JP2002510678A - Fungicidal compounds containing hydroxyme or hydrazone groups - Google Patents

Abstract

(57) The present invention provides a compound represented by the general formula (I): Wherein G is a group G1-G9: And the other substituents are as defined in the description.) And compositions containing the same. The present invention also relates to a method for treating a plant using the above compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to new compounds containing a hydroxyme or hydrazone group, a process for their preparation, their use as fungicides, in particular in the form of fungicidal compositions, and crop plants using these compounds or compositions. The present invention relates to a method for controlling pathogenic fungi.

[0002] Many compounds having a bactericidal action are already known and widely used. For example, EP-A-046348 and EP-A-370629 describe, inter alia, fungicidal compounds having a hydroxyme or hydrazone function.

[0003] EP-A-02299694, WO-A-96 / 33164 and JP-090
No. 31048 also describes similar fungicidal compounds.

However, all of these compounds have disadvantages that are well known to users of such compounds. That is, it is a problem that is encountered when trying to combat diseases caused by fungi of plants, such as compounds having low activity, effective only against diseases caused by relatively weak fungi, low selectivity, toxicity, that is, ecological pollution.

In other words, known fungicidal compounds have low activity and / or a relatively narrow spectrum of activity. For example, users need to use multiple products (substances) to eradicate various fungal species that attack plants, but need to be familiar with their spectra and application rates exactly. Also, the use of multiple substances is contrary to cultivation treatment methods which today recommend that the application amount be as low as possible for environmental protection purposes.

Furthermore, the use of large amounts of fungicides and / or a plurality of different fungicides often results in harm to cultivated crops (fungicide toxicity).

[0007] When large amounts of fungicides are used in treating fungal diseases, bacterial species that are resistant to these substances may appear.

It is an object of the present invention to provide a new compound system with a broad spectrum of action against crop phytopathogenic fungi.

It is another object of the present invention to provide a new compound system which can solve certain problems and has a broad spectrum of action against phytopathogenic fungi in crops.

Another object of the present invention is to provide new compound systems which are active at low doses and have a broad spectrum of action against phytopathogenic fungi in crops.

Another object of the present invention is to provide a new compound system having a broad and improved action spectrum against cultivated phytopathogenic fungi.

Another object of the present invention is to provide an improved broad spectrum of action against phytopathogenic fungi on crops such as cereals, rice, fruit trees, forest trees, grapes, organic crops, vegetables, solanaceae and sugar beet. And to provide a new compound system.

Surprisingly, it has been found that these objects can be realized in whole or in part by compounds having a heterocyclic motif linked to a hydroxyme or hydrazone function as described in the present invention. .

The present invention provides a compound of the general formula (I)

[0015]

Embedded image A compound having a heterocyclic motif A bonded to a hydroxyme or hydrazone functional group, wherein G is selected from the following groups G1 to G9:

[0016]

Embedded image In each group, n represents 0 or 1, Q ₁ is a nitrogen atom or a CH group, Q ₂ is an oxygen or sulfur atom, Q ₃ is an oxygen or sulfur atom, Q ₄ is nitrogen or CR ₁₁ Q ₅ is an oxygen, sulfur atom or NR ₁₂ group; Y is an oxygen, sulfur atom or amino (NH) or oxyamino (ONH) group; W ₁ is an oxygen, sulfur atom or sulfinyl (SO ) Or sulfonyl (SO ₂ )
W ₂ is an oxygen atom or an NR ₁₃ group, p represents 0, 1 or 2, A is 5 to 10 atoms (1 to 4 of which are oxygen, sulfur or nitrogen atoms) Wherein each sulfur or nitrogen atom is optionally oxidized to the form of an N-oxide or sulfoxide group), and represents a mono- or bicyclic aromatic heterocyclic group having The heterocyclic group is bonded to a carbon atom which is substituted by R ₁ and R ₂ groups when p = 1 or p = 2, or W ₂ by a carbon atom or a nitrogen atom when p = 0. And optionally the heterocyclic group is 1 to 5 groups X ₁ and / or X ₂ and / or X ₄ and / or X ₅ , preferably 1 to 3 X ₁ and / or Substituted by X ₂ and / or X ₃ X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each independently a hydrogen atom, a halogen atom, or a hydroxyl, mercapto, nitro, thiocyanic acid, azide, cyano or pentafluorosulfonyl group, or lower. Alkyl, lower haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl, cyanoalkoxy, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl,
Alkylsulfonyl, haloalkylsulfonyl, alkoxysulfonyl, or lower cycloalkyl, lower halocycloalkyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio, or amino, N-alkylamino, N, N-dialkyl Amino, acylamino, aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, or acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxycarbonyl And the group X ₁ is optionally 5-7 with R ₁₃ when W ₂ is an NR ₁₃ group.
The members of the ring, if the case is p = 1 ring 5-7 membered together with _{R 1} or p = 2, may form a ring of 5 to 7 membered together with R _{'1, X 6} is A hydrogen atom, a halogen atom, or a lower alkyl, a lower haloalkyl, an alkoxy, a haloalkoxy, or a cyano or a nitro group, and R ₁ and R ₂ are each independently a hydrogen atom, a lower alkyl, a lower haloalkyl group, a lower cycloalkyl A lower halocycloalkyl group, an alkoxyalkyl, a haloalkoxyalkyl, an alkylthioalkyl, a haloalkylthioalkyl, a cyanoalkyl group, or a cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N
, N-dialkylcarbamoyl, lower alkoxycarbonyl, alkylthiocarbonyl, haloalkoxycarbonyl, alkylthiothiocarbonyl, or aminoalkyl, N-alkylaminoalkyl, N, N-dialkylaminoalkyl, acylaminoalkyl, or R ₁ and R ₂ together form a divalent group, such as an alkylene group optionally substituted by one or more halogen atoms, and optionally by one or more lower alkyl groups. R ₃ is a hydrogen atom, a lower alkyl, a lower haloalkyl group, a lower cycloalkyl,
Lower cycloalkyl group, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, haloalkylthioalkyl, cyanoalkyl group, or nitro, cyano, acyl, carboxy, carbamoyl, N-alkylcarbamoyl, N , N-Dialkylcarbamoyl, lower alkoxycarbonyl, 3-oxetanyloxycarbonyl, alkylthiocarbonyl, haloalkoxy-carbonyl, alkoxythiocarbonyl, haloalkoxy-thiocarbonyl, alkylthiothiocarbonyl groups, or alkenyl, alkynyl, N, N-dialkylamino , An N, N-dialkylaminoalkyl group, or an optionally substituted phenyl or benzyl group; R ₄ is lower alkyl, lower haloalkyl group, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl group, or alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino group, and R ₅ and R ₆ are each independently lower. R ₇ represents a lower alkyl, a lower haloalkyl, an alkoxyalkyl, a haloalkoxyalkyl, an alkenyl, or an alkynyl group; R ₈ represents a lower alkyl, a lower haloalkyl, an alkoxyalkyl, a haloalkoxyalkyl, an alkenyl, or an alkynyl; , formyl, or an acyl group, R ₉ is a hydrogen atom, a lower alkyl, a lower haloalkyl group, a lower cycloalkyl group, a lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, a Kenyir, an alkynyl group, R ₁₀ is a halogen atom, a lower alkyl group, lower haloalkyl group, lower cycloalkyl, lower halocycloalkyl group, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, R ₁₁ and R ₁₂ are each independently a hydrogen atom, a lower alkyl, a lower alkyl group, a lower cycloalkyl, a lower halocycloalkyl, an alkoxyalkyl, a haloalkoxyalkyl, an alkenyl, an alkynyl group, ₁₃ is a hydrogen atom, a lower alkyl, a lower haloalkyl group, lower cycloalkyl, lower halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkylthioalkyl, Haroaruki Thioalkyl groups, optionally substituted allyl groups, optionally substituted propargyl groups, optionally substituted benzyl groups, or acyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, lower alkoxy -Carbonyl, haloalkoxycarbonyl, alkoxythio-carbonyl, haloalkoxythiocarbonyl, alkylthiothiocarbonyl, or optionally substituted alkylsulfonyl, haloalkylsulfonyl, arylsulfonyl, Q ₂ and R ₄ are both halogen, A 5- to 7-atom ring having 2-3 oxygen and / or nitrogen atoms, optionally substituted by one or more groups such as lower alkyl or lower haloalkyl groups, and Such compounds of formula (I) may form salts, metal complexes and metalloid complexes.

In the case of compounds of the formula (I) in which A represents a monovalent or divalent aromatic heterocyclic radical as defined above, and the radicals X ₁ and / or X ₂ and / or X ₄ and / or at least one of X ₅ is hydroxy, mercapto, amino, N- alkylamino or is N- acylamino, the compound, the hydroxy, mercapto, amino, N- alkylamino or N- acylamino group protons It may be possible to accept a chemically equilibrated tautomeric form resulting from the transfer of Tautomeric forms of such compounds are included within the scope of the present invention. The invention may also include tautomeric forms of the compounds of formula (I) wherein p = 0 and W ₂ is NR ₁₃ and R ₁₃ is a hydrogen atom. Such tautomeric forms are particularly described in Elguero, C .; Martin, A .; R. Katrit
zky et P.K. Academic Press, New by Linda
The book "The customs," published in 1976 by York.
m of heterocycles, Advances in Hetero
cyclic Chemistry, Supplement 1 ", pages 1-4.

In the text of the present invention, the term “hydroxym group” refers to (O—C ＝ N—O
With a true “hydroxyme group” (with a linkage) (with an S—C ＝ N—O linkage)
Also included are thiohydroxyme groups. Similarly, the term “hydrazone group” has (O-
Included are true "hydrazone groups" (with C = NN linkages) as well as "thiohydrazone groups" (with SC = NN linkages).

For compounds of formula (I) where p = 2, the group — (CR₁R₂)₂Is a group-(CR ₁ R₂)-(CR '₁R '₂) (Where R '₁And R '₂Are each other
Standing and R₁And R₂Independently of R₁And R₂Has the same definition as ₁ , R₂) And (R '₁, R '₁) May be the same or different)
Should be included.

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

A halogen atom means a fluorine, chlorine, bromine or iodine atom; an adjective "lower" describes an organic group; a cycloalkyl where the adjective "lower" means 3 to 6 carbon atoms Means that, except for the group, this group has 1 to 6 carbon atoms,-the alkyl group may be straight-chain or branched,-the halogenated alkyl group may be one or May contain a plurality of identical or different halogen atoms, -acyl group means alkylcarbonyl, or cycloalkylcarbonyl, -adjective lower for acyl refers to the alkyl or cycloalkyl portion of this group, - alkylene group, m = 2 to 5 a is group _{(CH 2) m} - means.

When the amino group is disubstituted, two substituents are of 5 or 6 atoms,
It may form a saturated or unsaturated nitrogen-containing heterocyclic ring.-When the carbamoyl group is disubstituted, the two substituents are atoms 5 or 6
May form a saturated or unsaturated nitrogen-containing heterocycle-the expression "optionally substituted" as referring to organic groups applies to the various groups which constitute this group -The radicals and alkyl, alkenyl and alkynyl groups in the corresponding description and claims are, unless stated otherwise, straight-chain or branched and contain up to 6 carbon atoms.

Preferred embodiments of the invention are those in which the product of formula (I) further exhibits any of the following features, separately or in combination:

That is, n is 0, p is 0, 1 or 2, Q ₂ is an oxygen atom, and / or Q ₃ is an oxygen atom, and / or Q ₄ is nitrogen, and / or Or Q ₅ is an oxygen atom, W ₁ is an oxygen or sulfur atom, W ₂ is a hydrogen atom or an alkylamino, haloalkylamino, alkoxyalkylamino, allylamino group, Y is a hydrogen atom, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are each independently a hydrogen atom, a lower alkyl group, a halogen atom or a cyano, trifluoromethyl, methoxy or nitro group, and R ₁ and R ₂ are each independently hydrogen Atom, lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl, cyano, cyanoalkyl, N-alkylaminoalkyl , N, N- dialkylaminoalkyl, acyl aminoalkyl, lower alkoxycarbonyl, a N- alkylcarbamoyl or N, N- dialkylcarbamoyl group, R ₃ is a hydrogen atom, a lower alkyl, lower cycloalkyl, lower haloalkyl, alkoxyalkyl A group, preferably a methyl, ethyl, propyl, isopropyl, cyclopropyl or methoxymethyl group, wherein R ₄ is a lower alkyl, alkoxy, alkylamino, dialkylamino group, preferably methyl, ethyl, propyl, methoxy, ethoxy, methylamino Or an ethylamino group, R ₅ , R ₆ , R ₈ and R ₉ are each independently of the other, lower alkyl,
Lower haloalkyl group, preferably methyl, fluoromethyl, difluoromethyl,
R ₇ is a lower alkyl or lower haloalkyl group, preferably methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2,2 or a trifluoromethyl, ethyl, 2,2,2-trifluoroethyl or propyl group. , 2-trifluoroethyl, propyl, or allyl or propargyl; R ₁₀ is chlorine, lower alkyl, lower haloalkyl, preferably methyl;
An alkoxy, alkylthio group, preferably methoxy or methylthio, wherein R ₁₁ and R ₁₂ are each independently a lower alkyl, a lower haloalkyl,
R ₁₃ is a hydrogen atom, a lower alkyl, a lower haloalkyl, an alkoxyalkyl, an alkoxyalkyl, an allyl, a propargyl group,
A is a haloalkoxyalkyl, allyl, propargyl, benzyl group, wherein A is a group X ₁ and / or _{1 to} 5 derived from one of the following rings (i) to (v) by removal of a hydrogen atom: X ₂ and / or X ₃ and / or X ₄ and / or X ₅ and X ₆ , preferably from groups optionally substituted by _{1 to} 3 groups X ₁ and / or X ₂ and / or X ₃ Selected, a 5-membered ring described by formula (i)

[0025]

Embedded image Wherein B ¹ , B ² , B ³ , B ⁴ in each group of the list are selected from carbon, nitrogen, oxygen and sulfur, said list comprising 0-3 carbon atoms, 0-1 sulfur atom ,
A 6-membered ring comprising from 0 to 1 oxygen atom and from 0 to 4 nitrogen atoms, or-described by formula (ii)

[0026]

Embedded image Wherein D ¹ , D ² , D ³ , D ⁴ , D ⁵ in each group of the list are selected from carbon or nitrogen atoms, said list comprising 1 to 4 carbon atoms and 1 to 4 nitrogen atoms Or 6-membered fused bicyclic rings described by formula (iii)

[0027]

Embedded image Wherein E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ ,
E ⁸ is selected from carbon or nitrogen atoms, said list comprises from 4 to 7 carbon atoms and 1 to 4 nitrogen atoms, or - the formula (iv) is a 6-membered ring and one is described by 5-membered condensed ring

[0028]

Embedded image Wherein J ¹ , J ² , J ³ , J ⁴ , J ⁵ , J ⁶ in each group of the list are selected from carbon or nitrogen atoms, said list comprising 3 to 6 carbons and 0 to 3 And L ¹ , L ² , L ³ in each group of the list are selected from carbon, nitrogen, oxygen or sulfur atoms, said list comprising from 0 to 3 carbon atoms, from 0 to 1 It contains a sulfur atom, 0 to 1 oxygen atom and 0 to 3 nitrogen atom, and J ¹ , J ² , J ³ , J ⁴ , J ⁵ , J ⁶ , L ¹ , L ^{1 2} ,
L ³ is the list is selected to include from 3 to 8 carbon atoms, or - two rings fused to each 5-membered described by formula (v)

[0029]

Embedded image In the formula, M ¹ , M ² , M ³ in each group of the list represent carbon, nitrogen, oxygen or sulfur atom, and the list contains 0 to 3 carbon atoms, 0 to 1 sulfur atom, 0 to 1 One oxygen atom and 0-3 nitrogen atoms, wherein T ¹ , T ² , T ³ in each group of the list represent a carbon, nitrogen, oxygen or sulfur atom, said list comprising 0-3 Containing a carbon atom, 0-1 sulfur atom, 0-1 oxygen atom and 0-3 nitrogen atom, Z represents a carbon or nitrogen atom, M ¹ , M ² , M ³ , T ¹ , T ² and T ³ are selected such that the list contains 0 to 6 carbon atoms.

Naturally, in each of the above formulas (i), (ii), (iii), (iv) and (v), when the group representing a carbon or nitrogen atom is p = 1 or 2, Has a free valence of bonding A to a carbon atom substituted by R ₁ and R ₂ groups, or a group representing a carbon atom bonds A to W ₂ group when p = 0 Has free valence.

Among the various forms mentioned above, the following forms will be combined and selected separately.

