双(3-氨基-4-羟基苯基)双酚醚类化合物的合成

doi:10.3724/SP.J.1095.2013.20501

摘要/Abstract

摘要： 以双酚化合物及对卤苯酚为起始原料，经用苄基保护、乌尔曼成醚、选择性硝化和还原脱保护4步反应，合成了具有双酚芳香醚结构的4个新型聚苯并噁唑单体：双(3-氨基-4-羟基苯基)双酚醚类化合物的盐酸盐。确定了乌尔曼成醚反应的最佳工艺条件，证明硝化反应只发生在对卤苯酚苄保护基的邻位，改进了还原脱保护反应的成盐及后处理条件，提高了产物的质量和收率，4步反应总收率可达54.0%。采用红外光谱、核磁共振H谱和高分辨质谱表征了每步产物的化学结构。

关键词: 聚苯并噁唑单体, 乌尔曼反应, 双氨基羟基苯基双酚醚, 合成

Abstract: Four monomers of polybenzoxazole having the structure of bisphenol aromatic ether, bis(3-amino-4-hydroxyphenyl) bisphenol ether, were prepared from bisphenols and 4-chloro(or bromo)-phenol by successive 4 steps of synthetic routes including benzyl protection, Ullmann reaction, selective nitrification and reduction-deprotection. The effect of reaction conditions on the Ullmann reaction was investigated. The high region selection of the nitrification is confirmed. The process of after-treatment of the reduction-deprotection was optimized and the quality and yield of the product were improved. The total yield of 4 steps reaction can reach up to 54.0%. The target compound and its intermediates were characterized by means of IR, 1H NMR and HRMS.

Key words: monomer of polybenzoxazole, Ullmann reaction, bis(aminohydroxyphenyl) bisphenol ether, synthesis

中图分类号:

O625

张前锋, 唐安斌, 黄杰, 马寒冰, 杨玉川. 双(3-氨基-4-羟基苯基)双酚醚类化合物的合成[J]. 应用化学, DOI: 10.3724/SP.J.1095.2013.20501.

ZHANG Qianfeng1, TANG Anbin1,2*, HUANG Jie2, MA Hanbing1, YANG Yuchuan2. Synthesis of Bis(3-amino-4-hydroxyphenyl) Bisphenol Ether[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2013.20501.

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