Process for preparing an unsaturated carboxylic acid salt using an aryloxide

Patent metadata

Field	Value
Publication number	US-9758461-B2
Application number	US-201515311011-A
Country	US
Kind code	B2
Filing date	May 13, 2015
Priority date	May 16, 2014
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

Abstract

Catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt, wherein an alkene and carbon dioxide are reacted in the presence of a carboxylation catalyst and in the presence of a specific aryloxide to obtain the α,β-ethylenically unsaturated carboxylic acid salt, the carboxylation catalyst being a transition metal complex. The process allows for efficient preparation of α,β-ethylenically unsaturated carboxylic acid derivatives from CO 2 and an alkene.

First claim

The invention claimed is:

1. A catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt, the catalytic process comprising reacting an alkene and carbon dioxide in the presence of a carboxylation catalyst and an aryloxide to obtain the α,β-ethylenically unsaturated carboxylic acid salt,
wherein:
the carboxylation catalyst is a transition metal complex;
the aryloxide corresponds to formula (I):

R is selected from the group consisting of F, Cl, Br, I, a C 1 -C 16 -alkyl, and a C 3 -C 16 -cycloalkyl, and two vicinal R groups may constitute a C 3 -C 5 -hydrocarbylene bridge that is optionally substituted by one to four substituents which are independently selected from the group consisting of F, Cl, Br, I, a C 1 -C 16 -alkyl, and a C 3 -C 16 -cycloalkyl;
n is an integer selected from 1 to 5; and
at most two R groups are F.

2. The catalytic process according to claim 1 , wherein two vicinal R groups constitute an unsaturated C 4 -hydrocarbylene bridge that is optionally substituted by one to four substituents which are independently selected from the group consisting of F, Cl, Br, I, ua C 1 -C 16 -alkyl, and a C 3 -C 16 -cycloalkyl.

3. The catalytic process according to claim 1 , wherein:
the aryloxide corresponds to one of the formulae (Ia), (Ib), and (Ic):

o is 0, 1, 2, or 3;
p is 0, 1, or 2;
q is 0, 1, or 2;
the sum of o, p, and q is at least 1;
r, s, t, u, v, and w are 0 or integers;
the sum of r and u is 0, 1, 2, or 3;
the sum of s and v is 0, 1, or 2;
the sum oft and w is 0, 1, or 2; and
R 1 is selected from the group consisting of Br, I, a C 1 -C 16 -alkyl, and a C 3 -C 16 -cycloalkyl.

4. The catalytic process according to claim 3 , wherein the aryloxide corresponds to the formula (Ia), in which the sum of p and q is at most 3.

5. The catalytic process according to claim 3 , wherein:
the aryloxide corresponds to the formula (Ia);
p is at most 1;
q is at most 2; and
the sum of p and q is 1 or 2.

6. The catalytic process according to claim 3 , wherein R 1 is a C 1 -C 16 -alkyl or a C 3 -C 16 -cycloalkyl.

7. The catalytic process according to claim 1 , wherein:
the aryloxide corresponds to one of the formulae (Ia-1), (Ia-2), and (Ia-3):

x is 0, 1, or 2;
R 2 is methyl; and
R 3 is independently a C 1 -C 16 -alkyl or a C 3 -C 16 -cycloalkyl.

8. The catalytic process according to claim 7 , wherein:
the aryloxide corresponds to formula (Ia-2) or (Ia-3); and
x is 1 or 2.

9. The catalytic process according to claim 7 , wherein:
the aryloxide corresponds to formula (Ia-2) with F being ortho to O − ; and
x is 1 or 2.

10. The catalytic process according to claim 1 , wherein the aryloxide is an alkali metal, an alkaline earth metal or a zinc aryloxide.

11. The catalytic process according to claim 1 , wherein the aryloxide is selected from the group consisting of sodium 2-fluorophenolate, sodium 3-fluorophenolate, sodium 4-fluorophenolate, sodium 2,6-difluorophenolate, sodium 2,4-difluorophenolate, sodium 2-chlorophenolate, sodium 3-chlorophenolate, sodium 4-chlorophenolate, sodium 2-fluoro-4-methylphenolate, sodium 2-methylphenolate, sodium 2,6-dimethylphenolate, and sodium 1-naphtholate.

