Abstract: The intermediates 4-[(2,4-dihydroxyl-5-nitrobenzophenonel) carbamoyl]-2,6-di-hydroxyl methyl benzoate (2,6-DH-MNC),4-(5-nitro-6-hydroxy-2-benzoxazolyl-2,6-dhydroxy methyl benzoate (2,6-DH-MNB) and the final product 4-[(2,4-dihydroxyl-5-nitrobenzophenonel)carbamoyl]-2,6-dihydroxyl methyl benzoate (2,6-DH-MAB) were successfully synthesized through a series of reactions,including acylchloride,acylation,dehydration cyclization and catalytic hydrogenation reduction reaction by using 2,6-dihydro mono-methyl terephthalate and 4-amino-6-nitroresorcinol hydrochloride (ANR·HCl) as materials. The optimized dehydration cyclization and catalytic hydrogenation reduction conditions were obtained. The experimental results showed that with diethylene glycol dimethyl ether as solvent and polyphosphoric acid (PPA) as dehydrant for the dehydration cyclization reaction,the yield of 2,6-DH-MNB was 74.15% and the purity was 98.76% as determined by HPLC,when w (2,6-DH-MNB):w (PPA)was 1:6,the content of P₂O₅ in PPA was 83%,the reaction temperature at 140℃ and the reaction time was 8h. Then N,N-dimethylformamide was used as solvent,the yield of 2,6-DH-MAB was 81.42% based on 2,6-DH-MNB and the purity was 99.69% as determined by HPLC with w (5%Pd/C):w (2,6-DH-MNB)=1:20,reaction temperature 60℃,reaction time 3h,pressure of hydrogen 0.5-1.0MPa.

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, hydrogenation reduction reaction

摘要： 研究了以2,6-二羟基-1-甲酯-1,4-苯二酸(α酯)与4-氨基-6-硝基间苯二酚盐酸盐(ANR·HCl)为原料经酰氯化、N-酰化、环合和催化加氢还原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-苯甲酸甲酯(2,6-DH-MNC)和4-(6-羟基-5-硝基-2-苯并 唑基)-2,6-苯甲酸甲酯(2,6-DH-MNB)及2,6-二羟基改性PBO的AB型新单体4-(5-氨基-6-羟基-2-苯并 唑基)-2,6-二羟基苯甲酸甲酯(2,6-DH-MAB),并对环合和催化还原加氢的反应条件进行了优化。结果表明:对于环合反应,以二乙二醇二甲醚为溶剂,多聚磷酸(PPA)为脱水剂,PPA中P₂O₅质量分数83%,w(2,6-DH-MNC):w(PPA)=1:6,反应温度140℃,反应时间8h,2,6-DH-MNB收率74.15%,HPLC纯度98.76%;催化加氢还原反应,以N,N-二甲基甲酰胺(DMF)为溶剂,w(5%Pd/C):w(2,6-DH-MNB)=1:20,氢气压力0.5~1MPa和温度60℃下反应3h得到2,6-DH-MAB,HPLC纯度99.69%,收率81.42%。中间体和产物结构经FT-IR、13C NMR、¹H NMR和ESI-MS表征确认。

关键词: 4-[(2,4-二羟基-5-硝基苯基)氨甲酰基]-2,6-二羟基苯甲酸甲酯, 4-(5-氨基-6-羟基-2-苯并 唑基)-2,6-二羟基苯甲酸甲酯, 环合反应, 加氢还原反应