4-(6-羟基-5-硝基-2-苯并唑基)-2,6-二羟基苯甲酸的合成

doi:10.16085/j.issn.1000-6613.2018-0959

化工进展 ›› 2019, Vol. 38 ›› Issue (02): 1062-1067.DOI: 10.16085/j.issn.1000-6613.2018-0959

4-(6-羟基-5-硝基-2-苯并唑基)-2,6-二羟基苯甲酸的合成

董斌, 付聪, 吴纯鑫, 张建庭, 金宁人, 赵德明

浙江工业大学化学工程学院, 浙江杭州 310014

收稿日期:2018-05-09 修回日期:2018-09-17 出版日期:2019-02-05 发布日期:2019-02-05
通讯作者: 赵德明,博士,副教授。
作者简介:董斌(1992-),男,硕士研究生,研究方向为有机合成。
基金资助:
江苏省重大科技计划支撑项目（BE2011129）；浙江省教育厅项目（Y201121211）。

Synthesis of 4-(6-hydroxy-5-nitro-2-benzoxazolyl)-2,6-dihydroxybenzoic acid

DONG Bin, FU Cong, WU Chunxin, ZHANG Jianting, JIN Ningren, ZHAO Deming

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2018-05-09 Revised:2018-09-17 Online:2019-02-05 Published:2019-02-05

摘要/Abstract

摘要： 研究了以2，6-二羟基对苯二甲酸（2，6-DH-TA）与4-氨基-6-硝基间苯二酚盐酸盐（ANR·HCl）为原料经酰氯化和N-酰化一锅法及环合等一系列反应合成得到中间体4-[（2，4-二羟基-5-硝基苯基）氨甲酰基]-2，6-二羟基苯甲酸（2，6-DH-NCA）和2，6-二羟基改性PBO的AB型酸类新单体的关键前体4-（6-羟基-5-硝基-2-苯并唑基）-2，6-二羟基苯甲酸（2，6-DH-NBA），并对其反应条件进行了优化。结果表明：对于酰氯化和N-酰化一锅法反应，以1，4-二氧六环为酰氯化溶剂，SOCl₂为酰氯化试剂，酰氯化时间2h，N-酰化溶剂为4-甲基2-戊酮，N-酰化温度105℃，N-酰化时间4h，N-酰化缚酸剂为三乙胺，n（2，6-DH-TA）：n（ANR·HCl）：n（SOCl₂）：n（三乙胺）=1.0：1.0：2.0：0.5，经乙醇精制，2，6-DH-NCA收率80.31%，HPLC纯度（质量分数）98.57%；环合反应，以二乙二醇二甲醚为溶剂，多聚磷酸（PPA）为脱水剂，PPA中P₂O₅质量含量85%，w（2，6-DH-NCA）：w（PPA）=1：8.6，反应温度135℃，反应时间6h，2，6-DH-NBA收率83.76%，HPLC纯度99.25%。中间体和产物结构经FTIR、¹H NMR和EI-MS表征确认。

