【作者】 吴作林；

【导师】 吴祖望；

【作者基本信息】 大连理工大学 ， 应用化学， 2004， 硕士

【摘要】 胡椒胺(3，4-亚甲二氧基苯胺)和N-乙基胡椒胺(N-乙基-3，4-亚甲二氧基苯胺)是一类重要的染料、医药中间体。本论文主要研究了胡椒胺和N-乙基胡椒胺的合成方法，通过正交实验，提出了优化合成工艺。 以亚甲二氧基苯为原料，以稀硝酸为硝化剂，在45～50℃反应，制得了纯度≥99的3，4-亚甲二氧基硝基苯，该反应的收率为95.5％。 以乙醇为溶剂，3，4-亚甲二氧基-硝基苯在Raney Ni的催化下，加氢还原合成胡椒胺，原料转化率＞99％，胡椒胺选择性在90％左右，其主要副产物是N-乙基胡椒胺。加氢在甲苯中进行时，3，4-亚甲二氧基硝基苯的转化率＞96％，而胡椒胺选择性接近100％。 以3，4-亚甲二氧基-硝基苯为原料，乙醛为烷化剂，在乙醇溶剂中Raney Ni催化下，通过还原烷基化合成N-乙基胡椒胺，硝基胡椒环的转化率100％，胡椒胺的转化率97％，N-单烷化选择性90％，主要副产为N，N-二乙基胡椒胺。 上述还原烷基化反应以甲苯代替乙醇为溶剂合成N-乙基胡椒胺时，在正交设计试验得出的优化条件下，硝基胡椒环的转化率100％，胡椒胺的转化率98％，N-单烷化选择性97％。此工艺具有，加氢还原和N-乙基化同釜连续反应，原料转化率和产物选择性优异的特点。更多还原

【Abstract】 An investigation of the preparation of N-ethyl-3,4-methylene dioxy-aniline3,4-methylenedioxy-aniline and N-ethyl-3,4-methylenedioxyaniline are two important intermediates for prepare dyes and medicines. Their synthetic technique have been studied. The optimum synthesis condition was set by the orthogonal design method.Nitration of 1,2-methylenedioxybenzene with dilute nitric acid at 40~45癈, 3,4-methylenedioxy-nitrobenzene with high purity and a yield of 95.5% is obtained.Hydrogenation of 3,4-methylenedioxy-nitrobenzene by Raney Ni catalysis in ethanol, over than 99% conversion ratio of nitro compound and 90% selectivity of 3,4-methylenedioxyaniline are achieved, the main by-products is the ethylated derivative N-ethyl- 3,4-methylenedioxyaniline. If the hydrogenation is carried on same condition but with toluene as the solvent, 96% conversion ratio and near 100% selectivity of 3,4-methylene dioxyaniline is given.Reductive alkylation of 3,4-methylenedioxy-nitrobenzene with acetaldehyde and hydrogen by Raney Ni as a catalyst and alcohol as the solvent, near 100% conversion ratio of nitro compound and over than 97% conversion of 3,4-methylenedioxyaniline is achieved, the selectivity is 90%. If the reductive alkylation is carried on toluene solvent, the conversion ratio are 100% and 98% respectively, and the selectivity of N-ethyl-3,4-methylenedioxyaniline is 97%. Both high conversion and high selectivity are given.更多还原