Method for preparing 4-substituted oxyphenol compound

An oxyphenol and compound technology, applied in the field of organic synthesis, can solve the problems of poor selectivity for synthesizing 4-substituted oxyphenol, difficult recovery of solvent and hydroquinone, complicated process, etc., and avoid side reactions and reaction steps. Short, highly selective effects

Active Publication Date: 2015-07-01
SHANGHAI ZHONGHUA TECH CO LTD
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  • Abstract
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  • Claims
  • Application Information

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Problems solved by technology

[0002] Patent documents DE2908937, US4246419, US4266063, US4302242, US4216007 and Australian Journal of Chemistry, 48 (8), 1503-9; 1995 reported the synthesis of hydroquinone and 2-chloro-5-trifluoromethylpyridine derivatives, However, the selectivity is poor, and the yield is only 45%
The literature US4555575 and Synthetic Communications, 23 (20), 2845-9; 1993 discloses that methoxyphenol is condensed with halides, and then deprotected under acidic catalysis to synthesize, and the literature involves the methyl of hydroquinone Three-step reaction of protection, ether formation reaction and demethylation protection, the process is complicated and the total yield is low
Patent JP2006036739A discloses that methanol / toluene mixed liquid is used as solvent, and the selectivity of hydroquinone is controlled by dropwise adding aqueous sodium hydroxide solution to synthesize 4-(3,3-dichloroallyloxy)phenol. Long, the process is loaded down with trivial details, yield is only 74.2%
In the above-mentioned documents, it is reported that the selectivity of synthesizing 4-substituted oxyphenol is relatively poor, and the reaction yield is not high. The post-treatment all adopts the method of directly importing into water, without reclaiming hydroquinone, and then extracting, resulting in a large amount of waste water. Solvent and Difficult recovery of hydroquinone, cost surge

Method used

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  • Method for preparing 4-substituted oxyphenol compound

Examples

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Embodiment 1

[0034] Example 1 Synthesis of 4-(5-trifluoromethylpyridyl-2-oxygen)phenol

[0035] The synthetic reaction formula is:

[0036]

[0037] The specific synthesis is as follows: add 6.0g of sodium hydroxide, 11.1g of hydroquinone, 8.0g of sodium bisulfite and 50g of DMF to the reaction bottle, then raise the temperature, and add dropwise 9.2g of 2-chloro-5-trifluoroform under temperature control at 90°C Basepyridine, add dropwise in about 1 hour, after dropping, keep warm at 90°C for 5 hours, after the conversion of raw materials is complete, distill and concentrate the reaction solution under reduced pressure, add 100ml of toluene after completion, stir for 1 hour, filter, and recover hydroquinone. Add 100ml of 5% sodium hydroxide aqueous solution to the toluene phase to extract twice, separate the water phase, add hydrochloric acid dropwise at a temperature of 25-30°C to acidify to pH 5-6, stir for 30 minutes, filter and dry to obtain 12.5g of 4-(5-tri Fluoromethylpyridyl-2-...

Embodiment 2

[0038] Example 2 Synthesis of 4-(5-trifluoromethylpyridyl-2-oxygen)phenol

[0039] After adding 86.8g of potassium hydroxide, 166.5g of hydroquinone, 88.5g of sodium bisulfite and 500g of DMF into the reaction flask, the temperature was raised, and 92g of 2-chloro-5-trifluoromethylpyridine was added dropwise at a temperature of 50°C, about 1 The dropwise addition was completed within 1 hour. After the dropwise completion, the reaction was carried out at 90°C for 5 hours. After the conversion of the raw materials was completed, the reaction solution was concentrated by distillation under reduced pressure. After the completion, 1000ml of toluene was added, stirred for 1 hour, filtered, and hydroquinone was recovered. Add 1000ml of 5% sodium hydroxide aqueous solution to the toluene phase to extract twice, separate the water phase, add hydrochloric acid dropwise at a temperature of 25-30°C to acidify to pH 5-6, stir for 30 minutes, filter and dry to obtain 128.8g of 4-(5-tri Fluo...

Embodiment 3

[0040] Example 3 Synthesis of 4-(5-trifluoromethylpyridyl-2-oxygen)phenol

[0041] The operation method is the same as in Example 1, and the solvent is replaced with DMSO to obtain a product content of 97.8% and a yield of 96.9%. Recover hydroquinone 5.3g, content 94.8%.

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Abstract

The invention belongs to the field of organic synthesis, and relates to a method for preparing a 4-substituted oxyphenol compound. The method comprising the following steps: condensing hydroquinone and a halogen compound in a polar aprotic solvent in a reducing agent and metal alkali system to obtain the 4-substituted oxyphenol compound; removing the solvent after the above reaction, adding a non-polar solvent, filtering, washing, and recovering the raw material hydroquinone; and washing the obtained filtrate through using water, extracting by using an alkaline solution, and adjusting the pH value of the obtained extract solution to obtain the 4-substituted oxyphenol compound. The method has the advantages of short route, simple operation, high selectivity, high yield, good atom economy, high product content, recovery convenience and recycling of the raw material, reduction of three wastes and the cost, and suitableness for industrial production.

Description

technical field [0001] The invention belongs to the field of organic synthesis and relates to a method for preparing 4-substituted oxyphenol compounds. Background technique [0002] Patent documents DE2908937, US4246419, US4266063, US4302242, US4216007 and Australian Journal of Chemistry, 48 (8), 1503-9; 1995 reported the synthesis of hydroquinone and 2-chloro-5-trifluoromethylpyridine derivatives, However, the selectivity is poor, and the yield is only 45%. The literature US4555575 and Synthetic Communications, 23 (20), 2845-9; 1993 discloses that methoxyphenol is condensed with halides, and then deprotected under acidic catalysis to synthesize, and the literature involves the methyl of hydroquinone The three-step reaction of protection, ether formation reaction and demethylation protection has complicated process and low overall yield. Patent JP2006036739A discloses that methanol / toluene mixed liquid is used as solvent, and the selectivity of hydroquinone is controlled b...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/643C07C43/23C07C41/16
CPCC07C41/01C07D213/643C07C43/23
Inventor 杨丙连耿丽文任忠宝丁亚伟张则勇
Owner SHANGHAI ZHONGHUA TECH CO LTD
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