2-methyl-4- [2- [1 - (1 - (phenyl) ethyl-oxyimino) ethyloxymethyl] -phenyl] -3H-1,2, 4-triazol-3-one

0.4 g of (Z) -2,4-dihydro-5-methoxy-2-methyl-4- [2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] -phenyl] -3H-1 , 2,4-triazol-3-one are dissolved in 20 ml of anhydrous toluene. The reaction medium is brought to reflux for 13 hours under ultraviolet irradiation. The medium is concentrated to give 0.4 g of a yellow oil. Chromatography on silica allows 0.18 g of the expected compound, of stereochemistry (E), to be isolated in the form of a light yellow oil. n _D = 1.5310 (21 ° C).

Example 5:

Preparation of (E) -2- [2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] - phenyl] -2-methyl methoxyacetate

Step 1:

Preparation of methyl 2- (2-acetoxymethylphenyl) -2-oxoacetate

A mixture of 25 g of methyl 2- (2-bromomethylphenyl) -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 re-extracted with ether. After purification by chromatography on silica, 1 1 g of the expected product is obtained. n _D : 1.5292 (25 ° C).

2nd step:

Preparation of methyl 2- (2-acetoxymethylphenyl) -2-hydroxyacetate

11 g of the above compound are loaded into 150 ml of methanol. After cooling in 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 and the methanolic phase is concentrated. After re-extraction, washing with an aqueous sodium bicarbonate solution and drying, 10.5 g of the expected product are isolated in the form of an oil yellow. NMR (CDCI3): 2.10 s, 3H; 3.72, s 3H; 5.28, AB. 1H: 5.42, s. 1 H: 7.25- 7.45, m, 4H).

Step 3: Preparation of methyl 2- (2-acetoxymethylphenyl) -2-methoxyacetate

1.5 g of silver oxide are added to 1 g of the preceding compound and 11.36 g of methyl iodide in solution in 200 ml of N-methylpyrrolidone.

After heating at 40 ° C for 2 days, the reaction mixture is filtered, diluted with water and re-extracted with ether. After purification by chromatography on silica, 2.5 g of the expected compound are obtained in the form of a yellow oil.

Step 4:

Preparation of methyl 2- (2-bromomethylphenyl) -2-methoxyacetate

Gas hydrobromic acid is bubbled at a temperature between 0 and 5 ° C. in a solution of 0.5 g of the above compound in 10 ml of dichloromethane. After concentration and purification by chromatography on silica, 0.25 g of a yellow NMR liquid (CDCl3) is obtained: 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 5:

Preparation of (E) -2- [2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] - phenyl] -2-methyl methoxyacetate

A mixture of 0.125 g of N- (1- (phenyl) ethyloxy) acetamide, 0.2 g of methyl 2- (2-bromomethylphenyl) -2-methoxyacetate and 0.234 g of cesium carbonate in 15 ml of acetonitrile are heated for 4 hours at reflux. After purification by chromatography on silica, 0.1 g of the expected compound, of stereochemistry (E), is obtained in the form of a 50:50 mixture of two diastereoisomers. n _D : 1.5330 (25 ° C). Example 6:

Preparation of (E, E) -2- [2- [1- (N2-benzyl-N2-methylhydrazono) ethyloxy-methyl] phenyl] -3-methyl methoxyacrylate

Step 1 :

Preparation of N ^ -benzyl-N ^ -methylacethydrazide

5.4 ml of acetyl chloride are poured dropwise onto a mixture, strongly stirred at room temperature, of 9.4 g of 1-methyl-1-benzylhydrazine prepared according to Synth. Comm. (1990), 20, 185, dissolved in 50 ml of ether and 2.76 g of sodium hydroxide dissolved in 25 ml of water. After 2 hours of reaction, the reaction mixture is decanted and the organic phase treated in the usual way. After purification by chromatography on silica, 8.36 g of the expected product is obtained in the form of a yellow oil. NMR (CDCI3): 2.5, s, 3H; 2.95, bs, 2H; 3.62, s, 2H; 7.25-7.45, m, 5H.

2nd step:

Preparation of (E, E) -2- [2- [1- (T ^ 2.b _enZ yi ^. \ | F2. _M ethylhydrazono) ethyloxy-methyl] phenyl] -3-methyl methoxyacrylate.

3 g of (E) -2- (2-bromomethylphenyl) -3-methyl methoxyacrylate dissolved in 90 ml of dry dimethylformamide are gradually added at 20 ° C in a mixture of 2.06 g of N2-benzyl-N-- methylacethydrazide obtained as above and 1.3 g of potassium tert-butoxide in 60 ml of dry dimethylformamide. After 5 hours of reaction, the mixture is poured into 300 ml of water and reextracted several times with ethyl acetate. After purification by chromatography on silica, 70 mg of the expected product, of stereochemistry (E, E), is obtained in the form of a honey. NMR (CDCl3): 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 (E, Z) -2- [2- [1 - (1 - (phenyl) ethyloxyimino) ethyloxymethyl] - phenyl] -4,4,4-trifluorobut-2-enoate Step 1:

Preparation of methyl 3-hydroxy-2- [2- (methyl) phenyl] -4,4,4-trifluorobutanoate

To 200 ml of lithium diisopropylamide (1M in dry tetrahydrofuran) and cooled to -70 ° C, 28.75 g (0.15 mole) of 2- [2- (methyl) phenyl] acetate are added dropwise. methyl in solution in 100 ml of dry tetrahydrofuran. Is bubbled in the reaction medium, dry trifluoroacetaldehyde prepared according to J. Chem. Éduc (1975), 52, 131, for 1 h. After 3 hours of stirring at -70 ° C, the medium is poured into 500 ml of water and 200 ml of 1M hydrochloric acid, reextracted with ethyl acetate and dried. Evaporation of the solvents leaves 37 g of a yellow oil which is distilled under reduced pressure (E = 1 15-120 ° C under 4 mmHg; these expressions denote the boiling point under a pressure expressed in mm of mercury) to give 35.60 g of a colorless oil. After purification by chromatography on silica, 21.26 g of a sy anti mixture are obtained in a 70:30 ratio of the expected compound. The majority diastereomer of configuration syn, can be isolated pure and crystallized: ⁴ J _HH = 5 Hz; Mp 58 ° C.

