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Method for synthesizing 1,2-cyclohexanediol by cyclohexene under selenium catalysis

A technology of cyclohexene and selenium compounds, which is applied in the field of synthesis of important organic intermediate 1,2-cyclohexanediol, can solve problems such as limiting application prospects, consuming large solvents, and limited profits, and achieves reduction in use costs and recycling Take advantage of the simplicity of the process

Inactive Publication Date: 2012-06-20
JIANGSU YANGNONG CHEM GROUP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The profit of bulk chemical products is limited, therefore, the cost of the catalyst in this method severely limits the application prospect of this reaction
(2) This document does not consider the practical application of industry, but only tried the oxidation reactions of common olefins in several laboratories, and did not involve the oxidation of cyclohexene to 1,2-cyclohexanediol, which is more important in industrial production.
(3) The concentration of the reaction solution in this method is only 0.25mol / L (calculated based on the organic solvent acetonitrile, water is not considered, and it is lower if water is considered, only 0.0625mol / L), such a low concentration of the reaction solution makes the actual production Need to consume a lot of solvent and severely restrict the production capacity
(4) The catalyst is for one-time use and has not been recycled

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Add cyclohexene (16.4g, 0.2 mol), diphenyldiselenide (62.4 mg, 0.2 mmol) and acetonitrile (20 mL) into a 100 mL round bottom flask, and stir for 10 min. Add 27.5% hydrogen peroxide solution (25g, 0.2mol) and stir at 30°C for 24h. After the reaction is over, distill under normal pressure at 80-100°C to remove the solvent acetonitrile, water and unreacted raw material cyclohexene; after cooling down to below 50°C, gradually reduce the pressure to 15 mmHg, and start heating when the vacuum is stable, and collect 110 From the fraction at ~120°C, 18.4 g of 1,2-cyclohexanediol was distilled off. Yield 79%.

[0024] Cyclohexene (16.4 g, 0.2 mol) and acetonitrile (20 mL) were added to the distillation residue again, and stirred for 10 min. Add 27.5% hydrogen peroxide solution (25g, 0.2mol) and stir at room temperature for 24h. After the reaction, distill at 80-100°C under normal pressure to remove the solvent and unreacted raw materials; then distill at 120°C under reduced p...

Embodiment 2～5

[0028] With 4,4'-p-difluorodiphenyl diselenide (p-FC 6 h 4 Se) 2 , 4,4'- p-dimethyl diphenyl diselenide (p-MeC 6 h 4 Se) 2 , phenyl selenite PhSe(O)OH, 4-fluorophenyl selenite p-FC 6 h 4 Se(O)OH was used as a catalyst instead of diphenyl diselenide, and other conditions were the same as in Example 1. The experimental results are shown in Table 2.

[0029] Table 2 Effect of catalyst

[0030] catalyst 4,4'-p-difluorodiphenyl diselenide 4,4'-p-Dimethyldiphenyldiselenide Benzene selenite p-Fluorophenyl selenous acid Product yield / % 83 75 86 80

Embodiment 6～8

[0032] The acetonitrile solvent was replaced with ethanol, water, and acetic acid, and other conditions were the same as in Example 1. The experimental results are shown in Table 3.

[0033] Table 3 The influence of solvent

[0034] solvent ethanol water acetic acid Product yield / % 72 55 76

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PUM

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Abstract

The invention provides a method for synthesizing 1,2-cyclohexanediol by cyclohexene under selenium catalysis. The method comprises the following steps of: taking cyclohexene as a raw material, taking a selenium compound as a catalyst, and taking hydrogen peroxide as an oxidant; carrying out reaction at a temperature of 15-80 DEG C in the presence of a solvent, wherein a mole ratio of the hydrogen peroxide to the cyclohexene is (0.5-1.5): 1, the mole fraction of the selenium compound and the cyclohexene is 0.1-1 percent, and the concentration of the reaction solution based on a solvent calculation is 1-20 mol / L. Furthermore, the production can be continuously carried out by adding the raw materials for the next turn into reaction residues. After the reaction, the solvent and non-reacted raw materials are respectively recycled by distillation and a product is refined. The selenium compound is selected from diselenide, selenious acid, and phenyl, fluoro-phenyl, tolyl substitutes and the like of the diselenide amd the selenious acid. The solvent is selected from acetonitrile, water, ethanol and acetic acid. The method disclosed by the invention has the advantages of simple process flow, temper reaction conditions, and high yield (the highest yield can be up to 92 percent). The method is efficient, clean and environment-friendly and further has the characteristics of simple components in a reaction system, easiness of product purification, and easiness of recycling the solvent and the catalyst.

Description

technical field [0001] The present invention relates to the synthetic method of important organic intermediate 1,2-cyclohexanediol, more specifically, relates to the method for preparing 1,2-cyclohexanediol from cyclohexene. Background technique [0002] 1,2-cyclohexanediol (1,2-cyclohexanediol) is an important intermediate in chemical production, which can be used to synthesize polyester, diacrylate, epoxy resin diluent, catechol, etc. [0003] 1,2-cyclohexanediol can be prepared from cyclohexene: first, it is oxidized to obtain epoxy compounds, and then hydrolyzed to finally generate 1,2-cyclohexanediol. However, this method often requires the use of chemical oxidants such as m-chloroperbenzoic acid (MCPBA) when oxidizing cyclohexene. In addition to the production of products, the reaction will also generate a large number of by-products, and the atom economy is poor. The reaction process of cyclohexene epoxidation to prepare 1,2-cyclohexanediol is as follows: [0004] ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C35/14C07C29/48
CPCY02P20/584
Inventor 俞磊丁克鸿顾志强杨树斌缪荣荣王刚董海妹
Owner JIANGSU YANGNONG CHEM GROUP
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