WO2004074280A1 - Pyridine derivatives as fungicidal compounds - Google Patents
Pyridine derivatives as fungicidal compounds Download PDFInfo
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- WO2004074280A1 WO2004074280A1 PCT/EP2004/002381 EP2004002381W WO2004074280A1 WO 2004074280 A1 WO2004074280 A1 WO 2004074280A1 EP 2004002381 W EP2004002381 W EP 2004002381W WO 2004074280 A1 WO2004074280 A1 WO 2004074280A1
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- alkyl
- halogen atoms
- halogenoalkyl
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- 0 C*IN/C1=C(\*(C)C)/*(*)C*C/*=C1\*(C)C(C)C Chemical compound C*IN/C1=C(\*(C)C)/*(*)C*C/*=C1\*(C)C(C)C 0.000 description 8
- YPZLKLYZFOSSPW-UHFFFAOYSA-N O=C(c1c(C(F)(F)F)nccc1)NCCc(ncc(C(F)(F)F)c1)c1Cl Chemical compound O=C(c1c(C(F)(F)F)nccc1)NCCc(ncc(C(F)(F)F)c1)c1Cl YPZLKLYZFOSSPW-UHFFFAOYSA-N 0.000 description 1
- BFROETNLEIAWNO-UHFFFAOYSA-N OC(c1cccnc1C(F)(F)F)=O Chemical compound OC(c1cccnc1C(F)(F)F)=O BFROETNLEIAWNO-UHFFFAOYSA-N 0.000 description 1
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
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- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C07D405/00—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
- 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
- C07D405/12—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 linked by a chain containing hetero atoms as chain links
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- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D411/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
Definitions
- the present invention relates to novel N-[2-(2-pyridinyl)ethyl]carboxamides " derivatives, their process of 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.
- the present invention relates to N-[2-(2- pyridinyl)ethyl]carboxamide derivative of general formula (I):
- - X may be an oxygen atom or a sulphur atom
- - Y may be the same or different and may be a halogen atom, a nitro group, a cyano group, a hydroxy, a carboxyl group, a Cj-Cs-alkyl, a d-C ⁇ -halogenoalkyl having 1 to 5 halogen atoms, a CrCg-alkylamino, a di-CrCg-alkylamino, a Cj-Cg-alkoxy, a Cj-C 6 -halogenoalkoxy having 1 to 5 halogen atoms, a Cj-Cg-alkylthio, a -C ⁇ - halogenoalkylthio having 1 to 5 halogen atoms, a C 2 -Cg-alkenyloxy, a C 2 -Cg- halogenoalkenyloxy having 1 to 5 halogen atoms,
- R 1 may be a hydrogen atom, a cyano group, a nitro group, a forrnyl group, a -C ⁇ - alkyl, a Ct-C ⁇ -alkylcarbamoyl, a C 2 -C -alkenyl, a C 2 -C 6 -alkynyl, a - - halogenoalkyl having 1 to 7 halogen atoms, a Ci- -alkoxy-d-C ⁇ -alkyl, a C ⁇ -C 6 - cyanalkyl, a Q-Ce-aminoalkyl, a C 3 -C 6 -cycloalkyl, a Cr -alkylcarbonyl, a Q-C 6 - halogenalkylcarbonyl having 1 to 5 halogen atoms, a Ct-Ce-alkoxy-Q-Crr alkylcarbonyl, a Cj-C
- - n maybe 1, 2, 3 or 4;
- Het represents an optionally substituted 5-, 6- or 7-membered non-fused heterocycle with one, two or three heteroatoms which may be the same or different; Het being linked by a carbon atom.
- - halogen means fluorine, bromine, chlorine or iodine
- - heteroatom means N, O or S.
- X represents an oxygen atom or a sulphur atom.
- X represents an oxygen atom.
- the 2-pyridyl may be substituted in every position by (Y) n , in which Y and n are as defined above.
- the present invention relates to N-[2-(2-pyridinyl)ethyl]carboxamide derivative of general formula (I) in which the different characteristics may be chosen alone or in combination as being :
- n is 1 or 2. More preferably n is 2.
- At least one of the Y substituent is a halogen atom, a CpCg-alkyl, a Ci-C ⁇ -halogenoalkyl having 1 to 5 halogen atoms or a C ⁇ -C 6 -alkoxy-C ⁇ -C 6 - alkylcarbonyl. More preferably, at least one of the Y substituent is a - - halogenoalkyl having 1 to 5 halogen atoms. Even more preferably, at least one of the Y substituent is -CF 3 .
- Het of the compound of general formula (I) may be a five membered ring non-fused heterocycle.
- Specific examples of compounds of the present invention where Het is a five membered heterocycle include : * Het represents a heterocycle of the general formula (II)
- R and R may be the same or different and may be a hydrogen atom, a halogen atom, an amino group, a nitro group, a Cj-C 4 -alkyl or a C 1 -C 4 -halogenoalkyl having 1 to 5 halogen atoms;
- R 4 may be a hydrogen atom, a halogen atom, a nitro group, a C 1 -C 4 -alkyl or a C ⁇ -C 4 -halogenoalkyl having 1 to 5 halogen atoms.
- - R s may be a hydrogen atom, a halogen atom , a C ⁇ -C 4 -alkyl or a Cj-C - halogenoalkyl having 1 to 5 halogen atoms
- - R 6 and R7 6 may be the same or different and may be a hydrogen atom, a halogen atom, an amino group, a C ⁇ -C 4 -alkyl or a C ⁇ -C 4 -halogenoalkyl having 1 to 5 halogen atoms.
- - R 8 may be a halogen atom, a C ⁇ -C 4 -alkyl or a C ⁇ -C 4 -halogenoalkyl having 1 to 5 halogen atoms
- - R 9 may be a hydrogen atom, a C 1 -C -alkyl or a Q-Gt-halogenoalkyl having 1 to 5 halogen atoms.
- R 10 and R 11 may be the same or different and may be a hydrogen atom, a halogen atom, a C ⁇ -C 4 -alkyl, a Q- -halogenoalkyl having 1 to 5 halogen atoms, a C 1 -C -alkylthio, a C)-C 4 -alkylsulphonyl, a phenyl optionally substituted by a halogen atom or a Q-Q-alkyl or a pyridyl otpionally substituted by a halogen atom or a Q- C 4 -alkyl; and
- R 12 may be a hydrogen atom, a halogen atom, a cyano group, a Cj-C 4 -alkyl, a C ! -C 4 -halogenoalkyl having 1 to 5 halogen atoms or a Q-Q-halogenoalkoxy having 1 to 5 halogen atoms.
- R 13 and R 14 may be the same or different and may be a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl, a Q ⁇ -alkyloxy or a C 1 -C 4 -halogenoalkyl having 1 to 5 halogen atoms;
- R 15 may be a hydrogen atom, a halogen atom, a C ⁇ -C 4 -alkyl or a Q-Gt- halogenoalkyl having 1 to 5 halogen atoms.
- - R 16 may be a hydrogen atom, a halogen atom, a cyano group, a C 1 -C 4 -alkyl or a C ⁇ -C -halogenoalkyl having 1 to 5 halogen atoms;
- - R 17 and R 19 may be the same or different and may be a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl or a d-d-halogenoalkyl having 1 to 5 halogen atoms;
- R 18 may be a hydrogen atom, a cyano group, a Cj-C 4 -alkyl, a d-C 4 - halogenoalkyl having 1 to 5 halogen atoms, a C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, a hydroxy- C 1 -C 4 -alkyl, a CrC 4 -alkylsulphonyl, a di(C ⁇ -C -alkyl)aminosulphonyl, a d-C 6 - alkylcarbonyl, a phenylsulphonyl optionally substituted by a halogen atom or a Q- C -alkyl, or a benzoyl optionally substituted by a halogen atom or a Cj-C -alkyl.
- - R >20 may be a hydrogen atom, a cyano group, a Q-Q-alkyl, a C 1 -C 4 - halogenoalkyl having 1 to 5 halogen atoms, a C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, a hydroxy- C ⁇ -C 4 -alkyl, a C ⁇ -C 4 -alkylsulphonyl, a di(C 1 -C 4 -alkyl)aminosulphonyl, a C ⁇ -C 6 - alkylcarbonyl, a phenylsulphonyl optionally substituted by a halogen atom or a Q- C4-alkyl, or a benzoyl optionally substituted by a halogen atom or a Q ⁇ - lkyl; and
- R - R , R and R may be the same or different and may be a hydrogen atom, a halogen atom, a cyano group, a d-Q-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms or a d-d-alkylcarbonyl.
- - R 24 may be a hydrogen atom or a C ⁇ -C 4 -alkyl; and - R 25 may be a halogen atom, a d-C4-alkyl or a d-C 4 -halogenoalkyl having 1 to 5 halogen atoms.
- - R 26 may be a hydrogen atom or a C ⁇ -C 4 -alkyl
- R 27 may be a halogen atom, a d-d-alkyl, a d-C4-halogenoalkyl having 1 to 5 halogen atoms or a phenyl optionally substituted by a halogen atom or a C 1 -C 4 - alkyl.
- - R 28 may be a hydrogen atom, a halogen atom, an amino group, a cyano group, a C 1 -C 4 -alkylamino 3 a di-(C ⁇ -C 4 -alkyl)amino 3 a C 1 -C 4 -alkyl, a d-Gj- halogenoalkyl having 1 to 5 halogen atoms or a phenyl optionally substituted by a halogen atom or a d-C ⁇ -alkyl; and - R 29 may be a halogen atom, a C 1 -C 4 -alkyl or a C ⁇ -C 4 -halogenoalkyl having
- - R 30 may be a hydrogen atom, a halogen atom, an amino group, a cyano group, a C ⁇ -C 4 -alkylamino, a di-(C ⁇ -C 4 -alkyl)amino, a C ⁇ -C4-alkyl or a C1-C 4 - halogenoalkyl having 1 to 5 halogen atoms; and -R 31 may be a halogen atom, a C ⁇ -C4-alkyl or a C 1 -C -halogenoalkyl having 1 to 5 halogen atoms.
- - R may be a hydrogen atom, a halogen atom, a cyano group, a nitro group, a d-C 4 -alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, a C 3 -C 6 - cycloalkyl, a C]-C 4 -alkoxy, a C ⁇ -C 4 -halogenoalkoxy having 1 to 5 halogen atoms, a d-d-alkylthio, a C 1 -C 4 -halogenoalkylthio having 1 to 5 halogen atoms, an aminocarbonyl group or an aminocarbonyl-C 1 -C 4 -alkyl; - R may be a hydrogen atom, a halogen atom, a cyano group, a nitro group, a d-d-alkyl, a d-Q-alkoxy or a d-C
- R 34 may be a hydrogen atom, a phenyl, a C 1 -C 4 -alkyl, a C 1 -C 4 - halogenoalkyl having 1 to 5 halogen atoms, a hydroxy-d-C -alkyl, a d-Cg-alkenyl, a C 3 -C 6 -cycloalkyl, a C ⁇ -C 4 -alkylthio-C ⁇ -C 4 -alkyl, a C ⁇ -C 4 -halogenoalkylthio-C 1 -C 4 - alkyl having 1 to 5 halogen atoms, a C ⁇ -C 4 -alkoxy-C 1 -C 4 -alkyl or a d-C 4 - halogenoalkoxy-d-C 4 -alkyl having 1 to 5 halogen atoms.
- - R may be a hydrogen atom, a halogen atom, a cyano group, a nitro group, a d-C 4 -alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a C 3 -C 6 - cycloalkyl, a C ⁇ -C 4 -alkoxy, a d-Q-halogenoalkoxy having 1 to 5 halogen atoms, a d ⁇ -alkylthio, a C ⁇ -C4-halogenoalkylthio having 1 to 5 halogen atoms, an aminocarbonyl or an aminocarbonyl-d-d-alkyl; - R 36 may be a hydrogen atom, a halogen atom, a cyano group, a d-C -alkyl, a C ⁇ -C4-alkoxy, a d-d-halogenoalkoxy having 1 to 5 halogen
- R 37 may be a hydrogen atom, a C ⁇ -C 4 -alkyl, a C ⁇ -C 4 -halogenoalkyl having 1 to 5 halogen atoms, a hydroxy-C ⁇ -C 4 -alkyl, a C 2 -C 6 -alkenyl, a C 3 -C 6 -cycloalkyl, a C ⁇ -C4-alkylthio-C ⁇ -C4-alkyl, a C ⁇ -C4-halogenoalkylthio-C 1 -C 4 -alkyl having 1 to 5 halogen atoms, a C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, a C ⁇ -C 4 -halogenoalkoxy-C 1 -C 4 -alkyl having 1 to 5 halogen atoms or a phenyl optionally substituted by a halogen atom, a d-C -alkyl
- -R may be a hydrogen atom, a halogen atom, a cyano group, a nitro group, a d-C -alkyl, a d-C 4 -halogenoalkyl having 1 to 5 halogen atoms, a C 3 -C 6 -cycloalkyl, a C ⁇ -C 4 -alkoxy, a C ⁇ -C -halogenoalkoxy having 1 to 5 halogen atoms, a C1-C 4 - alkylthio, a Ci-Q-halogenoalkylthio having 1 to 5 halogen atoms, an aminocarbonyl, or an ammocarbonyl-C ⁇ -C 4 -alkyl;
- - R may be a hydrogen atom, a halogen atom, a cyano group, a Cj-C 4 -alkyl, a d-C4-alkoxy, a Ci-d-alkylthio or a Ci-d-halogenoalky having 1 to 5 halogen atoms;
- R 40 may be a hydrogen atom, a phenyl, a benzyl, a Ci-d-alkyl, a d-d- halogenoalkyl having 1 to 5 halogen atoms, a hydroxy-d-Q-alkyl, a C 2 -C 6 -alkenyl, a C 3 -C 6 -cycloalkyl, a d-d-alkylthio-Ci-d-alkyl, a C ⁇ -C 4 -halogenoalkylthio-C ⁇ -C 4 - alkyl having 1 to 5 halogen atoms, a C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, a d-C - halogenoalkoxy-d-d-alkyl having 1 to 5 halogen atoms.
- R 41 and R 42 may be the same or different and may be a hydrogen atom, a halogen atom, a Ci-d-alkyl or a Cj-C -halogenoalkyl having 1 to 5 halogen atoms.
- R 43 and R 4 may be the same or different and may be a hydrogen atom, a halogen atom, a d-C -alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a phenyl optionally substituted by a halogen atom or a Ci-d-alkyl, or a heterocyclyl optionally substituted by a halogen atom or a d-d-alkyl.