2nd step:

Preparation of (E) -2- [2- (methyl) phenyl] -4,4,4-trifluorobut-2-enoate

To 9.34 g of the symanti mixture of 3-hydroxy-2- [2- (methyl) phenyl] -4,4,4- methyl trifluorobutanoate obtained as above, in solution in 40 ml of diethyl ether, 9 , 34 g of triphenylphosphine. 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 20 ° C. then the triphenylphosphine oxide is filtered. The filtrate is distilled in a ball oven to give 7 g of the expected compound, of stereochemistry (E), in the form of a colorless liquid. nr 1.4722 (20 ° C).

Step 3:

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

Step 4:

Preparation of methyl (E, Z) -2- [2- [1 - (1 - (phenyl) ethyloxyimino) ethyloxymethyl] - phenyl] -4,4,4-trifluorobut-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-enenoate obtained as above are added successively, and 1.76 g of carbonate of cesium and brings the reaction medium to reflux for 2 hours. After cooling, the medium is poured into 100 ml of water, re-extracted with ethyl acetate, dried and then concentrated to provide 1.7 g of a yellow oil. Chromatography on silica allows 0.4 g of the expected compound, of stereochemistry (E, Z), to be isolated in the form of a yellow oil. n _D - 1.5251 (20 ° C).

Example 8:

Preparation of (E, E) -2- [2- [1 - (1 - (phenyl) ethyloxyimino) ethyloxymethyl] - phenyl] -4,4,4-trifluorobut-2-enoate

In a manner analogous to the process described in Example 2, isomerized

130 mg of (E, Z) -2- [2- [1- (1 - (phenyl) ethyloxyimino) ethyloxymethyl] -phenyl] -

4,4,4-methyl trifluorobut-2-enoate at reflux of toluene in the presence of acetic acid. Chromatography on silica makes it possible to isolate 70 mg of the expected compound, of stereochemistry (E, E), in the form of a yellow oil. n _D = 1.5107 (26 ° C). Example 9:

Preparation of (E, E) -2-methoxyimino-N-methyl-2- [2- [1- (1- (N-methyl-carbamoyl) - 1 - (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] acetamide

Step 1:

Preparation of methyl 2-bromo-2-phenylpropanoate

To 9.58 g of methyl 2-phenylpropanoate in solution in 120 ml of carbon tetrachloride, 10.7 g of N-bromosuccinimide, 0.1 g of benzoyl peroxide are added and the medium is brought to reflux for 4 hours. After cooling, the succinimide is filtered and the organic phase washed with 0.1N sodium thiosulfate, with water and dried. Evaporation of the solvent leaves 13.5 g of an orange oil which is distilled in a ball oven (E = 175 ° C under 5 mmHg) to give 12.5 g of the expected compound in the form of a colorless liquid. n _D - 1, 5478 (19 ° C).

2nd step:

Preparation of N- [1- (methoxycarbonyl) -1- (phenyl) ethyloxy] acetamide

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 ° C., 2.43 g of sodium methoxide in portions. The medium is heated for 8 h at 40 ° C. After evaporation of the methanol, the residue is taken up in 50 ml of water, reextracted with ethyl acetate and dried. Evaporation of the solvents leaves 12 g of a colorless 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. F - 94 ° C.

Step 3: Preparation of (E, Z) -2-methoxyimino-2- [2- [l- (l- (methoxycarbonyl) -l-

(phenyl) ethyloxyimino) ethyloxymethyl] phenyl] methyl acetate

5.7 g of N- [1- (methoxycarbonyl) -1- (phenyl) ethyloxy] acetamide obtained as above, are dissolved in 50 ml of anhydrous acetonitrile. We add successively 6.87 g of (E) -2-methoxyimino-2- [2- (bromomethyl) phenyl] methyl acetate, and 9.38 g of cesium carbonate and brings the reaction medium to reflux for 4 hours. After cooling, the cesium salts are filtered and the filtrate concentrated to provide 12 g of a brown oil. Chromatography on silica allows 4.5 g of the expected compound, of stereochemistry (E, Z), to be isolated in the form of a white solid. Mp 108 ° C.

Step 4:

Preparation of methyl (E, E) -2-methoxyimino-2- [2- [1- (1- (methoxycarbonyl) -l- (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] acetate

In a manner analogous to the process described in Example 2, 3.5 g of (E, Z) -2-methoxyimino-2- [2- [1- (1- (methoxycarbonyl) -l- (phenyl) are isomerized) ) ethyloxyimino) ethyloxymethyl] phenyl] methyl acetate at reflux of toluene in the presence of acetic acid. Recrystallization of the crude solid from diisopropyl ether makes it possible to isolate 3.2 g of the expected compound, of stereochemistry (E, E). as a white solid. F- 1 17 ° C.

