Grunwald-Winstein Analysis - Isopropyl Chloroformate Solvolysis Revisited
Abstract
:1. Introduction
2. Results and Discussion
3. Conclusions
4. Experimental
Acknowledgments
References and Notes
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Solvent (%)b | 1 @ 25.0 °C; 105k, s−1c,d | 1 @ 40.0 °C; 105k, s−1e | NTe | YClf | % Acidc,f |
---|---|---|---|---|---|
100% MeOH | 4.19 ± 0.10g | 15.4 ± 0.1 | 0.17 | −1.2 | 96 ± 2 |
90% MeOH | 8.28 ± 0.09 | 30.7 ± 0.6 | −0.01 | −0.20 | 97 ± 1 |
80% MeOH | 13.4 ± 0.4 | 49.7 ± 0.6 | −0.06 | 0.67 | 88 ± 3 |
70% MeOH | 76.6 ± 0.8 | −0.40 | 1.46 | 94 ± 2 | |
60% MeOH | 120 ± 6 | −0.54 | 2.07 | 91 ± 2 | |
100% EtOH | 1.09 ± 0.04h | 5.41 ± 0.01 | 0.37 | −2.50 | 93 ± 3 |
90% EtOH | 2.36 ± 0.09 | 10.8 ± 0.1 | 0.16 | −0.90 | 91 ± 2 |
80% EtOH | 3.92 ± 0.14 | 18.6 ± 0.2 | 0.00 | 0.00 | 91 ± 1 |
70% EtOH | 5.53 ± 0.26 | 31.3 ± 0.1 | −0.20 | 0.80 | 89 ± 2 |
60% EtOH | 51.3 ± 0.1 | −0.39 | 1.38 | 87 ± 5 | |
50% EtOH | 96.5 ± 0.3 | −0.58 | 2.02 | 90 ± 2 | |
90% Acetone | 0.331 ± 0.025 | 1.08 ± 0.03 | −0.35 | −2.39 | 78 ± 3 |
80% Acetone | 1.19 ± 0.04 | 4.27 ± 0.03 | −0.37 | −0.80 | 86 ± 5 |
70% Acetone | 2.59 ± 0.08 | 11.8 ± 0.2 | −0.42 | 0.17 | 81 ± 2 |
60% Acetone | 28.8 ± 0.2 | −0.52 | 1.00 | 85 ± 1 | |
97% TFE (w/w) | 12.3 ± 0.3 | 71.6 ± 0.7 | −3.30 | 2.83 | 67 ± 1 |
90% TFE (w/w) | 13.9 ± 0.4 | 74.7 ± 0.8 | −2.55 | 2.85 | 72 ± 1 |
70% TFE (w/w) | 19.7 ± 0.7 | 117 ± 3 | −1.98 | 2.96 | 80 ± 3 |
50% TFE (w/w) | 33.5 ± 0.04 | −1.73 | 3.16 | ||
80T-20E | 3.26 ± 0.07 | 21.3 ± 0.7 | −1.76 | 1.89 | 68 ± 1 |
60T-40E | 1.41 ± 0.10 | 7.87 ± 0.06 | −0.94 | 0.63 | 72 ± 1 |
40T-60E | 0.964 ± 0.023 | 3.76 ± 0.03 | −0.34 | −0.48 | |
20T-80E | 0.757 ± 0.014 | 3.16 ± 0.06 | 0.08 | −1.42 | |
100% H2O | 218 ± 1i | 1622 ± 4i | −1.38 | 4.57 | 98j |
99.3% HCOOH | 28.2 ± 0.1k | 172 ± 2k | −2.44l | 3.20l | |
97%HFIP (w/w) | 146 ± 2 | 563 ± 16d,m | −5.26 | 5.17 | |
90%HFIP (w/w) | 63.2 ± 2.9 | 246 ± 12d,m | −3.84 | 4.41 | |
70%HFIP (w/w) | 60.1 ± 2.4 | −2.94 | 3.83 | ||
50%HFIP (w/w) | 71.0 ± 3.0 | −2.49 | 3.8 |
Solvent (%)a | 105k, s−1b | 105 ki, s−1c | 105 (k–ki), s−1 | 105k, s−1e | 105 ki, s−1f | 105 (k–ki), s−1 |
---|---|---|---|---|---|---|
