FR2798929A1 - NEW OPTICALLY ACTIVE FUNGICIDE COMPOUNDS - Google Patents

Abstract

The invention concerns optically active compounds, and fungicide compositions containing them, of general formula (I) wherein: G is selected among the following groups (G1 to G9). The invention also concerns methods for treating plants using said compounds.

Description

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

A large number of fungicidal compounds are already known and widely used. By way of example, patent applications EP-A-0 463 488, EP-A-0 370 629 and EP-A-0 821 667 describe, in particular, fungicidal compounds comprising a hydroximic or hydrazonic function.

All the fungicides described in these patent applications are in racemic form. However, crop treatment methods today recommend the lowest possible application rates. Thus, in the case where a compound has in its structure one or more centers of asymmetry, it may be advantageous to choose one or other of the isomers or diastereoisomers. Indeed, it is known that in some cases only one of the two optical isomers has the proper activity of the racemic compound. By way of example, mention may be made of EP-A-0 551 048 and EP-A-0 629 616 respectively presenting racemic compounds and their enantiomers.

One of the advantages of using an optical isomer and not racemic is obvious and logical for both economic and ecological reasons: the activity of the racemic being contained in a single isomer, the doses applied will be theoretically halved, this being highly recommended for the treatment methods advocated today, as discussed above. The racemic compounds comprising a hydroximic or hydrazonic function, whose optically active isomers are the subject of the present invention, are described in the international patent application not yet published.

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 PCT / FR 99/00753. Surprisingly, it has now been discovered that one of the optical isomers of these compounds has a biological activity which is much greater than that of the other isomer and that of the racemic mixture.

An object of the present invention is therefore to provide a new family of compounds useful for the fight against fungal diseases of crops.

Another object of the present invention is to provide novel compounds having a hydroximic or hydrazonic function, active at a reduced dose compared with those of the corresponding racemic compounds.

Another object of the present invention is to propose a novel family of optically active 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, corn, cereals, fruit trees, vines, oilseeds, vegetable crops, solanées and beetroot, as well as the genetically modified counterparts of these crops.

It has now been found that these objects can be achieved, in whole or in part, by means of the products of the invention, which are optically active compounds having a heterocyclic unit associated with a hydroximic or hydrazonic function.

The present invention thus relates to optically active compounds comprising a heterocyclic unit associated with a hydroximic or hydrazonic function, of general formula (I):

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dans lesquels : # n représente 0 ou 1 ; # Q, est l'atome d'azote ou le groupe CH ; # Q2 est l'atome d'oxygène ou de soufre ; # Q3 est l'atome d'oxygène ou de soufre ; # Q4 est l'atome d'azote ou le groupe CR11 ; # Q5 est l'atome d'oxygène, de soufre ou le groupe NR,2 ; # Y est l'atome d'oxygène, de soufre ou le groupe amino (NH) ou oxyamino (ONH) ; et # W1 est l'atome d'oxygène, de soufre ou les groupes sulfinyle (SO) ou sulfonyle (SO2); # W2 est l'atome d'oxygène ou le groupe NR13 ; in which G is selected from groups G1 to G9:

in which: # n represents 0 or 1; # 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 CR11 group; # Q5 is the oxygen atom, sulfur atom or NR group, 2; # Y is the oxygen atom, sulfur atom or the amino (NH) or oxyamino (ONH) group; and # W1 is oxygen, sulfur or sulfinyl (SO) or sulfonyl (SO2) groups; # W2 is the oxygen atom or the NR13 group;

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# p represents 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; optionally being in the oxidized state as an N-oxide or sulfoxide group, which radical is attached to the carbon atom substituted by the groups
R 1 and R 2, which radical is optionally substituted with 1 to 5 radicals; preferably 1 to 3 radicals X, and / or X2 and / or X3; # X ,, X2 and X3 are independently of each other a hydrogen atom, a halogen atom; or a hydroxy, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl group; or lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkoxysulfonyl; or lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio; amino, 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,

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# R 1 and R 2 are different from each other and represent a hydrogen atom, a lower alkyl group, a lower haloalkyl group, a lower cycloalkyl group, a lower halocycloalkyl group, an alkoxyalkyl group, a haloalkoxyalkyl group, an alkylthioalkyl group or a haloalkylthioalkyl group; cyanoalkyl; cyano, acyl, carboxy, carbamoyl, N-alkyl-carbamoyl,
N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; or an 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 a or more lower alkyl groups; # R3 is a hydrogen atom, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; a nitro, cyano, acyl, carboxy, carbamoyl group,
N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, 3-oxetanyloxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; or an alkenyl, alkynyl, N, N-dialkylamino group,
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;

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 # R5 and R6 represent independently of each other a lower alkyl or lower haloalkyl group; # R7 is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl; # R8 is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, formyl, acyl; # R9 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl; # RIO is a halogen atom, 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 a hydrogen atom, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, an optionally substituted allyl group, an optionally substituted propargyl group, a benzyl group optionally substituted; or an acyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl group; or

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 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; # the asterisk (*) indicated on the general formula means that the carbon atom carrying the radicals R1 and R2 is an asymmetric carbon; as well as the salts, the metal and metalloid complexes of the optically active compounds of formula (I) as just 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, and / or X2 and / or X3 is a hydroxyl group , mercapto, amino, N-alkylamino or N-acylamino, this compound may be capable of admitting a tautomeric form in chemical equilibrium, resulting from the proton displacement of said hydroxy, mercapto, amino, N-alkylamino or N-acylamino group. The tautomeric forms of such compounds are within the scope of the invention. Such tautomeric forms are in particular described in the book "The tautomerism of heterocycles, Advances in Heterocyclic Chemistry, Supplement 1" by J. Elguero, C.

Martin, A. R. 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 O-C = N-O) and the "thiohydroximic group" (with the sequence S-C = N-O). In the same way, the name "hydrazonic group" includes both the "hydrazonic group" strict (with the sequence O-C = N-N) that the "thiohydrazonic group" (with the sequence S-C = N-N).

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In the case of the compounds of formula (I) for which p = 2, the radical - (CR, R2) 2- must be understood as being the radical - (CR1R2) - (CR'1R'2) -, where R ' 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.

It is understood that when p = 2, each of the carbon atoms bearing respectively the radicals (R 1, R 2) and (R '1; R' 2) have an asymmetric center. It follows that the compounds for which p = 2 each have four optical isomers, two of which are diastereoisomers of the other two.

