化学学报 ›› 2004, Vol. 62 ›› Issue (9): 869-874. 上一篇    下一篇

研究论文

3,7-二硝基二苯并环状卤鎓盐在碱性条件下的反应机理研究

李文玲, 潘仙华, 朱耘玑, 侯自杰   

  1. 兰州大学有机化学研究所,应用有机化学国家重点实验室,兰州,730000
  • 投稿日期:2003-08-11 修回日期:2004-01-02 发布日期:2014-02-17
  • 通讯作者: 侯自杰,E-mail:houzj@lzu.edu.cn E-mail:houzj@lzu.edu.cn

Study on the Reaction Mechanism of 3,7-Dinitrodibenzohalonium Salts under Basic Conditions

LI Wen-Ling, PAN Xian-Hua, ZHU Yun-Ji, HOU Zi-Jie   

  1. Institute of Organic Chemistry and State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000
  • Received:2003-08-11 Revised:2004-01-02 Published:2014-02-17

研究了3,7-二硝基二苯并溴五环盐(1a)与一些伯胺及仲胺的反应,其主要产物6 (2-溴-2'-烷氨基-4,4'-二硝基联苯)与次要产物7 (2-溴-3'-烷氨基-4,4'-二硝基联苯)互为位置异构体,这一结果支持一个以苯炔类化合物(4)为中间体的反应机理.进而用蒽成功地捕获了一系列3,7-二硝基二苯并环状卤鎓盐(1a~1c)在碱性条件下形成的苯炔类中间体,为上述机理提供了强有力的证明.

关键词: 3,7-二硝基二苯并环状卤鎓盐, 胺, 蒽, 苯炔, 捕获, 反应机理

Reactions of 3,7 dinitrodibenzobromolium salt (1a) with primary and secondary amines were studied.The result that the major products 6a~6e (2 bromo 2' alkylamino 4,4' dinitrobiphenyl) and the minor products 7a~7e (2 bromo 3' alkylamino 4,4' dinitrobiphenyl) are regioisomers supports a mechanism with the substituted benzyne 4 as the intermediate.It provides powerful backing for this mechanism that the formed benzyne intermediates of some 3,7 dinitrodibenzohalonium salts (1a~1c) under basic conditions were successfully trapped using anthracene.The structures of the trapped products 8a~8c were established by 1H NMR, MS and IR spectroscopy.The crystal and molecular structure of 8a was determined by X ray analysis.The dihedral angle between two phenyl rings of the biphenyl part of 8a is 77°, showing that 8a is an axial chiral molecule.

Key words: 3,7-dinitrodibenzohalonium salt, amine, anthracene, benzyne, trap, reaction mechanism