- R 45 and w may be the same or different and may be a hydrogen atom, a halogen atom, a d-d-alkyl or a Ci-d-halogenoalkyl having 1 to
- R 47 may be a halogen atom, a Ci-d-alkyl or a C 1 -C 4 - halogenoalkyl having 1 to 5 halogen atoms.
- - R 48 may be a halogen atom, a Ci-d-aikyl or a C ⁇ -C 4 -halogenoalkyl having 1 to 5 halogen atoms
- - R 49 may be a hydrogen atom, a d-d-alkyl, a C ⁇ -C 4 -halogenoalkyl having 1 to 5 halogen atoms, or a phenyl optionally substituted by a halogen atom or a C 1 -C - alkyl.
- R 50 may be a halogen atom, a Cj-C -alkyl or a C 1 -C 4 - halogenoalkyl having 1 to 5 halogen atoms.
- Het of the compound of general formula (I) may be a six membered ring non-fused heterocycle.
- Specific examples of compounds of the present invention where Het is a six membered heterocycle include :
- - R 51 may be a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a d-Q-alkyl, a Ci-Q-halogenoalkyl having 1 to 5 halogen atoms, a C 1 -C 4 - alkoxy, a Ci-d-alkylthio, a d-d-halogenoalkylfhio having 1 to 5 halogen atoms or a d-d-halogenoalkoxy having 1 to 5 halogen atoms; n
- R 52 , R 53 and R 54 which may be the same or different, may be a hydrogen atom, a halogen atom, a cyano group, a d-d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a d-d-alkoxy, a d-d-alkylthio, a d-d-halogenoalkoxy having 1 to 5 halogen atoms, a d-d-alkylsulphinyl or a d-d-alkylsulphonyl.
- - R may be a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a d-d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a C ⁇ -C 4 -alkoxy, a d-d-alkylthio, a d-d-alkenylfhio a d-d- halogenoalkylthio having 1 to 5 halogen atoms, a d-d-halogenoalkoxy having 1 to 5 halogen atoms, a phenyloxy optionally substituted by a halogen atom or a d-d- alkyl, or a phenylthio optionally substituted by a halogen atom or a d-d-alkyl;
- R 56 , R 57 and R 58 which may the same or different, may be a hydrogen atom, a halogen atom, a cyano group, a Ci-d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a d-d-alkoxy, a Ci-d-alkylthio, a Ci-d-halogenoalkoxy having 1 to 5 halogen atoms, a d-d-alkylsulphinyl, a d-d-alkylsulphonyl or a N- morpholine optionally substituted by a halogen atom or a d-d-alkyl, or a thienyl optionally substituted by a halogen atom or a d-d-alkyl.
- R 59 , R 60 , R 61 and R 62 which may be the same or different, may be a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a d-d- alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, a Ci-d-alkoxy, a C 1 -C4- alkylthio, a d-d-halogenoalkylthio having 1 to 5 halogen atoms, a d-d- halogenoalkoxy having 1 to 5 halogen atoms, a d-d-alkylsulphinyl or a C 1 -C 4 - alkylsulphonyl.
- - R 63 may be a hydrogen atom, a halogen atom, a d-d-alkyl or a d-d- halogenoalkyl having 1 to 5 halogen atoms;
- R 64 may be a hydrogen atom, a d-d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a C[-C 6 -alkoxycarbonyl, a benzyl optionally substituted by 1 to 3 halogen atoms, a benzyloxycarbonyl optionally substituted by 1 to 3 halogen atoms or a heterocyclyl.
- - R may be a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a Ci-d-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, a C 1 -C 4 - alkoxy, a d-d-alkylthio, a d-d-halogenoalkylthio having 1 to 5 halogen atoms or a d-d-halogenoalkoxy having 1 to 5 halogen atoms;
- R 66 may be a hydrogen atom, a d-d-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms or a benzyl.
- - X 1 may be a sulphur atom, -SO-, -SO 2 - or -CH 2 -; - R 67 may be a Ci-d-alkyl or a d-d-halogenoalkyl having 1 to 5 halogen atoms; and
- R 68 and R 69 may be the same or different and may be a hydrogen atom or a d-d-alkyl.
- R , 70 may be a Ci-d-alkyl or a d-d-halogenoalkyl having 1 to 5 halogen atoms;
- R may be a C ⁇ -C 4 -alkyl or a C ⁇ -C 4 -halogenoalkyl having 1 to 5 halogen atoms.
- R » 72 may be a hydrogen atom, a halogen atom, a Ci-d-alkyl or a Ci-d-halogenoalkyl having 1 to 5 halogen atoms.
- the present invention also relates to a process for the preparation of the compound of general formula (I).
- a process for the preparation of compound of general formula (I) as defined above which comprises reacting a carboxylic acid derivative of the general formula (A) ⁇
- - G may be a halogen atom, a hydroxy group or a C ⁇ -C 6 -alkoxy; with a 2-pyridine derivative of general formula (B)
- Y, R 1 and n are as defined above; in the presence of a catalyst if G is a hydroxy or a d-C 6 -alkoxy group, or in the presence of an acid binder if G is a halogen atom.
- the process for the preparation of compound of general formula (I) is carried out in the presence of a catalyst if G is a hydroxy or a d-C 6 -alkoxy group.
- Suitable catalyst includes the coupling reagents dicyclohexylcarbodiimide, N,N'-carbonyldimidazole, bromotripyrrolidinophosphonium hexafluorophosphate and trimethylaluminium.
- the process for the preparation of compound of general formula (I) is carried out in the presence of an acid binder if G is a halogen atom.
- Suitable acid binder includes carbonates, aqueous alkali or tertiary amines.
- the present invention also relates to another process for the preparation of the compound of general formula (I).
- a second process for the preparation of compound of general formula (I) as defined above which comprises reacting a carboxylic acid anhydride derivative of general formula (C)
- - Het is as defined above; - W may be defined as Het or a d-d-alkyl; with a 2-pyridine derivative of the formula (D)
- R 1 and n are each as defined above; in the presence of a reducing agent.
- the second process for the preparation of compound of general formula (I) is carried out in the presence of a reducing agent.
- a reducing agent includes H 2 and NaBH*.
- 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 the skilled worker will be able to adapt this method according to the specifics of each of the compounds, which it is desired to synthesise. For example, the above mentioned processes may be carried out in the presence of a diluent if appropriate. If appropriate, the second process for the preparation of compound of general formula (I) may also be carried out in the presence of a catalyst such as NiCl 2 -H 2 O or CoCl 3 -H 2 O.
- a catalyst such as NiCl 2 -H 2 O or CoCl 3 -H 2 O.
- - Z may be the same or different and may be a halogen atom, a nitro group, a cyano group, a hydroxy, a carboxyl group, a d-Cg-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, a C ⁇ -C 6 -halogenoalkoxy having 1 to 5 halogen atoms, a Cj-Cg- alkylthio, a Cj-d-halogenoalkylthio having 1 to 5 halogen atoms, a C 2 -Cg- alkenyloxy, a C 2 -Cg-halogenoalkenyloxy having 1 to 5 halogen atoms, a C 3 -Cg- alkinyloxy, a C 3 -Cg-halogenoalkinyloxy having 1 to 5 halogen atoms, a C 3 -Cg- cycloalkyl, a C
- - Z 1 may be a halogen atom or a d-Cg-alkyl
- the present invention also relates to a fungicidal composition
- a fungicidal composition comprising an effective amount of an active material of general formula (I).
- a fungicidal composition comprising, as an active ingredient, an effective amount of a compound of general formula (I) as defined above and an agriculturally acceptable carrier or filler.
- the term "support” denotes a natural or synthetic, organic or inorganic material with which the active material is combined 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 may be a solid or a liquid.
- 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 may also be used.
- composition may also comprise additional components.
- the composition may 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.
- polyacrylic acid salts lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts
- polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines substituted phenols (in particular alkylphenols or
- the presence of at least one surfactant is generally essential when the active material and/or the inert support are water-insoluble and when the vector agent for the application is water.
- surfactant content may be between 5% and 40% by weight.
- additional components may also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents.
- the active materials can be combined with any solid or liquid additive, which complies with the usual formulation techniques.
- the composition according to the invention may contain from 0.05 to 99% (by weight) of active material, preferably 10 to 70% by weight.
- compositions according to the present invention can be used in various forms such as aerosol dispenser, bait (ready for use), bait concentrate, block bait, 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, grain bait, granular bait, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, plate bait, powder for dry seed treatment, scrap bait, seed coated with a pesticide, smoke candle, smoke cartridge, smoke generator, smoke pellet, smoke rodlet, smoke tablet, smoke tin, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), tracking powder, ultra low volume (ulv) liquid, ultra low volume (ulv) suspension, vapour releasing product, water dispersible granules
- compositions include not only compositions which 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 which must be diluted before they are applied to the crop.
- the compounds of the invention can also be mixed with one or more insecticides, fungicides, bactericides, attractant acaricides or pheromones or other compounds with biological activity.
- the mixtures thus obtained have a broadened spectrum of activity.
- the mixtures with other fungicides are particularly advantageous.
- the fungicidal compositions of the present invention can be used to curatively or preventively control the phytopathogenic fungi of crops.
- a method for curatively or preventively controlling the phytopathogenic fungi of crops characterised in that a fungicidal composition as hereinbefore defined is applied to the seed, the plant and/or to the fruit of the plant or to the soil in which the plant is growing or in which it is desired to grow.
- the composition as used against phytopathogenic fungi of crops comprises an effective and non-phytotoxic amount of an active material of general formula (I).
- effective and non-phytotoxic amount means an amount of composition according to the invention which is sufficient to control or destroy the fungi present or liable to appear on the crops, and which 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 combated, the type of crop, the climatic conditions and the compounds included in the fungicidal composition according to the invention. This amount can be determined by systematic field trials, which are within the capabilities of a person skilled in the art.
- the method of treatment according to the present invention is useful to treat propagation material such as tubers and 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 present invention can also be useful to treat the overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruits of the concerned plant.
- cotton Among the plants targeted by the method according to the invention, mention may be made of cotton; flax; vine; fruit crops such as Rosaceae sp. (for instance pip fruits such as apples and pears, but also stone fruits such as apricots, almonds and peaches), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp.
- Rosaceae sp. for instance pip fruits such as apples and pears, but also stone fruits such as apricots, almonds and peaches
- Ribesioidae sp. Juglandaceae sp.
- Betulaceae sp. Anacardiaceae sp., F
- Rubiaceae sp. for instance banana trees and plantins
- Rubiaceae sp. Theaceae sp., Sterculiceae sp., Rutaceae sp.
- leguminous crops such as Solanaceae sp. (for instance tomatoes), Liliaceae sp., Asteraceae sp. (for instance lettuces), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp., Papilionaceae sp. (for instance peas), Rosaceae sp. (for instance strawberries); big crops such as Graminae sp.
- Asteraceae sp. for instance sunflower
- Cruciferae sp. for instance colza
- Papilionaceae sp. for instance soja
- Solanaceae sp. for instance potatoes
- Chenopodiaceae sp. for instance beetroots
- horticultural and forest crops as well as genetically modified homologues of these crops.
- - wheat as regards controlling the following seed diseases: fusaria (Microdochium nivale and Fusarium roseum), stinking smut (Tilletia caries, Tilletia controversa or Tilletia indica), septoria disease (Septoria nodorum) and loose smut;
- cereal eyespot fXapesia yallundae, Tapesia acuiformis
- - barley as regards controlling the following seed diseases: net blotch (Pyrenophora graminea, Pyrenophora teres and Cochliobolus sativus), loose smut (Ustilago nudd) and fusaria (Microdochium nivale and Fusarium roseum); - barley, as regards controlling the following diseases of the aerial parts of the plant: cereal eyespot (Tapesia yallundae), net blotch (Pyrenophora teres and Cochliobolus sativus), powdery mildew (Erysiphe graminis forma specie hordei), dwarf leaf rust (Puccinia hordei) and leaf blotch (Rhynchosporium secalis);
- tuber diseases in particular Helminthosporium solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani), mildew (Phytopthora infestans) and certain viruses (virus Y);
- peas protein yielding crops, for example peas, as regards controlling the following seed diseases: anthracnose (Ascochyta pisi, Mycosphaerella pinodes), fusaria (Fusarium oxysporum), grey mould (Botrytis cinerea) and mildew (Peronospora pisi) ;
- rape oil-bearing crops, for example rape, as regards controlling the following seed diseases: Phoma lingam, Alternaria brassicae and Sclerotinia sclerotiorum;
- - corn as regards controlling seed diseases: (Rhizopus sp., Penicillium sp., Trichoderma sp., Aspergillus sp., and Gibberellafujikuroi); - flax, as regards controlling the seed disease: Alternaria linicola; - forest trees, as regards controlling damping-off (Fusarium oxysporum, Rhizoctonia solani);
- blast disease Magnetic aporthe grised
- bordered sheath spot Rhizoctonia solani
- - leguminous crops as regards controlling the following diseases of seeds or of young plants grown from seeds: damping-off and collar rot (Fusarium oxysporum, Fusarium roseum, Rhizoctonia solani, Pythium sp.);
- Cercospora beticol ⁇ Cercospora beticol ⁇
- powdery mildew Erysiphe beiicol ⁇
- leaf spot Ramularia beticold
- the fungicide composition according to the present 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 of the present 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 material usually applied in the treatment according to the present invention is generally and advantageously between 10 and 800 g/ha, preferably between 50 and 300 g ha for applications in foliar treatment.
- the dose of active material applied is generally and advantageously between 2 and 200 g per 100 kg of seed, preferably between 3 and 150 g per 100 kg of seed in the case of seed treatments. It is clearly understood that the doses indicated above are given as illustrative examples of the invention. A person skilled in the art will know how to tailor the application doses according to the nature of the crop to be treated.
- the fungicidal composition according to the present invention may also be used in the treatment of genetically modified organisms with the compounds according to the invention or the agrochemical compositions according to the invention.
- Genetically modified plants are plants into whose genome a heterologous gene encoding a protein of interest has been stably integrated.
- the expression "heterologous gene encoding a protein of interest” essentially means genes which give the transformed plant new agronomic properties, or genes for improving the agronomic quality of the transformed plant.