Moreover, the following generic terms are used with the following meanings: # the halogen atom signifies the fluorine, chlorine, bromine or iodine atom, # the adjective "lower" qualifying an organic radical, means that this radical has from 1 to 6 carbon atoms, with the exception of the cycloalkyl radical where the adjective "lower" means from 3 to 6 carbon atoms, # the alkyl radicals may be linear or branched, # the alkyl radicals halogenated compounds may have one or more identical or different halogen atoms, # the acyl radical means alkylcarbonyl, or cycloalkylcarbonyl, # the lower adjective qualifying the term acyl applies to the alkyl or cycloalkyl part of this radical, # the alkylene radical denotes the radical - (CH2) m - where m = 2 to 5, # when the amino radical is disubstituted, the two substituents 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, 5 or
6 atoms, # the expression "optionally substituted" qualifying an organic group applies to the different radicals constituting this group.

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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: # n is equal to 0; # 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, # X ,, X2, X3 and X4 are independently of each other a hydrogen atom, a lower alkyl group, a halogen atom, or the cyano, trifluoromethyl, methoxy, nitro, # R1 and R2 radicals are different from each other and are 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 hydrogen, lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl or methoxymethyl radical, # R4 is a lower alkyl, alkoxy, alkylamino or dialkylamino group, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino or ethylamino radical, # R5, R6, R8 and R9 are, independently of one another, a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl or ethyl radical,
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,

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dans laquelle chacun des groupes de la liste B1, B2, B3,
B4, est choisi parmi les atomes de carbone, d'azote, d'oxygène et de soufre de telle sorte que ladite liste comprenne de 0 à 3 atomes de carbone, de 0 à 1 atome de soufre, de 0 à 1 atome d'oxygène et de 0 à 4 atomes d'azote ; ou bien un cycle à 6 maillons décrit par la formule (ii) :

dans laquelle chacun des groupes de la liste D1, D2, D3,
D4, D5, est choisi parmi les atomes de carbone ou d'azote de telle sorte que ladite liste comprenne de 1 à 4 atomes de carbone et de 1 à 4 atomes d'azote ; ou bien, deux cycles fusionnés à 6 maillons chacun, décrits par la formule (iii) : # R10 is a chlorine atom, lower alkyl, lower haloalkyl, preferably methyl, alkoxy, alkylthio, preferably methoxy, or methylthio, # R11 and R12 are independently of each other a lower alkyl group , lower haloalkyl, alkoxyalkyl, allyl, propargyl, # R13 is hydrogen, lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl, benzyl, #A is selected from a radical, optionally substituted with 1 with 5 radicals, preferably with 1 to 3 X radicals; and / or X2 and / or X3, derived by removal of a hydrogen atom from one of the following rings (i) to (v): a 5-membered ring described by formula (i):

in which each of the groups of the list B1, B2, B3,
B4 is chosen from carbon, nitrogen, oxygen and sulfur atoms such that said list comprises from 0 to 3 carbon atoms, from 0 to 1 sulfur atom, from 0 to 1 atom oxygen and 0 to 4 nitrogen atoms; or a 6-membered ring described by formula (ii):

in which 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 nitrogen atoms; or two fused rings with 6 links each, described by formula (iii):

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dans laquelle chacun des groupes de la liste E1, E2, E3,
E4, E5, E6, E, E8 est choisi parmi les atomes de carbone ou d'azote de telle sorte que ladite liste comprenne de 4 à 7 atomes de carbone et de 1 à 4 atomes d'azote ; ou bien un cycle à 6 maillons et un cycle à 5 maillons fusionnés décrits par la formule (iv) :

dans laquelle : - chacun des groupes de la liste J1, J2, J3, J4, J5, J6 est choisi parmi les atomes de carbone ou d'azote de telle sorte que ladite liste comprenne de 3 à 6 atomes de carbone, et de 0 à 3 atomes d'azote ; et - chacun des groupes de la liste LI, L2, L3 est choisi parmi les atomes de carbone, d'azote, d'oxygène ou de soufre de telle sorte que ladite liste comprenne de 0 à 3 atomes de carbone, de 0 à 1 atome de soufre, de 0 à 1 atome d'oxygène et de 0 à 3 atomes d'azote ; et - chacun des groupes de la liste JI, J2, J3, J4, J5, J6, L1,
L2, L3 est choisi de telle façon que ladite liste comprenne de 3 à 8 atomes de carbone ; ou bien deux cycles fusionnés à 5 maillons chacun décrits par la formule (v) :

dans laquelle : - chacun des groupes de la liste MI, M2, M3, représente

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

in which: each of the groups of the list J1, J2, J3, J4, J5, J6 is chosen from carbon or nitrogen atoms such that said list comprises from 3 to 6 carbon atoms, and from 0 to at 3 nitrogen atoms; and each of the groups of the list LI, 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, 0 to 1 oxygen atom and 0 to 3 nitrogen atom; and each of the groups of the list JI, J2, J3, J4, J5, J6, L1,
L 2, L 3 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 MI, M2, M3, represents

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 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 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 in such a way that 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 by the groups R1 and R2.

Among the above variants, the following variants will be chosen more particularly in isolation: # W1 is the oxygen atom, # R1, different from R2, is the hydrogen atom or the methyl radical, # R2, different R 1 is hydrogen, lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N, N-dialkylcarbamoyl, # A represents a heterocyclic radical, optionally substituted with 1 to 5 radicals, preferably with 1 to 3 radicals XI 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;

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1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl;
1,3,4-thiadiazolyl; 1,2,3-triazolyl; 1,2,4-triazolyl; tetrazolyl; pyridyl; pyrimidinyl; pyrazinyl;
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.

Advantageously, compounds of formula (I) having the following variants are furthermore preferred: # G is the group G1 or G2 or G3 or G7, # W is the oxygen atom, # W2 is the atom of oxygen, p = 1, # RI is different from R2 and represents hydrogen, # R2 represents lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl,
N, N-lower dialkylcarbamoyl, #A optionally substituted with 1 to 3 X, and / or X 2 and / or X 3 radicals, is selected from one of the following heterocycles: pyridyl; pyridazinyl; pyrimidinyl; pyrazinyl;
1,3,5-triazinyl; 1,2,4-triazinyl;

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   quinolinyl; furanyl; pyrolyl; thiophenyl; oxazolyl; isoxazolyl; thiazolyl; isothiazolyl; imidazolyl; pyrazolyl.

