The Electronic Structure of Vinyl Ethers and Sulfides with Interrupted Conjugation Examined by Photoelectron Spectroscopy

Abstract

Suunnzary. Photoelectron spectroscopy has been used to examine the conseqncnces of steric inhibition of conjugation in a distorted vinyl sulfide and vinyl ether. Based upon the degree of interaction a deviation from coplanarity of 70"-75" is calculated for 9-oxabicyclo[3.3.ljnon-l-ene (3) and approximately 75"-80" for the sulfur analog 6 .Twisting two conjugated, individually planar n-systems K and S by an angle @ES with respect to each other produce:; changes in the electronic structure of the molecule R-S. Within the framework of a simple HXO-type model these changes are linked to the decrease of the crossteri-u,

Photoelectron spectra of psychotropic drugs. 1. Phenethylamines, tryptamines, and LSD

“…As can be seen from the data in Table II, a good correlation exists between the lower IP's of the substituted toluenes and their corresponding phenethylamines. The absence of anomalies within this series indicates that the amino group of Journal of the American Chemical Society / 99:13 / June 22,1977 (12) 7.69 ± 0.08 8.25 ± 0.08 9.63 ± 0.08 9.25 ±0.16…”

“…Temperature-dependent photoelectron spectroscopy reveals that the lower energy form, which corresponds to the "planar" conformation, has a vertical IP of 8.02 eV, while the higher energy "perpendicular" conformation has a vertical IP of 8.55 eV.21 While similar evidence on anisóle is unavailable, the photoelectron spectra of certain bicyclic enol ethers show that an ether oxygen attached to a double bond raises the IP of the x orbital of the alkene, if the oxygen "p-type" lone pair is prevented from conjugating with the 7 orbital. 22 In 3,4-dimethoxyphenethylamine, both methoxyls may be "planar", while the 4-methoxyl group cannot be planar in mescaline. Recent neutron diffraction studies on a related compound, trimethoprim, indicate that the central methoxyl is rotated 101 °out of plane; that is, the 4-methoxyl is only 110…”