CA2268021A1 - 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 from crops using these compounds or compositions.
Derivatives with an lnxroximic function used for control crop phytopathogenic fungi are known in particular from EP 463488 and EP 370629.
An object of the present invention is therefore to propose a new family of compounds comprising the hydrox: imic or hydrazonic function useful as fungicides.
Another object of the present invention is to propose a new family of compounds comprising the hydroximic or hydrazonic function having a broad spectrum of action on phytopathogenic fungi in crops.
2o Another object of the present invention is to propose a new family of compounds comprising the hydroximic or hydrazonic function having a broad spectrum of action on crop pathogenic fungi to solve the specific problems encountered.
Another object of the present invention is to propose 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 propose a new family of compounds comprising the hydroximic or hydrazonic function having a broad spectrum of action improved on phytopathogenic fungi of cultures such as rice, cereals, fruit trees, vines and beets.
It has been found that these objects can be achieved in whole or in part, by the compounds described in the present invention.

WO 98/1551

2 PCT / FR97 / 01774 General definition of the invention The invention relates to compounds comprising the hydro ~ imique or hydrazonic of general formula (I) R, X, Xa W, ~~ Wz p X2 (I)

3 io in which G is chosen from the groups Gl to G9 Rs ~ R4 Rs ~ R4 Rs R4 'he' II ' 5 4 R5 - \ / R4 / R4 R (CH2) n ~ R (CH2) n ~ R7 R4 R10 ~ Q3 R10 Q3 Qy 04 ~ 45 1 s G7 G8 G9 wherein n = Y or 1 2o Q 1 is the nitrogen atom or the CH group, .._. ~ ... ... . .. ~, WO 98115512 PCT / FIt97 / 01774 Q2 is the oxygen or sulfur atom.
Q3 is the oxygen or sulfur atom.
Q ~ l is the nitrogen atom or the group CRl 1, QS is the oxygen, sulfur atom or the NR12 group>
Y is the oxygen, sulfur or amino (NH) or oxyamino group (ONH) W 1 is the oxygen or sulfur atom or the sulfinyl groups (SO) or 1o sulfonyl (S02, W2 is the oxygen atom or the NRI group ;, p = 1 when W2 is the oxygen atom, p = 0 or 1 when W2 is the group NF: 1 ~.
X 1, X ~, X3 are independently of each other a hydro ~~ ene atom, a halogen atom; or hydroxy, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl; a lower alkyl group, lower haloalkyl, alkoxy, 2o haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyle, haloalkoxyalkyle, alkylthioalkyle, haloalkylthioalkyle, cyanoalkyle, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfmyl, alkylsulfonyl, haloalkylsulfonyl, alkoxysulfonyl;
or a lower cycloalkyl, lower halocycloalkyl or alkenyl group, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio; or an amino group, N-alkylamino, N, N-dialkylamino, acylamino, aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl; or a carboxy, carbamoyl, N-alkylcarbamoyl, N, N- group dialkylcarbamoyl, lower alkoxycarbonyl; or, 3o an acyl group;
X4 is a hydrogen atom, a: halogen atom; or lower alkyl, lower haloalkyl, alkoxy, haloalkoxy; or cyano, nitro radicals,

4 R1, R ~ are independently of each other a hydro atom; ene, a rump lower alkyl, lower haloalkyl, cycloalkyl group inferior, lower halocycloalkyl, an alkoxyaikyl, haloalkoxyalkyle group, s alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; or a cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N, N- group dialkylcarbamoyl, a lower alkoxycarbonyl group, alkylthiocarbonyl, haloalkoxycarbonyle, alkoxythiocarbonyle, haloalkoxythiocarbonyle, alkylthio-thiocarbonyl; or 1 o an aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl group, acylaminoalkyl R1 and R ~ can together form a divalent radical as a group alkvlene, optionally substituted by one or more halogen atoms, Optionally substituted with one or more lower alkyl groups, R ~ is a hydrogen atom, a lower alkyl, haloalkyl group lower, a lower cycloalkyl group, lower halocycloalkyl, a group alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyle, haloalkoxyalkyle, 2o alkylthioalkyle, haloalkylthioalkyle, cyanoalkyle; or a vitro, cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxy-carbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; or Alkenyl, alkynyl, N, N-dialkyiamino, N, N-dialkylaminoalkyl;
or an optionally substituted phenyl or benzyl group, R4 is a lower alkyl group, lower haloalkyl, a group Lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl; or an alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino group, R ~, R6 is independently of each other a lower alkyl group, lower haloalkyl, R ~ is a lower alkyl, lower haloalkyl, alkoxyalkyl group, haloalkoxyalkyle, alkenyl, alkynyle, Rg is a lower alkyl, lower haloalkyl, alkoxyalkyl group, haloalkoxyalkyle, alkenyl, alkynyle, formyle, acyle, R9 is the hydrogen atom, a lower alkyl group, lower haloalkyl group, a lower cycloalkyl, lower halocycloalkyl or alkoxyalkyl group, o haloalkoxyalkyle, alkenyl, alkynyl, Rlp is a halogen atom, a lower alkyl, haloalkyl group lower, lower cycloalkyl, lower halocycloalkyl. a group alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkvlsulfinvle, haloalkylsulfinyl, alkvlsulfonyle, haloalkylsulfonyle, R 1 1, R 1 ~ are independently of each other the hydrogen atom, a lower alkyl group, lower haloalkyl group, cycloalkyl group inferior, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, Rl ~ is hydrogen, lower alkyl, haloalkyl inferior.
a lower cycloalkyl, lower halocycloalkyl or alkoxyalkyl group, haloaIkoxyalkyle, alkylthioalkyle, haloalkylthioalkyle, an allyl group optionally substituted, an optionally substituted propar gyle group, a optionally substituted benzyl group; or an acyl group, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, alkoxy-lower carbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythio-carbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; or an alkylsulfonyl, haloalkylsulfonyl, optionally arylsulfonyl group 3o substituted, provided that when W2 and Q2 are the oxygen atom and G represents the group G1, then RS is other than an alkyl group, and R4 is other than an alkoxy group, all: ylamino, dialkvlamino, and R ~ is other than a hydro ~~ ene atom. a group alkyl, haloall: yl, a cycloalkyl group, halocycloalkyle, a group alkoxyalkyle, haloalkoxyalkyle, alkylthioalkyle, cyanoalkyle, alényle, alcvnyle, dialkylaminoalkyl, or an optionally substituted phenyl or benzyl group.
as well as the salts, metal and metalloid complexes of the compounds of formula (I) as just defined.
In the text of the present invention, the name "

1 o hydroximic "includes both" hydroximic group "(with the strict the enchantment OC = NO) than the "thiohydroximic group" (with the enchantment SC = NO). Of the group same way, the name "

hydrazonic "includes both" hydrazonic group "(with the strict thiohydrazonic enchantment "(with OC = NN) that enchantment the group is SC = NN).

In addition, the following generic terms are used with following meanings 20 - the halogen atom means the fluorine, chlorine, bromine atom or diode, - the adjective "lower" qualifying an organic radical, means that this radical has 1 to 6 carbon atoms, with the exception of the cycloalkvle radical where the adjective "lower" means from 3 to 6 carbon atoms, - the alkyl radicals can be linear or branched, 25 - the halogenated alkyl radicals may contain one or more atoms of identical or different halogens, the acyl radical signifies alkylcarbonyl, or cycloalkylcarbonyl, - the lower adjective qualifying the term acyl applies to the alkyl part or cycloalkyl of this radical, 30 - 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.

WO 98l15512 PCT / FR97 / 01774 Preferred embodiments of the invention are those products of formula (I) also have one and / or the other of the characteristics following taken individually or in combination n = yes p = 1 Q2 is the oxygen atom, and or Q3 is the oxygen atom, and / or Q4 is the nitrogen atom, and / or Q ~ is the oxygen atom;
lo WI is the oxygen or sulfur atom W2 is the oxygen atom or an alkylamino, haloalkylamino group, alkoxyalkylamino, allylamino, Y is the oxygen atom, XI, X2. X3 and X4 are independently of each other an atom 1 has hydrogen. a lower alkyl group, a halogen atom. where the radicals cyano, trifluoromethyl, methoxy, RI and R2 are independently the u: n of the other a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyle, N-alkylaminoalkyle, N, N-dialkylaminoalkyle, 2o acylaminoalkyl, lower alkoxycarbonyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, R; is hydrogen, lower alkyl, cycloalkyl lower, lower haloalkyl, alkoxyalkyl, preferably a radical methyl.
ethyl, propyl, isopropyl, cyclopropyl, methoxymethyl, R4 is a lower alkyl, alkoxy, alkylamino, dialkylamino group, of preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino radical, ethy lamino, R5, R6, Rg and R9 are independently of each other an alkyl group lower, lower haloalkyl, preferably a methyl radical, fluoromethyl, 3o difluoromethyl, trifluoromethyl, ethyl, 2;, 2,2-trifluoroethyl, propyl, R ~ is a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl, difluorom ~ ethyl, trifluoromethyl, ethyl radical, 2,2,2-trifluoroethyl, propyl, an allyl group, propargyl, R 10 is a chlorine atom, a lower alkyl, lower haloalkyl group.
preferably methyl, an alkoxy or alkylthio group, preferably methoxy, methylthio, Rl 1 and R12 are independently of each other a lower alkyl group, lower haloalkyl, alkoxyalkyle, allyl, propargyle, R 13 is hydrogen, lower alkyl, haloalkyl inferior, alkoxyalkyle, haloalkoxyalkyIe, allyl, propargyle, benzyle.
Among the previous variants, we will choose more particularly the to the following variants taken individually in combination W 1 is the oxygen atom, Rl is the hydrogen atom or the methyl radical, R2 is a hydrogen atom or a lower alkyl group, cyano.
cvanoalkyle, alkoxyalkyle, N, N-dialkylaminoalkyle, lower alkoxycarbonyle, 1 a N, lower N-dialkyl-carbamoyl, Even more particularly preferred compounds are those where.
substituents W 1 and W2 are in trans position (see below) relative to the double bond -C (RI) = N-.
The compounds of general formula (I) and the compounds optionally usable as intermediaries in the preparation processes, and which will defined when describing these processes, may exist under one or several forms of geometric isomers according to the number of double bonds of compound. The compounds of general formula (I) where G is the group G 1, G2 or G3 may have four different stereoisomers denoted (E, E), (E, Z), (Z, E), (Z, Z) depending on the configuration of the two double bonds. E and Z notation can be replaced by the terms syn and anti, or cis and trans respectively. We is will report in particular to the work of E.Eliel and S.Wilen "Stereochemistry of 3o Organic Compounds "Ed. Wiley (1994} for description and use of these ratings.
By convention, in the case of the present invention, the names (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 with the second letter the configuration of the hvdroximic or hydrazonic group.
The compounds of general formula (1) where G is the group G4 to G9 can have two different stereoisomers noted (E) or (Z) depending on the configuration of the hydroximic or hydrazonic group.
The compounds of general formula (I) and the compounds optionally usable as intermediaries in the preparation processes, and which will defined when describing these. processes, can exist under one or several forms of optical or chiral isomers depending on the number of centers asymmetric of the compound. The invention therefore relates equally to all isomers optics as their racemic mixtures and the corresponding diastereoisomers mixed or separated. I_a separation of. diastereoisomers and / or isomers optics can be performed according to methods known per se (E.Eliel ibid.).
t5 Preparation processes The compounds of the present invention of general formula (I) and the compounds which may be used as: intermediates in processes preparation, can be prepared by rr ~ oins one of the methods of preparation general described below: method A to L.
The preparation of reagents used in one or other of the methods of general preparation, is usually known per se and is usually described specifically in the prior art or in such a way that humans of art can adapt it to the desired goal. The prior art usable by humans art to establish the conditions for the preparation of reagents, can be found in of many general chemistry works such as "Advanced Organic Chemistry"
by J.March, Ed. Wiley (1992), "Methode: n der organischen Chemie" (Houben-Weyl), Ed. Georg Thieme Verlag or the "Chemical Abstracts" Ed. American Chemical Society as well as in accessible computer databases to the public.

