Process involving cross metathesis of olefins

Patent metadata

Field	Value
Publication number	US-10144720-B2
Application number	US-201515120802-A
Country	US
Kind code	B2
Filing date	Mar 13, 2015
Priority date	Mar 13, 2014
Publication date	Dec 4, 2018
Grant date	Dec 4, 2018

Abstract

A method of forming a macrocyclic musk compound comprising the steps of:—
i) cross-metathesizing a first olefin and a second olefin in the presence of a homogeneous transition metal catalyst comprising an alkylidene ligand, to form a statistical mixture of a hetero-dimer intermediate of said first and second terminal olefin, and homo-dimers ii) separating the hetero-dimer from the statistical mixture of hetero- and homo-dimers iii) and cyclizing the hetero-dimer intermediate to form the macrocyclic musk compound.

First claim

The invention claimed is:

1. A method of forming a macrocyclic musk compound comprising the steps of:
i) cross-metathesizing a first olefin and a second olefin in the presence of a homogeneous transition metal catalyst comprising an alkylidene ligand, to form a statistical mixture of a hetero-dimer intermediate of said first and second terminal olefin, and homo-dimers
ii) separating the hetero-dimer from the statistical mixture of hetero- and homo-dimers
iii) and cyclizing the hetero-dimer intermediate to form the macrocyclic musk compound,
wherein,

both the first and the second olefins are olefins with a terminal double bond; and
the second olefin has the formula (II)

wherein R 7 is a branched or non-branched alkyl moiety having 1 to 5 carbon atoms and m is an integer from 1 to 10.

2. A method according to claim 1 wherein the first olefin has the formula (I)

wherein:
OR 2 is a protected hydroxyl group, which is selected from: an alkyl ether group, an ester group, a silyl ether group, and a carbonate group;
R 3 is H or methyl; and,
n is an integer from 1-8.

3. A method according to claim 1 , wherein the hetero-dimer has the formula

4. A method according to claim 1 , wherein the hetero-dimer has the formula

5. A method according to claim 1 , wherein the hetero-dimer has the formula

6. A method according to claim 1 , wherein the first olefin and second olefin are reacted in a 1:x molar ratio to produce a ratio of hetero-dimer:first homo-dimer:second homo-dimer of 2x:1:1x 2 , where X is an integer or a number having a fractional part, which is greater than 1.

7. A method according to claim 1 , wherein the hetero-dimer is formed in admixture with a protected alcohol homo-dimer and a carboxylic acid ester homo-dimer.

8. A method according to claim 7 , wherein the mixture of the hetero-dimer, the protected alcohol homo-dimer and the carboxylic acid homo-dimer is formed in a respective molar ratio of 2:1:1.

9. A method according to claim 1 , wherein the hetero-dimer is separated from the homo-dimers by distillation at a temperature of 100 to 220 degrees centigrade and a pressure of 1 to 10 mbar.

10. A method according to claim 1 , wherein the homo-dimers are recycled by metathesis with ethylene to regenerate the first and second olefins.

11. A method according to claim 10 wherein the homo-dimers are treated with ethylene gas at a pressure of 1 bar to 20 bar.

12. A method according to claim 1 , wherein the hetero-dimer is cyclized by trans-esterification.

13. A method according to claim 12 wherein, if the hetero-dimer contains a protected alcohol group, it is first de-protected by hydrolysis before being subjected to cyclization by trans-esterification.

14. A method of forming E/Z 9-ambrettolide according to the method according to claim 1 .

15. A method of forming E/Z 9-ambrettolide according to claim 14 , wherein the E/Z ratio is from 80:20 to 90:10.

16. A method according to claim 15 wherein the E/Z ratio is 85:15.

17. A method according to claim 1 , wherein the catalyst is a molybdenum or tungsten catalyst containing an alkylidene ligand.

18. A method according to claim 1 , wherein the catalyst is a compound according to the formula:

wherein
M=Mo or W; R 1 is aryl, heteroaryl, alkyl, or heteroalkyl; which may be substituted;
R 2 and R 3 can be the same or different and each is hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; which may be substituted;
R 5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, which may be substituted; and
R 4 is a residue R 6 —X—, wherein
X═O and R 6 is aryl, which may be substituted; or
X═S and R 6 is aryl, which may be substituted; or
X═O and R 6 is (R 7 , R 8 , R 9 )Si; wherein R 7 , R 8 , R 9 are alkyl or phenyl, which may be substituted; or
X═O and R 6 is (R 10 , R 11 , R 12 )C, wherein R 10 , R 11 , R 12 are independently selected from phenyl, alkyl; which may be substituted;

or,
R 4 and R 5 are linked together and are bound to M via oxygen.

19. A hetero-dimer having the formula:

wherein R 7 is a branched or non-branched alkyl moiety having 1 to 5 carbon atoms.

20. A hetero-dimer having the formula:

wherein OR 2 is a protected hydroxyl group and R 7 is a branched or non-branched alkyl moiety having 1 to 5 carbon atoms.

21. The hetero-dimer according to claim 20 having the formula:

22. A method according to claim 1 , wherein:
R 7 is methyl or ethyl.

23. A method according to claim 1 , wherein:
m is 7.

Assignees

• Givaudan Sa
• Givaudan Sa

Inventors

• Davey Paul Nicholas
• Lovchik Martin Alan
• Goeke Andreas
• Lorincz Krisztian
• Toth Florian
• Ondi Levente

Classifications

• C07C69/734

  Ethers · CPC title

• C07C67/343

  by increase in the number of carbon atoms · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07D313/00 Primary

  Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom · CPC title

• C11B9/0084

  the hetero rings containing more than six atoms · CPC title