WO2013156559A1 - N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives - Google Patents
N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives Download PDFInfo
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- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
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- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
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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)CARBOXAMIDE
DERIVATIVES
DESCRIPTION
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.
In international patent application WO-2007/087906 certain N-cycloalkyl-N-benzyl-carboxamid' generically embraced in a broad disclosure of numerous compounds of the following formula:
wherein A represents a carbo-linked, partially saturated or unsaturated, 5-membered heterocyclyl group, Z1 represents a substituted or non-substituted C3-C7-cycloalkyl group, n is equal to 1 to 5 and X can represent various substituents among which a substituted or non-substituted pyridinyl or pyridinyloxy group. However, there is no explicit disclosure or suggestion to select in this document of any such derivative wherein X can represent a substituted or non-substituted heterocycyl group. In international patent application WO-2009/01 6220 certain N-cycloalkyl-N-benzyl-thiocarboxamides are generically embraced in a broad disclosure of numerous compounds of the following formula:
wherein A represents a carbo-linked, partially saturated or unsaturated, 5-membered heterocyclyl group, T can represent S, Z1 represents a substituted or non-substituted C3-C7-cycloalkyl group, n is equal to 1 to 5 and X can represent various substituents among which a substituted or non-substituted pyridinyl or pyridinyloxy group. However, there is no explicit disclosure or suggestion to select in this document of any such derivative wherein X can represent a substituted or non-substituted heterocycyl group.
In international patent application WO-201 0/130767 certain N-cycloalkyl-N-benzyl-carboxamides or thiocarboxamides are generically embraced in a broad disclosure of numerous compounds of the following formula:
wherein X1 and X2 represent a fluorine of a chlorine atom, T can represent O or S, Z1 represents a substituted or non-substituted -cycloalkyl group, Y can represent CR5 and R1 , R2, R3, R4 or R5 can, independently, represent various substituents among which a substituted or non-substituted pyridinyl or pyridinyloxy group. However, there is no explicit disclosure or suggestion to select in this document of any such derivative wherein R1 or R2 or R3 or R4 or R5 can represent a substituted or non-substituted heterocycyl group.
In international patent application WO-2009/024342 certain N-(substituted phenyl)methylene-carboxa- mides are generically embraced in a broad disclosure of numerous compounds of the following formula:
wherein Ri represents a Ci -C4-alkyl group, R2 represents a Ci-C4-haloalkyl group, B can represent a phenyl group that can be substituted by various substituents among which a substituted or non substituted phenyl group or a substituted or non substituted phenoxy group, and R15 can represent hydrogen or a C3-C7-cycloalkyl group with the proviso that B is different from phenyl if R15 represents a C3-C7-cycloalkyl group. Therefore, there is no disclosure in this document of any such derivative wherein R15 can represent a C3-C7-cycloalkyl group and B be simultaneously a substituted phenyl group.
Accordingly, the present invention provides a N-cycloalkyl-N-[(heterocyclylphenyl)methylene](thio) carboxamide of formula (I)
(I)
wherein
• A represents a carbo-linked, unsaturated or partially saturated, 5-membered heterocyclyl group that can be substituted by up to four groups R that can be the same or different ;
• T represents O or S ;
• n represents 0, 1 , 2, 3 or 4 ;
· L represents a direct bond, CZ4Z5, O, S, SO, S02 or NZ6 ;B represents a saturated, partially saturated or unsaturated, monocyclic or fused bicyclic 3-, 4-, 5-, 6-, 7-, 8-, 9-, or 10-membered ring comprising from 1 up to 4 heteroatoms selected in the list consisting of N, O, S, that can be substituted by up to 6 groups Y which can be the same or different ; with the proviso that B does not represent a pyridyl ring when L represents a direct bond or an oxygen atom
· Z1 represents a non-substituted C3-C7-cycloalkyl or a C3-C7-cycloalkyl substituted by up to 1 0 atoms or groups that can be the same or different and that can be selected in the list consisting of halogen atoms, cyano, CrC8-alkyl, CrC8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, CrC8-alkoxy, CrC8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, Ci -C8-alkoxycarbonyl, Ci - C8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different, Ci -C8-alkylaminocarbonyl or di-Ci -C8-alkylaminocarbonyl ;
• Z2 and Z3, which can be the same or different, represent a hydrogen atom ; substituted or non- substituted Ci -C8-alkyl ; substituted or non-substituted C2-C8-alkenyl ; substituted or non- substituted C2-C8-alkynyl ; cyano ; isonitrile ; nitro ; a halogen atom ; substituted or non- substituted CrC8-alkoxy ; substituted or non-substituted C2-C8-alkenyloxy ; substituted or non- substituted C2-C8-alkynyloxy ; substituted or non-substituted C3-C7-cycloalkyl ; substituted or non-substituted Ci -C8-alkylsulfanyl ; substituted or non-substituted Ci -C8-alkylsulfonyl ; substituted or non-substituted Ci -C8-alkylsulfinyl ; amino ; substituted or non-substituted Ci -C8-alkylamino ; substituted or non-substituted di-Ci -C8-alkylamino ; substituted or non- substituted CrC8-alkoxycarbonyl ; substituted or non-substituted Ci -C8-alkylcarbamoyl ; substituted or non-substituted di-CrC8-alkylcarbamoyl ; or substituted or non-substituted N- Ci -C8-alkyl-Ci -C8-alkoxy-carbamoyl ; or
• Z2 and Z3 together with the carbon atom to which they are linked can form a substituted or non-substituted cycloalkyl ; or
• Z3 and the substituent X vicinal to the point of attachment of the phenyl ring, together with the consecutive carbon atoms to which they are linked, can form a substituted or non-substituted 5-, 6- or 7-membered, partly saturated, carbo- or heterocycle comprising up to 3 heteroatoms and Z2 is as herein-described ; Z4 and Z5 independently represent a hydrogen atom ; a halogen atom ; cyano ; substituted or non-substituted CrC8-alkyl ; CrC8-halogenoalkyl having
1 to 5 halogen atoms ; substituted or non-substituted Ci -C8-alkoxy; substituted or non- substituted Ci -C8-alkylsulfanyl ; or substituted or non-substituted Ci -C8-alkoxycarbonyl ; or
Z4 and Z5 together with the carbon atom to which they are linked can form a C(=0) carbonyl group ;
Z6 represents a hydrogen atom ; a substituted or non-substituted CrC8-alkyl ; a CrC8- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted C2-C8-alkenyl ; C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted C3-C8-alkynyl ; C3-C8- halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted C3-C7-cycloalkyl ; C3-C7-halogeno-cycloalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted C3-C7- cycloalkyl-CrC8-alkyl ; formyl ; substituted or non-substituted CrC8-alkylcarbonyl ; Ci -C8- halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted CrC8-alkoxycarbonyl ; CrC8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non- substituted Ci -C8-alkylsulfonyl ; CrC8-halogenoalkylsulfonyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted benzyl ; or substituted or non-substituted phenylsulfonyl ;X independently represents a halogen atom ; nitro ; cyano ; isonitrile ; hydroxy ; amino ; sulfanyl ; pentafluoro-A6-sulfanyl ; formyl ; formyloxy ; formylamino ; substituted or non-substituted (hydroxyimino)-Ci -C8-alkyl ; substituted or non- substituted (Ci -C8-alkoxyimino)-Ci -C8-alkyl ; substituted or non-substituted (C2-C8- alkenyloxyimino)-Ci -C8-alkyl ; substituted or non-substituted (C2-C8-alkynyloxyimino)-Ci -C8- alkyl ; substituted or non-substituted (benzyloxyimino)-Ci -C8-alkyl ; carboxy ; carbamoyl ; N- hydroxycarbamoyl ; carbamate ; substituted or non-substituted CrC8-alkyl ; CrC8- halogenoalkyl having 1 to 9 halogen atoms ; substituted or non-substituted C2-C8-alkenyl ; C2- C8-halogenoalkenyl having 1 to 9 halogen atoms ; substituted or non-substituted C2-C8- alkynyl ; C2-C8-halogenoalkynyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci -C8-alkoxy ; CrC8-halogenoalkoxy having 1 to 9 halogen atoms ; substituted or non- substituted Ci -C8-alkylsulfanyl ; CrC8-halogenoalkylsulfanyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylsulfinyl ; Ci -C8-halogenoalkylsulfinyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci -C8-alkylsulfonyl ; Ci -C8- halogenoalkylsulfonyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci -C8- alkylamino ; substituted or non-substituted di-Ci -C8-alkylamino ; substituted or non-substituted C2-C8-alkenyloxy ; C2-C8-halogenoalkenyloxy having 1 to 9 halogen atoms ; substituted or non-substituted C3-C8-alkynyloxy ; C2-C8-halogenoalkynyloxy having 1 to 9 halogen atoms ; substituted or non-substituted C3-C7-cycloalkyl ; C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms ; substituted or non-substituted (C3-C7-cycloalkyl)-Ci -C8-alkyl ; substituted or non-substituted C4-C7-cycloalkenyl ; C4-C7-halogenocycloalkenyl having 1 to 9 halogen atoms ; substituted or non-substituted (C3-C7-cycloalkyl)-C2-C8-alkenyl ; substituted or non- substituted (C3-C7-cycloalkyl)-C2-C8-alkynyl ; substituted or non-substituted tri(CrC8)alkylsilyl ; substituted or non-substituted tri(Ci -C8)alkylsilyl-Ci -C8-alkyl ; substituted or non-substituted Ci -C8-alkylcarbonyl ; CrC8-halogenoalkylcarbonyl having 1 to 9 halogen atoms ; substituted
or non-substituted CrC8-alkylcarbonyloxy ; Ci-C8-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms ; substituted or non-substituted Ci-C8-alkylcarbonylamino ; CrC8- halogenoalkylcarbonylamino having 1 to 9 halogen atoms ; substituted or non-substituted Ci- C8-alkoxycarbonyl ; CrC8-halogenoalkoxycarbonyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci-C8-alkyloxycarbonyloxy ; Ci-C8-halogenoalkoxycarbonyloxy having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylcarbamoyl ; substituted or non- substituted di-CrC8-alkylcarbamoyl ; substituted or non-substituted CrC8- alkylaminocarbonyloxy ; substituted or non-substituted di-Ci-C8-alkylaminocarbonyloxy ; substituted or non-substituted N-(CrC8-alkyl)hydroxy carbamoyl ; substituted or non- substituted CrC8-alkoxycarbamoyl ; substituted or non-substituted N-(Ci-C8-alkyl)-CrC8- alkoxycarbamoyl ; aryl that can be substituted by up to 6 groups Q which can be the same or different ; aryl-CrC8-alkyl that can be substituted by up to 6 groups Q which can be the same or different ; aryl-C2-C8-alkenyl that can be substituted by up to 6 groups Q which can be the same or different ; aryl-C2-C8-alkynyl that can be substituted by up to 6 groups Q which can be the same or different ; aryloxy that can be substituted by up to 6 groups Q which can be the same or different ; arylsulfanyl that can be substituted by up to 6 groups Q which can be the same or different ; arylamino that can be substituted by up to 6 groups Q which can be the same or different ; aryl-CrC8-alkyloxy that can be substituted by up to 6 groups Q which can be the same or different ; aryl-Ci-C8-alkylsulfanyl that can be substituted by up to 6 groups Q which can be the same or different ; aryl-CrC8-alkylamino that can be substituted by up to 6 groups Q which can be the same or different ; pyridinyl which can be substituted by up to 4 groups Q ; or pyridinyloxy which can be substituted by up to 4 groups Q ;
Y independently represents a halogen atom ; cyano ; hydroxy ; amino ; sulfanyl ; substituted or non-substituted Ci-C8-alkyl ; CrC8-halogenoalkyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci-C8-alkoxy ; Ci-C8-halogenoalkoxy having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylsulfanyl ; Ci-C8-halogenoalkylsulfanyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylsulfinyl ; Ci-C8-halogenoalkylsulfinyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylsulfonyl ; Ci-C8- halogenoalkylsulfonyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8- alkylamino ; substituted or non-substituted di-Ci-C8-alkylamino ; substituted or non-substituted CrC8-alkylcarbonyl ; CrC8-halogenoalkylcarbonyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkoxycarbonyl ; CrC8-halogenoalkoxycarbonyl having 1 to 9 halogen atoms ; or aryl that can be substituted by up to 6 groups Q which can be the same or different ;
Q independently represents a halogen atom, cyano, nitro, substituted or non-substituted d- C8-alkyl, Ci-C8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, substituted or non-substituted Ci-C8-alkoxy, Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, substituted or non-substituted CrC8- alkylsulfanyl, Ci-C8-halogenoalkylsulfanyl comprising up to 9 halogen atoms that can be the same or different, substituted or non-substituted tri(Ci-C8)alkylsilyl, substituted or non-
substituted tri(Ci-C8)alkylsilyl-Ci-C8-alkyl, substituted or non-substituted (Ci-C8-alkoxyimino)- Ci -C8-alkyl , or substituted or non-substituted (benzyloxyimino)-Ci-C8-alkyl ;
• R independently represents hydrogen atom ; halogen atom ; nitro ; cyano ; hydroxy ; amino ; sulfanyl ; pentafluoro-A6-sulfanyl ; substituted or non-substituted (Ci-C8-alkoxyimino)-Ci -C8- alkyl ; substituted or non-substituted (benzyloxyimino)-Ci -C8-alkyl ; substituted or non- substituted Ci-C8-alkyl ; Ci-C8-halogenoalkyl having 1 to 9 halogen atoms ; substituted or non- substituted C2-C8-alkenyl ; C2-C8-halogenoalkenyl having 1 to 9 halogen atoms ; substituted or non-substituted C2-C8-alkynyl ; C2-C8-halogenoalkynyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkoxy ; CrC8-halogenoalkoxy having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylsulfanyl ; CrC8-halogenoalkylsulfanyl having
1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylsulfinyl ; CrC8- halogenoalkylsulfinyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci-C8- alkylsulfonyl ; CrC8-halogenoalkylsulfonyl having 1 to 9 halogen atoms ; substituted or non- substituted CrC8-alkylamino ; substituted or non-substituted di-Ci-C8-alkylamino ; substituted or non-substituted C2-C8-alkenyloxy ; substituted or non-substituted C3-C8-alkynyloxy ; substituted or non-substituted C3-C7-cycloalkyl ; C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms ; substituted or non-substituted tri(Ci-C8)alkylsilyl ; substituted or non- substituted CrC8-alkylcarbonyl ; CrC8-halogenoalkylcarbonyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkoxycarbonyl ; CrC8-halogenoalkoxycarbonyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci -C8-alkylcarbamoyl ; substituted or non- substituted di-CrC8-alkylcarbamoyl ; phenoxy ; phenylsulfanyl ; phenylamino ; benzyloxy ; benzylsulfanyl ; or benzylamino ;
as well as its salts, N-oxides, metal complexes, metalloid complexes and optically active isomers or geometric isomers thereof.
Unless indicated otherwise, a group or a substituent that is substituted according to the invention can be substituted by one or more of the following groups or atoms: a halogen atom ; nitro ; hydroxyl ; cyano ; isonitrile ; amino ; sulfanyl ; a pentafluoro- 6-sulfanyl group ; formyl ; formyloxy ; formylamino ; carbamoyl ; N-hydroxycarbamoyl ; carbamate ; (hydroxyimino)-Ci-C6-alkyl ; Ci-C8- alkyl ; a tri(CrC8-alkyl)silyl ; C3-C8-cycloalkyl ; CrC8-halogenoalkyl having 1 to 5 halogen atoms ; a C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms ; C2-C8-alkenyl ; C2-C8-alkynyl ; C2-C8- alkenyloxy ; C2-C8-alkynyloxy ; CrC8-alkylamino ; di-CrC8-alkylamino ; CrC8-alkoxy ; CrC8- halogenoalkoxy having 1 to 5 halogen atoms ; CrC8-alkylsulfanyl ; CrC8-halogenoalkylsulfanyl having 1 to 5 halogen atoms ; C2-C8-alkenyloxy ; C2-C8-halogenoalkenyloxy having 1 to 5 halogen atoms ; C3-C8-alkynyloxy ; C3-C8-halogenoalkynyloxy having 1 to 5 halogen atoms ; CrC8- alkylcarbonyl ; CrC8-halogenoalkylcarbonyl having 1 to 5 halogen atoms ; CrC8-alkylcarbamoyl ; di-CrC8-alkylcarbamoyl ; N-CrC8-alkyloxycarbamoyl ; CrC8-alkoxycarbamoyl ; N-CrC8-alkyl-Ci - C8-alkoxycarbamoyl ; CrC8-alkoxycarbonyl ; CrC8-halogenoalkoxycarbonyl having 1 to 5 halogen atoms ; CrC8-alkylcarbonyloxy ; CrC8-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms ; Ci-C8-alkylcarbonylamino ; Ci-C8-halogenoalkylcarbonylamino having 1 to 5 halogen atoms ; Ci-
Cs-alkylaminocarbonyloxy ; di-Ci -C8-alkylaminocarbonyloxy ; Ci -C8-alkyloxycarbonyloxy ; CrC8- alkylsulfanyl ; Ci -C8-halogenoalkylsulfanyl having 1 to 5 halogen atoms; CrC8-alkylsulfinyl ; CrC8- halogenoalkylsulfinyl having 1 to 5 halogen atoms ; Ci -C8-alkylsulfonyl ; Ci -C8-halogenoalkyl- sulfonyl having 1 to 5 halogen atoms ; Ci -C8-alkylaminosulfamoyl ; di-Ci -C8-alkylaminosulfamoyl ; (Ci -C6-alkoxyimino)-Ci -C6-alkyl ; (Ci -C6-alkenyloxyimino)-Ci -C6-alkyl ; (Ci -C6-alkynyloxyimino)-Ci - C6-alkyl ; 2-oxopyrrolidin-1 -yl ; (benzyloxyimino)-Ci -C6-alkyl ; Ci -C8-alkoxyalkyl ; CrC8- halogenoalkoxyalkyl having 1 to 5 halogen atoms ; benzyloxy ; benzylsulfanyl ; benzylamino ; aryloxy ; arylsulfanyl or arylamino.
According to the invention, the following generic terms are generally used with the following meanings:
• halogen means fluorine, chlorine, bromine or iodine ,
carboxy means -C(=0)OH ;
carbonyl means -C(=0)- ;
carbamoyl means -C(=0)NH2 ;
N-hydroxycarbamoyl means -C(=0)NHOH ;
SO represents a sulfoxide group ;
S02 represents a sulfone group ;
heteroatom means sulfur, nitrogen or oxygen ;
methylene means the diradical -CH2- ;
• an alkyl group, an alkenyl group and an alkynyl group as well as moieties containing these terms, can be linear or branched ;
• halogenated groups, notably haloalkyl, haloalkoxy and cycloalkyl groups, can comprise up to nine identical or different halogen atoms ;
• the term "aryl" means phenyl or naphthyl ;
• In the case of an amino group or the amino moiety of any other amino-containing group, substituted by two substituents that can be the same or different, the two substituents together with the nitrogen atom to which they are linked can form a heterocyclyl group, preferably a 5- to 7-membered heterocyclyl group, that can be substituted or that can include other hetero atoms, for example a morpholino group or piperidinyl group.
• Where a compound of the invention can be present in tautomeric form, such a compound is understood hereinabove and hereinbelow also to include, where applicable, corresponding tautomeric forms, even when these are not specifically mentioned in each case.
Any of the compounds of the present invention can exist in one or more optical or chiral isomer forms depending on the number of asymmetric centres in the compound. The invention thus relates equally to all the optical isomers and to their racemic or scalemic mixtures (the term "scalemic" denotes a mixture of enantiomers in different proportions) and to the mixtures of all the possible stereoisomers, in all proportions. The diastereoisomers and/or the optical isomers can be separated according to the methods which are known per se by the man ordinary skilled in the art.
Any of the compounds of the present invention can also exist in one or more geometric isomer forms
depending on the number of double bonds in the compound. The invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions. The geometric isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.
Any of the compounds of the present invention can also exist in one or more geometric isomer forms depending on the relative position (syn/anti or cis/trans) of the substituents of the chain or ring. The invention thus relates equally to all syn/anti (or cis/trans) isomers and to all possible syn/anti (or cis/trans) mixtures, in all proportions. The syn/anti (or cis/trans) isomers can be separated according to general methods, which are known per se by the man ordinary skilled in the art.
