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.