SK45699A3 - Fungicides with hydroximic and hydrazonic groups - Google Patents

Abstract

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

Description

Hydroxime and hydrazone derivatives, process for their preparation and fungicidal compositions containing them

Technical field

The invention relates to novel compounds containing hydroxime or hydrazone functional groups, to their use as fungicides, in particular in the form of a fungicidal composition, and to a method for combating phytopathogenic fungi in crops using the compounds or compositions.

BACKGROUND OF THE INVENTION

The use of derivatives containing a hydroximic functional group for combating phytopathogenic fungi in crops is known, in particular from patents EP 463 488 and EP 370 629.

SUMMARY OF THE INVENTION

Thus, one feature of the present invention is to propose a new class of fungicidally usable compounds that contain hydroxime or hydrazone functional groups.

It is a further feature of the present invention to provide a novel class of compounds containing hydroxime or hydrazone functional groups having a broad spectrum of activity on phytopathogenic fungi in crops.

It is a further feature of the present invention to provide a novel class of compounds containing hydroxime or hydrazone functional groups having a broad spectrum of activity on phytopathogenic fungi in crops, thereby preventing specific problems occurring.

Another feature of the present invention is to propose a new class of compounds containing hydroxime or hydrazone functional groups that improve the spectrum of activity on phytopathogenic fungi in crops.

It is a further feature of the present invention to provide a novel class of compounds containing hydroxime or hydrazone functional groups which improve the spectrum of activity on phytopathogenic fungi in crops such as rice, cereals, fruit trees, vines and beetroot.

It has been found that this objective can be achieved either wholly or partially by the compounds described in the present invention.

The present invention provides compounds having a hydroxim or hydrazone functionality of formula I

(I)

R ⁵ O>

'Q

R ⁴

Q ²

R ⁵ S 'Q

R ⁴

Q ²

R®

R ⁴

Q2

R®CL .N. , R ⁴ R ⁵ S, _{in the;} N, R ⁴ S (CH ₂₎ r <γ ^ (CH,) ^ γ

Q2 Q2

-IN

Q2

where n is 0 or 1,

Q ¹ is a nitrogen atom or a CH group,

Q ² is an oxygen atom or a sulfur atom,

Q ³ is an oxygen atom or a sulfur atom,

Q ⁴ is nitrogen or CR ¹¹ ,

Q ⁵ is an oxygen or sulfur atom or an NR ¹² group,

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

W ¹ is an oxygen or sulfur atom or a sulfinyl (SO) or sulfonyl (SO2) group,

W ² is O or NR ¹³ , p is 1 when W ² is O, p is 0 or 1 when W ² is NR ¹³ ,

X ¹ , X ² and X ³ are each independently hydrogen, halogen or hydroxyl, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl, lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, halo, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthio4alkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, lower alkyl, haloalkylsulfonyl, alkoxy, haloalkylsulfonyl, lower alkyl, haloalkylsulfonyl, alkoxyalkyl alkenyloxy, alkynyloxy, alkenylthio or alkynylthio, or amino, N-alkylamino, N, N-dialkylamino, acylamino, aminoalk alkyl, N-alkylaminoalkyl, Ν, Ν-dialkylaminoalkyl or acylaminoalkyl, or carboxyl, carbamoyl, N-alkylcarbamoyl, Ν, dial-dialkylcarbamoyl or lower alkoxycarbamoyl, or acyl,

X ⁴ is a hydrogen atom, a halogen atom or a lower alkyl group, a lower haloalkyl group, an alkoxy group or a haloalkoxy group, or a cyano or nitro group,

R ¹ and R ² are independently hydrogen, lower alkyl or lower haloalkyl, lower cycloalkyl or lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl or cyanoalkyl, or cyano, or cyano; carboxyl, carbamoyl, N-alkylcarbamoyl or Ν, Ν-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or alkylthiocarbonyl, alkylthiocarbonyl, -dialkylaminoalkyl or acylaminoalkyl,

R ¹ and R ² together may form a divalent radical such as an alkylene group optionally substituted by one or more halogen atoms or optionally substituted by one or more lower alkyl groups,

R ³ is hydrogen, lower alkyl or lower haloalkyl, lower cycloalkyl or lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, cyano, thio, thio, acyl, carboxyl, carbamoyl, N-alkylcarbamoyl, Ν, Ν-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl, or alkylthiocarbonyl, N-alkylcarbamoyl, -dialkylamino or Ν, Ν-dialkylaminoalkyl, or optionally substituted phenyl or benzyl,

R ⁴ is lower alkyl or lower haloalkyl, lower cycloalkyl, lower halocycloalkyl or alkoxyalkyl, or alkoxy, haloalkoxy, alkylthio, alkylamino or dialkylamino,

R ⁵ or R ⁶ are independently lower alkyl or lower haloalkyl,

R ⁷ is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl,

R ⁸ is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, formyl or acyl,

R ⁹ is a hydrogen atom, a lower alkyl group or a lower haloalkyl group or a lower cycloalkyl group, a lower halocycloalkyl group, an alkoxyalkyl group, a haloalkoxyalkyl group, an alkenyl group or an alkynyl group,

R ¹⁰ is halogen, lower alkyl or lower haloalkyl, lower cycloalkyl or lower halocycloalkyl or alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfonyl or haloalkylsulfonyl, alkylsulfonyl, alkylsulfonyl

R ( ¹¹⁾ and R ( ¹²⁾ independently of one another are hydrogen, lower alkyl or lower haloalkyl or lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl,

R ¹³ is hydrogen, lower alkyl or lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl or haloalkylthioalkyl, optionally substituted allyl, optionally substituted propargyl, or optionally substituted, or substituted,

Ί acyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxythiocarbonyl or alkylthiothiocarbonyl, or alkylsulfonyl, haloalkylsulfonyl, or

An optionally substituted arylsulfonyl group, provided that when W ¹ is a sulfur atom and W ² is a nitrogen atom, then R ³ is not an alkylthio group, when W ² and Q ² are an oxygen atom, and when G is a group G ¹ , then R R ⁵ is other than alkyl and R ⁴ is other than alkoxy, alkylamino or dialkylamino and R ³ is other than hydrogen, alkyl or haloalkyl, cycloalkyl or halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, cyanoalkyl, cyanoalkyl an alkenyl group, an alkynyl group or a dialkylaminoalkyl group or an optionally substituted phenyl group or a benzyl group, as well as metal salts and complexes and complexes thereof. compounds of formula I as defined above.

As used herein, the term "hydroxime group includes both" the hydroxime group per se (with the sequence O-C = N-O) and the "thiohydroxime group (with the sequence

S-C-N-O). Similarly, the term "hydrazone group includes both" the hydrazone group as such (with the sequence O-C = N-N) and the "thiohydrazone group (with the sequence S-C = N-N).

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

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

- the term "lower" defining an organic radical means a radical containing from 1 to 6 carbon atoms, with the exception of the cycloalkyl radical, where the adjective "lower" means that the radical contains from 3 to 6 carbon atoms,

- the alkyl radicals may be straight or branched,

- haloalkyl radicals may contain one or more identical or different halogen atoms,

- the adjective "lower delimiting acyl radical" refers to the alkyl or cycloalkyl moiety thereof,

- alkylene residue means a residue - (CfoJnu where m is 2 to 5,

- when the amine residue is disubstituted, both substituents may form a saturated or unsaturated nitrogen heterocycle of 5 or 6 atoms,

when the carbamoyl radical is disubstituted, both substituents may form a saturated or unsaturated nitrogen heterocycle of 5 or 6 atoms.

Preferred according to the invention are compounds of the formula I having one and / or more of the following characteristics, singly or in combination:

n is 0 or 1,

P is Ir

Q ² is an oxygen atom, and / or Q ³ is an oxygen atom, and / or Q ⁴ is a nitrogen atom, and / or Q ⁵ is an oxygen atom,

W ¹ is an oxygen atom or a sulfur atom,

W ² is an oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino or allylamino group,

Y is an oxygen atom,

X ¹ , X ² , X ³ and X ⁴ are each independently hydrogen, lower alkyl, halogen or cyano, trifluoromethyl or methoxy,

R ¹ and R ² are each 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,

R ³ is hydrogen, lower alkyl, lower cycloalkyl, lower haloalkyl, or alkoxyalkyl, preferably methyl, ethyl, propyl, isopropyl, cyclopropyl or methoxymethyl.

R ⁴ is lower alkyl, alkoxy, alkylamino or dialkylamino, preferably methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, methylamino or ethylamino,

R ⁵ , R ⁶ , R ⁸ and R ⁹ are independently lower alkyl or lower haloalkyl, preferably methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl or propyl,

I

R ⁷ is lower alkyl or lower haloalkyl, preferably methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl or propyl, or allyl or propargyl

R ¹⁰ is chloro, lower alkyl or lower haloalkyl, preferably methyl, or alkoxy or alkylthio, preferably methoxy or methylthio,

R ¹¹ and R ¹² are independently lower alkyl, lower haloalkyl, alkoxyalkyl, allyl or propargyl,

R ¹³ is hydrogen or lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl or benzyl.

Of these variants, the following variants are particularly preferred, individually or in combination:

W ¹ is an oxygen atom,

R ¹ is hydrogen or methyl,

R ² is hydrogen or lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl or lower Ν, Ν-dialkylcarbamoyl.

Particularly preferred are compounds in which the substituents W ¹ and W ² are in the trans position (see below) relative to the double bond -C (R ³ ) = N-.

The compounds of formula (I) and compounds which may optionally be used as intermediates in the methods of preparation and described in these methods may exist in one or more forms of geometric isomers depending on the number of double bonds in the compound. Compounds of formula I wherein G is G ¹ , G ^2, or G ³ may contain four different stereoisomers, designated as (E, E), (E, Z), (Z, E) or (Z, Z). , depending on the configuration of the two double bonds. The designations E and Z may be replaced by syn and anti or cis and trans. Attention is drawn in particular to E. Eliel and S. Wilen, "Stereochemistry of Organic Compounds, published by Wiley (1994), which describes and uses these labels.

Usually, in the case of the present invention in terms (E, E), (E, Z), (Z, E) and (Z, Z), the first letter is a double bond configuration of G ¹ , G ² or G ³ and the second letter is a configuration hydroxy or hydrazone groups.

Compounds of formula I wherein G is G ⁴ to G ⁹ may contain two different stereoisomers designated (E) and (Z), depending on the configuration of the hydroxime or hydrazone group.

The compounds of formula (I) and compounds which may optionally be used as intermediates in the methods of preparation and described in these methods may exist in one or more optical or chiral isomeric forms depending on the number of asymmetric centers in the compound. The invention thus relates equally to all optical isomers and their racemic mixtures and to the corresponding diastereoisomers either in a mixture or in separated form. Diastereoisomers and / or optical isomers can be resolved by generally known methods (see E. Eliel, ibid.).

The compounds of the formula I according to the invention and the compounds which can optionally be used as intermediates in the preparation processes can be prepared according to at least one of the processes described below as processes A to L.

The preparation of the reagents used in the general methods of preparation is generally known and is generally described in the art, or can be customized by the skilled artisan according to the desired objective. The prior art that skilled artisans can use to determine the conditions for the preparation of compounds can be found in many general chemistry books such as J. March, "Advanced Organic Chemistry published by Wiley (1992)," Methoden der organischen Chemie (Houben- Weyl), published by Georg Thieme Verlag, "Chemical Abstracts" published by the American Chemical Society, as well as in publicly available computer databases.

Method A

The present invention further provides a process for the preparation of compounds of formula (I) wherein G is one of G ¹ to G ⁹ and the other substituents are as defined above by reacting a compound of formula (IIA).

(HA) wherein G is one of G ¹ to G ⁹ , wherein G ¹ to G ⁹ are as defined in formula (I), X ⁴ is as defined in formula (I), V ¹ is halogen (preferably chlorine or bromo), an alkylsulfonate group or a haloalkylsulfonate group (preferably a methylsulfonate or trifluoromethylsulfonate group) or an arylsulfonate group (preferably a 4-methylphenylsulfonate group), with a compound of formula IIIA

(IIIA) wherein W ¹ , W ² , R ¹ , R ² , R ³ , R ¹³ , x ¹ , x ² , X ³ and p have the meaning given in formula I, in the presence of an organic or inorganic base, in the absence or in presence of a solvent. The reaction is usually carried out at a temperature comprised between -80 ° C and 180 ° C (preferably between 0 ° C and 150 ° C) or the boiling point of the solvent used, the appropriate solvent for this reaction may be an aliphatic hydrocarbon such as pentane, hexane , heptane or octane, an aromatic hydrocarbon such as benzene, toluene, xylenes or halogenated benzenes, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane or dimethoxyethane, a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane or 1, 1,1-trichloroethane, an ester such as methyl acetate or ethyl acetate, a nitrile such as acetonitrile, propionitrile or benzonitrile, a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or dimethylsulfoxide, or water. Mixtures of these solvents may also be used.

