Readily available tetrachloro-2-aza-1,3-butadienes enter into directed cyclocondensation reaction with N-phenyl-1,2-cyclopentanediamine which leads to regioselective cyclopentane annulation by the 1,3,5-triazepine. The formation of the 1,3,5-triazepine derivatives was confirmed proved by 1H- and 13C-NMR spectral study, elemental analysis and, in one case, single-crystal x-ray crystallographic study.
The quantum-chemical modeling mechanism of the [4+2]-cycloaddition reaction of 2,3 dimethylbuta-1,3-diene and methyl acrylate was conducted. Its qualitative aspects were analyzed at the molecular level by the program MOPAC2012 and semiempirical method RM1. The potential energy surfaces of 2,3 dimethylbuta-1,3-diene and methyl acrylate [4+2] cycloaddition possible reaction pathways were constructed by restricted and unrestricted Hartree-Fock approximation. It has been established that the molecule of the final product methyl-3,4-dimethylcyclohex-3-encarboxylate has the half-chair shape, wherein the carboalkoxyl group is in the exo-orientation. Interaction between molecules of 2,3 dimethylbuta-1,3-diene and methyl acrylate occurs by a two-step mechanism more likely than one-step, since the activation parameters of this interaction maximum coincide with the experimental data.
Two potential energy surfaces 1 2A1 and 1 2B1 for linear geometry of F-H-Br system have been computed with aug-cc-pVQZ basis set using dynamically weighted state averaged MCSCF followed by MRCI-F12 method. State 1 2A1 has smaller barrier height (3.49 kcal/mol) than 1 2B1. (13.6 kcal/mol). The latter has deep van der Waals well in Br-HF valley (2.12 kcal/mol).