Method for producing alkylated aromatic amide derivative

1. A method for producing an alkylated aromatic amide of the following Formula (4), the method comprising a process of allowing an aromatic amide of the following Formula (1) and a haloalkyl compound of the following Formula (3) to react with each other in the presence of a base and a metal salt selected from the group consisting of iron metal salts showing a valency of two, copper metals showing a valency of one, and samarium (II) iodide:

wherein, in Formula (1), each X is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a C1-C4 alkoxy group, or a dimethylamino group;

m is an integer from 1 to 4, and n1 is an integer from 1 to 4;

G 1 is an oxygen atom or a sulfur atom;

Y is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsulfonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, or an acetylamino group;

A is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsulfonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, a C1-C4 alkylaminocarbonyl group, a methylsulfinyl C1-C4-alkylamino-carbonyl group, a methylsulfonyl C1-C4-alkylamino-carbonyl group, an acetylamino group, or

an unsubstituted phenyl group, or a phenyl group having one or more substituents, which may be the same or different, selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsulfonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, an acetylamino group, and a phenyl group, or

an unsubstituted heterocyclic group, or a heterocyclic group having one or more substituents, which may be the same or different, selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsulfonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, an acetylamino group, and a phenyl group, or

a group of the following Formula (2):

wherein, in Formula (2), G 2 is an oxygen atom or a sulfur atom;

R 1 is a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group; and

Q 1 is a C1-C6 alkyl group, a C1-C6 haloalkyl group, or

an unsubstituted phenyl group, or a phenyl group having one or more substituents, which may be the same or different, selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsulfonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, an acetylamino group, and a phenyl group, or

an unsubstituted heterocyclic group, or a heterocyclic group having one or more substituents, which may be the same or different, selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsulfonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, an acetylamino group, and a phenyl group; and

the heterocyclic group in A of Formula (1) and in Q 1 of Formula (2) is a pyridyl group, a pyridin-N-oxide group, a pyrimidinyl group, a pyridazyl group, a pyrazyl group, a furyl group, a thienyl group, an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a triazolyl group, a pyrrolyl group, a pyrazolyl group, or a tetrazolyl group:

Z 1 —Xa  (3)

wherein, in Formula (3), Z 1 is a C1-C6 alkyl group or a C1-C4 haloalkyl group; and Xa is an iodine atom or a bromine atom:

wherein, in Formula (4), n2 is an integer from 1 to 4; Z 1 has the same definition as Z 1 in Formula (3), and X, m, G 1 , Y, and A have the same definitions as X, m, G 1 , Y, and A in Formula (1), respectively.

2. The production method according to claim 1 , wherein the aromatic amide of Formula (1) is an aromatic amide of the following Formula (5) and the alkylated aromatic amide of Formula (4) is an alkylated aromatic amide of the following Formula (6):

wherein, in Formula (5), each of Y 1 , Y 2 , Y 3 , and Y 4 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, or a C1-C4 haloalkylsulfonyl group;

and X, m, G 1 , and A have the same definitions as X, m, G 1 , and A in Formula (1), respectively:

wherein, in Formula (6), Z 1 has the same definition as Z 1 in Formula (3); and Y 1 , Y 2 , Y 3 , Y 4 , X, m, G 1 , and A have the same definitions as Y 1 , Y 2 , Y 3 , Y 4 , X, m, G 1 , and A in Formula (5), respectively.

3. The production method according to claim 2 , wherein the aromatic amide of Formula (5) is an aromatic amide of the following Formula (7) and the alkylated aromatic amide of Formula (6) is an alkylated aromatic amide of the following Formula (8):

wherein, in Formula (7), G 2 , Q 1 , and R 1 have the same definitions as G 2 , Q 1 , and R 1 in Formula (2), respectively; and X, m, G 1 , Y 1 , Y 2 , Y 3 , and Y 4 have the same definitions as X, m, G 1 , Y 1 , Y 2 , Y 3 , and Y 4 in Formula (5) above, respectively:

wherein, in Formula (8), Z 1 has the same definition as Z 1 in Formula (3); and Y 1 , Y 2 , Y 3 , Y 4 , X, m, G 1 , G 2 , Q 1 , and R 1 have the same definitions as Y 1 , Y 2 , Y 3 , Y 4 , X, m, G 1 , G 2 , Q 1 , and R 1 in Formula (7), respectively.

4. A method for producing a halogenated aromatic amide of the following Formula (10), the method comprising:

a process of obtaining an alkylated aromatic amide of Formula (8) by the production method according to claim 3 , and

a process of halogenating the alkylated aromatic amide of Formula (8) under a basic condition:

wherein, in Formula (10), Z 2 is a halogen atom; and X, m, G 1 , G 2 , Q 1 , R 1 , Y 1 , Y 2 , Y 3 , and Z 1 have the same definitions as X, m, G 1 , G 2 , Q 1 , R 1 , Y 1 , Y 2 , Y 3 , and Z 1 in Formula (8), respectively; and

wherein, in Formula (8), Y 4 is a hydrogen atom.

