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Dimerization of Cyclopentadiene

A similar Diels-Alder system that is more easily studied is the dimerization of 1,3cyclopentadiene shown below. The H for this reaction is almost 10 kcal/mole lower than that of the butadiene + ethene addition, reflecting strain in the tricyclic product. The S, on the other hand, is roughly 10 eu less negative as a result of the fixed cisoid orientation of the diene.
H = -18.4 kcal/mole S = -34 cal/ K mole G = -8.3 kcal/mole kcal/mole H = +15 kcal/mole S = -32 cal/ K mole G = +24.5 kcal/mole kcal/mole

At room temperature cyclopentadiene slowly dimerizes, the exergonic G corresponding to an equilibrium constant of 106 in favor of the dimer. The G prohibits immediate reaction, but a sample of pure cyclopentadiene at room temperature slowly dimerizes over a week or two. Consequently, the short shelf life of the synthetically important monomer demands that it be freshly prepared just before it is used in a reaction. This is easily accomplished by heating the dimer to just below its boiling point (170 C) and collecting the lower boiling monomer (b.p. 42 C) as it is formed. Although the G for dimerization is still negative at 170 C (-3.3 kcal/mole), it has been substantially lowered by the TS factor, permitting a significant equilibrium concentration of the monomer to be achieved. The availability of activation parameters for this reaction makes it possible to explore further details of the reaction path. The stereospecificity of the DielsAlder reaction implies a single step transformation, and the exothermic character of the reaction requires an enthalpy profile similar to that shown on the right. TheHammond Postulate, which uses H as an indicator, suggests that the transition state would resemble the reactants more than the products. However, the similar magnitude and sign of S and S requires the transition state to have a structure very similar to the dimer product. This disagreement is a warning that the Hammond postulate was intended to be used for reaction profiles involving high energy intermediates., and is probably inappropriate for single step reactions such as SN2 substitutions and the Diels-Alder cycloaddition.