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 geometrical isomers (E, E), (E, Z), (Z, E), (Z, Z) depending on the configuration of the two double bonds. The notation E and Z can be replaced respectively by the terms syn and anti, or cis and trans. In particular, reference is made to E. Eliel and S. Wilen's book "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.

Even more preferred compounds are those wherein the substituents W 1 and W 2 are in the trans (E) position with respect to the C (R 3) = N- double bond and the double bond of the Gl, G 2 and G 3 groups is also trans configuration (E).

According to a preferred variant of the invention, the optically active compounds according to the invention correspond to the general formula (Ia):

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cas particuliers des composés optiquement actifs de formule (I) pour lesquels G est le groupement Gl, p est égal à 1, Q2, W, et W2 représentent chacun l'atome d'oxygène, R, représente l'atome d'hydrogène et A représente le radical pyridyle, et # R2 représente un groupe alkyle inférieur, cyano, cyanoalkyle, ou alkoxyalkyle ; # R3 est un atome d'hydrogène, un groupe alkyle inférieur, cycloalkyle inférieur, haloalkyle inférieur, alkoxyalkyle, de préférence un radical méthyle, éthyle, propyle, isopropyle, butyle, isobutyle, tert-butyle, cyclopropyle, ou méthoxyméthyle, # R4 est un groupe alkyle inférieur, alkoxy, alkylamino, dialkylamino, de préférence un radical méthyle, éthyle, propyle, méthoxy, éthoxy, méthylamino, ou éthylamino, # R5 représente un groupe alkyle inférieur, haloalkyle inférieur, de préférence un radical méthyle, fluorométhyle, difluorométhyle, trifluorométhyle, éthyle, 2,2,2-trifluoroéthyle, propyle ou isopropyle, # X1, X2, X3 et X4 sont indépendamment les uns des autres un atome d'hydrogène, un groupe alkyle inférieur, un atome d'halogène, ou les radicaux cyano, trifluorométhyle, méthoxy, ou nitro ; les deux doubles liaisons éthyléniques étant de configuration trans (ou()), l'astérisque indiquant le carbone asymétrique conférant au composé son activité optique, ainsi que les sels, les complexes métalliques et métalloïdiques des composés optiquement actifs de formule (la) tels qu'ils viennent d'être définis.

particular cases of the optically active compounds of formula (I) for which G is the group G1, p is equal to 1, Q2, W and W2 each represent the oxygen atom, R represents the hydrogen atom and A represents the pyridyl radical, and # R2 represents a lower alkyl, cyano, cyanoalkyl, or alkoxyalkyl group; # R3 is a hydrogen atom, a lower alkyl group, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, preferably a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclopropyl, or methoxymethyl radical, # R4 is a lower alkyl, alkoxy, alkylamino, dialkylamino group, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino or ethylamino radical, # R5 represents a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl or difluoromethyl group; , trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl or isopropyl, # X1, X2, X3 and X4 are independently of each other a hydrogen atom, a lower alkyl group, a halogen atom, or the cyano, trifluoromethyl, methoxy or nitro radicals; the two ethylenic double bonds being of trans (or ()) configuration, the asterisk indicating the asymmetric carbon conferring on the compound its optical activity, as well as the salts, the metal and metalloid complexes of the optically active compounds of formula (Ia) such that they have just been defined.

According to the invention, the following optically active compounds are also preferred:

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#le (+)-(E,E)-2-(2-{ 1-[(2-pyridyl)éthyloxyimino]-1-cyclopropylméthyloxyméthyl}phényl)-3-méthoxypropénoate de méthyle, 9 le (-)-(E,E)-2-(2-{ 1-[(2-pyridyl)éthyloxyimino]-1-cyclopropylméthyloxyméthyl}phényl)-3-méthoxypropénoate de méthyle, #le (+)-(E,E)-2-(2-{1-[(2-pyridyl)propyloxyimino]-1-cyclopropylméthyloxyméthyl}phényl)-3-méthoxypropénoate de méthyle, #le (-)-(E,E)-2-(2-{1-[(2-pyridyl)propyloxyimino]-1-cyclopropylméthyloxyméthyl}phényl)-3-méthoxypropénoate de méthyle, #le (+)-(E,E)-2-(2-{ 1-[(2-pyridyl)propyloxyimino]propyloxyméthyl}phényl)-3-méthoxypropénoate de méthyle, #le (-)-(E,E)-2-(2-{ 1-[(2-(2-pyridyl)propyloxyimino]propyloxy- méthyl}phényl) -3-méthoxypropénoate de méthyle, # le (+)-(E,E)-2-(2-{I-[(2-pyridyl)propyloxyimino]isobutyl- oxyméthyl}phényl)-3-méthoxypropénoate de méthyle, et # le (-)-(E,E)-2-(2-{ 1-[(2-pyridyl)propyloxyimino]isobutyl- oxyméthyl}phényl)-3-méthoxypropénoate de méthyle, ainsi que leurs sels, complexes métalliques et métalloïdiques [0026] Un composé optiquement actiftout particulièrement préféré dans le cadre de la présente invention est le (-)-(E,E)-2-(2-{1-[(2-pyridyl) propyloxyimino]

-1-cyclopropylméthyloxyméthyl}phényl)-3-méthoxypropénoate de méthyle, dénommé par la suite composé (A).

Methyl (-) (+) - (E, E) -2- (2- {1 - [(2-pyridyl) ethyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate 9 (-) - (E) Methyl 2- (2- {1 - [(2-pyridyl) ethyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate, ## (+) - (E, E) -2- (2) Methyl {1 - [(2-pyridyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate, ## (-) - (E, E) -2- (2- {1 - [(2- methyl pyridyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate, #le (+) - (E, E) -2- (2- {1 - [(2-pyridyl) propyloxyimino] propyloxymethyl} phenyl) Methyl 3-methoxypropenoate, methyl (-) - (E, E) -2- (2- {1 - [(2- (2-pyridyl) propyloxyimino] propyloxy-methyl} phenyl) -3-methoxypropenoate methyl (+) - (E, E) -2- (2- {I - [(2-pyridyl) propyloxyimino] isobutyloxymethyl} phenyl) -3-methoxypropenoate, and # (-) - ( E, E) -2- (Methyl 2- {1 - [(2-pyridyl) propyloxyimino] isobutyloxymethyl} phenyl) -3-methoxypropenoate, as well as their salts, [0026] An optically active compound, especially preferred in the context of the present invention is (-) - (E, E) -2- (2- {1 - [(2-pyridyl) propyloxyimino]

Methyl 1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate, hereinafter referred to as compound (A).

