Catalytic oxidation of 3,5,5-trimethylcyclohexa-3-ene-1-one (β-isophorone) with hydrogen peroxide to afford 2,6,6-trimethyl-2-cyclohexene-1,4-dione (keto-isophorone)

Patent metadata

Field	Value
Publication number	US-10093605-B2
Application number	US-201715822607-A
Country	US
Kind code	B2
Filing date	Nov 27, 2017
Priority date	Dec 2, 2016
Publication date	Oct 9, 2018
Grant date	Oct 9, 2018

Abstract

The present invention provides a novel process for producing 2,6,6-trimethyl-2-cyclohexene-1,4-dione (keto-isophorone) by catalytic oxidation of 3,5,5-trimethylcyclohexa-3-ene-1-one (β-isophorone) with hydrogen peroxide as the oxidant. In particular, the novel process includes phase transfer reagent in a biphasic system including an organic phase and an aqueous phase wherein the biphasic system includes 1) a tungsten polyoxyometallate as catalyst and hydrogen peroxide, and/or 2) a mixture of a) a mineral acid, b) hydrogen peroxide, and c) a metal tungstate.

First claim

The invention claimed is:

1. A process for producing keto-isophorone, the process comprising the step of oxidizing β-isophorone in the presence of a catalyst and hydrogen peroxide in a one-pot synthesis, in the presence of a phase transfer reagent in a biphasic system comprising
A) an organic phase
and
B) an aqueous phase
wherein the biphasic system comprises:
1) a tungsten polyoxyometallate as catalyst and hydrogen peroxide,
and/or
2) a mixture of
a) a mineral acid,
b) hydrogen peroxide, and
c) a metal tungstate.

2. The process according to claim 1 , wherein the oxidizing is performed at a temperature of from 30 to 120° C.

3. The process according to claim 1 , wherein the ratio of β-isophorone to H 2 O 2 is from 1:0.7 to 1:3 wt %.

4. The process according to claim 1 , wherein the ratio of organic phase to aqueous phase varies from 1:10 to 5:1 wt %.

5. The process according to claim 1 , wherein the hydrogen peroxide concentration in the aqueous phase is from 1 to 50 wt %.

6. The process according to claim 1 , wherein the molar ratio of catalyst to hydrogen peroxide is from 1:10 to 1:400 wt %.

7. The process according to claim 1 , wherein the phase transfer agent is selected from the group consisting of quaternary ammonium salts, tertiary amines or quaternary phosphonium salts, alone or in mixtures.

8. The process according to claim 7 , wherein the phase transfer agent is selected from the group consisting of dodecyltrimethylammonium salts, hexadecyltrimethylammonium salts, octadecyltrimethylammonium salts, methyltributylammonium salts, methyltrioctylammonium salts, dodecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, tributylamine, trioctylamine, alkyl-, benzyl- and phenylphosphonium salts, alone or in mixtures.

9. The process according to claim 1 , wherein the mineral acid is selected from the group consisting of phosphoric acid, phosphorous acid, polyphosphoric acid, pyrophosphoric acid, alone or in mixtures.

10. The process according to claim 1 , further wherein the metal tungstate is selected from the group consisting of sodium tungstate, potassium tungstate, and ammonium tungstate.

11. The process according to claim 1 , wherein the biphasic system consists of sodium tungstate, phosphoric acid and a phase transfer reagent.

12. The process according to claim 1 , wherein the phase transfer agent is trioctylamine.

13. The process according to claim 1 , wherein the oxidizing is performed at temperatures of from 50 to 80° C.

14. The process according to claim 1 , wherein the ratio of β-isophorone to H 2 O 2 is from 1:1 to 1:2.2 wt %.

15. The process according to claim 1 , wherein the ratio of organic phase to aqueous phase varies from 1:4 to 2:1 wt %.

16. The process according to claim 1 , wherein the H 2 O 2 concentration in the aqueous phase is from 2 to 30 wt %.

17. The process according to claim 1 , wherein the molar ratio of catalyst to H 2 O 2 is from 1:50 to 1:200 wt %.

18. The process according to claim 2 , wherein the mineral acid is selected from the group consisting of phosphoric acid, phosphorous acid, polyphosphoric acid, pyrophosphoric acid, alone or in mixtures, are employed as the mineral acids.

19. The process according to claim 2 , wherein sodium, potassium and/or ammonium tungstate.

20. The process according to claim 7 , wherein the phase transfer agent is selected from the group consisting of di-tert-butylmethylphosphonium tetrafluoroborate, benzyltriphenylphosphonium chloride and triphenylbutylphosphonium chloride, alone or in mixtures.

Assignees

• Evonik Degussa Gmbh

Inventors

• Bajus Stephanie
• Cassens Jan
• Döring Jens
• Nitz Jörg-Joachim
• Kohlstruk Stephan
• Jansen Robert

Classifications

• C07C45/28 Primary

  of CHx-moieties · CPC title

• C07C45/294

  with hydrogen peroxide · CPC title

• C07C2601/16

  the ring being unsaturated · CPC title

• C07C49/603

  of a six-membered ring, e.g. quinone methides · CPC title