2-羟基-4-(5,6-二硝基-1H-苯并[2,3-d]咪唑-2-基)苯甲酸甲酯的合成探索  

Synthesis of methyl 2-hydroxyl-4-(5,6-dinitro-1H-benzo[2,3-d] imidazole-2-yl)benzoate

作　　者：张青龙[1] 金宁人[1] 杨健[1] 张清义[1] 张建庭[1] 

机构地区：[1]浙江工业大学化学工程与材料学院,浙江杭州310014

出　　处：《化工进展》2014年第3期744-748,757,共6页Chemical Industry and Engineering Progress

基　　金：江苏省科技支撑计划(BE 2011129);浙江省教育厅科研项目(Y201121211)

摘　　要：以4,5-二硝基邻苯二胺和2-羟基对苯二甲酸单甲酯为起始原料,设计并成功采用一锅法合成出2-羟基-4-(5,6-二硝基-1H-苯并[2,3-d]咪唑-2-基)苯甲酸甲酯(MHDIB)。以50 mL二乙二醇二甲醚为溶剂,1.5 g的2-羟基对苯二甲酸单甲酯和2.5 g SOCl2在80℃反应2 h制2-羟基-4-氯羰基苯甲酸甲酯。室温下快速向反应体系中加入1.56 g 4,5-二硝基邻苯二胺,并于85℃反应1 h后加入3.52 g多聚磷酸,回流反应1 h后水析出粗产品,经乙醇重结晶得到纯度为93.67%的黄色针状产物,产率为17.82%。产物经IR、MS、1H NMR的准确定性和表征,作为AB型新单体的前体可应用于羟基改性PBI纤维即聚2-羟基-1,4-亚苯基-2,6-苯并[2,3-d:5',6'-d']二咪唑(H-PBI)的创新研究。A novel compound , methyl 2-hydroxyl-4-（5,6-dinitro-1H-benzo[2,3-d]imidazole-2-yl）benzoate（MHDIB）,was designed and synthesized from 4,5-dinitro-1,2-benzenediamine and methyl 2-hydroxy-4-carboxybenzoate.The one-pot synthesis method was adopted in synthesis of MHDIB . With 50mL diethylene glycol dimethyl ether as vehicle,methyl 2-hydroxy-4-（chlorocarbonyl）benzoate was synthesized from 1.5 g methyl 2-hydroxy-4-carboxybenzoate and 2.5 g SOCl2 at 80 ℃,reaction time was 2 hours. At room temperature,1.56 g 4,5-Dinitro-o-phenylenediamine was added rapidly into the reaction system and 2 hours reaction time at 85 ℃. 3.52 g polyphosphoric acid was added and MHDIB was synthesized at reflux temperature for 1h.The preciptate formed was recrystallized with ethanol and yellow needles were obtained. Product yield was 17.82% and purity was 93.67%.The product was qualitatively exact and the structure was characterized by IR,ESI-MS,1H NMR. It was used to prepare a new AB-type monomer of high-performance polymer modified by orderly hydroxy , poly 2-hydroxy-1,4-phenylene-2,6-benzo[2,3-d：5＆#39;,6＆#39;-d＆#39;] diimidazole（H-PBI）.

关 键 词：2-羟基-4-(5 6-二硝基-1H-苯并2 3-d咪唑-2-基)苯甲酸甲酯 4 5-二硝基邻苯二胺 羟基改性PBI纤维 聚合 合成 纯化 methyl 2-hydrox yl-4-(5 6-dinitro-1H-benzo[2 3-d]imidazole-2-yl)benzoate(MHDIB) 

分 类 号：TQ253.2[化学工程—有机化工]