【作者】 张志超；

【导师】 张英菊； 吕小兵；

【作者基本信息】 大连理工大学 ， 应用化学， 2006， 硕士

【摘要】 本论文以Salen型配合物为亲电试剂和季铵盐（或有机碱）为亲核试剂组成二元催化体系,研究了二硫化碳和环氧烷烃、二硫化碳和环硫烷烃以及二氧化碳和吖丙啶在该体系催化下的环加成反应。 合成了一系列烷基、卤素取代的Salen型西佛碱,与三乙基铝反应制得催化剂SalenAlEt;与Co（OAc）₂反应生成的SalenCo（Ⅱ）配合物再与酸作用,经氧化后得到SalenCo（Ⅲ）配合物,原位用于催化环加成反应。以环氧丙烷为原料,与硫氰化钾反应制得中间体环硫丙烷;环氧丙烷与氨水或有机胺反应,开环后采用Wenker方法制备1-甲基吖丙啶及1,2-二甲基吖丙啶等中间体用于环加成反应。 制备的催化剂及环加成反应产物的结构分别用¹H NMR及FT IR进行了表征,合成的吖丙啶等中间体用气相色谱检验了纯度并用¹H NMR表征了结构。 亲电—亲核二元催化体系（SalenAlEt/季铵盐）可以在温和条件下催化二硫化碳和环氧丙烷反应。考察了催化剂用量、投料比、反应温度和时间等条件对环加成反应的影响。探索出最佳反应条件:100℃,PO/CS₂/Cat.=1000/200/1,9hrs,在此条件下环加成反应产率可达94%。控制反应条件可以在一定范围内改变主产物及各组份的含量。 在SalenCo（Ⅲ）/季铵盐催化体系下,吖丙啶与二氧化碳的环加成反应得到相应的两种区域异构体。以1,2-二甲基吖丙啶为底物时,与二氧化碳反应首次得到了3,4-二甲基噁唑烷-2-酮。更多还原

【Abstract】 Salen-type complex and quaternary halide or organic bases were used as the binary catalyst in the cycloadditon of carbon disulfide and epoxide, carbon disulfide and episulfide, carbon dioxide and aziridines, respectively.A series of alkyl, halogen substituted Schiff base ligands were prepared. SalenAlEt, fromed by the reaction of H₂Salen and Et3Al, was employed in the cycloadditon of carbon disulfide and epoxide （or episulfide）. SalenCo（II） complexes derived from the reaction of H2Salen ligand and Co（OAc）2, were oxided to afford the SalenCo（III） complexes in the presence of acid under an atmosphere of oxygen. It was used in the cycloaddition of aziridines and carbon dioxide in situ. -Propylene oxide was used as the starting material for the preparation of episulfide. Also, propylene oxide was ring-opened after the reaction of ammonium or amine to afford the p-amino alcohol. Then the p-amino alcohol was transformed into the corresponding aziridine through Wenker method.All the catalysts and the products of the catalytic reaction were characterized by ¹H NMR and FT IR. The purities of the aziridines were tested by Gas Chromatography and their structures were determined by ¹H NMR.This electrophile-nucleophile catalytic system （SalenAlEt/quaternary ammonia salt） was effective for the coupling reaction of carbon disulfide and epoxide under mild conditions. A series of factors such as the amount of catalyst, the ratio of the substrates, temperature, time etc were investigated. The optimized condition was determined: 100℃, PO/CS2/Cat.=1000/200/1, 9hrs, with a yield of 94%. The major product and its ratio could be varied according to different conditions employed.In the coupling reaction of aziridine and carbon dioxide which was catalyzed by SalenCo（III）/quaternary system, two regioselective products were obtained. Compound 3, 4-dimethyloxazolidin-2-one was reported the first time and its structure was determined by ¹H NMR when 1, 2-dimethylaziridine was used as substrate.更多还原