PBIO关键中间体5-氨基-2,4-二硝基苯酚的合成

Synthesis of 5-amino-2,4-dinitrophenol as key intermidiate for poly (p-phenylene-2-benzoimidazol-6-oxazole)

系统地研究了以4,6-二硝基间二氯苯(DCDNB)为原料经单水解后氨解两步反应制备聚对亚苯基苯并咪口恶二唑(PBIO)的关键中间体5-氨基-2,4-二硝基苯酚(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150℃下使用氨水压力氨解另一个氯基合成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、1HNMR、13CNMR及MS等定性确认,合成过程已呈现有机污染少、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。

A novel synthesis route and technique of 5-amino-2,4-dinitrophenol（ADNP）as key intermediate for poly（p-phenylene-2-benzoimidazol-6-oxazole）（PBIO）were studied systematically.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 hydrolysis of DCDNB at 100 ℃ with aqueous NaOH.In the second step,CDNP was ammonolyzed under pressure at 150 ℃ using dioxane as solvent yielding the target product.The prepared ADNP was identified by FTIR,1H NMR,13C 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.