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A kind of method for selective oxidation of ethylbenzene compounds

A compound and selective technology, which is applied in the preparation of organic compounds, chemical instruments and methods, and the preparation of carbonyl compounds by oxidation, can solve the problems of poor safety, difficult activation, non-compliance, etc., and avoid the use of toxic and harmful organic reagents, The effect of low peroxide content and novel reaction mode

Active Publication Date: 2022-06-21
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 kind of method for selective oxidation of ethylbenzene compounds
  • A kind of method for selective oxidation of ethylbenzene compounds
  • A kind of method for selective oxidation of ethylbenzene compounds

Examples

Experimental program
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Effect test

Embodiment 1

[0033] In a 100 mL agate ball mill jar, 1.51 g (10 mmol) of 4-nitroethylbenzene, 0.0004 g (0.0005 mmol) of 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin cobalt(II), 2.57 g (20 mmol) of 70% t-butyl hydroperoxide aqueous solution and 4.53 g of anhydrous sodium sulfate were mixed uniformly, and the ball mill jar was sealed. 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%...

Embodiment 2

[0035] In a 100 mL agate ball mill jar, 1.51 g (10 mmol) of 4-nitroethylbenzene, 0.0020 g (0.0025 mmol) of 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin cobalt(II), 2.57 g (20 mmol) of 70% t-butyl hydroperoxide aqueous solution and 4.53 g of anhydrous sodium sulfate were mixed uniformly, and the ball mill jar was sealed. 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 30%...

Embodiment 3

[0037] In a 100 mL agate ball mill jar, 1.51 g (10 mmol) of 4-nitroethylbenzene, 0.0008 g (0.0010 mmol) of 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin cobalt(II), 2.57 g (20 mmol) of 70% t-butyl hydroperoxide aqueous solution and 4.53 g of anhydrous sodium sulfate were mixed uniformly, and the ball mill jar was sealed. 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 28%...

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Abstract

A method for the selective oxidation of ethylbenzene compounds, said method comprising: placing ethylbenzene compounds shown in formula (I), metal porphyrin catalysts, an oxidizing agent, and a dispersant in a ball milling tank, sealing the ball milling tank, and , ball milling at a speed of 100 to 800rpm for 3 to 24 hours, during the ball milling process, stop the ball milling once every 1 to 3 hours, release the gas in the ball mill tank, after the reaction is completed, the reaction mixture is post-treated to obtain the phenyl ethyl alcohol shown in formula (II) Ketone compounds; the invention realizes the oxidative transformation of ethylbenzene and its derivatives through solid-phase ball milling, the reaction method is novel, the operation is convenient, and the energy consumption is low; organic solvents and other additives are not needed, and the use of toxic and harmful organic reagents is effectively avoided. Green and environmental protection; low peroxide content, high safety factor; high selectivity of acetophenone and its derivatives, in line with the current social needs of green chemical processes, environmentally compatible chemical processes, and biocompatible chemical processes.

Description

(1) Technical field [0001] The invention relates to a new method for preparing acetophenone compounds by selective oxidation of ethylbenzene compounds, and belongs 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 Process Research & D...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B41/06C07C201/12C07C205/45C07C45/28C07C49/78C07C49/76C07C49/784C07C51/373C07C65/32C07C49/807C07C49/84C07C49/67C07C253/30C07C255/56
CPCC07B41/06C07C201/12C07C45/28C07C51/373C07C253/30C07C2602/10C07C205/45C07C49/78C07C49/76C07C49/784C07C65/32C07C49/807C07C49/84C07C49/67C07C255/56
Inventor 佘远斌刘磊沈海民
Owner ZHEJIANG UNIV OF TECH
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