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 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.