Bulletin of the Korean chemical society | |
Rate and Product Studies of 5-Dimethylamino-Naphthalene-1-Sulfonyl Chloride under Solvolytic Conditions | |
Han Joong Koh1  Suk Jin Kang1  | |
关键词: 5-Dimethylamino-naphthalene-1-sulfonyl 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-dimethylamino-naphthalene-1-sulfonyl chloride ((CH3)2NC10H6SO2Cl, 1) in 31 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 0.96 ± 0.09 and 0.53 ± 0.03 for l and m, respectively; the correlation coefficient value was 0.955. These l and m values can be considered to support an SN2 reaction pathway having a transition state (TS) structure similar to that of the benzenesulfonyl chloride reaction. This interpretation is further supported by the activation parameters, i.e., relatively small positive ΔH≠ (12.0 to 15.9 kcal·mol−1) and large negative ΔS≠ (−23.1 to −36.3 cal·mol−1·K−1) values, and the solvent kinetic isotope effects (SKIEs, 1.34 to 1.88). Also, the selectivity values (S = 1.2 to 2.9) obtained in binary solvents are consistent with the proposed mechanism.
【 授权许可】
Unknown
【 预 览 】
Files | Size | Format | View |
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RO201912010245300ZK.pdf | 527KB | download |