Rate-Product Correlations for the Solvolysis of 5-Nitro-2-Furoyl Chloride

Bulletin of the Korean chemical society

Dildar Ali¹  Hojune Choi¹  Han Joong Koh¹  In Sun Koo¹  Kiyull Yang¹ 

关键词: 5-Nitro-2-furoyl chloride;    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 5-nitro-2-furoyl chloride (5-NO2(C4H2O)-2-COCl, 1) in 27 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with sensitivity values of 1.20 ± 0.05 and 0.37 ± 0.02 for l and m, respectively. The activation enthalpies (ΔH≠) were 5.63 to 13.0 kcal·mol−1 and the activation entropies (ΔS≠) were −25.9 to −43.4 cal·mol−1·K−1, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, kMeOH/kMeOD) of 2.65 was also in accord with the SN2 mechanism and was possibly assisted using a general-base catalysis. The product selectivity (S) for solvolysis of 1 in alcohol/water mixtures was 1.2 to 11, which is also consistent with the proposed bimolecular reaction mechanism.

【 授权许可】

Unknown