Ethynylphenylamidine compound or salt thereof, method for producing same, and fungicide for agricultural and horticultural use
An object of the present invention is to provide a novel fungicide having an excellent fungicidal activity. The compound used as the fungicide of the present invention is an ethynylphenylamidine compound or a salt thereof, the compound being represented by Formula (1): wherein R 1 and R 2 are each hydrogen or C 1-12 alkyl, or R 1 and R 2 may be bonded together to form C 1-7 alkylene; R 3 is hydrogen or C 1-4 alkylthio; R 4 , R 5 , R 6 , and R 7 are each hydrogen, halogen, etc.; and R 8 is hydrogen, C 1-20 alkyl, C 3-8 cycloalkyl, C 1-4 haloalkyl, phenyl, a heterocyclic group, or —(CH 2 )n-Si(R 9 )(R 10 )(R 11 ) wherein R 9 , R 10 , and R 11 are each C 1-6 alkyl, and n is an integer of 0 or 1.
1. An ethynylphenylamidine compound or a salt thereof, the compound being represented by Formula (1):
wherein R 1 and R 2 are each hydrogen or C 1-12 alkyl, or R 1 and R 2 may be bonded together to form C 2-7 alkylene;
R 3 is hydrogen or C 1-4 alkylthio;
R 4 , R 5 , R 6 , and R 7 are each hydrogen, halogen, C 1-4 alkyl, C 1-4 haloalkyl, or C 1-4 haloalkoxy; and
R 8 is hydrogen; C 1-20 alkyl optionally substituted on the alkyl group with one or more substituents independently selected from the group consisting of C 1-4 alkoxy, hydroxy, cyano, phenyl, phenoxy, and optionally substituted heterocyclic groups; C 3-8 cycloalkyl; C 1-4 haloalkyl; phenyl optionally substituted on the phenyl ring with one to five substituents independently selected from the group consisting of halogen, C 1-6 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, and phenoxy; a heterocyclic group optionally substituted on the heterocyclic ring with one or more substituents independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, and optionally substituted heterocyclic groups; or —(CH 2 )n-Si(R 9 )(R 10 )(R 11 ) wherein R 9 , R 10 , and R 11 are each C 1-6 alkyl, and n is an integer of 0 or 1.
2. The ethynylphenylamidine compound or a salt thereof according to claim 1 , wherein the ethynylphenylamidine compound is represented by Formula (1) wherein R 3 is hydrogen.
3. The ethynylphenylamidine compound or a salt thereof according to claim 1 , wherein the ethynylphenylamidine compound is represented by Formula (1) wherein R 1 and R 2 are each C 1-12 alkyl.
4. The ethynylphenylamidine compound or a salt thereof according to claim 1 , wherein the ethynylphenylamidine compound is represented by Formula (1) wherein R 4 or R 7 is halogen or C 1-4 alkyl.
5. The ethynylphenylamidine compound according to claim 1 , wherein the ethynylphenylamidine compound is represented by Formula (1) wherein R 8 is hydrogen; C 1-12 alkyl optionally substituted on the alkyl group with one or more substituents independently selected from the group consisting of C 1-4 alkoxy, hydroxy, cyano, and phenyl; C 3-8 cycloalkyl; phenyl optionally substituted on the phenyl ring with one to five substituents independently selected from the group consisting of halogen, C 1-6 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, and phenoxy; a heterocyclic group; or —(CH 2 )n-Si(R 9 )(R 10 )(R 11 ) wherein R 9 , R 10 , R 11 , and n are as defined in claim 1 .
6. A method for producing an ethynylphenylamidine compound or a salt thereof, the compound being represented by Formula (1):
wherein R 1 and R 2 are each hydrogen or C 1-12 alkyl, or R 1 and R 2 may be bonded together to form C 2-7 alkylene;
R 3 is hydrogen or C 1-4 alkylthio;
R 4 , R 5 , R 6 , and R 7 are each hydrogen, halogen, C 1-4 alkyl, C 1-4 haloalkyl, or C 1-4 haloalkoxy; and
R 8 is hydrogen; C 1-20 alkyl optionally substituted on the alkyl group with one or more substituents independently selected from the group consisting of C 1-4 alkoxy, hydroxy, cyano, phenyl, phenoxy, and optionally substituted heterocyclic groups; C 3-8 cycloalkyl; C 1-4 haloalkyl; phenyl optionally substituted on the phenyl ring with one to five substituents independently selected from the group consisting of halogen, C 1-6 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, and phenoxy; a heterocyclic group optionally substituted on the heterocyclic ring with one or more substituents independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, and optionally substituted heterocyclic groups; or —(CH 2 )n-Si(R 9 )(R 10 )(R 11 ) wherein R 9 , R 10 , and R 11 are each C 1-6 alkyl, and n is an integer of 0 or 1;
the method comprising:
reacting a phenylamidine compound represented by Formula (2):
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are as defined above, and L is a leaving group, with an acetylene compound represented by Formula (3):
wherein R 8 is as defined above, in the presence of a palladium catalyst and a base.
