Geminal dinitro compounds

Geminal dinitro compounds, " ct-nitro sulfones, " ct-nitro esters, or ct-nitro nitnles react v/ith anions derived from nitro ilkanes to give the Spj l products, as shovmin Eqs. 5.28, 5.29, 5.30 and 5.31, respecdvely fSecdon 7.1. ... 

Asaro, M. F. Nakayama, I. Wilson, R. B. Formation of sterically hindered primary vicinal diamines from vicinal and geminal dinitro compounds. /. Org. Chem. 1992, 57, 778-782. Rodriguez, H. Marquez, A. Chuaqui, C. A. Gomez, B. Oxidation of mesoionic oxazolones by oxygen. Tetrahedron 1991, 47, 5681-5688. Heras, M. Ventura, M. Linden, A. Villal-gordo, J. M. Reaction of a-iminomethylene amino esters with mono- and bidentate nucleophiles a straightforward route to 2-amino-lH-5-imidazolones. Tetrahedron 2001, 57, 4371—4388. 

Aliphatic geminal dinitro compounds are obtained by oxidative nitration of mononitro compounds with silver nitrate and sodium nitrite in an alkaline medium.165... 

Vytautas G, Garver LC, Kurt B (1990) Synthesis of geminal dinitro compounds. US Patent 4,910,322, 1990... 

As a final observation of Table III, one finds that the nitro group BDE for geminal dinitro compounds, i.e., CH2(N02)2 and NH(N02)2 are only slightly weaker than the corresponding mononitro compounds. 

Radical anions of geminal nitro compounds in DMF cleave rapidly to nitrite and a radical which initiate a free radical chain in which a v/c-dinitro compound is formed [43]. Radical anions of other a-substituted nitroalkanes may cleave either the nitro group or the other substituent 1-cyano-l-nitrocyclohexane thus splits off nitrite whereas 1-nitrocyclo-hexyl p-tolyl sulfone loses p-tolylsulfinate [44]. 

A.V. Fokin, Yu. N. Studnev, L. D. Kuznetsova, Syntheses Based on (N,N-Difluoroamino)Dinitro Acetonitrile, Russ. Chem. Bull., 45(1996) 1952-1954. A.V. Fokin, Yu Studnev, A.I. Rapkin, L.D. Kuznetsova Geminal(difluoroamino) Nitro Compounds Russ. Chem. Bull., 45(1996) 2547-2550. 

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