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

Suitable inorganic or organic bases suitable for this reaction include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium or calcium hydroxide, alkali metal or alkaline earth metal alkoxides, such as tertiary - potassium butoxide, alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride or cesium hydride, alkali metal or alkaline earth metal carbonates or bicarbonates, such as sodium carbonate, potassium carbonate or calcium carbonate or sodium bicarbonate, potassium bicarbonate, or calcium bicarbonate, organic bases which are preferably nitrogenous such as pyridine, alkylpyridines, alkylamines such as trimethylamine, triethylamine. or diisopropylethylamine, azaderivatives 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 ratio of compounds of formula IIA to compounds of formula IIIA. However, it is preferable to choose a molar ratio of IIIA / IIA between

0.1 and 10, preferably 0.5 to 2.

The compounds of the general formula (IIIA) are novel and also form the subject of the invention.

Depending on the conditions used, the compounds of the formula I are obtained in the form of a variable mixture of isomers (E) and (Z) or in the form of a single isomer (E) and a single isomer 14 (Z), depending on the configuration of the hydroxime or hydrazone group. If desired, the compounds of formula I and the (E) or (Z) configuration, depending on the configuration of the hydroxime or hydrazone group, can be isolated and purified by known methods such as extraction, crystallization or chromatography.

Hydroxamic or thiohydroxamic acids of formula IIIA wherein W ² is an oxygen atom and p is 1, or hydrazonic acids or thiohydrazonic acids of formula IIIA wherein W ² is NR ¹³ and p is 0 or 1, W ¹ , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² and X ³ are as defined in formula (I), may be obtained by reacting a compound of formula (IV)

H, N

I R ¹ ^ ^X1 N 2- ^ ^X2 (IV) R 2 R ¹³ , X ¹ , X ² , X ³ and p have meaning given I

with a compound of formula V

(V) wherein W ¹ and R ³ are as defined in formula I, U ¹ is a halogen atom (preferably hydroxyl, benzyloxy, lower chlorine or bromine) or lower alkoxy or alkylthio or amino or O (C = O) R ^a , wherein R ^a has the same meaning as R ³ given in formula I and is the same or different from R ³ , preferably a halogen atom; in which case the compound of formula V is an acid halide.

The condensation of a compound of formula IV with a compound of formula V is carried out in the presence of an organic or inorganic base or a dehydrating agent such as carboxylic acid anhydrides, preferably acetic anhydride or propionic anhydride, in the absence or presence of a solvent. The general conditions for the condensation of the compound of the formula IV with the compound of the formula V are similar or the same as the conditions for the condensation of the compound of the formula IIA and the compound of the formula IIIA and are known according to "Houben-Weyl, ibid.

- * Volume E5, p. 1144 - 1149

Hydroxamic acids of formula IIIA wherein W ² is an oxygen atom and p is 1, or hydrazonic acids of formula IIIA wherein W ² is a group NR ¹³ and p is 1, W ¹ , R ¹ , R ² , R ³ , R ¹³ , X , X and X are as defined in formula I, may also be prepared by reacting a compound of formula VI i

wherein R ¹ , R ² , X ¹ , x ² and X ³ have the meanings given in the general formula - * I and U ² is a halogen atom (preferably a chlorine or bromine atom) or an alkylsulfonate group (preferably a methylsulfonate or trifluoromethylsulfonate group), with a hydroxamic acid derivative in which W ² is an oxygen atom, or a hydrazonic acid derivative in which W ² is a NR ¹³ group, wherein R ³ and R ¹³ are as defined in formula I, formula VIIa.

(VII)

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

The general conditions for the condensation of the compound of formula VII with the compound of the formula VII are similar to or the same as the conditions for the condensation of the compound of the formula IIA and the compound of the formula IIIA.

Compounds of formulas IV, V, VI and VII wherein W ¹ , W ² , R ¹ , R ² , R ³ , R ¹³ , x ¹ , x ² , X ³ and p are as defined in formulas I and U ¹ and U ² have the same meaning as described in Method A, and can be prepared according to known procedures.

Compounds of formula (IIA) wherein G is one of G ¹ to G ⁹ , wherein G ¹ to G ⁹ are as defined in formula (I), X ⁴ is as defined in formula (I), V ¹ is halogen (preferably chloro or bromo), an alkylsulfonate group (preferably a methylsulfonate or trifluoromethylsulfonate group) or an arylsulfonate group (preferably a 4-methylphenylsulfonate group) are referred to by the generic term "benzyl halide derivatives" in the remainder of the description of the preparation process.

The benzyl halide derivatives of formula (IIA) wherein V ¹ is a halogen atom (preferably chlorine or bromine) may be prepared by halogenation of a compound of formula (VIII)

wherein G is one of G ¹ to G ⁹ , wherein G ¹ to G ⁹ are as defined in formula I and X ⁴ is as defined in formula I.

The halogenation of the compounds of formula VIII can be carried out by a free-radical, thermal or photochemical method, and these different methods are not mutually exclusive, with N-haloacetamide such as N-bromosuccinimide, N-chlorosuccinimide or N-bromoacetamide in an inert solvent such as benzene or carbon tetrachloride. with or without the presence of a free radical initiator, at a temperature of from 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 IIA, wherein V ¹ is a halogen atom (preferably a chlorine or bromine atom), can also be prepared by halogenating the compounds of formula IIB

wherein G is one of G ¹ to G ⁹ , wherein G ¹ to G ⁷ are as defined in formula I and R ⁴ is alkylamino or dialkylamino, G ⁸ and G ⁹ are as defined in formula I, X ⁴ has the meaning given to it in general. of formula I and W ² is an oxygen atom, a halogenating agent such as thionyl chloride, phosphorus oxychloride or phosphorus tribromide according to J. March, ibid., pages 431-433 or a lithium halide / mesyl halide / collidine reagent according to J. Org. Chem., 36, 3044 (1971).

Benzyl halide derivatives of formula IIA wherein V ¹ is a halogen atom (preferably chlorine or bromine atom) can also be prepared by cleavage of a compound of formula IIC

(IIC) wherein G is one of G ¹ to G ⁹ , wherein G ¹ to G ⁷ are as defined in formula I and R ⁴ is alkylamino or dialkylamino, G ⁸ and G ⁹ are as defined in formula I X ⁴ is as defined in formula I, W ² is an oxygen atom and P is a hydroxy protecting group such as an ester, preferably an acetic or benzoic ester, or an ether, preferably methyl ether, methoxymethyl ether, phenylether or benzyl ether (for selection and preparation) see, for example, W. Greene and P. Wuts, Protective Groups in Organic Synthesis, published by Wiley (1991)), by treatment with Lewis acid such as boron tribromide or anhydrous acids such as hydrogen chloride. This cleavage reaction is known in particular from EP 525 516.

The benzyl halide derivatives of formula IIA and compounds of formulas VIII, IIB and IIC can be prepared by known methods. These various methods or prior art related to this issue are described below for Methods J, K and L.

Method B

Compounds of formula I wherein G is one of G ¹ to G ⁹ , wherein G ¹ to G ⁷ are as defined in formula I and R ⁴ is amino, alkylamino or dialkylamino, G ⁸ and G ⁹ are as defined above in formula (I), X ⁴ is as defined in formula (I), may be prepared by reacting a compound of formula (IIB) wherein G is one of G ¹ to G ⁹ , wherein G ¹ to G ² G ⁷ are as defined in formula I and R ⁴ is amino, alkylamino or dialkylamino, G ⁸ and G ⁹ are as defined in formula I, X ⁴ is as defined in formula I and W ¹ is an oxygen atom or an atom sulfur with a compound of formula IIIB

wherein W ² , R ¹ , R ² , R ³ , R ¹³ , x ¹ , x ² , X ³ and p are as defined in formula I, U ³ is a halogen atom, preferably a chlorine atom, the double bond in the group U ³ -C (R ³ ) = NW ² - may have stereochemistry (E) or (Z).

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

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

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

There is no strict limitation on the ratio of compounds of formula IIB to compounds of formula IIIB. Preferably, however, the molar ratio IIIB / IIB is chosen between 0.1 and 10, preferably 0.5 to 2.

Depending on the conditions used, the compounds of the formula I are obtained in the form of a variable mixture of isomers (E) and (Z) or in the form of a single isomer (E) and a single isomer (Z), depending on the configuration of the hydroxime or hydrazone group. If desired, the compounds of formula I and the (E) or (Z) configuration, depending on the configuration of the hydroxime or hydrazone group, can be isolated and purified by known methods such as extraction, crystallization or chromatography.

Compounds of formula IIIB are prepared by known methods such as J. Org. Chem. 50, 993 (1985); J. Org. Chem. 36, 234 (1971) and Chem. Abstr. 73, 34750 s (1970).

Method C

The present invention also provides thiohydroxamic acids of formula IIIA wherein W ¹ is sulfur and W ² is oxygen, or thiohydrazonic acids of formula IIIA wherein W ¹ is sulfur and W ² is NR ¹³ , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² , X ³ and p are as defined in formula I.

They can be obtained by thionation of hydroxamic acids of formula IIIA, wherein W ¹ is an oxygen atom and W ² is an oxygen atom, or hydrazonic acids of formula IIIA, wherein W ¹ is an oxygen atom and W ² is NR ¹³ , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² , X ³ and p have the meaning given in formula (I) using a thionating agent such as phosphorus pentasulfide or Lawesson's reagent in the same or similar manner as described in "Houben-Weyl" , Volume E5, pp. 1279-1280 and Synthesis 1984, 829.

Method D

Compounds of formula I wherein G is G ³ , Q ² is oxygen, R ⁴ is alkoxy, alkylamino or dialkylamino, the other substituents are as defined in formula I and R ⁶ is lower alkyl or lower haloalkyl may be prepared by a process comprising reacting a compound of formula IX

where R ⁴ is alkoxy, alkylamino or dialkylamino, the other substituents are as defined in formula I, with the Wittig-Horner reagent of formula XA

R ⁶ -CH ₂ -P (= O) (OR ^b ) 2 (XA) wherein R ⁶ is a lower alkyl group or a lower haloalkyl group, R ^b is a lower alkyl group, a phenyl or benzyl group, or alternatively with a Wittig reagent of general of formula XB

R ⁶ -CH 2 -P (R ^d ) 3 ⁺ Hal '(XB) wherein R ⁶ is lower alkyl or lower haloalkyl, R ^d is optionally substituted phenyl, Hal' is a halide ion, by treatment with one or more equivalents of base such as are alkali metal or alkaline earth metal alkoxides, preferably sodium ethoxide, sodium methoxide or potassium tert-butoxide, or alkali metal or alkaline earth metal hydrides, preferably sodium hydride or potassium hydride, or by treatment with an organometallic derivative such as alkyllithium, preferably butyllithium, alkylmagnesium halides or lithium diisopropylamide, in an aprotic solvent such as ethers, preferably diethyl ether or tetrahydrofuran, at a temperature of from -78 ° C to 50 ° C, preferably from -70 ° C to 20 ° C, according to J. March, ibid., pages 956-963 or according to WO 95/29896.

The Wittig-Horner reagents of formula (XA) and the Wittig reagents of formula (XB) can be obtained according to conventional methods.

Method E

Compounds of formula I wherein G is G ¹ or θ ² / Q ¹ is nitrogen or CH, Q ² is oxygen, R ⁴ is alkoxy, alkylamino or dialkylamino, the other substituents being as defined in formula I and R ⁵ is a lower haloalkyl group, can be prepared by the method of reacting a compound of formula XI

wherein T is an oxygen atom and M is an alkali metal or alkaline earth metal ion, Q ¹ is a nitrogen atom or CH, R ⁴ is an alkoxy, alkylamino or dialkylamino group, W ¹ , W ² , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² , x ³ , x ⁴ and p are as defined in formula I, with a halogenated compound of the formula CHq (Hal) 4- _q wherein q is 1 or 2 and Hal is a halogen atom, wherein the atoms the halogen may be the same or different and at least one of them is a chlorine or bromine atom, in a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or dimethylsulfoxide, in the presence or absence of a catalytic amount of iodide ion. 20 ° C and 250 ° C, preferably between 25 ° C and 150 ° C, or at the boiling point of the solvent. This reaction is described in particular in patents DE 4 424 788 and WO 96/06072.

