TW201348243A - N-cycloalkyl-N-[(trisubstitutedsilylphenyl)methylene]-(thio)carboxamide derivatives - Google Patents

Abstract

The present invention relates to fungicidal N-cycloalkyl-N-[(trisubstitutedsilylphenyl)methylene] carboxamide derivatives and their thiocarbonyl derivatives, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.

Description

N-cycloalkyl-N-[(trisubstituted nonylalkylphenyl)methylene]-(thio)carbamamine derivatives

The present invention relates to a fungicidal N-cycloalkyl-N-[(trisubstituted nonylalkylphenyl)methylene]-formamide derivative and a thiocarbonyl derivative thereof, a preparation method thereof and a preparation thereof Intermediate compounds thereof, their use as fungicides (specifically in the form of fungicidal compositions) and methods of using such compounds or compositions thereof to control phytopathogenic fungi in plants.

In the international patent application WO-2007/087906, some N-cycloalkyl-N-benzyl-carbamamine systems are generally included in the broad disclosure of a number of compounds of the formula:

Wherein A represents a partially saturated or unsaturated 5-membered heterocyclic group of a carbon linkage, Z ¹ represents a substituted or unsubstituted C ₃ -C ₇ cycloalkyl group, n is equal to 1 to 5 and X may represent various substituents (wherein One is tris(C ₁ -C ₈ alkyl)decyl). However, any such derivative in which X may represent a substituted or unsubstituted dialkyl(hetero)aryldecyl group is not explicitly disclosed or suggested in this document.

In the international patent application WO-2009/016220, some N-cycloalkyl-N-benzyl-thiocarbamamine systems are generally included in the broad disclosure of a number of compounds of the formula:

Wherein A represents a partially saturated or unsaturated 5-membered heterocyclic group of a carbon linkage, T represents S, Z ¹ represents a substituted or unsubstituted C ₃ -C ₇ cycloalkyl group, n is equal to 1 to 5 and X represents A variety of substituents (one of which is a tri(C ₁ -C ₈ alkyl)decylalkyl group). However, any such derivative in which X may represent a substituted or unsubstituted dialkyl(hetero)aryldecyl group is not explicitly disclosed or suggested in this document.

In the international patent application WO-2010/130767, some N-cycloalkyl-N-benzyl-formamide or thiocarbamide series are generally included in the broad disclosure of a number of compounds of the formula:

Wherein X ¹ and X ² represent a fluorine or chlorine atom, T may represent O or S, Z ¹ represents a substituted or unsubstituted C ₃ -C ₇ cycloalkyl group, and Y may represent CR ⁵ and R ¹ , R ² , R ³ , R ⁴ or R ⁵ may independently represent various substituents (one of which is a substituted or unsubstituted tri(C ₁ -C ₈ alkyl)decylalkyl group). However, it is not explicitly disclosed or suggested in this document to select any such derivative in which R ¹ or R ² or R ³ or R ⁴ or R ⁵ may represent a substituted or unsubstituted dialkyl(hetero)arylalkylalkyl group. .

Accordingly, the present invention provides a N-cycloalkyl-N-[(trisubstituted nonylalkylphenyl)methylene]-(thio)carbamamine derivative of the formula (I), and a salt thereof, an N-oxide, Metal complexes, metalloid complexes and their optically active isomers or geometric isomers:

among them. A represents a carbon-bonded unsaturated or partially saturated 5-membered heterocyclic group which may be substituted with up to 4 groups R which may be the same or different; T represents O or S; n represents 0, 1, 2, 3 or 4; B represents an aryl group which may be substituted with up to 5 identical or different groups Y or represents a hetero atom comprising from 1 to 4 groups selected from N, O, S and may be up to 6 identical or different groups Y-substituted unsaturated monocyclic or fused bicyclic 5-, 6-, 7-, 8-, 9-, 10-membered ring; Z ¹ represents a non-substituted C ₃ -C ₇ cycloalkyl, or up to 10 identical or different atoms or groups substituted with the C ₃ -C ₇ cycloalkyl and such optional atom or group consisting of a halogen atom , cyano, C ₁ -C ₈ alkyl, C ₁ -C ₈ haloalkyl, C ₁ -C ₈ alkoxy, containing up to 9 identical or different halogen atoms, containing up to 9 identical or different halo C ₁ -C ₈ atoms haloalkoxy, C ₁ -C ₈ alkoxycarbonyl group, comprising up to 9 identical or different halogen atoms, halo C ₁ -C ₈ alkoxycarbonyl, C ₁ -C ₈ alkylamino a carbonyl group and a di-C ₁ -C ₈ alkylaminocarbonyl group; Z ² and Z ³ (which may be the same or different) represent a hydrogen atom, a substituted or unsubstituted C ₁ -C ₈ alkyl group, a substituted or unsubstituted C ₂ -C ₈ alkenyl group, substituted Or unsubstituted C ₂ -C ₈ alkynyl, cyano, isonitrile, nitro, halogen atom, substituted or unsubstituted C ₁ -C ₈ alkoxy, substituted or unsubstituted C ₂ -C ₈ alkenyloxy, substituted or unsubstituted C ₂ -C ₈ alkynyloxy, substituted or unsubstituted C ₃ -C ₇ cycloalkyl, substituted or unsubstituted C ₁ -C ₈ -alkylthio, substituted or unsubstituted C ₁ -C ₈ alkanesulfonyl, substituted or unsubstituted C ₁ -C ₈ alkylsulfinyl, amine, substituted or unsubstituted C ₁ -C ₈ alkylamino, substituted or unsubstituted di-C ₁ -C ₈ alkylamino, substituted or unsubstituted C ₁ -C ₈ alkoxycarbonyl, substituted or unsubstituted C ₁ -C ₈ alkyl amine acyl, substituted or unsubstituted bis C ₁ -C ₈ alkyl amine acyl or substituted or unsubstituted alkyl group of the NC ₁ -C ₈ -C ₁ -C ₈ alkoxy-amine methyl hydrazino; or. Z ² and Z ³ together with a carbon atom to which they are attached may form a substituted or unsubstituted C ₃ -C ₇ cycloalkyl group; The substituent X adjacent to the Z ³ and the phenyl ring attachment point together with the continuous carbon atom to which it is attached may form a substituted or unsubstituted 5-, 6- or 7-membered partially saturated carbocyclic ring or contain up to 3 impurities. a heterocyclic ring of an atom and Z ² is described herein; Z ⁴ and Z ⁵ independently represent a substituted or unsubstituted C ₁ -C ₈ alkyl group; X independently represents a halogen atom, a nitro group, a cyano group, an isonitrile, a hydroxyl group, an amine group, a thio group, a pentafluoro-λ ⁶ -thio group, a decyl group, a methyl methoxy group, a formamidine group, a substituted or Unsubstituted (hydroxyimino)-C ₁ -C ₈ alkyl, substituted or unsubstituted (C ₁ -C ₈ alkoxyimino)-C ₁ -C ₈ alkyl, substituted or Unsubstituted (C ₂ -C ₈ oxyimido)-C ₁ -C ₈ alkyl, substituted or unsubstituted (C ₂ -C ₈ alkynoxyimino)-C ₁ -C ₈ Alkyl, substituted or unsubstituted (benzyloxyimino)-C ₁ -C ₈ alkyl, carboxy, aminemethanyl, N-hydroxylamine, carboxylic acid, substituted or not the substituted C ₁ -C ₈ alkyl group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkyl, substituted or non-substituted C ₂ -C ₈ alkenyl group, having 1-9 halogen atoms, halo C ₂ -C ₈ alkenyl group, a substituted or non-substituted C ₂ -C ₈ alkynyl group having a C 1 to 9 halogen atoms, halo ₂ -C ₈ alkynyl group, a substituted or unsubstituted C ₁ of -C ₈ alkoxy group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkoxy, substituted or non-substituted C ₁ -C ₈ alkylthio group having a C 1 to 9 halogen atoms, ₁ -C ₈ haloalkylthio Substituted or non-substituted C ₁ -C ₈ alkyl sulfinyl group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkyl sulfinyl group, a substituted or unsubstituted of C ₁ -C ₈ Alkylsulfonyl, C ₁ -C ₈ halosulfonyl having 1 to 9 halogen atoms, substituted or unsubstituted C ₁ -C ₈ alkylamino group, substituted or unsubstituted di C ₁ -C ₈ alkyl group, a substituted or non-substituted C ₂ -C ₈ alkenyloxy group having a C 1 to 9 halogen atoms, halo ₂ -C ₈ alkenyloxy, substituted or non-substituted C ₃ -C ₈ alkynyloxy, C ₂ -C ₈ haloalkoxy group having 1 to 9 halogen atoms, substituted or unsubstituted C ₃ -C ₇ cycloalkyl group, C having 1 to 9 halogen atoms _3- C ₇ halocycloalkyl, substituted or unsubstituted (C ₃ -C ₇ cycloalkyl)-C ₁ -C ₈ alkyl, substituted or unsubstituted C ₄ -C ₇ cycloalkenyl a C ₄ -C ₇ halocycloalkenyl group having 1 to 9 halogen atoms, a substituted or unsubstituted (C ₃ -C ₇ cycloalkyl)-C ₂ -C ₈ alkenyl group, substituted or unsubstituted Substituted (C ₃ -C ₇ cycloalkyl)-C ₂ -C ₈ alkynyl, substituted or unsubstituted tri(C ₁ -C ₈ )alkyldecyl, substituted or unsubstituted tri C ₁ -C ₈ )alkylnonanyl -C ₁ -C ₈ alkyl, substituted or unsubstituted C ₁ -C ₈ alkylcarbonyl, C ₁ -C ₈ haloalkylcarbonyl having 1 to 9 halogen atoms, substituted or unsubstituted C ₁ -C ₈ alkylcarbonyloxy group, C ₁ -C ₈ haloalkylcarbonyloxy group having 1 to 9 halogen atoms, substituted or unsubstituted C ₁ -C ₈ alkylcarbonylamino group, having 1 to 9 halogen C ₁ -C ₈ halogen atoms, alkylcarbonyl group, substituted or non-substituted C ₁ -C ₈ alkoxycarbonyl group having a C 1 to 9 halogen atoms, halo ₁ -C ₈ alkoxycarbonyl group, a substituted or the unsubstituted C ₁ -C ₈ alkoxycarbonyl group having a C 1 to 9 halogen atoms, halo ₁ -C ₈ alkoxycarbonyl group, a substituted or unsubstituted alkyl group of C ₁ -C ₈ amine Mercapto, substituted or unsubstituted di-C ₁ -C ₈ alkylamine carbenyl, substituted or unsubstituted C ₁ -C ₈ alkylaminocarbonyloxy, substituted or unsubstituted a C ₁ -C ₈ alkylaminocarbonyloxy group, a substituted or unsubstituted N-(C ₁ -C ₈ alkyl)hydroxylamine carbenyl group, a substituted or unsubstituted C ₁ -C ₈ alkoxyamine methyl acyl, substituted or non-substituted N- (C ₁ -C ₈ alkyl) -C ₁ -C ₈ alkoxy carbamoyl acyl, may be up to six identical or different A substituted aryl group of the group Q, may be up to six identical or different substituents of the group Q C ₁ -C ₈ aralkyl, may be up to 6 identical or different radicals Q of C ₂ -C ₈ substituted aryl An alkenyl group, a C ₂ -C ₈ aralkynyl group which may be substituted with up to 6 identical or different groups Q, an aryloxy group which may be substituted with up to 6 identical or different groups Q, up to 6 An arylthio group substituted with the same or different group Q, an arylamine group which may be substituted with up to 6 identical or different groups Q, a C ₁ -C ₈ aryl group which may be substituted with up to 6 identical or different groups Q alkoxy, it may be up to six identical or different substituents of the group Q C ₁ -C ₈ aralkyl group, may be up to six identical or different substituents of the group Q C ₁ -C ₈ aralkyl amine a pyridyl group which may be substituted with up to 4 groups of Q, a pyridyloxy group which may be substituted with up to 4 groups of Q; Y independently represents a halogen atom, a cyano group, a hydroxyl group, an amine group, a thio group, a substituted or unsubstituted C ₁ -C ₈ alkyl group, a C ₁ -C ₈ haloalkyl group having 1 to 9 halogen atoms, substituted or non-substituted C ₁ -C ₈ alkoxy group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkoxy, substituted or non-substituted C ₁ -C ₈ alkylthio, a C ₁ -C ₈ haloalkylthio group having 1 to 9 halogen atoms, a substituted or unsubstituted C ₁ -C ₈ alkylsulfinyl group, a C ₁ -C ₈ halogen having 1 to 9 halogen atoms alkyl sulfinyl group, a substituted or unsubstituted alkyl of C ₁ -C ₈ acyl sulfo, having a C 1 to 9 halogen atoms, sulfo ₁ -C ₈ haloalkyl acyl, substituted or non-substituted C ₁ -C ₈ alkoxy group, a substituted or unsubstituted bis C ₁ -C ₈ alkyl group, a substituted or unsubstituted of C ₁ -C ₈ alkylcarbonyl group having a C 1 to 9 halogen atoms ₁ halo -C ₈ alkylcarbonyl group, a substituted or unsubstituted of C ₁ -C ₈ alkoxycarbonyl group having a C 1 to 9 halogen atoms, halo ₁ -C ₈ alkoxycarbonyl group, may be up to six identical or different An aryl group substituted by a group Q; Q independently represent a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group of C ₁ -C _8, comprising up to 9 identical or different halogen atoms, C ₁ -C ₈ haloalkyl, substituted or unsubstituted of C ₁ -C ₈ alkoxy group, comprising up to 9 identical or different halogen atoms, C ₁ -C ₈ haloalkoxy, substituted or non-substituted C ₁ -C ₈ alkylthio a C ₁ -C ₈ haloalkylthio group containing up to 9 identical or different halogen atoms, a substituted or unsubstituted tri(C ₁ -C ₈ )alkyldecanealkyl group, substituted or unsubstituted three (C ₁ -C ₈₎ alkyl silicon -C ₁ -C ₈ alkyl group, a substituted or non-substituted (C ₁ -C ₈ alkoxy imino) -C ₁ -C ₈ alkyl or substituted Or unsubstituted (benzyloxyimido)-C ₁ -C ₈ alkyl; R independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amine group, a thio group, a pentafluoro-λ ⁶ -thio group, a substituted or unsubstituted (C ₁ -C ₈ alkoxyimine) (1)-C ₁ -C ₈ alkyl, substituted or unsubstituted (benzyloxyimino)-C ₁ -C ₈ alkyl, substituted or unsubstituted C ₁ -C ₈ alkyl, having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkyl, substituted or non-substituted C ₂ -C ₈ alkenyl group having a C 1 to 9 halogen atoms ₂ -C ₈ - halo alkenyl, substituted or non-substituted C ₂ -C ₈ alkynyl group having a C 1 to 9 halogen atoms ₂ -C ₈ - alkynyl, halogen, substituted or non-substituted C ₁ -C ₈ alkoxy group having 1 to 9 halogen atoms, C ₁ -C ₈ haloalkoxy, substituted or non-substituted C ₁ -C ₈ alkylthio, having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkylthio, substituted or non-substituted C ₁ -C ₈ alkyl sulfinyl group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkyl sulfinyl group, a substituted or unsubstituted of C ₁ -C ₈ Alkylsulfonyl, C ₁ -C ₈ halosulfonyl having 1 to 9 halogen atoms, substituted or unsubstituted C ₁ -C ₈ alkylamino group, substituted or unsubstituted di C ₁ -C ₈ Alkylamino group, a substituted or non-substituted C ₂ -C ₈ alkenyloxy, substituted or non-substituted C ₃ -C ₈ alkynyl group, a substituted or non-substituted C ₃ -C ₇ cycloalkyl a C ₃ -C ₇ -halocycloalkyl group having 1 to 9 halogen atoms, a substituted or unsubstituted tris(C ₁ -C ₈ )alkyldecyl group, substituted or unsubstituted C ₁ a -C ₈ alkylcarbonyl group, a C ₁ -C ₈ haloalkylcarbonyl group having 1 to 9 halogen atoms, a substituted or unsubstituted C ₁ -C ₈ alkoxycarbonyl group, C ₁ - having 1 to 9 halogen atoms C ₈ haloalkoxycarbonyl, substituted or unsubstituted C ₁ -C ₈ alkylamine carbenyl, substituted or unsubstituted di C ₁ -C ₈ alkylamine carbenyl, phenoxy, A phenylthio group, an anilino group, a benzyloxy group, a benzylthio group or a benzylamino group.

