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

Article abstract of DOI:10.1246/bcsj.55.1348

The high-pressure kinetic study of the title reaction was carried out at 25 deg 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.