W₁Is an oxygen atom, R₁Is a hydrogen atom or a methyl group, R₂Is a hydrogen atom or lower alkyl, cyano, cyanoalkyl, alkoxya
Alkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, lower
A is an N, N-dialkyl-carbamoyl group, A is optionally a group X 1 to 5 as defined above₁And / or X ₂ And / or X₃And / or X₄And / or X₅, Preferably one
3 groups X₁And / or X₂And / or X₃Complex replaced by
Represents a cyclic group and A is selected from the following list: -furanyl, pyrrolyl, thiophenyl, -pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl
, Isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadia
Zolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,
2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadia
Zolyl, 1,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4
, -Triazolyl, tetrazolyl, -pyridinyl, -pyrimidinyl, pyrazinyl, pyridazinyl, 1,2,3-triazinyl
1,2,4-triazinyl, 1,3,5-triazinyl, 1,2,3,4-te
Trazinyl, 1,2,3,5-tetrazinyl, 1,2,4,5-tetrazinyl, -benzimidazolyl, indazolyl, benzotriazolyl, benzoxa
Zolyl, 1,2-benzisoxazolyl, 2,1-benzisoxazolyl, ben
Zothiazolyl, 1,2, -benzoisothiazolyl, 2,1-benzoisothiazoly
1,2,3-benzoxaziazolyl, 1,2,5-benzoxaziazolyl,
1,2,3-benzothiadiazolyl, 1,2,5-benzothiadiazolyl, -quinolyl, isoquinoleyl-quinoxazolinyl, quinazolinyl, cinnolyle
Or fetalazyl, pteridinyl, benzotriazinyl, -1,5-naphthyridinyl, 1,6-naphthyridinyl, 1,7-naphthyl
Dinyl, 1,8-naphthyridinyl, -imidazo [2,1-b] thiazolyl, thieno [3,4-b] pyridinyl
, Purines, pyrrolo [1,2-b] thiazolyl.

Advantageously, compounds of the formula (I) which further have the following characteristics are preferred: That is, W ₁ is an oxygen atom, R ₁ is a hydrogen atom or a methyl group, a hydrogen atom or a lower alkyl, cyano, cyanoalkyl, alkoxyalkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, lower N, N
A dialkyl-carbamoyl group, wherein optionally 1 to 5 groups X ₁ and / or X ₂ and / or X ₃ and / or X ₄ and / or X ₅ , preferably 1 to 3 groups X the a that is substituted by ₁ and / or _{X 2} and / or _{X 3} is selected from one of the following heterocyclic rings, i.e., - pyridinyl, - pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 1 , 2,4-Triazinyl, -quinolynyl, isoquinolinyl, -furanyl, pyrrolyl, thiophenyl, -oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl.

Particular preference is given to compounds of the formula (I) which furthermore have the following characteristics: Sand
Chi, W₁Is an oxygen atom, R₁Is a hydrogen atom or a methyl group, R₂Is a hydrogen atom or lower alkyl, cyano, cyanoalkyl, alkoxya
Alkyl, N, N-dialkylaminoalkyl, lower alkoxycarbonyl, lower
An N, N-dialkyl-carbamoyl group; optionally 1 to 5 groups X₁And / or X₂And / or X₃and
/ Or X₄And / or X₅, Preferably 1 to 3 groups X₁And / or X ₂ And / or X₃A represents a pyridinyl group.

In the present invention, compounds of formula (I) which are of particular interest are those wherein G represents G ₁ , G ₂ or G ₃ , G ₁ is a preferred group G and other substituents are as defined above. A compound which is a substituent as described above.

Finally, the following compounds of formula (I) are preferred. That is,-(E, E) -2 (2- {1-[(2-pyridinyl) methyloxyimino]-
Methyl 1-cyclopropyl-methyloxymethyldiphenyl) -3-methoxypropenoate,-(E, E) -2 (2- {1- [1- (2-pyridinyl) propyloxyimino] 1-1-cyclo) Methyl propyl-methyloxymethyl {phenyl) -3-methoxypropenoate,-(E, E) -2 (2- {1- [1- (1-pyridinyl) propyloxyimino] propyloxomethyl} phenyl) -3 Methyl-methoxypropenoate, and methyl (-E, E) -2 (2- {1- [1- (2-pyridinyl) propyloxyimino] isobutyl-oxymethyl} phenyl) -3-methoxypropenoate, and And metal or metalloid complexes.

Even more particularly preferred compounds are those wherein the substituents W ₁ and W ₂ are double bonds -C
_(R 3) = is a compound in the trans position (see below) to the N-.

The compounds of the general formula (I) and optionally the intermediates which can be used as intermediates in the preparation processes according to the invention and which are defined in the description of these processes, are characterized by the double bond of the compound Depending on the number, it may exist in one or more geometric isomeric forms.
Compounds of general formula (I) in which G is G1, G2 or G3 are labeled (E, E), (E, Z), (Z, E), (Z, Z) according to the configuration of the double bond. Or four different geometric isomers. The symbols E and Z may be replaced by the terms syn and anti, or cis and trans, respectively. In particular, the description and use of these symbols is described by Wiley (1994) E.C. Eliel and S.M. Willen's "Stereochemistry of Organ"
ic Compounds ".

By convention, in the case of the present invention, the symbols (E, E), (E, Z), (Z, E)
, (Z, Z) indicate that the first character is a double bond arrangement of a G1, G2 or G3 group,
The second letter indicates the configuration of the hydroxyme or hydrazone group.

The compounds of general formula (I) wherein G is a G4-G9 group include two different geometric isomers, labeled (E) or (Z), depending on the configuration of the hydroxyme or hydrazone group. May be.

Compounds of general formula (I), and optionally compounds which will be available as intermediates in the preparation processes and will be defined in the description of these processes, include all compounds of the compounds Depending on the number of asymmetric centers, it may exist in one or more optical or chiral isomeric forms. The present invention therefore relates to all optical isomers and their racemic or scalemiques mixtures (scalemiques).
es means enantiomeric mixtures in different ratios) as well as all possible stereoisomeric mixtures in all ratios. The separation of diastereoisomers and / or optical isomers can be carried out in a manner known per se (E
. Eliel ibid. ).

PREPARATION METHODS The compounds of the general formula (I) of the present invention and optionally the compounds which can be used as intermediates in the preparation methods of the present invention are prepared by at least one of the following general preparation methods A to K: obtain.

The preparation of the reagents to be used by any of the general preparation methods is generally known per se and is usually described in the prior art specifically or as such can be adapted by a person skilled in the art to the desired purpose. ing.

Conventional techniques that can be used by those skilled in the art to set conditions for preparing reagents are described in M
Arch's “Advanced Organic Chemistry” (Wi
ley, 1992), “Method der organischen.
Chemic "(Houben-Weyl) Georg Thieme Ve
rlag or “Chemical Abstracts”, Amierca
It can be found in a number of general chemical books, such as published by the Chemical Society, as well as in publicly available information databases.

Method AG Compounds of general formula (I) in which G is one of the groups G1 to G9 and the other substituents have the definitions given above can be prepared in the presence of an organic or inorganic base in the presence of a solvent. A compound of formula (II) A in the presence or presence

[0046]

Embedded image (Wherein G is one of G1 to G9 groups, G1 to G9 groups have the same definition as defined for formula (I), and X ₆ is the same as defined for formula (I) V ₁ is a halogen atom (preferably chlorine or bromine), an alkylsulfonate or haloalkylsulfonate (preferably methylsulfonate or trifluoromethylsulfonate), an arylsulfonate (preferably 4-methylphenylsulfonate) group And a compound of formula (III) A:

[0047]

Embedded image (Wherein W ₁ , W ₂ , R ₁ , R ₂ , R ₃ , p and A have the same definitions as given for formula (I)). . The reaction is generally carried out at a temperature between -80 and 180C (preferably between 0 and 150C) or at the boiling point of the solvent used. Suitable solvents for this reaction are pentane, hexane, heptane, aliphatic hydrocarbons such as octane, benzene, toluene, various xylenes, aromatic hydrocarbons such as various halogenobenzenes, diethyl ether, di-isopropyl ether tetrahydrofuran, Dioxane, ethers such as dimethoxyethane, dichloromethane, chloroform, 1,2-dichloroethane, halogenated hydrocarbons such as 1,1,1-trichloroethane, methyl acetate, esters such as ethyl acetate, acetonitrile, propionitrile, Nitriles such as benzonitrile, dimethylformamide,
Dipolar aprotic solvents such as dimethylacetamide, N-methylpyrrolidone, dimethylprorylene, dimethylsulfoxide, or water. Mixtures of these various solvents can also be used.

The reaction time varies depending on the conditions used, and is generally 0.1 to 48 hours.

Suitable organic or inorganic bases for this reaction include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide or calcium hydroxide, tert- (third) Alkali metal and alkaline earth metal alcoholates such as potassium butyrate, alkali metal and alkaline earth metal hydrides such as sodium hydride, potassium hydride or cesium hydride, sodium carbonate, potassium carbonate, calcium carbonate or bicarbonate Alkali and alkaline earth metal carbonates and bicarbonates such as sodium, potassium or calcium bicarbonate, organic bases, preferably nitrogen-containing organic bases, for example
Pyridine, alkylpyridine, trimethylamine, triethylamine or di-
Alkylamines such as isopropylethylamine, 1,5-diazabicyclo [
Aza derivatives such as 4.3.0] non-5-ene or 1,8-diazabicyclo [5.4.0] undec-7-ene.

There is no strict limit on the ratio for the compounds of Formula (II) A and Formula (III) A. However, (III) A / (II) A is 0.1-10, preferably 0
. Suitably a molar ratio of between 5 and 2 is chosen.

Depending on the conditions used, the compounds of the general formula (I) may be in the form of various mixtures of isomers (E) and (Z), depending on the arrangement of the hydroxyme or hydrazone groups, or of the isomer (E) alone or It is obtained in the form of the body (Z) alone. If necessary,
The compounds of the general formula (I) and the compounds of the configuration (E) or (Z) due to the configuration of the hydroxy or hydrazone groups can be isolated and purified by methods known per se, for example by extraction, crystallization or chromatography. Good.

Compounds of formula (III) A, wherein W ₁ , W ₂ , R ₁ , R ₂ , R ₃ , p and A have the same definitions as given for formula (I), are represented by the formula (IV) Compound

[0053]

Embedded image Wherein W ₂ , R ₁ , R ₂ , p and A have the same definitions as given for formula (I), and a compound of formula (V)

[0054]

Embedded image Wherein W ₁ and R are ₃ , have the same definitions as given for formula (I), and U ₁ is a halogen atom (preferably chlorine or bromine), or hydroxy, lower alkoxy or benzyloxy, lower Alkylthio, amino, N-alkylamino, N, N-dialkylamino, N-acylamino, N, N-acylalkylamino or —O (C ＝ O) R _a group, wherein R _a has the same definition as R ₃ And is the same as or different from R ₃ , U ₁ is preferably a halogen atom, and has the formula (V
) Compounds represent acid halides).

The condensation of the compound of the formula (IV) with the compound of the formula (V) is generally carried out in the presence of an organic or inorganic base or by dehydration such as a carboxylic anhydride, preferably acetic anhydride or propionic anhydride. It is performed in the presence or absence of a solvent in the presence of a reagent. formula(
The general conditions for the condensation of a compound of formula (IV) with a compound of formula (V) are similar or identical to the condensation conditions between a compound of formula (II) A and a compound of formula (III) A, As such, "Houben-Weyl" ibid. Volume E5,11
It is known from pages 44-1149.

W ₁ is an oxygen atom and W ₂ , R ₁ , R ₂ , R ₃ , p and A have the same definition as given for formula (I), hydroxymic acid or hydrazone of formula (III) A Derivatives of the acids are also compounds of formula (VI)

[0057]

Embedded image Wherein R ₁ , R ₂ , p and A have the same definitions as given for formula (I), and V ₁ is a halogen atom (preferably chlorine or bromine), an alkylsulfonate or a haloalkylsulfonate (preferably Is methylsulfonate or trifluoromethylsulfonate) or arylsulfonate (preferably 4
-Methylphenylsulfonate)), and formula (VII)

[0058]

Embedded image Of W ₂ and R ₃ having the same definition as given for formula (I).

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

The general conditions for the condensation of a compound of formula (VI) with a compound of formula (VII) are those of formula (I)
I) The conditions for the condensation of a compound of A with a compound of formula (III) A are similar or identical, and as such are described in "Houben-Weyl" ibid. Volume E5,1
Known from pages 144-1149.

Derivatives of hydroxymic acid of formula (III) A, wherein W ₁ and W ₂ are oxygen atoms, p = 1 or 2, and A has the same definition as given for formula (I), Compound of formula (VIII)

[0062]

Embedded image (Wherein R ₁ , R ₂ and A have the same definition as shown for formula (I) and p = 1 or 2), and W ₂ is an oxygen atom, and R ₃ is a group represented by the formula ( It can be obtained by a process comprising contacting with a hydroxymic acid derivative of the formula (VII) having the same definition as given for I).

A compound of formula (VII) wherein W ₂ is an oxygen atom and R ₃ has the same definition as given for formula (I) and R ₁ , R ₂ and A are as defined for formula (I) Condensation with a compound of formula (VIII) having the same definition is generally carried out with carbodi-imide or bis-alkoxycarbonyl azoic derivatives or bis- (N, N-dialkyl) carbamoyl azoic derivatives, preferably diethyl azodicarboxylate and In the presence of a binding agent such as a trialkylphosphine or a derivative of a triarylphosphine, preferably triphenylphosphine, ethers, especially diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, halogenated hydrocarbons, especially dichloromethane, chloroform , 1,2
The reaction is carried out in the absence or in the presence of aprotic solvents such as dichloroethane, 1,1,1-trichloroethane, nitriles, in particular acetonitrile, propionitrile, benzonitrile. Mixtures of these various solvents can also be used. The reaction is generally carried out at a temperature of -80 to 120C (preferably 0 to 60C) or at the boiling point of the solvent.

The reaction time varies depending on the conditions used, but is generally 0.1 to 48 hours. There is no strict limit on the ratio for the compounds of formula (VII) and formula (VIII). However, if (VII) / (VIII) A is between 0.1 and 10, preferably 0
. It is preferred to choose a molar ratio of 5 to 2.

The general conditions for this condensation can be found in various publications, especially in Synthesis (198
1), 1 et Org. Prep. Proced. Int (1996), 28
, 127.

W ₁ , W ₂ , R ₁ , R ₂ , R ₃ , p and A have the same definitions as given for formula (I), and U ₁ and V ₁ are the definitions given for method A Compounds of formula (IV), formula (V), formula (VI), formula (VII) and formula (VIII) having the same definition as for example Tetrahedron (1995) for compounds of formula (IV)
), 51, 11473 and Tetrahedron Lett. (1996)
, 37. , 8045 and Expression (VI) in Synthesis (1980)
, 746.

The compounds of the formula (VI) and of the formula (VIII) are in particular known per se,
Chemistry of heterocyclic compounds "
volumes 1-52, J. Mol. Published by Wiley & Sons and "Adv
ances in heterocyclic chemistry ”volu
mes 1-70, published by Academic Press.

G is one of the groups G1 to G9, wherein the groups G1 to G9 have the same definition as given for formula (I) and X ₆ has the same definition as given for formula (I) Has a definition,
V ₁ is a halogen atom (preferably chlorine or bromine), an alkylsulfonate (preferably methylsulfonate or trifluoromethylsulfonate), an arylsulfonate (preferably 4-methylphenylsulfonate) group,
I) Compounds of A are collectively referred to as "halogenated derivatives of benzyl" in the description of the process for preparing catabolic.

The benzyl halide derivative of the formula (II) A wherein V ₁ is a halogen atom (preferably chlorine or bromine) is a compound of the formula (IX)

[0070]

Embedded image (Wherein G is one of G1 to G9 groups, G1 to G9 groups have the same definition as defined for formula (I), and X ₆ is the same as defined for formula (I) May be obtained by halogenation of

The halogenation of the compound of formula (IX) is described in J. March ibid. pages
In accordance with 689-697, by a radical, thermal or photochemical method, each method does not repel one another, but with an N-halogenoacetamide such as N-bromosuccinimide, N-chlorosuccinimide, N-bromoacetamide. In an inert solvent such as benzene or carbon tetrachloride or in the absence of a solvent, with or without free radical initiator, at 20-170 ° C., preferably 80-170 ° C.
It can be performed at 100 ° C.

The benzyl halide derivative of the formula (II) A wherein V ₁ is a halogen atom (preferably chlorine or bromine) is also a compound of the formula (II) B

[0073]

Embedded image (Wherein G is one of G1 to G9 groups, G1 to G7 groups have the same definitions as given for formula (I), R ₄ is an alkylamino, dialkylamino group, G8 And the groups G9 have the same definitions as given for formula (I), X ₆ has the same definitions as given for formula (I), and W ₁ is an oxygen atom); . March ibid. With halogenating agents such as thionyl chloride, phosphorous oxytrichloride, phosphorous tribromide according to pages 431 to 433; Org. C
hem. (1971), 36, 3044, by halogenation with a lithium halide / methyl halide / collidine reagent.