Unless otherwise indicated, a substituted group or substituent according to the invention may be substituted by one or more of the following groups: a halogen atom, a nitro group, a hydroxyl group, a cyano group, an isonitrile, an amine group, a sulfur Base, pentafluoro-λ ⁶ -thio, methionyl, methyl methoxy, methionine, amine carbaryl, N-hydroxylamine, urethane, (hydroxyimino)- C ₁ -C ₆ alkyl, C ₁ -C ₈ alkyl, tri(C ₁ -C ₈ alkyl)decyl, C ₃ -C ₈ cycloalkyl, C ₁ -C having 1 to 5 halogen atoms _8- haloalkyl; C ₃ -C ₈ halocycloalkyl having 1 to 5 halogen atoms, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₂ -C ₈ alkenyloxy, C ₂ -C ₈ alkynyloxy, C ₁ -C ₈ alkylamino, di-C ₁ -C ₈ alkylamino, C ₁ -C ₈ alkoxy group having a C 1 to 5 halogen atoms, haloalkoxy of ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio group having a C 1 to 5 halogen atoms ₁ -C ₈ haloalkylthio, C ₂ -C ₈ alkenyloxy group having a C 1 to 5 halogen atoms of ₂ - C ₈ haloalkenyl group, C ₃ -C ₈ alkynyl group having C ₃ -C ₈ haloalkynyl group having 1 to 5 halogen atoms, C ₁ -C ₈ alkylcarbonyl group, having 1 to 5 halogen atoms halo C ₁ -C ₈ alkylcarbonyl, C ₁ -C ₈ alkyl amine acyl, C ₁ -C ₈ alkyl amine acyl, NC ₁ -C ₈ alkoxy carbamoyl acyl, C ₁ -C ₈ alkoxy acyl carbamoyl, NC ₁ -C ₈ alkyl -C ₁ -C ₈ alkyl oxygen carbamoyl acyl, C ₁ -C ₈ alkoxycarbonyl group having a C 1 to 5 halogen atoms, halo ₁ -C ₈ alkoxycarbonyl, C ₁ -C ₈ alkoxy carbonyl group having 1 to 5 halogen atoms the C ₁ -C ₈ haloalkoxy-carbonyl group, C ₁ -C ₈ alkylcarbonyl group having a C 1 to 5 halogen atoms, halo ₁ -C ₈ alkylcarbonyl group, C ₁ -C ₈ alkylamino carbonyloxy, di-C ₁ -C ₈ alkylamino carbonyloxy, C ₁ -C ₈ alkoxycarbonyl group, C ₁ -C ₈ alkylthio group having a C 1 to 5 halogen atoms ₁ -C ₈ haloalkylthio, C ₁ -C ₈ alkyl sulfinyl group having a C 1 to 5 halogen atoms ₁ -C ₈ haloalkyl sulfinyl group, sulfo C ₁ -C ₈ alkyl acyl having 1 to C ₁ -C ₈ haloalkylsulfonyl, C ₁ -C ₈ alkylaminosulfonyl, di-C ₁ -C ₈ alkylaminosulfonyl, (C ₁ -C) ₆ alkoxyimino)-C ₁ -C ₆ alkyl, (C ₁ -C ₆ oxyimido)-C ₁ -C ₆ alkyl, (C ₁ -C ₆ alkynoxyimino)- C ₁ -C ₆ alkyl, 2-sided oxypyrrolidin-1-yl, (benzyloxyimino)-C ₁ -C ₆ alkyl, C ₁ -C ₈ alkoxyalkyl, having 1 to 5 halogen atoms C ₁ -C ₈ haloalkoxy group, a benzyl group, a benzyl group, a benzyl group, aryloxy group, arylthio group, or an aryl group.

According to the present invention, the following general terms generally have the following meanings: Halogen means fluorine, chlorine, bromine or iodine; carboxyl means -C(=O)OH; carbonyl means -C(=O)-; aminemethanyl means -C(=O)NH ₂ ;N- Hydroxyaminocarbamyl means -C(=O)NHOH; SO represents an anthracenylene group; SO ₂ represents a fluorenyl group; hetero atom means sulfur, nitrogen or oxygen; methylene means a divalent group -CH ₂ - ;. Alkyl, alkenyl and alkynyl groups and part of the groups comprising these terms may be straight-chain or branched; Halogenated groups (especially haloalkyl, haloalkoxy and cycloalkyl) may contain up to 9 identical or different halogen atoms; The term "aryl" means phenyl or naphthyl; In the case of an amine group or any other group member group containing an amine group, the group may be substituted by two identical or different substituents which may form a hetero atom together with a nitrogen atom to which they are attached a cyclic group (preferably a 5- to 7-membered heterocyclic group) which may be substituted or may include other heteroatoms such as morpholinyl or piperidinyl; Where a compound of the invention may be in a tautomeric form, it is understood that in the context the compound includes, where possible, the corresponding tautomeric form (even when such forms are not specifically mentioned in each case).

Any of the compounds of the invention may exist in one or more optical or palmeromeric forms depending on the number of asymmetric centers in the compound. Thus, the present invention is equally directed to all optical isomers and racemic or partially racemic mixtures thereof (the term "partially racemic" means a mixture of enantiomers in different proportions) and all possible stereoisoties in all ratios. a mixture of structures. The non-stereoisomers and/or optical isomers may be isolated according to methods known per se to those skilled in the art.

Any of the compounds of the invention may also exist in one or more geometric isomers depending on the number of double bonds in the compound. Thus, the invention is equally concerned with all geometric isomers and all possible mixtures in all ratios. The geometric isomers can be separated according to the general methods known to those skilled in the art.

Any of the compounds of the invention may also exist in one or more geometric isomers depending on the relative position of the substituents in the chain or ring (ipsilateral/reverse or cis/trans). Thus, the invention is equally directed to all ipsilateral/reverse (cis/trans) isomers and all possible ipsilateral/reverse (cis/trans) mixtures in all ratios. The equivalent side/reverse (cis/trans) isomer can be isolated according to the general methods known to those skilled in the art.

Preferred compounds of the invention are those compounds of formula (I) wherein A is selected from the group consisting of:

Wherein: R ¹ to R ³ (lines may be same or different) represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, C comprising up to 9 identical or different halogen atoms, _l - C ₅ haloalkyl, a substituted or unsubstituted of C ₁ -C ₅ alkoxy or contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkoxy;

Wherein: R ⁴ to R ⁶ (lines may be same or different) represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, C comprising up to 9 identical or different halogen atoms, _l - C ₅ haloalkyl, a substituted or unsubstituted of C ₁ -C ₅ alkoxy or contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkoxy;

Wherein: R ⁷ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl, substituted or unsubstituted the substituted C ₁ -C ₅ alkoxy or contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkoxy; R ⁸ represents a hydrogen atom or a substituted or non-substituted C ₁ -C ₅ alkyl;

Wherein: R ⁹ to R ¹¹ (which may be the same or different) represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, an amine group, a substituted or unsubstituted C ₁ -C ₅ alkoxy, substituted or non-substituted C ₁ -C ₅ alkylthio group, comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl, or contain up to 9 identical or different halogen a C ₁ -C ₅ haloalkoxy group of an atom;

Wherein: R ¹² and R ¹³ (same or different and may be based) represents a hydrogen atom, a halogen atom, a substituted or unsubstituted of C ₁ -C ₅ alkyl, substituted or unsubstituted of C ₁ -C ₅ alkoxy a base, an amine group, a C ₁ -C ₅ haloalkyl group containing up to 9 identical or different halogen atoms or a C ₁ -C ₅ haloalkoxy group containing up to 9 identical or different halogen atoms; R ¹⁴ represents hydrogen Atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, an amine group, containing up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl, or contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkoxy;

Wherein: R ¹⁵ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, and contains up to 9 identical or different halogen atoms, C ₁ -C ₅ alkoxy group or a halogen comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ¹⁶ and R ¹⁸ (lines may be same or different) represent hydrogen atom, a halogen atom, a substituted or unsubstituted of C ₁ -C ₅ alkoxycarbonyl group, a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 identical or different halogen atoms, C ₁ - a C ₅ haloalkoxy group or a C ₁ -C ₅ haloalkyl group containing up to 9 identical or different halogen atoms; R ¹⁷ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group;

Wherein: R ¹⁹ represents a hydrogen atom or a C ₁ -C ₅ alkyl group; and R ²⁰ to R ²² (which may be the same or different) represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group or a C ₁ -C ₅ haloalkyl group containing up to 9 identical or different halogen atoms;

Wherein: R ²³ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ²⁴ represents hydrogen atom or a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl;

Wherein: R ²⁵ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ²⁶ represents hydrogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl;

Wherein: R ²⁷ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ²⁸ represents hydrogen Atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a C ₁ -C ₅ haloalkyl group containing up to 9 identical or different halogen atoms, containing up to 9 identical or different halogen atoms a C ₁ -C ₅ haloalkoxy group, an amine group, a substituted or unsubstituted C ₁ -C ₅ alkylamino group or a substituted or unsubstituted bis(C ₁ -C ₅ alkyl)amino group;

Wherein: R ²⁹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, and contains up to 9 identical or different halogen atoms, C ₁ -C ₅ alkoxy group or a halogen comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ³⁰ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted of C _{a 1-} C ₅ alkyl group, a C ₁ -C ₅ haloalkyl group containing up to 9 identical or different halogen atoms, a C ₁ -C ₅ haloalkoxy group containing up to 9 identical or different halogen atoms, an amine group a substituted or unsubstituted C ₁ -C ₅ alkylamino group or a substituted or unsubstituted bis(C ₁ -C ₅ alkyl)amino group;

Wherein: R ³¹ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; R ³² represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group or contains up to 9 C ₁ -C ₅ haloalkyl groups of the same or different halogen atoms; R ³³ represents a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted C ₁ -C ₅ alkyl group, substituted or unsubstituted the C ₁ -C ₅ alkoxy group, comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ alkoxy group or a halogen comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl, ;

Wherein: R ³⁴ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₃ -C ₅ cycloalkyl group, and contains up to 9 identical or different a C ₁ -C ₅ haloalkyl group of a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, a substituted or unsubstituted C ₂ -C ₅ alkynyloxy group or containing up to 9 identical Or a C ₁ -C ₅ haloalkoxy group of a different halogen atom; R ³⁵ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a cyano group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, a substituted or unsubstituted of C ₁ -C ₅ alkylthio group, comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl, comprising up to 9 identical Or a C ₁ -C ₅ haloalkoxy group of a different halogen atom, an amine group, a substituted or unsubstituted C ₁ -C ₅ alkylamino group or a substituted or unsubstituted bis (C ₁ -C ₅ alkyl group) An amine group; R ³⁶ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group;

Wherein: R ³⁷ and R ³⁸ (same or different and may be based) represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 identical or different halogen atoms, C ₁ - C ₅ haloalkyl, substituted or unsubstituted C ₁ -C ₅ alkoxy or substituted or unsubstituted C ₁ -C ₅ -alkylthio; R ³⁹ represents a hydrogen atom or substituted or not Substituted C ₁ -C ₅ alkyl;

Wherein: R ⁴⁰ and R ⁴¹ (same or different and may be based) represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or C comprising up to 9 identical or different halogen atoms, _l - C ₅ haloalkyl;

Wherein: R ⁴² and R ⁴³ (same or different and may be based) represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, C comprising up to 9 identical or different halogen atoms, _l - C ₅ haloalkyl or amine group;

Wherein: R ⁴⁴ and R ⁴⁵ (which may be the same or different) represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group or a C ₁ - containing up to 9 identical or different halogen atoms. C ₅ haloalkyl;

Wherein: R ⁴⁷ represents a hydrogen atom, a halogen atom, a substituted or non-substituted C ₁ -C ₅ alkyl or contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ⁴⁶ represents hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl, or a substituted or unsubstituted of C ₁ - C ₅ alkylthio;

Wherein: R ⁴⁹ and R ⁴⁸ (which may be the same or different) represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group. a C ₁ -C ₅ haloalkoxy group containing up to 9 identical or different halogen atoms or a C ₁ -C ₅ haloalkyl group containing up to 9 identical or different halogen atoms;

Wherein: R ⁵⁰ and R ⁵¹ (same or different and may be based) represents a hydrogen atom, a halogen atom, a substituted or unsubstituted of C ₁ -C ₅ alkyl, substituted or unsubstituted of C ₁ -C ₅ alkoxy a C ₁ -C ₅ haloalkoxy group containing up to 9 identical or different halogen atoms or a C ₁ -C ₅ haloalkyl group containing up to 9 identical or different halogen atoms;

Wherein: R ⁵² represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl.

Wherein: R ⁵³ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl.

Wherein: R ⁵⁴ and R ⁵⁶ (same or may be different lines) represents a hydrogen atom, a halogen atom, a substituted or unsubstituted of C ₁ -C ₅ alkyl or C comprising up to 9 identical or different halogen atoms, _l - C ₅ haloalkyl; R ⁵⁵ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group;

Wherein: R ⁵⁷ and R ⁵⁹ (same or different and may be based) represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or C comprising up to 9 identical or different halogen atoms, _l - C ₅ haloalkyl; R ⁵⁸ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group;

Wherein: R ⁶⁰ and R ⁶¹ (which may be the same or different) represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group or a C ₁ - containing up to 9 identical or different halogen atoms. C ₅ haloalkyl; R ⁶² represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group;

Wherein: R ⁶⁵ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₃ -C ₅ cycloalkyl group, and contains up to 9 identical or different a C ₁ -C ₅ haloalkyl group of a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, a substituted or unsubstituted C ₂ -C ₅ alkynyloxy group or containing up to 9 identical Or a C ₁ -C ₅ haloalkoxy group of a different halogen atom; R ⁶³ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a cyano group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, a substituted or unsubstituted of C ₁ -C ₅ alkylthio group, comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl, comprising up to 9 identical Or a C ₁ -C ₅ haloalkoxy group, an amine group, a substituted or unsubstituted C ₁ -C ₅ alkylamino group or a di(C ₁ -C ₅ alkyl)amino group of a different halogen atom; R ⁶⁴ represents A hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group.

A more preferred compound of the invention is a compound of formula (I) wherein A is selected from the group consisting of A ² , A ⁵ , A ⁶ , A ¹⁰ and A ¹³ as defined herein.

The compounds of the present invention is based even more preferably wherein A ¹³ and A represents wherein R ³⁴ represents a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 identical or different halogen atoms, halo C ₁ -C ₅ Alkyl, substituted or unsubstituted C ₁ -C ₅ alkoxy; R ³⁵ represents a hydrogen atom or a halogen atom and R ³⁶ represents a substituted or unsubstituted C ₁ -C ₅ alkyl group (I) Compound.

The compounds of the present invention is based even more preferably wherein A ¹³ and A represents wherein R ³⁴ represents C ₁ -C ₅ alkyl group, containing up to 3 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ³⁵ represents hydrogen A compound of the formula (I) wherein an atom, a chlorine atom or a fluorine atom; and R ³⁶ represents a methyl group.

Other preferred compounds of the invention are those of formula (I) wherein T represents O.

Other preferred compounds of the present invention wherein the line Z ¹ represents a substituted or unsubstituted cyclopropyl in the formula (I) compound.

The present invention more preferably other compounds of the compounds wherein Z ¹ represents a non-substituted cyclopropyl or 2-C ₁ -C ₅ alkyl cyclopropyl formula (I).

Other even more preferably based compounds of the present invention wherein Z ¹ represents a non-substituted cyclopropyl of the formula (I) compound.

Other even more preferably based compounds of the present invention wherein Z ¹ represents a 2-methyl-cyclopropyl compound of formula (I).

Other preferred compounds of the invention are those compounds of formula (I) wherein Z ² and Z ³ independently represent a hydrogen atom or a methyl group.

More preferred compounds of the invention are those compounds of formula (I) wherein Z ² represents a hydrogen atom and Z ³ represents a hydrogen atom or a methyl group.

Other preferred compounds of the invention are those compounds of formula (I) wherein n represents 0, 1 or 2.

Other preferred compounds of the invention are those compounds of formula (I) wherein Z ⁴ and Z ⁵ independently represent an unsubstituted C ₁ -C ₈ alkyl group.

More preferred compounds of the invention are those compounds of formula (I) wherein Z ⁴ and Z ⁵ independently represent an unsubstituted C ₁ -C ₃ alkyl group.

The present invention even more preferably wherein the compound is Z ⁴ and Z ⁵ represents a methyl compound of formula (I).

Other preferred compounds of the invention are those wherein B represents a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted benzo A compound of formula (I) which is a thiophene ring, a substituted or unsubstituted furan ring or a substituted or unsubstituted benzofuran ring.

More preferred compounds of the invention are those wherein B represents a substituted or unsubstituted benzene ring, A compound of formula (I) which is substituted or unsubstituted naphthalene ring, substituted or unsubstituted thiophene ring.

Other preferred compounds of the present invention wherein X lines independently represent a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _8, comprising up to 9 identical or different halogen atoms, C ₁ -C ₈ haloalkyl , substituted or unsubstituted C ₃ -C ₇ cycloalkyl, tri(C ₁ -C ₈ alkyl)decyl, substituted or unsubstituted C ₁ -C ₈ alkoxy or substituted or not A compound of formula (I) substituted with a C ₁ -C ₈ alkylthio group.

Other preferred compounds of the invention are those wherein C independently represents a halogen atom, a substituted or unsubstituted C ₁ -C ₈ alkyl group, a C ₁ -C ₈ haloalkyl group comprising 9 identical or different halogen atoms, substituted or non-substituted C ₁ -C ₈ alkoxy, containing 9 identical or different halogen atoms, compound C ₁ -C ₈ haloalkoxy of formula (I).

