The neutral, cationic, and anionic structures of both prototropic tautomers of trans-and cis-urocanic acid [(E)-and (Z)-3-(l'H-imidazol-4'(5')-yl)propenoic acid, respectively] were studied by using semiempirical and ab initio gas-phase calculations. Potential energy surfaces of the structures were calculated by using the semiempirical AM1 method, and the geometries corresponding to global minima on these surfaces were optimized up to the MP2/6-31G* level of theory. The calculated protonation forms of each urocanic acid isomer have a planar molecular structure due to a delocalized r-electron system, and all of them prefer the s-trans conformation with respect to the bond between the imidazole and the propenoic acid moieties. The cis-urocanic acid structures are stabilized by an intramolecular hydrogen bond. The charged cis-urocanic acid isomers have a lower molecular energy than the corresponding trans-isomers, whereas the neutral molecules have, after inclusion of thermodynamic corrections, approximately the same energy. The cationic urocanic acid structures have about 2500 kJ tool -l lower energy than the anionic ones and about 1000 kJ mol -I lower energy than the neutral ones. The nonzwitterionic forms of the neutral urocanic acid isomers have about 200 kJ mol-~ lower energy than the zwitterionic ones. These energy differences are explained by the proton affinities of the imidazole and the propenoic acid moieties of the urocanic acid structures.
The 'H N M R spectra of isomeric 5,6-dimethyl-2oxo-l,4-dioxans have been recorded and the pertinent chemical shifts and coupling constants determined. The parameters indicate that both isomers exist as an equilibrium mixture of interconverting half chair ring conformations.
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