Process for preparing α-damascone

Patent metadata

Field	Value
Publication number	US-10150730-B2
Application number	US-201615753244-A
Country	US
Kind code	B2
Filing date	Aug 17, 2016
Priority date	Aug 18, 2015
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

Abstract

The present invention relates to a process for preparing 1-(2,6,6-trimethylcyclohex-2-en-1-yl)but-2-en-1-one, which comprises a) providing 6,10-dimethylundeca-1,5,9-trien-4-ol, b) oxidizing 6,10-dimethylundeca-1,5,9-trien-4-ol provided in step a) with an oxidizing agent in the presence of at least one organic nitroxyl radical, at least one nitrate compound and an inorganic solid to yield 6,10-dimethylundeca-1,5,9-trien-4-one, c) reacting the 6,10-dimethylundeca-1,5,9-trien-4-one obtained in step b) with an acid to yield 1-(2,6,6-trimethylcyclohex-2-en-1-yl)but-2-en-1-one.

First claim

We claim:

1. A process for preparing 1-(2,6,6-trimethylcyclohex-2-en-1-yl)but-2-en-1-one, comprising:
a) providing 6,10-dimethylundeca-1,5,9-trien-4-ol,
b) oxidizing the 6,10-dimethylundeca-1,5,9-trien-4-ol provided in step a) with an oxidizing agent, which is selected from the group consisting of hypochlorites, hydrogen peroxide and molecular oxygen, in the presence of at least one organic nitroxyl radical, at least one nitrate compound and an inorganic solid, which is selected from the group consisting of alkali metal halides and alkali earth metal halides, to yield 6,10-dimethylundeca-1,5,9-trien-4-one,
c) reacting the 6,10-dimethylundeca-1,5,9-trien-4-one obtained in step b) with an acid selected from mineral acids to yield 1-(2,6,6-trimethylcyclohex-2-en-1-yl)but-2-en-1-one.

2. The process of claim 1 , where the total amount of the at least one nitroxyl radical used in step b) is in the range of 1 to 50 mol-%, based on the amount of 6,10-dimethylundeca-1,5,9-trien-4-ol in the reaction mixture.

3. The process according to claim 1 , where the nitroxyl radical used in step b) is selected from the group consisting of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl compounds, 2-azaadamantane-N-oxyl compounds, (1,1,3,3-tetramethylisoindolin-2-yl)oxyl compounds, 9-azanoradamantane N-oxyl, 9-azabicyclo[3.3.1]nonane N-oxyl, 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide, diphenylnitroxyl, di-tert-butylnitroxyl and mixtures thereof.

4. The process of claim 1 , where the nitrate compound used in step b) is selected from the group consisting of transition metal nitrates, nitric acid (HNO 3 ) and mixtures thereof.

5. The process of claim 1 , where the nitrate compound used in step b) is selected from the group consisting of Fe(NO 3 ) 3 and nitric acid (HNO 3 ).

6. The process of claim 1 , where the total amount of the at least one nitrate compound used in step b) is in the range of 1 to 50 mol-%, based on the amount of 6,10-dimethylundeca-1,5,9-trien-4-ol in the reaction mixture.

7. The process of claim 1 , where the molar ratio of the at least one nitroxyl radical to the at least one nitrate compound used in step b) is in the range of 1:10 to 10:1.

8. The process of claim 1 , where the inorganic solid used in step b) is selected from the group consisting of LiF, LiCl, KF, KCl, NaF, NaCl and mixtures thereof.

9. The process of claim 1 , where the total amount of the inorganic solid used in step b) is in the range of 0.5 to 20% by weight, based on the amount of 6,10-dimethylundeca-1,5,9-trien-4-ol in the reaction mixture.

10. The process of claim 1 , where the oxidizing agent used in step b) is molecular oxygen.

11. The process of claim 1 , where the oxidizing agent used in step b) is present in excess, based on the amount of 6,10-dimethylundeca-1,5,9-trien-4-ol in the reaction mixture.

12. The process of claim 1 , where the acid used in step c) is selected from sulfuric acid and phosphoric acid.

13. The process of claim 1 , where the total amount of the acid used in step c) is in the range of 0.9 to 5 mol per 1 mol of 6,10-dimethylundeca-1,5,9-trien-4-one.

14. The process of claim 1 , where the at least one nitroxyl radical, the at least one nitrate compound and the inorganic solid are added to 6,10-dimethylundeca-1,5,9-trien-4-ol provided in step a).

15. The process of claim 1 , where the 6,10-dimethylundeca-1,5,9-trien-4-ol is provided by reacting 3,7-dimethylocta-2,6-dienal with an allylmagnesium compound.

Assignees

• Basf Se

Inventors

• Rüdenauer Stefan
• Fenlon Thomas
• Hindalekar Shrirang
• Pansare Nisha
• Roy Abhijeet Deb
• Swaminathan Vijay Narayanan

Classifications

• C07C2601/16

  the ring being unsaturated · CPC title

• C07C403/16 Primary

  not being part of —CHO groups · CPC title

• C07C49/203

  with only carbon-to-carbon double bonds as unsaturation · CPC title

• C07C45/39

  being a secondary hydroxyl group · CPC title