Nitroamines

MEDNA is an acronym for MEthyleneDi-iso-NitrosAmine (erroneously called methylenedi-nitroamine in Blatt, OSRD 2014 (1944) (see MEDINA... 

Nitroaminocompounds or Nitroamines. Compds containing both —N02 and —NH2 radicals attached to different C atoms, eg, nitroaniline, 02N.C6H4.NH2, etc. Nitroamines can be prepd either by the nitration of amines, or by partial reduction of nitrocompounds contg several —N02 groups. Another method is to treat a chloronitrocompound with ammonia, as in the prepn of dinitroaniiine... 

Nitroamines differ from Nitramines in that the latter contain either —NH.N02 or =N.NOa radicals, each attached to one C atom... 

N-Nitro substituted aromatic amines (XXXII) readily undergo rearrangement in the presence of mineral acids or Lewis acids in a variety of solvents and at temperatures around room temperature to give mainly ortho (XXXIII) but also in many cases significant amounts of the para (XXXIV) nitroamine. The reaction... 

White et al.1A have obtained similar kinetic results for the acid-catalysed rearrangement of N-nitro-N-methylaniline, i.e. a first-order dependence on the nitroamine with a linear H0 plot of slope 1.19 for phosphoric acid, and a deuterium solvent isotope effect of about three, although the results have only been presented in preliminary form. Further, an excellent Hammett a+ correlation was claimed for thirteen para substituted nitroamines which gave a p value of —3.9. Since it is expected that the rate coefficients would correlate with a (rather than different basicities of the amines, the a+ correlation implies that the amino nitrogen is electron-deficient in the transition state,... 

The aza-Henry reaction is the nucleophilic addition of nitroalkanes to imines to give nitroamine derivatives. This reaction was also studied with metal-based catalysts [164]. 

The nitroamine is decomposed explosively by cone, sulfuric acid. 

The crude product tends to explode spontaneously on storage, though the triple-distilled material appears stable on prolonged storage. Generally, such nitroamines are unstable and explode at 75°C or above. 

This is the structure assigned by Chem. Abs. to the claimed benzotriazolium nitroimidate below. The editor suspects they are right and that the nitroamine... 

It is the purpose of the series to review the field of organic nitro chemistry in its broadest sense by including structurally related classes of compounds such as nitroamines, nitrates, nitrones, and nitrile oxides. It is intended that the contributors, who are active investigators in various facets of the field, will provide a concise presentation of recent advances that have generated a renaissance in nitro chemistry research. 

Scheme 16 are easily distinguished by the different products obtained, and by the breaks in the LFER plots of the log ko values against mechanism changes.287 The O-protonation mechanism of Scheme 16 is preferred over the more obvious JV-protonation one on the basis of the observed m values.287 The further decomposition of the first-formed benzamide, benzene-sulfonamide and jV-nitroamine reaction products takes place as previously discussed. 

Stockbruegger RW, Cotton PB, Eugenides N, Bartholomew BA, Hill MJ, Walters CL Intragastric nitrites, nitroamines, and bacterial overgrowth during cimetidine treatment. Gut 1982 23 1048-1054. 

High selectivity is observed, and in aromatic compounds other substituents (C02R, OR, CN, halide) are not affected. Dinitro aromatics could be sequentially hydrogenated to nitroamines and diamines (105). [Some ruthenium and iron carbonyls were less effective (104)]. 

Silyl Nitronates in the Mannich Reaction The Mannich reaction with SENAs (Scheme 3.194) was also modified (459). This reaction in nonpolar solvents produced previously unavailable 3-nitroamines (331), which are unstable in water and other protic solvents. 

Similar features were found for N, C -coupling reactions of silyl derivatives of N-nitroamines (473a,b) and BENA (434a) (Scheme 3.252) (501). 

---