哌啶与靛红衍生物在 80% 甲醇水溶液中的熵控制反应

IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL
Mohamed A El-Rahman, Mahmoud F. Ibrahim, M. F. Fathalla, S. El-Sadany, Ezzat A. Hamed, A. Z. Omar
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引用次数: 0

摘要

在 80% 的甲醇水溶液中,5- 和 7-取代的异汀衍生物(H、Me、Cl、Br)与哌啶反应,得到了相应的 1-(2'-氨基-5'- 或 3'- 取代苯基)-2-(哌啶-1-基)乙烷-1,2-二酮衍生物。反应是通过亲核攻击 C-2 然后开环的过程进行的。反应呈二阶进行,等动力学温度为 169 K,表明反应受熵控制。恒定的 ∆G# 值、∆H# 与 ∆S# 的线性图、高温与低温的对数 kN 值图表明,所有取代基的反应机理是统一的。σo-Taft常数与对数kN值呈线性相关,ρ值为(2.01-1.86),这表明取代基的感应效应占主导地位,限速是四面体中间体T-的分解,而开环是由水催化的。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Entropy controlled reaction of piperidine with isatin derivatives in 80% aqueous methanol
The reactions of 5- and 7-substituted isatin derivatives (H, Me, Cl, Br) with piperidine in 80% aqueous methanol gave the corresponding 1-(2’-amino-5’- or 3’- substituted phenyl)-2-(piperidin-1-yl) ethane-1,2-dione derivatives. The reaction is proceeded through nucleophilic attack on C-2 followed by ring opening process. The reaction showed a second order and the isokinetic temperature is 169 K indicating that the reaction is entropy controlled. The constant ∆G# value, the linear plot of ∆H# versus ∆S#, plot of log kN values at high temperature versus those at low temperatures indicated that a unified mechanism of the reactions for all substituents. The σo-Taft's constants are linearly correlated with log kN values and the ρ values are (2.01–1.86) pointing out that inductive effect of substituent is predominant and the rate-limiting is the breakdown of the tetrahedral intermediate T− and the ring opening is catalyzed by water.
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来源期刊
CiteScore
2.10
自引率
0.00%
发文量
5
审稿时长
2.3 months
期刊介绍: The journal covers the fields of kinetics and mechanisms of chemical processes in the gas phase and solution of both simple and complex systems.
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