- compositions according to the present invention may also be used to curatively or preventively treat human and animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
- human and animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
- M+l means the molecular ion peak, plus or minus 1 a.m.u. (atomic mass units) respectively, as observed in mass spectroscopy and M (Apcl+) means the molecular ion peak as it was found via positive atmospheric pressure chemical ionisation in mass spectroscopy.
- Example 1 in vivo test on Alternaria brassicae (Leaf spot of crucifers):
- the active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/l.This suspension is then diluted with water to obtain the desired active material concentration. Radish plants (Pernot variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18-20°C, are treated at the cotyledon stage by spraying with the aqueous suspension described above.
- Plants, used as controls, are treated with an aqueous solution not containing the active material. After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of Alternaria brassicae spores (40,000 spores per cm ). The spores are collected from a 12- 13 -day-old culture.
- the contaminated radish plants are incubated for 6-7 days at about 18°C, under a humid atmosphere. Grading is carried out 6 to 7 days after the contamination, in comparison with the control plants.
- the active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/l.This suspension is then diluted with water to obtain the desired active material concentration.
- Wheat plants (Audace variety) in starter cups, sown on 50/50 peat soil-pozzolana substrate and grown at 12°C, are treated at the 1 -leaf stage (10 cm tall) by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material.
- the plants are contaminated by dusting them with Erysiphe graminis f. sp. tritici spores, the dusting being carried out using diseased plants. Grading is carried out 7 to 14 days after the contamination, in comparison with the control plants.
- the active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/1. This suspension is then diluted with water to obtain the desired active material concentration.
- Cucumber plants (Marketer variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18- 20°C, are treated at the cotyledon Zl l stage by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material. After 24 hours, the plants are contaminated by depositing drops of an aqueous suspension of Botrytis cinerea spores (150,000 spores per ml) on upper surface of the leaves. The spores are collected from a 15-day-old culture and are suspended in a nutrient solution composed of:
- the contaminated cucumber plants are settled for 5/7 days in a climatic room at 15-11°C (day/night) and at 80% relative humidity.
- the active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/1. This suspension is then diluted with water to obtain the desired active material concentration.
- Barley plants (Express variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 12°C, are treated at the 1-leaf stage (10 cm tall) by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material. After 24 hours, the plants are contaminated by spraying them 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 24 hours at about 20°C and at 100% relative humidity, and then for 12 days at 80% relative humidity.
- the active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/1. This suspension is then diluted with water to obtain the desired active material concentration.
- Cabbage plants (Eminence variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18-20°C, are treated at the cotyledon stage by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material.
- the plants are contaminated by spraying them with an aqueous suspension of Peronospora brassicae spores (50,000 spores per ml).
- the spores are collected from infected plant.
- the contaminated cabbage plants are incubated for 5 days at 20°C, under a humid atmosphere.
Abstract
Compound of general formula (I): Process for preparing this compound. Novel intermediate of general formula (E): for the preparation of compound of general formula (I) Fungicidal composition comprising a compound of general formula (I). Method for treating plants by applying a compound of general formula (I) or a composition comprising it.
Description
PYRIDINE DERIVATIVES AS FUNGICIDAL COMPOUNDS
The present invention relates to novel N-[2-(2-pyridinyl)ethyl]carboxamides" derivatives, their process of 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.
The international patent application WO 01/11965 discloses a broad family of fungicidal compounds which genetically covers the compounds according to the present invention. Nevertheless, the compounds according to the present invention are not specifically disclosed in this document and their activity as fungicides has not been tested.
It is always of high-interest in agriculture to use pesticidal compounds more active than the compounds already known by the man ordinary skilled in the art in order to decrease the quantity of active ingredient used by the farmer as to maintain an efficacy at least equivalent to compounds already known.
We have now found a new family of compounds selected in a broad family of compounds which possess the above mentioned characteristics.
Accordingly, the present invention relates to N-[2-(2- pyridinyl)ethyl]carboxamide derivative of general formula (I):
- R1 may be a hydrogen atom, a cyano group, a nitro group, a forrnyl group, a -Cδ- alkyl, a Ct-Cβ-alkylcarbamoyl, a C2-C -alkenyl, a C2-C6-alkynyl, a - - halogenoalkyl having 1 to 7 halogen atoms, a Ci- -alkoxy-d-Cδ-alkyl, a Cι-C6- cyanalkyl, a Q-Ce-aminoalkyl, a C3-C6-cycloalkyl, a Cr -alkylcarbonyl, a Q-C6- halogenalkylcarbonyl having 1 to 5 halogen atoms, a Ct-Ce-alkoxy-Q-Crr alkylcarbonyl, a Cj-C6-alkylsulfanyl or a CrCβ-halogenalkylsulfanyl having 1 to 5 halogen atoms;
- n maybe 1, 2, 3 or 4; and
- Het represents an optionally substituted 5-, 6- or 7-membered non-fused heterocycle with one, two or three heteroatoms which may be the same or different; Het being linked by a carbon atom.
In the context of the present invention :
- halogen means fluorine, bromine, chlorine or iodine;
- heteroatom means N, O or S.
According to the present invention, X represents an oxygen atom or a sulphur atom. Preferably, X represents an oxygen atom.
According to the present invention, the 2-pyridyl may be substituted in every position by (Y)n, in which Y and n are as defined above. Preferably, the present invention relates to N-[2-(2-pyridinyl)ethyl]carboxamide derivative of general formula (I) in which the different characteristics may be chosen alone or in combination as being :
- as regards n, n is 1 or 2. More preferably n is 2.
- as regards Y, at least one of the Y substituent is a halogen atom, a CpCg-alkyl, a Ci-Cό-halogenoalkyl having 1 to 5 halogen atoms or a Cι-C6-alkoxy-Cι-C6- alkylcarbonyl. More preferably, at least one of the Y substituent is a - - halogenoalkyl having 1 to 5 halogen atoms. Even more preferably, at least one of the Y substituent is -CF3.
- as regards the positions in which the 2-pyridyl is substituted, the 2-pyridyl is substituted in 3- and/or in 5-position. Even more preferably, the substituent in 5-position is -CF3.
According to the present invention, "Het" of the compound of general formula (I) may be a five membered ring non-fused heterocycle. Specific examples of compounds of the present invention where Het is a five membered heterocycle include : * Het represents a heterocycle of the general formula (II)
- R and R may be the same or different and may be a hydrogen atom, a halogen atom, an amino group, a nitro group, a Cj-C4-alkyl or a C1-C4-halogenoalkyl having 1 to 5 halogen atoms; and
- R4 may be a hydrogen atom, a halogen atom, a nitro group, a C1-C4-alkyl or a Cι-C4-halogenoalkyl having 1 to 5 halogen atoms.
* Het represents a heterocycle of the general formula (III)
* Het represents a heterocycle of the general formula (IV)
* Het represents a heterocycle of the general formula (V)
(V)
in which :
- R10 and R11 may be the same or different and may be a hydrogen atom, a halogen atom, a Cι-C4-alkyl, a Q- -halogenoalkyl having 1 to 5 halogen atoms, a C1-C -alkylthio, a C)-C4-alkylsulphonyl, a phenyl optionally substituted by a halogen atom or a Q-Q-alkyl or a pyridyl otpionally substituted by a halogen atom or a Q- C4-alkyl; and
- R12 may be a hydrogen atom, a halogen atom, a cyano group, a Cj-C4 -alkyl, a C!-C4-halogenoalkyl having 1 to 5 halogen atoms or a Q-Q-halogenoalkoxy having 1 to 5 halogen atoms.
* Het represents a heterocycle of the general formula (VI)
(VI) in which :
- R13 and R14 may be the same or different and may be a hydrogen atom, a halogen atom, a C1-C4-alkyl, a Q^-alkyloxy or a C1-C4-halogenoalkyl having 1 to 5 halogen atoms; and
- R15 may be a hydrogen atom, a halogen atom, a Cι-C4-alkyl or a Q-Gt- halogenoalkyl having 1 to 5 halogen atoms.
* Het represents a heterocycle of the general formula (VII)
- R16 may be a hydrogen atom, a halogen atom, a cyano group, a C1-C4-alkyl or a Cι-C -halogenoalkyl having 1 to 5 halogen atoms; - R17 and R19 may be the same or different and may be a hydrogen atom, a halogen atom, a C1-C4-alkyl or a d-d-halogenoalkyl having 1 to 5 halogen atoms; and
- R18 may be a hydrogen atom, a cyano group, a Cj-C4-alkyl, a d-C4- halogenoalkyl having 1 to 5 halogen atoms, a C1-C4-alkoxy-C1-C4-alkyl, a hydroxy- C1-C4-alkyl, a CrC4-alkylsulphonyl, a di(Cι-C -alkyl)aminosulphonyl, a d-C6- alkylcarbonyl, a phenylsulphonyl optionally substituted by a halogen atom or a Q- C -alkyl, or a benzoyl optionally substituted by a halogen atom or a Cj-C -alkyl.
* Het represents a heterocycle of the general formula (VIII)
- R >20 may be a hydrogen atom, a cyano group, a Q-Q-alkyl, a C1-C4- halogenoalkyl having 1 to 5 halogen atoms, a C1-C4-alkoxy-C1-C4-alkyl, a hydroxy- Cι-C4-alkyl, a Cι-C4-alkylsulphonyl, a di(C1-C4-alkyl)aminosulphonyl, a Cι-C6- alkylcarbonyl, a phenylsulphonyl optionally substituted by a halogen atom or a Q- C4-alkyl, or a benzoyl optionally substituted by a halogen atom or a Q^- lkyl; and
- R , R and R may be the same or different and may be a hydrogen atom, a halogen atom, a cyano group, a d-Q-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms or a d-d-alkylcarbonyl.
* Het represents a heterocycle of the general formula (IX)
- R24 may be a hydrogen atom or a Cι-C4-alkyl; and
- R25 may be a halogen atom, a d-C4-alkyl or a d-C4-halogenoalkyl having 1 to 5 halogen atoms.
* Het represents a heterocycle of the general formula (X)
- R27 may be a halogen atom, a d-d-alkyl, a d-C4-halogenoalkyl having 1 to 5 halogen atoms or a phenyl optionally substituted by a halogen atom or a C1-C4- alkyl.
* Het represents a heterocycle of the general formula (XI)
(XI) in which :
- R28 may be a hydrogen atom, a halogen atom, an amino group, a cyano group, a C1-C4-alkylamino3 a di-(Cι-C4-alkyl)amino3 a C1-C4-alkyl, a d-Gj- halogenoalkyl having 1 to 5 halogen atoms or a phenyl optionally substituted by a halogen atom or a d-C^-alkyl; and - R29 may be a halogen atom, a C1-C4-alkyl or a Cι-C4-halogenoalkyl having
1 to 5 halogen atoms.
* Het represents a heterocycle of the general formula (XII)
(XII) in which : - R30 may be a hydrogen atom, a halogen atom, an amino group, a cyano group, a Cι-C4-alkylamino, a di-(Cι-C4-alkyl)amino, a Cι-C4-alkyl or a C1-C4- halogenoalkyl having 1 to 5 halogen atoms; and
-R31 may be a halogen atom, a Cι-C4-alkyl or a C1-C -halogenoalkyl having 1 to 5 halogen atoms.
* Het represents a heterocycle of the general formula (XIII)
in which :
- R may be a hydrogen atom, a halogen atom, a cyano group, a nitro group, a d-C4-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, a C3-C6- cycloalkyl, a C]-C4-alkoxy, a Cι-C4-halogenoalkoxy having 1 to 5 halogen atoms, a d-d-alkylthio, a C1-C4-halogenoalkylthio having 1 to 5 halogen atoms, an aminocarbonyl group or an aminocarbonyl-C1-C4-alkyl; - R may be a hydrogen atom, a halogen atom, a cyano group, a nitro group, a d-d-alkyl, a d-Q-alkoxy or a d-C4-alkylthio; and
- R34 may be a hydrogen atom, a phenyl, a C1-C4-alkyl, a C1-C4- halogenoalkyl having 1 to 5 halogen atoms, a hydroxy-d-C -alkyl, a d-Cg-alkenyl, a C3-C6-cycloalkyl, a Cι-C4-alkylthio-Cι-C4-alkyl, a Cι-C4-halogenoalkylthio-C1-C4- alkyl having 1 to 5 halogen atoms, a Cι-C4-alkoxy-C1-C4-alkyl or a d-C4- halogenoalkoxy-d-C4-alkyl having 1 to 5 halogen atoms.
* Het represents a heterocycle of the general formula (XIV)
- R37 may be a hydrogen atom, a Cι-C4-alkyl, a Cι-C4-halogenoalkyl having 1 to 5 halogen atoms, a hydroxy-Cι-C4-alkyl, a C2-C6-alkenyl, a C3-C6-cycloalkyl, a Cι-C4-alkylthio-Cι-C4-alkyl, a Cι-C4-halogenoalkylthio-C1-C4-alkyl having 1 to 5 halogen atoms, a C1-C4-alkoxy-C1-C4-alkyl, a Cι-C4-halogenoalkoxy-C1-C4-alkyl having 1 to 5 halogen atoms or a phenyl optionally substituted by a halogen atom, a d-C -alkyl, a Cι-C4-alkoxyalkyl or a nitro group.
* Het represents a heterocycle of the general formula (XV)
-R may be a hydrogen atom, a halogen atom, a cyano group, a nitro group, a d-C -alkyl, a d-C4-halogenoalkyl having 1 to 5 halogen atoms, a C3-C6-cycloalkyl, a Cι-C4-alkoxy, a Cι-C -halogenoalkoxy having 1 to 5 halogen atoms, a C1-C4- alkylthio, a Ci-Q-halogenoalkylthio having 1 to 5 halogen atoms, an aminocarbonyl, or an ammocarbonyl-Cι-C4-alkyl;
- R may be a hydrogen atom, a halogen atom, a cyano group, a Cj-C4 -alkyl, a d-C4-alkoxy, a Ci-d-alkylthio or a Ci-d-halogenoalky having 1 to 5 halogen atoms;
- R40 may be a hydrogen atom, a phenyl, a benzyl, a Ci-d-alkyl, a d-d- halogenoalkyl having 1 to 5 halogen atoms, a hydroxy-d-Q-alkyl, a C2-C6-alkenyl, a C3-C6-cycloalkyl, a d-d-alkylthio-Ci-d-alkyl, a Cι-C4-halogenoalkylthio-Cι-C4- alkyl having 1 to 5 halogen atoms, a C1-C4-alkoxy-C1-C4-alkyl, a d-C - halogenoalkoxy-d-d-alkyl having 1 to 5 halogen atoms.
