TW201347673A - N-cycloalkyl-N-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives - Google Patents

Abstract

The present invention relates to fungicidal N-cycloalkyl-N-[(heterocyclylphenyl)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-[(heterocyclylphenyl)methylene]-(thio)carbamamine derivative N-CYCLOALKYL-N-

The present invention relates to fungicidal N-cycloalkyl-N-[(heterocyclylphenyl)methylene]carbamamine derivatives and thiocarbonyl derivatives thereof, processes for preparing the same, and intermediate compounds therefor, It is used as a fungicide, especially in the form of a fungicidal composition, and a method of controlling a phytopathogenic fungus of a plant using such a compound or a composition thereof.

In the international patent application WO-2007/087906, certain N-cycloalkyl-N-benzyl-formamides are generally encompassed by a wide variety 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, There are substituted or unsubstituted pyridyl or pyridyloxy groups. However, any such derivative in which X is selected to represent a substituted or unsubstituted heterocyclic group is not explicitly disclosed or indicated in this document.

In the international patent application WO-2009/016220, certain N-cycloalkyl-N-benzyl-thiocarbamamines are generally encompassed by a wide variety of compounds of the formula:

Wherein A represents a partially saturated or unsaturated 5-membered heterocyclic group of the 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 is Represents various substituents having a substituted or unsubstituted pyridyl or pyridyloxy group. However, any such derivative in which X is selected to represent a substituted or unsubstituted heterocyclic group is not explicitly disclosed or indicated in this document.

In the international patent application WO-2010/130767, certain N-cycloalkyl-N-benzyl-formamide or thioformamide are generally encompassed by a wide variety 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, Y may represent CR ⁵ , and R ¹ , R ² And R ³ , R ⁴ or R ⁵ may independently represent various substituents including a substituted or unsubstituted pyridyl or pyridyloxy group. However, 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 heterocyclic group is not explicitly disclosed or indicated in this document.

In the international patent application WO-2009/024342, certain N-(substituted phenyl)methylene-formamides are generally encompassed by a wide variety of compounds of the formula:

Wherein R ₁ represents a C ₁ -C ₄ alkyl group, R ₂ represents a C ₁ -C ₄ haloalkyl group, and B represents a phenyl group which may be substituted with various substituents, wherein a substituted or unsubstituted phenyl group or a A substituted or unsubstituted phenoxy group, and R ₁₅ may represent hydrogen or a C ₃ -C ₇ cycloalkyl group, with the proviso that if R ₁₅ represents a C ₃ -C ₇ cycloalkyl group, then B is different from the phenyl group. Thus, any such derivatives in which R ₁₅ may represent a C ₃ -C ₇ cycloalkyl group and B is a substituted phenyl group are not disclosed in this document.

Accordingly, the present invention provides an N-cycloalkyl-N-[(heterocyclylphenyl)methylene](thio)carbamamine of the formula (I)

Wherein ̇A represents an unsaturated or partially saturated 5-membered heterocyclic group of a carbon linkage which may be substituted with up to four groups R which may be the same or different; ̇T represents O or S; ̇n represents 0, 1, 2 , 3 or 4; ̇L represents a direct bond, CZ ⁴ Z ⁵ , O, S, SO, SO ₂ or NZ ⁶ ; B represents a saturation of 1 to 4 heteroatoms selected from the list consisting of N, O, S a partially saturated or unsaturated monocyclic or fused bicyclic 3, 4, 5, 6, 7, 8, 9 or 10 membered ring which may be substituted with up to 6 groups which may be the same or different, Y; when L is a direct bond or represents an oxygen atom, B represents a pyridyl ring not; ˙Z ¹ represents a non-substituted C ₃ -C ₇ cycloalkyl or substituted alkyl of up to 10 atoms or groups C ₃ -C _{a 7-} cycloalkyl group, which may be the same or different and optionally a list of the following: a halogen atom, a cyano group, a C ₁ -C ₈ alkyl group, containing up to 9 halogen atoms which may be the same or different the 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 alkoxy, a carbonyl group containing up to nine C atoms which may be the same or different _{a 1-} C ₈ haloalkoxycarbonyl group, a C ₁ -C ₈ alkylaminocarbonyl group or a di-C ₁ -C ₈ alkylaminocarbonyl group; ̇Z ² and Z ³ may be the same or different and represent a hydrogen atom; 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 group; substituted or unsubstituted C ₂ -C ₈ alkenyloxy group; 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 Alkylsulfonyl; substituted or unsubstituted C ₁ -C ₈ alkylsulfinyl; amine; substituted or unsubstituted C ₁ -C ₈ alkylamino; substituted or unsubstituted Substituted bis-C ₁ -C ₈ alkylamino; substituted or unsubstituted C ₁ -C ₈ alkoxycarbonyl; substituted or unsubstituted C ₁ -C ₈ alkylamine fluorenyl; a substituted or unsubstituted bis -C ₁ -C ₈ alkyl amine acyl; or substituted or non-substituted NC ₁ -C ₈ alkyl -C ₁ -C ₈ Group - carbamoyl acyl; ˙Z ² and Z ^3, or with the carbon atoms they are attached, may form a substituted or non-substituted C ₃ -C ₇ cycloalkyl; or ˙Z ³ and the phenyl ring The substituent X adjacent to the point of attachment together with the continuous carbon atom to which Z ³ and X are attached may form a substituted or unsubstituted 5, 6 or 7 member partially saturated carbocyclic or heterocyclic ring containing up to 3 heteroatoms. and Z ² as described herein; Z ⁴ and Z ⁵ independently represent a hydrogen atom; a halogen atom; a cyano group; a substituted or unsubstituted of C ₁ -C ₈ alkyl; C ₁ 1 having to 5 halogen atoms -C ₈ haloalkyl; substituted or unsubstituted C ₁ -C ₈ alkoxy; substituted or unsubstituted C ₁ -C ₈ alkylthio; or substituted or unsubstituted C ₁ -C ₈ alkoxycarbonyl; or ̇Z ⁴ and Z ⁵ together with the carbon atom to which they are attached form a C(=O)carbonyl group; ̇Z ⁶ represents a hydrogen atom; substituted or unsubstituted C ₁ -C ₈ An alkyl group; a C ₁ -C ₈ haloalkyl group containing up to 9 halogen atoms which may be the same or different; a substituted or unsubstituted C ₂ -C ₈ alkenyl group; containing up to 9 which may be the same or different C ₂ -C ₈ haloalkenyl group of a halogen atom; substituted or not a substituted C ₃ -C ₈ alkynyl group; a C ₃ -C ₈ haloalkynyl group containing up to 9 halogen atoms which may be the same or different; a substituted or unsubstituted C ₃ -C ₇ cycloalkyl group; Up to 9 C ₃ -C ₇ halocycloalkyl groups which may be the same or different halogen atoms; substituted or unsubstituted C ₃ -C ₇ cycloalkyl-C ₁ -C ₈ alkyl group; formazan group; substituted or non-substituted C ₁ -C ₈ alkylcarbonyl; can contain up to 9 identical or different halogen atoms C ₁ -C ₈ haloalkyl carbonyl group; substituted or non-substituted C ₁ -C ₈ Alkoxycarbonyl; C ₁ -C ₈ haloalkoxycarbonyl group containing up to 9 halogen atoms which may be the same or different; substituted or unsubstituted C ₁ -C ₈ alkylsulfonyl group; 9 C ₁ -C ₈ haloalkylsulfonyl groups which may be the same or different halogen atoms; substituted or unsubstituted benzyl groups; or substituted or unsubstituted phenylsulfonyl groups; X independently Halogen atom; nitro group; cyano group; isonitrile group; hydroxyl group; amine group; sulfur group; pentafluoro-λ ⁶ -thio group; formazan group; methyl methoxy group; formamidine group; substituted or unsubstituted (hydroxyimino)-C ₁ -C ₈ alkyl; substituted or not Substituted (C ₁ -C ₈ alkoxyimino)-C ₁ -C ₈ alkyl; substituted or unsubstituted (C ₂ -C ₈ oxyimino)-C ₁ -C _8- alkyl; substituted or unsubstituted (C ₂ -C ₈ alkynyloxyimido)-C ₁ -C ₈ alkyl; substituted or unsubstituted (benzyloxyimino)-C ₁ -C ₈ alkyl; carboxy; amine carbenyl; N-hydroxylamine carbenyl; carbamate; substituted or unsubstituted C ₁ -C ₈ alkyl; having 1 to 9 halogens atoms C ₁ -C ₈ haloalkyl; substituted or non-substituted C ₂ -C ₈ alkenyl group; a C 1 to having halogen atoms. 9 ₂ -C ₈ haloalkenyl; substituted or non-substituted C ₂ -C ₈ alkynyl; C ₂ -C ₈ haloalkynyl group having 1 to 9 halogen atoms; substituted or unsubstituted C ₁ -C ₈ alkoxy group; C having 1 to 9 halogen atoms ₁ -C ₈ haloalkoxy; substituted or non-substituted C ₁ -C ₈ alkylthio; having a C 1 to halogen atoms. 9 ₁ -C ₈ haloalkyl group; substituted or non- Substituted C ₁ -C ₈ alkylsulfinyl; C ₁ -C ₈ haloalkylsulfinyl having 1 to 9 halogen atoms; substituted or unsubstituted C ₁ -C ₈ alkylsulfonate醯 base; with 1 to a C ₁ -C ₈ haloalkylsulfonyl group of 9 halogen atoms; a substituted or unsubstituted C ₁ -C ₈ alkylamino group; a substituted or unsubstituted di-C ₁ -C ₈ alkyl group amino; substituted or non-substituted C ₂ -C ₈ alkenyl group; a C 1 to having halogen atoms. 9 ₂ -C ₈ alkenyl group, a halogen; substituted or non-substituted C ₃ -C ₈ alkynyl group; a C 1 to having halogen atoms. 9 ₂ -C ₈ alkynyl group, a halogen; substituted or non-substituted C ₃ -C ₇ cycloalkyl group; a C 1 to having halogen atoms. 9 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; having 1 to a C ₄ -C ₇ halocycloalkenyl group of 9 halogen atoms; a substituted or unsubstituted (C ₃ -C ₇ cycloalkyl)-C ₂ -C ₈ alkenyl group; substituted or unsubstituted (C _3- C ₇ cycloalkyl)-C ₂ -C ₈ alkynyl; substituted or unsubstituted tri(C ₁ -C ₈ )alkyldecylalkyl; substituted or unsubstituted tris(C ₁ -C ₈₎ alkyl silicon -C ₁ -C ₈ alkyl group; a substituted or unsubstituted of C ₁ -C ₈ alkylcarbonyl group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkyl carbonyl group; by Replace or not take The C ₁ -C ₈ alkylcarbonyloxy group; a C 1 to having halogen atoms. 9 ₁ -C ₈ alkylcarbonyloxy halogen; substituted or non-substituted C ₁ -C ₈ alkylcarbonyl group; having a C 1 to halogen atoms. 9 ₁ -C ₈ haloalkyl carbonyl group; substituted or non-substituted C ₁ -C ₈ alkoxycarbonyl group; a C 1 to having halogen atoms. 9 ₁ -C ₈ halo alkoxycarbonyl group; a substituted or unsubstituted of C ₁ -C ₈ alkoxycarbonyl group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkoxy-carbonyl group; a substituted or unsubstituted by Substituted C ₁ -C ₈ alkylamine carbenyl; substituted or unsubstituted di-C ₁ -C ₈ alkylamine carbenyl; substituted or unsubstituted C ₁ -C ₈ alkyl Aminocarbonyloxy; substituted or unsubstituted bis-C ₁ -C ₈ alkylaminocarbonyloxy; substituted or unsubstituted N-(C ₁ -C ₈ alkyl)hydroxylamine formazan Substituted or unsubstituted C ₁ -C ₈ alkoxyamine indenyl; substituted or unsubstituted N-(C ₁ -C ₈ alkyl)-C ₁ -C ₈ alkoxyamine A fluorenyl group; an aryl group which may be substituted with up to 6 groups which may be the same or different Q; an aryl group-C _{1 which} may be substituted with up to 6 groups which may be the same or different. -C ₈ alkyl; aryl-C ₂ -C ₈ alkenyl which may be substituted with up to 6 groups which may be the same or different; Q may be substituted with up to 6 groups which may be the same or different. a aryl-C ₂ -C ₈ alkynyl group; an aryloxy group which may be substituted with up to 6 groups which may be the same or different Q; an arylthio group which may be substituted with up to 6 groups Q which may be the same or different An arylamine group which may be substituted with up to 6 groups which may be the same or different, Q; an aryl-C ₁ -C ₈ alkoxy group which may be substituted with up to 6 groups which may be the same or different. may be up to 6 may be the same or different substituent groups of Q aryl -C ₁ -C ₈ alkylthio; may be up to 6 may be the same or different substituent groups of Q -C ₁ aryl group a -C ₈ alkylamino group; a pyridyl group which may be substituted with up to 4 groups of Q; or a pyridyloxy group which may be substituted with up to 4 groups of Q; ̇Y independently represents a halogen atom; a cyano group; ; amine; group; a substituted or unsubstituted of C ₁ -C ₈ alkyl group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkyl; substituted or non-substituted C ₁ -C ₈ alkoxy; C ₁ -C ₈ haloalkoxy having 1 to 9 halogen atoms; substituted or unsubstituted C ₁ a -C ₈ alkylthio group; a C ₁ -C ₈ haloalkylthio group having 1 to 9 halogen atoms; a substituted or unsubstituted C ₁ -C ₈ alkylsulfinyl group; having 1 to 9 a C ₁ -C ₈ haloalkylsulfinyl group of a halogen atom; a substituted or unsubstituted C ₁ -C ₈ alkylsulfonyl group; a C ₁ -C ₈ haloalkyl having 1 to 9 halogen atoms A sulfonyl group; a substituted or unsubstituted C ₁ -C ₈ alkylamino group; a substituted or unsubstituted bis-C ₁ -C ₈ alkylamino group; a 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; having 1 to 9 halogen atoms a C ₁ -C ₈ haloalkoxycarbonyl group; or an aryl group which may be substituted with up to 6 groups which may be the same or different Q; ̇Q independently represents a halogen atom, a cyano group, a nitro group, a substituted or an unsubstituted the substituted C ₁ -C ₈ alkyl group, may contain up to 9 identical or different halogen atoms C ₁ -C ₈ haloalkyl, a substituted or unsubstituted of C ₁ -C ₈ alkoxy, comprising multiple to 9 may be the same or different halogen atoms C ₁ -C ₈ haloalkoxy, substituted or non-take The C ₁ -C ₈ alkylthio group, comprising up to 9 halogen atoms may be the same or different C ₁ -C ₈ haloalkyl group, a substituted or unsubstituted ter (C ₁ -C ₈₎ Alkylalkyl, substituted or unsubstituted tri(C ₁ -C ₈ )alkyldecyl-C ₁ -C ₈ alkyl, substituted or unsubstituted (C ₁ -C ₈ alkoxy Amino)-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; Cyano; hydroxy; amine; thio; pentafluoro-λ ⁶ -thio; substituted or unsubstituted (C ₁ -C ₈ alkoxyimino)-C ₁ -C ₈ alkyl; substituted or non-substituted (benzyloxyimino group) -C ₁ -C ₈ alkyl; substituted or non-substituted C ₁ -C ₈ alkyl group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkyl; substituted or non-substituted C ₂ -C ₈ alkenyl group; a C 1 to having halogen atoms. 9 ₂ -C ₈ haloalkenyl; substituted or non-substituted C ₂ -C ₈ alkynyl a C ₂ -C ₈ haloalkynyl group having 1 to 9 halogen atoms; a substituted or unsubstituted C ₁ -C ₈ alkoxy group; a C ₁ -C ₈ haloalkane having 1 to 9 halogen atoms; oxygen ; Substituted or non-substituted C ₁ -C ₈ alkylthio; ₁ -C ₈ haloalkyl group having a C 1 to. 9 halogen atoms; a substituted or unsubstituted alkyl of C ₁ -C ₈ a sulfinyl group; a C ₁ -C ₈ haloalkylsulfinyl group having 1 to 9 halogen atoms; a substituted or unsubstituted C ₁ -C ₈ alkylsulfonyl group; having 1 to 9 a C ₁ -C ₈ haloalkylsulfonyl group of a halogen atom; a substituted or unsubstituted C ₁ -C ₈ alkylamino group; a substituted or unsubstituted di-C ₁ -C ₈ alkylamino group Substituted or unsubstituted C ₂ -C ₈ alkenyloxy; substituted or unsubstituted C ₃ -C ₈ alkynyloxy; substituted or unsubstituted C ₃ -C ₇ cycloalkyl; a C ₃ -C ₇ halocycloalkyl group of 1 to 9 halogen atoms; a substituted or unsubstituted tri(C ₁ -C ₈ )alkyldecane group; a substituted or unsubstituted C ₁ -C ₈ alkane carbonyl group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkyl carbonyl group; substituted or non-substituted C ₁ -C ₈ alkoxycarbonyl group; a C 1 to having halogen atoms. 9 ₁ -C ₈ -haloalkoxycarbonyl; substituted or unsubstituted C ₁ -C ₈ alkylamine carbenyl; substituted or unsubstituted bis-C ₁ -C ₈ alkylamine carbenyl; phenoxy; phenylthio; phenylamino; benzyloxy; benzylthio; or benzylamino; and salts, N-oxides, metal Compounds, metalloid complexes and optically active isomers or geometric isomers thereof.

Unless otherwise indicated, a substituted group or substituent according to the invention may be substituted with one or more of the following groups or atoms: a halogen atom; a nitro group; a hydroxyl group; a cyano group; an isonitrile group; an amine group; ; pentafluoro-λ ⁶ -thio; methyl sulfhydryl; methyl methoxy; methionine; amine carbhydryl; N-hydroxylamine decyl; urethane; (hydroxyimino) -C ₁ -C ₆ alkyl; C ₁ -C ₈ alkyl; tri(C ₁ -C ₈ alkyl)decylalkyl; C ₃ -C ₈ cycloalkyl; C ₁ - having 1 to 5 halogen atoms C 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 alkenyl; ₂ -C ₈ alkynyloxy; C ₁ -C ₈ alkylamino group; di-C ₁ -C ₈ alkylamino group; C ₁ -C ₈ alkoxy group; C ₁ - having 1 to 5 halogen atoms C ₈ haloalkoxy; C ₁ -C ₈ alkylthio; having a C 1 to 5 halogen atoms, haloalkyl of ₁ -C ₈ alkylthio; C ₂ -C ₈ alkenyl group; having 1-5 halogen atoms C ₂ -C ₈ haloalkenyl group; C ₃ -C ₈ alkynyl group; having a C 1 to 5 halogen atoms ₃ -C ₈ haloalkynyl group; C ₁ -C ₈ alkylcarbonyl; having C ₁ -C ₈ haloalkyl having 1 to 5 halogen atoms Alkylcarbonyl; C ₁ -C ₈ alkylamine carbenyl; di-C ₁ -C ₈ alkylamine carbenyl; NC ₁ -C ₈ alkoxyamine carbenyl; C ₁ -C ₈ alkoxy carbamoyl acyl; the NC ₁ -C ₈ alkyl -C ₁ -C ₈ alkoxy, carbamoyl acyl; C ₁ -C ₈ alkoxycarbonyl; having a C 1 to 5 halogen atoms ₁ -C ₈ halogen alkoxycarbonyl; C ₁ -C ₈ alkylcarbonyloxy group; having a C 1 to 5 halogen atoms ₁ -C ₈ haloalkyl carbonyl group; C ₁ -C ₈ alkylcarbonyl group; having 1 to C ₁ -C ₈ haloalkylcarbonylamino group of 5 halogen atoms; C ₁ -C ₈ alkylaminocarbonyloxy group; di-C ₁ -C ₈ alkylaminocarbonyloxy group; C ₁ -C ₈ alkoxycarbonyloxy; C ₁ -C ₈ alkylthio; having a C 1 to 5 halogen atoms ₁ -C ₈ haloalkyl group; C ₁ -C ₈ alkylsulfinyl acyl; having a a C ₁ -C ₈ haloalkylsulfinyl group having 5 halogen atoms; a C ₁ -C ₈ alkylsulfonyl group; a C ₁ -C ₈ haloalkylsulfonyl group having 1 to 5 halogen atoms; C ₁ -C ₈ alkylaminoamine sulfonyl; di-C ₁ -C ₈ alkylaminoamine sulfonyl; (C ₁ -C ₆ alkoxyimino)-C ₁ -C ₆ alkane group; (C ₁ -C ₆ alkylene oxyalkylene amine) -C ₁ -C ₆ alkyl; (C ₁ -C ₆ - alkynyl oxyalkylene amine) -C ₁ -C ₆ Group; a 2-oxoalkyl pyrrolidin-1-yl; (benzyloxycarbonylamino imino) -C ₁ -C ₆ alkyl; C ₁ -C ₈ alkoxyalkyl; having 1 to 5 halogen atoms C ₁ -C ₈ haloalkoxyalkyl; benzyloxy; benzylthio; benzylamino; aryloxy; arylthio or arylamine.

