The reactions in aqueous solution of -hydroxyalkyl radicals with para-substituted nitrobenzenes were studied by using product analysis, electron spin resonance, and pulse radiolysis techniques. At neutral pH the -hydroxyalkyl radicals are quantitatively oxidized to yield the corresponding ketones or aldehydes and H+, and the nitrobenzenes are reduced to the radical anions. The mechanism of this redox reaction depends strongly on the substituents on the -hydroxyalkyl radical (the electron donor) and on the nitrobenzene (the electron acceptor). In the case of -hydroxymethyl radical, the reaction proceeds by addition to the nitro group to produce an alkoxynitroxyl radical which can undergo an OH'-catalyzed heterolysis to give formaldehyde and the radical anion of the nitrobenzene. With the -hydroxyethyl radical, both addition and "electron transfer" take place, the fraction of electron transfer increasing with increasing electron-withdrawing power of the substituent. The (1) On leave from Department of Chemistry, Sardar Patel College, Secunderabad-500025, India.(2) For reviews see, e.g.; (a) Neta, P.
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