An experimental and theoretical approach to 5α-cholestan-6-spiro-1′,2′,4′-triazolidine-3′-one

The 5α-cholestan-6-one semicarbazone (1) on reaction with hydrogen peroxide at 0 °C affords selectively 5α-cholestan-6-spiro-1′,2′,4′-triazolidine-3′-one. (2) The structural assignment of the product was confirmed on the basis of its elemental, analytical and spectral analysis. The Hartree–Fock method using 6-31G* basis set was employed in order to explore the reaction mechanism. The results of the computational study show that the reaction proceeds through two radical intermediates formation. The different characteristics involved during the reaction were explained, firstly, the lower energy conformation of each molecule using total energy, hardness and dipole moment, and secondly, the explanation of the free radical mechanism, using frontier molecular orbital (FMO) theory, encoded electrostatic potential, spin electronic density and atomic charges. The localization of highest occupied molecular orbital (HOMO) or α-HOMO, lowest unoccupied molecular orbital (LUMO) or α-LUMO and the flow of atomic charges are in good agreement to support the present mechanism of the reaction. Stability and feasibility of all the optimized structures were supported by their respective fundamental frequencies and energy minima.