Preferred compounds according to the invention are compounds of formula (I) wherein A is selected in the list consisting of:
- a heterocycle of formula (A1)
(A1)
wherein :
R1 to R3 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; CrC5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted CrC5-alkoxy or Ci-C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A2)
wherein :
R4 to R6 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; CrC5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-Cs-alkoxy or Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A3)
R7 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -Cs-alkyl ; C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non- substituted Ci -Cs-alkoxy or Ci -Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
R8 represents a hydrogen atom or a substituted or non-substituted CrC5-alkyl ;
- a heterocycle of formula (A4)
(A4)
wherein :
R9 to R11 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -Cs-alkyl ; amino ; substituted or non-substituted Ci -Cs-alkoxy ; substituted or non-substituted CrC5-alkylsulfanyl ; CrC5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci -Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A5)
(A5)
wherein :
R12 and R13 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; substituted or non-substituted CrC5-alkoxy ; amino ; C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or C1 -C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
R14 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -Cs-alkyl ; substituted or non-substituted CrC5-alkoxy ; amino ; CrC5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci -Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A6)
(A6)
wherein :
R15 represents a hydrogen atom ; a halogen atom ; a cyano ; substituted or non-substituted C1 -C5- alkyl ; substituted or non-substituted CrC5-alkoxy ; CrC5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R16 and R18 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkoxycarbonyl ; substituted or non-substituted CrC5-alkyl ; d- Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R17 represent a hydrogen atom or substituted or non-substituted CrC5-alkyl ;
- a heterocycle of formula (A7)
(A7)
wherein :
R19 represents a hydrogen atom or a Ci -Cs-alkyl
R20 to R22 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -Cs-alkyl or Ci -Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A8)
(A8)
wherein :
R23 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R24 represents a hydrogen atom or substituted or non-substituted Ci -C5-alkyl or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;
- a heterocycle of formula (A9)
(A9)
wherein :
R25 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R26 represents a hydrogen atom ; substituted or non-substituted CrC5-alkyl or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; - a heterocycle of formula (A10)
(A10)
wherein :
R27 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -Cs-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R28 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C1 -C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci -Cs-alkylamino or substituted or non-substituted di(Ci -C5-alkyl)amino ;
- a heterocycle of formula (A11)
wherein :
R29 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -Cs-alkyl ; substituted or non-substituted CrC5-alkoxy ; CrC5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R30 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; C1 -C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted C Cs-alkylamino or substituted or non-substituted di(Ci -C5-alkyl)amino ;
- a heterocycle of formula (A12)
(A12)
wherein :
R31 represents a hydrogen atom or a substituted or non-substituted CrC5-alkyl
R32 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R33 represents a hydrogen atom ; a halogen atom ; a nitro ; substituted or non-substituted Ci -Cs-alkyl ; substituted or non-substituted CrC5-alkoxy ; CrC5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci -Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A13)
(A13)
wherein :
R34 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; substituted or non-substituted Cs-Cs-cycloalkyl ; Ci -Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted CrC5-alkoxy ; substituted or non-substituted C2-C5-alkynyloxy or Ci -Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
R35 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -C5-alkyl ; a cyano ; substituted or non-substituted CrC5-alkoxy ; substituted or non-substituted C1 -C5- alkylsulfanyl ; Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci -C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted Ci -Cs-alkylamino or substituted or non-substituted di(Ci -Cs- alkyl)amino;
R36 represents a hydrogen atom or substituted or non-substituted C rC5-alkyl ;
-a heterocycle of formula (A14)
(A14)
wherein :
R37 and R38 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; CrC5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci -C5-alkoxy or a substituted or non- substituted C1 -C5- alkylsulfanyl ;
R39 represents a hydrogen atom or substituted or non-substituted C i -Cs-alkyl ;
- a heterocycle of formula (A15)
(A15)
wherein :
R40 and R41 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -Cs-alkyl or Ci -Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A16)
(A16)
wherein :
R42 and R43 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -Cs-alkyl ; Ci -Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or amino ;
-a heterocycle of formula (A17)
(A17)
wherein :
R44 and R45 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; - a heterocycle of formula (A18)
(A18)
wherein :
R47 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or Ci -C halogenoalkyi comprising up to 9 halogen atoms that can be the same or different ;
R46 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -Cs-alkyl ; Ci -C halogenoalkyi comprising up to 9 halogen atoms that can be the same or different or substituted non-substituted CrC5-alkylsulfanyl ;
- a heterocycle of formula (A19)
(A19)
wherein :
R49 and R48 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; substituted or non-substituted Ci -C5-alkoxy ; C1 -C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; a heterocycle of formula (A20)
(A20)
wherein :
R50 and R51 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; substituted or non-substituted Ci -C5-alkoxy ; C1 -C5- halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
-a heterocycle of formula (A21 )
(A21 )
wherein :
R52 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
-a heterocycle of formula (A22)
(A22)
wherein :
R53 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
-a heterocycle of formula (A23)
(A23)
wherein :
R54 and R56 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R55 represents a hydrogen atom or substituted or non-substituted C rC5-alkyl ; -a heterocycle of formula (A24)
(A24)
wherein
R57 and R59 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or CrCs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R58 represents a hydrogen atom or substituted or non-substituted C rC5-alkyl ;
-a heterocycle of formula (A25)
(A25)
wherein :
R60 and R61 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or CrCs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R62 represents a hydrogen atom or substituted or non-substituted C rC5-alkyl ; -a heterocycle of formula (A26)
(A26)
wherein :
R65 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrCs-alkyl ; substituted or non-substituted C3-C5-cycloalkyl ; d -Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted d-Cs-alkoxy ; substituted or non-substituted C2-C5-alkynyloxy or CrC5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
R63 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrCs-alkyl ; a cyano ; substituted or non-substituted CrC5-alkoxy ; substituted or non-substituted CrC5- alkylsulfanyl ; Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; CrC5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non-substituted CrC5-alkylamino or di(CrC5-alkyl)amino;
R64 represents a hydrogen atom or substituted or non-substituted C rC5-alkyl.
More preferred compounds according to the invention are compounds of formula (I) wherein A is selected in the list consisting of A2 ; A5 ; A6 ; A10 and A13 as herein-defined.
Even more preferred compounds according to the invention are compounds of formula (I) wherein A
represents A13 wherein R34 represents a substituted or non-substituted CrC5-alkyl, C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non- substituted Ci -Cs-alkoxy ; R35 represents a hydrogen atom or a halogen atom and R36 represents a substituted or non-substituted Ci -C5-alkyl.
Even more preferred compounds according to the invention are compounds of formula (I) wherein A represents A13 wherein R34 represents CrC5-alkyl, CrC5-halogenoalkyl comprising up to 3 halogen atoms that can be the same or different ; R35 represents a hydrogen atom ; a chlorine atom ; or a fluorine atom ; and R36 represents a methyl.
Other preferred compounds according to the invention are compounds of formula (I) wherein T represents O.
Other preferred compounds according to the invention are compounds of formula (I) wherein Z1 represents a substituted or non-substituted cyclopropyl.
Other more preferred compounds according to the invention are compounds of formula (I) wherein Z1 represents a non-substituted cyclopropyl or a 2-CrC5-alkylcyclopropyl. Other even more preferred compounds according to the invention are compounds of formula (I) wherein Z1 represents a non-substituted cyclopropyl.
Other even more preferred compounds according to the invention are compounds of formula (I) wherein Z1 represents a 2-methylcyclopropyl.
Other preferred compounds according to the invention are compounds of formula (I) wherein Z2 and Z3 independently represent a hydrogen atom or a methyl.
More preferred compounds according to the invention are compounds of formula (I) wherein Z2 represents a hydrogen atom and Z3 represents a hydrogen atom or a methyl.
Other preferred compounds according to the invention are compounds of formula (I) wherein n represents 0, 1 or 2. Other preferred compounds according to the invention are compounds of formula (I) wherein L represents a direct bond.
Other preferred compounds according to the invention are compounds of formula (I) wherein L represents an oxygen atom.
Other preferred compounds according to the invention are compounds of formula (I) wherein L represents a methylene or a carbonyl group.
Other preferred compounds according to the invention are compounds of formula (I) wherein B represents a substituted or non-substituted oxiranyl ring; a substituted or non-substituted pyrrolyl ring; a substituted or non-substituted pyrazolyl ring; a substituted or non-substituted thienyl ring; a substituted or non-substituted benzothienyl ring; a substituted or non-substituted quinolinyl ring; a substituted or non-substituted isoquinolinyl ring ; a substituted or non-substituted furan ring; or a substituted or non-substituted benzofuran ring.
Other more preferred compounds according to the invention are compounds of formula (I) wherein B represents a substituted or non-substituted thienyl ring. Other more preferred compounds according to the invention are compounds of formula (I) wherein B represents a substituted or non-substituted benzothienyl ring.
Other preferred compounds according to the invention are compounds of formula (I) wherein X independently, represents a halogen atom ; substituted or non-substituted Ci -C8-alkyl ; CrC8- halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non-substituted C3-C7-cycloalkyl ; tri(Ci -Ce-alkyl)silyl; substituted or non-substituted Ci -C8-alkoxy; or substituted or non-substituted CrC8-alkylsulfanyl.
Other preferred compounds according to the invention are compounds of formula (I) wherein Y independently, represents a halogen atom ; substituted or non-substituted Ci -C8-alkyl ; CrC8- halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non-substituted CrC8-alkoxy ; CrC8-halogenoalkoxy comprising up to 9 halogen atoms which can be the same or different.
The above mentioned preferences with regard to the substituents of the compounds according to the invention can be combined in various manners. These combinations of preferred features thus provide sub-classes of compounds according to the invention. Examples of such sub-classes of preferred compounds according to the invention are:
- preferred features of A with preferred features of T, Z1 to Z3, n, X, L, B and Y;
- preferred features of T with preferred features of A, Z1 to Z3, n, X, L, B and Y;
- preferred features of Z1 with preferred features of A, T, Z2, Z3, n, X, L, B and Y;
- preferred features of Z2 with preferred features of A, T, Z1 ,Z3, n, X, L, B and Y;
- preferred features of Z3 with preferred features of A, T, Z1 , Z2, n, X, L, B and Y;
- preferred features of n with preferred features of A, T, Z1 to Z3, X, L, B and Y;
- preferred features of X with preferred features of A, T, Z1 to Z3, n, L, B and Y;
- preferred features of L with preferred features of A, T, Z1 to Z3, n, X, B and Y;
- preferred features of B with preferred features of A, T, Z1 to Z3, n, X, L and Y;
- preferred features of Y with preferred features of A, T, Z1 to Z3, n, X, L and B.
In these combinations of preferred features of the substituents of the compounds according to the invention, the said preferred features can also be selected among the more preferred features of each of A, T, Z1 to Z3, n, X, L, B and Y so as to form most preferred subclasses of compounds according to the invention.
The present invention also relates to a process for the preparation of the compound of formula (I). Thus, according to a further aspect of the present invention there is provided a process P1 for the preparation of a compound of formula (I) as herein-defined and wherein T represents O and that comprises reaction of an amine of formula (I I) or one of its salts:
(III)
wherein A is as herein-defined and U1 represents a leaving group selected in the list consisting of a halogen atom, a hydroxyl group, -ORa, -OC(=0)Ra, Ra being a substituted or non-substituted CrC6- alkyl, a substituted or non-substituted CrC6-haloalkyl, a benzyl, 4-methoxybenzyl or pentafluorophenyl group, or a group of formula 0-C(=0)A ; in the presence when needed or useful of a catalyst and in the presence of a condensing agent in case U1 represents a hydroxyl group, and in the presence of an acid binder in case U1 represents a halogen atom.
N-substituted amine derivatives of formula (I I) are known or can be prepared by known processes such as reductive amination of aldehydes or ketones (Bioorganics and Medicinal Chemistry Letters (2006), 16, 2014), or reduction of imines (Tetrahedron (2005), 61, 1 1689), or nucleophilic substitution of a halogen, mesylate or tosylate (Journal of Medicinal Chemistry (2002), 45, 3887).
Carboxylic acid derivatives of formula (II I) are known or can be prepared by known processes.
In case U1 represents a hydroxy group, process P1 according to the present invention is conducted in the presence of condensing agent. Suitable condensing agent may be selected in the non limited list consisting of acid halide former, such as phosgene, phosphorous tribromide, phosphorous trichloride, phosphorous pentachloride, phosphorous trichloride oxide or thionyl chloride; anhydride former, such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride; carbodiimides, such as Ν,Ν'-dicyclohexylcarbodiimide (DCC) or other customary condensing agents, such as phosphorous pentoxide, polyphosphoric acid, N,N'-carbonyl-
diimidazole, 2-ethoxy-N-ethoxycarbonyl-1 ,2-dihydroquinoline (EEDQ), triphenylphosphine/tetrachloro- methane, 4-(4,6-dimethoxy[1 .3.5]-triazin-2-yl)-4-methylmorpholinium chloride hydrate, bromo- tripyrrolidinophosphoniumhexafluorophosphate or propanephosphonic anhydride (T3P).
Process P1 according to the present invention may be conducted in the presence of a catalyst. Suitable catalyst may be selected in the list consisting of N,N-dimethylpyridin-4-amine, 1 -hydroxy- benzotriazole or N, N-dimethylformamide.
In case U1 represents a halogen atom, process P1 according to the present invention is conducted in the presence of an acid binder. Suitable acid binders for carrying out process P1 according to the invention are in each case all inorganic and organic bases that are customary for such reactions. Preference is given to using alkaline earth metal, alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide, alkali metal carbonates, such as caesium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, Ν,Ν-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethylpyridin-4-amine, diazabicyclooctane (DABCO), diazabicyclo-nonene (DBN) or diazabicycloundecene (DBU). It is also possible to work in the absence of an additional condensing agent or to employ an excess of the amine component, so that it simultaneously acts as acid binder agent.
Suitable solvents for carrying out process P1 according to the invention can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane; ethers, such as diethyl ether, diisopropyl ether, methyl t- butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2-diethoxyethane or anisole; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, Ν,Ν-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone, or hexamethylphosphoric triamide; alcohols such as methanol, ethanol, propanol, iso-propanol; esters, such as methyl acetate or ethyl acetate, sulfoxides, such as dimethyl sulfoxide, or sulfones, such as sulfolane. When carrying out process P1 according to the invention, the amine derivative of formula (I I) can be employed as its salt, such as chlorhydrate or any other convenient salt.
When carrying out process P1 according to the invention, 1 mole or an excess of the amine derivative of formula (I I) and from 1 to 3 moles of the acid binder can be employed per mole of the reagent of formula (I I I).
It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
According to a further aspect of the present invention, there is provided a second process P2 for the preparation of a compound of formula (I) wherein L represents a direct bond or a methylene group, as illustrated by the following reaction scheme:
(IV) (V) (I)
Process P2 wherein A, T, Z1 , Z2, Z3, n, X and B are as herein-defined, L represents a direct bond or a methylene group, U2 represents a halogen atom such as chlorine, bromine or iodine, or a triflate group and W1 represents a boron derivative such as a boronic acid, a boronic ester or a potassium trifluoroborate derivative.
The present invention therefore refers to a process P2 for preparing a compound of formula (I)
wherein A, T, Z1 , Z2, Z3, n, X and B are as defined in any one of claims 1 to 14 and L represents direct bond or a methylene group, characterized in that a compound of formula (IV)
(IV)
wherein A, T, Z1 , Z2, Z3, n, X are as defined above and U2 represents a halogen atom such as chlorine, bromine or iodine, or a triflate group,
is reacted with a compound of formula (V)
W— L
\
B
(V)
wherein L and B are as defined above and W1 represents a boron derivative such as a boronic acid, a boronic ester or a potassium trifluoroborate derivative. Process P2 can be performed in the presence of a transition metal catalyst such as palladium and if appropriate in the presence of a phosphine ligand or a N-heterocyclic carbene ligand and in the presence of a base and if appropriate in the presence of a solvent.
Compounds of formula (IV) can be prepared by known processes (WO-2007/087906 and WO- 201 0/130767) and the preparation of compounds of 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 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, tetrakis(triphenylphosphine)palladium, bis(dibenzylideneacetone)palladium , bis(triphenyl phosphine)palladium dichloride or 1 , 1 '-bis(diphenylphosphino) ferrocenepalladium(l l) chloride.
It is also possible to generate a palladium complex in the reaction mixture by separate addition to the reaction of a palladium salt and a ligand or salt, such as triethylphosphine, tri-tert-butylphosphine, tri- tert-butylphosphonium tetrafluoroborate, tricyclohexylphosphine, 2-(dicyclohexylphosphine)biphenyl, 2-(di-tert-butylphosphine)biphenyl, 2-(dicyclohexylphosphine)-2'-(N,N-dimethylamino)biphenyl, triphenyl-phosphine, tris-(o-tolyl)phosphine, sodium 3-(diphenylphosphino)benzenesulfonate, tris-2- (methoxy-phenyl)phosphine, 2,2'-bis(diphenylphosphine)-1 ,1 '-binaphthyl, 1 ,4- bis(diphenylphosphine)butane, 1 ,2-bis(diphenylphosphine) ethane, 1 ,4- bis(dicyclohexylphosphine)butane, 1 ,2-bis(dicyclohexylphosphine)-ethane, 2-(dicyclohexyl phosphine)- 2'-(N,N-dimethylamino)-biphenyl, 1 ,1 '-bis(diphenylphosphino)-ferrocene, (R)-(-)-1 -[(S)-2- diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine, tris-(2,4-tert-butyl-phenyl)phosphite or 1 ,3- bis(2,4,6-trimethylphenyl)imidazolium chloride.
It is also advantageous to choose the appropriate catalyst and/or ligand from commercial catalogues such as "Metal Catalysts for Organic Synthesis" by Strem Chemicals or "Phosphorous Ligands and Compounds" by Strem Chemicals.
Suitable bases for carrying out process P2 according to the invention can be inorganic and organic bases which are customary for such reactions. Preference is given to using alkaline earth metal or alkali metal hydroxides, such as sodium hydroxide, calcium hydroxide, potassium hydroxide or other ammonium hydroxide derivatives ; alkaline earth metal, alkali metal or ammonium fluorides such as
potassium fluoride, caesium fluoride or tetrabutylammonium fluoride ; alkaline earth metal or alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or caesium carbonate ; alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate or calcium acetate ; alkali metal alcoholates, such as potassium ter- butoxide or sodium ter-butoxide ; alkali metal phosphates, such as tri-potassium phosphate ; tertiary amines, such as trimethylamine, triethylamine, tributylamine, Ν,Ν-dimethylaniline, N,N- dicyclohexylmethylamine, N-methylpiperidine, Ν,Ν-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU) ; and also aromatic bases, such as pyridine, picolines, lutidines or collidines.
Suitable solvents for carrying out process P2 according to the invention can be customary inert organic solvents. Preference is given to using optionally halogen atomated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2- diethoxyethane or anisole ; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile ; amides, such as N,N-dimethylformamide, Ν,Ν-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide ; esters, such as methyl acetate or ethyl acetate, sulfoxides, such as dimethyl sulfoxide, or sulfones, such as sulfolane.
It can also be advantageous to carry out process P2 according to the invention, with a co-solvent such as water or an alcohol such as methanol, ethanol, propanol, i-propanol or t-butanol.
When carrying out process P2 according to the invention, 1 mole or an excess of compound of formula (V) and from 1 to 5 moles of base and from 0.01 to 20 mole percent of a palladium complex can be employed per mole of compound of formula (IV).
It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
According to a further aspect of the present invention, there is provided a third process P3 for the preparation of a compound of formula (I) wherein L represents a heteroatom, as illustrated by the following reaction scheme:
(VI) (VII) (I)
Process P3 wherein A, T, Z Z2, Z3, n, X and B are as herein-defined, U3 represents a halogen atom and L represents an oxygen atom, a sulfur atom or a mono-substituted or non-substituted nitrogen atom,
Process P3 according to the invention is performed in the presence of a base.
Compounds of formula (VI) can be prepared by known processes (WO-2007/087906 and WO- 201 0/130767) and the preparation of compounds of formula (VI I) is well known.
Suitable bases for carrying out process P3 according to the invention can be inorganic and organic bases which are customary for such reactions. Preference is given to using alkaline earth metal or alkali metal hydroxides, such as sodium hydroxide, calcium hydroxide, potassium hydroxide or other ammonium hydroxide derivatives ; alkaline earth metal, alkali metal or ammonium fluorides such as potassium fluoride, caesium fluoride or tetrabutylammonium fluoride ; alkaline earth metal or alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or caesium carbonate ; alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate or calcium acetate ; alkali metal alcoholates, such as potassium ter- butoxide or sodium ter-butoxide ; alkali metal phosphates, such as tri-potassium phosphate ; tertiary amines, such as trimethylamine, triethylamine, tributylamine, Ν,Ν-dimethylaniline, N,N- dicyclohexylmethylamine, N-methylpiperidine, Ν,Ν-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU) ; and also aromatic bases, such as pyridine, picolines, lutidines or collidines.
Other suitable bases for carrying out process P3 according to the invention can be amides or organometallic derivatives. Preference is given to alkali metal amides, such as sodium amide or potassium amide ; organic amides, such as lithium diisopropylamine (LDA), lithium hexamethyldisilazane (LiHMDS), potassium hexamethyldisilazane (KHMDS) or sodium hexamethyldisilazane (NaHMDS) ; organolithium derivatives, such as methyllithium, phenyllithium, butyllithium, sec-butyllithium, iso-butyllithium or tert-butyllithium.