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

5 G 1 to G9, the other substituents having the definition already indicated, can to be obtained by a process consisting in bringing a compound of formula into contact (II) A
o ~, X

(II) A
to in which G is one of the groups G 1 to G9, the groups G 1 to G9 having the same definition as those indicated for formula (I), X4 having the same definition than that indicated for formula (I), V 1 is a halogen atom (preferably chlorine or bromine), a ~ = cut alkylsulfonate or haloalkylsulfonate (preferably methylsulfonate or trifluoromethylsulfonate), arylsulfonate (preferably 4-methylphenylsulfonate), with a comliosé of formula (III) A
li RX ~
in / ~ r ~ 1 X2 W2 P ~ Xs (III) A
Wl, W2, R1, R2, R3, RI3, X1, 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 presence of a solvent. The reaction is usually carried out at a temperature between - 80 ~ C and 180 ~ C (preferably between 0 ~ C and 1 SO ~ C) or at point the solvent used. The appropriate solvent for this reaction can be a aliphatic hydrocarbon such as pentane, fhexane, heptane, octane; a aromatic hydrocarbon such as benzene, toluene, xylenes, halo ~~ enobenzenes; an ether such as diethyl ether, düsopropylether, tetrahydrofuran, dioxane, dimethoxyethane; halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane; an ester such as methyl acetate, ethyl acetate, a nitrite such as acetonitrile, propionitrile, Ifs benzonitrile; an aprotic solvent dipolar such as dimethylformamide, dimethylacetamide, Ia N-methylpyrrolidone, dimethylprolyleneurc: e, dimethylsulfoxide; or water.
Of mixtures of these different solvents can also be used.
The reaction time depends on the conditions used and is generally 1 o between 0.1 to 48 h.
As an appropriate organic or inorganic base for this reaction, may mention the alkali and alkaline earth metal hydroxides such as hydroxide sodium, potassium, cesium or calcium; metal alcoholates alkaline and alkaline earth such as potassium ter-butoxide, hydrides of alkali and alkaline earth metals, such as sodium hydride, potassium or cesium; carbonates and bicarbonates of alkali metals and alkalineeweux such as sodium carbonate, potassium carbonate, calcium or bicarbonate sodium, potassium or calcium; organic bases, preferably nitrogenous.
such as pyridine, alkylpyridines, alkylamines such as trimethylamine, triethylamine or düsopropylethylarnine, aza derivatives such as 1. ~ -diazabicyclo [4.3.0] non-S-ene or 1.8-diazabicyclo [i.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 ~ one molar ratio (III) A / (II) A of between 0.1 and 10, preferably 0.5 to 2.
Depending on the conditions used, the compounds of general formula (I) are obtained as a variable mixture of (E) and (Z) isomers or as a single isomer (E) or a single isomer (Z) depending on the group configuration hydroximic or hydrazonic. If necessary, the compounds of general formula (I) and configuration (E) or (Z) depending on the configuration of the group hydroximic or hydrazonic, can be isolated and purified according to known methods in itself such as for example extraction, crystallization or chromatography.

IZ
The hydroxamic or thiohydroxamic acids of formula (III) A where ~ U?
is the oxygen atom and p = 1 or the hydrazonic acids or thiohydrazonic of formula (III) A where W2 is the group NR13 and p = 0 or 1, Wl, RI, R ~, R ~, Rl ~.
X 1, X ~, X ~ having the same definition as that indicated for formula (I), can be obtained by a method of contacting a compound of formula (IV) R ~
H2 ~ X2 W2 p X3 (IV) W2, R1, R ~, R1 ~, X1, X ~, X ~ and p having the same definition as that 1 o indicated for formula (I), with a compound of formula (V) W ~ U ~
R3 (V) 5 W 1, R ~ having the same definition as that indicated for formula (I), L ' is a halogen atom (preferably chlorine or bromine), or a radical hydroxy, lower alkoxy or benzyloxy, lower alkylthio, amino, or the group -O (C = O) Ra, Ra having the same definition as that of R ~ indicated for the formula (I) and being identical to R3 or different, preferably a halogen atom, the 2o compound of formula (V) then being an acid halide.
Condensation between the compound of formula (IV) and the compound of formula (V) is carried out in the presence of an organic or inorganic base, or of a reagent dehydration such as carboxylic acid anhydrides, preferably Acetic anhydride or propionic anhydride, in the absence or in the presence of 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). ~~ where V'2 is the oxygen atom and p = 1 or the hydrazonic acids of formula (III) A where W2 is the group NR I ~
and p = 1, W 1, R1, R2, R3, R13, X1, 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 U
Xs (VI) 1 o R1, R ~, X l, X ~, X3 having the same definition as that indicated for the formula (I), and U ~ is a halogen atom (preferably chlorine or bromine), a alkylsulfonate group (preferably methylsulfonate or trifluoro-methylsulfonate), with a hydroxamic acid derivative: where W2 is the oxygen atom or a derivative of hydrazonic acid where W2 is the group NR13, R3 and R13 having the same definition than that indicated for formula (I), of formula (VII) H
~~~ W2-H

(VII) 2o The condensation between the compound of: formula (VI) and the compound of formula (VII) is carried out in the presence of an organic or inorganic base, in the 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.

1 ~ l The compounds of formula (IV)) formula (V), formula (VI) and formula (VII).
V 'I, ~. ~ ?. R 1, R2. R3, R l ;, X l, X2. X; and p having the same definition than indicated for formula (I), U 1 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 â
G9) groups G 1 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) and V 1 is a halogen atom (preferably chlorine or bromine), a group io alkylsulfonate (preferably methylsulfonate or trifluoromethyl-sulfonate), arylsulfonate (preferably 4-methylphenylsulfonate), will be by convention, for the rest of the description of the preparation methods, designated by term generic "benzyles halide derivatives".
The benzyl halide derivatives of formula (II) A where V 1 is an atom halogen (preferably chlorine or bromine) can be obtained by halogenation of a compound of formula (VIII) x4 ~ cH3 (VIII) 2o in which G is one of the groups G1 to G9, the groups G1 to G9 having the same definition as that indicated for formula (I), Xç having the same definition than that indicated for formula (I).
The halogenation of the compound of formula (VIII) can be carried out by radical, thermal or photochemical, the different processes not being mutually exclusive, by an N-haloacetamide such as N
bromosuccinimide, N-chlorosuccinimide, N-bromoacetamide, in a inert solvent such as benzene or carbon tetrachloride or in the absence of solvent with or without a free radical initiator at a temperature of 20 ~ C to l70 ~ C preferably from 80 ~ C to l00 ~ C according to J. March ibid. pages 689-697.

IS
The benzyl halide derivatives of formula (II) A where V 1 is an atom halogen (preferably chlorine or bromine) can also be obtained by halogenation of a compound of formula (II) B
~ W ~ H
X 'l' G (II) B
in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as indicated for formula (I) and R4 is the group alkylamino, dialkylamino, groups G8 and G9 having the same definition as 1 o that indicated for formula (I), X4 having the same definition as that indicated for formula (I), W 1 is the oxygen atom, with a halogenating agent such as thionyl chloride, oxvtrichloride phosphorus. phosphorus tribromide according to J. March ibid. pages 431-433 or with the lithium halide / mesyl halide / collidine reagent following t5 3.Org.Chem. (l971), 36.3044.
The benzyl halide derivatives of formula (II) A where V 1 is an atom halogen (preferably chlorine or bromine) can also be obtained by cleavage of a compound of formula (II) C
uWi_P

G
(II) C
in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as indicated for formula (I) and R4 is the group alkylamino, dialkylamino, groups G8 and G9 having the same definition as that indicated for the formula (I}, X4 having the same definition as that indicated for formula (I), W 1 is the oxygen atom, and P is a group protective alcohol function as an ester of preference; acetic or benzoic ference, or a ether preferably methyl, methoxymethyl, phenyl, benzyl, (we will bring back advantageously to the book "Protective Groups in Organic Svnthesis" by ~ '. Greene and P. W uts, Ed. Wiley (1991) for the choit and the preparation of said protective groups), with a Lewis acid like boron tribromide, or hydracids anhydrous like hydrogen chloride. This cleavage reaction is especially known 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 1 o in itself. These different methods or the related prior art will explained in methods J, K and L.
Method B
1 ~ The compounds of general formula (I) for which G is one of the groups G 1 to G9, the groups G 1 to G7 having the same definition as that indicated for the formula (I) and R4 is the amino, alkylamino, dialkylamino group or radical.
the groups G8 and G9 having the same definition as that indicated for the formula (I), X ~ having the same definition as that indicated for formula (I), can to be 2o obtained by a process consisting in bringing into contact a compound of formula (II) B in which G is one of the groups G 1 to G9, the groups G 1 to G7 having the same definition as that indicated for formula (I) and R4 is the group or amino radical, alkylamino, dialkylamino, groups G8 and G9 having the same definition as that indicated for formula (I), X ~ having the same definition than 25 that indicated for formula (I), and W 1 is the oxygen or sulfur, with a compound of formula (III) B
X ~
U3 N ~ R1 Xz Wz P Xa (III) B
3o W2, R1, R2, R3, R13, X1, X2, X3 and p having the same definition as that indicated for formula (I), U3 being a halogen atom preferably a atom of chlorine, the double bond U3-C (R3) = N-fJ ~ - 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 presence of a solvent. The reaction is usually performed at a temperature between - 80 ~ C and l 80 ~ C (preferably between 0 ~ C and 1 ~ 0 ~ C) or at the boiling point of the solvent used. The appropriate solvent for this reaction may be an ether such as diethyl ether, düsopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, a nitrile like acetonitrile, propionitrile, benzonitrile, a dipolar aprotic solvent such as ~ o dimethylformamide, dimethylacetarnide, N-methylpyrrolidone, dimethylprolylene urea, or dime; thylsulfoxide. 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.
~ 5 As an appropriate organic or inorganic base for this reaction, may mention the hydrides of alkali metals and: alkaline earth, as hydride of sodium, potassium or cesium, alkali metal alcoholates and alkaline-earthy, such as potassium tert-butoxide.
There is no strict limitation for the relative proportions of the compounds 2o of formula (II) B and of formula (III) B. It is however advantageous to choose one molar ratio (III) B / (II) B of between 0.1 and 10, preferably 0.5 to 2.
Depending on the conditions used, the compounds of general farmule (I) are obtained as a variable mixture of (E) and (Z) isomers or as a single isomer (E) or a single isomer (Z) depending on the group configuration 25 hydroximic or hydrazonic. If necessary, the compounds of formula general (I) and configuration (E) or (Z) depending on the configuration of the group hydroximic or hydrazonic, can be isolated and purified according to known methods in itself 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.
(197l), 36, 234, and Chem. Abstracts (1970), _ 13, 34750s.

Method C
The thiohydroxamic acids of formula (III) A where W 1 is the sulfur atom and W2 is the oxygen atom or the thiohydrazonic acids of formula (III) A
or Wl is the sulfur atom and W2 is the NRI group ;, Rl, R2, R3, R1 ~, Xl, 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 W 1 is the oxygen atom and W2 is the oxygen atom or the acids hydrazonics of form (III) A where W 1 is the oxygen atom and W2 is the group NR13, Rl, R2, R3, R13, Xl, X2. X3 and p having the same definition as that indicated for formula (I}, with thionating agents such as pentasulfide phosphorus or Lawesson's reagent in the same or similar way to the processes described in "Houben-Weyl" volume E ~, pages I279-l280 and Synthesis 1 s (1984}, 829.
