Normal alpha olefin synthesis using metathesis and dehydroformylation

Patent metadata

Field	Value
Publication number	US-10183899-B2
Application number	US-201615347833-A
Country	US
Kind code	B2
Filing date	Nov 10, 2016
Priority date	Nov 10, 2016
Publication date	Jan 22, 2019
Grant date	Jan 22, 2019

Abstract

The present invention discloses processes for producing normal alpha olefins, such as 1-hexene, 1-octene, and 1-decene, in a multistep synthesis scheme. Generally, a first normal alpha olefin is subjected to an olefin metathesis step to form a linear internal olefin, which is then subjected to an isomerization-hydroformylation step to form a linear aldehyde, which is then subjected to a dehydroformylation step to form a second normal alpha olefin.

First claim

I claim:

1. A process comprising:
(i) contacting a first normal alpha olefin having the structure CH 3 (CH 2 ) n HC═CH 2 and a metathesis catalyst system to form a linear internal olefin having the structure CH 3 (CH 2 ) n HC═CH(CH 2 ) n CH 3 ;
(ii) contacting the linear internal olefin with a hydroformylation catalyst system, carbon monoxide, and hydrogen to form a linear aldehyde having the formula CH 3 (CH 2 ) 2n+3 C(═O)H; and
(iii) contacting the linear aldehyde with a dehydroformylation catalyst system comprising i) a transition metal compound, a diphosphine, and a carboxylic acid or carboxylic acid derivative, or ii) a diphosphine transition metal compound complex and a carboxylic acid or carboxylic acid derivative, to form a second normal alpha olefin having the structure CH 3 (CH 2 ) 2n+1 HC═CH 2 ;
wherein n is an integer from 0 to 15.

2. The process of claim 1 , wherein n is an integer from 1 to 7.

3. The process of claim 1 , wherein the first normal alpha olefin comprises 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or any combination thereof.

4. The process of claim 1 , wherein the first normal alpha olefin comprises 1-hexene, and the second normal alpha olefin comprises 1-decene.

5. The process of claim 1 , wherein step (iii) comprises contacting the linear aldehyde with 1) the dehydroformylation catalyst system comprising i) the transition metal compound, the diphosphine, and the carboxylic acid or carboxylic acid derivative, or ii) the diphosphine transition metal compound complex and the carboxylic acid or carboxylic acid derivative, and 2) an aldehyde group acceptor to form the second normal alpha olefin.

6. The process of claim 5 , wherein the aldehyde group acceptor comprises an aliphatic mono-olefin hydrocarbon, an aliphatic di-olefin hydrocarbon, an aliphatic tri-olefin hydrocarbon, or any combination thereof.

7. The process of claim 5 , wherein a molar ratio of the aldehyde group acceptor to the linear aldehyde is in a range from 0.2:1 to 1,000:1.

8. The process of claim 5 , wherein n is an integer from 1 to 7.

9. The process of claim 1 , wherein the dehydroformylation catalyst system comprises a rhodium compound.

10. The process of claim 1 , wherein:
the diphosphine or the diphosphine of the diphosphine transition metal compound complex comprises a 1,6-bisphosphinylhexane, a substituted 1,6-bisphosphinylhexane, a (1,3-phenylenedi-1,1-ethanediyl)bis(phosphine), a substituted (1,3-phenylenedi-1,1-ethanediyl)bis(phosphine), a 1,8-anthracenediylbis(phosphine), a substituted 1,8-anthracenediylbis(phosphine), a 1,8-tetradecahydroanthracenediylbis(phosphine), or a substituted 1,8-tetradecahydroanthracenediylbis(phosphine), a (methylenedi-2,1-phenylene)bis(phosphine), a substituted (methylenedi-2,1-phenylene)bis(phosphine), a 9H-xanthene-4,5-diylbis(phosphine), or a substituted 9H-xanthene-4,5-diylbis(phosphine); and
the carboxylic acid or carboxylic acid derivative comprises benzoic acid or a substituted benzoic acid, or a salt or ester of benzoic acid or of a substituted benzoic acid.

11. The process of claim 1 , wherein
a molar ratio of the linear aldehyde to the transition metal of the transition metal compound or the diphosphine transition metal compound complex is in a range from 0.00001:1 to 0.05:1; and
a molar ratio of the transition metal of the transition metal compound or the diphosphine transition metal compound complex to the carboxylic acid or carboxylic acid derivative is in a range from 0.8:1 to 5:1.

12. The process of claim 1 , wherein the metathesis catalyst system is a metal oxide based metathesis catalyst system, a metal halide based metathesis catalyst system, a metal carbene based metathesis catalyst system, or any combination thereof.

13. The process of claim 1 , wherein the hydroformylation catalyst system comprises a rhodium compound, a cobalt compound, a ruthenium compound, an iridium compound, a platinum compound, a palladium compound, an iron compound, or any combination thereof.

14. A process comprising:
(a) contacting a linear internal olefin having the structure CH 3 (CH 2 ) p HC═CH(CH 2 ) q CH 3 with a hydroformylation catalyst system, carbon monoxide, and hydrogen to form a linear aldehyde having the formula CH 3 (CH 2 ) p + q +3C(═O)H; and
(b) contacting the linear aldehyde with a dehydroformylation catalyst system comprising i) a transition metal compound, a diphosphine, and a carboxylic acid or carboxylic acid derivative, or ii) a diphosphine transition metal compound complex and a carboxylic acid or carboxylic acid derivative, to form a normal alpha olefin having the structure CH 3 (CH 2 ) p+q+1 HC═CH 2 ;
wherein p and q independently are an integer from 0 to 15.

15. The process of claim 14 , wherein p and q independently are an integer from 1 to 7.

16. The process of claim 15 , wherein step (b) comprises contacting the linear aldehyde with 1) the dehydroformylation catalyst system comprising i) the transition metal compound, the diphosphine, and the carboxylic acid or carboxylic acid derivative, or ii) the diphosphine transition metal compound complex and the carboxylic acid or carboxylic acid derivative, and 2) an aldehyde group acceptor to form the normal alpha olefin.

17. The process of claim 14 , wherein the normal alpha olefin comprises 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof.

18. The process of claim 17 , wherein the diphosphine or the diphosphine of the transition metal compound complex has any one of the following structures:

wherein:
Ph is a phenyl group; and
each R independently is H or a C 1 to C 18 hydrocarbyl group.

19. The process of claim 14 , wherein the linear aldehyde and the dehydroformylation catalyst system are contacted in the presence of a polar solvent.

20. The process of claim 19 , wherein the normal alpha olefin comprises 1-hexene, 1-octene, 1-decene, or any combination thereof.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Bischof Steven M

Classifications

• C07C45/50

  by oxo-reactions · CPC title

• C07C6/04

  at a carbon-to-carbon double bond · CPC title

• C07C1/2076 Primary

  by a transformation in which at least one -C(=O)- moiety is eliminated · CPC title

• C07C1/22 Primary

  by reduction · CPC title

• C07C2531/22

  Organic complexes · CPC title