Method for manufacturing aromatic nitrile compound

Patent metadata

Field	Value
Publication number	US-12054448-B2
Application number	US-201917050255-A
Country	US
Kind code	B2
Filing date	Apr 26, 2019
Priority date	Apr 26, 2018
Publication date	Aug 6, 2024
Grant date	Aug 6, 2024

Abstract

The present invention provides a method for industrially producing a highly pure aromatic nitrile compound and a highly pure aromatic carboxylic acid compound safely and highly efficiently at low costs. Compound (2) is subjected to Willgerodt reaction in the presence of an additive as necessary, and the obtained amide compound (3) is hydrolyzed and neutralized to give carboxylic acid compound (4). Carboxylic acid compound (4) is reacted with a halogenating agent in the presence of a catalyst as necessary in an organic solvent, and further reacted with an amidating agent, and the obtained amide compound (5) or (6) is reacted with a dehydrating agent to give nitrile compound (1). Alternatively, carboxylic acid compound (4) is reacted with a halogenating agent and a compound represented by the formula R 6 SO 2 R 7 in the presence of a catalyst as necessary in an organic solvent to give nitrile compound (1). Np is a naphthyl group optionally having substituent(s), R 5 is an alkylene group having 1-3 carbon atoms, and other symbols are as described in the DESCRIPTION.

First claim

The invention claimed is:

1. A method for producing a nitrile compound represented by the formula (1′)

comprising the following step 1 and step 2B:
step 1:
subjecting a compound represented by the formula (2′)

to Willgerodt reaction in the presence of an additive as necessary to give a compound represented by the formula (3′)

and hydrolyzing and thereafter neutralizing the obtained compound to give a carboxylic acid compound represented by the formula (4′)

step 2B:
reacting the carboxylic acid compound represented by the aforementioned formula (4′), obtained in the aforementioned step 1, with a halogenating agent and a compound selected from the group consisting of sulfamide, sulfamic acid, and chlorosulfonyl isocyanate in the presence of a catalyst as necessary in an organic solvent to give a nitrile compound represented by the aforementioned formula (1′).

2. The method for producing a nitrile compound according to claim 1 , wherein the aforementioned halogenating agent is thionyl chloride, oxalyl chloride, sulfuryl chloride, phosphoryl chloride, phosphorus trichloride, phosphorus pentachloride, thionyl bromide, or phosphorus tribromide.

3. The method for producing a nitrile compound according to claim 1 , wherein the aforementioned catalyst is N,N-dimethylformamide, N-methylpyrrolidone, or N,N-dimethylacetamide.

4. The method for producing a nitrile compound according to claim 1 , wherein, in the aforementioned step 2B, the nitrile compound represented by the aforementioned formula (1′) is precipitated as crystals by adding water to a reaction mixture containing the nitrile compound represented by the aforementioned formula (1′).

5. The method for producing a nitrile compound according to claim 1 , wherein, in the aforementioned step 1, the compound represented by the aforementioned formula (3′) is obtained by subjecting the compound represented by the aforementioned formula (2′) to the Willgerodt reaction in the presence of molecular sieves, magnesium sulfate, p-toluenesulfonic acid, or methanesulfonic acid, thereby suppressing the production of a ketothioamide compound represented by the following formula

6. The method for producing a nitrile compound according to claim 1 , wherein, in the aforementioned step 1, the reaction product obtained by the hydrolysis is contacted with a hydrocarbon solvent; a hydrocarbon solvent is present during the aforementioned neutralization; or the reaction product obtained by the aforementioned neutralization is contacted with a hydrocarbon solvent.