According to the present invention, the following general terms are generally used in the following senses: ̇ halogen means fluorine, chlorine, bromine or iodine; carboxyl means -C(=O)OH; carbonyl means -C(=O)-; amine formazan The meaning is -C(=O)NH ₂ ; N-hydroxylamine carbenyl means -C(=O)NHOH; SO means a fluorenylene group; SO ₂ means a fluorenyl group; hetero atom means sulfur, nitrogen or oxygen Methylene means bis-CH ₂ -; decyl, alkenyl and alkynyl and the moiety containing these terms may be straight or branched; hydrazine halide, especially haloalkyl, haloalkoxy And a cycloalkyl group which may contain up to 9 identical or different halogen atoms; ̇ the term "aryl" means phenyl or naphthyl; oxime is an amino group substituted by two substituents which may be the same or different or any In the case of other amine moiety containing an amine group, the two substituents together with the nitrogen atom to which they are attached may form a heterocyclic group, preferably a 5 to 7 membered heterocyclic group, which may be substituted or may include Other heteroatoms such as N-morpholino or piperidinyl.

When the compounds of the invention may exist in tautomeric forms, such compounds are also to be understood above and in the following to include the corresponding tautomeric forms, as appropriate, even in each case without specifically mentioning such tautomers. When constructing the form.

Depending on the number of asymmetric centers in the compound, any of the compounds of the invention may exist in one or more optical or palmical isomer forms. Thus, the present invention is also directed to all optical isomers and racemic or non-racemic mixtures thereof (the term "non-racemic" means mixtures of enantiomers in different ratios) and in all ratios. a mixture of all possible stereoisomers. The diastereomers and/or optical isomers can be separated according to methods known per se to the person skilled in the art.

Depending on the number of double bonds in the compound, any of the compounds of the invention may also exist in one or more geometric isomeric forms. Accordingly, the invention is also to all geometric isomers and all possible mixtures in all ratios. Geometric isomers can be separated according to the general methods known to those of ordinary skill in the art. Depending on the relative position of the substituents of the chain or ring (ipsilateral/reverse or cis/trans), any of the compounds of the invention may also exist in one or more geometric isomers. Thus, the invention is equally directed to all ipsilateral/reverse (or cis/trans) isomers and all possible ipsilateral/reverse (or cis/trans) mixtures in all ratios. The ipsilateral/reverse (or cis/trans) isomers can be separated according to the general methods known to those of ordinary skill in the art.

The preferred compounds of the invention of formula (I), wherein A is selected from the list consisting of: - heterocycle of formula ^{(A. 1)} of

Wherein: R ¹ to R ³ may be the same or different and represent a hydrogen atom; a halogen atom; a substituted or unsubstituted of C ₁ -C ₅ alkyl; C comprising up to 9 identical or different halogen atoms _1-- C ₅ haloalkyl group; a substituted or unsubstituted of C ₁ -C ₅ alkoxy group or may comprise up to nine identical or different a halogen atoms C ₁ -C ₅ haloalkoxy; - of formula (A ² Heterocycle

Wherein: R ⁴ to R ⁶ may be the same or different and represent a hydrogen atom; a halogen atom; a substituted or unsubstituted of C ₁ -C ₅ alkyl; C comprising up to 9 identical or different halogen atoms _1-- C ₅ haloalkyl group; a substituted or unsubstituted of C ₁ -C ₅ alkoxy group or may comprise up to nine identical or different a halogen atoms C ₁ -C ₅ haloalkoxy; - of formula (A ³ Heterocycle

Wherein: R ⁷ represents a hydrogen atom; a halogen atom; a substituted or unsubstituted alkyl group of C ₁ -C _5; may contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl; substituted or unsubstituted of C ₁ -C ₅ alkoxy group or may comprise up to nine identical or different a halogen atoms C ₁ -C ₅ haloalkoxy; R ⁸ represents a hydrogen atom or a substituted or non-substituted C ₁ -C ₅ alkyl; - heterocyclic ring of formula (A ⁴ )

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 group; substituted or non-substituted C ₁ -C ₅ alkylthio; it can contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl, or comprising up to 9 may be the same or a C ₁ -C ₅ haloalkoxy group of a different halogen atom; - a heterocyclic ring of the formula (A ⁵ )

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; Amino group; C ₁ -C ₅ haloalkyl group containing up to 9 halogen atoms which may be the same or different or C ₁ -C ₅ haloalkoxy group containing up to 9 halogen atoms which may be the same or different; R ¹⁴ 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; containing up to 9 which may be the same or different the halogen atom of 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⁾ of the 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; containing 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 and a hydrogen atom; a halogen atom; a substituted or unsubstituted C ₁ -C ₅ alkoxycarbonyl group; a substituted or unsubstituted C ₁ -C ₅ alkyl group; containing up to 9 halogens which may be the same or different C ₁ -C ₅ atoms or haloalkoxy comprising up to 9 halogen atoms may be the same or different C ₁ -C ₅ haloalkyl group; R ¹⁷ represents a hydrogen atom or a substituted or unsubstituted of C ₁ - C ₅ alkyl; - heterocyclic ring of formula (A ⁷ )

Wherein: R ¹⁹ represents a hydrogen atom or a C ₁ -C ₅ alkyl group; 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 To a C ₁ -C ₅ haloalkyl group which may be the same or different halogen atom; - a heterocyclic ring of the formula (A ⁸ )

Wherein: R ²³ represents a hydrogen atom; a halogen atom; a substituted or unsubstituted alkyl group of C ₁ -C ₅ to 9 or a plurality may be the same or different halogen atoms C ₁ -C ₅ haloalkyl group; R ²⁴ It represents a hydrogen atom or a substituted or unsubstituted alkyl group of C ₁ -C ₅ to 9 or a plurality may be the same or different halogen atoms C ₁ -C ₅ haloalkyl group; - of formula (A ⁹⁾ of the heterocycle

Wherein: R ²⁵ represents a hydrogen atom; a halogen atom; a substituted or unsubstituted alkyl group of C ₁ -C ₅ to 9 or a plurality may be the same or different halogen atoms C ₁ -C ₅ haloalkyl group; R ²⁶ represents a hydrogen 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; - heterocycle of formula (A ¹⁰⁾ of

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 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 halogen atoms which may be the same or different; containing up to 9 C ₁ -C ₅ haloalkoxy group of the same or different halogen atom; amine group; substituted or unsubstituted C ₁ -C ₅ alkylamino group or substituted or unsubstituted bis (C ₁ -C _5- alkyl)amino group; - heterocyclic ring of formula (A ¹¹ )

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; containing up to 9 may be the same or halogen atoms different from 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 by the substituted C ₁ -C ₅ alkyl; may contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl; can contain up to 9 identical or different halogen atoms 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)amino group; - formula (A ¹² ) heterocyclic ring

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; the substituted C ₁ -C ₅ alkoxy; can contain up to 9 identical or different halogen atoms C ₁ -C ₅ alkoxy group or a halogen comprising up to 9 C may be the same or different halogen atoms ₁ -C ₅ haloalkyl; - heterocyclic ring of formula (A ¹³ )

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; containing up to 9 may be the same or a C ₁ -C ₅ haloalkyl group of a different 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 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; the substituted C ₁ -C ₅ alkoxy group; a substituted or unsubstituted of C ₁ -C ₅ alkylthio; can contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl, a C ₁ -C ₅ haloalkoxy group containing up to 9 halogen atoms which may be the same or different; an amine group; a substituted or unsubstituted C ₁ -C ₅ alkylamino group or a substituted or unsubstituted a bis(C ₁ -C ₅ alkyl)amino group; R ³⁶ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; - a heterocyclic ring of the formula (A ¹⁴ )

Wherein: R ³⁷ and R ³⁸ may be the same or different and represent a hydrogen atom; a halogen atom; a substituted or unsubstituted of C ₁ -C ₅ alkyl; C comprising up to 9 identical or different halogen atoms _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;-heterocyclic ring of formula (A ¹⁵ )

Wherein: R ⁴⁰ and R ⁴¹ may be the same or different and represent 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 _1-- C ₅ haloalkyl; - heterocyclic ring of formula (A ¹⁶ )

Wherein: R ⁴² and R ⁴³ may be the same or different and represent a hydrogen atom; a halogen atom; a substituted or unsubstituted of C ₁ -C ₅ alkyl; C comprising up to 9 identical or different halogen atoms _1-- C ₅ haloalkyl; or an amine group; - a heterocyclic ring of the formula (A ¹⁷ )

Wherein: R ⁴⁴ and R ⁴⁵ may be the same or different and represent 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 _1-- C ₅ haloalkyl; - heterocyclic ring of formula (A ¹⁸ )

Wherein: R ⁴⁷ represents a hydrogen atom; a halogen atom; a substituted or unsubstituted alkyl group of C ₁ -C ₅ to 9 or a plurality may be the same 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; may contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl, or a substituted or unsubstituted a C ₁ -C ₅ alkylthio group; a heterocyclic ring of the formula (A ¹⁹ )

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; It may comprise up to nine identical or different a 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; - of formula (A ²⁰ Heterocycle

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; It may comprise up to nine identical or different a 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; - of formula (A ²¹ Heterocycle

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 halogen atoms may be the same or different C ₁ -C ₅ haloalkyl group; - of formula (A ²² ) heterocyclic ring

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 halogen atoms may be the same or different C ₁ -C ₅ haloalkyl group; - of formula Heterocyclic ring of (A ²³ )

Wherein: R ⁵⁴ and R ⁵⁶ may be the same or different and represent 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 _1-- C ₅ haloalkyl; R ⁵⁵ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; - a heterocyclic ring of the formula (A ²⁴ )

Wherein: R ⁵⁷ and R ⁵⁹ may be the same or different and represent 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 _1-- C ₅ haloalkyl; R ⁵⁸ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; - a heterocyclic ring of the formula (A ²⁵ )

Wherein: R ⁶⁰ and R ⁶¹ may be the same or different and represent 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 _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 a C ₁ -C ₅ haloalkyl group of a different 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 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 not the substituted C ₁ -C ₅ alkoxy group; a substituted or unsubstituted of C ₁ -C ₅ alkylthio; can contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl, a C ₁ -C ₅ haloalkoxy group containing up to 9 halogen atoms which may be the same or different; an amine group; a substituted or unsubstituted C ₁ -C ₅ alkylamino group or a di(C ₁ -C _{A 5-} alkyl)amino group; R ⁶⁴ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group.

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

Even more preferred compounds of the invention are compounds of formula (I) wherein A represents A ¹³ wherein R ³⁴ represents substituted or unsubstituted C ₁ -C ₅ alkyl, containing up to 9 halogen atoms which may be the same or different a C ₁ -C ₅ haloalkyl group, a substituted or unsubstituted C ₁ -C ₅ alkoxy group; R ³⁵ represents a hydrogen atom or a halogen atom; and R ³⁶ represents a substituted or unsubstituted C ₁ -C ₅ alkyl.

Even more preferably the compounds of the invention of formula (I) compounds wherein A represents A ^{13 is} wherein R ³⁴ represents C ₁ -C ₅ alkyl group, may contain up to 3 identical or different halogen atoms C ₁ -C ₅ halogen An alkyl group; R ³⁵ represents a hydrogen 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 invention are those of formula (I) wherein Z ¹ represents a substituted or unsubstituted cyclopropyl group.

Other more preferred compounds of the invention are those of formula (I) wherein Z ¹ represents unsubstituted cyclopropyl or 2-C ₁ -C ₅ alkylcyclopropyl.

Other even more preferred compounds of the invention are those of formula (I) wherein Z ¹ represents an unsubstituted cyclopropyl group.

Further and even more preferred compounds of the invention are compounds of formula (I) wherein Z ¹ represents 2-methylcyclopropyl.

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

More preferably, the compound of the invention is a compound 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 of formula (I) wherein n represents 0, 1 or 2.

Other preferred compounds of the invention are those of formula (I) wherein L represents a direct bond.

Other preferred compounds of the invention are compounds of formula (I) wherein L represents an oxygen atom.

Other preferred compounds of the invention are those of formula (I) wherein L represents methylene or carbonyl.

Other preferred compounds of the invention are compounds of formula (I) wherein B represents substituted or unsubstituted oxiranyl ring; substituted or unsubstituted pyrrolyl ring; substituted or unsubstituted pyrazole Substituted or substituted thiophenyl ring; substituted or unsubstituted benzothienyl ring; substituted or unsubstituted quinolinyl ring; substituted or unsubstituted isoquinolyl Ring; substituted or unsubstituted furan ring; or substituted or unsubstituted benzofuran ring.

Other more preferred compounds of the invention are those of formula (I) wherein B represents a substituted or unsubstituted thienyl ring. Other more preferred compounds of the invention are those of formula (I) wherein B represents a substituted or unsubstituted benzothienyl ring.

Further preferred compounds of the invention are those of the formula (I), wherein X independently represents a halogen atom; a substituted or unsubstituted C ₁ -C ₈ alkyl group; C containing up to 9 halogen atoms which may be the same or different _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 alkane An oxy group; or a substituted or unsubstituted C ₁ -C ₈ alkylthio group.

Other preferred compounds of the invention are those of formula (I) wherein Y independently represents a halogen atom; a substituted or unsubstituted C ₁ -C ₈ alkyl group; C containing up to 9 halogen atoms which may be the same or different ₁ -C ₈ haloalkyl; substituted or non-substituted C ₁ -C ₈ alkoxy; can contain up to 9 identical or different halogen atoms C ₁ -C ₈ haloalkoxy.

The above preferences regarding the substituents of the compounds of the invention can be combined in various ways. Accordingly, combinations of such preferred features provide a subclass of the compounds of the invention. Examples of such subclasses of preferred compounds of this invention are: - preferred features of A with ¹ to Z ^3, preferably wherein n, X, L, B and Y, or T, Z; - T preferred feature of the A, Z ¹ to Z ³ , n, X, L, B and Y preferred features; - Z ¹ preferred features and A, T, Z ² , Z ³ , n, X, L, B and Y Preferred features; - preferred features of Z ² and preferred features of A, T, Z ¹ , Z ³ , n, X, L, B and Y; - preferred features of Z ³ and A, T, Z ¹ Preferred features of Z ² , n, X, L, B and Y; preferred features of -n and preferred features of A, T, Z ¹ to Z ³ , X, L, B and Y; Preferred features and preferred features of A, T, Z ¹ to Z ³ , n, L, B and Y; - preferred features of L and A, T, Z ¹ to Z ³ , n, X, B and Y Preferred features; - preferred features of B and preferred features of A, T, Z ¹ to Z ³ , n, X, L and Y; - preferred features of Y and A, T, Z ¹ to Z ³ Preferred features of n, X, L and B.

In such preferred combinations of features of the substituents of the compounds of the invention, the preferred features may also be selected from each of A, T, Z ¹ to Z ³ , n, X, L, B and Y. More preferred features are in the form of the best subclass of the compounds of the invention.

The invention also relates to a process for the preparation of a compound of formula (I).

Thus, according to another aspect of the present 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 one of the amines of formula (II) or a salt thereof:

Wherein Z ¹ , Z ² , Z ³ , n, X, L and B are as defined herein; reacted with a carboxylic acid derivative of formula (III):

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

The N-hydroxy 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 imines. Reduction (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.

If U ¹ represents a hydroxyl group, the process P1 of the invention is carried out in the presence of a condensing agent. Suitable condensing agents may be selected from a non-limiting list of the following: acid halide formers such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or sulphide chloride; Anhydride forming agent such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonium chloride; carbodiimide such as N,N'-dicyclohexylcarbodiimide (DCC) or other conventional condensing agents such as phosphorus pentoxide, polyphosphoric acid, N,N'-carbonyl-diimidazole, 2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ) ), triphenylphosphine/tetrachloromethane, chlorinated 4-(4,6-dimethoxy[1.3.5]-triazin-2-yl)-4-methylmorpholinium, hexafluorophosphate Bromo-tripyrrolidinophosphonium hexafluorophosphate or propanephosphonic anhydride (T3P).

Process P1 according to the invention can be carried out in the presence of a catalyst. Suitable catalysts may be selected from the list consisting of N,N-dimethylpyridin-4-amine, 1-hydroxy-benzotriazole or N,N-dimethylformamide.

If U ¹ represents a halogen atom, the process P1 of the invention is carried out in the presence of an acid binder. Suitable acid binders for carrying out the process P1 according to the invention are in each case all inorganic and organic bases customary for such reactions. Preference is given to using alkaline earth metals, alkali metal hydrides, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium butoxide or other ammonium hydroxide; Metal carbonates such as cesium carbonate, sodium carbonate, potassium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate; alkali metal or alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate; and tertiary amines such as trimethylamine, three Ethylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethylpyridin-4-amine, diazabicyclooctyl Alkane (DABCO), diazabicyclo-decene (DBN) or diazabicycloundecene (DBU).

It is also possible to operate or employ an excess of the amine component in the absence of other condensing agents to simultaneously act as an acid binder.

Suitable solvents for carrying out the process P1 according to the invention may be customary inert organic solvents. Preference is given to using aliphatic, alicyclic or aromatic hydrocarbons which are optionally halogenated, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decahydronaphthalene; chlorobenzene , dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ether, such as B Ether, diisopropyl ether, methyl tert-butyl ether, methyl third amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxy B Alkane or anisole; nitrile such as acetonitrile, propionitrile, n-butyronitrile or isobutyronitrile or benzonitrile; decylamine such as N,N-dimethylformamide, N,N-dimethylacetamide , N-methylformanilide, N-methylpyrrolidone or hexamethylphosphonium triamine; alcohols such as methanol, ethanol, propanol, isopropanol; esters such as methyl acetate or ethyl acetate; Aachen, such as dimethyl hydrazine; or hydrazine, such as guanidine.

When carrying out the process P1 according to the invention, the amine derivatives of the formula (II) can be used in the form of their salts, such as the hydrochloride or any other suitable salt.

When carrying out the process P1 according to the invention, the reagent of the formula (III) can be used in an amount of 1 mole or excess of the amine derivative of the formula (II) and a 1 to 3 molar acid binder.

It is also possible to use the reaction components in other ratios. Processing is performed by a known method.

According to another aspect of the present invention, there is provided a second method P2 for preparing a compound of formula (I) wherein L represents a direct bond or a methylene group, as illustrated by the following reaction scheme:

Method P2

Wherein A, T, Z ¹ , Z ² , Z ³ , n, X and B are as defined herein, L represents a direct bond or a methylene group, and U ² represents a halogen atom such as chlorine, bromine or iodine or trifluoromethanesulfonate. An acid ester group, and W ¹ represents a boron derivative, such as acid, An acid ester or a potassium trifluoroborate derivative.

Accordingly, the present invention relates to a process for the preparation of a compound of formula (I) P2

Wherein A, T, Z ¹ , Z ² , Z ³ , n, X and B are as defined in any one of claims 1 to 14, and L represents a direct bond or a methylene group, and the method P2 is characterized by (IV) compound

Wherein A, T, Z ¹ , Z ² , Z ³ , n, X are as defined above and U ² represents a halogen atom such as chlorobromo or iodine or a triflate group, reacted with a compound of formula (V),

Wherein L and B are as defined above and W ¹ represents a boron derivative, such as acid, An acid ester or a potassium trifluoroborate derivative.

Process P2 can be carried out in the presence of a transition metal catalyst such as palladium and, where appropriate, in the presence of a phosphine ligand or an N-heterocyclic carbene ligand and in the presence of a base and, where appropriate, in the presence of a solvent.

The compound of the formula (IV) can be produced by a known method (WO-2007/087906 and WO-2010/130767) and the preparation of the compound of the formula (V) is well known.

Process P2 according to the invention can be carried out in the presence of a catalyst, such as a metal salt or a complex. Suitable metal derivatives for this purpose are transition metal catalysts such as palladium. Suitable metal salts or complexes for this purpose are, for example, palladium chloride, palladium acetate, ruthenium (triphenylphosphine) palladium, bis(dibenzylideneacetone)palladium, bis(triphenylphosphine)dichloride Palladium or 1,1'-bis(diphenylphosphino)ferrocene palladium(II) chloride.

It is also possible to produce a palladium complex in the reaction mixture by separately adding the following to the palladium salt and the ligand or salt reactant: such as triethylphosphine, tri-tert-butylphosphine, tetrafluoro Tri-tert-butyl borohydride, tricyclohexylphosphine, 2-(dicyclohexylphosphine)biphenyl, 2- (di-tert-butylphosphine)biphenyl, 2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino)biphenyl, triphenyl-phosphine, ginseng (o-tolyl) Phosphine, sodium 3-(diphenylphosphino)benzenesulfonate, cis-2-(methoxy-phenyl)phosphine, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl , 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)ethane, 1,4-bis(dicyclohexylphosphine)butane, 1,2-double (two Cyclohexylphosphine)-ethane, 2-(dicyclohexylphosphine)-2'-(N,N-dimethylamino)-biphenyl, 1,1'-bis(diphenylphosphino)-di Ferrocene, (R)-(-)-1-[(S)-2-diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine, phosphite ginseng (2,4-t-butyl) -Phenyl) ester or 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride.

