Reactions of 5-nitrospiro[benzimidazole-2,1′-cyclohexane] 1,3-dioxide with nucleophiles

• Published in: Russian journal of organic chemistry Vol. 48; no. 3; pp. 399 - 410
• Main Authors: Samsonov, V. A., Gatilov, Yu. V., Savel’ev, V. A., Baranova, S. S.
• Format: Journal Article
• Language: English
• Published: Dordrecht SP MAIK Nauka/Interperiodica 01.03.2012; Springer Nature
• Subjects: Chemistry; Chemistry and Materials Science; Chemistry, Organic; Organic Chemistry; Physical Sciences; Science & Technology; Aniline Hydrochloride; Sodium Cyanide; Aromatic Amine; Benzimidazole; Cyclohexane; DERIVATIVES; 2H-BENZIMIDAZOLES; SYNTHONS
• ISSN: 1070-4280; 1608-3393
• DOI: 10.1134/S1070428012030116

Reactions of 5-nitrospiro[benzimidazole-2,1′-cyclohexane] 1,3-dioxide with aliphatic amines and sodium hydroxide resulted in removal of one N -oxide oxygen atom and formation of 4-alkylamino- or 4-hydroxy-substituted 5-nitrospiro[benzimidazole-2,1′-cyclohexane] 1-oxides, respectively. The title compound reacted with ammonia and methylamine in the presence of MnO 2 with conservation of both N -oxide moieties, and the products were 4-amino- and 4-methylamino-5-nitrospiro[benzimidazole-2,1′-cyclohexane] 1,3-dioxides. The reactions with aromatic amines were accompanied by removal of both N -oxide oxygen atoms with formation of N -aryl-5-nitrospiro[benzimidazole-2,1′-cyclohexane]-4-amines. In the reactions of 5-nitrospiro-[benzimidazole-2,1′-cyclohexane] 1,3-dioxide with sodium azide and aromatic amine hydrochlorides nucleophilic replacement of the 5-nitro group by azido or arylamino occurred, in the first case both N -oxide fragments being conserved. The reactions with aromatic amine hydrochlorides afforded N -aryl-5-nitrospiro[benzimidazole-2,1′-cyclohexan]-4-amine 1-oxides. Treatment of 5-nitrospiro[benzimidazole-2,1′-cyclohexane] 1,3-dioxide with sodium cyanide led to the formation of 5-oxo-3,5-dihydrospiro[benzimidazole-2,1′-cyclohexane]-4-carbonitrile 1-oxide.