Synthesis of Polynitrocyclobutane Derivatives

Article abstract of DOI:10.1021/jo00273a019

The synthesis of polynitrocyclobutanes was studied.Oxidation of oximinocyclobutanes with hypochlorite followed by Zn reduction gave ethyl 3-nitrocyclobutanecarboxylate (4a), diethyl 3-nitrocyclobutane-1,1-dicarboxylate (4b), and 2,5,8,10-tetranitrodispiro<3.1.3.1>decane (4d) in 20-90percent yields.Oxidation of aminocyclobutanes with m-chloroperbenzoic acid gave 1-nitrocyclobutane (4e), 1,3-dinitrocyclobutane (4f), and 2,8-dinitrodispiro<3.1.3.1>decane (4c) in 20-40percent yields.Bromination of 4f gave 1,3-dibromo-1,3-dinitrocyclobutane (5).Addition of N2O4 to methyl orethyl bicyclo<1.1.0>butane-1-carboxylates gave methyl or ethyl 1,3-dinitrocyclobutanecarboxylates (7a,b) in 17percent and 40percent yields.Oxidative nitration of nitrocyclobutanes 4a,d,e gave the corresponding gem-dinitrocyclobutanes in 15-78percent yield. 1,1,3,3-Tetranitrocyclobutane (8f) and 1,1,3-trinitrocyclobutane (11) were obtained by similar oxidative nitration of 4f or 7a,b in 20-40percent yields.Dispirane 4c was converted similarly to 5,5,10,10-tetranitrodispiro<3.1.3.1>decane in 64percent yield.