Preferred substituents of the above compounds of the invention may be combined in a variety of ways. Accordingly, combinations of these preferred features provide a subgroup of the compounds of the invention. Examples of such preferred system of the present invention a subgroup of compounds of: - preferred features of A combination of T, Z ¹ to Z ^5, preferably wherein n, X, B and Y, or; - preferred features of T composition A, Preferred features of Z ¹ to Z ⁵ , n, X, B and Y; - preferred features of Z ^{1 are} preferred characteristics of combinations A, T, Z ² to Z ⁵ , n, X, B and Y; - Z ² preferred features combine A, T, Z ¹ , Z ³ to Z ⁵ , n, X, B and Y; - Z ³ preferred combination of features A, T, Z ¹ to Z ² , Z ⁴ to Z ⁵ , n, X, B and Y preferred features; - preferred characteristics of Z ⁴ combinations A, T, Z ¹ to Z ³ , Z ⁵ , n, X, B and Y; - Preferred characteristics of Z ^{5 are} preferred characteristics of combinations A, T, Z ¹ to Z ⁴ , n, X, B and Y; preferred combinations of - n are A, T, Z ¹ to Z ⁵ , X, B And preferred features of Y; - preferred features of X are preferred features of A, T, Z ¹ to Z ⁵ , n, B and Y; - preferred combinations of B are A, T, Z ¹ to Z ⁵ Preferred features of n, X, and Y; - preferred features of Y are combinations of A, T, Z ¹ to Z ⁵ , n, X, and B.

In combinations of such preferred features of the substituents of the compounds of the invention, such preferred ones may be selected among the preferred features of each of A, T, Z ¹ to Z ⁵ , n, X, B and Y. Characterized to form the best subgroup of the compounds of the invention.

The invention is also directed to a process for the preparation of a compound of formula (I). Thus, according to another aspect of the invention there is provided a process P1 for the preparation of a compound of formula (I) as defined herein and wherein T represents O and which comprises an amine of formula (II) or a salt thereof:

Wherein Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , n, X and B are as defined herein; and the carboxylic acid derivative of formula (III):

Wherein A is as defined herein and U ¹ represents a leaving group selected from the group consisting of ^a halogen atom, a hydroxyl group, -OR ^a , -OC(=O)R ^a , and R ^a is substituted or unsubstituted C ₁ -C ₆ alkyl, substituted or unsubstituted C ₁ -C ₆ haloalkyl, benzyl, 4-methoxybenzyl or pentafluorophenyl or an OC(=O)A group; And in the presence of a condensing agent (in the case where U ¹ represents a hydroxyl group), and in the presence of an acid binder (in the case where U ¹ represents a halogen atom).

The N-substituted amine derivatives of formula (II) are known or can be prepared by known methods, such as reductive amination of aldehydes or ketones (Bioorganics and Medicinal Chemistry Letters (2006), 16, 2014), or Reduction of amines (Tetrahedron (2005), 61, 11689), or nucleophilic substitution of halogen, mesylate or tosylate (Journal of Medicinal Chemistry (2002), 45, 3887).

The carboxylic acid derivative of the formula (III) is known or can be produced by a known method.

In the case where U ¹ represents a hydroxyl group, the method P1 of the present invention is carried out in the presence of a condensing agent. Suitable condensing agents may be selected from the following non-limiting groups: sulfhydryl halides (eg phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phos-phorous trichloride oxide) Or sulphite chloride, anhydride formations (eg ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride), carbodiimides (eg N, N) '-Dicyclohexylcarbodiimide (DCC)) or other commonly used condensing agents (eg, phosphorus pentoxide, polyphosphoric acid, N, N'-carbonyl-diimidazole, 2-ethoxy-N-ethoxycarbonyl- 1,2-dihydroquinoline (EEDQ), triphenylphosphine/tetrachloromethane, 4-(4,6-dimethoxy[1.3.5]-triazin-2-yl)-4-methyl Morpholine Chloride Hydrate, Bromo-Tripyrrolidinium Hexafluorophosphate or Propanephosphonic Anhydride (T3P)).

The method P1 of the present invention is carried out in the presence of a catalyst. Suitable catalysts may be selected from the group consisting of N,N-dimethylpyridin-4-amine, 1-hydroxy-benzotriazole or N,N-dimethylformamide.

In the case where U ¹ represents a halogen atom, the method P1 of the present invention is carried out in the presence of an acid binder. Acid binders suitable for carrying out the process P1 according to the invention are in each case all inorganic and organic bases customary for such reactions. Preferably, an alkaline earth metal, an alkali metal hydride, an alkali metal hydroxide or an alkali metal alkoxide (for example, sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium butoxide or other ammonium hydroxide) is used. ) an alkali metal carbonate (eg, cesium carbonate, sodium carbonate, potassium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate), an alkali metal or alkaline earth metal acetate (eg, sodium acetate, potassium acetate, calcium acetate) and a tertiary amine (eg, Trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethylpyridin-4-amine, two Azabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU)).

It can also be carried out in the absence of an additional condensing agent, or an excess of the amine component can be used, so that it acts as an acid binder at the same time.

Suitable solvents for carrying out the process P1 according to the invention can be customary inert organic solvents. It is preferred to use an aliphatic, alicyclic or aromatic hydrocarbon which is halogenated as desired, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorine Benzene, dichloro Benzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl third amyl ether, dioxins Alkane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitrile, such as acetonitrile, propionitrile, n- or isobutyronitrile or benzonitrile; For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or trimethylamine hexamethylphosphate; alcohol, for example Methanol, ethanol, propanol, isopropanol; esters such as methyl acetate or ethyl acetate; hydrazine (such as dimethyl hydrazine) or hydrazine (such as cyclobutyl hydrazine).

When carrying out the process P1 of the present invention, the amine derivative of the formula (II) can be used in the form of its salt (for example, a hydrochloride or any other conventional salt).

When the method P1 of the present invention is carried out, 1 mol or an excess of the amine derivative of the formula (II) and 1 to 3 mol acid binder may be used per mol of the (III) reagent.

Reaction components in other ratios can also be used. Processing is performed by a known method.

According to another aspect of the present invention, there is provided a second method P2 of the preparation of a compound of formula (I) wherein T represents S, starting from a compound of formula (I) wherein T represents O, and is illustrated according to the following reaction scheme:

Method P2

Wherein A, Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , n, X and B are as defined herein.

The process P2 of the present invention is carried out in the presence of a thiocarbonating agent.

An initial guanamine derivative of formula (I) wherein T represents O can be prepared according to method P1.

The thiocarbonating agent suitable for carrying out the process P2 of the present invention may be sulfur (S), hydrosulfuric acid (H ₂ S), sodium sulfide (Na ₂ S), sodium hydrosulfide (NaHS), boron trisulfide (B ₂ S). ₃ ), sulfurized bis(diethylaluminum) ((AlEt ₂ ) ₂ S), ammonium sulfide ((NH ₄ ) ₂ S), phosphorus pentasulfide (P ₂ S ₅ ), Lawesson's reagent (2,4- Bis(4-methoxyphenyl)-1,2,3,4-dithiadiphosphetane-2,4-disulfide) or polymer supported thiocarbonylating agent (eg Journal of the Chemical Society, as described in Perkin 1 (2001), 358), may optionally be carried out in the presence of a catalytic amount or a stoichiometric or excess base (e.g., inorganic and organic base). It is preferred to use an alkali metal carbonate such as sodium carbonate, potassium carbonate, potassium hydrogencarbonate or sodium hydrogencarbonate; a heterocyclic aromatic base such as pyridine, picoline, lutidine or trimethylpyridine; and tertiary An amine such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylpyridin-4-amine or N-methyl-piperidine.

Suitable solvents for carrying out the process P2 according to the invention may be customary inert organic solvents. It is preferred to use an aliphatic, alicyclic or aromatic hydrocarbon which is halogenated as desired, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorine Benzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl third amyl Ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane; nitrile, such as acetonitrile, propionitrile, n- or isobutyronitrile or benzonitrile; sulfur-containing solvent For example, cyclobutyl hydrazine or carbon disulfide.

When carrying out the process P1 according to the invention, a sulfur equivalent of 1 mole or excess of the thiocarbonating agent and 1 to 3 moles of base per mole of the melamine reaction (I) can be used.

Reaction components in other ratios can also be used. Processing is performed by a known method.

The processes P1 and P2 of the present invention are generally carried out under atmospheric pressure. It can also be operated under high pressure or reduced pressure.

When the processes P1 and P2 of the present invention are carried out, the reaction temperatures can be varied within a relatively wide range. Generally, such processes are carried out at temperatures between 0 ° C and 200 ° C (preferably 10 ° C to 150 ° C). One way to control the temperature of the process of the invention is to use microwave technology.

Typically, the reaction mixture is concentrated under reduced pressure. Any impurities that may still be present in the residue can be eliminated by known methods such as chromatography or crystallization.

It is processed by a common method. Usually, the reaction mixture is treated with water and separated The organic phase was concentrated and dried under reduced pressure. If appropriate, any impurities which may still be present in the remaining residue can be removed by conventional methods such as chromatography, crystallization or distillation.

The compounds of the present invention can be prepared according to the general preparation methods described above. However, it should be understood that those skilled in the art can use this method based on their general knowledge and available public literature, depending on the characteristics of each compound desired to be synthesized.

In still another aspect, the invention relates to a compound of formula (II) useful as an intermediate compound or material in the process of the invention. Accordingly, the present invention provides a compound of formula (IIa) and acceptable salts thereof:

Wherein Z ² , Z ³ , Z ⁴ , Z ⁵ , n, X and B are as defined herein. The N-cyclopropylamine derivative of the formula (IIa) can be produced according to a known method. Preferred compounds of the formula (IIa) according to the invention are: -N-{2-[dimethyl(phenyl)decyl]benzyl}cyclopropylamine; -N-{2-[(4-chlorophenyl)( Dimethyl)decyl]benzyl}cyclopropylamine; -N-{2-[biphenyl-4-yl(dimethyl)decyl]benzyl}cyclopropylamine; - N-{2-[dimethyl (4-phenoxyphenyl)nonanyl]benzyl}cyclopropylamine; -N-{2-[dimethyl(1-naphthyl)decyl]benzyl}cyclopropylamine; - N-{2-[ Dimethyl(2-thienyl)nonanyl]benzyl}cyclopropylamine; -N-{2-[(6-methoxypyridin-3-yl)(dimethyl)decyl]benzyl}cyclopropylamine .

In another aspect, the invention is also directed to a fungicidal composition comprising an effective and non-phytotoxic amount of an active compound of formula (I).

The expression "effective and non-phytotoxic amount" means that the composition of the invention is sufficient to control or destroy the fungus present or readily present on the crop without causing any significant phytotoxicity in the crop. The amount of sexual symptoms. The amount can vary over a wide range depending on the fungus to be controlled, the type of crop, the climatic conditions and the compounds included in the fungicide composition of the invention. This amount can be determined by systematic field trials within the capabilities of those skilled in the art.

Thus, according to the present invention there is provided a fungicide composition comprising as an active ingredient an effective amount of a compound of formula (I) as defined herein and an agriculturally acceptable carrier, carrier or filler.

According to the invention, the term "carrier" denotes a natural or synthetic organic or inorganic compound which combines or combines the active compound of formula (I) to make it easier to apply, in particular, to the plant part. Therefore, this carrier is generally inert and should be agriculturally acceptable. The carrier can be either solid or liquid. Examples of suitable carriers include clay, natural or synthetic silicates, vermiculite, resins, waxes, solid fertilizers, water, alcohols (specifically butanol), organic solvents, minerals and vegetable oils and derivatives thereof. Mixtures of such carriers can also be used.

The compositions of the present invention may also contain other components. In particular, the composition may additionally comprise a surfactant. The surfactant can be an ionic or nonionic emulsifier, dispersant or wetting agent or a mixture of such surfactants. Mention may be made, for example, of polyacrylates, lignosulfonates, phenolsulfonates or naphthalenesulfonates, ethylene oxides with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (specific Alkyl phenol or aryl phenol), a sulfosuccinate salt, a taurine derivative (specifically, an alkyl taurate sulfonate), a polyoxyethylated alcohol or a phenol phosphate, a plurality of a fatty acid ester of an alcohol, and a derivative of the above compound containing a sulfate, a sulfonate, and a phosphate functional group. When the active compound and/or the inert carrier is water insoluble and when the vehicle for application is water, it is generally necessary to have at least one surfactant. Preferably, the surfactant level may range from 5% to 40% by weight of the composition.

Other components may also be included as needed, such as protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers, chelating agents. More generally, the active compounds can be combined with any solid or liquid additive that conforms to conventional formulation techniques.

In general, the compositions of the invention may comprise from 0.05 to 99% by weight of active compound, preferably from 10 to 70% by weight.

Compositions of the invention in various forms and formulations may be employed, such as aerosol dispensers, capsule suspensions, cold mist concentrates, powders, emulsifiers, oil-in-water emulsions, water-in-oil emulsions, encapsulated granules, microparticles Agent, treatment seed suspension with water, gas (under pressure), gas production product, granules, hot mist concentrate, large particles, micro particles, oil dispersible powder, oil miscible suspension, oil miscible liquid , paste, plant stick, dry seed treatment powder, pesticide coated seed, soluble concentrate, soluble powder, treatment seed solution, suspension concentrate (flowable concentrate), Ultra low volume (ULV) liquid, ultra low volume (ULV) suspension, water-dispersible granules or lozenges, water-dispersible powders for treating pulp, water-soluble granules or lozenges, water-soluble powders for treating seeds and Wet powder. Such compositions include not only ready-to-use compositions that can be applied directly to the plant or seed to be treated by suitable means, such as a spray or dusting device, but also concentrated commercial compositions that must be diluted prior to application to the crop.

The formulations may be prepared in a manner known per se, for example, from such active ingredients with at least one conventional extender, solvent or diluent, adjuvant, emulsifier, dispersant and/or binder or fixative, Aerosol, water repellent, (if appropriate) desiccant and UV stabilizer and (if appropriate) dyes and pigments, defoamers, preservatives, inorganic and organic thickeners, adhesives, gibberellins and other processing aids Mix with water. Depending on the type of formulation to be prepared, further processing steps such as wet milling, dry milling and granulation are necessary.

The active ingredient of the present invention may be present in its original state or in the form of its (commercial) formulation and the use of such other formulations formed by mixing other (known) active ingredients, such as insecticides, attractants, no Progesting agents, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers, safeners and/or chemical pheromones.

The compounds of formula (I) and fungicide compositions of the present invention are useful for the curative or prophylactic control of phytopathogenic fungi in plants or crops.

Thus, according to another aspect of the present invention, there is provided a method for the curative or prophylactic control of a phytopathogenic fungus in a plant or crop, characterized in that a compound of the formula (I) or a fungicide composition of the invention is applied. To the fruit of the seed, plant or plant or to the soil in which the plant has been planted or planted.

The treatment method of the present invention can also be used to treat propagation material (such as tubers or rhizomes) and can also treat seeds, seedlings or transplanted seedlings and plants or transplanted plants. This processing method can also be used to process the root. The treatment method of the present invention can also be used to treat aerial parts of plants, such as the trunk, stem or stalk, leaves, flowers and fruits of plants of interest.

According to the invention, all plants and plant parts can be treated. By plant, it means all plants and plant populations, such as wild plants, cultivars and plant varieties that need and are not needed (whether protected by plant variety or plant breeder rights). Cultivars and plant varieties may be conventionally supplemented or supplemented by one or more biotechnological methods (eg, using double haploid, protoplast fusion, random and directed mutagenesis, molecular or genetic markers) or bioengineering and genetic engineering methods. Plants obtained by breeding and breeding methods. The relevant part of the plant means all above-ground and underground parts and organs of the plant, such as buds, flowers, flowers and roots, examples of which are leaves, needles, stems, branches, flowers, fruiting bodies, fruits and Seeds, and roots, bulbs and rhizomes. Crops and asexual and reproductive material (such as cuttings, bulbs, rhizomes, runners and seeds) also belong to the plant part.

Among the plants which can be protected by the method of the invention, mention may be made of major crops such as corn, soybean, cotton, Brassica oilseeds (for example Brassica napus (for example, canola)) , Brassica rapa, B. juncea (eg mustard (mustard) and brown mustard (Brassica carinata)), rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet, durum wheat Various fruits and vegetables of flax, vine and various plant groups, such as Rosaceae sp. (such as pome fruits (such as apples and pears) and stone fruits (such as apricots, cherries, almonds and peaches), berries ( For example, strawberry)), Ribesioidae sp., Juglandaceae sp., birch Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Polygonaceae (Lauraceae sp.), Musaceae sp. (such as banana tree and plant seedling), Rubiaceae sp. (such as coffee), Theaceae sp., Sterculiceae sp. , Rutaceae sp. (eg lemon, orange and grapefruit), Solanaceae sp. (eg tomato, potato, pepper, eggplant), Liliaceae sp., Compositiae sp .) (eg lettuce, artichokes and chicory - including chicory root, endive or chicory), Umbelliferae sp. (eg carrot, celery, celery and root celery), Cucurbitaceae sp. (eg cucumbers - including pickled cucumbers, pumpkins, watermelons, gourds and melons), Alliaceae sp. (eg onions and leeks), Cruciferae sp. (eg white cabbage, red cabbage, blue and white) Vegetables, white cauliflower, Brussels sprouts, Chinese cabbage, kohlrabi, radish, wasabi, cress, Shandong cabbage, legumes (Leguminosae) Sp.) (for example, peanuts, peas and kidney beans - such as green beans and broad beans), Chenopodiaceae sp. (such as amaranth, leaf beet, spinach, beetroot), Malvaceae (such as white bamboo shoots) ), Asparagaceae (eg asparagus); horticultural crops and forest crops; ornamental plants, and genetically engineered homologs of such crops.