»

Compounds of formula XI wherein T is oxygen and M is an alkali or alkaline earth ion, Q ¹ is nitrogen, R ⁴ is alkoxy, alkylamino or dialkylamino, W ¹ , W ² , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² , X ³ , X ⁴ and p are as defined in formula (I), can be readily prepared from compounds of formula (IX) wherein R ⁴ is alkoxy, alkylamino or dialkylamino; reported in Formula I by the action of hydroxylamine and a base according to J. March, ibid., pages 906-907.

Compounds of formula XI wherein T is oxygen and M is an alkali or alkaline earth ion, Q ¹ is CH, R ⁴ is alkoxy, alkylamino or dialkylamino, W ¹ , W ² , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² , X ³ , X ⁴ and p have the meanings given in formula (I), can be prepared, in particular, as described in EP 176 826.

* Method F • Compounds of formula I wherein G is G ⁴ , where n 'is 1, Q ² is oxygen, R ⁴ is alkoxy, alkylamino. or a dialkylamino group and the other substituents as defined in formula I may be prepared by reacting a compound of formula XIIA

(XIIA) wherein R ⁴ is alkoxy, alkylamino or dialkylamino and the other substituents are as defined in formula I, with a compound of formula XIII

In ¹

OR ⁵ (xiii) wherein V ¹ is a halogen atom (preferably a chlorine or bromine atom), R ⁵ has the meaning given in formula I, soils, soils, by treatment with one or more base equivalents such as alkali or alkaline earth metal hydroxides, alkali metal or alkali metal alkoxides alkali metal or alkali 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 salt, in an aprotic solvent such as ethers, preferably diethyl ether or tetrahydrofuran, at temperature from -78 ° C to 40 ° C, preferably between -20 ° C and 25 ° C.

Compounds of formula XIIA wherein R ⁴ is alkoxy, alkylamino or dialkylamino and the other substituents are as defined in formula I may be prepared by reaction of a compound of formula XIIB

(XIIB) wherein R ⁴ is alkoxy, alkylamino or dialkylamino, X ⁴ is as defined in formula I, V ¹ is halogen (preferably chlorine or bromine) or alkylsulfonate (preferably methylsulfonate or trifluoromethylsulfonate) or arylsulfonate ( preferably a 4-methylphenylsulfonate group), with a compound of formula (IIIA) wherein W ¹ , W ² , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² , X ³ and p are as defined in Formula I.

The general condensation conditions for the compounds of formula XIIB with the compound of formula IIIA are similar to or the same as the condensation conditions for the compound of formula IIA and the compound of formula IIIA, and

- they are described in method A.

Compounds of formula XIIB can be prepared according to EP 498 396.

Method G

Compounds of formula I wherein G is G ¹ to G ⁷ and R ⁴ is alkylamino or dialkylamino and the other substituents are as defined in formula I may be prepared by reacting a compound of formula I, wherein G is G ¹ to G ⁷ and R ⁴ is alkoxy or alkylthio and the other substituents are as defined in formula I, with an alkylamine or dialkylamine, preferably methylamine, in an alcoholic solvent such as methanol, ethanol, propanol or isopropanol , at a temperature of from - 50 ° C to 100 ° C or at the boiling point of the solvent used. In general, it is preferred to use an excess of from 1 to 5 equivalents, preferably 1.1 to 2 equivalents, of alkylamine or dialkylamine relative to the compound of formula I wherein G is G ¹ to G ⁷ and R ⁴ is alkoxy or alkylthio and the other substituents have as defined in formula I.

Method H

Compounds of formula I wherein W ¹ is sulfoxide (SO) or sulfone (SO 2), G is one of G ¹ , G ³ , G ⁴ and G ⁶ to G ⁹ , Q 2 and Q ³ are oxygen atoms and the others the substituents having the meanings given in formula (I), may be prepared by oxidation of compounds of formula (I) wherein W ¹ is a sulfur atom, G is one of G ¹ , G ³ , G ⁴ and G ⁶ to G ⁹ , Q ² and Q ³ are oxygen and the other substituents are as defined in formula I, using one or more equivalents of an oxidizing agent such as organic peroxides, preferably peracetic acid or 3-chloroperbenzoic acid, inorganic peroxides and 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

Compounds of formula I prepared according to Method A or Method B can be obtained with atoms or groups W ¹ and W ² , wherein W ¹ and W ² have the meaning given in formula I, in the cis position (see above) with respect to the double bond -C (R ³ ) = N (hydroxime or hydrazone group).

Isomers of formula I with atoms or groups W ¹ and W ² in the trans position due to the double bond -C (R 3) = N- (hydroxy or hydrazone group) can be prepared from the cis isomers by heating in a solvent, preferably under irradiation with ultraviolet light , with or without a catalyst, in particular with an acid catalyst. The reaction time is chosen such that the total conversion of the cis isomer to the trans isomer occurs. The reaction is usually carried out at a temperature between 0 ° C and the boiling point of the solvent. An appropriate solvent for this reaction may be an aliphatic hydrocarbon such as pentane, hexane, heptane or octane, an aromatic hydrocarbon such as benzene, toluene or xylenes, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane or dimethoxyethane, a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane or 1,1,1-trichloroethane, ester such as methyl acetate or ethyl acetate, nitrile such as acetonitrile, propionitrile or benzonitrile, alcohol such as methanol, ethanol, propanol or isopropanol, dipolar aprotic a solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or dimethylsulfoxide, or water. Mixtures of these various solvents can also be used.

The solvent is preferably an aromatic solvent such as toluene or xylenes, or an ether such as diisopropyl ether. The catalyst, preferably the acid catalyst, is selected from anhydrous acids such as hydrogen chloride, carboxylic acids such as acetic acid, propionic acid or trifluoroacetic acid, sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, or 4-methylphenylsulfonic acid, or sulfuric acid.

Method J

I (Benzyl halide derivatives of formula IIA and the like)

The benzyl halide derivatives of formula IIA and the compounds of formulas VIII, IIB and IIC can be prepared according to a number of known methods.

Non-limiting and non-limiting examples include various patents describing processes for preparing benzyl halide derivatives of formula IIA or compounds of formulas VIII, IIB and IIC.

Benzyl halide derivatives of formula IIA and the like, wherein G is G ¹ or G ² with (E) or (Z) stereochemistry, can be prepared according to patents EP 426 460, EP 398 692, EP 617 014, EP 585 751, EP 487 409, EP 535 928 and DE 4 305 502.

Benzyl halide derivatives of formula IIA similar where G is a G ³ group with (E) or (Z) stereochemistry are known from WO 96/16943.

Benzyl halide derivatives of formula IIA and the like, wherein G is a group G ⁴ , G ⁵ or G ⁶ , are known from patents EP 498 396, EP 619 301 and WO 93/15046.

Benzyl halide derivatives of formula IIA and the like, wherein G is a group G ⁷ , are known from patents WO 95/27693 and WO 96/07633.

Benzyl halide derivatives of formula IIA and the like, wherein G is G ⁸ or G ⁹ , are known from WO 96/14009.

Method K

Compounds of formula I wherein W ¹ , W ² , R ¹ , R ² , R ³ , XI, X ² , X ³ , X ⁴ and p are as defined in formula I and G is G ⁷ may be prepared in the following manner, which is also the essence of the present invention.

This process consists in the intermediates of formula (IIIA) wherein the groups W ¹ , W ² , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² , X ³ and p are as defined in formula I, reacted with compounds of formula IIA wherein G is G ⁷ , X ⁴ is as defined in formula I and V ¹ is halogen, preferably chlorine or bromine, according to the procedure described in Method A.

Compounds of formula IIA wherein G is G ⁷ , X ⁴ · is as defined in formula I and V ¹ is halogen, preferably chlorine or bromine, can be prepared by cleavage of a compound of formula XIVA

(XIVA) wherein Y, X ⁴ , Q ² , R ⁴ and R ⁸ are as defined in formula I and R ^c is a hydrogen atom or a lower alkyl group optionally substituted by one or more halogen atoms, or an alkoxy group, an optionally substituted benzyl group or an optionally substituted aryl group, by reaction with a halogenating agent.

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

The halogenating agents used may be, for example, Lewis acids such as aluminum chloride or boron trichloride. or halogenated acids such as hydrogen chloride or hydrogen bromide. The halogenating agent is used in equimolar amounts or in excess. Compounds of the formula XIVA, wherein Y, X ^4, Q ^2, R ⁴ and R ⁸ are as for formula I and R ^c is hydrogen or lower alkyl, optionally substituted by one or more halogen or alkoxy, optionally substituted a benzyl group or an optionally substituted aryl group may be prepared by alkylation of compounds of formula XIVB

(XIVB) wherein Y, X ⁴ , Q ² , R ⁴ and R ⁸ are as defined in formula (I) and R ^c is a hydrogen atom or a lower alkyl group optionally substituted by one or more halogen atoms, or an alkoxy group optionally substituted by a benzyl group or an optionally substituted aryl group.

As the alkylating agent, an alkyl halide or acyl halide or sulfonate of formula XV can be used

R 1 -V ¹ (XV) wherein R ⁸ is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, formyl or acyl and V ¹ is halogen (preferably chlorine or bromine) or alkylsulfonate (preferably trifluoromethylsulfonate) ) or an arylsulfonate group, in the presence of a silver derivative such as silver salts or oxides, according to J. Chem. Soc. 1969, 2372 and Bull. Chem. Soc. Jpn. 51, 866 (1978). The reaction is carried out in a dipolar aprotic solvent, for example amides such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, at a temperature between -70 ° C and 180 ° C, preferably between -30 ° C and 80 ° C.

Compounds of formula XIVB wherein Y, X ⁴ , Q ² and R ⁴ are as defined in formula I and R ^c is as defined in formula XIVA may be prepared by reduction of compounds of formula XIVC

wherein Y, X ⁴ , Q ² and R ⁴ are as defined in formula (I) and R ^c is as defined in formula (XIVA) using a reducing agent such as an alkali metal or alkaline earth metal hydride, preferably sodium borohydride, in an alcohol such as methanol, ethanol, propanol, isopropanol, butanol or tert-butanol, according to J. March, ibid., page 910.

Compounds of formula XIVC wherein Y, X ⁴ , Q ² and R ⁴ have t

as defined in formula (I) and R ^(c) as defined in formula (XIVA), may be prepared by reacting a compound of formula (XIVD)

And (XIVD)

Q 2 wherein Y, X ⁴ , Q ² and R ⁴ are as defined in formula I and V ¹ is a halogen atom, preferably a chlorine or bromine atom, with an inorganic carboxylate such as formate, acetate or propionate, or other inorganic salt of lower alkylcarboxylic acids, wherein the alkyl group may be optionally substituted by one or more halogen or alkoxy or optionally substituted phenyl, or alternatively from salts of optionally substituted benzoic acid, according to J. March, ibid., page 398.

The reaction is preferably carried out in a dipolar aprotic solvent such as amides, preferably formamide, acetamide, dimethylacetamide or N-methylpyrrolidone, at a temperature ranging from 0 ° C to the boiling point of the solvent used.

Compounds of formula XIVD can be obtained according to known procedures as described in EP 374 811.

Method L

Compounds of formula I wherein W ¹ , W ² , R ¹ , r ² , R ³ , X ¹ , X ² , X ³ , X ⁴ and p are as defined in formula I and G is G ³ and R ⁶ is a trifluoromethyl group, and can also be prepared according to the following process, which is also an aspect of the invention.

The process consists in reacting intermediates of formula (IIIA) wherein W ¹ , W ² , R ¹ ,

R 2, R ³ , R ¹³ , X ¹ , X ² , X ³ and p are as defined in formula I with compounds of formula IIA wherein G is G ³ , R ⁶ is trifluoromethyl, X ⁴ , R ⁴ and Q ² are as defined in formula I and V ¹ is a halogen atom, preferably a chlorine or bromine atom, according to the procedure described in Method A.

Compounds of formula IIA wherein G is G ³ , R ⁶ is trifluoromethyl, X ⁴ , R ⁴ and Q ² are as defined in formula I and V ¹ is halogen, preferably chlorine or bromine, can be prepared by halogenation compounds of formula VIII wherein G is G ³ , R ⁶ is trifluoromethyl, X ⁴ , R ⁴ and Q ² are as defined in formula I according to the procedure described in Method A.

