Electron spin resonance studies. Part XVIII. Reactions of some aldehydes and ketones, the corresponding oximes, and some nitroalkane anions with the titanium(III)–hydroxylamine system
Abstract
When solutions of titanium(III) chloride, hydroxylamine, and one of a number of aldehydes or ketones are mixed, shortly before passage of the combined solution through the cavity of an e.s.r. spectrometer, the spectrum of a radical of the type R1R2C(OH)–NH–O· is observed; evidently the adduct R1R2C(OH)–NHOH, which mediates in oxime formation, is both formed and oxidised exceptionally rapidly. These radicals are also formed by addition of the hydroxyl radical to oximes, at both pH 1 and 9, and analogous radicals are formed by the addition of the amino-radical to oximes. Both ·OH and ·NH2 also add readily to the anions derived from some nitroalkanes. The hyperfine splitting constants of the radicals which have been examined are discussed.