Method for producing 2,7-octadien-1-OL

Patent metadata

Field	Value
Publication number	US-9315433-B2
Application number	US-201414778798-A
Country	US
Kind code	B2
Filing date	Mar 26, 2014
Priority date	Mar 27, 2013
Publication date	Apr 19, 2016
Grant date	Apr 19, 2016

Abstract

Provided is a simple and industrially advantageous method for producing 2,7-octadien-1-ol, in which an expensive palladium catalyst is recovered in high efficiency and the reaction rate per atom of palladium is enhanced. Specifically, provided is a method for producing 2,7-octadien-1-ol by subjecting butadiene and water to a telomerization in the presence of a palladium catalyst containing a water-soluble triarylphosphine having two or more sulfonate groups in the molecule and a palladium compound, a tertiary amine, and carbon dioxide, including a step of mixing the telomerization solution obtained by the telomerization with an organic solvent having a dielectric constant at 25° C. of 2 to 18, followed by carrying out phase separation in the presence of carbon dioxide, thereby obtaining 2,7-octadien-1-ol from an organic phase while recovering an aqueous phase including the palladium catalyst. By this production method, the selectivity for 2,7-octadien-1-ol is enhanced.

First claim

The invention claimed is:

1. A method for producing 2,7-octadien-1-ol, comprising:
subjecting butadiene and water to a telomerization in the presence of a palladium catalyst, a tertiary amine and carbon dioxide, the palladium catalyst comprising a water-soluble triarylphosphine and a palladium compound, the water-soluble triarylphosphine comprising two or more sulfonate groups;
mixing a telomerization solution obtained by the telomerization with an organic solvent having a dielectric constant of 2 to 18 at 25° C. to form a liquid having an aqueous phase and an organic phase; and
carrying out phase separation of the liquid in the presence of carbon dioxide by recovering the 2,7-octadien-1-ol from the organic phase while retaining the palladium catalyst in the aqueous phase.

2. The method of according to claim 1 , wherein the water-soluble triarylphosphine is represented by the following general formula (I):

wherein:
R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms;
R 7 , R 8 , and R 9 each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
p, q, and r each independently represent an integer of 0 to 2;
M's may be the same as or different from each other, and each M represents a cation of a metal atom belonging to Group 1 or an ammonium cation derived from a tertiary amine where the total number of carbon atoms of a group bonded to the nitrogen atom of the tertiary amine is 3 to 27;
n represents 0 or 1; and
sulfonate groups (—SO 3 M) are each at a meta-binding position or a para-binding position to the phosphorous atom of the water-soluble triarylphosphine.

3. The method according to claim 2 , wherein:
R 1 , R 3 , R 5 , R 7 , R 8 , and R 9 each independently represent a hydrogen atom, a methyl group, or a methoxy group;
R 2 , R 4 , and R 6 are a hydrogen atom;
M's each independently represent a cation of an alkali metal atom or the ammonium cation derived from a tertiary amine; and
the sulfonate groups (—SO 3 M) are each at the meta-binding position to the phosphorous atom of the water-soluble triarylphosphine.

4. The method according to claim 2 , wherein:
R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent a hydrogen atom, a methyl group, or a methoxy group;
p, q, and r are each 0;
M's each independently represent a cation of a lithium atom, a cation of a sodium atom, a cation of a potassium atom, or the ammonium cation derived from a tertiary amine; and
the sulfonate groups (—SO 3 M) are each at a diagonal binding position of R 1 , R 3 , or R 5 on the benzene ring.

5. The method according to claim 4 , wherein:
R 1 , R 3 , and R 5 are all the same as each other and each represent a hydrogen atom or a methyl group;
p, q, and r are each 0, and
M's are the same as each other and each represent a cation of a lithium atom, a cation of a sodium atom, a cation of a potassium atom, or the ammonium cation derived from a tertiary amine.

6. The method according to claim 2 , wherein:
at least two of R 1 , R 3 , and R 5 are each an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

7. The method according to claim 6 , wherein at least two of R 1 , R 3 , and R 5 are each a methyl group.

8. The method according to claim 2 , wherein M is an ammonium cation derived from a tertiary amine where the total number of carbon atoms of a group bonded to the nitrogen atom of the tertiary amine is 5 to 24.

9. The method according to claim 8 , wherein M is an ammonium cation derived from a tertiary amine wherein the total number of carbon atoms of a group bonded to the nitrogen atom of the tertiary amine is 5 to 7.

10. The method according to claim 1 , wherein the phase separation is carried out at a temperature of 130° C. or lower and a total pressure, after introduction of carbon dioxide, of 0.1 MPa (gauge pressure) or more.

11. The method according to claim 10 , wherein the phase separation is carried out at a temperature of 5° C. to 90° C., and a total pressure, after introduction of carbon dioxide, of 0.5 MPa to 3 MPa (gauge pressure).

12. The method according to claim 1 , wherein the telomerization is carried out at a temperature of 130° C. or lower and a total pressure, after introduction of carbon dioxide, of 0.5 MPa (gauge pressure) or more.

13. The method according to claim 1 , wherein at least a part of the palladium catalyst in the aqueous phase is reused in the telomerization.

Assignees

• Kuraray Co

Inventors

• Yoshikawa Tatsuya
• Tsuji Tomoaki

Classifications

• C07C29/86

  by liquid-liquid treatment · CPC title

• C07C33/02

  Acyclic alcohols with carbon-to-carbon double bonds · CPC title

• C07C29/46 Primary

  by diene-synthesis · CPC title

• C07C31/36

  the halogen not being fluorine · CPC title

• C07C29/36

  increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal · CPC title