The optically active compounds of general formulas (I) and (Ia) as well as the compounds which may optionally be used as intermediates in the preparation processes, and which will be defined on the occasion of the description of these processes, may therefore exist under one or more forms of optical or chiral isomers depending on the number of asymmetric centers of the compound. The invention therefore relates to all optical isomers as well as mixtures of all possible stereoisomers in all proportions, except for racemic mixtures.

The preparation of optically active compounds according to the present invention can be carried out in several ways. Among these various methods, methods (1) and (2) described below are preferred. It is understood that all methods

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 to prepare the optically active compounds according to the invention are suitable. Methods (1) and (2) below are presented by way of example to illustrate the present invention.

Thus, according to a first method (1), the optically active compounds of the invention can be prepared from their racemic mixtures. These racemic mixtures are themselves prepared as described in the unpublished international patent application PCT / FR 99/00753 or by adapting the synthetic methods described in application EP-A-0 821 667.

The racemic mixtures are then resolved into optically active compounds according to the invention according to standard techniques known per se for the separation of enantiomers and / or diastereoisomers. Among these conventional separation techniques, those described in the book by E. Eliel and S. Wilen "Stereochemistry of Organic Compounds" Ed Wiley (1994). It is also possible to carry out separations on chiral columns, or else by techniques of recrystallization, enantiomeric enrichment or so-called swaying techniques, described for example in the patent application WO 95/08522, these various methods of course being able to be combined. .

According to a second general method (2), the optically active compounds according to the invention can be prepared directly by asymmetric synthesis, that is to say by including the asymmetric carbon chirality during the course of the synthesis. This method of preparation has the advantage of only leading to the only desired optical isomer.

However, in the case in particular of the compounds of formula (I) for which p = 2 and having two centers of chirality, it may be advantageous to combine an asymmetric synthesis according to process (2) with a final separation of the different optical isomers according to process (1). The use of one or other of these methods or a combination of the two processes, for the preparation of optically active compounds according to the invention, is well known to those skilled in the art who will know how to use the techniques the most appropriate according to the nature of the compound (s) to be synthesized.

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For the general preparation method (2), the asymmetric syntheses used can advantageously be inspired by the syntheses of the racemic compounds described in the applications. The reagents used in one or other of the general preparation methods as well as their Preparations are usually known per se and are usually specifically described in the prior art or in such a way that one skilled in the art can adapt it to the desired purpose. The prior art usable by those skilled in the art for establishing the reagent preparation conditions can be found in many general chemistry publications such as J. March, J. Wiley (1992), "Advanced Organic Chemistry", "Methoden der organischen Chemie" (Houben-Weyl), Ed. Georg Thieme Verlag or "Chemical Abstracts" Ed.

American Chemical Society as well as publicly available computer databases.

dans lequel les intermédiaires (II), (IIR) et (IIS) comportent les radicaux R2, X1, X2 et X3 tels que décrits précédemment pour les composés de formule (la), cette étape, dite réaction de Mitsunobu, étant réalisée en présence de triphénylphosphine, dans le tétrahydrofurane par exemple, conduit aux deux énantiomères (IIR) et (IIS), qui peuvent être séparés par des techniques classiques de séparation telles que celles exposées ci-dessus pour le procédé général (1). In order to illustrate the general process (2) described above, the optically active compounds of formula (Ia) may, for example, be prepared according to the following scheme:

in which the intermediates (II), (IIR) and (IIS) contain the radicals R2, X1, X2 and X3 as described above for the compounds of formula (Ia), this step, called the Mitsunobu reaction, being carried out in the presence triphenylphosphine, in tetrahydrofuran for example, leads to the two enantiomers (IIR) and (IIS), which can be separated by conventional separation techniques such as those set out above for the general process (1).

Each of these two enantiomers is then engaged in the synthesis leading to the final product. The intermediate (IIR) leads to the (R) isomer of formula (Ia),

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schéma dans lequel : - l'ensemble des composés de formule (IIR), (IIIR), (IVR), (VIR) et (IaR) comportent les radicaux R2, R3, R4, R5, X1, X2 X3, et X4 tels que décrits précédemment pour les composés de formule (la), - l'étape 2 est réalisée en présence d'hydrate d'hydrazine, dans l'éthanol ; - l'étape 3 est réalisée en présence de pyridine et de chlorure d'éthanoyle, dans le dichlorométhane ; - l'étape 4 est réalisée en présence de carbonate de césium, à reflux d'acétonitrile, puis, sans isoler le composé (VIR), - l'étape 5 est réalisée en présence d'acide acétique, dans le toluène. intermediate (IIS) leading meanwhile to the isomer (S) of formula (la). The diagram below indicates, for example, the preparation of the isomer (R) of formula (Ia):

scheme in which: - all the compounds of formula (IIR), (IIIR), (IVR), (VIR) and (IaR) comprise the radicals R2, R3, R4, R5, X1, X2 X3, and X4 such as previously described for the compounds of formula (Ia), step 2 is carried out in the presence of hydrazine hydrate, in ethanol; step 3 is carried out in the presence of pyridine and ethanoyl chloride in dichloromethane; step 4 is carried out in the presence of cesium carbonate, with reflux of acetonitrile, and then, without isolating the compound (VIR), step 5 is carried out in the presence of acetic acid, in toluene.

The following example makes it possible to illustrate, without limitation, a process for preparing an optically active compound according to the invention. The example below shows the synthesis of the compound (A), i.e. the

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(-)-(E,E)-2-(2- {1 - [(2-pyridyl) propyloxyimino] -1 -cyclopropylméthyloxyméthyl} phényl) -3-méthoxypropénoate de méthyle, ainsi que son antipode optique, c'est-àdire le (+)-(E,E)-2-(2-{ 1-[(2-pyridyl) propyloxyimino]-1-cyclopropylméthyloxyméthyl}phényl)-3-méthoxypropénoate de méthyle(Composé (B)).