It is also advisable to select suitable catalysts and/or ligands from the commercial catalogue, such as "Metal Catalysts for Organic Synthesis" by Strem Chemicals or "Phosphorous Ligands and Compounds" by Strem Chemicals. )".

Suitable bases for carrying out the process P2 according to the invention may be inorganic and organic bases customary for such reactions. Preference is given to using alkaline earth or alkali metal hydroxides, such as sodium hydroxide, calcium hydroxide, potassium hydroxide or other ammonium hydroxide derivatives; alkaline earth metals, alkali metal or ammonium fluorides, such as potassium fluoride, fluorination铯 or tetrabutylammonium fluoride; alkaline earth metal or alkali metal carbonate such as sodium carbonate, potassium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate or cesium carbonate; alkali metal or alkaline earth metal acetate such as sodium acetate, potassium acetate or Calcium acetate; an alkali metal alkoxide such as potassium third butoxide or sodium butoxide; an alkali metal phosphate such as tripotassium phosphate; a tertiary amine such as trimethylamine, triethylamine, tributylamine, N, N - dimethylaniline, N,N-dicyclohexylmethylamine, N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU); and an aromatic base such as pyridine, picoline, lutidine or trimethylpyridine.

Suitable solvents for carrying out the process P2 according to the invention may be customary inert organic solvents. Preferred use of halogen atomized aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, Toluene or decahydronaphthalene; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers such as diethyl ether, diisopropyl ether, methyl tertidine Ether, methyl tertiary amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitrile, such as acetonitrile, propionitrile , n-butyronitrile or isobutyronitrile or benzonitrile; decylamine, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methyl Pyrrolidone or hexamethylphosphonium triamine; esters such as methyl acetate or ethyl acetate; hydrazine, such as dimethyl hydrazine; or hydrazine, such as cyclobutyl hydrazine.

It is also preferred to carry out the process P2 according to the invention using a cosolvent such as water or an alcohol such as methanol, ethanol, propanol, isopropanol or tert-butanol.

When carrying out the process P2 according to the invention, one mole or excess of the compound of the formula (V) and from 1 to 5 moles of base and from 0.01 to 20 moles of palladium complex can be used per mole of the compound of formula (IV).

It is also possible to use the reaction components in other ratios. Processing is performed by a known method.

According to another aspect of the present invention, there is provided a third method P3 for preparing a compound of formula (I) wherein L represents a hetero atom, as illustrated by the following reaction scheme:

Method P3

Wherein A, T, Z ¹ , Z ² , Z ³ , n, X and B are as defined herein, U ³ represents a halogen atom and L represents an oxygen atom, a sulfur atom or a monosubstituted or unsubstituted nitrogen atom.

The process P3 according to the invention is carried out in the presence of a base.

The compound of the formula (VI) can be produced by a known method (WO-2007/087906 and WO-2010/130767) and the preparation of the compound of the formula (VII) is well known.

Suitable bases for carrying out the process P3 according to the invention may be inorganic and organic bases customary for such reactions. Preferred use of alkaline earth metals or alkali metal hydroxides, such as sodium hydroxide, hydrogen and oxygen Calcium, potassium hydroxide, or other ammonium hydroxide derivative; alkaline earth metal, alkali metal or ammonium fluoride, such as potassium fluoride, barium fluoride or tetrabutylammonium fluoride; alkaline earth metal or alkali metal carbonate, Such as sodium carbonate, potassium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate or cesium carbonate; alkali metal or alkaline earth metal acetate such as sodium acetate, potassium acetate or calcium acetate; alkali metal alkoxide such as potassium third butoxide or third Sodium butoxide; alkali metal phosphates such as tripotassium phosphate; tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dicyclohexylmethylamine, N -methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU); Alkaloids such as pyridine, picoline, lutidine or trimethylpyridine.

Other suitable bases for carrying out the process P3 according to the invention may be aminides or organometallic derivatives. Preferred are alkali metal amides such as sodium or potassium amide; organic amides such as lithium diisopropylamide (LDA), lithium hexamethyldiazepine (LiHMDS), potassium hexamethyldioxazone ( KHMDS) or sodium hexamethyldisilazane (NaHMDS); an organolithium derivative such as methyl lithium, phenyl lithium, butyl lithium, second butyl lithium, isobutyl lithium or tert-butyl lithium.

Suitable solvents for carrying out the process P3 according to the invention may be customary inert organic solvents. Preference is given to using aliphatic, alicyclic or aromatic hydrocarbons which are halogenated as appropriate, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl Triamyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitrile such as acetonitrile, propionitrile, n-butyronitrile or different Butyronitrile or benzonitrile; decylamine, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformamide, N-methylpyrrolidone or hexamethyl An amino ester; an ester such as methyl acetate or ethyl acetate; an anthracene such as dimethyl hydrazine; or an anthracene such as cyclobutyl hydrazine.

When carrying out the process P3 according to the invention, the compound of the formula (VI) can be used in an amount of 1 mole or excess of the compound of the formula (VII) and 1 to 5 moles of base per mole of the compound of the formula (VI).

It is also possible to use the reaction components in other ratios. Processing is performed by a known method.

According to another aspect of the present invention, there is provided a fourth method P4 for preparing a compound of formula (I) according to the following reaction scheme:

Method P4

Wherein A, Z ¹ , Z ² , Z ³ , n, X, L and B are as defined herein and when p is 1, W ² represents a boron derivative, such as acid, An acid ester or a potassium trifluoroborate derivative; or when p is 3, W ² represents Bi.

The compound of the formula (IX) can be produced by a known method.

The process P4 of the invention is carried out in the presence of copper (II) acetate.

Suitable bases for carrying out the process P4 according to the invention may be inorganic and organic bases customary for such reactions. Preference is given to using alkaline earth or alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate or cesium carbonate; alkali metal phosphates such as tripotassium phosphate; tertiary amines such as trimethylamine, triethylamine, Tributylamine, N,N-dimethylaniline, N,N-dicyclohexylmethylamine, N-methylpiperidine, N,N-dimethylaminopyridine; and aromatic bases such as pyridine, A Pyridine, lutidine or trimethylpyridine.

Other suitable bases for carrying out the process P4 according to the invention may be the organic bases customary for such reactions. Preferential use of organic amides such as lithium diisopropylamide (LDA), lithium hexamethyldiazepine (LiHMDS), potassium hexamethyldioxane (KHMDS) or sodium hexamethyldisilazane (NaHMDS) .

Suitable ligands for carrying out the process P4 according to the invention may be the organic bases customary for such reactions. Preference is given to using aromatic bases such as pyridine, picoline, lutidine, trimethylpyridine, 2,2'-bipyridine or 1,10-morpholine; and tertiary amines such as trimethylamine, triethylamine , Tributylamine, N,N-dimethylaniline, N,N-dicyclohexylmethylamine, N-methylpiperidine, N,N-dimethylaminopyridine.

Suitable solvents for carrying out the process P4 according to the invention may be customary inert organic solvents. Preference is given to using aliphatic, alicyclic or aromatic hydrocarbons which are halogenated as appropriate, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl Triamyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitrile such as acetonitrile, propionitrile, n-butyronitrile or different Butyronitrile or benzonitrile; decylamine, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphonium triamine; ester, Such as methyl acetate or ethyl acetate; anthraquinones such as dimethyl hydrazine; or hydrazine, such as cyclobutyl hydrazine.

When carrying out the process P4 according to the invention, one mole or a mixture of the compound of the formula (IX) can be used per mole of the compound of the formula (VIII).

When carrying out the process P4 according to the invention, from 1 to 3 moles or excess of base per mole of the compound of formula (VIII). A combination of bases may also be employed in various ratios as appropriate.

When carrying out the process P4 according to the invention, the compound of the formula (VIII) can be used without a ligand or with a 0.1 to 1 molar ligand.

When carrying out the process P4 according to the invention, from 0.1 to 2.5 moles or excess of copper (II) acetate per mole of the compound of formula (VIII).

It is also possible to use the reaction components in other ratios. Processing is performed by a known method.

The secondary guanamine of formula (VIII) can be prepared, for example, according to the following reaction scheme:

Wherein A, T, Z ¹ , Z ² , Z ³ , n, X and B are as defined herein, and - when U ² represents a halogen atom such as chlorine, bromine or iodine or a triflate group, and W ¹ represents a boron derivative such as acid, In the case of an acid ester or a potassium trifluoroborate derivative, L represents a direct bond or a methylene group (step a); or - when U ³ represents a halogen atom, L represents an oxygen atom, a sulfur atom or a mono- or unsubstituted group. A nitrogen atom (step b).

The tertiary guanamine of formula (IV) can be prepared, for example, according to the following reaction scheme:

Wherein A, T, Z ¹ , Z ² , Z ³ , n and X are as defined herein, U ² represents a halogen atom such as chlorine, bromine or iodine or a triflate group, and - when p is 1 W ² represents a boron derivative such as acid, An acid ester or a potassium trifluoroborate derivative; or - when p is 3, W ² represents Bi.

Derivatives of formula (X) or formula (XI) are known or can be prepared by known methods (WO-2012/052490).

Step a can be performed according to method P2, step b can be performed according to method P3, and step c can be performed according to method P4.

According to another aspect of the present invention, there is provided a fourth method P5 wherein the compound of the formula (I) wherein T represents O is used as a starting material and the compound of the formula (I) wherein T represents S is prepared according to the following reaction scheme. :

Method P5

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

The process P5 according to the invention is carried out in the presence of a vulcanizing agent.

The starting guanamine derivatives of formula (I) wherein T represents O can be prepared according to methods P1, P2, P3 and P4.

Suitable vulcanizing agents for carrying out the process P5 according to the invention may be sulfur (S), hydrogen sulphate (H ₂ S), sodium sulphide (Na ₂ S), sodium hydrosulfide (NaHS), boron trisulfide (B ₂ S ₃ ) , bis(diethylaluminum) sulfide ((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 vulcanizing agent, such as Journal of the Chemical Society , as described in Perkin 1 (2001), 358, in the presence of a catalytic amount or a stoichiometric or excess base such as inorganic and organic bases. Preference is given to using alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate; heterocyclic aromatic bases such as pyridine, picoline, lutidine, trimethylpyridine; and tertiary amines, Such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylpyridin-4-amine or N-methyl-piperidine.

Suitable solvents for carrying out the process P5 according to the invention may be customary inert organic solvents. excellent First using aliphatic, alicyclic or aromatic hydrocarbons which are halogenated as appropriate, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decahydronaphthalene; chlorobenzene , dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl third An ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane; a nitrile such as acetonitrile, propionitrile, n-butyronitrile or isobutyronitrile or benzonitrile; A sulfur-containing solvent such as cyclobutyl hydrazine or carbon disulfide.

When carrying out the process P5 according to the invention, a sulfur equivalent of 1 mole or excess vulcanizing agent and 1 to 3 moles of base per mole of the melamine reaction (I) can be used.

It is also possible to use the reaction components in other ratios. Processing is performed by a known method.

The processes P1, P2, P3, P4 and P5 according to the invention are generally carried out under atmospheric pressure. It is also possible to operate under pressure or reduced pressure.

When carrying out the processes P1, P2, P3, P4 and P5 according to the invention, the reaction temperature can be varied within a relatively wide range. Generally, such processes are carried out at temperatures ranging from -75 ° C to 200 ° C, preferably from 10 ° C to 150 ° C. The manner in which the temperature of the process of the invention is controlled is the use of microwave technology.

In general, the reaction mixture is concentrated under reduced pressure. The remaining residue can be released from any impurities that may still be present by known methods such as chromatography or crystallization.

It is processed by a conventional method. In general, the reaction mixture is treated with water, and the organic phase is separated and concentrated under reduced pressure. Where appropriate, the remaining residue can be released from any impurities that may still be present by conventional methods such as chromatography, crystallization or distillation.

The compounds of the invention can be prepared according to the general preparation methods described above. Nonetheless, it should be understood that based on the general knowledge and available disclosures, those skilled in the art will be able to modify this method depending on the particularity of each compound to be synthesized.

In another aspect, the invention relates to a compound of formula (II) which is useful as an intermediate compound or substance in the process of the invention.

Accordingly, the present invention provides a compound of formula (IIa) and an acceptable salt thereof:

Wherein Z ² , Z ³ , n and X are as defined herein, and L is a direct bond and B ¹ is a substituted or unsubstituted oxiranyl ring, a substituted or unsubstituted thiophene ring, A substituted or unsubstituted benzothienyl ring, a substituted or unsubstituted furan ring or a substituted or unsubstituted benzofuran ring, with the limitation that (IIa) does not mean:

- N-[2-(2-furyl)benzyl]cyclopropylamine

- N-[2-(2-furyl)-4,5-dimethoxybenzyl]cyclopropylamine

- N-[2-(3-Bromo-2-furyl)-4,5-dimethoxybenzyl]cyclopropylamine

- N-[2-(3-Bromo-2-furyl)benzyl]cyclopropylamine

- N-[2-(3-furyl)benzyl]cyclopropylamine

- N-[2-(2-Thienyl)benzyl]cyclopropylamine

- N-[4,5-Dimethoxy-2-(2-thienyl)benzyl]cyclopropylamine.

Accordingly, the present invention provides a compound of formula (IIb) and an acceptable salt thereof:

Wherein Z ² , Z ³ , n and X are as defined herein, and L is a direct bond and B ¹ is a substituted or unsubstituted oxiranyl ring, a substituted or unsubstituted thiophene ring, A substituted or unsubstituted benzothienyl ring, a substituted or unsubstituted furan ring or a substituted or unsubstituted benzofuran ring, with the limitation that (IIb) does not mean:

- N-[3-(2-furyl)benzyl]cyclopropylamine

- N-[5-(2-furyl)-2-methoxybenzyl]cyclopropylamine

- N-[4-Fluoro-3-(2-furyl)benzyl]cyclopropylamine

- N-[2-Fluoro-5-(2-furyl)benzyl]cyclopropylamine

- N-[2-Fluoro-5-(3-furyl)benzyl]cyclopropylamine

- N-[3-(3-Bromo-2-furyl)-4-fluorobenzyl]cyclopropylamine

- N-[3-(3-Bromo-2-furyl)benzyl]cyclopropylamine

- N-[5-(3-Bromo-2-furyl)-2-fluorobenzyl]cyclopropylamine

- N-[5-(3-Bromo-2-furyl)-2-methoxybenzyl]cyclopropylamine

- N-[3-(3-furyl)benzyl]cyclopropylamine

- N-[3-(2-Thienyl)benzyl]cyclopropylamine

- N-[4-Fluoro-3-(2-thienyl)benzyl]cyclopropylamine

- N-[2-Fluoro-5-(2-thienyl)benzyl]cyclopropylamine

- N-[2-methoxy-5-(2-thienyl)benzyl]cyclopropylamine

5-{5-[(Cyclopropylamino)methyl]-2-fluorophenyl}thiophene-2-carbonitrile.

The N-cyclopropyl derivative of the formula (IIa) or the formula (IIb) can be produced according to a known method.

Preferably, the compound of formula (IIa) of the present invention is:

- N-[5-Chloro-2-(2-furyl)benzyl]cyclopropylamine

- N-[5-Chloro-2-(2-thienyl)benzyl]cyclopropylamine

- N-[2-(3-Thienyl)benzyl]cyclopropylamine

- N-{1-[2-(3-Thienyl)phenyl]ethyl}cyclopropylamine

- N-[5-Chloro-2-(3-thienyl)benzyl]cyclopropylamine

- N-[2-(5-Chloro-2-thienyl)benzyl]cyclopropylamine

- N-[5-Chloro-2-(5-chloro-2-thienyl)benzyl]cyclopropylamine.

Preferably, the compound of formula (IIb) of the present invention is:

- N-[2-chloro-5-(2-furyl)benzyl]cyclopropylamine

- N-[2-chloro-5-(2-thienyl)benzyl]cyclopropylamine

- N-[2-chloro-5-(3-thienyl)benzyl]cyclopropylamine

- N-[2-chloro-5-(5-chloro-2-thienyl)benzyl]cyclopropylamine.

In another aspect, the invention relates to a compound of formula (X) which is useful as an intermediate compound or substance in the process of the invention.

Accordingly, the present invention provides a compound of formula (Xa):

Wherein Z ² and Z ^{3 are} as defined herein, A represents A ¹³ , X ^a1 represents a halogen atom; substituted or unsubstituted C ₁ -C ₈ alkyl; contains up to 9 halogen atoms which may be the same or different. 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 unsubstituted C ₁ -C ₈ alkylthio, X ^a2 represents hydrogen or X ^a1 , and U ² represents a halogen atom such as chlorine, bromine or iodine or a triflate Base, whose constraint is (Xa) does not mean:

- N-(2,5-Dichlorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide

- N-[1-(2,5-Dichlorophenyl)ethyl]-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide

- N-[2-(2,5-Dichlorophenyl)propan-2-yl]-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamidine amine

- N-[1-(2,5-Dichlorophenyl)cyclopropyl]-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide

- 5-Chloro-N-[1-(2,5-dichlorophenyl)ethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide

- 5-Chloro-N-[2-(2,5-dichlorophenyl)propan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyridyl Oxazol-4-carboxamide

- 5-Chloro-N-[1-(2,5-dichlorophenyl)cyclopropyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide

- 5-Chloro-N-(2,5-dichlorobenzyl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide

- N-(5-Bromo-2-fluorobenzyl)-1,3,5-trimethyl-1H-pyrazole-4-carboxamide

- N-(5-bromo-2-fluorobenzyl)-3,5-dimethyl-1H-pyrazole-4-carboxamide

- 1-Methyl-N-[1-(2,4,5-trichlorophenyl)ethyl]-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide

- 3-(Difluoromethyl)-1-methyl-N-[1-(2,4,5-trichlorophenyl)ethyl]-1H-pyrazole-4-carboxamide

- N-(5-Chloro-2-fluorobenzyl)-1-methyl-5-propoxy-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide

- N-(2,5-Dichlorobenzyl)-1-methyl-5-propoxy-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide.

Preferably, the compound of formula (Xa) of the present invention is:

- N-(5-Chloro-2-ethylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide

- N-(5-Chloro-2-isopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide

- N-[5-Chloro-2-(trifluoromethyl)benzyl]-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide

- N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-methyl Guanamine.

The most preferred compound of the formula (Xa) of the present invention is:

- N-(5-Chloro-2-isopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide.

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

The expression "effective and non-phytotoxic amount" means an amount of the composition of the invention sufficient to control or destroy the fungus present or readily occurring on the crop without causing any significant phytotoxic symptoms of the crop. 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, such amounts may vary within wide limits. This amount can be determined by systematic field trials within the skill of 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 is combined or associated with an active compound of formula (I) to make it easier to apply, in particular to a plant part. Therefore, the carrier is generally inert and should be agriculturally acceptable. The carrier can be a solid or a liquid. Examples of suitable carriers include clay, natural or synthetic silicates, cerium oxide, resins, waxes, solid fertilizers, water, alcohols (especially butanol), organic solvents, mineral oils, 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, phenolsulfonic acids or naphthalenesulfonates, polyethylene oxides with fatty alcohols or polycondensates with fatty acids or with fatty amines, substituted phenols (especially alkylphenols) Or aryl phenol), a salt of a sulfonated succinate, a taurine derivative (especially an alkyl taurate), a polyoxyethylated alcohol or a phosphate of a phenol, a fatty acid ester of a polyhydric alcohol, and a sulfuric acid containing Derivatives of the above compounds having a salt, sulfonate and phosphate function. When the active compound and/or the inert carrier are insoluble in water and when the vector agent applied is water, it is generally necessary to have at least one surfactant. Preferably, the surfactant level can range from 5% to 40% by weight of the composition.

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

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

The compositions of the present invention can be used in a variety of forms and formulations, such as aerosol dispensers, capsule suspensions, cold mist concentrates, spreadable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, Encapsulated granules, fine granules, flowable concentrate for seed treatment, gas (under pressure), gas producing products, granules, hot mist concentrate, large granules, granules, oil dispersible powder, can be mixed with oil Dissolvable flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with insecticide, soluble concentrate, soluble powder, Solution for seed treatment, suspension concentrate (flowable concentrate), ultra low volume (ULV) liquid, ultra low volume (ULV) suspension, water dispersible granule or lozenge, water for slurry treatment Dispersible powder, water-soluble granules or troches, water-soluble powders for seed treatment, and wettable powders. Such compositions include not only compositions that are intended to be applied to the plant or seed to be treated by means of a suitable device, such as a spray or dusting device, but also a concentrated commercial composition that must be diluted prior to application to the crop.

Formulations may be prepared in a manner known per se, for example by mixing the active ingredient with at least one conventional extender, solvent or diluent, adjuvant, emulsifier, dispersant and/or binder or fixative, Wetting agents, water repellents, desiccants and UV stabilizers, and, where appropriate, dyes and pigments, defoamers, preservatives, inorganic and organic thickeners, adhesives, gibberellin and other processing aids And water. Depending on the type of formulation to be prepared, additional processing steps such as wet milling, dry milling and granulation are required.

