Process for the epoxidation of a tetrasubstituted alkene

Patent metadata

Field	Value
Publication number	US-11072593-B2
Application number	US-201716309478-A
Country	US
Kind code	B2
Filing date	Jun 1, 2017
Priority date	Jun 15, 2016
Publication date	Jul 27, 2021
Grant date	Jul 27, 2021

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 performic acid prepared in situ from formic acid 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 formic acid 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 performic acid prepared in situ from formic acid and hydrogen peroxide in the presence of at least one buffering agent
wherein the tetrasubstituted alkene is terpinolene of the formula (Ia)

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

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

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

4. The process according to claim 1 wherein the buffering agent is selected from alkali metal and alkaline earth metal phosphates, alkali metal and alkaline earth metal formates and any combination thereof.

5. The process according to claim 1 wherein the buffering agent is selected from alkali metal phosphates.

6. The process according to claim 1 wherein the buffering agent is selected from di-(alkali metal) hydrogen phosphates.

7. The process according to claim 1 wherein the reaction is carried out in the presence of at least one inert organic solvent.

8. The process according to claim 7 wherein the inert organic solvent is selected from non-halogenated aliphatic hydrocarbons, non-halogenated cycloaliphatic hydrocarbons, non-halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, amides, ethers, esters, ketones, nitriles and any combination thereof.

9. The process according to claim 7 wherein the inert organic solvent is selected from non-halogenated inert organic solvents.

10. The process according to claim 1 wherein the temperature is from 0 to 70° C.

11. The process according to claim 1 wherein the terpinolene epoxide of formula (IIa) is further converted via limonene-4-ol to terpinene-4-ol.

12. The process according to claim 1 , wherein the terpinolene epoxide of formula (IIa), limonene-4-ol or terpinene-4-ol 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

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

Classifications

• B01J19/0086

  Processes carried out with a view to control or to change the pH-value; Applications of buffer salts; Neutralisation reactions · CPC title

• C07D303/04

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

• C07D493/08

  Bridged systems · CPC title

• C07D301/16 Primary

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