Step 5: Preparation of (E, E) -2-methoxyimino-N-methyl-2- [2- [1- (1- (methoxycarbonyl) -1- (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] acetamide

A 3.2 g of (E, E) -2-methoxyimino-2- [2- [1- [(1- (methoxycarbonyl) -l- (phenyl) - ethyloxyimino) ethyloxymethyl] phenyl] methyl acetate obtained as below above, dissolved in 70 ml of methanol, 14 ml of 40% by weight methylamine in water are added and the mixture is stirred vigorously at 20 ° C. for 4 hours. The methanol is evaporated 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 (E, E), in the form of a colorless oil. n _D = 1.5390 (19 ° C).

Step 6:

Preparation of (E, E) -2-methoxyimino-N-methyl-2- [2- [1 - (1 - (N-methyl-carbamoyl) - 1 - (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] acetamide A 0.88 g of (E, E) -2-methoxyimino-N-methyl-2- [2- [l- (l-

(methoxycarbonyl) -1- (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] acetamide obtained as above, in solution in 20 ml of anhydrous N-methylpyrrolidone, 0.16 g of 60% sodium hydride is added. The medium is cooled to 0 ° C and methylamine gas 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 adding IN hydrochloric acid and the aqueous phase reextracted with ethyl acetate, washed with water and dried. Evaporation of the solvents leaves 1.0 g of a colorless oil. After purification by chromatography on silica, 0.15 g of the expected compound, of stereochemistry (E, E) is obtained, in the form of a colorless oil which crystallizes progressively. M = 152 ° C.

Example 10: Preparation of (E, Z) -2- [2- [1- (1- (methoxycarbonyl) -1- (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] -4,4,4-trifluorobut-2- methyl enoate

1.54 g of N- [1- (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 (E) -2- [2- (bromomethyl) -phenyl] -4,4.4- methyl trifluorobut-2-enoate obtained according to step 3 of Example 7 are added successively, and 2.33 g of cesium carbonate and brings the reaction medium to 50 ° C for 7 hours. After cooling, the cesium salts are filtered and the medium is concentrated to provide 3.2 g of a yellow oil. Chromatography on silica makes it possible to isolate 1.5 g of the expected compound, of stereochemistry (E, Z), in the form of a yellow oil. Rf = 0.19 (heptane / ethyl acetate 3/1).

Example 11:

Preparation of (E, E) -2- [2- [1 - (1 - (methoxycarbonyl) - 1 - (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] -4,4,4-trifluorobut-2-enenoate

In a manner analogous to the process described in Example 2, 1.15 g of (E, Z) -2- [2- [l- (l- (methoxycarbonyl) -l- (phenyl) ethyloxyimino) ethyloxy) is isomerized - methyl] phenyl] -4,4,4-methyl trifluorobut-2-enoate at the reflux of toluene in presence of acetic acid. Recrystallization of the crude solid from diisopropyl ether makes it possible to isolate 0.85 g of the expected compound, of stereochemistry (E, E), in the form of a white solid. F ^* = 82 ° C.

Example 12:

Preparation of (Z) -2,4-dihydro-5-methoxy-2-methyl-4- [2- [1 - (1 - (methoxycarbonyl) - 1 - (phenyl) ethyloxyimino) ethyloxymethyl] -phenyl] - 3 H- 1, 2, 4-triazol-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 acetonitrile. 2.39 g of 4- [2- (bromomethyl) phenyl] -2,4-dihydro-5-methoxy-2-methyl-3H-1,2,3,4-triazol-3-one and 3.13 are added successively. g of cesium carbonate and brings the reaction medium to reflux for 2 hours. After cooling, the salts are filtered, washed with acetonitrile and the organic fractions are concentrated to give 4.4 g of a yellow oil. By chromatography on silica, 2.21 g of the expected compound, of stereochemistry (Z), are isolated, in the form of a yellow oil which crystallizes progressively. Mp 110 ° C.

Example 13:

Preparation of (E) -2,4-dihydro-5-methoxy-2-methyl-4- [2- [1- (l- (methoxycarbonyl) - 1 - (phenyl) ethyloxyimino) ethyloxymethyl] -phenyl] - 3H- 1, 2,4-triazol-3 - one

2.07 g of (Z) -2,4-dihydro-5-methoxy-2-methyl-4- [2- [1- (1- (methoxycarbonyl) -1- (phenyl) ethyloxyimino) ethyloxymethyl] - phenyl] -3H-1,2,4-triazol-3-one are dissolved in 10 ml of anhydrous toluene. 0.5 ml of acetic acid is added and the reaction medium is brought to reflux for 52 hours under ultraviolet irradiation. The medium is diluted with 20 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 stereochemistry (E), in the form of a light yellow oil which gradually crystallizes. Mp 110 ° C. Example 14:

Preparation of (E) -N-methoxycarbonyl-N-methoxymethyl-2- [1- (1- (phenyl) - ethyloxyimino) ethyloxymethyl] aniline

Step 1 :

Preparation of (E) -N-methoxycarbonyl-2- [1- (1- (phenyl) ethyloxyimino) - ethyloxymethyl] aniline

6.5 g of N- (1- (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 cesium carbonate are added successively and the reaction medium is brought to reflux for 2 hours. After cooling, the salts are filtered, washed with acetonitrile and the filtrate is concentrated to give 10 g of an orange oil. Chromatography on silica allows 1.0 g of the expected compound, of stereochemistry (E), to be isolated in the form of a yellow oil. n _D = 1.5571 (22 ° C).

