Pressure Effect on Reaction Rate of Cycloaddition of Tetracyanoethylene with α-Methylstyrene in Some Aprotic Solvents

Abstract

Abstract The high-pressure kinetic study of the title reaction was carried out at 25 °C up to 1500 bar in carbon tetrachloride, chloroform, 1,2-dichloroethane, and acetonitrile, taking into account the role of the EDA complex formation. The dipole moment at the transition state is as large as 8.5±0.5 debye by Kirkwood’s electrostatic model. The solvent effect is also ascribable to the polarity change upon activation. The intrinsic volume of activation is −27±3 cm3/mol for the cycloadding process and −3.3±3 cm3/mol for the reverse reaction.