维生素E的催化合成路线分析

引用本文: 王哲, 毛善俊, 李浩然, 王勇. 维生素E的催化合成路线分析[J]. 物理化学学报, 2018, 34(6): 598-617. doi: 10.3866/PKU.WHXB201711231 shu

Citation: WANG Zhe, MAO Shanjun, LI Haoran, WANG Yong. How to Synthesize Vitamin E[J]. Acta Physico-Chimica Sinica, 2018, 34(6): 598-617. doi: 10.3866/PKU.WHXB201711231 shu

维生素E的催化合成路线分析

浙江大学化学系催化研究所，浙江大学-新和成研发中心，杭州 310028

作者简介:

王勇，浙江大学化学系教授，催化研究所所长。中组部“万人计划”青年拔尖人才及国家优秀青年基金获得者。2002年本科毕业于湘潭大学化工学院，2007年博士毕业于浙江大学化工系。作为项目负责人承担多项国家及省部级项目。王勇课题组致力于新材料在传统多相催化反应、能源转化等方面的应用，所研发的多个催化剂在工业上得到应用;

通讯作者: 王勇, chemwy@zju.edu.cn

基金项目:
国家自然科学基金(21622308, 91534114, 21376208)资助项目

摘要: 维生素E具有多种特异的生理活性，同时也是一种优良的抗氧化剂，已经逐渐成为维生素领域中的焦点，市场需求不断增加。目前合成维生素E占据市场的80%以上，提升维生素E的产量和生产效率势在必行。天然维生素E包括四种生育酚类物质和四种生育三烯酚类物质，其中α-生育酚含量最大，生理活性也最高。本综述简要介绍α-生育酚的合成路线，其中包括2, 3, 5-三甲基氢醌和异植物醇的合成以及它们二者缩合的反应。本文着重阐述路线的设计和催化剂的选择，并对存在的问题及潜在的解决办法进行评述和展望。

关键词:

English

How to Synthesize Vitamin E

ZJU-NHU United R & D Center, Institute of Catalysis, Department of Chemistry, Zhejiang University, Hangzhou 310028, P. R. China

Corresponding author: WANG Yong, Email: chemwy@zju.edu.cn; Tel.: +86-571-88273551

Received Date: 11 October 2017
Accepted Date: 17 November 2017
Revised Date: 16 November 2017
Available Online: 15 June 2018
Fund Project:
The project was supported by the National Natural Science Foundation of China (21622308, 91534114, 21376208)

Abstract: Vitamin E compounds are biologically active and are frequently used as antioxidants. The demand for Vitamin E compounds has increased significantly in recent years, and at present, more than 80% of the market demand for Vitamin E is fulfilled by its synthetic counterparts. Therefore, it is imperative to increase the production of Vitamin E. Vitamin E compounds contain tocopherol and tocotrienol derivatives, and α-tocopherol, which dominates the sound, is the most biologically active. This review covers the methods of preparation of α-tocopherol, focusing on the synthesis routes, chemical reactions, and corresponding catalysts. The synthesis of Vitamin E, including preparation of 2, 3, 5-trimethylhydroquinone (TMHQ), preparation of isophytol, and condensation of TMHQ and isophytol are discussed in detail. The disadvantages and issues related to the preparation methods are also included. In general, the preparation of TMHQ comprises three steps: (1) methylation of m-cresol to 2, 3, 6-trimethylphenol, (2) oxidation of 2, 3, 6-trimethylphenol to 2, 3, 5-trimethylbenzoquione (TMBQ), and (3) hydrogenation of TMBQ to TMHQ. Recently, a novel and attractive method using isophorone, which can be produced by self-condensation of acetone, as a source for synthesizing TMHQ has been developed. Among these procedures, it is important to attain high selectivity in the oxidative reactions, including oxidation of 2, 3, 6-trimethylphenol and isophorone (α-isophorone or β-isophorone), and to replace H₂O₂, a common oxidant, by oxygen or air. One of the methods of preparation of isophytol using citral as a source has been abandoned because of shortage of oil of litsea cubeba, which is a natural source of citral. Linalool, produced from 6-methyl-5-hepten-2-one, is a key intermediate in the main process of preparation of isophytol. Both BASF SE and Roche have developed effective methods for the preparation of 6-methyl-5-hepten-2-one, respectively. Semi-hydrogenation of alkynols plays a key role in the whole process. The selectivity, especially at high conversion is directly related to the profit; therefore, it is of great importance for industries. The condensation of TMHQ and isophytol is essentially a Friedel-Crafts alkylation reaction catalyzed by acids. Similar reactions include methylation of m-cresol. Bronsted acids are usually effective for these reactions; however, it is difficult to recover these catalysts from the homogeneous systems. Therefore solid acid has a great potential in this area and it is also a promising topic to reduce the loss of acid sites when using acid-immobilized catalysts. The supply of various sources of the reactants and the local policy need to be considered while choosing an appropriate method for the preparation of Vitamin E.

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沈阳化工大学材料科学与工程学院沈阳 110142

维生素E的催化合成路线分析

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How to Synthesize Vitamin E

Corresponding author: WANG Yong, Email: chemwy@zju.edu.cn; Tel.: +86-571-88273551

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中国化学会秘书处

维生素E的催化合成路线分析

通讯作者: 王勇, chemwy@zju.edu.cn

English

How to Synthesize Vitamin E

Corresponding author: WANG Yong, Email: chemwy@zju.edu.cn; Tel.: +86-571-88273551

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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