Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis
Abstract
:1. Introduction
2. Results and Discussion
3. Conclusions
4. Experimental Section
Acknowledgments
References and Notes
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Solvent (%)a | 1 @ 25.0 °C; 105k, s−1b | NTc | YCld | k1/k2e | Etf | Phg |
---|---|---|---|---|---|---|
100% MeOH | 1.99 ± 0.11h | 0.17 | −1.2 | 0.47 | 0.26 | 0.042 |
90% MeOH | 5.06 ± 0.24 | −0.01 | −0.20 | 0.61 | ||
80% MeOH | 24.7 ± 0.3 | −0.06 | 0.67 | 1.84 | 0.40 | |
100% EtOH | 1.21 ± 0.06i | 0.37 | −2.50 | 1.11 | 0.19 | 0.026 |
90% EtOH | 3.32 ± 0.17 | 0.16 | −0.90 | 1.41 | 0.21 | 0.029 |
80% EtOH | 13.7 ± 0.7j | 0.00 | 0.00 | 3.49 | 0.37 | 0.029 |
70% EtOH | 42.1 ± 1.3 | −0.20 | 0.80 | 7.61 | 0.029 | |
90% Acetone | 0.153 ± 0.004k | −0.35 | −2.39 | 0.46 | ||
70% Acetone | 1.21 ± 0.06 | −0.42 | 0.17 | 0.47 | ||
97% TFE (w/w) | 49.8 ± 2.5l | −3.30 | 2.83 | 4.05 | 260 | 5.9 |
90% TFE (w/w) | 69.5 ± 2.1 | −2.55 | 2.85 | 5.00 | 171 | 0.50 |
70% TFE (w/w) | 212 ± 18m | −1.98 | 2.96 | 10.76 | 89 | |
80T-20E | 14.5 ± 0.8 | −1.76 | 1.89 | 4.45 | 0.10 | |
60T-40E | 3.75 ± 0.18 | −0.94 | 0.63 | 2.66 | 0.033 | |
50T-50E | 2.81 ± 0.02 | −0.64 | 0.60 | |||
40T-60E | 1.55 ± 0.16 | −0.34 | −0.48 | 1.61 | ||
20T-80E | 1.09 ± 0.13 | 0.08 | −1.42 | 1.44 | ||
97%HFIP (w/w) | 376 ± 17 | −5.26 | 5.17 | 2.58 | 253 | |
90%HFIP (w/w) | 437 ± 28n | −3.84 | 4.41 | 6.91 | 357 | 16 |
70%HFIP (w/w) | 659 ± 39o | −2.94 | 3.83 | 10.97 | 183 | 0.22p |
Substrate | na | lb | mb | cc | Rd | Fe | Mechanism |
---|---|---|---|---|---|---|---|
PhOCOClf | 49 | 1.66 ± 0.05 | 0.56 ± 0.03 | 0.15 ± 0.07 | 0.980 | 568 | A-E |
PhSCSClg | 31 | 0.69 ± 0.05 | 0.95 ± 0.03 | 0.18 ± 0.05 | 0.987 | 521 | SN1 |
PhOCSClh | 9 | 1.88 ± 0.28 | 0.56 ± 0.15 | 0.38 ± 0.15 | 0.950 | 28 | A-E |
18 | 0.34 ± 0.05 | 0.93 ± 0.09 | −2.54 ± 0.34 | 0.955 | 77 | SN1 | |
PhSCOCli | 16 | 1.74 ± 0.17 | 0.48 ± 0.07 | 0.19 ± 0.23 | 0.946 | 55 | A-E |
6 | 0.62 ± 0.08 | 0.92 ± 0.11 | −2.29 ± 0.13 | 0.983 | 44 | SN1 | |
EtOCOClj | 28 | 1.56 ± 0.09 | 0.55 ± 0.03 | 0.19 ± 0.24 | 0.967 | 179 | A-E |
7 | 0.69 ± 0.13 | 0.82 ± 0.16 | −2.40 ± 0.27 | 0.946 | 17 | SN1 | |
EtSCOClk | 19 | 0.66 ± 0.08 | 0.93 ± 0.07 | −0.16 ± 0.31 | 0.961 | 96 | SN1 |
MeOCOCll | 19 | 1.59 ± 0.09 | 0.58 ± 0.05 | 0.16 ± 0.07 | 0.977 | A-E | |
MeSCOClm | 12 | 1.48 ± 0.18 | 0.44 ± 0.06 | 0.08 ± 0.08 | 0.949 | 40 | A-E |
8 | 0.79 ± 0.06 | 0.85 ± 0.07 | −0.27 ± 0.18 | 0.987 | 95 | SN1 | |
i-PrOCOCln | 9 | 1.35 ± 0.22 | 0.40 ± 0.05 | 0.18 ± 0.07 | 0.960 | 35 | A-E |
16 | 0.28 ± 0.04 | 0.59 ± 0.04 | −0.32 ± 0.06 | 0.982 | 176 | fragmentation-ionization | |
i-PrSCOClo | 19 | 0.38 ± 0.11 | 0.72 ± 0.09 | −0.28 ± 0.10 | 0.961 | 97 | SN1 |
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D’Souza, M.J.; Mahon, B.P.; Kevill, D.N. Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis. Int. J. Mol. Sci. 2010, 11, 2597-2611. https://doi.org/10.3390/ijms11072597
D’Souza MJ, Mahon BP, Kevill DN. Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis. International Journal of Molecular Sciences. 2010; 11(7):2597-2611. https://doi.org/10.3390/ijms11072597
Chicago/Turabian StyleD’Souza, Malcolm J., Brian P. Mahon, and Dennis N. Kevill. 2010. "Analysis of the Nucleophilic Solvation Effects in Isopropyl Chlorothioformate Solvolysis" International Journal of Molecular Sciences 11, no. 7: 2597-2611. https://doi.org/10.3390/ijms11072597