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Method for preparing 2-(1-adamantyl)-4-bromophenol

A technology of adamantyl and bromophenol, which is applied in chemical instruments and methods, preparation of organic compounds, chemical recovery, etc., can solve the problems of waste water, three wastes in the process, low recovery rate, etc., and achieve high yield and simple process , the effect of simple operation

Inactive Publication Date: 2011-01-26
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, since a large amount of acetic acid is used as a diluent, this production process requires more alkali to neutralize acetic acid and sulfuric acid, so not only more waste water is produced, but also a large amount of new waste sodium acetate
[0004] With the improvement of environmental protection standards for chemical production in society, the shortcomings of the currently known production process of 2-(1-adamantyl)-4-bromophenol appear to be more prominent.
Some people try to replace concentrated sulfuric acid with recyclable strong organic acids, such as trifluoroacetic acid and trifluoromethanesulfonic acid. However, trifluoroacetic acid and trifluoromethanesulfonic acid are expensive, corrosive, highly volatile, and have low recovery rates. Its related technology is not suitable for industrial production of 2-(1-adamantyl)-4-bromophenol

Method used

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  • Method for preparing 2-(1-adamantyl)-4-bromophenol
  • Method for preparing 2-(1-adamantyl)-4-bromophenol

Examples

Experimental program
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Effect test

Embodiment 1

[0020] (1) Soak 530 grams of D001 sodium-type cation exchange resin (water content 40%) with 500 milliliters of 30% sulfuric acid aqueous solution, filter after 12 hours and wash the resin with deionized water until the eluent is neutral; then vacuum (100mmHg ) to dry the resin, soak the resin with 300 grams of glacial acetic acid for 1 hour, and filter it with suction; then repeat the soaking and suction filtration once, and dry the obtained resin at 100°C for 3 hours in vacuum (10mmHg) to obtain H-type strongly acidic ion exchange resin Catalyst D001 315 grams.

[0021] (2) Add 315 grams of H-type strongly acidic ion exchange resin catalyst D001 obtained in step (1), 173 grams (1.0 mole) of p-bromophenol, 1-adamantane to a 2-liter three-necked flask equipped with a mechanical stirring device at room temperature 157 grams (1.03 moles) of acid and 780 grams of glacial acetic acid, heated to 100 ° C, stirred for 3 hours; after cooling to room temperature, 105 grams of acetic an...

Embodiment 2

[0023] (1) Same as embodiment 1.

[0024] (2) Add 315 grams of the H-type strong acid ion exchange resin catalyst obtained in step (1) to a 2-liter three-necked flask equipped with a mechanical stirring device at room temperature, 173 grams (1.0 mole) of p-bromophenol, 1-adamantanic acid 157 grams (1.03 moles) and 780 milliliters of recovered acetic acid, heated to 100°C, and stirred for 3 hours; after cooling to room temperature, 105 grams of acetic anhydride was added to the reaction mixture, stirred for half an hour, and the ion exchange resin was recovered by filtration, and the mother liquor was recovered by distillation 825 grams of acetic acid; the residue was dissolved in 2 liters of petroleum ether at 60-90°C for thermal recrystallization to obtain 295 grams of product 2-(1-adamantyl)-4-bromophenol with a molar yield of 96%. Product melting point: 147~148 o C, HPLC purity 99.6%. The recovered ion exchange resin, acetic acid and recrystallization mother liquor are al...

Embodiment 3

[0028] (1) Soak 530 grams of 001 (732) sodium type cation exchange resin (water content 40%) with 500 ml of 30% sulfuric acid aqueous solution, filter after 12 hours and wash the resin with deionized water until the eluent is neutral, vacuum (100mmHg) to dry the resin, soak the resin with 300g of glacial acetic acid for 1 hour, and then filter it; then repeat the soaking and suction filtration once, and dry the obtained resin at 100°C for 3 hours under vacuum (10mmHg) to obtain H-type strong acidity 330 grams of ion exchange resin catalyst.

[0029] (2) Add 330 grams of H-type strong acid ion exchange resin catalyst obtained in step (1), 173 grams (1.0 mole) of p-bromophenol, 1-adamantanic acid to a 2-liter three-necked flask equipped with a mechanical stirring device at room temperature 157 grams (1.03 moles) and 800 grams of glacial acetic acid, heated to 100 ° C, stirred and reacted for 5 hours; after cooling to room temperature, 105 grams of acetic anhydride was added to t...

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Abstract

The invention relates to a method for preparing 2-(1-adamantyl)-4-bromophenol, belonging to the technical field of fine chemical industry. The method is characterized in that 4-bromophenol reacts with 1-adamantanol in acetic acid under the catalysis of acidic ion exchange resin to form the target product 2-(1-adamantyl)-4-bromophenol in high selectivity, and water is a byproduct; after the reaction, the byproduct water can react with an equal amount of acetic anhydride to be converted into the acetic acid which is used as a solvent and can be recycled; and the ion exchange resin catalyst can also be recycled after being filtered and dried, thereby realizing zero discharge in the whole preparation processes. The invention has the advantages of simple and environment-friendly processes, high yield and simple operation; the acetic acid and the ion exchange resin can be directly recycled after being treated, thereby realizing the zero discharge in the production processes; and the molar yield of the product 2-(1-adamantyl)-4-bromophenol can reach 92-99%, and the purity can reach more than 99%.

Description

[0001] technical field [0002] The invention belongs to the technical field of fine chemicals and relates to a preparation method of a pharmaceutical intermediate 2-(1-adamantyl)-4-bromophenol. Background technique [0003] 2-(1-adamantyl)-4-bromophenol is an intermediate in the production of the acne drug adapalene, and its early production technology is the "1-adamantane catalyzed by concentrated sulfuric acid" disclosed in U.S. Patent (U.S.Patent) 4717720 Alkylation of alcohols with p-bromophenol in dichloromethane or dichloroethane at room temperature". Although the reaction conditions of this production technology are mild, it not only has the problem of phenolsulfonic acid by-products formed by the reaction of concentrated sulfuric acid and p-bromophenol, thus consuming raw materials such as p-bromophenol and concentrated sulfuric acid, but also needs to use alkali to neutralize the sulfuric acid after the reaction. And, a large amount of waste water and inorganic s...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C39/42C07C37/16
CPCY02P20/584
Inventor 邹刚王楠王荣华
Owner EAST CHINA UNIV OF SCI & TECH
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