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Preparation method of 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone and intermediate thereof as well as preparation method of intermediate

A technology of cyclopropyl methyl ketone and cyclopropyl, which is applied in the preparation of carbon-based compounds, heterocyclic compounds, organic compounds, etc., can solve the problems of major safety problems, large amount of boron trifluoride, etc., Achieve the effect of high product content and simple process

Active Publication Date: 2012-07-25
JIANGSU CHENGYANG GROP SCI CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, due to the large amount of boron trifluoride, there are still major safety problems

Method used

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  • Preparation method of 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone and intermediate thereof as well as preparation method of intermediate
  • Preparation method of 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone and intermediate thereof as well as preparation method of intermediate
  • Preparation method of 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone and intermediate thereof as well as preparation method of intermediate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] The sodium tert-butoxide solution prepared from 5.6g sodium metal and 150mL tert-butanol was added dropwise to 17.0g cyclopropyl methyl ketone and 48.0g α-chloro-p-chlorophenylacetic acid methyl ester under ice-water bath cooling In the mixture, control the temperature of the system between 15°C and 20°C; after the addition, stir and react at 20°C to 30°C for 4 hours; evaporate most of the tert-butanol under reduced pressure, and after cooling to room temperature, add 100mL of water and 100mL of di Chloromethane, static until the layers were separated, the aqueous layer was extracted with 30 mL×2 dichloromethane, the combined organic layers were washed with water and dried over anhydrous magnesium sulfate to obtain methyl glycidate (IV, R=methyl) solution.

[0042] After desolventizing the above solution, methyl glycidate IV (R=methyl) can be obtained: EIMS (m / z): 268 (M+2), 266 (M); 1 H NMR: δ0.20-0.50(m, 4H), 0.71(m, 1H), 1.34(s, 3H), 3.69(s, 3H), 7.13(d, J=8.1Hz, 2H)...

Embodiment 2

[0046] Use 8.0g potassium tert-butoxide, 35mL tert-butanol, 4.2g cyclopropyl methyl ketone and 13.0g α-chloroethyl p-chlorophenylacetate as raw materials, refer to the method of Example 1, obtain 12.2g Ethyl glycidate (IV, R=ethyl): EIMS (m / z): 282 (M+2), 280 (M); 1 H NMR: δ0.20-0.50(m, 4H), 0.72(m, 1H), 1.30(t, J=6.3Hz, 3H), 1.33(s, 3H), 4.09(q, J=6.3Hz, 2H ), 7.15 (d, J=8.2Hz, 2H), 7.22 (d, J=8.2Hz, 2H).

Embodiment 3

[0048] The glycidic acid methyl ester (IV, R=methyl) solution obtained by repeating Example 1 was added dropwise to a solution composed of 18.0g potassium hydroxide and 120mL methanol, and the resulting mixture was stirred at room temperature for 6 hours; under cooling in an ice-water bath, Slowly add 120mL of water and stir for 2 hours; then add dropwise 30% hydrochloric acid to adjust the pH to 3~4, and continue to stir for 4 hours at room temperature; let the layers stand, extract the aqueous layer with 40mL of dichloromethane, combine the organic layers, and add 5% bicarbonate Wash with aqueous sodium solution, then wash with water until neutral, and remove the solvent to obtain 34.2 g of crude product 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone (I), which is a translucent red liquid with a chromatographic analysis content of 93.4% , yield 76.6%.

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Abstract

The invention discloses a preparation method of 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone (I) and an intermediate thereof as well as the preparation method of the intermediate. The preparation method of 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone (I) comprises the following steps of: carrying out Darzen condensation reaction on alpha-halo-p-chlorophenylacetate (II) and acetylcyclopropane (III) as raw materials in the presence of alkaline to prepare glycidic ester (IV); and carrying out basic hydrolysis on the obtained glycidic ester (IV) to be converted to a corresponding glycerate (V), and further carrying out decarboxylation reaction under acidic conditions to prepare 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone (I) as a bactericide cyproconazole intermediate. The preparation method is simple in process, the three-step reaction can be realized through continuous operation or 'one-pot method'; and the product 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone (I) is high in content and suitable for large-scale development.

Description

technical field [0001] The invention belongs to the field of chemistry and chemical engineering, and relates to a preparation method of 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone, an intermediate and a preparation method of the intermediate. Background technique [0002] 1-(4-Chlorophenyl)-2-cyclopropyl-1-propanone (I) is an important intermediate of the fungicide cyproconazole. [0003] [0004] The early disclosed preparation method (US4973767, US4664696) is to take p-chlorobenzaldehyde as raw material, synthesize 1-(4-chlorophenyl)-3-butene-1-alcohol by reacting with chloropropene Grignard reagent, and then combine with Dibromomethane is subjected to cyclopropanation to obtain 1-(4-chlorophenyl)-2-cyclopropylethanol, which is converted into corresponding 4-chlorophenylcyclopropylmethyl ketone through oxidation, and further reacts with methyl iodide at the carbonyl The α-position introduces a methyl group to obtain 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone (I); also...

Claims

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Application Information

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IPC IPC(8): C07C49/813C07C45/61C07C45/58
Inventor 徐尚成徐明华王晓军郭丽琴万琴
Owner JIANGSU CHENGYANG GROP SCI CO LTD
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