The active ingredient of the present invention may be present as it is or in the form of its (commercial) formulation and The use of such formulations in the form of a mixture with other (known) active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, Fungicides, growth regulators, herbicides, fertilizers, safeners and/or semiochemicals.

The compounds of the formula (I) according to the invention and the fungicide compositions are useful for the phytopathogenic fungi for the therapeutic or prophylactic control of plants or crops.

According to another aspect of the present invention, there is provided a method for the therapeutic or prophylactic control of a phytopathogenic fungus of a plant or crop, characterized in that a compound of the formula (I) or a fungicide composition of the invention is applied to Seeds, plants or fruits applied to plants or applied to plants where plants are grown or where plants need to be grown.

The treatment method of the present invention can also be applied to the treatment of propagation material, such as tubers or rhizomes, as well as seeds, seedlings or transplanted seedlings and plants or transplanted plants. This processing method can also be applied to processing roots. The treatment method of the present invention can also be applied to the treatment of aerial parts of plants, such as the trunk, stem or stem, leaves, flowers and fruits of related plants.

According to the invention, all plants and plant parts can be treated. Plant means all plants and plant populations, such as wild plants, cultivars and plant varieties that are needed and undesirable (whether or not protected by the plant variety or the rights of the plant breeder). Cultivars and plant varieties may be plants obtained by conventional breeding and breeding methods, which may be supplemented or supplemented by one or more biotechnological methods, such as by using double haploid, protoplast fusion, random And directed mutation induction, molecular or genetic markers or by bioengineering and genetic engineering methods. Plant parts mean all above-ground and underground parts and organs of plants, such as buds, leaves, flowers and roots, such as leaves, needles, stems, branches, flowers, fruit bodies, fruits and seeds, as well as roots, bulbs and rhizomes. . Crops as well as vegetative and sexually propagated materials (such as cuttings, bulbs, rhizomes, long stalks and seeds) are also part of the plant.

Among the plants which can be protected by the method of the invention, mention may be made of major field crops such as corn, soybean, cotton, and kale oilseeds (such as Brassica napus (for example, mustard), phthalocyanine ( Brassis rapa ), Brassica ( B.juncea ) (such as mustard) and Brassica carinata (), rice, wheat, sugar beet, sugar cane, oats, rye, barley, millet, triticale, flax, vine and various plants A variety of fruits and vegetables, such as Rosaceae sp. (such as pome fruit, such as apples and pears; and stone fruit, such as apricots, cherries, almonds, and peaches; berry fruits, such as strawberries) ), Ribesioidae sp. , Juglandaceae sp. , Betulaceae sp. , Anacardiaceae sp. , Fagaceae sp. , Moraceae sp. , Oleaceae sp. , Actinidaceae sp. , Lauraceae sp. , Musaceae sp. (eg banana tree and planting) Lin), Rubiaceae sp. ( Rubiaceae sp. (eg coffee), Theaceae sp. , Sterculiceae sp. , Rutaceae sp. (eg lemon, citrus and grapefruit); Solanaceae sp. (eg tomato, potato, pepper, eggplant), Liliaceae sp. , Compositiae sp. (eg lettuce, artichoke and chicory, including root chicory, chicory or common chicory), umbrella Umbelliferae sp. (eg carrot, parsley, celery and root celery), Cucurbitaceae sp. (eg cucumber (including pickled cucumber), pumpkin, watermelon, gourd and melon), onion species ( Alliaceae sp.) (such as onion and leeks), Cruciferae sp. (such as white cabbage, red cabbage, broccoli, broccoli, Brussels sprouts, cabbage, broccoli, radish, horseradish, water Parsley, Chinese cabbage, Leguminosae sp. (such as peanuts, peas and beans, beans such as vine and broad beans), Chenopodiaceae sp. (eg fodder beet, leaf beet, spinach, beetroot) ), Malvaceae (Malvaceae) (such as okra), aspartate (Asparagaceae) (e.g. asparagus); horticultural and forest crops; ornamental plants; and such genetically modified crops of the homologs.

The treatment methods of the invention can be used to treat genetically modified organisms (GMOs), such as plants or seeds. Genetically modified plants (or transgenic plants) have been stabilized as heterologous genes A plant integrated into the genome. The expression "heterologous gene" basically means providing or assembling outside the plant and when introduced into the nucleus, chloroplast or mitochondrial genome by expressing a related protein or polypeptide or by using, for example, antisense technology, cosuppression technology or RNA interference -RNAi technology) A gene that down-regulates or silences other genes present in a plant to confer novel or improved agronomic or other properties to the transformed plant. A heterologous gene located in the genome is also referred to as a transgenic gene. A transgene that is defined by its specific location in the plant genome is referred to as a transformation or transgenic event.

The treatment of the present invention may also produce a superadditive ("synergistic") effect depending on the plant species or plant cultivar, its location and growth conditions (soil, climate, nutrient period, foodstuff). Thus, for example, it is possible to achieve a reduction in the amount of application and/or broadening of the range of activity and/or enhanced activity of the active compounds and compositions which can be used according to the invention, better plant growth, enhanced tolerance to high or low temperatures. Tolerance to drought or water or soil salt content, enhanced flowering efficiency, easier harvesting, accelerated maturation, higher harvest yield, larger fruit, higher plant height, greener leaf color, early flowering, harvest The product has higher quality and/or higher nutritional value, higher sugar concentration in the fruit, better storage stability and/or processability of the harvested product, and these effects exceed the actual expected effect.

The active compound combination of the invention may also have a potentiating effect in plants at a particular application rate. Therefore, it is also suitable for mobilizing plant defense systems against the invasion of inappropriate microorganisms. This may be one of the reasons for the enhanced activity of the combination of the invention, for example against fungi, where appropriate. In the context of the present invention, a plant-enhancing (resistance-inducing) substance is understood to mean a substance or combination of substances capable of stimulating a plant's defense system in such a way that when subsequently inoculated with an inappropriate microorganism, the treated plant shows a pair These microorganisms are substantially resistant to the extent. In the context of the present invention, an inappropriate microorganism is understood to mean a phytopathogenic fungus, a bacterium and a virus. Thus, the materials of the invention can be used to protect plants from attack by the aforementioned pathogens for a certain period of time after treatment. The period of time to achieve protection is generally extended from one day to ten days after the treatment of the active compound by the plant, preferably from one day to seven days.

Plants and plant cultivars which are preferably treated according to the invention include all plants (whether obtained by breeding and/or biotechnological means) having genetic material which confers particularly advantageous and useful traits on such plants.

It is also preferred that the plants and plant cultivars treated in accordance with the present invention are resistant to one or more biological stresses, that is, the plants exhibit animal and microbial pests (such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, Better defense against viruses and/or viruses.

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 plants which are resistant to one or more abiotic stresses. Abiotic stress conditions can include, for example, drought, low temperature exposure, heat exposure, osmotic pressure, flooding, high soil salinity, high mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, and shade avoidance .

Plants and plant cultivars which may also be treated according to the invention are characterized by their plants having improved yield characteristics. Increases in the yield of such plants can be the result, for example, of improved plant physiology, growth and development (such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthetic synthesis, increased germination efficiency, and accelerated maturation). In addition, yield can be affected by improved plant line types (under stress and non-stress conditions), including (but not limited to) early flowering, flowering control of hybrid seed production, seedling vigor, plant size, internode number and distance Root growth, seed size, fruit size, pod size, number of pods or ears, number of seeds per pod or ear, seed quality, higher seed filling, lower seed Dispersion, lower pod cracking, and lodging resistance. Other yield traits include seed composition such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability, and better storage stability.

Examples of plants having the above traits are not listed in detail in Table A.

Plants which can be treated according to the invention are hybrid plants which have exhibited heterosis or hybrid viability characteristics which generally result in higher yield, vigor, health and resistance to biotic and abiotic stresses. Such plants are usually produced by crossing a male sterile male parental line (parent) of another inbreeding with a male fertile parental line (parent) of another close relative. Hybrid seeds are typically harvested from male sterile plants and sold to growers. Male sterile plants are sometimes produced (eg, in corn) from emasculated spikes (ie, mechanically removed male reproductive organs (or male flowers)), but male sterility is more often the result of genetic determinants in the plant genome. In this case, and especially when the seed is the desired product harvested from the hybrid plant, it is generally useful to ensure that the male fertility of the hybrid plant is fully restored. This can be achieved by ensuring that the male parents have appropriate fertility restorer genes that are capable of restoring the male fertility of the hybrid plants containing the genetic determinants responsible for male sterility. The genetic determinant of male sterility can be located in the cytoplasm. Examples of cytoplasmic male sterility (CMS) are described, for example, in the genus Amaranthus (WO 92/05251, WO 95/09910, WO 98/27806, WO 05/002324, WO 06/021972 and US 6,229,072). However, the genetic determinant of male sterility 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 way of obtaining male sterile plants is described in WO 89/10396, wherein, for example, ribonuclease (such as barnase) is selectively expressed in the stapum cells of the stamens. Fertility can then be restored by expressing a ribonuclease inhibitor such as barstar in the tapetum cells (e.g., WO 91/02069).

Plants or plant cultivars (obtained by plant biotechnology methods (such as genetic engineering)) which can be treated according to the invention are herbicide tolerant plants, i.e. plants which are tolerant to one or more established herbicides. Such plants may be conferred by genetic transformation or by selection This herbicide tolerance is obtained by mutating plants.

Herbicide-tolerant plants are, for example, glyphosate-tolerant plants, i.e. plants which are tolerant to the herbicide glyphosate or a salt thereof. Plants can be tolerant to glyphosate in different ways. For example, a glyphosate resistant plant can be obtained by transforming a plant with a gene encoding 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene of Salmonella typhimurium (mutant CT7) (Comai et al., 1983, Science 221, 370-371), and the CP4 gene of Agrobacterium sp. (Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), encoding Petunia EPSPS (Shah et al., 1986, Science 233, 478-481), tomato EPSPS (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289) or the gene of Eleusine EPSPS (WO 01/66704). It can also be a mutant EPSPS as described in, for example, EP 0837944, WO 00/66746, WO 00/66747 or WO 02/26995. 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 the expression of a gene encoding a glyphosate acetyltransferase, as described 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 mutations of the above genes, for example as described 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, and 11/312,866. Nos. 11/315,678, 12/421,292, 11/400,598, 11/651,752, 11/681,285, 11/605,824, 12/468,205, 11/760,570, 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 in, for example, U.S. Patent Application Serial Nos. 11/588,811, 11/185,342, 12/364,724, 11/185,560, or 12/423,926.

Other herbicide resistant plants are, for example, plants which are tolerant to herbicides which inhibit branylamine synthase, such as bialaphos, phosphinothricin or glufosinate. Such plants can be obtained by expressing an enzyme which detoxifies the herbicide or a mutant glutamate synthase which is resistant to inhibition, as described in U.S. Patent Application Serial No. 11/760,602. One such effective detoxifying enzyme is an enzyme encoding a glufosinate acetyltransferase (such as a bar or pat protein of a Streptomy species). Plants which exhibit exogenous phosphinothricin acetyltransferase are 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 No. 7,112,665.

Other herbicide tolerant plants are also plants which are tolerant to herbicides which inhibit hydroxyphenylpyruvate dioxygenase (HPPD). Hydroxyphenylpyruvate dioxygenase is an enzyme that catalyzes the conversion of p-hydroxyphenylpyruvate (HPP) to homogentisate. Plants that are tolerant 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, as described in 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, tolerance to HPPD inhibitors can also be obtained by transforming plants with genes encoding certain enzymes that enable the formation of homogentisate. Such plants and genes are described in WO 99/34008 and WO 02/36787. Plant tolerance to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme having prephenate dehydrogenase (PDH) activity plus a gene encoding a HPPD-resistant enzyme, as in WO 2004/024928 Said. In addition, plants can be weeded against HPPD inhibitors by adding genes encoding enzymes capable of metabolizing or degrading HPPD inhibitors, such as the CYP450 enzymes shown in WO 2007/103567 and WO 2008/150473, to the plant genome. The agent is more tolerant.

Other herbicide resistant plants are plants that are tolerant to acetate lactate synthase (ALS) inhibitors. ALS inhibitors are known to include, for example, sulfonylurea, imidazolinone, triazolopyrimidine, pyrimidinyloxy(thio)benzoate and/or sulfonylaminocarbonyltriazolinone herbicide. Known ALS Different mutations of the enzyme (also known as acetamidine hydroxyacid synthase, AHAS) confer tolerance to different herbicide and herbicide groups, such as, for example, Tranel and Wright (2002, Weed Science 50: 700-712) and in the United States. Patent Nos. 5,605,011, 5,378,824, 5,141,870 and 5,013,659. The sulphate-resistant urethrazole plant and the imidazolinone-resistant plant are described in U.S. Patent Nos. 5,605,011, 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 imidazolinone-resistant plants are also described in, for example, 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 . Other sulfonylurea-resistant and imidazolinone-resistant plants are also described in, for example, WO 07/024782 and U.S. Patent Application Serial No. 61/288,958.

Other plants that are tolerant to imidazolinones and/or sulfonylureas can be obtained by induction of mutations, selection in cell culture in the presence of herbicides, or mutation breeding, such as, for example, US patents on soybeans. 5, 084, 082, WO 97/41218 to rice, U.S. Patent No. 5,773,702, to WO 99/057965, to U.S. Pat.

Plants or plant cultivars (obtained by genetic engineering engineering plant biotechnology methods) which can also be treated according to the invention are plants which are resistant to insect transfer genes, i.e. plants which are resistant to attack by certain target insects. Such plants can be obtained by genetic transformation or by selection of plants containing mutations conferring such insect resistance.

An "insect-resistant transgenic plant" as used herein includes any plant comprising at least one transgene comprising a coding sequence encoding:

1) Insecticidally crystalline proteins from Bacillus thuringiensis or insecticidal fractions thereof, such as those listed by Crickmore et al. (1998, Microbiology and Molecular Biology Reviews, 62: 807-813) and by Crickmore et al. (2005) An insecticidal crystal protein or an insecticidal part thereof, such as the Cry protein class Cry1Ab, which is updated in the B. thuringiensis nomenclature (online: http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/) , 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 U.S. Patent Application Serial No. 12/ As described in 249,016; or

2) a crystal protein or a part thereof from Bacillus thuringiensis which is insecticidal in the presence of a second other crystal protein or a part thereof from Bacillus thuringiensis, such as a binary toxin composed of Cry34 and Cry35 crystal proteins (Moellenbeck et al. 2001). , Nat. Biotechnol. 19: 668-72; Schnepf et al. 2006, Applied Environm. Microbiol. 71, 1765-1774) or a binary toxin consisting of Cry1A or Cry1F protein and Cry2Aa or Cry2Ab or Cry2Ae protein (US Patent Application) 12/214,022 and EP 08010791.5); or

3) a hybrid insecticidal protein comprising a portion of a different insecticidal crystal protein from Bacillus thuringiensis, such as a hybrid of the protein of 1) above or a hybrid of the protein of 2) above, such as the Cry1A.105 protein produced by the corn event MON98034 (WO 2007/027777); or

4) The protein of any one of the above 1) to 3), wherein some (especially 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 this is due to changes introduced into the coding DNA during selection or transformation, such as the Cry3Bb1 protein in maize event MON863 or MON88017, or the Cry3A protein in maize event MIR604;

5) Insect-secreting proteins or insecticidal parts from Bacillus thuringiensis or Bacillus cereus , such as http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html a vegetative insecticidal (VIP) protein, such as a protein from the VIP3Aa protein class; or

6) a secreted protein from Bacillus thuringiensis or Cactus bacillus, which is insecticidal in the presence of a second secreted protein from Bacillus thuringiensis or Cactus bacillus, such as a binary toxin composed of VIP1A and VIP2A proteins (WO 94/21795); or

7) a hybrid insecticidal protein comprising a portion derived from a different secreted protein of Bacillus thuringiensis or Cactus, such as a hybrid of the proteins of 1) above or a hybrid of the proteins of 2) above;

8) The protein of any of the above 5) to 7), wherein some (especially 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 this is due to changes in the coding DNA introduced during selection or transformation (while still encoding insecticidal proteins), such as the VIP3Aa protein in cotton event COT102; or

9) a secreted protein from Bacillus thuringiensis or Cactus bacterium, which is insecticidal in the presence of a crystal protein from Bacillus thuringiensis, such as a binary toxin composed of VIP3 and Cry1A or Cry1F (US Patent Application No. 61/126083 and No. 61/195019), or a binary toxin composed 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 (especially 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 The scope, and/or this is due to the introduction of changes in the coding DNA during selection or transformation (while still encoding insecticidal proteins).

Of course, an insect-resistant transgenic plant as used herein 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 contains more than one transgene encoding a protein of any of the above categories 1 to 10 to expand upon the use of different proteins for different target insect species Delaying the insect resistance of plants by affecting the range of target insect species, or by using different proteins that are insecticidal to the same target insect species but have different modes of action, such as different receptor binding sites that bind to insects. development of.

An "insect-resistant transgenic plant" as used herein additionally includes any plant comprising at least one of a transgenic gene comprising a sequence which produces a double-stranded RNA (which inhibits the growth of the pest when ingested by a plant pest). It is described, for example, in WO 2007/080126, WO 2006/129204, WO 2007/074405, WO 2007/080127 and WO 2007/035650.

Plants or plant cultivars (obtained by genetically engineered plant biotechnology methods) that are also treated according to the invention are also tolerant to abiotic stresses. Such plants can be obtained by genetic transformation or by selection of plants containing mutations conferring such resistance to stress. Particularly suitable pressure-resistant plants include:

1) Plants containing a transgenic gene capable of reducing 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 as described in EP 06009836.5.

2) A plant comprising a stress-tolerant transgenic gene capable of reducing 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 (including nicotinamide, nicotinic acid phosphoribosyltransferase, nicotinic acid mononucleotide adenosine transferase, containing a nicotine indoleamine adenine dinucleotide rescue synthesis pathway, Plants that are resistant to stress-enhancing transgenic genes, such as, for example, EP 04077624.7, WO 2006/133827, PCT/EP07/002433, EP, of nicotine indoleamine adenine dinucleotide synthase or nicotine indole phosphoribosyltransferase) Said in 1999263 or WO 2007/107326.

Plants or plant cultivars (obtained by genetically engineered plant biotechnology methods) which can also be treated according to the invention show the quantity, quality and/or storage of harvested products Changes in the stability of the storage and/or changes in the characteristics of the specific components of the harvested product, such as:

1) Synthetic modified starch transgenic plant having physical and chemical characteristics (especially amylose content or amylose/amylopectin ratio, compared with synthetic starch in wild type plant cells or plants, The degree of branching, average chain length, side chain distribution, viscosity behavior, gel strength, starch particle size, and/or starch particle morphology are altered to make it more suitable for a particular application. Transgenic plants of such synthetically modified starches are 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 94/04693, WO 94/09144, WO 94/11520, WO 95/35026, WO 97/20936.

2) Synthesis of non-starch carbohydrate polymers or synthetic and non-genetically modified wild-type plants A transgenic plant of a non-starch carbohydrate polymer having altered properties compared to a compound. Examples are plants which produce polyfructose, in particular inulin and polydextrose-type polyfructose, as disclosed in EP 0 663 956, WO 96/01904, WO 96/21023, WO 98/39460 and WO 99/24593; a plant of 1,4-glucan, 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; A plant having an alpha-1,6 branched alpha-1,4-glucan, as disclosed in WO 00/73422; a plant producing a cyclical tetrasaccharide, such as, for example, WO 00/47727, WO 00/73422 , as disclosed in EP 06077301.7, US 5,908,975 and EP 0728213.

3) A transgenic plant that produces 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) a transgenic plant or a hybrid plant, such as an onion having characteristics such as "highly soluble solid content", "low irritancy" (LP) and/or "long shelf life" (LS), such as US Patent Application No. As described in 12/020,360 and 61/054,026.

Plants or plant cultivars (which may be obtained by genetic engineering engineering plant biotechnology methods) which may also be treated according to the invention are plants having altered fiber characteristics, such as cotton plants. Such plants can be obtained by genetic transformation or by selecting plants containing mutations that confer such altered fiber characteristics, and such plants include:

a) A plant containing an altered form of the cellulase synthase gene, such as a cotton plant, as described in WO 98/00549.

b) Plants containing altered forms of rsw2 or rsw3 homologous nucleic acids, such as cotton plants, as described in WO 2004/053219.

c) Plants with increased expression of sucrose phosphate synthase, such as cotton plants, as described in WO 01/17333.

d) plants with increased expression of sucrose synthase, such as cotton plants, such as WO Said in 02/45485.

e) a plant in which the timing of fibroblast-based intercellular filament gating is changed, for example, by a fiber-selective β-1,3-glucanase down-regulation, such as a cotton plant, as described in WO 2005/017157 or as EP 08075514.3 or U.S. Patent Application Serial No. 61/128,938.

f) A plant having, for example, a fiber which undergoes a change in reactivity by the performance of an N-acetylglucosamine transferase gene (including the nodC and chitin synthase genes), as described in WO 2006/136351.

