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Preparation method of alpha-monochlorinated ketone compound

A monochloroketone and compound technology, applied in the field of organic compound preparation, can solve the problems of generating a large amount of dust, expensive, high temperature, etc., and achieve the effects of easy recovery, high selectivity and mild reaction conditions

Inactive Publication Date: 2013-12-18
HUANGSHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Use dichlorhydantoin because of chlorination reagent, cheap, easy to use, but above-mentioned method also has following deficiency: used more expensive p-toluenesulfonic acid as catalyzer in the reaction, and produced a large amount of acid waste liquids; Use 300~400 When the silica gel is used as the catalyst, a large amount of dust is generated during the operation, and the reaction needs to be carried out at a higher temperature

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Embodiment 1: the preparation of α-chloroacetophenone

[0021] Mix 5mmol of acetophenone, 0.5mmol of ammonium sulfate, 9.75mL of methanol and 0.25mL of water, add 2.5mmol of dichlorohydantoin solid in 3 batches, and react at 20°C for 8 hours. Then, the solvent was recovered by rotary evaporation, 10 mL of ethyl acetate was added, ammonium sulfate was recovered by suction filtration, the organic layer was washed three times with 30 mL of water, and dried over anhydrous sodium sulfate. Filtration and rotary evaporation gave 0.72 g of ɑ-chloroacetophenone as a white solid with a yield of 93%. mp: 51-53°C (Lit: 51-52°C). 1 H NMR (CDCl 3 ,500MHz)δ4.72(s,2H,CH 2 Cl), 7.51(t, J=7.8Hz, 2H, ArH), 7.63(t, J=7.8Hz, 1H, ArH), 7.96-7.98(m, 2H, ArH).

Embodiment 2

[0022] Embodiment 2: the preparation of α-chloro-4-methoxyacetophenone

[0023] Mix 5mmol of 4-methoxyacetophenone, 2.0mmol of ammonium sulfate, 5mL of ethanol and 5mL of water, add 2.5mmol of dichlorohydantoin solid in 3 batches, and react at 20°C for 5 hours. Then, the solvent was recovered by rotary evaporation, 10 mL of ethyl acetate was added, ammonium sulfate was recovered by suction filtration, the organic layer was washed three times with 30 mL of water, and dried over anhydrous sodium sulfate. Filtration and rotary evaporation gave 0.83g of a white solid ɑ-chloro-4-methoxyacetophenone with a yield of 89%. mp: 94-96°C (Lit: 96-98°C). 1 H NMR (CDCl 3 ,500MHz)δ3.80(s,3H,CH 3 ),4.77(s,2H,CH 2 Cl), 7.51(t, J=7.8Hz, 2H, ArH), 7.63(t, J=7.8Hz, 1H, ArH), 7.96-7.98(m, 2H, ArH).

Embodiment 3

[0024] Embodiment 3: the preparation of α-chloro-4-methylacetophenone

[0025] Mix 5 mmol of 4-methylacetophenone, 5 mmol of ammonium sulfate, 9.5 mL of isopropanol, and 0.5 mL of water, add 5 mmol of dichlorohydantoin solids in 7 batches, and react at 30°C for 6 hours. Then, the solvent was recovered by rotary evaporation, 10 mL of ethyl acetate was added, ammonium sulfate was recovered by suction filtration, the organic layer was washed three times with 30 mL of water, and dried over anhydrous sodium sulfate. Filtration and rotary evaporation gave 0.78 g of a white solid ɑ-chloro-4-methylacetophenone, with a yield of 92%. mp: 53-55°C (Lit: 54-55°C). 1 H NMR (CDCl 3 ,500MHz)δ2.41(s,3H,CH 3 ),4.69(s,2H,CH 2 Cl), 7.21(d, J=8.1Hz, 2H, ArH), 7.83(d, J=8.1Hz, 2H, ArH). Example 4: Preparation of α-chloro-4-chloroacetophenone

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Abstract

The invention relates to a preparation method of an alpha-monochlorinated ketone compound which is prepared from a carbonyl compound and a chlorinated reagent by an alpha-monochlorinated reaction under catalysis of an ammonium salt. By adopting the preparation method, the ammonium salt is taken as a catalyst to carry out the alpha-monochlorinated reaction instead of strong acids such as p-toluenesulfonic acid or silica gel, so as to achieve the effects of mild reaction condition, high selectivity and high yield; the ammonium salt is easily recovered, and can be repeatedly used. Raw materials including cheap imidazolidinedione and the ammonium salt are selected by the chlorination method disclosed by the invention, so that the alpha-monochlorinated ketone compound is safe and non-toxic, free of irritation, free of emission of acid waste liquid, and close to the requirements of green chemistry. Therefore, industrial production is easily achieved; the preparation method has a broad application prospect.

Description

technical field [0001] The invention belongs to the technical field of organic compound preparation, and in particular relates to a preparation method of α-monochloroketone compounds. Background technique [0002] Various α-monochloroketone compounds are important intermediates of fine chemicals such as medicine and pesticides. Their preparation method is usually direct chlorination by carbonyl compounds, wherein the chlorination reagents include chlorine gas, chlorinated inorganic salts, chlorinated thionyl chloride, and N-chlorosuccinimide. Chlorine gas and some inorganic salts have poor selectivity, are highly corrosive to equipment, cause large pollution, and are inconvenient to use. However, N-chlorosuccinimide is expensive and difficult to promote in industry. 1,3-Dichloro-5,5-dimethylhydantoin (abbreviated as dichlorohydantoin or DCDMH) is a new type of disinfectant that has also recently been used in chlorinated agents. Chlorination reactions of carbonyl compounds ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B39/00C07C45/63C07C49/80C07C49/84C07C201/12C07C205/45C07C67/307C07C69/72C07C69/738C07C69/63C07C205/56
Inventor 郑祖彪韩冰冰
Owner HUANGSHAN UNIV
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