The treatment methods of the invention can be used to treat genetically modified organisms (GMOs), such as plants or seeds. A genetically modified plant (or transgenic plant) refers to a plant that has stably integrated a heterologous gene into its genome. The expression "heterologous gene" basically means to provide or combine with the outside of a plant and when introduced into the nuclear, chloroplast or mitochondrial genome, by expressing the desired protein or polypeptide or by downregulating other genes present in the plant or It is silent (using, for example, antisense technology, co-suppression techniques, or RNA interference (RNAi) techniques) to confer agronomic or other traits on the transformed plants that are novel or improved. A heterologous gene located in the genome is also referred to as a transgene. Defining a transgene at a particular location in the plant genome is referred to as a transformation or transgenic event.

Depending on the plant species and plant cultivars, their geographic and growing conditions (soil, climate, growing season, diet), the treatment of the present invention may also result in a superadditive ("synergistic") effect. Thus, for example, reducing the rate of application and/or expanding the spectrum of activity and/or increasing the activity of the active compounds and compositions used according to the invention, improving plant growth, increasing tolerance to high or low temperatures, increasing drought or water or Tolerance of soil salt content, increase flowering rate, easier harvesting, accelerated maturation, increase yield, increase fruit, increase plant height, deepen leaf green, early flowering, improve harvest product quality and/or improve nutritional value, Increasing the sugar concentration in the fruit, increasing the storage stability and/or processing possibilities of the harvested product, etc., exceeds the actual expected effect.

At some application rates, the active compound combinations of the invention may also have a potentiating effect in plants. Therefore, they are also suitable for mobilizing the plant's defense system against attacks by unwanted microorganisms. If appropriate, this may be one of the reasons for the enhanced activity of the combination of the invention (e.g., against fungi). In this context, it is understood that a fortified (inducible resistance) substance means a substance or combination of substances that can stimulate a plant defense system such that the treated plant can be contacted with an undesired microorganism later. Such microorganisms show substantial resistance. In this context, it is understood that undesired microorganisms mean phytopathogenic fungi, bacteria and viruses. Thus, plants of the invention can be used to protect plants from attack by the pathogens described above for a specific period of time after treatment. After treatment of the plants with the active compounds, the effective period of protection is generally from 1 to 10 days, preferably from 1 to 7 days.

Plants and plant cultivars that are more suitable for treatment in accordance with the present invention include all plants (whether obtained by breeding and/or biotechnological methods) having genetic material that confers particularly advantageous useful traits on such plants.

Plants and plant cultivars which are also suitable for treatment according to the invention are resistant to one or more biological stresses, that is to say that the plants exhibit better defense against animal and microbial pests, such as nematodes, insects, mites, plant pathogenicity. Fungi, bacteria, viruses and/or viroids.

Examples of nematode-resistant plants are described, for example, in U.S. Patent Application Serial Nos. 11/765,491, 11/765,494, 10/926,819, 10/782,020, 12/032,479, 10/783,417, 10 /782,096, 11/657,964, 12/192,904, 11/396,808, 12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886 No. 12/364,335, 11/763,947, 12/252,453, 12/209,354, 12/491,396 or 12/497,221.

Plants and plant cultivars which may also be treated according to the invention are those which are resistant to one or more abiotic stresses. Abiotic stress conditions can include, for example, drought, low temperature exposure, thermal exposure, osmotic stress, flooding, high soil salinity, high mineral concentration exposure, ozone exposure, high light exposure, limited utilization of nitrogen nutrients, phosphorus nutrients Limited utilization, avoiding shade.

Plants and plant cultivars which may also be treated according to the invention are plants which are characterized by enhanced yield characteristics. The high yield of such plants can be, for example, the result of improved plant physiology, growth and development, such as water use efficiency, water retention, improved nitrogen utilization, enhanced carbon assimilation, improved photosynthesis, improved germination rate And accelerate maturity. It can also affect yield by improving plant structure (under stress and non-stress conditions), including (but not limited to) early flowering, flowering control for seed production, seedling vigor, plant size, internode number and distance, root Growth, seed size, fruit size, pod size, pod or panicle number, seed number/pod or ear, seed quality, enhanced seed plumpness, reduced seed dispersibility, reduced pod cracking, and lodging resistance. Other yield traits include seed composition (eg, carbohydrate content, oil content and composition), nutritional value, reduced anti-nutritional compounds, improved processability, and better storage stability.

Plant examples having the above traits are not listed in detail in Table A.

Plants that can be treated by the present invention have been shown to produce hybrids that are generally superior in yield, vigor, health, and resistance to biotic and abiotic stresses, or hybrid vigor. Things. Such plants are usually obtained by crossing a homologous male sterile parent (maternal) with another homologous male sterile parent (parent). Hybrid seeds are typically harvested from these male sterile plants and sold to growers. Male sterile plants can sometimes be obtained by emasculation (ie mechanical removal of such male reproductive organs (or male flowers)), but more often by genetic determinants in the genome of the plant. Male infertility results. In this case, and especially when the seed is intended to be harvested from the hybrid plant, it is generally necessary to ensure that the male fertility of the hybrid plant can be fully restored. This can be accomplished by ensuring that the male parent has a suitable fertile restorer gene (which can restore the male fertility of the hybrid plant and contains a genetic stator responsible for male fertility). The male fertility genetic stator can be located in the cytoplasm. Examples of cytoplasmic male fertility (CMS) are described, for example, in Brassica species (WO 92/05251, WO 95/09910, WO 98/27806, WO 05/002324, WO 06/021972, and US 6,229,072). . However, the male fertility genetic stator can also be located in the nuclear genome. Male sterile plants can also be obtained by plant biotechnology methods such as genetic engineering. A particularly useful method for obtaining a male sterile plant is described in WO 89/10396, in which, for example, a ribonuclease (eg, a bacillus RNase) is selectively expressed in the velvet cell layer. in. Subsequently, fertility can be restored by expressing a ribonuclease inhibitor (e.g., barstar) (e.g., WO 91/02069) in cells of the velvet layer.

Plants or plant cultivars (obtained by plant biotechnology methods (e.g., genetic engineering) that can be treated in accordance with the present invention are plants that are tolerant to herbicide plants, i.e., can tolerate one or more specified herbicides. Such plants can be obtained by gene transformation or by selecting plants containing mutants that confer tolerance to the herbicide.

Herbicide-tolerant plant lines such as glyphosate-tolerant plants, ie plants which are tolerant to the herbicide glyphosate or a salt thereof. Plants can be rendered tolerant to glyphosate via various methods. For example, a glyphosate-tolerant plant can be obtained by transforming a plant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). An example of such EPSPS genes is the AroA gene (mutant CT7) of Salmonella typhimurium bacteria (Comai et al. Human 1983, Science 221, 370-371), CP4 gene of Agrobacterium sp. bacteria (Barry et al. 1992, Curr. Topics Plant Physiol. 7, 139-145), gene encoding petunia EPSPS (Shah Et al. 1986, Science 233, 478-481), a gene encoding tomato EPSPS (Gasser et al. 1988, J. Biol. Chem. 263, 4280-4289) or a gene encoding Eleusine EPSPS (WO 01/66704) ). It can also be a mutant EPSPS, as described, for example, in EP 0837944, WO 00/66746, WO 00/66747 or WO 02/26995. The glyphosate-tolerant plants can also be obtained by the expression of a gene encoding a glyphosate oxidoreductase, as described in U.S. Patent Nos. 5,776,760 and 5,463,175. Glyphosate-tolerant plants can also be obtained by expressing a gene encoding a glyphosate acetyltransferase, as described, for example, in WO 02/36782, WO 03/092360, WO 05/012515, and WO 07/024782. . Glyphosate-tolerant plants can also be obtained by selecting plants containing naturally occurring mutants of the above genes, as described, for example, in WO 01/024615 or WO 03/013226. Plants that exhibit an EPSPS gene that confers glyphosate tolerance are described, for example, in U.S. Patent Application Serial Nos. 11/517,991, 10/739,610, 12/139,408, 12/352,532, 11/312,866. No. 11/315,678, 12/421,292, 11/400,598, 11/651,752, 11/681,285, 11/605,824, 12/468,205, 11/760,570, Nos. 11/762,526, 11/769,327, 11/769,255, 11/943801 or 12/362,774. Plants comprising other genes that confer tolerance to glyphosate, such as decarboxylase genes, are described, for example, in U.S. Patent Application Serial Nos. 11/588,811, 11/185,342, 12/364,724, 11/185,560. No. 12/423,926.

Other herbicide tolerant plant lines are for example plants which are tolerant to herbicides which inhibit the enzyme glutamine indoleamine synthase, such as bialaphos, phosphinothricin or glufosinate. Such plants can be obtained by an enzyme which exhibits a detoxifying herbicide or a mutant glutamine indole synthase which is resistant to inhibition, as described, for example, in U.S. Patent Application Serial No. 11/760,602. An effective detoxifying enzyme encoding glufosinate An enzyme that transfers an enzyme (for example, a bar or pat protein from Streptomyces). A plant line exhibiting an exogenous glufosinate acetyltransferase is described, for example, in U.S. Patent Nos. 5,561,236, 5,648,477, 5,646,024, 5,273,894, 5,637,489, 5,276,268, 5,739,082, 5,908,810. And in No. 7,112,665.

Other herbicide tolerant plants are also plants that are tolerant to herbicides that inhibit hydroxyphenylpyruvate dioxygenase (HPPD). Hydroxyphenylpyruvate dioxygenase is an enzyme that catalyzes the reaction of conversion of hydroxyphenylpyruvate (HPP) to black uric acid. Plants that are resistant to HPPD inhibitors can be transformed with a gene encoding a naturally occurring anti-HPPD enzyme or a gene encoding a mutant or chimeric HPPD enzyme, such as WO 96/38567, WO 99/24585, WO 99/24586, WO It is described in 2009/144079, WO 2002/046387 or US 6,768,044. Although HPPD inhibitors inhibit native HPPD enzymes, plants can also be transformed with genes encoding specific enzymes that form black uric acid to obtain tolerance to HPPD inhibitors. Such plants and gene lines are described in WO 99/34008 and WO 02/36787. Genes encoding enzymes with prephenate dehydrogenase (PDH) activity can also be used to transform plants to improve plant tolerance to HPPD inhibitors, in addition to genes encoding HPPD-tolerant enzymes, such as WO 2004/024928 Said in the middle. In addition, plants can be more tolerant to HPPD by adding genes encoding enzymes that can metabolize or degrade HPPD inhibitors, such as the CYP450 enzymes shown in WO 2007/103567 and WO 2008/150473, to the genome of plants. - Inhibitor herbicide.

Another plant that is tolerant to herbicide plant lines to acetate lactate synthase (ALS) inhibitors. Known ALS inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pyrimidinyloxy(thio)benzoates, and/or sulfonamide carbonyl triazolinone herbicides. It is known that different mutations in the ALS enzyme (also known as acetamidine lactate synthetase, AHAS) confer tolerance to different herbicides and herbicide groups, such as, for example, Tranel and Wright (2002, Weed Science 50:700). -712) and U.S. Patent Nos. 5,605,011, 5,378,824, 5,141,870 and 5,013,659. Production methods that are resistant to sulfonium urea plants and tolerant to imidazolinone plants are described in U.S. Patent No. 5,605,011 No. 5,013,659, 5,141,870, 5,767,361, 5,731,180, 5,304,732, 4,761,373, 5,331,107, 5,928,937 and 5,378,824, and International Publication No. WO 96/33270. Other tolerant imidazolinone plants are also described, for example, in WO 2004/040012, WO 2004/106529, WO 2005/020673, WO 2005/093093, WO 2006/007373, WO 2006/015376, WO 2006/024351 and WO 2006/060634 in. Other sulfonamide-resistant and imidazolinone-resistant plants are also described in, for example, WO 07/024782 and U.S. Patent Application Serial No. 61/288,958.

Cell cultures can be selected by mutagenesis in the presence of a herbicide, or by mutation breeding to obtain other plants that are resistant to imidazolinone and/or sulfonylurea, for example, U.S. Patent No. 5,084,082 (for soybeans), WO 97/41218 (for rice), US Patent No. 5,773,702 and WO 99/057965 (for sugar beet), US Patent No. 5,198,599 (for lettuce) or WO 01/065922 (for sunflower) Said.

Plants or plant cultivars (obtained by plant biotechnology methods (e.g., genetic engineering)) that may also be treated in accordance with the present invention are insect-resistant transgenic plants, i.e., plants that are resistant to attack by a particular target insect. Such plants can be obtained by gene transformation or by selecting a plant containing a mutant that confers resistance to the insect.

As used herein, an "insect-resistant transgenic plant" includes any plant comprising at least one transgene comprising a coding sequence encoding the following proteins:

1) an insecticidal crystalline protein derived from Bacillus thuringiensis or an insecticidal fraction thereof, for example as set forth by Crickmore et al. (1998, Microbiology and Molecular Biology Reviews, 62: 807-813) and by Crickmore et al. 2005) Insect crystalline protein or its insecticidal fraction, such as the Cry protein class, as updated by the S. sinensis nomenclature (website: http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/) Proteins Cry1Ab, Cry1Ac, Cry1B, Cry1C, Cry1D, Cry1F, Cry2Ab, Cry3Aa or Cry3Bb or an insecticidal moiety thereof (e.g., EP 1999141 and WO 2007/107302), or such proteins encoded by synthetic genes, such as described in U.S. Patent Application Serial No. 12/249,016;

2) a crystalline protein derived from S. cerevisiae or a part thereof having an insecticidal activity in the presence of a second other crystalline protein or a part thereof from S. cerevisiae, for example, a binary toxin composed of Cry34 and Cry35 crystalline proteins (Moellenbeck et al. Human, 2001, Nat. Biotechnol. 19: 668-72; Schnepf et al., 2006, Applied Environm. Microbiol. 71, 1765-1774) or a binary toxin composed of Cry1A or Cry1F protein and Cry2Aa or Cry2Ab or Cry2Ae protein ( U.S. Patent Application Serial No. 12/214,022 and EP 08010791.5); or

3) Hybrid insecticidal proteins comprising a portion of different insecticidal crystalline proteins from S. cerevisiae, such as the hybrid of the protein of 1) above or the hybrid of the protein of 2) above, for example from the maize line MON89034 (WO 2007/027777) Producing a Cry1A.105 protein; or

4) The protein of any one of the above 1) to 3), wherein some (specifically 1 to 10) amino acids have been replaced by another amino acid to obtain higher insecticidal activity against the target insect species And/or expanding the range of affected target insect species and/or because of changes introduced into the coding DNA during selection or transformation, such as the Cry3Bb1 protein in maize line MON863 or MON88017 or the Cry3A protein in maize line MIR604;

5) Insecticidal secreted proteins from S. or Bacillus cereus or insecticidal parts thereof, for example at http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip. a vegetative insecticidal (VIP) protein listed on html, such as a protein from the VIP3Aa protein class; or

6) an insecticidal secreted protein from S. suis or Bacillus cereus in the presence of a second secreted protein from S. cerevisiae or Bacillus cereus, for example by VIP1A And a binary toxin composed of the VIP2A protein (WO 94/21795); or

7) a hybrid insecticidal protein comprising a portion of a different secreted protein from S. cerevisiae or Bacillus cereus, such as a hybrid of a protein of 1) above or a hybrid of a protein of 2) above;

8) The protein of any one of the above 5) to 7), wherein some (specifically 1 to 10) amino acids have been replaced by another amino acid to obtain higher insecticidal activity against the target insect species and / or expanding the range of affected target insect species and / or because of changes introduced into the coding DNA during selection or transformation (although still encoding insecticidal proteins), such as the VIP3Aa protein in cotton line COT102; or

9) an insecticidal secreted protein from S. cerevisiae or Bacillus cereus in the presence of a crystalline protein from S. cerevisiae, such as a binary toxin consisting of VIP3 and Cry1A or Cry1F (US Patent Application No. 61) /126083 and 61/195019) or a binary toxin consisting of a VIP3 protein and a Cry2Aa or Cry2Ab or Cry2Ae protein (U.S. Patent Application Serial No. 12/214,022 and EP 08010791.5).

10) The protein of the above 9), wherein some (specifically 1 to 10) amino acids have been replaced by another amino acid to obtain higher insecticidal activity against the target insect species and/or to expand the affected target Insect species range and/or because of changes introduced into the coding DNA during selection or transformation (although still encoding insecticidal proteins).

