Journal
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
Volume 13, Issue 1, Pages 665-682Publisher
MDPI
DOI: 10.3390/ijms13010665
Keywords
solvolysis; nucleophilicity; ionizing power; gamma-Methyl-beta-alkynyl chloroformate; 2-butyn-1-yl-chloroformate; aryl chloroformate; 2-methoxyphenyl chloroformate; Grunwald-Winstein equation; Linear Free Energy Relationships (LFERs)
Funding
- National Center for Research Resources (NCRR), a component of the National Institutes of Health (NIH) [2 P2O RR016472-12]
- National Science Foundation (NSF) [EPS-0814251, 0960503]
- State of Delaware (DE)
- NASA/Delaware [NNG05GO92H]
- Direct For Biological Sciences
- Div Of Biological Infrastructure [0960503] Funding Source: National Science Foundation
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The specific rates of solvolysis of 2-butyn-1-yl-chloroformate (1) and 2-methoxyphenyl chloroformate (2) are studied at 25.0 degrees C in a series of binary aqueous-organic mixtures. The rates of reaction obtained are then analyzed using the extended Grunwald-Winstein (G-W) equation and the results are compared to previously published G-W analyses for phenyl chloroformate (3), propargyl chloroformate (4), p-methoxyphenyl choroformate (5), and p-nitrophenyl chloroformate (6). For 1, the results indicate that dual side-by-side addition-elimination and ionization pathways are occurring in some highly ionizing solvents due to the presence of the electron-donating gamma-methyl group. For 2, the analyses indicate that the dominant mechanism is a bimolecular one where the formation of a tetrahedral intermediate is rate-determining.
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