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Novel cycloalkane catalytic oxidation method promoted with copper porphyrin

A technology for catalytic oxidation and naphthenic hydrocarbons, applied in chemical instruments and methods, oxidation preparation of carboxylic acids, oxidation reaction preparation, etc., can solve the problems of poor product selectivity, low substrate conversion rate, low yield, etc., and achieve oxidation product selection. The effect of high performance, low catalyst dosage and low reaction temperature

Inactive Publication Date: 2019-03-12
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, at present, the catalytic oxidation of naphthenes generally has the disadvantages of low substrate conversion rate, poor product selectivity, and low yield, especially with clean O 2 For the oxidation process of the oxidant, the above disadvantages are more obvious, especially the product selectivity is low
The root cause is that the low selectivity of oxidation products in the catalytic oxidation of naphthenes is mainly due to the fact that the intermediate product cycloalkyl hydroperoxide generated in the oxidation process is mainly transformed into cycloalkyl alcohols, cycloalkyl ketones and alkyl diacids through thermal decomposition. hard to control

Method used

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  • Novel cycloalkane catalytic oxidation method promoted with copper porphyrin

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] In a 100mL stainless steel autoclave with a tetrafluoroethylene liner, dissolve 1.5mg of 5,10,15,20-tetrakis(p-chlorophenyl)porphyrin cobalt(II) in 50.0g of cyclohexane, and close the autoclave kettle. Stir to raise the temperature to 120°C, pass O 2 to 1.4MPa, at 120°C, 1.4MPaO 2 The reaction was stirred under pressure for 8.0 h, stirred and cooled to room temperature in an ice-water bath. Open the autoclave, filter the obtained reaction mixture, wash the obtained solid with 3 × 5mL cyclohexane, and dry it under vacuum at 60°C, which is adipic acid. The yield of HPLC analysis is 0.32%, and the yield of cyclohexanol is 1.45% by GC analysis of the filtrate. %, cyclohexanone yield 1.49%.

Embodiment 2

[0020] In a 100mL stainless steel autoclave with a tetrafluoroethylene liner, dissolve 1.5mg of 5,10,15,20-tetra(p-chlorophenyl)porphyrin copper (II) in 50.0g of cyclohexane, and close the autoclave kettle. Stir to raise the temperature to 120°C, pass O 2 to 1.4MPa, at 120°C, 1.4MPaO 2 The reaction was stirred under pressure for 8.0 h, stirred and cooled to room temperature in an ice-water bath. The autoclave was opened, and the resulting reaction mixture was analyzed by HPLC and GC, and adipic acid, cyclohexanol and cyclohexanone were not detected.

Embodiment 3

[0022] In a 100 mL stainless steel autoclave with a tetrafluoroethylene liner, 1.5 mg of 5,10,15,20-tetrakis(p-chlorophenyl)porphyrin cobalt(II) and 1.5 mg of 5,10,15,20- Tetrakis(p-chlorophenyl)porphyrin copper(II) was dissolved in 50.0 g of cyclohexane, and the autoclave was closed. Stir to raise the temperature to 120°C, pass O 2 to 1.4MPa, at 120°C, 1.4MPa O 2 The reaction was stirred under pressure for 8.0 h, stirred and cooled to room temperature in an ice-water bath. Open the autoclave, filter the obtained reaction mixture, wash the obtained solid with 3×5mL cyclohexane, and dry it under vacuum at 60°C, which is adipic acid. The yield of HPLC analysis is 0.15%, and the yield of cyclohexanol is 1.92% by GC analysis of the filtrate. %, cyclohexanone yield 1.64%.

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Abstract

The invention discloses a cycloalkane catalytic oxidation method promoted with copper porphyrin, which comprises the following steps of mixing cycloalkane, a main catalyst and a cocatalyst, performingreaction for 2-48 h under the conditions that the temperature is 100-160 DEG C and O2 pressure is 0.8-2 MPa, and then performing aftertreatment on a reaction liquid to obtain alkyl diacid, cycloalkylalcohol and cycloalkyl ketone as oxidative products. The novel cycloalkane catalytic oxidation method involved is high in selectivity of oxidative products, low in reaction temperature and less in dosage of catalyst, is environmentally friendly by taking O2 as an oxidant, can highly selectively realize cycloalkane catalytic oxidation and also has the advantages of simpleness in operation, no useof an organic solvent and the like.

Description

(1) Technical field [0001] The invention relates to a new method for catalytic oxidation of naphthenes promoted by copper porphyrin, which belongs to the field of catalytic organic synthesis. (2) Background technology [0002] Catalytic oxidation of naphthenes is an important chemical transformation process. The oxidation products cycloalkyl alcohols and cycloalkyl ketones are not only important chemical intermediates, but also can be further oxidized to prepare alkyl diacids, which are used to prepare various An important precursor of a polymer material. At the same time, the cycloalkane oxidation process can also generate alkyldiacids, which can be directly used in the preparation of various polymer materials. For example, the main products of cyclohexane catalytic oxidation, cyclohexanol and cyclohexanone, can be further oxidized to obtain adipic acid, an important precursor for the production of nylon-66 and nylon-6, and the market demand is very large (Angew.Chem.Int.E...

Claims

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Application Information

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IPC IPC(8): C07C55/14C07C55/12C07C55/02C07C51/31C07C35/08C07C35/06C07C35/20C07C29/50C07C49/403C07C49/395C07C49/413C07C45/33
CPCC07C29/50C07C45/33C07C51/313C07C2601/08C07C2601/14C07C2601/18C07C55/14C07C55/12C07C55/02C07C35/08C07C35/06C07C35/20C07C49/403C07C49/395C07C49/413
Inventor 佘远斌张龙沈海民
Owner ZHEJIANG UNIV OF TECH
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