PBIO关键中间体5-氨基-2,4-二硝基苯酚的合成.pdf

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2010年第29卷第12期
CHEMICAL INDUSTRY AND ENGINEERING PROGRESS
2379
parsee cohen
研究开发
PBIO关键中间体5-氨基-2,4-二硝基苯酚的合成
金宁人,侯晓华,毛连城,金婷婷,张建庭,赵德明
(浙江工业大学化学工程与材料学院,浙江杭州310032)
摘要:系统地研究了以4.6-二硝基间二氟苯( DCIDNB)为原料经单水解后氟解两步反应制备聚对亚苯基苯并
咪恶二唑(PBIO)的关键中间体5-氪基-2,4-ニ硝基苯酚(ADNP)的合成新路线及其优化条件。结果表明:采
用NaOH在水溶剂中100℃回流下进行两个氯基的选择单水解反应,制得纯度98%以上的高收率5-氯-2,4-二硝
基苯酚(CDNP;以1,4-二氧六环为溶剂,在150C下使用氨水压力領解另一个氯基合成ADNP,经精制后获
得纯度98.5%以上、总收率达73.6%(以 DCDNB计)的产品,产品经IR、'HNMR、1CNMR及MS等定性确
认,合成过程巳呈现有机污染少、操作方便、产品质量优异、经济性良好及易于产业化等特色,为进一步研发
合成新型高性能材料PBIO及其新单体提供技术基础及中间体来源
关键词:5-基-2,4-二硝基苯酚;PBIO关键中间体;合成新方法;4,6-二硝基间二氟苯;单水解氨解
中图分类号:TQ316.342
文献标志码:A
文章编号:1000-6613(2010)12-2379-07
Synthesis of 5-amino-2, 4-dinitrophenol as key intermidiate for poly
p-phenylene-2-benz0imidazol-6-oxazole
JIN Ningren, HOU Xiaohua, MAO Liancheng, N Tingting, ZHANG ianting, ZAO Deming
K College of Chemical Engineering and Materials Science, Zhejiang University of Technology
Hangzhou 310032, Zheji
China))
Abstract: A novel synthesis route and technique of 5-amino-2 4-dinitrophenol(ADNP)as key
intermediate for poly (p-phenylene-2-benzoimidazo1-6-oxazole)(PBIO )were studied systematicall
ADNP was economically prepared by a two-step reaction from 4, 6-dinitro-1, 3-dichlorobenzene
DCDNB with 73.6% total yield and 98.5% purity. In the first step, 5-chloro-2 4-dinitrophenol
CDNP )was obtained with high yield by the selective hydrol ysis of DCDNB at 100 C with aqueous
NAOH. In the second step, CDNP was ammonolyzed under pressure at 150 C using dioxane as
solvent yielding the target product. The prepared ADNP was identified by FTIR, H NMR, C NMR
and MS. This process for ADNP synthesis has advantages of simple operation procedure, lower organic
pollution, excellent product quality, good economy and easy industrialization etc, which provides
convenience for further development of PBIO high-preformance materials
Key words: 5-amino-2, 4-dinitrophenol PBIO key intermediate; novel synthesis; 4, 6-dinitro-1
dichlorobenzene; mono-hydrolysis and ammonolysis
PBIO即聚对亚苯棊苯并咪恶二唑poly(p-普纤维轴向抗压性能,见式(1)。PBO纤维是采用
phenylene-2- benzimidazol-6-0 azole)的缩写,它与
PBO(聚对亚苯基苯并二唑)分子的基本结构相收稿日期,2000修改稿日期:201006
基金项目:江苏省科技攻关重大项目(BE2006077)资助。
同,只是将PBO重复单元中的一个氧原子O一变
第一作者及联系人简介:金宁人(1954-),男,教授。电话
换为氮氢原子NHI一、从而在分子链间形成氢键改0571-8808E-mailcnhzjnth(@mailhz.zi.cn