FR2777003A1 - NEW FUNGICIDE COMPOUNDS - Google Patents

Abstract

The invention concerns fungicide compounds of general formula (I) and compositions containing them, wherein G is selected among the groups (G1) to (G9), the other substituents being such as defined in the description. The invention also concerns plant treatment methods using said compounds.

Description

New fungicidal compounds
The present invention relates to novel compounds having a hydroximic or hydrazonic function, and a process for their preparation. their use as fungicides, especially in the form of fungicidal compositions, and methods for controlling phytopathogenic fungi of cultures using these compounds or compositions.

A large number of fungicidal compounds are already known and widely used. For example, patent applications EP-A-0463488 and
EP-A-370629 describe in particular fungicidal compounds comprising a hydroximic or hydrazonic function.

 Of all the fungicides known to date, the user of such compounds, that is to say the one confronted with the problems of controlling fungal diseases of plants, has at its disposal only effective compounds on a relatively weak range of fungal diseases.

 In other words, the known fungicidal compounds have a relatively narrow spectrum of activity. In order to eradicate all the different species of fungi attacking plants, the user must therefore use several products whose exact spectrum and application rates must be known.

 The use of several products is moreover contrary to the methods of treatment of crops recommended today, where the application doses must be as low as possible.

 An object of the present invention is to provide a novel family of compounds having a broad spectrum of action on phytopathogenic fungi cultures.

 Another object of the present invention is to provide a new family of compounds having a broad spectrum of action on phytopathogenic fungi cultures to solve the specific problems encountered.

 Another object of the present invention is to provide a new family of compounds having a broad spectrum of improved action on plant pathogenic fungi.

 Another object of the present invention is to propose a novel family of compounds having a broad spectrum of improved action on phytopathogenic fungi of crops such as cereals, rice, fruit trees, forest trees, grapevine, oilseed crops , vegetable crops, solanées and beets.

 Another object of the present invention is to propose a new family of compounds comprising a heterocyclic unit associated with the hydroximic or hydrazonic function, having a broad spectrum of action on the phytopathogenic fungi of crops such as rice, cereals, fruit trees. , vines, oilseeds, vegetable crops, solanées and beets.

 Surprisingly, it has been found that these objects can be made in whole or in part by compounds having a heterocyclic unit associated with the hydroximic or hydrazonic function, such as those described in the present invention.

dans laquelle G est choisi parmi les groupes G1 à G9:

General definition of the invention:
The invention relates to compounds comprising a heterocyclic unit associated with the hydroximic or hydrazonic function, of general formula (I):

in which G is selected from groups G1 to G9:

wherein
n represents 0 or I
Q is the nitrogen atom or the CH group,
Q2 is the oxygen or sulfur atom,
Q3 is the oxygen or sulfur atom,
Q4 is the nitrogen atom or the CR group, 1,
Q5 is the oxygen atom, the sulfur atom or the NR12 group,
Y is the oxygen, sulfur or amino (NH) or oxyamino (ONH) group.

W1 is the oxygen atom, sulfur atom or the sulfinyl (SO) or sulphonyl (SO2) groups,
W2 is the oxygen atom or the group NR13,
p represents 0, 1 or 2,
A represents a mono or bicyclic aromatic heterocyclic radical containing from 5 to 10 atoms, of which 1 to 4 are heteroatoms chosen from oxygen, sulfur or nitrogen atoms, each sulfur or nitrogen atom being optionally in the oxidized state in the form of an N-oxide or sulfoxide group, which radical is attached to the carbon atom substituted by the groups R 1 and R 2 in the case where p = 1 or p = 2, or attached to the W2 group in the case where p = 0 by a carbon or nitrogen atom, which radical is optionally substituted with 1 to 5 radicals, preferably with 1 to 3 radicals X and / or X2 and / or X3,
X1, X2 and X3 are independently of each other a hydrogen atom, a halogen atom; or
hydroxy, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl; or
lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsul finyl, alkylsulfonyl, haloalkyl sulfonyl, alkoxysulfonyl; or
lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio; or
an amino group, N-alkylamino, N, N-dialkylamino, acylamino, aminoalkyl,
N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl; or
an acyl, carboxy, carbamoyl, N-alkylcarbamoyl group,
N, N-dialkylcarbamoyl, lower alkoxycarbonyl
X4 is a hydrogen atom, a halogen atom; or
lower alkyl, lower haloalkyl, alkoxy, haloalkoxy; or
cyano radicals, nitro,
R1 and R2 are independently of each other hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; or
cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl,
N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; or
aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, or
R1 and R2 may together form a divalent radical such as an alkylene group, optionally substituted by one or more halogen atoms, optionally substituted with one or more lower alkyl groups,
R3 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; or
nitro, cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, 3-oxetanyloxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; or
an alkenyl, alkynyl, N, N-dialkylamino, N, N-dialkylaminoalkyl or
an optionally substituted phenyl or benzyl group,
R4 is lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl; or
an alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino group,
R5 and R5 independently of one another represent a lower alkyl or lower haloalkyl group,
R 1 is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,
R8 is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, formyl, acyl,
R 1 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,
R1 is halogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl,
R11 and R12 are, independently of each other, hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,
R13 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, optionally substituted allyl group, optionally substituted propargyl group, optionally substituted benzyl group ; or
acyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; or
an alkylsulfonyl, haloalkylsulfonyl, optionally substituted arylsulfonyl group,
Q2 and R4 may together form a ring of 5 to 7 atoms containing 2 to 3 oxygen and / or nitrogen atoms, optionally substituted with one or more radicals such as halogen, lower alkyl or lower haloalkyl,
as well as the salts, the metal and metalloid complexes of the compounds of formula (I) as they have just been defined.

When the compound of formula (I) is such that A represents a mono or bicyclic aromatic heterocyclic radical as defined above, and when at least one of the radicals X 1 and / or X 2 and / or X 3 is a hydroxyl group, mercapto, ammo, N-alkylamino or N-acylamino, this compound may be capable of admitting a tautomeric form in chemical equilibrium, resulting from the displacement of the proton of said hydroxy group. mercapto, amino, N-alkylamino or N-acylamino. The tautomeric forms of such compounds are within the scope of the invention. Also included in the invention are the possible tautomeric forms of the compounds of formula (I) wherein p = O and W2 is NR13, wherein R13 is hydrogen. Such tautomeric forms are in particular defined in the book "The tautomerism of heterocycles, Advances in Heterocyclic Chemistry,
Supplement 1 "by J. Elguero, Martin C., AR Katritzky and P. Linda, edited by
Academic Press, New York, 1976, pages 1-4.

In the text of the present invention, the term "hydroximic group" includes both the strict "hydroximic group" (with the sequence OC = NO) and the "thiohydroximic group" (with the sequence
SC = NO). In the same way, the name "hydrazonic group" includes both the "hydrazonic group" strict (with the sequence OC = NN) that the "thiohydrazonic group" (with the sequence SC = NN).

In the case of the compounds of formula (I) for which p = 2, the radical - (CR 1 R 2) 2 - must be understood as being the radical - (CR 1 R 2) - (CR ', R' 2) -, where R '1 and
R'2 have the same definitions as R1 and R2 respectively, the pairs of radicals (R1; R2) and (R'1;R'2) being identical or different.

In addition, the following generic terms are used with the following meanings
The halogen atom means the fluorine, chlorine, bromine or iodine atom,
The "lower" objective qualifying an organic radical means that this radical has 1 to 6 carbon atoms, with the exception of the cycloalkyl radical, where the term "lower" means from 3 to 6 carbon atoms,
the alkyl radicals can be linear or branched,
the halogenated alkyl radicals may comprise one or more identical or different halogen atoms,
the acyl radical means alkylcarbonyl, or cycloalkylcarbonyl,
- the lower term qualifying the term acyl applies to the alkyl or cycloalkyl part of this radical,
the alkylenic radical denotes the radical - (CH2) m - where m = 2 to 5,
when the amino radical is disubstituted, the two substituents may constitute a saturated or unsaturated nitrogen heterocycle of 5 or 6 atoms,
when the carbamoyl radical is disubstituted, the two substituents may constitute a saturated or unsaturated nitrogen heterocycle of 5 or 6 atoms,
The expression "optionally substituted" qualifying an organic group applies to the different radicals constituting this group.

Preferred embodiments of the invention are those in which the products of formula (I) additionally have one and / or the other of the following characteristics taken separately or in combination:
nestégalàO;
pestal at 0, 1 or 2;
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;
W, is the oxygen or sulfur atom
W2 is the oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino, allylamino group,
Y is the oxygen atom,
X1, X2, X3 and X4 are, independently of one another, a hydrogen atom, a lower alkyl group, a halogen atom, or the cyano, trifluoromethyl, methoxy or nitro radicals,
R1 and R2 are each independently hydrogen, lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, alkoxycarbonyl; lower, N-alkylcarbamoyl, or N, N-dialkylcarbamoyl,
R3 is a hydrogen atom, a lower alkyl group, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl or methoxymethyl radical,
R4 is lower alkyl, alkoxy, alkylamino, dialkylamino, preferably methyl, ethyl, propyl, methoxy, ethoxy, methylamino, or ethylamino,
R5, R6, R5 and R6 are independently lower alkyl, lower haloalkyl, preferably methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, or propyl,
R 1 is lower alkyl, lower haloalkyl, preferably methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl, allyl, or propargyl,
Rlo is a chlorine atom, lower alkyl, lower haloalkyl, preferably methyl, alkoxy, alkylthio, preferably methoxy, or methylthio,
R11 and R12 are independently lower alkyl, lower haloalkyl, alkoxyalkyl, allyl, propargyl,
R, 3 is hydrogen, lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl, benzyl,
A is chosen from a radical, optionally substituted with 1 to 5 radicals, preferably with 1 to 3 radicals X1 and / or X2 and / or X3, derived, by elimination of a hydrogen atom, from one of the rings; (i) to (v):
a 5-link cycle described by formula (i)

wherein each of the groups of the list B1, B2, B3, B4 is selected from carbon, nitrogen, oxygen and sulfur so that said list comprises from 0 to 3 carbon atoms, from 0 to 1 sulfur atom, 0 to 1 oxygen atom and 0 to 4 nitrogen atom; or
a 6-link cycle described by formula (ii):

wherein each of the groups of the list D1, D2, D3, D4, D5 is selected from carbon or nitrogen atoms such that said list comprises from 1 to 4 carbon atoms and from 1 to 4 carbon atoms. nitrogen; or else, two fused rings with 6 links each, described by formula (iii):

in which each of the groups of the list E1, E2, E3, E4, E5, E6 E7, E8 is selected from carbon or nitrogen atoms such that said list comprises from 4 to 7 carbon atoms and from 1 to at 4 nitrogen atoms; or
a 6-link and a 5-link fused ring described by formula (iv)

in which:
- each of the groups of the list J1 J2 J3, J4, J5. J6 is selected from carbon or nitrogen atoms such that said list comprises from 3 to 6 carbon atoms, and from 0 to 3 nitrogen atoms; and
each of the groups of the list L1, L2, L3 is chosen from carbon, nitrogen, oxygen or sulfur atoms such that said list comprises from 0 to 3 carbon atoms, from 0 to 1 atom sulfur, from 0 to 1 oxygen atom and from 0 to 3 nitrogen atoms; and
each of the groups of the list J1, J2 J3 J4 J5 J6 L1 L2. L3 is chosen such that said list comprises from 3 to 8 carbon atoms; or
two fused rings with 5 links each described by the formula (v)

in which:
each of the groups of the list M1, M2, M3 represents the carbon, nitrogen, oxygen or sulfur atoms, such that said list comprises from 0 to 3 carbon atoms, from 0 to 1 atom of sulfur, from 0 to 1 oxygen atom and from 0 to 3 nitrogen atoms;
each of the groups of the list T1, T2, T3 represent the carbon, nitrogen, oxygen or sulfur atoms such that said list comprises from 0 to 3 carbon atoms, from 0 to 1 sulfur atom from 0 to 1 oxygen atom and from 0 to 3 nitrogen atoms;
Z represents the carbon or nitrogen atom;
each of the groups of the list M1, M2, M3, T1, T2, T3 is chosen such that the said list comprises from 0 to 6 carbon atoms.

It is understood that in formulas (i), (ii), (iii), (iv), (v) above, a group representing a carbon or nitrogen atom carries the free valence which connects A to the carbon atom substituted with the groups R1 and R2 in the case where p = 1 or 2; or
a group representing a carbon atom carries the free valence that connects A to the group W2 in the case where p = O.

Among the preceding variants, the following variants will be chosen more particularly in isolation:
W1 is the oxygen atom,
R1 is the hydrogen atom or the methyl radical,
R2 is hydrogen, lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N, N-lower dialkylcarbamoyl,
A represents a heterocyclic radical, optionally substituted with 1 to 5 radicals, preferably with 1 to 3 radicals X and / or X 2 and / or X 3 as defined above, chosen from the following list
furanyl; pyrolyl; thiophenyl;
pyrazolyl; imidazolyl; oxazolyl; isoxazolyl; thiazolyl;
isothiazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl;
1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,3-thiadiazolyl;
1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl; 1,3,4-thiadiazolyl;
1,2,3-triazolyl; 1,2,4-triazolyl tetrazolyl;
pyridyl;
pyrimidinyl; pyrazinyl; pyridazinyl; 1,2,3-triazinyl;
1,2,4-triazinyl; 1,3,5-triazinyl; 1,2,3,4-tetrazinyl;
1,2,3,5-tetrazinyl; 1,2,4,5-tetrazinyl;
benzimidazolyl; indazolyl; benzotriazolyl; benzoxazolyl;
1,2-benzisoxazolyl; 2,1-benzisoxazolyl; benzotiazolyl;
1,2-benzisothiazolyl; 2,1-benzisothiazolyl; 1,2,3-benzoxadiazolyl;
1,2,5-benzoxadiazolyl; 1,2,3-benzothiadiazolyl;
1,2,5-benzothiadiazolyl;
quinolinyl; isoquinolinyl;
quinoxazolinyl; quinazolinyl; cinnolyl or phthalazyl; pteridinyl;
benzotriazinyl;
1,5-naphthyridinyl; 1,6-naphthyridinyl; 1,7-naphthyridinyl;
1,8-naphthyridinyl;
imidazo [2,1-b] thiazolyl; thieno [3,4-b] pyridyl; purine; pyrolo [1,2-
b] thiazolyl.

