The effect of pressure on the Diels-Alder reaction was investigated. The observed activation volume was found to have a significant correlation with the activation free energy of the reaction. A correlation diagram between the activation volume and the activation free energy was proposed. By this diagram, the position of the transition state in the Diels-Alder reaction was discussed, and the activation volume was suggested to be a good diagnostic probe for the position of the transition state. The importance of the contribution of the volume contraction resulting from secondary orbital interaction to the apparent activation volume was pointed out.
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Seguchi et al. (1974) studied this question.
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