Process for the preparation of limonene-4-ol

Patent metadata

Field	Value
Publication number	US-10538470-B2
Application number	US-201615571987-A
Country	US
Kind code	B2
Filing date	Apr 22, 2016
Priority date	May 8, 2015
Publication date	Jan 21, 2020
Grant date	Jan 21, 2020

Abstract

The present invention relates to a process for the preparation of limonene-4-ol by an epoxide ring opening isomerization of terpinolene epoxide.

First claim

The invention claimed is:

1. A process for the preparation of limonene-4-ol of formula (II)

comprising subjecting a selective epoxide ring opening isomerization to a terpinolene epoxide of formula (I)

in the presence of a sulfonic acid and an organic base as a catalyst.

2. The process of claim 1 , wherein the sulfonic acid is selected from the group consisting of (C 1 -C 14 )-alkylsulfonic acids, halo-(C 1 -C 6 )-alkylsulfonic acids, (C 1 -C 6 )-alkyl-(C 6 -C 10 )-arylsulfonic acids, camphorsulfonic acid and any mixture thereof.

3. The process of claim 1 , wherein the sulfonic acid is selected from the group consisting of methane sulfonic acid, dodecyl sulfonic acid, trifluoromethane sulfonic acid, p-toluene sulfonic acid, 2-naphthalene sulfonic acid, camphorsulfonic acid and any mixture thereof.

4. The process of claim 1 , wherein the base is selected from the group consisting of tertiary amines, pyridine, substituted pyridines, bicyclic amines and any mixture thereof.

5. The process of claim 1 , wherein the base is selected from the group consisting of trimethylamine, triethylamine, tributylamine, N,N-diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, N-methyl imidazole, pyridine, collidine, lutidine, picoline, N,N-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-en, 1,5-diazabicyclo[4.3.0]non-5-ene and 1,4-diazabicyclo[2.2.2]octan.

6. The process of claim 1 , wherein the base is selected from the group consisting of triethylamine and N,N-dimethylaminopyridine.

7. The process of claim 1 , wherein the base is used in the form of a free base or in the form of a salt with a sulfonic acid that may be the same or different to the sulfonic acid used as the catalyst.

8. The process of claim 7 , wherein the base is used in the form of a salt with methanesulfonic acid or p-toluene sulfonic acid.

9. The process of claim 1 , wherein the molar ratio of the sulfonic acid used as the catalyst to terpinolene epoxide is from 0.01:1 to 0.5:1.

10. The process of claim 1 , wherein the molar ratio of the sulfonic acid used as the catalyst to the organic base calculated as a free base is from 4:1 to 1.01:1.

11. The process of claim 1 , wherein the isomerization is carried out in an inert organic solvent.

12. The process of claim 11 , wherein the solvent is selected from the group consisting of aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, halogenated aromatic hydrocarbons, carboxylic acid esters, ethers, ketones and nitriles.

13. The process of claim 1 , wherein the isomerization is carried out at −10 to 60° C.

14. The process of claim 1 , wherein limonene-4-ol is further reduced to give terpinene-4-ol.

15. The process of claim 1 , wherein terpinolene epoxide of formula (I) is prepared via epoxidation of terpinolene.

16. A process for preparing (±)-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, comprising preparing limonene-4-ol of formula (II) in accordance with claim 1 .

17. The process of claim 16 , further comprising hydrogenating limonene-4-ol to afford terpinene-4-ol.

18. The process of claim 17 , further comprising treating terpinene-4-ol successively or concurrently with an oxidizing agent and an acid in an inert solvent to effect epoxidation and cyclization to give (±)-2-exo-hydroxy-1-methyl-4-isopropyl-7-oxabicyclo[2.2.1]heptane.

19. The process of claim 18 , further comprising reacting (±)-2-exo-hydroxy-1-methyl-4-isopropyl-7-oxabicyclo[2.2.1]heptane with a compound of the formula WCH 2 L wherein W is 2-methylphenyl and L is a leaving group to afford (±)-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
• Kraus Helmut
• Goetz Roland
• Narayanan Sukunath
• Rishinaradamangalam Chidambaram

Classifications

• C07C29/56 Primary

  by isomerisation · CPC title

• C07D493/08

  Bridged systems · CPC title

• C07C29/17

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

• C07C2601/16

  the ring being unsaturated · CPC title