Method D
The compounds of general formula (I) for which G is the group G3, Q2 2o being the oxygen atom, R4 being the alkoxy, alkylamino group, dialkylamino, the other substituents having the same definition as that indicated for the formula (I) and R6 is a lower alkyl or lower haloalkyl group, may be obtained by a process consisting in bringing a compound of formula (IX) into contact R ~ X ~
W1 ~~ X2 Ra Ra Rz O
25 (IX) in which R4 is the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for the formula (I}, WO 98I15512 PCT / FR97l01774 with a Wittig-Horner reagent of formula (X) A
R6-CbI2-P (= O) (ORb) 2 (X) A
R6 being a lower alkyl group or a lower haloalkyl group, Rb being a lower aikyl, phenyl or benzyl group, or with a Wittig reagent of formula (X) B
lo R6-CH2-P (Rd) 3 ~~; Hal- (X) B
R6 being a lower alkyl or lower haloalkyl group, Rd being a optionally substituted phenyl group, Rial- being a halide ion, per share of one or more equivalents. of a base like the alcoholates of I ~ alkali or alkaline earth metals, preferably sodium fethylate. the sodium methylate or potassium tert-butoxide, metal hydrides alkaline and alkaline earth, preferably sodium or sodium hydroxide potassium, of a organometallic derivative such as the preferred alkyllithians butyllithium, the alkylmagnesium halides or lithium dopropopropylamide in a 2o aprotic solvent such as ethers preferably diethyl ether or tetrahydrofuran at a temperature of - 78 ~ C to 50 ~ C preferably - 70 ~ C to ~ C according to J. March ibid. pages 9S6-963 or patent WO 929896.
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 (lf) for which G is the group Gl or G2, Q 1 being the nitrogen atom or the group; CH, Q2 being the oxygen atom, Rç
3o being the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for formula (I) and R5 is a group lower haloalkyl, can be obtained by a process of in contact a compound of formula (XI) R Xy y W ~ ~ X2 X4 ~ ~ W2 P X3 MT ~ R4 R3 Rz O
(XI) in which T is the oxygen atom and M an alkaline or alkaline ion earthy, Q 1 being the nitrogen atom or the CH group, R4 being the alkoxy group, 5 alkylamino, dialkylamino, W 1, W2, R 1, R2, R3, R 13, X 1, X2, X3, X4 and p having the same definition as that indicated for formula (I), with a halogenated compound of formula CHq (Hal) 4-q where q = 1 or 2 and Hal denotes the halogen atoms identical or different between them and one of which of them at least is the chlorine or bromine atom, 10 in a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolylene urea, or the dimethyl sulfoxide in the presence or absence of a catalytic amount of iodide ion, at a temperature between -20 ~ C and 250 ~ C preferably 25 ~ C to 1 ~ 0 ~ C
or at reflux of the solvent. This reaction is described in particular in the DE patents 15 4424788 and WO 9606072.
The compounds of formula (XI) in which T is the oxygen atom and M a alkaline or alkaline earth ion, Q1 being the nitrogen atom, R4 being the Group alkoxy, alkylamino, dialkylamino, W 1, W2, Rl, R2, R3, R1 ~, X 1, X2, X ;, X4 and 2o p having the same definition as that indicated for formula (I), can to 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 than that indicated for formula (I), by 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 a alkaline or alkaline earth ion, Q 1 being the group CH, R4 being the group alkoxy, alkylamino, dialkylamino, Wl, W2, R1, R2, R3, R13, Xl, X2, X3, X4 and p having the same definition as that indicated for formula (I) can be especially 3o prepared in a similar manner 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,: EZ4 being the alkoxy group, alkylamino, dialkylamino, other substituents having the same definition as that indicated for formula (I), can be obtained by reaction between a compound of formula (XII) A:
R, HN \ 'R4 R3 R
1I I ~ z O
(XII) A
wherein R4 is the group; alkoxy. alkylamino, dialkylamino, the other substituents having the same definition as that indicated for the formula (I), with a reagent of formula (XIII):
V1 SRS (XIII) in which V 1 is a halogen atom (preferably chlorine or bromine), RS having the same definition as that indicated for formula (I), by the action of one or more base equivalents such as the hydroxides of 2o alkali or alkaline earth metals, alkali metal alcoholates or alkaline earthy, alkali metal and alkaline earth hydrides, carbonates and the bicarbonates of alkali or alkaline earth metals, possibly in the presence a phase transfer catalyst such as a quaternary ammonium, in a aprotic solvent such as ethers preferably diethyl ether or tetrahydrofuran at a temperature of -78 "C to 40 ~ C preferably included Between - -20 and 25 ~ C.
The compounds of general formula (XII) A, in which R4 is the group alkoxy, alkylamino, dialkylamino, 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
Ra (XII) B
in which R4 is the alkoxy, alkylamino, dialkylamino group, X4 before the same definition as that indicated for formula (I), V 1 is a halogen atom (preferably chlorine or bromine), a group alkylsulfonate (preferably methylsulfonate or trifluoromethylsulfonate), an ~ lsulfonate (preferably 4-methylphenylsulfonate), with a compound of formula (III) A, VVI, W2, Rl, R ~, R ~, R13, Xl, X ~, X3, and p having the same definition as that indicated for formula (I).
The general conditions of condensation between the compound of formula 1 ~ {XII) B and compound, of formula (III) A are similar or identical to 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 the 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 G 1 to G7 and R4 is the alkoxy or alkylthio group, the other substituents having the same definition as that indicated for the formula (I}, with an alkylamine or dialkylamine, preferably methylamine, in a 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 solvent selected. II
is generally advantageous to use an excess of 1 to 5 equivalents of preference 1.1 to 2 equivalents of alkyl or dialkylamine relative to the compound of formula general (I) for which G is the group G 1 to G7 and R4 is the alkoxy group or alkylthio, the other substituents having the same definition as that indicated for formula (I).
to Method H
The compounds of general formula (I) for which W 1 is the group sulfoxide (SO) or sulfone (S02) and G being one of the groups G1, G3, G ~, G6 to G9, Q2 and Q3 being the oxygen atom, the other substituents having the same definition than that indicated for formula (I), can be obtained by oxidation of the compounds of general formula (I) for which WI is the atom of sulfur, G being one of the groups Gl, G3, G4, G6 to G9, Q2 and Q3 being the atom of oxygen, the other substituents having the same definition as that indicated for formula (I), using one or more equivalent of an oxidizing agent such as the 2o organic peroxides, preferably peracetic acid, 3-chloroperbenzoic acid, mineral peroxides, hydroperoxides such as hydrogen peroxide, mineral oxychlorides or oxygen, in the presence or not of a catalyst in an inert solvent according to J. March ibid. pages 1201-l203.
Method I
The compounds of general formula (I) prepared according to method A or the method B can be obtained with atoms or groups W 1 and W2, WI and W2 having the same meaning as for: Formula (I), in the cis position (see more 3o high) with respect to the double bond -C (R3) = N- (hydroximic group or hydrazonic).
The isomers of general formula (I) with the atoms or group W 1 and W2 in trans position with respect to the double bond -C (R3) = N- (group hydroximic or hydrazonic) can be prepared from cis isomers by heating in a solvent preferably under ultraviolet irradiation, with or as the absence of a catalyst, in particular an acid catalyst. The reaction time is chosen 2 ~
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 appropriate solvent for this reaction can be a aliphatic hydrocarbon such as pentane, hexane, heptane, octane; a aromatic hydrocarbon such as benzene, toluene, xylenes, an ether such as diethyl ether, dopropopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane; a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane; an ester like methyl acetate, ethyl acetate; a nitrite such as acetonitrile, 1 o propionitrile, benzonitrile; an alcohol such as methanol, ethanol, propanol, isopropanol; a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolylene urea, dimethyl sulfoxide; 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 like düsopropyléther. The catalyst, preferably a acid catalyst, will be chosen from anhydrous hydracids such as chloride hydrogen, carboxylic acids like acetic acid, acid propionic, trifluoroacetic acid, sulfonic acids such as acid methanesulfonic, trifluoromethanesulfonic, 4-metllylphenylsulphonic 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 many methods known per se.
Mention will be made, by way of examples, nonlimiting and not exhaustive, of various 3o patents describing the processes for the preparation of halide derivatives of benzyles of formula (II) A or compounds of formula (VIII) or 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 G 1 or G2 of stereochemistry (E) or (Z), can be prepared according to what which is described in patents EP 426460, EP 398692, EP 6170I4, EP 585751, EP
487409, EP 535928. DE 4305502, Benzyl halide derivatives of formula (II) A and the like where G
is the group G3 of stereochemistry (E) or (Z), are known according to the patent WO
9616943, The benzyl halide derivatives of formula (II) A and the like where G
is the group G4, G5 or G6, are known according to patents EP 498396, EP
61930l, WO 9315046, Benzylca halide derivatives of formula (II) A and the like where G
~ o is ie group G7, are known according to patents WO 9527693, WO 9607633, Benzylfa 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, W ?.
R1, R2, R3, X1, X2, X3, X4 and p having the lr ~ same meaning as for the fornmle (I) and G is the group G7 can also be prepared from the process according to which is also the object of the present invention.
2o This process consists in putting in contact the intermediaries of formula general (III) A in which the groups W1, W2, R1, R2, R3, R13, X1, X ~. X3, and p have the same meaning as for formula (I), with a compound of general formula (II) A for which G is the group G7, X4 having the same definition as that given for formula (I) and V 1 is a halogen atom preferably chlorine or bromine according to the process described in the method A.
The compounds of general formula ((I) A for which G is the group G7, X4 having the same definition as that indicated for formula (I) and V 1 is a 3o halogen atom preferably chlorine or bromine can be obtained by reaction for cleavage of the compounds of formula (XIV) A

OCORc v RQ

(XIV) A
in which Y, X4, Q2, R4 and Rg have the same meaning as for the 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 optionally substituted benzyl, optionally substituted aryl, by reaction with a halogenating agent.
This reaction can be carried out at a temperature between -30 ~ C and ~ 0 ~ C in an inert solvent. By inert solvent is meant a hydrocarbon to aliphatic like pentane, hexane cyclohexane and ether oil; or an aromatic compound such as toluene, xylenes; or compounds chlorinated such as methylene chloride, chloroform, 1,1,1-trichloroethane and chlorobenzene; or ethers such as diethyl ether, isopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran; or well a ~ 5 nitrite such as acetonitrile or propionitrile, or an alcohol such as the methanol, ethanol, n-propanol, isopropanol, butanol and tertiobutanol; or either dimethylsulfoxide, or dimethylformamide or a mixture of these solvents.
As halogenating agent, an acid of 2 ~ Lewis such as Aluminum chloride, Boron trichloride, or a hydracid halogenated like hydrogen chloride or hydrogen bromide. The agent halogenation will be in equimolar amount or in excess.
The compounds of formula (XIV) A in which Y, X4, Q2, R4 and Rg have the 25 same meaning as for formula (I) and Rc is a hydrogen atom or one lower alkyl group optionally substituted by one or more halogens or an alkoxy group, an optionally substituted benzyl, an optionally aryl substituted, can be obtained by alkylation of the compounds of formula (XIV) B

2î
OCORc (XIV) B
in which Y, Xq., Q2 and R4 have the same meaning as for the formula (I) and Rc is a hydrogen atom or a lower alkyl group eventually substituted by one or more halogens or an alkoxy group, a benzyl optionally substituted, optionally substituted aryl.
As the alkylating agent, an alkyl halide or sulfonate will be used or acyl of formula (XV}:
to Rg-Vl (XV) wherein Rg is a lower alkyl, lower haloalkyl group.
alkoxyalkyl, haloalkoxyalkyle, formyl or acyl, and V 1 is an atom halogen (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), 51, 866. The reaction is conducted in a dipolar aprotic solvent such as amides such as 2o dimethylformamide, dimethylacetamide, N-methylpyrolidone at a temperature between - 70 ~ C and 180 '~ C, preferably between - 30 ~ C and ~ C.