Methyl (-) - (E, E) -2- (2- {1 - [(2-pyridyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate, as well as its optical antipode, that is, that is methyl (+) - (E, E) -2- (2- {1 - [(2-pyridyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate (Compound (B)).

tout d'abord le composé racémique (E,E)-2-(2-(1-(1-(2-pyridyl)propyloxyimino)-1- cyclopropyl-méthyloxyméthyl)phényl)-3-méthoxypropénoate de méthyle, selon le mode opératoire décrit dans la demande de brevet international non encore publiée PCT/FR 99/00753, exemple 9 et repris ci-dessous :

The method used follows the general method (1) described above. We prepare

firstly the racemic compound (E, E) -2- (2- (1- (1- (1-pyridyl) propyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -3-methoxypropenoic acid methyl, depending on the mode procedure described in the international patent application not yet published PCT / FR 99/00753, Example 9 and repeated below:

Example of preparation of racemic methyl (E, E) -2- (2- {1- [1- (2-pyridyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate.

 # Step 1: 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-pyridyl) propyloxy) phthalimide in the form of a white solid. F = 123C.

 # Step 2: 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, 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

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 The aqueous phase is reextracted with ethyl acetate, the organic phases are combined, dried and then evaporated to give 11.65 g of crude reaction product 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 at 0 ° C., and the reaction mixture is then 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 product 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 0-1- (2-pyridyl) propyl cyclopropanecarboxamate in the form of a white solid. F = 79 C.

 # Step 3: Preparation of (E, E) -2- (Methyl 2- (1- (1- (1-pyridyl) propyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -3-methoxypropenoate.

For 4 hours under an inert atmosphere, 6.1 g of 0-1- (2-pyridyl) propyl cyclopropanecarboxamate, 7.89 g of (E) -2- (2- (2- (4 -) -) are stirred in 100 ml of acetonitrile at reflux. bromomethyl) phenyl) -
Methyl 3-methoxypropenoate and 9.02 g of cesium carbonate.

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
100 C 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 in the form of a brown oil. nD = 1.5366 (24.0 ° C).

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Example of separation of the racemic column chiral.

4 g of racemic product obtained in the preceding example of preparation are applied to a Chiracel 05 chiral column (10 micrometers, 250 × 4.6 mm) with a heptane / ethanol mixture in proportions of 85:15 (volume percentages) as eluent. The flow rate is set at 1 ml / min. The detection is carried out by an ultraviolet probe of wavelength 238 nm. 1.84 g of dextrorotatory isomer Compound (B) and 1.99 g of levorotatory isomer Compound (A) are thus obtained, with the following characteristics: Compound (B): Retention time: 8.8 min
Rotation power aD = +21.5 Enantiomeric excess: 99.5% Compound (A): Retention time: 11.2 min
Rotation power aD = -19.9 Enantiomeric excess: 99% [0039] 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.

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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, acid esters 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

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 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 solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, wettable powders (or powder to spray).

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 defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as carrier, water or a liquid organic 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.

By way of example, here is a concentrated suspension composition: # EXAMPLE SC 1: - active ingredient 500 g - polyethoxylated tristyrylphenol phosphate 50 g - polyethoxylated alkylphenol 50 g - sodium polycarboxylate 20 g - ethylene glycol 50 g - organopolysiloxane oil ( antifoam) 1 g - polysaccharide 1.5 g - water 316.5 g

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Wettable powders (or spray powder) are usually prepared to contain from 20 to 95% active ingredient, and usually contain, in addition to the solid carrier, from 0 to 30% of a wetting agent, 3 to 20% of a dispersing agent, and, when necessary, 0.1 to 10% of one or more stabilizers and / or other additives, such as penetrants, 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 to be sprayed): # Example PM 1 - active ingredient 50% - ethoxylated fatty alcohol (wetting agent) 2.5% - ethoxylated phenylethylphenol (dispersing agent) 5% - chalk (inert carrier) 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% - calcium lignosulfonate neutral (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:

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 - active substance 75% - wetting agent 1.50% - dispersing agent 8% - calcium carbonate (inert filler) q. s.p. 100% # Example PM 4: - active ingredient 90% - ethoxylated fatty alcohol (wetting agent) 4% - ethoxylated phenylethylphenol (dispersing agent) 6% # Example PM 5: - active ingredient 50% - mixture of anionic and nonionic surfactants ionic (wetting agent) 2.5% - sodium lignosulfonate (dispersing agent) 5% - kaolinic clay (inert carrier) 42.5% [0053] The aqueous dispersions and emulsions, for example the compositions obtained by diluting using 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, with an apparent density generally of between approximately 0.3 and 0.6, have a particle size generally of between approximately 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 can be mineral

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 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 an alkaline polynaphthalene sulphonate. or alkaline earth metal or an alkaline or alkaline earth lignosulfonate, the remainder being nonionic or anionic wetting agents such as an alkaline or alkaline earth metal alkyl naphthalene sulfonate. 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 ingredient is mixed with
10% urea beads. 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 alkylnaphthalenesulphonate) 2% - dispersing agent (sodium polynaphthalenesulphonate) 8% - inert load insoluble in water (kaolin) 15%

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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, maneb, mancozeb, diflumetorim, ethirimol, benomyl, cymoxanil, fenpropidin, fenpropimorph, triadimefon, captan, captafol, folpel, thiophanate, thiabendazole, phosetyl-Al, chlorothalonil, dichloran, metalaxyl, iprodione, oxadixyl, vinchlozoline, tebuconazole, bromuconazole , triticonazole, difenconazole, diniconazole, metconazole, penconazole, propiconazole, prochloraz, 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, tr icyclazole, fluzilazole, flutolanil, guazatine, hexaconazole, hymexazol, isoprothiolane, kazugamycin, pencycuron, phthalide, pyroquilon, tetraconazole, thifluzamide, carboxin.

Another subject of the invention is a method of controlling, as a curative or preventive measure, phytopathogenic fungi of crops, characterized in that it is applied to the soil where plants grow or are likely to grow, on

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 the leaves and / or fruits of the plants or on the seeds of the plants, an effective (agronomically effective) and non-phytotoxic amount 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 fought, 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.

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

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

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.

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The products and compositions according to the invention can also be applied as a foliar application to vegetable crops, that is to say on the foliage, flowers, fruits and / or trunks of the plants concerned.

Among the plants targeted by the method according to the invention, mention may be made of rice, maize, cotton, cereals, such as wheat, barley, triticale, fruit trees, in particular apple, pear, peach, vine, banana, orange, lemon, etc ..., oilseed crops, for example, rapeseed, sunflower, vegetable crops, tomatoes, peas, salads, solanées, for example potato, beetroot, flax, and forest trees, as well as genetically modified counterparts of these crops.

