Process for the epoxidation of a tetrasubstituted alkene

Patent metadata

Field	Value
Publication number	US-10640477-B2
Application number	US-201716309475-A
Country	US
Kind code	B2
Filing date	Jun 1, 2017
Priority date	Jun 15, 2016
Publication date	May 5, 2020
Grant date	May 5, 2020

Abstract

This invention relates to a process for the epoxidation of a tetrasubstituted alkene such as terpinolene to the corresponding epoxide such as terpinolene epoxide by reacting the tetrasubstituted alkene with peracetic acid prepared in situ from acetic anhydride and hydrogen peroxide in the presence of at least one buffering agent. Further, the invention relates to the use of an oxidizing agent comprising hydrogen peroxide and acetic anhydride for the in-situ epoxidation of a tetrasubstituted alkene.

First claim

The invention claimed is:

1. A process for the epoxidation of a tetrasubstituted alkene to the corresponding epoxide comprising reacting the tetrasubstituted alkene with peracetic acid prepared in situ from acetic anhydride and hydrogen peroxide in the presence of at least one buffering agent wherein the hydrogen peroxide is used as an aqueous solution and the reaction is carried out in the presence of at least one inert organic solvent selected from non-halogenated aromatic hydrocarbons, and wherein the tetrasubstituted alkene contains one additional carbon-carbon double bond being trisubstituted.

2. The process of claim 1 , wherein the buffering agent is selected from the group consisting of salts of inorganic acids, salts of organic acids and any combination thereof.

3. The process of claim 1 , wherein the buffering agent is a salt selected from the group consisting of phosphates, formates, acetates, carbonates, citrates, sulfates and any combination thereof.

4. The process claim 1 , wherein the buffering agent is selected from the group consisting of alkali metal and alkaline earth metal phosphates, alkali metal and alkaline earth metal acetates, alkali metal and alkaline earth metal carbonates and any combination thereof.

5. The process of claim 1 , wherein the molar ratio of hydrogen peroxide to acetic anhydride is from 2.0:1.9 to 1.1:1.05.

6. The process of claim 1 , wherein the temperature is from 0 to 50° C.

7. The process of claim 1 , wherein the tetrasubstituted alkene is terpinolene of the formula (Ia):

and the corresponding epoxide is terpinolene epoxide of formula (IIa)

8. The process according to claim 7 , wherein the terpinolene epoxide of formula (IIa) is further subjected to an epoxide ring opening isomerization leading to limonene-4-ol.

9. The process according to claim 8 , wherein limonene-4-ol is further reduced to give terpinene-4-ol.

10. 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 the terpinolene epoxide of formula (IIa) in accordance with claim 7 .

11. The process of claim 10 , further comprising subjecting terpinolene epoxide of formula (IIa) to an epoxide ring opening isomerization to give limonene-4-ol.

12. The process of claim 11 further comprising hydrogenating limonene-4-ol to afford terpinene-4-ol.

13. The process of claim 12 , 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.

14. The process of claim 13 , 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

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

Classifications

• C07D301/16 Primary

  formed in situ, e.g. from carboxylic acids and hydrogen peroxide · CPC title

• C07D303/04 Primary

  containing only hydrogen and carbon atoms in addition to the ring oxygen atoms · CPC title

• C07D493/08

  Bridged systems · CPC title