Method of preparing a thiomethylphenol derivative

Patent metadata

Field	Value
Publication number	US-12486223-B2
Application number	US-202117911886-A
Country	US
Kind code	B2
Filing date	Oct 18, 2021
Priority date	Oct 30, 2020
Publication date	Dec 2, 2025
Grant date	Dec 2, 2025

Abstract

A method of preparing a thiomethylphenol derivative is disclosed, the method including: (a) carrying out a primary reaction of a phenol derivative represented by the following Chemical Formula 2, a mercaptan derivative represented by R 4 SH, and paraformaldehyde at a reaction temperature T 1 under conditions in which a heterocyclic base having 3 to 10 carbon atoms and an acid are simultaneously present; and (b) carrying out a secondary reaction at a reaction temperature T 2 to prepare a thiomethylphenol derivative represented by the following Chemical Formula 1, wherein T 1 <T 2 is satisfied.

First claim

The invention claimed is:

1 . A method of preparing a thiomethylphenol derivative, comprising:
(a) carrying out a primary reaction of a phenol derivative represented by the following Chemical Formula 2, a mercaptan derivative represented by R 4 SH, and paraformaldehyde at a reaction temperature T 1 under conditions in which a heterocyclic base having 3 to 10 carbon atoms and an acid are simultaneously present; and (b) carrying out a secondary reaction at a reaction temperature T 2 to prepare a thiomethylphenol derivative represented by the following Chemical Formula 1; wherein 95° C.<T 1 +5° C.<T 2 <120° C. is satisfied,

wherein,
R 1 and R 2 are each independently selected from hydrogen, deuterium, a C 1 to C 16 straight or branched alkyl group, a C 5 to C 16 cycloalkyl group or a C 5 to C 16 aromatic-containing alkyl group, and —CH 2 SR 3 ,
R 3 and R 4 are each independently selected from a C 1 to C 16 straight or branched alkyl group, a C 5 to C 16 cycloalkyl group, or a C 5 to C 16 aromatic-containing alkyl group,
R 11 and R 22 are each independently selected from hydrogen, deuterium, a C 1 to C 16 straight or branched alkyl group, a C 5 to C 16 cycloalkyl group or a C 5 to C 16 aromatic-containing alkyl group,
n is 0 or 1.

2 . The method of claim 1 , wherein steps (a) and (b) are each carried out for 1 to 5 hours.

3 . The method of claim 1 , wherein step (a) is carried out in the presence of 0.5 to 50.0 equivalents by weight of a solvent based on 1 equivalent by weight of the phenol derivative.

4 . The method of claim 3 , wherein the solvent is water or an alcohol.

5 . The method of claim 1 , wherein 0.01 to 0.50 equivalents by weight of the heterocyclic base are used based on 1 equivalent by weight of the phenol derivative in step (a).

6 . The method of claim 1 , wherein the base in step (a) is at least one selected from the group consisting of pyrrole, pyrrolidine, imidazole, pyridine, piperidine, piperazine and pyrazine.

7 . The method of claim 1 , wherein 0.01 to 0.90 equivalents by weight of the acid are used based on 1 equivalent by weight of the phenol derivative in step (a).

8 . The method of claim 1 , wherein the acid in step (a) is at least one selected from the group consisting of chlorous acid, phosphoric acid, arsenic acid, chloroacetic acid, hydrofluoric acid, nitrous acid, formic acid, benzoic acid, hydrazoic acid, acetic acid, propionic acid and carbonic acid.

9 . The method of claim 1 , wherein 2.0 to 6.0 equivalents by weight of the mercaptan derivative are used based on 1 equivalent by weight of the phenol derivative in step (a).

10 . The method of claim 1 , wherein 2.0 to 6.0 equivalents by weight of the paraformaldehyde are used based on 1 equivalent by weight of the phenol derivative in step (a).

11 . The method of claim 1 , further comprising, after step (b), (c) a purification step of washing an organic layer formed after the reaction of step (b) with an acid.

12 . The method of claim 11 , wherein the acid in step (c) has a pKa of 2.0 or higher.

13 . The method of claim 12 , wherein the acid in step (c) is at least one selected from the group consisting of chlorous acid, phosphoric acid, arsenic acid, chloroacetic acid, hydrofluoric acid, nitrous acid, formic acid, benzoic acid, hydrazoic acid, acetic acid, propionic acid and carbonic acid.

14 . The method of claim 11 , further comprising (d) washing with a base or water after step (c).

15 . The method of claim 14 , wherein the base in step (d) is at least one selected from the group consisting of anhydrous sodium carbonate, anhydrous sodium percarbonate and anhydrous sodium hydrogen carbonate.

16 . The method of claim 14 , further comprising, after step (d), (e) isolating the thiomethylphenol derivative represented by Chemical Formula 1 by concentration under reduced pressure at 90 to 120° C. for 1 to 5 hours.

17 . The method of claim 16 , wherein the isolated thiomethylphenol derivative has an APHA value of less than 75 after standing at 120° C. for 72 hours.

Assignees

• Korea Kumho Petrochemical Co Ltd

Inventors

• Roh Kee Yoon
• Jang Sang Hun
• Choi Jung Hei

Classifications

• C07C319/14 Primary

  of sulfides · CPC title

• C07C315/02 Primary

  by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides · CPC title

• C07C323/18

  having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton · CPC title

• C07C323/16 Primary

  the carbon skeleton containing six-membered aromatic rings · CPC title