4-(6-羟基-5-硝基-2-苯并唑基)-2,6-二羟基苯甲酸的合成
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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,SOCl_2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(SOCl_2)∶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。
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 successfullysynthesized through a series of reactions, including one pot reaction of the acylchlorination and N-acylation, 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 experimentalconditions of one pot reaction of acylchlorination and N-acylation and the dehydration cyclization wereobtained. For the one pot reaction of acylchlorination and N-acylation, with the 1, 4-dioxane asacylchlorination solvent and SOCl_2 as acylchlorination reagent, the acylchlorination time was 2h; with thetriethylamine as the deacid reagent of N-acylation, the temperature of N-acylation at 105℃ and thereaction time was 4h, n(2,6-DH-TA)∶n(ANR·HCl)∶n(SOCl_2)∶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 ofPPA 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.
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 successfullysynthesized through a series of reactions, including one pot reaction of the acylchlorination and N-acylation, 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 experimentalconditions of one pot reaction of acylchlorination and N-acylation and the dehydration cyclization wereobtained. For the one pot reaction of acylchlorination and N-acylation, with the 1, 4-dioxane asacylchlorination solvent and SOCl_2 as acylchlorination reagent, the acylchlorination time was 2h; with thetriethylamine as the deacid reagent of N-acylation, the temperature of N-acylation at 105℃ and thereaction time was 4h, n(2,6-DH-TA)∶n(ANR·HCl)∶n(SOCl_2)∶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 ofPPA 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.
引文
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[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 onsynthesis of 4, 5-diamino-2-hydroxybenzoic acid[J]. ChemicalIndustry and Engineering Progress, 2017, 36(3):1059-1066.
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[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.
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[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 inmodification 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 plasma-treated 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 ofpoly-p-phenylene(PBO)fiber with kinking damage[J]. ProcediaStructural Integrity, 2016, 2:293-300.
[5] LIU Z, ZENG Q, CHEN P, et al. Comparison of effects on PBO fiber byair 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 onstructures and properties of poly(p-phenylene benzobisoxazole)(DHPBO)fibers during dry-jet wet-spinning process[J]. Science inChina Series E:Technological Sciences, 2009, 52(4):906-909.
[7] ZHANG T, HU D, JIN J, et al. Improvement of surface wettability andinterfacial 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. Polybenzoxazolepolymer 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 ABmonomers of dihydroxyl modified PBO[J]. Chemical Industry andEngineering 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 newAB-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 noveltechnology 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 hydroxymodified 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 onsynthesis of 4, 5-diamino-2-hydroxybenzoic acid[J]. ChemicalIndustry 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 ABmonomers of amino modified PBO[J]. Chemical Industry andEngineering 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.