Of course, as used herein, an insect-resistant transgenic plant also includes any plant comprising a combination of genes encoding a protein of any of the above categories 1 to 10. In one embodiment, the insect-resistant plant comprises more than one transgene encoding a protein of any of the above categories 1 to 10, and when different proteins for different target insect species are used, the range of affected target insect species can be expanded, It is possible to delay the development of insect resistance by using different proteins that kill the same target insect species but have different modes of action (eg, binding to different receptor binding sites in insects).

As used herein, "anti-insect transgenic plants" additionally include at least one type of Any plant of the gene, once expressed by the sequence of the transgene, will inhibit the growth of the pest once it is ingested by the plant pest, as described, for example, in WO 2007/080126, WO 2006/129204, It is described in WO 2007/074405, WO 2007/080127 and WO 2007/035650.

Plants or plant cultivars (obtained by plant biotechnology methods (eg, genetic engineering)) that can also be treated in accordance with the present invention are resistant to abiotic stresses. Such plant lines can be obtained by genetic transformation or by selecting plants containing mutants that confer such stress resistance. Particularly useful stress tolerant plants include:

1) Plants containing a transgene which reduces the expression and/or activity of a poly(ADP-ribose) polymerase (PARP) gene in a plant cell or plant, such as WO 00/04173, WO/2006/045633, EP 04077984.5 or EP 06009836.5 Said in the middle.

2) A plant comprising a stress tolerance enhancing transgene which reduces the expression and/or activity of a PARG encoding gene of a plant or plant cell, as described, for example, in WO 2004/090140.

3) Plant functional enzymes encoding the nicotinamide adenine dinucleotide salvage synthesis pathway (including nicotinamide, nicotinate phosphoribosyltransferase, niacin single nucleotide adenosyltransferase, nicotinamide gland) Plants that enhance stress tolerance transgenes of purine dinucleotide synthase or nicotinamide phosphoribosyltransferase), for example, EP 04077624.7, WO 2006/133827, PCT/EP07/002433, EP 1999263 or WO Said in 2007/107326.

Plants or plant cultivars (obtained by plant biotechnology methods (eg genetic engineering)) which may also be treated according to the invention may exhibit altered yield, quality and/or storage stability of the harvest product and/or alteration of specific components of the harvest product The nature of, for example:

1) A transgenic plant capable of synthesizing modified starch, wherein the modified starch has a physical and chemical property, specifically an amylose content or an amylose/amylopectin, compared to a starch synthesized by a wild type plant cell or a plant. The ratio, degree of branching, average chain length, side chain distribution, viscosity properties, gel strength, starch granule size, and/or starch granule morphology have changed, and thus are more suitable for a particular application. The transgenic plant line of the synthetically modified starch is disclosed, for example, in EP 0571427, WO 95/04826, EP 0719338, WO 96/15248, WO 96/19581, WO 96/27674, WO 97/11188, WO 97/26362, WO 97/32985, WO 97/42328, WO 97/44472, WO 97/45545, WO 98/27212, WO 98/40503, WO 99/58688, WO 99/58690, WO 99/58654, WO 00/08184, WO 00/08185, WO 00/08175, WO 00/28052, WO 00/77229, WO 01/12782, WO 01/12826, WO 02/101059, WO 03/071860, WO 2004/056999, WO 2005/030942, WO 2005/030941, WO 2005/095632, WO 2005/095617, WO 2005/095619, WO 2005/095618, WO 2005/123927, WO 2006/018319, WO 2006/103107, WO 2006/108702, WO 2007/009823, WO 00/22140, WO 2006/063862, WO 2006/072603, WO 02/034923, EP 06090134.5, EP 06090228.5, EP 06090227.7, EP 07090007.1, EP 07090009.7, WO 01/14569, WO 02/79410, WO 03/33540, WO 2004/078983, WO 01/19975, WO 95/26407, WO 96/34968, WO 98/20145, WO 99/12950, WO 99/66050, WO 99/53072, US 6,734, 341, WO 00/11192, WO 98/22604, WO 98/32326, WO 01/98509, WO 01/ 98509, WO 2005/002359, US 5,824,790, US 6,013,861, WO 9 4/04693, WO 94/09144, WO 94/11520, WO 95/35026, WO 97/20936;

2) A transgenic plant that can synthesize a non-starch carbohydrate polymer or a synthetic non-starch carbohydrate polymer that has improved properties over a genetically modified wild type plant. Examples are plants which produce polyfructose, in particular inulin and fructan type, as disclosed in EP 0663956, WO 96/01904, WO 96/21023, WO 98/39460 and WO 99/24593; , 4-glucan-producing plants, as disclosed in WO 95/31553, US 2002031826, US 6,284,479, US 5,712,107, WO 97/47806, WO 97/47807, WO 97/47808, and WO 00/14249; 1,6 branches α- Plants of 1,4-glucan, as disclosed in WO 00/73422; plants which produce alternan, such as in WO 00/47727, WO 00/73422, EP 06077301.7, US 5,908,975 and EP 0728213 reveal;

3) Transgenic plants which produce hyaluronic acid, as disclosed in, for example, WO 2006/032538, WO 2007/039314, WO 2007/039315, WO 2007/039316, JP 2006304779, and WO 2005/012529.

4) Transgenic plants or hybrid plants, for example, having onions such as "highly soluble solids content", "low irritancy" (LP) and/or "long stability" (LS), as described in U.S. Patent Application Serial No. 12/020,360 And as described in No. 61/054,026.

Plants or plant cultivars (obtainable by plant biotechnology methods (e.g., genetic engineering)) which may also be treated in accordance with the present invention are plants having improved fiber characteristics, such as cotton plants. Such plants can be obtained by genetic transformation or by selection of plants containing mutants which confer such improved fiber characteristics and include: a) plants containing modified forms of the cellulose synthase gene, such as cotton plants, such as Said in WO 98/00549; b) plants of modified form containing rsw2 or rsw3 homologous nucleic acids, such as cotton plants, as described in WO 2004/053219; c) plants which enhance the expression of sucrose phosphate synthase, such as cotton plants , as described in WO 01/17333; d) plants that enhance the expression of sucrose synthase, such as cotton plants, as described in WO 02/45485; e) altering the timing of intercellular filamentation at the base of fibroblasts (eg via A plant, such as a cotton plant, that is degraded by a fiber-selective β-1,3-glucanase, as described in WO 2005/017157 or as described in EP 0 807 551 4.3 or US Patent Application No. 61/128,938; Plants with improved reactivity (eg, via fibers expressing the N-acetylglucosamine transferase gene (including the nodC and chitin synthase genes)), such as cotton plants Said as described in WO 2006/136351.

Plants or plant cultivars (obtainable by plant biotechnology methods (e.g., genetic engineering)) which may also be treated in accordance with the present invention are plants having improved oil distribution characteristics, such as canola or related Brassica plants. Such plants can be obtained by genetic transformation or by selecting plants containing mutants which confer such improved oil distribution characteristics, and include: a) plants which produce oils having a high oleic acid content, such as canola plants, , for example, as described in US Pat. No. 5,969,169, US Pat. A plant which produces an oil having a low concentration of a saturated fatty acid, such as a canola plant, as described in, for example, U.S. Patent No. 5,434,283, or U.S. Patent Application Serial No. 12/668,303.

Plants or plant cultivars (obtainable by plant biotechnology methods (e.g., genetic engineering)) which may also be treated in accordance with the present invention are plants having improved seed rupture characteristics, such as rapeseed or related Brassica plants. Such plants can be obtained by genetic transformation or by selecting plants containing mutants that confer such improved seed rupture characteristics, and include plants having delayed or reduced seed rupture, such as canola plants, such as U.S. Patent Application Serial No. 61 /135,230, WO09/068313 and WO10/006732.

Particularly useful transgenic plant lines that can be treated in accordance with the present invention contain a combination of transformation events or transformation events (such as those in the United States Department of Agriculture (USDA) Animal and Plant Health Inspection Service (APHIS), regardless of such applications Plants that have been approved or are still pending. This information is readily available from APHIS (4700 River Road Riverdale, MD 20737, USA), for example on its website (URL http://www.aphis.usda.gov/brs/not_reg.html). At the filing date of this application, APHIS pending or APHIS approved non-regulated status applications are those listed in Table B with the following information:

- Application: The identification number of the application. The technical content of such conversion events may be based on this application number, see individual application documents obtained from APHIS (e.g., on the APHIS website). These are incorporated herein by reference.

- Application extension: Refer to the previous application for extension.

- Agency: The name of the entity submitting the application.

- Normative objects: Plant species of interest.

- Transgenic phenotype: The traits conferred on such plants by transformation events.

- Conversion event or line: The name of the event (sometimes referred to as a work item) that requires this unregulated status.

- APHIS literature: Various documents published by APHIS relating to this application and possibly requested by APHIS.

Other particularly useful plant families containing a single conversion event or combination of conversion events are shown, for example, in databases from various national or local regulatory agencies (see for example http://gmoinfo.jrc.it/gmp_browse.aspx and http:// Www.agbios.com/dbase.php).

Particularly useful transgenic plant lines which can be treated according to the invention contain plants for combinations of transformation events or transformation events, and such transformation events are shown, for example, in databases of various national or regional regulatory agencies and include lines 1143-14A (cotton, insects) Control, not deposited, as described in WO 2006/128569); line 1143-51B (cotton, insect control, unregistered, described in WO 2006/128570); line 1445 (cotton, herbicide tolerant, unregistered, described in US-A 2002-120964 or WO 02/034946); line 17053 (rice, herbicide tolerant, accession number PTA-9843, described in WO 2010/117737); line 17314 (rice, herbicide tolerant, accession number PTA- 9844, described in WO 2010/117735); line 281-24-236 (cotton, insect control - herbicide tolerant, accession number PTA-6233, described in WO 2005/103266 or US-A 2005-216969); 3006-210-23 (cotton, insect control - herbicide tolerant, accession number PTA-6233, described in US-A 2007-143876 or WO 2005/103266); line 3272 (corn, quality traits, accession number PTA-9972, described in WO 2006/098952 or US-A 2006-230473); line 40416 (corn, insect control - herbicide tolerance) Agent, accession number ATCC PTA-11508, described in WO 2011/075593); line 43A47 (corn, insect control - herbicide tolerant, accession number ATCC PTA-11509, described in WO 2011/075595); line 5307 (corn , insect control, accession number ATCC PTA-9561, described in WO 2010/077816); strain ASR-368 (糠草, herbicide tolerant, ATCC PTA-4816, described in US-A 2006-162007 or WO 2004/ 053062); Line B16 (corn, herbicide tolerant, not deposited, described in US-A 2003-126634); line BPS-CV127-9 (soybean, herbicide tolerant, accession number NCIMB No. 41603, described in WO 2010 /080829); line CE43-67B (cotton, insect control, accession number DSM ACC2724, described in US-A 2009-217423 or WO2006/128573); line CE44-69D (cotton, insect control, unregistered, described in US-A 2010-0024077); line CE44-69D (cotton, insect control, not deposited, described in WO 2006/12857 1)) line CE46-02A (cotton, insect control, not deposited, described in WO 2006/128572); strain COT102 (cotton, insect control, unregistered, described in US-A 2006-130175 or WO 2004/039986 Medium); line COT202 (cotton, insect control, unregistered, described in US-A 2007-067868 or WO 2005/054479); line COT203 (cotton, insect control, not deposited, described in WO 2005/054480); Line DAS40278 (corn, herbicide tolerant, accession number ATCC PTA-10244, described in WO 2011/022469); line DAS-59122-7 (corn, insect control - herbicide tolerant, accession number ATCC PTA 11384, described in US -A 2006-070139); strain DAS-59132 (corn, insect control - herbicide tolerant, not deposited, described in WO 2009/100188); strain DAS68416 (soybean, herbicide tolerant, accession number ATCC PTA-10442, Described in WO 2011/066384 or WO 2011/066360); line DP-098140-6 (corn, herbicide tolerant, accession number ATCC PTA-8296, described in US-A 2009-137395 or WO 2008/112019); line DP-305423-1 (soybean, quality traits, unregistered, described in US-A 2008-312082 or WO 2008/054747); line DP-32138-1 (corn, hybrid system, storage No. ATCC PTA-9158, described in US-A 2009-0210970 or WO 2009/103049); line DP-356043-5 (soybean, herbicide tolerant, accession number ATCC PTA-8287, described in US-A 2010-0184079 Or WO 2008/002872); line EE-1 (eggplant, insect control, not deposited, described in WO 2007/091277); line FI117 (corn, herbicide tolerant, accession number ATCC 209031, described in US-A 2006) -059581 or WO 98/044140); line GA21 (corn, herbicide tolerant, accession number ATCC 209033, described in US-A 2005-086719 or WO 98/044140); line GG25 (corn, herbicide tolerant, deposited No. ATCC 209032, described in US-A 2005-188434 or WO 98/044140); line GHB119 (cotton, insect control - herbicide tolerant, accession number ATCC PTA-8398, described in WO 2008/151780); line GHB614 (cotton, herbicide tolerant, accession number ATCC PTA-6878, described in US-A 2010-050282 or WO 2007/017186); line GJ11 (jade , herbicide tolerant, accession number ATCC 209030, described in US-A 2005-188434 or WO 98/044140); line GM RZ13 (sugar beet, virus resistance, accession number NCIMB-41601, described in WO 2010/076212 Medium); line H7-1 (sugar beet, herbicide tolerant, accession number NCIMB 41158 or NCIMB 41159, described in US-A 2004-172669 or WO 2004/074492); strain JOPLIN1 (wheat, disease-resistant, unregistered) , described in US-A 2008-064032; strain LL27 (soybean, herbicide tolerant, accession number NCIMB 41658, described in WO 2006/108674 or US-A 2008-320616); strain LL55 (soybean, herbicide tolerant, Accession number NCIMB 41660, described in WO 2006/108675 or US-A 2008-196127); strain LLcotton 25 (cotton, herbicide tolerant, accession number ATCC PTA-3343, described in WO 03/013224 or US-A 2003-097687 Medium); strain LLRICE06 (rice, herbicide tolerant, accession number ATCC-23352, described in US 6,468,747 or WO 00/026345); strain LLRICE 601 (rice, resistant to Herbs, accession number ATCC PTA-2600, described in US-A 2008-2289060 or WO 00/026356); line LY038 (corn, quality traits, accession number ATCC PTA-5623, described in US-A 2007-028322 or WO 2005/061720); strain MIR162 (corn, insect control, accession number PTA-8166, described in US-A 2009-300784 or WO 2007/142840); line MIR 604 (corn, insect control, unregistered, description In US-A 2008-167456 or WO 2005/103301); line MON 15985 (cotton, insect control, accession number ATCC PTA-2516, described in US-A 2004-250317 or WO 02/100163); line MON810 (corn , insect control, not deposited, as described in US-A 2002-102582); line MON863 (corn, insect control, accession number ATCC PTA-2605, described in WO 2004/011601 or US-A 2006-095986); MON87427 (corn, pollination control, accession number ATCC PTA-7899, described in WO 2011/062904); line MON87460 (corn, stress tolerance, accession number ATCC PTA-8910, described in WO 2009/111263 or US-A 2011-0138504); strain MON87701 (soybean, insect control, accession number ATCC PTA-8194, [US-A 2009-130071 or WO 2009/064652); strain MON87705 (soybean, quality traits - herbicide tolerant, accession number ATCC PTA-9241, described in US-A 2010-0080887 or WO 2010/037016) Line MON87708 (soybean, herbicide tolerant, accession number ATCC PTA9670, described in WO 2011/034704); line MON 87754 (soybean, quality traits, accession number ATCC PTA-9385, described in WO 2010/024976); MON87769 (soybean, quality trait, accession number ATCC PTA-8911, described in US-A 2011-0067141 or WO 2009/102873); strain MON88017 (corn, insect control - herbicide tolerant, accession number ATCC PTA-5582, description In US-A 2008-028482 or WO 2005/059103); line MON 88913 (cotton, herbicide tolerant, accession number ATCC PTA-4854, described in WO 2004/072235 or US-A 2006-059590); line MON89034 (Maize, insect control, accession number ATCC PTA-7455, described in WO 2007/140256 or US-A 2008- 260932); line MON89788 (soybean, herbicide tolerant, accession number ATCC PTA-6708, described in US-A 2006-282915 or WO 2006/130436); strain MS11 (canola, pollination control - herbicide tolerant, storage number ATCC PTA-850 or PTA-2485, described in WO 01/031042); line MS8 (canola, pollination control - herbicide tolerant, accession number ATCC PTA-730, described in WO 01/041558 or US-A 2003-188347 Medium); line NK603 (corn, herbicide tolerant, accession number ATCC PTA-2478, described in US-A 2007-292854); line PE-7 (rice, insect control, unregistered, described in WO 2008/114282 ); line RF3 (canola, pollination control - herbicide tolerant, accession number ATCC PTA-730, described in WO 01/041558 or US-A 2003-188347); strain RT73 (canola, herbicide tolerant, unregistered, description In WO 02/036831 or US-A 2008-070260); line T227-1 (sugar beet, herbicide tolerant, not deposited, as described in WO 02/44407 or US-A 2009-265817); line T25 ( Corn, herbicide tolerant, not deposited, as described in US-A 2001-029014 or WO 01/051654); line T304-40 (cotton, insect control - herbicide tolerant, storage No. ATCC PTA-8171, described in US-A 2010-077501 or WO 2008/122406); line T342-142 (cotton, insect control, unregistered, described in WO 2006/128568); line TC1507 (corn, insect) Control - herbicide tolerant, not deposited, as described in US-A 2005-039226 or WO 2004/099447; strain VIP1034 (corn, insect control - herbicide tolerant, accession number ATCC PTA-3925, described in WO 03/052073 Medium); line 32316 (corn, insect control - herbicide tolerant, accession number PTA-11507, described in WO 2011/084632); line 4114 (corn, insect control - herbicide tolerant, accession number PTA-11506, described in WO 2011/084621).