关键词: 2,6-二羟基对苯二甲酸, 4-(6-羟基-5-硝基-2-苯并唑基)-2,6-二羟基苯甲酸, 环合反应, 一锅法

Abstract: The intermediate 4-[(2,4-dihydroxy-5-nitrophenyl)carbamoyl]-2,6-dihydroxy-benzoic acid (2,6-DH-NCA) and a key precursor of AB-type acid new monomer of 2,6-dihydroxyl modified PBO 4-(6-hydroxy-5-nitro-2-benzoxazolyl)-2,6-dihydroxybenzoic acid (2,6-DH-NBA) were successfully synthesized through a series of reactions, including one pot reaction of the acylchlorination and Nacylation, and the dehydration cyclization reaction by using 2,6-dihydroxyterephthalic acid (2,6-DH-TA) and 4-amino-6-nitroresorcinol hydrochloride (ANR·HCl) as materials. The optimal experimental conditions of one pot reaction of acylchlorination and N-acylation and the dehydration cyclization were obtained. For the one pot reaction of acylchlorination and N-acylation, with the 1, 4-dioxane as acylchlorination solvent and SOCl₂ as acylchlorination reagent, the acylchlorination time was 2h; with the triethylamine as the deacid reagent of N-acylation, the temperature of N-acylation at 105℃ and the reaction time was 4h, n(2,6-DH-TA):n(ANR·HCl):n(SOCl₂):n(triethylamine) was 1.0:1.0:2.0:0.5, the yield of 2,6-DH-NCA was 80.31% and the purity was 98.57% as determined by HPLC. For the dehydration cyclization reaction, with the diethylene glycol dimethyl ether as solvent and the polyphosphoric acid(PPA) as dehydrant, and the content of P₂O₅ in PPA of 85%, the reaction temperature at 135℃, the reaction time was 6h, w(2,6-DH-NCA):w(PPA) was 1:8.6, the yield of 2,6-DH-NBA was 83.76%, and the purity was 99.25% as determined by HPLC.

Key words: 2,6-dihydroxyterephthalic acid, 4-(6-hydroxy-5-nitro-2-benzoxazolyl)-2,6-dihydroxybenzoic acid, cyclization, one pot reaction

中图分类号:

TQ226.14

董斌, 付聪, 吴纯鑫, 张建庭, 金宁人, 赵德明. 4-(6-羟基-5-硝基-2-苯并唑基)-2,6-二羟基苯甲酸的合成[J]. 化工进展, 2019, 38(02): 1062-1067.

DONG Bin, FU Cong, WU Chunxin, ZHANG Jianting, JIN Ningren, ZHAO Deming. Synthesis of 4-(6-hydroxy-5-nitro-2-benzoxazolyl)-2,6-dihydroxybenzoic acid[J]. Chemical Industry and Engineering Progress, 2019, 38(02): 1062-1067.