Compounds of formula VIII wherein G is G ³ , R ⁶ . X is a trifluoromethyl group, X ⁴ , R ⁴ and Q ² are as defined in formula (I), can be prepared by dehydrating compounds of formula (XVI)

wherein X ⁴ , R ⁴ and Q ² are as defined in formula I, using a dehydrating agent such as anhydrous acids (preferably sulfuric acid), their alkali metal or alkaline earth metal salts (preferably potassium hydrogen sulphate), or anhydrides such as phosphorus pentoxide, according to J. March, ibid., pages 1011 et seq., or Chem. Ber. 119, 2233 (1986), or phosphorus oxychloride, alkylsulfonate chlorides (preferably methylsulfonate or trifluoromethylsulfonate) or arylsulfonate chlorides (preferably 4-methylphenylsulfonate), in the presence of nitrogenous bases such as pyridine, alkylpyridines or alkylamines such as trimethylamine, triethylamine or triethylamine or triethylamine Tetrahedron: Asymmeters of dialkyldiazodicarboxylates (preferably in the presence of a triarylphosphine, such as diphenylphosphine, according to J. Org Chem. 49, 1430 (1984)).

1, 521 (1990) or diethyldiazodicarboxylate)

This reaction is carried out in the absence or presence of a solvent. The reaction is usually carried out at a temperature between -80 ° C and 180 ° C (preferably between 0 ° C and 150 ° C) or at the boiling point of the solvent used. The relevant solvent in this reaction may be a halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane, l ^1, 1,1-trichloroethane; an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane or dimethoxyethane, a nitrile such as acetonitrile, propionitrile or benzonitrile, a nitrogenous base such as pyridine or alkylpyridines, a dipolar aprotic solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone dimethylsulfonamide; . Mixtures of these solvents may also be used.

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

Compounds of formula XVI wherein X ⁴ , R ⁴ and Q ² are as defined in formula I may be prepared by an aldol condensation reaction of compounds of formula XVII

(XVII) wherein X ⁴ , R ⁴ and Q ² are as defined in formula I, with trifluoroacetaldehyde gas, by treatment with one or more base equivalents, such as alkali metal or metal hydrides. alkaline earth metals, preferably sodium hydride or potassium hydride, alkali metal or alkaline earth metal alkoxides, organometallic derivatives such as alkyl lithium, preferably butyllithium, alkylmagnesium halides or amides of alkali or alkaline earth metals such as lithium diisopropylamide or lithium hexamethyldisilazilazeazilazeazilazilaz ethers, preferably diethyl ether or tetrahydrofuran, at a temperature of from -78 ° C to 50 ° C, preferably - 70 ° C to 20 ° C.

The present invention further provides fungicidal compositions comprising an effective amount of at least one active compound of formula (I).

The fungicidal compositions according to the invention contain, in addition to the active compound of the formula I, agriculturally acceptable solid or liquid carriers and / or surface-active substances which are also agriculturally acceptable. In particular, conventional inert carriers and conventional surfactants are used. These. the compositions include not only compositions ready for application to plants or seeds to be treated with a suitable device such as a spray or dusting device, but also concentrated commercial compositions which must be diluted before application to the crop.

These compositions according to the invention may also contain other components of any kind, such as protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, masking agents, and the like. In general, the active compounds can be combined with any solid or liquid additives which comply with conventional formulation techniques.

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

As used herein, the term "carrier" refers to a natural or synthetic organic or inorganic material with which the active ingredient is combined to facilitate application to parts of plants. Thus, this carrier is generally inert and should be agriculturally acceptable. This carrier 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 the ionic or non-ionic type or a mixture of these surfactants. For example, polyacrylic acid salts, ligninsulfonic acid salts, phenolsulfonic acid salts or naphthalenesulfonic acid salts, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (especially alkylphenols or arylphenols), sulfosuccinic acid ester salts, (especially alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyols, and derivatives of said compounds containing a sulfate, sulfonate and phosphate functionality. The presence of at least one surfactant is usually suitable when the active agent and / or the inert carrier are insoluble in water and if the carrier for application is water.

The compositions for agricultural use according to the invention may contain the active ingredient in a very wide range, from 0.05% to 95% by weight. The surfactant content is preferably between 5% and 40% by weight. Unless otherwise indicated herein, percentages are by weight.

As such, the compositions of the invention are in completely different solid or liquid forms.

Solid form preparations include dusting powders (up to 100% active ingredient) and granules, in particular granules obtained by extrusion, compression, impregnation of a granular carrier or granular powder (active ingredient content here being between 0.5 and 80% for recent cases).

The fungicidal compositions according to the invention may also be used in the form of dusting powders, compositions containing 50 g of active ingredient and 950 g of talc, compositions containing 20 g of active ingredient, 10 g of finely divided silica and 970 g of talc. These ingredients are mixed together and ground and the mixture applied by dusting.

Liquid form preparations or forms intended for administration as liquid formulations include solutions, in particular water-soluble concentrates, emulsions, concentrated suspensions and wettable powders (or powders for spraying).

Concentrated suspensions which can be applied by spraying are prepared so as to obtain a stable, non-settled liquid product and usually contain from 10 to 75% of active ingredient, from 0.5 to 15% of surfactants, from 0.1 up to 10% of thixotropic agents, from 0 to 10% of suitable additives such as antifoams, corrosion inhibitors, stabilizers, penetration agents and adhesives, and as a carrier a water or organic liquid in which the active ingredient is insoluble or only slightly soluble. Certain organic solids or inorganic salts can be dissolved in the carrier to prevent sedimentation or are antifreeze agents for water.

The following is an example of the composition of a concentrated suspension:

Example CS1

- active substance 500 g

-Polyethoxylated tristyrylphenol phosphate 50 g

- Polyethoxylated alkylphenol 50 g

- polysodium carboxylate 20 g

- ethylene glycol 50 g

- polyorganosiloxane oil (anti-foaming) 1 g

- polysaccharide 1.5 g

- water 316.5 g

Wettable powders (or powders for spraying) are usually prepared containing 20 to 95% of the active ingredient and usually contain, in addition to the solid carrier, from 0 to 30% of a wetting agent, from 3 to 20% of a dispersant and from 0.1 to 30%. 10% of one or more stabilizers and / or other additives, such as penetration agents, adhesives, anti-caking agents, colorants, etc.

In the preparation of sprayable powders or wettable powders, the active ingredients are intimately mixed with the additives in suitable mixers and ground in mills or other suitable mixers. This yields sprayable powders with a preferable wettability and suspension formulations. These can be suspended in water at any desired concentration, and these suspensions are very preferably used for application, for example, to plant leaves or seeds.

The various compositions of wettable powders (or spray powders) are given below as examples:

Example WP1

- active substance %

ethoxylated fatty alcohol (wetting agent) 2.5

- ethoxylated phenylethylphenol (dispersant) 5

- chalk (inert carrier) 42.5

Example WP2

- the active substance

- Synthetic branched-type C ₁₃ oxoalcohol, ethoxylated with 8 to 10 ethylene oxide units (wetting agent) 0,75

- neutral calcium lignosulfonate (dispersant) 12

- calcium carbonate (inert filler) qs 100%

%%

%

Example WP3

This wettable powder contains the same ingredients as the previous example, but in the following proportions:

- the active substance

wetting agent 1.5

- dispersing agent 8

- calcium carbonate (inert filler) qs 100

Example WP4

- the active substance

ethoxylated fatty alcohol (wetting agent) 4

- ethoxylated phenylethylphenol (dispersant) 6

Example WP5

- the active substance

Mixture of anionic and nonionic surfactants (wetting agent) 2,5

- sodium lignosulfonate (dispersant) 5

- kaolin clay (inert carrier) 42,5% for%%

%%

%%

%%

Aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder of the invention with water, are also within the 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 "mayonnaise".

The fungicidal compositions of the invention may be formulated in the form of water-dispersible granules, which are also within the scope of the invention.

These dispersible granules with a bulk density typically between about 0.3 and about 0.6 have a particle size generally between about 150 and about 2000 µm, and preferably between 300 and 1500 µm.

The active ingredient content of these granules is generally between about 1% and about 95% and preferably between 25% and 90%.

The remainder of the granules consists of a solid carrier and optionally a surfactant which provides the granules with water dispersibility. These granules may be essentially of two different types depending on whether the carrier is water soluble or insoluble. If the carrier is water-soluble, it may have an inorganic or preferably organic origin. Excellent results are obtained with urea. If the carrier is insoluble, it preferably has an inorganic origin, such as kaolin or bentonite. Then, it is preferred to use surfactants (in a proportion of 2% to 20% by weight of the granules) of which more than half consist, for example, of at least one dispersing anionic or alkali metal or alkaline earth metal lignosulfonate, and the remainder consisting of non-ionic or anionic wetting agents such as an alkali metal or alkaline earth metal alkyl naphthalenesulfonate.

an alkali metal reagent such as an alkaline earth polynaphthalenesulfonate; or

In addition, other adjuvants, such as antifoams, may optionally be used.

The granules of the invention can be prepared by mixing the desired ingredients and then granulating by known methods (granulator, fluid bed, sprayer, extrusion, etc.). The process usually ends by crushing and then sieving to a selected particle size within the stated range. It is also possible to use the granules obtained by the above process and then impregnate with the active ingredient-containing composition.

They are preferably obtained by extrusion as described in the following examples:

Example DG1: Dispersible granules by weight of active ingredient and 10% urea pellets are mixed together in a mixer. The mixture is then ground in a toothed roller crusher. A powder is obtained which is moistened with about 8% by weight of water. The wet powder is extruded in a perforated roller extruder. A granulate is obtained which is dried and then crushed and sieved so that only granules with a size between 150 and 2000 μπι are obtained.

Example DG2: Dispersible granules

The following ingredients are mixed together in the blender:

- active substance 75%

- wetting agent (sodium alkylnaphthalenesulfonate) 2%

- dispersant (polysodium naphthalenesulfonate) 8%

- water-insoluble inert filler (kaolin) 15%

The mixture is granulated on a fluid bed in the presence of water and then dried, crushed and sieved to give granules between 0.15 and 0.80 mm in size.

These granules may be used alone or as a solution or dispersion in water to obtain the desired dosage. They can also be used for the preparation of combinations with other active substances, in particular fungicides, in the form of wettable powders, granules or aqueous suspensions.

The compounds of the invention may also be mixed with one or more insecticides, fungicides, bactericides, attractants, acaricides or pheromones, or other compounds having biological activity. The mixtures thus obtained have a broad spectrum of activity. Particularly preferred are mixtures with other fungicides, in particular mixtures with carbendazim, thiuram, dodine, maneb, mancozeb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimephone, captan, captafol, folpet, folpel, thiopendolil, thiopendolil, thiopendolil, thiopendolil , metalaxyl, iprodione, oxadixyl, vinchlozolin, tebuconazole, difenconazole, diniconazole, metconazole, penconazole, propiconazole, prochloraz, fenarimol, triadimenol, furalaxyl, with copper derivatives such as copper hydroxide and probenazole, copper oxyenazole.

The compositions of the invention are useful for the treatment of cereal seeds (wheat, rye, triticale and especially barley), potatoes, cotton, peas, oilseed rape, maize or flax, or alternatively forest tree seeds (especially resinous trees).

It should be noted that the term "seed treatment" refers to grain treatment in the terminology used by those skilled in the art. Application techniques are well known to those skilled in the art and can be used routinely. For example, thin coatings or coatings may be mentioned.

A further object of the invention is a method of treating or preventing phytopathogenic fungi on crops by applying an effective (agriculturally effective) and non-phytotoxic amount of an active compound of the formula I, preferably in the form of a fungicidal composition according to the invention, to plant seeds or leaves or to the soil in which the plants grow or where they need to grow.

The term &quot; effective and non-phytotoxic amount &quot; means an amount of a composition of the invention that is sufficient to control or destroy fungi present on crops and that does not cause any apparent symptom of phytotoxicity on these crops. This amount can vary widely, depending on the fungi to be exterminated, the type of crop, the climatic conditions and the compounds contained in the fungicidal composition of the invention. This amount can be determined by systematic field trials, as is known to those skilled in the art.

Finally, the invention relates to a method of preventive or curative protection of a variety of plant products as well as of a plant. of fungal diseases which comprises coating these products with an effective and non-phytotoxic amount of a composition according to the invention.

A variety of plant products is understood to mean, in particular, seeds or grains and noises.

I

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

As already mentioned, methods of coating a variety of plant products, especially seeds, are well known and include, in particular, thin film coating or coating techniques.

