4,5-二氨基-2-羟基苯甲酸的合成工艺
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摘要
以对氨基水杨酸(ASA)为原料先经酰化、硝化和水解制备关键中间体4-氨基-2-羟基-5-硝基苯甲酸(AHNA),然后硝基还原合成聚苯并咪唑新单体4,5-二氨基-2-羟基苯甲酸(DAHBA)。结果表明:ASA在乙酸中先后用乙酐进行酰化和用HNO3硝化、20~30℃各反应3h,获得收率为70.9%、纯度为97.28%的4-乙酰胺基-2-羟基-5-硝基苯甲酸(AHNBA);AHNBA在盐酸水溶液中,水解回流反应4h,制得关键中间体AHNA,其收率为79.5%、纯度99.21%;以水为溶剂,AHNA在Pd/C催化下水合肼回流还原30min合成出DAHBA,收率为55.3%、纯度98.84%。产物的分子结构经过FTIR、1H NMR、13C NMR、ESI-MS等表征与确认,为提高聚对苯撑苯并二噁唑(PBO)的复合粘结、轴向抗压和耐光性能提供关键共聚单体的技术与来源。
In this paper,the key intermediate 4-amino-2-hydroxy-5-nitro benzoic acid(AHNA)was successfully synthesized by the acylation reaction of 4-aminosalicylic acid(ASA),then nitration and acid hydrolysis. A new polybenzimidazole monomer 4,5-diamino-2-hydroxybenzoic acid(DAHBA)was prepared by the reduction reaction of AHNA. The results showed that,using acetic acid as solvent,after ASA was first acylated with acetic anhydride and then nitrated with nitric acid for 3 hours,4-acetamido-2-hydroxy-5-nitro benzoic acid(AHNBA)was obtained with the total yield of 70.9% and the purity of 97.28%. The key intermediate AHNA was synthesized by the acid hydrolysis of AHNBA for 4 hours at reflux. AHNA was obtained with the yield of 79.5% and the purity of 99.21%. DAHBA of 98.84% purity was obtained by reduction of AHNA using hydrazine hydrate,Pd/C and reflux 30 min in the water with the yield of 55.3%. The structure of DAHBA was identified by FTIR,1H NMR,13 C NMR,and ESI-MS. Meanwhile,it could also provide the key monomer and technical source for the synthesis of the HI-PBO fiber with good performance of composite adhesiveness,axial compressive and light resistance.
In this paper,the key intermediate 4-amino-2-hydroxy-5-nitro benzoic acid(AHNA)was successfully synthesized by the acylation reaction of 4-aminosalicylic acid(ASA),then nitration and acid hydrolysis. A new polybenzimidazole monomer 4,5-diamino-2-hydroxybenzoic acid(DAHBA)was prepared by the reduction reaction of AHNA. The results showed that,using acetic acid as solvent,after ASA was first acylated with acetic anhydride and then nitrated with nitric acid for 3 hours,4-acetamido-2-hydroxy-5-nitro benzoic acid(AHNBA)was obtained with the total yield of 70.9% and the purity of 97.28%. The key intermediate AHNA was synthesized by the acid hydrolysis of AHNBA for 4 hours at reflux. AHNA was obtained with the yield of 79.5% and the purity of 99.21%. DAHBA of 98.84% purity was obtained by reduction of AHNA using hydrazine hydrate,Pd/C and reflux 30 min in the water with the yield of 55.3%. The structure of DAHBA was identified by FTIR,1H NMR,13 C NMR,and ESI-MS. Meanwhile,it could also provide the key monomer and technical source for the synthesis of the HI-PBO fiber with good performance of composite adhesiveness,axial compressive and light resistance.
引文
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[2]李晨.改性PBO新单体的合成探索及AB型PBO新单体制备的产业化[D].杭州:浙江工业大学,2014.LI C.Exploratory synthesis of modified PBO new monomer and industrialization of preparing new AB-type PBO monomer[D].Hangzhou:Zhejiang University of Technology,2014.
[3]谢钟清,王晓蕾,田杰,等.PBO纤维表面改性研究进展[J].工程塑料应用,2015(1):115-119.XIE Z Q,WANG X L,TIAN J,et al.Research progress on surface modification of PBO fiber[J].Engineering Plastics Application,2015(1):115-119.
[4]WOLFE J F,SYBERT P D.Liquid crystalline polymer compositions,process and products:US4533692A[P].1985-08-05.
[5]金宁人,何彪,金菁.4-(5-氨基-6-羟基苯并噁唑-2-基)苯甲酸铵及其制备与应用:102977045A[P].2013-03-20.JING N R,HE B,JIN Q.Synthesis and application of4-(5-amino-6-hydroxybenzoxazole-2-yl)benzoic acid ammonium:102977045A[P].2013-03-20.
