Terminally selective metathesis of polyenes derived from natural oil
View Patent ↗Methods of carrying out metathesis reactions of natural oil-derived polyenes (e.g., dienes and trienes), including functionalized polyenes, are generally disclosed herein. In some embodiments, the dienes or trienes contain a terminal carbon-carbon double bond, and the metathesis reaction is selective toward reaction of the terminal carbon-carbon double bonds in the polyene. Compounds made by such methods are also generally disclosed herein.
1. A method for forming a dimer by olefin metathesis, the method comprising:
providing a reactant composition comprising a terminally unsaturated diene, which is methyl 9,12-tridecadienoate; and
self-metathesizing the terminally unsaturated diene, methyl 9,12-tridecadienoate, in the presence of a metathesis catalyst at the terminal double bond of the terminally unsaturated diene to form a product composition comprising 1,24-dimethyl 9,12,15-tetracosatriendioate;
provided that the terminally unsaturated diene, methyl 9,12-tridecadienoate, is derived from a natural oil.
2. The method of claim 1 , comprising hydrogenating the 1,24-dimethyl 9,12,15-tetracosatriendioate to form 1,24-dimethyl tetracosanedioate.
3. The method of claim 2 , comprising converting the 1,24-dimethyl tetracosanedioate to form 1,24-tetracosanedioic acid.
4. The method of claim 3 , wherein the converting comprises hydrolysis.
5. The method of claim 3 , wherein the converting comprises saponification followed by acidification.
6. A method for forming a dimer by olefin metathesis, the method comprising:
providing a reactant composition comprising a terminally unsaturated diene, which is methyl 9,12-tridecadienoate, and methyl 9-decenoate; and
cross-metathesizing the terminally unsaturated diene, methyl 9,12-tridecadienoate, and the methyl 9-decenoate in the presence of a metathesis catalyst at the terminal double bond of the terminally unsaturated diene to form a product composition comprising 1,21-dimethyl 9,12-heneicosadiendioate;
provided that the terminally unsaturated diene, methyl 9,12-tridecadienoate, or the methyl 9-decenoate is derived from a natural oil.
7. The method of claim 6 , comprising hydrogenating the 1,21-dimethyl 9,12-heneicosadiendioate to form 1,21-dimethyl heneicosanedioate.
8. The method of claim 7 , comprising converting the 1,21-dimethyl heneicosanedioate to form 1,21-heneicosanedioic acid.
9. The method of claim 8 , wherein the converting comprises hydrolysis.
10. The method of claim 8 , wherein the converting comprises saponification followed by acidification.