Oxidizing method of cycloalkane compound

Abstract

The invention discloses an oxidizing method of a cycloalkane compound. The oxidizing method comprises the following steps of using the cycloalkane compound as the raw material, and catalyzing by a catalysis system to oxidize under the oxygen-containing atmosphere, so as to obtain the corresponding cycloketone compound and cyclitol compound, wherein the catalysis system comprises a cyclic organic nitrogen and oxygen free radical precursor and a metal cerium salt; the cyclic organic nitrogen and oxygen free radical precursor is selected from the following four structures; in the formulae, R1, R2and R3 are independently selected from hydrogen atom, alkyl, cycloalkyl, aryl, heterocycle, hydroxyl, nitryl, or halogen, or at least two of R1, R2 and R3 form loops; the metal cerium salt is selected from soluble salt of trivalent cerium and / or soluble salt of tetravalent cerium. The oxidizing method has the advantages that the conditions are mild, and the safety is high; on the basis of higherconversion rate of cycloalkane compound, the selectivity of the target products, such as cycloketone compound and cyclitol compound, is improved. The formulae are shown in the attached figure.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to an oxidation method of cycloalkane compounds. Background technique [0002] Cyclic ketones and cyclic alcohols are important chemical raw materials, widely used in industries such as synthetic rubber, fiber industrial coatings, medicine, pesticides and organic solvents. For example, the mixture of cyclohexanone and cyclohexanol (KA oil) can be used to prepare caprolactone, adipic acid, caprolactam, etc., and can also be used as a solvent and emulsifier. Today, there are three main processes for producing cyclohexanone: liquid-phase oxidation of cyclohexane, hydrogenation of phenol and partial hydrogenation of cyclohexane. Among them, the cyclohexane liquid-phase oxidation method is the most important process for the industrial production of cyclohexanone, accounting for more than 90%. However, this production process is also considered to be one of the least efficient of all ch...

AI Technical Summary

Problems solved by technology

However, the production process is also considered to be the least efficient of all chemical industrial processes

There are generally three methods for cyclohexane liquid-phase oxidation in industry: (1) Catalytic oxidation using cobalt salt as a catalyst. This method has a high conversion rate of cyclohexane, but it is easy to foul the reactor due to the formation of cobalt adipate , has been basically eliminated

(2) Boric acid catalytic oxidation method, this method has high infrastructure investment, high energy consumption, very complicated process, difficult operation, and easy to cause serious blockage of reaction equipment and pipelines

(3) Catalyst-free oxidation method with air direct oxidation, this method effectively avoids the problem of reactor fouling, but the process is complex, with many intermediate steps, low cyclohexane conversion rate, and high energy consumption

Although this method can prepare cyclohexanol and cyclohexanone with high selectivity, the conversion rate of cyclohexane is extremely low, less than 1%.

[0007] It can be seen that most of the currently reported processes for the oxidation of cyclohexane to KA oil need to be carried out under harsh conditions such as high pressure and ultraviolet light.

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