Among the diseases of plants or crops which can be controlled by the method of the present invention, mention may be made of: powdery mildew diseases such as wheat powdery mildew, for example, caused by Blumeria graminis; Podosphaera diseases), for example caused by Podosphaera leucotricha; Sphaerotheca diseases, for example caused by Sphaerotheca fuliginea; Uncinula diseases, for example Caused by Uncinula necator; rust, for example: Gymnosporangium diseases, for example caused by Gymnosporangium sabinae; Hemileia diseases, such as rust from coffee (Hemileia vastatrix); Phakopsora diseases, for example caused by Phakopsora pachyrhizi or Phakopsora meibomiae; Puccinia diseases, for example Caused by Puccinia recondite, Puccinia graminis or Puccinia striiformis; Uromyces diseases, for example, caused by Uromyces appendiculatus; Oomycete diseases, such as: Albugo diseases, for example, caused by Albugo candida; Bremia diseases, for example caused by Bremia lactucae; Peronospora diseases, for example caused by Peronospora pisi or P. brassicae; Phytophthora diseases, for example caused by Phytophthora infestans; Plasmopara diseases, for example caused by Plasmopara viticola; Pseudoperonospora diseases, For example, caused by Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium diseases, for example, caused by Pythium ultimum; leafspot disease, leaf blister (leaf blotch disease) and leaf blight disease, for example, Alternaria diseases, such as Alternaria so Lani) causes; Cercospora diseases, for example caused by Cercospora beticola; Cladiosporum diseases, for example caused by Cladiosporium cucumerinum; Helminthosporosis (Cochliobolus diseases), for example caused by Cochliobolus sativus (conidia: Drechslera, synonym: Helminthosporium) or Cochliobolus miyabeanus; Colletotrichum diseases, For example, caused by Colletotrichum lindemuthanium; Cycloconium diseases, for example, caused by Cycloconium oleaginum; Diaporthe diseases, for example, by citrus compartments Caused by the genus (Diaporthe citri); Elsinoe diseases, for example caused by Elsinoe fawcettii; Gloeosporium diseases, for example, Gloeosporium laeticolor Causing; Glomerella diseases, for example caused by Glomerella cingulata; Guignardia diseases, for example caused by Guignardia bidwelli; Leptosphaeria diseases, for example, from Leptosphaeria maculans, Pseudomonas aeruginosa ( Leptosphaeria nodorum); Magnaporthe diseases, for example caused by Magnaporthe grisea; Mycosphaerella diseases, such as Mycosphaerella graminicola, Mycosphaerella arachidicola ), caused by Mycosphaerella fijiensis; Phaeosphaeria diseases, for example, caused by Phaeosphaeria nodorum; Pyrenophora diseases, such as by a circular nucleus Caused by Pyrenophora teres or Pyrenophora tritici repentis; Ramularia diseases, for example caused by Ramularia collocygni or Ramularia areola; Fusarium disease (Rhynchosporium diseases), for example caused by Rhynchosporium secalis; Diseases (Septoria diseases), for example caused by Septoria apii or Septoria lycopercisi; Typhula diseases, for example caused by Typhula incarnata ; Venturia diseases, for example caused by Venturia inaequalis; root, sheath and stem diseases, such as: Corticium diseases, for example, Corticium graminearum Cause; Fusarium diseases, for example caused by Fusarium oxysporum; Gaeumannomyces diseases, for example caused by Gaeumannomyces graminis; Rhizoctonia disease ( Rhizoctonia diseases), for example caused by Rhizoctonia solani; Sarocladium diseases, for example caused by Sarocladium oryzae; Sclerotium diseases, for example from rice Caused by Sclerotium oryzae; Tapesia diseases, such as caused by Tapesia acuformis; Thielaviopsis diseases, for example caused by Thielaviopsis basicola; ear and inflorescence diseases, for example: Alternaria diseases, for example caused by Alternaria spp.; Aspergillosis (Aspergillus diseases), for example caused by Aspergillus flavus; Cladosporium diseases, for example caused by Cladosporium spp.; Claviceps diseases, for example, by C. sphaeroides (Claviceps purpurea); Fusarium diseases, for example caused by Fusarium culmorum; Gibberella diseases, such as Gibberella zeae; Cloud-shaped diseases (Monographella) Diseases, for example caused by Monographella nivalis; smut and smut, for example: Sphacelotheca diseases, for example caused by Sphacelotheca reiliana; Tilletia diseases, for example caused by Tilletia caries; black powder fungus disease (Urocystis dise Ases), for example caused by Urocystis occulta; Ustilago diseases, for example caused by Ustilago nuda; fruit rot and fungal diseases, eg Aspergillus Diseases, for example caused by Aspergillus flavus; Botrytis diseases, for example caused by Botrytis cinerea; Penicillium diseases, for example by Penicillium expansum Cause; Rhizopus diseases, for example caused by Rhizopus stolonifer; Sclerotinia diseases, for example caused by Sclerotinia sclerotiorum; Verticilium diseases , for example, caused by Verticilium alboatrum; seed, soil-borne decay, mold, wither, decay, and collapse: Alternaria diseases, such as caused by Alternaria brassicicola ; Aphanomyces diseases, for example caused by Aphanomyces euteiches; Ascocci Yta diseases), for example caused by Ascochyta lentis; aspergillus diseases, for example caused by Aspergillus flavus; Cladosporium diseases, for example by Cladosporium herbarum Caused by; Cochliobolus diseases, for example caused by Cochliobolus sativus (conidia: Drechslera, Bipolaris synonym: Helminthosporium ); Colletotrichum diseases, for example (Colletotrichum coccodes) tomato caused by Colletotrichum; Fusarium disease (Fusarium diseases), e.g. caused by a yellow Fusarium (Fusarium culmorum); damage scab (Gibberella diseases), for example, caused by Gibberella zeae (Gibberella zeae); Beauveria graminis (Macrophomina diseases), e.g. caused by Beauveria bean shells (Macrophomina phaseolina); snow mold (Monographella diseases), for example, wheat caused by snow mold (Monographella nivalis); green mycosis (Penicillium diseases), for example extended Penicillium (Penicillium expansum) caused; Phoma diseases (Phoma diseases), e.g. Phoma (Phoma lingam) caused; Phomopsis disease (Phomopsis diseases), for example, from soybeans Phomopsis (Phomopsis sojae) caused; Phytophthora infestans disease (Phytophthora diseases), for example, caused by Phytophthora cactorum (Phytophthora cactorum) Pyrenophora diseases, for example caused by Pyrenophora graminea ; Pyricularia diseases, for example caused by Pyricularia oryzae ; Pythium diseases , for example, caused by Pythium ultimum ; Rhizoctonia diseases, for example, caused by Rhizoctonia solani ; Rhizopus diseases, such as Rhizopus oryzae Caused by; Sclerotium diseases, for example caused by Sclerotium rolfsii ; Septoria diseases, for example caused by Septoria nodorum ; Typhula diseases, for example caused by Typhula incarnata ; Verticillium diseases, for example by Verticillium ( Vert Icillium dahliae ); canker, broom, and dieback diseases, such as Nectria diseases, such as caused by the dry cell, Nectria galligena Fusarium wilt, for example: Monilinia diseases, for example caused by Monilinia laxa; leaf blister or leaf curl disease, for example: Exobasidium diseases, for example by bad Caused by Exobasidium vexans; Taphrina diseases, for example caused by Taphrina deformans; degenerative diseases of woody plants, such as Esca disease, such as by grape es Caused by Phaemoniella clamydospora; Eutypa dyeback, for example caused by Eutypa lata; Ganoderma diseases, such as caused by Ganoderma boninense; hard holes Rigidoporus diseases, for example caused by Rigidoporus lignosus; flower and seed diseases, such as Botrytis diseases, for example by Botrytis c Inerea); tuber diseases, such as: Rhizoctonia diseases, such as caused by Rhizoctonia solani; Helminthosporium diseases, such as Helminthosporium solani Caused by; swollen diseases, such as: Plasmodiophora diseases, such as caused by Plamodiophora brassicae; diseases caused by bacterial microorganisms, such as: Xanthomonas, such as rice white leaves Xanthomonas campestris pv. oryzae; Pseudomonas, such as Pseudomonas syringae pv. lachrymans; Erwinia, such as Erwinia Amylovora).

The compositions of the present invention can also be used to combat fungal diseases that are readily grown on or in wood. The term "wood" means all types of wood species and all types of processed products of this wood species intended for construction, such as solid wood, high density wood, laminates and plywood. The method of treating wood according to the present invention is primarily in contact with a compound of the invention or a composition of the invention; this includes, for example, direct application, spraying, dipping, injecting or any other suitable method.

When the leaves are treated, the dosage of the active compound usually applied in the treatment method of the invention is usually and advantageously from 10 to 800 g/ha, preferably from 50 to 300 g/ha. When the seed is treated, the dose of the active substance applied is usually and advantageously 2 to 200 g / 100 kg of seed, preferably 3 to 150 g / 100 kg of seed.

It is to be expressly understood that the dosages indicated herein are provided as an illustrative example of the method of the invention. Those skilled in the art will know how to adapt these applied doses (especially Depending on the nature of the plant or crop to be treated).

The compounds or mixtures according to the invention can also be used for the preparation of curative or prophylactic treatment of human or animal fungal diseases such as, for example, mycosis, skin diseases, blemishes and candidiasis or by Aspergillus spp. (eg, diseases caused by Aspergillus fumigatus).

The invention further relates to the use of a compound of formula (I) as defined herein for the control of phytopathogenic fungi.

The invention further relates to the use of a compound of formula (I) as defined herein for the treatment of a transgenic plant.

The invention further relates to the use of a compound of formula (I) as defined herein for the treatment of seeds and seeds of transgenic plants.

The invention further relates to a process for the manufacture of a composition for controlling phytopathogenic harmful fungi, characterized in that a derivative of the formula (I) as defined herein is admixed with a bulking agent and/or a surfactant.

Various aspects of the invention will now be described with reference to the following list of compound examples and the following formula or example of potency.

Table 1 illustrates, by way of non-limiting example, the compounds of formula (I) of the present invention:

Wherein A can be selected from the group consisting of A-G1, A-G2, A-G3, A-G4, A-G5, A-G6, A-G7, A-G8 and A-G9:

Wherein ^* represents the point of attachment of the group A to the (thio)carbonyl group.

In Table 1, unless otherwise indicated, M+H(ApcI+) means the ion peak of the molecule plus 1 a.m.u. (atomic mass unit) as observed in mass spectrometry via normal atmospheric pressure chemical ionization.

In Table 1, the logP value is measured by HPLC (High Performance Liquid Chromatography) on a reverse phase column (C 18) according to EEC Directive 79/831 Annex V.A8 using the following method: temperature: 40 ° C; Mobile phase: a linear gradient of 0.1% aqueous formic acid and acetonitrile; 10% acetonitrile to 90% acetonitrile.

Calibration was performed using unbranched alkan-2-ones (containing from 3 to 16 carbon atoms) with known logP values (measured using linear interpolation between the retention times of the two consecutive alkanones). The maximum lambda value and the peak value of the chromatographic signal were measured using a UV spectrum from 200 nm to 400 nm.

In Table 1, "position" indicates the point of attachment of the -Si(Z ⁴ Z ⁵ )-B residue to the benzene ring.

Table 2 illustrates, by way of non-limiting example, an example of a compound of formula (II) of the present invention:

In Table 2, M+H (ApcI+) and logP are as defined for Table 1.

In Table 2, "position" indicates the point of attachment of the -Si(Z ⁴ Z ⁵ )-B residue to the benzene ring.

Table 3 provides a selected number from Table 1 or Table 2, the NMR data of the compound ⁽¹ H).

The ¹ H-NMR data for the selected examples (at 400 Mhz in DMSO-d ₆ ) are presented as a list of ¹ H-NMR peaks. Each signal peak lists the value (ppm) and the signal strength in parentheses.

The intensity of the steep signal is related to the signal height (cm) in the NMR spectral printing example and shows the actual relationship of the signal strength. In the case of a wide peak signal, several peaks or intermediate signals can be produced and their relative intensities compared to the strongest signal in the spectrum.

The ¹ H-NMR peak list is similar to the classical ¹ H-NMR spectrum and therefore typically contains all of the peaks listed in the classical NMR analysis. Further, these may show, for example, a solvent, a stereoisomer of the target compound (which is also an object of the present invention), and/or a classical ¹ H-NMR spectrum signal of an impurity peak. To show the compound signal in the Δ range of solvent and/or water, the ordinary peak of the solvent (such as the peak of DMSO in DMSO-d6 and the water peak) is shown in our ¹ H-NMR peak list and usually has an average height. strength.

The peaks and/or impurity peaks of the stereoisomers of the target compound are generally on average lower than the peak of the target compound (e.g., > 90% purity). Such stereoisomers and/or impurities may be typical for a particular process. Therefore, its peaks can help confirm the reproducibility of our system through the "by-product fingerprint".

The peaks of the target compound are calculated by a skilled person using known methods (MestreC, ACD simulation, but also the expected value of empirical evaluation), and an intensity filter can be additionally used to separate the peaks of the target compounds as needed. This separation will be similar to the acquisition of correlation peaks in classical ¹ H-NMR analytical methods.

Further details of the NMR data content for the peak list can be found in the publication "Citation of NMR Peak List Data within Patent Applications" of Research Disclosure Library No. 564025.

The following examples illustrate, in a non-limiting manner, the preparation and efficacy of the compounds of formula (I) of the present invention. force.

Preparation Example 1 : N-cyclopropyl-N-{2-[dimethyl(phenyl)decyl]benzyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-methyl Method for preparing decylamine (Compound I.1)

Step 1: Method for preparing 2-[dimethyl(phenyl)decyl]benzaldehyde

12 mL (19.3 mmol) of a 1.6 M butyllithium solution was slowly added to a cooled solution of 5 g (19.3 mmol) of 1-bromo-2-(diethoxymethyl)benzene in 40 mL of diethyl ether. The reaction mixture was stirred at ambient temperature for 1 hour. After slowly adding 4.28 g (25 mmol) of chloro(dimethyl)phenyl decane, the reaction mixture was stirred at ambient temperature for additional 2 hours, then poured onto a mixture of ice and 40 mL of 1N HCl and stirred overnight. The aqueous layer was extracted with 2 x 50 mL ethyl acetate. The organic layer was washed twice with concentrated aqueous NaCl and dried over magnesium sulfate. Column chromatography (gradient n-heptane / ethyl acetate) on silica gel yielding 4.65 g (100% yield) of 2-[dimethyl(phenyl)decyl]benzaldehyde as a colorless oil (M+ H=241).

Step 2: Preparation of N-{2-[dimethyl(phenyl)decylalkyl]benzyl}cyclopropylamine (Compound II.1)

1.15 mL (16.6 mmol) of cyclopropylamine, 5 g of 3Å molecular sieve and 1.19 mL (20.8 mmol) of acetic acid were sequentially added to a solution of 2 g (8.3 mmol) of 2-[dimethyl(phenyl)decylalkyl]benzaldehyde in 60 mL of methanol. in. The reaction mixture was stirred at reflux for 3.5 hours. The reaction mixture was then cooled to 0.degree. C. and 0.78 g (12.5 mmol) of sodium cyanoborohydride was slowly added and the reaction mixture was stirred for 2 hours under reflux. The cooled reaction mixture was then filtered through a pad of Celite. The filter cake was rinsed twice with 60 mL of methanol and the methanol extract was concentrated in vacuo. Then 100 mL of water was added to the residue and the pH was adjusted to 12 using 1N aqueous sodium hydroxide. The aqueous layer was extracted with 2 x 50 mL ethyl acetate. The organic layer was washed twice with concentrated aqueous NaCl and dried over magnesium sulfate to yield 1.95 g (yield: 83% yield - 6% purity) of N-{2-[dimethyl (phenyl) decane. Base] benzyl} cyclopropylamine brown oil. (M+H=282).