More particularly, among the plants targeted by the method according to the invention, mention may be made of: # wheat, as regards the fight against the following seed diseases: fusariosis (Microdochium 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 mitespot (Pseudocercosporella herpotrichoides), the foot-and-mouth disease (Gaeumannomyces graminis), the Fusarium blight (F. culmorum, F. graminearum), rhizoctonia (Rhizoctonia cerealis), powdery mildew (Erysiphe graminis forma specie tritici), rust (Puccinia striiformis and Puccinia recondita), and septoria (Septoria tritici and Septoria nodorum); # wheat and barley, with regard to the fight against bacterial and viral diseases, for example barley yellowing of barley.

# barley, as regards the control of the following seed diseases: helminthosporiosis (Pyrenophora graminea,
Pyrenophora teres and Cochliobolus sativus), naked smut (Ustilago nuda) and fusariosis (Microdochium nivale and Fusarium roseum), barley, as regards the control of the following diseases of the aerial parts of the plant: (Pseudocercosporella herpotrichoids), helminthosporiosis (Pyrenophora teres

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Cochliobolus sativus), powdery mildew (Erysiphe graminis forma specie hordei), dwarf rust (Puccinia hordei) and rhynchosporiosis (Rhynchosporium secalis); # the potato, as regards the control of tuber diseases (in particular Helminthosporium solani, Phoma tuberosa,
Rhizoctonia solani, Fusarium solani) and some viruses (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, with regard to the control of the following seed diseases: Phoma lingam and Alternaria brassicae; # corn, as regards the fight against seed diseases: (Rhizopus sp., Penicillium sp., Trichoderma sp.,
Aspergillus sp. and Gibberellafujikuroi); # flax, with regard to the fight against seed disease:
Alternaria linicola; # forest trees, with regard to the control of furrow (Fusarium oxysporum, Rhizoctonia solani).

In the case of plant treatments, the dose of composition applied is, in general and advantageously, between 10 and 800 g / ha, preferably 50 to 300 g / ha of active material for applications in foliar treatment.

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.

It is understood that the doses indicated above are illustrative examples of the invention. Those skilled in the art will be able to adapt the application doses according to the nature of the culture to be treated.

<Desc / Clms Page number 32>

It has been surprisingly found that the optically active compounds according to the invention have greater efficacy than their optical antipode and also a higher efficiency than their corresponding racemic. The following tests present the results, in percentages of effectiveness, obtained on 7-day persistence tests on different diseases of wheat and barley.

#Composé (C) : (',)-2-(2-{l-[l-(2-pyridyl)propyloxyimino]-l- cyclopropylméthyloxyméthyl}phényl)-3-méthoxypropénoate de méthyle (racémique), décrit dans l'exemple de préparation ci-dessus. The tested products are:

# Compound (C): methyl (racemic) 2- (2- {1- [1- [1- (2-pyridyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate, described in US Pat. example of preparation above.

 # Compound (B): (+) - (E, E) -2- (2- {1 - [(2-pyridyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate, dextrorotatory isomer of the compound (C).

 # Compound (A): (-) - (E, E) -2- (Methyl 2- {I - [(2-pyridyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate, levorotatory isomer of the compound (C).

In order to demonstrate the quite surprising effect of the optically active compounds of the present invention, and for comparison, similar tests were carried out on a compound of similar structure (described in EP-A-0 821 667 already mentioned above, example 16), racemic, as well as on its dextrorotatory and laevorotatory isomers prepared by chiral column separation as described above.

The products of the comparative tests are: # Compound (C '): (E, E) -2- {2- [1- (1-Phenyl) ethoxyimino] -1-ethyloxymethyl} phenyl) -3-methoxypropenoate of methyl (racemic ).

 # Compound (B '): methyl (+) - (E, E) -2- {2- [1- (1-phenyl) ethoxyimino] -1-ethyloxymethyl} phenyl) -3-methoxypropenoate, dextrorotatory isomer of the compound (C ').

 # Compound (A '): (-) - (E, E) - Methyl 2- {2- [1- (1-phenyl) ethoxyimino] -1-ethyloxymethyl} phenyl) -3-methoxypropenoate, Levogyric isomer of the compound (C ').

<Desc / Clms Page number 33>

The results, presented in the following table, clearly show: # the superiority, in terms of effectiveness, of the compound (A) compared to all the other compounds tested; # the total absence of difference in effectiveness for the comparative compounds (A '), (B') and (C).

Table of results: Persistence tests at 7 days (Results in% of effectiveness)

<Tb>
<tb> Compound <SEP> Doses <SEP> (g / ha) <SEP> Oidium <SEP> Oidium <SEP> Rust <SEP> Brown <SEP> Septoria
<tb> Barley <SEP> Wheat <SEP> Wheat <SEP> nodorum <SEP> Wheat <SEP>
<tb> 31 <SEP> 0 <SEP> 75 <SEP> 85 <SEP> 50
<tb> (A) <SEP> 62 <SEP> 60 <SEP> 80 <SEP> 90 <SEP> 50
<tb> 125 <SEP> 50 <SEP> 98 <SEP> 90 <SEP> 80
<tb> 250 <SEP> 60 <SEP> 98 <SEP> 100 <SEP> 90
<tb> 31 <SEP> 0 <SEP> 20 <SEP> 40 <SEP> 0
<tb> (B) <SEP> 62 <SEP> 0 <SEP> 20 <SEP> 60 <SEP> 0
<tb> 125 <SEP> 40 <SEP> 30 <SEP> 60 <SEP> 25
<tb> 250 <SEP> 50 <SEP> 85 <SEP> 60 <SEP> 25
<tb> 31 <SEP> 0 <SEP> 50 <SEP> 60 <SEP> 75
<tb> (C) <SEP> 62 <SEP> 0 <SEP> 75 <SEP> 70 <SEP> 75
<tb> 125 <SEP> 20 <SEP> 80 <SEP> 85 <SEP> 75
<tb> 250 <SEP> 50 <SEP> 90 <SEP> 100 <SEP> 75
<tb> 62 <SEP> 100 <SEP> 50 <SEP> 70 <SEP> 60
<tb> (A ') <SEP> 125 <SEP> 100f <SEP> 50 <SEP> 80 <SEP> 60
<tb> 250 <SEP> 100f <SEP> 60 <SEQ> 85 <SEP> 70
<tb> 62 <SEP> Phytotoxic <SEP> 70 <SEP> 70 <SEP> 50
<tb> (B ') <SEP> 125 <SEP> Phytotoxic <SEP> 80 <SEP> 80 <SEP> 50
<tb> 250 <SEP> Phytotoxic <SEP> 80 <SEP> 80 <SEP> 50
<tb> 62 <SEP> 90 <SEP> 50 <SEP> 75 <SEP> 50
<tb> (C ') <SEP> 125 <SEP> 95f <SEP> 70 <SEP> 85 <SEP> 70
<tb> 250 <SEP> 100f <SEP> 85 <SEP> 85 <SEP> 80
<Tb>