* Het represents a heterocycle of the general formula (XVI)
* Het represents a heterocycle of the general formula (XVII)
* Het represents a heterocycle of the general formula (XVIII)
5 halogen atoms.
* Het represents a heterocycle of the general formula (XIX)
* Het represents a heterocycle of the general formula (XX)
in which : - R48 may be a halogen atom, a Ci-d-aikyl or a Cι-C4-halogenoalkyl having 1 to 5 halogen atoms; and - R49 may be a hydrogen atom, a d-d-alkyl, a Cι-C4-halogenoalkyl having 1 to 5 halogen atoms, or a phenyl optionally substituted by a halogen atom or a C1-C - alkyl.
* Het represents a heterocycle of the general formula (XXI)
According to the present invention, "Het" of the compound of general formula (I) may be a six membered ring non-fused heterocycle. Specific examples of compounds of the present invention where Het is a six membered heterocycle include :
* Het represents a heterocycle of the general formula (XXII)
- R52, R53 and R54, which may be the same or different, may be a hydrogen atom, a halogen atom, a cyano group, a d-d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a d-d-alkoxy, a d-d-alkylthio, a d-d-halogenoalkoxy having 1 to 5 halogen atoms, a d-d-alkylsulphinyl or a d-d-alkylsulphonyl.
* Het represents a heterocycle of the general formula (XXIII)
(XXIII) in which :
- R may be a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a d-d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a Cι-C4-alkoxy, a d-d-alkylthio, a d-d-alkenylfhio a d-d- halogenoalkylthio having 1 to 5 halogen atoms, a d-d-halogenoalkoxy having 1 to 5 halogen atoms, a phenyloxy optionally substituted by a halogen atom or a d-d- alkyl, or a phenylthio optionally substituted by a halogen atom or a d-d-alkyl;
- R56, R57 and R58, which may the same or different, may be a hydrogen atom, a halogen atom, a cyano group, a Ci-d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a d-d-alkoxy, a Ci-d-alkylthio, a Ci-d-halogenoalkoxy having 1 to 5 halogen atoms, a d-d-alkylsulphinyl, a d-d-alkylsulphonyl or a N- morpholine optionally substituted by a halogen atom or a d-d-alkyl, or a thienyl optionally substituted by a halogen atom or a d-d-alkyl.
* Het represents a heterocycle of the general formula (XXIV)
(XXIV) in which R59, R60, R61 and R62, which may be the same or different, may be a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a d-d- alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, a Ci-d-alkoxy, a C1-C4- alkylthio, a d-d-halogenoalkylthio having 1 to 5 halogen atoms, a d-d-
halogenoalkoxy having 1 to 5 halogen atoms, a d-d-alkylsulphinyl or a C1-C4- alkylsulphonyl.
* Het represents a heterocycle of the general formula (XXV)
- R64 may be a hydrogen atom, a d-d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a C[-C6-alkoxycarbonyl, a benzyl optionally substituted by 1 to 3 halogen atoms, a benzyloxycarbonyl optionally substituted by 1 to 3 halogen atoms or a heterocyclyl.
* Het represents a heterocycle of the general formula (XXVI)
- R may be a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a Ci-d-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, a C1-C4- alkoxy, a d-d-alkylthio, a d-d-halogenoalkylthio having 1 to 5 halogen atoms or a d-d-halogenoalkoxy having 1 to 5 halogen atoms;
- R66 may be a hydrogen atom, a d-d-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms or a benzyl.
* Het represents a heterocycle of the general formula (XXVII)
- X1 may be a sulphur atom, -SO-, -SO2- or -CH2-;
- R67 may be a Ci-d-alkyl or a d-d-halogenoalkyl having 1 to 5 halogen atoms; and
- R68 and R69 may be the same or different and may be a hydrogen atom or a d-d-alkyl.
* Het represents a heterocycle of the general formula (XXVIII)
70
,R
\
(XVIII) in which :
R , 70 may be a Ci-d-alkyl or a d-d-halogenoalkyl having 1 to 5 halogen atoms;
* Het represents a heterocycle of the general formula (XXIX)
(XXIX) in which :
71
R may be a Cι-C4 -alkyl or a Cι-C4-halogenoalkyl having 1 to 5 halogen atoms.
* Het represents a heterocycle of the general formula (XXX)
The present invention also relates to a process for the preparation of the compound of general formula (I). Thus, according to a further aspect of the present invention there is provided a process for the preparation of compound of general formula (I) as defined above, which comprises reacting a carboxylic acid derivative of the general formula (A)
ϋ
O
G X Het
(A) in which : - Het is as defined above;
- G may be a halogen atom, a hydroxy group or a Cι-C6-alkoxy; with a 2-pyridine derivative of general formula (B)
According to the present invention, the process for the preparation of compound of general formula (I) is carried out in the presence of a catalyst if G is a hydroxy or a d-C6-alkoxy group. Suitable catalyst includes the coupling reagents dicyclohexylcarbodiimide, N,N'-carbonyldimidazole, bromotripyrrolidinophosphonium hexafluorophosphate and trimethylaluminium.
According to the present invention, the process for the preparation of compound of general formula (I) is carried out in the presence of an acid binder if G is a halogen atom. Suitable acid binder includes carbonates, aqueous alkali or tertiary amines.
The present invention also relates to another process for the preparation of the compound of general formula (I). Thus, according to a further aspect of the present invention there is provided a second process for the preparation of compound of general formula (I) as defined above, which comprises reacting a carboxylic acid anhydride derivative of general formula (C)
(C) in which :
- Het is as defined above;
- W may be defined as Het or a d-d-alkyl; with a 2-pyridine derivative of the formula (D)
According to the present invention, the second process for the preparation of compound of general formula (I) is carried out in the presence of a reducing agent. Suitable reducing agent includes H2 and NaBH*.
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 the skilled worker will be able to adapt this method according to the specifics of each of the compounds, which it is desired to synthesise. For example, the above mentioned processes may be carried out in the presence of a diluent if appropriate. If appropriate, the second process for the preparation of compound of general formula (I) may also be carried out in the presence of a catalyst such as NiCl2-H2O or CoCl3-H2O.
Certain of the intermediate compounds used for the preparation of compound of general formula (I) are novel. Therefore, the present invention also relates to novel intermediate compound useful for the preparation of compound of general formula
(I). Thus, according to the present invention, there is provided a novel compound of general formula (E) :
- Z1 may be a halogen atom or a d-Cg-alkyl;
- R1 and n are as defined above.
The present invention also relates to a fungicidal composition comprising an effective amount of an active material of general formula (I). Thus, according to the present invention, there is provided a fungicidal composition comprising, as an active ingredient, an effective amount of a compound of general formula (I) as defined above and an agriculturally acceptable carrier or filler. In the present specification, the term "support" denotes a natural or synthetic, organic or inorganic material with which the active material is combined 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 may 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 may also be
"UScu..
The composition may also comprise additional components. In particular, the composition may 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 may be made, for example, of polyacrylic acid salts, lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic 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 sulphosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the above compounds containing sulphate, sulphonate and phosphate functions. The presence of at least one surfactant is generally essential when the active material and/or the inert support are water-insoluble and when the vector agent for the application is water. Preferably, surfactant content may be between 5% and 40% by weight.
Optionally, additional components may also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active materials can be combined with any solid or liquid additive, which complies with the usual formulation techniques. In general, the composition according to the invention may contain from 0.05 to 99% (by weight) of active material, preferably 10 to 70% by weight.
Compositions according to the present invention can be used in various forms such as aerosol dispenser, bait (ready for use), bait concentrate, block bait, 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, grain bait, granular bait, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, plate bait, powder for dry seed treatment, scrap bait, seed coated with a pesticide, smoke candle, smoke cartridge, smoke generator, smoke pellet, smoke rodlet, smoke tablet, smoke tin, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), tracking powder, ultra low volume (ulv) liquid, ultra low volume (ulv) suspension, vapour releasing product, 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 which 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 which must be diluted before they are applied to the crop.
The compounds of the invention can also be mixed with one or more insecticides, fungicides, bactericides, attractant acaricides or pheromones or other compounds with biological activity. The mixtures thus obtained have a broadened spectrum of activity. The mixtures with other fungicides are particularly advantageous.
The fungicidal compositions of the present invention can be used to curatively or preventively control the phytopathogenic fungi of crops. Thus, according to a further aspect of the present invention, there is provided a method for curatively or preventively controlling the phytopathogenic fungi of crops characterised in that a fungicidal composition as hereinbefore defined is applied to the seed, the plant and/or to
the fruit of the plant or to the soil in which the plant is growing or in which it is desired to grow.
The composition as used against phytopathogenic fungi of crops comprises an effective and non-phytotoxic amount of an active material of general formula (I). The expression "effective and non-phytotoxic amount" means an amount of composition according to the invention which is sufficient to control or destroy the fungi present or liable to appear on the crops, and which 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 combated, the type of crop, the climatic conditions and the compounds included in the fungicidal composition according to the invention. This amount can be determined by systematic field trials, which are within the capabilities of a person skilled in the art.
The method of treatment according to the present invention is useful to treat propagation material such as tubers and 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 present invention can also be useful to treat the overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruits of the concerned plant.
Among the plants targeted by the method according to the invention, mention may be made of cotton; flax; vine; fruit crops such as Rosaceae sp. (for instance pip fruits such as apples and pears, but also stone fruits such as apricots, almonds and peaches), 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 plantins), Rubiaceae sp., Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemons, oranges and grapefruits); leguminous crops such as Solanaceae sp. (for instance tomatoes), Liliaceae sp., Asteraceae sp. (for instance lettuces), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp., Papilionaceae sp. (for instance peas), Rosaceae sp. (for instance strawberries); big crops such as Graminae sp. (for instance maize, cereals such as wheat, rice, barley and triticale), Asteraceae sp. (for instance sunflower), Cruciferae sp. (for instance colza), Papilionaceae sp. (for instance soja), Solanaceae sp. (for instance potatoes), Chenopodiaceae sp. (for instance beetroots); horticultural and forest crops; as well as genetically modified homologues of these crops. Among the plants and the possible diseases of these plants targeted by the method according to the present invention, mention may be made of :
- wheat, as regards controlling the following seed diseases: fusaria (Microdochium nivale and Fusarium roseum), stinking smut (Tilletia caries, Tilletia controversa or Tilletia indica), septoria disease (Septoria nodorum) and loose smut;
- wheat, as regards controlling the following diseases of the aerial parts of the plant: cereal eyespot (fXapesia yallundae, Tapesia acuiformis), take-all
(Gaeumannomyces graminis), foot blight (F. culmorum, F. graminearum), black speck (Rhizoctonia cerealis), powdery mildew (Erysiphe graminis forma specie tritici), rusts (Puccinia striiformis and Puccinia reconditd) and septoria diseases (Septoria tritici and Septoria nodorum); - wheat and barley, as regards controlling bacterial and viral diseases, for example barley yellow mosaic;
- barley, as regards controlling the following seed diseases: net blotch (Pyrenophora graminea, Pyrenophora teres and Cochliobolus sativus), loose smut (Ustilago nudd) and fusaria (Microdochium nivale and Fusarium roseum); - barley, as regards controlling the following diseases of the aerial parts of the plant: cereal eyespot (Tapesia yallundae), net blotch (Pyrenophora teres and Cochliobolus sativus), powdery mildew (Erysiphe graminis forma specie hordei), dwarf leaf rust (Puccinia hordei) and leaf blotch (Rhynchosporium secalis);
- potato, as regards controlling tuber diseases (in particular Helminthosporium solani, Phoma tuberosa, Rhizoctonia solani, Fusarium solani), mildew (Phytopthora infestans) and certain viruses (virus Y);
- potato, as regards controlling the following foliage diseases: early blight (Alternaria solani), mildew (Phytophthora infestans);
- cotton, as regards controlling the following diseases of young plants grown from seeds: damping-off and collar rot (Rhizoctonia solani, Fusarium oxysporum) and black root rot (Thielaviopsis basicola);
- protein yielding crops, for example peas, as regards controlling the following seed diseases: anthracnose (Ascochyta pisi, Mycosphaerella pinodes), fusaria (Fusarium oxysporum), grey mould (Botrytis cinerea) and mildew (Peronospora pisi) ;
- oil-bearing crops, for example rape, as regards controlling the following seed diseases: Phoma lingam, Alternaria brassicae and Sclerotinia sclerotiorum;
- corn, as regards controlling seed diseases: (Rhizopus sp., Penicillium sp., Trichoderma sp., Aspergillus sp., and Gibberellafujikuroi); - flax, as regards controlling the seed disease: Alternaria linicola;
- forest trees, as regards controlling damping-off (Fusarium oxysporum, Rhizoctonia solani);
- rice, as regards controlling the following diseases of the aerial parts: blast disease (Magnaporthe grised), bordered sheath spot (Rhizoctonia solani); - leguminous crops, as regards controlling the following diseases of seeds or of young plants grown from seeds: damping-off and collar rot (Fusarium oxysporum, Fusarium roseum, Rhizoctonia solani, Pythium sp.);
- leguminous crops, as regards controlling the following diseases of the aerial parts: grey mould (Botrytis sp.), powdery mildews (in particular Erysiphe cichoracearum, Sphaerotheca fuliginea and Leveillula taurica), fusaria (Fusarium oxysporum, Fusarium roseum), leaf spot (Cladosporium sp.), alternaria leaf spot (Alternaria sp.), anthracnose (Colletotrichum sp.), septoria leaf spot (Septoria sp.), black speck (Rhizoctonia solani), mildews (for example Bremia lactucae, Peronospora sp., Pseudoperonospora sp., Phytophthora sp.); - fruit trees, as regards diseases of the aerial parts: monilia disease (Monilia fructigenae, M. laxά), scab (Venturia inaequalis), powdery mildew (Podosphaera leucoiricha);
- vine, as regards diseases of the foliage: in particular grey mould (Botrytis cinered), powdery mildew (Uncinula necalor), black rot (Guignardia biwelli) and mildew (Plasmopara viticold);
- beetroot, as regards the following diseases of the aerial parts: cercospora blight (Cercospora beticolά), powdery mildew (Erysiphe beiicolά), leaf spot (Ramularia beticold).
