Synthetic method

Patent metadata

Field	Value
Publication number	US-9908826-B2
Application number	US-201515115591-A
Country	US
Kind code	B2
Filing date	Jan 28, 2015
Priority date	Jan 30, 2014
Publication date	Mar 6, 2018
Grant date	Mar 6, 2018

Abstract

The invention relates to a method of alkene metathesis. In the method, at least one monoalkene is subjected to ethenolysis in the presence of a diene. The invention also relates to the use of a diene to promote an ethenolysis reaction conducted on a monoalkene.

First claim

The invention claimed is:

1. A method of ethenolysis of a monoalkene, comprising introducing into a reaction vessel a monoalkene, ethylene and a diene, and subjecting the monoalkene to ethenolysis in the presence of an alkylidene ruthenium alkene metathesis catalyst and the diene, wherein the diene consists only of carbon and hydrogen atoms; and/or is cyclic; and wherein the metathesis catalyst comprises two ligands P 1 and P 2 , which may be the same or different and are of formula P(R 1 ) 3 , in which P is a phosphorus atom coordinated to the ruthenium and each R 1 is independently an optionally substituted alkyl, cycloalkyl, alkoxy or cycloalkyloxy group; or two R 1 groups within one P 1 or P 2 ligand and the phosphorus atom to which they are attached constitute an optionally substituted bicycloalkane phosphino.

2. The method of claim 1 , wherein the monoalkene is optionally esterified selected from a monounsaturated fatty acid and a monounsaturated fatty acid ester.

3. The method of claim 2 , wherein the fatty acid comprises from 4 to 28 carbon atoms.

4. The method of claim 2 wherein the fatty acid is selected from the group consisting of oleic acid, sapienic acid, palmitoleic acid, myristoleic acid or erucic acid.

5. The method of claim 4 , wherein the fatty acid is oleic acid.

6. The method of claim 2 , wherein the fatty acid is esterified.

7. The method of claim 6 , wherein the esterified fatty acid is an alkyl ester.

8. The method of claim 2 , wherein the monoalkene is methyl oleate.

9. The method of claim 1 , wherein a carbon atom of the carbon-carbon double bond of the monoalkene is tethered to an aromatic moiety.

10. The method of claim 9 , wherein the aromatic moiety is an aromatic alcohol.

11. The method of claim 9 , wherein the method comprises the ethenolysis of cashew nut shell liquid, or one or more components thereof.

12. The method of claim 11 wherein the method comprises the ethenolysis of a monoalkene component of cardanol.

13. The method of claim 11 , wherein the method comprises the ethenolysis of

14. The method of claim 11 , wherein a product of the ethenolysis reaction is 1-octene.

15. The method of claim 11 , wherein a product of the ethenolysis reaction is 3-Non-8-enylphenol.

16. The method of claim 15 further comprising hydrogenating 3-Non-8-enylphenol resulting in 3-nonylphenol and ethoxylating the resultant 3-nonylphenol to provide ethoxy-3-nonylphenol or oligoethoxy-3-nonylphenol, in which the oligoethoxy substituent is of formula —(OCH 2 CH 2 ) n OH, wherein n is an integer of between 1 and 20.

17. The method of claim 1 , wherein the catalyst is of formula (I):

wherein:
P 1 and P 2 are as defined in claim 1 ;
X 1 and X 2 are anionic ligands, which may be the same or different; and
A is an alkylidene group.

18. The method of claim 1 , wherein each R 1 is independently a C 5-10 cycloalkyl group.

19. The method of claim 1 , wherein at least one of ligands P 1 and P 2 is tricyclohexylphosphine.

20. The method of claim 1 , wherein both ligands P 1 and P 2 are the same.

21. The method of claim 1 , wherein the alkylidene group is a moiety of formula=CR y R z and (i) one of R y and R z is hydrogen and the other of R y and R z is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, carboxyalkyl, alkoxy, alkenyloxy, alkynyloxy and alkoxycarbonyl, or (ii) each of R y and R z is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl carboxyalkyl, alkoxy, alkenyloxy, alkynyloxy and alkoxycarbonyl, or (iii) R y and R z together form a saturated, unsaturated or aromatic cyclic or bicyclic moiety.

22. The method of claim 21 wherein the alkylidene group is optionally substituted indenylidene.

23. The method of claim 22 wherein the alkylidene group is a phenyl-substituted indenylidene.

24. The method of claim 22 wherein the alkylidene group is 3-phenyl-1H-inden-1-ylidene.

25. The method of claim 24 wherein the catalyst is a dihalo(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine) ruthenium (II).

26. The method of claim 25 wherein the catalyst is a dichloro(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine) ruthenium (II).

27. The method of claim 21 wherein the alkylidene group is phenylidene.

28. The method of claim 1 , wherein the diene is 1,4-cyclohexadiene.

29. The method of claim 1 , wherein the diene consists only of carbon and hydrogen atoms, and comprises 4-10 carbon atoms.

30. The method of claim 29 , wherein the diene comprises 6-8 carbon atoms.

31. The method of claim 1 , wherein the diene is selected from the group consisting of 1,4-hexadiene, 1,5-cyclooctadiene and 1,7-octadiene.

Assignees

• Univ Court Univ St Andrews
• Univ Court Univ St Andrews

Inventors

• Julis Jennifer
• Bartlett Stuart
• Cole Hamilton David John

Classifications

• Y02P30/20

  using bio-feedstock · CPC title

• C07C6/06

  at a cyclic carbon-to-carbon double bond · CPC title

• B01J2531/821

  Ruthenium · CPC title

• C07C6/02 Primary

  Metathesis reactions at an unsaturated carbon-to-carbon bond · CPC title

• B01J31/2278

  Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts · CPC title