Nitroxide chemistry. Part IV. Reaction of bistrifluoromethyl nitroxide with aldehydes

Abstract

Bistrifluoromethyl nitroxide abstracts aldehydic hydrogen atoms from acetaldehyde, propionaldehyde, pivalaldehyde, benzaldehyde, m- and p-tolualdehyde, terephthalaldehyde, and pentafluorobenzaldehyde with great ease, to give NN-bistrifluoromethylhydroxylamine and the corresponding (bistrifluoromethylamino-oxy)carbonyl-alkane or -arene in almost quantitative yields. Basic hydrolysis of the carbonyl compounds ArCO₂·N(CF₃)₂(Ar = Ph or C₆F₅) yields the corresponding arenecarboxylic acids, and attack of bistrifluoromethyl nitroxide on the phenyl compound at elevated temperature leads to nuclear substitution with the formation of (bistrifluoromethylamino-oxy)[(bistrifluoromethylamino-oxy)carbonyl]benzenes.