The compounds of formula (XIV) B in which Y, Xq, Q2 and R ~ 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

$ 2 OCORc (XIV) C
in which Y, X4, Q2 and R ~ have the same meaning as for the formula (I) and Rc has the same meaning as for compound (XIV) A, using a agent reducing agent such as an alkaline or alkaline earth hydride, preferably the sodium borohydride in an alcohol such as methanol, ethanol, propanol, isopropanol. butanol, tertiobutanol according to J. March ibid. page 9l0.
The compounds of formula (XIV) C in which Y, X4, Q2 and R ~. have the to same meaning as for formula (I) and Rc has the same meaning that for compound (XIV) A, can be obtained by a method of contacting a compound of formula (XIV) D
Vy Az (XIV) D
in which Y, X4, Q2 and R4 have the same meaning as for the formula (I) and V 1 is a halogen atom, preferably chlorine or bromine, with a mineral carboxylate such as a formate, an acetate, a propionate 2o or other mineral salt of lower alkylcarboxylic acid, the group of which alkyl can be optionally substituted by one or more halogens or a group alkoxy or an optionally substituted phenyl, or else a benzoic acid salt possibly substituted according to J.March ibid.p398.
The reaction is preferably carried out in an aprotic solvent dipolar such as amides preferably formamide, acetamide, WO 98/15512 PCT / F'R97 / 01774 dimethylacetamide, N-methylpyrrolidine, at a temperature ranging from 0 ~ to solvent reflux.
Compounds (XIV) D are obtained according to methods known per se s as described in patent EP 37481 1.
Method L:
The compounds of general formula (I) in which the groups W 1, W2, to R l, R ~, R3, X l, X2, X3, X4 and p having the same meaning as for the formula (I) and G is the group G3, and R6 is the trifluoromethyl radical can be also prepared from the following process which is also the subject of the present invention.
This process consists in putting in contact the intermediaries of formula General (III) A in which the groups W1, W2, R1, R ~, R3, R13, Xl, X ~, X3, and p have the same meaning as for formula (I), with a compound of general formula (II) A for which G is the group G3, R6 is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I) and V 1 is preferably a halogen atom chlorine or 2o bromine according to the process described in method A.
The compounds of general formula (I: I) A for which G is the group G3, R6 is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I) and V 1 is preferably a halogen atom chlorine or 25 bromine can be obtained by halogenation compounds of general formula (VIII) for which G is the group G3, R6 is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I), according to the process described in method A.
The compounds of general formula ('JIII) for which G is the group G3, R6 is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated for formula (I), can be obtained by dehydration of compounds of formula (XVI):

X4, CH3 ~ i ~ 2 (XVI) in which X4, R4 and Q2 have the same meaning as for the formula (I), 5 using a dehydrating agent such as anhydrous hydracids (of preferably sulfuric acid), their alkali or alkaline earth salts (of preference potassium hydrogen sulfate) or anhydrides such as anhydride phosphoric according to J. March ibid. pages 10l1 et seq. or Chem.Ber.
(1986), 119. 2233, or phosphorus oxvtrichloride, chlorides of alkyl sulfonates 10 (preferably methylsulfonate or trifluoromethylsulfonate), chlorides of arylsulfonates (preferably 4-methylphenylsulfonate) in the presence of a based nitrogen like pyridine, alkylpyridines, alkylamines like trimethylamine, triethylamine or düsoprylethylamine Tetrahedron: Asymmetry (1990), 1.52 l, or dialkyldiazodicarboxylates (from 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 solvent 20 used. The suitable solvent for this reaction can be a hydrocarbon halogenated such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,1, -trichloroethane, an ether such as diethyl ether, düsopropyléther, tetrahydrofuran, dioxane, dimethoxyethane, a nitrile like acetonitrile, propionitrile, benzonitrile, a nitrogenous base such as pyridine, 25 alkylpyridines, a dipolar aprotic solvent such as dimethylformamide, the dimethylacetamide, N-methylpyrrolidone, dimethylprolylene urea, or the dimethyl sulfoxide. Mixtures of these different solvents can also be to be used.
The reaction time depends on the conditions used and is generally 3o between 0.1 to 48 h.

The compounds of general formula (: KVI) in which X, ~, R ~ 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):
X4 ~ CH3 Ra ~ '~ 2 (XVII) in which X4, Rç and Q2 have the same meaning as for the formula (I j, lo with the gaseous trifluoroacetaldehyde, by the action of one or more equivalents of a base such as hydrides of alkali and alkaline earth metals, preferably sodium hydride or potassium, alkali and alkaline earth alcoholates, of a derivative organometallic like the preferred alkyllithians butyllithium, alkyl magnesium halides or alkali metal amides and alkaline earth metals such as lithium propylamide or lithium amide hexamethyldisilazane, in an aprotic solvent such as ethers of 2o preferably diethyl ether or tetrahydrofvrane at a temperature of - 78 ~ C to 50 ~ C preferably - 70 ~ C to 20 ~ C ' The invention also relates to fungicidal compositions comprising a 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), the solid or liquid supports, acceptable in agriculture and / or surfactants also 3o acceptable in agriculture. In particular, the supports can be used inert and usual and the usual surfactants. These compositions not only cover ready-to-apply compositions the plant or seed to be treated using a suitable device, such as spraying or dusting device, but also concentrated commercial compositions which must be diluted before application on culture.
These fungicidal compositions according to the invention may contain also all kinds of other ingredients such as, for example, colloids protectors, adhesives, thickeners, thixotropic agents, lo penetration agents, stabilizers, sequestrants, etc ... More generally the active ingredients can be combined with all solid or liquid additives corresponding to the usual techniques of the formulation.
In general, the compositions according to the invention ~ 5 usually contain 0.05 to 95% (by weight) of active ingredient, one or more solid or liquid supports and, optionally, one or several surfactants.
By the term "support", in the present description, is meant a organic or mineral, natural or synthetic matter, with which 20 the active ingredient 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 agents surfactants. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic acids or naphthalenesulfonic, polycondensates of ethylene oxide on 3o fatty alcohols or fatty acids or fatty amines, substituted phenols (in particular alkylphenols or arylphenols), ester salts of sulfosuccinic acids, taurine derivatives (in particular alkyltaurates), phosphoric esters of alcohols or of polyoxyethylated phenols, esters of fatty acids and polyols, sulfate derivatives) sulfonates and phosphates of the compounds previous. The presence of at least one surfactant is generally essential when the active ingredient and / or the support inert are not soluble in water and that the carrier agent the application is water.
Thus, the compositions for agricultural use according to the invention may contain the active ingredient within very wide limits, ranging from 0.05% to 95% (by weight). Their surfactant content is advantageously between 5% and 40% by weight. Unless stated otherwise the percentages given in this description are weight percentages.
These compositions according to the invention are themselves under fairly diverse forms, solid or liquid.
As forms of solid compositions, mention may be made of powders for dusting (active ingredient content up to 100%) and the granules, in particular those obtained by extrusion, by compaction, by impregnation of a granulated support, by granulation from a powder (the active ingredient 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; we can also use compositions comprising 50 g of active material and 950 g of talc; we can also use compositions comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; we mix and grind these constituents 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, especially water soluble concentrates, emulsions, concentrated suspensions, wettable powders (or spray powder).
Concentrated suspensions, applicable for spraying, are prepared so as to obtain a product which is stable and does not settle not and they usually contain 10 to 75% active ingredient, 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 a carrier, water or an organic liquid in which active ingredient is sparingly or not soluble: certain materials organic solids or mineral salts can be dissolved in the support to help prevent sedimentation or as antifreeze for the water.
1o As an example, here is a suspension composition concentrated Example SC 1 - active ingredient 500 g - polythoxyl tristyrylphnol phosphate 50 g alkylphnol polythoxyl 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%
active ingredient, and they usually contain, in addition to the carrier solid, 0-30% wetting agent, 3-20% wetting agent dispersant, 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 ...
3o To obtain spray powders or wettable powders, we thoroughly mix the active ingredients in the appropriate mixers with additional substances and we grind with mills or other suitable shredders. This gives spray powders whose wettability and suspension are advantageous; we 3 ~
can suspend them with water, ~ any desired concentration and these suspensions can be used very advantageously in particular for application for example on plant leaves or on seeds.
As an example, here are various powder compositions wettable (or spray powders) Example PM 1 - active ingredient 50%
to - ethoxylated fatty alcohol (wetting agent) 2.5%
- ethoxylated phenylethylphenol (dispersing agent) S%
- chalk (inert support) 42.5%
Example PM 2 IS - active ingredient 10%
- branched type oxo synthetic alcohol, C13 ethoxylated by 8 to ethylene oxide (wetting agent) 0.75%
- neutral calcium lignosulfonate (agent dispersant) 12 - calcium carbonate (inert filler) qs 100 Example PM 3 This wettable powder contains the same ingredients as in the previous example, in the proportions below - active ingredient 75%
- wetting agent '1.50%
- dispersing agent 8%
- calcium carbonate (inert filler) qs 100%
3o Example PM 4 - active ingredient 90%
- ethoxylated fatty alcohol (wetting agent :) 4%
- ethoxylated phenylethylphenol (dispersing agent) 6%

Example PM ~
- active ingredient 50%
- mixture of anionic surfactants and non-ionic (wetting agent) 2.5%
- sodium lignosulfonate (dispersing agent) 5%
- kaolin clay (inert support) 42.5%
Aqueous dispersions and emulsions, for example o compositions obtained by diluting a wettable powder with water according to the invention are included in the general framework of the present invention. The emulsions can be of the water-in-oil or oil- type.
in the water and they can have a thick consistency like that a "mayonnaise".
a The fungicidal compositions according to the invention can be formulated as water dispersible granules also included in the context of the invention.
These dispersible granules, of generally apparent density between about 0.3 and 0.6 have a particle size 20 generally between approximately 1 ~ 0 and 2000 and preferably between 300 and 1500 microns.
The active ingredient content of these granules is generally between approximately 1% and 95 ~ rb, and preferably between 25% and 90%.
25 The rest of the granule is essentially composed of a filler solid and optionally surfactant additives giving the granule water dispersibility properties. These granules can be essentially of two distinct types depending on whether the charge selected is soluble or not in water. When the filler is water-soluble, it can 30 be mineral or, preferably, organic. We got excellent results with urea. In the case of an insoluble filler, this is preferably mineral, such as kaolin or bentonite. She is then advantageously accompanied by surfactants (at a reasonable from 2 to 20% by weight of the granule) of which more than half is, for example, consisting of at least one dispersing agent. essentially anionic, such as an alkaline or alkaline earth polynaphthalene sulfonate or an alkali or alkaline earth lignosulfonate, the rest being by nonionic or anionic wetting agents such as an alkyl alkaline or alkaline earth naphthalene sulfonate.
In addition, although it is not essential, one can add other adjuvants such as defoamers.
The granule according to the invention can be prepared by mixing necessary ingredients then granulation according to several techniques in 1 o known ones (bezel, fluid bed, atomizer, extrusion, etc ...). We completed generally by crushing followed by amassing to the size of particle chosen within the limits mentioned above. We can still use granules obtained as above and then impregnated with a composition containing the active ingredient.
~ 5 Preferably, it is obtained by extrusion, operating as shown in the examples below.
Example GD1: Dispersible granules In a mixer, 90% by weight of active material is mixed 20 and 10% urea pearls. The mixture is then ground in a - pins. A powder is obtained which is moistened with approximately 8% by weight of water. The wet powder is extruded in a perforated roller. We obtain a granule which is dried, then crushed and sieved, so as to keep respectivemf ~ nt only the granules of a 25 dimension between 150 and 2000 microns.