Suitable solvents for carrying out process P3 according to the invention can be customary inert organic solvents. Preference is given to using optionally halogen atomated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform,
carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2- diethoxyethane or anisole ; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile ; amides, such as N,N-dimethylformamide, Ν,Ν-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide ; esters, such as methyl acetate or ethyl acetate, sulfoxides, such as dimethyl sulfoxide, or sulfones, such as sulfolane.
When carrying out process P3 according to the invention, 1 mole or an excess of compound of formula (VI I) and from 1 to 5 moles of base can be employed per mole of compound of formula (VI).
It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
According to a further aspect according to the invention, there is provided a fourth process P4 for the preparation of a compound of formula (I), according to the following reaction scheme :
(VIII) (IX) (I)
Process P4 wherein A, Z1 , Z2, Z3, n, X, L and B are as herein-defined and W2 represents a boron derivative such as a boronic acid, a boronic ester or a potassium trifluoroborate derivative when p is 1 , or W2 represents Bi when p is 3.
Compounds of formula (IX) can be prepared by known processes.
Process P4 according to the invention is performed in the presence of copper(l l) acetate.
Suitable bases for carrying out process P4 according to the invention can be inorganic and organic bases which are customary for such reactions. Preference is given to using alkaline earth metal or alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or caesium carbonate ; alkali metal phosphates, such as tri-potassium phosphate ; tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, Ν,Ν-dicyclohexylmethylamine, N-methylpiperidine, Ν,Ν-dimethylaminopyridine ; and also aromatic bases, such as pyridine, picolines, lutidines or collidines.
Other suitable bases for carrying out process P4 according to the invention can be organic bases which are customary for such reactions. Preference is given to using organic amides such as lithium diisopropylamine (LDA), lithium hexamethyldisilazane (LiHM DS), potassium hexamethyldisilazane (KHM DS) or sodium hexamethyldisilazane (NaHM DS).
Suitable ligands for carrying out process P4 according to the invention can be organic bases which are customary for such reactions. Preference is given to using aromatic bases such as pyridine, picolines, lutidines, collidines, 2,2'-bipyridine or 1 ,1 0-phenanthroline ; and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, Ν,Ν-dimethylaniline, N,N-dicyclohexylmethylamine, N-methylpiperidine, N,N-dimethylaminopyridine.
Suitable solvents for carrying out process P4 according to the invention can be customary inert organic solvents. Preference is given to using optionally halogen atomated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2- diethoxyethane or anisole ; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile ; amides, such as N,N-dimethylformamide, Ν,Ν-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide ; esters, such as methyl acetate or ethyl acetate, sulfoxides, such as dimethyl sulfoxide, or sulfones, such as sulfolane.
When carrying out process P4 according to the invention, 1 mole or an excess of compound of formula (IX) can be employed per mole of compound of formula (VI II).
When carrying out process P4 according to the invention, 1 to 3 mole or an excess of base can be employed per mole of compound of formula (VI I I). If suitable, a combination of bases in various ratio can also be employed. When carrying out process P4 according to the invention, no ligand or 0.1 to 1 mole of ligand can be employed per mole of compound of formula (VI I I).
When carrying out process P4 according to the invention, 0.1 to 2.5 mole or an excess of copper(l l) acetate can be employed per mole of compound of formula (VI I I).
It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
Secondary amides of formula (VI I I) can be, for example, prepared according to the following reaction scheme :
(XI) (VII) wherein A, T, Z1 , Z2, Z3, n, X and B are as herein-defined, and
- L represents a direct bond or a methylene group when U2 represents a halogen atom such as chlorine, bromine or iodine, or a triflate group, and W1 represents a boron derivative such as a boronic acid, a boronic ester or a potassium trifluoroborate derivative (step a) ; or
- L represents an oxygen atom, a sulfur atom or a mono-substituted or non-substituted nitrogen atom when U3 represents a halogen atom (step b).
Tertiary amides of formula (IV) can be, for example, prepared according to the following reaction schem
(X) (IX) (IV)
Wherein A, T, Z1 , Z2, Z3, n and X are as herein-defined, U2 represents a halogen atom such as chlorine, bromine or iodine, or a triflate group, and
- W2 represents a boron derivative such as a boronic acid, a boronic ester or a potassium trifluoroborate derivative when p is 1 , or
- W2 represents Bi when p is 3.
Derivatives of formula (X) or formula (XI) are known or can be prepared by known processes (WO- 2012/052490).
Step a can be performed according to process P2, step b can performed according to process P3 and step c can be performed according to process P4.
According to a further aspect according to the invention, there is provided a fourth process P5 for th preparation of a compound of formula (I) wherein T represents S, starting from a compound of formul (I) wherein T represents O and illustrated according to the following reaction scheme :
(I)
Process P5 wherein A, Z1 , Z2, Z3, n, X, L and B are as herein-defined.
Process P5 according to the invention is performed in the presence of a thionating agent.
Starting amide derivatives of formula (I) wherein T represents O can be prepared according to processes P1 , P2, P3 and P4.
Suitable thionating agents for carrying out process P5 according to the invention can be sulfur (S), sulfhydric acid (H2S), sodium sulfide (Na2S), sodium hydrosulfide (NaHS), boron trisulfide (B2S3), bis(diethylaluminium) sulfide ((AIEt2)2S), ammonium sulfide ((N H4)2S), phosphorous pentasulfide (P2S5), Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1 ,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent such as described in Journal of the Chemical Society, Perkin 1 (2001 ), 358, in the optionally presence of a catalytic or stoichiometric or excess amount, quantity of a base such as an inorganic and organic base. Preference is given to using alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate ; heterocyclic aromatic bases, such as pyridine, picoline, lutidine, collidine ; and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, Ν,Ν-dimethylaniline, N,N-dimethylpyridin-4-amine or N-methyl-piperidine.
Suitable solvents for carrying out process P5 according to the invention can be customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane, ethers, such as diethyl ether, diisopropyl ether, methyl t- butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane or 1 ,2-diethoxyethane, nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile, sulfurous solvents, such as sulfolane or carbon disulfide.
When carrying out process P5 according to the invention, 1 mole or an excess of the sulfur equivalent of the thionating agent and from 1 to 3 moles of the base can be employed per mole of the amide reactant (I).
It is also possible to employ the reaction components in other ratios. Work-up is carried out by known methods.
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 elevated or reduced pressure.
When carrying out processes P1 , P2, P3, P4 and P5 according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, these processes are carried out at temperatures from - 75 °C to 200 °C, preferably from 10 °C to 150 °C. A way to control the temperature for the processes according to the invention is to use microwave technology.
In general, the reaction mixture is concentrated under reduced pressure. The residue that remains can be freed by known methods, such as chromatography or crystallization, from any impurities that can still be present.
Work-up is carried out by customary methods. Generally, the reaction mixture is treated with water and the organic phase is separated off and, after drying, concentrated under reduced pressure. If appropriate, the remaining residue can, be freed by customary methods, such as chromatography, crystallization or distillation, from any impurities that may still be present.
The compound according to the present invention can be prepared according to the general processes of preparation described above. It will nevertheless be understood that, on the basis of his general knowledge and of available publications, the skilled worker will be able to adapt this method according to the specifics of each of the compounds, which it is desired to synthesize.
Still in a further aspect, the present invention relates to compounds of formula (I I) useful as intermediate compounds or materials for the process of preparation according to the invention. The present invention thus provides compounds of formula (Ma.) as well as their acceptable salts:
(lla)
wherein Z2, Z3, n and X are as herein-defined, and L is a direct bond and B1 is a substituted or non- substituted oxiranyl ring, a substituted or non-substituted thienyl ring, a substituted or non-substituted benzothienyl ring, a substituted or non-substituted furan ring, or a substituted or non-substituted benzofuran ring,
providing that (I la) does not represent :
- N-[2-(2-furyl)benzyl]cyclopropanamine
- N-[2-(2-furyl)-4,5-dimethoxybenzyl]cyclopropanamine
- N-[2-(3-bromo-2-furyl)-4,5-dimethoxybenzyl]cyclopropanamine
- N-[2-(3-bromo-2-furyl)benzyl]cyclopropanamine
- N-[2-(3-furyl)benzyl]cyclopropanamine
- N-[2-(2-thienyl)benzyl]cyclopropanamine
- N-[4,5-dimethoxy-2-(2-thienyl)benzyl]cyclopropanamine.
The present invention thus provides compounds of formula (lib) as well as their acceptable salts:
providing that (l ib) does not represent :
- N- ■[3- ■(2-furyl)benzyl]cyclopropanamine
- N- ■[5- ■(2-furyl)-2-methoxybenzyl]cyclopropanamine
- N- ■[4- ■fluoro-3-(2-furyl)benzyl]cyclopropanamine
- N- ■[2- ■fluoro-5-(2-furyl)benzyl]cyclopropanamine
- N- ■[2- ■fluoro-5-(3-furyl)benzyl]cyclopropanamine
- N- ■[3- ■(3-bromo-2-furyl)-4-fluorobenzyl]cyclopropanamine
- N- ■[3- ■(3-bromo-2-furyl)benzyl]cyclopropanamine
- N- ■[5- ■(3-bromo-2-furyl)-2-fluorobenzyl]cyclopropanamine
- N- ■[5- ■(3-bromo-2-furyl)-2-methoxybenzyl]cyclopropanamine
- N- ■[3- -(3-furyl)benzyl]cyclopropanamine
- N- ■[3- ■(2-thienyl)benzyl]cyclopropanamine
- N- ■[4- ■fluoro-3-(2-thienyl)benzyl]cyclopropanamine
- N- ■[2- ■fluoro-5-(2-thienyl)benzyl]cyclopropanamine
- N- ■[2- ■methoxy-5-(2-thienyl)benzyl]cyclopropanamine
- 5-{5-[(cyclopropylamino)methyl]-2-fluorophenyl}thiophene-2-carbonitrile.
N-cyclopropyl derivatives of formula (l la) or formula (l ib) can be prepared according to known methods.
Preferred compounds of formula (l la) according to the invention are :
- N-[5-chloro-2-(2-furyl)benzyl]cyclopropanamine
- N-[5-chloro-2-(2-thienyl)benzyl]cyclopropanamine
- N-[2-(3-thienyl)benzyl]cyclopropanamine
- N-{1 -[2-(3-thienyl)phenyl]ethyl}cyclopropanamine
- N-[5-chloro-2-(3-thienyl)benzyl]cyclopropanamine
- N-[2-(5-chloro-2-thienyl)benzyl]cyclopropanamine
- N-[5-chloro-2-(5-chloro-2-thienyl)benzyl]cyclopropanamine. Preferred compounds of formula (l ib) according to the invention are :
- N-[2-chloro-5-(2-furyl)benzyl]cyclopropanamine
- N-[2-chloro-5-(2-thienyl)benzyl]cyclopropanamine
- N-[2-chloro-5-(3-thienyl)benzyl]cyclopropanamine
- N-[2-chloro-5-(5-chloro-2-thienyl)benzyl]cyclopropanamine.
Still in a further aspect, the present invention relates to compounds of formula (X) useful as intermediate compounds or materials for the process of preparation according to the invention. The present invention thus provides compounds of formula (Xa) :
(Xa)
wherein Z2 and Z3 are as herein-defined, A represents A13 , Xa1 represents a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non-substituted C3-C7-cycloalkyl ; tri(Ci-C8- alkyl)silyl; substituted or non-substituted CrC8-alkoxy; or substituted or non-substituted CrC8- alkylsulfanyl, Xa2 represents hydrogen or Xa1 , and U2 represents a halogen atom such as chlorine, bromine or iodine, or a triflate group,
providing that (Xa) does not represent :
- N-(2,5-dichlorobenzyl)-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide
- N-[1 -(2,5-dichlorophenyl)ethyl]-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide - N-[2-(2,5-dichlorophenyl)propan-2-yl]-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4- carboxamide
- N-[1 -(2,5-dichlorophenyl)cyclopropyl]-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4- carboxamide
- 5-chloro-N-[1 -(2,5-dichlorophenyl)ethyl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide
- 5-chloro-N-[2-(2,5-dichlorophenyl)propan-2-yl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4- carboxamide
- 5-chloro-N-[1 -(2,5-dichlorophenyl)cyclopropyl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4- carboxamide
- 5-chloro-N-(2,5-dichlorobenzyl)-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide
- N-(5-bromo-2-fluorobenzyl)-1 ,3,5-trimethyl-1 H-pyrazole-4-carboxamide
- N-(5-bromo-2-fluorobenzyl)-3,5-dimethyl-1 H-pyrazole-4-carboxamide
- 1 -methyl-N-[1 -(2,4,5-trichlorophenyl)ethyl]-3-(trifluoromethyl)-1 H-pyrazole-4-carboxamide
- 3-(difluoromethyl)-1 -methyl-N-[1 -(2,4,5-trichlorophenyl)ethyl]-1 H-pyrazole-4-carboxamide
- N-(5-chloro-2-fluorobenzyl)-1 -methyl-5-propoxy-3-(trifluoromethyl)-1 H-pyrazole-4-carboxamide
- N-(2,5-dichlorobenzyl)-1 -methyl-5-propoxy-3-(trifluoromethyl)-1 H-pyrazole-4-carboxamide.
Preferred compounds of formula (Xa) according to the invention are :
- N-(5-chloro-2-ethylbenzyl)-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide
- N-(5-chloro-2-isopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide
- N-[5-chloro-2-(trifluoromethyl)benzyl]-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4- carboxamide
- N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4- carboxamide.
Most preferred compounds of formula (Xa) according to the invention are :
- N-(5-chloro-2-isopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide.
In a further aspect, the present invention also relates 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 composition according to the invention that is sufficient to control or destroy the fungi present or liable to appear on the cropsand that does not entail any appreciable symptom of phytotoxicity for the said crops. Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the climatic conditions and the compounds included in the fungicide composition according to the invention. This amount can be determined by systematic field trials that are within the capabilities of a person skilled in the art.
Thus, according to the invention, there is provided a fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) as herein defined and an agriculturally acceptable support, carrier or filler.
According to the invention, the term "support" denotes a natural or synthetic, organic or inorganic compound with that the active compound of formula (I) is combined or associated to make it easier to apply, notably to the parts of the plant. This support is thus generally inert and should be agriculturally acceptable. The support can be a solid or a liquid. Examples of suitable supports include clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, water, alcohols, in particular butanol, organic solvents, mineral and plant oils and derivatives thereof. Mixtures of such supports can also be used.
The composition according to the invention can also comprise additional components. In particular, the composition can further comprise a surfactant. The surfactant can be an emulsifier, a dispersing agent or a wetting agent of ionic or non-ionic type or a mixture of such surfactants. Mention can be made, for example, of polyacrylic acid salts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyolsand derivatives of the above compounds containing sulfate, sulfonate and phosphate functions. The presence of at least one surfactant is generally essential when the active compound and/or the inert support are water-insoluble and when the vector agent for the application is water. Preferably, surfactant content can be comprised from 5% to 40% by weight of the composition.
Optionally, additional components can also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active compounds can be combined with any solid or liquid additive, that complies with the usual formulation techniques.
In general, the composition according to the invention can contain from 0.05 to 99% by weight of active compound, preferably 1 0 to 70% by weight. Compositions according to the invention can be used in various forms and formulations such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra low volume (ULV) liquid, ultra low volume (ULV) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder. These compositions include not only compositions that are ready to be applied to the plant or seed to be treated by means of a suitable
device, such as a spraying or dusting device, but also concentrated commercial compositions that must be diluted before application to the crop.
The formulations can be prepared in a manner known per se, for example by mixing the active ingredients with at least one customary extender, solvent or diluent, adjuvant, emulsifier, dispersant, and/or binder or fixative, wetting agent, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, dyes and pigments, antifoams, preservatives, inorganic and organic thickeners, adhesives, gibberellins and also further processing auxiliaries and also water. Depending on the formulation type to be prepared further processing steps are necessary, e.g. wet grinding, dry grinding and granulation.
The inventive active ingredients may be present as such or in their (commercial) formulations and in the use forms prepared from these formulations as 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 formula (I) and the fungicide composition according to the invention can be used to curatively or preventively control the phytopathogenic fungi of plants or crops.
Thus, according to a further aspect of the invention, there is provided a method for curatively or preventively controlling the phytopathogenic fungi of plants or crops characterised in that a compound of formula (I) or a fungicide composition according to the invention is applied to the seed, the plant or to the fruit of the plant or to the soil wherein the plant is growing or wherein it is desired to grow.
The method of treatment according to the invention can also be useful to treat propagation material such as tubers or rhizomes, but also seeds, seedlings or seedlings pricking out and plants or plants pricking out. This method of treatment can also be useful to treat roots. The method of treatment according to the invention can also be useful to treat the overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruit of the concerned plant.
According to the invention all plants and plant parts can be treated. By plants is meant all plants and plant populations such as desirable and undesirable wild plants, cultivars and plant varieties (whether or not protectable by plant variety or plant breeder's rights). Cultivars and plant varieties can be plants obtained by conventional propagation and breeding methods which can be assisted or supplemented by one or more biotechnological methods such as by use of double haploids, protoplast fusion, random and directed mutagenesis, molecular or genetic markers or by
bioengineering and genetic engineering methods. By plant parts is meant all above ground and below ground parts and organs of plants such as shoot, leaf, blossom and root, whereby for example leaves, needles, stems, branches, blossoms, fruiting bodies, fruits and seed as well as roots, corms and rhizomes are listed. Crops and vegetative and generative propagating material, for example cuttings, corms, rhizomes, runners and seeds also belong to plant parts.
Among the plants that can be protected by the method according to the invention, mention may be made of major field crops like corn, soybean, cotton, Brassica oilseeds such as Brassica napus (e.g. canola), Brassica rapa, B. juncea (e.g. mustard) and Brassica carinata, rice, wheat, sugarbeet, sugarcane, oats,
rye, barley, millet, triticale, flax, vine and various fruits and vegetables of various botanical taxa such as Rosaceae sp. (for instance pip fruit such as apples and pears, but also 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. (for instance banana trees and plantings), Rubiaceae sp. (for instance coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemons, oranges and grapefruit) ; Solanaceae sp. (for instance tomatoes, potatoes, peppers, eggplant), Liliaceae sp., Compositiae sp. (for instance lettuce, artichoke and chicory - including root chicory, endive or common chicory), Umbelliferae sp. (for instance carrot, parsley, celery and celeriac), Cucurbitaceae sp. (for instance cucumber - including pickling cucumber, squash, watermelon, gourds and melons), Alliaceae sp. (for instance onions and leek), Cruciferae sp. (for instance white cabbage, red cabbage, broccoli, cauliflower, brussel sprouts, pak choi, kohlrabi, radish, horseradish, cress, Chinese cabbage), Leguminosae sp. (for instance peanuts, peas and beans beans - such as climbing beans and broad beans), Chenopodiaceae sp. (for instance mangold, spinach beet, spinach, beetroots), Malvaceae (for instance okra), Asparagaceae (for instance asparagus); horticultural and forest crops; ornamental plants; as well as genetically modified homologues of these crops.
The method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds. Genetically modified plants (or transgenic plants) are plants of which a heterologous gene has been stably integrated into genome. The expression "heterologous gene" essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology or RNA interference - RNAi - technology). A heterologous gene that is located in the genome is also called a transgene. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the active compounds and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, bigger fruits, larger plant height, greener leaf color, earlier flowering, higher quality and/or a higher nutritional value of the harvested products, higher sugar concentration within the fruits, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.
At certain application rates, the active compound combinations according to the invention may also have a strengthening effect in plants. Accordingly, they are also suitable for mobilizing the defense system of the plant against attack by unwanted microorganisms. This may, if appropriate, be one of the reasons of the enhanced activity of the combinations according to the invention, for example against fungi. Plant- strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances or combinations of substances which are capable of stimulating the defense system of plants in such a way that, when subsequently inoculated with unwanted microorganisms, the treated plants display a substantial degree of resistance to these microorganisms. In the present case, unwanted microorganisms are to be understood as meaning phytopathogenic fungi, bacteria and viruses. Thus, the substances according to the invention can be employed for protecting plants against attack by the abovementioned pathogens within a certain period of time after the treatment. The period of time within which protection is effected generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.
Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means).
Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.