Advantageously, compounds of formula (I) having the following variants are furthermore preferred:
W1 is the oxygen atom,
R1 is the hydrogen atom or the methyl radical,
R2 is hydrogen, lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N, N-lower dialkylcarbamoyl,
in which A, optionally substituted with 1 to 5 radicals, preferably with 1 to 3 radicals X1 and / or X2 and / or X3, is chosen from one of the following heterocycles:
pyridyl;
pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4
triazinyl;
quinolinyl; isoquinolinyl;
furanyl; pyrolyl; thiophenyl;
oxazolyl; isoxazolyl; thiazolyl; isothiazolyl; imidazolyl
pyrazolyl.

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

The compounds of general formula (I) and the compounds which may be used as intermediates in the preparation processes, and which will be defined on the occasion of the description of these processes, may exist in one or more forms of geometric isomers. according to the number of double bonds of the compound. The compounds of general formula (I) in which G is the group G1, G2 or G3 may comprise four different geometric isomers (E, E), (E, 7), (Z, E), (Z, Z) the configuration of the two double bonds. The notation E and Z can be replaced respectively by the terms syn and anti, or cis and trans. We will refer in particular to the work of E.Eliel and S.Wilen "Stereochemistry of
Organic Compounds "Ed. Wiley (1994) for the description and use of these notations.

 By convention, in the case of the present invention, the denominations (E, E), (E, Z), (Z, E) and (Z, Z) denote by the first letter the configuration of the double bond of the group G1 , G2 or G3, and by the second letter the configuration of the hydroximic or hydrazonic group.

 The compounds of general formula (I) in which G is the group G4 to G9 may comprise two different geometric isomers denoted (E) or (Z) according to the configuration of the hydroximic or hydrazonic group.

 The compounds of general formula (I) and the compounds which may be used as intermediates in the preparation processes, and which will be defined on the occasion of the description of these processes, may exist in one or more forms of optical isomers. or chiral depending on the number of asymmetric centers of the compound. The invention thus relates to all optical isomers as well as their racemic or scalemic mixtures (a scalemic term is a mixture of enantiomers in different proportions), as well as mixtures of all possible stereoisomers in all proportions. The separation of the diastereoisomers and / or optical isomers can be carried out according to the methods known per se (E.Eliel ibid.).

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

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

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

in which G is one of groups G1 to G9, groups G1 to G9 having the same definition as those indicated for formula (I), X4 having the same definition as that indicated for formula (I),
V is a halogen atom (preferably chlorine or bromine), an alkylsulfonate or haloalkylsulfonate group (preferably methylsulfonate or trifluoromethylsulfonate), arylsulfonate (preferably 4-methylphenylsulfonate), with a compound of formula (III) A:

W 1, W 2, R 1, R 2, R 3, R 13, X 1, X 2, X 3, p and A having the same definition as that indicated for formula (I),
in the presence of an organic or inorganic base, in the absence or in the presence of a solvent. The reaction is generally carried out at a temperature between -80 ° C. and 1800 ° C. (preferably between 0 ° C. and 1500 ° C.) or at the boiling point of the solvent used. The appropriate solvent for this reaction may be an aliphatic hydrocarbon such as pentane, hexane, heptane, octane; an aromatic hydrocarbon such as benzene, toluene, xylenes, halobenzenes; an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane; a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane; an ester such as methyl acetate, ethyl acetate, a nitrile such as acetonitrile, propionitrile, benzonitrile; a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolylene urea, dimethylsulfoxide; or water. Mixtures of these different solvents can also be used.

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

 Suitable organic or inorganic bases for this reaction include alkali and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide or calcium hydroxide; alkali and alkaline earth metal alkoxides such as potassium tert-butoxide, alkali and alkaline earth metal hydrides, such as sodium, potassium or cesium hydride; alkali and alkaline-earth metal carbonates and bicarbonates, such as sodium carbonate and potassium carbonate. calcium or sodium bicarbonate, potassium or calcium; organic bases, preferably nitrogenous, such as pyridine, alkylpyridines, alkylamines such as trimethylamine, triethylamine or di-isopropylethylamine, aza derivatives such as 1,5-diazabicyclo [4.3.0] non-5-ene or 1,8-diazabicyclo [5.4.0] undec-7-ene.

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

 Depending on the conditions used, the compounds of general formula (I) are obtained in the form of a variable mixture of isomers (E) and (Z) or a single isomer (E) or a single isomer (Z) following the configuration of the hydroximic or hydrazonic group. If necessary, the compounds of general formula (I) and of configuration (E) having the same definition as that of R3 indicated for formula (I) and being identical to R3 or different, U1 being preferably a halogen atom, the compound of formula (V) then representing an acid halide.

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

The derivatives of hydroxamic acids or of hydrazonic acids of formula (III) A where W1 is the oxygen atom, W2, R1, R2, R3, R13, X1, X2, X3, p and A having the same definition that indicated for the formula (I), can also be obtained by a process consisting in bringing into contact a compound of formula (VI):

R1, R2, X1, X2, X3, p and A having the same definition as that indicated for formula (I), and U2 is a halogen atom (preferably chlorine or bromine), an alkylsulfonate group (preferably methylsulfonate or trifluoromethylsulfonate),
with a hydroxamic acid or hydrazonic acid derivative, W2, R3 and R13 having the same definition as that indicated for formula (I), of formula (VII):

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

 The general conditions of condensation between the compound of formula (VI) and the compound of formula (VII) are similar or identical to the condensation conditions between the compound of formula (II) A and the compound of formula (III) A and are known per se according to "Houben-Weyl" volume E5, pages 1148-1149.

The hydroxamic acid derivatives of formula (III) A wherein W 1 and W 2 are the oxygen atom and p = 1 or 2; R1, R2, R3, R13, X1, X2, X3 and A having the same definition as that indicated for formula (I), may be obtained by a process comprising contacting a compound of formula (VIII):

R1, R1, X1, X2, X3 and A having the same definition as that indicated for formula (I) and p = 1 or 2,
with a hydroxamic acid derivative of formula (VII) where W 2 is the oxygen atom, R 3 having the same definition as that indicated for formula (I),
The condensation between the compound of formula (VII), W2 being the oxygen atom, R, having the same definition as that indicated for formula (I), and the compound of formula (VIII). R 1, R 2, X 1, X 2, X 3 and A having the same definition as that indicated for formula (I), is carried out in the presence of a coupling agent such as carbodi-imides or bis-alkoxycarbonylazo or bis-alkoxycarbonylazo derivatives; (N, Ndialkyl) carbamoylazo, preferably diethyl azodicarboxylate and a trialkylphosphine or triarylphosphine, preferably triphenylphosphine, in the absence or in the presence of an aprotic solvent, such as ethers including diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane such as halogenated hydrocarbons including dichloromethane, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane; as nitriles including acetonitrile, propionitrile, benzonitrile. Mixtures of these different solvents can also be used.

 The reaction is generally carried out at a temperature of between -80 ° C. and 1200 ° C. (preferably between 0 ° C. and 600 ° C.) or at the boiling point of the solvent used. The reaction time depends on the conditions used and is generally between 0.1 to 48 hours.

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

 The general conditions of this condensation are described in several journals, notably Synthesis (1981), 1 and Org. Prep. Procedé. Int (1996), 28, 127.

 The compounds of formula (IV), formula (V), formula (VI), formula (VII) and formula (VIII), W1, W2, R1, R2, R3, R13, X1, X2, X3, p and A having the same definition as that indicated for formula (I), U1 and U2 having the same definition as that indicated in method A can be prepared according to methods known per se, for example Tetrahedron (1995), 51, 11473 and Tetrahedron Lett. (1996), 37, 8045 for compounds of formula (IV) and Synthesis (1980), 746 for compounds of formula (VI).

 The compounds of formula (VI) and of formula (VIII) may more particularly be prepared according to a very large number of processes known per se and described in "The chemistry of heterocyclic compounds" volumes 1 to 52, Ed.

J.Wiley & Sons, and "Advances in heterocyclic chemistry" volumes 1 to 70, Ed.

Academic Press.

Compounds of formula (II) A in which G is one of groups G1 to G9, groups G1 to G9 having the same definition as that indicated for formula (I), X4 having the same definition as that indicated for formula (I) and VI is a halogen atom (preferably chlorine or bromine), an alkylsulphonate group (preferably methylsulphonate or trifluoromethylsulphonate), arylsulphonate (preferably 4-methylphenylsulphonate), will be by convention, for the following descriptionc preparation methods, designated by the generic term "benzyl halide derivatives"
The benzyl halide derivatives of formula (II) A where V1 is a halogen atom (preferably chlorine or bromine) may be obtained by halogenation of a compound of formula (IN):

 wherein G is one of G1 to G9, with G1 to G9 being as defined for formula (I), X4 being as defined for formula (I).

The halogenation of the compound of formula (IX) can be carried out by radical, thermal or photochemical means, the various processes not being exclusive of each other, by an N-haloacetamide such as
N-bromosuccinimide, N-chlorosuccinimide, N-bromoacetamide, in an inert solvent such as benzene or carbon tetrachloride or in the absence of a solvent with or without a free radical initiator at a temperature of 20 ° C to 170 ° C preferably from 80 ° C. to 100 ° C. according to J.March ibid. pages 689-697.

The benzyl halide derivatives of formula (II) A where V is a halogen atom (preferably chlorine or bromine) may also be obtained by halogenation of a compound of formula (II) B:

wherein G is one of G1 to G9, wherein G1 to G7 are as defined for formula (I) and R4 is alkylamino, dialkylamino, G8 and G9 having the same definition as that indicated for formula (I), X4 having the same definition as that indicated for formula (I), W1 is the oxygen atom,
with a halogenating agent such as thionyl chloride, phosphorus oxytrichloride, phosphorus tribromide according to J.March ibid. pages 431-433 or with the lithium halide / mesyl halide / collidine reagent according to J. Org.

Chem. (1971), 36.3044.

The benzyl halide derivatives of formula (II) A in which V1 is a halogen atom (preferably chlorine or bromine) may also be obtained by cleavage of a compound of formula (II) C:

wherein G is one of G1 to G9, wherein G1 to G7 are as defined for formula (I) and R4 is alkylamino, dialkylamino, G8 and G9 having the same definition as that indicated for the formula (I), X4 having the same definition as that indicated for the formula (1), W is the oxygen atom, and P is a protecting group of the alcohol function as an ester of preferably acetic or benzoic acid, or an ether, preferably methyl, methoxymethyl, phenyl, benzyl (it is advantageous to refer to the "Protective Groups in Organic Synthesis" of
W. Greene and P. Wuts, Ed Wiley (1991) for the selection and preparation of said protective groups),
with a Lewis acid such as boron tribromide, or anhydrous hydracids such as hydrogen chloride. This cleavage reaction is in particular known from patent EP 525516
The benzyl halide derivatives of formula (II) A and the compounds of formula (IX), (II) B and (II) C may be prepared according to methods known per se. These different methods or the related prior art will be explained in method K.

Method B:
The compounds of general formula (I) for which G is one of groups G1 to G9, the groups G1 to G7 having the same definition as that indicated for formula (I) and R4 is the group or radical amino, alkylamino, dialkylamino, the groups G8 and G9 having the same definition as that indicated for formula (I),
X4 having the same definition as that indicated for the formula (1), can be obtained by a process consisting in bringing into contact a compound of the formula (II) B in which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that indicated for formula (I) and R4 is the group or amino, alkylamino, dialkylamino radical, the groups G8 and G9 having the same definition as that indicated for formula (I), X4 having the same definition as indicated for formula (I), and W1 is the oxygen or sulfur atom,
with a compound of formula (III) B

 W2, R1, R2, R3, R13, X1, X2, X3, p and A having the same definition as that indicated for formula (I), U3 being a halogen atom, preferably a chlorine atom, the double bond U3-C (R3) = N-W2- which can be of stereochemistry (E) or (Z).

 This reaction is conducted in the presence of an organic or inorganic base, in the absence or in the presence of a solvent. The reaction is generally carried out at a temperature between -80 ° C. and 180 ° C. (preferably between 0 ° C. and 1 ° C.) or at the boiling point of the solvent used. The appropriate solvent for this reaction may be an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, a nitrile such as acetonitrile, propionitrile, benzonitrile, a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolylene urea, or dimethylsulfoxide. Mixtures of these different solvents can also be used.

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

 Suitable organic or inorganic bases for this reaction are alkali and alkaline earth metal hydrides, such as sodium, potassium or cesium hydride, alkali and alkaline earth metal alkoxides, such as tert- potassium butylate.

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

 Depending on the conditions used, the compounds of general formula (I) are obtained in the form of a variable mixture of isomers (E) and (Z) or a single isomer (E) or a single isomer (Z) following the configuration of the hydroximic or hydrazonic group. If necessary, the compounds of general formula (I) and of configuration (E) or (Z) according to the configuration of the hydroximic or hydrazonic group, can be isolated and purified according to methods known per se, 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.

(l971), 36, 234, and Chem. Abstracts (1970), 73, 34750s.

Method C:
The thiohydroxamic acid derivatives of formula (III) A where W1 is the sulfur atom and W2 is the oxygen atom or the thiohydrazonic acid derivatives of formula (III) A where W1 is the sulfur atom and W2 is NR13, R1, R1, R3, R13, X1, X2, X3, p and A having the same definition as that indicated for formula (I), are also the subject of the present invention.

 They can be obtained by thionation of the hydroxamic acids of formula (III) A where W1 is the oxygen atom and W2 is the oxygen atom or the hydrazonic acids of formula (III) A where W1 is the atom of oxygen and W2 is NR13, R1, R2, R3, R3, X1, N2, X3, p and A having the same definition as that for formula (I), with thionation agents such as pentasulfide phosphorus or Lawesson's reagent in a manner identical or similar to the methods described in "Houben-Weyl" volume E5, pages 1279-1280 and Synthesis (1984), 829.

