Electrochemical Reactions and Mechanisms in Organic Chemistry

CHAPTER 11

REDUCTION OF NITRO, NITROSO, AZO AND AZOXY GROUPS

Nitro- and Nitroso-compounds Radical-Anions

Reduction of nitrocompounds involves a series of one-electron additions and chemical steps and an important reaction intermediate is the nitrosocompound. The redox properties of nitro- and nitroso-compounds will be discussed first. Some values of reduction potentials for nitrocompounds are collected in Table 11.1.

TABLE 11.1

Polarographic half-wave potentials for nitrocompounds in aqueous ethanol, pH 13. The radical-anion is formed reversibly so that E½ = E°

Substrate	E½ V vs. sce	Ref.
2-Methyl-2-nitropropane	−1.09	[1]
Nitrobenzene	−0.70	[2]
ω-Nitrostyrene	−0.40	[3]

The radical-anions of aliphatic nitrocompounds are detectable ...