Table 1.
Reaction parameters of the reaction of organic carbonates with NaSH
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|---|---|---|---|---|---|
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| |||||
| Substrate | 1a | 1b | 1c | 1d | 1e |
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| R group | CH3 | CH2CF3 | 4-NO2-Ph | Ph | 4-OMe-Ph |
| pKa (ROH) | 15.54 | 12.46 | 7.15 | 9.98 | 10.21 |
| NaSHa | 4.8(4) | 90.5(8) | 230(50) | 49(8) | 6(2) |
| k (M−1s−1)b | 0.018(2) | 0.362(3) | 0.9(2) | 0.21(3) | 0.023(7) |
| Hydrolysisc | 2.7(1) | 21.5(1) | 60(20) | 16(2) | 4(1) |
| Ratio | 1.8:1 | 4.22:1 | 3.7:1 | 3.0:1 | 1.4:1 |
Initial rates (10−10 × M/s). Reaction monitored by UV-vis kinetics at 401 nm.
a
Conditions: 25 μM 1, 1000 μM NaSH, pH 7.4 PBS
b
Calculated from concentrations of 1 and NaSH.
c
Conditions: 25 μM 1, pH 7.4 PBS.