Method D:
The compounds of general formula (I) for which G is the group G3, Q2 being the oxygen atom, R4 being the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for the formula (I and R6 is a lower alkyl or lower haloalkyl group, may be obtained by a process comprising contacting a compound of formula (X):

in which R4 is the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for formula (I),
with a Wittig-Horner reagent of formula (XI) A:
R6-CH2-P (= O) (ORb) 2 (XI) A
R 1 being a lower alkyl or lower haloalkyl group, Rb being a lower alkyl, phenyl or benzyl group,
or with a Wittig reagent of formula (XI) B:
R6-CH2-P (Rd) 3+; Hal- (XI) B
R6 is a lower alkyl or lower haloalkyl group, Rd being an optionally substituted phenyl group, Hal being a halide ion,
by the action of one or more equivalents of a base such as alkali metal or alkaline earth alcoholates, preferably sodium ethoxide, sodium methoxide or potassium tert-butoxide, alkali metal and alkaline earth metal hydrides preferably sodium or potassium hydride, an organometallic derivative such as alkyllithiums, preferably butyllithium, alkylmagnesium halides or lithium di-isopropylamide in an aprotic solvent such as ethers, preferably diethylether or tetrahydrofuran; at a temperature of -78 ° C. to 50 ° C., preferably -70 ° C. to 20 ° C., according to J.March ibid. pages 956-963 or WO 9529896.

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

Method E:
Compounds of general formula (I) for 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, dialkylamino group, the other substituents having the same definition as that indicated for the formula (I) and R5 is a lower haloalkyl group, can be obtained by a process comprising contacting a compound of formula (XII) with:

in which T is the oxygen or sulfur atom, M is an alkaline or alkaline-earth ion, Q1 being the nitrogen atom or the CH group, R4 being the alkoxy, alkylamino, dialkylamino, W1, W2 group, R1, R1, R3, R13, X1, N2, X3, X4, p and A having the same definition as that indicated for formula (I),
with a halogenated compound of formula CHq (Hal) 4q where q = 1 or 2 and Hal denotes the same or different halogen atoms and at least one of which is the chlorine or bromine atom ,
in a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolylene urea, or dimethylsulfoxide in the presence or absence of a catalytic amount of iodide ion, at a temperature between -20 C and 250 C preferably at 25 ° C. to 150 ° C. or at reflux of the solvent. This reaction is especially described in the patents
DE 4424788 and WO 9606072.

The compounds of formula (XII) in which T is the oxygen atom and M an alkaline or alkaline earth ion, Q being the nitrogen atom, R4 being the alkoxy, alkylamino, dialkylamino, W1, W2 group, R1, R2, R3, R13, X1, X2, X3, N4 p and A having the same definition as that indicated for formula (I), can be easily obtained from compounds of formula (N), wherein R4 is the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition as that indicated for formula (I), by the action of hydroxylamine and a base according to
J.March ibid. pages 906-907.

 The compounds of formula (XII) in which T is the oxygen atom and M is an alkaline or alkaline earth metal, QO is CH, R4 being alkoxy, alkylamino, dialkylamino, W1, W2, R1, R2 , R3, R13, X1, X2, X3, X4, p and A having the same definition as that indicated for the formula (I) can in particular be prepared in a manner similar to EP 176826.

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

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

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

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

wherein R4 is alkoxy, alkylamino, dialkylamino, X4 having the same definition as given for formula (I),
V is a halogen atom (preferably chlorine or bromine), an alkylsulphonate group (preferably methylsulphonate or trifluoromethylsulphonate), arylsulphonate (preferably 4-methylphenylsulphonate),
with a compound of formula (III) A, W 1, W 2, R 1, R 2, R 3, R 13, X 1, X 2, X 3, p and A having the same definition as that indicated for formula (I).

 The general conditions of condensation between the compound of formula (XIII) B and compound of formula (III) A are similar or identical to the condensation conditions between the compound of formula (II) A and compound of formula (III) A described in US Pat. method A.

 The compounds of general formula (XIII) B can be obtained according to patent EP 498396.

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

Method H:
The compounds of general formula (I) for which W 1 is the sulfoxide (SO) or sulfone (SO 2) group and G being one of the groups G 1, G 3, G 4, G 6 to G 9, Q 2 and Q 3 being the atom oxygen, the other substituents having the same definition as that indicated for the formula (I), can be obtained by oxidation of the compounds of general formula (I) for which W 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 as that indicated for formula (I), using one or more equivalents oxidation agents such as organic peroxides, preferably peracetic acid, 3-chloroperbenzoic acid, mineral peroxides, hydroperoxides such as hydrogen peroxide, inorganic oxychlorides or oxygen, in the presence or absence of a catalyst in an inert solvent according to J.March ibid. pages 1201-1203.

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

in which G is one of groups G1 to G9, groups G1 to G9 having the same definition as that indicated for formula (I), X4, W1, W2, R3 and R13 having the same definition as those indicated for formula (I),
with a compound of formula (VI), R1, R2, X1, X2, X3, p and A having the same definition as that indicated for formula (I), and U2 is a halogen atom (preferably chlorine or bromine ), an alkylsulphonate group (preferably methylsulphonate or trifluoromethylsulphonate).

 The condensation between the compound of formula (XV) A and the compound of formula (VI) 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 (XV) A and the compound of formula (VI) are similar or identical to the condensation conditions between the compound of formula (VII) and the compound of formula (VI) described in the method AT.

Compounds of formula (NV) A wherein G is one of groups G1 to
G9, the groups G1 to G9 having the same definition as that indicated for the formula (I), X4, W1, W2, R3 and R13 having the same definition as those indicated for the formula (I), are also subject to the present invention.

They can be obtained by cleavage of a compound of formula (XV) B:

in which G is one of groups G1 to G9, the groups G1 to G9 having the same definition as those indicated for formula (I), X4, W1, W2, R3 and R1R having the same definition as those indicated for formula (I), and P is a protecting group of the hydroxyl function such as a preferably acetic or benzoic ester, a silylated ether such as trialkylsilyl ether, dialkylarylsilyl ether, alkyldiarylsilyl ether or triarylsilyl ether, preferably isopropyldimethyl silyl ether, triethylsilyl ether, tert-butyldimethylsilyl ether, trityldimethylsilyl ether, tert-butyldiphenylsilyl ether, methyldiisopropylsilyl ether, methyldi-tert-butylsilyl ether or tri-isopropylsilyl ether, or an ether such as triarylmethyl ether, preferably triphenylmethyl ether, di- (4-methoxyphenyl) ) phenylmethyl ether or 4-methoxyphenyldiphenylmethyl ether, or a protecting group of the amino function such as an alkoxycarbonyl group, preferably tert-butyloxycarbonyl or benzyloxycarbonyl (this list is not limiting and reference will be made to the work of W.Greene and P.Wuts (ibid.) for the choice of said protective groups),
with a cleavage agent specific for the protecting group P. The specific cleavage conditions of each protecting group P are known per se according to W. Greene and P. Wuts (ibid.) and Synthesis (1985), 817.

 Compounds of formula (XV) B in which G is one of the groups <RTI ID =

The general conditions of condensation between the compound of formula (II) A and the compound of formula (XVI) are similar or identical to the condensation conditions between the compound of formula (II) A and the compound of formula (III) A described in method A and are known per se according to "Houben-Weyl" volume
E5, pages 1148-1149.

The compounds of formula (XVI), W1, W2, R3 and R13 having the same definition as those indicated for formula (I) and P being a protecting group for the hydroxyl function or a group protecting the amino function, may be prepared by condensation of a compound of formula (XVII):

W2 and R13 having the same definition as those indicated for formula (1) and
P being a protecting group of the hydroxyl function or a protective group of the mono function,
with a compound of formula (V), W1, R3 having the same definition as that indicated for formula (I), U1 is a halogen atom (preferably chlorine or bromine), or a hydroxy, lower alkoxy or benzyloxy radical; , lower alkylthio, ammo, N-alkylamino, N, N-dialkylamino, N-acylamino, N, N-acylalkylamino or the group -O (C = O) Ra, Ra having the same definition as that of R3 indicated for the formula (I) and being identical to R, or different, U1 is preferably a halogen atom, the compound of formula (V) then representing an acid halide.

 The general conditions of condensation between the compound of formula (XVII) and the compound of formula (V) are similar or identical to the condensation conditions between the compound of formula (IV) and the compound of formula (V) described in method A .

 The compounds of formula (XVII) can be prepared according to methods known per se.

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

 The isomers of general formula (I) with the atoms or group W1 and W2 in trans position relative to the double bond -C (R3) = N- (hydroximic or hydrazonic group) can be prepared from cis isomers by heating in a solvent, preferably under ultraviolet irradiation, with or in the absence of a catalyst, in particular an acid catalyst. The reaction time is chosen so as to obtain a total conversion of the cis isomer to 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 may be an aliphatic hydrocarbon such as pentane, hexane, heptane, octane; an aromatic hydrocarbon such as benzene, toluene, xylenes, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane; a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane; an ester such as methyl acetate, ethyl acetate; a nitrile such as acetonitrile, propionitrile, benzonitrile; an alcohol such as methanol, ethanol, propanol, isopropanol; a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprolylene urea, dimethylsulfoxide; or water. Mixtures of these different solvents can also be used.

 The solvent will preferably be an aromatic solvent such as toluene or xylenes or an ether such as diisopropyl ether. The catalyst, preferably an acidic catalyst, will be chosen from anhydrous hydrosaccharides such as hydrogen chloride, carboxylic acids such as acetic acid, propionic acid, trifluoroacetic acid, sulphonic acids such as methanesulphonic acid, trifluoromethanesulfonic, 4-methylphenylsulphonic or sulfuric acid.

Method K:
(Derivatives of benzyl halides of formula (II) A and the like)
The benzyl halide derivatives of formula (II) A and the compounds of formula (IX), (II) B and (II) C may be prepared according to a very many methods known per se.

Nonlimiting and non-exhaustive examples include various patents describing the processes for preparing benzyl halide derivatives of formula (II) A or compounds of formula (IX) 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 G1 or G2 of stereochemistry (E) or (Z), can be prepared according to the patent EP 426460, EP 398692 , EP 617014, EP 585751, EP 487409, EP 535928, DE 4305502,
The benzyl halide derivatives of formula (II) A and the like, where G is the group G1 or G2 of stereochemistry (E) or (Z) and Q2 and R4 together form a ring of 5 to 7 atoms containing 2 to 3 oxygen and / or nitrogen atoms, are known according to the patent WO 9504728,
The benzyl halide derivatives of formula (II) A and the like, where G is the G3 group 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 619301,
WO 9315046,
The benzyl halide derivatives of formula (II) A and the like. where G is the group G7, are known according to the patents WO 9527693, WO 9607633,
The benzyl halide derivatives of formula (II) A and the like, where G is the group G8 or G9, are known according to the patent WO 9514009.

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

 The fungicidal compositions according to the invention comprise, in addition to the active ingredient of formula (I), solid or liquid carriers which are acceptable in agriculture and / or surfactants which are also acceptable in agriculture. In particular, the inert and conventional supports and the usual surfactants can be used. These compositions not only cover the compositions ready to be applied to the plant or seed to be treated by means of a suitable device, such as a spraying or dusting device, but also the commercial concentrated compositions which must be diluted before application to Culture.

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

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

 By the term "carrier" in this specification is meant an organic or inorganic material, natural or synthetic, with which the active ingredient is combined to facilitate its application to parts of the plant. This support is therefore generally inert and must be acceptable in agriculture. The support may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, especially butanol, etc.).

 The surfactant may be an emulsifier, dispersant or wetting agent of ionic or nonionic type or a mixture of such surfactants. There may be mentioned, for example, salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines. substituted phenols (especially alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (especially alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols, esters of and polyols, sulfates, sulfonates and phosphates-based derivatives of the foregoing compounds. The presence of at least one surfactant is generally indispensable when the active ingredient and / or the inert carrier are not soluble in water and the application carrier agent 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 content of surfactant is advantageously between 5% and 40% by weight. Unless otherwise indicated, the percentages given in this description are percentages by weight.

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

 As forms of solid compositions, mention may be made of dusting powders (with an active matter content of up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation from a powder (the content of active material 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 dusting powders; it is also possible to use compositions comprising 50 g of active material and 950 g of talc; it is also possible to use compositions comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and milled 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 the solutions. in particular water-soluble concentrates, emulsions, concentrated suspensions, wettable powders (or powder for spraying).

 The concentrated suspensions, applicable in spraying, are prepared in such a way as to obtain a stable fluid product which does not settle and usually contain from 10 to 75% of active substance, from 0.5 to 15% of surfactants, from 0 to 1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as antifoams, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as carrier, water or an organic liquid in which the active ingredient is little or not soluble: some organic solids or mineral salts can be dissolved in the support to help prevent sedimentation or as antifreezes for water.

For example, here is a concentrated suspension composition
Example SC 1:
active ingredient 500 g
- polyethoxylated tristyrylphenol phosphate 50 g
polyethoxylated alkylphenol 50 g
- sodium polycarboxylate 20 g
- ethylene glycol 50 g
- organopolysiloxane oil (antifoam) lg
- polysaccharide 1.5 g
water 316.5 g
Wettable powders (or spray powder) are usually prepared to contain from 20 to 95% active ingredient, and usually contain, in addition to the solid support, from 0 to 30% of a wetting agent, at 20% of a dispersing agent, and, when necessary, from 0.1 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, dyes, etc.

 In order to obtain the spraying powders or wettable powders, the active ingredients in the appropriate mixers are intimately mixed with the additional substances and milled with suitable mills or other mills. Spray powders are thus obtained, the wettability and suspension of which are advantageous; they can be suspended with water at any desired concentration and these suspensions are very advantageously used especially for application for example on the leaves of plants or on seeds.

By way of example, here are various compositions of wettable powders (or powders for spraying):
Example PM 1
- active ingredient 50%
- ethoxylated fatty alcohol (wetting agent) 2.5%
- ethoxylated phenylethylphenol (dispersing agent) 5%
- chalk (inert support) 42.5%
Example PM 2:
- active ingredient 10%
- oxo synthetic alcohol of branched type, C13 ethoxylated with 8 to 10 ethylene oxide (wetting agent) 0.75%
- neutral calcium lignosulfonate (dispersing agent) 12%
- calcium carbonate (inert filler) qs 100%
Example PM 3:
This wettable powder contains the same ingredients as in the previous example, in the following proportions:
- active ingredient 75%
- wetting agent 1.50%
- dispersing agent 8%
- calcium carbonate (inert filler) qs 100%
Example PM 4:
- active ingredient 90%
- ethoxylated fatty alcohol (wetting agent) 4%
- ethoxylated phenylethylphenol (dispersing agent) 6%
Example PM 5:
- active ingredient 50%
- mixture of anionic and nonionic surfactants (wetting agent)
2.5%
- sodium lignosulfonate (dispersing agent) 5%
- kaolinic clay (inert support) 42.5%
The aqueous dispersions and emulsions, for example the compositions obtained by diluting with water a wettable powder according to the invention, are included in the general scope of the present invention. The emulsions may be of the water-in-oil or oil-in-water type and may have a thick consistency such as that of a "mayonnaise".