Claims (17)

1. Optically active compounds of general formula (I): wherein G is selected from groups G1 to G9: wherein: # n represents 0 or 1; # Q1 is the nitrogen atom or the CH group; # Q2 is the oxygen or sulfur atom; # Q3 is the oxygen or sulfur atom; # Q4 is the nitrogen atom or the CR11 group; # Q5 is the oxygen, sulfur or NR12 group; Y is the oxygen atom, sulfur atom or the amino (NH) or oxyamino (ONH) group; and # W is oxygen, sulfur or sulfinyl (SO) or sulfonyl (SO 2) groups; # Wz is the oxygen atom or the NR13 group; # p represents 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; optionally being 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, which radical is optionally substituted with 1 to 5 radicals; preferably with 1 to 3 radicals X1 and / or X2 and / or X3; # X ,, X2 and X3 are independently of each other a hydrogen atom, a halogen atom; or a hydroxy, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl group; or lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkoxysulfonyl; or lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio; amino, N-alkylamino, N, N-dialkylamino, acylamino, aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl; or an acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl group; # X4 is a hydrogen atom, a halogen atom; or lower alkyl, lower haloalkyl, alkoxy, haloalkoxy; or the cyano, nitro, # R, and R2 radicals are different from each other and represent a hydrogen atom, a lower alkyl group, a lower haloalkyl group, a lower cycloalkyl group, a lower halocycloalkyl group, an alkoxyalkyl group or a haloalkoxyalkyl group; alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl; cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl; or an 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 a or more lower alkyl groups; # R3 is a hydrogen atom, 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 group; or an optionally substituted phenyl or benzyl group; # R4 is lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl; or an alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino group; # R5 and R6 represent independently of each other a lower alkyl or lower haloalkyl group; # R7 is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl; # R8 is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, formyl, acyl; # R9 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl; # R10 is halogen, lower alkyl, 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; R 3 is hydrogen, lower alkyl, lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, optionally substituted allyl group, an optionally substituted propargyl group, an optionally substituted benzyl group; or an acyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl group; 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; # the asterisk (*) indicated on the general formula means that the carbon atom carrying the radicals R 1 and R 2 is an asymmetric carbon; as well as the salts, the metal and metalloid complexes of the optically active compounds of formula (I) as just defined.  2. Optically active compounds according to claim 1, having one or more of the following characteristics taken alone or in combination: # n is 0; # 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, <Desc / Clms Page number 39>  # X1, X2, X3 and X4 are independently of each other a hydrogen atom, a lower alkyl group, a halogen atom, or the cyano, trifluoromethyl, methoxy, nitro, # R1 and R2 radicals are different from one another; from each other and represent a hydrogen atom, a lower alkyl group, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, lower alkoxycarbonyl, N-alkylcarbamoyl, or N, N-dialkylcarbamoyl, # R3 is hydrogen, lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl or methoxymethyl radical, # R4 is a lower alkyl, alkoxy, alkylamino or dialkylamino group, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino or ethylamino radical, # R5, R6, R8 and R9 are, independently of one another, a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl, difluoromethyl, trifluoromethyl or ethyl radical, 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, # R10 is a chlorine atom, lower alkyl, lower haloalkyl, preferably methyl, alkoxy, alkylthio, preferably methoxy, or methylthio, # R11 and R12 are independently of each other a lower alkyl, lower haloalkyl, alkoxyalkyl, allyl, propargyl, # R13 is hydrogen, lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl, benzyl, #A is selected from a radical, optionally substituted with 1 to 5 radicals, preferably 1 to 3 radicals X, and / or X 2 and / or X 3, <Desc / Clms Page number 40>  derived, by removal of a hydrogen atom, from one of the following rings (i) to (v): a 5-membered ring described by formula (i):

   in which each of the groups of the list BI, B2, B3, B4 is chosen from carbon, nitrogen, oxygen and sulfur atoms such that said list comprises from 0 to 3 carbon atoms, from 0 to 1 sulfur atom, from 0 to 1 atom oxygen and 0 to 4 nitrogen atoms; or a 6-membered ring described by formula (ii):

 in which 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 nitrogen atoms; or 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, E, E8 is selected from carbon or nitrogen atoms such that said list comprises from 4 to 7 carbon atoms and from 1 to 4 nitrogen atoms; or a 6-membered and a 5-membered fused ring described by formula (iv): <Desc / Clms Page number 41>

 in which: each of the groups of the list J1, J2, J3, J4, J5, j6 is chosen from carbon or nitrogen atoms such that said list comprises from 3 to 6 carbon atoms, and from 0 to at 3 nitrogen atoms; and each of the groups of the list LI, 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, 0 to 1 oxygen atom and 0 to 3 nitrogen atom; and each of the groups of the list J1, J2, J3, J4, J5, J6, L1, L 2, L 3 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 sulfur atom, 0 to 1 oxygen atom and 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; <Desc / Clms Page number 42>  each of the groups of the list M1, M2, M3, TI, T2, T3 is chosen in such a way that said list comprises from 0 to 6 carbon atoms.  3. Optically active compounds according to claims 1 or 2, having one or more of the following characteristics taken alone or in combination: # W, is the oxygen atom, # RI, different from R2, is the hydrogen atom or the methyl radical, ## STR3 ##, different from R 1, is a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N, N-dialkyl-lower carbamoyl group; # A represents a heterocyclic radical, optionally substituted with 1 to 5 radicals, preferably with 1 to 3 X radicals, 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; <Desc / Clms Page number 43> 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.  4. Optically active compounds according to one of claims 1 to 3, having the following variants: # G is the group G1 or G2 or G3 or G7, # W1 is the oxygen atom, # W2 is the atom of oxygen, p = 1, # R, is different from R2 and represents hydrogen, # R2 represents lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, N, N-lower dialkylcarbamoyl, #A optionally substituted with 1 to 3 radicals X1 and / or X2 and / or X3, is selected 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.  5. Optically active compounds according to one of claims 1 to 4, of general formula (la): <Desc / Clms Page number 44>

