Metathesis reactions with cardanol and/or anacardic acid

Patent metadata

Field	Value
Publication number	US-9670109-B2
Application number	US-201314428013-A
Country	US
Kind code	B2
Filing date	Sep 11, 2013
Priority date	Sep 14, 2012
Publication date	Jun 6, 2017
Grant date	Jun 6, 2017

Abstract

The invention provides a method of alkene metathesis comprising contacting at least a first alkene, which is cardanol and/or anacardic acid, with an alkylidene ruthenium alkene metathesis catalyst comprising two ligands P 1 and P 2 , which may be the same or different and of formula P(R 1 ) 3 , in which P is a phosphorus atom coordinated to the ruthenium ion and each R 1 is independently an optionally substituted alkyl or alkoxy group; or two R 1 groups within one P 1 or P 2 ligand constitute an optionally substituted bicycloalkyl.

First claim

The invention claimed is:

1. A method of preparing 3-non-8-enylphenol by ethenolysis comprising:
contacting at least a first alkene, which is cardanol, with an alkylidene ruthenium alkene metathesis catalyst according to formula (I):

wherein: ligands P 1 and P 2 may be the same or different and of formula P(R 1 ) 3 , in which P is a phosphorus atom coordinated to the ruthenium ion and each R 1 is independently a C 5-10 cycloalkyl group; X 1 and X 2 are anionic ligands, which may be the same or different; and A is an alkylidene group.

2. The method of claim 1 wherein the method comprises the ethenolysis of cashew nut shell liquid.

3. The method of claims 1 wherein the method comprises the self metathesis of a trienic component of cashew nut shell liquid.

4. The method of claim 3 wherein the trienic component is of formula (III):

wherein —R′ is a hydrocarbyl chain of the following formula, wherein * indicates the end of the bond through which the hydrocarbyl chain is attached to the aromatic ring:

5. A method of preparing ethoxy-3-nonylphenol or oligoethoxy-3-nonylphenol from the 3-non-8-enylphenol produced in claim 1 further comprising hydrogenating the 3-non-8-enylphenol and ethoxylating the resultant 3-nonylphenol to provide ethoxy-3-nonylphenol or oligoethoxy-3-nonylphenol, in which the -oligoethoxy substituent is of formula (OCH2CH2)nOH, wherein n is an integer of between 1 and 20.

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

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

8. The method of claim 1 wherein the alkylidene group is a moiety of formula ═CR y R Z and in which one of R y and R z may be hydrogen and either or both of Ry and Rz may be alkyl, alkenyl, alkynyl, aryl carboxyalkyl, alkoxy, alkenyloxy, alkynyloxy or alkoxycarbonyl, or R y and R z together form a saturated, unsaturated or aromatic cyclic or bicyclic moiety.

9. The method of claim 8 wherein R y is hydrogen, alkyl or aryl and R z is alkyl, alkenyl or aryl.

10. The method of claim 8 wherein the alkylidene group is optionally substituted indenylidene.

11. The method of claim 10 wherein the alkylidene group is a phenyl-substituted indenylidene.

12. The method of claim 10 wherein the alkylidene group is 3-phenyl-1H-inden-1-ylidene.

13. The method of claim 12 wherein the catalyst is a dihalo(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine) ruthenium (II).

14. The method of claim 13 wherein the catalyst is a dichloro(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine) ruthenium (II).

Assignees

• Univ Court Univ St Andrews

Inventors

• Julis Jennifer
• Cole-Hamilton David John
• Cazin Catherine

Classifications

• C07C1/20 Primary

  starting from organic compounds containing only oxygen atoms as heteroatoms · CPC title

• C07C41/03

  by reaction of oxirane rings with hydroxy groups · CPC title

• C07C37/50

  by reactions decreasing the number of carbon atoms (C07C37/04, C07C37/045, C07C37/055, C07C37/08 take precedence) · CPC title

• C07C39/19

  containing carbon-to-carbon double bonds but no carbon-to-carbon triple bonds · CPC title

• C07C2531/22

  Organic complexes · CPC title