V ₁ is a halogen atom (preferably chlorine or bromine) V The benzyl halide derivative of the formula (II) A is also a compound of the formula (II) C

[0075]

Embedded image (Wherein G is one of G1-G9 groups, G1-G7 groups have the same definitions as given for formula (I), R ₄ is an alkylamino, dialkylamino group, G8 And the G9 group have the same definitions as given for formula (I), X ₆ has the same definition as given for formula (I), W ₁ is an oxygen atom,
And P is preferably an acetic acid ester or a benzoic acid ester, or an atomic group which preferably protects an alcohol function such as methyl ether, methoxymethyl ether, phenyl ether, benzyl ether (published by Wiley (199)).
1) W. Greene and P.M. Wuts's book "Protective G"
loops in Organic Synthesis)) and a Lewis acid such as boron tribromide, or a hydrogen anhydride such as hydrogen chloride. This fission reaction is known in particular from EP 525516. ing.

The derivatives of the benzyl halide of the formula (II) A and the compounds of the formulas (IX), (II) B and (II) C may be prepared by methods known per se. These various methods or their related prior art are described in detail in Method K.

Method B G is one of the G1 to G9 groups, wherein the G1 to G7 groups have the same definitions as given for formula (I), and R ₄ is an alkylamino, dialkylamino group, G8
And the G9 group have the same definition as given for formula (I), and X ₆ is of the formula (I
A) a compound of general formula (I) having the same definition as given for G)
Group G9, groups G1 to G7 have the same definitions as given for formula (I), R ₄ is an alkylamino, dialkylamino group, and groups G8 and G9 are of the formula (I) Has the same definition as given for X, X ₆ has the same definition as given for formula (I), W ₁ is hydrogen or a sulfur atom (II) B, and formula (III) Compound of B

[0078]

Embedded image Wherein W ₂ , R ₁ , R ₂ , R ₃ , p and A have the same definitions as given for formula (I), and V ₁ is a halogen atom (preferably chlorine or bromine), an alkyl A sulfonate or haloalkylsulfonate (preferably methylsulfonate or trifluoromethylsulfonate), or an arylsulfonate (
Preferably a 4-methylphenylsulfonate) group, a double bond V ₁ -C (R ₃ ) =
N-W 2 _- it may be obtained by a method comprising contacting the stereochemistry (E) or a (Z)).

The reaction is generally carried out in the absence or presence of an organic or inorganic base, in the absence or presence of a solvent. The reaction is generally carried out at a temperature of -80 to 180 ° C (preferably 0 to 1).
(50 ° C.) or at the boiling point of the solvent used. Suitable solvents for this reaction are ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, acetonitrile, nitriles such as propionitrile, benzonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylprothyl. It may be a dipolar aprotic solvent such as ryleneurea or dimethylsulfoxide. Mixtures of these various solvents can also be used.

The reaction time varies depending on the conditions used, but is generally 0.1 to 48 hours.

Suitable organic or inorganic bases for this reaction include hydrides of alkali or alkaline earth metals such as sodium hydride, potassium hydride, cesium hydride, potassium tert- (tert.) Butyrate. Alcoholates of such alkali metals or alkaline earth metals can be mentioned.

There is no strict limit on the ratio for both compounds of formulas (II) B and (III) B. However, 0.1 to 10, preferably 0.5 to 2, (II) B / (
III) It is appropriate to choose the B molar ratio.

Depending on the conditions of use, the compounds of the general formula (I) can, depending on the configuration of the hydroxyme or hydrazone group, be mixed in various forms of isomers (E) and (Z), or of isomer (E) alone or It is obtained in the form of a mixture of the body (Z) alone. If necessary,
The compounds of the general formula (I) and the compounds of the configuration (E) or (Z) due to the configuration of the hydroxy or hydrazone groups can be isolated and purified by methods known per se, for example by extraction, crystallization or chromatography. Good.

Compounds of general formula (III) B are described, for example, in J. Am. Org. Chem. (1985
), 50, 993, J. Mol. Org. Chem. (1971), 36, 234, 36
, And Chem. It is prepared according to methods known per se, such as Abstracts (1970), 73, 34750s.

Method C A thiohydroxamic acid derivative of the compound of formula (III) A, wherein W ₁ is a sulfur atom and W ₂ is an oxygen atom, or W ₁ is a sulfur atom and W ₂ is the definition given for formula (I) NR ₁₃ , R ₁ , R ₂ , R ₃ , R ₁₃ , p and the thiohydrazonic acid derivative of the formula (III) A, which has the same definition as, are also an object of the present invention.

These are described in “Houben-Weryl” volume E5, 1279-
1280, and Synthesis (1984), 829.
By the same or similar methods, thiol such as phosphorus pentasulfide or Lawesson's reagent
W using a nation reagent₁Is an oxygen atom and W₂Is an oxygen atom
Samic acid or W₁Is an oxygen atom and W₂Is W₁Is a sulfur atom and W₂Is the expression (
NR having the same definitions as given for I)₁₃, R₁, R₂, R₃, R ₁₃ Of the thiohydrazonic acids of the formula (III) A, which are groups p, A and A
Can be obtained by

Method D G is a G3 group, Q ₂ is an oxygen atom, R ₄ is an alkoxy, alkylamino, dialkylamino group, other substituents having the same definitions as given for formula (I), ₆ is lower alkyl or lower haloalkyl, the compound of the general formula (I) is a compound of the formula (X)

[0088]

Embedded image (Wherein R ₄ is an alkoxy, alkylamino, dialkylamino group, formula (I)
And a Wittig-Horner reagent R ₆ —CH ₂ —P (＝ O) (OR _b ) ₂ (XI) A of the formula (XI) A. ₆ is a lower alkyl or lower haloalkyl group, _Rb is a lower alkyl, phenyl or benzyl group), or a Wittig reagent of the formula (XI) B R ₆ —CH ₂ —P (R _d ) ₃ ⁺ ; ^- (XI) B (wherein, _{R 6} is lower alkyl or lower haloalkyl group, a phenyl group which is optionally substituted _{R d} is, Hal ^- is a halide ion) with, J. March ibid. 956-963 or WO9529896
, In an aprotic solvent such as an ether, preferably diethyl ether or tetrahydrofuran, at -78 to 50C, preferably -70 to 20C.
Alkali or alkaline earth metal alcoholates, preferably sodium ethylate, sodium methylate or potassium tert-butylate, alkali metal or alkaline earth metal hydrides, preferably sodium or potassium hydride, at a temperature of It can be obtained by a method involving contact by the action of one or more equivalents of a base such as an alkyl lithium, preferably butyl lithium, an alkyl magnesium halide or a lithium di-isopropylamidate organometallic derivative.

A Wittig-Horner reagent of formula (XI) A and a Wit of formula (XI) B
The tig reagent can be obtained by a method known per se.

[0090] Method E G is G1 or G2, _{Q 1} is a nitrogen atom or a CH group, _{Q 2} represents an oxygen atom, _{R 4} is alkoxy, alkylamino, dialkylamino, the same definition given for formula (I) And R ₅ is lower haloalkyl, the compound of general formula (I) is a compound of formula (XII)

[0091]

Embedded image (Wherein, T is an oxygen or sulfur atom, M is an alkali ion or an alkaline earth ion, Q1 is a nitrogen atom or a CH group, R ₄ is an alkoxy or dialkylamino group, and W ₁ , W ₂ , R ₁ , R ₂ , R ₃ , X ₆ , p and A have the same definitions as those given for formula (I), and formula CH _q (Hal) _4-q (where q = 1 or 2, Hal is Dimethylformamide, in the presence or absence of a catalytic amount of iodide ions, the same or different from each other, at least one of which represents a halogen atom which is a chlorine or bromine atom). -20 to 250 ° C in an aprotic solvent such as dimethylacetamide, N-methylpyrrolidone, dimethylprolylenurea, or dimethylsulfoxide. Preferably, it can be obtained by a method at a temperature of 25 to 150 ° C. This reaction is particularly D
E4424788 and WO 96/06072.

T is an oxygen atom, M is an alkali ion or an alkaline earth ion, Q₁Is a nitrogen source
Child, R₄Is an alkoxy, alkylamino, dialkylamino group;₁, W ₂ , R₁, R₂, R₃, R₄, X₆, P and A are the definitions given for formula (I)
A compound of formula (XII) having the same definition as₄Is alkoxy, alkyl
Mino, dialkylamino group, having the same definition as given for formula (I)
Compounds of formula (X) which are other substituents include hydroxyamine and Mar
chibid. It can be easily obtained by the action of a base according to pages 906-907.
Wear.

T is an oxygen atom, M is an alkali ion or an alkaline earth ion, Q ₁ is a CH group, R ₄ is an alkoxy, alkylamino, dialkylamino group, and W ₁ , W ₂ , R ₁ , R ₂ , Compounds of formula (XII) wherein R ₃ , R ₄ , X ₆ , p and A have the same definitions as given for formula (I) can be prepared in particular in a manner analogous to EP-A-0178826. .

Method F G is a G4 group with n = 1, Q ₂ is an oxygen atom, R ₄ is an alkoxy, alkylamino, dialkylamino group, other substitutions having the same definitions as given for formula (I) The compound of general formula (I) which is a group is a compound of formula (XIII) A

[0095]

Embedded image (Wherein R ₄ is an alkoxy, alkylamino, dialkylamino group, formula (I)
And the other substituents having the same definitions as those described for) and a reagent of the formula (XIV)

[0096]

Embedded image (Where V ₁ is a halogen atom (preferably chlorine or bromine), R ₅ has the same definition as given for formula (I)) and optionally a phase transfer catalyst such as a quaternary ammonium. Hydroxides of alkali metals or alkaline earth metals in the presence, in an aprotic solvent such as an ether, preferably diethyl ether or tetrahydrofuran, at a temperature of -78 to 40C, preferably -20 to 25C, It can be obtained by a reaction by the action of at least one equivalent of a base such as an alkali metal or alkaline earth metal alcoholate, an alkali metal or alkaline earth metal hydride, an alkali metal or alkaline earth metal carbonate and a bicarbonate.

Compounds of general formula (XIII) A wherein R ₄ is an alkoxy, alkylamino, dialkylamino group or other substituent having the same definition as given for formula (I) are represented by general formula (XIII) Compound of B

[0098]

Embedded image (Where R₄Is an alkoxy, alkylamino, dialkylamino group, and X ₆ Is another substituent having the same definition as that given for formula (I),₁Represents a halogen atom (preferably chlorine or bromine), an alkyl sulfonate (
Preferably methylsulfonate or trifluoromethylsulfonate),
Is an arylsulfonate (preferably 4-methylphenylsulfonate) group
) And W₁, W₂, R₁, R₂, R₃, P and A are as defined for formula (I)
It can be obtained by reaction with a compound of formula (III) A having the same definition.

The general condensation conditions for a compound of formula (XIII) B with a compound of formula (III) A are
Similar or identical to the condensation conditions of the compound of formula (II) A and the compound of formula (III) A described in method A.

Compounds of general formula (XIII) B may be obtained according to EP-A-0 498 396.

Method G G is a G1-G7 group, R ₄ is an alkylamino, dialkylamino group, a compound of the formula (
General formula (I) which is another substituent having the same definition as that described for I)
A) a compound of general formula (I) wherein G is a G1 to G7 group and R ₄ is alkoxy or alkylthio, another substituent having the same definition as given for formula (I); It can be obtained by a process comprising contacting an amine or dialkylamine, preferably methylamine, in an alcoholic solvent such as methanol, ethanol, propanol or isopropanol at a temperature of -50 to 100 ° C or at the boiling point of the selected solvent. it can. G is a G1 group, and R ₄ is a compound of general formula (I) wherein R ₄ is alkoxy or alkylthio, another substituent having the same definition as that given for formula (I). Or it is generally good to use an excess of 1 to 5 equivalents, preferably 1.1 to 2 equivalents of dialkylamine.

Method H W ₁ is sulfoxide (SO) or sulfone (SO ₂ ), G is G1, G3, G
4 is one of G6~G9 group, Q ₂ and Q ₃ is an oxygen atom, the formula (I) other general formula is a substituent having a same definition given for (I) compounds,
W ₁ is a sulfur atom, G is G1, G3, G4, is one of G6~G9 group, _{Q 2} and _{Q 3} other substituents having the same definition given for oxygen atom, the formula (I) Group of the compound of general formula (I) March ibid. 1201-12
Organic peroxides, preferably peracetic acid, 3-chloroperbenzoic acid, metal peroxides, hydroperoxides such as hydrogen peroxide, in the presence or absence of a catalyst in an inert solvent according to page 03 By oxidation with an equivalent amount or more of an oxidizing agent such as

Method IG is a compound of general formula (I), which is one of the G1 to G9 groups, the other substituents having the definitions given above,

[0104]

Embedded image (Wherein G is one of the G1 to G9 groups, the G1 to G9 groups have the same definition as shown for formula (I), and X ₆ , W ₁ , W ₂ and R ₃ are R ₁ , R ₂ , p and A have the same definitions as given for formula (I), and V ₁ is a halogen atom (preferably Is chlorine or bromine), an alkylsulfonate or haloalkylsulfonate (preferably methylsulfonate or trifluoromethylsulfonate) group, or an arylsulfonate (preferably 4
-Methylphenylsulfonate) group can be obtained by methods involving contact with a compound of formula (VI).

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

The general conditions for the condensation of the compound of formula (XV) A with the compound of formula (VI) are similar or similar to those for the condensation of the compound of formula (VII) with the compound of formula (VI) described in method A Are identical.

G is one of the G1 to G9 groups, wherein the G1 to G9 groups have the same definitions as given for formula (I), and X ₆ , W ₁ , W ₂ and R ₃ have the formula (I) Compounds of (XV) A having the same definitions as given for I) are also an object of the present invention.

These are compounds of the formula (XV) B

[0109]

Embedded image (Wherein G is one of the G1 to G9 groups, the G1 to G9 groups have the same definition as shown for formula (I), and X ₆ , W ₁ , W ₂ and R ₃ are Has the same definition as given for (I), wherein P is preferably an ester such as an acetate or a benzoate, a trialkylsilyl ether, a dialkylarylsilyl ether, an alkyldiarylsilyl ether or a triarylsilyl ether Preferably, isopropyl dimethylsilyl ether, triethylsilyl ether, tert-butyldimethylsilyl ether, trityldimethylsilyl ether, tert-butyldiphenylsilylether, methyldiisopropylsilylether, methyldi-tert-butylsilylether or tri-isopropylsilylether Like siri Protecting groups for hydroxyl functions such as etherified ethers or ethers such as triarylmethyl ethers, preferably triphenylmethyl ether, di- (4-methoxyphenyl) -phenylmethyl ether or 4-methoxyphenyldiphenylmethyl ether. Or an alkoxycarbonyl group,
Preference is given to protecting groups for amino functions such as tert-butyloxycarbonyl or benzyloxycarbonyl (this list is not limiting and the choice of said protecting groups can be found in the works of W. Green and P. Wuts (ibid). ) Using the specific elimination of each protecting group P. Each protecting group P
The specific desorption conditions of Green and P.M. Wuts (ibid) and S
syntheses (1985), 817.

G is one of the G1 to G9 groups, wherein the G1 to G9 groups have the same definitions as given for formula (I), and X ₆ , W ₁ , W ₂ and R ₃ have the formula (I) Compounds of the formula (XV) having the same definitions as given for I), wherein P is a protecting group for a hydroxyl function or an amino function, are also an object of the invention.

In these compounds, G is one of G1 to G9 groups, and G1 to G9 groups have the formula (I)
Has the same definitions as given for X, X ₆ has the same definitions as given for formula (I), and V ₁ is a halogen atom (preferably chlorine or bromine), an alkylsulfonate or a haloalkylsulfonate A compound of formula (II) A which is a (preferably methylsulfonate or trifluoromethylsulfonate) group or an arylsulfonate (preferably 4-methylphenylsulfonate) group, and a compound of formula (XVI)

[0112]

Embedded image Wherein W ₁ , W ₂ and R ₃ have the same definition as given for formula (I), and P is a protecting group for a hydroxyl function or a protecting group for an amino function. Obtained by reaction.

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

General conditions for the condensation of a compound of formula (II) A with a compound of formula (XVI) are described in Method A
Or the same as the condensation conditions of the compound of formula (II) A and the compound of formula (III) A described in "Houben-Weryl" volume E5,114
It is known per se from pages 8-1149.

W ₁ , W ₂ and R ₃ have the same definitions as given for formula (I),
Is a protecting group for a hydroxyl function or a protecting group for an amino function, of the formula (XVI)
Is a compound of formula (XVII)

[0116]

Embedded image Wherein W ₂ has the same definition as given for formula (I) and P is a protecting group for a hydroxyl function or a protecting group for an amino function, wherein W ₁ , R ₃ are of the formula ( Has the same definition as given for I), wherein U ₁ is a halogen atom (preferably chlorine or bromine), or hydroxy, lower hydroxy or benzyloxy, lower alkylthio, amino, N-alkylamino, N, N- Dialkylamino, N-diacylamino, N, N-acylalkylamino group or —O (C ＝ O)
R _a group, wherein R _a has the same definition as that of R _a shown for formula (I);
Formula (V), which is the same as or different from R ₃ and wherein U ₁ is preferably a halogen atom
It can be prepared by condensation with a compound (thus the compound of formula (V) is a halide of an acid).