Example GD2: Dispersible granules In a mixer, the following constituents are mixed - active ingredient 75%
30 - wetting agent (sodium alkylnaphthalene sulfanate) 2%
- dispersing agent (sodium polynaphthalene sulfanate) 8%
- inert filler insoluble in water (kaolin) 15%

WO 98I15512 PCT / FIt97101774 This mixture is granulated in a fluid bed) in the presence of water, then dried.
crushed and sieved so as to obtain granules of dimension 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 associations with other materials active) including 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 a or more insecticides, fungicides, bactericides, attractant acaricides or pheromones or other compounds with biological activity. Mixtures thus obtained have a broad spectrum activity. Mixtures with other fungicides are particularly beneficial, especially t 5 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, 20 letebuconazole, difenconazole, diniconazole, lemetconazole, penconazole, propiconazole, prochloraz, fenarimol, triadimenol, furalaxyl, copper derivatives like hydroxide and oxychloride, probenazole.
The compositions according to the invention are useful for treating 25 cereal seeds (wheat, rye, triticale and barley in particular), from potato, cotton, peas, rapeseed, corn, flax or even seeds of forest trees (especially conifers).
It should be noted in this connection that in the jargon of the skilled person, the seed treatment actually refers to the treatment of 3o seeds. Application techniques are well known to those of skill in the art.
profession and they can be used without disadvantage in the context of the present invention. Mention may be made, for example, of lamination or the coating.

Another subject of the invention is a method of control. as a curative or preventive, against phytopathogenic fungi in crops, characterized in that one applies to the seeds of plants or on the leaves of plants or on the soils where we do or where we want grow plants, an effective amount (agronomically effective) and non-phytotoxic 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" is meant a amount of composition according to the invention sufficient to allow the to control or destroy the fungi present or susceptible to appear on the cultures, and not entailing for said cultures any notable symptom of phytotoxicity. Such an amount is likely to vary within wide limits depending on the fungus to be controlled, the type of culture, climatic conditions, and the compounds included in the fungicidal composition according to the invention. This quantity can be determined by systematic field trials, within the reach of the skilled person.
The invention finally relates to a method of protection as preventive or curative of plant propagation products, as well 2o that resulting plants, against fungal diseases, characterized in that said products are covered with an effective dose and non-phytotoxic of a composition according to the invention.
Among the multiplication products of the plants concerned, may include in particular seeds or seeds, and tubers.
It is preferred to implement the method according to the invention in the seed case.
As indicated above, the procedures for recovery of plant propagating products, in particular seeds, are well known in the art and are particularly appealing film-coating or coating techniques :.
The products and compositions according to the invention can also apply as a foliar application on plant crops.
Among the plants targeted by the method according to the invention, it is possible to to quote:

- wheat, as regards the control of the following diseases seeds: Fusarium wilt (rLlodicrochium nivale and Fuscrrium rosezrm), caries (Tilletia caries. Tilletia controversa or Tilletia indica), septoria leaf spot (Septoria nodorum};
5 - wheat, as regards the fight against the following diseases of the aerial parts of the plant: the footwell (Pseudocercosporella herpotrichoides), the scald-scald (Gaezrmannomyces graminis), the Fusarium head blight (F culmorum, F. graminearum), rhizoctonia (Rhizoctonia cerealis), powdery mildew (Erysiphe graminis forma specie tritici), 10 rusts (Puccinia strüformis and Pz ~ ccinia recondita) and septoria (Septoria tritici and Septoria nodorum);
- wheat and barley, as regards disease control bacterial and viral, for example dwarfing jaundice from barley.
- barley. with regard to the control of the following diseases ~ 5 of the seeds: helminthosporioses (Pyrenophora graminea, Pvr-enophora teres and Cochl iobolzrs sativus), naked smut (Ustilago nzrda) and fusarium wilt (Microdochium nivale and Fusarium rosezrm), - barley, as regards the fight against the following diseases of the aerial parts of the plant: the footwell (Psez ~ docercosporella 20 herpotrichoFa'es), helminthosporioses (Pyrenophora teres et Cochliobolus sativus), powdery mildew (Erysiphe graminis forma specie hordei), dwarf rust (Puccinia hordei) and rhynchosporiosis (Rhynchosporium secalis);
- the potato, as regards the fight against diseases 25 of the tuber (in particular Helminthosporium solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani) and certain viral infections (virus Y);
- cotton, as regards the fight against the following diseases young plants grown from seed: seedlings and neck necrosis (Rhizoctonia solani, Fusarium oxysporum), 30 black root rot (Thielaviopsis basicola);
- pea, as regards the fight against the following diseases seeds: anthracnose (Ascochyta pisi, Mycosphaerella pinodes), Fusarium wilt (Fusarium oxysporum), gray mold (Botrytis cinerea);

dl - rapeseed, as regards the fight against the following diseases seeds: Phoma lingam and: 4lternaricr brassiccte;
- maize, as regards the fight against diseases of seeds: (Rhizopus sp., Penicillitem sp., Trichoderma sp., Aspergillus sp. and Gibberella fi jikuroi);
- flax, as regards the fight against seed disease Alternaria linicola;
- forest trees, with regard to the fight against melting seedlings (Ftcsarium oxysporum, Rhizoctoni a .solani).
1 o Wheat and barley are the most suitable plants for processing of the method according to the invention.
The dose of composition applied is. in general so advantageous such that the dose of active material is between 2 and t 5,200 g of active ingredient per 100 kg of seed, preferably between 3 and I ~ 0 g per l00 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 in leaf treatment.
The following examples illustrate the present invention Example 1 Preparation of (Z) -N-methoxy-N-methoxycarbonyl-2- [I - (I - (phenyl) ethyl-oxyimino) ethyloxymethyl] aniline 1.47 g of N- (I- (phenyl) ethyloxy) acetamide are dissolved in 30 ml anhydrous acetonitrile. 2.26 g of 2-bromo-methyl-N- are successively added methoxy-N-methoxycarbonylaniline and 2.67 g of cesium carbonate and bears the 3o reaction medium at reflux for 2 hours. After cooling, the salts are filtered, washed with acetonitrile which provides an organic solution which concentrated, and thus 3.2 g of a red oil are obtained. This oil is taken up in water, re-extracted three times with ethyl acetate to give after drying and evaporation 2.63 g of dark yellow oil. Chromatography on silica isolates 0.6 g of the expected compound, of stereochemistry (Z), in the form of a yellow oil. np =
l.5270 (2 3 ~ C) (these expressions denote the refractive index at 23 ~ C in using as light the D line of sodium).
Example 2 Preparation of (E) -N-methoxy-N-methoxycarbonyl-2- [1- (I - (phenyl) ethyl-oxyimino) ethyloxymethyl] aniline io 0.4 g of (Z) -N-methoxy-N-methoxycarbonyl-2- [1- (1- (phenyl) ethyloxy-imino) ethyloxymethyl) aniline are dissolved in 25 ml of anhydrous toluene. After addition of a few drops of acetic acid, the reaction medium is brought to reflux during 2 hours. The medium is poured into 50 ml of water, the toluene phase East decanted, washed until neutral and dried, which gives 0.4 g of an oil yellow.
5 Chromatography on silica allows 0.33 g of the expected compound to be isolated, stereochemistry (E), in the form of a light yellow oil which crystallizes gradually. F = 70 ~ C (this point denotes the point of merger).
2o Example 3 Preparation of (Z) -2,4-dihydro-5-methoxy-2-methyl-4- [2- [i - (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 25 anhydrous acetonitrile. 5.96 g of 4- [2- (bromo-methyl) phenyl] -2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one and 7.82 g cesium carbonate and brings the reaction medium to boiling at reflux while 4 hours. After cooling, the salts are filtered, washed with acetonitrile then them organic fractions are concentrated to give 7.0 g of an orange oil.
By 3o chromatography on silica, 0.82 g of the expected compound, stereochemistry (Z), in the form of a yellow oil. Rf = 0.24 (heptane / ethyl acetate 1 /
3). (We denotes by this the retention coefficient on a chromatography plate in layer thin silica).

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) ethyloxy-imino) ethyloxymethyl] -phenyl] -3H-1,2,4-tr: iazol-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 oil yellow. Chromatography on silica perrr ~ and isolate 0.18 g of the compound expected, o stereochemistry (E), in the form of a light yellow oil. np = 1.5310 (21 ~ C).
Example 5:
Preparation of (E) -2- [2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] -methyl phenyl] -2-methoxyacetate Step 1:
Preparation of methyl 2- (2-acetoxymethylphenyl) -2-oxoacetate 2o A mixture of 2 ~ g of 2- (2-t ~ romomethylphenyl) -2-methyl oxoacetate, 9.57 g of potassium acetate and O,: ig of potassium iodide is worn at reflux for 3 hours in 150 ml of dimethylformamide. After cooling and dilution with water, the reaction mixture is re-extracted to ether.
After purification by chromatography on silica, 11 g of the product are obtained expected. np: 1.5292 (25 ~ C).
2nd step:
Preparation of methyl 2- (2-acetoxymethylphEinyl) -2-hydroxyacetate 11 g of the above compound are loaded into 150 ml of methanol. After cooling in an ice bath, add 0.4 g of borohydride sodium and stir 30 min at 0 ~ C. 5 ml of acetic acid are then added and the phase methanolic. After re-extraction, washing with an aqueous solution of bicarbonate sodium and drying, 10.5 g of the expected product are isolated in the form of a oil WO 98I15512 PCTlFR97 / 01774 yellow. NMR (CDCI3): 2.10 s. 3H; 3.72, s 3H; i.28, AB, 1H: 5.42) s, 1H; 7.?~-7.4 ~, m, 4i-I).
Step 3:
Preparation of methyl 2- (2-acetoxymethylphenyl) -2-methoxyacetate A 10 g of the above compound and 13.36 g of methyl iodide in solution in 200 ml of N-methylpyrrolidone, 1.5 g of d oxide are added over 1 hour 'silver.
After heating at 40 ~ C for 2 days, the reaction mixture is filtered, diluted to water and re-extract with ether. After purification by chromatography on silica, we 2, ~ g of the expected compound are obtained in the form of a yellow oil.
Step 4:
Preparation of methyl 2- (2-bromomethylphenyl) -2-methoxyacetate Is bubbled at a temperature between 0 and 5 ~ C, acid hydrobromic gas 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 liquid RVfN (CDCl3) is obtained: 3.42 s, 3H;
3.7, s 3H; 4.55, d, 1H; 4.82, d, 1H; 5.20, s, 1H; 7.25-7.5 ~, m 4H.
Step â:
Preparation of (E) -2- [2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] -methyl phenyl) -2-methoxyacetate A mixture of 0.125 g of N- (1- (phenyl) ethyloxy) acetamide, 0.2 g of 2-(2-bromomethylphenyl) -2-methyl methoxyacetate and 0.234 g carbonate cesium in IS ml of acetonitrile are heated for 4 hours at reflux. After purification by chromatography on silica, 0.1 g of the compound is obtained expected, 3o of stereochemistry (E), in the form of a 50:50 mixture of two diastereoisomers.
nD: 1.5330 (25 ~ C).

WO 98l15512 PCT / P'R97 / 01774 ~ l: i Example 6 Preparation of (E, E) ~ 2- [2- [1- (N ~~ -benzyl-N ~ -methylhydrazono) ethyloxy-methyl methylphenyl] -3-methyl methoxyacrylate Step 1:
Preparation of N2-benzyl-N2-methylacethydrazide 5.4 ml of acetyl chloride are added dropwise onto a mixture strongly stirred at room temperature, 9.4 g of 1-methyl-1-benzylhvdrazine t0 prepared according to Synth. Comm. (1990) .20, 1.8 ~, in solution in 50 ml of ether and of 2.76 g of sodium hydroxide dissolved in 25 ml of water. After 2 hours of reaction, the mixed the reaction is decanted and the organic phase treated in the usual way.
We after purification by chromatography on silica, 8.36 g of product is obtained expected as a yellow oil. NMR (CDCl3): 2, ~, s, 3I-I; 2.95, bs, 2H; 3.62, s, 2H;
t5 7.2 ~ -7.45, m. SH.
2nd step:
Preparation of (E, E) -2- [2- [1- (N- ~ -benzyl-N2-methylhydrazono) ethyloxy-methyl methyl] phenyl] -3-methoxyacrylate.