Examples of nematode resistant plants are described in e.g. US Patent Application Nos 1 1 /765,491 , 1 1 /765,494, 10/926,81 9, 1 0/782,020, 12/032,479, 1 0/783,417, 1 0/782,096, 1 1 /657,964, 12/1 92,904, 1 1 /396,808, 12/1 66,253, 12/1 66,239, 12/1 66, 124, 12/1 66,209, 1 1 /762,886, 12/364,335, 1 1 /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 may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
Plants and plant cultivars which may also be treated according to the invention, are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance. Further 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 with the above-mentioned traits are non-exhaustively listed in Table A. Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses). Such plants are typically made by crossing an inbred male-sterile parent line (the female parent) with another inbred male-fertile parent line (the male parent). Hybrid seed is typically harvested from the male sterile plants and sold to growers. Male sterile plants can sometimes (e.g. in corn) be produced by detasseling, i.e. the mechanical removal of the male reproductive organs (or males flowers) but, more typically, male sterility is the result of genetic determinants in the plant genome. In that case, and especially when seed is the desired product to be harvested from the hybrid plants it is typically useful to ensure that male fertility in the hybrid plants is fully restored. This can be accomplished by ensuring that the male parents have appropriate fertility restorer genes which are capable of restoring the male fertility in hybrid plants that contain the genetic determinants responsible for male-sterility. Genetic determinants for male sterility may be located in the cytoplasm. Examples of cytoplasmic male sterility (CMS) were for instance described in Brassica species (WO 92/05251 , WO 95/09910, WO 98/27806, WO 05/002324, WO 06/021972 and US 6,229,072). However, genetic determinants for 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 means of obtaining male-sterile plants is described in WO 89/1 0396 in which, for example, a ribonuclease such as barnase is selectively expressed in the tapetum cells in the stamens. Fertility can then be restored by expression in the tapetum cells of a ribonuclease inhibitor such as barstar (e.g. WO 91 /02069).
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.
Herbicide-resistant plants are for example glyphosate-tolerant plants, i.e. plants made tolerant to the herbicide glyphosate or salts thereof. Plants can be made tolerant to glyphosate through different means. For example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium (Comai et al., 1 983, Science 221 , 370-371 ), the CP4 gene of the bacterium Agrobacterium sp. (Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the genes encoding a Petunia EPSPS (Shah et al., 1986, Science 233, 478-481 ), a Tomato EPSPS (Gasser et al., 1 988, J. Biol. Chem. 263, 4280-4289), or an Eleusine EPSPS (WO 01 /66704). It can also be a mutated EPSPS as described in for example EP 0837944, WO 00/66746, WO 00/66747 or WO02/26995. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate oxido-reductase enzyme as described in
U.S. Patent Nos. 5,776,760 and 5,463, 1 75. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate acetyl transferase enzyme as described in for example 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-mentioned genes, as described in for example WO 01 /024615 or WO 03/013226. Plants expressing EPSPS genes that confer glyphosate tolerance are described in e.g. US Patent Application Nos 1 1 /51 7,991 , 10/739,61 0, 12/139,408, 12/352,532, 1 1 /312,866, 1 1 /315,678, 12/421 ,292, 1 1 /400,598, 1 1 /651 ,752, 1 1 /681 ,285, 1 1 /605,824, 12/468,205, 1 1 /760,570, 1 1 /762,526, 1 1 /769,327, 1 1 /769,255, 1 1 /943801 or 12/362,774. Plants comprising other genes that confer glyphosate tolerance, such as decarboxylase genes, are described in e.g. US patent applications 1 1 /588,81 1 , 1 1 /1 85,342, 12/364,724, 1 1 /185,560 or 12/423,926.
Other herbicide resistant plants are for example plants that are made tolerant to herbicides inhibiting the enzyme glutamine synthase, such as bialaphos, phosphinothricin or glufosinate. Such plants can be obtained by expressing an enzyme detoxifying the herbicide or a mutant glutamine synthase enzyme that is resistant to inhibition, e.g. described in US Patent Application No 1 1 /760,602. One such efficient detoxifying enzyme is an enzyme encoding a phosphinothricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous
phosphinothricin acetyltransferase are for example described 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; 5,908,81 0 and 7, 1 12,665.
Further herbicide-tolerant plants are also plants that are made tolerant to the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase (H PPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is transformed into homogentisate. Plants tolerant to H PPD-inhibitors can be transformed with a gene encoding a naturally-occurring resistant HPPD enzyme, or a gene encoding a mutated or chimeric HPPD enzyme as described in WO 96/38567, WO 99/24585, WO 99/24586, WO 2009/144079, WO 2002/046387, or US 6,768,044.. Tolerance to HPPD-inhibitors can also be obtained by transforming plants with genes encoding certain enzymes enabling the formation of homogentisate despite the inhibition of the native HPPD enzyme by the H PPD-inhibitor. Such plants and genes are described in WO 99/34008 and WO 02/36787. Tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme having prephenate deshydrogenase (PDH) activity in addition to a gene encoding an HPPD-tolerant enzyme, as described in WO 2004/024928. Further, plants can be made more tolerant to H PPD-inhibitor herbicides by adding into their genome a gene encoding an enzyme capable of metabolizing or degrading H PPD inhibitors, such as the CYP450 enzymes shown in WO 2007/103567 and WO 2008/150473.
Still further herbicide resistant plants are plants that are made tolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pryimidinyoxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinone herbicides. Different mutations in the ALS enzyme (also known as acetohydroxyacid synthase, AHAS) are known to confer tolerance to different herbicides and groups of herbicides, as described for example in Tranel and
Wright (2002, Weed Science 50:700-712), but also, in U.S. Patent No. 5,605,01 1 , 5,378,824, 5, 141 ,870, and 5,013,659. The production of sulfonylurea-tolerant plants and imidazolinone-tolerant plants is described in U.S. Patent Nos. 5,605,01 1 ; 5,013,659; 5, 141 ,870; 5,767,361 ; 5,731 , 1 80;
5,304,732; 4,761 ,373; 5,331 , 107; 5,928,937; and 5,378,824; and international publication WO 96/33270. Other imidazolinone-tolerant plants are also described in for example WO 2004/040012, WO 2004/1 06529, WO 2005/020673, WO 2005/093093, WO 2006/007373, WO 2006/015376, WO 2006/024351 , and WO 2006/060634. Further sulfonylurea- and imidazolinone-tolerant plants are also described in for example WO 07/024782 and US Patent Application No 61 /288958.
Other plants tolerant to imidazolinone and/or sulfonylurea can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or mutation breeding as described for example for soybeans in U.S. Patent 5,084,082, for rice in WO 97/4121 8, for sugar beet in U.S. Patent 5,773,702 and WO 99/057965, for lettuce in U.S. Patent 5, 198,599, or for sunflower in WO 01 /065922.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.
An "insect-resistant transgenic plant", as used herein, includes any plant containing at least one transgene comprising a coding sequence encoding:
1 ) an insecticidal crystal protein from Bacillus thuringiensis or an insecticidal portion thereof, such as the insecticidal crystal proteins listed by Crickmore et al. (1 998, Microbiology and Molecular Biology Reviews, 62: 807-813), updated by Crickmore et al. (2005) at the Bacillus thuringiensis toxin nomenclature, online at:
http://www.lifesci. Sussex. ac.uk/Home/Neil_Crickmore/Bt/), or insecticidal portions thereof, e.g., proteins of the Cry protein classes Cry1 Ab, Cry1 Ac, Cry1 B, Cry1 C, Cry1 D, Cry1 F, Cry2Ab,
Cry3Aa, or Cry3Bb or insecticidal portions thereof (e.g. EP 1999141 and WO 2007/107302), or such proteins encoded by synthetic genes as e.g. described in and US Patent Application No 12/249,01 6 ; or
2) a crystal protein from Bacillus thuringiensis or a portion thereof which is insecticidal in the presence of a second other crystal protein from Bacillus thuringiensis or a portion thereof, such as the binary toxin made up of the Cry34 and Cry35 crystal proteins (Moellenbeck et al. 2001 , Nat. Biotechnol. 1 9: 668-72; Schnepf et al. 2006, Applied Environm. Microbiol. 71 , 1765-1 774) or the binary toxin made up of the Cry1 A or Cry1 F proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins (US Patent Appl. No. 12/214,022 and EP 08010791 .5); or 3) a hybrid insecticidal protein comprising parts of different insecticidal crystal proteins from
Bacillus thuringiensis, such as a hybrid of the proteins of 1 ) above or a hybrid of the proteins of 2) above, e.g., the Cry1 A.105 protein produced by corn event MON89034 (WO
2007/027777) ; or
4) a protein of any one of 1 ) to 3) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect
species, and/or to expand the range of target insect species affected, and/or because of changes introduced into the encoding DNA during cloning or transformation, such as the Cry3Bb1 protein in corn events MON863 or MON8801 7, or the Cry3A protein in corn event MIR604; or
5) an insecticidal secreted protein from Bacillus thuringiensis or Bacillus cereus, or an insecticidal portion thereof, such as the vegetative insecticidal (VI P) proteins listed at:
http://www.lifesci. Sussex. ac.uk/home/Neil_Crickmore/Bt/vip. html, e.g., proteins from the VI P3Aa protein class; or
6) a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a second secreted protein from Bacillus thuringiensis or B. cereus, such as the binary toxin made up of the VI P1 A and VI P2A proteins (WO 94/21 795); or
7) a hybrid insecticidal protein comprising parts from different secreted proteins from Bacillus thuringiensis or Bacillus cereus, such as a hybrid of the proteins in 1 ) above or a hybrid of the proteins in 2) above; or
8) a protein of any one of 5) to 7) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes introduced into the encoding DNA during cloning or transformation (while still encoding an insecticidal protein), such as the VI P3Aa protein in cotton event COT1 02; or 9) a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a crystal protein from Bacillus thuringiensis, such as the binary toxin made up of VI P3 and Cryl A or Cry1 F (US Patent Appl. No. 61 /126083 and 61 /1 9501 9), or the binary toxin made up of the VI P3 protein and the Cry2Aa or Cry2Ab or Cry2Ae proteins (US Patent Appl. No. 12/214,022 and EP 0801 0791 .5).
10) a protein of 9) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes introduced into the encoding DNA during cloning or transformation (while still encoding an insecticidal protein)
Of course, an insect-resistant transgenic plant, as used herein, also includes any plant comprising a combination of genes encoding the proteins of any one of the above classes 1 to 10. In one embodiment, an insect-resistant plant contains more than one transgene encoding a protein of any one of the above classes 1 to 1 0, to expand the range of target insect species affected when using different proteins directed at different target insect species, or to delay insect resistance development to the plants by using different proteins insecticidal to the same target insect species but having a different mode of action, such as binding to different receptor binding sites in the insect.
An "insect-resistant transgenic plant", as used herein, further includes any plant containing at least one transgene comprising a sequence producing upon expression a double-stranded RNA which upon
ingestion by a plant insect pest inhibits the growth of this insect pest, as described e.g. in WO
2007/080126, WO 2006/129204, WO 2007/074405, WO 2007/080127 and WO 2007/035650.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance. Particularly useful stress tolerance plants include:
1 ) plants which contain a transgene capable of reducing the expression and/or the activity of poly(ADP-ribose) polymerase (PARP) gene in the plant cells or plants as described in WO 00/04173, WO/2006/045633, EP 04077984.5, or EP 06009836.5.
2) plants which contain a stress tolerance enhancing transgene capable of reducing the expression and/or the activity of the PARG encoding genes of the plants or plants cells, as described e.g. in WO 2004/090140.
3) plants which contain a stress tolerance enhancing transgene coding for a plant-functional enzyme of the nicotineamide adenine dinucleotide salvage synthesis pathway including nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide adenyl transferase, nicotinamide adenine dinucleotide synthetase or nicotine amide
phosphorybosyltransferase as described e.g. in EP 04077624.7, WO 2006/133827,
PCT/EP07/002433, EP 1 999263, or WO 2007/1 07326.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product such as :
1 ) transgenic plants which synthesize a modified starch, which in its physical-chemical characteristics, in particular the amylose content or the amylose/amylopectin ratio, the degree of branching, the average chain length, the side chain distribution, the viscosity behaviour, the gelling strength, the starch grain size and/or the starch grain morphology, is changed in comparison with the synthesised starch in wild type plant cells or plants, so that this is better suited for special applications. Said transgenic plants synthesizing a modified starch are disclosed, for example, in EP 0571427, WO 95/04826, EP 071 9338, WO 96/15248, WO 96/1 9581 , WO 96/27674, WO 97/1 1 188, WO 97/26362, WO 97/32985, WO 97/42328, WO 97/44472, WO 97/45545, WO 98/27212, WO 98/40503, W099/58688, WO 99/58690, WO 99/58654, WO 00/081 84, WO 00/08185, WO 00/081 75, WO 00/28052, WO 00/77229, WO 01 /12782, WO 01 /12826, WO 02/1 01059, WO 03/071 860, WO 2004/056999, WO
2005/030942, WO 2005/030941 , WO 2005/095632, WO 2005/09561 7, WO 2005/09561 9, WO 2005/09561 8, WO 2005/123927, WO 2006/01 8319, WO 2006/1 03107, WO 2006/1 08702, 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 02/7941 0, 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
00/1 1 192, WO 98/22604, WO 98/32326, WO 01 /98509, WO 01 /98509, WO 2005/002359, US 5,824,790, US 6,01 3,861 , WO 94/04693, WO 94/09144, WO 94/1 1 520, WO 95/35026, WO 97/20936
2) transgenic plants which synthesize non starch carbohydrate polymers or which synthesize non starch carbohydrate polymers with altered properties in comparison to wild type plants without genetic modification. Examples are plants producing polyfructose, especially of the inulin and levan-type, as disclosed in EP 0663956, WO 96/01904, WO 96/21023, WO 98/39460, and WO 99/24593, plants producing alpha- 1 ,4-glucans as disclosed in WO 95/31553, US 2002031 826, US 6,284,479, US 5,71 2, 1 07, WO 97/47806, WO 97/47807, WO 97/47808 and WO 00/14249, plants producing alpha-1 ,6 branched alpha-1 ,4-glucans, as disclosed in WO 00/73422, plants producing alternan, as disclosed in e.g. WO 00/47727, WO 00/73422, EP 06077301 .7, US 5,908,975 and EP 0728213,
3) transgenic plants which produce hyaluronan, as for example disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO 2007/03931 6, J P 2006304779, and WO
2005/01 2529.
4) transgenic plants or hybrid plants, such as onions with characteristics such as 'high soluble solids content', low pungency' (LP) and/or long storage' (LS), as described in US Patent Appl. No. 12/020,360 and 61 /054,026.
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics and include:
a) Plants, such as cotton plants, containing an altered form of cellulose synthase genes as described in WO 98/00549
b) Plants, such as cotton plants, containing an altered form of rsw2 or rsw3 homologous nucleic acids as described in WO 2004/05321 9
c) Plants, such as cotton plants, with increased expression of sucrose phosphate synthase as described in WO 01 /17333
d) Plants, such as cotton plants, with increased expression of sucrose synthase as described in WO 02/45485
e) Plants, such as cotton plants, wherein the timing of the plasmodesmatal gating at the basis of the fiber cell is altered, e.g. through downregulation of fiber-selective β-1 ,3- glucanase as described in WO 2005/01 7157, or as described in EP 08075514.3 or US Patent Appl. No. 61 /128,938
f) Plants, such as cotton plants, having fibers with altered reactivity, e.g. through the expression of N-acetylglucosaminetransferase gene including nodC and chitin synthase genes as described in WO 2006/136351
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics and include:
a) Plants, such as oilseed rape plants, producing oil having a high oleic acid content as described e.g. in US 5,969, 1 69, US 5,840,946 or US 6,323,392 or US 6,063,947 b) Plants such as oilseed rape plants, producing oil having a low linolenic acid content as described in US 6,270,828, US 6,1 69, 190, or US 5,965,755
c) Plant such as oilseed rape plants, producing oil having a low level of saturated fatty acids as described e.g. in US Patent No. 5,434,283 or US Patent Application No 12/668303
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering as described in US Patent Appl. No. 61 /135,230 WO09/068313 and W01 0/006732.
Particularly useful transgenic plants which may be treated according to the invention are plants containing transformation events, or combination of transformation events, that are the subject of petitions for non-regulated status, in the United States of America, to the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) whether such petitions are granted or are still pending. At any time this information is readily available from APH IS (4700 River Road Riverdale, MD 20737, USA), for instance on its internet site (U RL
http://www. aphis. usda.gov/brs/not_reg. html). On the filing date of this application the petitions for nonregulated status that were pending with APHIS or granted by APHIS were those listed in table B which contains the following information:
Petition : the identification number of the petition. Technical descriptions of the transformation events can be found in the individual petition documents which are obtainable from APH IS, for example on the APHIS website, by reference to this petition number. These descriptions are herein incorporated by reference.
Extension of Petition : reference to a previous petition for which an extension is requested.
Institution : the name of the entity submitting the petition.
- Regulated article : the plant species concerned.
Transgenic phenotype : the trait conferred to the plants by the transformation event.
Transformation event or line : the name of the event or events (sometimes also designated as lines or lines) for which nonregulated status is requested.
APH IS documents : various documents published by APHIS in relation to the Petition and which can be requested with APHIS.
Additional particularly useful plants containing single transformation events or combinations of transformation events are listed for example in the databases from various national or regional regulatory agencies (see for example http://gmoinfo.jrc.it/gmp_browse.aspx and
http://www.agbios.com/dbase.php).