Step 3: N-cyclopropyl-N-{2-[dimethyl(phenyl)decyl]benzyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamidine Amine method

195 mg (1 mmol) of 195 mg (1.1 mmol) of 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carbonyl chloride in 2 mL of anhydrous tetrahydrofuran was added to 4 mL of anhydrous tetrahydrofuran. A mixture of N-{2-[dimethyl(phenyl)decylalkyl]benzyl}cyclopropylamine and 0.154 mL (1.1 mmol) of triethylamine. The reaction mixture was stirred under reflux for 2 hours. The reaction mixture was deposited on an acidic alumina cartridge (2 g) eluting with ethyl acetate. Concentrate and perform column chromatography on silica gel (gradient: n-heptane / ethyl acetate) to yield 113 mg (24% yield) of N-cyclopropyl-N-{2-[dimethyl (phenyl) An oil of decyl]benzyl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (M+H=422).

General Process Example 2: Formula (I) Indoleamine in Chemspeed ^TM Thiocarbonylation reaction on the device

In 13mL Chemspeed ^TM bottle, weighed 0.27mmol of phosphorous pentasulfide (P ₂ S _5). 3 mL of 0.18 M decylamine (I) (0.54 mmol) in dioxane was added and the mixture was heated under reflux for 2 hr. This temperature was then cooled to 80 C and 2.5 mL of water was added. The mixture was heated again at 80 C for 1 hour. Then 2 mL of water was added and the reaction mixture was extracted twice with 4 mL dichloromethane. The organic phase was deposited on a basic alumina cartridge (2 g) and eluted twice with 8 mL dichloromethane. The solvents were removed and the crude thioguanamine derivative was analyzed by LCMS and NMR. The less pure compound is further purified by preparative LC.

Example A: In vivo testing of Sphaerotheca fuliginea (melon powdery mildew)

The method of preparing the active component is homogenized in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active material.

Cucumber plants ("Vert petit de Paris" variety) were sown on a 50/50 peat soil-pozzolana substrate in a breeding cup and grown at 24 °C. At the Z11 cotyledon stage, the active ingredients prepared as described above were used. Spray treatment. Use acetone without the active material Plants treated with a mixture of /tween/DMSO/water were used as a control group.

After 24 hours, the cotyledons were sprayed with an aqueous suspension of Xanthium sinensis spores (100 000 spores/mL) to contaminate the plants. These spores are collected from infected plants. The contaminated cucumber plants are cultured at about 20 ° C and 70-80% relative humidity.

The score (% of efficacy) was scored 12 days after the contamination, compared with the control plants.

Under these conditions, good (at least 70%) to full protection was observed at a 500 ppm dose of the active ingredient of the compound of Table A below:

Example B: In vivo testing of Pyrenophora teres (barley mesh spot)

The method of preparing the active component is homogenized in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active material.

The barley plant ("Plaisant" variety) was sown on a 50/50 peat soil-pozzolana substrate in a breeding cup and grown at 22 ° C. At the 1 leaf stage (height 10 cm), the active group prepared as described above was used. Spray treatment. Plants treated with a mixture of acetone/tween/DMSO/water without the active material were used as a control group.

After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of the nucleus spores (12,000 spores/mL). The spores were collected from a 12 day culture. The contaminated barley plants were cultured for 48 hours at about 20 ° C and 100% relative humidity. And then incubated at 20 ° C and 70-80% relative humidity for 12 days.

The score (% of efficacy) was scored 14 days after the contamination, compared with the control plants.

Under these conditions, good (at least 70%) to excellent (at least 90%) protection was observed at a 500 ppm dose of the active ingredient of the compound of Table B below:

Example C: In vivo testing of Puccinia recondita (leaf rust)

The method of preparing the active component is homogenized in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active material.

Wheat plants ("Scipion" varieties) were sown on a 50/50 peat soil ash matrix in a breeding cup and grown at 22 ° C. At the 1 leaf stage (height 10 cm), the active ingredients prepared as described above were used. Spray treatment. Plants treated with a mixture of acetone/tween/DMSO/water without the active material were used as a control group.

After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Puccinia recondita spores (100 000 spores/mL). The spores were collected from infected plants and suspended in water containing 10% Tween 80 (2.5 mL/L). The contaminated wheat plants were incubated at about 20 ° C and 100% relative humidity for 24 hours and then incubated at 20 ° C and 70-80% relative humidity for 10 days.

The score (% of efficacy) was scored 12 days after the contamination, compared with the control plants.

Under these conditions, good (at least 70%) to excellent (at least 90%) protection was observed at a 500 ppm dose of the active ingredient with the following Table C compound:

Example D: In vivo prophylactic test against Alternaria brassicae (radish leaf spot)

The method of preparing the active component is homogenized in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active material.

Radish plants ("Pernod Clair" varieties) were sown on a 50/50 peat soil pozzolan substrate in a breeding cup and grown at 17 °C, and sprayed with the active ingredients prepared as described above during the cotyledon stage. Plants treated with a mixture of acetone/tween/DMSO/water without the active material were used as a control group.

After 24 hours, the plants were contaminated by spraying the cotyledons with an aqueous suspension of the black spot spores (50,000 swores/mL). These spores were collected from 15 day cultures. The contaminated radish plants are grown at about 20 ° C and 100% relative humidity.

The score (% of efficacy) was scored 6 days after the contamination, compared with the control plants.

Under these conditions, good (at least 70%) to full protection was observed at 500 ppm of the active ingredient of the compound of Table D below:

Example E: In vivo pretreatment of Botrytis cinerea (Botrytis cinerea) Anti-test

The method of preparing the active component is homogenized in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active material.

Cucumber plants ("Vert petit de Paris" variety) were sown on a 50/50 peat soil pozzolan substrate in a breeding cup and grown at 24 °C, and sprayed with the active ingredients prepared as described above during the Z11 cotyledon stage. . Plants treated with a mixture of acetone/tween/DMSO/water without the active material were used as a control group.

After 24 hours, the plants were contaminated with a water-sustained suspension of cryopreserved P. pyogenes spores (50,000 spores/mL) to contaminate the plants. The spores were suspended in a nutrient solution consisting of 10 g/L PDB, 50 g/L D-fructose, 2 g/L NH ₄ NO ₃ and 1 g/L KH ₂ PO ₄ . The contaminated cucumber plants are grown at about 17 ° C and 90% relative humidity.

The score (% of efficacy) was scored 4 to 5 days after the contamination, compared with the control plants.

Under these conditions, good (at least 70%) protection was observed at 500 ppm of the active ingredient of the compound of Table E below:

Example F: In vivo prophylaxis test for Septoria tritici (wheat)

The method of preparing the active component is homogenized in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active material.

Wheat plants ("Scipion" varieties) were sown on a 50/50 peat soil ash matrix in a breeding cup and grown at 22 ° C. At the 1 leaf stage (height 10 cm), the active ingredients prepared as described above were used. Spray treatment. Plants treated with a mixture of acetone/tween/DMSO/water without the active material were used as a control group.

After 24 hours, cryopreserved wheat sphaeroides (500 000 spores/mL) The aqueous suspension sprays the leaves to contaminate the plants. The contaminated wheat plants were grown for 72 hours at about 18 ° C and 100% relative humidity, and then cultured for 21 days at 90% relative humidity.

The score (% of efficacy) was scored 24 days after the contamination, compared with the control plants.

Under these conditions, good (at least 70%) to full protection was observed at 500 ppm of the active ingredient of the compound of Table F below:

Example G: Right _{Puccinia solani} In vivo prophylaxis test (Uromyces appendiculatus)

The method of preparing the active component is homogenized in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active material.

The bean plant ("Saxa" variety) was sown on a 50/50 peat soil pozzolan substrate in a breeding cup and grown at 24 ° C. At the 2-leaf stage (height 9 cm), the active ingredient spray prepared as described above was used. deal with. Plants treated with a mixture of acetone/tween/DMSO/water without the active material were used as a control group.

After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of P. sylvestris (150 000 spores/mL). The spores were collected from contaminated plants and suspended in water containing 10% Tween 80 (2.5 mL/L). The contaminated bean plants were cultured at about 20 ° C and 100% relative humidity for 24 hours, followed by incubation at 20 ° C and 70-80% relative humidity for 10 days.

The score (% of efficacy) was scored 11 days after the contamination, and compared with the control plants.

Under these conditions, good (at least 70%) to full protection was observed at 500 ppm of the active ingredient of the compound of Table G below:

Claims (22)