3 g of (E) -2- (2-bromomethylphenyl) -3-methyl methoxyacrylate dissolved in 90 ml of dry dimethylformamide are added gradually at 20 ~ C in a mixture of 2.06 g of N2-benzyl-N2-methylacethydrazide obtained as below above and 1.3 g of potassium tert-butoxide in 60 ml of dimethylformamide dry. After 5 hours of reaction, the mixture: is poured into 300 ml of water and would reexamine several times with ethyl acetate. After purification by chromatography sure 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 (E, Z) -2- [2- [I - (1- (phenyl) ethyloxyimino) ethyloxymethyl] -methyl phenyl] -4,4,4-trifluorobut-2-enoate Step 1:
Preparation of 3-hydroxy-2 - [? - (methyl) phenyl] -4,4,4-trilluorobutanoate methyl To 200 ml of lithium dopropopropylamide (1 M in tetrahydrofuran dry) and cooled to -70 ~ C, 28.7 g (0.1 ~ mole) are added dropwise from 2- [2-(methyl) phenyl] methyl acetate in solution in l00 ml of tetrahydrofuran dry. Is bubbled in the reaction medium, dry trifluoroacetaldehyde prepared according to J.Chem.Educ. (197S), 52, 131, for 1 h. After 3 hours 1 o of stirring at -70 ~ C, the medium is poured over 500 ml of water and 200 ml acid 1 M hydrochloric acid, re-extracted with ethyl acetate and dried. Evaporation of solvents leaves 37 g of a yellow oil which is distilled under reduced pressure (E =
11 ~ -120 ~ C under 4 mmHg; these expressions denote the boiling point under a pressure expressed in rrun of mercury) to give 35.60 g of an oil colorless. After purification by chromatography on silica, 2 are obtained I, 26 a of a syn: anti mixture in a 70:30 ratio of the expected compound. The major diastereoisomer of syn configuration, can be isolated pure and crystallized:
4JHH = ~ Hz; F = 58 ~ C.
2o Step 2:
Preparation of (E} -2- [2- (methyl) phenyl] -4,4,4-trifluorobut-2-enoate methyl At 9.34 g of the syn: anti mixture of 3-hydroxy-2- [2- (methyl) phenyl] -4,4,4-25 methyl trifluorobutanoate obtained as above, dissolved in 40 ml of diethyl ether, 9.34 g of triphenylphosphine are added. The medium is cooled to 0 ~ C
and 6.19 g of diethyl azodicarboxylate are added dropwise. The middle 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 3o stereochemistry (E), in the form of a colorless liquid. nD: 1.4722 (20 ~ C).
Step 3:
Preparation of (E) -2- [2- (bromomethyl) phenyl] -4,4,4-trilluorobut-2-enoate methyl .4 7 g of (E) -2- [2- (methyl) phenyl] -4,4.4-trifluorobut -? - methyl enenoate obtained as above, in solution in l00 ml of carbon tetrachloride, we add 5.34 g of N-bromosuccinimide, 0.1 g of benzoyl peroxide and wear the s medium at 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 (l ~), contaminated with approximately I ~ ~,% of the starting compound.
l0 Step 4:
Preparation of (E, Z) -2- [2- [1- (1-phenyl) ethyloxyimino) ethyloxymethyl] -phenyl] -4,4,4-trifluorobut-2-enoate of méi: hyle 0.8 g of N- (1- (phenyl) ethyloxy) acetamide is dissolved in 20 ml of aceto-15 anhydrous nitrile. 1.4 ~ g of (E) -2- [2- (bromomethyl) - are added successively methyl phenyl] -4,4,4-trifluorobut-2-enoate obtained as above, and I, 76 g cesium carbonate and brings the reaction medium to reflux for 2 hours.
After cooling, the medium is poured into 100 ml of water, re-extracted to acetate ethyl, dried and then concentrated to provide 1.7 g of a yellow oil. A
2o chromatography on silica allows 0.4 g of the expected compound to be isolated, stereochemistry (E, Z), in the form of a yellow oil. nD = 1.52 I (20 ~ C).
Example 8 Preparation of (E, E) -? - [2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] -Methyl phenyl] -4,4,4-trifluorobut-2-enoate In a manner analogous to the process described in Example 2, isomerized l 30 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 acid 30 acetic. Chromatography on silica isolates 70 mg of the compound expected, of stereochemistry (E, E), in the form of a yellow oil. nD = 1.5107 (26 ~ C).

Example 9 Preparation of (E, E) -2-methoxyimino-N-methyl-2- [2- [1- (1- (N-methvl-carbamoyie) -1- (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] acetamide Step 1:
Preparation of methyl 2-bromo-2-phenylpropanoate A 9 ~ 8 g of methyl 2-phenylpropanoate in solution in 120 ml of carbon tetrachloride, 10.7 g of N-bromosuccinimide, 0.1 g of ~ o benzoyl peroxide and brings the medium to reflux for 4 hours. After cooled The succinimide is filtered and the organic phase washed with thiosulfate.
of 0.1 N sodium with water and dried. Evaporation of the solvent leaves 13.
oil orange which is distilled in a ball oven (E = 175 ~ C under 5 mmHg) to give l 2.5 g of the expected compound in the form of a colorless liquid. nD = 1 g478 (19 ~ C).
l5 2nd step:
Preparation of N- [1- (methoxycarbonyl) -1- (phenyl) ethyloxy] acetamide To a solution of 12.16 g of methyl 2-bromo-2-phenylpropanoate 20 obtained as above, and 3.7 ~ g of acetohydroxamic acid in 60 ml of anhydrous methanol heated to 40 ~ C, 2.43 g of sodium methylate are added per 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, re-extracted with acetate ethyl and dried. Evaporation of the solvents leaves 12 g of a colorless oil which crystallizes 25 gradually. 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 solid white. F = 94 ~ C.
Step 3:
Preparation of (E, Z) -2-methoxyimino-2- [2- [1- (1- (methoxycarbonyl) -1-(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-methoxyirr ~ ino -? - [2- (bromomethyl) phenyl]
acetate methyl, 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 isolates 4.5 g of the expected compound, of stereochemistry (E, Z), in the form of a solid white. F = 108 ~ C.
Step 4:
Preparation of (E, E) -2-methoxyimino-2- [2- [1- (1- (methoxycarbonyl) -1-(phenyl) ethyloxyimino) ethyloxymethyl] phenyl] methyl acetate In a manner analogous to the process described in Example 2, isomerized 3.5 g of (E, Z) -2-methoxyimino-2- [2- [1- (1-f methoxycarbonyl) -1-(phenyl) ethyloxy-imino) ethyloxymethyl] phenyl] methyl acetate at reflux of toluene in presence acetic acid. Recrystallization of the crude solid from ether isopropyl, allows to isolate 3.2 g of the expected compound, of stereochemistry (E, E). form of a solid white. F = 117 ~ C.
Step ~:
Preparation of (E, E) -2-methox; yimino-N-methy l-2- [2- [1- (I - (methoxy-carbonyl) -1- (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] acetamide 3.2 g of (E, E) -2-methoxyimino-2- [2- [1- (1- (methoxycarbonyl) -1- (phenyl) -ethyloxyimino) ethyloxymethyl] phenyl] methyl aceaate obtained as below 2s above, dissolved in 70 ml of methanol, 14 ml of methylamine are added to 40 by weight in water and stirred strongly at 20 ~ C for 4 hours. Methanol East 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), as a colorless oil. np = 1.5390 (19 ~ C).
Step 6:
Preparation of (E, E) -2-methoxyimino-N-methyl-2- [2- [1- (1- (N-methyl-carbamoyl) -1- (phenyl) ethyloxyirnino) ethyloxymethyl] phenyl] acetamide ~ 0 At 0.88 ~ from (E, E) -2-methoxyimino-N-methyl-2- [2- [I - (1-(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 of the gaseous methylamine is introduced by bubbling for 30 min. The middle reaction is stirred at 0 ~ C for 3 hours and then poured into 100 ml of water. The pH
is brought to 6 by adding 1N hydrochloric acid and the aqueous phase re-extracted by ethyl acetate, washed with water and dried. Evaporation of solvents leaves 1.0 g colorless oil. After purification by chromatography on silica, obtains 0.1 ~ g of the expected compound, of stereochemistry (E, E), in the form of an oil colorless which crystallizes progressively. F = 152 ~ C.
Example 10 1 ~ Preparation of (E, Z) -2- [2- [1- (I - (methoxycarbonyl) -I - (phenyl) ethvloxy-methyl imino) ethyloxymethyl] phenyl] -4,4,4-trifluorobut-2-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 acetonitrile anhydrous. We successively add 2.1 g of (E) -2- [2- (bromomethyI) -phenyl] -4,4,4-methyl trifluorobut-2-enoate obtained according to step 3 of Example 7, and 2.33; of cesium carbonate and brings the reaction medium to 50 ~ C for 7 hours.
After cool-tight, cesium salts are filtered and the medium is concentrated for supply 3.2 g of a yellow oil. Chromatography on silica allows to isolate 1 ~, ~
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) ethyloxy-methyl imino) ethyloxymethyl] phenyl] -4,4,4-trifluorobut-2-enoate In a manner analogous to the process described in Example 2, isomerized 1.15 g (E, Z) -2- [2- [1- (1- (methoxycarbonyl) -1-(phenyl) ethyloxyimino) ethyloxy-methyl] phenyl] -4,4,4-methyl trifluorobut-2-enoate at reflux of toluene in presence of acetic acid. Recrystallization of the crude solid from ether düsopropylic, allows to isolate 0.8 ~ g of the expected compound, stereochemistry (E, E), as a white solid. F = 82 ~ C.
Example 12 Preparation of (Z) -2,4-dihydro-5-methoxy-2-methyl-4- [2- [1- (1- (methoxy-carbonyl) -1- (phenyl) ethyloxyimino} ethyloxymethyl] -phenyl] -3 H-1,2,4-triazo 1-3-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 acetonitrile anhydrous. We successively add 2.39 g of 4- [2- (bromomethyl) phenyl] -2,4-dihvdro- ~ -methoxy-2-methyl-3H-1,2,4-triazol-3-one fa 3, 13 g of cesium carbonate and brings the reaction medium to reflux for 2 hours. After cooling, the salts are filtered, washed with acetonitrile then the organic fractions are concentrated to give 4.4 g of a yellow oil. By chromatography on silica, we isolate 2.21 g of the expected compound, of stereochemistry (Z), in the form of a yellow oil which crystallizes gradually. F = 110 ~ C.
2o Example 13 Preparation of (E) -2,4-dihydro-5-m ~ ethoxy-2-methyl-4- [2- [1- (1- (methoxy-carbonyl) -1- (phenyl) ethyloxyimino) ethyloxymethyl] -phenyl] -3 H-1,2,4-triazol-3-one 2.07 g of (Z) -2,4-dihydro-5-m.ethoxy-2-methyl-4- [2- [1- (1- (methoxy-carbonyl} -1- (phenyl) ethyloxyimino) ethyloxymethyl] -phenyl] -3H-1,2,4-triazol-3-one are dissolved in 10 ml of anhydrous toluene. 0.5 ml of acid is added acetic 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 the water, 3o dried and concentrated to give 2 g of a: yellow oil. Chromatography sure silica allows to isolate 0.17 g of the expected compound, of stereochemistry (E}, under form a light yellow oil which gradually crystallizes. F = 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, ~ g of N- (1- (phenyl) ethyloxy) acetamide are dissolved in 150 ml anhydrous acetonitrile. 8.8 g of N- (2- {bromo-methyl) phenyl) methyl carbamate and 14.1 g of cesium carbonate and carries the reaction medium at reflux for 2 hours. After cooling, the salts are filtered, washed with acetonitrile and the filtrate is concentrated to give 10 g of an oil orange. Chromatography on silica allows 1.0 g of the compound to be isolated expected, of stereochemistry (E), in the form of a yellow oil. np = l, ~ 71 (22 ~ C).