 particular cases of the optically active compounds of formula (I) for which G is the group G1, p is equal to 1, Q2, W and W2 each represent the oxygen atom, R1 represents the hydrogen atom and A represents the pyridyl radical, and # R2 represents a lower alkyl, cyano, cyanoalkyl, or alkoxyalkyl group; # R3 is a hydrogen atom, a lower alkyl group, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, preferably a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclopropyl, or methoxymethyl radical, # R4 is a lower alkyl, alkoxy, alkylamino, dialkylamino group, preferably a methyl, ethyl, propyl, methoxy, ethoxy, methylamino or ethylamino radical, # R5 represents a lower alkyl, lower haloalkyl group, preferably a methyl, fluoromethyl or difluoromethyl group; , trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, propyl or isopropyl, # X1, X2, X3 and X4 are independently of each other a hydrogen atom, a lower alkyl group, a halogen atom, or the cyano, trifluoromethyl, methoxy or nitro radicals; the two ethylenic double bonds being of trans (or ()) configuration, the asterisk indicating the asymmetric carbon conferring on the compound its optical activity, as well as the salts, the metal and metalloid complexes of the optically active compounds of formula (Ia) such that they have just been defined. <Desc / Clms Page number 45>  6. Compounds according to one of claims 1 to 5, called:

 # (+) - (E, E) -2- (2- {1 - [(2-pyridyl) ethyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoic acid, # (-) - (E, E) Methyl 2- (2- {1 - [(2-pyridyl) ethyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate, # (+) - (E, E) -2- (2-) Methyl {1 - [(2-pyridyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate

 # (-) - (E, E) -2- (2- {1 - [(2-pyridyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoic acid, # (+) - (E, E) Methyl 2- (1- {1 - [(2-pyridyl) propyloxyimino] propyloxymethyl} phenyl) -3-methoxypropenoate, # (-) - (E, E) -2- (2- {1 - [( Methyl 2- (2-pyridyl) propyloxyimino] propyloxymethyl} phenyl) -3-methoxypropenoate,

 # (+) - (E, E) -2- (2- [- [(2-pyridyl) propyloxyimino] isobutyloxymethyl} phenyl] -3-methoxypropenoate methyl, and # (-) - (',) - 2- Methyl 2- {1 - [(2-pyridyl) propyloxyimino] isobutyloxymethyl} phenyl) -3-methoxypropenoate, and salts thereof, metal and metalloid complexes 7. Optically active compound according to one of claims 1 to 6 which is

 Methyl (-) - (E, E) -2- (2- {1 - [(2-pyridyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -3-methoxypropenoate, and its salts, metal complexes and metalloidics.  8. Fungicidal compositions comprising an effective amount of at least one active ingredient according to one of the preceding claims.  9. Fungicidal compositions according to claim 8 comprising, in addition to an active ingredient according to any one of claims 1 to 7, solid or liquid carriers, acceptable in agriculture and / or surfactants also acceptable in agriculture.  10. Fungicidal compositions according to one of claims 8 or 9 comprising from 0.05 to 95% by weight of active ingredient. <Desc / Clms Page number 46>  11. Control method, curative or preventive, against phytopathogenic fungi cultures, characterized in that it is applied, preferably in the form of fungicidal composition, on the soil where grow or where are likely to grow the plants, on the leaves and / or fruits of plants or on the seeds of plants, an agronomically effective and non-phytotoxic amount of an active ingredient according to one of claims 1 to 7.  12. Process according to claim 11, in which rice, corn, cotton, cereals, such as wheat, barley, triticale, fruit trees, apple, pear, peach, grapevine, banana, orange, and lemon trees are treated. , oilseed crops, rapeseed, sunflower, vegetable crops, tomatoes, peas, salads, solanea, potato, beet, flax, and forest trees, as well as genetically modified counterparts of these crops.  13. A method for the preventive or curative treatment of the multiplication products of plants, as well as plants resulting therefrom, against fungal diseases, characterized in that said products are coated with an effective and non-phytotoxic dose of a compound or a composition according to one of the preceding claims.  14. A method according to claim 13 in which the seeds of cereals, wheat, rye, triticale and barley, potato, cotton, peas, rapeseed, maize, flax or tree seeds are treated. foresters, or genetically modified seeds of these plants.  15. Method according to one of claims 11 to 14 wherein the wheat or barley is treated.  16. Method according to one of claims 13 to 15 wherein the dose of active ingredient 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. <Desc / Clms Page number 47>  17. Method according to one of claims 11,12 or 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 foliar treatments.  18. Process for the preparation of optically active compounds according to one of claims 1 to 7, characterized in that the racemic mixture is resolved by separation on a chiral column, or by recrystallization or by enantiomeric enrichment or by combination of one or more of these techniques.  19. Process for the preparation of optically active compounds according to one of claims 1 to 7, characterized in that it is an asymmetric synthesis process, optionally followed by separation of the products obtained on a chiral column, or by recrystallization or by enantiomeric enrichment or by combination of one or more of these techniques.  20. Process for the preparation of optically active compounds according to one of claims 5 to 7, characterized in that it follows the following asymmetric synthesis scheme:

 in which the intermediates (II), (IIR) and (IIS) have the radicals R2, X ,, X2 and X3 according to claim 5, the intermediates (IIR) and (IIS) being then separated, and then one of the two intermediates is engaged in the process of the following scheme (process for the intermediate (IIR) shown below): <Desc / Clms Page number 48>

 wherein: - all the compounds of formula (IIR), (IIIR), (IVR), (VIR) and (IaR) have the radicals R2, R3, R4, R5, X1, X2 X3, and X4 as described previously in claim 5, - step 2 is carried out in the presence of hydrazine hydrate, in ethanol; step 3 is carried out in the presence of pyridine and ethanoyl chloride in dichloromethane; step 4 is carried out in the presence of cesium carbonate, with reflux of acetonitrile, and then, without isolating the compound (VIR), step 5 is carried out in the presence of acetic acid, in toluene.