5. An aromatic amide of the following Formula (7):

wherein, in Formula (7), each X is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a C1-C4 alkoxy group, or a dimethylamino group;

m is an integer from 1 to 4;

each of G 1 and G 2 is an oxygen atom;

Y 1 is a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, or a C1-C4 haloalkylsulfonyl group, each of Y 2 and Y 3 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group, Y 4 is a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, or a C1-C4 haloalkylsulfonyl group, provided that at least one of Y 1 or Y 4 is not a hydrogen atom;

R 1 is a C1-C6 alkyl group or a C1-C6 haloalkyl group;

Q 1 is a C1-C6 alkyl group, a C1-C6 haloalkyl group, or

an unsubstituted phenyl group, or a phenyl group having one or more substituents, which may be the same or different, selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsufonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, an acetylamino group, and a phenyl group, or

an unsubstituted heterocyclic group, or a heterocyclic group having one or more substituents, which may be the same or different, selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsulfonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, an acetylamino group, and a phenyl group; and

the heterocyclic group is a pyridyl group, a pyridin-N-oxide group, a pyrimidinyl group, a pyridazyl group, a pyrazyl group, a furyl group, a thienyl group, an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a triazolyl group, a pyrrolyl group, a pyrazolyl group, or a tetrazolyl group.

6. An alkylated aromatic amide of the following Formula (9):

wherein, in Formula (9), each X is a fluorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, a C1-C4 alkoxy group, or a dimethylamino group;

m is an integer from 1 to 3;

each of G 1 and G 2 is an oxygen atom;

each of Y 1 , Y 2 , and Y 3 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, or a C1-C4 haloalkylsulfonyl group;

Z 1 is a C1-C6 haloalkyl group;

R 1 is a C1-C6 alkyl group or a C1-C6 haloalkyl group;

Q 1 is a C1-C6 haloalkyl group, or

an unsubstituted phenyl group, or a phenyl group having one or more substituents, which may be the same or different, selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsulfonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, an acetylamino group, and a phenyl group, or

an unsubstituted heterocyclic group, or a heterocyclic group having one or more substituents, which may be the same or different, selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsulfonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, an acetylamino group, and a phenyl group; and

the heterocyclic group is a pyridyl group, a pyridin-N-oxide group, a pyrimidinyl group, a pyridazyl group, a pyrazyl group, a furyl group, a thienyl group, an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a triazolyl group, a pyrrolyl group, a pyrazolyl group, or a tetrazolyl group.

7. The alkylated aromatic amide according to claim 6 , wherein, in Formula (9), Y 1 is a C1-C2 haloalkyl group, each of Y 2 and Y 3 is a hydrogen atom, Z 1 is a C1-C6 fluoroalkyl group, and X is a halogen atom.

8. An aromatic amide of the following Formula (7′):

wherein, in Formula (7′), each of G 1 and G 2 is an oxygen atom;

Y 1 is a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, or a C1-C4 haloalkylsulfonyl group, each of Y 2 and Y 3 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group, Y 4 is a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, or a C1-C4 haloalkylsulfonyl group, provided that at least one of Y 1 or Y 4 is not a hydrogen atom;

R 1 is a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group;

Q 1 is a C1-C6 alkyl group, a C1-C6 haloalkyl group, or

an unsubstituted phenyl group, or a phenyl group having one or more substituents, which may be the same or different, selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsufonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, an acetylamino group, and a phenyl group, or

an unsubstituted heterocyclic group, or a heterocyclic group having one or more substituents, which may be the same or different, selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 haloalkenyl group, a C2-C4 alkynyl group, a C2-C4 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a C1-C4 haloalkylthio group, a C1-C4 alkylsulfinyl group, a C1-C4 haloalkylsulfinyl group, a C1-C4 alkylsulfonyl group, a C1-C4 haloalkylsulfonyl group, an arylsulfonyl group, a C1-C4 alkylamino group, a di-C1-C4-alkylamino group, a cyano group, a nitro group, a hydroxyl group, a C1-C4 alkylcarbonyl group, a C1-C4 haloalkylcarbonyl group, a C1-C4 alkylcarbonyloxy group, a C1-C4 alkoxycarbonyl group, an acetylamino group, and a phenyl group; and

the heterocyclic group is a pyridyl group, a pyridin-N-oxide group, a pyrimidinyl group, a pyridazyl group, a pyrazyl group, a furyl group, a thienyl group, an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a triazolyl group, a pyrrolyl group, a pyrazolyl group, or a tetrazolyl group.

9. The alkylated aromatic amide according to claim 7 , wherein, in Formula (9), Y 1 is a trifluoromethyl group, each of Y 2 and Y 3 is a hydrogen atom, Z 1 is a heptafluoroisopropyl group, and X is a halogen atom.