Particularly useful transgenic plants which may be treated according to the invention are plants containing transformation events, or a combination of transformation events, and that are listed for example in the databases for various national or regional regulatory agencies including Event 1 143- 14A (cotton, insect control, not deposited, described in WO 2006/128569); Event 1 143-51 B (cotton, insect control, not deposited, described in WO 2006/128570); Event 1445 (cotton, herbicide tolerance, not deposited, described in US-A 2002-120964 or WO 02/034946); Event 1 7053 (rice, herbicide tolerance, deposited as PTA-9843, described in WO 201 0/1 1 7737); Event 17314 (rice, herbicide tolerance, deposited as PTA-9844, described in WO 201 0/1 1 7735); Event 281 -24-236 (cotton, insect control - herbicide tolerance, deposited as PTA-6233, described in WO 2005/1 03266 or US-A 2005- 216969); Event 3006-21 0-23 (cotton, insect control - herbicide tolerance, deposited as PTA-6233, described in US-A 2007-143876 or WO 2005/1 03266); Event 3272 (corn, quality trait, deposited as PTA-9972, described in WO 2006/098952 or US-A 2006-230473); Event 4041 6 (corn, insect control - herbicide tolerance, deposited as ATCC PTA-1 1508, described in WO 201 1 /075593); Event 43A47 (corn, insect control - herbicide tolerance, deposited as ATCC PTA-1 1509, described in WO
201 1 /075595) ; Event 5307 (corn, insect control, deposited as ATCC PTA-9561 , described in WO 201 0/07781 6) ; Event ASR-368 (bent grass, herbicide tolerance, deposited as ATCC PTA-481 6, described in US-A 2006-1 62007 or WO 2004/053062); Event B1 6 (corn, herbicide tolerance, not deposited, described in US-A 2003-126634); Event BPS-CV127-9 (soybean, herbicide tolerance, deposited as NCIMB No. 41 603, described in WO 201 0/080829); Event CE43-67B (cotton, insect control, deposited as DSM ACC2724, described in US-A 2009-21 7423 or WO2006/128573); Event CE44-69D (cotton, insect control, not deposited, described in US-A 2010-0024077); Event CE44-69D (cotton, insect control, not deposited, described in WO 2006/128571 ); Event CE46-02A (cotton, insect control, not deposited, described in WO 2006/128572); Event COT1 02 (cotton, insect control, not deposited, described in US-A 2006-1301 75 or WO 2004/039986); Event COT202 (cotton, insect control, not deposited, described in US-A 2007-067868 or WO 2005/054479); Event COT203 (cotton, insect control, not deposited, described in WO 2005/054480); Event DAS40278 (corn, herbicide tolerance, deposited as ATCC PTA-1 0244, described in WO 201 1 /022469); Event DAS-59122-7 (corn, insect control - herbicide tolerance, deposited as ATCC PTA 1 1384 , described in US-A 2006- 070139); Event DAS-59132 (corn, insect control - herbicide tolerance, not deposited, described in WO 2009/1001 88) ; Event DAS6841 6 (soybean, herbicide tolerance, deposited as ATCC PTA-1 0442, described in WO 201 1 /066384 or WO 201 1 /066360); Event DP-098140-6 (corn, herbicide tolerance, deposited as ATCC PTA-8296, described in US-A 2009-137395 or WO 2008/1 1201 9); Event DP- 305423-1 (soybean, quality trait, not deposited, described in US-A 2008-312082 or WO 2008/054747); Event DP-32138-1 (corn, hybridization system, deposited as ATCC PTA-9158, described in US-A 2009-021 0970 or WO 2009/103049); Event DP-356043-5 (soybean, herbicide tolerance, deposited as ATCC PTA-8287, described in US-A 2010-01 84079 or WO 2008/002872); Event EE-1 (brinjal, insect
control, not deposited, described in WO 2007/091277); Event FI 1 1 7 (corn, herbicide tolerance, deposited as ATCC 209031 , described in US-A 2006-059581 or WO 98/044140) ; Event GA21 (corn, herbicide tolerance, deposited as ATCC 209033, described in US-A 2005-08671 9 or WO 98/044140) ; Event GG25 (corn, herbicide tolerance, deposited as ATCC 209032, described in US-A 2005-188434 or WO 98/044140); Event GHB1 1 9 (cotton, insect control - herbicide tolerance, deposited as ATCC PTA-8398, described in WO 2008/151 780); Event GHB614 (cotton, herbicide tolerance, deposited as ATCC PTA-6878, described in US-A 2010-050282 or WO 2007/0171 86); Event GJ 1 1 (corn, herbicide tolerance, deposited as ATCC 209030, described in US-A 2005-188434 or WO 98/044140); Event GM RZ13 (sugar beet, virus resistance , deposited as NCIMB-41 601 , described in WO 201 0/076212) ; Event H7-1 (sugar beet, herbicide tolerance, deposited as NCIMB 41 158 or NCIMB 41 159, described in US-A 2004-1 72669 or WO 2004/074492); Event JOPLIN 1 (wheat, disease tolerance, not deposited, described in US-A 2008-064032); Event LL27 (soybean, herbicide tolerance, deposited as
NCIMB41 658, described in WO 2006/1 08674 or US-A 2008-32061 6) ; Event LL55 (soybean, herbicide tolerance, deposited as NCIMB 41 660, described in WO 2006/1 08675 or US-A 2008-1 96127); Event LLcotton25 (cotton, herbicide tolerance, deposited as ATCC PTA-3343, described in WO 03/013224 or US-A 2003-097687); Event LLRICE06 (rice, herbicide tolerance, deposited as ATCC-23352, described in US 6,468,747 or WO 00/026345); Event LLRICE601 (rice, herbicide tolerance, deposited as ATCC PTA-2600, described in US-A 2008-2289060 or WO 00/026356); Event LY038 (corn, quality trait, deposited as ATCC PTA-5623, described in US-A 2007-028322 or WO 2005/061720); Event MIR162 (corn, insect control, deposited as PTA-81 66, described in US-A 2009-300784 or WO
2007/142840) ; Event M I R604 (corn, insect control, not deposited, described in US-A 2008-1 67456 or WO 2005/1 03301 ); Event MON15985 (cotton, insect control, deposited as ATCC PTA-251 6, described in US-A 2004-25031 7 or WO 02/1 001 63); Event MON81 0 (corn, insect control, not deposited, described in US-A 2002-1 02582); Event MON863 (corn, insect control, deposited as ATCC PTA-2605, described in WO 2004/01 1 601 or US-A 2006-095986); Event MON87427 (corn, pollination control, deposited as ATCC PTA-7899, described in WO 201 1 /062904); Event MON87460 (corn, stress tolerance, deposited as ATCC PTA-891 0, described in WO 2009/1 1 1263 or US-A 201 1 -0138504); Event MON87701 (soybean, insect control, deposited as ATCC PTA-81 94, described in US-A 2009- 130071 or WO 2009/064652); Event MON87705 (soybean, quality trait - herbicide tolerance, deposited as ATCC PTA-9241 , described in US-A 201 0-0080887 or WO 201 0/037016); Event MON87708 (soybean, herbicide tolerance, deposited as ATCC PTA9670, described in WO
201 1 /034704) ; Event MON87754 (soybean, quality trait, deposited as ATCC PTA-9385, described in WO 201 0/024976); Event MON87769 (soybean, quality trait, deposited as ATCC PTA-891 1 , described in US-A 201 1 -0067141 or WO 2009/1 02873) ; Event MON88017 (corn, insect control - herbicide tolerance, deposited as ATCC PTA-5582, described in US-A 2008-028482 or WO 2005/059103); Event MON88913 (cotton, herbicide tolerance, 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 tolerance, deposited as ATCC PTA-6708, described in US-A 2006-282915 or WO
2006/130436) ; Event MS1 1 (oilseed rape, pollination control - herbicide tolerance, deposited as ATCC
PTA-850 or PTA-2485, described in WO 01 /031042) ; Event MS8 (oilseed rape, pollination control - herbicide tolerance, deposited as ATCC PTA-730, described in WO 01 /041558 or US-A 2003- 188347); Event NK603 (corn, herbicide tolerance, deposited as ATCC PTA-2478, described in US-A 2007-292854) ; Event PE-7 (rice, insect control, not deposited, described in WO 2008/1 14282); Event RF3 (oilseed rape, pollination control - herbicide tolerance, deposited as ATCC PTA-730, described in WO 01 /041558 or US-A 2003-188347); Event RT73 (oilseed rape, herbicide tolerance, not deposited, described in WO 02/036831 or US-A 2008-070260); Event T227-1 (sugar beet, herbicide tolerance, not deposited, described in WO 02/44407 or US-A 2009-265817); Event T25 (corn, herbicide tolerance, not deposited, described in US-A 2001 -029014 or WO 01 /051 654); Event T304-40 (cotton, insect control - herbicide tolerance, deposited as ATCC PTA-8171 , described in US-A 201 0-077501 or WO 2008/122406); Event T342-142 (cotton, insect control, not deposited, described in WO
2006/128568) ; Event TC1507 (corn, insect control - herbicide tolerance, not deposited, described in US-A 2005-039226 or WO 2004/099447); Event VI P1 034 (corn, insect control - herbicide tolerance, deposited as ATCC PTA-3925., described in WO 03/052073), Event 3231 6 (corn, insect control- herbicide tolerance,deposited as PTA-1 1507, described in WO 201 1 /084632), Event 41 14
(corn, insect control-herbicide tolerance, deposited as PTA-1 1506, described in WO 201 1 /084621 ).
Among the diseases of plants or crops that can be controlled by the method according to the invention, mention can be made of :
Powdery mildew diseases such as :
Blumeria diseases, caused for example by Blumeria graminis ;
Podosphaera diseases, caused for example by Podosphaera leucotricha ;
Sphaerotheca diseases, caused for example by Sphaerotheca fuliginea ;
Uncinula diseases, caused for example by Uncinula necator ;
Rust diseases such as :
Gymnosporangium diseases, caused for example by Gymnosporangium sabinae ;
Hemileia diseases, caused for example by Hemileia vastatrix ;
Phakopsora diseases, caused for example by Phakopsora pachyrhizi or Phakopsora meibomiae ; Puccinia diseases, caused for example by Puccinia recondite, Puccinia graminis or Puccinia striiformis;
Uromyces diseases, caused for example by Uromyces appendiculatus ;
Oomycete diseases such as :
Albugo diseases caused for example by Albugo Candida;
Bremia diseases, caused for example by Bremia lactucae ;
Peronospora diseases, caused for example by Peronospora pisi ox P. brassicae ;
Phytophthora diseases, caused for example by Phytophthora infestans ;
Plasmopara diseases, caused for example by P\asmopara viticola ;
Pseudoperonospora diseases, caused for example by Pseudoperonospora humuli or
Pseudoperonospora cubensis ;
Pythium diseases, caused for example by Pythium ultimum ;
Leafspot, leaf blotch and leaf blight diseases such as :
Alternaria diseases, caused for example by Alternaria solani ;
Cercospora diseases, caused for example by Cercospora beticola ;
Cladiosporum diseases, caused for example by Cladiosporium cucumerinum ;
Cochliobolus diseases, caused for example by Cochliobolus sativus (Conidiaform: Drechslera, Syn: Helminthosporium) or Cochliobolus miyabeanus ;
Colletotrichum diseases, caused for example by Colletotrichum lindemuthanium ;
Cycloconium diseases, caused for example by Cycloconium oleaginum ;
Diaporthe diseases, caused for example by Diaporthe citri ;
Elsinoe diseases, caused for example by Elsinoe fawcettii ;
Gloeosporium diseases, caused for example by Gloeosporium laeticolor ;
Glomerella diseases, caused for example by Glomerella cingulata ;
Guignardia diseases, caused for example by Guignardia bidwelli ;
Leptosphaeria diseases, caused for example by Leptosphaena maculans ; Leptosphaena nodorum ; Magnaporthe diseases, caused for example by Magnaporthe grisea ;
Mycosphaerella diseases, caused for example by Mycosphaerella graminicola ; Mycosphaerella arachidicola ; Mycosphaerella fijiensis ;
Phaeosphaeria diseases, caused for example by Phaeosphaeria nodorum ;
Pyrenophora diseases, caused for example by Pyrenophora teres, or Pyrenophora tritici repentis ;
Ramularia diseases, caused for example by Ramularia collocygni , or Ramularia areola ;
Rhynchosporium diseases, caused for example by Rhynchosporium secalis ;
Septoria diseases, caused for example by Septoria apii ox Septoria lycopercisi ;
Typhula diseases, caused for example by Typhula incarnata ;
Venturia diseases, caused for example by Venturia inaequalis ;
Root, Sheath and stem diseases such as :
Corticium diseases, caused for example by Corticium graminearum ;
Fusarium diseases, caused for example by Fusarium oxysporum ;
Gaeumannomyces diseases, caused for example by Gaeumannomyces graminis ;
Rhizoctonia diseases, caused for example by Rhizoctonia solani ;
Sarocladium diseases caused for example by Sarocladium oryzae;
Sclerotium diseases caused for example by Sclerotium oryzae;
Tapesia diseases, caused for example by Tapesia acuformis ;
Thielaviopsis diseases, caused for example by Thielaviopsis basicola ;
Ear and panicle diseases such as :
Alternaria diseases, caused for example by Alternaria spp. ;
Aspergillus diseases, caused for example by Aspergillus flavus ;
Cladosporium diseases, caused for example by Cladosporium spp. ;
Claviceps diseases, caused for example by Claviceps purpurea ;
Fusarium diseases, caused for example by Fusarium culmorum ;
Gibberella diseases, caused for example by Gibberella zeae ;
Monographella diseases, caused for example by Monographella nivalis ; Smut and bunt diseases such as :
Sphacelotheca diseases, caused for example by Sphacelotheca reiliana ;
Tilletia diseases, caused for example by Tilletia caries ;
Urocystis diseases, caused for example by Urocystis occulta ;
Ustilago diseases, caused for example by Ustilago nuda ;
Fruit rot and mould diseases such as :
Aspergillus diseases, caused for example by Aspergillus flavus ;
Botrytis diseases, caused for example by Botrytis cinerea ;
Penicillium diseases, caused for example by Penicillium expansum ;
Rhizopus diseases caused by example by Rhizopus stolonifer
Sclerotinia diseases, caused for example by Sclerotinia sclerotiorum ;
Verticilium diseases, caused for example by Verticilium alboatrum ;
Seed and soilborne decay, mould, wilt, rot and damping-off diseases :
Alternaria diseases, caused for example by Alternaria brassicicola ;
Aphanomyces diseases, caused for example by Aphanomyces euteiches ;
Ascochyta diseases, caused for example by Ascochyta lentis ;
Aspergillus diseases, caused for example by Aspergillus flavus ;
Cladosporium diseases, caused for example by Cladosporium herbarum ;
Cochliobolus diseases, caused for example by Cochliobolus sativus ;
(Conidiaform: Drechslera, Bipolaris Syn: Helminthosporium) ;
Colletotrichum diseases, caused for example by Colletotrichum coccodes ;
Fusarium diseases, caused for example by Fusarium culmorum ;
Gibberella diseases, caused for example by Gibberella zeae ;
Macrophomina diseases, caused for example by Macrophomina phaseolina
Monographella diseases, caused for example by Monographella nivalis ;
Penicillium diseases, caused for example by Penicillium expansum ;
Phoma diseases, caused for example by Phoma lingam ;
Phomopsis diseases, caused for example by Phomopsis sojae ;
Phytophthora diseases, caused for example by Phytophthora cactorum ;
Pyrenophora diseases, caused for example by Pyrenophora graminea ;
Pyricularia diseases, caused for example by Pyricularia oryzae ;
Pythium diseases, caused for example by Pythium ultimum ;
Rhizoctonia diseases, caused for example by Rhizoctonia solani ;
Rhizopus diseases, caused for example by Rhizopus oryzae ;
Sclerotium diseases, caused for example by Sclerotium rolfsii ;
Septoria diseases, caused for example by Septoria nodorum ;
Typhula diseases, caused for example by Typhula incarnata ;
Verticillium diseases, caused for example by Verticillium dahliae ;
Canker, broom and dieback diseases such as :
Nectria diseases, caused for example by Nectria galligena ;
Blight diseases such as :
Monilinia diseases, caused for example by Monilinia laxa ;
Leaf blister or leaf curl diseases such as :
Exobasidium diseases caused for example by Exobasidium vexans ;
Taphrina diseases, caused for example by Taphrina deformans ;
Decline diseases of wooden plants such as :
Esca diseases, caused for example by Phaemoniella clamydospora ;
Eutypa dyeback, caused for example by Eutypa lata ;
Ganoderma diseases caused for example by Ganoderma boninense ;
Rigidoporus diseases caused for example by Rigidoporus lignosus ;
Diseases of Flowers and Seeds such as :
Botrytis diseases caused for example by Botrytis cinerea ;
Diseases of Tubers such as :
Rhizoctonia diseases caused for example by Rhizoctonia solani ;
Helminthosporium diseases caused for example by Helminthosporium solani ;
Club root diseases such as :
Plasmodiophora diseases, cause for example by Plamodiophora brassicae ;
Diseases caused by Bacterial Organisms such as :
Xanthomonas species for example Xanthomonas campestris pv. oryzae ;
Pseudomonas species for example Pseudomonas syringae pv. lachrymans ;
Erwinia species for example Erwinia amylovora.
The composition according to the invention may also be used against fungal diseases liable to grow on or inside timber. The term "timber" means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood. The method for treating timber according to the invention mainly consists in contacting one or more compounds according to the invention or a composition according to the invention ; this includes for example direct application, spraying, dipping, injection or any other suitable means.
The dose of active compound usually applied in the method of treatment according to the invention is generally and advantageously from 1 0 to 800 g/ha, preferably from 50 to 300 g/ha for applications in foliar treatment. The dose of active substance applied is generally and advantageously from 2 to 200 g per 1 00 kg of seed, preferably from 3 to 150 g per 1 00 kg of seed in the case of seed treatment. It is clearly understood that the doses indicated herein are given as illustrative examples of the method according to the invention. A person skilled in the art will know how to adapt the application doses, notably according to 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 composition useful to curatively or preventively treat human or animal fungal diseases such as, for
example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
The present invention further relates to the use of compounds of the formula (I) as herein defined for the control of phytopathogenic fungi.
The present invention further relates to the use of compounds of the formula (I) as herein defined for the treatment of transgenic plants.
The present invention further relates to the use of compounds of the formula (I) as herein defined for the treatment of seed and of seed of transgenic plants.
The present invention further relates to a process for producing compositions for controlling phytopathogenic harmful fungi, characterized in that derivatives of the formula (I) as herein defined are mixed with extenders and/or surfactants.
The various aspects of the invention will now be illustrated with reference to the following table of compound examples and the following preparation or efficacy examples.
Table 1 illustrates in a non-limiting manner examples of compounds of formula (I) according to the invention :
A-G1 A-G2 A-G3
A-G4 A-G5 A-G6 A-G7 wherein * denotes the point of attachment the group A to the (thio)carbonyl moiety. In table 1 , unless otherwise specified, M+H (Apcl+) means the molecular ion peak plus 1 a.m.u. (atomic mass unit) as observed in mass spectroscopy via positive atmospheric pressure chemical ionisation.
In table 1 , the logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18), using the method described below :
Temperature: 40 °C ; Mobile phases : 0.1 % aqueous formic acid and acetonitrile ; linear gradient from 10% acetonitrile to 90% acetonitrile.
Calibration was carried out using unbranched alkan-2-ones (comprising 3 to 1 6 carbon atoms) with known logP values (determination of the logP values by the retention times using linear interpolation between two successive alkanones). lambda-max-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.
In table 1 , "position" denotes the point of attachment of the -L-B residue to the phenyl ring.
Table 1
Note: Me : methyl ; iPr : isopropyl
Table 2 illustrates in a non limiting manner examples of compounds of formula (Ha) according to the invention,
wherein L is a direct bond and B1 is a substituted or non-substituted oxiranyl ring, a substituted or non- substituted thienyl ring, a substituted or non-substituted benzothienyl ring, a substituted or non- substituted furan ring, or a substituted or non-substituted benzofuran ring,
In table 2, M+H (Apcl+) and logP are defined as for table 1 .
In table 2, "position" denotes the point of attachment of the -L-B1 residue to the phenyl ring.
Table 2
Table 3 illustrates in a non limiting manner examples of compounds of formula (lib) according to the invention,
wherein L is a direct bond and B1 is a substituted or non-substituted oxiranyl ring, a substituted or non- substituted thienyl ring, a substituted or non-substituted benzothienyl ring, a substituted or non- substituted furan ring, or a substituted or non-substituted benzofuran ring
(lib)
In table 3, M+H (Apcl+) and logP are defined as for table 1 .
In table 3, "position" denotes the point of attachment of the -L-B1 residue to the phenyl ring.
Table 3
wherein Z2 and Z3 are as herein-defined, A represents A13 , Xa1 represents a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non-substituted C3-C7-cycloalkyl ; tri(CrC8-alkyl)silyl; substituted or non- substituted Ci-Cs-alkoxy; or substituted or non-substituted Ci-Cs-alkylsulfanyl, Xa2 represents hydrogen or Xa1 , and U2 represents a halogen atom such as chlorine, bromine or iodine, or a triflate group,
(Xa)
In table 4, M+H (Apcl+) and logP are defined as for table 1 . wherein A can be selected in the list consisting of the following groups : A-G1 .
A-G1
Table 4 :
Note: Et : ethyl ; iPr : isopropyl
Table 5 provides the NM R data (1 H) of a selected number of compounds from table 1 .
The 1 H-NM R data of selected examples are stated in the form of 1 H-NM R peak lists. For each signal peak, the δ value in ppm and the signal intensity in brackets are listed.
Intensity of sharp signals correlates with the height of the signals in a printed example of a NM R spectrum in cm and shows the real relations of signal intensities. From broad signals several peaks or the middle of the signal and their relative intensity in comparison to the most intensive signal in the spectrum can be shown.
The 1 H-NM R peak lists are similar to classical 1 H-NM R prints and contain therefore usually all peaks, which are listed at classical NM R-interpretation. Additionally they can show like classical 1 H-NMR prints signals of solvents, stereoisomers of the target compounds, which are also object of the invention, and/or peaks of impurities. To show compound signals in the delta-range of solvents and/or water the usual peaks of solvents, for example peaks of DMSO in DMSO-d6 and the peak of water are shown in our 1 H- NMR peak lists and have usually on average a high intensity.
The peaks of stereoisomers of the target compounds and/or peaks of impurities have usually on average a lower intensity than the peaks of target compounds (for example with a purity >90%). Such stereoisomers and/or impurities can be typical for the specific preparation process. Therefore their peaks can help to recognize the reproduction of our preparation process via "side-products-fingerprints".
An expert, who calculates the peaks of the target compounds with known methods (MestreC, ACD- simulation, but also with empirically evaluated expectation values), can isolate the peaks of the target compounds as needed optionally using additional intensity filters. This isolation would be similar to relevant peak picking at classical 1 H-NM R interpretation.
Further details of NMR-data description with peak lists can be found in the publication "Citation of NMR Peaklist Data within Patent Applications" of the Research Disclosure Database Number 564025.
