Production method of asymmetric chain carbonate

Patent metadata

Field	Value
Publication number	US-10774028-B2
Application number	US-201615774829-A
Country	US
Kind code	B2
Filing date	Nov 22, 2016
Priority date	Nov 24, 2015
Publication date	Sep 15, 2020
Grant date	Sep 15, 2020

Abstract

A method for producing an asymmetric chain carbonate by reacting an alcohol with a halocarbonate ester compound in the presence of a basic magnesium salt.

First claim

The invention claimed is:

1. A method for producing an asymmetric carbonate, the method comprising
reacting an alcohol represented by Formula (1):
R 1 OH  (1):

wherein, in Formula (1), R 1 is an organic group,

with a halocarbonate ester compound represented by Formula (2):
XCOOR 2   (2):

wherein, in Formula (2), X is a halogen atom; and R 2 is an organic group different from R 1 ,

in the presence of a salt to produce an asymmetric carbonate represented by Formula (3):
R 1 OCOOR 2   (3):

wherein R 1 and R 2 are as defined above;

wherein the organic group in R 1 is selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and a heteroaryl group,
wherein the organic group in R 2 is independently selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a heteroaryl group,
wherein the organic group in R 1 and R 2 are independently optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a fluorinated alkyl group, an aryl group, and a heteroatom-containing group,
wherein the heteroatom-containing group is a group containing N, O, or S, and
wherein the salt is selected from the group consisting of magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium hydrogen carbonate, magnesium acetate, calcium oxide, calcium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium acetate, strontium oxide, strontium hydroxide, strontium carbonate, strontium hydrogen carbonate, strontium acetate, barium oxide, barium hydroxide, barium carbonate, barium hydrogen carbonate, barium acetate, and mixtures thereof.

2. The production method according to claim 1 ,
wherein R 1 is an alkyl group,
R 2 is an alkyl group different from R 1 , and
R 1 and R 2 are optionally substituted with a fluorine atom.

3. The production method according to claim 2 ,
wherein R 1 is an alkyl group having 20 or less carbon atoms, and
R 2 is an alkyl group having 20 or less carbon atoms that is different from R 1 .

4. The production method according to claim 2 ,
wherein R 1 is an alkyl group having 10 or less carbon atoms, and
R 2 is an alkyl group having 10 or less carbon atoms that is different from R 1 .

5. The production method according to claim 1 ,
wherein the heteroatom-containing group is selected from the group consisting of an amino group, an amide group, a hydroxy group, an ether group, an ester group, a thiol group, and a SH group.

6. The production method according to claim 1 ,
wherein R 1 is an alkyl group, and
R 2 is an alkyl group that is different from R 1 ,
R 1 is substituted with fluorine atom, and
R 2 is substituted with a fluorine atom.

7. The production method according to claim 1 ,
wherein R 1 is an alkyl group having 2 or less carbon atoms, and
R 2 is an alkyl group having 2 or less carbon atoms that is different from R 1 .

8. The production method according to claim 1 ,
wherein R 1 is selected from the group consisting of —CH 3 , —CH 2 CH 3 , —CH 2 —O—CH 3 , —CH 2 —CH 2 —O—CH 3 , —C 6 H 5 , —CF 3 , —CF 2 H, —CFH 2 , —CH 2 CF 3 , —CH 2 CF 2 H, —CH 2 CFH 2 , —CF 2 CF 3 , —CF 2 CF 2 H, —CF 2 CFH 2 , —CFHCF 3 , —CFHCF 2 H, —CFHCFH 2 , —CH(CF 3 ) 2 , —CH 2 C 2 F 3 , —CH 2 CF 2 CF 3 , —CH 2 CF 2 CF 2 H, —CF 2 CF 2 CF 3 , —CHFCH 3 , and —CF 2 CH 3 .

9. The production method according to claim 1 ,
wherein R 2 is selected from the group consisting of —CH 3 , —CH 2 CH 3 , —CH(CH 3 ) 2 , —CH 2 CF 3 , and —CH 2 C 2 H 5 .

10. The production method according to claim 1 ,
wherein R 1 is an alkyl group having 20 or less carbon atoms,
R 2 is an alkyl group having 20 or less carbon atoms that is different from R 1 , and
R 1 and R 2 are optionally substituted with a fluorine atom.

11. The production method according to claim 1 ,
wherein R 1 is an alkyl group having 10 or less carbon atoms,
R 2 is an alkyl group having 10 or less carbon atoms that is different from R 1 , and
R 1 and R 2 are optionally substituted with a fluorine atom.

12. The production method according to claim 1 ,
wherein R 1 is an alkyl group having 2 or less carbon atoms,
R 2 is an alkyl group having 2 or less carbon atoms that is different from R 1 , and
R 1 and R 2 are optionally substituted with a fluorine atom.

13. The production method according to claim 1 ,
wherein the salt is selected from the group consisting of magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium hydrogen carbonate, magnesium acetate, and mixtures thereof.

14. The production method according to claim 1 ,
wherein the salt is selected from the group consisting of calcium oxide, calcium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium acetate, and mixtures thereof.

15. The production method according to claim 1 ,
wherein the salt is selected from the group consisting of strontium oxide, strontium hydroxide, strontium carbonate, strontium hydrogen carbonate, strontium acetate, and mixtures thereof.

16. The production method according to claim 1 ,
wherein the salt is selected from the group consisting of barium oxide, barium hydroxide, barium carbonate, barium hydrogen carbonate, barium acetate, and mixtures thereof.

17. A method for producing an asymmetric carbonate, the method comprising
reacting an alcohol represented by Formula (1):
R 1 OH  (1):

wherein, in Formula (1), R 1 is an organic group,

with a halocarbonate ester compound represented by Formula (2):
XCOOR 2   (2):

wherein, in Formula (2), X is a halogen atom; and R 2 is an organic group different from R 1 ,

in the presence of an inorganic base and a desiccant to produce an asymmetric carbonate represented by Formula (3):
R 1 OCOOR 2   (3):

wherein, in Formula (3), R 1 and R 2 are as defined above;

wherein the organic group in R 1 and R 2 are independently selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and a heteroaryl group,
wherein the organic group in R 1 and R 2 are independently optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a fluorinated alkyl group, an aryl group, and a heteroatom-containing group, and
wherein the heteroatom-containing group is a group containing N, O, or S.

18. The production method according to claim 17 ,
wherein R 1 is an alkyl group,
R 2 is an alkyl group different from R 1 , and
R 1 and R 2 are optionally substituted with a fluorine atom.

19. The production method according to claim 17 ,
wherein the inorganic base is at least one selected from the group consisting of carbonates of alkali metals, hydroxides of alkali metals, oxides of magnesium, oxides of alkaline earth metals, hydroxides of magnesium, hydroxides of alkaline earth metals, carbonates of magnesium, carbonates of alkaline earth metals, acetates of magnesium, and acetates of alkaline earth metals.

20. The production method according to claim 17 ,
wherein the desiccant is at least one selected from the group consisting of neutral calcium salts, zeolite, silica gel, alumina, and activated carbon.

Assignees

• Daikin Ind Ltd

Inventors

• Hamada Tomohito
• Okada Michiaki
• Yamauchi Akiyoshi
• Kishikawa Yosuke

Classifications

• C07C69/96

  Esters of carbonic or haloformic acids · CPC title

• C07C68/02 Primary

  from phosgene or haloformates · CPC title