Table 3.

Correlation of the specific rates of solvolysis of benzyl, alkenyl, and alkynyl chloroformates (ROCOCl) using the extended (Eqn. 4) form of the Grunwald-Winstein equation^a.

R in ROCOCl	nb	lc	mc	cc	l/m	Rd	Fe
C6H5CH2-	15	1.95 ± 0.16	0.57 ± 0.05	0.16 ± 0.15	3.42	0.966	83
	11	0.25 ± 0.05	0.66 ± 0.06	−2.05 ± 0.11f	0.38	0.976	80
p-NO2C6H4CH2-	19	1.61 ± 0.09	0.46 ± 0.04	0.04 ± 0.22	3.50	0.975	157
CH2=CH-	12	1.67 ± 0.19	0.31 ± 0.07	0.10 ± 0.09	5.38	0.941	35
	5	0.80 ± 0.03	0.59 ± 0.01	−1.31 ± 0.03f	1.36	0.999	578
CH2=C(CH3)-	50g	1.54 ± 0.06	0.54 ± 0.03	0.05 ± 0.06	2.85	0.968	347
CH2=CH-CH2-	28	1.43 ± 0.13	0.52 ± 0.03	0.10 ± 0.06	2.75	0.954	127
	7	0.93 ± 0.12	0.66 ± 0.14	−0.84 ± 0.30f	1.41	0.974	36
H-C≡C-CH2-	22	1.37 ± 0.10	0.47 ± 0.07	0.11 ± 0.11	2.91	0.970	152
CH3-C≡C-CH2-	14h	1.50 ± 0.15	0.49 ± 0.08	0.15 ± 0.10	3.06	0.956	58

^aWhen two entries are given for a substrate, the first refers to what is believed to be predominantly addition-elimination reaction and the second to the region with what is believed to be predominantly ionization reaction.

^bNumber of solvents.

^cWith associated standard error.

^dMultiple correlation coefficient.

^eF-test value.

^fSince the k_o value (80% ethanol) is not available for the ionization reaction, log k was plotted and the intercept is (c + log k_o), a close approximation to an estimate for log k_o for ionization reaction.

^gOmitting the (above the plot) data point for 97% HFIP.

^hOmitting data points in HFIP-H₂O mixtures (above the plot).