苯并咪唑类方酸菁染料的合成与理论研究-有机化学专业论文.docxVIP

摘要 万方数据 摘要 本文中，首次报道了一种在强碱条件下选择性一步合成苯并咪唑类 1,2-方 酸菁的方法，产率最高可达 89%。实验结果如下： (1)苯并咪唑盐与方酸二乙酯反应只能在强碱(有机强碱：EtONa、DBU 无 机强碱：CsCO3、KOH 和 NaOH)存在的条件下顺利进行，并且反应产物是 1,2- 位取代的方酸菁染料(3a-3b)，表现出高度的区域选择性。 (2)通过理论计算模拟了1,2,3-三甲基苯并咪唑盐(1b)与方酸二乙酯的整个反 应过程，结果表明只有在强碱条件下苯并咪唑盐容易脱去质子生成2-亚甲基苯并 咪唑亲核试剂(PRa)；并且模拟的两条可能反应路径中生成1,2-SQs的I-A路径的最 高能垒比生成1,3-SQs的I-B路径的低得多，是最佳的反应路径。 (3)通过分离得到反应中间体 PRb，与 2-甲基-1,3-二苄基苯并咪唑盐(1a)在 强碱 EtONa 催化下反应得到不对称的 1,2-位取代方酸菁染料(3c),证明上述 I-A 反应路径的合理性。 关键词：方酸菁染料；1,2-位取代；选择性合成； 强碱催化；理论计算 I ABSTRACT ABSTRACT In this study, a regioselective method of synthesis of 1, 2-benzimidazole SQs in the presence of strong base has been firstly proposed, and the yield is up 89%. The laboratory findings are listed as blow: the reaction between benzimidazolium salt and diethyl squarate can been promoted efficiently in the presence of strong bases (organic base: EtONa、DBU, inorganic base: CsCO3、KOH and NaOH)，and the product is 1,2- substituted SQs (3a-3b), being found to be highly regioselective。 The overall process of the reaction between 1,2,3-trimethyl-benzimida- zolium （ 1b ） and diethyl squarate have been simulated employing theoretical calculation. Results indicate that nucleophile benzimidazole methylene (PRa) is easier to form by deprotonating in the condition of strong base; Also among the two simulated reaction pathways, the highest activation barrier of I-A pathway forming 1,2-SQs is low than that of I-B forming 1,3-SQs, meaning that I-A is the optimal pathway of this reaction. Unsymmetrical 1,2-SQ(3c) has been synthetized from 1,3-dibenzyl -2-methyl-benzimidazolium chloride(1a) and the separated PRb intermediate in the presence of strong base EtONa as catalyst, which demonstrates that the I-A pathway is of great rationality. Key words: SQs; 1, 2-substituted; Regioselective synthesis; strong base catalyst; theoretical calculation II 目录 目 录  HYPERLINK \l _bookmark0 第一章 绪 论 .........................................................................................................