The general conditions for the condensation of a compound of formula (XVII) with a compound of formula (V) are similar or identical to the conditions for condensation of a compound of formula (IV) with a compound of formula (V) described in method A It is.

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

Method J According to Method A or Method B, the general formula (I) having W ₁ and W ₂ atoms or groups
Wherein W ₁ and W ₂ have the same meanings as for formula (I) and a double bond —C (R ₃ ) = N— (hydroxyme or hydrazone group). In the cis position (see above).

The isomers of general formula (I) having W ₁ and W ₂ atoms in the trans position with respect to the double bond —C (R ₃ ) = N- (hydroxyme or hydrazone group) are preferably UV It can be prepared from the cis isomer by heating in a solvent under irradiation, in the presence or absence of a catalyst, especially an acidic catalyst. The reaction time is chosen such that a complete conversion from the cis isomer to the trans isomer takes place. The reaction is generally carried out at a temperature between 0 ° C. and the boiling point of the solvent. Suitable solvents for this reaction are aliphatic hydrocarbons such as pentane, hexane, heptane, octane, aromatic hydrocarbons such as benzene, toluene, xylene, diethyl ether, diisopropyl ether, tetrohydrofuran, dioxane, dimethyloxy. Ethers such as ethane, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and 1,1,1-trichloroethane, esters such as methyl acetate and ethyl acetate, acetonitrile, propionitrile and benzonitrile Such as nitriles, alcohols such as methanol, ethanol, propanol and isopropyl; and dipolar non-polymers such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylproryleneurea and dimethylsulfoxide. Tons of solvent or water, and the like. Mixtures of these various solvents can also be used.

The solvent is preferably an aromatic hydrocarbon such as toluene or xylene or an ether such as diisopropyl ether. Catalysts which are preferably acidic catalysts include hydrogen anhydride such as hydrogen chloride, carboxylic acids such as acetic acid, propionic acid and trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid and 4-methylphenylsulfonic acid. You will choose between sulfonic or sulfuric acid.

Method K (Derivatives of Benzyl Halide of Formula (II) A and Analogs thereof) Benzyl halide derivatives of formula (II) A and compounds of formulas (IX), (II) B and (II) C It can be prepared according to numerous methods known per se.

For example, without limitation and without exhaustion, the preparation of benzyl halide derivatives of formula (II) A or compounds of formula (IX) or compounds of formula (II) B or compounds of formula (II) C Each patent that describes the method is listed. G is a G1 or G2 group of stereochemistry (E) or (Z), the benzyl halide derivative of formula (II) A and analogs thereof are described in EP-A-0426460,
EP-A-0398692, EP-A-0617014, EP-A-05857
51, EP-A-0487409, EP-A-0535928, DE-4055
02 can be prepared.

G is a G1 or G2 group of stereochemistry (E) or (Z), and Q ₂ and R ₄ are both 5-7 membered rings containing 2-3 oxygen and / or nitrogen atoms The benzyl halide derivative of formula (II) A and its analogs forming
-A-95 / 04728.

The benzyl halide derivatives of the formula (II) A and analogues thereof in which G is G3 in stereochemistry (E) or (Z) are known from WO9616943. Formula (G) in which G is a G4, G5 or G6 group II) Benzyl halide derivatives of A and analogs thereof are described in EP-A-0498396, EP-A-0619301.
Benzyl halide derivatives of the formula (II) A wherein G is a G7 group and analogues thereof are known from WO9527693, WO96073633, G is a G8 or G9 group Benzyl halide derivatives of the formula (II) A and analogs thereof are known from WO-A-95 / 14009.

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

Quite surprisingly, it has been found that the compounds of the formula (I) according to the invention are fungicidal compounds which are active against a wide range of crop phytopathogenic fungi.

This activity exerted extremely excellent effects even when a small amount of the compound of the formula (I) was used.

Also, for compounds having such activity (broad spectrum of action and low use), the compounds of formula (I) are surprisingly non-phytotoxic or very low. That is, these compounds have very good selectivity for fungi.

Finally, the compounds of the formula (I) can also be said to have a very favorable effect on the environment in terms of no or negligible ecological pollution.

The fungicidal compositions according to the invention comprise a compound of formula (I) or an agriculturally acceptable salt thereof or a metal or metalloid complex of this compound in association with an agriculturally acceptable solid or liquid carrier and / or Or also with agriculturally acceptable surfactants. In particular, conventional inert carriers and conventional surfactants can be used. These compounds fall within the category of compositions prepared for application to the plants or seeds to be treated using suitable equipment such as dusting or dusting equipment, as well as before use on crops. Also included are commercial concentrated compositions to be diluted.

The fungicidal compositions according to the invention may also contain all kinds of other ingredients, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers, masking agents. Good. More generally, the active substances can be mixed with all kinds of solid or liquid additives corresponding to the usual preparation techniques.

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

In the present disclosure, “carrier” refers to a natural or synthetic organic or inorganic substance mixed with an active substance to facilitate application of the active substance to each part of a plant.
Thus, in general, the carrier is inert and should be agriculturally acceptable. The carrier can be solid (clay, natural or synthetic silicate, silica, resin, wax, solid fertilizer, etc.) or liquid (water, alcohol, especially butanol, etc.).

The surfactant may be an ionic or non-ionic emulsifier, dispersant, wetting agent or mixture as a surfactant. For example, salts of polyacrylic acid, salts of linosulphonic acid, salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide on fatty alcohols or fatty acids or fatty amines, substituted phenols (especially alkylphenols or Arylphenols), salts of sulfosuccinates, derivatives of taurine (particularly alkyl taurates), phosphates of alcohols or polyethylated phenols, esters of fatty acids and polyols, sulfate, sulfonate and phosphate functional groups of the above compounds And derivatives thereof. If the active substance and / or the inert carrier is not soluble in water, and if the application agent is water, it is essential that at least one surfactant is present.

Thus, the agricultural compositions of the present invention can contain the active substance in a very wide range, from 0.05 to 95% (by weight). The surfactant content is advantageously between 5 and 40% by weight. Unless otherwise specified, percentages given herein are percent by weight.

These compositions according to the invention are themselves in a wide variety of solid or liquid forms.

Solid compositions can include powders for dusting (up to 100% active substance content) and, in particular, granules obtained from extrusion, compaction, penetration of granule carriers, granulation from powders ( In the latter case, the content of active substance in these granules is from 0.5 to
80%).

The fungicidal composition according to the invention further comprises 50 g of active substance in powder form for dusting.
A composition comprising 950 g of talc, and a composition comprising 20 g of active substance, 10 g of finely divided silica and 970 g of talc can also be used. These components are mixed and ground, and the mixture is dusted.

When used, a liquid composition form or a form for forming a liquid composition includes:
There are concentrates, thick suspensions, wettable powders (or sprayable powders) which are soluble in solutions, in particular water, emulsions.

Concentrated suspensions which can be used by spraying are prepared in such a way as to obtain stable fluid substances which do not precipitate, which are usually from 10 to 75% of active substance, 0.5 to 15% of surfactant,
0.1 to 10% thixotropic agent, 0 to 10% suitable additives, colloid inhibitors, stabilizers, penetrants and adhesives as antifoaming agents, as a carrier, hardly soluble in water or active substances or It contains organic liquids that do not dissolve at all (some solid organic substances or inorganic salts may be soluble in the carrier to prevent settling or as an antifreeze for water).

As an example, a concentrated suspension is shown here.

Example SC1-500 g of active substance-50 g of polyethoxylated tristyryl phosphate phosphate-50 g of polyethoxylated alkylphenol-20 g of sodium polycarboxylate-50 g of ethylene glycol-1 g of organic polysiloxane oil (antifoaming agent) 1 g-polysaccharide 5g-water 316.5g Wetting powders (or powders for spraying) are usually prepared so as to contain 20-95% of the active substance and usually, in addition to the solid carrier, 0-30% of a wetting agent, It contains from 3 to 20% of the agent, if necessary one or several stabilizers and / or other additives, as penetrants, adhesives or antimotants, coloring agents and the like.

To obtain a sprayable or wettable powder, the active substance is mixed well with the additives in suitable admixtures and turned into a powder by means of a mill or other suitable pulverizer. In this way, a powder for spraying which is rich in wettability and advantageous for suspension is obtained. This is suspended in water to the desired concentration. The suspensions thus formed are particularly advantageous, for example, when used on plant leaves and seeds.

By way of example, various compositions of wettable powders (or sprayable powders) are given here.

Example PM1-Active substance 50%-Ethoxylated fatty alcohol (wetting agent) 2.5%-Ethoxylated phenylethylphenol (dispersant) 5%-Chalk (inert carrier) 42.5%

Example PM2-Active substance 10%-Branched synthetic oxo alcohol at C13 ethoxylated with 8-10 ethylene oxide (wetting agent) 0.75%-Neutral calcium lignosulphonate (dispersing agent) 12%- Calcium carbonate (inert filler) q. s. p. 100%

Example PM3 This wettable powder contains the same components as Example PM2 in the following proportions: -Active substance 75%-wetting agent 1.50%-dispersant 8%-calcium carbonate (inert filler) q. s. p. 100%

Example PM4-90% active substance-4% ethoxylated fatty alcohol (wetting agent)-6% ethoxylated phenylethylphenol

Example PM5-50% active-mixture of anionic and nonionic surfactants (wetting agent) 2.5%-sodium lignosulphonate (dispersant) 5%-kaolin clay (inert carrier) 42.5 %

Aqueous dispersions or emulsions, for example compositions obtained by diluting a powder according to the invention with water, are included within the general framework of the invention. Emulsions may be of the water-in-oil or oil-in-water type and may have a thick viscosity such as "mayonnaise".

The composition of the germicidal composition according to the present invention may be determined in the form of granules dispersed in water, which are also included in the present invention.

[0153] These dispersible granules generally have an apparent density of about 0.3 to 0.6 and generally have a particle size of about 150 to 2000, preferably 300 to 1500.
Micron.

The active substance content of these particles is generally around 1-90%, preferably 25%
~ 90%.

The rest of the granules are mainly solid fillers and, in some cases, surfactant adjuvants that impart the granules dispersibility in water. In particular, these granules may be of two different types, depending on whether the filler is soluble or insoluble in water. If the filler is water-soluble, it may be inorganic or, preferably, organic. We got great results with Urea. In the case of insoluble fillers, minerals such as kaolin or bentonite are preferred. A surfactant is then advantageously included (approximately 2 to 20% by weight of the granules), more than half of which are in particular alkaline or alkaline earth polynaphthalene sulphonates or alkaline or alkaline earth linosulphonates. It is composed of at least one dispersant, and the remaining part is composed of a nonionic or anionic wetting agent.

Further, although not essential, other auxiliaries, such as antifoams, may be added.

The granules according to the invention may be prepared by mixing the necessary ingredients and then by several methods known per se (granulators, fluid beds, sprayers, extruders, etc.). Finally, it is usually ground and sieved to selected particle sizes within the following limits: Granules impregnated with a composition containing an active substance obtained by the above method can also be used.

Preferably, extrusion is performed by operating as shown in the following examples.

Example GD1: Dispersible Granules In a mixer, 90% by weight of active substance and 10% of urea are mixed and beaded. The mixture is then ground in a broyur a broche and the resulting powder is wetted with approximately 8% by weight of water. The moistened powder is extruded in an extruder with perforated rollers. The obtained granules are dried, crushed and sieved, and
Adjust to a size of 000 microns.

Example GD2: Dispersible granules The following ingredients are mixed in a mixing machine.

-75% active substance-2% wetting agent (sodium alkylnaphthalenesulfonate)-8% dispersant (sodium polynaphthalenesulfonate)-15% water-insoluble filler (kaolin) 15% The mixture is granulated in a fluid bed, dried and ground, and then sieved to obtain granules having a size of 0.15 to 0.80 mm.

These granules may be used alone or in the form of a solution or dispersion having a necessary content in water. It may also be used to prepare formulations with wettable powders or other active substances in granular or aqueous suspension form, especially fungicides.

The compounds of the present invention may comprise one or more insecticides, fungicides, disinfectants, acaricides, arthropodicides, anti-nematodes, attractants or pheromones or other biologically active compounds. Mixing is also possible. The mixture thus obtained has a broad-spectrum activity. Mixtures with other fungicides, such as carbendazim, thiram, dietofencarb, dozine, maneb, mancozeb, diflumetrim, etirimol, benomyl, simoxanil, fenpropidine, fenpropimorph, triadimefon, captan, captafor, phorper, thiophanate, Thiabendazol, phosphoric acid and its derivatives such as phostyl-A1, chlorothalonil, copper-based fungicide composition, dichlorane, metal axyl, iprodione,
Phenamidone, oxadixyl, vinclozolin, tebuconazole, bromuconazole, triticonazole, difenconazole, dinicosol, metconazole, penconazole, propiconazole, prochloraz, fenarimol, triazimenol,
Derivatives of copper as furalaxyl, hydroxide and oxychloride, probenazole, azoxystrobin, kresoxim-methyl, epoxyconazole, famoxadone, picosixistrbin, fludioxyonyl, pyrimethanil, nepalipyrim, cyprodinil, quinoxyfen, Ferimzone, Fluazinam, Trifluoxystrobin, Dimethomorph, Discostrobin, Benalaxyl, Blasticidin-S, Fluquinconazole, Tricyclicleazole, Fludirazol, Derivatives of valinamide such as iprovalicarb, Flutoranil, Guazatine, Hexaconazole, Himexazol, Isopromithiolan, Isopromithiolane , Peniculones, phthalides, pyroquilone, tetraconazole, thifluzamide, and mixtures with carboxin. It is effective.

The compositions according to the invention can also be used, for example, in cereals (especially wheat, rye, triticale,
Barley), potatoes, cotton, peas, rapeseed, corn, flax seeds, and seeds of forest trees (especially conifers).

In this regard, it is noted that for seed treatment terms in the jargon of those skilled in the art, reference is made to general seed treatment. The application techniques are sufficiently known to the person skilled in the art and can be used without disadvantage within the framework of the present invention. This includes, for example, film cling (pel
licage) or a coating process.

Another object of the present invention is a method for treating or preventing crops against phytopathogenic fungi, the method comprising the steps of growing seeds, leaves or stems of plants or the possibility of growing these plants. Soil with plants, preferably in the form of a fungicidal composition according to the invention, of an active substance of formula (I) or any of the agriculturally acceptable salts, or also of a metal or metalloid complex of an agriculturally acceptable compound It is characterized in that it is treated by applying, spraying or injecting a nontoxic effective amount (an effective amount for crops).

“No effective amount and no phytotoxicity” is sufficient to allow for the control or control of fungi present or possibly present in the crop and is significant for said crop. Refers to the amount of the composition according to the invention that does not cause any significant signs of phytotoxicity. Such amounts can vary widely depending on the fungi to be controlled, the type of crop, the weather conditions, and the compounds contained in the fungicidal composition according to the invention. This amount may be determined by a person skilled in the art using field-tested test methods.

Finally, the present invention relates to a method of protection for treating or preventing the reproductive products of plants and the resulting plants against fungal diseases, the method comprising the steps of: It is characterized in that it is covered with a non-phytotoxic amount of the composition according to the invention.

Among the plant propagation products concerned in this connection, mention may in particular be made of seeds and tubers.

As mentioned above, methods for coating plant propagation products, especially seeds, are well known in the prior art and are performed in particular by techniques such as filming or coating.

The products and compositions according to the invention are applied to the foliage part for plant crops.

