Normal alpha olefin synthesis using dehydroformylation or dehydroxymethylation
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.
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.