An Efficient Preparation of 4-Nitrosoaniline from the Reaction of Nitrobenzene with Alkali Metal Ureates
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This paper describes the synthesis of alkali metal salts of urea (ureates) and their application to the direct preparation of 4-nitrosoaniline from nitrobenzene via nucleophilic aromatic substitution of hydrogen. Sodium and potassium ureates were readily prepared from the reaction of urea with sodium hydride, metal methoxides, and metal hydroxides. The effect of ureates as nucleophiles on the conversion of nitrobenzene to 4-nitrosoaniline was investigated and compared with that of a urea-metal hydroxide mixture. It was found that the ureates were superior for producing 4-nitrosoaniline owing to their higher thermal stability of the ureate. The ureate obtained from the treatment of urea with sodium hydride gave the highest yield for the preparation of 4-nitrosoaniline. The ureates generated from the reaction of urea with metal hydroxide also gave high yields of 4-nitrosoaniline. Catalytic hydrogenation of 4-nitrosoaniline afforded polymer-grade 1,4-benzenediamine in quantitative yield.
Abstract
This paper describes the synthesis of alkali metal salts of urea (ureates) and their application to the direct preparation of 4-nitrosoaniline from nitrobenzene via nucleophilic aromatic substitution of hydrogen. Sodium and potassium ureates were readily prepared from the reaction of urea with sodium hydride, metal methoxides, and metal hydroxides. The effect of ureates as nucleophiles on the conversion of nitrobenzene to 4-nitrosoaniline was investigated and compared with that of a urea-metal hydroxide mixture. It was found that the ureates were superior for producing 4-nitrosoaniline owing to their higher thermal stability of the ureate. The ureate obtained from the treatment of urea with sodium hydride gave the highest yield for the preparation of 4-nitrosoaniline. The ureates generated from the reaction of urea with metal hydroxide also gave high yields of 4-nitrosoaniline. Catalytic hydrogenation of 4-nitrosoaniline afforded polymer-grade 1,4-benzenediamine in quantitative yield.
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