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本文用量子化学的MNDO方法对N-(苯亚甲基)苯胺、N-(苯亚甲基)-2-甲苯胺与N-(4-硝基苯亚甲基)-2-甲氧基苯胺Schiff碱汞化反应区域选择性进行了研究,结果表明,在其稳定构象下,芳胺环上的电荷密度大于苯基亚甲基环,故汞化反应发生在芳胺环上;分子中亚胺氮原子的电荷密度最大,在汞化反应过程中,亚胺氮原子首先与醋酸汞配位,然后再进行邻位亲电进攻,生成邻位汞化产物;而在N-(苯亚甲基)-2-甲苯胺分子中,邻位甲基阻碍了亚胺氮原子与汞原子的配位作用,故无邻位汞化产物生成。计算结果与实验结果一致,并进一步支持了已经提出的反应机理。
In this paper, quantum chemistry MNDO method for the N- (benzylidene) aniline, N- (benzylidene) -2-toluidine N- (4-nitrobenzylidene) -2-methoxy The results showed that the charge density of the aromatic amine ring was larger than that of the phenylmethylidene ring under the stable conformation, so the mercury reaction occurred on the aromatic amine ring. In the molecule The charge density of the imine nitrogen atom is the largest. During the amalgamation reaction, the imine nitrogen atom is first coordinated with mercuric acetate and then the ortho-electrophilic attack to generate the ortho-mercurial product. In the N- Methyl) -2-toluidine, the ortho-methyl group hinders the coordination between the imine nitrogen atom and the mercury atom, so there is no formation of ortho-mercurial. The calculated results agree well with the experimental results and further support the proposed reaction mechanism.