Evaluation of Electronic Effects in the Solvolyses of p-Methylphenyl and p-Chlorophenyl Chlorothionoformate Esters

Table 2

Correlations of the specific rates of solvolysis of 1–8 using the extended Grunwald-Winstein equation (1).

Substrate	𝑛^a	𝑙^b	𝑚^b	𝑐^b	𝑅^c	𝐹^d	𝑙/𝑚	Mechanism
1 e	9	1.88 ± 0.28	0.56 ± 0.15	0.38 ± 0.15	0.950	28	3.36	A-E
	18	0.34 ± 0.05	0.93 ± 0.09	−2.54 ± 0.34	0.955	77	0.37	S N1
2 f	49	1.66 ± 0.05	0.56 ± 0.03	0.15 ± 0.07	0.980	568	2.96	A-E
3 e	31	0.69 ± 0.05	0.95 ± 0.03	0.18 ± 0.05	0.987	521	0.72	S N1
4 g	16	1.74 ± 0.17	0.48 ± 0.07	0.19 ± 0.23	0.946	55	3.62	A-E
	6	0.62 ± 0.08	0.92 ± 0.11	−2.29 ± 0.13	0.983	44	0.67	S N1
5 h	22	1.32 ± 0.13	0.39 ± 0.08	−0.02 ± 0.10	0.952	95	3.38	A-E
6	13^i	1.63 ± 0.31	0.46 ± 0.10	0.30 ± 0.12	0.881	17	3.54	A-E
	7^j	0.45 ± 0.13	1.07 ± 0.14	−2.25 ± 0.20	0.986	69	0.42	S N1
7	13^i	1.79 ± 0.16	0.45 ± 0.07	−0.05 ± 0.09	0.966	69	3.98	A-E
8 k	10	1.76 ± 0.28	0.54 ± 0.15	0.34 ± 0.15	0.943	28	3.26	A-E
	5	0.53 ± 0.18	0.89 ± 0.18	−2.66 ± 0.35	0.967	15	0.60	S N1

^a𝑛 is the number of solvents. ^bWith associated standard error. ^cCorrelation coefficient. ^d𝐹-test value. ^eValues taken from [26, 27]. ^fValues taken from [25, 26]. ^gValues taken from [28]. ^hValues taken from [49]. ⁱExcluding the data points in aqueous HFIP, aqueous TFE, and 80T-20E in regression calculations. ^jUsing only the data points in aqueous HFIP, aqueous TFE, and 80T-20E in regression calculations. ^kValues taken from [40].