7. A method for producing an ethynylphenylamidine compound or a salt thereof, the compound being represented by Formula (1):
wherein R 1 and R 2 are each hydrogen or C 1-12 alkyl, or R 1 and R 2 may be bonded together to form C 2-7 alkylene;
R 3 is hydrogen or C 1-4 alkylthio;
R 4 , R 5 , R 6 , and R 7 are each hydrogen, halogen, C 1-4 alkyl, C 1-4 haloalkyl, or C 1-4 haloalkoxy; and
R 8 is hydrogen; C 1-20 alkyl optionally substituted on the alkyl group with one or more substituents independently selected from the group consisting of C 1-4 alkoxy, hydroxy, cyano, phenyl, phenoxy, and optionally substituted heterocyclic groups; C 3-8 cycloalkyl; C 1-4 haloalkyl; phenyl optionally substituted on the phenyl ring with one to five substituents independently selected from the group consisting of halogen, C 1-6 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, and phenoxy; a heterocyclic group optionally substituted on the heterocyclic ring with one or more substituents independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, and optionally substituted heterocyclic groups; or —(CH 2 )n-Si(R 9 )(R 10 )(R 11 ) wherein R 9 , R 10 , and R 11 are each C 1-6 alkyl, and n is an integer of 0 or 1;
the method comprising:
reacting an ethynylaniline compound represented by Formula (4):
wherein R 4 , R 5 , R 6 , R 7 , and R 8 are as defined above, with an ortho-ester compound represented by Formula (5):
wherein R 3 is as defined above, and B 1 and B 2 are each C 1-4 alkyl or C 3-8 cycloalkyl, in the presence of an acid; and
reacting the produced compound with an amine compound represented by Formula (6):
wherein R 1 and R 2 are as defined above.
8. A method for producing an ethynylphenylamidine compound or a salt thereof, the compound being represented by Formula (1):
wherein R 1 and R 2 are each hydrogen or C 1-12 alkyl, or R 1 and R 2 may be bonded together to form C 2-7 alkylene;
R 3 is hydrogen or C 1-4 alkylthio;
R 4 , R 5 , R 6 , and R 7 are each hydrogen, halogen, C 1-4 alkyl, C 1-4 haloalkyl, or C 1-4 haloalkoxy; and
R 8 is hydrogen; C 1-20 alkyl optionally substituted on the alkyl group with one or more substituents independently selected from the group consisting of C 1-4 alkoxy, hydroxy, cyano, phenyl, phenoxy, and optionally substituted heterocyclic groups; C 3-8 cycloalkyl; C 1-4 haloalkyl; phenyl optionally substituted on the phenyl ring with one to five substituents independently selected from the group consisting of halogen, C 1-6 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, and phenoxy; a heterocyclic group optionally substituted on the heterocyclic ring with one or more substituents independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, and optionally substituted heterocyclic groups; or —(CH 2 )n-Si(R 9 )(R 10 )(R 11 ) wherein R 9 , R 10 , and R 11 are each C 1-6 alkyl, and n is an integer of 0 or 1;
the method comprising:
reacting an ethynylaniline compound represented by Formula (4):
wherein R 4 , R 5 , R 6 , R 7 , and R 8 are as defined above, with an amide compound represented by Formula (7):
wherein R 1 , R 2 , and R 3 are as defined above, in the presence of a halogenating agent.
9. A method for producing an ethynylphenylamidine compound or a salt thereof, the compound being represented by Formula (1):
wherein R 1 and R 2 are each hydrogen or C 1-12 alkyl, or R 1 and R 2 may be bonded together to form C 2-7 alkylene;
R 3 is hydrogen or C 1-4 alkylthio;
R 4 , R 5 , R 6 , and R 7 are each hydrogen, halogen, C 1-4 alkyl, C 1-4 haloalkyl, or C 1-4 haloalkoxy;
R 8 is hydrogen; C 1-20 alkyl optionally substituted on the alkyl group with one or more substituents independently selected from the group consisting of C 1-4 alkoxy, hydroxy, cyano, phenyl, phenoxy, and optionally substituted heterocyclic groups; C 3-8 cycloalkyl; C 1-4 haloalkyl; phenyl optionally substituted on the phenyl ring with one to five substituents independently selected from the group consisting of halogen, C 1-6 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, and phenoxy; a heterocyclic group optionally substituted on the heterocyclic ring with one or more substituents independently selected from the group consisting of halogen, C 1-4 alkyl, C 1-4 haloalkyl, and optionally substituted heterocyclic groups; or —(CH 2 )n-Si(R 9 )(R 10 )(R 11 ) wherein R 9 , R 10 , and R 11 are each C 1-6 alkyl, and n is an integer of 0 or 1;
the method comprising:
reacting an ethynylaniline compound represented by Formula (4):
wherein R 4 , R 5 , R 6 , R 7 , and R 8 are as defined above, with an aminoacetal compound represented by Formula (8):
wherein R 1 , R 2 , R 3 , B 1 , and B 2 are as defined above, in the presence of an acid.
10. An agricultural and horticultural fungicide comprising the ethynylphenylamidine compound or a salt thereof according to claim 1 as an active ingredient.