Rate and Product Studies on the Solvolyses of Allyl Chloroformate

Bulletin of the Korean chemical society

Han Joong Koh¹  Suk Jin Kang¹ 

关键词: Allyl chloroformate;    Extended grunwald-winstein equation;    SN2 mechanism;    Solvent kinetic isotope effect;    Product selectivity;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

The solvolysis rate constants of allyl chloroformate (CH2=CHCH2OCOCl, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with the sensitivity values of 0.93 ± 0.05 and 0.41 ± 0.02 for l and m, respectively. These l and m values can be considered to support a SN2 reaction pathway. The activation enthalpies (ΔH≠) were 12.5 to 13.4 kcal·mol−1 and the activation entropies (ΔS≠) were −34.4 to −37.3 cal·mol−1·K−1, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, kMeOH/kMeOD) of 2.16 was also in accord with the SN2 mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.

【 授权许可】

Unknown