2nd step Preparation of (E) -N-methoxycarbonyl-N-methoxymethy l-2- [1- (1- (phenyl) -ethyloxyimino) ethyloxymethyl] aniline A 1.0 g of (E} -N-methoxycarbonyl-2- [1- (1- (phenyl) ethyloxyimino) ethyl l-oxymethyl] aniline, obtained as above, dissolved in 20 ml of anhydrous tetrahydrofuran, 0.33 g of potassium ter-butoxide is added. After mn of stirring at 20 ~ C, 0.32 ml of bromomethyl methyl ether is added and stirring min at 20 ~ C. The reaction medium is poured into l00 ml of brine, re-extracted at ethyl acetate, washed with water and dried. Evaporation of solvents leaves 1.2 g of yellow oil. Chromatography on silica allows 1.0 g of the compound to be isolated expected, of stereochemistry (E), in the form of a yellow oil. nD = 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 ~ 3 A 0.88 g of (E, E) -2-methoxyimino-N-methyl-2- [2- [1- (1-(methoxycarbonyl) -1- (phenyl) ethyloxyimino) ethyloxymethyl] phenyl] acetamide obtained as described in step ~ of the exe: mple 9, dissolved in 20 ml of NOT-anhydrous methylpyrrolidone, 0.2'7 g of sodium amide is added. The middle reaction is heated to 5 ~ ~ C for 3 hours and then poured into 100 ml of water.
The pH is brought to 7 by adding 1N hydrochloric acid and the aqueous phase re-extracted with ethyl acetate, washed with water and dried over magnesium sulfate.
Evaporation of the solvents leaves 0.6 g of a yellow oil. A crushing by a minimum of propopropyl ether makes it possible to obtain 0.31 g of the expected compound 10 as a white solid. F = 144 ~ C.
Example 16 Preparation of (E, E) -2- [2- [1- (1- (p: hényl) ethyloxyimino} ethyloxymethyl] -methyl phenyl] -but-2-enoate ! 5 Step 1 Preparation of (E, Z) -2- [2- [1- (1- (pl'nenyl) ethyloxyimino) ethyloxymethyl] -methyl phenyl] -but-2-enoate 20 1.1 g of N- (1- (phenyl) ethyloxy) acetarnide are dissolved in ~ 0 ml of aceto-anhydrous nitrile. 1.6 g of {E) -2- [2- (bromomethyl) - are successively added methyl phenyl] -but-2-enoate prepared according to US 54,606,068, and 2.11 g of cesium carbonate and brings the reaction medium to reflux for 4 hours.
After cooling, the medium is filtered through celite and the celite washed at 25 acetonitrile. After concentration, chromatography on silica of the oil residual allows to isolate 1.0 g of the compost; expected, of stereochemistry (E, Z), under form of a yellow oil. Rf = 0.67 (heptane! Ethyl acetate 1/1).
2nd step Preparation of (E, E) -2- [2- [1- (1- (pllenyl) ethyloxyimino) ethyloxymethyl] -methyl phenyl] -but-2-enoate In a manner analogous to the process described in Example 2, isomerized 1.0 g of (E, Z) -2- [2- [1- (1- (phenyl) ethyloxyimino) ethyloxymethyl] -phenyl] -but-WO 98l15512 PCTlFR97 / 01774 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. np = 1.5460 (24 ~ C).
Example B1: In vivo test on Plasmopara viticola (downy mildew):
An aqueous suspension of the active material is prepared by fine grinding.
test having the following composition:
- 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.
t ~ This aqueous suspension is then diluted with water so as to get the desired ppm (part per million) concentration.
Vine cuttings (Vins vinifera), Chardonnay variety, are cultivated in buckets. When these plants are 2 months old (stage 8 to 10 leaves.
height 10 to 15 cm), they are treated by spraying using 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 with spraying of an aqueous suspension of Plasmopara viticola spores get from a culture of 4-5 days, then suspended at a rate of I
00,000 units per cm3.
Contaminated plants are then incubated for two days at 18 ~ C approximately, in an atmosphere saturated with humidity then for five days at 20-22 ~ C approximately under 90-100% relative humidity.
Reading is done seven days after contamination, in comparison with control plants.
Under these conditions, a good protection is observed at a dose of 5 ppm.
(at least 75%) or total with the following compounds: 1, 4, 5 and 9.

Example B2: In vivo test on Pc ~ ccinia recondita (wheat rust):
An aqueous suspension of the active material is prepared by fine grinding.
test having the following composition:
5 - active ingredient: 60 mg - Tween 80 surfactant (oleate of polyoYyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml - acetone: 5 ml - make up to 60 ml of water.
I o This aqueous suspension is then diluted with water so as to get the desired ppm (part per million) concentration.
Wheat (Scipio variety), in pots, sown on a peat soil substrate pozzolan 50 / Q0 and maintained at 12 ~ C, is treated at the 1 leaf stage (10 cm height) by spraying the above aqueous suspension.
15 Plants used as controls are treated with an aqueous solution.
not containing the active ingredient.
After 24 hours, each plant is contaminated with a spray of aqueous suspension of spores (150,000 spores per cm3) of Puccinicr recondita.
This suspension is obtained from contaminated plants.
2o Contaminated wheat plants are then incubated for 24 hours at around 20 ~ C, in an atmosphere saturated with humidity, then for seven to fourteen days at 60% relative humidity.
The reading is done between the 5th and the 15th day after contamination, in comparison with control plants.
25 Under these conditions, 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 material is prepared by fine grinding.
test having the following composition:
- active ingredient: 60 mg WO 98/15512 PCTlFR97 / 01774 - a ~~ ent surfactant Tween 80 (oate derivative polyo ~ cyethylenated sorbitan) diluted: 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 ppm (part per million) concentration.
Wheat (Scipion variety) in pots, sown on a peat soil substrate pozzolan Q0 / 50 and maintained at 12 ~ C, is treated at the 1 leaf stage (10 cm height) by spraying the above aqueous suspension.
1 o Plants, used as controls are treated with an aqueous solution born not containing the active ingredient.
After 24 hours, each plant is contaminated with a spray of aqueous suspension of spores (500,000 spores per cm3) of Septoria tritici, Les spores are harvested from a seven day old culture.
Contaminated wheat plants are incubated for 72 hours at ~ C approximately, in a humid atmosphere then for twenty days at 90% humidity relative.
Reading is done twenty-one days after contamination. in comparison with control plants.
2o In 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, ~, 6, 9, 14 and 16.
Example B4: In vivo test on Septoria nodorum (wheat septoria):
An aqueous suspension of the active material is prepared by fine grinding.
test having the following composition:
- 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 ppm (part per million) concentration.

~ 7 Wheat (Scipion variety) in pots, sown on a peat soil substrate pozzolan Q0150 and maintained at 12 ~ C, is treated at the 1 leaf stage (10 cm 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 with a spray of aqueous suspension of spores (500,000 spores per cm 3) of Septoria nodorum.
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 fourteen days at 90 relative humidity.
Reading takes place two weeks after contamination, in comparison with Control plants.
Under these conditions, a good protection is observed at a dose of 40 ppm.
IS (at least 75%} or total with the following compounds: I. 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 is prepared by fine grinding.
test having the following composition:
- 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 ppm (part per million) concentration.
Wheat (Audace variety) in pots, sown on a peat soil substrate pozzolan 50 / S0 and maintained at 12 ~ C, is treated at the 1 leaf stage (10 cm 3o 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 Erisyphus spores graminis, the dusting being carried out using diseased plants.

Reading takes place seven to fourteen days after contamination. in comparison with 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, 9, 11, 14 and 16.
Example B6: In vivo test on Erisyphe graminis fsp hordei (powdery mildew barley):
An aqueous suspension of the active material is prepared by fine grinding.
to test with the following composition:
- active ingredient: 60 mg - Tween 80 surfactant (oleate of polyoxyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml - acetone: 5 ml 1 s - make up to 60 ml of water.
This aqueous suspension is then diluted with water so as to obtain the desired ppm (part per million) concentration.
Barley (Express variety) in pots, sown on a peat soil substrate pozzolan Q0 / 50 and maintained at 12 ~ C, is treated at the 1 leaf stage (10 cm 2o 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 sprinkled with Erisyphus spores gramihis, the dusting being carried out using diseased plants.
25 Reading takes place seven to fourteen days after contamination, in comparison with 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, 4, 5, 14 and 16.
3o Example B7: In vivo test on Pyrenophora teres (helmintosporiosis of barley):
An aqueous suspension of the active material is prepared by fine grinding.
test having the following composition:

~ 9 - active ingredient: 60 mg - Tween 80 surfactant (oleate of polyoxyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml - acetone: 5 mi - make up to 60 ml of water.
This aqueous suspension is then diluted with water so as to obtain the concentration in ppm (part per million; l desired.
Barley (Express variety), in pots, sown on a peat soil substrate pozzolan 50/50 and maintained at 12 ~ C, is treated at the 1 leaf stage (10 cm lo 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 with a spray of aqueous suspension of spores (12,000 spores per cm3) of Pyrenophora teres.
This suspension is obtained from contaminated plants.
Contaminated barley plants are then incubated for 24 hours at around 20 ~ C, in an atmosphere saturated with humidity, then for seven to fourteen days at 80% relative humidity.
Reading takes place between the 5th and the 1st day - after contamination, in 2o comparison with 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, 4, 5, 6, 7, 9, 10, 11, 14, 15 and 16.

Claims (29)

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

in which G is chosen from the groups G1 to G9:
~ ~ ~ ~ ~ ~ wherein n=0 or 1 Q1 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 C0R11 group, Q5 is oxygen, sulfur or NR12 group, Y is the oxygen, sulfur atom or the amino (NH) or oxyamin o group (ONH);
W1 is the oxygen atom. sulfur or sulphinyl groups (SO) or sulfonyl (SO2), 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 NR13 group, X1, X2. X3 are independently of each other a hydrogen atom, a halogen atom; Where a hydroxy, mercapto, vitro, thiocyanato, azido, cyano or pentafluorosulfonyl; lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkoxysulfonyl;
Where lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio; Where an amino, N-alkylamino, N,N-dialkylamino, acylamino, aminoalkyl, N-alkylaminoalkyl, N,N-dialkylaminoalkyl, acylaminoalkyl; Where a carboxy, carbamoyl, N-alkylcarbamoyl group, N,N-dialkylcarbamoyl, lower alkoxycarbonyl; Where an acyl group;
X4 is a hydrogen atom, a halogen atom; Where lower alkyl, lower haloalkyl, alkoxy, haloalkoxy; Where cyano and nitro radicals, R1, R2 are independently of each other a hydrogen atom, a lower alkyl, lower haloalkyl, cycloalkyl lower, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; Where a cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl group, N,N-dialkylcarbamoyl, lower alkoxycarbonyl group, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; Where an aminoalkyl, N-alkylaminoalkyl, N,N-dialkylaminoalkyl group, acylaminoalkyl, R1 and R2 can together form a divalent radical as a group alkylene, optionally substituted by one or more halogen atoms, optionally substituted by one or more lower alkyl groups, R3 is hydrogen, lower alkyl, haloalkyl lower cycloalkyl, lower halocycloalkyl, a band alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; Where a nitro, cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxy-carbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; Where an alkenyl, alkynyl, N,N-dialkylamino, N,N-dialkylaminoalkyl group;
Where an optionally substituted phenyl or benzyl group, R4 is lower alkyl, lower haloalkyl, a group lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl; Where an alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, R5, R6 is independently lower alkyl, lower haloalkyl, R7 is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, R8 is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, formyl, acyl, R9 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, R10 is halogen, lower alkyl, haloalkyl lower. lower cycloalkyl, lower halocycloalkyl, a band alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfuryl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, R11, R12 are independently of each other the hydrogen atom, a lower alkyl, lower haloalkyl, cycloalkyl lower, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, R13 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, an allyl group optionally substituted, an optionally substituted propargyl group, a optionally substituted benzyl group; Where an acyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl group, lower alkoxy-carbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythio-carbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; Where an alkylsulfonyl, haloalkylsulfonyl, arylsulfonyl group optionally substituted, provided that when W2 and Q2 are the oxygen atom and G represents the group G1, then R5 is other than an alkyl group, and R4 is other than an alkoxy group, alkylamino, dialkylamino, and R3 is other than hydrogen, a group alkyl, haloalkyl, a cycloalkyl group, halocycloalkyl, a group alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, cyanoalkyl, alkenyl, alkynyl, dialkylaminoalkyl, or an optionally substituted phenyl or benzyl group, as well as salts, metal and metalloid complexes, isomers optical and geometric properties of the compounds of formula (I) as it has just been 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 nitrogen atom, and/or Q5 is the oxygen atom;
W1 is the oxygen or sulfur atom, W2 is the oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino, allylamino, Y is the oxygen atom. 3. Compounds according to one of the preceding claims in which X1, X2, X3 and X4 are independently of each other a hydrogen atom, a lower alkyl group, a halogen atom, or cyano radicals,.