The products and compositions of the invention can also be applied to the leaves of crop plants.

Among the selected plants for which the method according to the invention is suitable:

- wheat, for the control of the following seed diseases: fusariosis (Microdochium nivale and Fusarium roseum), stinking sieve (Tilletia caries, Tilletia controversa or Tilletia indica) and spotting (Septoria nodorum),

- wheat, for the control of the following diseases of the aerial parts of the plants: steblolam (Gaeumannomyces graminis), mold (F.

culiaorum and F. graminearum), blotches (Rhizoctonia cerealis), powdery mildew (Erysiphe graminis form specie tritici), corn rust (Puccinia striiformis and Puccinia recondita) and septoriosis (Septoria tritici and Septoria nodorum),

- wheat and barley as regards control, bacterial viral diseases such as yellow mosaic barley disease,

- barley as regards the control of the following seed diseases: brown spots of barley (Pyrenophora graminea, Pyrenophora teres and Cochliobolus sativus), dusty barley (Ustilago nuda) and fusariosis (Microdochium nivale and Fusarium roseum),

- barley as regards diseases of the aerial parts of the plants: steblolam (Pseudocercosporella herpotrichoides), brown barley (Pyrenophora teres and Cochliobolus sativus), powdery mildew (Erysiphe graminis form specie hordei), barley rust (Puospinium spp.) .

- potatoes for the control of tuber diseases (in particular Helminthosporium solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani) and certain viruses (Y virus),

- cotton as regards the following diseases of young plants grown from seed: withering and mold (Rhizoctonia solani, Fusarium oxysporum) and black rot (Thielaviopsis basicola),

- peas as regards the following seed diseases: anthracnose (Ascochyta pisi, Mycosphaerella pinodes), fusarium (Fusarium oxysporum) and gray mold (Botrytis cinerea),

- oilseed rape as regards the following seed diseases: Phoma lingam and Alternaria brassicae,

- maize for the following seed diseases: Rhizopus sp., Penicillium sp., Trichoderma sp., Aspergillus sp. and Gibberella fujikuroi, lan as regards the control of seed disease: Alternaria linicola,

- forest trees with regard to wilting control (Fusarium oxysporum, Rhizoctonia solani).

Wheat and barley are suitable plants for carrying out the methods of the invention.

A suitable dose of the composition administered is generally such that the dose of active compound is between 2 and 200 g of active compound per 100 kg of seed, preferably between 3 and 150 g per 100 kg, in the case of seed treatment.

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

The present invention is further illustrated by the following examples.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Preparation of (Z) -N-methoxy-N-methoxycarbonyl-2- {1- [1- (phenyl) ethyloxyimino] ethyloxymethyl} aniline

1.47 g of N- [1- (phenyl) ethyloxy] acetamide is dissolved in 30 ml of anhydrous acetonitrile. 2.26 g of 2-bromomethyl-N-methoxycarbonylaniline and 2.67 g of cesium carbonate are added sequentially and the reaction mixture is refluxed for 2 hours. After cooling, the salts were filtered off and washed with acetonitrile to give a concentrated organic solution and 3.2 g of a red oil. The oil was taken up in water and re-extracted three times with ethyl acetate to give 2.63 g of a dark yellow oil after drying and evaporation.

Silica chromatography yields 0.6 g of the expected compound with stereochemistry (Z) as a yellow oil, n _D »1.5270 (23 ° C) (this is the refractive index at 23 ° C using light as the light) sodium D-line).

Example 2

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

0.4 g of (Z) -N-methoxy-N-methoxycarbonyl-2- {1- [1- (phenyl) ethyloxyimino] ethyloxymethyl} aniline is dissolved in 25 ml of anhydrous toluene. After addition of a few drops of acetic acid, the reaction mixture was heated to reflux for 2 hours. The mixture is poured into 50 ml of water and the toluene phase is separated after settling, washed neutral and dried to give 0.4 g of a yellow oil.

Chromatography on silica affords 0.33 g of the expected compound with stereochemistry (E) as a pale yellow oil which crystallizes gradually. Mp 70 ° C.

Example 3

Preparation of (Z) -2,4-dihydro-5-methoxy-2-methyl-4- (2- (1- (1- (phenyl) ethyloxyimino) ethyloxymethyl) phenyl) -3H-1,2,4-triazole- 3-one

3.58 g of N- [1- (phenyl) ethyloxy] acetamide are dissolved in 40 ml of anhydrous acetonitrile. 5.96 g of 4- [2- (bromomethyl) phenyl] -2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one and 7.82 g are gradually added. The reaction mixture was heated to reflux for 4 hours. After cooling, the salts are filtered off and washed with acetonitrile, and the organic fraction is then concentrated to give 7.0 g of an orange-colored oil. After chromatography on silica, 0.82 g of the expected compound with stereochemistry (Z) is isolated as a yellow oil. Rf = 0.24 (1/3 heptane / ethyl acetate) (corresponds to the retention coefficient on a thin-layer chromatography plate).

Example 4

Preparation of (E) -2,4-dihydro-5-methoxy-2-methyl-4- (2- {1- [1- (phenyl) ethyloxyimino] ethyloxymethyl} phenyl) -3H-1,2,4-triazole- 3-one

0.4 g of (Z) -2,4-dihydro-5-methoxy-2-methyl-4- (2- {1- [1- (phenyl) ethyloxyimino] ethyloxymethyl} phenyl) -3H-1,2, 4-Triazol-3-one is dissolved in 20 ml of anhydrous toluene. The reaction mixture is heated at reflux for 13 hours, irradiating with ultraviolet light. The reaction mixture was concentrated to give 0.4 g of a yellow oil.

Chromatography on silica isolates 0.18 g of the expected compound with stereochemistry (E) as a pale yellow oil, n _D = 1.5310 (21 ° C).

Example 5

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

Stage 1

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

A mixture of 25 g of methyl 2- (2-bromomethylphenyl) -2-oxoacetate, 9.57 g of potassium acetate and 0.5 g of potassium iodide in 150 ml of dimethylformamide was heated at reflux for 3 hours. After cooling and dilution with water, the reaction mixture is re-extracted with ether. Purification by silica chromatography gives 11 g of the expected product, n _D = 1.5292 (25 ° C).

Stage 2

Preparation of methyl 2- (2-acetoxymethylphenyl) -2-hydroxyacetate g of the compound prepared in the previous step is taken up in 150 ml of methanol. After cooling in an ice bath, 0.4 g of sodium borohydride is added and the mixture is stirred at 0 ° C for 30 minutes. 5 ml of acetic acid are then added and the methanol phase is concentrated. After re-extraction, washing, with aqueous sodium bicarbonate solution and drying, 10.5 g of the expected product is isolated as a yellow oil. NMR (CDC1 _3): 2.10 (s, 3H), 3.72 (s, 3H), 5.28 (AB, 1H), 5.42 (s, 1H), 7.25 to 7.45 ( m, 4H).

Stage 3

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

1.5 g of silver oxide are added over 1 hour to 10 g of the compound prepared in the preceding step and 11.36 g of methyl iodide dissolved in 200 ml of N-methylpyrrolidone. After heating at 40 ° C for 2 hours, the reaction mixture was filtered, diluted with water and re-extracted with ether. After purification by chromatography on silica, 2.5 g of the expected compound are obtained in the form of a yellow oil.

Stage 4

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

Hydrogen bromide is added to a solution of 0.5 g of the compound obtained in the preceding step in 10 ml of dichloromethane at a temperature between 0 ° C and 5 ° C. After concentration and purification by silica chromatography, 0.25 g of a yellow liquid is obtained. NMR (CDCl 3): 3.42 (s, 3H), 3.75 (s, 3H), 4.55 (d, 1H), 4.82 (d, 1H), 5.20 (s, 1H),

7.25 - 7.55 (m, 4H).

Stage 5

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

A mixture of 0.125 g of N- [1- (phenyl) ethyloxy] acetamide, 0.2 g of methyl 2- (2-bromomethylphenyl) -2-methoxyacetate and 0.234 g of cesium carbonate in 15 ml of acetonitrile is heated to reflux for 4 hours. Purification by silica chromatography yields 0.1 g of the expected compound with stereochemistry (E) as a 50/50 mixture of two diastereomers, n _D = 1.5330 &lt; -1 &gt; (25 [deg.] C).

Example 6

Preparation of methyl (E, E) -2- {2- [1- (N ² -benzyl-N ² -methylhydrazono) ethyloxymethyl] phenyl} -3-methoxyacrylate

Stage 1

Preparation of N ² -benzyl-N ² -methylacethydrazide

5.4 ml of acetyl chloride are added dropwise at room temperature to a vigorously stirred mixture of 9.4 g of 1-methyl-1-benzylhydrazine prepared according to Synth. Commun. 20, 185 (1990), dissolved in 50 ml of ether and 2.76 g of sodium hydroxide dissolved in 50 ml of water. The reaction is allowed to proceed for 2 hours, then the phases in the reaction mixture are separated by settling and the organic phase is worked up in the usual manner. After purification by chromatography on silica, 8.36 g of the expected product is obtained in the form of a yellow oil. NMR (CDCl 3): 2.5 (s, 3H), 2.95 (broad s, 2H), 3.62 (s, 2H), 7.25-7.45 (m, 5H).

Stage 2

Preparation of methyl (E, E) -2- {2- [1- (N ² -benzyl-N ² -methylhydrazono) ethyloxymethyl] phenyl} -3-methoxyacrylate

To a mixture of 2.06 g of N ² -benzyl-N ² -methylacethydrazide obtained in the preceding step and 1.3 g of potassium tert-butoxide in 60 ml of anhydrous dimethylformamide at 20 ° C is gradually added 3 g of methyl (E) -2. - (2-bromomethylphenyl) -3-methoxyacrylate dissolved in 90 ml of anhydrous dimethylformamide. The reaction was allowed to proceed for 5 hours and the mixture was poured into 300 mL of water and re-extracted several times with ethyl acetate. Purification by silica chromatography gives 70 mg of the expected product with stereochemistry (E, E) as a syrup. NMR (CDC1 _3): 1.88 (s, 3H), 2.42 (s, 3H), 3.66 (s, 3H), 3 m, 68 (s, 2H), 3.72 (s, 3H) 4.93 (s, 2H); 7.10-7.50 (m, 9H); 7.47 (s, 1H).

Example 7

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

Stage 1

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

28.75 g (0.15 mol) of methyl 2- [2- (methyl) phenyl] acetate dissolved in 100 ml of anhydrous tetrahydrofuran is added dropwise to 200 ml of lithium diisopropylamide (1 M in anhydrous tetrahydrofuran) and cooled to - 70 “C. Anhydrous trifluoroacetaldehyde prepared according to J. Chem. Educ. 52, 131 (1975). The reaction mixture was stirred at -70 ° C for 3 hours, then poured into 500 ml of water and 200 ml of 1 M hydrochloric acid, re-extracted with ethyl acetate and dried. Evaporation of the solvents afforded 37 g of a yellow oil which was distilled under reduced pressure (bp 115-120 ° C at 533 Pa) to give 35.60 g of a colorless oil. After purification by chromatography on silica gel, 21.26 g of the expected compound is obtained in the form of a syn: anti mixture in a ratio of 70:30. The main diastereoisomer having the syn configuration can be isolated in pure form and recrystallized.

⁴ Jhh = 5 Hz, mp 58 ° C.

Stage 2

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

To 9.14 g of the syn: anti-methyl 3-hydroxy-2- [2- (methyl) phenyl] -4,4,4-trifluorobutanoate mixture obtained in the previous step dissolved in 40 ml of diethyl ether is added 9.34 g of triphenylphosphine. The reaction mixture was cooled to 0 ° C and 6.19 g of diethyl azodicarboxylate was added dropwise. The reaction mixture is stirred for 15 hours at 20 ° C and the triphenylphosphine oxide is filtered off. The filtrate is distilled in a round-bottomed flask to give 7 g of the expected compound with stereochemistry (E) as a colorless liquid, nD = 1.4772 ( 20 ^e C).

Stage 3

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

To 7 g of methyl (E) -2- [2- (methyl) phenyl] -4,4,4-trifluorobut-2-enoate obtained in the previous step dissolved in 100 ml of carbon tetrachloride is added 5.34 g of N-bromosuccinimide and 0.1 g of benzoyl peroxide and the reaction mixture was heated at reflux for 2 hours. After cooling, the succinimide is filtered off and the organic phase is washed with water and dried. Evaporation of the solvent gave 8.63 g of the expected compound with stereochemistry (E) contaminated with about 15% of the starting compound.

