The Effect of Light on Electron-Transfer Substitution at a Saturated Carbon Atom

Article abstract of DOI:10.1021/jo00390a026

Quantum yields have been determined for four electron-transfer substitution reactions at a saturated carbon atom: azide and quinuclidine dispacement of chloride ion from p-nitrocumyl chloride, azide displacement of nitrite ion from α,p-dinitrocumene, and displacement of nitrite ion from ethyl α-nitroisobutyrate by the salt of 2-nitropropane.The values range from 3.5 for the quinuclidine-p-nitrocumyl chloride reaction to 6000 for the azide-p-nitrocumyl chloride reaction.A study of the wavelength dependence of the quantum yields supports the view that photochemical initiation involves a charge-transfer complex between the nucleophile and the compound in which substitution takes place