Preparation method of 2-hydroxyl-4-substituted arone compound

A technology for aryl ketones and compounds, which is applied in the field of preparation of 2-hydroxy-4-substituted aryl ketone compounds, can solve the problems of unsuitability for large-scale industrial production, difficulty in product separation and purification, and excessive production of three wastes, etc., and achieve excellent solubility properties , low process pollution and low cost

Active Publication Date: 2013-11-27
BEIJING GREENCHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Therefore, the Fries rearrangement of the process uses the metal catalyst aluminum trichloride, which makes it difficult to separate and purify the product, produces a lot of three wastes, corrodes the equipment, and pollutes the environment. Moreover, the aluminum trichloride explodes when it encounters water during post-reaction treatment, which is dangerous to a certain extent. A small number of times, so it is not suitable for large-scale industrial production

Method used

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  • Preparation method of 2-hydroxyl-4-substituted arone compound
  • Preparation method of 2-hydroxyl-4-substituted arone compound
  • Preparation method of 2-hydroxyl-4-substituted arone compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0070] Preparation of 2-hydroxy-4-bromoacetophenone

[0071]

[0072] (1) Preparation of [sulfuric acid][triethylamine 4-butylammonium sulfonate][zinc oxide] ionic liquid

[0073] Under stirring conditions, 9.4g of 1,4-butane sultone was slowly added dropwise to 7.0g of triethylamine, reacted at 80°C for 2h, cooled to 25°C, filtered with suction, and the filter cake was washed 3 times with ethanol. Dry under vacuum to obtain triethylamine butane sulfonate inner salt.

[0074] Under an ice bath, mix the 15.8 g of triethylamine butane sulfonate in the deionized water solution obtained in the previous step with 6.5 g of sulfuric acid, react at 50°C for 3 hours, cool, and dry in vacuo to obtain [sulfuric acid][triethylamine 4-butylammonium sulfonate] intermediate of ionic liquid.

[0075] Under stirring conditions, add 5.2 g of zinc oxide and 21.3 g of the [sulfuric acid] [triethylamine 4-butylammonium sulfonate] ionic liquid intermediate obtained in the previous step into deionized wate...

Embodiment 2

[0083] Preparation of 2-hydroxy-4-methoxypropiophenone

[0084]

[0085] (1) Preparation of [sulfuric acid][dipropylamine 4-butylammonium sulfonate][copper oxide] ionic liquid

[0086] Under stirring conditions, 21.7g of 1,4-butane sultone was slowly added dropwise to 16.1g of dipropylamine, reacted at 70°C for 2h, cooled to 25°C, filtered with suction, and the filter cake was washed 3 times with ethanol and vacuum After drying, the inner salt of dipropylamine butane sulfonate is obtained.

[0087] Under an ice bath, mix the 36.7g deionized aqueous solution of dipropylamine butane sulfonate obtained in the previous step with 15.2g sulfuric acid, react at 60°C for 5h, cool, and dry in vacuo to obtain [sulfuric acid][dipropylamine 4- Butylammonium sulfonate] Intermediate of ionic liquid.

[0088] Under stirring conditions, add 11.8 g of copper oxide and 49.7 g of the [sulfuric acid] [dipropylamine 4-butylammonium sulfonate] ionic liquid intermediate obtained in the previous step into d...

Embodiment 3

[0096] Preparation of 2-hydroxy-4-methylphenylbenzophenone

[0097]

[0098] (1) Preparation of [sulfuric acid][dipropylamine 4-butylammonium sulfonate][copper oxide] ionic liquid

[0099] Under stirring conditions, 14.1g of 1,4-butane sultone was slowly added dropwise to 10.4g of dipropylamine, reacted at 70°C for 2h, cooled to 25°C, filtered with suction, and the filter cake was washed 3 times with ethanol and vacuum After drying, the inner salt of dipropylamine butane sulfonate is obtained.

[0100] Under an ice bath, mix 23.8g of dipropylamine butane sulfonate in the deionized water solution obtained in the previous step with 9.8g of sulfuric acid, react at 60°C for 5h, cool, and dry in vacuo to obtain [sulfuric acid][dipropylamine 4- Butylammonium sulfonate] Intermediate of ionic liquid.

[0101] Under stirring conditions, add 7.2 g of copper oxide and 32.2 g of the [sulfuric acid] [dipropylamine 4-butylammonium sulfonate] ionic liquid intermediate obtained in the previous step ...

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Abstract

The invention discloses a preparation method of a 2-hydroxyl-4-substituted arone compound. A Bronsted-Lewis dual acidic ionic liquid is taken as a catalyst to catalyze 3-substituted phenolic ester to undergo a Fries rearrangement reaction. The Bronsted-Lewis dual acidic ionic liquid catalyst is a quaternary ammonium salt ionic liquid containing dual acidity, contains a Lewis acid site of copper ions or zinc ions and a Bronsted acid site of a sulfonic group. The Bronsted acid site of the sulfonic group takes the quaternary ammonium salt as a cation and adopts a sulfate radical as an anion. The dual acidic ionic liquid catalyst has strong catalytic activity, high reaction selectivity, and an ortho product with high yield and high purity can be obtained. The reaction aftertreatment is simple and safe, has less pollution, and the catalyst can be used repeatedly. Specifically, the raw material 3-substituted phenolic ester of the Fries rearrangement reaction can be obtained by reaction of 3-substituted phenol with an acylation reagent acyl chloride.

Description

Technical field [0001] The invention relates to a method for preparing a 2-hydroxy-4-substituted aromatic ketone compound, which belongs to the technical field of organic synthesis. Background technique [0002] Aromatic ketones are important intermediates for the synthesis of fine chemicals, medicines and pesticides, and surfactants. Among them, 2-hydroxy-4-substituted aryl ketones are mainly used for the synthesis of antiarrhythmic drugs-propafenone hydrochloride and sulfonamide anti-arrhythmic drugs. Intermediates of fungal drugs, anti-allergic diseases and anti-hepatitis C virus drugs. [0003] The current literature reports that the method for synthesizing 2-hydroxy-4-substituted aryl ketone compounds is to use 3-substituted phenol as a raw material, firstly undergo an acylation reaction with an acylating reagent to obtain a phenolic ester, which is then catalyzed by aluminum trichloride catalyst. Fries rearrangement yields 2-hydroxy-4-substituted aryl ketone. Therefore, the...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/825C07C45/51C07C49/84B01J31/26B01J31/28
Inventor 宫宁瑞
Owner BEIJING GREENCHEM TECH
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