Process for preparing a mixture of terpene alcohols

Patent metadata

Field	Value
Publication number	US-10266468-B2
Application number	US-201716079152-A
Country	US
Kind code	B2
Filing date	Feb 16, 2017
Priority date	Feb 26, 2016
Publication date	Apr 23, 2019
Grant date	Apr 23, 2019

Abstract

The present invention relates to a process for preparing a mixture of terpene alcohols comprising limonene-4-ol and terpinene-4-ol from terpinolene epoxide via an isomerization and/or hydrogenation reaction in the presence of a copper catalyst.

First claim

The invention claimed is:

1. A process for preparing a mixture of terpene alcohols comprising limonene-4-ol of formula (II)

and terpinene-4-ol of formula (III)

said process comprising contacting terpinolene epoxide of formula (I)

with hydrogen in the presence of at least one copper catalyst and at least one inert organic solvent selected from carboxylic acid esters.

2. The process of claim 1 , wherein the copper catalyst comprises copper chromite.

3. The process of claim 1 , wherein the copper catalyst comprises at least one promoter selected from the group consisting of alkali metals, alkaline earth metals, manganese, bismuth, iron and combinations thereof.

4. The process of claim 3 , wherein the promoter is selected from the group consisting of sodium, potassium, magnesium, calcium, barium, manganese, iron and combinations thereof.

5. The process of claim 1 , wherein the copper catalyst comprises at least one binder or support material selected from the group consisting of aluminum oxide (Al 2 O 3 ), silicon dioxide (SiO 2 ), titanium dioxide (TiO 2 ), zirconium dioxide (ZrO 2 ), sodium silicate, calcium silicate, magnesium silicate, graphite, clay, zeolite, molecular sieves, and mixtures thereof.

6. The process of claim 1 , wherein the carboxylic acid ester is selected from esters of the general formula R 1 COOR 2 wherein R 1 is hydrogen or a group selected from C 1 -C 4 -alkyl, C 3 -C 6 -cycloalkyl, C 6 -C 10 -aryl and C 6 -C 10 -aryl-C 1 -C 4 -alkyl and R 2 is a group selected from C 1 -C 4 -alkyl, C 3 -C 6 -cycloalkyl, C 6 -C 10 -aryl and C 6 -C 10 -aryl-C 1 -C 4 -alkyl, each of the aforementioned groups optionally being substituted with one or more substituents selected from C 1 -C 4 -alkoxy.

7. The process of claim 1 , wherein the carboxylic acid ester is selected from C 1 -C 4 -alkyl acetates.

8. The process of claim 1 , wherein the carboxylic acid ester is ethyl acetate.

9. The process of claim 1 , wherein the temperature is from 100 to 200° C.

10. The process of claim 1 , wherein the hydrogen pressure is from 2 to 10 bar.

11. The process of claim 1 , wherein said mixture is subjected to subsequent hydrogenation to give terpinene-4-ol of formula (III).

12. The process of claim 11 , wherein the hydrogenation is carried out in the presence of at least one nickel-containing catalyst.

13. The process of claim 12 , wherein the nickel-containing catalyst is Raney nickel.

14. The process of claim 1 , wherein terpinolene epoxide of formula (I) is prepared by epoxidation of terpinolene of the formula (IV)

15. The process of claim 1 , wherein said mixture or terpinene-4-ol of the formula (III) is further converted into (±)-2-exo-(2-Methylbenzyloxy)-1-methyl-4-isopropyl-7-oxabicyclo[2.2.1]heptane, any of its individual enantiomers or any non-racemic mixture thereof.

Assignees

• Basf Agro Bv

Inventors

• Wolf Bernd
• Rack Michael
• Benson Stefan
• Goetz Roland
• Kraus Helmut

Classifications

• C07D303/06

  in which the oxirane rings are condensed with a carbocyclic ring system having three or more relevant rings · CPC title

• C07C2601/16

  the ring being unsaturated · CPC title

• C07C35/18

  with unsaturation at least in the ring · CPC title

• C07C29/56 Primary

  by isomerisation · CPC title

• C07C29/17

  by hydrogenation of carbon-to-carbon double or triple bonds · CPC title