 The fungicidal compositions according to the invention may be formulated in the form of water-dispersible granules also included in the scope of the invention.

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

 The active ingredient content of these granules is generally between about 1% and 90%, and preferably between 25% and 90%.

 The rest of the granule is essentially composed of a solid filler and optionally surfactant adjuvants conferring on the granule properties of dispersibility in water. These granules can be essentially of two distinct types depending on whether the charge retained is soluble or not in water. When the filler is water soluble, it may be inorganic or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble filler, it is preferably mineral, such as kaolin or bentonite. It is then advantageously accompanied by surfactants (in a proportion of 2 to 20% by weight of the granule) of which more than half is, for example, constituted by at least one dispersing agent, essentially anionic, such as polynaphthalene. an alkali or alkaline earth metal sulphonate or an alkali or alkaline earth lignosulfonate, the remainder being nonionic or anionic wetting agents such as an alkaline or alkaline earth alkyl naphthalene sulphonate.

 On the other hand, although not essential, other adjuvants such as antifoam agents may be added.

 The granulate according to the invention can be prepared by mixing the necessary ingredients and then granulating according to several techniques known per se (dredger, fluid bed, atomizer, extrusion, etc.). It is generally finished by crushing followed by sieving at the chosen particle size within the limits mentioned above. It is also possible to use granules obtained as above and then impregnated with a composition containing the active ingredient.

 Preferably, it is obtained by extrusion, operating as indicated in the examples below.

Example GD1: Dispersible granules
In a mixer, 90% by weight of active material and 10% of urea beads are mixed. The mixture is then milled in a pin mill. A powder is obtained which is moistened with about 8% by weight of water. The wet powder is extruded in a perforated roll extruder. A granule is obtained which is dried, then crushed and sieved so as to keep only the granules with a size of between 150 and 2000 microns respectively.

Example GD2: Dispersible granules
In a mixer, the following constituents are mixed:
- active ingredient 75%
- wetting agent (sodium alkylnaphthalene sulphonate) 2%
- dispersing agent (sodium polynaphthalene sulphonate) 8%
- inert load insoluble in water (kaolin) 15%
This mixture is granulated in a fluid bed, in the presence of water, then dried, crushed and sieved so as to obtain granules with a size of between 0.15 and 0.80 mm.

 These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active ingredients, especially fungicides, the latter being in the form of wettable powders, or aqueous granules or suspensions.

 The compounds of the invention may also be mixed with one or more insecticides, fungicides, bactericides, attractant acaricides or pheromones or other compounds with biological activity. The mixtures thus obtained have broad spectrum activity. Mixtures with other fungicides are particularly advantageous, especially mixtures with carbendazim, thiram, diethofencarb, dodine, carousel, mancozeb, diflumetorim, ethirimol, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, captafol, folpel, thiophanate, thiabendazole, phosetyl-Al, chlorothalonil, dichioran, metalaxyl, iprodione, oxadixyl, vinchlozoline, tebuconazole, bromuconazole , triticonazole, difenconazole, diniconazole, metconazole, penconazole, propiconazole, prochioraz, fenarimol, triadimenol, furalaxyl, copper derivatives such as hydroxide and oxychloride, probenazole, azoxystrobin , kresoxymethyl, epoxyconazole, famoxadone, fludioxonyl, pyrimethanil, neparipyrim, cyprodinyl, quinoxyfen. ferimzone, fluazinam, dimethomorph, benalaxyl, blasticidin-S, fluquinconazole, tricyclazole, fluzilazole, flutolanil, guazatine, hexaconazole, hymexazol, isoprothiolane, kazugamycin, pencycuron, phthalide, pyroquilon, tetraconazole, thifluzamide, carboxin.

 The compositions according to the invention are useful for treating seeds of cereals (wheat, rye, triticale and barley in particular), potatoes, cotton, peas, rapeseed, corn, linseed or seeds of forest trees (especially softwood).

 It should be noted in this connection that in the jargon of the skilled person, the term "seed treatment" refers to the treatment of seeds. Application techniques are well known to those skilled in the art and can be used without disadvantage in the context of the present invention. For example, film-coating or coating may be mentioned.

 Another subject of the invention is a method for controlling curative or preventive fungi against phytopathogenic fungi in crops, characterized in that an effective amount (agronomically effective) is applied to plant seeds or to plant leaves. ) and non-phytotoxic of an active ingredient of formula (I), preferably in the form of a fungicidal composition according to the invention.

 By "effective and non-phytotoxic amount" is meant a quantity of composition according to the invention which is sufficient to allow the control or destruction of fungi present or likely to appear on the cultures, and which does not cause for said cultures any noticeable symptoms of phytotoxicity. Such an amount is likely to vary within wide limits depending on the fungus to be controlled. the type of culture, the climatic conditions, and the compounds included in the fungicidal composition according to the invention. This amount can be determined by systematic field tests, within the reach of the skilled person.

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

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

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

 As indicated above, the methods for recovering plant propagation products, in particular seeds, are well known in the art and make particular use of film-coating or coating techniques.

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

Among the plants targeted by the method according to the invention, mention may be made of:
- wheat, with regard to the control of the following seed diseases: fusariosis (Microdoclzium nivale and Fusarium roseum), caries (Tilletia caries, Tilletia controversa or Tilletia indica), septoria (Septoria nodorum);
- wheat, with regard to the control of the following diseases of the aerial parts of the plant: the pied-trunk (Pseudocercosporella herpotricholdes), the foot-and-mouth disease (Gaeumannomyces graminis), the Fusarium blight (F. culmorum,
F. graminearum), Rhizoctonia (Rhizoctonia cerealis), Orthic (Erysiphe graminis forma specie tritici), Rust (Puccinia striiformis and Puccinia recondita) and Septoria (Septoria tritici and Septoria nodorum)
- wheat and barley, as regards the fight against bacterial and viral diseases, for example barley yellowing of barley.

- barley, as regards the control of the following diseases of seeds
Helminthosporiosis (Pyrenophora graminea, Pyrenophoru teres and
Cochliobolus sativus), bare smut (Ustilago nuda) and fusariosis (Microdochium nivale and Fusarium roseum),
- the barley, with regard to the control of the following diseases of the aerial parts of the plant: the troglodyte (Pseudocercosporella herpotrichoides), the helminthosporiosis (Pyrenophora teres and Cochiiobolus sativus), the powdery mildew (Erysiphe seeds forma hordei spectrum) , dwarf rust (Puccinia hordei) and rhynchosporiosis (Rhynchosporium secalis):
- potatoes, as regards the control of tuber diseases (especially Helminthosporium solani, Phoma tube rosa, Rhizoctonia solani, Fusarium solani) and certain virus diseases (virus Y);
- cotton, with regard to the fight against the following diseases of young seed-derived plants: root fern and neck necrosis (Rhizoctonia solani, Fusarium oxysporum), black root rot (Thielaviopsis basicola)
- peas, as regards the control of the following seed diseases: anthracnose (Ascochyta pisi, Mycosphaerella pinodes), fusarium wilt (Fusarium oxysporum), gray mold (Botrytis cinerea);
- rapeseed, as regards the control of the following diseases of seeds: Phoma lingam and Alternaria brassicae;
- maize, as regards the control of seed diseases (Rhizopus sp., Penicillium sp., Trichoderma sp., Aspergillus sp. and Gibberella Ajikurol);
- flax, as regards the control of seed disease: Alternaria lincola;
- forest trees, with regard to the control of seeding furs (Fusarium oxysporum, Rhizoctonia solani).

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

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

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

The following examples illustrate the present invention
EXAMPLE 1 Preparation of Methyl (E, E) -2- (2- (i ((5-chloro-2-thiophenyl) methyloxyimino) ethoxymethyl) phenyl) -2-methoxyiminoethanoate
Step 1:
preparation of O- (5-chloro-2-thiophenyl) methyl acetohydroxamate
To a solution at room temperature of 23.6 g of O- (5-chloro-2-thiophenyl) methylhydroxylamine hydrochloride and 24.2 ml of pyridine in 200 ml of dichloromethane is added with stirring. acetyl. After 2 h, the reaction mixture is taken up in ethyl acetate, washed with water, dried over magnesium sulfate, concentrated and then purified by flash chromatography on silica, which gives 16.0 g of O- (5-chloro-2-thiophenyl) methyl acetohydroxamate as a pale yellow liquid. Rf = 0.18 (eluent: heptane / ethyl acetate 50/50) (where Rf denotes the retention coefficient on silica thin layer chromatography plate).

2nd step:
Preparation of (E, E) -2- (Methyl-2- (1 - ((5-chloro-2-thiophenyl) methyloxyimino) ethoxymethyl) phenyl) -2-methoxyiminoethanoate
A suspension of 2.10 g of methyl (E) -2- (2- (bromomethyl) phenyl) -2-methoxyiminoethanoate, 1.65 g of O- (5-chloro2-thiophenyl) methyl acetohydroxamate with 3, 20 g of cesium carbonate in 50 ml of acetonitrile is stirred at 500 ° C. for 3 h, then filtered and concentrated. The reaction medium is taken up in 20 ml of toluene containing a catalytic amount of acetic acid and stirred at 1000 ° C. for 4 hours. Concentration followed by purification by flash chromatography on silica gives 1.30 g of (E, E) -2- (2- (1 - ((5-chloro-2-thiophenyl) methyloxyimino) ethoxymethyl) phenyl) Methyl 2-methoxyiminoethanoate as a white solid. F = 630C (this expression denotes the melting point).

Example 2
Preparation of (E, E) -2- (2- (1 - ((5-chloro-2-thiophenyl) methyloxyimino) ethoxymethyl) phenyl) -2-methoxyimino-N-methylacetamide
0.80 g of methyl (E, E) -2- (2- (1 - ((5-chloro-2-thiophenyl) methyloxyimino) ethoxymethyl) phenyl) -2-methoxyiminoethanoate is stirred for 5 hours at room temperature. in 10 ml of a solution of methylamine [2M] in methyl alcohol. After evaporation, 0.88 g of (E, E) -2

2nd step :
Preparation of Methyl (E, E) -2- (2- (1 - ((3, 5-dimethyl-4-isoxazolyl) methyloxyimino) -cyclopropylmethyloxymethyl) phenyl) -3-methoxypropenoate
1.5 g of O- (3,5-dimethyl-4-isoxazolyl) methyl cyclopropanecarboxamate, 1.8 g of methyl (E) -2- (2- (bromomethyl) phenyl) -3-methoxypropenoate and 2, 5 g of cesium carbonate are stirred for 4 hours under an inert atmosphere in 10 ml of refluxing acetonitrile. After filtration of the cesium salts and evaporation of the solvent, the crude reaction product is stirred at 100 ° C. for 5 h in 15 ml of toluene containing 0.25 ml of glacial acetic acid. After neutralization with a buffer solution at pH = 7 followed by filtration on phase-separating paper and evaporation, flash chromatography on silica makes it possible to isolate 0.61 g of (E, E) -2- (2). Methyl (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -3-methoxypropenoate as a yellow oil. nD = 1.5300 (24.50C).

Example 4
Preparation of Methyl (E, E) -2- (2- (1 - ((3,5-dimethyl-4-isoxaaazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-methoxyiminoethanoate
Methyl (E, E) -2- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-methoxyiminoethanoate is prepared according to a procedure similar to that given in Example 3, step 2. 0.82 g of (E, E) -2- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl Methyl 2-methoxyiminoethanoate is thus obtained in the form of an orange oil from 4 g of O- (3,5-dimethyl-4-isoxazolyl) methyl cyclopropanecarboxamate and 4.8 g of (E) -2 Methyl (2- (bromomethyl) phenyl) -2-methoxyiminoethanoate. np = 1.5320 (25.7 ° C).

Example 5
Preparation of (E, E) -2- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethoxymethyl) phenyl) -2-methoxyimino-N-methylacetamide
(E, E) -2- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-methoxyimino-N-methylacetamide is prepared according to a procedure similar to that given in Example 2. 0.435 g of (E, E) -2 (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2- methoxyimino-N-methylacetamide is thus obtained in the form of a yellow oil from 0.4 g of (E, E) -2- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) Methyl 1-cyclopropylmethyloxymethyl) phenyl-2-methoxyiminoethanoate. n, = 1.5357 (26.1 C).

Example 6
Preparation of methyl (E) -N-methoxy-N- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) carbamate
Methyl (E) -N-methoxy-N- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethoxymethyl) phenyl) carbamate is prepared according to a procedure similar to that given in example 3, step 2. 0.366 g of (E) -N methoxy-N- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) Methyl carbamate is thus obtained in the form of an orange oil from 1.7 g of O- (3,5-dimethyl-4isoxazolyl) methyl cyclopropanecarboxamate and 1.95 g of N-methoxy-N- (2- (bromomethyl) phenyl) methyl carbamate. nD = 1.5266 (23.3 ° C).

Example?:
Preparation of methyl (E) -2- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-methoxyethanoate
Methyl (E) -2- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-methoxy ethanoate is prepared according to a similar procedure. to that given in Example 3, Step 2. 0.23 g of (E) -2- (2- (1 ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) Methyl 2-methoxyethanoate is thus obtained in the form of an orange oil from 1.7 g of O- (3,5-dimethyl-4isoxazolyl) methyl cyclopropanecarboxamate and 1.94 g of 2- (2- (bromomethyl) ) phenyl) -2-methoxyethanoate methyl. nD = 1.5277 (23.9 C).

