THE REACTION OF n-BUTYLAMINE AND BENZYLAMINE WITH SOME β-NITROSTYRENES, DIETHYL BENZALMALONATES, AND CINNAMALMALONONITRILES

Abstract

The relative rates of reaction of n-butylamine with 27 β-nitrostyrenes, 36 β-nitropropenylbenzenes, 20 β-nitrobutenylbenzenes and 7 related compounds, 11 diethyl benzalmalonates, and 4 cinnamalmalononitriles were measured in dioxane solution at 25 °C. In addition, the slower rates of reaction of benzylamine with 15 of these compounds were measured under identical conditions. The pseudo first order rate constants, koverall, for all the reactions were adequately represented by the expression[Formula: see text]where A and B are constants which, in general, could be correlated with Hammett sigma constants. A nitro group substituted in the ortho position or chlorines substituted in both ortho positions gave anomalous rate constants in some series but not in others. A mechanism is proposed for the amine additions.