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The Diels-Alder Reaction

The group of [4 + 2] cycloaddition reactions referred to as the Diels-Alder reaction constitute one of the most versatile and widely used synthetic methods. Stripped to its most basic components, this reaction is represented by the addition of 1,3-butadiene to ethene shown below. The standard state thermodynamic functions for this reaction may be calculated from the heats of formation and entropies of the components.

H = -40 kcal/mole

S = -43.6 cal/ K mole G = -27 kcal/mole kcal/mole

The exothermic nature of this reaction is the result of converting two weak -bonds into two stronger -bonds. The large negative entropy reflects the change from two independent reactant molecules to one product molecule, and the necessity of fixing the diene in a cisoid conformation. Both impose increasing order on the system. Because the entropy factor opposes the enthalpy change, the calculated G is smaller than H by 298*S/1000, but it still represents a strongly exergonic reaction. Despite the favorable overall energy change, this reaction has a substantial free energy of activation, and requires heating to take place. At 200 C the TS component increases to 20.6 kcal/mole, but G remains a strongly exergonic -19.4 kcal/mole. The calculated equilibrium constant favoring cyclohexene at this temperature is therefore greater than 1012. Functional substituents on the dienophile or diene reactants often lower the activation barrier, and in some cases spontaneous [4 + 2] additions may occur. Examples include: 1,3-butadiene + maleic anhydride, 1,3-cyclopentadiene + propenal, and 1,3-cyclohexadiene + dimethyl acetylenedicarboxylate. It is interesting to note that a commercial process for preparing 1,3-butadiene consists of passing gaseous cyclohexene over a red hot metal coil (ca. 900 C), as shown in the following equation.

G1173 = +40 (1173 * 43.6/1000) = -11.1 kcal/mole

This is the reverse of the Diels-Alder cycloaddition, and the thermodynamic functions for this reaction will have opposite signs to those defined above. Using these standard state functions, the success of this procedure can be explained. At 900 C (1173 K) the entropy component is larger than the enthalpy component, so the G for the decomposition is an exergonic -11.1 kcal/mole. This is equivalent to an equilibrium constant of 108, favoring the desired butadiene, which is easily separated from ethene thanks to its higher boiling point (-

4.5 C ). It should be noted that H and S are not constant at all temperatures, but do not normally suffer large changes.