The fungicide composition according to the present 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 of the present 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 material usually applied in the treatment according to the present invention is generally and advantageously between 10 and 800 g/ha, preferably between 50 and 300 g ha for applications in foliar treatment. The dose of active
material applied is generally and advantageously between 2 and 200 g per 100 kg of seed, preferably between 3 and 150 g per 100 kg of seed in the case of seed treatments. It is clearly understood that the doses indicated above are given as illustrative examples of the invention. A person skilled in the art will know how to tailor the application doses according to the nature of the crop to be treated.
The fungicidal composition according to the present invention may also be used in the treatment of genetically modified organisms with the compounds according to the invention or the agrochemical compositions according to the invention. Genetically modified plants are plants into whose genome a heterologous gene encoding a protein of interest has been stably integrated. The expression "heterologous gene encoding a protein of interest" essentially means genes which give the transformed plant new agronomic properties, or genes for improving the agronomic quality of the transformed plant.
The compositions according to the present invention may also be used to curatively or preventively treat human and animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
The aspects of the present invention will now be illustrated with reference to the following tables of compounds and examples. The following Tables A to V illustrate in a non-limiting manner examples of fungicidal compounds according to the present invention. In the following Examples, M+l (or M-l) means the molecular ion peak, plus or minus 1 a.m.u. (atomic mass units) respectively, as observed in mass spectroscopy and M (Apcl+) means the molecular ion peak as it was found via positive atmospheric pressure chemical ionisation in mass spectroscopy.
Table A
Compound R1 R2 R3 R4 γl γ2 ■γ-3 Y4 M+l
A-l H H H H CI H CF3 H 319 at l 35Cl
A-2 H NO2 H H CI H CF3 H 364 at 1 35C1
A-3 H H H Me CI H CF3 H 333 at 1 35C1
397 at 1 35C1
A-4 H H H Br CI H CF3 H and 1 79Br
Table B
Compound R1 R5 R6 R7 γl Y2 γ3 γ4 M (Apcl+) M+1
B-l H Me H H CI H CF3 H 333 at 1 35C1
4-
B-2 H CF3 chloro- H CI H CF3 H 497 at 2 35C1 phenyl
B-3 H H H H CI H CF3 H 319 at l 35Cl
B-4 H Me t-Bu H CI H CF3 H 389 at 1 35C1
B-5 H Me Ph H CI H CF3 H 409 at 1 35C1
4-
B-6 H Me chloro- H CI H CF3 H 443 at 2 35Cl phenyl
B-7 H Me Me H CI H CF3 H 347 at 1 35C1
B-8 H CF3 ' Me H CI H CF3 H 401 at 1 35C1
3-
496 at 2
B-9 H CF3 c loro- H CI H CF3 H 35C1 phenyl
B-10 H CF3 Ph H CI H CF3 H 463 at 1 35C1
B-ll H H H Me CI H CF3 H 333 at 1 35C1
B-12 H CF3 H H CI H CF3 H 387 at 1 35C1
B-13 H Me H H CI H CI H
B-14 H I H H CI H CF3 H 445 at 1 35C1
B-15 Cyclopropyl I H H CI H CF3 H 485 at 1 35C1
B-16 H Me Me H CI H CI Me 327 at 2 35C1
Compound R1 R5 R6 R7 Y1 γ2 γ3 γ4 M (Apcl+) M+1
B-17 H Me Me H F H F F 299
B-18 H I H H F H F F 397
B-19 H Me H H F H F F 285
B-20 H Me Me H F Me F F 313
B-21 H Me H H F Me F F 299
B-22 H I H H F Me F F 411
Table C
Compound R1 R10 Rn R12 Y1 γ2 γ3 γ4 M (Apcl+) M+1
C-l H H H H CI H CF3 H 335 at 1 35C1
C-2 H H H CI CI H CF3 H 369 at 2 35C1
C-3 H H H Me CI H CF3 H 349 at 1 35C1
C-4 H H SO Pr CI CI H CF3 H 475 at 2 35C1
412 at 1 35C1
C-5 H H H Br CI H CF3 H and 1 79Br
2-
C-6 H H H CI H CF3 H 412 at 1 35C1
Pyridy]
C-7 H Ph H H CI H CF3 H 41 1 at 1 35C1
C-8 H H SO2Me CI CI H CF3 H 446 at 1 35C1
C-9 H SMe SO2«Pr CI CI H CF3 H 521 at 2 35C1
C-10 H SMe SO2zPr I CI H CF3 H 612 at 1 35C1
C-11 H CI CI CI CI H CF3 H 436 at 4 35C1
C-12 H H H I CI H CF3 H 461 at 1 35C1
C-13 H H H I CI H CI H
C-14 H H H Me F H CI H 333 at 1 35C1
C-15 H H H I F H CI H 411 at 1 35C1
471 at 1 35C1
C-16 H H H I Br H CI H and 1 79Br
C-17 H H H I H H CI H 393 at 1 35C1
Compound R1 R10 Rn R12 Y1 Y2 γ3 Y4 M (Apcl+) M+1
C-18 H H H CI H H CI 427 at2 35Cl
C-19 H H H H H Me H 373
C-20 Cyclopropyl H H CI H CF3 H
C-21 H H H CI H CI Me 441 at 2 35C1
C-22 H H H CI H CI F 445 at 2 35C1
C-23 H H H F H CI F
C-24 H H H H H CF3 CI 461 at 1 35C1
C-25 H H H Me H H CF3 CI
C-26 H H H Me F H F F 301
C-27 H H H Br F H F F 365 at 1 79Br
C-28 H H H I F H F F 413
C-29 H H H Me F Me F F 315
C-30 H H H Br F Me F F 379 at 1 79Br
C-31 H H H I F Me F F 427
Table D
Compound R1 R13 R14 R1S Y1 Y Y4 M+1
D-l H CI OMe H CI H CF3 H 399 at 2 "CI
D-2 H H H H CI H CF3 H 335 at 1 35C1
D-3 H H H Me CI H CF3 H 349 at 1 35C1
D-4 H H H I CI H CF3 H 461 at 1 35C1
D-5 H H Me H CI H CF3 H 349 at 1 35C1
D-6 H H H I F H F F 413 at 1 35C1
D-7 H H H I F Me F F 427 at 1 35C1
Table E
Compound R1 R16 R17 R18 R19 Y1 Y2 Y M+1 M-l
E-l H H Me Me Me CI H CF3 H 358 at 1 35C1
E-2 H CF3 Me Me H CI H CF3 H 400 at l 3J53C/- l
E-3 H CF3 H Me H CI H 352
E-4 H CF3 H Me H CI Me F 366
Table F
Compound R1 R20 R21 R22 R23 Y1 Y2 Y3 Y4 M (APcI+) M+1
F-l H Me H H H CI H CF3 H 332 at 1 35C1
F-2 H H Me Ac Me CI H CF3 H 387 at l 35Cl
F-3 H Me H H I CI H CF3 H 458 at 1 35C1
Table G
Compound R1 R26 R27 Y1 M+1
G-l H H Ph CI H CF3 H 396 at 1 3 "5C, I
G-2 H Me CF3 CI H CF3 H 402 at 1 3 "5/CI
Table H
Compound R1 R28 R29 γl γ2 γ3 γ4 M+1
H-l H Me CF3 CI H CF3 H 418 at l 35Cl
H-2 H Me CHF2 CI H CF3 H 400 at 1 35C1
H-3 H Ph Me CI H CF3 H 426 at 1 35C1
H-4 H Me CF3 CI H CI H
H-S H Me CF3 CI H H CI 384 at 2 35Cl
H-6 H Me CF3 CI H Methoxyiminoethyl H 407 at 1 35C1
H-7 H Me CF3 CI H Ethoxyiminomethyl H 421 at 1 3SC1
H-8 H Me CF3 CI H Isopropoximinoethyl H 435 at 1 35C1
H-9 H Me CF3 CI H CI CI 418 at 3 35Cl
H-10 H Me CF3 F H CI H 368 at 1 35C1
H-11 Cyclopropyl Me CF3 CI H CF3 H 458 at 1 35C1
H-12 H Me CF3 F Me F F 384
H-13 H Me CF3 CI H CI Me 398 at 2 35C1
H-14 H Me CF3 F H F F 370
H-15 Cyclopropyl Me CHF2 CI H CF3 H 440 at 1 3 C1
H-16 H Me CHF2 F Me F F 366
Compound R1 R28 R29 Y1 γ2 Y3 γ4 M+1
409 at 1 35C1
H-17 H Me CHF2 CI H Br H and 1 79Br
H-18 H Me CHF2 Br H CF3 H 444 at 1 79Br
H-19 H Me CHF2 CI H CI Me 380 at 2 35Cl
H-20 H Me CHF2 CI H CI F 384 at 2 35Cl
H-21 H Me CHF2 F H F F 352
H-22 H Me CHF2 F H CI F 368 at 1 35C1
H-23 H Me CHF2 H H CF3 CI 400 at 1 35C1
Table I
Compound R1 R32 R33 R34 Y1 Y2 Y3 Y4 M(APcI+) M+1
1-1 H H Me t-Bu CI H CF3 H 389 at 1 35C1
1-2 H H Me Me CI H CF3 H 347 at 1 35C1
455 at 1 35C1
1-3 H Br NO2 Me CI H CF3 H and 1 79Br 1-4 H I H Me CI H CF3 H 459 at 1 35C1
Table J
J-l H H M Mee F F M Mee C Cll H H CF3 H 365 at 1 3SC
J-2 H H M Mee H H M Mee C Cll H H CF3 H 347 at 1 35C
J-3 H H C CHHFF22 H H M Mee C Cll H H CF3 H 383 at 1 35C
J-4 H H H H C CFF33 P Phh C Cll H H CF3 H 463 at 1 35C
J-5 H H H H C CFF33 4 4--cchhlloorroopphheennyyll C Cll H H CF3 H 497 at 2 35C
J-6 H H H H C Cll M Mee C Cll H H CF3 H 367 at 2 35C
J-7 H H H H M Mee 4 4--fflluuoorroopphheennyyll C Cll H H CF3 H 427 at 1 35C
4 4--
J-8 H H H H M Mee C Cll H H CF3 H 439 at 1 35C mmeetthhooxxyypphheennyyll
3-9 H H H H M Mee P Phh C Cll H H CF3 H 409 at 1 35C
J-10 H H H H M Mee 2 2--mmeetthhyyllpphheennyyll C Cll H H CF3 H 423 at 1 35C
J-11 H H H H nn--PPrr P Phh C Cll H H CF3 H 437 at 1 35C
J-12 H H H H nn--PPrr 4 4--cchhlloorroopphheennyyll C Cll H H CF3 H 471 at 2 35C
J-13 H H H H C CFF33 4 4--nniittrroopphheennyyll C Cll H H CF3 H 508 at 1 35C
J-14 H H M Mee M Mee M Mee C Cll H H CF3 H 361 at 1 35C
J-15 H H C Cll H H M Mee C Cll H H CF3 H 367 at 2 35C
J-16 H H I I H H M Mee C Cll H H CF3 H 459 at 1 35C
J-17 H H M Mee M Mee M Mee C Cll H H Cl H
J-18 H H M Mee F F M Mee C Cll H H Cl H 330 at 2 35C
J-19 H H M Mee H H M Mee C Cll H H Cl H
J-20 H H C CFF33 H H M Mee C Cll H H Cl Cl 401 at 3 35C
J-21 H H C CFF33 H H M Mee F F H H Cl H 351 at 1 35C
Compound R1 R35 R36 R37 Y1 γ2 γ3 γ4 M+1
J-22 H CF3 H Me Cl H H Cl 365 at 2 35(
J-23 Cyclopropyl CF3 H Me Cl H CF3 H 441 at 1 35(
J-24 H CF3 H Me H H CF3 Cl 401 at 1 35(
J-25 H CF3 H Me Cl H Cl Me 381 at 2 35C
J-26 H CF3 H Me Cl H Cl F 385 at 235(
J-27 H CF3 H Me F H F F 353
J-28 H CF3 H Me F Me F F 367
J-29 H CHF2 H Me Cl H Cl H
J-30 H CHF2 H Me H H Me H 295
« —^ A H CHF2 H Me H H Methoximinoethyl H 386 at 1 35C
J-32 H CHF2 H Me Me H Br H
J-33 H CHF2 H Me F H Cl H 333 at 1 35C
J-34 H CHF2 H Me Cl H Cl Cl 383 at 3 35C
J-35 H CHF2 H Me Cl H Methoximinoethyl H 372 at 1 35C
J-36 H CHF2 H Me H H Cl H
J-37 H CHF2 T 1J1 Me Cl H Ethoximinoethyl H 386 at 1 35C
J-38 H CHF2 H Me Cl H Isopropoximinoethyl H
393 at 1 35C
J-39 H CHF2 H Me Br H Cl H and 1 79Br
J-40 H CHF2 H Me F Me F F 349
J-41 Cyclopropyl CHF2 H Me Cl H CF3 423 at 1 35C
J-42 H CHF2 H Me H H CF3 383 at 1 35C
J-43 H CHF2 H Me Cl H Br
J-44 H CHF2 H Me F H Cl 351 at 1 35C
J-45 H CHF2 H Me Br H CF3 427 at 1 79B
J-46 H Me F Me Cl H Cl
Compound R1 R35 R36 R37 Y1 Y2 γ3 γ4 M+1
J-47 H Me F Me H H Me 277
J-48 H Me F Me Cl H Methoximinoethyl H
J-49 H Me F Me F H Cl H 315 at 1 35C
J-50 H Me F Me Cl H Cl Cl 365 at 3 35C
J-51 H Me F Me Cl H Methoximinoethyl H 354 at 1 35C
J-52 Cyclopropyl Me F Me Cl H CF3 H 405 at 1 35C
J-53 H Me F Me F H F H 317
J-54 H CF3 H Me Cl H CF3 H
J-55 H Fluorethyl H Me Cl H CF3 H
J-56 H Formyl H Me Cl H CF3 H
J-57 H Cl H Me Cl H CF3 H
J-58 H I H Me Cl H CF3 H
J-59 H Me H Me Cl H CF3 H
J-60 H CHC12 H Me Cl H CF3 H
J-61 H H Fluorethyl Me Cl H CF3 H
Table K
Compound R1 R38 R39 R 40 M+1
K-l H Me H t-Bu Cl H CF3 H 389 at 1 35C1 K-2 H t-Bu H Me Cl H CF3 H 334 at 1 35C1
K-3 H t-Bu H Benzyl Cl H CF3 H 465 at 1 35C1
K-4 H Me H Me Cl H CF3 H 347 at 1 35C1
K-5 H H H Ph Cl H CF3 H 395 at 1 35C1
439 at 1 35C1 -6 H Me Br Et Cl H CF3 H and 1 79Br
Table L
Compound R1 R41 R42 Y1 Y2 Y3 Y4 M+1
L-l H Me H Cl H CF3 H 394 at 1 35C1
Table M
Compound R1 R43 R 44 Yl γ2 γ3 γ4 M-1 M+1
4-methyl-
432 at
M-l H Me [l,2,3]thiadiazol- Cl H CF3 H 1 35C1
5-yl
348 at
-2 H Me Me Cl H CF3 H 1 35C1
408 at
M-3 H Ph Me Cl H CF3 H 1 35C1
444 at
1-4 H 2-chlorophenyl Me Cl H CF3 H 2 35C1
2,6- 478 at