Among the plants targeted by the method according to the invention, the following can be mentioned by way of example without limitation:

For the following diseases of wheat seeds: Red snow rot (Red snow rot McRodoc)
ium nivale and Fusarium roseum), smut (T
illletia caries, Tilletia converversa
Or Tilletia indica), barley hagare disease (Septori)
a nodorum)-For the following diseases of the above-ground parts of wheat plants: Damping-off disease (Goumanomyces)
, Root red snow rot (F. culmorum, F. graminearum),
Rhizoctonia cerealis, powdery mildew (Erys)
iphe graminis f. sp. tritici), rust (Pucc)
inia striiformis and Puccinia recondit
a) and barley Hagare disease (Septoria tritici and Sep
tria nodorum,-against bacterial and viral diseases of wheat and barley, such as barley chlorosis-against the following diseases of barley, seeds: Pyrenophora gra
minea, Pyrenophora teres and Cochliobol
us sativus), naked smut (Utilago nuda) and red snow rot (Microdochium nivale and Fusarium roseum), for the following diseases of the aerial parts of barley plants: Pseudocercosp
orella herpotrichoides), spot disease (Pyrenop)
hora teres and Cochliobolus sativus, powdery mildew (Erysiphe graminis f. sp hordei),
Leaf rust (Puccinia hordei) and scald disease (Rynchos)
porium secalis), against potato tuber diseases (especially Helminthosporium)
solani, Pharma tuberosa, Rhizoctonia so
lani, Fusarium solani and certain viral diseases (virus Y), for the following diseases of shoots emerging from cotton seeds: Root rot (Rhizoct)
onia solani, Fusarium oxysporum, Black rot (Thielaviopsis basicola)-For the following diseases of pea seeds: Ascochyta pi
si, Mycosphaerella pinodes, rot (Fusar)
ium oxysporum, Botrytis cinerea
-For the following diseases of rapeseed seeds: Pharmalingam and Alt
ernaria brassicae, for disease of corn seeds: (Rhizoopus sp., Pe
nicillium sp. , Trichoderma sp. , Asperg
illus sp. And Gebellaella fikuroi),-against flaxseed disease: Alternaria linicola,-against forest tree seedling rot (Fusarium oxysporum, Rh)
isoctonia solani), wheat and barley are preferred plants for application of the method according to the invention.

The dosage used for the compositions is, in the case of seed treatment, generally from 2 to 200 g, preferably from 3 to 150 g, of active substance per 100 kg of seed.

In the case of plant treatment, the treatment of foliage is generally from 10 to 800 g per hectare.
, Preferably 50 to 300 g per hectare.

The following examples are provided to illustrate the present invention.

Example 1 Preparation of methyl (E, E) -2- (2- {1-[(5-chloro-2-thiophenyl) methyloxyimino] -ethoxymethyl} phenyl) -2-methoxyiminoethaneate Step 1 Preparation of N-[(5-chloro-2-thiophenyl) methoxy] acetamido acid salt 23.6 g of O- (5-chloro-2-thiophenyl) methylhydroxylamine hydrochloride and 24 in 200 ml of dichloromethane. To a room temperature solution of 2 ml of pyridine, 7.1 ml of acetyl chloride are added with stirring. After 2 hours, the reaction medium is removed with ethyl acetate, washed with water, dried over magnesium sulfate and concentrated and purified on silica by flash chromatography. Thereby, 16.0 g
To give N-((5-chloro-2-thiophenyl) methoxy) acetamide as a pale yellow liquid. Rf = 0.18 (eluent: heptane / ethyl acetate 50/50)
(Rf represents the retention factor on silica thin layer chromatography plates).

Step 2 Preparation of methyl (E, E) -2- (2- {1-[(5-chloro-2-thiophenyl) methyloxyimino] -ethoxymethyl} phenyl) -2-methoxyiminoethaneate 2 .10 g of methyl (E) -2- [2- (bromomethyl) phenyl] -2-methoxyiminoethaneate and 1.65 g of acetohydroxamic acid O- (with 3.20 g of cesium carbonate in 50 ml of acetonitrile The suspension of 5-chloro-2-thiophenyl) methyl is stirred at 50 ° C. for 3 hours, then filtered and concentrated. The reaction medium is taken up in 20 ml of toluene containing a catalytic amount of acetic acid and stirred at 100 ° C. for 4 hours. Concentration and purification on silica by flash chromatography gave 1.30 g of (E, E) -2- (2- {1-[(5-chloro-2-thiophenyl) methyloxyimino] white solid. -Ethoxymethyldiphenyl)
This gives methyl 2-methoxyiminoethaneate. F = 63 ° C. (this formula represents the melting point).

Example 2 (E, E) -2- (2- {1-[(5-Chloro-2-thiophenyl) methyloxyimino] -ethoxymethyl} phenyl) -2-methoxyimino-N-methylacetamide Preparation of (E, E) in 10 ml of a solution of methylamine [2M] in methyl alcohol
-2- (2- {1-[(5-chloro-2-thiophenyl) methyloxyimino]
-Ethoxymethyldiphenyl) -2-methoxyiminoethaneate at room temperature for 5 hours.
Stir for hours. After evaporation, 0.88 g of (E, E) -2- (2-
{1-[(5-Chloro-2-thiophenyl) methyloxyimino] -ethoxymethyl} phenyl) -2-methoxyimino-N-methylacetamide is obtained.
n _D = 1.5710 (24.0 ° C.) (this equation represents the refractive index at 24.0 ° C. when using the D emission line of sodium as light).

Example 3 (E, E) -2- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl)
Preparation of methyl 3-methoxypropenoate Step 1 Preparation of N-[(3,5-dimethyl-4-isoxazolyl) -methoxy] cyclopropane-carboxamide 18 g of O- (3,5-dimethyl-4-isoxazolyl) methyl To a 0 ° C. cooled solution of hydroxylamine hydrochloride and 30.9 ml of triethylamine in 250 ml of dichloromethane is added dropwise 10.9 ml of cyclopropanecarboxylic acid chloride. The reaction medium obtained is stirred at room temperature for 16 hours and then neutralized with an aqueous buffer solution of pH = 7. The organic phase is dried, evaporated and recrystallized in diisopropyl ether. Thus, F = 92 ° C., white solid N-[(3,5-dimethyl-4-isoxazolyl) -methoxy] cyclopropane-carboxamide 1
2.9 g are obtained.

Step 2 (E, E) -2- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl)
Preparation of methyl 3-methoxypropenoate In 10 ml of refluxing acetonitrile, 1.5 g of O- (3,5-dimethyl-4-isoxazolyl) methyl cyclopropanecarboxamate and 1.8 g of (E
) Stir methyl-2- [2- (bromomethyl) phenyl] -3-methoxypropenoate and 2.5 g of cesium carbonate for 4 hours under an inert atmosphere. After filtration of the cesium salts and evaporation of the solvent, the reaction mass is stirred at 100 ° C. for 5 hours in 15 ml of toluene containing 0.25 ml of glacial acetic acid. neutralized with a buffered aqueous solution of pH = 7,
After filtration on a phase separation filter and evaporation, flash chromatography on silica gave 0.61 g of n _D = 1.5300 (24.5 ° C.), (E, E) as a yellow oil. -2- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl}
Methyl phenyl) -3-methoxypropenoate can be isolated.

Example 4 (E, E) -2- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl)
Preparation of methyl 2-methoxyiminoethaneate (E, E) -2- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl )
Methyl-2-methoxyiminoethaneate is prepared by a procedure similar to that shown in Step 2 of Example 3. Thus, 4 g of cyclopropane carboxamic acid O
-(3,5-dimethyl-4-isoxazolyl) methyl and 4.8 g of n _D = 1
. (E) -2- [2- (Bromomethyl) phenyl]-at 5320 (25.7 ° C)
From methyl 2-methoxyiminoethaneate, the properties of orange oil (E, E
Methyl) -2- (2- (1-((3,5-dimethyl-4-isoxazolyl) methyloxyimino) -1-cyclopropylmethyloxymethyl) phenyl) -2-methoxyiminoethaneate is obtained.

Example 5 (E, E) -2- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl)
Preparation of -2-methoxyimino-N-methylacetamide (E, E) -2- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl ｝ Phenyl)
-2-Methoxyimino-N-methylacetamide is prepared by a procedure similar to that shown in Example 2. Thus, 0.4 g of (E, E) -2- (2- ｛
1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1
-Methyl-cyclopropylmethyloxymethyl {phenyl) -2-methoxyiminoethanate gives (E, E) -2- (2- {1-[(3,5)
-Dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl {phenyl) -2-methoxyimino-N-methylacetamide. _{n D = 1.5357 (26.1 ℃)} .

Example 6 (E) -N-methoxy-N- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl}
Preparation of methyl phenyl) carbamate (E) -N-methoxy-N- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl}
Methyl phenyl) carbamate is prepared by a procedure similar to that shown in Step 2 of Example 3. Thus, 1.7 g of cyclopropanecarboxamic acid O-
From (3,5-dimethyl-4-isoxazolyl) methyl and 1.95 g of methyl N-methoxy-N- [2- (bromomethyl) phenyl] -carbamate, (E) -N having the properties of an orange oil was obtained. -Methoxy-N- (2- {1-[(3,5-
0.366 g of methyl dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl {phenyl) carbamate are obtained.
_{n D = 1.5266 (23.3 ℃)} .

Example 7 Preparation of methyl (E) -2- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -e} phenyl) -2-methoxyethanate ) -2- (2- {1-[(3,5-Dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -2
-Methyl methoxyethanoate is prepared by a procedure similar to that shown in Step 2 of Example 3. Thus, 1.7 g of cyclopropanecarboxamic acid O- (3
, 5-Dimethyl-4-isoxazolyl) methyl and 1.94 g of 2- [2- (
From methyl bromomethyl) phenyl] -2-methoxyethanate, 0.23 g of orange oil (E) -2- (2- {1-[(3,5-dimethyl-4
-Isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl {phenyl) -2-methoxyethaneate.

Example 8 (E, E) -2- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl)
Preparation of methyl 2-butenoate (E, E) -2- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyloxyimino] -1-cyclopropylmethyloxymethyl {phenyl}
Methyl-2-butenoate is prepared by a procedure similar to that shown in Step 2 of Example 3. Thus, 1.5 g of cyclopropanecarboxamic acid O- (3,5
-Dimethyl-4-isoxazolyl) methyl and 1.6 g of (E) -2- [2-
From (bromomethyl) phenyl] -2-butenoate, 0.66 g of a yellow oil having the properties of (E, E) -2- (2- {1-[(3,5-dimethyl-4-isoxazolyl) methyl] Oxiimino] -1-cyclopropylmethyloxymethyl
This gives methyl (phenyl) -2-butenoate.

Example 9 Methyl (E, E) -2- (2- {1- [1- (2-pyridinyl) propyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl} -3-methoxypropenoate Step 1 Preparation of N- [1- (2-pyridinyl) propyloxy] phthalimide 14.4 g of 2- (1-chloropropyl) pyridine, 15.1 g of N-hydroxyphthalimide and 280 ml of dimethylformamide A mixture of 12.8 g of potassium carbonate in the mixture was stirred for 7 hours at 80 ° C. The reaction material was partitioned between an aqueous phase and ethyl acetate, the aqueous phase was extracted with ethyl acetate, and the organic phase was extracted with a saturated aqueous solution of sodium chloride. Collect and wash, then dry and evaporate The solid obtained is recrystallized in di-isopropyl ether, which gives 11.52 g of Color solid N-
[1- (2-Pyridinyl) propyloxy] phthalimide is obtained. F = 12
3 ° C.

Step 2 Preparation of N- [1- (2-pyridinyl) propoxy] cyclopropanecarboxamide 20.4 g of N- [1- (2-pyridinyl) propyloxy] phthalimide and 4.34 g in 400 ml of ethanol Is stirred at 35 ° C. for 2 hours and then filtered. The filtrate is rinsed with ethanol and the mother liquor is collected, concentrated and reconstituted with ethyl acetate and saturated aqueous sodium chloride. The aqueous phase is re-extracted with ethyl acetate, the combined organic phases are dried and evaporated to give 11.65 g of reaction material. This is added to a solution of 12.17 ml of triethylamine in 120 ml of dichloromethane. Next, 7.98 ml of cyclopropanecarboxylic acid chloride are added dropwise at 0 ° C. and the reaction mixture is then stirred at room temperature for 1 hour. Next, a saturated aqueous solution of sodium chloride was added, the aqueous phase was extracted with dichloromethane, and the organic phase was collected.
Dry and evaporate. The material obtained was recrystallized in di-isopropyl ether and purified by flash chromatography on a silica column, whereby 13
g of N- [1- (2-pyridinyl) propoxy] cyclopropanecarboxamide as a white solid. F = 79 ° C.

Step 3 Methyl (E, E) -2- (2- {1- [1- (2-pyridinyl) propyloxyimino] -1-cyclopropyl-methyloxymethyl} phenyl} -3-methoxypropenoate Preparation of 6.1 g of O-1- (2-pyridinyl) propyl cyclopropanecarboxamate in 100 ml of refluxing acetonitrile and 7.89 g of (E) -2- [2-
Stir methyl (bromomethyl) phenyl] -3-methoxypropenoate and 9.02 g of cesium carbonate under an inert atmosphere for 4 hours. After filtering the cesium salt,
The filtrate is concentrated, reconstituted with aqueous solution and ethyl acetate, the organic phase is dried and evaporated. The reaction mass is purified by flash chromatography on silica. In 50 ml of toluene containing 0.50 ml of glacial acetic acid, the material obtained is
Stir at 00 ° C. for 6 hours. After neutralization with a buffered aqueous solution of pH = 7, filtration on a phase separation filter and evaporation, flash chromatography on silica gave 0.96 g of (E, E) -2 as a brown oil. -(2- ｛1- [1- (2-
Pyridinyl) propyloxyimino] -1-cyclopropylmethyloxymethyl {phenyl} -3-methoxypropenoate. n _D =
1.5366 (24.0 ° C).

Example 10 (E, E) -2- (2- {1- [1- (6-Methyl-2-pyridinyl) ethyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl} -2- Preparation of methyl methoxyiminoethaneate Step 1 Preparation of 2- (1-hydroxyethyl) -6-methylpyridine 15 g of 6-methylpyridine-2 in 100 ml of diethyl ether at −78 ° C.
-To the solution of carboxaldehyde, under an inert atmosphere, add 50 ml of Grignard bromomethyl [3M / diethyl ether]. After the addition, the reaction medium is stirred for 1 hour at room temperature. Separation of diethyl ether / hydrochloric acid [1N] was carried out and pH = 7.
The aqueous phase is neutralized with a buffer solution of the above and the organic phase is collected, dried over magnesium sulfate and evaporated to give 14.6 g of crude 2- (1-hydroxyethyl) as a yellow oil.
-6-Methylpyridine can be separated. Rf = 0.31 (heptane / ethyl acetate 30/70).

Step 2 Preparation of N- [1- (6-methyl-2-pyridinyl) ethyloxy] phthalimide 14.6 g of crude 2- (1-hydroxyethyl) -6-methylpyridine in 300 ml of tetrahydrofuran Dilute 19.1 g of N-hydroxyphthalimide and 30.7 g of triphenylphosphine. Next, 18.4 ml of diethyl azodicarboxylate are added dropwise with stirring under an inert atmosphere. The resulting reaction mixture is stirred at room temperature for 14 hours, evaporated and purified by flash chromatography on silica. This makes it possible to separate the binding substance and the solid mixture corresponding to the reduced diethyl azodicarboxylate as used in the next step. Rf = 0.59 (heptane / ethyl acetate 30/70)

Step 3 Preparation of O- [1- (6-Methyl-2-pyridinyl) ethyloxy] hydroxylamine N- [1- (6-Methyl-2-pyridinyl) ethyloxy] phthalimide as described above and reduced diethyl azodicarboxylate Is stirred in 200 ml of refluxing ethanol containing 5.8 g of hydrated hydrazine for 1 hour. The filtrate is washed with ethanol, the mother liquor is concentrated and reconstituted with diisopropyl ether. After three successive crystallizations, the suspended solution of diisopropyl ether is evaporated. This gives 8.4 g of O- [1- (6-methyl-2-pyridinyl) ethyl] hydroxylamine as a pale yellow oil. Rf = 0.23 (ethyl acetate 100).

Step 4 Preparation of N- [1- (6-methyl-2-pyridinyl) ethoxy] cyclopropanecarboxamide 8 g of O- [1- (6-methyl-2-pyridinyl) ethyl] hydroxylamine and 100 ml To a cooled solution of 9.6 ml of triethylamine in dichloromethane at 0 ° C., 6.2 ml of cyclopropanecarboxylic acid chloride are added dropwise under an inert atmosphere. The resulting reaction mixture is stirred at room temperature for 5 hours and then neutralized with an aqueous buffer solution at pH = 7. The organic phase is washed with a buffered aqueous solution at pH = 7 and the combined aqueous phases are extracted with ethyl acetate. After recombining and evaporating the organic phase, flash chromatography on silica gives 2.9 g of N- as a white solid.
[1- (6-Methyl-2-pyridinyl) ethoxy] cyclopropanecarboxamide is obtained. F = 134 ° C.

Step 5 (E, E) -2- (2- {1- [1- (6-Methyl-2-pyridinyl) ethyloxyimino] -1-cyclopropylmethyloxymethyl} phenyl) -2-methoxy Preparation of methyl iminoethanoate In 15 ml of refluxing acetonitrile, 1.3 g of O-1- (6-methyl-2-pyridinyl) ethyl cyclopropanecarbohydroxamate and 1.7 g of (E)
Stir methyl-2- [2- (bromomethyl) phenyl] -2-methoxyiminoethaneate and 2.3 g of cesium carbonate for 3 hours under an inert atmosphere. After filtration of the cesium salts and evaporation of the solvent, the reaction mass is stirred at 100 ° C. in 20 ml of toluene containing 0.24 ml of glacial acetic acid. After neutralization with a buffered aqueous solution of pH = 7, filtration on a phase separation filter, evaporation and flash chromatography on silica, 0.701 g of brown oily (E, E) -2 was obtained. − (2- ｛
Methyl 1- [1- (6-methyl-2-pyridinyl) ethyloxyimino] -1-cyclopropylmethyloxymethyl {phenyl) -2-methoxyiminoethaneate can be separated. _{n D = 1.5438 (24.2 ℃)} .