2nd step :

Preparation of (E) -N-methoxycarbonyl-N-methoxymethyl-2- [1- (1- (phenyl) - ethyloxyimino) ethyloxymethyl] aniline

To 1.0 g of (E) -N-methoxycarbonyl-2- [1- (1- (phenyl) ethyloxyimino) ethyl-oxymethyl] aniline, obtained as above, dissolved in 20 ml of anhydrous tetrahydrofuran, 0.33 g of potassium ter-butoxide. After 15 minutes of stirring at 20 ° C., 0.32 ml of bromomethyl methyl ether is added and the mixture is stirred for 30 minutes at 20 ° 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 leaves 1.2 g of a yellow oil. Chromatography on silica allows 1.0 g of the expected compound, of stereochemistry (E), to be isolated in the form of a yellow oil. n _D = 1.5402 (12 ° C).

Example 15:

Preparation of (E, E) -2-methoxyimino-N-methyl-2- [2- [1 - (1 - (carboxy) - 1 - (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] acetamide A 0.88 g of (E, E) -2-methoxyimino-N-methyl-2- [2- [l- (l- (methoxycarbonyl) - 1 - (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] acetamide obtained as described in l step 5 of Example 9, in solution in 20 ml of anhydrous N-methylpyrrolidone, 0.27 g of sodium amide is added. The reaction medium is heated at 55 ° C for 3 hours and then poured into 100 ml of water. The pH is brought to 7 by adding IN hydrochloric acid and the aqueous phase reextracted with ethyl acetate, washed with water and dried over magnesium sulfate. Evaporation of the solvents leaves 0.6 g of a yellow oil. Trituration with a minimum of diisopropyl ether gives 0.31 g of the expected compound in the form of a white solid. Mp 144 ° C.

Example 16:

Preparation of (E, E) -2- [2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] - phenyl] -but-2-enoate

Step 1 :

Preparation of (E, Z) -2- [2- [1 - (1 - (phenyl) ethyloxyimino) ethyloxymethyl] - phenyl] -but-2-enoate

1.1 g of N- (1- (phenyl) ethyloxy) acetamide are dissolved in 50 ml of anhydrous acetonitrile. 1.6 g of (E) -2- [2- (bromomethyl) - phenyl] -but-2-enoate, prepared according to US 5416068, and 2.1 1 g of cesium carbonate are added successively and the medium is carried reactiormel at reflux for 4 hours. After cooling, the medium is filtered through celite and the celite washed with acetonitrile. After concentration, chromatography on silica of the residual oil makes it possible to isolate 1.0 g of the expected compound, of stereochemistry (E, Z). as a yellow oil. Rf = 0.67 (heptane / ethyl acetate 1/1).

Step 2: Preparation of (E, E) -2- [2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] - phenyl] -but-2-enoate

In a manner analogous to the process described in example 2, 1.0 g of (E, Z) -2- [2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] -phenyl] -but is isomerized -2- methyl ene-oate at reflux of toluene in the presence of acetic acid. Evaporation of the solvent leaves 1.0 g of the expected compound, of stereochemistry (E, E), in the form of a pale yellow honey. n _D = 1.5460 (24 ° C).

Example B1: In vivo test on Plasmopara viticola (downy mildew):

An aqueous suspension of the active ingredient to be tested having the following composition is prepared by fine grinding: - active ingredient: 60 mg

- Tween 80 surfactant (oleate of polyoxyethylene derivative of sorbitan) diluted to 10% o in water: 0.3 ml

- acetone: 5 ml

- make up to 60 ml of water. This aqueous suspension is then diluted with water so as to obtain the desired concentration in ppm (parts per million).

Vine cuttings (Vitis vinifera), Chardonnay variety, are grown in pots. When these plants are 2 months old (8 to 10 leaf stage, 10 to 15 cm high), they are treated by spraying with the above aqueous suspension.

Plants, used as controls are treated with an aqueous solution not containing the active ingredient.

After drying for 24 hours, each plant is contaminated by spraying with an aqueous suspension of Plasmopara viticola spores obtained from a culture of 4-5 days, then suspended at the rate of 100,000 units per cm.

The contaminated plants are then incubated for two days at around 18 ° C, in an atmosphere saturated with humidity and then for five days at around 20-22 ° C under 90-100% relative humidity. The reading is done seven days after contamination, in comparison with the control plants.

Under these conditions, at the dose of 5 ppm, good (at least 75%) or total protection is observed 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 ingredient to be tested having the following composition is prepared by fine grinding: - active ingredient: 60 mg

- Tween 80 surfactant (oleate of polyoxyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml

- acetone: 5 ml

- make up to 60 ml of water. This aqueous suspension is then diluted with water so as to obtain the desired concentration in ppm (parts per million).

Wheat (Scipion variety), in pots, sown on a peat soil 50/50 and kept at 12 ° C, is treated at the 1 leaf stage (10 cm high) by spraying the above aqueous suspension. Plants, used as controls are treated with an aqueous solution not containing the active ingredient.

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. Contaminated wheat plants are then incubated for 24 hours at approximately 20 ° C, in an atmosphere saturated with humidity and then for seven to fourteen days at 60%> relative humidity.

The reading is between the 8 ^th and 15 ^th day after the contamination, in comparison with the control plants. Under these conditions, a good protection is observed at a dose of 40 ppm.

