Method for preparing acetophenone and its derivatives through selectively oxidizing ethylbenzene and its derivatives

A derivative, the technology of acetophenone, applied in the field of organic chemical industry and fine organic synthesis, can solve the problems of incomplete decomposition of peroxides, uneasy control of the reaction, high reaction temperature, etc., and achieve simple oxidation transformation, novel reaction mode, selective sex high effect

Active Publication Date: 2019-11-26
ZHEJIANG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, because molecular oxygen has good stability as an oxidizing agent and is not easy to be activated, the oxygen oxidation of ethylbenzene and its derivatives often requires the use of a large amount of transition metal catalysts or co-catalysts, and even higher reaction temperatures, high energy consumption, and difficult control of the reaction. ; At the same time, in the current catalytic oxidation process of ethylbenzene and its derivatives, the intermediate product peroxide is not completely decomposed and easy to enrich, which makes the current industrial synthesis route of acetophenone and its derivatives less safe and does not meet the current " Realistic needs of "green chemical process" and "safe chemical process"

Method used

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  • Method for preparing acetophenone and its derivatives through selectively oxidizing ethylbenzene and its derivatives
  • Method for preparing acetophenone and its derivatives through selectively oxidizing ethylbenzene and its derivatives

Examples

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Embodiment 1

[0023] In a 100mL agate ball mill jar, 1.51g (10mmol) 4-nitroethylbenzene, 0.0009g (0.0050mmol) cobalt acetate, 2.57g (20mmol) 70% t-butyl hydroperoxide aqueous solution and 4.53g anhydrous sulfuric acid Mix the sodium evenly, and seal the ball mill jar. At room temperature, the ball milling reaction was carried out at 600 rpm for 12.0 h, and the ball milling was stopped every 1.0 h to release the gas in the ball milling tank. After the reaction was completed, the resulting reaction mixture was dissolved in 30 mL of absolute ethanol, and stirred at room temperature for 30.0 min. Filter, wash the obtained filter cake with 2×10 mL of absolute ethanol, combine the ethanol solution, and dilute the obtained ethanol solution to 100 mL. Pipette 10 mL of the resulting solution, add internal standard 2-naphthoic acid, and perform liquid chromatography analysis. The conversion rate of 4-nitroethylbenzene was 27%, the selectivity of 4-nitroacetophenone was 92%, the selectivity of 1-(4-...

Embodiment 2

[0025] In a 100mL agate ball mill jar, 1.51g (10mmol) 4-nitroethylbenzene, 0.0044g (0.0250mmol) cobalt acetate, 2.57g (20mmol) 70% t-butyl hydroperoxide aqueous solution and 4.53g anhydrous sulfuric acid Mix the sodium evenly, and seal the ball mill jar. At room temperature, the ball milling reaction was carried out at 600 rpm for 12.0 h, and the ball milling was stopped every 1.0 h to release the gas in the ball milling tank. After the reaction was completed, the resulting reaction mixture was dissolved in 30 mL of absolute ethanol, and stirred at room temperature for 20.0 min. Filter, wash the obtained filter cake with 2×10 mL of absolute ethanol, combine the ethanol solution, and dilute the obtained ethanol solution to 100 mL. Pipette 10 mL of the resulting solution, add internal standard 2-naphthoic acid, and perform liquid chromatography analysis. The conversion rate of 4-nitroethylbenzene was 30%, the selectivity of 4-nitroacetophenone was 97%, the selectivity of 1-(4-...

Embodiment 3

[0027] In a 100mL agate ball mill jar, 1.51g (10mmol) 4-nitroethylbenzene, 0.0018g (0.0100mmol) cobalt acetate, 2.57g (20mmol) 70% t-butyl hydroperoxide aqueous solution and 4.53g anhydrous sulfuric acid Mix the sodium evenly, and seal the ball mill jar. At room temperature, the ball milling reaction was carried out at 600 rpm for 12.0 h, and the ball milling was stopped every 1.0 h to release the gas in the ball milling tank. After the reaction was completed, the resulting reaction mixture was dissolved in 30 mL of absolute ethanol, and stirred at room temperature for 50.0 min. Filter, wash the obtained filter cake with 2×10 mL of absolute ethanol, combine the ethanol solution, and dilute the obtained ethanol solution to 100 mL. Pipette 10 mL of the resulting solution, add internal standard 2-naphthoic acid, and perform liquid chromatography analysis. The conversion rate of 4-nitroethylbenzene was 28%, the selectivity of 4-nitroacetophenone was 96%, the selectivity of 1-(4-...

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Abstract

The invention discloses a method for preparing acetophenone and its derivatives through selectively oxidizing ethylbenzene and its derivatives. The method comprises the following steps: putting ethylbenzene and its derivatives, a cobalt (II) salt catalyst, an oxidizing agent and a dispersant in an agate ball milling tank, sealing the ball milling tank, carrying out ball milling at room temperatureunder a rotating speed of 100-800 rpm for 3.0-24.0 h, stopping the ball milling one time every 1.0-3.0 h, and discharging a gas in the ball milling tank; and dissolving the obtained reaction mixturein anhydrous ethanol after the reaction is finished, performing stirring at room temperature, filtering the obtained solution, washing the obtained solid with anhydrous ethanol, mixing the obtained ethanol solutions, and making the volume reach a constant value. The method provided by the invention has the advantages of small catalyst dosage, no solvents, no heating, low reaction temperature, lessenergy consumption, convenience in operation, high acetophenone selectivity, no obvious peroxide residue, high safety factor, and realization of selective and safe oxidative conversion of ethylbenzene and its various derivatives.

Description

[0001] (1) Technical field [0002] The invention relates to a method for preparing acetophenone and its derivatives through selective oxidation of ethylbenzene and its derivatives, belonging to the fields of organic chemical industry and fine organic synthesis. [0003] (2) Background technology [0004] Acetophenone and its derivatives are an important class of fine chemical intermediates, widely used in the synthesis of fine chemical products and high-end intermediates such as pharmaceuticals, pesticides, dyes, and analytical and detection reagents (WO 201611034971; Bioorganic & Medicinal Chemistry Letters 2019, 29: 525-528; Bioorganic Chemistry 2019, 82:360-377; ACS Applied Materials & Interfaces 2018, 10:44324-44335). At present, the synthesis of acetophenone and its derivatives is mainly based on ethylbenzene, 1-phenylethanol, styrene and its derivatives as raw materials through oxidation reactions (US20190002487; CN 108947846; Molecular Catalysis 2019, 469: 27- 39; Orga...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C201/12C07C205/45
CPCC07C201/12C07C205/45
Inventor 沈海民叶宏亮佘远斌
Owner ZHEJIANG UNIV OF TECH
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