Synthesis of terminal alkenes from internal alkenes via olefin metathesis

• US 8,501,973 B2
• Filed: 10/15/2007
• Issued: 08/06/2013
• Est. Priority Date: 10/13/2006
• Status: Active Grant

• Current Assignee: Wilmar Trading Pte., Ltd. (Wilmar International Limited)
• Original Assignee: Elevance Renewable Sciences Incorporated
• Inventors: Schrodi, Yann, Pederson, Richard L., Kaido, Hiroki, Tupy, Michael John
• Primary Examiner(s): Carr, Deborah D
• Application Number:
  US12/445,000
• Publication Number:
  US 20100145086A1
• Time in Patent Office: 2,122 Days
• Field of Search: 554/124
• US Class Current: 554/124
• CPC Class Codes: B01J 2231/54 Metathesis reactions, e.g. olefin metathesis
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 31/2278 Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 2531/22 Organic complexes
• CPC Class Codes: C07C 2531/24 Phosphines
• CPC Class Codes: C07C 6/04 at a carbon-to-carbon double bond
• CPC Class Codes: C07C 67/333 by isomerisation; by change of size of the carbon skeleton introduction or elimination of carboxyl groups C07C67/313, C07C67/32
• CPC Class Codes: C07C 67/475 by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
• CPC Class Codes: C07C 69/533 Monocarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C07C 69/73 of unsaturated acids

Abstract

This disclosure relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by an olefin metathesis catalyst. According to one aspect, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting, in the presence of a ruthenium alkylidene metathesis catalyst, an olefinic substrate comprised of at least one internal olefin with a cross metathesis partner comprised of an alpha olefinic reactant, under reaction conditions effective to allow cross-metathesis to occur, wherein the reaction conditions include a reaction temperature of at least 35° C. The methods, compositions, reactions and reaction systems herein disclosed have utility in the fields of catalysis, organic synthesis, and industrial chemistry.

Claims

1. A method for synthesizing a terminal olefin, the method comprising:

providing an olefinic substrate having at least one internal olefin;

providing an alpha olefin having at least 3 carbon atoms; and

contacting the olefinic substrate with the alpha olefin in the presence of less than approximately 100 ppm of a metathesis catalyst relative to the number of olefinic substrate double bonds, under reaction conditions effective to allow cross-metathesis to occur;

wherein the contacting yields a product having at least 10 wt % 9DA, and the catalyst has a TON_9DA of approximately 10,000 or greater.

2. The method of claim 1, wherein the reaction conditions effective to ensure that the olefinic substrate and the cross-metathesis partner are in liquid form.

3. The method of claim 1, wherein the internal olefin is selected from the group consisting of:

a C₈-C₂₄ monounsaturated compound, a C₈-C₂₄ monounsaturated segment, and combinations thereof.

4. The method of claim 1, wherein the olefinic substrate comprises a mixture of internal olefins.

5. The method of claim 4, wherein the internal olefins are selected from the group consisting of:

monoglycerides, diglycerides, triglycerides, and combinations thereof.

6. The method of claim 4, wherein the olefinic substrate is an oil or a compound derived from an oil.

7. The method of claim 1, wherein the olefinic substrate is a fatty acid ester.

8. The method of claim 1, wherein the olefinic substrate is a seed oil or a compound derived from a seed oil.

9. The method of claim 8, wherein the olefinic substrate is selected from the group consisting of:

canola oil, soybean oil, sunflower oil, safflower oil, cottonseed oil, castor oil, rapeseed oil, peanut oil, corn oil, olive oil, palm oil, sesame oil, grapeseed oil, fatty acid esters thereof, and combinations thereof.

10. The method of claim 1, wherein the alpha olefin is selected from the group consisting of:

mono-substituted olefins, di-substituted olefins, and combinations thereof.

11. The method of claim 10, wherein the alpha olefin contains one or two substituents each having 1 to about 10 carbon atoms.

12. The method of claim 10, wherein the alpha olefin is a mono-substituted olefin haying 1 to about 10 carbon atoms.

13. The method of claim 12, wherein the alpha olefin is selected from the group consisting of:

propene, 1-butene, 1-hexene, and combinations thereof.

14. The method of claim 1, wherein the alpha olefin has a solubility of at least 0.25 M in the olefinic substrate.

15. The method of claim 1, wherein the metathesis catalyst is a ruthenium alkylidene metathesis catalyst which has the structure of formula (IV):

19. The method of claim 1, wherein the contacting occurs in the presence of approximately 50 ppm or less of the catalyst.

20. The method of claim 1, wherein the contacting occurs in the presence of approximately 10 ppm or less of the catalyst.

21. The method of claim 1, wherein the contacting yields at least 20 wt % 9DA.

22. The method of claim 1, wherein the TON_9DA is approximately 20,000 or greater.

16. A method for synthesizing a terminal olefin, the method comprising:

contacting, under an inert or oxygen atmosphere and in the presence of a ruthenium alkylidene metathesis catalyst, an olefinic substrate comprised of at least one internal olefin with a cross metathesis partner comprised of an alpha olefin having at least 3 carbon atoms, under reaction conditions effective to ensure that the olefinic substrate and the cross-metathesis partner are in liquid form and to allow cross-metathesis to occur, wherein the catalyst is present in an amount ranging from about 1 ppm to about 100 ppm relative to the number of olefinic substrate double bonds.

17. The method of claim 16, wherein the method provides a terminal olefin having a turnover number of at least twice the turnover number obtained for an identical reaction in which ethylene is substituted for the alpha olefin.

18. The method of claim 16, wherein the method provides a terminal olefin having a turnover number of at least five times the turnover number obtained for an identical reaction in which ethylene is substituted for the alpha olefin.

23. A method for synthesizing a terminal olefin, the method comprising:

contacting, in the presence of a ruthenium alkylidene metathesis catalyst, an olefinic substrate comprised of at least one internal olefin with an alpha olefin having at least 3 carbon atoms, under reaction conditions effective to allow cross-metathesis to occur, wherein the ruthenium alkylidene metathesis catalyst is present in an amount of approximately 100 ppm or less and the method provides a terminal olefin having a turnover number of at least twice the turnover number obtained for an identical reaction in which ethylene is substituted for the alpha olefin, and wherein the ruthenium alkylidene metathesis catalyst has the structure of formula (IV);

24. The method of claim 23, wherein the turnover number is at least five times the turnover number obtained for an identical reaction in which ethylene is substituted for the alpha olefin.