1. Nitroxide chemistry. Part IV. Reaction of bistrifluoromethyl nitroxide with aldehydes
2. The literature contains conflicting reports on the susceptibility of benzene towards attack by (CF3)2NO· (II). Thus, while American investigators [W.D. Blackley and R.R. Reinhard, J. Amer. Chem. Soc., 87 (1965) 802] maintain that the nitroxide (II) is ‘not affected chemically’ by benzene, Russian workers, having noted evidence of a reaction during e.s.r. experiments [I.V. Miroshnichenko, G.M. Larin, S.P. Makarov and A.F. Videiko, Zhur. Strukt. Khim., 6 (1965) 776], claimed the slow (2–3 days at room temperature) formation of (CF3)2NOH and material believed to be 1,2,4-tris(bistrifluoromethylamino-oxy)benzene [S.P. Makarov, A.F. Videiko, T.V. Nikolaeva and M.A. Englin, Zhur. obshchei Khim., 37 (1967) 1975]; except for a reasonable elemental analysis (C,H,F and N) and a molecular weight value (method not given), evidence for the identity of this tri-substituted benzene appears restricted to formation in unspecified yield of a derivative produced via hydrolysis (hot KOH aq.) and stated to be 1,2,4-trihydroxybenzene on the basis of a melting point (145 °C) which does not compare well with a literature value (141 °C [J. Böeseken, Rec. Trav. Chim., 34 (1915) 272]. The latter Russian paper also contains a claim (based on elemental analysis) that the nitroxide (I) attacks fluorobenzene at room temperature to yield a bis(bistrifluoromethylamino-oxy) derivative of unknown orientation.
3. In our hands (R.E. Banks, D.L. Connell, R.N. Haszeldine and G. Shaw) the nitroxide (I) attacks benzene at 21 °C to yield (CF3)2NOH, (CF3)2NON(CF3)2 and a complex, multi-component, salmon pink, unidentified oil [containing carbonyl compounds (i.r. analysis)] that does not yield 1,2,4-trihydroxybenzene when heated with 10% aqueous KOH.
4. This method of preparation of (CF3)2NO−Na+ was pioneered by R.E. Banks and R.A. Hughes.