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A method for preparing acetophenone and its derivatives by selective oxidation of 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: 2022-06-17
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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  • A method for preparing acetophenone and its derivatives by selective oxidation of ethylbenzene and its derivatives
  • A method for preparing acetophenone and its derivatives by selective oxidation of ethylbenzene and its derivatives

Examples

Experimental program
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Effect test

Embodiment 1

[0019] In a 100 mL agate ball mill jar, mix 1.51 g (10 mmol) 4-nitroethylbenzene, 0.0009 g (0.0050 mmol) cobalt acetate, 2.57 g (20 mmol) 70% t-butyl hydroperoxide aqueous solution and 4.53 g anhydrous sulfuric acid Mix the sodium well 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, and the gas in the ball milling jar was released. After the reaction was completed, the obtained 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 solutions, and dilute the obtained ethanol solution to 100 mL. Pipette 10 mL of the obtained solution, add internal standard 2-naphthoic acid, and carry out liquid chromatography analysis. The conversion rate of 4-nitroethylbenzene was 27%, the selectivity of 4-nitroacetophenone was 92%, the sele...

Embodiment 2

[0021] In a 100 mL agate ball mill jar, mix 1.51 g (10 mmol) 4-nitroethylbenzene, 0.0044 g (0.0250 mmol) cobalt acetate, 2.57 g (20 mmol) 70% t-butyl hydroperoxide aqueous solution and 4.53 g anhydrous sulfuric acid Mix the sodium well 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, and the gas in the ball milling jar was released. After the reaction was completed, the obtained 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 solutions, and dilute the obtained ethanol solution to 100 mL. Pipette 10 mL of the obtained solution, add internal standard 2-naphthoic acid, and carry out liquid chromatography analysis. The conversion rate of 4-nitroethylbenzene was 30%, the selectivity of 4-nitroacetophenone was 97%, the sele...

Embodiment 3

[0023] In a 100 mL agate ball mill jar, mix 1.51 g (10 mmol) 4-nitroethylbenzene, 0.0018 g (0.0100 mmol) cobalt acetate, 2.57 g (20 mmol) 70% t-butyl hydroperoxide aqueous solution and 4.53 g anhydrous sulfuric acid Mix the sodium well 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, and the gas in the ball milling jar was released. After the reaction was completed, the obtained 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 solutions, and dilute the obtained ethanol solution to 100 mL. Pipette 10 mL of the obtained solution, add internal standard 2-naphthoic acid, and carry out liquid chromatography analysis. The conversion rate of 4-nitroethylbenzene was 28%, the selectivity of 4-nitroacetophenone was 96%, the sele...

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Abstract

A method for preparing acetophenone and derivatives thereof by selective oxidation of ethylbenzene and derivatives thereof, wherein ethylbenzene and derivatives thereof, cobalt (II) salt catalyst, oxidizing agent and dispersant are placed in an agate ball mill jar, sealed ball mill Tank, room temperature, ball milling at 100-800rpm for 3.0-24.0h, stop the ball milling every 1.0-3.0h, release the gas in the ball milling tank; after the reaction is completed, dissolve the obtained reaction mixture in absolute ethanol, stir at room temperature, filter, Wash the obtained solid with absolute ethanol, and combine the obtained ethanol solutions to constant volume. The invention uses less catalyst, does not use solvent, does not need heating, has low reaction temperature, less energy consumption, convenient operation, high selectivity of acetophenone, no obvious peroxide residue detected, high safety factor, and various Selective, safe oxidative transformation of ethylbenzene and its derivatives.

Description

(1) Technical field [0001] The invention relates to a method for preparing acetophenone and its derivatives by selective oxidation of ethylbenzene and derivatives thereof, belonging to the fields of organic chemical industry and fine organic synthesis. (2) Background technology [0002] Acetophenone and its derivatives are an important class of fine chemical intermediates, which are widely used in the synthesis of fine chemical products such as medicines, pesticides, dyes, analytical detection reagents, and high-end intermediates (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 mainly uses ethylbenzene, 1-phenethyl alcohol and styrene and their derivatives as raw materials, and is realized by oxidation reaction (US20190002487; CN 108947846; Molecular Catalysis 2019, 469: 27- 39; Organic Pr...

Claims

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Application Information

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Patent Type & Authority Patents(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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