Normal alpha olefin synthesis using dehydroformylation or dehydroxymethylation

Patent metadata

Field	Value
Publication number	US-11072569-B2
Application number	US-202016920835-A
Country	US
Kind code	B2
Filing date	Jul 6, 2020
Priority date	Feb 26, 2018
Publication date	Jul 27, 2021
Grant date	Jul 27, 2021

Abstract

The present invention discloses processes for producing normal alpha olefins, such as 1-hexene, 1-octene, 1-decene, and 1-dodecene in a multistep synthesis scheme from another normal alpha olefin. Also disclosed are reactions for converting aldehydes, primary alcohols, and terminal vicinal diols into normal alpha olefins.

First claim

What is claimed is:

1. A process comprising:
(i) conducting a dihydroxylation reaction of a first normal alpha olefin having the structure CH 3 (CH 2 ) n HC═CH 2 to form a terminal vicinal diol having the structure CH 3 (CH 2 ) n CH(OH)CH 2 OH; and
(ii) contacting the terminal vicinal diol with a catalyst composition to form a second normal alpha olefin having the structure CH 3 (CH 2 ) n−2 HC═CH 2 ;
wherein n is an integer from 2 to 33; and
wherein the catalyst composition comprises:
(I) a transition metal compound, a phosphine, and a heteroatomic acid or heteroatomic acid derivative; or
(II) a phosphine transition metal compound complex and a heteroatomic acid or heteroatomic acid derivative.

2. The process of claim 1 , wherein:
the second normal alpha olefin comprises 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof;
the transition metal compound or the transition metal compound of the phosphine transition metal compound complex comprises an olefin rhodium alkoxide complex; and
the heteroatomic acid or heteroatomic acid derivative comprises a carboxylic acid, an alcohol, a mineral acid, an ammonium salt, an amine, a thiol, or any combination thereof.

3. The process of claim 2 , wherein:
a molar ratio of the vicinal diol to the transition metal of the transition metal compound or the phosphine transition metal compound complex is in a range from about 2:1 to about 1000:1; and
the heteroatomic acid or heteroatomic acid derivative comprises benzoic acid or a substituted benzoic acid, or a salt or ester of benzoic acid or a substituted benzoic acid.

4. The process of claim 1 , wherein the catalyst composition further comprises an acceptor.

5. The process of claim 3 , wherein the acceptor comprises an enone, an enamine, an enol, an enamide, or any combinations thereof.

6. The process of claim 3 , wherein:
the second normal alpha olefin comprises 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof; and
a molar ratio of the acceptor to the vicinal diol is in a range from about 0.2:1 to about 1000:1.

7. The process of claim 6 , wherein a molar yield of the second normal alpha olefin is at least about 50%, based on the vicinal diol.

8. The process of claim 6 , wherein:
the transition metal compound or the transition metal compound of the phosphine transition metal compound complex comprises an olefin rhodium alkoxide complex; and
the heteroatomic acid or heteroatomic acid derivative comprises a carboxylic acid, an alcohol, a mineral acid, an ammonium salt, an amine, a thiol, or any combination thereof.

9. The process of claim 8 , wherein:
the heteroatomic acid or heteroatomic acid derivative comprises benzoic acid or a substituted benzoic acid, or a salt or ester of benzoic acid or a substituted benzoic acid.

10. 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 catalyst composition 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; and
wherein the catalyst composition comprises:
(I) a transition metal compound, a phosphine, a heteroatomic acid or heteroatomic acid derivative, and an acceptor; or
(II) a phosphine transition metal compound complex, a heteroatomic acid or heteroatomic acid derivative, and an acceptor.

11. The process of claim 10 , wherein:
the second normal alpha olefin comprises 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof; and
a molar ratio of the acceptor to the linear aldehyde is in a range from about 0.2:1 to about 1000:1.

12. The process of claim 11 , wherein the acceptor comprises an enone, an enamine, an enol, an enamide, or any combinations thereof.

13. The process of claim 11 , wherein:
a molar yield of the second normal alpha olefin is at least about 50%, based on the linear aldehyde;
the transition metal compound or the transition metal compound of the phosphine transition metal compound complex comprises an olefin rhodium alkoxide complex; and
the heteroatomic acid or heteroatomic acid derivative comprises a carboxylic acid, an alcohol, a mineral acid, an ammonium salt, an amine, a thiol, or any combination thereof.

14. The process of claim 11 , wherein:
the heteroatomic acid or heteroatomic acid derivative comprises benzoic acid or a substituted benzoic acid, or a salt or ester of benzoic acid or a substituted benzoic acid.

15. 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+3 C(═O)H; and
(b) contacting the linear aldehyde with a catalyst composition 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; and
wherein the catalyst composition comprises:
(I) a transition metal compound, a phosphine, a heteroatomic acid or heteroatomic acid derivative, and an acceptor; or
(II) a phosphine transition metal compound complex, a heteroatomic acid or heteroatomic acid derivative, and an acceptor.

16. The process of claim 15 , wherein:
the second normal alpha olefin comprises 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof; and
a molar ratio of the acceptor to the linear aldehyde is in a range from about 0.2:1 to about 1000:1.

17. The process of claim 16 , wherein the acceptor comprises an enone, an enamine, an enol, an enamide, or any combinations thereof.

18. The process of claim 16 , wherein:
a molar yield of the second normal alpha olefin is at least about 50%, based on the linear aldehyde;
the transition metal compound or the transition metal compound of the phosphine transition metal compound complex comprises an olefin rhodium alkoxide complex; and
the heteroatomic acid or heteroatomic acid derivative comprises a carboxylic acid, an alcohol, a mineral acid, an ammonium salt, an amine, a thiol, or any combination thereof.

19. The process of claim 16 , wherein:
the heteroatomic acid or heteroatomic acid derivative comprises benzoic acid or a substituted benzoic acid, or a salt or ester of benzoic acid or a substituted benzoic acid.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Bischof Steven M
• Dong Vy M
• Cruz Faben A
• Wu Xuesong
• Murphy Stephen Karl

Classifications

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• C07J9/00

  Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane · CPC title

• B01J2231/70

  Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues · CPC title

• C07C29/48

  by oxidation reactions with formation of hydroxy groups · CPC title

• B01J31/0271

  also containing elements or functional groups covered by B01J31/0201 - B01J31/0231 · CPC title