A compound of formula (I): Wherein A represents a carbon-linked unsaturated or partially saturated 5-membered heterocyclic group which may be substituted with up to 4 groups which may be the same or different R; T represents O or S; n represents 0, 1, 2, 3 or 4; B represents an aryl group which may be substituted with up to 5 groups which may be the same or different group Y, or represents a hetero atom containing 1 to 4 groups selected from N, O, S, and may be up to 6 Unsaturated monocyclic or fused bicyclic 5-, 6-, 7-, 8-, 9-, 10-membered ring substituted with the same or different group Y; Z ¹ represents unsubstituted C ₃ -C ₇ cycloalkyl , or up to 10 C ₃ -C ₇ cycloalkyl groups which may be substituted by the same or different atoms or groups and which may be optionally a halogen atom, a cyano group, a C ₁ -C ₈ alkyl group, or may be up to 9 identical or different halogen atoms, C ₁ -C ₈ haloalkyl, C ₁ -C ₈ alkoxy group, may contain up to 9 identical or different halogen atoms, C ₁ -C ₈ haloalkoxy , C ₁ -C ₈ alkoxycarbonyl group, it may contain up to 9 identical or different halogen atoms, halo C ₁ -C ₈ alkoxycarbonyl, C ₁ -C ₈ alkylaminocarbonyl group, and two C ₁ -C ₈ alkylamino a group consisting of carbonyl groups; Z ² and Z ³ may be the same or different and represent a hydrogen atom, a substituted or unsubstituted C _1- C ₈ alkyl, substituted or unsubstituted C ₂ -C ₈ alkenyl, substituted or unsubstituted C ₂ -C ₈ alkynyl, cyano, isonitrile, nitro, halogen atom, Substituted or unsubstituted C ₁ -C ₈ alkoxy, substituted or unsubstituted C ₂ -C ₈ alkenyloxy, substituted or unsubstituted C ₂ -C ₈ alkynyloxy, substituted or Unsubstituted C ₃ -C ₇ cycloalkyl, substituted or unsubstituted C ₁ -C ₈ sulfanyl, substituted or unsubstituted C ₁ -C ₈ alkanesulfonyl group, Substituted or unsubstituted C ₁ -C ₈ alkylsulfinyl, amine, substituted or unsubstituted C ₁ -C ₈ alkylamino, substituted or unsubstituted di-C ₁ -C ₈ alkane Amino, substituted or unsubstituted C ₁ -C ₈ alkoxycarbonyl, substituted or unsubstituted C ₁ -C ₈ alkylaminecarbamyl, substituted or unsubstituted di C ₁ -C ₈ alkylamine carbenyl or substituted or unsubstituted NC ₁ -C ₈ alkyl-C ₁ -C ₈ alkoxy-aminecarbamyl; or Z ² and Z ³ with a carbon atom attached thereto Forming a substituted or unsubstituted C ₃ -C ₇ cycloalkyl group together; or a substituent X adjacent to the Z ³ and the phenyl ring attachment point and linking them The continuous carbon atoms may together form a substituted or unsubstituted 5-, 6- or 7-membered partially saturated carbocyclic ring or a heterocyclic ring containing up to 3 heteroatoms, and Z ² is as described herein; Z ⁴ and Z ⁵ independently represent a substituted or non-substituted C ₁ -C ₈ alkyl; X independently represents a halogen atom, nitro, cyano, isonitrile, hydroxy, amino, thio, pentafluoro -λ ⁶ - thio , formazan, methyl methoxy, methionine, substituted or unsubstituted (hydroxyimino)-C ₁ -C ₈ alkyl, substituted or unsubstituted (C ₁ -C ₈ Alkoxyimino)-C ₁ -C ₈ alkyl, substituted or unsubstituted (C ₂ -C ₈ oxyimido)-C ₁ -C ₈ alkyl, substituted or unsubstituted (C ₂ -C ₈ alkynoxyimino)-C ₁ -C ₈ alkyl, substituted or unsubstituted (benzyloxyimino)-C ₁ -C ₈ alkyl, carboxy, aminecarboxamido , N- acyl-hydroxy-carbamoyl, carbamate, substituted or unsubstituted alkyl group of C ₁ -C _8, having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkyl, substituted or unsubstituted the substituted C ₂ -C ₈ alkenyl group having a C 1 to 9 halogen atoms, halo ₂ -C ₈ alkenyl group, a substituted or non-substituted C ₂ -C ₈ alkynyl group having 1-9 C ₂ -C ₈ alkynyl group a halogen atom, a substituted or unsubstituted of C ₁ -C ₈ alkoxy group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkoxy, substituted or non- the substituted C ₁ -C ₈ alkylthio group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkoxy group, a substituted or unsubstituted of C ₁ -C ₈ alkyl sulfinyl group having 1 to a C ₁ -C ₈ haloalkylsulfinyl group of a halogen atom, a substituted or unsubstituted C ₁ -C ₈ alkanesulfonyl group, a C ₁ -C ₈ haloalkylsulfonate having 1 to 9 halogen atoms Mercapto, substituted or unsubstituted C ₁ -C ₈ alkylamino, substituted or unsubstituted di-C ₁ -C ₈ alkylamino, substituted or unsubstituted C ₂ -C ₈ olefin group having a C 1 to 9 halogen atoms, halo ₂ -C ₈ alkenyloxy, substituted or non-substituted C ₃ -C ₈ alkynyl group having a C 1 to 9 halogen atoms, halo ₂ -C ₈ alkynyloxy, substituted or non-substituted C ₃ -C ₇ cycloalkyl group having a C 1 to 9 halogen atoms ₃ -C ₇ halocycloalkyl, substituted or non-substituted (C ₃ -C ₇ cycloalkyl) -C ₁ -C ₈ alkyl, substituted or non-substituted C ₄ -C ₇ cycloalkenyl group having a C 1 to 9 halogen atoms, halo ₄ -C ₇ cycloalkenyl, substituted Or not taken The (C ₃ -C ₇ cycloalkyl) -C ₂ -C ₈ alkenyl group, a substituted or non-substituted (C ₃ -C ₇ cycloalkyl) -C ₂ -C ₈ alkynyl group, a substituted or unsubstituted by Substituted tri(C ₁ -C ₈ )alkyldecyl, substituted or unsubstituted tri(C ₁ -C ₈ )alkyldecyl-C ₁ -C ₈ alkyl, substituted or unsubstituted the C ₁ -C ₈ alkylcarbonyl group having a C 1 to 9 halogen atoms, halo ₁ -C ₈ alkylcarbonyl group, a substituted or unsubstituted of C ₁ -C ₈ alkoxy carbonyl group having 1-9 halogen atoms the C ₁ -C ₈ haloalkoxy-carbonyl group, a substituted or unsubstituted of C ₁ -C ₈ alkylcarbonyl group having a C 1 to 9 halogen atoms, halo ₁ -C ₈ alkylcarbonyl group, a substituted or unsubstituted of C ₁ -C ₈ alkoxycarbonyl group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkoxy-carbonyl group, a substituted or unsubstituted of C ₁ -C ₈ alkoxycarbonyl group, a C ₁ -C ₈ haloalkoxycarbonyloxy group having 1 to 9 halogen atoms, a substituted or unsubstituted C ₁ -C ₈ alkylamine carbenyl group, a substituted or unsubstituted di C ₁ - C ₈ alkylamine carbenyl, substituted or unsubstituted C ₁ -C ₈ alkylaminocarbonyloxy, substituted or unsubstituted di-C ₁ -C ₈ alkylaminocarbonyloxy, Replaced Non-substituted N- (C ₁ -C ₈ alkyl) hydroxylamine methyl acyl, substituted or non-substituted C ₁ -C ₈ alkoxy carbamoyl acyl, substituted or non-substituted N- ( a C ₁ -C ₈ alkyl)-C ₁ -C ₈ alkoxyamine carbenyl group, an aryl group which may be substituted with up to 6 groups which may be the same or different groups Q, may be up to 6 may be the same or different groups a C ₁ -C ₈ aralkyl group substituted by a group Q, a C ₂ -C ₈ aralkenyl group which may be substituted with up to 6 groups which may be the same or different groups Q, may have up to 6 groups which may be the same or different Q a substituted C ₂ -C ₈ aralkynyl group, an aryloxy group which may be substituted with up to 6 groups which may be the same or different groups Q, an arylthio group which may be substituted with up to 6 groups which may be the same or different groups Q, Up to 6 arylamino groups which may be substituted with the same or different groups Q, up to 6 C ₁ -C ₈ aralkyloxy groups which may be substituted with the same or different groups Q, may be up to 6 identical or Q substituted with different radicals of C ₁ -C ₈ aralkyl group, may be up to six identical or different radicals may be substituted with group Q of the C ₁ -C ₈ aralkyl group, may be up to 4 groups a Q-substituted pyridyl group, a pyridyloxy group which may be substituted with up to 4 groups of Q; Y independently represents a halogen atom, a cyano group, a hydroxyl group, an amine , Thio, substituted or unsubstituted alkyl group of C ₁ -C _8, having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkyl, a substituted or unsubstituted of C ₁ -C ₈ alkoxy group, with a C 1 to 9 halogen atoms ₁ -C ₈ haloalkoxy, substituted or unsubstituted of C ₁ -C ₈ alkylthio group having a C 1 to 9 halogen atoms ₁ -C ₈ halogen alkylthio group, a substituted or unsubstituted of C ₁ -C ₈ alkyl sulfinyl group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkyl sulfinyl group, a substituted or unsubstituted of C sulfonic ₁ -C ₈ alkoxy group having a C 1 to 9 halogen atoms, sulfo ₁ -C ₈ haloalkyl acyl, substituted or non-substituted C ₁ -C ₈ alkyl group, a substituted or unsubstituted bis C ₁ -C ₈ alkyl group, a substituted or unsubstituted by the C ₁ -C ₈ alkylcarbonyl group having a C 1 to 9 halogen atoms, halo ₁ -C ₈ alkylcarbonyl group, a substituted or non-substituted C ₁ -C ₈ alkoxycarbonyl group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkoxy-carbonyl group, may be up to 6 may be the same or different substituents group Q of the aryl group; Q independently represent a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted of C ₁ -C ₈ alkyl group, may contain up to 9 identical or different halogen atoms, C ₁ - C ₈ haloalkyl, substituted or non-substituted C ₁ -C ₈ alkoxy group, may contain up to 9 identical or different halogen atoms, C ₁ -C ₈ haloalkoxy, substituted or unsubstituted the C ₁ -C ₈ alkylthio group, may contain up to 9 identical or different halogen atoms, C ₁ -C ₈ haloalkoxy group, a substituted or unsubstituted ter (C ₁ -C ₈₎ alkyl Silane , substituted or unsubstituted tri(C ₁ -C ₈ )alkyldecyl-C ₁ -C ₈ alkyl, substituted or unsubstituted (C ₁ -C ₈ alkoxyimino)- C ₁ -C ₈ alkyl or substituted or unsubstituted (benzyloxyimino)-C ₁ -C ₈ alkyl; R independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amine , thio, pentafluoro-λ ⁶ -thio, substituted or unsubstituted (C ₁ -C ₈ alkoxyimino)-C ₁ -C ₈ alkyl, substituted or unsubstituted ( group benzyloxyimino) -C ₁ -C ₈ alkyl, substituted or unsubstituted alkyl group of C ₁ -C _8, having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkyl, substituted or the unsubstituted C ₂ -C ₈ alkenyl group having a C 1 to 9 halogen atoms ₂ -C ₈ - alkenyl, halo, substituted or non-substituted C ₂ -C ₈ alkynyl group having 1-9 Halogen atom The C ₂ -C ₈ - alkynyl, halogen, substituted or non-substituted C ₁ -C ₈ alkoxy group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkoxy, substituted or non- the substituted C ₁ -C ₈ alkylthio group having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkoxy group, or a substituted of unsubstituted C ₁ -C ₈ alkyl sulfinyl group having 1 to a C ₁ -C ₈ haloalkylsulfinyl group of a halogen atom, a substituted or unsubstituted C ₁ -C ₈ alkanesulfonyl group, a C ₁ -C ₈ haloalkylsulfonate having 1 to 9 halogen atoms Mercapto, substituted or unsubstituted C ₁ -C ₈ alkylamino, substituted or unsubstituted di-C ₁ -C ₈ alkylamino, substituted or unsubstituted C ₂ -C ₈ olefin group, substituted or non-substituted C ₃ -C ₈ alkynyl group, a substituted or non-substituted C ₃ -C ₇ cycloalkyl group having a C 1 to 9 halogen atoms ₃ -C ₇ - halocycloalkyl alkyl, substituted or unsubstituted ter (C ₁ -C ₈₎ alkyl silicon alkyl, substituted or non-substituted C ₁ -C ₈ alkylcarbonyl group having 1-9 halogen atoms, a C ₁ -C ₈ haloalkyl carbonyl, substituted or non-substituted C ₁ -C ₈ alkoxycarbonyl group, with a C 1 to 9 halogen atoms, halo ₁ -C ₈ alkoxycarbonyl group, a substituted or non-substituted C ₁ -C ₈ alkylamine methyl fluorenyl, substituted or unsubstituted di C ₁ -C ₈ alkylamine methyl fluorenyl, phenoxy, phenylthio, anilino, benzyloxy, benzylthio Or a benzylamine group; and salts, N-oxides, metal complexes thereof, metalloid complexes thereof, and optically active isomers or geometric isomers thereof. The compound of claim 1, wherein the A is selected from the group consisting of: a heterocyclic ring of the formula (A ¹ ) Wherein: R ¹ to R ³ may be the same or different, represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 halogen atoms may be the same or different, a C ₁ -C ₅ haloalkyl, substituted or non-substituted C ₁ -C ₅ alkoxy or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkoxy; Wherein: R ⁴ to R ⁶ may be the same or different, represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 halogen atoms may be the same or different, a C ₁ -C ₅ haloalkyl, substituted or non-substituted C ₁ -C ₅ alkoxy or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkoxy; Wherein: R ⁷ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl, substituted or the unsubstituted C ₁ -C ₅ alkoxy or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkoxy; R ⁸ represents a hydrogen atom or a substituted or unsubstituted C ₁ of -C ₅ alkyl; Wherein: R ⁹ to R ¹¹ may be the same or different and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, an amine group, a substituted or unsubstituted C ₁ -C ₅ alkane. An oxy, substituted or unsubstituted C ₁ -C ₅ alkylthio group, containing up to 9 C ₁ -C ₅ haloalkyl groups which may be the same or different halogen atoms or containing up to 9 of the same or different halo a C ₁ -C ₅ haloalkoxy group of an atom; Wherein R ¹² and R ¹³ may be the same or different and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, An amine group, a C ₁ -C ₅ haloalkyl group containing up to 9 or different halogen atoms or a C ₁ -C ₅ haloalkoxy group containing up to 9 halogen atoms which may be the same or different; R ¹⁴ represents hydrogen Atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, an amine group, containing up to 9 halogen atoms which may be the same or different the C ₁ -C ₅ haloalkyl, or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkoxy; of formula (a ⁶⁾ heterocycle Wherein: R ¹⁵ represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, and contains up to 9 may be the same or different halogen atoms, C ₁ -C ₅ alkoxy group or a halogen comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ¹⁶ and R ¹⁸ may be the same or different, represent a hydrogen atom, a halogen atom, a substituted or unsubstituted of C ₁ -C ₅ alkoxycarbonyl group, a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 halogen atoms may be the same or different, a C ₁ a -C ₅ haloalkoxy group or a C ₁ -C ₅ haloalkyl group containing up to 9 or different halogen atoms; R ¹⁷ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; Wherein: R ¹⁹ represents a hydrogen atom or a C ₁ -C ₅ alkyl group; and R ²⁰ to R ²² may be the same or different and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group or a plurality of Up to 9 C ₁ -C ₅ haloalkyl groups which may be the same or different halogen atoms; formula (A ⁸ ) heterocyclic ring Wherein: R ²³ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ²⁴ represents a hydrogen atom or a substituted or non-substituted C ₁ -C ₅ alkyl group or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl; Wherein: R ²⁵ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ²⁶ represents a hydrogen atom, a substituted or unsubstituted of C ₁ -C ₅ alkyl group or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl; Wherein: R ²⁷ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ²⁸ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a C ₁ -C ₅ haloalkyl group containing up to 9 or different halogen atoms, containing up to 9 or the same or C ₁ -C ₅ haloalkoxy, amine, substituted or unsubstituted C ₁ -C ₅ alkylamino group or substituted or unsubstituted bis (C ₁ -C ₅ alkyl) of different halogen atoms Amine group Wherein: R ²⁹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, and contains up to 9 may be the same or different halogen atoms, C ₁ -C ₅ alkoxy group or a halogen comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ³⁰ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted a C ₁ -C ₅ alkyl group, a C ₁ -C ₅ haloalkyl group containing up to 9 identical or different halogen atoms, and C ₁ -C ₅ haloalkoxy containing up to 9 halogen atoms which may be the same or different a base, an amine group, a substituted or unsubstituted C ₁ -C ₅ alkylamino group or a substituted or unsubstituted bis(C ₁ -C ₅ alkyl)amino group; Wherein: R ³¹ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; R ³² represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group or contains up to 9 C ₁ -C ₅ haloalkyl groups which may be the same or different halogen atoms; R ³³ represents a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted C ₁ -C ₅ alkyl group, substituted or unsubstituted the substituted C ₁ -C ₅ alkoxy group, may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ alkoxy group or a halogen comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ Haloalkyl Wherein: R ³⁴ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₃ -C ₅ cycloalkyl group, and contains up to 9 may be the same or C ₁ -C ₅ haloalkyl, substituted or unsubstituted C ₁ -C ₅ alkoxy, substituted or unsubstituted C ₂ -C ₅ alkynyl or containing up to 9 a C ₁ -C ₅ haloalkoxy group which may be the same or different halogen atom; R ³⁵ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a cyano group, a substituted or unsubstituted group the C ₁ -C ₅ alkoxy, substituted or non-substituted C ₁ -C ₅ alkylthio group, may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl, comprising up to 9 C ₁ -C ₅ haloalkoxy groups, amine groups, substituted or unsubstituted C ₁ -C ₅ alkylamino groups or substituted or unsubstituted bis (C ₁ -) which may be the same or different halogen atoms a C ₅ alkyl)amino group; R ³⁶ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; Wherein: R ³⁷ and R ³⁸ may be the same or different, represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 halogen atoms may be the same or different, a C ₁ -C _5- haloalkyl, substituted or unsubstituted C ₁ -C ₅ alkoxy or substituted or unsubstituted C ₁ -C ₅ -alkylthio; R ³⁹ represents a hydrogen atom or substituted or unsubstituted C ₁ -C ₅ alkyl; Wherein: R ⁴⁰ and R ⁴¹ may be the same or different, represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 halogen atoms may be the same or different, a C ₁ -C _5- haloalkyl; Wherein: R ⁴² and R ⁴³ may be the same or different, represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 halogen atoms may be the same or different, a C ₁ -C _5- haloalkyl, or an amine group; Wherein: R ⁴⁴ and R ⁴⁵ may be the same or different, represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 halogen atoms may be the same or different, a C ₁ -C _5- haloalkyl; Wherein: R ⁴⁷ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ⁴⁶ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl, or a substituted or unsubstituted of C ₁ -C ₅ alkylthio; Wherein R ⁴⁹ and R ⁴⁸ may be the same or different and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, a C ₁ -C ₅ haloalkoxy group containing up to 9 or different halogen atoms or a C ₁ -C ₅ haloalkyl group containing up to 9 halogen atoms which may be the same or different; Wherein: R ⁵⁰ and R ⁵¹ may be the same or different and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group, a C ₁ -C ₅ haloalkoxy group containing up to 9 or different halogen atoms or a C ₁ -C ₅ haloalkyl group containing up to 9 halogen atoms which may be the same or different; Wherein: R ⁵² represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl; Wherein: R ⁵³ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl; Wherein: R ⁵⁴ and R ⁵⁶ may be the same or different, represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 halogen atoms may be the same or different, a C ₁ -C _5- haloalkyl; R ⁵⁵ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; Wherein: R ⁵⁷ and R ⁵⁹ may be the same or different, represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 halogen atoms may be the same or different, a C ₁ -C _5- haloalkyl; R ⁵⁸ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; Wherein: R ⁶⁰ and R ⁶¹ may be the same or different, represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C ₅ or comprising up to 9 halogen atoms may be the same or different, a C ₁ -C _5- haloalkyl; R ⁶² represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; a heterocyclic ring of the formula (A ²⁶ ) Wherein: R ⁶⁵ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a substituted or unsubstituted C ₃ -C ₅ cycloalkyl group, containing up to 9 may be the same or C ₁ -C ₅ haloalkyl, substituted or unsubstituted C ₁ -C ₅ alkoxy, substituted or unsubstituted C ₂ -C ₅ alkynyl or containing up to 9 a C ₁ -C ₅ haloalkoxy group which may be the same or different halogen atom; R ⁶³ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted C ₁ -C ₅ alkyl group, a cyano group, a substituted or unsubstituted group the C ₁ -C ₅ alkoxy, substituted or non-substituted C ₁ -C ₅ alkylthio group, may contain up to 9 identical or different halogen atoms, C ₁ -C ₅ haloalkyl, comprising up to 9 C ₁ -C ₅ haloalkoxy groups, amine groups, substituted or unsubstituted C ₁ -C ₅ alkylamino groups or di(C ₁ -C ₅ alkyl)amino groups which may be the same or different halogen atoms ; R ⁶⁴ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group. The compound of claim 2, wherein the A is selected from the group consisting of A ² , A ⁵ , A ⁶ , A ¹⁰ and A ¹³ . The compound of the requested item 3, wherein A represents ^{13 is} A, and wherein R ³⁴ represents a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 identical or different halogen atoms, C ₁ -C ₅ Haloalkyl, substituted or unsubstituted C ₁ -C ₅ alkoxy; R ³⁵ represents a hydrogen atom or a halogen atom, and R ³⁶ represents a substituted or unsubstituted C ₁ -C ₅ alkyl group. The compound of the requested item 4, wherein A represents ^{13 is} A, and wherein R ³⁴ represents C ₁ -C ₅ alkyl group, may contain up to 3 identical or different halogen atoms, C ₁ -C ₅ haloalkyl group; R ³⁵ represents a hydrogen atom, a chlorine atom or a fluorine atom; and R ³⁶ represents a methyl group. The compound of any one of claims 1 to 5, wherein T represents O. The compound of any one of claims 1 to 5, wherein Z ¹ represents a substituted or unsubstituted cyclopropyl group. The compound of claim 7, wherein Z ¹ represents an unsubstituted cyclopropyl or 2-C ₁ -C ₅ alkylcyclopropyl group. The compound of any one of claims 1 to 5, wherein Z ² and Z ³ independently represent a hydrogen atom or a methyl group. The compound of any one of claims 1 to 5, wherein n represents 0, 1, or 2. The compound of any one of claims 1 to 5, wherein Z ⁴ and Z ⁵ independently represent an unsubstituted C ₁ -C ₈ alkyl group. The compound of any one of claims 1 to 5, wherein B represents a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted thiophene ring, substituted or not a substituted benzothiophene ring, a substituted or unsubstituted furan ring or a substituted or unsubstituted benzofuran ring. A compound according to claim 12, wherein B represents a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted thiophene ring. A compound according to any one of items 1 to 5 as a request, wherein X independently represents a halogen atom, a substituted or unsubstituted alkyl group of C ₁ -C _8, comprising up to 9 halogen atoms may be the same or different, a C ₁ -C ₈ haloalkyl, substituted or unsubstituted C ₃ -C ₇ cycloalkyl, tri(C ₁ -C ₈ alkyl)decyl, substituted or unsubstituted C ₁ -C ₈ alkoxy A substituted or unsubstituted C ₁ -C ₈ alkylthio group. A compound according to any one of items 1 to 5 as a request, wherein Y independently represents a halogen atom, a substituted or unsubstituted of C ₁ -C ₈ alkyl, C ₁ comprising up to 9 identical or different halogen atoms, _{. 8} haloalkyl -C, substituted or _{unsubstituted. 1} of -C ₈ alkoxy C, comprising up to 9 may be the same or _{different. 1} halogen atoms -C ₈ haloalkoxy C group. A compound of formula (IIa): Wherein Z ² , Z ³ , Z ⁴ , Z ⁵ , n, X and B are as defined in any one of claims 1 to 15, and salts thereof. The compound of claim 16, which is selected from the group consisting of N-{2-[dimethyl(phenyl)decyl]benzyl}cyclopropylamine; N-{2-[(4-chlorophenyl) (dimethyl)decyl]benzyl}cyclopropylamine; N-{2-[biphenyl-4-yl(dimethyl)decyl]benzyl}cyclopropylamine; N-{2-[dimethyl ( 4-phenoxyphenyl)nonanyl]benzyl}cyclopropylamine; N-{2-[dimethyl(1-naphthyl)decyl]benzyl}cyclopropylamine; N-{2-[dimethyl (2-Thienyl)nonanyl]benzyl}cyclopropylamine; N-{2-[(6-methoxypyridin-3-yl)(dimethyl)decylalkyl]benzyl}cyclopropylamine. A fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) according to any one of claims 1 to 15 and an agriculturally acceptable carrier, carrier or filler. A method of controlling a phytopathogenic fungus of a crop, characterized in that an agronomically effective and substantially phytotoxic amount of a compound according to any one of claims 1 to 15 or a composition according to claim 18 is applied to plant growth Or soil that can grow, leaves of plants and/or seeds of fruits or plants. Use of a compound of formula (I) according to any one of claims 1 to 15 for controlling phytopathogenic harmful fungi. A method for producing a composition for controlling a phytopathogenic harmful fungus, characterized by comprising a derivative of the formula (I) according to any one of claims 1 to 15 and an extender and/or a boundary The surfactant is mixed. Use of a compound of formula (I) according to any one of claims 1 to 15 for the treatment of plants, seeds, transgenic plants or transgenic seeds.