Method for producing 3-arylpropionamide compound and 3-arylpropionic acid ester compound

Patent metadata

Field	Value
Publication number	US-11028056-B2
Application number	US-201816616596-A
Country	US
Kind code	B2
Filing date	May 30, 2018
Priority date	May 31, 2017
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

Abstract

The present invention provides a method for industrially producing: a pyrimidine compound having pest control efficacy; 2-[4-(trifluoromethyl)phenyl]ethylamine which is a production intermediate of the pyrimidine compound; a phenylethylamine compound useful as a pharmaceutical and agrochemical intermediate; and further a 3-arylpropionamide compound and a 3-arylpropionic acid ester compound useful as production intermediates of the phenylethylamine compound. The 3-arylpropionamide compound or the 3-arylpropionic acid ester compound can be efficiently and industrially produced in a single step by reacting a compound represented by formula (1)(wherein X represents a chlorine atom or a bromine atom; and Y represents an alkyl group optionally substituted with fluorine atom(s), a hydrogen atom, a fluorine atom, a cyano group, an alkylcarbonyl group, a dialkylamino group, or the like) with acrylamide or an acrylic acid ester in the presence of a metal catalyst and a reducing agent.

First claim

The invention claimed is:

1. A method for producing a compound represented by formula (2)

(wherein
Y represents an alkyl group optionally substituted with fluorine atom(s), an alkoxy group optionally substituted with fluorine atom(s), an alkoxyalkyl group optionally substituted with fluorine atom(s), an alkylthio group optionally substituted with fluorine atom(s), an alkylsulfonyl group optionally substituted with fluorine atom(s), a hydrogen atom, a fluorine atom, a cyano group, an alkylcarbonyl group, or a dialkylamino group; and
Z represents a NH 2
the method comprising
Step (a): reacting a compound represented by formula (1)

(wherein X represents a chlorine atom; and Y is the same as defined above)
with a compound represented by formula (5)

(wherein Z is the same as defined above)
in the presence of a nickel compound and zinc to produce the compound represented by formula (2).

2. A method for producing a compound represented by formula (2a)

(wherein Y represents an alkyl group optionally substituted with fluorine atom(s), an alkoxy group optionally substituted with fluorine atom(s), an alkoxyalkyl group optionally substituted with fluorine atom(s), an alkylthio group optionally substituted with fluorine atom(s), an alkylsulfonyl group optionally substituted with fluorine atom(s), a hydrogen atom, a fluorine atom, a cyano group, an alkylcarbonyl group, or a dialkylamino group)
the method comprising the following Step (a-1) and Step (b);
Step (a-1): reacting a compound represented by formula (1)

(wherein X represents a chlorine atom; and Y is the same as defined above)
with a compound represented by formula (5b)

(wherein R 2 represents a methyl group or an ethyl group)
in the presence of a nickel compound and zinc to produce a compound represented by formula (2b)

(wherein Y and R 2 are the same as defined above); and
Step (b): reacting the compound represented by formula (2b) with formamide in the presence of a strong base to produce the compound represented by formula (2a).

3. A method for producing a compound represented by formula (3)

(wherein Y represents an alkyl group optionally substituted with fluorine atom(s), an alkoxy group optionally substituted with fluorine atom(s), an alkoxyalkyl group optionally substituted with fluorine atom(s), an alkylthio group optionally substituted with fluorine atom(s), an alkylsulfonyl group optionally substituted with fluorine atom(s), a hydrogen atom, a fluorine atom, a cyano group, an alkylcarbonyl group, or a dialkylamino group)
the method comprising the following Step (a-2) or Step (c), and comprising the following Step (d):
Step (a-2): reacting a compound represented by formula (1)

(wherein X represents a chlorine atom; and Y is the same as defined above)
with a compound represented by formula (5a)

in the presence of a nickel compound and zinc to produce a compound represented by formula (2a)

(wherein Y is the same as defined above); or
Step (c): the following Step (a-1) and the following Step (b)
Step (a-1): reacting a compound represented by formula (1)

(wherein X represents a chlorine atom; and Y is the same as defined above)
with a compound represented by formula (5b)

(wherein R 2 represents a methyl group or an ethyl group)
in the presence of a nickel compound and zinc to produce a compound represented by formula (2b)

(wherein Y and R 2 are the same as defined above); and
Step (b): reacting the compound represented by formula (2b) with formamide in the presence of a strong base to produce a compound represented by formula (2a)

(wherein Y is the same as defined above); and
Step (d): subjecting the compound represented by formula (2a) to a Hofmann rearrangement to produce the compound represented by formula (3).

4. The method according to claim 3 , wherein the Step (d) is carried out in water in the presence of bromine or chlorine, and an alkali metal hydroxide.

5. The method according to claim 3 , wherein the Step (d) is a step of
subjecting the compound represented by formula (2a) to a Hofmann rearrangement in an alcohol represented by formula (6)
R 1 OH  (6)

(wherein R 1 represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group)
in the presence of bromine or chlorine, and an alkali metal alcoholate compound to produce a compound represented by formula (4)

(wherein Y and R 1 are the same as defined above)
and then
reacting the compound represented by formula (4) in the presence of a strong acid to produce the compound represented by formula (3).

6. The method according to claim 1 , wherein Y represents a 4-trifluoromethyl group.

7. A method for producing a compound represented by formula (8)

(wherein R 3 represents a hydrogen atom or a fluorine atom)
the method comprising the following Step (a-2) or the following Step (c)
Step (a-2): reacting a compound represented by formula (1)

(wherein X represents a chlorine atom; and Y represents a 4-trifluoromethyl group)
with a compound represented by formula (5a)

in the presence of a nickel compound and zinc to produce a compound represented by formula (2a)

(wherein Y is the same as defined above); or
Step (c): the following Step (a-1) and the following Step (b)
Step (a-1): reacting a compound represented by formula (1)

Assignees

• Sumitomo Chemical Co

Inventors

• Tanimura Shun
• Tanimoto Masaya
• Hagiya Koji

Classifications

• C07C269/00

  Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups [IMAGE cpc-sch-C07C-0964.gif], the nitrogen atom not being part of nitro or nitroso groups · CPC title

• C07C231/12 Primary

  by reactions not involving the formation of carboxamide groups · CPC title

• C07C209/58

  from or via amides · CPC title

• C07C67/347 Primary

  by addition to unsaturated carbon-to-carbon bonds · CPC title

• C07C211/29

  the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups · CPC title