Plants or plant cultivars (which may be obtained by genetic engineering engineering plant biotechnology methods) which are also treated according to the invention are plants which have altered oil profile, such as oilseed rape or related genus plant. Such plants can be obtained by genetic transformation or by selection of plants containing mutations that confer such altered oil profile characteristics, and such plants include:

a) A plant which produces an oil having a high oleic acid content, such as a sorghum plant, as described in, for example, US 5,969,169, US 5,840,946 or US 6,323,392 or US 6,063,947.

b) A plant which produces an oil having a low linoleic acid content, such as a sorghum plant, as described in US 6,270,828, US 6,169,190 or US 5,965,755.

c) A plant which produces an oil having a low content of a saturated fatty acid, such as a sorghum 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 (which may be obtained by plant biotechnological methods such as genetic engineering) which may also be treated according to the invention are plants which have altered granulating characteristics, such as mites or related genus. Such plants may be obtained by genetic transformation or by selection of plants containing mutations conferring the altered shattering characteristics of such alterations, and such plants include plants such as plants having delayed or reduced shredding properties, It is described in U.S. Patent Application Serial No. 61/135,230, WO 09/068313, and WO 10/006732.

A particularly suitable transgenic plant that can be treated in accordance with the present invention is a plant containing a combination of transformation events or transformation events, which is the United States Department of Agriculture (United States) Department of Agriculture; USDA) The subject matter of the non-regulated status of the Animal and Plant Health Inspection Service (APHIS), whether or not such application is authorized or still pending. This information is readily available from APHIS (4700 River Road Riverdale, MD20737, USA) at any time, for example on its Internet site (URL http://www.aphis.usda.gov/brs/not_reg.html) . On the filing date of this application, the application for non-regulated status with APHIS or authorized by APHIS is the application listed in Table B, which contains the following information:

- Application: The identification number of the application. A technical description of the conversion event can be found in the individual application documents, which can be obtained from APHIS, for example on the APHIS website. These descriptions are incorporated herein by reference.

- Extension of the application: Refer to the request to extend the previous application.

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

- Controlled items: related plant species.

- Transgenic gene phenotype: a trait that is imparted to a plant by a transformation event.

- Conversion event or line: The name of an event (sometimes called a line) that requires an unregulated state.

- APHIS documents: Various documents disclosed by APHIS related to the application, and which are subject to APHIS requirements.

Other particularly suitable plants containing a single conversion event or combination of conversion events are listed, for example, in a database of regulatory agencies in various countries or regions (see for example http://gmoinfo.jrc.it/gmp_browse.aspx and http://www. Agbios.com/dbase.php).

Plants that are particularly suitable for treatment according to the present invention are plants containing a combination of transformation events or transformation events, and are listed, for example, in a database of regulatory agencies of various countries or regions, including event 1143-14A (cotton, insect control). , not registered, described in WO 2006/128569); event 1143-51B (cotton, insect control, unregistered, described in WO 2006/128570); event 1445 (cotton, herbicide tolerant, unregistered, described in US-A 2002-120964 or WO 02/034946); event 17053 (rice, herbicide tolerant, deposited as PTA-9843, Described in WO 2010/117737); event 17314 (rice, herbicide tolerant, deposited as PTA-9844, described in WO 2010/117735); event 281-24-236 (cotton, insect control - herbicide tolerant, deposited Is PTA-6233, described in WO 2005/103266 or US-A 2005-216969); Event 3006-210-23 (cotton, insect control - herbicide tolerant, deposited as PTA-6233, described in US-A 2007- 143876 or WO 2005/103266); event 3272 (corn, quality traits, deposited as PTA-9972, described in WO 2006/098952 or US-A 2006-230473); event 40416 (corn, insect control - herbicide tolerant) , registered as ATCC PTA-11508, described in WO 2011/075593); event 43A47 (corn, insect control - herbicide tolerant, deposited as ATCC PTA-11509, described in WO 2011/075595); event 5307 (corn, Insect control, deposited as ATCC PTA-9561, described in WO 2010/077816); Event ASR-368 (bent grass, herbicide tolerant, deposited as ATCC PTA-4816, described in US-A 2006-162007 or WO 2004/053062); Event B16 (corn, herbicide tolerant, not deposited, described in US-A 2003-126634); Event BPS-CV127-9 (Soybean, herbicide tolerant, deposited as NCIMB 41603, described in WO 2010/080829); Event CE43-67B (cotton, insect control, deposited as DSM ACC2724, as described in US-A 2009-217423 or WO2006/128573 Event CE44-69D (cotton, insect control, unregistered, described in US-A 2010-0024077); event CE44-69D (cotton, insect control, unregistered, described in WO 2006/128571); event CE46 -02A (cotton, insect control, unregistered, described in WO 2006/128572); event COT 102 (cotton, insect control, unregistered, described in US-A 2006-130175 or WO 2004/039986); event COT202 ( Cotton, insect control, unregistered, described in US-A 2007-067868 or WO 2005/054479); event COT203 (cotton, insect control, unregistered, described in WO 2005/054480); event DAS 40278 (corn, Herbicide tolerant, deposited as ATCC PTA-10244, described in WO 2011/022469); Event DAS-59122-7 (corn, insect control - herbicide tolerant, deposited as ATCC PTA 11384, described in US-A 2006-070139 Event) DAS-59132 (corn, insect control - herbicide tolerant, not deposited, as described in WO 2009/100188); event DAS68416 (soybean, herbicide tolerant, deposited as ATCC PTA-10442, described in WO 2011/ 066384 or WO 2011/066360); event DP-098140-6 (corn, herbicide tolerant, deposited as ATCC PTA-8296, as described in US-A 2009-137395 or WO 2008/112019); event DP-305423- 1 (soybean, quality traits, not deposited, as described in US-A 2008-312082 or WO 2008/054747); event DP-32138-1 (corn, hybrid system, deposited as ATCC PTA-9158, described in US-A 2009-0210970 or WO 2009/103049); event DP-356043-5 (soybean, herbicide tolerant, deposited as ATCC PTA-8287, described in US-A 2010-0184079 or WO 2008/002872); event EE- 1 (eggplant, insect control, unregistered, described in WO 2007/091277); event FI117 (corn, herbicide tolerant, deposited as ATCC 209031, described in US-A 2006-05 Event 921 or WO 98/044140); event GA21 (corn, herbicide tolerant, deposited as ATCC 209033, described in US-A 2005-086719 or WO 98/044140); event GG25 (corn, herbicide tolerant, deposited as ATCC 209032, described in US-A 2005-188434 or WO 98/044140); event GHB119 (cotton, insect control - herbicide tolerant, deposited as ATCC PTA-8398, described in WO 2008/151780); event GHB614 ( Cotton, herbicide tolerant, deposited as ATCC PTA-6878, as described in US-A 2010-050282 or WO 2007/017186); Event GJ11 (corn, herbicide tolerant, deposited as ATCC 209030, described in US-A 2005- 188434 or WO 98/044140); event GM RZ13 (beet, anti-viral, deposited as NCIMB-41601, described in WO 2010/076212); event H7-1 (beet, herbicide tolerant, deposited as NCIMB 41158 or NCIMB 41159, described in US-A 2004-172669 or WO 2004/074492); event JOPLIN1 (wheat, disease-resistant, unregistered, described in US-A 2008-064032 Event LL27 (soybean, herbicide tolerant, deposited as NCIMB 41658, described in WO 2006/108674 or US-A 2008-320616); event LL55 (soybean, herbicide tolerant, deposited as NCIMB 41660, described in WO 2006 /108675 or US-A 2008-196127); event LLcotton 25 (cotton, herbicide tolerant, deposited as ATCC PTA-3343, described in WO 03/013224 or US-A 2003-097687); event LLRICE06 (rice, resistant Herbicide, deposited as ATCC-23352, described in US 6,468,747 or WO 00/026345); Event LLRICE 601 (rice, herbicide tolerant, deposited as ATCC PTA-2600, as described in US-A 2008-2289060 or WO 00/026356 Event LY038 (corn, quality traits, deposited as ATCC PTA-5623, described in US-A 2007-028322 or WO 2005/061720); event MIR162 (corn, insect control, deposited as PTA-8166, described in US-A 2009-300784 or WO 2007/142840); event MIR604 (corn, insect control, unregistered, described in US-A 2008-167456 or WO 2005/103301); event MON15985 (cotton, insect control, deposit) For ATCC PTA-2516, described in US-A 2004-250317 or WO 02/100163); event MON810 (corn, Kun Insect control, not registered, described in US-A 2002-102582); event MON863 (corn, insect control, deposited as ATCC PTA-2605, described in WO 2004/011601 or US-A 2006-095986); event MON87427 (Maize, pollination control, deposited as ATCC PTA-7899, described in WO 2011/062904); Event MON87460 (corn, stress resistant, deposited as ATCC PTA-8910, as described in WO 2009/111263 or US-A 2011-0138504 Event) MON87701 (soybean, insect control, deposited as ATCC PTA-8194, described in US-A 2009-130071 or WO 2009/064652); event MON87705 (soybean, quality traits - herbicide tolerant, deposited as ATCC PTA -9241, described in US-A 2010-0080887 or WO 2010/037016); event MON87708 (soybean, herbicide tolerant, deposited as ATCC PTA9670, described in WO 2011/034704); event MON87754 (soybean, quality trait, Deposited as ATCC PTA-9385, described in WO 2010/024976); Event MON87769 (soybean, quality traits, deposited as ATCC PTA-8911, described in US-A 2011-0067141 or WO 2009/102873); event MON88017 (corn, insect control - herbicide tolerant, deposited as ATCC PTA-5582, described in US-A 2008-028482 or WO 2005/059103); event MON88913 (cotton, herbicide tolerant, deposited as ATCC PTA-4854, described in WO 2004/072235 or US-A 2006-059590); event MON89034 (corn, insect control, deposited as ATCC PTA) -7455, described in WO 2007/140256 or US-A 2008-260932); event MON89788 (soybean, herbicide tolerant, deposited as ATCC PTA-6708, as described in US-A 2006-282915 or WO 2006/130436) Event MS11 (芸薹, pollination control - herbicide tolerant, deposited as ATCC PTA-850 or PTA-2485, described in WO 01/031042); event MS8 (芸薹, pollination control - herbicide tolerant, deposited as ATCC) PTA-730, described in WO 01/041558 or US-A 2003-188347); event NK603 (corn, herbicide tolerant, deposited as ATCC PTA-2478, described in US-A 2007-292854); event PE- 7 (rice, insect control, unregistered, described in WO 2008/114282); event RF3 (芸薹, pollination control - herbicide tolerant, deposited as ATCC PTA-730 Described in WO 01/041558 or US-A 2003-188347); event RT73 (芸薹, herbicide tolerant, not registered, described in WO 02/036831 or US-A 2008-070260); event T227-1 ( Beet, herbicide tolerant, not deposited, as described in WO 02/44407 or US-A 2009-265817; Event T25 (corn, herbicide tolerant, not deposited, as described in US-A 2001-029014 or WO 01/051654 Medium); Event T304-40 (cotton, insect control - herbicide tolerant, deposited as ATCC PTA-8171, described in US-A 2010-077501 or WO 2008/122406); event T342-142 (cotton, insect control, Unregistered, described in WO 2006/128568); Event TC1507 (corn, insect control - herbicide tolerant, not deposited, as described in US-A 2005-039226 or WO 2004/099447); event VIP1034 (corn, insect control) - herbicide tolerant, deposited as ATCC PTA-3925., described in WO 03/052073); event 32316 (corn, insect control - herbicide tolerant, deposited as PTA-11507, described in WO 2011/084632); Section 4114 (corn, insect control - herbicide tolerant, registered as PTA-11506, described in WO 2011/084621).

Among the plant or crop diseases which can be controlled by the method of the invention, mention may be made of: powdery mildew disease, such as, for example, Blumeria disease caused by Blumeria graminis ; for example Podosphaera disease caused by Podosphaera leucotricha ; for example, Sphaerotheca disease caused by Sphaerotheca fuliginea ; for example, by grape powdery mildew ( Uncinula disease caused by Uncinula necator ; rust disease such as, for example, Gymnosporangium disease caused by Gymnosporangium sabinae ; for example, Hemileia "Hamatiaia disease" caused by vastatrix ; for example, Phakopsora pachyrhizi or Phakopsora meibomiae caused by Phakopsora disease; for example, Puccinia serrata ( Puccinia recondite ), Puccinia graminis or Puccinia striiformi s ) caused by Puccinia disease; for example, Uromyces disease caused by Uromyces appendiculatus ; oomycete disease, such as, for example, white rust ( Albugo) Albugo disease caused by candida ; for example, Bremia disease caused by Bremia lactucae ; for example, by Peony downy mildew ( Peronospora pisi ) or Rhizoctonia solani ( P. brassicae) Peronospora disease; for example, Phytophthora disease caused by Phytophthora infestans ; for example, Plasmopara caused by Plasmopara viticola ( Plasmopara ) Disease; for example, Pseudoperonospora disease caused by Pseudoperonospora humuli or Pseudoperonospora cubensis ; for example, Pythium caused by Pythium ultimum (Pythium) Disease); leaf spot disease, leaf blotch disease, and leaf blight disease, such as: As indicated by Alternaria solani (Alternaria solani) causes the tenuis disease (Alternaria disease); for example, due to the beet Cercospora (Cercospora beticola) Cercospora disease (Cercospora disease); for example cucumerinum ( Cladiosporum cucumerinum caused by Cladiosporum disease; for example, Cochliobolus sativus (Conidiaform): Drechslera, synonym: Helminthosporium Helminthosporium)) or Cochliobolus disease caused by Cochliobolus miyabeanus ; for example, Colletotrichum disease caused by Colletotrichum lindemuthanium ; for example, from olive oil peafew Cycloconium disease caused by Cycloconium oleaginum; for example, Diaporthe disease caused by Diaporthe citri ; for example, sac caused by Elsinoe fawcettii Elsinoe disease; for example, anthracnose caused by Gloeosporium laeticolor ( Gloeospo ) Rium disease); for example, Glomerella disease caused by Glomerella cingulata ; for example, Guignardia disease caused by Guignardia bidwelli ; for example, from cruciferae Leptosphaeria maculans , Leptosphaeria disease caused by Leptosphaeria nodorum ; for example, Magnaporthe disease caused by Magnaporthe grisea ; For example, Mycosphaerella graminicola , Mycosphaerella arachidicola, Mycosphaerella fijiensis , Mycosphaerella disease; for example, caused by Phaeosphaeria nodorum the glume blotch (Phaeosphaeria disease); for example, due to of a Pyrenophora teres (Pyrenophora teres), or Agropyron Pyrenophora (Pyrenophora tritici repentis) Pyrenophora diseases (Pyrenophora disease); for example Kele Greek RAMULARIA bacteria ( Ramularia collocygni ) or sclerotia caused by Ramularia areola (Ramular Ia disease); for example, Rhynchosporium disease caused by Rhynchosporium secalis ; for example, a shell needle caused by Septoria apii or Septoria lycopercisi Septoria disease; for example, gray rot (Typhula disease) caused by Typhula incarnata ; for example, Venturia disease caused by Venturia inaequalis ; root , sheath and stem stem diseases, such as, for example, Corticium disease caused by Corticium graminearum ; for example, Fusarium caused by Fusarium oxysporum (Fusarium) Disease; for example, Gaeumannomyces disease caused by Gaeumannomyces graminis ; for example Rhizoctonia disease caused by Rhizoctonia solani ; for example, from rice Sarocladium disease caused by Sarocladium oryzae ; for example, Sclerotinia dung caused by Sclerotium oryzae (Sclerotium d) isease); e.g. caused by a needle's eye Vexans (Tapesia acuformis) eyespot (Tapesia disease); for example, due to the tobacco root rot (Thielaviopsis basicola) root rot (Thielaviopsis disease); panicle and panicle diseases, For example: Alternaria spp. caused by Alternaria spp .; for example Aspergillus disease caused by Aspergillus flavus ; for example caused by Cladosporium spp. Cladosporium mold (Cladosporium disease); for example ergot (Claviceps purpurea) Claviceps diseases (Claviceps disease) caused by the; e.g. from yellow Fusarium (Fusarium culmorum) strain of Fusarium diseases caused; for example Gibberella Gibberella zeae caused by Gibberella disease; for example, Monographella disease caused by Monographella nivalis ; smut disease and black smut disease (bunt disease), such as: for example, caused by a wire sorghum smut fungi (Sphacelotheca reiliana) of Head smut (Sphacelotheca disease); for example, a net wheat Tilletia Bacteria (Tilletia caries) causing the bunt (Tilletia disease); for example, due to the straw from the black smut (Urocystis occulta) smut (Urocystis disease); for example, Ustilago from barley (Ustilago nuda) caused Ustilago disease; fruit rot disease and mould disease such as, for example, aspergillosis caused by Aspergillus flavus; for example, gray mold caused by Botrytis cinerea Botrytis disease; for example, Penicillium disease caused by Penicillium expansum ; for example, Rhizopus disease caused by Rhizopus stolonifer ; for example, Sclerotinia sclerotiorum) Sclerotinia sclerotiorum causes of disease (Sclerotinia disease); for example Verticillium sp (Verticilium alboatrum) causes the Verticillium disease (Verticilium disease); rot and seed with the soil, mold, wilt, blight and damping-off diseases: for example, due to the strain of Alternaria brassicae (Alternaria brassicicola) tenuis disease; for example, a pea Aphanomyces primers (Aphanomyces euteiches) The nematocysts mildew (Aphanomyces disease); for example, due to of a lentil Ascochyta (Ascochyta lentis) disease Ascochyta (Ascochyta disease); for example, the disease caused by the Aspergillus flavus; for example, a multi-spore main branch (Cladosporium herbarum Caclosporium disease; for example, Helminthosporium caused by Helminthosporium ; (conidial form: Helminthosporium , Bipolaris , synonym : Helminthosporium ); for example, anthracnose caused by Colletotrichum coccodes ; for example, Fusarium caused by Fusarium oxysporum; for example, gibberellosis caused by Gibberella zeae; for example, by bean bulb Macrophomina phaseolina caused by Macrophomina disease; for example, Monographella disease caused by Monographella nivalis ; for example, penicillium caused by Penicillium expansum; the mildew caused, for example Phoma (Phoma disease) from the Brassica Phoma (Phoma lingam); Phomopsis e.g. caused the mold (Phomopsis disease) from soybeans Phomopsis (Phomopsis sojae) For example Phytophthora cactorum (Phytophthora cactorum) causes blight of (Phytophthora disease); for example, due to the strain of Pyrenophora (Pyrenophora graminea) Pyrenophora diseases; of e.g. caused by the fungus Pyricularia (Pyricularia oryzae) pear Pyricularia disease; for example, pyogenic disease caused by Pythium ultimum; for example, sclerotium caused by Rhizoctonia solani; for example, rhizopus caused by Rhizopus oryzae ; Sclerotium disease caused by Sclerotium rolfsii ; for example, scleroderma caused by Septoria nodorum ; for example, gray snow caused by Typhula incarnata Rot; for example, Verticillium disease caused by Verticillium dahliae ; canker disease, broom disease, and dieback disease, such as: the example caused by a cancer cluster pome red globosum (Nectria galligena) plexus disease Neocosmospora (Nectria disease); wilt (blight disease), such as: for example, caused by Sclerotinia stone chain (Monilinia laxa) chain Monilinia disease; leaf blister disease or leaf curl disease, such as, for example, Exobasidium disease caused by Exobasidium vexans ; deformity caused by, for example, outside the outer balloon bacteria (Taphrina deformans) capsule graminis (Taphrina disease); decline disease of woody plants (decline disease), such as: for example, caused by bacteria chlamydospores Pucci Virginia (Phaemoniella clamydospora) of Esca disease; for example, Eutypa dyeback caused by Eutypa lata ; for example, Ganoderma disease caused by Ganoderma boninense ; hard wood volvatus (Rigidoporus lignosus) caused by the hard volvatus disease (Rigidoporus disease); flower and seed diseases, such as: for example, caused by Botrytis cinerea it; tuber diseases, such as: for example Rhizoctonia solani Rhizoctonia causes the disease; for example solani Helminthosporium (Helminthosporium solani) causes the helminthosporium (Helminthosporium disease); clubroot (club root disease), such as: for example Plasmodiophora brassicae (Plamodiophora brassicae) causes the clubroot (Plasmodiophora disease); of a disease caused by the bacterial organisms, such as bacterial organisms such as: Xanthomonas (Xanthomonas species), such as rice bacterial leaf blight (Xanthomonas campestris pv. Oryzae); Pseudomonas species, such as Pseudomonas syringae pv. lachrymans; Erwinia species, such as Erwinia amylovora .

