Statistical Methods for the Investigation of Solvolysis Mechanisms Illustrated by the Chlorides of the Carbomethoxy Protecting Groups NVOC and FMOC
Table 1
Specific rates of solvolysis (k) of 1 in several binary solvents at 25.0°C and literature values for and .
Solvent (%)a
1 @ 25.0°C; 105k,
100% EtOH
73.6 ± 1.2
0.37
−2.50
90% EtOH
116 ± 5
0.16
−0.90
80% EtOH
147 ± 10
0.00
0.00
100% MeOH
125 ± 10
0.17
−1.2
90% MeOH
187 ± 22
−0.01
−0.20
80% MeOH
299 ± 14
−0.06
0.67
90% acetone
3.23 ± 0.15
−0.35
−2.39
80% acetone
11.6 ± 0.6
−0.37
−0.80
70% acetone
23.3 ± 0.2
−0.42
0.17
97% TFE (w/w)
0.056 ± 0.003
−3.30
2.83
90% TFE (w/w)
0.346 ± 0.025
−2.55
2.85
70% TFE (w/w)
3.39 ± 0.24
−1.98
2.96
50% TFE (w/w)
16.9 ± 0.7
−1.73
3.16
60T-40E
5.77 ± 0.23
−0.94
0.63
40T-60E
17.2 ± 1.0
−0.34
0.48
20T-40E
34.0 ± 2.0
0.08
−1.42
90% HFIP (w/w)
0.065 ± 0.002
−3.84
4.31
80% HFIP (w/w)
0.117 ± 0.021
−3.31
3.99
70% HFIP (w/w)
3.61 ± 0.10
−2.94
3.83
50% HFIP (w/w)
9.71 ± 0.22
−2.49
3.80
Substrate concentration of ca. 0.005 M; binary solvents on a volume-volume basis at 25.0°C, except for TFE-H2O and HFIP-H2O solvents which are on a weight-weight basis. T-E are TFE-ethanol mixtures. bWith associated standard deviation. cReferences [16, 17]. dReferences [18–20].