Table 5 : NMR peak lists
Sltnove 2.5032 (54.35); 2.4987 (39.28); 2.3298 (0.36); 0.6982 (0.80); 0.6793 (3.80);
0.6611 (3.84); 0.6505 (2.03); 0.6328 (1.12); 0.6147 (4.26); -0.0002 (3.50)
Fencyrque 8.4383 (2.00); 7.9531 (1.27); 7.6323 (1.63); 7.6266 (1.77); 7.6115 (2.38); 7.6058 (Mh)z (2.57); 7.5882 (2.71); 7.5857 (2.85); 7.5756 (2.90); 7.5731 (2.91); 7.5324 (0.48);
7.5246 (5.48); 7.5126 (0.55); 7.5037 (3.87); 7.4989 (3.18); 7.4963 (3.04); 7.4871 (6.14); 7.4816 (3.38); 7.3031 (1.43); 7.1671 (3.42); 7.1568 (2.93); 7.1477 (2.86);
DMSO
1.84 400 7.1442 (2.83); 7.1351 (2.55); 7.0312 (1.60); 4.7353 (8.60); 4.0028 (0.73); 3.9365 -d6
(16.00); 3.3358 (133.71); 2.8909 (10.35); 2.7317 (8.16); 2.5250 (0.88); 2.5118 (16.39); 2.5074 (32.26); 2.5029 (42.03); 2.4984 (30.16); 2.4939 (14.35); 0.7818 (0.61); 0.7639 (2.64); 0.7507 (2.70); 0.7465 (2.33); 0.7336 (0.85); 0.6453 (1.16); 0.6345 (2.93); 0.6275 (3.02); 0.6197 (2.22); 0.6059 (0.64); -0.0002 (1.48)
7.9520 (2.17); 7.6571 (3.04); 7.6517 (3.68); 7.6363 (4.83); 7.6308 (5.52); 7.6098 (6.12); 7.6074 (6.78); 7.5970 (6.92); 7.5947 (7.56); 7.5806 (1.61); 7.5553 (8.43); 7.5499 (8.91); 7.5408 (6.34); 7.5206 (4.24); 7.4993 (6.21); 7.4917 (6.69); 7.4449 (0.48); 7.4246 (0.33); 7.1718 (6.87); 7.1626 (6.81); 7.1592 (7.34); 7.1501 (6.69); 7.0414 (3.76); 6.9067 (1.88); 4.8291 (0.50); 4.7580 (1.91); 4.6485 (0.48); 4.6352 (0.44); 4.6023 (0.36); 3.8998 (14.91); 3.8399 (0.78); 3.3922 (0.36); 3.3824 (0.37);
DMSO
1.85 400 3.3705 (0.66); 3.3296 (446.02); 3.3149 (58.12); 3.2498 (0.42); 2.8904 (16.00);
-d6
2.8742 (1.83); 2.8000 (1.78); 2.7470 (0.46); 2.7307 (13.68); 2.7149 (1.87); 2.6755 (0.96); 2.6708 (1.30); 2.6665 (1.10); 2.5240 (3.19); 2.5108 (67.26); 2.5065 (139.91); 2.5020 (193.78); 2.4975 (157.95); 2.4931 (102.24); 2.3333 (0.87); 2.3288 (1.23); 2.3239 (1.01); 1.2329 (0.59); 0.5809 (9.05); 0.3909 (0.33); 0.3798 (0.32); 0.3741 (0.34); 0.2910 (0.33); 0.0082 (0.43); -0.0002 (12.46); -0.0085
(1.32); -0.0174 (1.15)
7.6619 (0.94); 7.6552 (3.05); 7.6455 (4.27); 7.6389 (3.35); 7.6291 (3.83); 7.5601 (2.83); 7.3903 (0.63); 7.3753 (1.44); 7.3599 (2.36); 7.3539 (2.44); 7.3370 (8.90); 7.3303 (10.89); 7.3200 (5.14); 7.3002 (2.96); 7.2733 (1.71); 7.2444 (2.35); 7.2307 (2.29); 7.1162 (1.60); 6.9369 (3.38); 6.7576 (1.66); 5.7585 (16.00); 4.7825 (1.14);
DMSO 4.7308 (1.87); 4.5964 (3.74); 4.5451 (2.30); 4.0407 (0.45); 4.0168 (0.45); 3.7932
1.86 300 (11.40); 3.7691 (2.40); 3.3246 (65.38); 2.5134 (7.55); 2.5074 (16.59); 2.5014 -d6
(23.21); 2.4953 (17.28); 2.4894 (8.57); 2.2340 (1.03); 1.9889 (1.92); 1.2454 (0.74); 1.1980 (0.56); 1.1743 (1.04); 1.1505 (0.53); 0.8583 (0.81); 0.8354 (0.40); 0.6912 (1.76); 0.6787 (1.71); 0.6112 (3.86); 0.5388 (1.11); 0.5221 (1.65); 0.5085 (1.84); 0.4935 (1.20); 0.4778 (0.92); 0.3179 (0.69); 0.2990 (1.35); 0.2793 (1.36); 0.2591 (0.60); 0.0107 (0.61); -0.0002 (19.88); -0.0112 (1.32); -0.0300 (0.53)
8.2069 (2.28); 7.6450 (0.60); 7.6354 (2.67); 7.6258 (2.96); 7.6191 (2.98); 7.6095 (2.95); 7.5589 (2.73); 7.5546 (3.19); 7.5492 (2.90); 7.5451 (2.46); 7.3785 (0.45); 7.3638 (1.02); 7.3503 (1.12); 7.3424 (1.95); 7.3203 (9.82); 7.3102 (6.62); 7.2819 (1.14); 7.2558 (1.86); 7.2466 (2.71); 7.2424 (2.76); 7.2303 (2.54); 7.2262 (2.55); 7.1811 (0.38); 7.0746 (3.43); 6.8938 (1.69); 5.7588 (10.28); 4.9653 (0.37); 4.9140
DMSO (0.40); 4.6610 (7.72); 4.5009 (0.61); 4.4485 (0.44); 3.9108 (16.00); 3.3252 (54.81);
1.87 300
-d6 2.5131 (8.04); 2.5072 (17.47); 2.5012 (24.33); 2.4952 (18.05); 2.4893 (9.03);
2.3828 (1.07); 1.9889 (0.73); 1.2460 (0.45); 1.1742 (0.38); 1.1162 (0.32); 0.8579 (0.46); 0.7279 (0.80); 0.7170 (0.82); 0.7074 (1.08); 0.6972 (0.94); 0.6514 (7.60); 0.6319 (4.26); 0.5295 (0.71); 0.5126 (1.19); 0.4995 (1.38); 0.4831 (0.89); 0.4700 (0.71); 0.3797 (0.79); 0.3616 (1.36); 0.3390 (1.44); 0.3195 (0.58); 0.0667 (0.34);
0.0107 (0.60); -0.0002 (20.43); -0.0110 (1.06)
7.6782 (1.85); 7.6685 (2.60); 7.6625 (2.51); 7.6526 (2.56); 7.5882 (2.71); 7.4648 (0.34); 7.4010 (0.81); 7.3907 (0.89); 7.3527 (7.16); 7.3351 (7.55); 7.2708 (2.64); 7.2568 (2.37); 7.1855 (1.02); 7.0056 (1.90); 6.8260 (1.01 ); 5.7590 (16.00); 4.7793 (0.43); 4.6614 (0.34); 4.6121 (0.34); 4.5572 (0.48); 4.5270 (0.47); 4.4856 (0.50);
DMSO
1.88 300 4.4481 (0.36); 3.8948 (10.42); 3.8731 (2.22); 3.8076 (1.07); 3.3281 (26.01);
-d6
2.5136 (3.24); 2.5078 (6.87); 2.5018 (9.46); 2.4958 (7.04); 2.4900 (3.51); 2.3032 (1.12); 1.9891 (0.97); 1.2345 (0.33); 1.1744 (0.50); 0.9057 (0.62); 0.8842 (0.61); 0.8583 (0.44); 0.6684 (1.80); 0.4787 (6.36); 0.4597 (5.71); 0.2306 (0.65); 0.2096 (1.27); 0.1892 (1.22); 0.1691 (0.55); 0.0106 (0.35); -0.0002 (7.26)
1.89 DMSO 400 7.9535 (2.13); 7.8799 (2.96); 7.7769 (2.93); 7.7635 (3.05); 7.6908 (2.54); 7.6854
2.6837 (0.90); 2.0744
The following examples illustrate in a non-limiting manner the preparation and efficacy of the compounds of formula (I) according to the invention. Preparation example 1 : preparation of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-N-[2-(3- methyloxetan-3-yl)benzyl]-1 H-pyrazole-4-carboxamide (compound 1.15)
Step 1 : preparation of N-[2-(3-methyloxetan-3-yl)benzyl]cyclopropanamine
To a cooled solution of 1 .94 g (34 mmol) of cyclopropylamine and 2.44 mL (42 mmol) of acetic acid, together with 9 g of 4A molecular sieves, in 50 mL of methanol, are added 3 g (1 7 mmol) of 2-(3- methyloxetan-3-yl)benzaldehyde. The reaction mixture is stirred for 3 hrs at reflux. The reaction mixture is then cooled to 0 °C and 1 .6 g (25 mmol) of sodium cyanoborohydride are slowly added and the reaction mixture is further stirred for 1 hr at reflux. The cooled reaction mixture is then filtered over a cake of diatomaceous earth. The cake is washed twice by 80 mL of methanol and the combined methanolic extracts are concentrated under vacuum. 100 mL of water are then added to the residue and the pH is adjusted to 12 with a 1 N aqueous solution of sodium hydroxide. The watery layer is extracted with 2 x 50 mL of ethyl acetate. The organic layer is washed twice by a concentrated aqueous solution of NaCI and dried over magnesium sulfate to yield after concentration 4.37 g of a yellow oil. Column chromatography on silica gel (gradient heptane/ethyl acetate) yields 2.44 g (62% yield) of N-[2-(3- methyloxetan-3-yl)benzyl]cyclopropanamine as a colorless oil. (M+H) = 21 8.
Step 2 : preparation of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-N-[2-(3-methyloxetan-3-yl) benzyl]-1 H-pyrazole-4-carboxamide
At ambient temperature, a solution of 1 95 mg (0.92 mmol) of 3-(difluoromethyl)-5-fluoro-1 -methyl-1 H- pyrazole-4-carbonyl chloride in 2 mL of dry tetrahydrofurane is added to a mixture of 200 mg (0.92 mmol) of N-[2-(3-methyloxetan-3-yl)benzyl]cyclopropanamine and 0.141 mL (1 .01 mmol) of triethylamine in 3 mL of dry tetrahydrofurane. The reaction mixture is stirred at ambient temperature for four days. The reaction mixture is then quenched by 0.1 mL of a 1 N solution of HCI in diethylether and solids are filtered off. The organic phase is concentrated under vacuum to yield 400 mg of a crude residue. Column chromatography on silica gel (gradient n-heptane/ethyl acetate) yields 314 mg (82% yield) of N- cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-N-[2-(3-methyloxetan-3-yl)benzyl]-1 H-pyrazole-4- carboxamide as an oil. 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-1 H-pyrazole-4-carboxamide (compound 1.4)
Step 1 : preparation of N-[5-chloro-2-(prop-1 -en-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H- pyrazole-4-carboxamide
To a suspension of 1 .55 g (3.55 mmol) of N-(2-bromo-5-chlorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5- fluoro-1 -methyl-1 H-pyrazole-4-carboxamide in a 20/1 mixture of toluene / water degassed with argon, are successively added 753 mg (4.25 mmol) of 4,4,5,5-tetramethyl-2-(prop-1 -en-2-yl)-1 ,3,2-dioxaborolane, 205 mg (0.71 mmol) of tricyclohexylphosphine, 167 mg (0.355 mmol) of palladium (II) acetate and 4.65 g (21 .3 mmol) of tri-potassium phosphate. The mixture is heated at 1 00 °C for 3 hrs. The reaction mixture is cooled to ambient temperature. 60 ml_ of water are added and the reaction mixture is extracted 3 times by ethyl acetate. The combined organic extracts are washed by a saturated aqueous solution of NaCI and dried over a phase-separator filter. The organic phase is concentrated under vacuum and the crude residue is purified by column chromatography on silica gel (gradient n-heptane/ethyl acetate) to yield 1 .01 g (72% yield) of a 68/32 mixture of N-[5-chloro-2-(prop-1 -en-2-yl)benzyl]-N-cyclopropyl-3- (difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide and N-cyclopropyl-3-(difluoromethyl)-N- [2, 5-di(prop-1 -en-2-yl)benzyl]-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide used as such in the next step. LogP = 3.96. (M+H) = 398. Step 2 : preparation of N-[5-chloro-2-(2-methyloxiran-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5- fluoro-1 -methyl-1 H-pyrazole-4-carboxamide
To a cooled solution of 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-1 H-pyrazole-4-carboxamide in 20 mL of dichloro- methane, are slowly added 1 .65 g (6.69 mmol) of 70% wt. m-chloroperbenzoic acid. The reaction mixture is stirred at ambient temperature for 2 hrs. The excess of oxidant is neutralized by addition of an aqueous solution of 2.47 g (12.6 mmol) of sodium hydrosulfite and the mixture is then extracted 3 times by dichloromethane. The combined organic extracts are washed by an aqueous solution of sodium hydrogenocarbonate and dried over a phase-separator filter. The organic phase is concentrated under vacuum and the crude residue is purified by column chromatography on silica gel (gradient n- heptane/ethyl acetate) to yield 1 83 mg (33% yield) of N-[5-chloro-2-(2-methyloxiran-2-yl)benzyl]-N- cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide. LogP = 3.19. (M+H) = 414.
Preparation example 3 : preparation of N-[5-(1 -benzothiophen-3-yl)-2-isopropylbenzyl]-N-cyclopropyl-3- (difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide (compound 1.157)
Step 1 : preparation of 1 -(5-chloro-2-isopropylphenyl)-N-hydroxymethanimine
To a solution of 1 g (5.47 mmol) of 5-chloro-2-isopropylbenzaldehyde in 12 mL of methanol are successively added 0.5 g (6 mmol) of sodium acetate and 41 9 mg (6 mmol) of hydroxylamine hydrochloride. The reaction mixture is stirred at ambient temperature for 6 hrs. The solvent is removed under vacuum and the residue is extracted by dichloromethane. The organic phase is filtered over a ChemElut™ cartridge and concentrated under vacuum to yield 1 .08 g (89% yield) of 1 -(5-chloro-2-isopropylphenyl)-N- hydroxymethanimine as a 8/92 mixture of two isomers. LogP = 2.90 (minor isomer) and 3.1 7 (major isomer). (M+H) = 1 98. Step 2 : preparation of 1 -(5-chloro-2-isopropylphenyl)methanamine
To a cooled solution of 1 .08 g (5.46 mmol) of 1 -(5-chloro-2-isopropylphenyl)-N-hydroxymethanimine in 18 mL of tetrahydrofuran are slowly added 21 mL (21 mmol) of a 1 M solution of the
borane:tetrahydrofuran complex in tetrahydrofuran. The reaction mixture is heated at reflux for 1 day. The excess of hydride is destroyed by addition of ethanol. A few mL of a 1 N aqueous solution of sodium hydroxyde are added and the reaction mixture is further heated at 70 °C for 30 min. The reaction mixture is diluted by water, extracted by terbutylmethylether. The organic phase is filtered over a ChemElut™ cartridge and concentrated under vacuum to yield 1 .30 g of 1 -(5-chloro-2-isopropylphenyl)methanamine used as such in the next step. LogP = 1 .20. (M+H) = 1 84.
Step 3 : preparation of N-(5-chloro-2-isopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4- carboxamide (compound Xa.1 )
At ambient temperature, 824 mg (3.87 mmol) of 3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4- carbonyl chloride are added to a mixture of 647 mg (3.52 mmol) of 1 -(5-chloro-2-isopropyl- phenyl)methanamine and 0.590 mL (4.23 mmol) of triethylamine in 7 mL of dry tetrahydrofuran. The reaction mixture is heated at reflux for 2 hrs. A few mL of water are added and the reaction mixture is filtered over a ChemElut™ cartridge and concentrated to give 1 .5 g of crude material as a yellow oil. The residue is purified by preparative H PLC (gradient acetonitrile/water + 0.1 % HC02H) to yield 360 mg (27% yield) of N-(5-chloro-2-isopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide as a white solid. LogP = 3.46. (M+H) = 360.
Step 4 : preparation of N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl- 1 H-pyrazole-4-carboxamide
In a dried Radleys™ vial, are added 63 mg (0.1 9 mmol) of N-(5-chloro-2-isopropylbenzyl)-3-(difluoro- methyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide, 35 mg (0.1 9 mmol) of copper(ll) acetate and 31 mg (0.096 mmol) of caesium carbonate. The vial is flushed with dry air and vigorously stirred for a few minutes. 0.5 mL of toluene is added together with 46 mg (0.58 mmol) of pyridine and 65 mg (0.38 mmol) of 2-cyclopropyl-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane. The vial is flushed again with dry air, sealed and heated at 1 00 °C for 1 day. HPLC-mass analysis of the reaction shows the formation of 4% (7% cv) of N- (5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4- carboxamide. 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-1 H-pyrazole-4-carboxamide
In a 5 mL microwave vial, 200 mg (0.5 mmol) of N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoro- methyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide are dissolved in 1 mL of acetonitrile. The vial is degassed with argon and 1 04 mg (0.75 mmol) of potassium carbonate dissolved in 1 mL of water are further added, followed by 1 06 mg (0.6 mmol) of 1 -benzothiophen-3-ylboronic acid and 6.5 mg (0.01 mmol) of 1 ,1 'Bis(di-ter-butylphosphino)(ferrocene)dichlorpalladium(ll). The microwave apparatus [Biotage Initiator™] is then heated at 130 °C for 20 minutes. The reaction mixture is cooled to ambient temperature, filtered, and extracted by ethyl acetate. The organic extract is dried over a ChemElut™ cartridge and concentrated under vacuum. The residue is purified by preparative HPLC (gradient acetonitrile/water + 0.1 % HC02H) to yield 75 mg (28% yield) of N-[5-(1 -benzothiophen-3-yl)-2-isopropyl- benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide as a brown oil. LogP = 5.1 7. (M+H) = 498.
Preparation example 4 : preparation of N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-N-[2-(4-methyl- 2-thienyl)benzyl]-1 H-pyrazole-4-carboxamide (compound 1.1 00)
In a Radleys™ vial, 200 mg (0.49 mmol) of N-(2-bromobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro- 1 -methyl-1 H-pyrazole-4-carboxamide are dissolved in 5 mL of dioxan together with 137 mg (0.99 mmol) of potassium carbonate dissolved in 0.5 mL of water. The vial is degassed with argon for 1 0 min. Are then added, 106 mg (0.74 mmol) of (4-methyl-2-thienyl)boronic acid and 1 15 mg (0.1 mmol) of tetrakis- (triphenylphosphine)palladium(O). The reaction mixture is heated at 1 00 °C for 8 hrs. The cooled mixture is filtered over a cake of diatomaceous earth. The filtrate is washed by an aqueous solution of potassium carbonate followed by a saturated aqueous solution of NaCI and dried over a ChemElut™ cartridge. The organic layer is concentrated to leave a residue that is purified by column chromatography on silica gel (gradient n-heptane/ethyl acetate) to yield 1 65 mg (71 % yield) of N-cyclopropyl-3-(difluoromethyl)-5- fluoro-1 -methyl-N-[2-(4-methyl-2-thienyl)benzyl]-1 H-pyrazole-4-carboxamide as a colorless oil. LogP = 3.99. (M+H) = 420.
General preparation example 5 : thionation of amide of formula (I) on Chemspeed™ apparatus
In a 13 mL Chemspeed™ vial is weighted 0.27 mmol of phosphorous pentasulfide (P2S5). 3 mL of a 0.1 8 M solution of the amide (I) (0.54 mmol) in dioxane is added and the mixture is heated at reflux for two hours. The temperature is then cooled to 80 °C and 2.5 mL of water are added. The mixture is heated at 80 °C for one more hour. 2 mL of water are then added and the reaction mixture is extracted twice by 4 mL of dichloromethane. The organic phase is deposited on a basic alumina cartridge (2 g) and eluted twice by 8 mL of dichloromethane. The solvents are removed and the crude thioamide derivative is analyzed by LCMS and NM R. Insufficiently pure compounds are further purified by preparative LC. Example A : in vivo preventive test on Blumeria praminis (barley)
Solvent: 49 parts by weight of N,N-dimethylacetamide
Emulsifier: 1 part by weight of alkylarylpolyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.
After the spray coating has been dried, the plants are dusted with spores of Blumeria graminis f.sp. hordei.
The plants are placed in the greenhouse at a temperature of approximately 1 8 °C and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.
The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 1 00% means that no disease is observed.
Under these conditions, excellent (at least 90%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table A :
Table A:
Example B : in vivo preventive test on Alternaria brassicae (leaf spot on radish)
The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.
Radish plants ("Pernod Clair" variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 1 7 °C, are treated at the cotyledon stage by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.
After 24 hours, the plants are contaminated by spraying the cotyledons with an aqueous suspension of
Alternaria brassicae spores (50 000 spores per mL). The spores are collected from a 15-day-old culture.
The contaminated radish plants are incubated at 20 °C and at 1 00% relative humidity.
Grading (% of efficacy) is carried out 6 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table B :
Table B:
Example C : in vivo preventive test on Botrytis cinerea (grey mould)
The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO and then diluted with water to obtain the desired active material concentration.
Gherkin plants ("Vert petit de Paris" variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 24 °C, are treated at the Z1 1 cotyledon stage by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.
After 24 hours, the plants are contaminated by spraying the cotyledons with an aqueous suspension of cryopreserved Botrytis cinerea spores (50 000 spores per mL). The spores are suspended in a nutrient solution composed of 1 0 g/L of PDB, 50 g/L of D-Fructose, 2 g/L of NH4N03 and 1 g/L of KH2P04. The contaminated gherkin plants are incubated at 1 7 °C and at 90% relative humidity.
Grading (% of efficacy) is carried out 4 to 5 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table C :
Table C:
Under the same conditions, good (at least 70%) to total protection is observed at a dose of 1 00 ppm of active ingredient with the following compounds from table C2 :
Table C2:
Example D : in vivo preventive test on Leptosphaena nodorum test (wheat)
Solvent: 49 parts by weight of N,N-dimethylacetamide
Emulsifier: 1 part by weight of alkylarylpolyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for preventive activity, young plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.
After the spray coating has been dried, the plants are sprayed with a spore suspension of Leptosphaena nodorum. The plants remain for 48 hours in an incubation cabinet at approximately 20 °C and a relative atmospheric humidity of approximately 100%.
The plants are placed in the greenhouse at a temperature of approximately 22 °C and a relative atmospheric humidity of approximately 80%.
The test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 1 00% means that no disease is observed.
Under these conditions, high (at least 80%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table D:
Example E : in vivo preventive test on Pyrenophora teres (barley)
The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.