Example 8
Preparation of Methyl (E, E) -2- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1cyclopropylmethyloxymethyl) phenyl) -2-butenoate
Methyl (E, E) -2- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-butenoate is prepared according to a procedure similar to that given in Example 3, Step 2. 0.66 g of (E, E) -2- (2- (1 - ((3,5-dimethyl-4-isoxazolyl) methyloxyimino) 1 -cyclopropylmethyloxymethyl) phenyl) -2 methyl butenoate is thus obtained in the form of a yellow oil from 1.5 g of O- (3,5-dimethyl-4-isoxazolyl) methyl cyclopropanecarboxamate and 1.6 g of (E, E) - 2- (2- (bromomethyl) phenyl) -2-butenoate methyl, nD = 1.5244 (25.6 ° C).

Example 9
Preparation of (E, E) -2- (Methyl 2- (1 - (2-pyridyl) propyloxyimino) -1-cyclopropyl methyloxymethyl) phenyl) -3-methoxypropenoate Etapel:
Preparation of N- (1- (2-pyridyl) propyloxy) phthalimide
A mixture of 14.4 g of 2- (1-chloropropyl) pyridine, 15.1 g of
N-hydroxyphthalimide and 12.8 g of potassium carbonate in 280 ml of dimethylformamide is stirred at 80 ° C. for 7 hours. The reaction crude is partitioned between an aqueous phase and ethyl acetate. The aqueous phase is extracted with ethyl acetate, the organic phases are combined and washed with a saturated aqueous solution of sodium chloride, and then dried and evaporated. The solid obtained is recrystallized from diisopropyl ether, which makes it possible to obtain 11.52 g of N- (1- (2-pyndyl) propyloxy) phthalimide in the form of a white solid. Mp = 123 ° C.

2nd step:
Preparation of 0-1- (2-pyridyl) propyl cyclopropanecarboxamate
A mixture of 20.4 g of N- (1- (2-pyridyl) propyloxy) phthalimide and 4.34 ml of hydrazine hydrate in 400 ml of ethanol is stirred at 35 ° C. for 2 h and then filtered. The filtrate is rinsed with ethanol, the mother liquors combined, concentrated and then taken up with ethyl acetate and saturated aqueous sodium chloride solution. The aqueous phase is reextracted with ethyl acetate, the organic phases are combined, dried and then evaporated to yield the
11.65 g of reaction crude which is added to a solution of 12.17 ml of triethylamine in 120 ml of dichloromethane. 7.98 ml of cyclopropanecarboxylic acid chloride are then added dropwise to OOC, and the reaction mixture is stirred for 1 hour at room temperature. A saturated aqueous solution of sodium chloride is then added, and the aqueous phase is extracted with dichloromethane, the organic phases are combined, dried and then evaporated. The crude obtained is recrystallized from diisopropyl ether and then purified by flash chromatography on a silica column, which makes it possible to obtain 13 g of cyclopropanecarboxamate of Ol- (2-pyridyl) propyl in the form of a white solid. F = 790C.

Step 3:
Preparation of Methyl (E, E) -2- (Methyl 2- (1- (1- (2-pyridyl) propyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -3-methoxypropenoate
6.1 g of cyclopropanecarboxamate of Ol- (2-pyridyl) propyie, 7.89 g of methyl (E) 2- (2- (bromomethyl) phenyl) -3-methoxypropenoate and 9.02 g of cesium carbonate are stirred for 4 hours under an inert atmosphere in 100 ml of refluxing acetonitrile. After filtration of the cesium salts, concentration of the filtrate and recovery with an aqueous solution and ethyl acetate, the organic phase is dried and evaporated. The crude reaction product is purified by flash chromatography on silica. The product obtained is stirred at 1000C for 6 h in 50 ml of toluene containing 0.50 ml of glacial acetic acid. After neutralization with a buffer solution at pH = 7 followed by filtration on phase-separating paper and evaporation, flash chromatography on silica makes it possible to isolate 0.96 g of (E, E) -2 (2- Methyl 1- (1 - (2-pyridyl) propyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl-3-methoxypropenoate as a brown oil. nD = 1.5366 (24.00C).

Example 10
Preparation of (E, E) -2- (methyl 2- (1- (1- (6-methyl-2-pyridyl) ethyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-methoxyiminoethanoate
Step 1:
Preparation of 2- (1-hydroxyethyl) -6-methylpyridine
To a solution of 15 g of 6-methylpyridine-2-carboxaldehyde in 100 ml of diethyl ether at -78 ° C., 50 ml of bromomethyl are added under an inert atmosphere.
Grignard [3M diethyl ether]. After the addition, the reaction medium is stirred at ambient temperature for 1 h. A partition of diethyl ether I hydrochloric acid [IN] followed by neutralization of the aqueous phase with a pH = 7 buffer solution and evaporation of the combined organic phases and dried over magnesium sulfate makes it possible to isolate 14.6 g of Crude 2- (1-hydroxyethyl) -6-methylpyridine as a yellow oil. Rf = 0.31 (heptane / ethyl acetate 30/70).

2nd step:
Preparation of N- (1- (6-methyl-2-pyridyl) ethyloxy) phthalimide
14.6 g of crude 2- (1-hydroxyethyl) -6-methylpyridine, 19.1 g of
N-hydroxyphthalimide and 30.7 g of triphenylphosphine are diluted in 300 ml of tetrahydrofuran. 18.4 ml of diethyl azodicarboxylate are then added dropwise with stirring and inert atmosphere. The reaction mixture obtained is stirred at ambient temperature for 14 h and then evaporated and purified by flash chromatography on silica, which makes it possible to isolate a solid mixture corresponding to the coupling product and the reduced diethyl azodicarboxylate, used as such in the reaction mixture. 'next step. Rf = 0.59 (heptane / ethyl acetate 30/70).

Step 3:
Preparation of O- (1- (6-methyl-2-pyridyl) ethyl) hydroxylamine
The preceding mixture of N- (1- (6-methyl-2-pyridyl) ethyloxy) phthalimide and of reduced diethyl azodicarboxylate is stirred in 200 ml of refluxing ethanol in the presence of 5.8 g of hydrate d. hydrazine for 1 hour. The filtrate is washed with ethanol, then the mother liquors are concentrated and taken up in diisopropyl ether. After 3 successive crystallizations, the supernatant solution of diisopropyl ether is evaporated, which makes it possible to obtain 8.4 g of O- (1- (6-methyl-2-pyridyl) ethyl) hydroxylamine in the form of an oil. pale yellow. Rf 0.23 (ethyl acetate 100).

Step 4:
Preparation of Oi (6-methyl-2-pyridyl) ethyl cyclopropanecarbohydroxamate
In a solution cooled to 0 ° C., 8 g of O- (1- (6-methyl-2-pyridyl) ethyl) hydroxylamine and 9.6 ml of triethylamine in 100 ml of dichloromethane are added dropwise under an inert atmosphere. 2 ml of cyclopropane carboxylic acid chloride. The reaction mixture obtained is stirred at room temperature for 5 h and then neutralized with a buffer solution pH = 7. The organic phase is washed with a buffer solution pH = 7, and the combined aqueous phases are extracted with sodium acetate. ethyl. After joining and evaporation of the organic phases, a flash chromatography on silica makes it possible to obtain 2.9 g of 0-1- (6-methyl-2-pyridyl) ethyl cyclopropanecarbohydroxamate in the form of a white solid. F = 134 C.

Step5:
Preparation of Methyl (E, E) -2- (2- (1 - (1 - (6-methyl-2-pyridyl) ethyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-methoxyiminoethanoate
1.3 g of O- (1- (6-methyl-2-pyridyl) ethyl cyclopropanecarbohydroxamate, 1.7 g of methyl (E) -2- (2- (bromomethyl) phenyl) -2-methoxyiminoethanoate and 2.3 The crude reaction product is stirred at 1000 ° C. in 20 ml of toluene containing 0.24 ml. of glacial acetic acid After neutralization with a pH = 7 buffer solution followed by filtration on phase-separating paper and evaporation, a flash chromatography on silica makes it possible to isolate 0.701 g of (E, E) - Methyl 2- (2- (1- (1- (6-methyl-2-pyridyl) ethyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-methoxyiminoethanoate as a brown oil nD = 1.5438 (24.2 C) .

The following examples for which W 1 and W 2 are the oxygen atom, X 4 is the hydrogen atom, p = 1, the groups G 1 and G 3 being of stereochemistry (E) and the substituents W and W 2 being in the trans position. (E-stereochemistry) relative to the -C (R3) = N- double bond are prepared in a manner identical to Examples 9 and 10, and illustrate the present invention.
(in the following table, cPr means cyclopropyl)

F (C) <SEP> or
<tb><SEP> Example <SEP> Gn <SEP> R1 <SEP> R2 <SEP> R3 <SEP> A
<tb><SEP> nD (TC)
<tb><SEP> G1 <SEP> H <SEP> H <SEP> Me <SEP> 2-pyridyl <SEP> honey
<tb><SEP> 11 <SEP> Q1 = CH <SEP>;<SEP> Q2 = O
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> H <SEP> H <SEP> Me <SEP> 2-pyridyl <SEP> 68
<tb><SEP> 12 <SEP> Q1 = N <SEP>;<SEP> Q2 = O
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> H <SEP> H <SEP> Me <SEP> 2-pyridyl <SEP> 1.5610
<tb><SEP> 13 <SEP> Q1 = N <SEP>;<SEP> Q2 = O <SEP>;<SEP> (23 C)
<tb><SEP> R6 = Me <SEP>;<SEP> R4 = NHMe
<tb><SEP> G1 <SEP> H <SEP> H <SEP> cPr <SEP> 2-pyridyl <SEP> honey
<tb><SEP> 14 <SEP> Q1 = N <SEP>;<SEP> Q2 = O
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> H <SEP> H <SEP> cPr <SEP> 2-pyridyl <SEP> 1.5560
<tb><SEP> 15 <SEP> Q1 = N <SEP>;<SEP> Q2 = O <SEP> (23 C)
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> H <SEP> H <SEP> cPr <SEP> 2-pyridyl <SEP> 1.5640
<tb><SEP> 16 <SEP> | <SEP> Q1 = N <SEP>;<SEP> Q2 = O <SEP>;<SEP> | <SEP> | <SEP> | <SEP> | <SEP> | <SEP> (23 C)
<tb><SEP> R6 = Me <SEP><SEP>;<SEP> R4 = NHMe
<tb><SEP> G8 <SEP> H <SEP> H <SEP> cPr <SEP> 2-pyridyl <SEP> honey
<tb><SEP> 17 <SEP> Q3 = O <SEP>;<SEP> Q4 = N
<tb><SEP> R9 = Me <SEP>;<SEP> R10 = OMe
<Tb>

F <SEP> (C) <SEP> or
<tb><SEP> Example <SEP> Gn <SEP> R1 <SEP> R2 <SEP> R3 <SEP> A
<tb><SEP> nD <SEP> (TC)
<tb><SEP> G3 <SEP> H <SEP> H <SEP> cPr <SEP> 2-pyridyl <SEP> 1.5540
<tb><SEP> 18 <SEP> Q2 = O; <SEP> (24 C)
<tb><SEP> R6 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G4 <SEP> H <SEP> H <SEP> cPr <SEP> 2-pyridyl <SEP> honey
<tb><SEP> 19 <SEP> Q2 = O <SEP>;<SEP> n = 0
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> H <SEP> H <SEP> Me <SEP> 3-pyridyl <SEP> 1.5562
<tb><SEP> 20 <SEP> Q1 = CH <SEP>;<SEP> Q2 = O <SEP> (24 C)
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> And <SEP> H <SEP> Me <SEP> 4-pyridyl <SEP> 1.5460
<tb><SEP> 21 <SEP> Q1 = CH <SEP>;<SEP> Q2 = O <SEP> (24 C)
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> And <SEP> H <SEP> cPr <SEP> 3-pyridyl <SEP> 1.5590
<tb><SEP> 22 <SEP> Q1 = CH <SEP>;<SEP> Q2 = O <SEP> (24 C)
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> H <SEP> H <SEP> cPr <SEP> 3-pyridyl <SEP> 1.5640
<tb><SEP> 23 <SEP> Q1 = CH <SEP>;<SEP> Q2 = O <SEP> (24 C)
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G3 <SEP> H <SEP> H <SEP> cPr <SEP> 3-pyridyl <SEP> 1.5528
<tb><SEP> 24 <SEP> Q2 = O <SEP>;<SEP> (23 C)
<tb><SEP> R6 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G3 <SEP> H <SEP> H <SEP> Me <SEP> 3-pyridyl <SEP> 1.5500
<tb><SEP> 25 <SEP> Q2 = O <SEP>;<SEP> (23 C)
<tb><SEP> R6 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> H <SEP> H <SEP> cPr <SEP> 3-pyridyl <SEP> 76
<tb><SEP> 26 <SEP> Q1 = N <SEP>;<SEP> Q2 = O
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<Tb>

F <SEP> (C) <SEP> or
<tb><SEP> Example <SEP> Gn <SEP> R1 <SEP> R2 <SEP> R3 <SEP> A
<tb><SEP> nD <SEP> (TC)
<tb><SEP> G3 <SEP> H <SEP> H <SEP> Me <SEP> 4-pyridyl <SEP> honey
<tb><SEP> 27 <SEP> Q2 = O <SEP>;
<tb><SEP> R6 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G3 <SEP> And <SEP> H <SEP> cPr <SEP> 2-pyridyl <SEP> 1.5410
<tb><SEP> 28 <SEP> Q2 = O <SEP>;<SEP> (22 C)
<tb><SEP> R6 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> And <SEP> H <SEP> cPr <SEP> 2-pyridyl <SEP> 1.5356
<tb><SEP> 29 <SEP> Q1 = N <SEP>;<SEP> Q2 = O <SEP> (24 C)
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> Me <SEP> H <SEP> cPr <SEP> 6-Me <SEP> 72
<tb><SEP> 30 <SEP> Q1 = CH <SEP>;<SEP> Q2 = O <SEP> 2-pyridyl
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G8 <SEP> And <SEP> H <SEP> cPr <SEP> 2-pyridyl <SEP> 1.5555
<tb><SEP> 31 <SEP> Q3 = O <SEP>;<SEP> Q4 = N <SEP> (23 C)
<tb><SEP> R9 = Me <SEP>;<SEP> R10 = OMe
<tb><SEP> G1 <SEP> And <SEP> H <SEP> cPr <SEP> 2-pyridyl <SEP> 1.5558
<tb><SEP> 32 <SEP> Q1 = N <SEP>;<SEP> Q2 = O <SEP>;<SEP> (23 C)
<tb><SEP> R6 = Me <SEP>;<SEP> R4 = NHMe
<tb><SEP> G4 <SEP> And <SEP> H <SEP> cPr <SEP> 2-pyridyl <SEP> 1.5320
<tb> 33 <SEP> Q2 = O <SEP>;<SEP> n = 0 <SEP> (23 C)
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> Me <SEP> H <SEP> cPr <SEP> 6-Me <SEP> 1,5520
<tb><SEP> 34 <SEP> Q1 = N <SEP>;<SEP> Q = O <SEP>;<SEP> 2-pyridyl <SEP> (23 C)
<tb><SEP> R6 = Me <SEP>;<SEP> R4 = NHMe
<tb><SEP> G1 <SEP> H <SEP> And <SEP> cPr <SEP> 4-pyridyl <SEP> honey
<tb><SEP> 35 <SEP> Q1 = CH <SEP>;<SEP> Q2 = O
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<Tb>

