【作者】 陈丽萍；

【导师】 洪三国；

【作者基本信息】 江西师范大学 ， 有机化学， 2003， 硕士

【摘要】 磺酸酯是一种使用广泛的化合物，常用作表面活化剂、离子交换树脂、染料、动物饲料、杀虫剂和医药品等。磺酸酯的化学反应对于现代有机化学基本概念的发展起着相当重要的作用。本文在对磺酸酯进行了大量的文献调研的基础上，综合叙述了磺酸酯的几种常用的制备方法，以及磺酸酯几类重要的化学变化，并大篇幅地对研究的中心反应—磺酸酯的热解反应进行了理论研究。 基于目标反应中反应体系的组成和大小，用MOPAC7.0软件和GAUSSAIN98程序中的计算方法(PM3和B3LYP)重点对2-吡啶磺酸乙酯、8-喹啉磺酸乙酯、8-喹啉磺酸异丙酯、甲基磺酸异丁酯和甲基磺酸新戊基酯五种磺酸酯的气相热解反应进行了理论研究，得出了较可信且有意义的结论，并首次在此类反应中提出紧密离子对过渡态机理。 研究结果表明，2-吡啶磺酸乙酯、8-喹啉磺酸乙酯、8-喹啉磺酸异丙酯、甲基磺酸异丁酯的热解反应都是经历了紧密离子对过渡态机理，C-O键的断裂是此类热解反应的关键，控制了该反应的反应速率，酯基中的β-H在反应过程中发生迁移，从β-C原子迁移到磺酸基中的O原子上，帮助C-O键的进一步裂解，直至产生烯烃。在甲基磺酸异丁酯的热解过程中还有重排反应发生，即β-C原子上的甲基在反应过程中发生迁移，产生非典型碳正离子与磺酸负离子构成的紧密离子对过渡态，甲基和β-H共同协助C-O键发生进一步断裂，从而产生几种丁烯异构体。随着烯烃的放出，遗留在反应容器中2-吡啶磺酸或8-喹啉磺酸继续发生分子内的酸碱中和反应，杂环上的氮原子起着碱的作用。 此外，还对三个有意义的气相热解反应(1．N-乙基，N-异丙基和N-叔丁基-2-氨基嘧啶的热解反应；2．N-乙基，N-异丙基和N-叔丁基-2-氨基吡嗪的热解反应；3．2-溴丙酸的气相热消除反应)的机理进行了理论研究，也给出了有意义的结论。更多还原

【Abstract】 Sulfonate esters are compounds that are used widely as surface active agent, ion-exchange resin, dye, pesticide and medicine. Reactions of sulfonate esters have played an important role in the development of many of the fundamental concepts on which modern organic chemistry. By quotation of a lot of papers, the preparation and some kinds of important reactions of sulfonate esters have been described in this paper. The theorical studies on the pyrolytic reactions of sulfonate esters, which is the central reaction in this paper, have also been discussed in detail.Based on the size and composing of reaction system, density functional theory and semi-empirical method are applied to investigate the mechanism of ethyl-2-pyridine sulfonate, ethyl-8-quinoline sulfonate, isopropyl-8-quinoline sulfonate, isobutyl methylsulfonate and neopentyl methylsulfonate, and an authentic and useful conclusion has been drawn. It is the first time that intimate ion-pair transition state has been brought forward in this kind of the reaction.The results obtained show that the process for the gas-phase pyrolysis of these sulfonate esters occur via an intimate ion-pair transition state, where the p-hydrogen atom of ethyl carbocation facilitates C-O bond cleavage, and the cleavage of C-O bond is rate determining. On the pyrolysis of isobutyl methylsulfonate, rearrangement reactions are detected, in which the methyl group is transferred from p-C atom to O atom of sulfonic group. Furthermore, the left 2-pyridine sulfonic acid or 8-quinoline sulfonic acid processes intramolecular acid-base neutralization.In addition, theoretical studies on the mechanism of three reactions (1.Gas-phase Pyrolytic Reactions of N-Ethyl, N-Isopropyl and N-t-Butyl Substituted 2-Aminopyrimidine; 2.Gas-phase Pyrolytic Reactions of N-Ethyl, N-Isopropyl and N-t-Butyl Substituted 2-Aminopyrazine; 3.Gas-phase Elimination of 2-Bromopropionic acid) have been done, and some significant results have also been gotten.更多还原