Barley plants ("Plaisant" variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 22 °C, are treated at the 1 leaf stage (1 0 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.
After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Pyrenophora teres spores (12 000 spores per ml_). The spores are collected from a 12-day-old culture. The contaminated barley plants are incubated for 48 hours at 20 °C and at 1 00% relative humidity, and then for 12 days at 20 °C at 70-80% relative humidity.
Grading (% of efficacy) is carried out 14 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table E :
Table E:
Under the same conditions, good (at least 70%) to excellent (at least 95%) protection is observed at a dose of 100 ppm of active ingredient with the following compounds from table E2 :
Table E2:
Under the same conditions, good (at least 70%) protection to high (at least 80%) protection is observed at a dose of 1 00 ppm of active ingredient with compounds of example 1.84 and 1.144, whereas no protection is observed with the pyridine analogue CM P1 disclosed in patent application WO-2007/087906 as in table E3:
Table E3:
CMP1 disclosed in international patent WO-2007/087906 corresponds to N-[2-chloro-4-(pyridin-3- yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide.
These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2007/087906. Example F : In vivo preventive test on Pyricularia orvzae (rice blast)
The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.
Rice plants ("Koshihikari" variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 26 °C, are treated at the 2 leaf stage (1 0 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.
After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Pyricularia oryzae spores (40 000 spores per ml_). The spores are collected from a 15-day-old culture and are suspended in water containing 2.5 g/L of gelatin. The contaminated rice plants are incubated at 25 °C and at 80% relative humidity.
Grading (% of efficacy) is carried out 6 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 70%) to high (at least 80%) protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table F :
Table F:
Example Efficacy
1.1 06 80
1.1 19 70
1.132 80
Example G : in vivo preventive test on Puccinia recondita (brown rust on wheat)
The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.
Wheat plants ("Scipion" variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 22 °C, are treated at the 1 leaf stage (1 0 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.
After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Puccinia recondita spores (100 000 spores per ml_). The spores are collected from an infected plant and are suspended in water containing 2.5 mL/L of Tween 80 at 10%. The contaminated wheat plants are incubated for 24 hours at 20 °C and at 1 00% relative humidity, and then for 1 0 days at 20 °C and at 70- 80% relative humidity.
Grading (% of efficacy) is carried out 12 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table G :
Table G:
Example Efficacy Example Efficacy Example Efficacy
1.1 75 1.75 94 1.122 98
I.3 94 1.76 93 1.123 94
I.4 98 1.77 93 1.130 81
I.5 98 1.78 93 1.131 75
I.27 100 1.79 75 1.132 83
I.28 94 1.86 98 1.136 98
I.29 81 1.87 75 1.137 88
I.48 75 1.88 94 1.138 94
I.50 100 1.1 00 100 1.139 94
I.54 80 1.1 01 100 1.141 86
I.55 95 1.1 02 100 1.143 88
I.56 78 1.1 03 95 1.144 75
1.66 94 1.1 04 95 1.145 88
1.67 100 1.1 05 100 1.154 75
1.68 94 1.1 12 83 1.155 75
1.69 94 1.1 14 72 1.156 81
1.70 78 1.1 19 100 1.157 98
1.73 100 1.120 100 1.158 81
1.74 94 1.121 94 1.1 68 81
Under the same conditions, good (at least 70%) to total protection is observed at a dose of 1 00 ppm of active ingredient with the following compounds from table G2 :
Table G2:
Under the same conditions, average (at least 60%) to excellent (at least 90%) protection is observed at a dose of 100 ppm and 500 ppm of active ingredient with compounds of example 1.77, 1.78 or 1.79, whereas poor (less than 40%) to no protection is observed with the pyridine analogue CMP2 disclosed in patent application WO-201 0/130767 as in table G3:
Table G3:
CMP2 disclosed in international patent WO-2010/130767 corresponds to 5-chloro-N-[2-chloro-4-(pyridin- 3-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-1 -methyl- 1 H-pyrazole-4-carboxamide.
These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2010/130767.
Example H : in vivo preventive test on Septoria tritici (wheat)
The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.
Wheat plants ("Scipion" variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 22 °C, are treated at the 1 leaf stage (1 0 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.
After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of cryopreserved Septoria tritici spores (500 000 spores per ml_). The contaminated wheat plants are incubated for 72 hours at 1 8 °C and at 1 00% relative humidity, and then for 21 days at 90% relative humidity.
Grading (% of efficacy) is carried out 24 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table H :
Table H:
Under the same conditions, good (at least 70%) to total protection is observed at a dose of 1 00 ppm of active ingredient with the following compounds from table H2 :
Table H2:
Example I : in vivo preventive test on Sphaerotheca fuli inea (powdery mildew on cucurbits)
The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO and then diluted with water to obtain the desired active material concentration.
Gherkin plants ("Vert petit de Paris" variety), sown in starter cups on a 50/50 peat soil-pozzolana substrate and grown at 24 °C, are treated at the Z1 1 cotyledon stage by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.
After 24 hours, the plants are contaminated by spraying the cotyledons with an aqueous suspension of Sphaerotheca fuliginea spores (1 00 000 spores per ml_). The spores are collected from infected plants. The contaminated gherkin plants are incubated at about 20 °C and at 70-80% relative humidity.
Grading (% of efficacy) is carried out 12 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table I :
Table I :
Under the same conditions, good (at least 70%) to total protection is observed at a dose of 1 00 ppm of active ingredient with the following compounds from table I2 :
Table I2:
Under the same conditions, total protection is observed at a dose of 100 ppm of active ingredient with compound of example 1.144, whereas no protection is observed with the pyridine analogue CM P1 disclosed in patent application WO-2007/087906 as in table I3:
Table I3:
CMP1 disclosed in international patent WO-2007/087906 corresponds to N-[2-chloro-4-(pyridin-3- yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide.
These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2007/087906.
Under the same conditions, excellent (at least 90%) to total protection is observed at a dose of 500 ppm of active ingredient with compound of example 1.139 (respectively 1.140, 1.141 , 1.144 and 1.145) whereas poor (less than 40%) protection or plant damages is observed with the pyridine analogue CMP3 (respectively CMP4, CMP5, CM P6 and CM P7) claimed in patent applications WO-2007/087906 or WO- 2010/130767 as in table I4:
Table I4:
CMP3 disclosed in international patent WO-201 0/130767 corresponds to N-[2-(6-chloropyridin-2- yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-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-1 H-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-1 H-pyrazole-4-carboxamide,
CMP6 disclosed in international patent WO-2007/087906 corresponds to N-[5-chloro-2-(6-chloropyridin-2- yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide, and
CMP7 disclosed in international patent WO-201 0/130767 corresponds to 5-chloro-N-[5-chloro-2-(6- chloropyridin-2-yl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-1 -methyl- 1 H-pyrazole-4-carboxamide.
These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2007/087906.
Example J : in vivo preventive test on Uromvces appendiculatus (bean rust)
The active ingredients tested are prepared by homogenization in a mixture of acetone/tween/DMSO, and then diluted with water to obtain the desired active material concentration.
Bean plants ("Saxa" variety), sown in starter cups on a 50/50 peat soil pozzolana substrate and grown at 24 °C, are treated at the 2 leaf stage (9 cm height) by spraying with the active ingredient prepared as described above. Plants, used as controls, are treated with the mixture of acetone/tween/DMSO/water not containing the active material.
After 24 hours, the plants are contaminated by spraying the leaves with an aqueous suspension of Uromyces appendiculatus spores (150 000 spores per ml_). The spores are collected from infected plants and are suspended in water containing 2.5 mL/L of Tween 80 at 10%. The contaminated bean plants are incubated for 24 hours at 20 °C and at 1 00% relative humidity, and then for 1 0 days at 20 °C and at 70- 80% relative humidity.
Grading (% of efficacy) is carried out 1 1 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 70%) to total protection is observed at a dose of 500 ppm of active ingredient with the following compounds from table J :
Table J:
Under the same conditions, good (at least 70%) to total protection is observed at a dose of 1 00 ppm of active ingredient with the following compounds from table J2 :
Table J2:
Example K : in vivo preventive test on Venturis inaegualis (apples)
Solvent: 24.5 parts by weight of acetone
24.5 parts by weight of N,N-dimethylacetamide
Emulsifier: 1 part by weight of alkylarylpolyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the causal agent of apple scab (Venturis inaequalis) and then remain for 1 day in an incubation cabinet at approximately 20 °C and a relative atmospheric humidity of 1 00%.
The plants are then placed in a greenhouse at approximately 21 °C and a relative atmospheric humidity of approximately 90%.
The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 1 00% means that no disease is observed.
Under these conditions, excellent (at least 90%) to total protection is observed at a dose of 1 00 ppm of active ingredient with the following compounds from table K :
Table K:
Example Efficacy
I.3 96
I.4 100
1.139 100
1.157 100
Claims
1 . A compound of formula (I)
(I)
wherein
• A represents a carbo-linked, unsaturated or partially saturated, 5-membered heterocyclyl group that can be substituted by up to four groups R that can be the same or different ;
• T represents O or S ;
· n represents 0, 1 , 2, 3 or 4 ;
• L represents a direct bond, CZ4Z5, O, S, SO, S02 or NZ6 ;B represents a saturated, partially saturated or unsaturated, monocyclic or fused bicyclic 3-, 4-, 5-, 6-, 7-, 8-, 9-, or 1 0-membered ring comprising from 1 up to 4 heteroatoms selected in the list consisting of N, O, S, that can be substituted by up to 6 groups Y which can be the same or different ; with the proviso that B does not represent a pyridyl ring when L represents a direct bond or an oxygen atom
• Z1 represents a non-substituted C3-C7-cycloalkyl or a C3-C7-cycloalkyl substituted by up to 1 0 atoms or groups that can be the same or different and that can be selected in the list consisting of halogen atoms, cyano, CrC8-alkyl, CrC8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, CrC8-alkoxy, CrC8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, CrC8-alkoxycarbonyl, CrC8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different, Ci-C8-alkylaminocarbonyl or di-Ci -C8-alkylaminocarbonyl ;
• Z2 and Z3, which can be the same or different, represent a hydrogen atom ; substituted or non- substituted Ci-C8-alkyl ; substituted or non-substituted C2-C8-alkenyl ; substituted or non- substituted C2-C8-alkynyl ; cyano ; isonitrile ; nitro ; a halogen atom ; substituted or non- substituted CrC8-alkoxy ; substituted or non-substituted C2-C8-alkenyloxy ; substituted or non- substituted C2-C8-alkynyloxy ; substituted or non-substituted C3-C7-cycloalkyl ; substituted or non- substituted Ci -C8-alkylsulfanyl ; substituted or non-substituted Ci -C8-alkylsulfonyl ; substituted or non-substituted Ci -C8-alkylsulfinyl ; amino ; substituted or non-substituted CrC8-alkylamino ; substituted or non-substituted di-Ci-C8-alkylamino ; substituted or non-substituted Ci -C8- alkoxycarbonyl ; substituted or non-substituted Ci -C8-alkylcarbamoyl ; substituted or non- substituted di-CrC8-alkylcarbamoyl ; or substituted or non-substituted N-CrC8-alkyl-Ci -C8- alkoxy-carbamoyl ; or • Z2 and Z3 together with the carbon atom to which they are linked can form a substituted or non- substituted cycloalkyl ; or
• Z3 and the substituent X vicinal to the point of attachment of the phenyl ring, together with the consecutive carbon atoms to which they are linked, can form a substituted or non-substituted 5-, 6- or 7-membered, partly saturated, carbo- or heterocycle comprising up to 3 heteroatoms and Z2 is as herein-described ; Z4 and Z5 independently represent a hydrogen atom ; a halogen atom ; cyano ; substituted or non-substituted CrC8-alkyl ; CrC8-halogenoalkyl having 1 to 5 halogen atoms ; substituted or non-substituted CrC8-alkoxy; substituted or non-substituted CrC8- alkylsulfanyl ; or substituted or non-substituted CrC8-alkoxycarbonyl ; or
• Z4 and Z5 together with the carbon atom to which they are linked can form a C(=0) carbonyl group ;
• Z6 represents a hydrogen atom ; a substituted or non-substituted CrC8-alkyl ; a CrC8- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted C2-C8-alkenyl ; C2-C8-halogenoalkenyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted C3-C8-alkynyl ; C3-C8-halogenoalkynyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non- substituted C3-C7-cycloalkyl ; C3-C7-halogeno-cycloalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted C3-C7-cycloalkyl-Ci-C8-alkyl ; formyl ; substituted or non-substituted CrC8-alkylcarbonyl ; CrC8-halogenoalkylcarbonyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-C8- alkoxycarbonyl ; CrC8-halogenoalkoxycarbonyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted Ci-C8-alkylsulfonyl ; Ci -C8- halogenoalkylsulfonyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted benzyl ; or substituted or non-substituted phenylsulfonyl ;X independently represents a halogen atom ; nitro ; cyano ; isonitrile ; hydroxy ; amino ; sulfanyl ; pentafluoro-A6-sulfanyl ; formyl ; formyloxy ; formylamino ; substituted or non-substituted (hydroxyimino)-Ci-C8-alkyl ; substituted or non-substituted (Ci-C8-alkoxyimino)-Ci -C8-alkyl ; substituted or non-substituted (C2-C8-alkenyloxyimino)-Ci-C8-alkyl ; substituted or non-substituted (C2-C8-alkynyloxyimino)-Ci-C8-alkyl ; substituted or non-substituted (benzyloxyimino)-Ci-C8-alkyl ; carboxy ; carbamoyl ; N-hydroxycarbamoyl ; carbamate ; substituted or non-substituted CrC8- alkyl ; CrC8-halogenoalkyl having 1 to 9 halogen atoms ; substituted or non-substituted C2-C8- alkenyl ; C2-C8-halogenoalkenyl having 1 to 9 halogen atoms ; substituted or non-substituted C2- C8-alkynyl ; C2-C8-halogenoalkynyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkoxy ; CrC8-halogenoalkoxy having 1 to 9 halogen atoms ; substituted or non-substituted Ci-C8-alkylsulfanyl ; CrC8-halogenoalkylsulfanyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci-C8-alkylsulfinyl ; Ci-C8-halogenoalkylsulfinyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylsulfonyl ; CrC8-halogenoalkylsulfonyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci-C8-alkylamino ; substituted or non-substituted di-CrC8-alkylamino ; substituted or non-substituted C2-C8-alkenyloxy ; C2-C8-halogenoalkenyloxy having 1 to 9 halogen atoms ; substituted or non-substituted C3-C8-alkynyloxy ; C2-C8- halogenoalkynyloxy having 1 to 9 halogen atoms ; substituted or non-substituted C3-C7- cycloalkyl ; C3-C7-halogenocycloalkyl having 1 to 9 halogen atoms ; substituted or non-substituted (C3-C7-cycloalkyl)-Ci -C8-alkyl ; substituted or non-substituted C4-C7-cycloalkenyl ; C4-C7- halogenocycloalkenyl having 1 to 9 halogen atoms ; substituted or non-substituted (C3-C7- cycloalkyl)-C2-C8-alkenyl ; substituted or non-substituted (C3-C7-cycloalkyl)-C2-C8-alkynyl ; substituted or non-substituted tri(Ci -C8)alkylsilyl ; substituted or non-substituted tri(Ci - C8)alkylsilyl-Ci -C8-alkyl ; substituted or non-substituted CrC8-alkylcarbonyl ; CrC8- halogenoalkylcarbonyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci -C8- alkylcarbonyloxy ; Ci -C8-halogenoalkylcarbonyloxy having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylcarbonylamino ; Ci -C8-halogenoalkylcarbonylamino having 1 to 9 halogen atoms ; substituted or non-substituted Ci -C8-alkoxycarbonyl ; CrC8- halogenoalkoxycarbonyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci -C8- alkyloxycarbonyloxy ; CrC8-halogenoalkoxycarbonyloxy having 1 to 9 halogen atoms ; substituted or non-substituted Ci -C8-alkylcarbamoyl ; substituted or non-substituted di-Ci -C8- alkylcarbamoyl ; substituted or non-substituted Ci -C8-alkylaminocarbonyloxy ; substituted or non- substituted di-Ci -C8-alkylaminocarbonyloxy ; substituted or non-substituted N-(Ci -C8- alkyl)hydroxy carbamoyl ; substituted or non-substituted Ci -C8-alkoxycarbamoyl ; substituted or non-substituted N-(Ci -C8-alkyl)-Ci -C8-alkoxycarbamoyl ; aryl that can be substituted by up to 6 groups Q which can be the same or different ; aryl-Ci -C8-alkyl that can be substituted by up to 6 groups Q which can be the same or different ; aryl-C2-C8-alkenyl that can be substituted by up to 6 groups Q which can be the same or different ; aryl-C2-C8-alkynyl that can be substituted by up to 6 groups Q which can be the same or different ; aryloxy that can be substituted by up to 6 groups Q which can be the same or different ; arylsulfanyl that can be substituted by up to 6 groups Q which can be the same or different ; arylamino that can be substituted by up to 6 groups Q which can be the same or different ; aryl-Ci -C8-alkyloxy that can be substituted by up to 6 groups Q which can be the same or different ; aryl-CrC8-alkylsulfanyl that can be substituted by up to 6 groups Q which can be the same or different ; aryl-Ci -C8-alkylamino that can be substituted by up to 6 groups Q which can be the same or different ; pyridinyl which can be substituted by up to 4 groups Q ; or pyridinyloxy which can be substituted by up to 4 groups Q ;
• Y independently represents a halogen atom ; cyano ; hydroxy ; amino ; sulfanyl ; substituted or non-substituted C rC8-alkyl ; CrC8-halogenoalkyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkoxy ; CrC8-halogenoalkoxy having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylsulfanyl ; CrC8-halogenoalkylsulfanyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci -C8-alkylsulfinyl ; Ci -C8-halogenoalkylsulfinyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci -C8-alkylsulfonyl ; CrC8-halogenoalkylsulfonyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci -C8-alkylamino ; substituted or non-substituted di-Ci -C8-alkylamino ; substituted or non-substituted CrC8-alkylcarbonyl ; CrC8- halogenoalkylcarbonyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8- alkoxycarbonyl ; Ci -C8-halogenoalkoxycarbonyl having 1 to 9 halogen atoms ; or aryl that can be substituted by up to 6 groups Q which can be the same or different ;
• Q independently represents a halogen atom, cyano, nitro, substituted or non-substituted Ci -C8- alkyl, CrC8-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different, substituted or non-substituted CrC8-alkoxy, Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different, substituted or non-substituted Ci-C8-alkylsulfanyl, Ci-C8- halogenoalkylsulfanyl comprising up to 9 halogen atoms that can be the same or different, substituted or non-substituted tri(CrC8)alkylsilyl, substituted or non-substituted tri(CrC8)alkylsilyl- Ci-C8-alkyl, substituted or non-substituted (Ci-C8-alkoxyimino)-Ci-C8-alkyl , or substituted or non-substituted (benzyloxyimino)-Ci-C8-alkyl ;
• R independently represents hydrogen atom ; halogen atom ; nitro ; cyano ; hydroxy ; amino ; sulfanyl ; pentafluoro-A6-sulfanyl ; substituted or non-substituted (Ci-C8-alkoxyimino)-Ci-C8-alkyl ; substituted or non-substituted (benzyloxyimino)-Ci-C8-alkyl ; substituted or non-substituted Ci-C8- alkyl ; CrC8-halogenoalkyl having 1 to 9 halogen atoms ; substituted or non-substituted C2-C8- alkenyl ; C2-C8-halogenoalkenyl having 1 to 9 halogen atoms ; substituted or non-substituted C2- C8-alkynyl ; C2-C8-halogenoalkynyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkoxy ; CrC8-halogenoalkoxy having 1 to 9 halogen atoms ; substituted or non-substituted Ci-C8-alkylsulfanyl ; Ci-C8-halogenoalkylsulfanyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylsulfinyl ; CrC8-halogenoalkylsulfinyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkylsulfonyl ; CrC8-halogenoalkylsulfonyl having 1 to 9 halogen atoms ; substituted or non-substituted Ci-C8-alkylamino ; substituted or non-substituted di-Ci-C8-alkylamino ; substituted or non-substituted C2-C8-alkenyloxy ; substituted or non- substituted C3-C8-alkynyloxy ; substituted or non-substituted C3-C7-cycloalkyl ; C3-C7- halogenocycloalkyl having 1 to 9 halogen atoms ; substituted or non-substituted tri(Ci-
C8)alkylsilyl ; substituted or non-substituted Ci-C8-alkylcarbonyl ; CrC8-halogenoalkylcarbonyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8-alkoxycarbonyl ; CrC8- halogenoalkoxycarbonyl having 1 to 9 halogen atoms ; substituted or non-substituted CrC8- alkylcarbamoyl ; substituted or non-substituted di-CrC8-alkylcarbamoyl ; phenoxy ; phenylsulfanyl ; phenylamino ; benzyloxy ; benzylsulfanyl ; or benzylamino ; as well as its salts, N-oxides, metal complexes, metalloid complexes and optically active isomers or geometric isomers thereof.
