2,3,3',4'-联苯四甲酸二酐的合成

doi:10.11944/j.issn.1000-0518.2016.08.150401

摘要/Abstract

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-PPh₃(PPh₃:三苯基膦)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。

关键词: 联苯四甲酸二酐, 合成, 交叉偶联, 聚酰亚胺

Abstract:

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.

Key words: biphenyltetracarboxylic dianhydride, synthesis, cross-coupling, polyimide

李玉邯, 吴强, 康传清, 郭海泉, 金日哲, 高连勋. 2,3,3',4'-联苯四甲酸二酐的合成[J]. 应用化学, 2016, 33(8): 900-904.

LI Yuhan, WU Qiang, KANG Chuanqing, GUO Haiquan, JIN Rizhe, GAO Lianxun. Synthesis of 2,3,3',4'-Biphenyltetracarboxylic Dianhydride[J]. Chinese Journal of Applied Chemistry, 2016, 33(8): 900-904.

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