Organic Chemistry International

Research Article

On the Importance of the Aromatic Ring Parameter in Studies of the Solvolyses of Cinnamyl and Cinnamoyl Halides

Table 1

Specific rates of solvolysis of 1, in several binary solvents at C and literature values for ( ) and ( ).
Solvent 1@ C; , s-1
100% MeOH0.9050.17−1.2
90% MeOH4.87−0.01−0.20
80% MeOH21.5−0.060.67
100% EtOH 0.37−2.50
90% EtOH 0.16−0.90
80% EtOH8.05e0.000.00
90% Acetone0.00731−0.35−2.39
97% TFE (w/w) −3.302.83
90% TFE (w/w) −2.552.85
80T-20E −1.761.89
60T-40E −0.940.63
40T-60E −0.34−0.48
20T-80E 0.08−1.42
Determined titrimetrically; typical error 4%. Substrate concentration of . 0.0052 M; binary solvents on a volume-volume basis at C, except for TFE- solvents which are on a weight-weight basis. T-E are TFE-ethanol mixtures. Value reported in Table 1 is the average obtained using k ( ) values at C of 0.409, 0.420, 0.418, and 0.417 from four independent runs. A value of 0.0839  is reported in the literature [23]. Value reported in Table 1 is the average obtained using k ( ) values at C of 2.26, 2.27, 2.30, and 2.30 from four independent runs. A value of 0.970  is reported in the literature [23]. Value reported in Table 1 is the average obtained using k ( ) values at C of 8.03, 8.03, 8.03, and 8.11 from four independent runs. A value of 4.73  has been reported in the literature [23]. Calculated from Arrhenius plots using k ( ) values at , − , and − C of 17.8, 8.9, and 4.0. Calculated from Arrhenius plots using k ( ) values at , − , and − C of 23.9, 10.2, and 5.4. Value reported in Table 1 is the average obtained using k ( ) values at C of 82.7, 83.1, 83.8, and 84.2 from four independent runs. A value of 84.8  is reported in the literature [23]. Value reported in Table 1 is the average obtained using k ( ) values at C of 14.1, 14.6, 14.6, and 14.7 from four independent runs. A value of 10.4 is reported in the literature [23]. Value reported in Table 1 is the average obtained using k ( ) values at C of 3.48, 3.50, 3.55, and 3.56 from four independent runs. A value of 1.91 is reported in the literature [23]. Value reported in Table 1 is the average obtained using k ( ) values at C of 1.09, 1.10, 1.13, and 1.14 from four independent runs. A value of 0.353 X is reported in the literature [23]. Refs. [9, 10]. Refs. [5, 6].