Stage 4

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

0.8 g of N- [1- (phenyl) ethyloxy] acetamide is dissolved in 20 ml of anhydrous acetonitrile. 1.45 g of methyl (E) -2- [2- (bromomethyl) phenyl] -4,4,4-trifluorobut-2-enoate obtained in the previous step and 1.76 g of cesium carbonate are added successively and the reaction mixture is stirred for 1 hour. at reflux for 2 hours. After cooling, the reaction mixture is poured into 100 ml of water and re-extracted with ethyl acetate, dried and then concentrated to give 1.7 g of a yellow oil. Silica chromatography elutes 0.4 g of the expected compound with stereochemistry (E, Z) as a yellow oil, n _D = 1.5251 (20 ° C).

Example 8

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

In a similar manner to that described in Example 2, 130 mg of methyl (E, Z) -2- (2- {1- [1- (phenyl) ethyloxyimino] ethyloxymethyl} phenyl) -4,4,4-trifluorobut-2- The enoate isomerized by boiling in toluene in the presence of acetic acid. Silica chromatography yields 70 mg of the expected compound with stereochemistry (E, E) as a yellow oil, n _D = 1.5107 (26 ° C).

Example 9

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

Stage 1

Preparation of methyl 2-bromo-2-phenylpropanoate

To 9.58 g of methyl 2-phenylpropanoate dissolved in 120 ml of carbon tetrachloride was added 10.7 g of N-bromosuccinimide and 0.1 g of benzoyl peroxide, and the reaction mixture was refluxed for 4 hours. After cooling, the succinimide is filtered off and the organic phase is washed with 0.1 N sodium thiosulphate and water and dried. Evaporation of the solvent yielded 13.5 g of an orange-colored oil which was distilled in a round-bottomed flask (boiling point 175 ° C at 666 Pa) to give 12.5 g of the expected compound as a colorless liquid, n _D 1 1, 5478 (19'C).

Stage 2

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

2.43 g of sodium methoxide are added in portions to a solution of 12.16 g of methyl 2-bromo-2-phenylpropanoate obtained in the preceding step and 3.75 g of acetohydroxamic acid in 60 ml of anhydrous methanol heated to 40 ° C. The reaction mixture was heated at 40 ° C for 8 hours. After evaporation of the methanol, the residue is taken up in 50 ml of water, re-extracted with ethyl acetate and dried. Evaporation of the solvents gave 12 g of a colorless oil which crystallized gradually. The solid is recrystallized from 100 ml of pentane / chloroform 4/1 to give 8.7 g of the expected compound as a white solid, m.p. 94 ° C.

Stage 3

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

5.7 g of the N- [1- (methoxycarbonyl) -1- (phenyl) ethyloxy] acetamide obtained in the previous step are dissolved in 50 ml of anhydrous acetonitrile. 6.87 g of methyl (E) -2-methoxyimino-2- [2- (bromomethyl) phenyl] acetate and 9.38 g of cesium carbonate are gradually added and the reaction mixture is refluxed for 4 hours. After cooling, the cesium salts are filtered off and the filtrate is concentrated to give 12 g of a brown oil. 4.5 g of the expected compound with stereochemistry (E, Z) are isolated by chromatography on silica as a white solid, m.p. 108 [deg.] C.

Stage 4

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

3.5 g of methyl- (E, Z) -2-methoxyimino-2- (2- {1- [1- (methoxy53 carbonyl) -1- (phenyl) ethyloxyimino] ethyloxymethyl) isomerized in a manner similar to that described in Example 2 phenyl) acetate by boiling in toluene in the presence of acetic acid. Recrystallization of the crude solid from diisopropyl ether isolated 3.2 g of the expected compound with stereochemistry (E, E) as a white solid, m.p. 117 ° C.

I

Stage 5

Preparation of (E, E) -2-methoxyimino-N-methyl-2- (2- {1- [1- (methoxycarbonyl) -1- (phenyl) ethyloxyimino] ethyloxymethyl} phenyl) acetamide ml 40% wt. of methylamine in water is added to 3.2 g of methyl (E, E) -2-methoxyimino-2- (2- {1- [1- (methoxycarbonyl) -1- (phenyl) ethyloxyimino] ethyloxymethyl) phenyl) acetate obtained in the previous step dissolved in 70 ml of methanol and stirred vigorously at 20 ° C for 4 hours, the methanol is evaporated and the residue is taken up in 50 ml of ethyl acetate, washed with water and dried. Evaporation of the solvents gave 3.33 g of the expected compound with stereochemistry (E, E) ¹ as a colorless oil, n _D = 1.5390 (19 ° C).

Stage 6

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

0.16 g of 60% sodium hydride is added to 0.88 g of (E, E) -2-methoxyimino-N-methyl-2- (2- {1- [1- (methoxycarbonyl) -1- (phenyl) ethyloxyimino] (ethyloxymethyl) phenyl) acetamide obtained in the previous step dissolved in 20 ml of anhydrous N-methylpyrrolidone. The reaction mixture was cooled to 0 ° C and methylamine gas was introduced over 30 minutes. The reaction mixture was stirred at 0 ° C for 3 hours and then poured into 100 mL of water. The pH is adjusted to 6 by addition of 1 N hydrochloric acid and the aqueous phase is reextracted with ethyl acetate, washed with water and dried. Evaporation of the solvents afforded 1.0 g of a colorless oil. Purification by silica chromatography gives 0.15 g of the expected compound with stereochemistry (E, E) as a colorless oil which crystallizes gradually. Melting point 152 ^e C.

Example 10

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

1.54 g of N- [1- (methoxycarbonyl) -1- (phenyl) ethyloxy] acetamide obtained according to Step 2 in Example 9 were dissolved in 20 ml of anhydrous acetonitrile. 2.1 g of methyl (E) -2- [2- (bromomethyl) phenyl] -4,4,4-trifluorobut-2-enoate obtained according to step 3 in Example 7 and 2.33 g of cesium carbonate are added successively and the reaction mixture is maintained at 50 ° C for 7 hours. After cooling, the cesium salts were filtered off and the reaction mixture was concentrated to give 3.2 g of a yellow oil. Chromatography on silica is isolated 1.5 g of the expected compound with the stereochemistry (E, Z) in the "I, a yellow oil, _Rf = 0.19 (3/1 heptane / ethyl acetate).

Example 11 ₍

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

In a similar manner to that described in Example 2, 1.15 g of methyl- (E, Z) -2- (2- {1- [1- (methoxycarbonyl) -1- (phenyl) ethyloxyimino] -ethyloxymethyl} phenyl) -4 The isomerization of 4,4,4-trifluorobut-2-enoate is by boiling in toluene in the presence of acetic acid. Recrystallization of the crude solid from diisopropyl ether isolated 0.85 g of the expected compound with stereochemistry (E, E) as a white solid, m.p. 82 ° C.

Example 12

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

1.9 g of N- [1- (methoxycarbonyl) -1- (phenyl) ethyloxy] acetamide obtained according to Step 2 in Example 9 were dissolved in 20 ml of anhydrous acetonitrile. 2.39 g of 4- [2- (bromomethyl) phenyl] -2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one and 3.13 g are gradually added. cesium carbonate and the reaction mixture was heated at reflux for 2 hours. After cooling, the salts were filtered off and washed with acetonitrile and the organic fraction was concentrated to give 4.4 g of a yellow oil. Chromatography on silica afforded 2.21 g of the expected compound with stereochemistry (Z) as a yellow oil which crystallized gradually. Melting point 110 ° C.

Example 13

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

2.07 g of (Z) -2,4-dihydro-5-methoxy-2-methyl-4- (2- {1- [1- (methoxycarbonyl) -1- (phenyl) ethyloxyimino] ethyloxymethyl} phenyl) -3H The 1,2,2-triazol-3-one is dissolved in 10 ml of anhydrous toluene. 0.5 ml of acetic acid is added and the reaction mixture is heated to reflux for 52 hours, irradiating with ultraviolet light. The reaction mixture was diluted with 20 mL of toluene, washed with water, dried and concentrated to give 2 g of a yellow oil. Chromatography on silica yields 0.17 g of the expected compound with stereochemistry (E) as a pale yellow oil which crystallizes gradually. Melting point 110 ° C.

Example 14

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

Stage 1

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

6.5 g of N- [1- (phenyl) ethyloxy] acetamide are dissolved in 150 ml of anhydrous acetonitrile. 8.8 g of methyl N- [2- (bromomethyl) phenyl] carbamate and 14.1 g of cesium carbonate are added sequentially and the reaction mixture is refluxed for 2 hours. After cooling, the salts are filtered off, washed with acetonitrile and the filtrate is concentrated to give 10 g of an orange-colored oil. Chromatography on silica yields 1.0 g of the expected compound with stereochemistry (E) as a yellow oil, n _D = 1.5571 (22 ° C).

Stage 2

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

To 1.0 g of (E) -N-methoxycarbonyl-2- {1- [1- (phenyl) ethyloxyimino] -ethyloxymethyl} aniline obtained in the previous step dissolved in 20 ml of anhydrous tetrahydrofuran is added 0.33 g of potassium tert-butoxide. . The reaction mixture is stirred at 20 ° C for 15 minutes, 0.32 ml of bromomethyl methyl ether is added and the mixture is stirred at 20 ° C for 30 minutes. The reaction mixture was poured into 100 ml of brine, re-extracted with ethyl acetate, washed with water and dried. Evaporation of the solvents gave a yellow oil (1.2 g). Chromatography on silica afforded 1.0 g of the expected compound with stereochemistry (E) as a yellow oil, n _D = 1.5402 (12 ° C).

Example 15

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

To 0.88 g of (E, E) -2-methoxyimino-N-methyl-2- (2- {1- [1- (methoxycarbonyl) -1- (phenyl) ethyloxyimino] ethyloxymethyl} phenyl) acetamide obtained according to Step 5 in Example 9 dissolved in 20 ml of anhydrous N-methylpyrrolidone was added 0.27 g of sodium amide. The reaction mixture is heated at 55 ° C for 3 hours and then poured into 100 ml of water. The pH was adjusted to 7 by addition of 1 N hydrochloric acid and the aqueous phase was re-extracted with ethyl acetate, washed with water and dried over magnesium sulfate. Evaporation of the solvents afforded 0.6 g of a yellow oil. Trituration with a minimum amount of diisopropyl ether gave 0.31 g of the expected compound as a white solid, m.p. 144 ° C.

Example 16

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

Stage 1

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

1.1 g of N- [1- (phenyl) ethyloxy] acetamide are dissolved in 50 ml of anhydrous acetonitrile. 1.6 g of methyl (E) -2- [2- (bromomethyl) phenyl] but-2-enoate prepared according to U.S. Pat. No. 5,416,068 and 2.11 g of cesium carbonate are added successively and the reaction mixture is heated to boiling point. under reflux for 4 hours. After cooling, the reaction mixture was filtered through Celite and the Celite was washed with acetonitrile. After concentration and chromatography on silica, 1.0 g of the expected compound with stereochemistry (E, Z) is obtained in the form of a yellow oil. R f = 0.67 (1/1 heptane / ethyl acetate).

Stage 2

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

In a similar manner to that described in Example 2, 1.0 g of methyl- (E, Z) -2- (2- (1- (1- (phenyl) ethyloxyimino) ethyloxymethyl) phenyl) but58

The 2-enoate isomerized by boiling in toluene in the presence of acetic acid. Evaporation of the solvent gave 1.0 g of the expected compound with stereochemistry (E, E) as a pale yellow syrup, n _D =

1.5460 (24 ° C).

Example BI

In vivo test for Plasmopara viticola

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

- active substance

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

- acetone

- made up to 60 ml with water.

mg

0.3 ml 5 ml

The desired aqueous suspension is then diluted with water to a concentration in parts per million.

so that it is obtained

The vine cuttings (Vitis vinifera), Chardonay variety, are cultivated in pots. When these plants are 2 months old (stage 8 to 10 leaves, height 10 to 15 cm), they are sprayed with said aqueous suspension.

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

After drying for 24 hours, each plant is contaminated by spraying with an aqueous spore suspension of Plasmopara viticola obtained from a 4-5 day old culture and then placed in suspension at 100,000 units per cm ³ .

The contaminated plants are then incubated for 2 days at about 18 ° C in a saturated atmosphere and then for 5 days at about 20-22 ° C at 90-100% humidity.

Evaluation is carried out 7 days after contamination by comparison with control plants.

