Department of Chemistry and Biochemistry, University of Wisconsin-Eau Claire, Eau Claire, WI, 54702, USA.
Chemistry. 2021 Nov 17;27(64):15829-15841. doi: 10.1002/chem.202101823. Epub 2021 Oct 13.
The name of Menshutkin is most frequently associated with his eponymous reaction (the quaternization of tertiary amines with alkyl halides). However, he made encyclopedic contributions to the field of reaction kinetics, where he carried out extensive studies of the effects of reactant structure on the rates of esterification of monohydric, dihydric and trihydric alcohols with monocarboxylic acids, and monobasic and dibasic carboxylic acids and anhydrides with monohydric alcohols. In these studies, he deduced an order of reactivity of alcohols in esterification on the basis of their reactions with acetic acid, and the effects of acid structure on the rates of esterification based on the reaction of the carboxylic acid with isobutyl alcohol. When his attention later turned to the substitution chemistry of amines, he defined the parameters that affected their reactions: anilines were less reactive than alkylamines, secondary more reactive than primary amines, and the reaction was accelerated by replacing benzene as a solvent with alcohols. The wide-ranging work of Menshutkin, the physical organic chemist, is discussed.
Menshutkin 的名字最常与他的同名反应（叔胺与卤代烷的季铵化）联系在一起。然而，他在反应动力学领域做出了百科全书式的贡献，在该领域他广泛研究了反应物结构对一元、二元和三元醇与一元羧酸、一元和二元羧酸以及一元醇与酐的酯化反应速率的影响。在这些研究中，他根据醇与乙酸的反应，推导出醇在酯化反应中的反应活性顺序，以及根据羧酸与异丁醇的反应，推导出酸结构对酯化反应速率的影响。当他后来将注意力转向胺的取代化学时，他确定了影响其反应的参数：苯胺的反应活性低于烷基胺，仲胺的反应活性高于伯胺，并且用醇代替苯作为溶剂会加速反应。本文讨论了物理有机化学家 Menshutkin 的广泛工作。