The compositions of the invention may also be used to combat fungal diseases that are readily developable on or in the wood. The term "wood" means all types of wood and all types of processing of the wood to be used in construction, such as compacts, high density wood, laminates and plywood. The method of treating wood according to the present invention is primarily directed to contacting one or more compounds of the invention or compositions of the invention; this includes, for example, direct application, spraying, dipping, injecting, or any other suitable means.

The dosage of the active compound which is usually applied in the treatment method of the present invention is generally from 10 to 800 g/ha, preferably from 50 to 300 g/ha, for application in the treatment of the leaves. The dose of active substance applied is generally from 2 to 200 g per 100 kg of seed, preferably from 3 to 150 g per 100 kg of seed, in the case of seed treatment.

It will be apparent that the dosages indicated herein are provided as illustrative examples of the methods of the invention. Those skilled in the art will know how to vary the dosage administered, 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 compositions suitable for the therapeutic or prophylactic treatment of human or animal fungal diseases such as mycosis, skin diseases, rickets and candidiasis or aspergillus A disease caused by Aspergillus spp. (such as 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 a compound of formula (I) as defined herein for use in the treatment of a transgenic group Due to the use of plants.

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

The invention further relates to a process for the preparation of a composition for the control of phytopathogenic harmful fungi, characterized in that a derivative of formula (I) as defined herein is admixed with extenders and/or surfactants.

Various aspects of the invention will now be described with reference to the examples of the compounds in the <RTIgt;

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

A can be selected from the list of the following groups: A-G1, A-G2, A-G3, A-G4, A-G5, A-G6 and A-G7:

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

In Table 1, unless otherwise stated, M+H(ApcI+) means a molecular ion peak as observed in mass spectrometry by positive atmospheric pressure chemical ionization plus 1 a.m.u. Quality unit).

In Table 1, the logP values were determined by HPLC (High Performance Liquid Chromatography) on a reverse phase column (C 18) using the method described below according to EEC Directive 79/831 Annex V.A8: Temperature : 40 ° C; mobile phase: 0.1% aqueous formic acid and acetonitrile; linear gradient: 10% acetonitrile to 90% acetonitrile.

Calibration was performed using an unbranched alkan-2-one (containing 3 to 16 carbon atoms) having a known logP value (measured by a linear interpolation between two consecutive alkanones using a linear interpolation method to determine the logP value). The λ maximum is determined using a UV spectrum of 200 nm to 400 nm and a peak of the chromatographic signal.

In Table 1, "position" indicates the point of attachment of the -L-B residue to the phenyl ring.

Table 2 illustrates, in a non-limiting manner, an example of a compound of the formula (IIa) of the present invention, wherein L is a direct bond and B ¹ is a substituted or unsubstituted oxiranyl ring, a substituted or unsubstituted thienyl group. a ring, a substituted or unsubstituted benzothienyl ring, a substituted or unsubstituted furan ring or a substituted or unsubstituted benzofuran ring,

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

In Table 2, "position" indicates the point of attachment of the -LB ¹ residue to the phenyl ring.

Table 3 illustrates, in a non-limiting manner, an example of a compound of the formula (IIb) of the present invention, wherein L is a direct bond and B ¹ is a substituted or unsubstituted oxiranyl ring, a substituted or unsubstituted thienyl group. Ring, substituted or unsubstituted benzothienyl ring, substituted or unsubstituted furan ring or substituted or unsubstituted benzofuran ring

In Table 3, M+H (ApcI+) and logP are as defined in Table 1.

In Table 3, "position" indicates the point of attachment of the -LB ¹ residue to the phenyl ring.

table 3:

Table 4 illustrates, in a non-limiting manner, an example of a compound of the formula (Xa) of the present invention, wherein Z ² and Z ^{3 are} as defined herein, A represents A ¹³ , X ^a1 represents a halogen atom; substituted or unsubstituted C ₁ - C ₈ alkyl; C ₁ -C ₈ haloalkyl containing up to 9 halogen atoms which may be the same or different; 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 unsubstituted C ₁ -C ₈ alkylthio, X ^a2 represents hydrogen or X ^a1 , and U ² represents a halogen atom such as chlorine, bromine or iodine or a triflate group,

In Table 4, M+H(ApcI+) and logP are as defined in Table 1.

A can be selected from the list of the following groups: A-G1.

Note: Et: ethyl; iPr: isopropyl

NMR data in Table 5 provides a number of selected compounds of Table ⁽¹ H).

The ¹ H-NMR data of the selected examples are presented in the form of a list of ¹ H-NMR peaks. For each signal peak, the delta value (ppm) and the signal strength in parentheses are listed.

The intensity of the sharp signal is associated with the signal height (cm) in the printed NMR spectrum example and shows the true relationship of the signal strength. The self-width signal can show several signal peaks or intermediate values and their relative intensities relative to the densest signals in the spectrum.

^{The 1} H-NMR peak list is similar to the classical ¹ H-NMR print and therefore typically contains all of the peaks listed in the classical NMR description. Alternatively, it can generally exhibit a solvent signal, a stereoisomer of the target compound (which is also the subject of the invention) and/or an impurity peak, as in a classical ¹ H-NMR print. To display compound signals in the range of δ of solvent and/or water, common solvent peaks (eg, DMSO peaks in DMSO-d6) and water peaks are shown in our ¹ H-NMR peak list and typically have high strength on average.

The peaks and/or peaks of the stereoisomers of the target compound generally have a lower average intensity compared to the peak of the target compound (e.g., having a purity greater than 90%). Such stereoisomers and/or impurities may be typical for a particular method of preparation. Therefore, its peak can be used to help identify the reproducibility of our manufacturing method via "by-product fingerprints".

An expert who calculates the peak of the target compound using known methods (MestreC, ACD simulation, and empirically evaluated expected values) can optionally separate the peak of the target compound as needed using other intensity filters. This separation will be similar to the correlation peaks in the classical ¹ H-NMR description.

Further details of the NMR data description with the peak list can be found in the publication "Citation of NMR Peak List Data within Patent Applications" of Research Publication 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.

Preparation Example 1 : Preparation of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[2-(3-methyloxetan-3-yl)benzyl -1H-pyrazole-4-carboxamide (Compound I.15) Step 1 : Preparation of N-[2-(3-methyloxetan-3-yl)benzyl]cyclopropylamine

To a cooled solution of 1.94 g (34 mmol) of cyclopropylamine and 2.44 mL (42 mmol) of acetic acid and 9 g of 4Å molecular sieve in 50 mL of methanol was added 3 g (17 mmol) of 2-(3-methyloxetan-3-yl) Benzaldehyde. The reaction mixture was stirred under reflux for 3 hours. The reaction mixture was then cooled to 0 ° C, and 1.6 g (25 mmol) of sodium cyanoborohydride was slowly added, and the reaction mixture was further stirred under reflux for 1 hour. The cooled reaction mixture was then filtered through a diatomaceous earth cake. The filter cake was washed twice with 80 mL of methanol and the combined methanol extracts were concentrated under vacuum. Take things. Then 100 mL of water was added to the residue and the pH was adjusted to 12 with 1N aqueous sodium hydroxide. The aqueous layer was extracted with 2 x 50 mL ethyl acetate. The organic layer was washed twice with aq. aq. EtOAc and dried over magnesium sulfate. Column chromatography (heptane/ethyl acetate gradient) gave 2.44 g (yield: 62% yield) of N-[2-(3-methyl oxetane-3-yl)benzyl as a colorless oil. ] Cyclopropylamine. (M+H) = 218.

Step 2 : Preparation of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[2-(3-methyloxetan-3-yl)benzyl ]-1H-pyrazole-4-carboxamide

Add 195 mg (0.92 mmol) of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl chloride in 2 mL of anhydrous tetrahydrofuran to 200 mg (0.92) at ambient temperature. Methyl) a mixture of N-[2-(3-methyloxetan-3-yl)benzyl]cyclopropylamine and 0.141 mL (1.01 mmol) of triethylamine in 3 mL anhydrous THF. The reaction mixture was stirred at ambient temperature for 4 days. The reaction mixture was then quenched with 1 mL EtOAc (EtOAc)EtOAc. The organic phase was concentrated in vacuo to give a crude material. Column chromatography (n-heptane / ethyl acetate gradient) gave 314 mg (yield: 82% yield) of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl as an oil. -N-[2-(3-Methyloxetan-3-yl)benzyl]-1H-pyrazole-4-carboxamide. LogP=1.94. (M+H) = 394.

Preparation Example 2 : Preparation of N-[5-chloro-2-(2-methyloxiran-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro -1-methyl-1H-pyrazole-4-carboxamide (Compound I.4) Step 1 : Preparation of N-[5-chloro-2-(prop-1-en-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl keto-1H-pyrazole-4-carboxamide

To 1.55 g (3.55 mmol) of N-(2-bromo-5-chlorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole- 4-Metformamide was added 753 mg (4.25 mmol) of 4,4,5,5-tetramethyl-2-(propan-1-) in a suspension of 20/1 toluene/water mixture by argon gas degassing. Alk-2-yl)-1,3,2-dioxaboron 205 mg (0.71 mmol) of tricyclohexylphosphine, 167 mg (0.355 mmol) of palladium(II) acetate and 4.65 g (21.3 mmol) of tripotassium phosphate. The mixture was heated at 100 ° C for 3 hours. The reaction mixture was cooled to ambient temperature. 60 mL of water was added and the reaction mixture was extracted three times with ethyl acetate. The combined organic extracts were washed with a saturated aqueous solution of NaCl and dried over a phase separation filter. The organic phase was concentrated in vacuo <RTI ID=0.0></RTI> tojjjjjjjj 1-en-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide and N- Cyclopropyl-3-(difluoromethyl)-N-[2,5-di(prop-1-en-2-yl)benzyl]-5-fluoro-1-methyl-1H-pyrazole- A 68/32 mixture of 4-methanamine was used as such in the next step. LogP=3.96. (M+H)=398.

Step 2 : N-[5-Chloro-2-(2-methyloxiran-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -Preparation of methyl-1H-pyrazole-4-carboxamide

To 0.5 g (1.26 mmol, 68% purity) of N-[5-chloro-2-(prop-1-en-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)- 5-Fluoro-1-methyl-1H-pyrazole-4-carboxamide A 1.65 g (6.69 mmol) of 70% by weight of m-chloroperbenzoic acid was slowly added to the cooled solution in 20 mL of dichloromethane. The reaction mixture was stirred at ambient temperature for 2 hours. The excess oxidizing agent was neutralized by adding 2.47 g (12.6 mmol) of an aqueous solution of sodium hydrogensulfite, and then the mixture was extracted three times with dichloromethane. The combined organic extracts were washed with aqueous sodium bicarbonate and dried over a phase separation filter. The organic phase was concentrated in vacuo <RTI ID=0.0></RTI> tojjjjjjjjj Methyl oxiran-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide. LogP=3.19. (M+H) = 414.

Preparation Example 3 : N-[5-(1-Benzothiophen-3-yl)-2-isopropylbenzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -Preparation of methyl-1H-pyrazole-4-carboxamide (Compound I.157) Step 1 : Preparation of 1-(5-chloro-2-isopropylphenyl)-N-hydroxymethylimine

To a solution of 1 g (5.47 mmol) of 5-chloro-2-isopropylbenzaldehyde in 12 mL of methanol was added 0.5 g (6 mmol) of sodium acetate and 419 mg (6 mmol) of hydroxylamine hydrochloride. The reaction mixture was stirred at ambient temperature for 6 hours. The solvent was removed under vacuum and the residue was extracted with dichloromethane. ChemElut ^TM cartridge organic phase was filtered and concentrated under vacuum to give 1.08 g (89% yield) of 1- (5-chloro-2-isopropyl-phenyl) -N- hydroxymethanimine, two isomers was 8/92 mixture of constructs. LogP = 2.90 (minor isomer) and 3.17 (major isomer). (M+H) = 198.

Step 2 : Preparation of 1-(5-chloro-2-isopropylphenyl)methylamine

Slow addition of borane: tetrahydrofuran complex in tetrahydrofuran to 1.08 g (5.46 mmol) of 1-(5-chloro-2-isopropylphenyl)-N-hydroxymethylimine in 18 mL of tetrahydrofuran 1 M solution 21 mL (21 mmol). The reaction mixture was heated under reflux for 1 day. Excess hydride was destroyed by the addition of ethanol. A few milliliters of 1 N aqueous sodium hydroxide solution was added, and the reaction mixture was further heated at 70 ° C for 30 minutes. The reaction mixture was diluted with water and extracted with aq. The organic phase was filtered through a pad of EtOAc (EtOAc ⁾ and concentrated in vacuo to give 1.30 g of 1-(5-chloro-2-isopropylphenyl)methylamine as the next step. LogP=1.20. (M+H) = 184.

Step 3 : N-(5-Chloro-2-isopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (Compound Xa .1) Preparation

824 mg (3.87 mmol) of 3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carbonyl chloride was added to 647 mg (3.52 mmol) 1-(5- at ambient temperature. A mixture of chloro-2-isopropyl-phenyl)methylamine and 0.590 mL (4.23 mmol) of triethylamine in 7 mL anhydrous THF. The reaction mixture was heated under reflux for 2 hours. A few milliliters of water was added and the reaction mixture was filtered with EtOAc (EtOAc ⁾ cartridge. By prep HPLC (acetonitrile / water + 0.1% HCO ₂ H gradient) the residue to give 360mg (27% yield) as a white solid of N- (5- chloro-2-isopropyl-benzyl) - 3-(Difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide. LogP = 3.46. (M+H)=360.

Step 4 : Preparation of N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4 -Procarbamide

63 mg (0.19 mmol) of N-(5-chloro-2-isopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide , 35mg (0.19mmol) of copper (II) acetate and 31mg (0.096mmol) of cesium carbonate was added to a dried Radleys ^TM vials. The vial was purged with dry air and stirred vigorously for a few minutes. Add 0.5 mL of toluene and 46 mg (0.58 mmol) of pyridine and 65 mg (0.38 mmol) of 2-cyclopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaboron . The vial was again purged with dry air, sealed and heated at 100 ° C for 1 day. HPLC-mass spectrometry analysis of the reaction showed formation of 4% (7% cv) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro- 1-Methyl-1H-pyrazole-4-carbamide. LogP=4.06. (M+H)=400.

Step 5 : Preparation of N-[5-(1-benzothiophen-3-yl)-2-isopropylbenzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-1H-pyrazole-4-carboxamide

200 mg (0.5 mmol) of N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl in a 5 mL microwave vial The benzyl-1H-pyrazole-4-carboxamide was dissolved in 1 mL of acetonitrile. The vial was degassed with argon, and 104 mg (0.75 mmol) of potassium carbonate dissolved in 1 mL of water was further added, followed by the addition of 106 mg (0.6 mmol) of 1-benzothiophen-3-yl group. Acid and 6.5 mg (0.01 mmol) of 1,1'-bis(di-t-butylphosphino)(ferrocene)dichloropalladium(II). Deg.] C followed by heating in a microwave apparatus 130. [Biotage Initiator ^TM] 20 minutes. The reaction mixture was cooled to ambient temperature, filtered andEtOAc evaporated. The organic extract was dried over a ChemElut ^(TM) cartridge and concentrated in vacuo. By prep HPLC (acetonitrile / water + 0.1% HCO ₂ H gradient) the residue was purified to give 75mg of a brown oil (28% yield) N- [5- (1- benzothiophen-3-yl) 2-Isopropyl-benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide. LogP=5.17. (M+H) = 498.

Preparation Example 4 : Preparation of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[2-(4-methyl-2-thienyl)benzyl]-1H -pyrazole-4-carboxamide (Compound I.100)

In Radleys ^TM vial, 200mg (0.49mmol) N- (2- bromobenzyl) -N- cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl -1H- pyrazolo 4-Methylguanamine was dissolved in 5 mL of dioxane together with 137 mg (0.99 mmol) of potassium carbonate dissolved in 0.5 mL of water. The vial was degassed with argon for 10 minutes. Subsequently, 106 mg (0.74 mmol) of (4-methyl-2-thienyl) was added. Acid and 115 mg (0.1 mmol) of ruthenium (triphenylphosphine) palladium (0). The reaction mixture was heated at 100 ° C for 8 hours. The cooled mixture was filtered through a diatomaceous earth cake. Sequentially with aqueous potassium carbonate, NaCl filtrate was washed with a saturated aqueous solution, and dried over ChemElut ^TM cartridge. The organic layer was concentrated to dryness crystals crystals eluted eluted eluted eluted 3-(Difluoromethyl)-5-fluoro-1-methyl-N-[2-(4-methyl-2-thienyl)benzyl]-1H-pyrazole-4-carboxamide. LogP=3.99. (M+H)=420.

General Preparation Example 5: at Chemspeed ^TM Sulfated formula (I) on the equipment

The 0.27mmol phosphorus pentasulfide (P ₂ S ₅₎ were weighed into 13mL Chemspeed ^TM vials. A solution of 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. The temperature was then lowered to 80 ° C and 2.5 mL of water was added. The mixture was further heated at 80 ° C for 1 hour. Then 2 mL of water was added and the reaction mixture was extracted twice with 4 mL of dichloromethane. The organic phase was deposited on a basic alumina cartridge (2 g) and was taken twice with 8 mL dichloromethane. The solvent was removed and the crude thioguanamine derivative was analyzed by LCMS and NMR. The under-purified compound was further purified by preparative LC.

Example A: In vivo prophylactic testing of Gramineae blight (barley)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkyl aryl polyglycol ether

To produce a suitable formulation of the active compound, 1 part by weight of the active compound or active compound combination is mixed with a defined amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test the prophylactic activity, a preparation of the active compound or combination of active compounds is applied to the young plants at a prescribed application rate.

After the spray coating has dried, the plants are sprinkled with spores of Blumeria graminis f . sp . hordei .

The plants are placed in a greenhouse at a temperature of about 18 ° C and about 80% relative atmospheric humidity to promote the development of mold vesicles.

The test was evaluated 7 days after the inoculation. 0% means the efficacy corresponding to the untreated control, while 100% means that no disease is observed.

Under these conditions, excellent protection (at least 90%) was observed to a complete protection at a dose of 500 ppm active ingredient from the following compounds of Table A:

Example B: In vivo prophylactic testing against Alternaria alternata (radish leaf spot)

The active ingredients tested were prepared by homogenization in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active substance.

The radish plants ("Pernod Clair" variety) were sown on a 50/50 peat soil pozzolan substrate in a starter cup and grown at 17 ° C, and the active ingredients prepared as described above were sprayed at the cotyledon stage. To handle. The plants used as controls were treated with a mixture of acetone/tween/DMSO/water without active substance.

After 24 hours, the plants were contaminated by spraying the cotyledons with an aqueous suspension of Alternaria alternata spores (50,000 spores per ml). Spores were collected from cultures of 15 days of age. The contaminated radish plants were grown at 20 ° C and 100% relative humidity.

Six days after the contamination, classification (% efficacy) was performed compared to the control plants.

Under these conditions, good protection (at least 70%) to complete protection was observed at doses of 500 ppm active ingredient with the following compounds from Table B:

Example C: In vivo prophylactic testing of Botrytis cinerea (Gold mold)

The active ingredients tested were prepared by homogenization in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active substance.

The cucumber plant ("Vert petit de Paris" variety) was sown on a 50/50 peat soil pozzolan substrate in a starter cup and grown at 24 ° C, and the active ingredients prepared as described above were sprayed at the Z11 cotyledon stage. To handle. The plants used as controls were treated with a mixture of acetone/tween/DMSO/water without active substance.

After 24 hours, the plants were contaminated by spraying the cotyledons with an aqueous suspension of cryopreserved spores of Botrytis cinerea (50,000 spores per ml). 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 were grown at 17 ° C and 90% relative humidity.

Grades (% efficacy) were compared to control plants 4 to 5 days after contamination.

Under these conditions, good protection (at least 70%) to complete protection was observed at doses of 500 ppm active ingredient from the following compounds from Table C:

Under the same conditions, good protection (at least 70%) to complete protection was observed at doses of 100 ppm active ingredient with the following compounds from Table C2:

Example D: In vivo prophylactic testing of the genus Corydalis (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkyl aryl polyglycol ether

To produce a suitable formulation of the active compound, 1 part by weight of the active compound or active compound combination is mixed with a defined amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test the prophylactic activity, a preparation of the active compound or combination of active compounds is applied to the young plants at a prescribed application rate.

After the spray coating has dried, the plants are sprayed with a spore suspension of the bacterium. The plants are maintained in an incubator at about 20 ° C and about 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 22 ° C and about 80% relative atmospheric humidity.

The test was evaluated 8 days after the inoculation. 0% means the efficacy corresponding to the untreated control, while 100% means that no disease is observed.

Under these conditions, a high degree of protection (at least 80%) to complete protection was observed at doses of 500 ppm active ingredient from the following compounds from Table D:

Example E: In vivo prophylactic testing of nucleus bacteria (barley)

The active ingredients tested were prepared by homogenization in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active substance.

