Gas-phase thermolysis of pyrazolines. 3. Electronic structure and gas-phase pyrolysis of 4-substituted 3,5,5-trialkyl-3,5-dihydro-4H-1,2,3-triazoles studied by photoelectron spectroscopy and semiempirical calculations.
The PE spectra of title compds. I (X = O, NMe, CH2; R = Me, CH2CMe3) have been recorded. The ionization potentials have been assigned to MOs on the basis of MNDO, AM1, and PM3 calcns. The most important occupied MOs are characterized as pNNN, pC:X, nN-3, nNN+, nNN- and nX. The gas-phase thermolyses of I have been studied by PE-controlled real-time gas anal. After extrusion of mol. nitrogen, the remaining reactive species cyclize to three-membered rings. At higher temps. and in flash vacuum pyrolysis, subsequent reactions lead to smaller acyclic compds.
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