Theoretical and experimental studies of 1,3-dipolar cycloaddition reactions between trimethylsilylazide and citral (geranial and neral)

The [3+2] cycloaddition reactions on citral which is the mixture of geranial 1 and neral 2 isomers have been performed to obtain interesting varieties of its derivatives. The probable 1,3-dipolar cycloaddition reactions between citral mixture (1 and 2) with trimethylsilylazide (TMS), the comparison of the citral mixture in the kinetic and thermodynamic reactions, the structural studies of the 1,2,3-triazoline products, carbine reactive intermediates and transition states are investigated. The reactions are studied and discussed by B3LYP/6-31G* method. The main configurations are performed with less steric restraint effects. The HOMO and LUMO orbital levels, Delta EHOMO-LUMO gaps, dipole moments, Mulliken charges, thermodynamic and kinetic stabilities in vacuum are investigated for the components by the density functional theory (DFT) B3LYP/6-31G* method. The elimination reactions of N-2 molecule from the 1,2,3-triazolines to produce aziridine products, the mechanisms, the biradical intermediates and the related transition states have been investigated as well by the use of B3LYP/6-31G* method. Some of the experimental results such ns FT-IR, H-1 NMR and GC-MS have been carried out in this study to pursue the course of the reactions.