F <SEP> (C) <SEP> or
<tb><SEP> Example <SEP> Gn <SEP> R1 <SEP> R2 <SEP> R3 <SEP> A
<tb><SEP> nD <SEP> (TC)
<tb><SEP> G4 <SEP> H <SEP> And <SEP> cPr <SEP> 4-pyridyl <SEP> honey
<tb><SEP> 36 <SEP> Q2 = O <SEP>;<SEP> n = 0
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> H <SEP> And <SEP> cPr <SEP> 4-pyridyl <SEP> honey
<tb><SEP> 37 <SEP> Q1 = N <SEP>;<SEP> Q2 = O
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<tb><SEP> G1 <SEP> Me <SEP> CN <SEP> cPr <SEP> 2-pyridyl <SEP> 1.5408
<tb><SEP> 38 <SEP> Q1 = N <SEP>;<SEP> Q2 = O <SEP> (21 C)
<tb><SEP> R5 = Me <SEP>;<SEP> R4 = OMe
<Tb>
Example 39
Preparation of Methyl (E, E) -2- (2- (1 - (1 - (6-methyl-3-pyridyl) -1- (methoxycarbonyl) ethyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-methoxyiminoethanoate
Step 1 :
Preparation of methyl 2-bromo-2- (6-methyl-3-pyridyl) propionate
A mixture of 14 g of methyl 2- (6-methyl-3-pyridyl) propionate 14 g of
N-bromosuccinimide and 1 g of benzoyl peroxide in 300 ml of carbon tetrachloride is stirred for 3 hours under illumination by a halogen lamp. After filtration. the organic solution is washed with a saturated aqueous solution of sodium chloride, then with a saturated aqueous solution of sodium thiosulfate, and again with a saturated aqueous solution of sodium chloride, dried and evaporated. Purification by flash chromatography on silica makes it possible to isolate 2.9 g of methyl 2-bromo-2- (6-methyl-3-pyridyl) propionate in the form of a brown oil. Rf = 0.38 (heptane / ethyl acetate 50/50).

Step 2: Preparation of 0-1 - (6-methyl-3-pyridyl) -1- (methoxycarbonyl) ethyl cyclopropanecarboxamate
A mixture of 2.9 g of methyl 2-bromo-2- (6-methyl-3-pyridyl) propionate, 1.13 g of cyclopropanecarboxamic acid and 0.6 g of sodium methoxide in 40 ml of methanol. The suspension of 0.57 g of cyclopropanecarboxamic acid and 0.3 g of sodium methanoate in 2 ml of methanol is then added, and the reaction mixture is stirred at 50 ° C. for 5 hours. 2 h After evaporation of the solvent, the crude reaction product is taken up in an aqueous solution and ethyl acetate, the organic phase is dried, evaporated and purified by flash chromatography on silica, which makes it possible to isolate 1, 7 g of 0-1- (6-methyl-3-pyridyl) -1- (methoxycarbonyl) ethyl cyclopropanecarboxamate as a brown solid, mp = 89 ° C.

Step 3:
Preparation of (E, E) -2- (methyl 2- (1- (1- (6-methyl-3-pyridyl) -1- (methoxycarbonyl) ethyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-methoxyiminoethanoate
1.4 g of 0-1- (6-methyl-3-pyridyl) -1- (methoxycarbonyl) ethyl cyclopropanecarboxamate, 1.43 g of (E) -2- (2- (bromomethyl) phenyl) -2-methoxyiminoethanoate. Methyl and 1.63 g of cesium carbonate are stirred for 7 hours under an inert atmosphere in 50 ml of refluxing acetonitrile. After filtration of the cesium salts and evaporation of the solvent, the crude reaction product is stirred at 50 ° C. for 5 h in 20 ml of toluene containing 0.25 ml of glacial acetic acid.

After neutralization with an aqueous solution of potassium carbonate followed by extraction of the aqueous phase with ethyl acetate and evaporation of the combined and dried organic phases, flash chromatography on silica makes it possible to isolate 0, 54 g of (E, E) -2- (2- (1- (1- (1- (6-methyl-3-pyridyl) -1 (methoxycarbonyl) ethyloxyimino) -1 -cyclopropylmethyloxymethyl) phenyl) -2-methyl-methoxyiminoethanoate in the form of a rosy solid. Mp = 95 ° C.

Example 40
Preparation of (E, E) -2- (Methyl 2- (1- (1 - (4-quinolyl) ethyloxyimino) ethyloxymethyl) phenyl) -2-methoxyiminoethanoate
Step 1 :
Preparation of (E, E) -2- (Methyl 2- (1- (tertbutyldimethylsilyloxyimino) ethyloxymethyl) phenyl) -2-methoxyiminoethanoate
A mixture of 1.89 g of O-tertbutyldimethylsilyl acetohydroxamate, 2.86 g of methyl (E) -2- (2- (bromomethyl) phenyl) -2-methoxyiminoethanoate and 3.91 g of cesium in 50 ml of acetonitrile is stirred at 50 ° C. for 5 h, then filtered and concentrated. Purification by flash chromatography on silica makes it possible to isolate 0.60 g of methyl (E, E) -2- (2- (1 - (tertbutyldimethylsilyloxyimino) ethyloxymethyl) phenyl) -2-methoxyiminoethanoate in the form of a white solid. F = 79 C.

* 2nd step :
Preparation of Methyl (E, E) -2- (2- (I - (Hydroxyimino) ethyloxymethyl) phenyl) -2-methoxyiminoethanoate
A mixture of 0.19 g of methyl (E, E) -2- (2- (1- (tertbutyldimethylsilyloxyimino) ethyloxymethyl) phenyl) -2-methoxyiminoethanoate, 0.086 g of acetic acid and 0.080 g of fluoride of Cesium in 10 ml of acetonitrile is stirred for 20 h at room temperature. Concentration followed by purification by flash chromatography on silica makes it possible to isolate 0.10 g of methyl (E, E) -2- (2- (1 (hydroxyimino) ethyloxymethyl) phenyl) -2-methoxyiminoethanoate in the form of a white solid. M.p. 112 ° C.

Step 3:
Preparation of (E, E) -2- (Methyl 2- (1- (1 - (4-quinolyl) ethyloxyimino) ethyloxymethyl) phenyl) -2-methoxyiminoethanoate
A mixture of 0.4 g of methyl (E, E) -2- (2- (1 - (hydroxyimino) ethyloxymethyl) phenyl) -2-methoxyiminoethanoate, 0.274 g of 4- (1-chloroethyl) quinoline and 0.513 g of cesium carbonate in 20 ml of acetonitrile is stirred at reflux for 5 h. After filtration and evaporation of the solvent, the crude reaction product is purified by flash chromatography on silica, which makes it possible to isolate 0.118 g of (E, E) -2- (2- (1 - (1- (4-quinolyl) ethyloxyimino methyl (ethyloxymethyl) phenyl) -2-methoxyiminoethanoate as a yellow honey. Rf = 0.41 (heptane / ethyl acetate 30/70).

Example 41:
Preparation of Methyl (E, E) -2- (2- (1 - ((3-Trifluoromethyl-2-pyridyl) oxyimino) -ethyloxymethyl) phenyl) -2-methoxyiminoethanoate
A mixture of 0.4 g of (E, E) -2- (2- (1 (hydroxyimino) ethyloxymethyl) phenyl) -2-methoxyiminoethanoate methyl (prepared according to the method described in the previous example), of 0.323 g of 2-bromo-3- (trifluoromethyl) pyridine and 0.513 g of cesium carbonate in 20 ml of acetonitrile is stirred at reflux for 5 h. After filtration and evaporation of the solvent, the crude reaction product is purified by flash chromatography on silica, which makes it possible to isolate 0.510 g of (E, E) -2- (2- (1- ((3-trifluoromethyl-2-pyridyl) Methyl (oxyimino) ethyloxymethyl) phenyl) -2-methoxyiminoethanoate as a white solid. Mp = 76 ° C.

Example 42
Preparation of Methyl (E, E) -2- (2- (1 - (2- (2-pyridyl) ethoxyimino) -1-cyclopropyl methyloxymethyl) phenyl) -3-methoxypropenoate
Step 1:
Preparation of N- (2 (-2-pyridyl) ethoxy) phthalimide
In a tricolor under an inert atmosphere are introduced 20 g of 2- (2-hydroxyethyl) pyridine, 29.2 g of N-hydroxyphthalimide, 47 g of triphenylphosphine and 450 ml of anhydrous THF. 29.4 ml of DEAD are then added dropwise with stirring. The THF is evaporated and the residue is taken up in diisopropyl ether and ethyl acetate to give a white precipitate which is recrystallized to give 14 g of the expected product.

2nd step :
Preparation of Methyl (E, E) -2- (2- (i - (2- (2-pyridyl) ethoxyimino) -1-cyclopropylmethyloxymethyl (1-phenyl) -3-methoxypropenoate
By repeating steps 2 and 3 described in Example 9 above, using the phthalimide prepared above, the expected compound is obtained in the form of a brown viscous liquid. nD = 1.5605 (21.40 ° C).

Example 43: Preparation of methyl (E) -N-methoxy-N- (2- (1 - (2- (2-pyridyl) ethoxyimino) -cyclopropylmethyloxymethyl) phenyl) carbamate
By repeating the procedure described in Example 42 above, but using methyl N-methoxy-N- (2- (bromomethyl) phenyl) carbamate instead of (E) -2- (2- (bromomethyl) phenyl) ) -3-methyl methoxypropenoate, the expected product is obtained in the form of an orange viscous liquid. nD = 1.5435 (21.5 ° C).

Example B1: In vivo test on Puccinia recondita (wheat rust):
Fine grinding is used to prepare an aqueous suspension of the active ingredient to be tested, having the following composition:
- active ingredient: 60 mg
surfactant Tween 80 (polyoxyethylene sorbitan derivatized oleate) diluted to 10% in water: 0.3 ml
- acetone: 5 ml
- complete with 60 ml of water.

 This aqueous suspension is then diluted with water to obtain the desired ppm (part per million) concentration.

 Wheat (variety Scipion), in buckets, sown on a 50/50 pozzolan peat soil substrate and maintained at 120C, is treated at the 1-leaf stage (10 cm high) by spraying the aqueous suspension above.

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

 After 24 hours, each plant is contaminated by spraying with an aqueous suspension of spores (150,000 spores per cm3) of Puccinia recondita.

This suspension is obtained from contaminated plants.

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

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

 Under these conditions, at a dose of 40 ppm, a good (at least 75%) or total protection is observed with the compounds of the following examples: 1, 2, 3, 4, 9, 11, 12, 13, 14, 15 , 16, 17, 18, 19 and 20. This is for example total with the compound of Example 9.

Example B2: In vivo test on Septoria tritici (septoria of wheat):
A fine aqueous milling of the active ingredient to be tested having the following composition is prepared by fine grinding
- active ingredient: 60 mg
surfactant Tween 80 (polyoxyethylene sorbitan derivative oleate) diluted to 10% in water: 0.3 ml
- acetone: 5 ml
- complete with 60 ml of water.

 This aqueous suspension is then diluted with water to obtain the desired ppm (part per million) concentration.

 Wheat (Scipion variety) in buckets, sown on a 50/50 pozzolan peat substrate and maintained at 12 ° C, is treated at the 1-leaf stage (10 cm high) by spraying the aqueous suspension above.

 Plants used as controls are treated with an aqueous solution that does not contain the active ingredient.

 After 24 hours, each plant is contaminated by spraying an aqueous suspension of spores (500,000 spores per cm3) of Septoria tritici. The spores are harvested from a seven-day old culture.

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

 The reading is done twenty-one days after the contamination, in comparison with the control plants.

 Under these conditions, a good (at least 75%) or total protection is observed at the 40 ppm dose with the following compounds: 1, 2, 3, 4, 9, 11, 12, 13, 14, 15, 16 , 17, 18, 19 and 20. This is for example total with the compound of Example 9.

Example B3: In vivo test on Septoria nodorum (wheat septoria):
Fine grinding is used to prepare an aqueous suspension of the active ingredient to be tested, having the following composition:
- active ingredient: 60 mg
surfactant Tween 80 (polyoxyethylene sorbitan derivative oleate) diluted to 10% in water: 0.3 ml
- acetone: 5 ml
- complete with 60 ml of water.

 This aqueous suspension is then diluted with water to obtain the desired ppm (part per million) concentration.

 Wheat (Scipion variety) in buckets, sown on a 50/50 pozzolan peat soil substrate and maintained at 12 ° C., is treated at the 1-leaf stage (10 cm high) by spraying the aqueous suspension above.

 Plants used as controls are treated with an aqueous solution that does not contain the active ingredient.

 After 24 hours, each plant is contaminated by spraying an aqueous suspension of spores (500,000 spores per cm3) of Septoria nodorum. The spores are harvested from a seven-day old culture.

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

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

 Under these conditions, a good protection (at least 75%) or total protection with the following compounds 1, 2, 3, 9, 11, 12, 13, 14, 15, 16, 17, is observed at the dose of 40 ppm. 18 and 19.

