双(3-氨基-4-羟基苯基)双酚醚类化合物的合成

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(口恶)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.%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.