(at least 75%) or total with the following compounds: 1, 2, 3, 4, 5, 6, 9, 14, 15 and

16.

Example B3: In vivo test on Septoria tritici (wheat septoria):

An aqueous suspension of the active ingredient to be tested having the following composition is prepared by fine grinding: - active ingredient: 60 mg - Tween 80 surfactant (oleate of polyoxyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml

- acetone: 5 ml

- make up to 60 ml of water. This aqueous suspension is then diluted with water so as to obtain the desired concentration in ppm (parts per million).

Wheat (Scipion variety) in pots, sown on a 50/50 peat soil pozzolan peat substrate and maintained at 12 ° C, is treated at the 1 leaf stage (10 cm in height) by spraying the above aqueous suspension. Plants, used as controls are treated with an aqueous solution not containing the active ingredient.

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. Contaminated wheat plants are incubated for 72 hours at

20 ° C approximately, in a humid atmosphere then for twenty days at 90% relative humidity.

The reading is done twenty-one days after the contamination, in comparison with the control plants. Under these conditions, a good protection is observed at a dose of 40 ppm.

(at least 75%) or total with the following compounds: 1, 2, 3, 4, 5, 6, 9, 14 and 16.

Example B4: In vivo test on Septoria nodorum (wheat septoria):

An aqueous suspension of the active material to be tested having the following composition is prepared by fine grinding:

- active ingredient: 60 mg

- Tween 80 surfactant (oleate of polyoxyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml - acetone: 5 ml

- make up to 60 ml of water.

This aqueous suspension is then diluted with water so as to obtain the desired concentration in ppm (parts per million). Wheat (Scipion variety) in pots, sown on a 50/50 peat soil pozzolan peat substrate and maintained at 12 ° C, is treated at the 1 leaf stage (10 cm in height) by spraying the above aqueous suspension.

Plants, used as controls are treated with an aqueous solution not containing the active ingredient.

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

Contaminated wheat plants are incubated for 72 hours at approximately 20 ° C, in a humid atmosphere and then for fourteen days at 90% relative humidity.

The reading is done fifteen days after contamination, in comparison with the control plants.

Under these conditions, at the dose of 40 ppm, good (at least 75%) or total protection is observed with the following compounds: 1, 2, 3, 4, 5, 6, 9, 14 and 16.

Example B5: In vivo test on Erisyphe graminis fsp tritici (wheat powdery mildew):

An aqueous suspension of the active material to be tested having the following composition is prepared by fine grinding:

- active ingredient: 60 mg

- Tween 80 surfactant (oleate of polyoxyethylene derivative of sorbitan) diluted to 10%> in water: 0.3 ml

- acetone: 5 ml - make up to 60 ml of water.

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

Wheat (Audace variety) in pots, sown on a peat soil 50/50 pozzolan earth and maintained at 12 ° C, is treated at the 1 leaf stage (10 cm in height) by spraying the above aqueous suspension

Plants, used as controls are treated with an aqueous solution not containing the active ingredient.

After 24 hours, the wheat plants are dusted with Erisyphe graminis spores, the dusting being carried out using diseased plants. The reading is made seven to fourteen days after contamination, in comparison with the control plants.

Under these conditions, at the dose of 40 ppm, good (at least 75%) or total protection is observed with the following compounds: 1, 2, 3, 4, 5, 9, 11, 14 and 16.

Example B6: In vivo test on Erisyphe graminis fsp hordei (barley powdery mildew):

An aqueous suspension of the active material to be tested having the following composition is prepared by fine grinding:

- active ingredient: 60 mg

- Tween 80 surfactant (oleate of polyoxyethylene derivative of sorbitan) diluted to 10% o in water: 0.3 ml

- acetone: 5 ml - make up to 60 ml of water.

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

Barley (Express variety) in pots, sown on a peat soil 50/50 pozzolan earth and maintained at 12 ° C, is treated at the 1 leaf stage (10 cm in height) by spraying the above aqueous suspension

Plants, used as controls are treated with an aqueous solution not containing the active ingredient.

After 24 hours, the barley plants are dusted with Erisyphe graminis spores, the dusting being carried out using diseased plants. The reading is made seven to fourteen days after contamination, in comparison with the control plants.

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

Example B7: In vivo test on Pyrenophora teres (barley helmintosporiosis):

An aqueous suspension of the active material to be tested having the following composition is prepared by fine grinding: - active ingredient: 60 mg

- Tween 80 surfactant (oleate of polyoxyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml

- acetone: 5 ml - make up to 60 ml of water.

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

Barley (Express variety), in pots, sown on a 50/50 peat earth peat substrate and maintained at 12 ° C. is treated at the 1 leaf stage (10 cm in height) by spraying the above aqueous suspension.

Plants, used as controls are treated with an aqueous solution not containing the active ingredient.

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

The contaminated barley plants are then incubated for 24 hours at approximately 20 ° C, in an atmosphere saturated with humidity and then for seven to fourteen days at 80% relative humidity.

The reading is between the 8 ^th and 15 ^th day after the contamination, in comparison with the control plants.

