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Novel method for zinc protoporphyrin promoted catalyzed oxidation of cycloalkanes

A technology for catalytic oxidation and naphthenic hydrocarbons, applied in chemical instruments and methods, oxidation reaction preparation, oxidation preparation of carboxylic acids, 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

Pending 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 method for zinc protoporphyrin promoted catalyzed oxidation of cycloalkanes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

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

Embodiment 2

[0020] In a 100mL stainless steel autoclave with a tetrafluoroethylene liner, 1.5 mg of 5,10,15,20-tetrakis (p-chlorophenyl) porphyrin zinc (II) was dissolved in 50.0 g of cyclohexane, and the high pressure was sealed. kettle. Stir and raise the temperature to 120℃, then pass in O 2 To 1.4MPa, at 120℃, 1.4MPaO 2 The reaction was stirred for 8.0h under pressure, and cooled to room temperature with stirring in an ice-water bath. The autoclave was turned on, and the resulting reaction mixture was analyzed by HPLC and GC. 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) zinc porphyrin (II) was dissolved in 50.0 g of cyclohexane, and the autoclave was sealed. Stir and raise the temperature to 120℃, then pass in O 2 To 1.4MPa, at 120℃, 1.4MPa O 2 The reaction was stirred for 8.0h under pressure, and cooled to room temperature with stirring in an ice-water bath. Turn on the autoclave and filter the resulting reaction mixture. The solid obtained is washed with 3×5 mL cyclohexane and dried under vacuum at 60°C to obtain adipic acid. The yield of HPLC analysis is 0.11%, and the yield of cyclohexanol is 1.96 by GC analysis of the filtrate. %, the yield of cyclohexanone is 1.56%.

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Abstract

The invention relates to a method for zinc protoporphyrin promoted catalyzed oxidation of cycloalkanes. The method comprises the following steps: mixing the cycloalkanes, a main catalyst and a cocatalyst, carrying out a reaction for 2 to 48 hours under the condition that the temperature is 100 DEG C to 160 DEG C and the O2 pressure is 0.8MPa to 2MPa, then, subjecting a reaction solution to aftertreatment, thereby obtaining oxidation products, i.e., alkyl diacid, cycloalkyl alcohol and cycloalkyl ketone. According to the novel method for catalyzed oxidation of the cycloalkanes, provided by theinvention, the selectivity of the oxidation products is high, the reaction temperature is low, and the consumption of catalysts is low; O2 serves as an oxidant, so that the method is environmentally friendly, and the catalyzed oxidation of the cycloalkanes is achieved in a high-selectivity manner; the novel method for catalyzed oxidation of the cycloalkanes further has the advantages that the operation is simple, no organic solvent is used, and the like.

Description

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

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C55/14C07C55/12C07C55/02C07C51/31C07C35/08C07C35/06C07C35/20C07C29/50C07C49/403C07C49/395C07C49/413C07C45/33
CPCC07C29/50C07C45/33C07C51/313C07C2601/18C07C2601/08C07C2601/14C07C55/14C07C55/12C07C55/02C07C35/08C07C35/06C07C35/20C07C49/403C07C49/395C07C49/413
Inventor 沈海民张龙佘远斌
Owner ZHEJIANG UNIV OF TECH
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