Pesticide thiazolyloxy substituted phenylamidine derivatives
View Patent ↗The present invention relates to aryloxy substituted phenylamidine derivatives of formula (I) wherein the substituents are as in the description, their process of preparation, their use as fungicide or insecticide active agents, particularly in the form of fungicide or insecticide compositions, and methods for the control of phytopathogenic fungi or damaging insects, notably of plants, using these compounds or compositions (I).
1. A phenyl-amidine derivative of formula (I):
wherein
R 1 represents H, a substituted or non substituted C 1 -C 12 -alkyl, a substituted or non substituted C 2 -C 12 -alkenyl, a substituted or non substituted C 2 -C 12 -alkynyl, SH or a substituted or non substituted S—C 1 -C 12 -alkyl;
R 2 represents methyl;
R 3 represents a substituted or non substituted C 2 -C 12 -alkyl, substituted or non substituted C 3 -C 6 -cycloalkyl, substituted or non substituted C 2 -C 12 -alkenyl, substituted or non substituted C 2 -C 12 -alkynyl, halogeno-C 1 -C 12 -alkyl; or
R 1 and R 2 , R 1 and R 3 or R 2 and R 3 can form together a substituted or non substituted 5- to 7-membered heterocycle;
R 4 represents a substituted or non substituted C 1 -C 12 -alkyl, a halogen atom, halogeno-C 1 -C 12 -alkyl, substituted or non substituted 0-C 1 -C 12 -alkyl or cyano;
R 5 represents H, a substituted or non substituted C 1 -C 12 -alkyl, a halogen atom, halogeno-C 1 -C 12 -alkyl, substituted or non substituted O—C 1 -C 12 -alkyl or cyano;
R 6 represents a heterocycle selected from the group consisting of
wherein
R 7 represents H, halogen, nitro, cyano; substituted or non substituted phenyl, substituted or non substituted benzyl; C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, C 1 -C 6 -halo-genalkyl, C 1 -C 6 -halogen-alkoxy or C 1 -C 6 -halogenalkylthio; C 1 -C 8 -alkyl-S(O) m R 11 ; C 1 -C 8 -alkyl-SO 2 NR 12 R 13 ; C 1 -C 8 -alkyl-COR 14 ; —CR 15 ═N—O—R 16 , S(O) m R 11 , SO 2 NR 12 R 13 , COR 14 ;
R 8 represents H, halogen, cyano; substituted or non substituted phenyl, substituted or non substituted benzyl; C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, C 1 -C 6 -halo-genalkyl, C 1 -C 6 -halogenalkoxy or C 1 -C 6 -halogenalkylthio; C 1 -C 8 -alkyl-COR 14 ; —CR 15 ═N—O—R 16 , COR 14 ;
R 7 and R 8 can form a carbocycle, which can be saturated, unsaturated or aromatic and substituted or non substituted by halogen, C 1 -C 4 -alkyl, C 1 -C 4 -halogenalkyl, or C 1 -C 4 -alkoxyalkyl;
R 9 represents H, halogen, cyano; phenyl substituted by F, Cl, Br, I, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy; substituted or non substituted benzyl; C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, C 1 -C 6 -halo-genalkyl, C 1 -C 6 -halogenalkoxy or C 1 -C 6 -halogenalkylthio; C 1 -C 8 -alkyl-COR 14 ; —CR 15 ═N—O—R 16 , COR 14 ;
R 10 represents H, halogen, cyano; substituted or non substituted phenyl, substituted or non substituted benzyl, substituted or non substituted pyridyl; C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, C 1 -C 6 -halogenalkyl, C 1 -C 6 -halogenalkoxy or C 1 -C 6 -halogenalkylthio; C 1 -C 8 -alkyl-S(O) m R 11 ; C 1 -C 8 -alkyl-SO 2 NR 12 R 13 ; C 1 -C 8 -alkyl-COR 14 ; —CR 15 ═N—O—R 16 , S(O) m R 11 , SO 2 NR 12 R 13 , COR 14 ;
m represents 0, 1 or 2;
R 11 represents C 1 -C 8 -alkyl, C 3 -C 6 -cycloalkyl;
R 12 represents H, C 1 -C 8 -alkyl, C 3 -C 6 -cycloalkyl;
R 13 represents H, C 1 -C 8 -alkyl, C 3 -C 6 -cycloalkyl;
R 14 represents H, substituted or non substituted, branched or linear C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy;
R 15 represents H, C 1 -C 8 -alkyl, C 3 -C 6 -cycloalkyl;
R 16 represents H, C 1 -C 8 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 8 -alkoxy, substituted or non substituted benzyl;
R 12 and R 13 can form a 5- or 6-membered heterocycle, which can further comprise one or more heteroatoms selected in the group consisting of O, N, and S;
R 15 and R 16 can form a heterocyclic 5- or 6-membered ring, optionally including at least one further heteroatom;
