Reaction of trans, trans-1,4-diphenylbutadiene and maleic anhydride. Substituent and solvent effects

Abstract

Diels–Alder adducts from X-substituted diphenylbutadienes (X =p-NMe₂, p-OMe, p-Me, m-Me, H, m-OMe, p-Cl, m-Cl, p-CN, and m-NO₂) and maleic anhydride, and from diphenylbutadiene and some dienophiles (N-methylmaleimide, N-phenylmaleimide, and 1,4-benzoquinone), have been prepared. Second-order rate constants and activation parameters for these reactions have been measured in m-xylene as solvent. The effects of some aprotic solvents (toluene, anisole, chlorobenzene, bromobenzene, benzonitrile, nitrobenzene, and NN-dimethylformamide) on the kinetics of diphenylbutadiene and maleic anhydride have been investigated. The stereospecificity of the endo-addition and the small substitutent and solvent effects on the reaction rate rule out the presence of a zwitterionic intermediate along the reaction co-ordinate. These results, together with the low activation enthalpies and the large negative entropies, can be interpreted in terms of the diradical or concerted mechanism, even though the latter seems to be more acceptable.