Reduction of 1.2.3-trimethoxy-5-nitrobenzene (VI) with zinc and calcium chloride or with zinc and ammonium chloride yielded 3,3',4,4',5,5'-hexamethoxyazoxybenzene. In zinc, ammonium chloride, and a controlled amount of nitrous acid, (VI) yielded a compound C,8H22N40,,Zn (IX), which appeared to be a stable complex of the dimer of 1.2,3-trimethoxy-5-nitrosobenzene and zinc nitrite. When treated with nitrous acid, (IX) yielded 2,5-dimethoxy-l,4-benzoquinone (V), but with hydrochioric acid gave a mixture of (V) and 4-hydroxyimino-2,6-dimethoxycyclohexa-2,5-dienone (IV). Since (V) is a product of the reaction of 1.2.3-trimethoxybenzene (I) with nitrous acid, it is proposed that 5-nitroso-I ,2,3-trimethoxybenzene (11) and (IV) are intermediates in the latter reaction and that they are formed, in turn, by nitrodeprotonation and acid hydrolytic demethoxylation, respectively.