Synthesis of 1,2-Naphthoquinone 1-Oxime O-Sulfate and Its Solvolytic Properties with or without Bivalent Copper

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1,2-Naphthoquinone 1-oxime O-sulfate (1) was synthesized by sulfation of 1-nitroso-2-naphthol with chlorosulfonic acid and N, N-dimethylaniline. The sodium salt of 1 was decomposed to form inorganic sulfate and 1-nitroso-2-naphthol in neutral (pH 4.9,80°) and acidic (0.1N HCl, 40°) conditions, with their half-lives of 380 and 140 min, respectively. In an alkaline medium (0.1N NaOH, 20°), the salt was instantaneously decomposed to give a quantitative amount of inorganic sulfate and a ring-cleaved product of 1,2-naphthoquinone 1-oxime moiety, and this product was identified as o-cyano-cis-cinnamic acid (2). The effect of Cu (II) on the hydrolysis of 1 was more accelerative in a neutral condition than in an acidic condition, resulting in the reduction of its half-life to 60 min. It was also observed that polar organic solvents such as pyridine, dioxan, and tetrahydrofuran markedly accelerated the hydrolysis of the triethylammonium salt of 1,in both neutral and acidic conditions. Reactivity of the triethylammonium and the pyridinium salts of 1 in trans-sulfation was examined in Me_2SO・pyridine (4 : 1), with or without Cu (II). As estimated by the formation of sulfated products from riboflavin, 1 had a much smaller reactivity than 8-quinolyl sulfate reported previously, although the effect of Cu (II) was accelerative on the reaction.
公益社団法人日本薬学会の論文
1977-06-25