100% MeOH | 15.4 | 1.5 | 13.9d | 4.19 | 0.12 | 4.07g |
90% MeOH | 30.7 | 5.1 | 25.6d | 8.28 | 0.46 | 7.82g |
80% MeOH | 49.7 | 16.2 | 33.5d | 13.4 | 1.53 | 11.9g |
70% MeOH | 76.6 | 39.5 | 37.1 | |||
60% MeOH | 120 | 83.2 | 36.8 | |||
100% EtOH | 5.41 | 0.29 | 5.1d | 1.09 | 0.021 | 1.07g |
90% EtOH | 10.8 | 2.2 | 8.6d | 2.36 | 0.18 | 2.18g |
80% EtOH | 18.6 | 6.8 | 11.9d | 3.92 | 0.61 | 3.31g |
70% EtOH | 31.3 | 17.8 | 13.5 | 5.53 | 1.73 | 3.8 |
60% EtOH | 51.3 | 35.5 | 15.8 | |||
50% EtOH | 96.5 | 76.1 | 20.4 | |||
90% Acetone | 1.08 | 0.30 | 0.78d | 0.33 | 0.020 | 0.31g |
80% Acetone | 4.27 | 1.93 | 2.34d | 1.19 | 0.18 | 1.01g |
70% Acetone | 11.8 | 6.9 | 4.9d | 2.59 | 0.680 | 1.91g |
60% Acetone | 28.8 | 19.9 | 8.9 | |||
97% TFE (w/w) | 71.6 | 60.4 | 12.3 | 12.2 | ||
90% TFE (w/w) | 74.7 | 87.6 | 13.9 | 15.4 | ||
70% TFE (w/w) | 117 | 134 | 19.7 | 21.1 | ||
50% TFE (w/w) | 33.5 | 29.6 | ||||
80T-20E | 21.3 | 36.0 | 3.26 | 5.08 | ||
60T-40E | 7.87 | 9.9 | 1.41 | 1.12 | ||
40T-60E | 3.76 | 3.03 | 0.7 | 0.96 | 0.280 | 0.68 |
20T-80E | 3.16 | 1.07 | 2.1 | 0.757 | 0.088 | 0.67 |
100% H2O | 1622 | 1514 | 218 | 229 | ||
99.3% HCOOH | 172 | 150 | 28.2 | 25.7 | ||
97%HFIP (w/w) | 563 | 523 | 146 | 179 | ||
90%HFIP (w/w) | 246 | 331 | 63.2 | 80.0 | ||
70%HFIP (w/w) | 60.1 | 54.1 | ||||
50%HFIP (w/w) | 71.0 | 58.1 |
Substrate | na | lb | mb | cc | Rd | Fe |
---|---|---|---|---|---|---|
1; 40.0 °C | 26f | 0.33 ± 0.03 | −0.11 ± 0.07 | 0.919 | 130 | |
0.21 ± 0.06 | 0.44 ± 0.04 | −0.02 ± 0.06 | 0.947 | 100 | ||
7g | 0.44 ± 0.12 | −0.56 ± 0.44 | 0.861 | 14 | ||
0.21 ± 0.04 | 0.58 ± 0.05 | −0.44 ± 0.16 | 0.987 | 74 | ||
11h | 0.41 ± 0.04 | −0.45 ± 0.12 | 0.964 | 117 | ||
0.20 ± 0.06 (0.014)i | 0.53 ± 0.05 | −0.33 ± 0.09 | 0.984 | 121 | ||
10j | 0.37 ± 0.02 | −0.43 ± 0.07 | 0.983 | 232 | ||
0.05 ± 0.11 (0.67)i | 0.41 ± 0.08 | −0.41 ± 0.10 | 0.984 | 105 | ||
9k | 0.36 ± 0.10 | 0.04 ± 0.14 | 0.803 | 13 | ||
1.05 ± 0.17 | 0.44 ± 0.04 | 0.15 ± 0.06 | 0.976 | 61 | ||
9k,l | 0.31 ± 0.13 | 0.03 ± 0.17 | 0.661 | 5 | ||
1.35 ± 0.22 | 0.40 ± 0.05 | 0.18 ± 0.07 | 0.960 | 35 | ||
16m | 0.38 ± 0.05 | −0.28 ± 0.13 | 0.911 | 69 | ||
0.28 ± 0.04 | 0.59 ± 0.04 | −0.32 ± 0.06 | 0.982 | 176 | ||
