Method for catalytic conversion of alkyl cyclohexanol and alkyl cyclohexanone from air oxidized alkyl cyclohexane

Abstract

A process for selectively oxidizing alkyl cyclohexane by air under the catalysis of mu-oxygen bimetal porphyrin, single-metal porphyrin, or their solid carried substance to become alkyl cyclohexanol and alkyl cyclohexanone is disclosed. Said alkyl cyclohexane may be methyl cyclohexane, ethyl cyclohexane, isopropyl cyclohexane, etc. Its advantages are low cost, high catalytic performance, low reaction temp (less than 200 deg.C) and high transform rate.

Description

Technical field:

[0001] The present invention relates to the method for catalytic air oxidation of alkyl cyclohexane to alkyl cyclohexanol and alkyl cyclohexanone Background technique

[0002] Alkyl cyclohexanol and alkyl cyclohexanone are widely used as important intermediates of medicine, pesticide and fine chemical industry because of their better fat solubility than cyclohexanol and cyclohexanone. At present, industrially, alkylcyclohexanols are mainly prepared by hydrogenation of corresponding alkylphenols, while alkylcyclohexanones are produced by nucleophilic substitution of cyclohexanone and halogenated hydrocarbons or by cyclohexenone and alkyl copper lithium The reagents are prepared by nucleophilic addition. WO0214255 discloses a method for preparing methylcyclohexanol by hydrogenating methylphenol, and CH595309 discloses a method for preparing methylcyclohexanone by directly hydrogenating methylphenol. These methods for preparing alkylcyclohexanol and alkylcycl...

Examples

Embodiment 1

[0018] With 3 mg of metalloporphyrins of general formula (I), R 1 =R 2 =R 3 =CH 3 , M=Mn, add 400ml of methylcyclohexane, and pass through 6atm air. The reactant was stirred at 130° C. for 4 hours, the conversion rate of methylcyclohexane was 18.2%, and the yield of alcohol and ketone in the reaction product was 95%.

Embodiment 2

[0020] With 1 mg of metalloporphyrins of general formula (II), R 1 =R 2 =R 3 =Cl,M 1 = M 2 =Fe, added to 500ml 1,4-dimethylcyclohexane, and 8atm air was introduced. The reactant was stirred at 160° C. for 4 hours, the conversion rate of 1,4-methylcyclohexane was 15.5%, and the yield of alcohol and ketone in the reaction product was 92%.

Embodiment 3

[0022] With 4 mg of metalloporphyrins of general formula (I), R 1 =R 2 =R 3 =Cl, M=Fe, and 15 mg CoCl 2 Add 500ml of methylcyclohexane, and pass through 10atm air. The reactant was stirred at 140° C. for 3 hours, the conversion rate of methylcyclohexane was 22.5%, and the yield of alcohol and ketone in the reaction product was 86%.

Technical field:

[0001] The present invention relates to the method for catalytic air oxidation of alkyl cyclohexane to alkyl cyclohexanol and alkyl cyclohexanone Background technique

[0002] Alkyl cyclohexanol and alkyl cyclohexanone are widely used as important intermediates of medicine, pesticide and fine chemical industry because of their better fat solubility than cyclohexanol and cyclohexanone. At present, industrially, alkylcyclohexanols are mainly prepared by hydrogenation of corresponding alkylphenols, while alkylcyclohexanones are produced by nucleophilic substitution of cyclohexanone and halogenated hydrocarbons or by cyclohexenone and alkyl copper lithium The reagents are prepared by nucleophilic addition. WO0214255 discloses a method for preparing methylcyclohexanol by hydrogenating methylphenol, and CH595309 discloses a method for preparing methylcyclohexanone by directly hydrogenating methylphenol. These methods for preparing alkylcyclohexanol and alkylcycl...

Examples

Embodiment 1

[0018] With 3 mg of metalloporphyrins of general formula (I), R 1 =R 2 =R 3 =CH 3 , M=Mn, add 400ml of methylcyclohexane, and pass through 6atm air. The reactant was stirred at 130° C. for 4 hours, the conversion rate of methylcyclohexane was 18.2%, and the yield of alcohol and ketone in the reaction product was 95%.

Embodiment 2

[0020] With 1 mg of metalloporphyrins of general formula (II), R 1 =R 2 =R 3 =Cl,M 1 = M 2 =Fe, added to 500ml 1,4-dimethylcyclohexane, and 8atm air was introduced. The reactant was stirred at 160° C. for 4 hours, the conversion rate of 1,4-methylcyclohexane was 15.5%, and the yield of alcohol and ketone in the reaction product was 92%.

Embodiment 3

[0022] With 4 mg of metalloporphyrins of general formula (I), R 1 =R 2 =R 3 =Cl, M=Fe, and 15 mg CoCl 2 Add 500ml of methylcyclohexane, and pass through 10atm air. The reactant was stirred at 140° C. for 3 hours, the conversion rate of methylcyclohexane was 22.5%, and the yield of alcohol and ketone in the reaction product was 86%.

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