期刊
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
卷 12, 期 8, 页码 4805-4818出版社
MDPI
DOI: 10.3390/ijms12084805
关键词
solvolysis; substituent effects; solvent effects; acylium cations
资金
- Engineering and Physical Sciences Research Council [EP/J003921/1] Funding Source: researchfish
- EPSRC [EP/J003921/1] Funding Source: UKRI
Rate constants and activations parameters are reported for solvolyses of p-Z-substituted benzoyl chlorides (1, Z = OMe, Me, H, and Cl) in 97% w/w hexafluoroisopropanol-water (97H). Additional kinetic data are reported for solvolyses in acetic and formic acids. Plots of log k vs. sigma(p) in 97H are consistent with previous research showing that a cationic reaction channel is dominant, even for solvolyses of 1, Z = NO2. A benzoyl cation intermediate was trapped by Friedel-Crafts reaction with 1,3,5-trimethoxybenzene in hexafluoroisopropanol. The results are explained by an S(N)2-S(N)1 spectrum of mechanisms with variations in nucleophilic solvent assistance. Ab initio calculations of heterolytic bond dissociation energies of various chloro-and fluoro-substituted and other benzoyl chlorides are correlated with log k for solvolyses.
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