Example 11 (E, E) -2- (2- {1- [1- (6-Methyl-3-pyridinyl) -1-)
Preparation of methyl (methoxycarbonyl) -ethyloxyimino] -1-cyclopropylmethyloxymethyldiphenyl) -2-methoxyiminoethaneate Step 1 Methyl 2-bromo-2- (6-methyl-3-pyridinyl) propionate Preparation of 14 g of methyl 2- (6-methyl-3-pyridinyl) propionate and 14 g
Of N-bromosuccinimide and 1 g of benzoyl peroxide in 300 ml of carbon tetrachloride are stirred for 3 hours under illumination with a halogen lamp. After filtration, the organic solution is washed with a saturated aqueous solution of sodium chloride and then with a saturated aqueous solution of sodium thiosulfate, washed again with a saturated aqueous solution of sodium chloride, dried and evaporated. Purification by flash chromatography on silica allows 2.9 g of maroon oily methyl 2-bromo-2- (6-methyl-3-pyridinyl) propionate to be isolated. Rf = 0.38 (heptane / ethyl acetate 50/5
0).

Step 2 2-{[cyclopropylcarbonyl] amino] oxy} -2- (6-methyl-
Preparation of methyl 3-pyridinyl) propionate 2.9 g of methyl 2-bromo-2- (6-methyl-3-pyridinyl) propionate, 1.13 g of cyclopropanecarboxamic acid, and 0.4 g of methanol in 40 ml of methanol. A mixture of 6 g of sodium methylate is heated at 50 ° C. for 5 hours. 2
0.57 g cyclopropanecarboxamic acid in 0.3 ml methanol and 0.3 g
Is added and the reaction mixture is stirred at 50 ° C. for a further 2 hours. After evaporation of the solvent, the reaction mass is taken up with aqueous solution and ethyl acetate, the organic phase is dried, evaporated and purified by flash chromatography on silica. Thereby, 1.7 g of methyl 2-{[cyclopropylcarbonyl] amino] oxy} -2- (6-methyl-3-pyridinyl) propionate as a brown solid can be separated. F = 89 ° C.

Step 3 (E, E) -2- (2- {1- [1- (6-methyl-3-pyridinyl) -1-)
Preparation of methyl (methoxycarbonyl) ethyloxyimino] -1-cyclopropylmethyloxymethyldiphenyl) -2-methoxyiminoethaneate In 50 ml of refluxing acetonitrile, 1.4 g of cyclopropanecarboxamic acid O-1- ( 6-methyl-3-pyridinyl) -1- (methoxycarbonyl) ethyl, 1.43 g of methyl (E) -2- [2- (bromomethyl) phenyl] -2-methoxyiminoethaneate and 1.63 g of methyl The cesium carbonate is stirred for 7 hours under an inert atmosphere. After filtration of the cesium salts and evaporation of the solvent, the reaction mass is stirred at 50 ° C. for 5 hours in 20 ml of toluene containing 0.25 ml of glacial acetic acid. Neutralize with an aqueous solution of potassium carbonate, extract the aqueous phase with ethyl acetate, evaporate the combined and dried organic phases and flash chromatograph on silica to obtain 0.54 g of a pink solid. (E, E) -2- (2- {1- [1- (6-methyl-3-pyridinyl) -1- (methoxycarbonyl) ethyloxyimino]-
Methyl 1-cyclopropylmethyloxymethyl {phenyl) -2-methoxyiminoethaneate can be separated. F = 95 ° C.

Example 12 of methyl (E, E) -2- (2- {1- [1- (N-oxide-2-pyridinio) ethyloxyimino] -ethoxymethyl} phenyl) -3-methoxypropenoate Preparation 200 mg of methyl (E, E) -2- (2- {1- [1- (2-pyridinyl) ethyloxyimino] -ethoxymethyl} phenyl) -3-methoxypropenoate (see Example 50) ) And 0.65 mg of methyltrioxorhenium in 1 ml of dichloromethane at room temperature were added to a 0.05% aqueous solution of 30% aqueous hydrogen peroxide.
9 ml are added dropwise. The resulting reaction mixture is stirred at room temperature for 24 hours, then p
Place in H = 7 buffer solution. The aqueous phase was extracted with dichloromethane, the organic phases were combined and evaporated, followed by flash chromatography on silica to give 172 mg of a colorless oily (E, E) -2- (2- {1- [ 1- (N-oxide-2-pyridinio) ethyloxyimino] -ethoxymethyldiphenyl)
This gives methyl -3-methoxypropenoate. n _D = 1.5629 (21.2 ° C.
).

Example 13 (E, E) -2- (2- {1- [1- (4-quinolyl) ethyloxyimino]
Preparation of methyl ethyloxymethyl) phenyl-2-methoxyiminoethaneate Step 1 (E, E) -2- {2- [1- (tert-butyldimethylsilyloxyimino) ethyloxymethyl] phenyl} -2-methoxy Preparation of methyl iminoethaneate 1.89 g of O-tert-butyldimethylsilyl acetohydroxamate;
A mixture of 2.86 g of methyl (E) -2- [2- (bromomethyl) phenyl] -2-methoxyiminoethanolate and 3.91 g of cesium carbonate in 50 ml of acetonitrile was stirred at 50 ° C. for 5 hours, Next, it is filtered and concentrated. Purification by flash chromatography on silica gave 0.60 g of (E, E) -2- {2- [1- (tert-butyldimethylsilyloxyimino) ethyloxy-methyl] phenyl} as a white solid. Methyl 2-methoxyiminoethaneate can be isolated.

Step 2 Preparation of methyl (E, E) -2- {2- [1- (hydroxyimino) ethyloxymethyl] phenyl} -2-methoxy-iminoethaneate 0.19 g of (E, E) -2 -{2- [1- (tert-butyldimethylsilyloxyimino) ethyloxymethyl] phenyl} -2-methoxyiminoethaneate, 0.086 g of acetic acid and 0.080 in 10 ml of acetonitrile
A mixture of g cesium fluoride is stirred at room temperature for 20 hours. After concentration, purification by flash chromatography on silica gave 0.10 g of (E, E) -2- {2- [1- (hydroxyimino) ethyloxymethyl] phenyl} -white solid. Methyl 2-methoxy-iminoethaneate can be isolated.

Step 3 (E, E) -2- (2- {2- [1- (4-quinolyl) ethyloxyimino]
Preparation of methyl ethyloxy-methyl {phenyl) -2-methoxyiminoethaneate 0.4 g of (E, E) -2- {2- [1- (hydroxyimino) ethyloxymethyl] phenyl} -2-methoxyiminoethane Methyl acid and 0.274 g of 4
-(1-Chloro-ethyl) -quinolein and 0.1% in 20 ml of acetonitrile.
A mixture of 513 g of cesium carbonate is stirred at reflux for 5 hours. After filtration and evaporation of the solvent, the reaction mass is purified by flash chromatography on silica.
Thereby, 0.118 g of yellow-honey-like (E, E) -2- (2- {1- [1- (
Methyl 4-quinolyl) ethyloxyimino] ethyloxymethyl {phenyl) -2-methoxyiminoethaneate can be isolated. Rf = 0.41 (heptane / ethyl acetate 30/70).

Example 14 Methyl (E, E) -2- (2- {1-[(3-trifluoromethyl-2-pyridinyl) oxyimino]-) ethyloxymethyl} phenyl) -2-methoxyiminoethaneate Preparation of 0.4 g of methyl (E, E) -2- {2- [1- (hydroxyimino) ethyloxymethyl] phenyl} -2-methoxyiminoethaneate (according to the method described in the previous example) Preparation), a mixture of 0.323 g of 2-bromo-3- (trifluoromethyl) pyridine and 0.513 g of cesium carbonate in 20 ml of acetonitrile are stirred at reflux for 5 hours. After filtration and evaporation of the solvent, the reaction mass is purified by flash chromatography on silica. Thereby, 0.
510 g of (E, E) -2- (2- {1-[(3-trifluoromethyl-2-pyridinyl) oxyimino] ethyloxymethyl} phenyl) -2-white solid
Methyl methoxyiminoethaneate can be isolated. F = 76 ° C.

Example 15 (E, E) -2- (2- {1- [2- (2-pyridinyl) ethoxyimino]-
Preparation of methyl 1-cyclopropyl-methyloxymethyldiphenyl) -3-methoxypropenoate Step 1 Preparation of N- [2 (-2-pyridinyl) ethoxy] phthalimide 20 g of 2- ( Charge 2-hydroxy-ethyl) pyridine, 29.2 g of N-hydroxyphthalimide, 47 g of triphenylphosphine and 450 ml of anhydrous THF. Next, 29.4 ml of DEA
Add D dropwise with stirring. The THF is evaporated and the residue is taken up in diisopropyl ether and ethyl acetate to give a white precipitate, which is recrystallized to give 14 g of the desired material.

Step 2 (E, E) -2- (2- {1- [2- (2-pyridinyl) ethoxyimino]-
Preparation of methyl 1-cyclopropyl-methyloxymethyldiphenyl) -3-methoxypropenoate By repeating steps 2 and 3 described in Example 9 and using the phthalimide prepared above, the desired Is obtained. n _D =
1.5605 (21.4 ° C).

Example 16 Preparation of methyl (E) -N-methoxy-N- (2- {1- [2- (2-pyridinyl) ethoxyimino] -1-cyclopropylmethyloxymethyl} phenyl) carbamate The operation method described in Example 15 above was repeated to obtain (E) -2- [2
-(Bromomethyl) phenyl] -3-methoxypropenoate instead of N-
The use of methyl methoxy-N- [2- (bromomethyl) phenyl] carbamate gives the desired substance as an orange viscous liquid. n _D = 1.54
35 (21.5 ° C).

The following examples are obtained by a similar procedure. In the following examples, the groups G1, G2
, G3 is due stereochemistry (E), the substituents _{W 1} and _{W 2} with respect to the double bond -C (R3) = N-, in the trans (stereochemistry E) position.

(In the table below, Pr is n-propyl, cPr is cyclopropyl, iPr
Represents isopropyl, sBu represents a secondary butyl group, and He represents n-hexyl. )

[0208]

[Table 1]

[0209]

[Table 2]

[0210]

[Table 3]

[0211]

[Table 4]

[0212]

[Table 5]

[0213]

[Table 6]

[0214]

[Table 7]

[0215]

[Table 8]

[0216]

[Table 9]

[0219]

[Table 10]

[0218]

[Table 11]

[0219]

[Table 12]

[0220]

[Table 13]

[0221]

[Table 14]

[0222]

[Table 15]

[0223]

[Table 16]

[0224]

[Table 17]

[0225]

[Table 18]

[0226]

[Table 19] Physicochemical analysis table of compound F: melting point (° C) n _D : refractive index (measuring temperature ° C) Rf: elution rate M: molecular peak

[0227]

[Table 20]

[0228]

[Table 21]

[0229]

[Table 22]

[0230]

[Table 23]

[0231]

[Table 24]

[0232]

[Table 25]

[0233]

[Table 26]

Example B1: In Vivo Test of Puccinia recondita (Wheat Rust) An aqueous suspension of the active material to be tested having the following composition is prepared by milling.

-Active material: 60 mg-Tween 80 surfactant (oleic acid ester of sorbitan polyoxyethylenated derivative) diluted to 10% with water: 0.3 ml-Acetone: 5 ml-Add 60 ml of water Dilute the suspension with water to obtain the desired ppm (parts per million).

Wheat in a container sown on a base layer of Pozzolanic 50/50 peat and kept at 12 ° C.
Step 1 (10 cm height) by spraying the above aqueous suspension
To process.

In this example and the following examples B2 to B7, the aqueous solution containing no active material
Treat seedlings used as controls.

After 24 hours, an aqueous suspension of Puccinia recondita spores (1
Each seedling is contaminated by spraying (150,000 spores per cm ³ ). This suspension is obtained from the contaminated seedlings.

Next, the contaminated wheat seedlings are incubated at a constant humidity of about 20 ° C. for 24 hours under a saturated humidity atmosphere, and then incubated at a relative humidity of 60% for 7 to 14 days.

Readings are taken between day 8 and day 15 after contamination in comparison to control seedlings.

In this and the following Examples B2 to B7, good protection (at least 7
The results observed in this situation at a dose of 40 ppm for 5%) or complete protection are listed in the results table below.

Example B2 In Vivo Testing of Septoria tritici (Wheat Spot) An aqueous suspension of the active material to be tested is prepared as in Example B1.

Wheat in a container, sown on a base layer of Pozzolanic 50/50 peat and kept at 12 ° C.
Step 1 (10 cm height) by spraying the above aqueous suspension
To process.

After 24 hours, an aqueous suspension of spores of Septoria tritici (1 cm ³ 500,000 spores per plant) to reduce the contamination of each seedling.
Do. The spores are collected from the culture that has passed for 7 days.

Next, the contaminated wheat seedlings are incubated at a constant temperature of about 20 ° C. for 72 hours in a humidity atmosphere, and then incubated at a relative humidity of 90% for 20 days.

At 21 days after the contamination, a reading is taken in comparison with the control seedlings.

Example B3 In Vivo Testing of Septoria nodorum (Wheat Spot) An aqueous suspension of the active material to be tested is prepared as in Example B1 above.

Wheat in a container, sown on a base layer of Pozzolanic 50/50 peat and kept at 12 ° C.
Step 1 (10 cm height) by spraying the above aqueous suspension
To process.

After 24 hours, each seedling is contaminated by spraying with an aqueous suspension of Septoria nodorum spores (500,000 spores per cm ³ ). The spores are harvested from the culture that has passed for 7 days.

Next, the contaminated wheat seedlings are incubated at a constant temperature of about 20 ° C. for 72 hours in a humidity atmosphere, and then at a constant humidity of 90% for 14 days.

On day 15 after contamination, a reading is taken in comparison with control seedlings.

Example B4: Erisiphe graminis fsp tritic
In vivo test of i (wheat powdery mildew) In the same manner as in Example B1, an aqueous suspension of the active material to be tested is prepared.

Wheat in a container, sown on a pozzolanic 50/50 peat base layer and kept at 12 ° C.
Audice variant) is treated in stage 1 (10 cm height) by spraying the above aqueous suspension.

Twenty-four hours later, wheat seedlings are sprinkled with Erysphe graminis spores. Spraying is performed using diseased seedlings.

Readings are taken between 7 and 14 days after contamination in comparison to control seedlings.

Example B5: Eryshphe graminis fsp hordei
In vivo test of (barley powdery mildew) An aqueous suspension of the test active material is prepared in the same manner as in Example B1 above.

Barley in a container, sown on a base layer of Pozzolanic 50/50 peat and kept at 12 ° C.
Express variant), by spraying the above aqueous suspension onto stage 1 (10 cm height)
To process.

Twenty-four hours later, barley seedlings are sprinkled with spores of Erisphe graminis. Spraying is performed using diseased seedlings.

Readings are taken between 7 and 14 days after contamination in comparison to control seedlings.

Example B6 In Vivo Test of Pyrenophora teres (Barley Leaf Spot) An aqueous suspension of the active material to be tested is prepared as in Example B1.

Barley in a container sown on a base layer of Pozzolanic 50/50 peat and kept at 12 ° C.
Express variant), by spraying the above aqueous suspension onto stage 1 (10 cm height)
To process.

After 24 hours, each seedling is sprayed with an aqueous suspension of Pyrenophora teres spores (12,000 spores per cm ³ ). This suspension is obtained from the contaminated seedlings.

Next, the contaminated barley seedlings are incubated at a constant temperature of about 20 ° C. for 24 hours in a saturated humidity atmosphere, and then at a relative humidity of 80% for a period of 7 to 14 days.

The readings are taken between day 8 and day 15 after contamination in comparison with control seedlings.

Example B7: Rynchosporium secalis (ryn of barley)
In vivo test of spores As in Example B1, an aqueous suspension of the active material under test is prepared.

Barley in a container, sown on a base layer of Pozzolanic 50/50 peat and kept at 12 ° C.
Express variant), by spraying the above aqueous suspension onto stage 1 (10 cm height)
To process.

Twenty-four hours later, each seedling is sprayed with an aqueous suspension of Rynchosporium secalis spores (800,000 spores per cm ³ ). This suspension is obtained from the contaminated seedlings.

Next, the contaminated barley seedlings are incubated at a constant temperature of about 20 ° C. for 24 hours under a saturated humidity atmosphere, and then incubated at a relative humidity of 80% for 7 to 14 days.

Readings are taken in comparison to control seedlings between days 8 and 15 after contamination.

Table of Test Results The "+" sign indicates 75% to 100% protection.