1; 25.0 °C | 24f | 0.31 ± 0.03 | −0.10 ± 0.07 | 0.923 | 127 | |
0.14 ± 0.08 (0.10)i | 0.40 ± 0.05 | −0.02 ± 0.08 | 0.933 | 71 | ||
10g | 0.52 ± 0.06 | −0.83 ± 0.22 | 0.952 | 78 | ||
0.12 ± 0.02 | 0.60 ± 0.03 | −0.81 ± 0.10 | 0.991 | 203 | ||
14h | 0.41 ± 0.03 | −0.48 ± 0.10 | 0.967 | 175 | ||
0.11 ± 0.07 (0.14)i | 0.48 ± 0.05 | −0.41 ± 0.10 | 0.973 | 99 | ||
13j | 0.40 ± 0.03 | −0.46 ± 0.09 | 0.970 | 176 | ||
0.05 ± 0.10 (0.66)i | 0.43 ± 0.08 | −0.44 ± 0.11 | 0.971 | 82 | ||
9k | 0.36 ± 0.10 | 0.10 ± 0.13 | 0.812 | 14 | ||
0.92 ± 0.23 | 0.42 ± 0.06 | 0.20 ± 0.08 | 0.953 | 30 | ||
9k,l | 0.34 ± 0.11 | 0.11 ± 0.14 | 0.765 | 10 | ||
1.01 ± 0.26 | 0.41 ± 0.06 | 0.22 ± 0.08 | 0.940 | 23 |
Substrate | na | lb | mb | cc | Rd | Fe |
---|---|---|---|---|---|---|
EtOCOClf | 28 | 1.56 ± 0.09 | 0.55 ± 0.03 | 0.19 ± 0.24 | 0.967 | 179 |
7 | 0.69 ± 0.13 | 0.82 ± 0.16 | −2.40 ± 0.27 | 0.946 | 17 | |
MeOCOClg | 19 | 1.59 ± 0.09 | 0.58 ± 0.05 | 0.16 ± 0.07 | 0.977 | |
4h | 49 | 1.66 ± 0.05 | 0.56 ± 0.03 | 0.15 ± 0.07 | 0.980 | 568 |
PhSCSCli | 31 | 0.69 ± 0.05 | 0.95 ± 0.03 | 0.18 ± 0.05 | 0.987 | 521 |
2j | 11 | 0.57 ± 0.03 | 0.05 ± 0.08 | 0.985 | 294 | |
11 | 0.08 ± 0.20 (0.71)i | 0.59 ± 0.05 | 0.06 ± 0.08 | 0.985 | 133 | |
3k | 19 | 0.47 ± 0.03 | −0.11 ± 0.19 | 0.970 | 274 | |
19 | 0.03 ± 0.07 (0.70)i | 0.48 ± 0.04 | −0.10 ± 0.19 | 0.971 | 130 |
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D’Souza, M.J.; Reed, D.N.; Erdman, K.J.; Kyong, J.B.; Kevill, D.N. Grunwald-Winstein Analysis - Isopropyl Chloroformate Solvolysis Revisited. Int. J. Mol. Sci. 2009, 10, 862-879. https://doi.org/10.3390/ijms10030862
D’Souza MJ, Reed DN, Erdman KJ, Kyong JB, Kevill DN. Grunwald-Winstein Analysis - Isopropyl Chloroformate Solvolysis Revisited. International Journal of Molecular Sciences. 2009; 10(3):862-879. https://doi.org/10.3390/ijms10030862
Chicago/Turabian StyleD’Souza, Malcolm J., Darneisha N. Reed, Kevin J. Erdman, Jin Burm Kyong, and Dennis N. Kevill. 2009. "Grunwald-Winstein Analysis - Isopropyl Chloroformate Solvolysis Revisited" International Journal of Molecular Sciences 10, no. 3: 862-879. https://doi.org/10.3390/ijms10030862