Extended Grunwald-Winstein Analysis - LFER Used to Gauge Solvent Effects in p-Nitrophenyl Chloroformate Solvolysis
Abstract
:1. Introduction
2. Results and Discussion
3. Conclusions
4. Experimental Section
Acknowledgments
References and Notes
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Solvent (%)a | 1; 105k(s−1)b | 2; 105k(s−1)c | 3; 105k(s−1)d | ||
---|---|---|---|---|---|
97% TFE (w/w) | 0.113±0.008 | 0.0570±0.0030 | 0.0300±0.0013 | −3.30 | 2.83 |
90% TFE (w/w) | 8.87±0.28 | 1.15±0.08 | 0.825±0.032 | −2.55 | 2.85 |
80% TFE (w/w) | 56.8±0.4 | 7.02±0.28 | 8.63±0.24 | −2.22 | 2.90 |
70% TFE (w/w) | 153±1.5 | 17.4±1.3 | 15.2±0.6 | −1.98 | 2.96 |
50% TFE (w/w) | 438±44 | 63.5±3.0 | 52.6±2.8 | −1.73 | 3.16 |
90T-10E (v/v) | 8.82±0.17 | −2.67 | 2.33 | ||
80T-20E (v/v) | 45.5±0.7 | 2.43±0.21 | 3.52±0.13 | −1.76 | 1.89 |
90%HFIP (w/w) | 1.20±0.06 | 0.166±0.004 | 0.172±0.007 | −3.84 | 4.31 |
70%HFIP (w/w) | 83.8±0.9 | 10.5±0.3 | 7.58±0.22 | −2.94 | 3.83 |
50%HFIP (w/w) | 277±2 | 31.6±0.6 | 24.9±0.5 | −2.49 | 3.80 |
Substrate | nb | ℓc | mc | cc | l/m | Rd | Fe |
---|---|---|---|---|---|---|---|
29f | 1.85±0.21 | 0.48±0.05 | 0.14±0.05 | 3.85 | 0.871 | 41 | |
1 | 39g | 1.68±0.06 | 0.46±0.04 | 0.074±0.08 | 3.65 | 0.976 | 363 |
38h | 1.69±0.07 | 0.46±0.04 | 0.074±0.08 | 3.67 | 0.974 | 323 | |
2 | 38h | 1.59±0.07 | 0.54±0.03 | 0.16±0.08 | 2.94 | 0.972 | 299 |
3 | 38h | 1.58±0.06 | 0.57±0.04 | 0.17±0.07 | 2.77 | 0.974 | 320 |
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D’Souza, M.J.; Shuman, K.E.; Carter, S.E.; Kevill, D.N. Extended Grunwald-Winstein Analysis - LFER Used to Gauge Solvent Effects in p-Nitrophenyl Chloroformate Solvolysis. Int. J. Mol. Sci. 2008, 9, 2231-2242. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms9112231
D’Souza MJ, Shuman KE, Carter SE, Kevill DN. Extended Grunwald-Winstein Analysis - LFER Used to Gauge Solvent Effects in p-Nitrophenyl Chloroformate Solvolysis. International Journal of Molecular Sciences. 2008; 9(11):2231-2242. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms9112231
Chicago/Turabian StyleD’Souza, Malcolm J., Kevin E. Shuman, Shannon E. Carter, and Dennis N. Kevill. 2008. "Extended Grunwald-Winstein Analysis - LFER Used to Gauge Solvent Effects in p-Nitrophenyl Chloroformate Solvolysis" International Journal of Molecular Sciences 9, no. 11: 2231-2242. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms9112231