有机化学 ›› 2019, Vol. 39 ›› Issue (7): 1996-2000.DOI: 10.6023/cjoc201901019 上一篇    下一篇

研究论文

次氯酸钠引发的α-羟基酯的自由基氧化

王茂昌a, 张宝华a, 丁凯b   

  1. a 上海大学化学与环境工程学院 上海 200444;
    b 中国科学院上海有机化学研究所 天然产物合成重点实验室 上海 200032
  • 收稿日期:2019-01-15 修回日期:2019-03-12 出版日期:2019-07-25 发布日期:2019-03-29
  • 通讯作者: 张宝华, 丁凯 E-mail:zhangbh@shu.edu.cn;dingkai@mail.sioc.ac.cn

Radical Oxidation of α-Hydroxyl Ester Initiated by Sodium Hypochlorite

Wang Maochanga, Zhang Baohuaa, Ding Kaib   

  1. a School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444;
    b CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2019-01-15 Revised:2019-03-12 Online:2019-07-25 Published:2019-03-29
  • Contact: 10.6023/cjoc201901019 E-mail:zhangbh@shu.edu.cn;dingkai@mail.sioc.ac.cn

次氯酸钠是一种绿色氧化试剂,可用于醇的氧化,但是对a-羟基酯的氧化较为困难.发展了一种以次氯酸钠为氧化剂,氢溴酸为添加剂的氧化方法,可以快速高效地完成a-羟基酯化合物的氧化.进一步研究发现自由基是反应的中间体,与传统的Stevens氧化拥有不同的机理.该方法也可以用于普通醇的氧化,并且对多羟基化合物的氧化具有很好的选择性.

关键词: 次氯酸钠, 绿色, 高效, 选择性

Sodium hypochlorite has been used as a green oxidant in oxidation of alcohols. However, the oxidation of a-hydroxyl ester via sodium hypochloriteis difficult under the same conditions. Herein, an efficient method is developed for the oxidation of a-hydroxyl ester with sodium hypochlorite in the presence of hydrogenbromide. In this case, a reaction mechanism was proposed with the formation of free radicals as reactive intermediates, which was different from the mechanism of traditional Stevens oxidation. The method is also applied to the oxidation of common secondary alcohol and has good selectivity for multi-hydroxyl compounds.

Key words: sodium hypochlorite, green, radical oxidation, selectivity