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A kind of method that catalytic oxidation alicyclic alcohol compound prepares alicyclic ketone

A technology for compounds and alicyclic alcohols is applied in the field of catalytic reaction systems for selectively oxidizing alicyclic alcohol compounds to prepare corresponding alicyclic ketones. Less by-products, mild reaction conditions and less environmental pollution

Inactive Publication Date: 2017-10-17
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Traditional oxidation methods use stoichiometric manganese dioxide, chromium trioxide, sodium hypochlorite, etc. as oxidants (Acc.Chem.Res.2002, 35, 728-737), this type of oxidation process will produce a large amount of waste residue, serious pollution; the development of using oxygen is The efficient catalytic oxidation system of oxygen source has always been a challenging problem
Catalytic systems with nitroxide radicals as key components exhibit high catalytic activity, and nitroxide radicals reported in open literature include 2,2,6,6-tetramethylpiperidine nitroxide radicals (TEMPO) , such as Chinese patent CN1796349A, CN1789225A respectively reported NaNO 2 / Br 2 / TEMPO,NaNO 2 / HCl / TEMPO and other catalytic systems, this type of system has high catalytic activity, but the halogen is highly corrosive, and it is easy to produce halogenated by-products with alcohol
Literature (Catal.Commun.2010,11,732) reported to VOSO 4 / TEMPO system, but due to the steric hindrance of secondary alcohols, the catalytic activity of secondary alcohols is significantly lower than that of primary alcohols

Method used

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  • A kind of method that catalytic oxidation alicyclic alcohol compound prepares alicyclic ketone
  • A kind of method that catalytic oxidation alicyclic alcohol compound prepares alicyclic ketone

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] 1.0g cyclohexanol, 2mol% (relative to the substrate cyclohexanol) azaadamantane type nitroxide free radical (I), 2mol% (relative to the substrate cyclohexanol) vanadyl sulfate, 5mL acetonitrile was added to The reactor was filled with oxygen at a pressure of 0.3 MPa, operated at 80°C for 3 hours, and then cooled to room temperature. Sampling was analyzed by gas chromatography, and the conversion rate of cyclohexanol was 99.5%, and the selectivity of cyclohexanone was 99.9%.

[0014] If use 2,2,6,6-tetramethylpiperidine nitroxide free radical to replace azaadamantane type nitroxide free radical (I), under the same reaction conditions of above-mentioned embodiment 1 (catalyst substrate ratio, reaction temperature , reaction time, oxygen partial pressure, solvent and consumption etc.), the conversion rate of cyclohexanol is only 67%. If the reaction time is further extended to 15 hours, the conversion of cyclohexanol reaches 91%. It can be seen that its oxidation efficie...

Embodiment 2

[0016] With 10g cyclohexanol, 1mol% (relative to the substrate cyclohexanol) azaadamantane type nitroxide radical (I), 1mol% (relative to the substrate cyclohexanol) vanadyl sulfate, 100mL acetonitrile was added to the reaction The kettle was filled with oxygen at a pressure of 0.5MPa, operated at 100°C for 10h and then cooled to room temperature. Sampling was analyzed by gas chromatography, and the conversion rate of cyclohexanol was 99.1%, and the selectivity of cyclohexanone was 99.9%.

Embodiment 3

[0018] With 1.76g 2-phenyl cyclohexanol, 0.05mol% (relative to the substrate 2-phenylcyclohexanol) azaadamantane type nitroxide free radical (II), 0.5mol% (relative to the substrate 2- Phenylcyclohexanol) vanadyl trichloride, 5mL of acetonitrile were added to the reaction kettle, filled with air pressure of 0.5MPa, operated at 80°C for 20h and then cooled to room temperature. Samples were analyzed by gas chromatography, and the conversion rate of 2-phenylcyclohexanol was 99.7%, and the selectivity of 2-phenylcyclohexanone was 99.8%.

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Abstract

The invention provides a method for catalytically oxidizing alicyclic alcohol compounds to prepare alicyclic ketones. The method uses air or oxygen as an oxidizing agent and a catalyst system composed of two components: azaadamantane-type nitroxide free radicals and vanadium oxide compounds. , highly selectively oxidize alicyclic alcohols to the corresponding alicyclic ketones at 50-120°C. Compared with 2,2,6,6-tetramethylpiperidine nitroxide radicals, azaadamantane-type nitroxide radicals are less affected by steric hindrance in the catalytic oxidation of secondary alcohols and are composed of vanadium oxide compounds. The catalyst system oxidizes alicyclic alcohols more efficiently. Compared with traditional quantitative chemical oxidation methods such as manganese dioxide, chromium trioxide, and sodium hypochlorite, this method has the characteristics of less by-products, mild reaction conditions, and less environmental pollution, and is highly practical and economical.

Description

technical field [0001] The invention relates to a method for preparing alicyclic ketone compounds, in particular to a catalytic reaction system for selectively oxidizing alicyclic alcohol compounds to prepare corresponding alicyclic ketones. Background technique [0002] Alicyclic ketones are important organic intermediates and have important applications in fine chemical industries such as medicine and spices. For example, p-acetylaminocyclohexanone can be used to synthesize thiazole compounds (such as the drug pramipexole for treating Parkinson's disease), and 4-methylcyclohexanone can be used to synthesize drug methylcyclonitrosourea. Selective oxidation of the corresponding alicyclic alcohols is an important method for the preparation of alicyclic ketones. Traditional oxidation methods use stoichiometric manganese dioxide, chromium trioxide, sodium hypochlorite, etc. as oxidants (Acc.Chem.Res.2002, 35, 728-737), this type of oxidation process will produce a large amount...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B41/06C07C45/39C07C49/403C07C49/657C07C231/12C07C233/32C07C221/00C07C225/20C07C49/395C07C49/463B01J31/36
CPCC07B41/06C07C45/39C07C221/00C07C231/12B01J27/053B01J27/06B01J27/198B01J27/25B01J31/0244B01J31/36B01J2231/70B01J35/19C07C49/403C07C49/657C07C233/32C07C225/20C07C49/395C07C49/463
Inventor 杜中田唐洋洋孙小万
Owner DALIAN UNIV OF TECH
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