12. The catalytic process according to claim 1 , wherein the aryloxide is selected from the group consisting of sodium 2-fluorophenolate, sodium 3-fluorophenolate, sodium 2-chlorophenolate, sodium 3-chlorophenolate, and sodium 2-fluoro-4-methylphenolate.

13. The catalytic process according to claim 1 , wherein:
R is independently selected from the group consisting of a C 1 -C 16 -alkyl and a C 3 -C 16 -cycloalkyl;
n is an integer from 2 to 5; and
one R is at position 2 and another R is at position 6 of the phenyl ring of general formula (I).

14. The catalytic process according to claim 13 , wherein:
R is independently a C 1 -C 6 -alkyl; and
n is 2 or 3.

15. The catalytic process according to claim 13 , wherein the aryloxide is a sodium aryloxide.

16. The catalytic process according to claim 1 , wherein the transition metal complex comprises a ligand selected from the group consisting of a bidentate P,P ligand, a bidentate P,N ligand, a bidentate P,O ligand and a P,carbene ligand.

17. The catalytic process according to claim 16 , wherein the ligand is a bidentate P,P ligand.

18. The catalytic process according to claim 1 , wherein the transition metal complex is a nickel or a palladium complex.

19. The catalytic process according to claim 1 , wherein:
the alkene is ethene; and
the α,β-ethylenically unsaturated carboxylic acid is acrylic acid.

20. The catalytic process according to claim 1 , wherein the alkene and the carbon dioxide are reacted in the presence of a reducing agent.

21. The catalytic process according to claim 1 , wherein the reacting occurs in the presence of a reaction medium comprising an aprotic organic solvent.

22. The catalytic process according to claim 21 , wherein the aprotic organic solvent is selected from the group consisting of
a cyclic alkyl ether having 4 to 8 carbon atoms,
a dialkyl ether having 2 to 12 carbon atoms,
a cycloalkyl alkyl ether having 4 to 12 carbon atoms,
an aryl alkyl ether having 7 to 16 carbon atoms,
a biaryl having 12 to 16 carbon atoms,
a diaryl oxide having 12 to 16 carbon atoms,
a C 1 -C 8 -alkyl ester of a C 6 -C 10 -aryl monocarboxylic acid,
a di-C 1 -C 8 -alkyl ester of a C 6 -C 10 -aryl dicarboxylic acid,
a dialkyl carbonate having 3 to 13 carbon atoms,
a diether consisting of an dioxyalkylene residue with 2 to 8 carbon atoms and two C 1 -C 8 -alkyl residues,
a benzene wherein 1 to 4 hydrogen atoms are substituted by 1 to 4 C 1 -C 4 -alkyl residues,
a halogenated benzene,
an alkane having 5 to 18 carbon atoms, and
mixtures thereof.

23. The catalytic process according to claim 1 , wherein:
the reacting occurs in the presence of a reaction medium;
the α,β-ethylenically unsaturated carboxylic acid salt is removed from the reaction medium;
the removal of the α,β-ethylenically unsaturated carboxylic acid salt from the reaction medium comprises a liquid-liquid phase separation into
a first liquid phase in which the α,β-ethylenically unsaturated carboxylic acid salt is enriched, and
a second liquid phase in which the carboxylation catalyst, unconverted aryloxide and an arylhydroxide byproduct are enriched; and

the first and second liquid phases are obtained by contacting the reaction medium with a polar solvent.

24. The catalytic process according to claim 1 , further comprising regenerating the aryloxide by adding an alkaline material.

Assignees

• Basf Se

Inventors

• Limbach Michael
• Lejkowski Michael
• Huguet Subiela Nuria
• Gordillo Alvaro
• Lindner Ronald
• Bru Roig Miriam
• Schunk Stephan A

Classifications

• C07C51/15 Primary

  by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis · CPC title