Terminally selective metathesis of polyenes derived from natural oil

Patent metadata

Field	Value
Publication number	US-10479755-B2
Application number	US-201615376239-A
Country	US
Kind code	B2
Filing date	Dec 12, 2016
Priority date	Oct 31, 2014
Publication date	Nov 19, 2019
Grant date	Nov 19, 2019

Abstract

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.

First claim

What is claimed is:

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.

Assignees

• Elevance Renewable Sciences

Inventors

• Wampler Keith M
• Uy Jane
• Cohen Steven A

Classifications

• C11C3/14

  by isomerisation {(isomerisation induced by hydrogenation C11C3/12)} · CPC title

• C07C67/475 Primary

  by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of [IMAGE cpc-sch-C07C-0963.gif] groups between different molecules · CPC title

• C11C1/04

  by hydrolysis · CPC title

• C07C69/602

  Dicarboxylic acid esters having at least two carbon-to-carbon double bonds · CPC title

• C07C69/593

  Dicarboxylic acid esters having only one carbon-to-carbon double bond · CPC title