Under these conditions, good (at least 75%) or complete protection was observed at a dose of 5 ppm for the following compounds: 1, 4, 5 and 9.

Example B2

In vivo test for Puccinia recondita (wheat rust)

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

- active substance

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

- acetone

I

- made up to 60 ml with water.

mg

0.3 ml 5 ml

The desired aqueous suspension is then diluted with water to a concentration in parts per million.

so that it is obtained

Wheat (Scipion variety) in pots sown on a 50/50 polan peat substrate and maintained at 12 ° C is treated at stage 1 of the leaf (10 cm high) by spraying with said aqueous suspension.

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

solution,

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

The contaminated wheat plants are then incubated for 24 hours at about 20 ° C in a saturated atmosphere and then for 7-14 days at 60% relative humidity.

Evaluation is performed between day 8 and day 15 after contamination by comparison with control plants.

Under these conditions, good (at least 75 =) or complete protection was observed at a dose of 40 ppm for the following compounds: 1, 2, 3, 4, 5, 6, 9, 14, 15 and 16.

Example B3

In vivo test for Septoria tritici (wheat septoriosis)

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

- the active substance is 60 mg

- Tween 80 surfactant (polyoxyethylene sorbitan oleate derivative) diluted to 10% in water 0,3 ml

- acetone 5 ml

- made up to 60 ml with water.

The aqueous suspension is then diluted with water to give the desired concentration in ppm (parts per million).

Wheat (variety Scipion) in pots sown on a 50/50 pocolane peat substrate and maintained at 12 ° C is treated at stage 1 of the leaf (10 cm high) by spraying with said aqueous suspension.

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

After 24 hours, each plant is contaminated by spraying with an aqueous spore suspension (500,000 spores per cm ³ ) of Septoria tritici. Spores are obtained from a 7 day old culture.

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

Evaluation is carried out 21 days after contamination by comparison with control plants.

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

Example B4

In vivo test for Septoria nodorum (wheat septoriosis)

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

60 mg surfactant Tween 80 (polyoxyethylene derivative diluted to 10% in water)

- acetone

- made up to 60 ml with water.

sorbitan oleate)

0.3 ml 5 ml

The desired aqueous suspension is then diluted with water to a concentration in parts per million.

so that it is obtained

Wheat (variety Scipion) in pots sown on a 50/50 pocolane peat substrate and maintained at 12 ° C is treated at stage 1 of the leaf (10 cm high) by spraying with said aqueous suspension.

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

After 24 hours, each plant is contaminated by spraying with an aqueous spore suspension (500,000 spores per cm ³ ) of Septoria nodorum. Spores are obtained from a 7 day old culture.

The contaminated wheat plants are incubated for 72 hours at about 20 ° C in a humid atmosphere and then for 14 days at 90% relative humidity.

Evaluation is carried out 15 days after contamination by comparison with control plants.

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

Example B5

In vivo test for Erisyphe graminis f sp tritici

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

- active substance

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

- acetone

- made up to 60 ml with water.

mg

0.3 ml 5 ml

This desired aqueous suspension is then diluted with water to a concentration in parts per million.

so that it is obtained

Wheat (Audace variety) in pots sown on 50/50 · pocolane peat substrate and maintained at 12 ° C is treated at stage 1 of the leaf (10 cm high) by spraying with the said aqueous suspension.

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

After 24 hours, each wheat plant is contaminated by spraying with spores of Erisyphe graminis by spraying the infected plants.

Evaluation is carried out 7-14 days after contamination by comparison with control plants.

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

Example B6

I

In vivo test for Erisyphe graminis fsp hordei (barley powdery mildew)

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

- the active substance is 60 mg

- surfactant Tween 80 sorbitol oleate)

0.3 ml of 5 ml is then diluted with water to obtain (parts per million).

in pots sown at 50/50 maintained at 12 ° C with 10 cm) by spraying with said aqueous suspension.

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

After 24 hours, barley plants are sprayed with spores of Erisyphe graminis by spraying with the infected plants.

Evaluation is carried out 7-14 days after contamination by comparison with control plants.

Under these conditions, good (at least 75 -) or complete protection was observed at a dose of 40 ppm for the following compounds: 1, 2, 4, 5, 14 and 16.

(polyoxyethylenated derivative diluted to 10% in water

- acetone

- made up to 60 ml with water.

This aqueous suspension was the desired concentration in ppm

Barley (Variety Express) pocolán peat substrate and treated in stage 1 leaf (height

Example B7

In vivo test for Pyrenophora teres (brown spot of barley)

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

- active substance

- Tween 80 surfactant (polyoxyethylene sorbitan oleate derivative) diluted to 10% in water - acetone mg

0.3 ml 5 ml

- made up to 60 ml with water.

The aqueous suspension is then diluted with water to give the desired concentration in ppm (parts per million).

Barley (variety Express), seeded in pots pocolán on 50/50 peat substrate and maintained at 12 C, ^e 'I, treated at the 1-(10 cm tall) by spraying with the aqueous suspension.

Plants used as controls are treated with an aqueous solution containing no active ingredient.

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

The contaminated barley plants are incubated for 24 hours at about 20 ^e C and saturated atmospheric humidity, and then for 7 to 14 days at a relative humidity of 80%.

Evaluation is performed between day 8 and day 15 after contamination by comparison with control plants.

Under these conditions, good (at least 75%) or complete protection at 40 ppm was observed for the following compounds: 1, 2, 4, 5, 6, 7, 9, 10, 11, 14, 15 and 16.

Claims (29)