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
2. A phenyl-amidine derivative of formula (I) according to claim 1 wherein
R 1 represents H, C 1 -C 12 -alkyl or SH; or
R 2 represents methyl; or
R 3 represents C 2 -C 12 -alkyl, C 2 -C 12 -alkenyl; C 3 -C 6 -cycloalkyl; or
R 2 and R 3 can form together a substituted or non substituted 5- to 7-membered heterocycle; or
R 4 represents C 1 -C 12 -alkyl, a halogen atom or trifluoromethyl; or
R 5 represents H, C 1 -C 12 -alkyl, a halogen atom or trifluoromethyl; or
R 7 represents H, Cl, Br, I, nitro, cyano; phenyl; phenyl substituted by F, Cl, Br, I, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy; benzyl; benzyl substituted by F, Cl, Br, I, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy; C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -halo-genalkyl, C 1 -C 4 -halogenalkoxy or C 1 -C 4 -halogenalkylthio; C 1 -C 4 -alkyl-S(O) m R 11 ; C 1 -C 4 -alkyl-SO 2 NR 12 R 13 ; C 1 -C 4 -alkyl-COR 14 ; —CR 15 ═N—O—R 16 , S(O) m R 11 , SO 2 NR 12 R 13 , COR 14 ; or
R 8 represents H, Cl, Br, I, cyano; phenyl; phenyl substituted by F, Cl, Br, I, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy; benzyl; benzyl substituted by F, Cl, Br, I, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy; C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkyl-thio, C 1 -C 4 -halo-genalkyl, C 1 -C 4 -halogenalkoxy or C 1 -C 4 -halogenalkylthio; C 1 -C 4 -alkyl-COR 14 ; —CR 15 ═N—O—R 16 , COR 14 ; or
R 9 represents Cl, Br, I, cyano; phenyl substituted by F, Cl, Br, I, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy; benzyl; benzyl substituted by F, Cl, Br, I, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy; C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -halogenalkyl, C 1 -C 4 -halogenalkoxy or C 1 -C 4 -halogenalkylthio; C 1 -C 4 -alkyl-COR 14 ; —CR 15 ═N—O—R 16 , COR 14 ; or
R 10 represents H, Cl, Br, I, cyano; phenyl; phenyl substituted by F, Cl, Br, I, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy; benzyl; benzyl substituted by F, Cl, Br, I, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy; pyridyl; pyridyl substituted by F, Cl, Br, I, C 1 -C 4 -alkyl, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy; C 1 -C 6 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -halogenalkyl, C 1 -C 4 -halogenalkoxy or C 1 -C 4 -halogen-alkylthio; C 1 -C 4 -alkyl-S(O) m R 11 ; C 1 -C 4 -alkyl-SO 2 NR 12 R 13 ; C 1 -C 4 -alkyl-COR 14 ; —CR 15 ═N—O—R 16 , S(O) m R 11 , SO 2 NR 12 R 13 , COR 14 ; or
R 15 represents H, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl; or
R 16 represents H, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, benzyl; benzyl substituted by halogen, C 1 -C 4 -alkyl or C 1 -C 4 -halogenoalkyl
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
3. A phenyl-amidine derivative of formula (I) according to claim 1 wherein
R 1 represents H or C 1 -C 12 -alkyl; or
R 3 represents a non substituted C 2 -C 4 -alkyl, C 3 -C 4 -alkenyl or cyclopropyl; or
R 2 and R 3 can form together a 6-membered heterocycle; or
R 4 represents a non substituted C 1 -C 12 -alkyl, a fluorine or a chlorine atom; or
R 5 represents a non substituted C 1 -C 12 -alkyl, a fluorine or a chlorine atom
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
4. A phenyl-amidine derivative of formula (I) according to claim 1 wherein
R 1 represents H or methyl; or
R 3 represents ethyl, n-propyl, i-propyl, propenyl or allyl; or
R 2 and R 3 can form together a pipiridinyl or a pyrolidinyl; or
R 4 represents methyl and ethyl; or
R 5 represents methyl or ethyl
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
5. A phenyl-amidine derivative of formula (I)
wherein
R 1 represents H, a substituted or non substituted C 1 -C 12 -alkyl, a substituted or non substituted C 2 -C 12 -alkenyl, a substituted or non substituted C 2 -C 12 -alkynyl, SH, or a substituted or non substituted S—C 1 -C 12 -alkyl;
R 2 and R 3 form together a 2-alkylated-pyrolidinyl;
R 4 represents a substituted or non substituted C 1 -C 12 -alkyl, a halogen atom, halogeno-C 1 -C 12 -alkyl, substituted or non substituted O—C 1 -C 12 -alkyl, or cyano;
