固体酸催化酰基化高选择性合成间三氟甲基苯乙酮

摘要间三氟甲基苯乙酮是合成农药肟菌酯的关键中间体,同时也是合成医药、染料等其他化学品的重要原料。目前已报道的合成路线大多存在工艺复杂、环境污染大、危险性高等问题。研究了以乙酰氯为酰化剂,在负载型固体酸催化作用下,由三氟甲苯为原料一步生成间三氟甲基苯乙酮的Friedel-Crafts酰基化反应。重点考察了催化剂活性组分负载量、反应温度以及反应溶剂对催化制备三氟甲基苯乙酮的影响规律。确定了以FeCl₃为活性组分,γ-Al₂O₃为负载体,二氯乙烷为溶剂,催化剂加入量为10%,在50 ℃下进行回流反应的优化工艺条件。目标产物三氟甲基苯乙酮的选择性可达99%,三氟甲苯的单程转化率为15.5%。通过XPS、BET以及NH₃-TPD对所制备FeCl₃/γ-Al₂O₃负载型固体酸进行了表征分析,初步探讨了催化反应机理。该合成方法操作简便、催化剂成本低、后处理过程环境友好,具有工业化应用潜力。

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	李彬
	王文钧
	姜爽
	张天永

关键词：固体酸催化傅克酰基化反应间三氟甲基苯乙酮三氟甲苯高选择性

Abstract： m-Trifluoromethyl acetophenone(TFAP) is a key intermediate in the synthesis of trifloxystrobin, and also an important raw material for the synthesis of other chemicals such as pharmaceuticals and dyes. Most of the synthesis routes that have been reported presently suffer from complex processes, high environmental pollution and high risk. In this paper, we investigated the Friedel-Crafts acylation reaction for preparation of m-trifluoromethyl acetophenone from trifluorotoluene with acetyl chloride as the acylating agent in one step based on the loaded solid acid catalyst, which focused on the effects of catalyst loading, reaction temperature and reaction solvent on the catalytic preparation of trifluoromethy lacetophenone. The optimal process conditions were determined for the reflux reaction at 50 ℃ with FeCl₃ as the active component, γ-Al₂O₃ as the carrier, dichloroethane as the solvent, and the catalyst addition of 10%. The selectivity of the target product trifluoromethyl acetophenone could reach 99%, and the one-way conversion of trifluorotoluene was 15.5%. The prepared FeCl₃/γ-Al₂O₃ loaded solid acids were characterized by XPS, BET and NH₃-TPD, and the possible catalytic reaction mechanism was proposed. The synthetic method is easy to operate, with low cost catalyst and environmentally friendly post-treatment process, which exhibiting good potential for industrial application.

Keywords： solid acid catalysis Friedel-Crafts acylation reaction m-trifluoromethyl acetophenone trifluoromethyl benzene high selectivity

Received 2023-04-28;

Fund:国家重点研发计划项目(2022YFB3603101);国家自然科学基金(22278315)。

Corresponding Authors: 张天永,教授,tyzhang@tju.edu.cn;姜爽,副教授,shuangjiang@tju.edu.cn。 Email: tyzhang@tju.edu.cn;shuangjiang@tju.edu.cn

About author: 李彬(1982—),男,博士,副教授,研究方向为精细化学品的绿色合成。

引用本文:

李彬, 王文钧, 姜爽, 张天永.固体酸催化酰基化高选择性合成间三氟甲基苯乙酮[J]. 化学工业与工程, 2025,42(2): 20-27

LI Bin, WANG Wenjun, JIANG Shuang, ZHANG Tianyong.Highly selective synthesis of m-trifluoromethyl acetophenone by catalytic acylation based on solid acid catalyst[J]. Chemcial Industry and Engineering, 2025,42(2): 20-27

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