2,3,3',4'-联苯四甲酸二酐的合成  

Synthesis of 2,3,3',4'-Biphenyltetracarboxylic Dianhydride

作　　者：李玉邯[1] 吴强[2] 康传清[2] 郭海泉[2] 金日哲[2] 高连勋[2] 

机构地区：[1]吉林工商学院食品工程学院,长春130507 [2]中国科学院长春应用化学研究所,长春130022

出　　处：《应用化学》2016年第8期900-904,共5页Chinese Journal of Applied Chemistry

基　　金：国家重点基础研究发展计划(973计划)课题(2014CB643603);吉林省重大科技攻关专项(20140203003GX);吉林省自然科学基金(20130101005JC)资助~~

摘　　要：报道了一种从卤代邻二甲苯偶联和液相氧化制备2,3,3',4'-联苯四甲酸二酐(3,4'-BPDA)的简便方法。以NiF2-PPh_3(PPh_3:三苯基膦)为催化体系,高效地实现了4-溴邻二甲苯格氏试剂与3-氯代邻二甲苯的交叉偶联反应,合成了2,3,3',4'-四甲基联苯(3,4'-TMDP),后者经液相氧化、高温脱水成酐制备了3,4'-BPDA,两步总产率达到74%。这条路线与从邻苯二甲酸二甲酯或混合氯代邻苯二甲酸二甲酯制备3,4'-BPDA相比,不涉及酯的水解及异构体的分离等过程,因此分离及环保方面具有非常明显的优势,同时合成路线更简便。A facile synthesis of 2,3,3＇,4＇-biphenyltetracarboxylic dianhydride through cross-coupling of halo- substituted orthoxylene and liquid-phase oxidation of the resulted tetramethylbiphenyl. 2, 3, 3＇, 4＇- Tetramethylbiphenyl （3,4＇-TMDP） was synthesized by cross-coupling of 4-bromo-1,2-dimethylbenzene and 3,4-dimethylphenylmagnesium bromide with NiF2-PPh3 （ PPh3 ：triphenylphosphine） as the catalyst and which was then converted to 2,3,3＇, 4＇-biphenyltetracarboxylic dianhydride （ 3,4＇- BPDA） by the oxidation and dehydration procedures. The overall yield reached to 74%. In comparison with the preparations of 3,4＇-BPDA from dimethyl phthalate or chlorinated dimethyl phthalate mixture, the method exhibits advantages in the separation and environmental benign because of the avoidance of the tedious hydrolysis step and the separation of isomers.

关 键 词：联苯四甲酸二酐 合成 交叉偶联 聚酰亚胺 

分 类 号：O625.5[理学—有机化学]