7. The method for producing a nitrile compound according to claim 1 , wherein the aforementioned step 2B is the following step 2B-1 or step 2B-2:
step 2B-1:
reacting the carboxylic acid compound represented by the aforementioned formula (4′) with a halogenating agent and a compound selected from the group consisting of sulfamide, sulfamic acid, and chlorosulfonyl isocyanate in the presence of a catalyst as necessary in an organic solvent at 80° C.-180° C. to give a nitrile compound represented by the aforementioned formula (1′),
wherein the amount of the halogenating agent is 1 mol-3 mol and the amount of the compound selected from the group consisting of sulfamide, sulfamic acid, and chlorosulfonyl isocyanate is 1 mol-3 mol, per 1 mol of the carboxylic acid compound represented by the aforementioned formula (4′), and the amount of the compound selected from the group consisting of sulfamide, sulfamic acid, and chlorosulfonyl isocyanate is 2%-20% larger than the amount of the halogenating agent;
step 2B-2:
reacting reaction starting material 1 which is a mixture of the carboxylic acid compound represented by the aforementioned formula (4′), a halogenating agent, a first organic solvent and, where necessary, a catalyst, with reaction starting material 2 which is a mixture of a compound selected from the group consisting of sulfamide, sulfamic acid, and chlorosulfonyl isocyanate and a second organic solvent at 80° C.-180° C. to give a nitrile compound represented by the aforementioned formula (1′),
wherein the amount of the halogenating agent is 1 mol-3 mol and the amount of the compound selected from the group consisting of sulfamide, sulfamic acid, and chlorosulfonyl isocyanate is 1 mol-3 mol, per 1 mol of the carboxylic acid compound represented by the aforementioned formula (4′), and the amount of the compound selected from the group consisting of sulfamide, sulfamic acid, and chlorosulfonyl isocyanate is 2%-20% larger than the amount of the halogenating agent.

8. The method for producing a nitrile compound according to claim 7 , wherein, in the aforementioned step 2B-1, the organic solvent is a sulfone solvent, and in the aforementioned step 2B-2, the first organic solvent is a hydrocarbon solvent or a sulfone solvent, and the second organic solvent is a sulfone solvent.

9. The method for producing a nitrile compound according to claim 7 , wherein, in the aforementioned step 2B-2, the preparation temperature of the reaction starting material 1 is 15° ° C.-65° C.

10. A method for producing a nitrile compound represented by the formula (1′)

comprising the following step 2B:
step 2B:
reacting a carboxylic acid compound represented by the formula (4′)

with a halogenating agent and a compound selected from the group consisting of sulfamide, sulfamic acid, and chlorosulfonyl isocyanate in the presence of a catalyst as necessary in an organic solvent to give a nitrile compound represented by the aforementioned formula (1′).

11. The method for producing a nitrile compound according to claim 10 , wherein the aforementioned halogenating agent is thionyl chloride, oxalyl chloride, sulfuryl chloride, phosphoryl chloride, phosphorus trichloride, phosphorus pentachloride, thionyl bromide, or phosphorus tribromide.

12. The method for producing a nitrile compound according to claim 10 , wherein the aforementioned catalyst is N,N-dimethylformamide, N-methylpyrrolidone, or N,N-dimethylacetamide.

13. The method for producing a nitrile compound according to claim 10 , wherein, in the aforementioned step 2B, the nitrile compound represented by the aforementioned formula (1′) is precipitated as crystals by adding water to a reaction mixture containing the nitrile compound represented by the aforementioned formula (1′).

14. The method for producing a nitrile compound according to claim 10 , wherein the step 2B is the following step 2B-1 or step 2B-2:
step 2B-1:
reacting a carboxylic acid compound represented by the aforementioned formula (4′) with a halogenating agent and a compound selected from the group consisting of sulfamide, sulfamic acid, and chlorosulfonyl isocyanate in the presence of a catalyst as necessary in an organic solvent at 80° C.-180° C. to give a nitrile compound represented by the aforementioned formula (1′),
wherein the amount of the halogenatin

Assignees

• Api Corp

Inventors

• Nagahama Masaki
• Oomiya Hideki
• Okado Daiki
• Taniike Hirotsugu

Classifications

• C07C51/60

  by conversion of carboxylic acids or their anhydrides {or esters, lactones, salts} into halides with the same carboxylic acid part · CPC title

• C07C303/34

  of amides of sulfuric acids · CPC title

• C07C231/02

  from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines · CPC title

• C07D295/182

  Radicals derived from carboxylic acids · CPC title

• C07C51/00

  Preparation of carboxylic acids or their salts, halides or anhydrides (of acids by hydrolysis of oils, fats or waxes C11C) · CPC title