2. A compound according to claim 1 wherein A is selected in the list consisting of:
- a heterocycle of formula (A1) 
(A1)
wherein :
R1 to R3 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted CrC5-alkoxy or Ci-C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; - a heterocycle of formula (A2)
wherein :
R4 to R6 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; CrC5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted CrC5-alkoxy or Ci -C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; - a heterocycle of formula (A3)
wherein :
R7 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non- substituted CrCs-alkoxy or CrCs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
R8 represents a hydrogen atom or a substituted or non-substituted d-Cs-alkyl ;
- a heterocycle of formula (A4) 
(A4)
wherein :
R9 to R11 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted d-Cs-alkyl ; amino ; substituted or non-substituted d-Cs-alkoxy ; substituted or non- substituted CrCs-alkylsulfanyl ; CrC5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci -C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; - a heterocycle of formula (A5) 
(A5)
wherein :
R12 and R13 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; substituted or non-substituted CrC5-alkoxy ; amino ; Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci-C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
R14 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; substituted or non-substituted Ci-C5-alkoxy ; amino ; Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or Ci-C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A6)
(A6)
wherein :
R15 represents a hydrogen atom ; a halogen atom ; a cyano ; substituted or non-substituted CrC5-alkyl ; substituted or non-substituted Ci-Cs-alkoxy ; Ci-Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R16 and R18 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkoxycarbonyl ; substituted or non-substituted CrC5-alkyl ; Ci-C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R17 represent a hydrogen atom or substituted or non-substituted CrC5-alkyl ;
- a heterocycle of formula (A7)
(A7)
wherein :
R19 represents a hydrogen atom or a CrC5-alkyl
R20 to R22 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; - a heterocycle of formula (A8) 
(A8)
wherein :
R23 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R24 represents a hydrogen atom or substituted or non-substituted CrC5-alkyl or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different;
- a heterocycle of formula (A9) 
(A9)
wherein :
R25 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R26 represents a hydrogen atom ; substituted or non-substituted CrC5-alkyl or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A10) 
(A10)
wherein :
R27 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R28 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci -C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non- substituted Ci -Cs-alkylamino or substituted or non-substituted di(Ci -C5-alkyl)amino ;
- a heterocycle of formula (A11) 
wherein :
R29 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -Cs-alkyl ; substituted or non-substituted CrC5-alkoxy ; Ci -C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R30 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci -C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non- substituted Ci -C5-alkylamino or substituted or non-substituted di(Ci -C5-alkyl)amino ;
- a heterocycle of formula (A12)
(A12)
wherein :
R31 represents a hydrogen atom or a substituted or non-substituted Ci -C5-alkyl
R32 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci -Cs-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R33 represents a hydrogen atom ; a halogen atom ; a nitro ; substituted or non-substituted Ci -Cs-alkyl ; substituted or non-substituted CrC5-alkoxy ; Ci -C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A13)
(A13)
wherein :
R34 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; substituted or non-substituted Cs-Cs-cycloalkyl ; Ci -Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted CrC5-alkoxy ; substituted or non-substituted C2-C5- alkynyloxy or Ci -C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; R35 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; a cyano ; substituted or non-substituted C rC5-alkoxy ; substituted or non-substituted CrC5-alkylsulfanyl ; C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; Ci -Cs-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non- substituted Ci -C5-alkylamino or substituted or non-substituted di(Ci -C5-alkyl)amino; R36 represents a hydrogen atom or substituted or non-substituted CrC5-alkyl ;
-a heterocycle of formula (A14)
(A14)
wherein :
R37 and R38 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted CrC5-alkoxy or a substituted or non-substituted CrC5- alkylsulfanyl ;
R39 represents a hydrogen atom or substituted or non-substituted CrC5-alkyl ;
- a heterocycle of formula (A15) 
(A15)
wherein :
R40 and R41 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-C5-alkyl or Ci-C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A16) 
(A16)
wherein :
R42 and R43 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; Ci-Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or amino ;
-a heterocycle of formula (A17) 
(A17) wherein :
R44 and R45 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
- a heterocycle of formula (A18) 
(A18)
wherein :
R47 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R46 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different or substituted or non- substituted Ci -C5-alkylsulfanyl ;
- a heterocycle of formula (A19) 
(A19)
wherein :
R49 and R48 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; substituted or non-substituted CrC5-alkoxy ; CrC5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or CrCs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; - a heterocycle of formula (A20)
(A20)
wherein :
R50 and R51 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; substituted or non-substituted CrC5-alkoxy ; CrC5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different or Ci -Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; -a heterocycle of formula (A21) 
(A21 )
wherein :
R52 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
-a heterocycle of formula (A22) 
(A22)
wherein :
R53 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or C1 -C5- halogenoalkyl comprising up to 9 halogen atoms that can be the same or different.
-a heterocycle of formula (A23)
(A23)
wherein :
R54 and R56 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl or Ci -C5-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R55 represents a hydrogen atom or substituted or non-substituted CrC5-alkyl ; -a heterocycle of formula (A24)
(A24)
wherein : R57 and R59 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or CrCs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R58 represents a hydrogen atom or substituted or non-substituted CrC5-alkyl ;
-a heterocycle of formula (A25)
(A25)
wherein :
R60 and R61 that can be the same or different represent a hydrogen atom ; a halogen atom ; substituted or non-substituted Ci-Cs-alkyl or CrCs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ;
R62 represents a hydrogen atom or substituted or non-substituted CrC5-alkyl ; -a heterocycle of formula (A26)
(A26)
wherein :
R65 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; substituted or non-substituted C3-C5-cycloalkyl ; C Cs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; substituted or non-substituted d-Cs-alkoxy ; substituted or non-substituted C2-C5- alkynyloxy or Ci-C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; R63 represents a hydrogen atom ; a halogen atom ; substituted or non-substituted CrC5-alkyl ; a cyano ; substituted or non-substituted CrC5-alkoxy ; substituted or non-substituted CrC5-alkylsulfanyl ; C1-C5- halogenoalkyi comprising up to 9 halogen atoms that can be the same or different ; Ci-C5-halogenoalkoxy comprising up to 9 halogen atoms that can be the same or different ; amino ; substituted or non- substituted Ci -Cs-alkylamino or di(Ci-C5-alkyl)amino;
R64 represents a hydrogen atom or substituted or non-substituted CrC5-alkyl.
3. A compound according to claim 2 wherein A is selected in the list consisting of A2 ; A5 ; A6 ; A10 and A13.
4. A compound according to claim 3 wherein A represents A13 wherein R34 represents a substituted or non-substituted CrC5-alkyl, CrCs-halogenoalkyl comprising up to 9 halogen atoms that can be the same or different ; or substituted or non-substituted CrC5-alkoxy ; R35 represents a hydrogen atom or a halogen atom and R36 represents a substituted or non-substituted CrC5-alkyl.
5. A compound according to anyone of claims 1 to 4 wherein T represents O.
6. A compound according to anyone of claims 1 to 5 wherein Z1 represents a substituted or non- substituted cyclopropyl.
7. A compound according to claim 6 wherein Z1 represents a non-substituted cyclopropyl or a 2-CrC5- alkylcyclopropyl.
8. A compound according to anyone of claims 1 to 7 wherein Z2 and Z3 independently represent a hydrogen atom or a methyl.
9. A compound according to anyone of claims 1 to 8 wherein n represents 0, 1 or 2.
10. A compound according to anyone of claims 1 to 9 wherein L represents a direct bond, an oxygen atom, a methylene or a carbonyl group.
11. A compound according to anyone of claims 1 to 10 wherein B represents a substituted or non- substituted oxiranyl ring; a substituted or non-substituted pyrrolyl ring; a substituted or non-substituted pyrazolyl ring; a substituted or non-substituted thienyl ring; a substituted or non-substituted benzothienyl ring; a substituted or non-substituted quinolinyl ring; a substituted or non-substituted isoquinolinyl ring ; a substituted or non-substituted furan ring; or a substituted or non-substituted benzofuran ring.
12. A compound according to claim 1 1 wherein B represents a substituted or non-substituted thienyl ring or a substituted or non-substituted benzothienyl ring.
13. A compound according to anyone of claims 1 to 12 wherein X independently, represents a halogen atom ; substituted or non-substituted CrC8-alkyl ; CrC8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non-substituted -cycloalkyl ; tri(Ci-Ce-alkyl)silyl; substituted or non-substituted CrC8-alkoxy; or substituted or non-substituted CrC8-alkylsulfanyl.
14. A compound according to anyone of claims 1 to 13 wherein Y independently, representsa halogen atom ; substituted or non-substituted CrC8-alkyl ; CrC8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non-substituted Ci-C8-alkoxy ; Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms which can be the same or different.
15. Process for preparing a compound of formula (I)
wherein A, T, Z1 , Z2, Z3, 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, characteriz of formula (IV)
(IV)
wherein A, T, Z1 , Z2, Z3, n, X are as defined above and U2 represents a halogen atom or a triflate group, is reacted with a compound of formula (V)
B
(V)
wherein L and B are as defined above and W1 represents a boron derivative.
16. Compound of formula (I la.)
providing that (Ma.) does not represent :
- N-[2-(2-furyl)benzyl]cyclopropanamine
- N-[2-(2-furyl)-4,5-dimethoxybenzyl]cyclopropanamine
- N-[2-(3-bromo-2-furyl)-4,5-dimethoxybenzyl]cyclopropanamine
- N-[2-(3-bromo-2-furyl)benzyl]cyclopropanamine
- N-[2-(3-furyl)benzyl]cyclopropanamine
- N-[2-(2-thienyl)benzyl]cyclopropanamine
- N-[4,5-dimethoxy-2-(2-thienyl)benzyl]cyclopropanamine,
as well as salts thereof.
17. A compound of formula (I la) according to claim 16 selected in the list consisting of:
- N-[5-chloro-2-(2-furyl)benzyl]cyclopropanamine - N-[5-chloro-2-(2-thienyl)benzyl]cyclopropanamine
- N-[2-(3-thienyl)benzyl]cyclopropanamine
- N-{1 -[2-(3-thienyl)phenyl]ethyl}cyclopropanamine
- N-[5-chloro-2-(3-thienyl)benzyl]cyclopropanamine
- N-[2-(5-chloro-2-thienyl)benzyl]cyclopropanamine
- N-[5-chloro-2-(5-chloro-2-thienyl)benzyl]cyclopropanamine.
18. Compound of formula (l ib)
(lib) wherein Z2, Z3, n and X are as defined in anyone of claims 1 to 14, and L is a direct bond and B1 is a substituted or non-substituted oxiranyl ring, a substituted or non-substituted thienyl ring, a substituted or non-substituted benzothienyl ring, a substituted or non-substituted furan ring, or a substituted or non- substituted benzofuran ring,
providing that (lib) does not represent :
- N- -[3- (2-furyl)benzyl]cyclopropanamine
- N- -[5- (2-furyl)-2-methoxybenzyl]cyclopropanamine
- N- -[4- ■fluoro-3-(2-furyl)benzyl]cyclopropanamine
- N- -[2- ■fluoro-5-(2-furyl)benzyl]cyclopropanamine
- N- -[2- ■fluoro-5-(3-furyl)benzyl]cyclopropanamine
- N- -[3- (3-bromo-2-furyl)-4-fluorobenzyl]cyclopropan amine
- N- ■[3- (3-bromo-2-furyl)benzyl]cyclopropanamine
- N- ■[5- (3-bromo-2-furyl)-2-fluorobenzyl]cyclopropan amine
- N- ■[5- (3-bromo-2-furyl)-2-methoxybenzyl]cyclopropanamine
- N- -[3- (3-furyl)benzyl]cyclopropanamine
- N- ■[3- (2-thienyl)benzyl]cyclopropanamine
- N- ■[4- ■fluoro-3-(2-thienyl)benzyl]cyclopropanamine
- N- ■[2- ■fluoro-5-(2-thienyl)benzyl]cyclopropanamine
- N- ■[2- ■methoxy-5-(2-thienyl)benzyl]cyclopropanamine
- 5-{5-[(cyclopropylamino)methyl]-2-fluorophenyl}thiophene-2-carbonitrile.
as well as salts thereof.
19. A compound of formula (l ib) according to claim 18 selected in the list consisting of:
- N-[2-chloro-5-(2-furyl)benzyl]cyclopropanamine
- N-[2-chloro-5-(2-thienyl)benzyl]cyclopropanamine
- N-[2-chloro-5-(3-thienyl)benzyl]cyclopropanamine
- N-[2-chloro-5-(5-chloro-2-thienyl)benzyl]cyclopropanamine.
20. Compound of formula (Xa)
A represents A13 ,
Xa1 represents a halogen atom ; substituted or non-substituted Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non-substituted C3- C7-cycloalkyl ; tri(CrC8-alkyl)silyl; substituted or non-substituted CrC8-alkoxy; or substituted or non- substituted Ci-C8-alkylsulfanyl,
Xa2 represents hydrogen, a halogen atom ; substituted or non-substituted CrC8-alkyl ; Ci-C8- halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non- substituted C3-C7-cycloalkyl ; tri(CrC8-alkyl)silyl; substituted or non-substituted CrC8-alkoxy; or substituted or non-substituted CrC8-alkylsulfanyl, and
U2 represents a halogen atom or a triflate group,
providing that (Xa) does not represent :
- N-(2,5-dichlorobenzyl)-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide
- N-[1 -(2,5-dichlorophenyl)ethyl]-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide - N-[2-(2,5-dichlorophenyl)propan-2-yl]-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide
- N-[1 -(2,5-dichlorophenyl)cyclopropyl]-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide
- 5-chloro-N-[1 -(2,5-dichlorophenyl)ethyl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide
- 5-chloro-N-[2-(2,5-dichlorophenyl)propan-2-yl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide
- 5-chloro-N-[1 -(2,5-dichlorophenyl)cyclopropyl]-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide - 5-chloro-N-(2,5-dichlorobenzyl)-3-(difluoromethyl)-1 -methyl-1 H-pyrazole-4-carboxamide
- N-(5-bromo-2-fluorobenzyl)-1 ,3,5-trimethyl-1 H-pyrazole-4-carboxamide
- N-(5-bromo-2-fluorobenzyl)-3,5-dimethyl-1 H-pyrazole-4-carboxamide
- 1 -methyl-N-[1 -(2,4,5-trichlorophenyl)ethyl]-3-(trifluoromethyl)-1 H-pyrazole-4-carboxamide
- 3-(difluoromethyl)-1 -methyl-N-[1 -(2,4,5-trichlorophenyl)ethyl]-1 H-pyrazole-4-carboxamide
- N-(5-chloro-2-fluorobenzyl)-1 -methyl-5-propoxy-3-(trifluoromethyl)-1 H-pyrazole-4-carboxamide
- N-(2,5-dichlorobenzyl)-1 -methyl-5-propoxy-3-(trifluoromethyl)-1 H-pyrazole-4-carboxamide,
as well as salts thereof.
21. A compound according to claim 20 selected in the list consisting of - N-(5-chloro-2-ethylbenzyl)-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide
- N-(5-chloro-2-isopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide
- N-[5-chloro-2-(trifluoromethyl)benzyl]-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4-carboxamide - N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-3-(difluoromethyl)-5-fluoro-1 -methyl-1 H-pyrazole-4- carboxamide.
22. A fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) according to claims 1 to 14 and an agriculturally acceptable support, carrier or filler.
23. A method for controlling phytopathogenic fungi of crops, characterized in that an agronomically effective and substantially non-phytotoxic quantity of a compound according to any one of claims 1 to 14 or a composition according to claim 21 is applied to the soil where plants grow or are capable of growing, to the leaves and/or the fruit of plants or to the seeds of plants.
24. Use of compounds of the formula (I) according to any one of claims 1 to 14 for the control of phytopathogenic harmful fungi.
25. Process for producing compositions for controlling phytopathogenic harmful fungi, characterized in that derivatives of the formula (I) according to any one of claims 1 to 14 are mixed with extenders and/or surfactants.
26. Use of compounds of the formula (I) according to any one of claims 1 to 14 for treatment of plants, seeds, transgenic plants or transgenic seeds..
Priority Applications (12)
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| CA2865599A CA2865599C (en) | 2012-04-20 | 2013-04-18 | N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives |
| KR1020147032119A KR102062517B1 (en) | 2012-04-20 | 2013-04-18 | N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives |
| BR112014025976-3A BR112014025976B1 (en) | 2012-04-20 | 2013-04-18 | compound, process for preparing a compound, fungicidal composition, method for controlling fungi, use of compounds and process for producing compositions for controlling fungi |
| UAA201412399A UA115663C2 (en) | 2012-04-20 | 2013-04-18 | N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives |
| AU2013251109A AU2013251109B2 (en) | 2012-04-20 | 2013-04-18 | N-cycloalkyl-N-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives |
| MX2014012449A MX2014012449A (en) | 2012-04-20 | 2013-04-18 | N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives. |
| JP2015506237A JP6109295B2 (en) | 2012-04-20 | 2013-04-18 | N-cycloalkyl-N-[(heterocyclylphenyl) methylene]-(thio) carboxamide derivatives |
| CN201380020863.9A CN104428294B (en) | 2012-04-20 | 2013-04-18 | N cycloalkyl N [(heterocyclyl phenyl) methylene] (thio) carboxamide derivative |
| EP13719444.5A EP2838893B1 (en) | 2012-04-20 | 2013-04-18 | N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives |
| US14/395,038 US10125126B2 (en) | 2012-04-20 | 2013-04-18 | N-cycloalkyl-N-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives |
| IL23516614A IL235166B (en) | 2012-04-20 | 2014-10-19 | N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives |
| US16/141,397 US20190092765A1 (en) | 2012-04-20 | 2018-09-25 | N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives |
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| EP12356010.4 | 2012-04-20 | ||
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| US201261675001P | 2012-07-24 | 2012-07-24 | |
| US61/675,001 | 2012-07-24 |
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| US16/141,397 Division US20190092765A1 (en) | 2012-04-20 | 2018-09-25 | N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives |
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| US (2) | US10125126B2 (en) |
| EP (1) | EP2838893B1 (en) |
| JP (1) | JP6109295B2 (en) |
| KR (1) | KR102062517B1 (en) |
| CN (1) | CN104428294B (en) |
| AR (1) | AR090763A1 (en) |
| AU (1) | AU2013251109B2 (en) |
| BR (1) | BR112014025976B1 (en) |
| CA (1) | CA2865599C (en) |
| CL (1) | CL2014002779A1 (en) |
| CO (1) | CO7131397A2 (en) |
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Cited By (4)
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| WO2014172191A1 (en) * | 2013-04-15 | 2014-10-23 | E. I. Du Pont De Nemours And Company | Fungicidal carboxamides |
| WO2015082586A1 (en) | 2013-12-05 | 2015-06-11 | Bayer Cropscience Ag | N-cycloalkyl-n-{[2-(1-substitutedcycloalkyl)phenyl]methylene}-(thio)carboxamide derivatives |
| WO2017093348A1 (en) * | 2015-12-02 | 2017-06-08 | Syngenta Participations Ag | Microbiocidal oxadiazole derivatives |
| US9949955B2 (en) | 2012-06-15 | 2018-04-24 | Glenmark Pharmaceuticals S.A. | Triazolone compounds as mPGES-1 inhibitors |
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| CN107531676A (en) * | 2015-04-13 | 2018-01-02 | 拜耳作物科学股份公司 | N cycloalkyl N (double heterocyclic radical ethylidene) (thio) carboxamide derivative |
| US11459340B2 (en) | 2018-09-18 | 2022-10-04 | Nikang Therapeutics, Inc. | Tri-substituted heteroaryl derivatives as Src homology-2 phosphatase inhibitors |
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Also Published As
| Publication number | Publication date |
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| CA2865599A1 (en) | 2013-10-24 |
| US20190092765A1 (en) | 2019-03-28 |
| UA115663C2 (en) | 2017-12-11 |
| CO7131397A2 (en) | 2014-12-01 |
| MX2014012449A (en) | 2015-01-19 |
| CN104428294B (en) | 2017-07-14 |
| BR112014025976B1 (en) | 2019-10-29 |
| US20150210678A1 (en) | 2015-07-30 |
| AU2013251109A1 (en) | 2014-12-04 |
| KR20150003820A (en) | 2015-01-09 |
| CA2865599C (en) | 2020-10-27 |
| EP2838893B1 (en) | 2019-03-13 |
| AR090763A1 (en) | 2014-12-03 |
| CN104428294A (en) | 2015-03-18 |
| BR112014025976A2 (en) | 2017-07-11 |
| US10125126B2 (en) | 2018-11-13 |
| JP2015520127A (en) | 2015-07-16 |
| JP6109295B2 (en) | 2017-04-05 |
| KR102062517B1 (en) | 2020-01-06 |
| AU2013251109B2 (en) | 2017-08-24 |
| CL2014002779A1 (en) | 2015-01-16 |
| EP2838893A1 (en) | 2015-02-25 |
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