对于两种羧酸的酮基脱羧的反应机理,β-酮酸在许多实验和理论研究中被认为是关键的中间体。α-位的氢原子是底物通过遵循该机理反应的必不可少的必要条件。然而,使用叔羧酸的分离观察结果与它不一致,并且在本文中重新讨论和讨论这些。用新戊酸获得的实验结果表明,该底物不会发生酮脱羧。相反,它在其他反应中被消耗,如分解成异丁烯,一氧化碳,和水(逆-Koch反应)。此外,羧酸异构化或失去碳原子,将叔羧酸转化为带有α-质子原子的羧酸。因此,后者适于通过β-酮酸途径反应。第二基板,2,2,5,5-四甲基己二酸,通过遵循相同的反Koch途径进行反应。主要产物是单羧酸2,2,5-三甲基-4-己烯酸(及其双键异构体),可能进一步转化为环烯酮或内酯。酮脱羧产物,观察到痕量的2,2,5,5-四甲基环戊酮(<0.2%产率)。因此,可以得出结论,观察到的实验结果进一步支持了通过β-酮酸中间体进行酮基脱羧的拟议机理。
For the reaction mechanism of the ketonic decarboxylation of two carboxylic acids, a β-keto acid is favored as key intermediate in many experimental and theoretical studies. Hydrogen atoms in the α-position are an indispensable requirement for the substrates to react by following this mechanism. However, isolated observations with tertiary carboxylic acids are not consistent with it and these are revisited and discussed herein. The experimental results obtained with pivalic acid indicate that the ketonic decarboxylation does not occur with this substrate. Instead, it is consumed in alternative reactions such as disintegration into isobutene, carbon monoxide, and water (retro-Koch reaction). In addition, the carboxylic acid is isomerized or loses carbon atoms, which converts the tertiary carboxylic acid into carboxylic acids bearing α-proton atoms. Hence, the latter are suitable to react through the β-keto acid pathway. A second substrate, 2,2,5,5-tetramethyladipic acid, reacted by following the same retro-Koch pathway. The primary product was the monocarboxylic acid 2,2,5-trimethyl-4-hexenoic acid (and its double bond isomer), which might be further transformed into a cyclic enone or a lactone. The ketonic decarboxylation product, 2,2,5,5-tetramethylcyclopentanone was observed in traces (<0.2 % yield). Therefore, it can be concluded that the observed experimental results further support the proposed mechanism for the ketonic decarboxylation via the β-keto acid intermediate.