Dithioester compound

Patent metadata

Field	Value
Publication number	US-11214546-B2
Application number	US-202017124919-A
Country	US
Kind code	B2
Filing date	Dec 17, 2020
Priority date	Dec 18, 2019
Publication date	Jan 4, 2022
Grant date	Jan 4, 2022

Abstract

An object of the present invention is to provide a dithioester compound capable of generating an alkoxy radical having high hydrogen abstraction ability. The present invention provides a dithioester compound represented by a formula (1). The dithioester compound according to the present invention is capable of generating an alkoxy radical (R 1 R 2 R 3 CO.) having high hydrogen abstraction ability. Thus, the dithioester compound according to the present invention can be suitably used as an additive (RAFT agent) when synthesizing a polymer material having a crosslinked structure.

[In the formula (1), R 1 to R 3 each independently represent an alkyl group having 1 or more carbon atoms, an alkenyl group having two or more carbon atoms, an alkynyl group having two or more carbon atoms, a hydrogen atom, or a halogen atom.]

First claim

The invention claimed is:

1. A dithioester compound represented by a formula (1):

wherein in the formula (1),
R 1 to R 3 each independently represent an alkyl group having 1 or more carbon atoms, an alkenyl group having two or more carbon atoms, or an alkynyl group having two or more carbon atoms; and
Z represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heterocyclyloxy group, an alkanoyl group, an aroyl group, a heterocyclylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclyloxycarbonyl group, an alkanoyloxy group, an aroyloxy group, a heterocyclylcarbonyloxy group, a carbamoyl group, a carboxy group, an alkylthio group, an arylthio group, an amino group, a cyano group, a dialkylphosphonate group, a diarylphosphonate group, a dialkylphosphinate group, a diarylphosphinate group, a cyanoalkyl group, a halogenated alkyl group, an alkylamino group, a hydrogen atom, or a halogen atom.

2. The dithioester compound according to claim 1 , wherein in the formula (1), R 1 to R 3 are an alkyl group having 1 or more carbon atoms.

3. A method for producing the dithioester compound according to claim 1 , comprising carrying out a reaction between a dithiocarboxylic acid metal salt represented by a formula (4) and an alcohol represented by a formula (5) in the presence of [bis(trifluoroacetoxy)iodo]benzene,

wherein in the formula (4),
Z represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heterocyclyloxy group, an alkanoyl group, an aroyl group, a heterocyclylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclyloxycarbonyl group, an alkanoyloxy group, an aroyloxy group, a heterocyclylcarbonyloxy group, a carbamoyl group, a carboxy group, an alkylthio group, an arylthio group, an amino group, a cyano group, a dialkylphosphonate group, a diarylphosphonate group, a dialkylphosphinate group, a diarylphosphinate group, a cyanoalkyl group, a halogenated alkyl group, an alkylamino group, a hydrogen atom, or a halogen atom;
M represents potassium, lithium, sodium, calcium, beryllium, zinc, copper, iron, magnesium, aluminum, cobalt, nickel, ammonium, a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation, a quaternary ammonium cation, a phosphonium cation, or a phosphazene cation; and
n represents an integer of 1 to 3,

wherein in the formula (5), R 1 to R 3 each independently represent an alkyl group having 1 or more carbon atoms, or an alkenyl group having two or more carbon atoms, or an alkynyl group having two or more carbon atoms.

4. The method according to claim 3 , wherein an amount of [bis(trifluoroacetoxy)iodo]benzene ranges from 0.01 mole to 20 moles with respect to 1 mole of the dithiocarboxylic acid metal salt.

5. The method according to claim 3 , wherein an amount of the alcohol ranges from 1 mole to 500 moles with respect to 1 mole of the dithiocarboxylic acid metal salt.

6. A dithioester compound represented by a formula (1):

wherein in the formula (1),
R 1 to R 3 each independently represent an alkyl group having 1 or more carbon atoms, an alkenyl group having two or more carbon atoms, an alkynyl group having two or more carbon atoms, or a halogen atom; and
Z represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an oxopyrrolidine-1-yl group, a methylphenylamino group, a methylpyridylamino group, a cyanomethyl group, a 2-cyanobutane-2-yl group, a 1-cyanoethane-1-yl group, a 2-cyanopropane-2-yl group, a 2-phenylpropane-2-yl group, a 1-cyano-1-phenylethane-1-yl group, a 2-(ethoxycarbonyl)propane-2-yl group, or a structure represented by formulae (11) to (16):

wherein in the formulae (11) to (16),
R 11 to R 16 represent an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, a hydrogen atom, or a halogen atom.

7. The dithioester compound according to claim 6 , wherein in the formula (1), R 1 to R 3 are an alkyl group having 1 or more carbon atoms.

8. The dithioester compound according to claim 6 , wherein the compound represented by the formula (1) is a compound represented by a formula (3):

wherein in the formula (3),
R 31 to R 33 each independently represent an alkyl group having 1 or more carbon atoms, an alkenyl group having two or more carbon atoms, an alkynyl group having two or more carbon atoms, or a halogen atom; and
X 1 to X 3 each independently represent an alkyl group having 1 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 6 or more carbon atoms, a hydrogen atom, or a halogen atom.

9. A method for producing the dithioester compound according to claim 6 , comprising carrying out a reaction between a dithiocarboxylic acid metal salt represented by a formula (4) and an alcohol represented by a formula (5) in the presence of [bis(trifluoroacetoxy)iodo]benzene,

wherein in the formula (4),
Z represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an oxopyrrolidine-1-yl group, a methylphenylamino group, a methylpyridylamino group, a cyanomethyl group, a 2-cyanobutane-2-yl group, a 1-cyanoethane-1-yl group, a 2-cyanopropane-2-yl group, a 2-phenylpropane-2-yl group, a 1-cyano-1-phenylethane-1-yl group, a 2-(ethoxycarbonyl)propane-2-yl group, or a structure represented by formulae (11) to (16),

wherein in the formulae (11) to (16),
R 11 to R 16 represent an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, a hydrogen atom, or a halogen atom;
M represents potassium, lithium, sodium, calcium, beryllium, zinc, copper, iron, magnesium, aluminum, cobalt, nickel, ammonium, a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation, a quaternary ammonium cation, a phosphonium cation, or a phosphazene cation; and
n represents an integer of 1 to 3,

wherein in the formula (5), R 1 to R 3 each independently represent an alkyl group having 1 or more carbon atoms, an alkenyl group having two or more carbon atoms, an alkynyl group having two or more carbon atoms, or a halogen atom.

10. The method according to claim 9 , wherein the dithiocarboxylic acid metal salt represented by the formula (4) is a dithiocarboxylic acid metal salt represented by a formu

Assignees

• Sumitomo Rubber Ind

Inventors

• Kaneko Takumi
• Shigemitsu Takahiro
• Shiga Kazuyoshi

Classifications

• C07D231/12 Primary

  with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms · CPC title