化工进展2016，Vol.35Issue(4)：1197-1202,6.DOI:10.16085/j.issn.1000-6613.2016.04.037
单氨基改性PBO的AB型新单体的合成
Synthesis of new AB monomers of amino modified PBO
摘要
Abstract
Using 4-methoxycarbonyl-2-nitro-benzoic acid (β-MNT) and 4-amino-6- nitroresorcinolhydrochloride (ANR·HCl) as the starting materials,we synthesized the intermediates 4-(5-nitro-6- hydroxybenzoxazole-2-yl)-3-nitro-methyl benzoate (3-NMNC),4-(5-nitro-6-hydroxybenzoxazole- 2-yl)-3-nitrobenzoate (3-NMNB),4-(5-nitro -6-hydroxy benzoxazole-2-yl)-3-aminobenzoic acid (3-NNBA) and the final product 4-(5-amino-6-hydroxy benzoxazole-2-yl)-3-aminobenzoic acid (3-AABA) through a series of reaction,including acylchloride,N-acylation,cyclization,hydrolysis and catalytichydrogenation reduction reaction. The optimal cyclization,hydrolysis and catalytichydrogenation reduction conditions were obtained. The experimental results for the cyclization reaction showed that taking diethyleneglycol dimethyl ether as solvent,the polyphosphoric acid(PPA) as dehydrant and the content of P2O5 in PPA of 84%,w(3-NMNC)∶w(PPA)=1∶9.5,the reaction temperature of 140℃ and the reaction time of 8h,we obtained the yield of 3-NMNB of 73.16% and its purity was 99.10% as determined by HPLC. The experimental results for the hydrolysis reaction showed that using ethanol and water as solvent,n(K2CO3)∶n(3-NMNB) = 1.8:1 and the reaction time of 2h,we got the yield of 3-NNBA of 74.19% and the purity was 98.59% as determined by HPLC. The experimental results for the hydrogenation reduction reaction showed that using methanol as solvent, w(10%Pd/C)∶w(3-NNBA)=1∶20,pressure of hydrogen of 1.0 MPa,reaction temperature of 80℃, reaction time of 5h,we had the yield of 3-AABA of 65.08% based on 3-NNBA and the purity was 99.43% as determined by HPLC.关键词
4-(5-硝基-6-羟基-2-苯并/唑基)-3-硝基苯甲酸甲酯/4-(5-氨基-6-羟基-2-苯并/唑基)-3-氨基苯甲酸/环合反应/水解反应/加氢还原反应Key words
4-((2,4-dihydroxyl-5-nitrobenzophenonel)carbamoyl)-2,6-dihydroxyl methyl benzoate/4-(5-nitro-6-hydroxy-2-benzoxazolyl-2,6-dyhydroxy methyl benzoate/cyclization reaction/hydrolysis reaction/hydrogenation reduction reaction分类
化学化工引用本文复制引用
赵德明,吴锋,陈中海,吴纯鑫,张建庭,金宁人..单氨基改性PBO的AB型新单体的合成[J].化工进展,2016,35(4):1197-1202,6.基金项目
江苏省重大科技计划支撑项目（BE2011129）及浙江省教育厅项目（Y201121211）。 （）