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

Claims

1. Compounds comprising the hydroximic or hydrazonic function of general formula (I):

(D in which G is chosen from groups Gl to G9:

Gl G2 G3

G4 G5 G6

G7 G8 G9

in which: n = 0 or 1 Q l is the nitrogen atom or the CH group, Q2 is the oxygen or sulfur atom, Q3 is the oxygen or sulfur atom, Q4 is the nitrogen atom or the CR group _] \, Q5 is the oxygen or sulfur atom or the group NR12,

Y is the oxygen or sulfur atom or the amino (NH) or oxyamino (ONH) group;

Wl is the oxygen or sulfur atom or the sulfinyl (SO) or sulfonyl (SO2) groups,

W2 is the oxygen atom or the NR13 group,

p = 1 when W2 is the oxygen atom, p = 0 or 1 when W2 is the group NR13,

X], X2-X3 are, independently of each other, a hydrogen atom, a halogen atom; or a hydroxy, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl group; a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyle, alkylthioalkyle, haloalkylthioalkyle, cyanoalkyle, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl; or a lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio group; or an amino, N-alkylamino, N, N-dialkylamino, acylamino, aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl group; or a carboxy, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl group; or an acyl group;

X4 is a hydrogen atom, a halogen atom; or a lower alkyl, lower haloalkyl, alkoxy, haloalkoxy group; or the cyano, nitro, R], R2 are, independently of each other, a hydrogen atom, a lower alkyl group, lower haloalkyl, a lower cycloalkyl group, lower halocycloalkyl, an alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl group; or a cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl group, a lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthio-thiocarbonyl group; or an aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl group,

R \ and R2 may together form a divalent radical such as an alkylene group, optionally substituted by one or more halogen atoms, optionally substituted by one or more lower alkyl groups,

R3 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; or a nitro, cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxy-carbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl group; or an alkenyl, alkynyl, N, N-dialkylamino, N, N-dialkylaminoalkyl group; or an optionally substituted phenyl or benzyl group,

R4 is lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl; or an alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino group,

R5, Rg is independently of each other a lower alkyl, lower haloalkyl group, R7 is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl group. alkenyl, alkynyl,

Rg is a lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl group. alkenyl, alkynyl, formyl, acyl,

R9 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,

RjO is a halogen atom, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkvlsulfinyl, alkylsulfonyl. haloalkylsulfonyl,

R _] , R _j 2 are, independently of each other, a hydrogen atom, a lower alkyl group, lower haloalkyl, a lower cycloalkyl group, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl.

R _j 3 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, optionally substituted allyl group, optionally substituted propargyl group, benzyl group optionally substituted; or an acyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl group; or an optionally substituted alkylsulfonyl, haloalkylsulfonyl, arylsulfonyl group,

provided that: when W2 and Q2 are the oxygen atom and G represents the group Gl, then R5 is other than an alkyl group, and R4 is other than an alkoxy group, alkylamino, dialkylamino, and R3 is other than hydrogen, alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, cyanoalkyl, alkenyl, alkynyl, dialkylaminoalkyl, or phenyl or benzyl possibly substituted,

as well as the salts, the metallic and metalloid complexes, the optical and geometric isomers of the compounds of formula (I) as just defined.

2. Compounds according to claim 1 in which n = 0 or 1, p = 1 and / or Q2 is the oxygen atom, and / or Q3 is the oxygen atom, and / or Q4 is the atom nitrogen, and / or Q5 is the oxygen atom;

Wl is the oxygen or sulfur atom,

W2 is the oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino, allylamino group, Y is the oxygen atom.

3. Compounds according to one of the preceding claims, in which X _] , X2, X3 and X4 are, independently of each other, a hydrogen atom, a lower alkyl group, a halogen atom, or the cyano, trifluoromethyl radicals, methoxy.

4. Compounds according to one of the preceding claims, in which R _j and R2 are, independently of each other, a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyl, N- group. alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, lower alkoxycarbonyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl,

R3 is a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl group, preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl, methoxymethyl radical, R4 is a lower alkyl, alkoxy, alkylamino, dialkylamino group, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino, ethylamino radical, R5, Rg, Rg and R9 are, independently of each other, a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl,

R7 is a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl radical. trifluoromethyl, ethyl, 2,2,2- trifluoroethyl, propyl, an allyl group, propargyl,

RjO is a chlorine atom, a lower alkyl group, lower haloalkyl, preferably methyl, an alkoxy group, alkylthio, preferably methoxy, methylthio, Rj j and Ri 2 are independently a lower alkyl group, lower haloalkyl, alkoxyalkyle, allyl, propargyle,

Ri 3 is the hydrogen atom, a lower alkyl, lower haloalkyl, alkoxyalkyl group. haloalkoxyalkyle, allyl, propargyle, benzyle.

5. Compounds according to one of the preceding claims in which

Wl is the oxygen atom,

Rj is the hydrogen atom or the methyl radical,

R2 is a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N.N-dialkylaminoalkyl, lower alkoxycarbonyl, N.N-dialkyl-carbamoyl group.

6. Compounds according to one of the preceding claims in which the substituents W1 and W2 are in the trans position with respect to the double bond -C (R ₃ ) = N-.

7. Fungicidal compositions comprising an effective amount of at least one active ingredient according to one of the preceding claims.

8. Fungicidal compositions according to claim 7 comprising, in addition to the active material of formula (I), solid or liquid supports, acceptable in agriculture and / or surfactants also acceptable in agriculture.

9. Fungicidal compositions according to one of claims 7 or 8 comprising from 0.05 to 95% by weight of active material.

10. A method of preventive or curative control against phytopathogenic fungi of cultures, characterized in that one applies to the seeds of plants or on the leaves of plants or on the soils where one does or where one wishes to grow plants, an agronomically effective and non-phytotoxic amount of at least one active ingredient or of a fungicidal composition containing an active ingredient of formula (I) as defined in claim 1

11. A process for the preventive or curative treatment of plant multiplication products, as well as of the resulting plants, against fungal diseases, characterized in that said products are covered with an effective and non-phytotoxic dose of compound or of composition according to one of the preceding claims.