M-5 H Me Cl H CF3 H dichlorophenyl 3 35C1
2-chloro-6- 462 at
M-6 H Me Cl H CF3 H fluorophenyl 2 35C1
444 at
M-7 H 4-chlorophenyl Me Cl H CF3 H 1 35C1
Table N
Compound R1 R45 R46 γl Y2 γ3 Y4 M+1
N-l H H H Cl H CF3 H 320 at 1 35C1
Table O
Compound R1 R48 R49 γl Y2 γ3 γ4 M+1
O-l H Me Ph Cl H CF3 H 410 at 1 35C1
Table P
Compound R1 R50 Y1 γ2 γ3 Y4 M+1
P-l H Me Cl H CF3 H 351 at 1 35C1
Table 0
10
Compound R1 R51 R52 R53 R54 Y1 Y2 Y3 Y4 M (APeI+) M+1
-l H Cl H CF3 H Cl H CF3 H 432 at 2 35C1
Q-2 H Cl H H Cl Cl H CF3 H 397 at 3 35C1
Q-3 H Me H H H Cl H CF3 H 344 at 1 35C1
Table R
Compound R1 R1 55 R 56 R 57 R58 γl γ2 γ3 γ4 M
M+1 (Apcl+)
364 at
R-l H Cl H H H Cl H CF3 H
2 35C1
R-2 H Cl H H H Cl H Cl H
390 at
R-3 H SEt H H H Cl H CF3 H 1 35C1
364 at
H H Cl H H Cl H CF3 H
2 35C1
330 at
R-5 H H H H H Cl H CF3 H 1 35C1
438 at
R-6 H SPh H H H Cl H CF3 H 1 35C1
4-chloro- 456 at
E-7 H H H H Cl H CF3 H phenoxy 2 35C1
2- 412 at
R-8 H H H H Cl H CF3 H ieny 1 1 35C1
N- 415 at
R-9 H H H H Cl H CF3 H rV [orph< 1 35C1
344 at
R-10 H Me H H H Cl H CF3 H 1 35C1 3-
402 at
R-ll H propenyl- H H H Cl H CF3 H 1 35C1 sulfinyl
M
Compound R1 R55 R56 R57 R58 Y1 γ2 Y3 Y4 M+1 (Apcl+)
404 at
R-12 H SnPr H H H Cl H CF3 H 135C1 n-pentyl- 432 at
R-13 H H H H Cl H CF3 H sulfinyl 135C1
415 at 3
R-14 H Cl Cl F H Cl H CF3 H 35C1
412 at
R-15 H Me CFj H H Cl H CF3 H 135C1
355 at
R-16 H CN H H H Cl H CF3 H 135C1
378 at
R-17 H Cl Me H H Cl H CF3 H 235C1
398 at
R-18 H CF3 H H H Cl H CF3 H 135C1
348 at
R-19 H F H H H Cl H CF3 H 135C1
398 at
R-20 H H H H CF3 Cl H CF3 H 135C1
397 at 3 398 at
R-21 H Cl Cl H H Cl H CF3 H 35C1 335C1
398 at
WX22 H Cl H Cl H Cl H CF3 H 35C1 335C1
367 at
R-23 H Cl H H H Cl H 1 -methoximinoethyl H 235C1
314 at
R-24 H Cl H H H F H Cl H 235C1
345 at
R-25 H NH2 H H H Cl H CF3 H 135C1
408 at
135C1
R-26 H Br H H H Cl H CF3 H and 1 79Br
456 at
R-27 H H H H H Cl H CF3 H 135C1
M
Compound R1 R55 R56 R57 R58 Y1 Y2 M+1 (Apcl+)
362 at
R-28 H SH H H H Cl H CF3 H 135C1
364 at
R-29 H H H H Cl H Cl H 435C1
353 at
R-30 H H H H Cl H Methoximinoethyl H 235C1
367 at
R-31 H H H H Cl H Ethoximinoethyl H 235C1
296 at
R-32 H H H H H H Cl H 235C1
418 at
-33 Cyclopropyl C H H Cl H CF3 H
235C1
466 at
R-37 H Cl H CF3 Cl H CF3 H 335C1
344 at
1-35 H Me H H F 135C1
330 at
R-36 H Me H H F H 135C1
Table S
Compound R1 R59 R60 R61 R62 γl γ2 γ3 Y4 M+1
S-l H H Cl Cl H Cl H CF3 H 398 at 3 35C1
S-2 H H Me Cl H Cl H CF3 H 378 at 2 35C1
S-3 H H OMe Cl H Cl H CF3 H 330 at 2 35C1
S-4 H H H H H Cl H CF3 H 3DO 8 1 -
S-5 H H H Cl H Cl H CF3 H 364 at 2 35C1
S-6 H NH2 H H H Cl H CF3 H 345 at 1 35C1
S-7 H I H H H Cl H CF3 H 456 at 1 35C1
408 at 1 35C1
§-8 H Br H H H Cl H CF3 H and 1 79Br
Table T
Compound R1 R1 63 R 64 γl γ2 M+1
T-l H H Benzyloxycarbonyl Cl H CF3 H 470atl 3"5/Cl
4-trifluormethyl- ,-
T-2 H H Cl H CF3 H 482atl35Cl pyrimidin-2-yl
Table ϋ
Compound R1 R65 R66 γι γ2 γ3 y4 M+1
U-l H H Benzyl Cl H CF3 H 428 at 135C1
Table V
Compound R1 R67 R68 R69 X1 Y1 γ2 γ3 Y4 M+1
V-l H Me H H S Cl H CF3 H 367 at 1 35C1
V-2 H CF3 H H S Cl H CF3 H 421 at 1 35C1
V-3 H CF3 Me H s Cl H CF3 H 435 at 1 35C1
V- H CF3 H Me s Cl H CF3 H 435 at 1 35C1
V-5 H CHF2 H H s Cl H CF3 H
V-6 H Me H H s Cl H Cl H
V-7 H Me H H s Cl H Cl Cl 521 at 3 35C1
V-8 H Me H H s Cl H Metho: ximinomethyl H 356 at 1 35C1
V-9 H Me H H s F H Cl H 3 J 8.1 1 l
V-10 H Me H H s Cl H H Cl 333 at 2 35C1
V-ll H CF3 H H s H H Me H 333
V-12 Cyclopropyl Me H H s Cl H CF3 H 407 at 1 35C1
V-13 Cyclopropyl CF3 H H s Cl H CF3 H 461 at 1 35C1
V-14 H CF3 H H s F H F F 373
V-15 H Me H H s F H F F 319
V-16 H CF3 H H s F Me F F 387
V-17 H Me H H s F Me F F 333
Examples of process for preparation of the compound of general formula (I)
Example A : Preparation of N-[2-(3-Chloro-5-trifluoromethyl-pyridϊn-2-yl)- ethyn-2-trifluoromethyl-nicotinamide
A solution of 204 mg (1 mmol) of 2-trifluormethyl nicotinic acid, 200 mg (0.9 mmol) of 2-(3-chloro-5-trifluormethyl-pyridin-2-yl)-ethylamine and 620 mg (1.3 mmol) of bromotripyrrolidinophosphonium hexafluorophosphate and 230 mg (1.8 mmol) N,N-Diisopropylethylamine in 8 ml methylene chloride is stirred for 20 h at room temperature.
The mixture is diluted with 10 ml water, separated and the methylene chloride phase is washed with sat. NH4C1 solution and water. The organic phase is dried over sodium sulfate. After evaporation of the solvent the residue is purified by column chromatography over silica-gel (eluantihexane/ethylacetate = 10:1 to 1:1). Yield: 370 mg (98%).
Example B : Preparation of 2-Chloro--V-f2-(3-£hloro-5-trifluorometfayl-pγridin- 2-vD-ethyll-6-methyl-nicotmanude
A solution of 161 mg (0.7 mmol) 2-chloro-6-methylnictotinyl chloride, 160 mg (0.7 mmol) 2-(3-chloro-5-trifluormethyl-pyridin-2-yl)-ethylamine hydrochloride and 236 mg (1.7 mmol) sodium carbonate in 8 ml acetonitrile is stirred for 3 days at room temperature.
The mixture is diluted with 5ml water and 5 ml ethylacetate, separated and the organic phase is washed with sat. NH C1 solution and water. The organic phase is dried over sodium sulfate and evaporated. Yield: 200 mg (62%).
Example C : Preparation of l-Methyl-3-trifluoromethyl-liT-pyrazole-4- carboxylic acid [2-(3-chloro-5-trifluoromethyl-pyridin-2-vI)-ethyll -amide
132 mg (3.5 mmol) of sodium borohydrate is added in small portions to a solution of 370 mg (1.0 mmol) l-methyl-3-trifluoromethyl-lH-pyrazole-4-carboxylic acid-anhydride, 110 mg (0.5 mmol) (3-chloro-5-trifluormethyl-pyridin-2-yl)- acetonitrile and 120 mg (0.5 mmol) Nickel(II) chloride hexahydrate in 5 ml of acetonitrile at 0°C. Stirring was continued at room temperature for 4 hours.
After evaporation of the solvent, the residue is purified by column chromatography over silica-gel (eluantihexane/ethylacetatβ = 10:1 to 1:1). Yield: 80 mg (40%).
Examples of biological activity of the compound of general formula (I)
Example 1: in vivo test on Alternaria brassicae (Leaf spot of crucifers):
The active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/l.This suspension is then diluted with water to obtain the desired active material concentration. Radish plants (Pernot variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18-20°C, are treated at the cotyledon stage by spraying with the aqueous suspension described above.
Plants, used as controls, are treated with an aqueous solution not containing the active material. After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of Alternaria brassicae spores (40,000 spores per cm ). The spores are collected from a 12- 13 -day-old culture.
The contaminated radish plants are incubated for 6-7 days at about 18°C, under a humid atmosphere. Grading is carried out 6 to 7 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 50%) to total protection is observed at a dose of 330ppm with the following compounds : AS, A-4, B-2, B-4, B-5, B-7, B-8, B-9, B-10, B-13, B-14, B-16, C-2, CS, C-5, C-6, C-8, C-12, C-13, C-14, C-16, C-18, C-21, C-23, D-4, D-5, ES, E-4, F-3, G-l, H-l, H-2, H-4, H-6, H-7, H-17, H-19, H- 22, H-23, 1-1, IS, J-l, J-2, J-3, J-4, J-5, J-6, J-12, J-13, J-19, J-22, J-24, J-25, J-26, JS1, J-32, J-33, J-35, J-36, JS7, J-38, JS9, J-41, J-43, J-45, J-47, J-49, J-50, J-51, J-52, J-53, J-55, KS, KS, K-6, M -2, M-4, M-5, M-6, N-1, O-l, Q-l, Q-2, R-1, R-5, R-6, R-7, R-10, R-ll, R-13, R-14, R-15, R-23, R-24, R-26, R-30, RSI, S-2, S-5, V-1, V-6, V-7, V-8, V-12.
Example 2: in vivo test on Erysiphe graminis f. sp. tritici (wheat powdery mildew):
The active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/l.This suspension is then diluted with water to obtain the desired active material concentration.
Wheat plants (Audace variety) in starter cups, sown on 50/50 peat soil-pozzolana substrate and grown at 12°C, are treated at the 1 -leaf stage (10 cm tall) by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material.
After 24 hours, the plants are contaminated by dusting them with Erysiphe graminis f. sp. tritici spores, the dusting being carried out using diseased plants. Grading is carried out 7 to 14 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 50%) to total protection is observed at a dose of 330ppm with the following compounds : A-4, B-4, B-8, C-2, C-3, C-12, D- 4, F-l, H-l, H-2, H-4, H-20, IS, J-l, J-2, JS, J-19, J-20, J-31, J-37, J-40, J-55, J- 57, J-58, J-59, J-61, K-l, M-5, M-6, R-JR-IO R-26, R-29, V-7.
Example 3: in vivo test on Botrytis cinerea (encumber Grey mould):
The active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/1. This suspension is then diluted with water to obtain the desired active material concentration.
Cucumber plants (Marketer variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18- 20°C, are treated at the cotyledon Zl l stage by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material. After 24 hours, the plants are contaminated by depositing drops of an aqueous suspension of Botrytis cinerea spores (150,000 spores per ml) on upper surface of the leaves. The spores are collected from a 15-day-old culture and are suspended in a nutrient solution composed of:
• 20 g/L of gelatin • 50 g/L of cane sugar
• 2 g/L of NH4NO3
• l g/L ofKH2PO4
The contaminated cucumber plants are settled for 5/7 days in a climatic room at 15-11°C (day/night) and at 80% relative humidity.
Grading is carried out 5/7 days after the contamination, in comparison with the control plants. Under these conditions, good (at least 50%) to total protection is observed at a dose of 330ppm with the following compounds :B-7, B-8, B-13, B-14, C-3, C-12, C-13, C-14, C-15, C-16, D-4, D-5, E-4, H-l, H-2, H-4, H-7, H-9, H-22, J- 1, J-2, JS, J-19, J-31, J-32, J-33, JS4, J-35, J-37, J-39, J-43, J-44, R-1, R-10, R-23, R-24, R-26, RSI, V-l, V-8.
Example 4: in vivo test on Pyrenophora teres (Barley Net blotch):
The active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/1. This suspension is then diluted with water to obtain the desired active material concentration.