Hydroxime and hydrazone derivatives of the general formula I wherein G is selected from groups G ¹ to G ⁹ Q ² R ⁵ CL / N. .R ⁴ W ' Q ² R ⁵ S., R 4 (chj ^ γ Q 2 ^{R 7 X} Y ⁴ Q2 b R8y> IN ^R1 W 9 Q ² Q ⁴ -N _xo R9 • where G ⁷ G ⁸ n is C or 1, Q ¹ is nitrogen or CH, Q ² is an oxygen atom or a sulfur atom, Q ³ is an oxygen atom or a sulfur atom, Q ⁴ is nitrogen or CR ¹¹ , Q ⁵ is an oxygen or sulfur atom or an NR ¹² group, Y is an oxygen or sulfur atom or an amino (NH) or oxyamino (ONH) group, W ¹ is an oxygen or sulfur atom or a sulfinyl (SO) or sulfonyl (SO2) group, W ² is O or NR ¹³ , p is 1 when W ² is O, p is 0 or 1 when W ² is NR ¹³ , X ¹ , X ² and X ³ are each independently hydrogen, halogen or hydroxyl, mercapto, nitro, thiocyanato, azido, cyano or pentafluorosulfonyl, lower alkyl, lower haloalkyl, alkoxy, haloalkoxy, halo, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkoxyalkyl, haloalkylsulfonyl, alkoxyalkyl, haloalkylsulfonyl, alkoxyalkyl, haloalkylsulfonyl, alkoxyalkyl , alkynyloxy, alkenylthio or alkynylthio, or amino, N-alkylamino, N, N-dialkylamino, acylamino, aminoalky an alkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl or acylaminoalkyl group, or a carboxyl, carbamoyl, N-alkylcarbamoyl, Ν, Ν-dialkylcarbamoyl or lower alkoxycarbamoyl group, or an acyl group, X ⁴ is a hydrogen atom, a halogen atom or a lower alkyl group, a lower haloalkyl group, an alkoxy group or a haloalkoxy group, or a cyano or nitro group, R ¹ and R ² are independently hydrogen, lower alkyl or lower haloalkyl, lower cycloalkyl or lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl or cyanoalkyl, or », cyano; , carboxyl, carbamoyl, N-alkylcarbamoyl or Ν, Ν-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl alkyl or alkylthiothiocarbonyl, alkylthiocarbonyl, -dialkylaminoalkyl or acylaminoalkyl, R ¹ and R ² together may form a divalent radical such as an alkylene group optionally substituted by one or more halogen atoms or optionally substituted by one or more lower alkyl groups, R ³ is hydrogen, lower alkyl or lower haloalkyl, lower cycloalkyl or lower halocycloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, cyano, thio, thio, acyl, carboxyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkoxythiocarbonyl, haloalkoxythiocarbonyl or alkylthiothiocarbonyl, or alkenyl, alkynyl, N, N-dialkylamino, alebo, dialkylamino, or prípadne-dialkylamino; a group or a benzyl group, R ⁴ is lower alkyl or lower haloalkyl, lower cycloalkyl, lower halocycloalkyl or alkoxyalkyl, or alkoxy, haloalkoxy, alkylthio, alkylamino or dialkylamino, R ⁵ or R ⁶ are independently lower alkyl or lower haloalkyl; R ⁷ is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl, R ⁸ is lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, alkynyl, formyl or acyl, R ⁹ is a hydrogen atom, a lower alkyl group or a lower haloalkyl group or a lower cycloalkyl group, a lower halocycloalkyl group, an alkoxyalkyl group, a haloalkoxyalkyl group, an alkenyl group or an alkynyl group, R ¹⁰ is halogen, lower alkyl or lower haloalkyl, lower cycloalkyl or lower halocycloalkyl or alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfonyl or haloalkylsulfonyl, alkylsulfonyl, alkylsulfonyl R ( ¹¹⁾ and R ( ¹²⁾ independently of one another are hydrogen, lower alkyl or lower haloalkyl or lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl or alkynyl, R ¹³ is hydrogen, lower alkyl or lower haloalkyl, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl or haloalkylthioalkyl, optionally substituted allyl I, optionally substituted propargyl or optionally substituted benzyl, or acyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxythiocarbonyl or alkylthiothiocarbonyl, or alkylsulfonyl; a substituted arylsulfonyl group, provided that when W ¹ is a sulfur atom and W ² is a nitrogen atom, then R ³ is not an alkylthio group, when W ² and Q ² are an oxygen atom, and when G is a group G ¹ then R ⁵ is other than alkyl and R ⁴ is other than alkoxy, alkylamino or dialkylamino and R ³ is other than hydrogen, alkyl or haloalkyl, cycloalkyl or halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, cyanoalkyl , alkenyl, alkynyl or dialkylaminoalkyl or optionally substituted phenyl or benzyl, wherein the term lower alkyl means a radical of 1 to 6 carbon atoms, as well as salts and metal complexes and metal complexes of these compounds of formula I, such as defined. »· Compounds according to claim 1, wherein n is 0 or 1, p is 1 and / or Q ² is an oxygen atom, and / or Q ³ is an oxygen atom, and / or Q ⁴ is a nitrogen atom, and / or Q ⁵ is oxygen atom, W ¹ is an oxygen atom or a sulfur atom, W ² is an oxygen atom or an alkylamino, haloalkylamino, alkoxyalkylamino or allylamino group, Y is an oxygen atom. Compounds according to any one of the preceding claims, wherein X ¹ , X ² , X ^3, and X ⁴ are each independently hydrogen, lower alkyl, halogen or cyano, trifluoromethyl or methoxy. Compounds according to one of the preceding claims, wherein R ¹ and R ² are each independently hydrogen, lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyl, N-alkylaminoalkyl, Ν, ky-dialkylaminoalkyl, acylaminoalkyl, lower alkoxycarbonyl , N-alkylcarbamoyl or Ν, Ν-dialkylcarbamoyl, R ³ is hydrogen, lower alkyl, lower cycloalkyl, lower haloalkyl, or alkoxyalkyl, preferably methyl, ethyl, propyl, cyclopropyl or methoxymethyl. R ⁴ is lower alkyl, alkoxy, alkylamino or dialkylamino, preferably methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, methylamino or ethylamino, R ⁵ , R ⁶ , R ⁸ and R ⁹ are independently lower alkyl or lower haloalkyl, preferably methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl or propyl, R ⁷ is lower alkyl or lower haloalkyl, preferably methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl or propyl, or allyl or propargyl, R ¹⁰ is chloro, lower alkyl or lower haloalkyl, preferably methyl, or alkoxy or alkylthio, preferably methoxy or methylthio, R ¹¹ and R ¹² are independently lower alkyl, lower haloalkyl, alkoxyalkyl, allyl or propargyl, R ¹³ is hydrogen or lower alkyl, lower haloalkyl, alkoxyalkyl, haloalkoxyalkyl, allyl, propargyl or benzyl. Compounds according to one of the preceding claims, W ¹ is an oxygen atom, R ¹ is hydrogen or methyl, R ² is hydrogen or lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylamino72 alkyl group, a lower alkoxycarbonyl group or a lower N, N-dialkylcarbamoyl. Compounds according to one of the preceding claims, wherein W ¹ and W ² are in the trans position with respect to the double bond -C (R ³ ) = N-. Fungicidal compositions, characterized in that they contain an effective amount of at least one active substance according to one of the preceding claims. Fungicidal compositions according to claim 7, characterized in that they contain, in addition to the active compound of the formula I, agriculturally acceptable solid or liquid carriers and / or surface-active substances which are also agriculturally acceptable. Fungicidal compositions according to claim 7 or 8, characterized in that they contain from 0.05 to 95% by weight of active ingredient. • 10. A method of preventing or treating phytopathogenic fungi in crops comprising:. apply an agriculturally effective and non-phytotoxic amount of at least one active ingredient or fungicidal composition comprising the active ingredient of the formula I as defined in claim 1 to plant seeds or plant leaves or to the soil where the plants grow or need to grow. A method for the preventive or therapeutic treatment of a variety of plant products as well as plants derived therefrom against fungal diseases, characterized in that the products are coated with an effective and non-phytotoxic dose of a compound or composition according to one of the preceding claims. Method according to claim 11, characterized in that rice, cereals, fruit trees, vines or beetroot are treated. Method according to claim 11 or 12, characterized in that wheat or barley is treated. Method according to claim 11, characterized in that cereal seed, potato sowing, cotton seed, pea seed, rape seed, corn or flax seed or forest tree seed are treated. Method according to one of the preceding claims, characterized in that a dose of active compound of between 20 and 200 g of active compound per 100 kg of seed, preferably between 3 and 150 g per 100 kg, is applied in the case of seed treatment. Method according to one of Claims 10 to 14, characterized in that a dose of active substance of between 10 and 800 g of active substance per hectare, preferably between 50 and 300 g of active substance per hectare, is applied in the case of leaf treatment. Process for the preparation of compounds according to claims 1 to 6, characterized in that a compound of the formula IIA is reacted wherein G is one of the groups G ¹ to G ⁹ , wherein the groups G ¹ to G ⁹ are as defined in claims 1 to 6 X ⁴ is as defined in claims 1 to 6; V ¹ is halogen (preferably chlorine or bromine), alkylsulfonate or haloalkylsulfonate. group IIIA (IIIA) (preferably methylsulfonate or trifluoromethylsulfonate group) or arylsulfonate group (preferably 4-methylphenylsulfonate group), with a compound of formula HR ¹ r'V'-H R 3 R 2 wherein W ¹ , W ² , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² , X ³ and p are as defined in claims 1 to 6, wherein the benzyl halide derivatives of formula IIA wherein V ¹ is a halogen atom (preferably a chlorine or bromine atom) are prepared halogenating compounds of formula IIB W ¹ -H (IIB) wherein G is one of G ¹ to G ⁹ , wherein G ¹ to G ⁷ are as defined in claims 1 to 6 and R ⁴ is alkylamino or dialkylamino, G ⁸ and G ⁹ are as defined X ¹ is as defined in any one of claims 1 to 6 and W ¹ is an oxygen atom, a halogenating agent such as thionyl chloride, phosphorus oxychloride or phosphorus tribromide, or a lithium halide / mesyl halide / collidine reagent, or - cleavage of a compound of formula IIC (IIC) G wherein G is one of G ¹ to G ⁹ , wherein G ¹ to G ⁷ are as defined in claims 1 to 6 and R ⁴ is an alkylamino or dialkylamino group, G ⁸ and G ⁹ are as defined in claims 1 to 6 X ⁴ is as defined in claims 1 to 6, W ¹ is an oxygen atom and P is a hydroxy protecting group such as an ester, preferably an acetic or benzoic acid ester, or an ether, preferably methyl ether, methoxymethyl ether, phenylether or benzyl ether A Lewis acid such as boron tribromide or anhydrous acid such as hydrogen chloride. Compounds of formula IIIA (IIIA) wherein W ¹ , W ² , R ¹ , R ² , R ³ , X ¹ , X ² , X ³ and p are as defined in claims 1 to 6, except for compounds wherein W ² is -NR ¹³ and compounds wherein R ³ is phenyl, benzyl, alkoxy or alkylthio. A process for the preparation of compounds according to claims 1 to 6, wherein G is one of G ¹ to G ⁹ , wherein G ¹ to G ⁷ are as defined in claims 1 to 6 and R ⁴ is amino, alkylamino or dialkylamino, groups G ⁸ and G ⁹ are as defined in claims 1 to 6 and X ⁴ is as defined in claims 1 to 6, characterized in that a compound of formula IIB (IIB) is reacted wherein G is one of G ¹ to G ⁹ wherein G ¹ to G ⁷ are as defined in claims 1 to 6 and R ⁴ is an amino, alkylamino or dialkylamino group, G ⁸ and G ⁹ are as defined in claims 1 to 6, X ⁴ is as defined in the claims 1 to 6 and W ¹ is an oxygen or sulfur atom with a compound of formula IIIB (IIIB) wherein W ² , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² , X ³ and p are as defined in the claims 1 to 6, U ³ is a halogen atom, preferably a chlorine atom, wherein the double bond in the group U ³ -C (R ³ ) = NW ² - has the stereochemistry (E) or (Z). A process for preparing compounds according to claims 1 to 6, wherein G is G ³ , Q ² is oxygen, R ⁴ is alkoxy, alkylamino or dialkylamino, the other substituents are as defined in claims 1 to 6 and R ⁶ is lower alkyl or a lower haloalkyl group, characterized in that a compound of formula IX (IX) wherein R ⁴ is alkoxy, alkylamino or dialkylamino and the other substituents are as defined in claims 1 to 6, is reacted with a Wittig-Horner reagent of formula XA R ⁶ -CH 2 -P (= O) (OR ^b ) 2 (XA) wherein R ⁶ is lower alkyl or lower haloalkyl and R ^b is lower alkyl, phenyl or benzyl, or alternatively with a Wittig reagent of formula XB R ⁶ -CH 2 -P (R ^d ) 3 ⁺ Hal (XB) While R ⁶ is a lower alkyl group or a lower haloalkyl group, R ^d is an optionally substituted phenyl group and Hal 1 is a halide ion. A process for preparing compounds according to claims 1 to 6, wherein G is G ¹ or G ² , Q ¹ is nitrogen or CH, Q ² is oxygen, R ⁴ is alkoxy, alkylamino or dialkylamino, the other substituents being as defined above in claims 1 to 6 and R ⁵ is a lower haloalkyl group, characterized in that a compound of formula XI is reacted wherein T is an oxygen atom and M is an alkali or alkaline earth metal ion, Q ¹ is a nitrogen atom or a CH group, R ⁴ is alkoxy, alkylamino or dialkylamino, W ¹ , W ² , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² , X ³ , X ⁴ and p are as defined in claims 1 to 6 with halogenated a compound of formula CH _q (Hal) _{4 q} , wherein q is 1 or 2 and Hal is a halogen atom, wherein the halogen atoms may be the same or different and at least one of them is chlorine or bromine. A process for the preparation of compounds according to claims 1 to 6, wherein G is a G ⁴ group, wherein n is 1, Q ² is an oxygen atom, R ⁴ is an alkoxy, alkylamino or dialkylamino group and the other substituents are as defined in claims 1 to 6; by reacting a compound of formula XIIA (XIIA) wherein R ⁴ is alkoxy, alkylamino or dialkylamino and the other substituents are as defined in claims 1 to 6 with a compound of formula XIII In ¹ OR ⁵ (XIII) wherein V ¹ is halogen (preferably chlorine or bromine) and R ⁵ is as defined in claims 1 to 6. A process for the preparation of compounds according to claims 1 to 6, wherein G is G ¹ to G ⁷ and R ⁴ is alkylamino or dialkylamino, the other substituents being as defined in claims 1 to 6, characterized in that a compound of formula I is reacted Wherein G is G ¹ to G ⁷ and R ⁴ is alkoxy or alkylthio and the other substituents are as defined in claims 1 to 6, with alkylamine or dialkylamine. A process for the preparation of compounds according to claims 1 to 6, wherein W ¹ is a sulfoxide group (SO) or a sulfone group (SO 2) and G is one of G ¹ , G ³ , G ⁴ and G ⁶ to G ⁹ , Q ² and Q ³ are an oxygen atom, the other substituents are as defined in claims 1 to 6, characterized in that a compound of formula I is oxidized wherein W ¹ is a sulfur atom, G is one of G ¹ , G ³ , G ⁴ and G ⁶ to G ⁹ , Q ² and Q ³ are oxygen, the other substituents being as defined in claims 1 to 6, using one or more equivalents of the oxidizing agent. A process for the preparation of compounds according to claims 1 to 6, wherein the groups W ¹ , W ² , R ¹ , R ² , R ³ , X ¹ , X ² , X ³ , X ⁴ and p are as defined in claims 1 to 6 and G. is a group G ⁷ , characterized in that the intermediate of formula IIIA is reacted HR ¹ - W ² - () _P R 3 R 2 (IIIA) wherein the groups W ¹ , W ² , R ¹ , R ² , R ³ , R ¹³ , X ¹ , x ² , X ³ and p have the meaning given in claims 1 to 6, with a compound of formula IIA (IIA) wherein G is G ⁷ , X ⁴ is as defined in claims 1 to 6 and V ¹ is a halogen atom, preferably a chlorine or bromine atom. A process for the preparation of compounds according to claims 1 to 6, wherein the groups W ¹ , W ² , R ¹ , R ² , R ³ , X ¹ , X ² , X ³ , X ⁴ and p are as defined in claims 1 to 6 and G. is a group G ³ and R ⁶ is a trifluoromethyl group characterized by reacting a compound of formula IIIA with a compound of formula IIA (IIIA) X ³ and p are as defined in (IIA) wherein G is G ³ , R ⁶ is trifluoromethyl, X ⁴ , R ⁴ and Q ² are as defined in claims 1 to 6 and V ¹ is halogen, preferably chlorine or bromine. A process for the preparation of compounds of formula IIIA according to claim 18, wherein W ² is an oxygen atom and p is 1, W ¹ , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² and X ³ have meaning stated in claims 1 to 6, mark the task clothes m that is allowed to react general compound of formula IV R ¹ / - ' , .X ^{1 2} W ² - -ο _Ρ - <Π ^ ^x2 (IV) R2 '- ^ _X 3 wherein W ² , R ¹ , R ² , R ¹³ , X ¹ , X ² , X ³ and p are as defined in claims 1 to 6, with a compound of formula V (V) wherein W ¹ and R ³ are as defined in the claims 1 to 6, U ¹ is halogen (preferably chlorine or bromine) or hydroxyl, lower alkoxy or benzyloxy, lower alkylthio or amino, or -O (C = O) R ^a , where R ^a has the same meaning as R 1 ³ given in claims 1 to 6, which may be the same or different from ^R3, preferably a halogen atom, a compound of formula V is thus an acid halide. A process for the preparation of compounds of formula (IIIA) according to claim 18, wherein W ² is an oxygen atom and p is 1, or hydrazone Acids of formula IIIA wherein W ² is NR ¹³ and p is 1, *** W ¹ , R ¹ , R ² , R ³ , R ¹³ , X ¹ , X ² and X ³ are as defined in the claims 1 to 6, characterized in that a compound of formula VI (VI) is reacted wherein R ¹ , R ² , X ¹ , X ² and X ³ are as defined in claims 1 to 6 and U ^2; is halogen (preferably chlorine or bromine) or 'alkyl sulfonate (preferably methanesulfonate radical ^or: trifluoro- methylsulfonate group), a hydroxamic acid derivative J, wherein W ² is O, or is a derivative of hydrazone J, wherein W ² is NR ¹³ , R ³ a R ¹³ are as defined in claims 1 to 6 of formula VII W ² —H (VII) A process for the preparation of compounds of formula IIIA according to claim 18, wherein W ¹ is a sulfur atom and W ² is an oxygen atom, or thiohydrazonic acids of formula IIIA according to claim 18 where W ¹ is a sulfur atom and W ² is a group NR ^13, R ^1, R ^2, R ³ , R ¹³ , X ¹ X ² , X ³ and p have the meaning stated in the claims 1 to 6, v y denoted by t that are thionizing hydroxamic an acid of formula IIIA wherein W ¹ is an oxygen atom and W ² is an oxygen atom, or hydrazonic acids of formula IIIA wherein W ¹ is an oxygen atom and W ² is a group NR ¹³ , R ¹ , R ² , R ³ , R ¹³ X ¹ , X ² , X ³ and p are as defined in claims 1 to 6 using a thionating agent.