trifluoromethyl, methoxy. 4. Compounds according to one of the preceding claims in which R1 and R2 are independently of each other a hydrogen atom, a group lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, blue, cyanoalkyl, N-alkylaminoalkyl, N,N-dialkylaminoalkyl, acylaminoalkyl, lower alkoxycarbonyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, R3 is hydrogen, lower alkyl, cycloalkyl lower, lower haloalkyl, alkoxyalkyl, preferably a radical methyl, ethyl, propyl, isopropyl, cyclopropyl, methoxymethyl, R4 is lower alkyl, alkoxy, alkylamino, dialkylamino, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino radical, ethylamino, R5, R6, R8 and R9 are independently an alkyl group lower. lower haloalkyl, preferably a methyl radical, fluoromethyl, ditluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl, R7 is lower alkyl, lower haloalkyl, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl, allyl, propargyl, R10 is chlorine, lower alkyl, lower haloalkyl, preferably methyl, an alkoxy, alkylthio, preferably methoxy, methylthio, R11 and R12 are independently lower alkyl, lower haloalkyl, alkoxyalkyl, allyl, propargyl, R13 is hydrogen, lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl, benzyl. 5. Compounds according to one of the preceding claims in which W1 is the oxygen atom, R1 is the hydrogen atom or the methyl radical, R2 is hydrogen or lower alkyl, cyano, cyanoalkyl, aikoxyalkyl, N,N-dialkylaminoalkyl, lower alkoxycarbonyl, N,N-dilower alkylcarbamoyl. 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 connection -C(R3)=N-. 7. Fungicidal compositions comprising an effective amount of at least one active material according to one of the preceding claims. 8. Fungicidal compositions according to claim 7 comprising, in addition to the active ingredient 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. Preventive or curative control method against fungi plant pathogens of crops, characterized in that one applies to the seed plants or on the leaves of plants or on the ground where one makes or where one wishes to grow the plants, an agronomically effective quantity and Nope phytotoxic of at least one active ingredient or of a fungicidal composition containing an active ingredient of formula (I) as defined in the claim 1 11. Process for preventive or curative treatment of the products of multiplication of plants, as well as resulting plants, against fungal diseases, characterized in that the said products are covered with a dose effective and non-phytotoxic compound or composition according to one of previous claims. 12. Process according to claim 11, in which the rice, the cereals, fruit trees, vines and beets. 13. Method according to one of claims 11 or 12 in which one treats wheat or barley. 14. Process according to claim 11, in which the seeds are treated cereals, potatoes, cotton, peas, rapeseed, corn, flax Where still the seeds of forest trees. 15. Method according to one of the preceding claims in which the dose of active ingredient applied is between 20 and 200 g of active ingredient per 100 kg of seed, preferably between 3 and 150 g per 100 kg for seed treatments. 16. Method according to one of claims 10 to 14 wherein the dose of active ingredient applied is between 10 and 800 g of active ingredient by hectare, preferably between 50 and 300 g of active ingredient per hectare in the case foliar treatments. 17. Process for the preparation of the compounds according to one of the claims 1 to 6 consisting in bringing a compound of formula (II)A into contact:

in which G is one of the groups G1 to G9, the groups G1 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 to 6, V1 is a halogen atom (preferably chlorine or bromine), a group alkylsulfonate or haloalkylsulfonate f preferably methylsulfonate or trifluoromethylsulfonate), arylsulfonate (preferably 4-methylphenylsulfonate), with a compound of formula (III)A

W1, W2, R1, R2, R3, R13, X1, X2, X3 and p having the same definition as that indicated in one of claims 1 to 6, benzyl halide derivatives of formula (II)A where V1 is an atom of halogen (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 given in claims 1 to 6 and R4 is the alkylamino, dialkylamino group, the groups G8 and G9 having the same definition as that indicated in claims 1 to 6, X4 having the same definition as that indicated in claims 1 to 6, W1 is the oxygen atom, with a halogenating agent such as thionyl chloride, oxytrichloride phosphorus, phosphorus tribromide or with the halide reagent of lithium / mesyl halide / collidine; Where - 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 given in claims 1 to 6 and R4 is the band alkylamino, dialkylamino, the groups G8 and G9 having the same definition as that indicated in claims 1 to 6, X4 having the same definition as that indicated in claims 1 to 6, W1 is the oxygen atom, and P is a protecting group of the alcohol function as an ester preferably acetic acid or benzoic acid, or an ether, preferably methyl, methoxymethyl, phenyl, benzyl, with a Lewis acid such as boron tribromide, or hydracids anhydrous such as hydrogen chloride. 18. Compounds of formula (III)A
in which W1, W2, R1, R2, R3, R13, X1, X2, X3 and p having the same definition than that given in one of claims 1 to 6. 19. Process for preparing compounds according to one of claims 1 to 6 for which G is fun 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 amino, alkylamino, dialkylamino group or radical, 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, consisting in bringing a compound of formula (II)B into contact 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 amino, alkylamino, dialkylamino group or radical, 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 is the oxygen or sulfur atom, with a compound of formula (III)B
W2, R1, R2, R3, R13, X1, X2, X3 and p having the same definition as that indicated in one of claims 1 to 6, U3 being a halogen atom of preferably a chlorine atom, the double bond U3-C(R3)=N-W2- possibly being of stereochemistry (E) or (Z). 20. Process for the preparation of compounds according to one of claims 1 to 6 in 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 than that indicated in one of claims 1 to 6 and R6 is a lower alkyl or lower haloalkyl group, consisting in bringing into contact a compound of formula (IX):

in which R4 being the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as given in any of the claims 1 to 6, with a Wittig-Horner reagent of formula (X)A:
R6-CH2-P(=O)(OR b)2 (X)A
R6 being a lower alkyl or lower haloalkyl group, R b being a lower alkyl, phenyl or benzyl group, or with a Wittig reagent of formula (X)B:
R6-CH2-P(Rd)3+; Hal-(X)B
R6 being a lower alkyl or lower haloalkyl group, R d being a optionally substituted phenyl group, Hal- being a halide ion. 21. Process for the preparation of compounds according to one of the claims 1 to 6 in which G is the group G1 or G2, Q1 being the nitrogen atom or the CH group, Q2 being the oxygen atom, R4 being the alkoxy, alkylamino group, dialkylamino, 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 into contact a compound of formula (XI):

in which T is the oxygen atom and M an alkaline or alkaline-earth ion, Q1 being the nitrogen atom or the CH group, R4 being the alkoxy group, alkylamino, dialkylamino, W1, W2, R1, R2, R3, R13, X1, 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 designates the identical or different halogen atoms, one of which of them at least is the atom of chlorine or bromine. 22. Process for the preparation of compounds according to one of the claims 1 to 6 for which G is the group G4 in which n = 1, Q2 being the atom of oxygen, R4 being the group alkoxy, alkylamino, dialkylamino, the other substituents having the same definition as given in any of the claims 1 to 6, consisting in reacting a compound of formula (XII)A:

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

wherein V1 is a halogen atom (preferably chlorine or bromine}, R5 having the same definition as that indicated in one of the claims 1 to 6. 23. for which G is the group G1 to G7 and R4 is the group alkylamino or dialkylamino, the other substituents having the same definition that that indicated in one of claims 1 to 6, consisting in putting 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 that 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 the claims 1 to 6 where W1 is the sulfoxide (SO) or sulfone (SO2) group and G
being one of the groups G1, G3, G4, G6 to G9, Q2 and Q3 being the oxygen atom, the other substituents having the same definition as given in any of the claims 1 to 6, consisting of an oxidation of the compounds of general formula (I) to which W1 is the sulfur atom, G being one of the groups G1, G3, G4, G6 to G9, Q2 and Q3 being the oxygen atom, the other substituents having the same definition than that indicated in one of claims 1 to 6, by means of a equivalent or more than one oxidizing agent. 25. Process for the preparation of the compounds according to one of the claims 1 to 6 in which the groups W1, W2, R1, R2, R3, X1, X2, X3, X4 and p having the same meaning as in one of claims 1 to 6 and G is the group G7, consisting in bringing the intermediates of formula (III)A into contact:
(III)A
in which the groups W1, W2, R1, R2, R3, R13, X1, 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 V1 is a halogen atom of preferably chlorine or bromine. 26. Process for the preparation of the compounds according to one of the claims 1 to 6 in which the groups W1, W2, R1, R2, R3, X1, X2, X3, X4 and p having the same meaning as in one of claims 1 to 6 and G is the group G3, and R6 is the trifluoromethyl radical, consisting in bringing the composed of formula (III)A:

in which the groups W1, W2, R1, R2, R3, R13, X1, 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, R6 is the trifluoromethyl radical, X4, R4 and Q2 having the same definition as that indicated in one of the claims 1 at 6 and V1 is a halogen atom, preferably chlorine or bromine. 27. Process for the preparation of the compounds of formula (III)A, according to claim 18, where W2 is the oxygen atom and p = 1 or the acids hydrazones or thiohydrazones of formula (III)A, according to claim where W2 is the NR13 group and p = 0 or 1, W1, R1, R2, R3, R13, X1, 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:
W2, R1, R2, R13, X1, X2, X3 and p having the same definition as that indicated in one of claims 1 to 6, with a compound of formula (V) W1, R3 having the same definition as that indicated in one of the claims 1 to 6, U1 is a halogen atom (preferably chlorine or bromine), or a hydroxy, lower alkoxy or benzyloxy, lower alkylthio, amino, or the group -O(C=O)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, from preferably a halogen atom, the compound of formula (V) then being a acid halide. 28. Process for the preparation of the compounds of formula (III)A, according to claim 18, where W2 is the oxygen atom and p = 1 or the acids hydrazones of formula (III)A where W2 is the NR13 group and p = 1, W1, R1, R2, R3, R13, X1, X2, X3 having the same definition as that indicated in one of the claims 1 to 6, consisting in contacting a compound of formula (IV):
R1, R2, X1, X2, X3 having the same definition as that indicated in one of claims 1 to 6, and U2 is a halogen atom (preferably chlorine Where bromine), an alkylsulfonate group (preferably methylsulfonate or trifluoro-methylsulfonate), with a derivative of hydroxamic acid where W2 is the oxygen atom or a hydrazonic acid derivative where W2 is the NR13 group, R3 and R13 having the same definition than 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, where W1 is the sulfur atom and W2 is the oxygen atom or the thiohydrazonic acids of formula (III)A according to claim 18, wherein W1 is the sulfur atom and W2 is the group NR13, R1, R2, R3, R13, X1, X2, X3 and p having the same definition as that indicated in one of claims 1 to 6, consisting of a thionation of hydroxamic acids of formula (III)A where W1 is oxygen atom and W2 is oxygen atom or acids hydrazonics of formula (III)A where W1 is the oxygen atom and W2 is the group NR13, R1, R2, R3, R13, X1, X2, X3 and p having the same definition as given in moon of claims 1 to 6, with thionating agents.