Barley plants (Express variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 12°C, are treated at the 1-leaf stage (10 cm tall) by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material. After 24 hours, the plants are contaminated by spraying them 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 24 hours at about 20°C and at 100% relative humidity, and then for 12 days at 80% relative humidity. Grading is carried out 12 days after the contamination, in comparison with the control plants. Under these conditions, good (at least 50%) to total protection is observed at a dose of 330ppm with the following compounds : A-4, BS, B-7, B-8, B- 13, B-14, B-15, B-16, CS, C-5, C-12, C-13, C-14, C-15, C-16, C-17, C-20, C-22, C- 23, D-4, D-5, ES, E-4, FS, G-l, H-l, H-2, H-4, H-5, H-6, H-7, H-8, H-11, H-l 5, H- 17, H-l 9, H-20, H-22, H-23, 1-1, IS, J-l, J-2, JS, J-7, J-8, J-10, J-19, J-20, J-22, J- 23, J-24, J-25, J-26, J-31, J-32, J-33, J-34, J-35, J-36, J-37, J-39, J-40, J-41, J-42, J- 43, J-44, J-46, J-49, J-50, J-51, J-52, J-54, J-55, J-57, J-58, J-59, J-61, K-6, M-4, P- 1, R-1, R-9, R-10, R-14, R-15, R-23, R-26, RS0, RSI, S-2, V-1, V-7, V-8, V-ll, V-12, V-13.
Example 5: in vivo test on Peronospora brassicae (Cabbage downy mildew):
The active ingredient tested is prepared by potter homogenisation in a concentrated suspension type formulation at 100 g/1. This suspension is then diluted with water to obtain the desired active material concentration.
Cabbage plants (Eminence variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18-20°C, are treated at the cotyledon stage by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material.
After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of Peronospora brassicae spores (50,000 spores per ml). The spores are collected from infected plant. The contaminated cabbage plants are incubated for 5 days at 20°C, under a humid atmosphere.
Grading is carried out 5 days after the contamination, in comparison with the control plants.
Under these conditions, good (at least 50%) to total protection is observed at a dose of 330ppm with the following compounds :B-6,B-7, J-46 , J-59.
Under these conditions, the N-{l-ethylcarbamoyl-2-[3-chloro- 5-(trifluoromethyl)-2-pyridinyl]ethyl}-4-chlorobenzamide, the N-{l-ethylcarbamoyl- 2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl} -3-nitrobenzamide, the N- { 1 - ethylcarbamoyl-2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl}-2- bromobenzamide, the N- { 1 -methylcarbamoyl-2-[3-chloro-5-(trifluoromethyl)- 2-pyridinyl]ethyl}-4-methoxybenzamide and the N-{l-methylcarbamoyl- 2-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl } -4-phenylbenzamide disclosed by Patent Application WO 01/11965 (see respectively compounds 306, 307, 310, 315 and 316 in Table D) showed poor efficacy against Alternaria brassicae and Pyrenophora teres and no efficacy against Botrytis cinerea and Peronospora parasitica at 330 ppm.
Under these conditions, the N-{[3-chloro-5-(trifluoromethyl)-2-pyridinyl]- methyl} -5-thienylacetamide disclosed by Patent Application WO 01/11965 (see
compound 101 in table B) showed poor efficacy against Alternaria brassicae and no efficacy against Botrytis cinerea and Peronospora parasitica at 330 ppm.
Claims
Compound of general formula (I)
- X may be an oxygen atom or a sulphur atom;
- Y may be the same or different and may be a halogen atom, a nitro group, a cyano group, a hydroxy, a carboxyl group, a d-Cg-alkyl, a Cι-C6-halogeno alkyl having 1 to 5 halogen atoms, a d-Cg-alkylamino, a di-d-Cg-alkylamino, a d-Cg-alkoxy, a Cι-C -halogenoalkoxy having 1 to 5 halogen atoms, a d-Cg-alkylthio, a Ci-d- halogenoalkylthio having 1 to 5 halogen atoms, a C2-C8-alkenyloxy, a C2-d- halogenoalkenyloxy having 1 to 5 halogen atoms, a d-Cg-alkinyloxy, a C3-Cg- halogenoalkinyloxy having 1 to 5 halogen atoms, a d-Cg-cycloalkyl, a d-Cg- alkoxycarbonyl, a d-Cg-alkylsulphinyl, a d-Cg-alkylsulphonyl, a d-Cg-halo- genoalkylsulphinyl having 1 to 5 halogen atoms, a Ci-Q-halogenoalkylsulphonyl having 1 to 5 halogen atoms or a d-d-alkoximino-d-d-alkyl;
- R1 may be a hydrogen atom, a cyano group, a nitro group, a formyl group, a d-d- alkyl, a d-d-alkylcarbamoyl, a C2-C6-alkenyl, a C2-d-alkynyl, a d-d- halogenoalkyl having 1 to 7 halogen atoms, a d-d-alkoxy-d-d-alkyl, a d-d- cyanalkyl, a Ci-d-aminoalkyl, a C3-d-cycloalkyl, a Ci-d-alkylcarbonyl, a d-d- halogenalkylcarbonyl having 1 to 5 halogen atoms, a Ci-d-alkoxy-d-d- alkylcarbonyl, a d-C6-alkylsulfanyl or a Cι-C6-halogenalkylsulfanyl having 1 to 5 halogen atoms;
- n may be 1, 2, 3 or 4; and
- Het represents an optionally substituted 5-, 6- or 7-membered non-fused heterocycle with one, two or three heteroatoms which may be the same or different; Het being linked by a carbon atom.
2. A compound according to claim 1, characterised in that X represents an oxygen atom.
3. A compound according to claim 1 or 2, characterised in that n is 1 or 2.
4. A compound according to claim 3, characterised in that n is 2.
5. A compound according to any of the claims 1 to 4, characterised in that at least one of the Y substituent is a halogen atom, a Cj-Cg-alkyl, a d-d- halogenoalkyl having 1 to 5 halogen atoms or a d-Ce-alkoxy-d-d-alkylcarbonyl.
6. A compound according to claim 5, characterised in that at least one of the Y substituent is a d-d-halogenoalkyl having 1 to 5 halogen atoms.
7. A compound according to claim 6, characterised in that at least one of the Y substituent is -CF3.
8. A compound according to any of the claims 1 to 7, characterised in that the 2- pyridyl is substituted in 3- and/or in 5-position.
9. A compound according to claim 7 and 8, characterised in that the 2-pyridyl is substituted in 5-position by -CF3.
10. A compound according to any of the claims 1 to 9, characterised in that Het is a five membered ring heterocycle.
11. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (II)
12. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (III)
- R5 may be a hydrogen atom, a halogen atom , a Ci-d-alkyl or a d-d- halogenoalkyl having 1 to 5 halogen atoms; and
- R6 and R76 may be the same or different and may be a hydrogen atom, a halogen atom, an amino group, a Cj-d-alkyl or a d-d-halogenoalkyl having 1 to 5 halogen atoms.
13. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (IV)
- R may be a halogen, a Ci-d-alkyl or a Ci-d-halogenoalkyl having 1 to 5 halogen atoms; and
- R may be a hydrogen atom, a Ci-d-alkyl or a Ci-d-halogenoalkyl having 1 to 5 halogen atoms.
14. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (V)
(V) in which : - R10 and R11 may be the same or different and may be a hydrogen atom, a halogen atom, a Cι-C4-alkyl, a Cι-C4-halogenoalkyl having 1 to 5 halogen atoms, a d-d-alkylthio, a C1-C4-alkylsulphonyl a phenyl optionally substituted by a halogen atom or a C1-C4-alkyl or a pyridyl otpionally substituted by a halogen atom or a d- C4-alkyl; and
- R12 may be a hydrogen atom, a halogen atom, a cyano group, a d-C4-alkyl, a Cj-d-halogenoalkyl having 1 to 5 halogen atoms or a C1-C4-halogenoalkoxy having 1 to 5 halogen atoms.
15. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (VI)
- R and R1 may be the same or different and may be a hydrogen atom, a halogen atom, a d-d-alkyl, a Ci-d-alkyloxy or a d-d-halogenoalkyl having 1 to 5 halogen atoms; and
- R15 may be a hydrogen atom, a halogen atom, a d-d-alkyl or a d-d- halogenoalkyl having 1 to 5 halogen atoms.
16. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (VII)
- R1 may be a hydrogen atom, a halogen atom, a cyano group, a Ci-d-alkyl or a Ci-d-halogenoalkyl having 1 to 5 halogen atoms;
- R17 and R19 may be the same or different and may be a hydrogen atom, a halogen atom, a d-d-alkyl or a Ci-d-halogenoalkyl having 1 to 5 halogen atoms; and - R18 may be a hydrogen atom, a cyano group, a d-d-alkyl, a d-d- halogenoalkyl having 1 to 5 halogen atoms, a Ci-d-alkoxy-d-d-alkyl, a hydroxy- d-d-alkyl, a d-d-alkylsulphonyl, a di(Cι-C4-alkyl)aminosulphonyl, a d-d- alkylcarbonyl, a phenylsulphonyl optionally substituted by a halogen atom or a d- d-alkyl, or a benzoyl optionally substituted by a halogen atom or a Ci-d-alkyl.
17. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (VIII)
18. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (IX)
- R24 may be a hydrogen atom or a d-d-alkyl; and
- R may be a halogen atom, a d-d-alkyl or a Ci-d-halogenoalkyl having 1 to 5 halogen atoms.
19. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (X)
20. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (XI)
(XI) in which :
- R28 may be a hydrogen atom, a halogen atom, an amino group, a cyano group, a d-d-alkylamino, a di-(Cι-C4-alkyl)amino, a d-d-alkyl., a d-d- halogenoalkyl having 1 to 5 halogen atoms or a phenyl optionally substituted by a halogen atom or a d-d-alkyl; and
- R29 may be a halogen atom, a d-d-alkyl or a Ci-d-halogenoalkyl having 1 to 5 halogen atoms.
21. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (XII)
(XII) in which - R30 may be a hydrogen atom, a halogen atom, an amino group, a cyano group, a Ci-d-alkylamino, a di-(d-C4-alkyl)amino, a d-d-alkyl or a d-d- halogenoalkyl having 1 to 5 halogen atoms; and
-R31 may be a halogen atom, a d-d-alkyl or a d-d-halogenoalkyl having 1 to 5 halogen atoms.
22. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (XIII)
in which 
- R32 may be a hydrogen atom, a halogen atom, a cyano group, a nitro group, a Ci-d-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, a C3-C6- cycloalkyl, a Ci-d-alkoxy, a d-d-halogenoalkoxy having 1 to 5 halogen atoms, a d-d-alkylthio, a d-d-halogenoalkylthio having 1 to 5 halogen atoms, an aminocarbonyl group or an aminocarbonyl-d-d-alkyl;
- R may be a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C j -d-alkyl, a C \ -d-alkoxy or a C i -d-alkylthio ; and
- R34 may be a hydrogen atom, a phenyl, a C[-C4 -alkyl, a Ci-d- halogenoalkyl having 1 to 5 halogen atoms, a hydroxy-Ci-d-alkyl, a C2-d-alkenyl, a d-d-cycloalkyl, a d-d-alkylthio-d -d-alkyl, a d-d-halogenoalkylthio-d-d- alkyl having 1 to 5 halogen atoms, a d-d-alkoxy-d -d-alkyl or a d-d- halogenoalkoxy-d-d-alkyl having 1 to 5 halogen atoms.
23. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (XIV)
- R36 may be a hydrogen atom, a halogen atom, a cyano group, a d-d-alkyl, a d-d-alkoxy, a Ci-d-halogenoalkoxy having 1 to 5 halogen atoms or a d-d- alkylthio; and
- R37 may be a hydrogen atom, a d-d-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, a hydroxy-d -d-alkyl, a C2-d-alkenyl, a C3-C6-cycloalkyl, a d-d-alkylthio-d-d-alkyl, a Ci-d-halogenoalkylthio-d -d-alkyl having 1 to 5 halogen atoms, a d-d-alkoxy-Ci -d-alkyl, a Ci-d-halogenoalkoxy-d -d-alkyl having 1 to 5 halogen atoms or a phenyl optionally substituted by a halogen atom, a d-d-alkyl, a d-d-alkoxyalkyl or a nitro group.
24. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (XV)
-R38 may be a hydrogen atom, a halogen atom, a cyano group, a nitro group, a d-d-alkyl, a Ci-d-halogβnoalkyl having 1 to 5 halogen atoms, a d-d-cycloalkyl, a d-d-alkoxy, a d-d-halogenoalkoxy having 1 to 5 halogen atoms, a C1-C4- alkylthio, a Ci-d-halogenoalkylthio having 1 to 5 halogen atoms, an aminocarbonyl, or an aminocarbonyl-d-d-alkyl;
- R39 may be a hydrogen atom, a halogen atom, a cyano group, a Ci -d-alkyl, a d-d-alkoxy, a d-d-alkylthio or a Cι-C4-halogenoalky having 1 to 5 halogen atoms; - R40 may be a hydrogen atom, a phenyl, a benzyl, a d-d-alkyl, a d-d- halogenoalkyl having 1 to 5 halogen atoms, a hydroxy-d -d-alkyl, a C2-C6-alkenyl, a C3-C6-cycloalkyl, a Ci-d-alkylthio-d-d-alkyl, a d-d-halogenoalkylthio-Ci-d- alkyl having 1 to 5 halogen atoms, a Ci-d-alkoxy-Ci-d-alkyl, a d-d- halogenoalkoxy-d -d-alkyl having 1 to 5 halogen atoms.
25. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (XVI)
26. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (XVII)
in which R43 and R44 may be the same or different and may be a hydrogen atom, a halogen atom, a Ci-d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a phenyl optionally substituted by a halogen atom or a d-d -alkyl, or a heterocyclyl optionally substituted by a halogen atom or a d-C4-alkyl.
27. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (XVIII)
in which R45 and R46 may be the same or different and may be a hydrogen atom, a halogen atom, a d-C -alkyl or a Ci-d-halogenoalkyl having 1 to
5 halogen atoms.
28. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (XIX) 
in which R47 may be a halogen atom, a Ci -d-alkyl or a C1-C4- halogenoalkyl having 1 to 5 halogen atoms.
29. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (XX)
- R48 may be a halogen atom, a d-d-alkyl or a d-d-halogβnoalkyl having 1 to 5 halogen atoms; and
- R49 may be a hydrogen atom, a Ci -d-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, or a phenyl optionally substituted by a halogen atom or a C1-C4- alkyl.