[6]常伟.杂萘联苯共聚苯并咪唑及其离子交联膜的制备[D].大连:大连理工大学,2013.CHANG W.Preparation of copolybenzimidazole and ionic cross-linked membranes containing phthalazinone moieties[D].Dalian:Dalian University of Technology,2013.
[7]张精安,郑盛润,苏成勇.微波辅助合成3,4-二氨基苯甲酸[J].精细石油化工,2006,23(3):6-9.ZHANG J A,ZHENG S R,SU C Y.Synthesis of 3,4-diaminobenzoic acid under microwave irradiation[J].Speciality Petrochemicals,2006,23(3):6-9.
[8]金宁人,郑志国,刘晓锋,等.AB型顺式聚对苯撑苯并二唑新单体的合成与应用研究[J].江苏化工,2007,35(3):23-30.JING N R,ZHENG Z G,LIU X F,et al.New AB-PBO monomers&their synthesis,characterization and application[J].Jiangsu Chemical Industry,2007,35(3):23-30.
[9]吴纯鑫,李婷婷,赵德明,等.2,6-二氨基-3-硝基甲苯的合成[J].化工进展,2014,33(8):2165-2169.WU C X,LI T T,ZHAO D M,et al.Synthesis of 2,6-diamido-3-nitrotoluene[J].Chemical Industry and Engineering Progress,2014,33(8):2165-2169.
[10]孔祥夫,杨松.2-甲氧基-5-硝基苯甲酸中硝基的还原[J].广州化工,2011,39(10):54-55.KONG X F,YANG S Reduction nitro group in 2-methoxy-5-nitrobenzoic acid[J].Guangzhou Chemical Industry,2011,39(10):54-55.
[11]李春圆.氮杂环蕃的合成与分子识别研究[D].西安:西北大学,2007.LI C Y.The synthesis and molecular recognition of azacyclophanes[D].Xi’an:Northwestern University,2007.
[12]原友志,唐家邓,岑均达.琥珀酸普卡必利的合成[J].中国医药工业杂志,2012,43(1):5-8.YUAN Y Z,TANG J D,CENG J D.Synthesis of prucalopride monosuccinate[J].Chinese Journal of Pharmaceuticals,2012,43(1):5-8.
[13]He R,Bai Y,Yu Z H,et al.Diversity-oriented synthesis for novel,selective and drug-like inhibitors for a phosphatase from mycobacterium tuberculosis[J].Medchemcomm,2014,5(10):1496-1499.
[14]秦欣荣,陈书明.2-乙氧基-4-氨基-5-氯苯甲酸的合成新方法及其中间体:101538217A[P].2009-09-23.QING X R,CHEN S M.Novel synthesis method of2-ethoxy-4-amino-5-chlorobenzoic acid and its intermediate:101538217A[P].2009-09-23.
[15]付强.硝基苯胺类红色基的合成研究[D].天津:天津大学,2006.FU Q.Study on the synthesis of red bases of nitroaniline[D].Tianjin:Tianjin University,2006.
[16]成健.不同硝化体系中3,5-二硝基吡唑的合成[D].南京:南京理工大学,2007.CHEN J.Synthesis of 3,5-dinitropyrazole in the different nitration system[D].Nanjing:Nanjing University of Science and Technology,2007.
[17]龚艳,林鹿,孙勇,等.脱羧反应途径及其机制的研究进展[J].化学与生物工程,2008,25(4):1-6.GONG Y,LIN L,SUN Y,et al.Research progress of pathways and mechanisms of decarboxylation[J].Chemistry&Bioengineering,2008,25(4):1-6.
[18]胡阳,李敬芬.药物中间体5-硝基-2-羟基-苯甲酸的合成方法改进[J].河南化工,2013,30(17):27-29.HU Y,LI J F.Synthetic method improvement of the medicine intermediate 5-nitryl-2-hydroxyl-benzoic acid[J].Henan Chemical Industry,2013,30(17):27-29.
[19]张铸勇,祁国珍.精细有机合成单元反应[M].2版.上海:华东理工大学出版社,2003:162-187.ZHANG Z Y,QI G Z.Fine organic synthesis unit reaction[M].2nd ed.Shanghai:East China University of Science and Technology Press,2003:162-187.
[20]孙乐大,张广明,沈晓文.一种阿立必利盐酸盐的制备方法:101066968B[P].2007.11.07.SUN L D,ZHANG G M,SHEN X W.A alizapride hydrochloride preparation method:101066968B[P].2007.11.07.
[21]梁国旗.水合肼还原芳硝基物的研究及其在活性染料中间体合成中的应用[D].上海:东华大学,2014.LIANG G Q.Study on reduction of aromatic nitro compounds with hydrazine hydrate and its application in synthesis of active dye intermediates[D].Shanghai:Donghua University,2014.