巯基苯并咪唑及其类似物互变异构的理论研究ATheoreticalStudy.PDF

2007 年第65 卷 化 学 学 报 Vol. 65, 2007 第16 期, 1561～1567 ACTA CHIMICA SINICA No. 16, 1561～1567 ·研究论文· 2-巯基苯并咪唑及其类似物互变异构的理论研究 国永敏 李宝宗* (苏州大学独墅湖校区化学化工学院 苏州 215123) 摘要 采用B3LYP/6-311G**方法, 计算了2-巯基苯并咪唑及其类似物(2-巯基苯并噁唑、2-巯基苯并噻唑、2-羟基苯并 咪唑、2-羟基苯并噁唑、2-羟基苯并噻唑以及2-巯基咪唑、2-巯基噁唑、2-巯基噻唑、2-羟基咪唑、2-羟基噁唑、2-羟 基噻唑) 的(硫)醇式与(硫)酮式结构进行质子迁移的3 种可能途径: (a)分子内质子迁移; (b)水助质子迁移; (c) 甲醇助质子 迁移．结果表明, 途经b 和c 所需要的活化能较小, 氢键在降低反应活化能方面起重要作用．采用PCM 方法研究了反 应体系的溶剂化效应．结果表明孤立分子、一水合物和一甲醇合物的最稳定异构体相同, 都为(硫)酮式, 与气相结论一 致．溶剂化效应对异构化能垒的影响较小. 关键词 2-巯基苯并咪唑; 2-巯基咪唑; 互变异构; 密度泛函理论方法; 自洽反应场 A Theoretical Study on Tautomerism of 2-Mercaptobenzimidazole and Its Analogues GUO, Yong-Min LI, Bao-Zong* (School of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215123) Abstract The processes of the proton transfer between the thione (keto) tautomer and the thiol (enol) tautomer of 2-mercaptobenzimidazole and its analogues (2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-hydroxybenzimidazole, 2-hydroxybenzoxazole, 2-hydroxybenzothiazole, 2-mercaptoimidazole, 2-mer- captooxazole, 2-mercaptothiazole, 2-hydroxyimidazole, 2-hydroxyoxazole and 2-hydroxythiazole) were in- vestigated by density functional theory at B3LYP/6-311G** level. The three possible reaction pathways: (a) intramolecular proton transfer; (b) water-assisted intermolecular transfer and (c) methanol-assisted intermo- lecular transfer were investigated. The calculated results showed that the processes (b) and (c) had lower ac-