30. A compound according to claim 10, characterised in that Het represents a heterocycle of the general formula (XXI)
31. A compound according to any of the claims 1 to 9, characterised in that Het is a six membered heterocycle.
32. A compound according to claim 31, characterised in that Het represents a heterocycle of the general formula (XXII) 
in which :
- R51 may be a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a d-d-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, a d-d- alkoxy, a d-d-alkylthio, a d-d-halogenoalkylthio having 1 to 5 halogen atoms or a d-d-halogenoalkoxy having 1 to 5 halogen atoms;
- R52, R53 and R54, which may be the same or different, may be a hydrogen atom, a halogen atom, a cyano group, a Ci-d-alkyl, a Ci-d-halogenoalkyl having 1 to 5 halogen atoms, a d-d-alkoxy, a Ci-d-alkylthio, a d-d-halogenoalkoxy having 1 to 5 halogen atoms, a Ci-d-alkylsulphinyl or a d-d-alkylsulphonyl.
33. A compound according to claim 31, characterised in that Het represents a heterocycle of the general formula (XXIII)
(XXIII) in which :
- R ι55 may be a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a d-d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a d-d- alkoxy, a d-C5-alkylthio, a C2-d-alkenylthio a d-d-halogenoalkylthio having 1 to 5 halogen atoms, a d-d-halogenoalkoxy having 1 to 5 halogen atoms, a phenyloxy optionally substituted by a halogen atom or a Ci -d-alkyl, or a phenylthio optionally substituted by a halogen atom or a Ci -d-alkyl;
- R , R and R , which may the same or different, may be a hydrogen atom, a halogen atom, a cyano group, a d -d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a d-d-alkoxy, a Ci-d-alkylthio, a Ci-d-halogenoalkoxy having 1 to 5 halogen atoms, a Ci-d-alkylsulphinyl, a Ci-d-alkylsulphonyl, a N-morpholine optionally substituted by a halogen atom or a Cι-C -alkyl, or a thienyl optionally substituted by a halogen atom or a Cι-C4-alkyl.
34. A compound according to claim 31, characterised in that Het represents a heterocycle of the general formula (XXIV)
(XXIV)
in which R59, R60, R61 and R62, which may be the same or different, may be a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a d-d- alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a d-d-alkoxy, a d-d- alkylthio, a d-d-halogenoalkylthio having 1 to 5 halogen atoms, a C1-C4- halogenoalkoxy having 1 to 5 halogen atoms, a Ci-d-alkylsulphinyl or a C1-C4- alkylsulphonyl.
35. A compound according to claim 31, characterised in that Het represents a heterocycle of the general formula (XXV)
- R » 63 may be a hydrogen atom, a halogen atom, a Ci-d-alkyl or a d-d- halogenoalkyl having 1 to.5 halogen atoms;
- R64 may be a hydrogen atom, a d-d-alkyl, a d-d-halogenoalkyl having 1 to 5 halogen atoms, a Cι-C6-alkoxycarbonyl, a benzyl optionally substituted by 1 to 3 halogen atoms, a benzyloxycarbonyl optionally substituted by 1 to 3 halogen atoms or a heterocyclyl.
36. A compound according to claim 31, characterised in that Het represents a heterocycle of the general formula (XXVI)
37. A compound according to claim 31, characterised in that Het represents a heterocycle of the general formula (XXVII)
- R67 may be a d-d-alkyl or a Ci-d-halogenoalkyl having 1 to 5 halogen atoms; and
- R 8 and R may be the same or different and may be a hydrogen atom or a d-d-alkyl.
38. A compound according to claim 31, characterised in that Het represents a heterocycle of the general formula (XXVIII)
(XVIII) in which :
- R70 may be a Ci-d-alkyl or a d-d-halogenoalkyl having 1 to 5 halogen atoms;
39. A compound according to claim 31, characterised in that Het represents a heterocycle of the general formula (XXIX)
(XXIX) in which : - R71 may be a Ci -d-alkyl or a Ci-d-halogenoalkyl having 1 to 5 halogen atoms.
40. A compound according to claim 31, characterised in that Het represents a heterocycle of the general formula (XXX)
41. A process for the preparation of compound of general formula (I) according to any of the claims 1 to 40, which comprises reacting a carboxylic acid derivative of the general formula (A)
- Het is as defined above;
- G may be a halogen atom, a hydroxy group or a d-d-alkoxy; with a 2-pyridine derivative of general formula (B)
42. A process according to claim 41, characterised in that the catalyst may be dicyclohexylcarbodiimide, N,N'-carbonyldimidazole, bromotripyrrolidinophosphonium hexafluorophosphate or trimethylaluminium.
43. A process according to claim 42, characterised in that the acid binder may be a carbonate, an aqueous alkali or a tertiary amine.
44. A process for the preparation of compound of general formula (I) according to any of the claims 1 to 40, which comprises reacting a carboxylic acid anhydride derivative of general formula (C)
- Het is as defined above;
- W may be defined as Het or a d-d-alkyl; with a 2-pyridine derivative of the formula (D)
45. A process according to claim 44, characterised in that the reducing agent is H2 or NaBFL.
46. Compound of general formula (E) :
47. Fungicidal composition comprising an effective amount of a compound according to any of the claims 1 to 40 and an agriculturally acceptable support.
48. Fungicidal composition according to claim 47 further comprising a surfactant.
49. Fungicidal composition according to either of claims 47 and 48, comprising from 0.05% to 99% by weight of active material.
50. Method for preventively or curatively combating the phytopathogenic fungi of crops, characterised in that an effective and non-phytotoxic amount of a composition according to any of the claims 46 to 48 is applied to the plant seeds or to the plant leaves and/or to the fruits of the plants or to the soil in which the plants are growing or in which it is desired to grow them.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI0406465A BRPI0406465B1 (en) | 2003-02-19 | 2004-02-12 | compounds, processes for the preparation of a compound, fungicidal composition and method for preventive or curative combating of phytopathogenic fungi |
| MXPA05008705A MXPA05008705A (en) | 2003-02-19 | 2004-02-12 | Pyridine derivatives as fungicidal compounds. |
| AT04710397T ATE497957T1 (en) | 2003-02-19 | 2004-02-12 | PYRIDINE DERIVATIVES AS FUNGICIDAL COMPOUNDS |
| EP04710397A EP1597252B1 (en) | 2003-02-19 | 2004-02-12 | Pyridine derivatives as fungicidal compounds |
| US10/545,364 US7754741B2 (en) | 2003-02-19 | 2004-02-12 | Pyridine derivatives as fungicidal compounds |
| CA2516186A CA2516186C (en) | 2003-02-19 | 2004-02-12 | Pyridine derivatives as fungicidal compounds |
| DE602004031326T DE602004031326D1 (en) | 2003-02-19 | 2004-02-12 | PYRIDINE DERIVATIVES AS FUNGICIDAL COMPOUNDS |
| JP2006501983A JP4630271B2 (en) | 2003-02-19 | 2004-02-12 | Pyridine derivatives as bactericidal compounds |
| KR1020057015235A KR101084022B1 (en) | 2003-02-19 | 2004-02-12 | Pyridine derivatives as fungicidal compounds |
| IL169527A IL169527A (en) | 2003-02-19 | 2005-07-04 | Pyridine derivatives and process for their preparation |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03356029A EP1449841A1 (en) | 2003-02-19 | 2003-02-19 | New fungicidal compounds |
| EP03356029.3 | 2003-02-19 |
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| Publication Number | Publication Date |
|---|---|
| WO2004074280A1 true WO2004074280A1 (en) | 2004-09-02 |
Family
ID=32731621
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2004/002381 WO2004074280A1 (en) | 2003-02-19 | 2004-02-12 | Pyridine derivatives as fungicidal compounds |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US7754741B2 (en) |
| EP (2) | EP1449841A1 (en) |
| JP (1) | JP4630271B2 (en) |
| KR (1) | KR101084022B1 (en) |
| CN (1) | CN100402525C (en) |
| AT (1) | ATE497957T1 (en) |
| BR (1) | BRPI0406465B1 (en) |
| CA (1) | CA2516186C (en) |
| DE (1) | DE602004031326D1 (en) |
| ES (1) | ES2360627T3 (en) |
| IL (1) | IL169527A (en) |
| MX (1) | MXPA05008705A (en) |
| PL (1) | PL218548B1 (en) |
| WO (1) | WO2004074280A1 (en) |
| ZA (1) | ZA200504957B (en) |
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| AR064565A1 (en) * | 2007-01-03 | 2009-04-08 | Bayer Cropscience Sa | DERIVATIVES OF N-METILCARBOXAMIDE, A PROCEDURE FOR THEIR PREPARATION, A FUNGITIVE COMPOSITION THAT UNDERSTANDS THEM AND A METHOD FOR COMBATING FITOPATOGEN FUNDS THAT USES THEM. |
| JP5341084B2 (en) | 2007-08-03 | 2013-11-13 | エフ．ホフマン−ラ ロシュ アーゲー | Pyridinecarboxamide and benzamide derivatives as TAAR1 ligands |
| TWI504395B (en) | 2009-03-10 | 2015-10-21 | Substituted 3-amino-2-mercaptoquinoline as a KCNQ2 / 3 modifier | |
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| TW201038565A (en) | 2009-03-12 | 2010-11-01 | Gruenenthal Gmbh | Substituted 2-mercapto-3-aminopyridines as KCNQ2/3 modulators |
| TWI461197B (en) | 2009-03-12 | 2014-11-21 | 2-mercaptoquinoline-3-carboxamide as a KCNQ2 / 3 modifier | |
| PL2609083T3 (en) | 2010-08-27 | 2015-07-31 | Gruenenthal Gmbh | Substituted 2-oxy-quinoline-3-carboxamides as kcnq2/3 modulators |
| EP2609084A1 (en) | 2010-08-27 | 2013-07-03 | Grünenthal GmbH | Substituted 2-amino-quinoline-3-carboxamides as kcnq2/3 modulators |
| KR101983979B1 (en) | 2010-08-27 | 2019-05-30 | 그뤼넨탈 게엠베하 | Substituted 2-oxo- and 2-thioxo-dihydroquinoline-3-carboxamides as kcnq2/3 modulators |
| JP5976649B2 (en) | 2010-09-01 | 2016-08-24 | グリュネンタール・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Substituted 1-oxo-dihydroisoquinoline-3-carboxamides as KCNQ2 / 3 modulators |
| JP6218734B2 (en) | 2012-08-30 | 2017-10-25 | 国立大学法人 東京大学 | Internal parasite control agent |
| US10076116B2 (en) * | 2013-10-16 | 2018-09-18 | Bayer Cropscience Aktiengesellschaft | N-cycloalkyl-N-(biheterocyclymethylene)-(thio)carboxamide derivatives |
| CN111484448A (en) * | 2020-05-11 | 2020-08-04 | 中国农业科学院农业质量标准与检测技术研究所 | Fluopyram hapten, preparation method and application thereof, and antibody and method for detecting fluopyram |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1386965A (en) * | 1971-03-29 | 1975-03-12 | Aron Md Samuel J | 4-nitro pyridine -1- oxide derivatives nad compositions containing the same |
| WO2000021934A1 (en) * | 1998-10-15 | 2000-04-20 | Astrazeneca Ab | Compounds |
| WO2001011965A1 (en) | 1999-08-18 | 2001-02-22 | Aventis Cropscience Gmbh | Fungicides |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1316667A (en) * | 1969-05-26 | 1973-05-09 | Xerox Corp | Benzobrazanquinone pigments |
| CA2036163C (en) * | 1990-02-14 | 2001-06-19 | Makoto Sunagawa | Novel beta-lactam compounds and their production |
| JP3005045B2 (en) * | 1990-02-14 | 2000-01-31 | 住友製薬株式会社 | Novel β-lactam compound and method for producing the same |
| WO1995006034A1 (en) * | 1993-08-24 | 1995-03-02 | Medivir Ab | Compounds and methods for inhibition of hiv and related viruses |
| PT1204643E (en) * | 1999-08-20 | 2008-09-15 | Dow Agrosciences Llc | Fungicidal heterocyclic aromatic amides and their compositions, methods of use and preparation |
| FR2827286A1 (en) * | 2001-07-11 | 2003-01-17 | Aventis Cropscience Sa | New 3,4-disubstituted pyridine-2-carboxylic acid derivatives, useful as broad-spectrum plant fungicides and medicinal antifungal agents |
-
2003
- 2003-02-19 EP EP03356029A patent/EP1449841A1/en not_active Withdrawn
-
2004
- 2004-02-12 CN CNB2004800042371A patent/CN100402525C/en not_active Expired - Fee Related
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-
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- 2005-06-17 ZA ZA200504957A patent/ZA200504957B/en unknown
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1386965A (en) * | 1971-03-29 | 1975-03-12 | Aron Md Samuel J | 4-nitro pyridine -1- oxide derivatives nad compositions containing the same |
| WO2000021934A1 (en) * | 1998-10-15 | 2000-04-20 | Astrazeneca Ab | Compounds |
| WO2001011965A1 (en) | 1999-08-18 | 2001-02-22 | Aventis Cropscience Gmbh | Fungicides |
Non-Patent Citations (1)
| Title |
|---|
| WROBEL ET AL., BULLETIN OF THE POLISH ACADEMY OF SCIENCES CHEMISTRY, vol. 35, no. 1-2, 1987, pages 21 - 29 |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1597252A1 (en) | 2005-11-23 |
| CN1751039A (en) | 2006-03-22 |
| BRPI0406465A (en) | 2005-12-06 |
| EP1597252B1 (en) | 2011-02-09 |
| IL169527A (en) | 2011-12-29 |
| KR20050101558A (en) | 2005-10-24 |
| ZA200504957B (en) | 2006-04-26 |
| US20060052366A1 (en) | 2006-03-09 |
| ATE497957T1 (en) | 2011-02-15 |
| CA2516186A1 (en) | 2004-09-02 |
| JP2006517948A (en) | 2006-08-03 |
| PL218548B1 (en) | 2014-12-31 |
| US7754741B2 (en) | 2010-07-13 |
| EP1449841A1 (en) | 2004-08-25 |
| DE602004031326D1 (en) | 2011-03-24 |
| CA2516186C (en) | 2012-07-31 |
| BRPI0406465B1 (en) | 2016-12-27 |
| ES2360627T3 (en) | 2011-06-07 |
| CN100402525C (en) | 2008-07-16 |
| JP4630271B2 (en) | 2011-02-09 |
| PL376620A1 (en) | 2006-01-09 |
| MXPA05008705A (en) | 2005-10-05 |
| KR101084022B1 (en) | 2011-11-16 |
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