Method for producing menthones from isopulegol in the gas phase

Patent metadata

Field	Value
Publication number	US-9856199-B2
Application number	US-201515123325-A
Country	US
Kind code	B2
Filing date	Mar 6, 2015
Priority date	Mar 7, 2014
Publication date	Jan 2, 2018
Grant date	Jan 2, 2018

Abstract

The present invention relates to a process for reacting isopulegol to menthone in the gas phase and to the use of the reaction products thus prepared as additives in foods, cosmetics, pharmaceutical products, tobacco formulations, household products, and laundry care products.

First claim

We claim:

1. A process for making menthone comprising contacting a carrier gas that includes isopulegol in the gas phase with an activated oxidic copper catalyst, optionally comprising at least one element selected from aluminum, manganese, barium, chromium, calcium, or iron, and optionally isolating a menthone-containing reaction product.

2. The process according to claim 1 , wherein a copper catalyst is activated with hydrogen, or with hydrogen and an alcohol to form the activated oxidic copper catalyst.

3. The process according to claim 1 , wherein the activated, oxidic copper catalyst includes copper present in the +I or +II oxidation state.

4. The process according to claim 1 , wherein the carrier gas comprises nitrogen, argon or a mixture thereof.

5. The process according to claim 1 , wherein the isopulegol comprises an enantiomer of the formula I

6. The process according to claim 1 , wherein the reaction is carried out at a temperature of 150-250° C.

7. The process according to claim 1 , wherein the activated, oxidic copper catalyst comprises copper and at least one further element selected from aluminum, manganese, barium, chromium, calcium, or iron, each in elemental form and/or as oxides.

8. The process according to claim 7 , in which the oxides are present as single-element oxides, double oxides, multiple oxides, or mixtures thereof.

9. The process according to claim 1 , wherein the activated, oxidic copper catalyst has a fraction of at least 20% up to 100 wt % of copper compound, based on the dry mass of the catalyst.

10. The process according to claim 1 , wherein the activated, oxidic copper catalyst is selected from one of the following compositions:
a) 30-40% copper oxide, 10-25% aluminum oxide, 10-25% manganese oxide, and 30-40% aluminum copper oxide,
b) 30-45% copper oxide, 10-25% aluminum oxide, 10-20% manganese oxide, and 30-40% aluminum copper oxide,
c) 60.0-65.0% chromium copper oxide (Cr 2 CuO 4 ), 20.0-25.0% copper oxide, 5.0-10.0% barium oxide, 1,0-5.0% graphite, 1.0% dichromium trioxide, and 1.0% chromium trioxide,
d) 60.0-70.0% chromium copper oxide (Cr 2 CuO 4 ), 20.0-30.0% copper oxide, 1.0-5.0% manganese dioxide, 1.0-5.0% silicic acid (sodium salt), 1.0-5.0% graphite, and 0.0-0.5% copper chromate,
e) 55.0-65.0% chromium copper oxide (Cr 2 CuO 4 ), 20.0-30.0% copper oxide, 5.0-10.0% silicon dioxide, 5.0-10.0% silicic acid (sodium salt), and 1.0-5.0% graphite,
f) 41.0-46.0% chromium copper oxide (Cr 2 CuO 4 ), 25.0-35.0% aluminum oxide, 13.0-17.0% copper oxide, and 10.0-13.0% barium chromate,
g) 55.0-65.0% copper oxide, 25.0-35.0% calcium silicate, 5.0-10.0% palygorskite ([Mg(Al 0.5 -1Fe 0-0.5 )]Si 4 (OH)O 10.4 H 2 O ), 1.0-5.0% graphite, 1.0-5.0% silicon dioxide, and 0.5-1.5% silica (crystalline), or
h) any one mixture of catalyst compositions a) to g), in each case in wt %, based on the dry mass of the catalyst.

11. The process according to claim 2 , wherein the catalyst is activated with hydrogen and an alcohol, added simultaneously or one before the other, in any order, optionally with a carrier gas stream.

12. The process according to claim 11 , in which the carrier gas is nitrogen or argon and optionally comprises up to 10 vol % of hydrogen.

13. The process according to claim 11 , wherein the alcohol used for the activation is selected from saturated or mono- or polyunsaturated, straight-chain or branched or cyclic, aliphatic or aromatic monools or polyols, or combinations thereof.

14. The process according to claim 11 , wherein the alcohol used for the activation comprises at least one primary and/or secondary OH group.

15. The process according to claim 13 wherein the alcohol is a C 3 -C 16 alcohol.

16. The process according to claim 5 , wherein the reaction product comprises menthone and/or isomenthone with a fraction of more than 80% of the enantiomer with (R) configuration at the methyl carbon.

17. The process according to claim 1 , wherein the reaction product menthone and/or isomenthone is present in at least 99% enantiomerically pure form.

18. The process according to claim 1 , wherein the oxidic copper catalyst comprises a double mixed oxide selected from 30%-40% aluminium copper oxide, or 41% to 70% chromium copper oxide.

19. A process for making menthone comprising contacting a carrier gas that includes isopulegol in the gas phase with an activated oxidic copper catalyst, the copper catalyst activated with hydrogen, or with hydrogen and an alcohol, and optionally comprising at least one metal selected from aluminum, manganese, barium, chromium, calcium, or iron, each metal as an oxide, elemental form, or a mixture thereof, to provide a menthone-containing reaction product that includes menthone and isomenthone, each with at least 80% stereoselectivity of (R) configuration at the methyl carbon.

20. A method of producing a consumer product comprising menthone additive, wherein the menthone additive is produced by a process comprising contacting a carrier gas that includes isopulegol in the gas phase with an activated oxidic copper catalyst, the catalyst optionally comprising at least one element selected from aluminum, manganese, barium, chromium, calcium, or iron, isolating a menthone-containing reaction product (methone additive), and adding the menthone additive to the consumer product selected from the group consisting of foods, cosmetics, pharmaceutical products, tobacco formulations, household products, and laundry care products.

21. The method of claim 20 , wherein the menthone product that is added to the consumer product includes menthone and isomenthone, each with at least 80% stereoselectivity of (R) configuration at the methyl carbon.

Assignees

• Basf Se

Inventors

• Hickmann Volker
• Rüdenauer Stefan
• Dehn Martine
• Keller Andreas
• Renz Stephanie
• Schneider Daniel

Classifications

• C07C49/407

  Menthones · CPC title

• C07C45/298

  with manganese derivatives · CPC title

• C07C45/29

  of hydroxy groups · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• A61Q19/00

  Preparations for care of the skin · CPC title