参考文献 17

[1]	李芝华, 李慧, 刘兰兰, 等. 高性能PBO纤维表面改性及抗紫外光性能研究功能材料[J].功能材料, 2018, 49(1):1112-1116. LI Zhihua, LI Hui, LIU Lanlan, et al. Surface modification and UV resistance of high performance PBO fibers[J]. Journal of Functional Materials, 2018, 49(1):1112-1116.
[2]	卢姍姍, 王艳红, 胡桢, 等. 聚对苯撑苯并双唑纤维改性技术的研究进展[J].合成纤维工业, 2018, 41(1):47-51. LU Shanshan, WANG Yanhong, HU Zhen, et al.Research progress in modification technique of poly(p-phenylene-2, 6-benzobisoxazole) fiber[J]. China Synthetic Fiber Industry, 2018, 41(1):47-51.
[3]	JIA C X, WANG Q, CHEN P. Wet ability assessment of plasmatreated PBO fibers based on thermogravimetric analysis[J]. International Journal of Adhesion and Adhesives, 2017, 74:123-130.
[4]	HORIKAWA N, KAWANO Y, MIYAJIMA T, et al. Tensile strength of poly-p-phenylene (PBO) fiber with kinking damage[J]. Procedia Structural Integrity, 2016, 2:293-300.
[5]	LIU Z, ZENG Q, CHEN P, et al. Comparison of effects on PBO fiber by air and oxygen dielectric barrier discharge plasma[J]. Vacuum, 2015, 121:152-158.
[6]	ZHANG T, JIN J, HU D, et al. Effect of coagulation temperature on structures and properties of poly(p-phenylene benzobisoxazole) (DHPBO) fibers during dry-jet wet-spinning process[J]. Science in China Series E:Technological Sciences, 2009, 52(4):906-909.
[7]	ZHANG T, HU D, JIN J, et al. Improvement of surface wettability and interfacial adhesion ability of poly(p-phenylene benzobisoxazole) (PBO) fiber by incorporation of 2,5-dihydroxyterephthalic acid (DHTA)[J]. European Polymer Journal, 2009, 45(1):302-307.
[8]	江建明, 金俊弘, 杨胜林. 含有羟基基团的聚苯并二唑聚合物及其制备方法:CN1594398[P]. 2005-03-16. JING Jianming, JIN Junhong, YANG Shenglin. Polybenzoxazole polymer containing hydroxyl group and preparation method:CN1594398[P]. 2005-03-16.
[9]	赵德明, 陈龙, 宋嘉彬, 等. 2,6-二羟基改性PBO的AB型新单体的合成[J]. 化工进展, 2015, 34(2):519-523, 533. ZHAO Deming, CHEN Long, SONG Jiabin, et al. Synthesis of new AB monomers of dihydroxyl modified PBO[J]. Chemical Industry and Engineering Progress, 2015, 34(2):519-523, 533.
[10]	宋嘉彬. AB型二羟基改性PBO新单体制备工艺研究及其应用探索[D]. 杭州:浙江工业大学, 2016. SONG Jiabin. Synthetic technique of dihydroxyl modified PBO new AB-type monomers and exploration of its application[D]. Hangzhou:Zhejiang University of Technology, 2016.
[11]	毛连城, 蔡丽霞, 张建庭, 等. 高纯度AB型PBO新单体的合成新工艺研究[J]. 浙江工业大学学报, 2009, 37(4):381-385. MAO Liancheng, CAI Lixia, ZHANG Jianting, et al. Study on novel technology for preparation of high-purity AB-PBO monomer[J]. Journal of Zhejiang University of Technology, 2009, 37(4):381-385.
[12]	金宁人, 李晨, 胡晓峰, 等. AB型羟基改性PBO单体及其合成新技术[J]. 化工学报, 2015, 66(5):1955-1963. JIN Ningren, LI Chen, HU Xiaofeng, et al. AB monomers of hydroxy modified PBO and its novel synthesis technology[J]. CIESC Journal, 2015, 66(5):1955-1963.
[13]	金宁人, 胡建民, 王学杰. AB型聚对苯撑苯并二恶唑新单体及其制备与应用:CN200410093359[P]. 2004-07-27. JIN Ningren, HU Jianmin, WANG Xuejie. New AB-PBO monomers & their synthesis, characterization and application:CN200410093359[P]. 2004-07-27.
[14]	何威威, 金宁人, 陈汉庚, 等. 4,5-二氨基-2-羟基苯甲酸的合成工艺[J]. 化工进展, 2017, 36(3):1059-1066. HE Weiwei, JIN Ningren, CHEN Hangeng, et al. Research on synthesis of 4, 5-diamino-2-hydroxybenzoic acid[J]. Chemical Industry and Engineering Progress, 2017, 36(3):1059-1066.
[15]	赵德明, 吴锋, 陈中海, 等. 单氨基改性PBO的AB型新单体的合成[J]. 化工进展, 2016, 35(4):1197-1202. ZHAO Deming, WU Feng, CHEN Zhonghai, et al. Synthesis of new AB monomers of amino modified PBO[J]. Chemical Industry and Engineering Progress, 2016, 35(4):1197-1202.
[16]	陈荣业. 有机合成工艺优化[M]. 北京:化学工业出版社, 2006. CHEN Rongye. Organic synthesis process optimization[M]. Beijing:Chemical Industry Press, 2006.
[17]	王利民, 邹刚. 精细有机合成工艺[M]. 北京:化学工业出版社, 2008. WANG Limin, ZOU Gang. Fine organic synthesis process[M]. Beijing:Chemical Industry Press, 2008.

4-(6-羟基-5-硝基-2-苯并唑基)-2,6-二羟基苯甲酸的合成

Synthesis of 4-(6-hydroxy-5-nitro-2-benzoxazolyl)-2,6-dihydroxybenzoic acid

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