有机化学 ›› 2018, Vol. 38 ›› Issue (10): 2736-2740.DOI: 10.6023/cjoc201805044 上一篇    下一篇

研究简报

铜催化醛肟脱水/贝克曼重排选择性可切换反应

范昕a,b, 易容a,b, 王芳c, 张旭a,b, 徐清a,b, 俞磊a,b   

  1. a 扬州大学广陵学院 扬州 225000;
    b 扬州大学化学化工学院 扬州 225002;
    c 扬州工业职业技术学院 扬州 225127
  • 收稿日期:2018-05-22 修回日期:2018-06-11 发布日期:2018-06-15
  • 通讯作者: 张旭,E-mail:zhangxu@yzu.edu.cn;俞磊,E-mail:yulei@yzu.edu.cn E-mail:zhangxu@yzu.edu.cn;yulei@yzu.edu.cn
  • 基金资助:

    国家自然科学基金(No.21202141)、江苏省高校优势学科项目及广陵学院自然科学基金(No.ZKZD17005)资助项目.

Copper-Catalyzed Selectivity-Switchable Dehydration/Beckmann Rearrangement Reactions of Aldoxime

Fan Xina,b, Yi Ronga,b, Wang Fangc, Zhang Xua,b, Xu Qinga,b, Yu Leia,b   

  1. a Guangling College, Yangzhou University, Yangzhou 225000;
    b School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002;
    c Yangzhou Polytechnology Institute, Yangzhou 225127
  • Received:2018-05-22 Revised:2018-06-11 Published:2018-06-15
  • Contact: 10.6023/cjoc201805044 E-mail:zhangxu@yzu.edu.cn;yulei@yzu.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21202141), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) and the Natural Science Foundation of Guangling College (No. ZKZD17005).

廉价金属铜,可催化醛肟的脱水反应,生成有机腈.该反应在腈类溶剂中发生,并且使用二氧化锰作助催化剂,三苯基膦作配体.如果使用水作溶剂,则会发生贝克曼重排,生成酰胺.这种选择性随溶剂切换的有趣反应,为合成相关有用的有机化合物提供了简便方法,兼具学术与实用价值.

关键词: 醛肟, 脱水, 贝克曼重排, 腈, 酰胺

It was found that, copper as a cheap metal, could well catalyze the dehydration reaction of aldoximes to organonitriles in nitrile solvent by using MnO2 as the co-catalyst and PPh3 as the ligand. In contrast, instead of organonitriles, the Cu-catalyzed reactions of the aldoximes in water led to amides, which were the products of the Beckmann rearrangements. These interesting selectivity-switchable reactions afford easy accesses to the related useful organic compounds and may be of both academic and practical values.

Key words: aldoxime, dehydration, Beckmann rearrangement, nitrile, amide