A CALCULATIONAL AND ULTRAVIOLET PHOTOELECTRON SPECTROSCOPIC STUDY OF DISTORTED AMIDES

Distorted amides 3,4-dihydro-2-oxo-1,4-ethanoquinoline (1a), 3,4-dihyd ro-2-oxo-1,4-propanoquinoline (1b), 3,3,4,5-tetrahydro-2-oxo-1,5-ethan obenzazepine (1c), and 3,3,4,5-tetrahydro-2-oxo-1,5-propanobenzazepine (1d) and the model compounds 2,N-dimethyl-acetanilide (2a), 2,N,N-tri methylaniline (3), and benzoquinuclidine (4) have been studied calcula tionally and with He(I) ultraviolet photoelectron spectroscopy. We fin d good agreement between experimentally obtained ionization energies f or 1b, 1c, 1d, 2a, 3, and 4 and values calculated with HAM/3 using the equilibrium geometries obtained at the WF/6-31G* level of theory. An excellent correlation between experimental ionization energies and or bital energies from Becke3LYP/6-31+G calculations led to the characte rization of the highest occupied molecular orbitals for these compound s and for 1a, whose photoelectron spectrum could not be obtained due t o its reactivity in the solid state.