[0271]

[Table 27]

[0272]

[Table 28]

[0273]

[Table 29]

[0274]

[Table 30]

[0275]

[Table 31]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 43/50 A01N 43/50 Q 4C056 43/647 43/647 4H006 43/80 101 43/80 101 4H011 C07C 251/48 C07C 251/48 C07D 213/64 C07D 213/64 213/89 213/89 215/14 215/14 221/04 221/04 231/12 231/12 D 235/14 235/14 239/26 239 / 26 249/02 249/02 261/08 261/08 271/08 271/08 275/02 275/02 277/24 277/24 333/16 333/16 333/28 333/28 473/00 473/00 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG) , AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM , AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL , PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Jerry Yuz, Bansan France, F-69009 Lyon, Li-Louis Bouquet, 39 (72) Inventor Altoma , Benoit, France, F-69004 Lyon, Lyre-Jiacar, 74 (72) Inventor Perez, Jozefev France, F-69009 Lyon, Lyue Ernesto Fabregue, Allee-de, 19 (72) Inventor Villier, Allan F-69370 Saint-Deid-Jay-au-Mont-d'Or, Chouman des Zes, France 18 (72) Inventor Ball, Jean-Pierre F-69009 Lyon, Cille Man Dou Monpla, 9 (72) Inventor Sawai Nobumitsu 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Japan Rhone-Poulin Petrochemical Agro Co., Ltd. Ami Research Institute (72) Inventor Sakurai Tadashi Ibaraki, Japan 8-3-1 Chuo, Ami-cho, Inashiki-gun Rh ヌ ne-Poulein Petrochemical Agro Co., Ltd. A terminology in the Ami Research Laboratory 4C023 BA04 4C031 BA02 4C033 AA10 AA17 AD06 AD17 4C034 CB01 4C055 AA01 AA17 BA02 BA03 BA05 BA27 CA01 CA02 CA13 CA27 CA39 DA01 4C056 AA01 AB01 AC01 AD01 AE03 FA14 4H006 AA01 AA02 AB03 AD33 BA04 BA29 BA51 BB12 BB14 BB21 BB30 BC10 TA04 4H011 AA01 BA01 BB09 BB10 BC05 BC08 BC18 BC19 DA14 DD03 DH03

Claims (36)

