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Method for quick synthesis of alpha-single chloro-ketone compounds

A technology of dichloroketones and compounds, applied in the field of rapid synthesis of α, to achieve the effects of high yield, reduced emissions, and high selectivity

Inactive Publication Date: 2009-05-13
EAST CHINA NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The selectivity of the chlorination reaction is a challenge in the synthesis reaction, and the product obtained in most cases is a mixture of monochloride and dichloride

Method used

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  • Method for quick synthesis of alpha-single chloro-ketone compounds
  • Method for quick synthesis of alpha-single chloro-ketone compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Example 1: Selective Dichlorination of Acetophenone

[0025] 2.8g choline chloride (20mmol), 3.4g p-toluenesulfonic acid (20mmol), placed in a single-neck bottle, nitrogen protection, stirring, heating in an oil bath at 100°C for 40 minutes, slowly cooling for 8 hours, forming a colorless transparent room temperature eutectic.

[0026] Add acetophenone (10mmol), acetonitrile 0.5ml, dichlorohydantoin (11mmol) to the above eutectic, stir at room temperature for 30 minutes, stop stirring. Add 30ml of butyl ether for extraction, separate the organic layer, wash the organic layer with 20ml of water three times, extract the aqueous layer with 10ml of butyl ether, combine the organic layers, and dry over magnesium sulfate. After filtration and rotary evaporation, 1.8 g of light yellow liquid was obtained, which was the dichlorinated product of acetophenone. Yield: 95%. 1 H NMR (CDCl 3 , 500MHz): δ 6.69 (s, 1H, CHCl 2 ), 7.52(t, J=7.8Hz, 2H, ArH), 7.65(t, J=7.4Hz, 1H, ArH)...

Embodiment 2

[0027] Embodiment 2: the selective dichlorination of p-chloroacetophenone

[0028] 2.8g choline chloride (20mmol), 2.4g p-toluenesulfonic acid (14mmol), placed in a single-neck bottle, nitrogen protection, stirring, heating in an oil bath at 100°C for 40 minutes, slowly cooling for 8 hours, forming a colorless transparent room temperature eutectic.

[0029] Add p-chloroacetophenone (10mmol), acetonitrile 1ml, and dichlorohydantoin (10mmol) to the above eutectic mixture, stir at room temperature for 30 minutes, and stop stirring. Add 30ml of butyl ether for extraction, separate the organic layer, wash the organic layer with 20ml of water three times, extract the aqueous layer with 10ml of butyl ether, combine the organic layers, and dry over magnesium sulfate. After filtration and rotary evaporation, the light yellow liquid obtained is the dichlorinated product of p-chloroacetophenone. Yield: 94%. M.p.52-54°C (literature 54-56°C).

Embodiment 3

[0030] Example 3: Selective Dichlorination of Ethyl 4-Nitrobenzoylacetate

[0031] 2g of choline chloride (14mmol), 3.4g of p-toluenesulfonic acid (20mmol), placed in a single-necked bottle, protected by nitrogen, stirred, heated in an oil bath at 100°C for 40 minutes, and slowly cooled for 8 hours to form a colorless transparent solution at room temperature. eutectic.

[0032] Add ethyl 4-nitrobenzoylacetate (10 mmol), 0.5 ml of acetonitrile, and dichlorohydantoin (15 mmol) to the above eutectic mixture, stir at room temperature for 30 minutes, and stop stirring. Add 30ml of butyl ether for extraction, separate the organic layer, wash the organic layer with 20ml of water three times, extract the aqueous layer with 10ml of butyl ether, combine the organic layers, and dry over magnesium sulfate. After filtration and rotary evaporation, 1.8 g of a light yellow liquid was determined to be the dichlorinated product of ethyl 4-nitrobenzoylacetate. Yield: 92%.

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Abstract

The invention provides a method for quickly synthesizing alpha, alpha-dichloro ketone compounds, and relates to a method for quickly synthesizing an alpha, alpha-dichloro product of a carbonyl compound. The method comprises the following steps: weighing choline hydrochloride and paratoluenesulfonic acid according to the molar ratio of between 7 to 3 and 3 to 7; placing the choline hydrochloride and the paratoluenesulfonic acid into a single-neck bottle to be protected by nitrogen, be stirred, and be heated in oil bath for 40 minutes at a temperature of between 10 and 100 DEG C, and slowly cooling the reactant for 8 hours to form a colorless transparent eutectic solution; then weighing the eutectic solution and the carbonyl compound according to the molar ratio of between 5 to 1 and 1 to 1, wherein the dosage of halogenated hydantoin is 1 to 3 times of the molar weight of the carbonyl compound, and the dosage of acetonitrile is 1 to 10 percent of the volume of the eutectic solution; adding the carbonyl compound, the acetonitrile, and the dichloro-hydantoin into the eutectic solution to be stirred and reacting at room temperature for 30 minutes, and stopping stirring; and finally, extracting, drying, filtering and distilling reactant to obtain the alpha, alpha-dichloro product. The method has the advantages of high reaction speed, high selectivity, high yield, no acid pollution, eutectic solution reutilization, and has better economic and social benefits and industrialized prospect.

Description

technical field [0001] The present invention relates to a method for rapidly synthesizing α,α-dichloroketone compounds, in particular to the highly selective and rapid synthesis of various carbonyl compounds using 1,3-dichloro-5,5-dimethylhydantoin The method for synthesizing dichlorinated products belongs to the technical field of preparation of fine chemical products. Background technique [0002] The α, α-dichloro products of various carbonyl compounds are important intermediates in organic synthesis, and are widely used in the synthesis of functional chemicals such as medicines and pesticides. Existing chlorination methods mainly use chlorine gas (Rarjohn N., Rogier E., "The vapor-phase chlorination of aliphatic ketones", J.Org.Chem.1946, 11, 781), chlorine-containing inorganic salts, and NCS. Chlorine gas and some chlorine-containing inorganic salts are highly toxic and inconvenient to use, while NCS and some chlorine-containing inorganic salts are expensive and diffic...

Claims

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Application Information

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IPC IPC(8): C07B39/00C07C45/63C07C49/80C07C69/72C07C201/12
Inventor 邹新琢陈梓湛朱伟
Owner EAST CHINA NORMAL UNIVERSITY
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