Example B4: In vivo test on Erisyphus graminis fsp tritici (wheat powdery mildew):
Fine grinding is used to prepare an aqueous suspension of the active ingredient to be tested, having the following composition:
- active ingredient: 60 mg
surfactant Tween 80 (polyoxyethylene sorbitan derivative oleate) diluted to 10% in water: 0.3 ml
- acetone: 5 ml
- complete with 60 ml of water.

 This aqueous suspension is then diluted with water to obtain the desired ppm (part per million) concentration.

Wheat (variety Audace) in buckets, sown on a 50/50 pozzolan soil peat substrate and maintained at 120C, is treated at the 1-leaf stage (10 cm high) by spraying the aqueous suspension above
Plants used as controls are treated with an aqueous solution that does not contain the active ingredient.

 After 24 hours, the wheat plants are sprinkled with spores of Erisyphus grlminis, the dusting being carried out with diseased plants.

 The reading is done seven to fourteen days after the contamination, in comparison with the control plants.

 Under these conditions, a good (at least 75%) or total protection is observed at the dose of 40 ppm with the following compounds: 1,2,3,4, 9, 14 and 15.

Example B5: In vivo test on Erisyphe graminis frp horde (barley powdery mildew):
A fine aqueous milling of the active ingredient to be tested having the following composition is prepared by fine grinding
- active ingredient: 60 mg
surfactant Tween 80 (polyoxyethylene sorbitan derivative oleate) diluted to 10% in water: 0.3 ml
- acetone: 5 ml
- complete with 60 ml of water.

 This aqueous suspension is then diluted with water to obtain the desired ppm (part per million) concentration.

 Barley (variety Express) in buckets, sown on a 50/50 pozzolan soil peat substrate and maintained at 120C, is treated at the 1-leaf stage (10 cm high) by spraying the aqueous suspension above.

 Plants used as controls are treated with an aqueous solution that does not contain the active ingredient.

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

 The reading is done seven to fourteen days after the contamination, in comparison with the control plants.

 Under these conditions, a good (at least 75%) or total protection is observed at the dose of 40 ppm with the following compounds: 2, 4, 9, 14, 16, 17 and 18.

Example B6: In vivo test on Pyrenophoru teres (barley helminthosporiosis)
Fine grinding is used to prepare an aqueous suspension of the active ingredient to be tested, having the following composition:
- active ingredient: 60 mg
surfactant Tween 80 (polyoxyethylene sorbitan derivative oleate) diluted to 10% in water: 0.3 ml
- acetone: 5 ml
- complete with 60 ml of water.

 This aqueous suspension is then diluted with water to obtain the desired ppm (part per million) concentration.

 Barley (variety Express), in buckets, sown on a 50/50 pozzolan soil peat substrate and maintained at 120C, is treated at the 1-leaf stage (10 cm high) by spraying the aqueous suspension above.

 Plants used as controls are treated with an aqueous solution that does not contain the active ingredient.

 After 24 hours, each plant is contaminated by spraying an aqueous suspension of spores (12,000 spores per cm3) of Pyrenophora teres. This suspension is obtained from contaminated plants.

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

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

 Under these conditions, a good (at least 75%) or total protection is observed at the dose of 40 ppm with the following compounds: 1 2, 3 9 4, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20. It is for example 98% with the compound of Example 9.

Example B7: In vivo test on Rynchosporium secalis (rynchosporiosis of barley)
Fine grinding is used to prepare an aqueous suspension of the active ingredient to be tested, having the following composition:
- active ingredient: 60 mg
surfactant Tween 80 (polyoxyethylene sorbitan derivative oleate) diluted to 10% in water: 0.3 ml
- acetone: 5 ml
- complete with 60 ml of water.

 This aqueous suspension is then diluted with water to obtain the desired ppm (part per million) concentration.

 Barley (variety Express), in buckets, sown on a 50/50 pozzolan soil peat substrate and maintained at 120C, is treated at the 1-leaf stage (10 cm high) by spraying the aqueous suspension above.

 Plants used as controls are treated with an aqueous solution that does not contain the active ingredient.

After 24 hours, each plant is contaminated by spraying with an aqueous suspension of spores (800 000 spores per cm3) of Rynchosporium secalis
This suspension is obtained from contaminated plants.

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

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

 Under these conditions, a good (at least 75%) or total protection is observed at the dose of 40 ppm with the following compounds: 2, 13, 14, 15, 16 and 20.

Claims (34)

 as well as the salts, the metal and metalloid complexes of the compounds of formula (I) as they have just been defined.  Q2 and R4 may together form a ring of 5 to 7 atoms containing 2 to 3 oxygen and / or nitrogen atoms, optionally substituted with one or more radicals such as halogen, lower alkyl or lower haloalkyl,  an alkylsulfonyl, haloalkylsulfonyl, optionally substituted arylsulfonyl group,  acyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; or  R13 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, optionally substituted allyl group, optionally substituted propargyl group, optionally substituted benzyl group ; or  R11 and R12 are, independently of one another, hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower cycloocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,  R1 is halogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl,  RO is the hydrogen atom. lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,  R8 is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, formyl, acyl,  R7 is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl,  R5 and R6 independently of one another are lower alkyl or lower haloalkyl,  an alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino group,  R4 is lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl; or  an optionally substituted phenyl or benzyl group,  an alkenyl, alkynyl, N, N-dialkylamino, N, N-dialkylaminoalkyl or  nitro, cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, NnN-dialkylcarbamoyl, lower alkoxycarbonyl, 3-oxetanyloxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; or  R3 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; or  R1 and R2 may together form a divalent radical such as an alkylene group, optionally substituted by one or more halogen atoms, optionally substituted with one or more lower alkyl groups,  aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, or N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; or  cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl,  R 1 and R 2 are, independently of each other, hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; or  the cyano radicals, nitre,  lower alkyl, lower haloalkyl, alkoxy, haloalkoxy; or  X4 is a hydrogen atom, a halogen atom; or N, N-dialkylcarbamoyl, lower alkoxycarbonyl;  an acyl, carboxyl, carbamoyl, N-alkylcarbamoyl group, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl; or  an amino group, N-alkylamino, N, N-dialkylamino, acylamino, aminoalkyl,  lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio; or  lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkoxysulfonyl; or  hydroxy, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl; or  X1, X2 and X3 are independently of each other a hydrogen atom, a halogen atom; or  A represents a mono or bicyclic aromatic heterocyclic radical containing from 5 to 10 atoms, of which 1 to 4 are heteroatoms chosen from oxygen, sulfur or nitrogen atoms, each sulfur or nitrogen atom being optionally in the oxidized state in the form of an N-oxide or sulfoxide group, which radical is attached to the carbon atom substituted by the groups R 1 and R 2 in the case where p = 1 or p = 2, or attached to the W2 group in the case where p = 0 by a carbon or nitrogen atom, which radical is optionally substituted with 1 to 5 radicals, preferably with 1 to 3 radicals Xl and / or X2 and / or X3,  p represents 0, 1 or 2,  W2 is the oxygen atom or the group NR13,  W is the oxygen atom. sulfur or sulfinyl (SO) or sulphonyl (su2) groups,  Y is the oxygen atom, sulfur atom or the amino (NH) or oxyamino (ONH) group,  Q5 is the oxygen atom, the sulfur atom or the NR12 group,  Q4 is the nitrogen atom or the CR11 group,  Q3 is the oxygen or sulfur atom,  Q2 is the oxygen or sulfur atom,  Q is the nitrogen atom or the CH group,  in which: n represents 0 or 1

 wherein G is selected from groups G1 to G9

 1. Compounds of general formula (I):  Compounds according to claim 1, having one or more of the following characteristics taken singly or in combination:  p is 0, 1 or 2;  Q2 is the oxygen atom, and / or Q3 is the oxygen atom, and / or Q4 is the nitrogen atom, and / or Q5 is the oxygen atom;  Wl is the oxygen or sulfur atom  W2 is the oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino, allylamino group,  Y is the oxygen atom,  X1, 2, X3 and X4 are, independently of one another, a hydrogen atom, a lower alkyl group, a halogen atom, or the cyano, trifluoromethyl, methoxy or nitro radicals,  R1 and R2 are independently hydrogen, lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, lower alkoxycarbonyl, N-alkylcarbamoyl, or N, N-dialkylcarbamoyl,  R3 is a hydrogen atom, a lower alkyl group, lower cycloalkyl, lower haloalkyl. alkoxyalkyl, preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl or methoxymethyl radical,  R 1 is lower alkyl, alkoxy, alkylamino, dialkylamino, preferably methyl, ethyl, propyl, methoxy, ethoxy, methylamino, or ethylamino,  R5, R6, R8 and R9 are independently of each other lower alkyl, lower haloalkyl, preferably methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, or propyl,  R7 is lower alkyl, lower haloalkyl, preferably methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl, allyl, or propargyl,  Rlo is a chlorine atom, lower alkyl, lower haloalkyl, preferably methyl, alkoxy, alkylthio, preferably methoxy, or methylthio,  R11 and R12 are independently lower alkyl, lower haloalkyl, alkoxyalkyl, allyl, propargyl,  R + is hydrogen, lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl, benzyl,  A is chosen from a radical, optionally substituted with 1 to 5 radicals, preferably with 1 to 3 radicals X1 and / or X2 and / or N3, derived, by elimination of a hydrogen atom, from one of the rings; (i) to (v):  a 5-link cycle described by formula (i):

 a 6-link cycle described by formula (ii)  wherein each of the groups of the list B1, B2, B3, B41 is selected from carbon, nitrogen, oxygen and sulfur atoms such that said list comprises from 0 to 3 carbon atoms, from 0 to at 1 sulfur atom, from 0 to 1 oxygen atom and from 0 to 4 nitrogen atom; or

 two fused rings with 6 links each, described by formula (iii):  wherein each of the groups in the list D1, D2, D3, D4, D5 is selected from carbon or nitrogen atoms such that said list comprises from 1 to 4 carbon atoms and from 1 to 4 carbon atoms. nitrogen; or,

 a 6-link and a 5-link fused ring described by formula (iv)  in which each of the groups of the list E1, E2, E3, E4, E5, E6, E7, E8 is selected from carbon or nitrogen atoms such that said list comprises from 4 to 7 carbon atoms and from I to 4 nitrogen atoms; or

 two fused rings with 5 links each described by the formula (v)  each of the groups of the list J1, J2, J3, J4, J6, L1, L2, L3 is chosen in such a way that said list comprises from 3 to 8 carbon atoms; or  - each of the groups of the list L, L2. L3 is chosen from carbon, nitrogen, oxygen or sulfur atoms such that said list comprises from 0 to 3 carbon atoms, from 0 to 1 sulfur atom, from 0 to 1 oxygen atom and from 0 to 3 nitrogen atoms; and  each of the groups in the list J, J 2, J 3, J 4, J 5, J 6 is chosen from carbon atoms or nitrogen atoms, such that said list comprises from 3 to 6 carbon atoms, and from 0 to 3 carbon atoms; 'nitrogen; and  in which  as well as their salts, and metal and metalloid complexes.  each of the groups of the list M1, M2, M3, T, T2, T3 is chosen in such a way that said list comprises from 0 to 6 carbon atoms;  Z represents the carbon or nitrogen atom;  each of the groups of the list T, T2, T3 represent the carbon, nitrogen, oxygen or sulfur atoms, such that said list comprises from 0 to 3 carbon atoms, from 0 to 1 sulfur atom; from 0 to 1 oxygen atom and from 0 to 3 nitrogen atoms;  each of the groups of the list M1, M2, M3 represents the carbon, nitrogen, oxygen or sulfur atoms, such that said list comprises from 0 to 3 carbon atoms, from 0 to 1 atom of sulfur, from 0 to 1 oxygen atom and from 0 to 3 nitrogen atoms;  in which :  Compounds according to claims 1 or 2, having one or more of the following characteristics taken alone or in combination  W1 is the oxygen atom,  R, is the hydrogen atom or the methyl radical,  R2 is hydrogen, lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N, N-lower dialkylcarbamoyl,  A represents a heterocyclic radical, optionally substituted with 1 to 5 radicals, preferably with 1 to 3 radicals X 1 and / or X 2 and / or X 3 as defined above, chosen from the following list  furanyl; pyrolyl; thiophenyl;  pyrazolyl; imidazolyl; oxazolyl; isoxazolyl; thiazolyl;  isothiazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl  1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,3-thiadiazolyl;  1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl; 1,3,4-thiadiazolyl;  1,2,3-triazolyl; 1,2,4-triazolyl; tetrazolyl;  pyridyl;  pyrimidinyl; pyrazinyl; pyridazinyl; 1,2,3-triazinyl;  1,2,4-triazinyl; 1,3,5-triazinyl; 1,2,3,4-tetrazinyl; 1,2,3,5-tetrazinyl; 1,2,4,5-tetrazinyl;  benzimidazolyl; indazolyl; benzotriazolyl; benzoxazolyl;  1,2-benzisoxazolyl; 2,1-benzisoxazolyl; benzothiazolyl;  1,2-benzisothiazolyl; 2,1-benzisothiazolyl; 1,2,3-benzoxadiazolyl;  1,2,5-benzoxadiazolyl; 1,2,3-benzothiadiazolyl;  1,2,5-benzothiadiazolyl;  quinolinyl; isoquinolinyl;  quinoxazolinyl; quinazolinyl; cinnolyl or phthalazyl; pteridinyl  benzotriazinyl;  1,5-naphthyridinyl; 1,6-naphthyridinyl; 1,7-naphthyridinyl  1,8-naphthyridinyl;  imidazo [2,1-b] thiazolyl; thieno [3,4-b] pyridyl; purine; pyrolo [1,2-  b] thiazolyl.  as well as their salts, and metal and metalloid complexes.  4. Compounds according to one of claims I to 3, having the following variants:  W1 is the oxygen atom,  R1 is the hydrogen atom or the methyl radical,  R2 is hydrogen, lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N, N-lower dialkylcarbamoyl,  A, optionally substituted with 1 to 5 radicals, preferably with 1 to 3 radicals X 1 and / or X 2 and / or X 3, is chosen from one of the following heterocycles  pyridyl;  pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4  triazinyl;  quinolinyl; isoquinolinyl;  furanyl; pyrolyl; thiophenyl;  oxazolyl; isoxazolyl; thiazolyl; isothiazolyl; imidazolyl  pyrazolyl.  as well as their salts, and metal and metalloid complexes.  5. Compounds according to one of claims I to 4, having the following variants:  W, is the oxygen atom,  R1 is the hydrogen atom or the methyl radical,  R2 is hydrogen, lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N, N-lower dialkylcarbamoyl,  A, optionally substituted with 1 to 5 radicals, preferably with 1 to 3 radicals X1 and / or X2 and / or X3, represents the pyridyl radical:  as well as their salts, and metal and metalloid complexes.  6. Compound according to one of claims I to 5, chosen from  methyl (E, E) -2- (2- (1 - ((2-pyridyl) methyloxyimino) -1-cyclopropyl methyloxymethyl) phenyl) -3-methoxypropenoate,  (E, E) -2- (2- (1- (1 - (2-pyridyl) propyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -3-methoxypropenoic acid methyl ester, (E, E) - Methyl 2- (2- (1- (1- (2-pyridyl) propyloxyimino) propyloxymethyl) phenyl) -3-methoxypropenoate, and  methyl (E, E) -2- (2- (1- (i (2-pyridyl) propyloxyimino) isobutyloxymethyl) phenyl) -3-methoxypropenoate,  as well as their salts, and metal and metalloid complexes.  7. Fungicidal compositions comprising an effective amount of at least one active ingredient according to one of the preceding claims.  8. Fungicidal compositions according to claim 7 comprising, in addition to the active ingredient of formula (I), solid or liquid carriers, 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 ingredient.  10. A method for preventive or curative control of phytopathogenic fungi in crops, characterized in that an agronomically effective and non-phytotoxic amount of at least one material is applied to plant seeds or to plant leaves. active ingredient or a fungicidal composition containing an active ingredient of formula (I) as defined in one of claims 1 to 6.  11. A method for the preventive or curative treatment of plant propagation products, and plants resulting therefrom, against fungal diseases, characterized in that said products are covered with an effective and non-phytotoxic dose of compound or composition according to one of the preceding claims.  12. The method of claim 11 wherein the cereals are processed. rice, fruit trees, forest trees, vines, oilseeds, vegetable crops, solanées or beet.  13. Method according to one of claims 11 or 12 wherein is treated rice, wheat, barley, rye, triticale, fruit trees, maize, cotton, flax, rapeseed, grapevine. , forest trees, peas, potatoes or beets.  14. Method according to one of claims 11 to 13 wherein the wheat or barley is treated.  15. Process according to claim 10 in which the seeds of cereals, potatoes, cotton, peas, rapeseed, maize, flax or the seeds of forest trees are treated.  16. Method according to one of claims 10 to 15 wherein the dose of active material applied is between 2 and 200 g of active ingredient per 100 kg of seed, preferably between 3 and 150 g per 100 kg in the case of seed treatments.  17. Method according to one of claims 10 to 15 wherein the dose of active ingredient applied is between 10 and 800 g of active ingredient per hectare, preferably between 50 and 300 g of active ingredient per hectare in the case of treatments foliar.  18. Process for the preparation of the compounds according to one of claims 1 to 6 consisting in bringing into contact a compound of formula (II) A

