Method for producing organic mercapto compound or intermediate thereof, (poly)thiol component, polymerizable composition for optical material, molded product, optical material, and lens

Patent metadata

Field	Value
Publication number	US-11897835-B2
Application number	US-201917043307-A
Country	US
Kind code	B2
Filing date	Mar 29, 2019
Priority date	Mar 30, 2018
Publication date	Feb 13, 2024
Grant date	Feb 13, 2024

Abstract

A method for producing an organic mercapto compound or an intermediate thereof according to the present invention has a reaction step of reacting an alcohol compound including a sulfur atom with a thioamide compound having a structure in which an organic group is bonded to at least one bonding hand of a thioamide group, under acidic conditions.

First claim

The invention claimed is:

1. A method for producing an organic mercapto compound or an intermediate thereof, comprising:
a reaction step of reacting an alcohol compound including a sulfur atom with a thioamide compound having a structure in which an organic group is bonded to at least one bonding hand of a thioamide group, under acidic conditions.

2. The method for producing an organic mercapto compound or an intermediate thereof according to claim 1 ,
wherein a topological polar surface area of the thioamide compound is 10.00 to 51.00 Å 2 .

3. The method for producing an organic mercapto compound or an intermediate thereof according to claim 1 ,
wherein the thioamide compound is represented by General Formula (2),

wherein in Formula (2), R 1 is a monovalent organic group having 1 to 30 carbon atoms, which optionally be substituted, R 2 and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 15 carbon atoms, and any two groups in the group consisting of R 1 , R 2 , and R 3 optionally be bonded to each other to form a heterocyclic ring having 3 to 10 carbon atoms.

4. The method for producing an organic mercapto compound or an intermediate thereof according to claim 3 ,
wherein, in the compound represented by General Formula (2), R 1 is a monovalent aryl group having 6 to 10 carbon atoms, which optionally be substituted, a monovalent aliphatic group having 1 to 10 carbon atoms, which optionally be substituted, or a monovalent heteroaryl group having 3 to 10 carbon atoms, which optionally be substituted, and substituents of these groups optionally include a hetero atom, and
R 2 and R 3 are hydrogen atoms or R 2 and R 3 are bonded to each other to form a nitrogen-containing heterocyclic ring having 3 to 10 carbon atoms.

5. The method for producing an organic mercapto compound or an intermediate thereof according to claim 1 ,
wherein the alcohol compound is represented by General Formula (1),
Q 1 OH n   (1)

wherein in Formula (1), Q 1 is an n-valent organic group including a sulfur atom and having 1 to 30 carbon atoms, and n is an integer of 1 to 10.

6. The method for producing an organic mercapto compound or an intermediate thereof according to claim 3 ,
wherein the alcohol compound is represented by General Formula (1), and
the reaction step comprises a step of reacting the alcohol compound represented by General Formula (1) with the thioamide compound represented by General Formula (2) under acidic conditions to obtain a thioester represented by General Formula (4A) as an intermediate via an isothioamide compound represented by General Formula (3A) or a salt thereof,
Q 1 OH n   (1)

wherein in Formula (1), Q 1 is an n-valent organic group including a sulfur atom and having 1 to 30 carbon atoms, and n is an integer of 1 to 10

wherein in Formula (3A), R 1 , R 2 , and R 3 respectively have the same meanings as those in General Formula (2), Q 2A has the same meaning as Q 1 in General Formula (1), and n has the same meaning as n in General Formula (1)
Q 3A (SC(═O)—R 1 ) n (4A)

wherein in General Formula (4A), n has the same meaning as n in General Formula (1), R 1 has the same meaning as R 1 in General Formula (2), and Q 3A has the same meaning as Q 1 in General Formula (1).

7. The method for producing an organic mercapto compound or an intermediate thereof according to claim 6 ,
wherein the step of obtaining the organic mercapto compound or an intermediate thereof is a step of obtaining the thioester via the salt of the isothioamide represented by General Formula (3A), and
an acid dissociation constant pKa of the salt of the isothioamide is less than 4, and at least one of R 1 and R 2 in General Formula (2) is a hydrogen atom.

8. The method for producing an organic mercapto compound or an intermediate thereof according to claim 3 ,
wherein the alcohol compound is represented by General Formula (1), and
the reaction step comprises
a step of reacting the alcohol compound represented by General Formula (1) with the thioamide compound represented by General Formula (2) under acidic conditions to obtain isothioamidonium represented by General Formula (3B) as an intermediate, and
a step of obtaining an organic mercapto compound from the isothioamidonium under basic conditions,
Q 1 OH n   (1)

wherein in Formula (1), Q 1 is an n-valent organic group including a sulfur atom and having 1 to 30 carbon atoms, and n is an integer of 1 to 10

wherein in Formula (3B), le has the same meaning as R 1 in General Formula (2), Q 2B has the same meaning as Q 1 in General Formula (1), and n has the same meaning as n in General Formula (1).

9. The method for producing an organic mercapto compound or an intermediate thereof according to claim 8 ,
wherein an acid dissociation constant pKa of the isothioamidonium is 4 or more and 14 or less.

10. The method for producing an organic mercapto compound or an intermediate thereof according to claim 1 , the method further comprising:
a step of obtaining an organic mercapto compound under a condition of reacting the alcohol compound with the thioamide compound.

11. A method for manufacturing a molded product, the method comprising:
a step of obtaining an organic mercapto compound by the method for producing an organic mercapto compound according to claim 1 , or a step of obtaining an organic mercapto compound from an intermediate of the organic mercapto compound obtained by the method according to claim 1 ;
a step of mixing the obtained organic mercapto compound and an iso(thio)cyanate compound to prepare a polymerizable composition; and
a step of injecting and curing the polymerizable composition in a mold.

Assignees

• Mitsui Chemicals Inc

Inventors

• Kuboi Hironori
• Ohshimizu Kaoru

Classifications

• C07C319/08 Primary

  by replacement of hydroxy groups or etherified or esterified hydroxy groups · CPC title

• B29C45/0001

  characterised by the choice of material · CPC title

• B29D11/00009

  Production of simple or compound lenses · CPC title

• C07C327/22

  having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms · CPC title

• C08G18/3876

  containing mercapto groups · CPC title