Model reaction for a synthesis of streptamine.

Abstract

Part I. trans,trans-1,3-Diacetamido-2-nitrocyclohexane (IV) was prepared from trans,trans-1,3-diacetoxy-2-nitrocyclohexane (II) by reaction with ammonia followed by acetylation. The configuration of IV was determined by studies of the n.m.r. spectra of two derivatives, trans,trans -2-amino-1,3-diacetamidocyclohexane (V) and trans,trans-1,2,3-triacetamidocyclohexane (VI). Permanganate oxidation of compound IV gave 2,6-diacetamidocyclohexanone (VII), whose 2,4-dinitrophenylhydrazone (VIII) was also prepared. The ketone VII was reduced by sodium borohydride and yielded trans,trans-2,6-diacetamidocyclohexanol (IX), whose configuration was confirmed by its n.m.r. spectrum and by that of its derivative, trans,trans-2,6-diacetamidocyclohexanol acetate (XI). The Clemmensen reduction of compound VII was investigated as a possible route to 1,3-diacetamidocyclohexane (XII). Action of ammonia followed by N-acetylation converted deoxynitro-scyllo-inositol pentaacetate (XIII) into 1,3-diacetamido-2-deoxy-2-nitro-scyllo-inositol (XIV). Part II. 3-Phthalidylnitromethane (XIII) was allowed to react with triethylamine in anhydrous methylene chloride to give 2-(2-nitrovinyl) benzoate ion (XIV) as suggested by the ultraviolet spectrum. Upon subsequent addition of diazomethane two products were isolated, neither of which had retained the nitro group and only one of which contained methoxyl. Possible molecular formulas for these products are discussed.