Barley plants ("Plaisant" varieties) were sown on a 50/50 peat soil ash matrix in a starter cup and grown at 22 ° C, at the 1 leaf stage (10 cm height) by spraying as described above The active ingredient is prepared for treatment. The plants used as controls were treated with a mixture of acetone/tween/DMSO/water without active substance.

After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of the nucleus spores (12,000 spores per ml). Spores were collected from 12 day old cultures. The contaminated barley plants were incubated at 20 ° C and 100% relative humidity for 48 hours, followed by incubation at 20 ° C, 70-80% relative humidity for 12 days.

Fractionation (% efficacy) was performed 14 days after the contamination compared to the control plants.

Under these conditions, good protection (at least 70%) to complete protection was observed at doses of 500 ppm active ingredient with the following compounds from Table E:

Under the same conditions, good protection (70%) to excellent protection (at least 95%) was observed at doses of 100 ppm active ingredient with the following compounds from Table E2:

Under the same conditions, good protection (at least 70%) to high protection (at least 80%) was observed at doses of 100 ppm active ingredient of the compounds of Examples I.84 and I.144, while the patents in Table E3 No protection was observed in the case of the pyridine analog CMP1 disclosed in application WO-2007/087906:

CMP1 disclosed in International Patent No. WO-2007/087906 corresponds to N-[2-chloro-4-(pyridin-3-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-1 -Methyl-1H-pyrazole-4-carboxamide.

These results show that the compounds of the invention have much better biological activity than the structurally closest compounds disclosed in WO-2007/087906.

Example F: In vivo prophylactic testing of Pyricularia oryzae (rice fever)

The active ingredients tested were prepared by homogenization in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active substance.

Rice plants ("Koshihikari" variety) were sown on a 50/50 peat soil pozzolan substrate in a starter cup and grown at 26 ° C, and the active ingredients prepared as described above were sprayed at the 2-leaf stage (10 cm height) by spraying To handle. The plants used as controls were treated with a mixture of acetone/tween/DMSO/water without active substance.

After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Pyricularia oryzae spores (40,000 spores per ml). Spores were collected from the 15 day old culture and suspended in water containing 2.5 g/L gelatin. The contaminated rice plants were grown at 25 ° C and 80% relative humidity.

Six days after the contamination, classification (% efficacy) was performed compared to the control plants.

Under these conditions, good protection (at least 70%) to high protection (at least 80%) was observed at doses of 500 ppm active ingredient from the following compounds of Table F:

Example G: In vivo prevention of Puccinia recondita (wheat brown rust) Sex test

The active ingredients tested were prepared by homogenization in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active substance.

The wheat plant ("Scipion" variety) was sown on a 50/50 peat soil pozzolan substrate in a starter cup and grown at 22 ° C, and the active ingredient prepared as described above was sprayed at the 1 leaf stage (10 cm height) by spraying. To handle. The plants used as controls were treated with a mixture of acetone/tween/DMSO/water without active substance.

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

Fractionation (% efficacy) was performed 12 days after the contamination compared to the control plants.

Under these conditions, good protection (at least 70%) to complete protection was observed at doses of 500 ppm active ingredient from the following compounds from Table G:

Under the same conditions, good protection (at least 70%) to complete protection was observed at doses of 100 ppm active ingredient with the following compounds from Table G2:

Under the same conditions, an average protection (at least 60%) to an excellent protection (at least 90%) was observed at doses of 100 ppm and 500 ppm active ingredient of the compound of Examples I.77, I.78 or I.79, A poor protection (less than 40%) was observed to no protection in the case of the pyridine analog CMP2 as disclosed in the patent application WO-2010/130767.

CMP2 disclosed in International Patent No. WO-2010/130767 corresponds to 5-chloro-N-[2-chloro-4-(pyridin-3-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl) Base)-1-methyl-1H-pyrazole-4-carboxamide.

These results show that the compounds of the invention have much better biological activity than the structurally closest compounds disclosed in WO-2010/130767.

Example H: In vivo prophylactic testing of Septoria tritici (wheat)

The active ingredients tested were prepared by homogenization in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active substance.

Wheat plants ("Scipion" varieties) were sown on a 50/50 peat soil ash matrix in a starter cup and grown at 22 °C, at the 1 leaf stage (10 cm height) by spraying as described above The active ingredient is prepared for treatment. The plants used as controls were treated with a mixture of acetone/tween/DMSO/water without active substance.

After 24 hours, the plants were contaminated by spraying the leaves on a frozen suspension of the aqueous suspension of the genus Aspergillus sp. (500,000 spores per ml). The contaminated wheat plants were incubated at 18 ° C and 100% relative humidity for 72 hours and then incubated at 90% relative humidity for 21 days.

Grading (% efficacy) was compared to control plants 24 days after contamination.

Under these conditions, good protection (at least 70%) to complete protection was observed at doses of 500 ppm active ingredient with the following compounds from Table H:

Under the same conditions, good protection (at least 70%) to complete protection was observed at doses of 100 ppm active ingredient with the following compounds from Table H2:

Example I: In vivo prophylactic testing of powdery mildew of the monofilament shell (Gourd powdery mildew)

The active ingredients tested were prepared by homogenization in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active substance.

The cucumber plant ("Vert petit de Paris" variety) was sown on a 50/50 peat soil-pozzolana substrate in a starter cup and grown at 24 °C, and the activity prepared as described above was sprayed at the Z11 cotyledon stage. Ingredients to deal with. The plants used as controls were treated with a mixture of acetone/tween/DMSO/water without active substance.

After 24 hours, the plants were contaminated by spraying the cotyledons with an aqueous suspension of spores of P. sphaeroides (100,000 spores per ml). Spores are collected from infected plants. The contaminated cucumber plants are grown at about 20 ° C and 70-80% relative humidity.

Fractionation (% efficacy) was performed 12 days after the contamination compared to the control plants.

Under these conditions, good protection (at least 70%) to complete protection was observed at doses of 500 ppm active ingredient from the following compounds of Table I:

Under the same conditions, good protection (at least 70%) to complete protection was observed at doses of 100 ppm active ingredient with the following compounds from Table I2:

Under the same conditions, complete protection is observed at a dose of 100 ppm of the active ingredient of the compound of Example I.144, as is the case of the pyridine analog CMP1 as disclosed in the patent application WO-2007/087906, which is incorporated herein by reference. No protection observed below:

CMP1 disclosed in International Patent No. WO-2007/087906 corresponds to N-[2-chloro-4-(pyridin-3-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-1 -Methyl-1H-pyrazole-4-carboxamide.

These results show that the compounds of the invention have much better biological activity than the structurally closest compounds disclosed in WO-2007/087906.

Excellent protection (at least 90%) was observed under the same conditions at a dose of 500 ppm active ingredient of the compound of Example I.139 (correspondingly, I.140, I.141, I.144 and I.145) Observed to the case of the pyridine analog CMP3 (respectively, CMP4, CMP5, CMP6 and CMP7) as claimed in the patent application WO-2007/087906 or WO-2010/130767, as shown in Table I4. Poor protection (less than 40%) or plant damage:

CMP3 disclosed in International Patent No. WO-2010/130767 corresponds to N-[2-(6-chloropyridin-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5- Fluoro-1-methyl-1H-pyrazole-4-carboxamide; CMP4 disclosed in International Patent WO-2007/087906 corresponds to N-[2-(6-chloropyridin-2-yl)benzyl] -N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide; CMP5 disclosed in International Patent WO-2010/130767 corresponds to 5-chloro- N-[2-(6-chloropyridin-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide; CMP6 disclosed in International Patent No. WO-2007/087906 corresponds to N-[5-chloro-2-(6-chloropyridin-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide; and CMP7 disclosed in International Patent WO-2010/130767 corresponds to 5-chloro-N-[5-chloro-2-(6-chloro) Pyridin-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide.

These results show that the compounds of the invention have much better biological activity than the structurally closest compounds disclosed in WO-2007/087906.

Example J: In vivo prophylactic testing of bean rust (bean rust)

The active ingredients tested were prepared by homogenization in a mixture of acetone/tween/DMSO, followed by dilution with water to obtain the desired concentration of active substance.

Bean plants ("Saxa" variety) were sown on a 50/50 peat soil pozzolan substrate in a starter cup and grown at 24 ° C, and the active ingredients prepared as described above were sprayed at the 2-leaf stage (9 cm height) by spraying. To handle. The plants used as controls were treated with a mixture of acetone/tween/DMSO/water without active substance.

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

Eleven days after the contamination, the fractionation (% efficacy) was performed compared to the control plants.

Under these conditions, good protection (at least 70%) to complete protection was observed at doses of 500 ppm active ingredient from the following compounds from Table J:

Under the same conditions, good protection (at least 70%) to complete protection was observed at doses of 100 ppm active ingredient with the following compounds from Table J2:

Example K: In vivo prophylactic testing of apple scab (Apple)

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkyl aryl polyglycol ether

To produce a suitable formulation of the active compound, 1 part by weight of active compound is mixed with a defined amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test the prophylactic activity, the active compound preparation is sprayed onto the young plants at a prescribed application rate. After the spray coating has dried, the plant is inoculated with an aqueous conidia suspension of the apple scab pathogenic factor (Apple black spot), which is then maintained in an incubator at about 20 ° C and 100% relative atmospheric humidity. day.

The plants are then placed in a greenhouse at about 21 ° C and about 90% relative atmospheric humidity.

The test was evaluated 10 days after inoculation. 0% means the efficacy corresponding to the untreated control, while 100% means that no disease is observed.

Under these conditions, excellent protection (at least 90%) was observed to a complete protection at doses of 100 ppm active ingredient from the following compounds of Table K:

Claims (26)

