硒催化环己烯氧化制备1,2-环己二醇进展

doi:10.6023/cjoc202501008

摘要/Abstract

环己烯是一种易得的化工原料, 可通过苯选择性加氢来制备. 与环己烷相比, 引入烯烃官能团可使环己烯更易被氧化, 且反应位点选择性更佳. 因此, 环己烯氧化反应是合成尼龙-66系列产品及中间体的关键步骤, 有很好的工业应用价值. 近年来, 硒催化技术发展迅速, 与金属催化相比, 硒元素易代谢, 对生态安全, 且其催化氧化过程通常使用过氧化氢与分子氧为清洁的氧化剂, 对环境友好. 硒催化环己烯氧化技术, 有望应用于尼龙中间体合成中, 对均相以及非均相硒催化剂在该反应中的应用进行了综述, 从科学角度阐述其原理, 并对其产业化应用前景进行了展望.

关键词: 硒, 催化, 氧化, 环己烯, 尼龙

Cyclohexene is an easily available chemical raw material that can be prepared by selective hydrogenation of benzene. Compared with cyclohexane, the introduction of the alkene functional group makes cyclohexene more active and can be oxidized with better selectivity. Therefore, the oxidation reaction of cyclohexene is the key step for the synthesis of nylon-66 series products and their intermediates. In recent years, selenium catalysis technology has developed rapidly. Compared with metal catalysis, selenium is easily metabolized and ecologically safe, and its catalytic oxidation process usually uses hydrogen peroxide and molecular oxygen as clean oxidants, which are environmentally friendly. The selenium-catalyzed oxidation technology of cyclohexene is expected to be applied in the synthesis of nylon intermediates. The relevant progresses including both homogeneous and heterogeneous catalysis are reviewed, the principle from a scientific perspective is expounded and prospects for its industrial application are provided.

Key words: selenium, catalysis, oxidation, cyclohexene, nylon

引用此文

雍达明, 袁广树, 刘永红, 张旭. 硒催化环己烯氧化制备1,2-环己二醇进展[J]. 有机化学, 2025, 45(8): 2767-2772.

Daming Yong, Guangshu Yuan, Yonghong Liu, Xu Zhang. Progress in Selenium Catalyzed Oxidation of Cyclohexene to Produce 1,2-Cyclohexanediol[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2767-2772.

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图/表 8

图式1. 环己烯在催化量二苯基二硒醚存在下被过氧化氢氧化

Scheme 1. Oxidation of cyclohexene by H2O2 in the presence of catalytic amount of (PhSe)2

图式2. 各种二硒醚与硒醚的合成

Scheme 2. Synthesis of the diselenides and selenides

图式3. 硒催化反应中硒活性物种的核磁共振研究

Scheme 3. 77Se NMR study of the active selenium species in catalysis

图式4. 硒催化环己烯氧化制备1,2-己二醇反应机理

Scheme 4. Mechanism of the selenium-catalyzed oxidation of cyclohexene to produce 1,2-cyclohexanediol

图式5. 聚苯乙烯负载硒酸催化剂制备

Scheme 5. Preparation of polystyrene supported selenic acid catalyst

图式6. 聚苯乙烯负载硒酸催化环己烯氧化制备1,2-环己二醇

Scheme 6. Preparation of 1,2-cyclohexanediol catalyzed by polystyrene supported selenic acid

图式7. 聚硒醚合成

Scheme 7. Synthesis of the polyselenide

图式8. 环己烯氧化“羟基自由基泵”机理

Scheme 8. “Hydroxyl radical pump” mechanism for the oxidation of cyclohexene

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