Preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone

A technology of cyclopropyl propionic acid and cyclopropyl methyl ketone, which is applied in the field of preparation of 1--2-cyclopropyl-1-propanone, can solve the problem of strict water content in the reaction system, complicated operation, chlorophenylacetonitrile Easy self-polymerization and other problems, to achieve the effect of cheap and easy-to-obtain raw materials and solvents, high yield, and reduce three wastes

Active Publication Date: 2013-10-30
HUNAN HAILI HIGH TECH IND GRP
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  • Abstract
  • Description
  • Claims
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AI Technical Summary

Problems solved by technology

[0007] RUSS2350597 discloses a seven-step reaction to synthesize 1-(4-chlorophenyl)-2-cyclopropyl-1- The method of acetone has a total yield of 86%, but the reaction steps are long, the operation is complicated, and p-chlorophenylacetonitrile is easy to self-polymerize
[0008] CN101786948 discloses a method for obtaining 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone through condensation, hydrogenation and oxidation using cyclopropyl methyl ketone, p-chlorophenylacetonitrile and sodium hydride as raw materials , this method also needs to use sodium hydride, which has strict requirements on the water content of the reaction system, unsafe factors exist in the magnesium powder reduction operation, p-chlorophenylacetonitrile is easy to self-polymerize, and is not suitable for industrialized large-scale production

Method used

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  • Preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone
  • Preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone
  • Preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Add 28.3g (0.22mol) of dimethyl sulfate, 136g of dimethyl sulfide, and 16.9g (0.20mol) of cyclopropylmethyl ketone into a 500mL three-necked flask with a stirring and reflux tube, reflux at 40°C for 1 hour, and dissolve the hydrogen Sodium oxide 17.8g (0.44mol) was added in portions within 1 hour, and the reflux reaction was continued for 2 hours. After the reaction is finished, neutralize with 10% dilute hydrochloric acid, stand to separate the phases, and reclaim dimethyl sulfide by distillation of the organic phase under normal pressure. 18.6 g of the still liquid is 2-cyclopropyl-2-methyloxirane, with a content of 96.2 % (gas chromatography), yield 93.2%.

[0030] Add 18.6g of 2-cyclopropyl-2-methyloxirane to a 100mL three-necked flask, add 0.6g of anhydrous zinc chloride at room temperature, stir for 4 hours, add 16g (0.23mol) of 50% hydrogen peroxide dropwise at room temperature , After adding in 1 hour, the reaction was continued for 3 hours, and the conversion ...

Embodiment 2

[0033] Add 28.3g (0.22mol) of dimethyl sulfate, 170g of dimethyl sulfide, and 16.9g (0.20mol) of cyclopropylmethyl ketone into a 500mL three-necked flask with a stirring and reflux tube, reflux at 40°C for 1 hour, and dissolve the hydrogen Sodium oxide 18.6g (0.46mol) was added in portions within 1 hour, and the reflux reaction was continued for 2 hours. Neutralize with 10% dilute hydrochloric acid after reaction finishes, stand to separate phases, organic phase normal pressure distillation reclaims dimethyl sulfide, still liquid 18.9g is 2-cyclopropyl-2-methyloxirane, content 96.5 % (gas chromatography), yield 95.0%.

[0034] Add 18.9g of 2-cyclopropyl-2-methyloxirane to a 100mL three-necked flask, add 0.7g of anhydrous zinc chloride at room temperature, stir for 6 hours, add dropwise 18.2g (0.26mol) of 50% Hydrogen peroxide was added in 1 hour, and the reaction was continued for 3 hours, and the conversion of 2-cyclopropylpropionaldehyde was complete as detected by liquid c...

Embodiment 3

[0037] Add 28.3g (0.22mol) of dimethyl sulfate, 170g of dimethyl sulfide, and 16.9g (0.20mol) of cyclopropylmethyl ketone into a 500mL three-necked flask with a stirring and reflux tube, reflux at 40°C for 1 hour, and dissolve the hydrogen Sodium oxide 19.4g (0.48mol) was added in portions within 1 hour, and the reflux reaction was continued for 3 hours. After the reaction is finished, neutralize with 10% dilute hydrochloric acid, stand to separate phases, and reclaim dimethyl sulfide by atmospheric distillation of the organic phase. 19.2 g of the still liquid is 2-cyclopropyl-2-methyloxirane, with a content of 96.1 % (gas chromatography), yield 94.1%.

[0038] Add 19.2g of 2-cyclopropyl-2-methyloxirane to a 100mL three-necked flask, add 0.96g of anhydrous zinc chloride at room temperature, stir for 6 hours, add dropwise 19.7g (0.28mol) of 50% Hydrogen peroxide was added in 1 hour, and the reaction was continued for 4 hours, and the conversion of 2-cyclopropylpropionaldehyde wa...

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Abstract

The invention discloses a preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone. The preparation method comprises the steps that: (1) cyclopropyl methyl ketone, dimethyl sulfate, dimethyl sulfide and sodium hydroxide take epoxidation reaction to obtain 2-cyclopropyl-2-methyl propylene oxide; (2) the 2-cyclopropyl-2-methyl propylene oxide is catalyzed and re-ranged by anhydrous zinc chloride at the room temperature to obtain 2-cyclopropyl propionaldehyde; (3) the 2-cyclopropyl propionaldehyde is oxidized by 40 percent oxydol at the room temperature to obtain 2-cyclopropyl monoprop; (4) the 2-cyclopropyl monoprop and thionyl chloride take reaction to obtain 2-cyclopropyl propionyl chloride; (5) the 2-cyclopropyl propionyl chloride takes reaction with chlorobenzene and anhydrous aluminum trichloride to obtain the 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone with the content being 98.0 percent to 98.7 percent, and the total yield is 80.0 percent to 83.1 percent. The preparation method has the advantages that the steps are simple, raw materials are cheap and are easy to obtain, easy-self-ignition compounds are not used, organic solvents are not used in the steps (2) and (3), three wastes are few, and the preparation method is suitable for industrialization.

Description

technical field [0001] The invention relates to a preparation method of 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone. Background technique [0002] 1-(4-Chlorophenyl)-2-cyclopropyl-1-propanone, English name 1-(4-Chlorophenyl)-2-Cyclopropylpropanon-1 is an important compound for the synthesis of triazole low-toxicity and high-efficiency fungicide cycloconazole Intermediate, molecular formula: C 12 h 13 ClO, molecular weight: 208.68 Molecular structural formula: [0003] [0004] Its purity and yield directly affect the production cost and product quality of cyproconazole. The currently reported methods mainly include the following. [0005] US4664696 discloses a method for obtaining 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone by reacting 4-chlorophenylcyclopropylmethyl ketone with sodium hydride and methyl iodide in a DMF solvent. The 4-chlorophenyl cyclopropyl methyl ketone is obtained by chlorinating cyclopropyl acetic acid to obtain cyclopropyl acetyl chloride, an...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C49/813C07C45/46
Inventor 王宇毛春晖徐建兵陈明杨彬
Owner HUNAN HAILI HIGH TECH IND GRP
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