Normal alpha olefin synthesis using dehydroformylation or dehydroxymethylation

Patent metadata

Field	Value
Publication number	US-10723672-B2
Application number	US-201916283892-A
Country	US
Kind code	B2
Filing date	Feb 25, 2019
Priority date	Feb 26, 2018
Publication date	Jul 28, 2020
Grant date	Jul 28, 2020

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 dehydroxymethylation process comprising:
contacting a saturated linear C 3 -C 36 hydrocarbon primary alcohol with a catalyst composition to form a C 2 -C 35 normal alpha olefin;
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 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 1 , wherein the normal alpha olefin is a C 4 -C 16 normal alpha olefin.

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

5. The process of claim 4 , 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.

6. The process of claim 4 , wherein the acceptor comprises a mono-olefin compound, a di-olefin compound, a tri-olefin compound, or any combination thereof.

7. The process of claim 6 , wherein a molar ratio of the acceptor to the primary alcohol is in a range from about 0.2:1 to about 1000:1.

8. The process of claim 7 , wherein the acceptor is a heteroatomic olefin compound.

9. The process of claim 4 , wherein the normal alpha olefin is 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, or any combination thereof.

10. The process of claim 9 , wherein a molar ratio of the primary alcohol 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.

11. The process of claim 4 , wherein:
the step of contacting is performed in a solvent at a temperature from about 0° C. to about 150° C.; and
the normal alpha olefin is a C 4 -C 16 normal alpha olefin.

12. The process of claim 4 , wherein a molar yield of the normal alpha olefin is at least about 30%, based on the primary alcohol.

13. A dehydroxymethylation process comprising:
contacting a saturated linear C 4 -C 36 hydrocarbon terminal vicinal diol with a catalyst composition to form a C 2 -C 34 normal alpha olefin;
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.

14. The process of claim 13 , 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.

15. The process of claim 13 , wherein the catalyst composition further comprises an acceptor selected from a mono-olefin compound, a di-olefin compound, a tri-olefin compound, or any combination thereof.

16. The process of claim 15 , wherein a molar ratio of the acceptor to the vicinal diol is in a range from about 0.2:1 to about 1000:1.

17. The process of claim 16 , 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.

18. The process of claim 17 , wherein:
a molar yield of the normal alpha olefin is at least about 50%, based on the vicinal diol; and
the normal alpha olefin is a C 4 -C 16 normal alpha olefin.

19. A dehydroformylation process comprising:
contacting a saturated linear C 3 -C 36 hydrocarbon aldehyde with a catalyst composition to form a C 2 -C 35 normal alpha olefin;
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.

20. The process of claim 19 , wherein:
the catalyst composition further comprises an acceptor;
a molar ratio of the acceptor to the aldehyde is in a range from about 0.2:1 to about 1000:1; and
the normal alpha olefin is 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, or any combination thereof.

Assignees

• Chevron Phillips Chemical Co Lp
• Chervon Phillips Chemical Company Lp

Inventors

• Bischof Steven M
• Dong Vy M
• Murphy Stephen Karl

Classifications

• C07C29/03

  by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 (by simultaneous introduction of -OH groups and halogens C07C29/64) · CPC title

• C07C67/297

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups · 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

• C07C2601/20

  the ring being twelve-membered · CPC title

• C07C29/48

  by oxidation reactions with formation of hydroxy groups · CPC title