R 5 represents H, a substituted or non substituted C 1 -C 12 -alkyl, a halogen atom, halogeno-C 1 -C 12 -alkyl, substituted or non substituted O—C 1 -C 12 -alkyl, or cyano;
R 6 represents a heterocycle selected from the group consisting of
R 7 represents H, halogen, nitro, cyano, substituted or non substituted phenyl, substituted or non substituted benzyl, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, C 1 -C 6 -halo-genalkyl, C 1 -C 6 -halogen-alkoxy, C 1 -C 6 -halogenalkylthio, C 1 -C 8 -alkyl-S(O) m R 11 , C 1 -C 8 -alkyl-SO 2 NR 12 R 13 , C 1 -C 8 -alkyl-COR 14 , —CR 15 ═N—O—R 16 , S(O) m R 11 , SO 2 NR 12 R 13 , or COR 14 ;
R 8 represents H, halogen, cyano, substituted or non substituted phenyl, substituted or non substituted benzyl, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, C 1 -C 6 -halo-genalkyl, C 1 -C 6 -halogenalkoxy, C 1 -C 6 -halogenalkylthio, C 1 -C 8 -alkyl-COR 14 , —CR 15 ═N—O—R 16 , or COR 14 ;
R 7 and R 8 can form a carbocycle, which can be saturated, unsaturated or aromatic and substituted or non substituted by halogen, C 1 -C 4 -alkyl, C 1 -C 4 -halogenalkyl, or C 1 -C 4 -alkoxyalkyl;
R 9 represents H, halogen, cyano, substituted phenyl, substituted or non substituted benzyl, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, C 1 -C 6 -halogenalkyl, C 1 -C 6 -halogenalkoxy, C 1 -C 6 -halogenalkylthio, C 1 -C 8 -alkyl-COR 14 , —CR 15 ═N—O—R 16 , or COR 14 ;
R 10 represents H, halogen, cyano, substituted or non substituted phenyl, substituted or non substituted benzyl, substituted or non substituted pyridyl, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, C 1 -C 6 -halogenalkyl, C 1 -C 6 -halogenalkoxy, C 1 -C 6 -halogenalkylthio, C 1 -C 8 -alkyl-S(O) m R 11 , C 1 -C 8 -alkyl-SO 2 NR 12 R 13 , C 1 -C 8 -alkyl-COR 14 , —CR 15 ═N—O—R 16 , S(O) m R 11 , SO 2 NR 12 R 13 , or COR 14 ;
m represents 0, 1, or 2;
R 11 represents C 1 -C 8 -alkyl or C 3 -C 6 -cycloalkyl;
R 12 represents H, C 1 -C 8 -alkyl or C 3 -C 6 -cycloalkyl;
R 13 represents H, C 1 -C 8 -alkyl or C 3 -C 6 -cycloalkyl;
R 14 represents H, substituted or non substituted, branched or linear C 1 -C 8 -alkyl, or C 1 -C 8 -alkoxy;
R 15 represents H, C 1 -C 8 -alkyl or C 3 -C 6 -cycloalkyl;
R 16 represents H, C 1 -C 8 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 8 -alkoxy, or substituted or non substituted benzyl;
R 12 and R 13 can form a 5- or 6-membered heterocycle, which can further comprise one or more heteroatoms selected in the group consisting of O, N, and S;
R 15 and R 16 can form a heterocyclic 5- or 6-membered ring, optionally including at least one further heteroatom;
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
6. A phenyl-amidine derivative of formula (I) according to claim 5 wherein R 2 and R 3 form together a 2-methyl-pyrolidinyl
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
7. A phenyl-amidine derivative of formula (I) according to claim 1 , wherein
R 1 represents hydrogen;
R 2 represents methyl;
R 3 represents ethyl, n-propyl, i-propyl, propenyl or allyl;
R 4 represents methyl or ethyl; and
R 5 represents methyl or ethyl
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
8. A phenyl-amidine derivative of formula (I) according to claim 1 , wherein
R 1 represents hydrogen;
R 2 represents methyl;
R 3 represents ethyl;
R 4 represents methyl; and
R 5 represents methyl
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
9. A phenyl-amidine derivative of formula (I) according to claim 1 , wherein
R 1 represents hydrogen;
R 2 represents methyl;
R 3 represents ethyl;
R 4 represents methyl;
R 5 represents methyl; and
R 6 represents the following:
wherein R 9 represents phenyl substituted by F, Cl, Br, I, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
10. A phenyl-amidine derivative of formula (I) according to claim 9 , wherein
R 9 represents phenyl substituted by F, Cl, Br, or I
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
11. A phenyl-amidine derivative of formula (I) according to claim 10 , wherein