 with a compound of formula (III) A  V1 is a halogen atom, an alkylsulfonate or haloalkylsulfonate group, arylsulfonate,  wherein G is one of G1 to G9, with G1 to G9 having the same definition as in claim 1, X4 having the same definition as in claim 1,  in the presence of an organic or inorganic base, in the absence or in the presence of a solvent, at a temperature of between -80 ° C. and 180 ° C. or at the boiling point of the solvent used, the reaction time depending on the conditions used generally ranging from 0.1 to 48 hours.  W1, W2, R1, R2, R3, R13, X1, X2, X3, p and A having the same definition as that given in claim 1,  19. Process for the preparation of the compounds of formula (III) A according to claim 18, wherein W1, W2, R1, R2, R3, R13, X1, X2, X3, p and A have the same definition as that indicated in FIG. claim 1 comprising contacting a compound of formula (IV):

 with a compound of formula (V):  W2, R1, R2, R13, X1, X2, X3, p and A having the same definition as that given in claim 1,  the condensation between the compound of formula (IV) and compound of formula (v) being carried out in the presence of an organic or inorganic base, or a dehydration reagent, in the absence or in the presence of a solvent. N-acylamino, N, N-acylalkylamino or the group -O (C = O) Ra, Ra having the same definition as that of R3 indicated in claim 1 and being identical to R3 or different,  W1 and R3 having the same definition as that indicated in claim 1, wherein U1 is a halogen atom, or a hydroxy, lower alkoxy or benzyloxy, lower alkylthio, amino, N-alkylamino, N, N-dialkylamino radical,  20. Process for the preparation of hydroxamic acid derivatives or of hydrazonic acids of formula (III) A according to claim 18, wherein W is the oxygen atom, W2, R1, R2, R3, R13, X1, X2, X3, p and A having the same definition as that indicated in claim 1, comprising contacting a compound of formula (VI):

 with a hydroxamic acid derivative or hydrazonic acid W2, R3 and R13 having the same definition as that indicated in claim 1, of formula (VII)  R1, R2, X1, X2, X3, p and A having the same definition as that indicated in claim 1, and U2 being a halogen atom, an alkylsulfonate group,  the condensation between the compound of formula (VI) and the compound of formula (VII) being carried out in the presence of an organic or inorganic base in the absence or in the presence of a solvent.  21. Process for the preparation of the hydroxamic acid derivatives of formula (III) A according to claim 18, wherein W1 and W2 are the oxygen atom and p = 1 or 2; R1, R2, R3, R13, X1, X2, X3 and A having the same definition as that given in claim 1, comprising contacting a compound of formula (VIII):

 22. Process for the preparation of the benzyl halide derivatives of formula (II) A according to claim 18, wherein V1 is a halogen atom by halogenation of a compound of formula (IX):  with a hydroxamic acid derivative of formula (VII) according to claim 18, wherein W2 is oxygen, R3 having the same definition as that indicated in claim 1,  R1, R2, X1, X2, X3 and A having the same definition as that given in claim 1 and p = 1 or 2,

 the benzyl halide derivatives of formula (II) A where V is a halogen atom which can also be obtained by halogenation of a compound of formula (II) B:  the halogenation of the compound of formula (IX), which may be carried out by radical, thermal or photochemical means, by an N-haloacetamide, in an inert solvent or in the absence of a solvent with or without a free radical initiator at a temperature from 20 "C to 1700,  wherein G is one of G1 to G9, with G1 to G9 having the same definition as in claim 1 X4 having the same definition as in claim 1,

 with a compound of formula (III) B  23. Process for the preparation of the compounds according to one of claims 1 to 6 for which G is one of the groups G1 to G9, the groups G1 to G7 having the same definition as that indicated in claim 1 and R4 being the group or amino, alkylamino, dialkylamino radical, the groups G8 and G9 having the same definition as that of claim 1, X4 having the same definition as that of claim 1, comprising contacting a compound of formula (II) B in wherein G is one of G1 to G9, with G1 to G7 having the same definition as in Claim 1 and R4 being amino, alkylamino, dialkylamino, or G8 and G9 having the same definition as that indicated in claim 1, X4 having the same definition as that of claim 1, wherein W is the oxygen or sulfur atom,  with a halogenating agent or with the lithium halide / mesyl halide / collidine reagent,  wherein G is one of G1 to G9, wherein G1 to G7 are as defined in claim 1 and R4 is alkylamino, dialkylamino, G8 and G9 having the same definition as indicated in claim 1, X4 having the same definition as that indicated in claim 1 W being the oxygen atom,  this reaction being carried out in the presence of an organic or inorganic base, in the absence or in the presence of a solvent, at a temperature of between -80 ° C. and 180 ° C. or at the boiling point of the solvent used.  W2, R1, R2, R3, R13, X1, X2, X3, p and A having the same definition as that indicated for formula (I), U3 being a halogen atom, preferably a chlorine atom, the double bond U3-C (R3) = N-W2- which can be of stereochemistry (E) or (Z),  24. Derivatives of thiohydroxamic or thiohydrazonic acids of formula (III) A:

 where W1 is the sulfur atom and W2 is the oxygen atom or the group NR13, R1, R2, R3, R13, X1, X, X3, p and A having the same definition as that indicated in claim 1 .  25. Process for the preparation of the compounds according to one of claims 1 to 6 for which G is the G3 group, Q2 being the oxygen atom, R4 being the alkoxy, alkylamino, dialkylamino group, the other substituents having the same definition. that indicated in claim 1 and R6 being lower alkyl or lower haloalkyl, comprising contacting a compound of formula (X)

 by the action of one or more equivalents of a base in an aprotic solvent at a temperature of -78 C to 50 C.  R6 is a lower alkyl or lower haloalkyl group, Rd being an optionally substituted phenyl group, Hal being a halide ion,  R6-CH2-P (Rd) 3+; Hal- (XI) B  or with a Wittig reagent of formula (XI) B  R6 being a lower alkyl or lower haloalkyl group, Rb being a lower alkyl, phenyl or benzyl group,  R6-CH2-P (= O) (ORb) 2 (XI) A  with a Wittig-Horner reagent of formula (XI) A:  wherein R4 is alkoxy, alkylamino, dialkylamino, the other substituents having the same definition as in claim 1,  26. A process for the preparation of compounds according to one of the claims in claim 1 and R5 is a lower haloalkyl group, comprising contacting a compound of formula (XII):

 in a dipolar aprotic solvent, at a temperature of between -20 ° C. and 250 ° C. or at reflux of the solvent.  with a halogenated compound of formula CHq (Hal) 4q where q = 1 or 2 and Hal denotes the same or different halogen atoms and of which at least one of them is the chlorine or bromine atom ,  wherein T is oxygen or sulfur, M is an alkali or alkaline earth ion, Q is N or CH, R4 is alkoxy, alkylamino, dialkylamino, W1, W2 , R1, R2, R3, R13, X1, X2, X3, X4, p and A having the same definition as that given in claim 1,  27. Process for the preparation of the compounds according to one of claims 1 to 6, for which G is the group G4 in which n = 1, Q2 being the oxygen atom, R4 being the alkoxy, alkylamino, dialkylamino group, Other substituents having the same definition as that given in claim 1, by reaction between a compound of formula (XIII) A:

 in which R4 is alkoxy, alkylamino, dialkylamino, the other substituents having the same definition as that indicated in claim 1, with a reagent of formula (XIV):

 the compounds of general formula (XIII) A, wherein R4 is the alkoxy alkylamino group, dialkylamino, the other substituents having the same definition as that indicated in claim 1, obtainable by reaction of a compound of general formula (XIII ) B:  by action of one or more base equivalents, optionally in the presence of a phase transfer catalyst, in an aprotic solvent at a temperature of -780C to 40C,  in which V, is a halogen atom, R5 having the same definition as that indicated in claim 1, R3, R3, X1, X2, X3, p and A having the same definition as that indicated in claim 1.  with a compound of formula (III) A according to claim 16, W1, W2, R1, R2,  Vl being a halogen atom, an alkylsulfonate group, arylsulfonate,  wherein R4 is alkoxy, alkylamino, dialkylamino, X4 having the same definition as that in claim 1,  28. Process for the preparation of the compounds of formula (I) according to one of claims 1 to 6, for which G is the group G1 to G7 and R4 is the alkylamino or dialkylamino group, the other substituents having the same definition as that indicated in claim 1, comprising contacting a compound of the general formula (I) according to claim 1 wherein G is the group G1 to G7 and R4 are alkoxy or alkylthio, the other substituents having the same definition as that in claim 1,  with an alkylamine or dialkylamine, in an alcoholic solvent, at a temperature of -50 ° C to 100 ° C or at the boiling point of the solvent.  29. Process for the preparation of the compounds according to one of claims 1 to 6, for which 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 that indicated in claim 1, by oxidation of the compounds of general formula (I) according to claim 1 for which W1 is the sulfur atom, G being one of G1, G3, G4, G6 to G9, Q2 and Q3 being oxygen, the other substituents having the same definition as that given in claim 1, by means of an equivalent or more than one oxidizing agent, in the presence or absence of a catalyst in an inert solvent.  30. Process for the preparation of the compounds according to one of claims 1 to 6, for which G is one of the groups G1 to G9, the other substituents having the same definition as in claim 1, of bringing into contact a compound of formula (XV) A:

 the condensation between the compound of formula (XV) A and the compound of formula (VI) being carried out in the presence of an organic or inorganic base, in the absence or in the presence of a solvent.  with a compound of formula (VI), R1, R2, X1, X2, X3, p and A having the same definition as that indicated in claim 1, and U2 is a halogen atom, an alkylsulfonate group,  in which G is one of groups G1 to G9, groups G1 to G9 having the same definition as that in claim 1, X4, W1, W2, R3 and R13 having the same definition as those indicated in claim 1 ,  31. Compounds of formula (XV) A:

 wherein G is one of G1 to G9, wherein G1 to G9 are as defined in claim 1, X4, W1, W2, R3 and R13 are as defined in claim 1 .  32. Process for the preparation of the compounds of formula (XV) A according to claim 31 consisting in cleaving a compound of formula (XV) B:

 with a cleavage agent specific for the protective group P.  wherein G is one of G1 to G9, wherein G1 to G9 are as defined in claim 1, wherein X4, W1, W2, R3 and R13 are as defined in claim 1 and P is a protecting group for the hydroxyl function, or a protecting group for the amino function,  33. Compounds of formula (XV) B:

 wherein G is one of G1 to G9, wherein G1 to G9 are as defined in claim 1, X4, W1, W2, R3 and R13 are as defined in claim 1 and P is a protecting group for the hydroxyl function or a protecting group for the amino function.  34. Process for the preparation of the compounds of formula (XV) B according to claim 33 consisting in reacting a compound of formula (II) A according to claim 18 in which G is one of groups G1 to G9, groups G1 to G9 having the same definition as those given in claim 1, X4 having the same definition as that indicated in claim 1 and V1 being a halogen atom, an alkylsulfonate or haloalkylsulfonate group, arylsulfonate,  with a compound of formula (XVI):

 the condensation between the compound of formula (II) A and the compound of formula (XVI) being carried out in the presence of an organic or inorganic base, in the absence or presence of a solvent.  W1, W2, R3 and R13 having the same definition as those indicated in claim 1 and P being a hydroxyl protecting group or a protecting group of the amino function,