摘要
在升温条件下 ,二苯胺和三氯化磷反应 ,产物经水解、氧化得次膦酸 :1 0 -羟基 -5 ,1 0 -二氢磷杂吖嗪 -1 0 -氧化物 (产率 4 5 % ) .经酰化后 ,与甲醇钠作用 ,生成相应的次膦酸甲酯 .次膦酸甲酯经 Na H处理后 ,在1 2 0℃下发生甲基迁移 ,形成 5 -甲基次膦酸 (产率 6 2 % ) .用 4 5倍摩尔量的硝化剂将 5 -甲基次膦酸硝化 ,得到双硝基产物 (产率 5 9% ) .在 5 % Pd/C催化下 ,双硝基产物又被氢气还原 .考察催化剂用量对该还原反应的影响 ,并在最佳催化剂用量时得到 2 ,8-二氨基 -1 0 -羟基 -5 -甲基 -5 ,1 0 -二氢磷杂吖嗪 -1 0 -氧化物 (产率70 % ) .用 NMR,IR和质谱确定了所合成的 5个中间体结构 .对合成的氨基化合物进行 Salmonella/mam-malian microsome assay测试 ,结果表明 ,该氨基化合物表现为非诱变性 .
Diphenylamine and phosphorus trichloride interacted on each other at slow-elevated temperatures and then the brown solution obtained was treated with H 2O, followed by oxidization to produce a phosphinic acid, viz, 10-hydroxy-5,10-dihydrophenophosphazine-10-oxide(yield 45%) which could be converted to a methyl phosphinate in yield 70% by reacting with SOCl 2 and then with MeONa in MeOH. After being treated with NaH in anhydrous DMF and then heating the reaction mixture to 120 ℃, the methyl phosphinate obtained above could also be transformed into N-methyl phosphinic acid with a yield of 62%. On nitrating the new phosphinic acid with 45 equimolar amount of nitrating agent, a dinitro compound will be obtained in a yield 59%. And this dinitro compound could further be reduced to 2,8-diamino-10-hydroxy-5-methyl-5,10-dihydrophenophosphazine-10-oxide with hydrogen over 5% Pd/C. The effect of the amount of 5% Pd/C on the hydrogenation was investigated and the title compound was ultimately synthesized in a yield 70% by using the optimum amount of catalyst. All five intermediates obtained from this study were identified by NMR and mass spectroscopy. The title compound was proved to be a nonmutagenic aromatic diamine via Salmonella/mammalian microsome assay.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2003年第7期1210-1215,共6页
Chemical Journal of Chinese Universities
基金
国家自然科学基金 (批准号 :2 9972 0 0 6 )
河南省教育厅骨干教师基金
郑州轻工业学院科研基金资助