R 9 represents phenyl substituted by Cl or Br or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
12. A phenyl-amidine derivative of formula (I) according to claim 1 , wherein
R 1 represents hydrogen;
R 2 represents methyl;
R 3 represents i-Pr;
R 4 represents methyl;
R 5 represents methyl; and
R 6 represents the following:
wherein R 10 represents CF 3
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
13. A phenyl-amidine derivative of formula (I) according to claim 5 , wherein
R 1 represents hydrogen;
R 4 represents methyl; and
R 5 represents methyl;
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
14. A phenyl-amidine derivative of formula (I) according to claim 1 , wherein
R 1 represents hydrogen;
R 2 represents methyl;
R 3 represents ethyl, propyl, i-Pr, n-Pr, or butyl;
R 4 represents methyl;
R 5 represents H or methyl; and
R 6 represents the following:
15. A phenyl-amidine derivative of formula (I):
wherein
R 1 represents H, a substituted or non substituted C 1 -C 12 -alkyl, a substituted or non substituted C 2 -C 12 -alkenyl, a substituted or non substituted C 2 -C 12 -alkynyl, SH, or a substituted or non substituted S—C 1 -C 12 -alkyl;
R 2 represents methyl;
R 3 represents a substituted or non substituted C 2 -C 12 -alkyl, substituted or non substituted C 3 -C 6 -cycloalkyl, substituted or non substituted C 2 -C 12 -alkenyl, substituted or non substituted C 2 -C 12 -alkynyl, halogeno-C 1 -C 12 -alkyl; or
R 1 and R 2 , R 1 and R 3 , or R 2 and R 3 can form together a substituted or non substituted 5- to 7-membered heterocycle;
R 4 represents a substituted or non substituted C 1 -C 12 -alkyl, a halogen atom, halogeno-C 1 -C 12 -alkyl, substituted or non substituted 0-C 1 -C 12 -alkyl, or cyano;
R 5 represents H, a substituted or non substituted C 1 -C 12 -alkyl, a halogen atom, halogeno-C 1 -C 12 -alkyl, substituted or non substituted O—C 1 -C 12 -alkyl, or cyano;
R 6 represents the following:
wherein
R 9 represents H, halogen, cyano, phenyl substituted by F, Cl, Br, I, C 1 -C 4 -halogenoalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -halogenoalkoxy; substituted or non substituted benzyl, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio, C 1 -C 6 -halo-genalkyl, C 1 -C 6 -halogenalkoxy, C 1 -C 6 -halogenalkylthio, C 1 -C 8 -alkyl-COR 14 , —CR 15 ═N—O—R 16 , or COR 14 ;
R 14 represents H, substituted or non substituted, branched or linear C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy;
R 15 represents H, C 1 -C 8 -alkyl or C 3 -C 6 -cycloalkyl;
R 16 represents H, C 1 -C 8 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 8 -alkoxy, or substituted or non substituted benzyl; and
R 15 and R 16 can form a heterocyclic 5- or 6-membered ring, optionally including at least one further heteroatom;
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
16. A phenyl-amidine derivative of formula (I) according to claim 15 , wherein
R 1 represents hydrogen;
R 2 represents methyl;
R 3 represents methyl, ethyl, propyl, i-Pr, n-Pr, or butyl;
R 4 represents methyl;
R 5 represents methyl; and
R 9 represents a phenyl substituted by F, Cl, Br, or I;
or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
17. A phenyl-amidine derivative of formula (I) according to claim 16 , wherein R 9 is phenyl substituted by chlorine or bromine; or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof.
18. A method for controlling phytopathogenic fungi of crops, comprising applying an agronomically effective and substantially non-phytotoxic quantity of a phenyl-amidine derivative or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof according to claim 1 to soil where a plant is growing or is capable of growing, to leaves and/or to fruit of a plant or to seeds of a plant.
19. A method for controlling damaging insects comprising applying a phenyl-amidine derivative of formula (I) or a salt, an N-oxyde, a metallic complex, a metalloidic complex and/or an optically active or geometric isomer thereof according to claim 1 to seed, a plant and/or to fruit of a plant or to soil wherein a plant is growing or wherein said plant is desired to grow.