Nucleophilic substitution reactions of cinnamoyl chlorides with anilines in acetonitrile and acetonitrile–methanol mixtures

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Abstract
Kinetic studies on the solvolysis (in McOH–MeCN mixtures) and aminolysis (with anilines in McCN) of cinnamoyl chlorides have been carried out at 25.0 °C. The relatively large negative values of ρY +=–0.9 –1.5 for the methanolysis are consistent with a dissociative SN2-like mechanism. For the aminolysis, the ρY values are positive (ρY= 0.52 1.64) and ρX values range from –1.68 to –2.51 in acetonitrile. The positive values of βX= 0.6–0.9 and ρXY= 0.88 in acetonitrile, and isotope effect data suggest that the aminolysis proceeds by a stepwise mechanism with rate-limiting breakdown of the tetrahedral intermediate, T±. It is noted that in the acyl-transfer reactions proceeding by rate-limiting departure of the leaving group from the tetrahedral intermediate the signs of both ρY and ρXY are positive and the reactivity–selectivity principle (RSP) is valid in general.

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