12. The method of claim 1 1 wherein treating rice, cereals, fruit trees, vines and beet.

13. Method according to one of claims 1 1 or 12 in which the wheat or barley is treated.

14. The method of claim 11 wherein the seeds of cereals, potatoes, cotton, peas, rapeseed, corn, flax or even seeds of forest trees are treated.

15. Method according to one of the preceding claims wherein the dose of active material applied is between 20 and 200 g of active material per 100 kg of seed, preferably between 3 and 150 g per 100 kg in the case of treatments of seeds.

16. Method according to one of claims 10 to 14 wherein the dose of active material applied is between 10 and 800 g of active material per hectare, preferably between 50 and 300 g of active material per hectare in the case of treatments. foliar.

17. Process for the preparation of the compounds according to one of claims to 6, consisting in bringing a compound of formula (II) A into contact:

in which G is one of the groups Gl to G9, the groups Gl to G9 having the same definition as those indicated in one of Claims 1 to 6, X4 having the same definition as that indicated in one of Claims 1 at 6,

Vj is a halogen atom (preferably chlorine or bromine), an alkylsulfonate or haloalkylsulfonate group (preferably methylsulfonate or trifluoromethylsulfonate), arylsulfonate (preferably 4-methylphenylsulfonate), with a compound of formula (III) A:

(III) A Wl, W2, Ri, R2, R3, R13, X], X2, X3 and p having the same definition as that indicated in one of Claims 1 to 6, the benzyl halide derivatives of formula (II) A where V] is a halogen atom (preferably chlorine or bromine) being obtained: - by halogenation of 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 indicated in Claims 1 to 6 and R4 is the group alkylamino, dialkylamino, the groups G8 and G9 having the same definition that that indicated in claims 1 to 6, X4 having the same definition as that indicated in claims 1 to 6, W] is the oxygen atom, with a halogenating agent such as thionyl chloride, phosphorus oxytrichloride , phosphorus tribromide or with the lithium halide / mesyl halide / collidine reagent; or

- by cleavage of a compound of formula (II) C:

in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that indicated in claims 1 to 6 and R4 is the alkylamino, dialkylamino group, the groups G8 and G9 having the same definition as that indicated claims 1 to 6, X4 having the same definition as that indicated claims 1 to 6, Wj is the oxygen atom, and P is a protective group of the alcohol function like an ester preferably acetic or benzoic, or an ether, preferably methyl, methoxymethyl, phenyl, benzyl, with a Lewis acid such as boron tribromide, or anhydrous hydracids such as hydrogen chloride.

18. Compounds of formula (III) A:

(III) A in which W1, W2, R, R2, R3, R13, X, X2, X3 and p having the same definition as that indicated in one of claims 1 to 6.

19. Process for the preparation of compounds according to one of claims

1 to 6 for which G is one of the groups Gl to G9, the groups Gl to G7 having the same definition as that indicated in one of claims 1 to 6 and R4 is the group or radical amino, alkylamino, dialkylamino, groups G8 and G9 having the same definition as that indicated in one of claims 1 to 6, X4 having the same definition as that indicated in one of claims 1 to 6, consisting in bringing into contact 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 indicated in one of claims 1 to 6 and R4 is the group or radical amino, alkylamino, dialkylamino, the groups G8 and G9 having the same definition as that indicated in one of claims 1 to 6, X4 having the same definition as that indicated in one of claims 1 to 6. and Wj is the oxygen or sulfur atom, with a compound of formula (III) B:

(III) B

W2, R], R2, R3, Ri 3, X], X2, X3 and p having the same definition as that indicated in one of Claims 1 to 6, U3 being a halogen atom preferably a chlorine atom , the double bond U3-C (R3) = N-W2- can be of stereochemistry (E) or (Z).

20. Process for the preparation of compounds according to one of claims

1 to 6 for which G is the group G3, Q2 being the oxygen atom, R4 being the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated in one of claims 1 to 6 and Rg is a lower alkyl or lower haloalkyl group, consisting in bringing a compound of formula (IX) into contact:

(IX) in which R4 is the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated in one of claims 1 to 6,

with a Wittig-Horner reagent of formula (X) A:

Rg-CH ₂ -P (= 0) (OR _b ) ₂ (X) A

Rg being a lower alkyl or lower haloalkyl group, R ^ being a lower alkyl, phenyl or benzyl group,

or with a Wittig reagent of formula (X) B:

Rg-CH ₂ -P (R _d ) 3 ⁺ ; Hal ^" (X) B

Rg being a lower alkyl or lower haloalkyl group, R i being an optionally substituted phenyl group, Hal ^" being a halide ion.

21. Process for the preparation of compounds according to one of claims

1 to 6 for which G is the Gl or G2 group, Ql being the nitrogen atom or the CH group, Q2 being the oxygen atom, R4 being the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated in one of claims 1 to 6 and R5 is a lower haloalkyl group, consisting in bringing a compound of formula (XI) into contact:

(XI) in which T is the oxygen atom and M an alkali or alkaline earth ion, Ql being the nitrogen atom or the CH group, R4 being the alkoxy, alkylamino, dialkylamino, Wl, W2, Ri group, R2, R3, R13, X \, X2, X3, X4 and p having the same definition as that indicated in one of claims 1 to 6, with a halogen compound of formula CHq (Hal) 4_q where q = 1 or 2 and Hal denotes the halogen atoms which are identical to or different from one another and at least one of which is the chlorine or bromine atom.