[Claims] 1. A compound of the general formula (I): Wherein G is a group G1-G9: Wherein n represents 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 a nitrogen atom or a group CR ₁₁ , Q ₅ is an oxygen atom or a sulfur atom or a group NR ₁₂ , Y is an oxygen atom or a sulfur atom or an amino group (NH) or an oxyamino group (ONH), and W ₁ Is an oxygen atom or a sulfur atom or a sulfinyl group (SO) or a sulfonyl group (SO ₂ ); W ₂ is an oxygen atom or a group NR ₁₃ ; p represents 0, 1 or 2; Atoms, of which 1-4 atoms are heteroatoms selected from oxygen, sulfur or nitrogen, including sulfur or nitrogen. Each is a monocyclic or bicyclic aromatic heterocyclic group, optionally in the oxidation state in the form of an N-oxide group or a sulfoxide group, wherein the heterocyclic group is, when p = 1 or p = 2, Is attached to a carbon atom substituted by groups R ₁ and R ₂ ;
In the case of p = 0 is linked to a group _{W 2} with carbon or nitrogen atom, said heterocyclic group 1-5 radicals _{X 1} and / or _{X 2} and / or _{X 3} and / or _{X 4} And / or X ₅ , preferably optionally substituted by 1-3 groups X ₁ and / or X ₂ and / or X ₃ , wherein X ₁ , X ₂ , X ₃ , X ₄ and X ₅ are each other Independently a hydrogen atom, a halogen atom;
Or hydroxy group, mercapto group, nitro group, thiocyanate group, azide group, cyano group or pentafluorosulfonyl group; or lower alkyl group, lower haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, haloalkylthio group, alkoxyalkyl Group, haloalkoxyalkyl group, alkylthioalkyl group, haloalkylthioalkyl group, cyanoalkyl group, sialalkoxy group, cyanoalkylthio group, alkylsulfinyl group, haloalkylsulfinyl group, alkylsulfonyl group, haloalkylsulfonyl group, alkoxysulfonyl group; or lower Cycloalkyl group, lower halocycloalkyl group, alkenyl group, alkynyl group, alkenyloxy group, alkynyloxy group, alkenylthio group, alkynylthi Or an amino group, N-alkylamino group, N, N-dialkylamino group, acylamino group, aminoalkyl group, N-alkylaminoalkyl group, N, N-dialkylaminoalkyl group, acylaminoalkyl group; or acyl Group, carboxy group, carbamoyl group, N-alkylcarbamoyl group, N
, An N-dialkylcarbamoyl group or a lower alkoxycarbonyl group; the group X ₁ optionally forms a 5- to 7-membered ring together with R ₁₃ when W ₂ is a group NR ₁₃ ; Forms a 5- to 7-membered ring with R ₁ , and when p = 2, R
_'1 together form a 5-7 membered ring, X ₆ is a hydrogen atom or a halogen atom; or a lower alkyl group, lower haloalkyl group, an alkoxy group, a haloalkoxy group; or a cyano group, a nitro group, R ₁ And R ₂ are each independently a hydrogen atom, a lower alkyl group, a lower haloalkyl group, a lower cycloalkyl group, a lower halocycloalkyl group, an alkoxyalkyl group, a haloalkoxyalkyl group, an alkylthioalkyl group, a haloalkylthioalkyl group, a cyanoalkyl Or a cyano group, acyl group, carboxy group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, lower alkoxycarbonyl group, alkylthiocarbonyl group, haloalkoxycarbonyl group, alkoxythiocarbonyl group, haloalkoxy Thio Carbonyl group, alkylthio-thiocarbonyl group;
Or an aminoalkyl group, an N-alkylaminoalkyl group, an N, N-dialkylaminoalkyl group, an acylaminoalkyl group, or R ₁ and R ₂ together form one or more lower alkyl groups. R ₃ can be a hydrogen atom, a lower alkyl group, a lower haloalkyl group, a lower cycloalkyl group, a lower alkyl group, such as an optionally substituted alkylene group optionally substituted by one or more halogen atoms. Halocycloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, haloalkylthio group, alkoxyalkyl group, haloalkoxyalkyl group, alkylthioalkyl group, haloalkylthioalkyl group, cyanoalkyl group;
Or nitro group, cyano group, acyl group, carboxy group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, lower alkoxycarbonyl group, 3-oxetanyloxycarbonyl group, alkylthiocarbonyl group, haloalkoxycarbonyl group Or an alkoxythiocarbonyl group, a haloalkoxythiocarbonyl group, an alkylthiothiocarbonyl group; or an alkenyl group, an alkynyl group, an N, N-dialkylamino group, an N, N-dialkylaminoalkyl group; or a substituted or unsubstituted phenyl group or a benzyl group, R ₄ is a lower alkyl group, lower haloalkyl group, a lower cycloalkyl group, a lower halocycloalkyl group, an alkoxyalkyl group; or an alkoxy group, a haloalkoxy group, an alkylthio group, a Kiruamino group, a dialkylamino group, R ₅ and R ₆ are each independently a lower alkyl group or a lower haloalkyl group, R ₇ is a lower alkyl group, a lower haloalkyl group, alkoxyalkyl group, haloalkoxy group, R ₈ is a lower alkyl group, a lower haloalkyl group, an alkoxyalkyl group, a haloalkoxyalkyl group, an alkenyl group, an alkynyl group, a formyl group, an acyl group; R ₉ is a hydrogen atom; A lower alkyl group, a lower haloalkyl group, a lower cycloalkyl group, a lower halocycloalkyl group, an alkoxyalkyl group, a haloalkoxyalkyl group, an alkenyl group, and an alkynyl group; R ₁₀ represents a hydrogen atom, a lower alkyl group, a lower haloalkyl group; , Lower cycloalkyl group, lower halo A cycloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, an alkylsulfinyl group, a haloalkylsulfinyl group, an alkylsulfonyl group, and a haloalkylsulfonyl group; R ₁₁ and R ₁₂ independently of one another are a hydrogen atom, An alkyl group, a lower haloalkyl group, a lower cycloalkyl group, a lower halocycloalkyl group, an alkoxyalkyl group, a haloalkoxyalkyl group, an alkenyl group, and an alkynyl group; R ₁₃ is a hydrogen atom, a lower alkyl group, a lower haloalkyl group, Lower cycloalkyl group, lower halocycloalkyl group, alkoxyalkyl group, haloalkoxyalkyl group, alkylthioalkyl group, haloalkylthioalkyl group, substituted or unsubstituted allyl group, substituted or unsubstituted propal Benzyl group, substituted or unsubstituted benzyl group; or acyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, lower alkoxycarbonyl group, alkylthiocarbonyl group, haloalkoxycarbonyl group, alkoxythiocarbonyl group, haloalkoxy Thiocarbonyl group,
An alkylthiocarbonyl group; or a substituted or unsubstituted alkylsulfonyl group, a haloalkylsulfonyl group, an arylsulfonyl group, wherein Q ₂ and R ₄ together represent one or more of a halogen, a lower alkyl group or a lower haloalkyl group. Can form a ring of 5-7 atoms containing 2-3 oxygen and / or nitrogen atoms optionally substituted by groups] and salts of the compounds of formula (I) as defined above, metal complexes and Metalloid complex. 2. One or more of the following features: n is equal to 0; p is equal to 0, 1 or 2; 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 group, a haloalkylamino group, an alkoxyalkyl X is an oxygen atom; X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and X ₆ are independently of each other, a hydrogen atom, a lower alkyl group, a halogen atom or a cyano group, fluoromethyl group, a methoxy group is the nitro group; R ₁ and R _2, independently of one another, a hydrogen atom, a lower alkyl group, lower cycloalkyl group, a lower haloalkyl group, alkoxyalkyl , A cyano group, a cyanoalkyl group, an N-alkylaminoalkyl group, an N, N-dialkylaminoalkyl group, an acylaminoalkyl group, a lower alkoxycarbonyl group, an N-alkylcarbamoyl group or an N, N-dialkylcarbamoyl group; R ₃ is a hydrogen atom, a lower alkyl group, lower cycloalkyl group, a lower haloalkyl group, an alkoxyalkyl group, preferably is a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group or a methoxymethyl group; R ₄ Is a lower alkyl group, an alkoxy group, an alkylamino group, a dialkylamino group, preferably a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group,
R ₅ , R ₆ , R ₈ and R ₉ are each independently a lower alkyl group, a lower haloalkyl group, preferably a methyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group; R ₇ is a lower alkyl group, a lower haloalkyl group, preferably a methyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, an ethyl group, a 2,2,2-trifluoroethyl group or a propyl group. Group, ethyl group, 2,2
, 2-trifluoromethyl, propyl, allyl or propargyl; R ₁₀ is chlorine, lower alkyl, lower haloalkyl, preferably methyl, or alkoxy, alkylthio, preferably methoxy or R ₁₁ and R ₁₂ are each independently a lower alkyl group, a lower haloalkyl group, an alkoxyalkyl group, an allyl group, or a propargyl group; R ₁₃ is a hydrogen atom, a lower alkyl group, a lower haloalkyl group, an alkoxy group. A is an alkyl group, a haloalkoxyalkyl group, an allyl group, a propargyl group, or a benzyl group; A is a ring represented by the following formulas (i) to (v), that is, a formula (i): Wherein each of the groups B ¹ , B ² , B ³ , B ^{4 in} the list represents 0-3 carbon atoms, 0-1 sulfur atoms, 0-1 oxygen atoms and 0 Selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom so as to contain four nitrogen atoms]; a 5-membered ring represented by the formula (ii): [In the formula, each of the groups D ¹ , D ² , D ³ , D ⁴ , and D ^{5 in} the list is a group in which the list is 1-
Selected from a carbon atom and a nitrogen atom so as to contain 4 carbon atoms and 1-4 nitrogen atoms]; a six-membered ring represented by the formula (iii): Wherein each of the groups E ¹ , E ² , E ³ , E ⁴ , E ⁵ , E ⁶ , E ⁷ , E ⁸ of the list is such that the list has 4-7 carbon atoms and 1-4 carbon atoms. Selected from a carbon atom and a nitrogen atom so as to include a nitrogen atom]; a fused ring of two 6-membered rings; formula (iv): Wherein each of the groups J ¹ , J ² , J ³ , J ⁴ , J ⁵ , J ^{6 in} the list is such that the list contains 3-6 carbon atoms and 0-3 nitrogen atoms. Each of the groups L ¹ , L ² , L ^{3 in} the list is selected from the group consisting of 0-3 carbon atoms, 0
Selected from carbon, nitrogen, oxygen and sulfur to contain -1 sulfur, 0-1 oxygen and 0-3 nitrogen; groups J ¹ , J ² , Each of J ³ , J ⁴ , J ⁵ , J ⁶ , L ¹ , L ² , L ³ is selected such that said list contains from ³ to 8 carbon atoms. A fused ring of and one 5-membered ring; Formula (v): Wherein each of the groups M ¹ , M ² , M ^{3 in} the list is 0-3 carbon atoms, 0-1 sulfur atoms, 0-1 oxygen atoms and 0-3 And each of the groups T ¹ , T ² , T ^{3 in} the list is selected from the group consisting of 0-3 carbon atoms, 0
Z is selected from carbon, nitrogen, oxygen and sulfur to include -1 sulfur, 0-1 oxygen and 0-3 nitrogen; and Z represents a carbon or nitrogen. , Each of the list groups M ¹ , M ² , M ³ , T ¹ , T ² , T ³ is such that the list is 0-
Selected from the group consisting of 6 carbon atoms] and 1-5 groups X ₁ and / or ₁ derived by removing a hydrogen atom from one of
Or X ₂ and / or X ₃ and / or X ₄ and / or X ₅ , preferably 1
Is selected from the group that is optionally substituted by -3 radicals X ₁ and / or X ₂ and / or X _3: a alone or in compound according to claim 1, characterized in that it comprises in combination as well as their Salts, metal complexes and metalloid complexes of 3. One or more of the following features:₁Is an oxygen atom; R₁Is a hydrogen atom or a methyl group; R₂Represents a hydrogen atom or a lower alkyl group, a cyano group, a cyanoalkyl group,
Coxyalkyl group, N, N-dialkylaminoalkyl group, lower alkoxycar
A is a carbonyl group, a lower N, N-dialkyl-carbamoyl group; A is 1-5 groups X as defined above₁And / or X₂And / or X ₃ And / or X₄And / or X₅, Preferably 1-3 groups X₁And / or
Is X₂And / or X₃Represents a heterocyclic group optionally substituted by: A represents the following list: furanyl; pyrrolyl; thiophenyl; pyrazolyl; imidazolyl; oxazolyl; isoxazolyl; thiazolyl;
Isothiazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl
1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl;
3-thiadiazolyl; 1,2,4-thiadiazolyl; 1,2,5-thiadiazoli
1,3,4-thiadiazolyl; 1,2,3-triazolyl; 1,2,4-tol
1,4,3-Triazinyl; 1,2,3-Triazinyl; 1,2,3-Triazinyl;
1,4-triazinyl; 1,3,5-triazinyl ;; 1,2,3,4-tetra
1,2,3,5-tetrazinyl; 1,2,4,5-tetrazinyl; benzimidazolyl; indazolyl; benzotriazolyl; benzoxazolyl
1,2-benzisoxazolyl; 2,1-benzisoxazolyl; ben
Zothiazolyl; 1,2-benzisothiazolyl; 2,1-benzisothiazolyl
1,2,3-benzooxadiazolyl; 1,2,5-benzooxadiazolyl
1,2,3-benzothiadiazolyl; 1,2,5-benzothiadiazolyl; quinoleyl; isoquinoleyl; quinoxazolinyl; quinazolinyl; cinnolyl or phthalazyl;
1,5-naphthyridinyl; 1,6-naphthyridinyl; 1,6-naphthyridinyl;
1,8-naphthyridinyl; imidazo [2,1-b] thiazolyl; thieno [3,4-b] pyridinyl;
Or a compound selected from the group consisting of: pyrrolo [1,2-b] thiazolyl; alone or in combination.
And their salts, metal complexes and metalloid complexes. 4. The following characteristics: W ₁ is an oxygen atom; R ₁ is a hydrogen atom or a methyl group; R ₂ is a hydrogen atom or a lower alkyl group, a cyano group, a cyanoalkyl group, an alkoxyalkyl A is a group, N, N-dialkylaminoalkyl group, lower alkoxycarbonyl group, lower N, N-dialkyl-carbamoyl; A is 1-5 groups X ₁ and / or X ₂ and / or X ₃ and / or Or X ₄ and / or X ₅ , preferably a heterocyclic group optionally substituted by 1-3 groups X ₁ and / or X ₂ and / or X ₃ , wherein A is a heterocycle: pyridinyl Pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl;
Furanyl; pyrrolyl; thiophenyl; oxazolyl; isoxazolyl; thiazolyl; isothiazolyl; imidazolyl; pyrazolyl; And the salts, metal complexes and metalloid complexes thereof. 5. The following characteristics: W ₁ is an oxygen atom; R ₁ is a hydrogen atom or a methyl group; R ₂ is a hydrogen atom or a lower alkyl group, a cyano group, a cyanoalkyl group, an alkoxyalkyl A N, N-dialkylaminoalkyl group, a lower alkoxycarbonyl group, a lower N, N-dialkyl-carbamoyl group; 1-5 groups X ₁ and / or X ₂ and / or X ₃ and / or X ₄ and / or
Or A, optionally substituted by X ₅ , preferably 1-3 groups X ₁ and / or X ₂ and / or X ₃ represents a pyridinyl group: 5. And the salts, metal complexes and metalloid complexes thereof. 6. The compound according to claim 1, wherein G is selected from G1, G2 and G3. 7. The compound according to claim 1, wherein G represents G1. 8. Methyl- (E, E) -2- (2- {1-[(2-pyridinyl) methyloxyimino] -1-cyclopropyl-methyloxymethyl} phenyl) -3-methoxypropenoate Methyl- (E, E) -2- (2- {1- [1- (2-pyridinyl) propyloxyimino] -1-cyclopropyl-methyloxymethyl} phenyl) -3-methoxypropenoate; methyl -(E, E) -2- (2- {1- [1- (2-pyridinyl) propyloxyimino] propyloxymethyl} phenyl) -3-methoxypropenoate and methyl- (E, E) -2- (2- {1- [1- (2-pyridinyl) propyloxyimino] isobutyl-oxymethyl} phenyl) -3-methoxypropenoate And their salts, metal complexes and metalloid complexes according to the Motomeko 1 7 any one of. 9. An active ingredient comprising at least one compound of the formula (I) according to claim 1 or an agriculturally acceptable salt thereof or a metal of said agriculturally acceptable compound. A fungicidal composition comprising an effective amount of a complex or metalloid complex. 10. In addition to the compound of formula (I) or an agriculturally acceptable salt thereof or an active ingredient comprising a metal complex or a metalloid complex of said agriculturally acceptable compound, an agriculturally acceptable solid or 10. The fungicidal composition according to claim 9, which comprises a liquid carrier and / or a surfactant which is also agriculturally acceptable. 11. The fungicidal composition according to claim 9, comprising 0.05-95% by weight of the active ingredient. 12. A metal or metalloid complex of at least one compound of formula (I) according to claim 1, or one of its agriculturally acceptable salts, or a compound of said agriculturally acceptable compound, or Plant seed by spraying, spraying or injecting a fungicidal composition comprising an active ingredient of formula (I) according to any one of claims 1 to 8 in a non-phytotoxic agronomically effective amount. A method for controlling or preventing phytopathogenic fungi, which comprises treating cultivated soil, leaves or stems, or cultivated soil or planned cultivated soil of these plants. 13. A plant-enhancing substance against fungal diseases, characterized by coating the plant-enhancing substance with a compound or composition according to any one of claims 1 to 12 at an effective application rate that is not phytotoxic. A method for the prophylactic or therapeutic treatment of the plant obtained. 14. The method according to claim 13, wherein cereals, rice, fruit trees, forest trees, grapes, oil crops, intensively grown vegetables, eggplants or sugar beet are treated. 15. Rice, wheat, barley, rye, triticale, fruit tree,
15. The method according to claim 13 or 14, wherein corn, cotton, flax, rapeseed, grapes, forest trees, peas, potatoes or sugar beet are treated. 16. The method according to claim 13, wherein wheat or barley is treated. 17. The method according to claim 12, wherein cereals, potatoes, cotton, peas, rapeseed, corn, flax seeds or forest tree seeds are treated. 18. The application rate of the active ingredient to be sprayed in the seed treatment is 10 seeds.
Method according to any of claims 12 to 17, characterized in that the active ingredient is 2-200 g per 0 kg, preferably 3-150 g of active ingredient per 100 kg of seeds. 19. The application rate of the active ingredient applied in the case of foliar treatment is 10 to 800 g of active ingredient per hectare, preferably 5 to 5 active ingredients per hectare.
18. The method according to any one of claims 12 to 17, wherein the weight is 0-300 g. 20. A compound of the formula (II) A: Wherein, G is any one of the groups G1-G9, groups G1-G9 are the same as defined in claim 1, _{X 6} have the same meanings as defined in claim 1, _{V 1} is hydrogen An atom, an alkylsulfonate group, a haloalkylsulfonate group or an arylsulfonate group], and a compound of formula (III) A: Wherein W ₁ , W ₂ , R ₁ , R ₂ , R ₃ , p and A have the same meanings as defined in claim 1) in the presence of an organic base or an inorganic base. At or in the presence, at temperatures ranging from -80 ° C to 180 ° C or up to the boiling point of the solvent used, a reaction time depending on the reaction conditions used, generally requiring a reaction time of 0.1-48 hours. The method for producing a compound according to any one of claims 1 to 8, comprising contacting the compound. 21. The compound of formula (III) A according to claim 20, wherein W ₁ , W ₂ , R ₁ , R ₂ , R ₃ , p and A have the same meanings as defined in claim 1. A method of manufacture comprising a compound of formula (IV): Wherein W ₂ , R ₁ , R ₂ , p and A have the same meanings as defined in claim 1, and a compound of the formula (V): [Wherein, W ₁ and R ₃ are the same as defined in claim 1, and U ₁ is a halogen atom, or a hydroxy group, a lower alkoxy group or a benzyloxy group, a lower alkylthio group, an amino group, an N-alkyl Amino group, N, N-dialkylamino group,
An N-acylmiano group, an N, N-acylalkylamino group, or a group -O (C = O
) R _a , wherein R _a has the same meaning as defined in R ₃ of claim 1 and may be the same as or different from R ₃ ), and a compound of the formula (IV) and a compound of the formula (V )) In the presence of an organic or inorganic base or a dehydrating reagent in the absence or presence of a solvent. 22. In the formula, W1 is an oxygen atom, and W ₂ , R ₁ , R ₂ , R ₃ ,
21. A process for the preparation of a hydroxamic acid or hydrazonic acid derivative of a compound of formula (III) A according to claim 20, wherein p and A have the same meanings as defined in claim 1, wherein Wherein R ₁ , R ₂ , p and A have the same meanings as defined in claim 1 and V ₁ is a halogen atom, an alkylsulfonate group or an arylsulfonate group, and a compound of the formula (VII): Formula 13 Wherein W ₂ and R ₃ are as defined in claim 1, and contacting the compound of formula (VI) with the compound of formula (VII). A method comprising condensing in the presence of a base or an inorganic base, in the absence or presence of a solvent. 23. The method according to claim 20, wherein W ₁ and W ₂ are oxygen atoms, p is 1 or 2, and R ₁ , R ₂ , R ₃ and A are as defined in claim 1. A method for producing a hydroxamic acid derivative of the formula (III) A according to
: Wherein R ₁ , R ₂ and A have the same meanings as defined in claim 1 and p is 1 or 2, and a hydroxamic acid derivative of the formula (VII) according to claim 18 [
W2 in the formula is an oxygen atom, the method R ₃ is comprising contacting the the same meanings as defined claim 1]. 24. The compound according to claim 20, wherein V ₁ represents a halogen atom.
II) A process for preparing a benzyl halide derivative of A, comprising a compound of formula (IX): Wherein, G represents any one of groups G1-G9, groups G1-G9 are the same as defined in claim 1, X ₆ have the same meanings as defined claim 1] halogen compounds Wherein in the presence or absence of a free radical initiator, in an inert solvent or in the absence of a solvent, radically by N-halogenoacetamide at a temperature of 20 ° C. to 170 ° C. To thermally or photochemically halogenate a compound of formula (IX) or to prepare a benzyl halide derivative of formula (II) A, wherein V ₁ represents a halogen atom, a compound of formula (IIB) : [Wherein, G represents any one of groups G1-G9, groups G1-G7 are as defined in claim 1, R ₄ is an alkylamino group, a dialkylamino group, and the group G
8 and G9 are the same as defined in claim 1, X ₆ have the same meanings as defined in claim 1, W1 is lithium halogenating agent or a halogenated compound of an oxygen atom] /
A method of halogenating with a mesyl halide / collidine reagent. 25. In the formula, G represents any one of the groups G1-G9, and the group G1-G9
G7 has the same meaning as defined in claim 1, R ₄ is amino, alkylamino, a group or a group such as dialkylamino, group G8 and G9 are the same as defined in claim 1, X ₆ is claim The method for producing a compound according to any one of claims 1 to 8, which has the same definition as that of the compound (I), wherein G is any one of groups G1 to G9. , the group G1-G7 has the same meaning as defined in claim 1, R ₄ is amino, alkylamino, a group or a group such as dialkylamino, group G8 and G9 are the same as defined in claim 1, X ₆ has the same meaning as defined in claim 1, wherein W ₁ is an oxygen atom or a sulfur atom], and a compound of the formula (III) B: [Wherein, W ₂ , R ₁ , R ₂ , R ₃ , R ₁₃ , X ₁ , X ₂ , X ₃ , p and A have the same meanings as in the definition of the formula (I), and V ₁ is a halogen atom, preferably Is a chlorine atom or an alkyl- or arylsulfonate group, and a double bond V ₁ -C (R ₃ ) =
N—W ₂ — represents a stereochemistry (E) or (Z)] at -80 ° C. in the presence of an organic or inorganic base, in the absence or presence of a solvent.
From 180 to 180 ° C or to the boiling point of the solvent used. 26. A compound of the formula (III) A: Wherein W ₁ is a sulfur atom, W ₂ is an oxygen atom or a group NR ₁₃ ,
R ₁ , R ₂ , R ₃ , R ₁₃ , p and A have the same meanings as defined in claim 1], wherein the thiohydroxamic acid or thiohydrazonic acid derivative is used. 27. In the formula, G is a group G3, Q ₂ is an oxygen atom, R ₄ is an alkoxy group, an alkylamino group, a dialkylamino group, and the other substituents are as defined in claim 1. The method for producing a compound according to any one of claims 1 to 8, wherein R ₆ is a lower alkyl group or a lower haloalkyl group, which has the same meaning as the formula (X): Wherein R ₄ is an alkoxy group, an alkylamino group, a dialkylamino group, and the other substituents are as defined in claim 1; and a compound of the formula (XI) A
R ₆ —CH ₂ —P (＝ O) (OR _b ) ₂ (XI) A wherein R ₆ is a lower alkyl group or a lower haloalkyl group, and R _b is a lower alkyl group, a phenyl group or a benzyl group. Or a formula (XI) B: R ₆ —CH ₂ —P (R _d ) ₃ ⁺ ; Hal ⁻ (XI) B, wherein R ₆ is a lower alkyl group or a lower haloalkyl. a group, R _d is phenyl substituted or unsubstituted, Hal ^- is contacting the Wittig reagent is a halide ion], -78 ° C. to 1 equivalent or more equivalents of a base in an aprotic solvent Reacting at a temperature ranging from to 50 ° C. 28. wherein G is a group G1 or G2 and Q is₁Is a nitrogen atom or
Is a CH group, Q₂Is an oxygen atom, and R₄Is an alkoxy group, an alkylamino
A dialkylamino group, and the other substituents are as defined in claim 1.
, R₅Is a lower haloalkyl group; the compound according to any one of claims 1 to 8,
A process for the preparation of a product comprising a compound of formula (XII): Wherein T is an oxygen atom or a sulfur atom, and M is an alkali metal ion or
Alkaline earth metal ion, Q₁Is a nitrogen atom or a CH group;₄Is
An alkoxy group, an alkylamino group, a dialkylamino group,₁, W₂, R ₁ , R₂, R₃, X₆, P and A are as defined in claim 1],
Formula CH_q(Hal)_4-q[Wherein q = 1 or 2, Hal is the same as each other, or
Represents different halogen atoms, at least one of which is a chlorine atom or a bromine atom
A) in a dipolar aprotic solvent at -20 ° C to 25 ° C.
Contacting at a temperature ranging up to 0 ° C. or the reflux temperature of the solvent
. 29. In the formula, G is a group G4, n = 1, Q ₂ is an oxygen atom, R ₄ is an alkoxy group, an alkylamino group, a dialkylamino group,
The process for producing a compound according to any one of claims 1 to 8, wherein the other substituents are as defined in claim 1, wherein the compound has the formula (XIII) A: Wherein R ₄ is an alkoxy group, an alkylamino group or a dialkylamino group, and the other substituents are as defined in claim 1; and a compound of the formula (XIV)
: Wherein V ₁ is a halogen atom and R ₅ has the same meaning as defined in claim 1) and one or more equivalents of a base optionally in the presence of an aprotic Reacting by acting at a temperature in the range of -78 ° C to 40 ° C in a solvent, wherein the compound of the general formula (XIII) A wherein R4 is an alkoxy group, an alkylamino group, a dialkylamino group , And other substituents are as defined in claim 1], but have the general formula (XIII) B: Wherein R ₄ is an alkoxy group, an alkylamino group, a dialkylamino group, X ₆ is as defined in claim 1, and V ₁ is a halogen atom, an alkylsulfonate group or an arylsulfonate group. A compound and a compound of the formula (III) A according to claim 16, wherein W ₁ , W ₂ , R ₁ , R ₂ , R ₃ , R ₁₃ , X ₁ , X ₂ ,
X ₃ , p and A have the same meanings as defined in claim 1]. 30. A be any one G is group G1-G7 in formula, wherein R ₄ is an alkyl amino group or a dialkylamino group, and the other substituents are the same as defined in claim 1 a process for preparing a compound of formula (I) according to any one of items 1 8, G in the formula represents one of the groups G1-G7, R ₄ is an alkoxy group or an alkylthio group Wherein the other substituents are as defined in claim 1, and the compound of formula (I) and an alkylamine or dialkylamine in an alcohol solvent from -50 ° C to 100 ° C or up to the boiling point of the solvent. Contacting at a temperature in the range of 31. W in the formula₁Is a sulfoxide group (SO) or a sulfone group (
SO₂), G is any one of G1, G3, G4, G6-G9 and Q ₂ And Q₃Is an oxygen atom, and the other substituents are the same as defined in claim 1.
9. A method for producing a compound according to any one of claims 1 to 8, wherein₁But
A sulfur atom, and G is any one of G1, G3, G4, G6-G9,
Q₂And Q₃Is an oxygen atom, and the other substituents are as defined in claim 1.
The compound of the formula (I) according to claim 1 is treated with one or more equivalents of an oxidizing agent.
Oxidation in an inert solvent in the presence or absence of a catalyst.
Way. 32. The preparation of a compound according to any one of claims 1 to 8, wherein G is one of the groups G1-G9, and the other substituents are as defined in claim 1. A method comprising the steps of formula (XV) A: [Wherein, G is one of groups G1-G9, and the groups G1-G9 are as defined in claim 1, and X ₆ , W ₁ , W ₂ , R ₃ and R ₁₃ are the same as those in claim 1. Is synonymous with the definition)
And a compound of the formula (VI) wherein R ₁ , R ₂ , p and A are as defined in claim 1, and V ₁ is a halogen atom, an alkylsulfonate group or an arylsulfonate group. A compound of the formula (XV) A and a compound of the formula (VI) in the presence of an organic or inorganic base, in the absence or presence of a solvent. 33. Formula (XV) A: [Wherein, G is one of groups G1-G9, groups G1-G9 are as defined in claim 1, and X ₆ , W ₁ , W ₂ and R ₃ are as defined in claim 1 Is a compound of the formula: 34. The process for preparing a compound of formula (XV) A according to claim 33, wherein the compound of formula (XV) B: [Wherein, G is a group G1-G9, the groups G1-G9 are as defined in claim 1, X ₆ , W ₁ , W ₂ and R ₃ are as defined in claim 1, P is a protecting group for a hydroxyl function or a protecting group for an amino function]. 35. A compound of the formula (XV) B; [Wherein, G is a group G1-G9, the groups G1-G9 are as defined in claim 1, X ₆ , W ₁ , W ₂ and R ₃ are as defined in claim 1, P is a protecting group for a hydroxyl function or a protecting group for an amino function]. 36. The process for preparing a compound of formula (XV) B according to claim 35, wherein the compound of formula (II) A according to claim 20 wherein G is a group G1-G9. , groups G1-G9 are the same as defined in claim 1, X ₆ have the same meanings as defined in claim 1, V ₁ represents a halogen atom, alkyl sulfonate group, a halo alkyl sulfonate group or an aryl sulfonate group] of A compound having the formula (XVI): Wherein W ₁ , W ₂ and R ₃ are as defined in claim 1, and P is a protecting group for a hydroxyl function or a protecting group for an amino function.
A method comprising condensing a compound of the formula (II) A and a compound of the formula (XVI) in the presence of an organic or inorganic base, in the absence or presence of a solvent.