应用化学 ›› 2009, Vol. 26 ›› Issue (09): 1040-1044.

• 研究论文 • 上一篇    下一篇

5-硝基-6-羟基-2-(对甲氧羰基苯基)苯并噁唑的合成

张建庭1,毛连城1,王嘉安1,胡建民2,金宁人1   

  1. (1.浙江工业大学化学工程与材料学院 杭州 310014;2.杭州鼎龙科技有限公司 杭州)
  • 收稿日期:2008-08-20 修回日期:2009-01-04 出版日期:2009-09-10 发布日期:2009-09-10
  • 通讯作者: 金宁人,男,教授; E-mail:cnhzjnrh@mail.hz.zj.cn; 研究方向:有机合成中间体化学,功能高分子及新单体
  • 基金资助:
    江苏省科技攻关重大项目(BE2006077)

Sythesis of Methyl 4-(5-nitro- 6-hydroxybenzoxazol-2-yl)benzoate

ZHANG Jian-Ting1, MAO Lian-Cheng1, WANG Jia-An1, HU Jian-Min2, JIN Ning-Ren1   

  1. (1.College of Chemical Engineering and Materials Science,Zhejiang University of Technology,Hangzhou 310014;2.Hangzhou Dragon Chemical Co. Ltd,Hangzhou)
  • Received:2008-08-20 Revised:2009-01-04 Published:2009-09-10 Online:2009-09-10

摘要:

研究了以关键中间体4-氨基-6-硝基间苯二酚盐酸盐(ANR·HCl)和对苯二甲酸单甲酯(MTA)为原料,分别经酰氯化、缩合、环合分步或原位合成AB型新单体前体——4-(5-硝基-6-羟基-2-苯并噁唑基)苯甲酸甲酯(MNB)的技术。 反应优化条件:在甲基异丁基酮溶剂中,n(ANR·HCl)∶n(MTA)=1.00∶1.03,115 ℃缩合反应2.5 h;m(ANR·HCl)∶m(PPA)=1.00∶3.25的多聚磷酸(PPA),120  ℃环合8.5 h;MNB收率75.68%(以ANR·HCl计),HPLC测定ω(MNB)=96.32%。 产物结构经1H NMR和IR确证。

关键词: 均缩聚路线, 5-硝基-6-羟基-2-(对甲氧羰基苯基)苯并噁唑, 酰氯化, 缩合, 环合, 一锅原位合成

Abstract:

To achieve industrialization of the New AB-type poly (p-phenylene benzobizoxazole) (PBO)’s homogeneous polycondensation. The AB-type monomer precursor──methyl 4-(5-nitro- 6-hydroxybenzoxazol -2-yl)benzoate’s(MNB)synthesis process was studied , and MNB’s synthesis route using 4-amino-6-nitroresorcinol hydrochloride (ANR•HCl) and 4-(methoxycarbonyl)benzoic acid (MTA) as raw materials was developed by acyl chlorination、condensation and cyclization separately or one-pot synthesis. The optimum conditions were as follows: 4-methyl-2-pentanone as solvent, Feed ratio (mol ratio) of ANR•HCl / MTA was 1.00/1.03, condensation reaction at 115 ℃ for 2.5 h. Cyclization reaction at 120 ℃ for 8.5 h after adding PPA as dehydrating agent which the feed ratio (mass ratio) of ANR•HCl / PPA was 1.00/3.25, the product was obtained with a yield of 75.68% and the purity of MNB without further purification was 96.32% by HPLC method. Structures of the products were characterized by 1HNMR and IR.

Key words: homogeneous polycondensation, methyl 4-(5-nitro-6-hydroxybenzoxazol-2-yl)benzoate, acyl-chlorination, condensation reaction, cyclization reaction, one-pot synthesis

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