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 four groups R which may be the same or different; T represents O or S; n represents 0, 1, 2, 3 or 4; L represents a direct ^{bond, CZ 4 Z 5, O,} S, SO, SO 2 or NZ ^6; B represents containing from 1 to 4 selected from the group consisting of N, the saturated hetero atoms list of O, S composition, the partially saturated or An unsaturated monocyclic or fused bicyclic 3, 4, 5, 6, 7, 8, 9 or 10 membered ring which may be substituted with up to 6 groups which may be the same or different Y; the limitation is when L represents direct when a bond or an oxygen atom, B represents a pyridyl ring not; Z ¹ represents a non-substituted C ₃ -C ₇ cycloalkyl or substituted alkyl of up to 10 atoms or groups C ₃ -C ₇ cycloalkyl, which other atoms or groups may be the same or different and are selected from the list consisting of: a halogen atom, a cyano group, C ₁ -C ₈ alkyl group, may contain 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, comprising up to 9 It may be the same or different halogen atoms, C ₁ -C ₈ haloalkoxy of Carbonyl group, C ₁ -C ₈ alkyl aminocarbonyl or di -C ₁ -C ₈ alkylamino-carbonyl group; Z ² and Z ³ may be the same or different, represent a hydrogen atom; a substituted or unsubstituted C ₁ of -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 alkylsulfanyl; substituted or unsubstituted C ₁ -C ₈ alkylsulfonyl Substituted or unsubstituted C ₁ -C ₈ alkylsulfinyl; amine; substituted or unsubstituted C ₁ -C ₈ alkylamino; substituted or unsubstituted bis-C ₁ -C ₈ alkyl group; a substituted or unsubstituted of C ₁ -C ₈ alkoxycarbonyl group; a substituted or unsubstituted of C ₁ -C ₈ alkyl amine acyl; substituted or non- Substituted bis-C ₁ -C ₈ alkylamine carbenyl; or substituted or unsubstituted NC ₁ -C ₈ alkyl-C ₁ -C ₈ alkoxy a carbylamine group; or Z ² and Z ³ together with the carbon atom to which they are attached may form a substituted or unsubstituted C ₃ -C ₇ cycloalkyl group; or Z ³ and a point of attachment to the phenyl ring The adjacent substituents X together with the consecutive carbon atoms to which they are attached may form a substituted or unsubstituted 5, 6 or 7 membered partially saturated carbocyclic or heterocyclic ring containing up to 3 heteroatoms, and Z ² Z ⁴ and Z ⁵ independently represent a hydrogen atom; a halogen atom; a cyano group; a substituted or unsubstituted C ₁ -C ₈ alkyl group; a C ₁ -C ₈ halogen having 1 to 5 halogen atoms; Alkyl; substituted or unsubstituted C ₁ -C ₈ alkoxy; substituted or unsubstituted C ₁ -C ₈ alkylthio; or substituted or unsubstituted C ₁ -C ₈ alkane An oxycarbonyl group; or Z ⁴ and Z ⁵ together with the carbon atom to which they are attached may form a C(=O)carbonyl group; Z ⁶ represents a hydrogen atom; a substituted or unsubstituted C ₁ -C ₈ alkyl group; 9 may be the same or different of halogen atom, C ₁ -C ₈ haloalkyl; substituted or non-substituted C ₂ -C ₈ alkenyl group; can contain up to 9 identical or different halogen atoms C ₂ - C ₈ haloalkenyl; substituted or unsubstituted C ₃ -C ₈ alkynyl; comprising up to 9 halogen atoms may be the same or different C ₃ -C ₈ haloalkynyl; substituted or non-substituted C ₃ -C ₇ cycloalkyl; comprising up to 9 C may be the same or different halogen atoms ₃ -C ₇ cycloalkyl, halogen; substituted or non-substituted C ₃ -C ₇ cycloalkyl, -C ₁ -C ₈ alkyl; methyl acyl; substituted or unsubstituted the substituted C ₁ -C ₈ alkylcarbonyl; can contain up to 9 identical or different halogen atoms C ₁ -C ₈ haloalkyl carbonyl group; substituted or non-substituted C ₁ -C ₈ alkoxy, a carbonyl group; a C ₁ -C ₈ haloalkoxycarbonyl group containing up to 9 halogen atoms which may be the same or different; a substituted or unsubstituted C ₁ -C ₈ alkylsulfonyl group; containing up to 9 a C ₁ -C ₈ haloalkylsulfonyl group of the same or different halogen atom; a substituted or unsubstituted benzyl group; or a substituted or unsubstituted phenylsulfonyl group; X independently represents a halogen atom; Nitro; cyano; isocyanyl; hydroxy; amine; thio; pentafluoro-λ ⁶ -thio; indolyl; methyl methoxy; methionine; substituted or unsubstituted (hydroxy imino) -C ₁ -C ₈ alkyl group; a substituted or unsubstituted (C ₁ -C ₈ alkoxyimino group) -C ₁ -C ₈ alkyl; substituted or non-substituted (C ₂ -C ₈ alkylene oxyalkylene amine) -C ₁ -C ₈ alkyl Substituted or unsubstituted (C ₂ -C ₈ alkynyloxyimido)-C ₁ -C ₈ alkyl; substituted or unsubstituted (benzyloxyimino)-C ₁ -C ₈ alkyl; carboxy; amine carbenyl; N-hydroxylamine carbenyl; carbamate; substituted or unsubstituted C ₁ -C ₈ alkyl; C having 1 to 9 halogen atoms ₁ -C ₈ haloalkyl; substituted or non-substituted C ₂ -C ₈ alkenyl; ₂ -C ₈ haloalkenyl group having a C 1 to halogen atoms. 9; substituted or non-substituted C ₂ - C ₈ alkynyl group; a C 1 to having halogen atoms. 9 ₂ -C ₈ haloalkynyl; substituted or non-substituted C ₁ -C ₈ alkoxy group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkoxy; substituted or non-substituted C ₁ -C ₈ alkylthio; having a C 1 to halogen atoms. 9 ₁ -C ₈ haloalkyl group; a substituted or unsubstituted of C _{a 1-} C ₈ alkylsulfinyl group; a C ₁ -C ₈ haloalkylsulfinyl group having 1 to 9 halogen atoms; a substituted or unsubstituted C ₁ -C ₈ alkylsulfonyl group; With 1 to 9 halogens Son halo C ₁ -C ₈ alkylsulfonyl group; a substituted or unsubstituted of C ₁ -C ₈ alkyl group; a substituted or unsubstituted bis -C ₁ -C ₈ alkylamino; substituted or non-substituted C ₂ -C ₈ alkenyl group; a C 1 to having halogen atoms. 9 ₂ -C ₈ alkenyl group, a halogen; substituted or non-substituted C ₃ -C ₈ alkynyl group; having a C 1 to halogen atoms. 9 ₂ -C ₈ alkynyl group, a halogen; substituted or non-substituted C ₃ -C ₇ cycloalkyl group; a C 1 to having halogen atoms. 9 ₃ -C ₇ cycloalkyl halo group; substituted or non-substituted (C ₃ -C ₇ cycloalkyl) -C ₁ -C ₈ alkyl; substituted or non-substituted C ₄ -C ₇ cycloalkenyl; having 1-9 halo C ₄ -C ₇ halocycloalkenyl; a substituted or unsubstituted (C ₃ -C ₇ cycloalkyl)-C ₂ -C ₈ alkenyl group; substituted or unsubstituted (C ₃ -C _{a 7} -cycloalkyl)-C ₂ -C ₈ alkynyl group; a substituted or unsubstituted tri(C ₁ -C ₈ )alkyldecane group; a substituted or unsubstituted tris(C ₁ -C ₈ ) alkane silicon alkyl group -C ₁ -C ₈ alkyl; substituted or non-substituted C ₁ -C ₈ alkylcarbonyl group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkyl carbonyl group; a substituted or unsubstituted Substituted C ₁ -C ₈ -alkylcarbonyloxy; C ₁ -C ₈ haloalkylcarbonyloxy having 1 to 9 halogen atoms; substituted or unsubstituted C ₁ -C ₈ alkylcarbonylamino group; having 1 to 9 a halogen atoms C ₁ -C ₈ haloalkyl carbonyl group; substituted or non-substituted C ₁ -C ₈ alkoxycarbonyl group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkoxy-carbonyl ; substituted or non-substituted C ₁ -C ₈ alkoxycarbonyl group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkoxy-carbonyl group; a substituted or unsubstituted C ₁ of -C ₈ alkylamine carbenyl; substituted or unsubstituted bis-C ₁ -C ₈ alkylamine carbenyl; substituted or unsubstituted C ₁ -C ₈ alkylaminocarbonyloxy Substituted or unsubstituted bis-C ₁ -C ₈ alkylaminocarbonyloxy group; substituted or unsubstituted N-(C ₁ -C ₈ alkyl)hydroxylamine carbenyl; substituted or Unsubstituted C ₁ -C ₈ alkoxyamine indenyl; substituted or unsubstituted N-(C ₁ -C ₈ alkyl)-C ₁ -C ₈ alkoxyamine indenyl; An aryl group substituted with up to 6 groups which may be the same or different, Q; an aryl-C ₁ -C ₈ alkyl group which may be substituted with up to 6 groups which may be the same or different. ; It may be up to 6 may be the same or different Q groups substituted aryl group of -C ₂ -C ₈ alkenyl group; may be up to 6 may be the same or different substituent groups of the aryl group Q -C ₂ - a C ₈ alkynyl group; an aryloxy group which may be substituted with up to 6 groups which may be the same or different Q; an arylthio group which may be substituted with up to 6 groups Q which may be the same or different; 6 arylamino groups which may be substituted with the same or different groups Q; aryl-C ₁ -C ₈ alkoxy groups which may be substituted with up to 6 groups which may be the same or different Q; may be up to 6 may be the same or different substituent groups of Q aryl -C ₁ -C ₈ alkylthio; may be up to 6 may be the same or different substituent groups of Q aryl -C ₁ -C ₈ alkyl An amino group; a pyridyl group which may be substituted with up to 4 groups of Q; or 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; ; substituted or non-substituted C ₁ -C ₈ alkyl group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkyl; substituted or non-substituted C ₁ -C ₈ alkoxy; having 1-9 halogen atoms C ₁ -C ₈ haloalkoxy; a substituted or unsubstituted alkyl group of C ₁ -C ₈ Group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkyl group; a substituted or unsubstituted of C ₁ -C ₈ alkylsulfinyl acyl; having a C 1 to _1. 9 halogen atoms -C ₈ haloalkylsulfinyl; substituted or unsubstituted C ₁ -C ₈ alkylsulfonyl; C ₁ -C ₈ haloalkylsulfonyl 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; substituted or unsubstituted C ₁ -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; a C ₁ -C ₈ halogen having 1 to 9 halogen atoms; alkoxycarbonyl group; or may be up to 6 may be the same or different substituent groups of the aryl group Q; Q independently represents a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted of C ₁ -C ₈ An alkyl group, a C ₁ -C ₈ haloalkyl group containing up to 9 halogen atoms which may be the same or different, a substituted or unsubstituted C ₁ -C ₈ alkoxy group, containing up to 9 may be the same or different a C ₁ -C ₈ haloalkoxy group of a halogen atom, a substituted or unsubstituted C ₁ -C ₈ alkane a thiol group, a C ₁ -C ₈ haloalkylthio group containing up to 9 halogen atoms which may be the same or different, a substituted or unsubstituted tri(C ₁ -C ₈ )alkyldecyl group, substituted Or unsubstituted tri(C ₁ -C ₈ )alkyldecane-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 group; Thio group; pentafluoro-λ ⁶ -thio group; substituted or unsubstituted (C ₁ -C ₈ alkoxyimino)-C ₁ -C ₈ alkyl group; substituted or unsubstituted (benzyl oxyalkylene amine) -C ₁ -C ₈ alkyl group; a substituted or unsubstituted alkyl group of C ₁ -C _{8; 1} -C ₈ haloalkyl. 9 having a C 1 to halogen atoms; or a substituted the unsubstituted C ₂ -C ₈ alkenyl group; having 1-9 C atoms, halogen of halide ₂ -C ₈ alkenyl group; a substituted or non-substituted C ₂ -C ₈ alkynyl group; with 1-9 halo C ₂ -C ₈ halogen atoms alkynyl group; a substituted or unsubstituted of C ₁ -C ₈ alkoxy group; a C 1 to having halogen atoms. 9 ₁ -C ₈ haloalkoxy; or a substituted The substituted C ₁ -C ₈ alkylthio; having 1-9 halogen atoms C ₁ -C ₈ haloalkyl group; a substituted or unsubstituted of C ₁ -C ₈ alkylsulfinyl acyl a C ₁ -C ₈ haloalkylsulfinyl group having 1 to 9 halogen atoms; a substituted or unsubstituted C ₁ -C ₈ alkylsulfonyl group; C ₁ having 1 to 9 halogen atoms _; -C ₈ haloalkylsulfonyl; substituted or unsubstituted C ₁ -C ₈ alkylamino; substituted or unsubstituted di-C ₁ -C ₈ alkylamino; substituted or not Substituted C ₂ -C ₈ alkenyloxy; substituted or unsubstituted C ₃ -C ₈ alkynyloxy; substituted or unsubstituted C ₃ -C ₇ cycloalkyl; having 1 to 9 halogens a C ₃ -C ₇ halocycloalkyl group; a substituted or unsubstituted tri(C ₁ -C ₈ )alkyldecylalkyl group; a substituted or unsubstituted C ₁ -C ₈ alkylcarbonyl group; to 9 halogen atoms C ₁ -C ₈ haloalkyl carbonyl group; substituted or non-substituted C ₁ -C ₈ alkoxycarbonyl; having a C 1 to 9 halogen atoms ₁ -C ₈ haloalkoxy carbonyl group; substituted or non-substituted C ₁ -C ₈ alkyl amine acyl; substituted or unsubstituted bis -C ₁ -C ₈ alkyl amine Phenoxy; phenylthio; phenylamino; benzyloxy; benzylthio; or benzylamino; and salts, N-oxides, metal complexes, metal-like complexes And optically active isomers or geometric isomers thereof. The compound of the requested item 1, wherein A is selected from the list consisting of: heterocyclyl of formula (A ¹⁾ of Wherein: R ¹ to R ³ may be the same or different, represent a hydrogen atom; a halogen atom; a substituted or unsubstituted of C ₁ -C ₅ alkyl; C comprising up to 9 identical or different halogen atoms _1-- C ₅ haloalkyl group; a substituted or unsubstituted of C ₁ -C ₅ alkoxy or comprising up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkoxy; of formula (A ²⁾ Heterocycle 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; may contain up to 9 identical or different halogen atoms C ₁ - C ₅ haloalkyl group; a substituted or unsubstituted of C ₁ -C ₅ alkoxy or comprising up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkoxy; of formula (A ³⁾ Heterocycle Wherein: R ⁷ represents a hydrogen atom; a halogen atom; a substituted or unsubstituted alkyl group of C ₁ -C _5; may contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl; substituted or unsubstituted of C ₁ -C ₅ alkoxy group or may comprise up to nine identical or different a halogen atoms C ₁ -C ₅ haloalkoxy; R ⁸ represents a hydrogen atom or a substituted or non-substituted C ₁ -C ₅ alkyl; heterocyclic ring of formula (A ⁴ ) 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 group; substituted or non-substituted C ₁ -C ₅ alkylthio; it can contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl, or comprising up to 9 may be the same or a C ₁ -C ₅ haloalkoxy group of a different halogen atom; a heterocyclic ring of the formula (A ⁵ ) 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; Amino group; C ₁ -C ₅ haloalkyl group containing up to 9 halogen atoms which may be the same or different or C ₁ -C ₅ haloalkoxy group containing up to 9 halogen atoms which may be the same or different; R ¹⁴ 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; containing up to 9 which may be the same or different the halogen atom of the C ₁ -C ₅ haloalkyl, or may contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkoxy; heterocycle of formula (A ⁶⁾ of 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; containing 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, a hydrogen atom; a halogen atom; a substituted or unsubstituted C ₁ -C ₅ alkoxycarbonyl group; a substituted or unsubstituted C ₁ -C ₅ alkyl group; containing up to 9 halogens which may be the same or different C ₁ -C ₅ atoms or haloalkoxy comprising up to 9 halogen atoms may be the same or different C ₁ -C ₅ haloalkyl group; R ¹⁷ represents a hydrogen atom or a substituted or unsubstituted of C ₁ - C ₅ alkyl; heterocyclic ring of formula (A ⁷ ) 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; heterocyclic ring of formula (A ⁸ ) Wherein: R ²³ represents a hydrogen atom; a halogen atom; a substituted or unsubstituted alkyl group of C ₁ -C ₅ to 9 or a plurality may be the same or different halogen atoms C ₁ -C ₅ haloalkyl group; R ²⁴ It represents a hydrogen atom, or a substituted or unsubstituted alkyl group of C ₁ -C ₅ to 9 or a plurality may be the same or different halogen atoms C ₁ -C ₅ haloalkyl group; heterocycle of formula (A ⁹⁾ of Wherein: R ²⁵ represents a hydrogen atom; a halogen atom; a substituted or unsubstituted alkyl group of C ₁ -C ₅ to 9 or a plurality may be the same or different halogen atoms C ₁ -C ₅ haloalkyl group; R ²⁶ represents a hydrogen atom; a substituted or unsubstituted alkyl group of C ₁ -C ₅ to 9 or a plurality may be the same or different halogen atoms C ₁ -C ₅ haloalkyl group; heterocycle of formula (A ¹⁰⁾ of 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 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 halogen atoms which may be the same or different; containing up to 9 C ₁ -C ₅ haloalkoxy group of the same or different halogen atom; amine group; substituted or unsubstituted C ₁ -C ₅ alkylamino group or substituted or unsubstituted bis (C ₁ -C heterocycle of formula (A ¹¹⁾ of; _alkyl) amino 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; containing up to 9 may be the same or halogen atoms different from 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 by the substituted C ₁ -C ₅ alkyl; may contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl; can contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkoxy; group; a substituted or unsubstituted of C ₁ -C ₅ alkyl substituted amino group or a substituted or unsubstituted bis (C ₁ -C ₅ alkyl) amino; of formula (A ¹² Heterocycle 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 not the substituted C ₁ -C ₅ alkoxy; can contain up to 9 identical or different halogen atoms C ₁ -C ₅ alkoxy group or a halogen comprising up to 9 C may be the same or different halogen atoms ₁ -C ₅ haloalkyl; heterocycle of formula (A ¹³ ) 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; containing up to 9 may be the same or a C ₁ -C ₅ haloalkyl group of a different 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 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; the substituted C ₁ -C ₅ alkoxy group; a substituted or unsubstituted of C ₁ -C ₅ alkylthio; can contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl, a C ₁ -C ₅ haloalkoxy group containing up to 9 halogen atoms which may be the same or different; an amine group; a substituted or unsubstituted C ₁ -C ₅ alkylamino group or a substituted or unsubstituted a bis(C ₁ -C ₅ alkyl)amino group; R ³⁶ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; a heterocyclic ring of the formula (A ¹⁴ ) Wherein: R ³⁷ and R ³⁸ may be the same or different, represent a hydrogen atom; a halogen atom; a substituted or unsubstituted of C ₁ -C ₅ alkyl; C comprising up to 9 identical or different halogen atoms _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; heterocyclic ring of formula (A ¹⁵ ) 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 C comprising up to 9 identical or different halogen atoms _1-- C ₅ haloalkyl; heterocycle of formula (A ¹⁶ ) Wherein: R ⁴² and R ⁴³ may be the same or different, represent a hydrogen atom; a halogen atom; a substituted or unsubstituted of C ₁ -C ₅ alkyl; C comprising up to 9 identical or different halogen atoms _1-- C ₅ haloalkyl; or amine; heterocycle of formula (A ¹⁷ ) 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 C comprising up to 9 identical or different halogen atoms _1-- C ₅ haloalkyl; heterocycle of formula (A ¹⁸ ) Wherein: R ⁴⁷ represents a hydrogen atom; a halogen atom; a substituted or unsubstituted alkyl group of C ₁ -C ₅ to 9 or a plurality may be the same 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; may contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl, or a substituted or unsubstituted a C ₁ -C ₅ alkylthio group; a heterocyclic ring of the formula (A ¹⁹ ) 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; may comprise up to nine identical or different a halogen atoms C ₁ -C ₅ haloalkoxy, or can comprise up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl; of formula (A ²⁰ Heterocycle 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; may comprise up to nine identical or different a halogen atoms C ₁ -C ₅ haloalkoxy, or can comprise up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl; of formula (A ²¹ Heterocycle Wherein: R ⁵² represents a hydrogen atom; a halogen atom; a substituted or unsubstituted alkyl group of C ₁ -C ₅ to 9 or a plurality may be the same or different halogen atoms C ₁ -C ₅ haloalkyl; of formula ( A ²² ) heterocyclic ring Wherein: R ⁵³ represents a hydrogen atom; a halogen atom; a substituted or unsubstituted alkyl group of C ₁ -C ₅ to 9 or a plurality may be the same or different halogen atoms C ₁ -C ₅ haloalkyl; of formula ( A ²³ ) heterocyclic ring 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 C comprising up to 9 identical or different halogen atoms _1-- C ₅ haloalkyl; R ⁵⁵ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; a heterocyclic ring of the formula (A ²⁴ ) 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 C comprising up to 9 identical or different halogen atoms _1-- C ₅ haloalkyl; R ⁵⁸ represents a hydrogen atom or a substituted or unsubstituted C ₁ -C ₅ alkyl group; a heterocyclic ring of the formula (A ²⁵ ) 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 C comprising up to 9 identical or different halogen atoms _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 a C ₁ -C ₅ haloalkyl group of a different 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 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 not the substituted C ₁ -C ₅ alkoxy group; a substituted or unsubstituted of C ₁ -C ₅ alkylthio; can contain up to 9 identical or different halogen atoms C ₁ -C ₅ haloalkyl, a C ₁ -C ₅ haloalkoxy group containing up to 9 halogen atoms which may be the same or different; an amine group; a substituted or unsubstituted C ₁ -C ₅ alkylamino group or a di(C ₁ -C _{A 5-} alkyl)amino group; 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 list consisting of A ² , A ⁵ , A ⁶ , A ¹⁰ and A ¹³ . The compound of the requested item 3, wherein A represents A ^{13 is} wherein R ³⁴ represents a substituted or unsubstituted alkyl group of C ₁ -C _5, comprising up to 9 C may be the same or different halogen atoms ₁ -C ₅ Haloalkyl, or 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 any one of claims 1 to 4, wherein T represents O. The compound of any one of claims 1 to 4, wherein Z ¹ represents a substituted or unsubstituted cyclopropyl group. The compound of claim 6, wherein Z ¹ represents an unsubstituted cyclopropyl or 2-C ₁ -C ₅ alkylcyclopropyl group. The compound of any one of claims 1 to 4, wherein Z ² and Z ³ independently represent a hydrogen atom or a methyl group. The compound of any one of claims 1 to 4, wherein n represents 0, 1, or 2. The compound of any one of claims 1 to 4, wherein L represents a direct bond, an oxygen atom, a methylene group or a carbonyl group. The compound of any one of claims 1 to 4, wherein B represents a substituted or unsubstituted oxiranyl ring; a substituted or unsubstituted pyrrolyl ring; a substituted or unsubstituted pyrazole Substituted or substituted thiophenyl ring; substituted or unsubstituted benzothienyl ring; substituted or unsubstituted quinolinyl ring; substituted or unsubstituted isoquinolyl Ring; substituted or unsubstituted furan ring; or substituted or unsubstituted benzofuran ring. The compound of claim 11, wherein B represents a substituted or unsubstituted thienyl ring or a substituted or unsubstituted benzothienyl ring. The compound according to any one of claims 1 to 4, wherein X independently represents a halogen atom; a substituted or unsubstituted C ₁ -C ₈ alkyl group; and C containing up to 9 halogen atoms which may be the same or different _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 alkane group; or substituted or non-substituted C ₁ -C ₈ alkylthio. The compound according to any one of claims 1 to 4, wherein Y independently represents a halogen atom; a substituted or unsubstituted C ₁ -C ₈ alkyl group; and C containing up to 9 halogen atoms which may be the same or different ₁ -C ₈ haloalkyl; substituted or non-substituted C ₁ -C ₈ alkoxy; can contain up to 9 identical or different halogen atoms C ₁ -C ₈ haloalkoxy. a method of preparing a compound of formula (I), Wherein A, T, Z ¹ , Z ² , Z ³ , n, X and B are as defined in any one of claims 1 to 14 and L represents a direct bond or a methylene group, the method being characterized by making the formula (IV) Compound Wherein A, T, Z ¹ , Z ² , Z ³ , n, X are as defined above and U ² represents a halogen atom or a triflate group, which is reacted with a compound of formula (V), Wherein L and B are as defined above and W ¹ represents a boron derivative. a compound of formula (IIa), Wherein Z ² , Z ³ , n and X are as defined in any one of claims 1 to 14, and L is a direct bond, and B ¹ is a substituted or unsubstituted oxiranyl ring, substituted or Unsubstituted thienyl ring, substituted or unsubstituted benzothienyl ring, substituted or unsubstituted furan ring or substituted or unsubstituted benzofuran ring, the condition is (IIa) no Represents: N-[2-(2-furyl)benzyl]cyclopropylamine N-[2-(2-furyl)-4,5-dimethoxybenzyl]cyclopropylamine N-[2-(3 -bromo-2-furanyl)-4,5-dimethoxybenzyl]cyclopropylamine N-[2-(3-bromo-2-furanyl)benzyl]cyclopropylamine N-[2-(3- Furanyl)benzyl]cyclopropylamine N-[2-(2-thienyl)benzyl]cyclopropylamine N-[4,5-dimethoxy-2-(2-thienyl)benzyl]cyclopropylamine, And its salt. A compound of the formula (IIa) according to claim 16 which is selected from the list consisting of N-[5-chloro-2-(2-furyl)benzyl]cyclopropylamine N-[5-chloro-2-( 2-thienyl)benzyl]cyclopropylamine N-[2-(3-thienyl)benzyl]cyclopropylamine N-{1-[2-(3-thienyl)phenyl]ethyl}cyclopropylamine N- [5-Chloro-2-(3-thienyl)benzyl]cyclopropylamine N-[2-(5-chloro-2-thienyl)benzyl]cyclopropylamine N-[5-chloro-2-(5- Chloro-2-thienyl)benzyl]cyclopropylamine. a compound of formula (IIb), Wherein Z ² , Z ³ , n and X are as defined in any one of claims 1 to 14, and L is a direct bond, and B ¹ is a substituted or unsubstituted oxiranyl ring, substituted or Unsubstituted thiophene ring, substituted or unsubstituted benzothienyl ring, substituted or unsubstituted furan ring or substituted or unsubstituted benzofuran ring, the restriction condition is (IIb) Represents: N-[3-(2-furyl)benzyl]cyclopropylamine N-[5-(2-furyl)-2-methoxybenzyl]cyclopropylamine N-[4-fluoro-3-( 2-furyl)benzyl]cyclopropylamine N-[2-fluoro-5-(2-furyl)benzyl]cyclopropylamine N-[2-fluoro-5-(3-furyl)benzyl]cyclopropylamine N-[3-(3-Bromo-2-furyl)-4-fluorobenzyl]cyclopropylamine N-[3-(3-bromo-2-furyl)benzyl]cyclopropylamine N-[5-( 3-bromo-2-furanyl)-2-fluorobenzyl]cyclopropylamine N-[5-(3-bromo-2-furyl)-2-methoxybenzyl]cyclopropylamine N-[3-( 3-furyl)benzyl]cyclopropylamine N-[3-(2-thienyl)benzyl]cyclopropylamine N-[4-fluoro-3-(2-thienyl)benzyl]cyclopropylamine N-[2 -Fluoro-5-(2-thienyl)benzyl]cyclopropylamine N-[2-methoxy-5-(2-thienyl)benzyl]cyclopropylamine 5-{5-[(cyclopropylamino) )methyl]-2-fluorophenyl}thiophene-2-carbonitrile, and salts thereof . A compound of the formula (IIb) according to claim 18, which is selected from the list consisting of N-[2-chloro-5-(2-furyl)benzyl]cyclopropylamine N-[2-chloro-5-( 2-thienyl)benzyl]cyclopropylamine N-[2-chloro-5-(3-thienyl)benzyl]cyclopropylamine N-[2-chloro-5-(5-chloro-2-thienyl)benzyl Base] cyclopropylamine. a compound of formula (Xa), Wherein Z ² and Z ^{3 are} as defined in any one of claims 1 to 14, A represents A ¹³ , X ^a1 represents a halogen atom; substituted or unsubstituted C ₁ -C ₈ alkyl; contains up to 9 C ₁ -C ₈ haloalkyl which may be the same or different halogen atom; substituted or unsubstituted C ₃ -C ₇ cycloalkyl; tri(C ₁ -C ₈ alkyl)decyl; substituted or not Substituted C ₁ -C ₈ alkoxy group; or substituted or unsubstituted C ₁ -C ₈ alkylthio group, X ^a2 represents hydrogen; halogen atom; substituted or unsubstituted C ₁ -C ₈ An alkyl group; a C ₁ -C ₈ haloalkyl group containing up to 9 halogen atoms which may be the same or different; a substituted or unsubstituted C ₃ -C ₇ cycloalkyl group; a tri(C ₁ -C ₈ alkyl group) a nonyl group; a substituted or unsubstituted C ₁ -C ₈ alkoxy group; or a substituted or unsubstituted C ₁ -C ₈ alkylthio group; U ² represents a halogen atom or a trifluoromethanesulfonate The restriction condition is that (Xa) does not mean: N-(2,5-dichlorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-methyl Indoleamine N-[1-(2,5-dichlorophenyl)ethyl]-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide N -[2-(2,5-dichlorophenyl)propan-2-yl]-3-(difluoromethyl) 5-)fluoro-1-methyl-1H-pyrazole-4-carboxamide N-[1-(2,5-dichlorophenyl)cyclopropyl]-3-(difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide 5-chloro-N-[1-(2,5-dichlorophenyl)ethyl]-3-(difluoromethyl )-1-methyl-1H-pyrazole-4-carboxamide 5-chloro-N-[2-(2,5-dichlorophenyl)propan-2-yl]-3-(difluoromethyl )-1-methyl-1H-pyrazole-4-carboxamide 5-chloro-N-[1-(2,5-dichlorophenyl)cyclopropyl]-3-(difluoromethyl)- 1-methyl-1H-pyrazole-4-carboxamide 5-chloro-N-(2,5-dichlorobenzyl)-3-(difluoromethyl)-1-methyl-1H-pyrazole 4-Methylguanamine N-(5-bromo-2-fluorobenzyl)-1,3,5-trimethyl-1H-pyrazole-4-carboxamide N-(5-bromo-2-fluoro Benzyl)-3,5-dimethyl-1H-pyrazole-4-carboxamide 1-methyl-N-[1-(2,4,5-trichlorophenyl)ethyl]-3- (trifluoromethyl)-1H-pyrazole-4-carbamide 3-(difluoromethyl)-1-methyl-N-[1-(2,4,5-trichlorophenyl)ethyl -1H-pyrazole-4-carbamide N-(5-chloro-2-fluorobenzyl)-1-methyl-5-propoxy-3-(trifluoromethyl)-1H-pyrazole 4-Methylguanamine N-(2,5-dichlorobenzyl)-1-methyl-5-propoxy-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, And its salt. The compound of claim 20, which is selected from the list consisting of N-(5-chloro-2-ethylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H -pyrazole-4-carboxamide N-(5-chloro-2-isopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4- Methionamine N-[5-chloro-2-(trifluoromethyl)benzyl]-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamidine amine. 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 14 and an agriculturally acceptable carrier, carrier or filler. A method for controlling a phytopathogenic fungus of a crop, characterized by applying an agronomically effective and substantially non-phytotoxic amount to a growing plant or a soil capable of growing the plant, a leaf of the plant and/or a fruit or a plant. The compound of any one of items 1 to 14 or the composition of claim 21. A use of a compound of formula (I) according to any one of claims 1 to 14 for controlling a phytopathogenic harmful fungus. A method of producing a composition for controlling a phytopathogenic harmful fungus, characterized in that a derivative of the formula (I) according to any one of claims 1 to 14 is mixed with a bulking agent and/or a surfactant. Use of a compound of formula (I) according to any one of claims 1 to 14 for the treatment of plants, seeds, transgenic plants or transgenic seeds.