3',5'-二溴-3-甲氧基-4-羟基偶氮苯合成、晶体结构与异构化性能

doi:10.3724/SP.J.1095.2014.40001

摘要/Abstract

摘要： 以4-氨基硝基苯为原料，通过溴代、重氮化去氨基、硝基还原和重氮偶合反应合成了3′,5′-二溴-3-甲氧基-4-羟基偶氮苯，并通过物理掺杂方法制备了3′,5′-二溴-3-甲氧基-4-羟基偶氮苯-聚甲基丙烯酸甲酯（PMMA）薄膜。利用元素分析、红外光谱、质谱、核磁共振和X射线单晶衍射等技术手段对标题化合物结构进行了表征。晶体结构分析表明，标题化合物晶体属于单斜晶系，C2/c空间群，晶胞参数为a=1.6182(3) nm，b=0.81847(16) nm，c=2.1945(4) nm，β=102.819(2) °，V=2.8342(10) nm3，Z=8，Dc=1.809 g/cm3，μ=5.719 mm-1，F(000)=1504，R1=0.0366，ωR2=0.0764，化合物分子呈反式平面构型，分子间存在的氢键和苯环π-π堆积作用使得其沿b轴方向形成了一维无限链状结构。用紫外-可见光谱对标题化合物在有机溶剂、聚合物中光致反-顺异构化反应和热回复异构化反应的速率常数进行了定量测试，异构化反应的速率常数的数量级为10-1～10-2 min-1。

关键词: 二溴-甲氧基-羟基偶氮苯, 晶体, 光致反-顺异构, 热回复, 速率常数

Abstract: Starting from 4-amino nitrobenzene, 3′,5′-dibromo-3-methoxy-4-hydroxyazobenzene 6 was synthesized via sequential reactions of dibromination, diazotization deamination, nitro-reduction and diazo coupling. Polymethyl methacrylate(PMMA) films containing azobenzene 6 were obtained by a physical doping process. The structure of the title compound was characterized by elemental analysis, FT-IR, MS(ESI), 1H NMR, 13C NMR, MS, especially by the X-ray single crystal diffraction. The crystal crystallizes in the monoclinic space group C2/c, with a=1.6182(3) nm, b=0.81847(16) nm, c=2.1945(4) nm, β=102.819(2) °, V=2.8342(10) nm3, Z=8, Dc=1.809 g/cm3, μ=5.719 mm-1, F(000)=1504, R1=0.0366 and ωR2=0.0764. The title compound exists in the trans-form. The intermolecular hydrogen bonds and π-π stacking between benzene rings contributes to one-dimensional infinite chain structure along b axis. By UV-Vis spectroscopy method, the reaction rate constants for trans-cis photoisomerization and cis-trans thermal back-isomerization are at the range of 10-1～10-2 min-1.

Key words: dibromo-methoxy-hydroxyazobenzene, crystal structure, trans-cis photoisomerization, thermal back-isomerization, rate constant

中图分类号:

O625.6

宋秀美, 冯宗财, 陈键侨, 汪朝阳, 冯翠娟, 卢扬丽. 3',5'-二溴-3-甲氧基-4-羟基偶氮苯合成、晶体结构与异构化性能[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.40001.

SONG Xiumei1,2, FENG Zongcai1*, CHEN Jianqiao3, WANG Zhaoyang2, FENG Cuijuan1, LU Yangli1. Synthesis, Crystal Structure and Isomerization Property of 3′,5′-Dibromo-3-methoxy-4-hydroxyazobenzene[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.40001.

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