A Study of Solvent Effects in the Solvolysis of Propargyl Chloroformate

Table 1

Specific rates of solvolysis (𝑘) of 1, in several binary solvents at 25.0°C and the literature values for (𝑁_𝑇) and (𝑌_𝐶𝑙).

Solvent (%)^a	1 at 25.0°C; 10^5𝑘, s^−1 b	𝑁T^c	𝑌Cl^d
100% MeOH	63.4±1.2	0.17	−1.2
90% MeOH	123±3	−0.01	−0.20
80% MeOH	178±10	−0.06	0.67
100% EtOH	35.0±0.8	0.37	−2.50
90% EtOH	53.9±1.2	0.16	−0.90
80% EtOH	66.7±1.6	0.00	0.00
70% EtOH	86.7±1.7	−0.20	0.80
95% Acetone	1.09±0.03	−0.49	−3.19
90% Acetone	2.46±0.10	−0.35	−2.39
80% Acetone	7.52±0.22	−0.37	−0.80
97% TFE (w/w)	0.0190±0.0007	−3.30	2.83
90% TFE (w/w)	0.342±0.007	−2.55	2.85
80% TFE (w/w)	1.72±0.01	−2.22	2.90
70% TFE (w/w)	4.78±0.07	−1.98	2.96
80T-20E	0.995±0.004	−1.76	1.89
60T-40E	3.31±0.01	−0.94	0.63
40T-60E	10.0±0.2	−0.34	−0.48
20T-80E	17.4±1.0	0.08	−1.42
97% HFIP (w/w)	0.00116±0.00009	−5.26	5.17
90% HFIP (w/w)	0.0426±0.0020	−3.84	4.41
80% HFIP (w/w)	0.821±0.003	−3.31	3.99
70% HFIP (w/w)	13.9±0.8	−2.94	3.83

^aSubstrate concentration of ca. 0.0052 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 [12–15].