22. Process for the preparation of compounds according to one of claims

1 to 6 for which G is the group G4 in which n = 1, Q2 being the oxygen atom, R4 being the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated in one of the Claims 1 to 6, consisting in reacting a compound of formula (XII) A:

in which R4 is the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for formula (I), with a reagent of formula (XIII):

V, OR ₅

(XIII)

in which Vi is a halogen atom (preferably chlorine or bromine), R5 having the same definition as that indicated in one of claims 1 to 6.

23. for which G is the group G1 to G7 and R4 is the alkylamino or dialkylamino group, the other substituents having the same definition as that indicated in one of claims 1 to 6, consisting in bringing a compound of general formula into contact (I) for which G is the group G 1 to G7 and R4 is the alkoxy or alkylthio group, the other substituents having the same definition as that indicated in one of claims 1 to 6, with an alkylamine or dialkylamine.

24. Process for the preparation of the compounds according to one of claims

1 to 6 for which Wl is the sulfoxide (SO) or sulfone (SO2) group and G being one of the groups Gl, G3, G4, G6 to G9, Q2 and Q3 being the oxygen atom, the other substituents having the same definition as that indicated in one of claims 1 to 6, consisting of an oxidation of the compounds of general formula (I) for which W1 is the sulfur atom, G being one of the groups Gl, G3, G4, G6 to G9, Q2 and Q3 being the oxygen atom, the other substituents having the same definition as that indicated in one of claims 1 to 6, using one equivalent or more of an agent d 'oxidation.

25. Process for preparing the compounds according to one of claims

1 to 6 in which the groups W1, W2, Ri, R2, R3, X], X2, X3, X4 and p having the same meaning as in one of claims 1 to 6 and G is the group G7, consisting of bringing the intermediaries of formula (III) A into contact:

(III) A in which the groups W1, W2, R \, R2, R3, R13, Xj, X2, X3, and p have the same meaning as in one of Claims 1 to 6, with a compound of general formula (II) A: for which G is the group G7, X4 having the same definition as that indicated in one of claims 1 to 6 and Vi is a halogen atom preferably chlorine or bromine.

26. Process for preparing the compounds according to one of claims

1 to 6 in which the groups W1, W2, R, R2, R3, X \, X2, X3, X4 and p having the same meaning as in one of claims 1 to 6 and G is the group G3, and Rg is the trifluoromethyl radical, consisting in bringing the compounds of formula (III) A into contact:

(III) A in which the groups W1, W2, Ri, R2, R3, R13, X], X2, X3, and p have the same meaning as in one of claims 1 to 6, with a compound of general formula (II) A:

for which G is the group G3, Rg is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated in one of claims 1 to 6 and V] is a halogen atom preferably chlorine or bromine.

27. A process for preparing the compounds of formula (III) A, according to claim 18, where W2 is the oxygen atom and p = 1 or the hydrazonic or thiohydrazonic acids of formula (III) A, according to claim 18 where W2 is the group NR13 and p = 0 or 1, Wl, R, R2, R3, R13, X \, X2, X3 having the same definition as that indicated in one of claims 1 to 6, consisting in bringing a compound of formula (IV) into contact:

H ₂

(IV)

W2, R}, R2, R] 3, X, X2, X3 and p having the same definition as that indicated in one of claims 1 to 6, with a compound of formula (V):

Wl, R3 having the same definition as that indicated in one of claims 1 to 6, Ul is a halogen atom (preferably chlorine or bromine), or a hydroxy, lower alkoxy or benzyloxy, lower alkylthio, amino, or the group -0 (C = 0) R _a , R _a having the same definition as that of R3 indicated in one of claims 1 to 6 and being identical to R3 or different, preferably a halogen atom, the compound of formula (V) then being an acid halide.

28. Process for preparing the compounds of formula (III) A, according to claim 18, where W2 is the oxygen atom and p = 1 or the hydrazonic acids of formula (III) A where W2 is the group NR13 and p = 1, Wl, R \, R2, R3, R 3, X], X2, X3 having the same definition as that indicated in one of Claims 1 to 6, consisting in bringing a compound of formula (VI) into contact :

Ri, R2, Xi, X2 _" X3 having the same definition as that indicated in one of claims 1 to 6, and U2 is a halogen atom (preferably chlorine or bromine), an alkylsulfonate group (preferably methylsulfonate or trifluoromethylsulfonate), with a hydroxamic acid derivative where W2 is the oxygen atom or a hydrazonic acid derivative where W2 is the group NR 3, R3 and R13 having the same definition as that indicated in one of claims 1 to 6 , of formula

(VII):

29. Process for the preparation of the compounds of formula (III) A, according to claim 18, in which W1 is the sulfur atom and W2 is the oxygen atom or the thiohydrazonic acids of formula (III) A according to claim 18 , where W1 is the sulfur atom and W2 is the group NR13, R], R2, R3, R13, X \, X2, X3 and p having the same definition as that indicated in one of claims 1 to 6, consisting of a thionation of the hydroxamic acids of formula (III) A where Wl is the oxygen atom and W2 is the oxygen atom or the hydrazonic acids of formula (III) A where Wl is the oxygen atom and W2 is the group NR13, R], R2, R3, R13, X], X2, X3 and p having the same definition as that indicated in one of claims 1 to 6, with thionating agents.