Method for producing mercaptophenol compound and intermediate of said compound

Patent metadata

Field	Value
Publication number	US-10851052-B2
Application number	US-201916761099-A
Country	US
Kind code	B2
Filing date	Feb 22, 2019
Priority date	Feb 27, 2018
Publication date	Dec 1, 2020
Grant date	Dec 1, 2020

Abstract

A production method in which a mercaptophenol compound is obtained using an industrially preferred sulfur atom introduction reaction, and intermediate compounds of the mercaptophenol compound are provided. A method for producing a mercaptophenol compound in which a phenyl carbamate compound is produced using a phenol compound as a raw material, and then a sulfur atom is regioselectively introduced by a reaction with sulfur monochloride, and a phenyl mercaptocarbamate compound is produced as an intermediate.

First claim

The invention claimed is:

1. A 5-mercaptophenyl carbamate compound represented by formula (1):

wherein R 1 and R 2 each independently represent a C 1 -C 4 alkyl group or a halogen atom,
R 3 and R 4 each independently represent a hydrogen atom, a C 1 -C 6 alkyl group that may be substituted with one or two or more identical or different halogen atoms, a C 2 -C 6 alkenyl group that may be substituted with one or two or more identical or different halogen atoms, a C 3 -C 6 cycloalkyl group that may be substituted with one or two or more identical or different halogen atoms, a C 1 -C 6 alkoxy group that may be substituted with one or two or more identical or different halogen atoms, a C 6 -C 10 aryl group that may be substituted with one or two or more identical or different substituents A, or a C 6 -C 10 aryl C 1 -C 4 alkyl group that may be substituted with one or two or more identical or different substituents A,
or R 3 and R 4 may together form a 4- to 8-membered ring by forming a divalent group selected from the group consisting of a C 3 -C 7 alkylene group that may be substituted with one or two or more identical or different substituents B, a —(C 1 -C 3 alkylene)-O—(C 1 -C 3 alkylene)- group that may be substituted with one or two or more identical or different substituents B, and a —(C 1 -C 3 alkylene)-NH—(C 1 -C 3 alkylene)- group that may be substituted with one or two or more identical or different substituents B,
the substituent A represents a C 1 -C 4 alkyl group or a halogen atom, and
the substituent B represents a C 1 -C 4 alkyl group, a halogen atom, or an oxo group.

2. The compound according to claim 1 , wherein in the formula (1),
R 1 and R 2 each independently represent a methyl group, a fluorine atom, or a chlorine atom, and
R 3 and R 4 each independently represent a methyl group, an ethyl group, a propyl group, or an isopropyl group.

3. A poly sulfide compound represented by formula (2):

wherein R 1 and R 2 each independently represent a C 1 -C 4 alkyl group or a halogen atom,
R 3 and R 4 each independently represent a hydrogen atom, a C 1 -C 6 alkyl group that may be substituted with one or two or more identical or different halogen atoms, a C 2 -C 6 alkenyl group that may be substituted with one or two or more identical or different halogen atoms, a C 3 -C 6 cycloalkyl group that may be substituted with one or two or more identical or different halogen atoms, a C 1 -C 6 alkoxy group that may be substituted with one or two or more identical or different halogen atoms, a C 6 -C 10 aryl group that may be substituted with one or two or more identical or different substituents A, or a C 6 -C 10 aryl C 1 -C 4 alkyl group that may be substituted with one or two or more identical or different substituents A,
or R 3 and R 4 may together form a 4- to 8-membered ring by forming a divalent group selected from the group consisting of a C 3 -C 7 alkylene group that may be substituted with one or two or more identical or different substituents B, a —(C 1 -C 3 alkylene)-O—(C 1 -C 3 alkylene)- group that may be substituted with one or two or more identical or different substituents B, and a —(C 1 -C 3 alkylene)-NH—(C 1 -C 3 alkylene)- group that may be substituted with one or two or more identical or different substituents B,
the substituent A represents a C 1 -C 4 alkyl group or a halogen atom,
the substituent B represents a C 1 -C 4 alkyl group, a halogen atom, or an oxo group, and
n represents an integer of 2 or more,
or a mixture thereof.

4. The polysulfide compound or the mixture thereof according to claim 3 , wherein in the formula (2),
R 1 and R 2 each independently represent a methyl group, a fluorine atom, or a chlorine atom,
R 3 and R 4 each independently represent a methyl group, an ethyl group, a propyl group, or an isopropyl group, and
n represents an integer in the range of 2 to 6.

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

wherein R 1 and R 2 each independently represent a C 1 -C 4 alkyl group or a halogen atom,
R 3 and R 4 each independently represent a hydrogen atom, a C 1 -C 6 alkyl group that may be substituted with one or two or more identical or different halogen atoms, a C 2 -C 6 alkenyl group that may be substituted with one or two or more identical or different halogen atoms, a C 3 -C 6 cycloalkyl group that may be substituted with one or two or more identical or different halogen atoms, a C 1 -C 6 alkoxy group that may be substituted with one or two or more identical or different halogen atoms, a C 6 -C 10 aryl group that may be substituted with one or two or more identical or different substituents A, or a C 6 -C 10 aryl C 1 -C 4 alkyl group that may be substituted with one or two or more identical or different substituents A,
or R 3 and R 4 may together form a 4- to 8-membered ring by forming a divalent group selected from the group consisting of a C 3 -C 7 alkylene group that may be substituted with one or two or more identical or different substituents B, a —(C 1 -C 3 alkylene)-O—(C 1 -C 3 alkylene)- group that may be substituted with one or two or more identical or different substituents B, and a —(C 1 -C 3 alkylene)-NH—(C 1 -C 3 alkylene)- group that may be substituted with one or two or more identical or different substituents B,
the substituent A represents a C 1 -C 4 alkyl group or a halogen atom,
the substituent B represents a C 1 -C 4 alkyl group, a halogen atom, or an oxo group, and
n represents an integer of 2 or more,
or a mixture thereof, comprising the following steps:
(i) a step of reacting a compound represented by formula (5):

wherein R 1 and R 2 are as defined above,
with a carbamoyl halide compound represented by formula (a):

wherein R 3 and R 4 are as defined above, and X represents a halogen atom,
in the presence of a base to produce a compound represented by formula (3):

wherein R 1 , R 2 , R 3 , and R 4 are as defined above; and
(ii) a step of subjecting the compound represented by the formula (3) to a reaction with a sulfur compound in the presence of an acid to produce the compound represented by the formula (2).

6. The method according to claim 5 , wherein R 1 and R 2 each independently represent a methyl group, a fluorine atom, or a chlorine atom,
R 3 and R 4 each independently represent a methyl group, an ethyl group, a propyl group, or an isopropyl group,
n represents an integer in the range of 2 to 6, and
X represents a chlorine atom.

7. The method according to claim 5 , wherein the base used in the step (i) is triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]-7-undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-(dimethylamino)-pyridine, 2,6-lutidine, or a mixture thereof.

8. The method according to claim 5 , wherein the acid used in the step (ii) is a Lewis acid.

9. A method for producing a 5-mercaptophenyl carbamate compound represented by formula (1):

Assignees

• Kumiai Chemical Industry Co

Inventors

• SAMBAI Kazuhiro

Classifications

• C07C323/20 Primary

  with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring · CPC title

• C07C319/24

  by reactions involving the formation of sulfur-to-sulfur bonds · CPC title

• C07C319/12

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

• C07C319/06 Primary

  from sulfides, hydropolysulfides or polysulfides · CPC title

• C07C271/44 Primary

  to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals · CPC title