Isonitramine

MEDINA in an acronym for MEthylene DINtrA-mine. In earlier literature it was called MEDNA (Ref 2), the latter name later used for the isomeric compd me thylenedi-isonitramine which was obtained by the action of nitric oxide on acet (Beil 1, 592) (See under MEDNA in this... 

It fonns expl heavy metal salts, which according to Urbanski, are weaker initiators than the corresponding metal salts of methylenedi-isonitramine. The decreasing order of brisance of these salts, when primed with MF, in the Pb plate test were Na, Ca, Ba, H and Pb Refs 1) T. Urbanski T, Wesolowski, Wiad-TechnUzbr 18, 28 (1932) 2) T. Urbanski,... 

In this reaction phenylhydroxylamine behaves like a secondary amine. To the class of nitrosohydroxylamines there belong also the so-called isonitramines and the compound of nitric oxide and potassium sulphite. 

The direct nitration of a primary amine to a nitramine with nitric acid or mixtures containing nitric acid is not possible due to the instability of the tautomeric isonitramine in strongly acidic solution (Equation 5.1). Secondary amines are far more stable under strongly acidic conditions and some of these can undergo electrophilic nitration with nitric acid in a dehydrating medium like acetic anhydride. 

Isonitramines are compounds having a general formula, R.N(OH).NO or likely... 

Traube s isonitramines , which are described later in this volume, are nitroso-hydroxylamines. 

Traube [15] prepared methylenedi-isonitramine, the isomer of methylenedinitramine, in the form of a sodium salt, by the action of nitric oxide on acetone, in the pres-... 

T. Urbanski, Zacharewicz and Pietrzyk [61] suggested the use of some methyl-enedi-isonitramine salts (CH2) (N202H)2 as primary explosives. 

The sodium salt of methylenedi-isonitramine was prepared by Traube [62] from acetone and nitric oxide in the presence of sodium alcoholate according to the following chain of reactions ... 

The sodium salt of methylenedi-isonitramine (II) is formed. In an aqueous solution this precipitates with the salts of heavy metals. Some of these salts (e.g. the thallium salt) have the properties of weak initiators. 

The structure of these compounds remained obscure for a long time. Traube originally assigned the structure —N—N—OH to the isonitramino group, but in further researches he found that isonitramines and the derivatives of nitrosohydro-xylamine which he prepared by the action of nitrous acid on -derivatives of hydro-xylamine were identical. He did not, however, draw from this any definite conclusions as to the structure of isonitramines in spite of the fact that by the synthesis of isonitraminoisobutyric acid, Gomberg [63] had confirmed the nitrosohydro-xylamine structure of the isonitramino group. 

Hantzsch [64] described isonitramines as compounds which have either the structure reported by Traube (I) or that of nitrosohydroxylamine (Ila) ... 

Hantzsch expressed the opinion that the active hydrogen in isonitramines is always combined with the oxygen atom whereas in nitramines it may be combined, in different tautomeric modifications, either with the nitrogen or the oxygen atom. 

However, on investigating the ultra-violet absorption spectra of methylenedi-isonitramine, R. N. Jones and Thorn [67] failed to detect a band characteristic of... 

Urbanski and Piskorz [60] found that the properties of methylenedi-isonitramine salt differ markedly from those of methylenedinitramine salt. They also established that methylenedi-isonitramine is not a tautomeric modification of methylenedinitramine. In their most recent work [70] they have confirmed the nitrosohydroxylamine structure of isonitramines by examining the infra-red absorption spectra. 

Under the influence of aqueous solutions of the water soluble salts of heavy metals the sodium salt of methylenedi-isonitramine gives precipitates of the salts of these metals. T. Urbanski, Zacharewicz and Pietrzyk [61] suggested the use of certain heavy metal salts as initiators. Particularly interesting properties were demonstrated by the thallous salt CH2(N202n)2. 

Some of the heavy metal salts of nitromethylisonitramine appear to have initiating properties, which are however considerably weakened by the presence of a nitro group. The salts of type III are therefore weaker initiators than the corresponding metal salts of methylenedi-isonitramine. 

Histrionicotoxins represent a unique structural class of alkaloids found only in dendrobatid frogs (see below). Somewhat similar hydroxy-azaspiro-undecanes, namely, sibirine, nitramine, and isonitramine, occur in certain plants of the genus Nitraria (cf. Ref. 70). 

Nitramine and isonitramine alkaloids of Nitraria spp., previously described as decahydroquinolines, are now considered to be the epimeric spiropiperidines (104 and (105) respectively (A.A. Ibragimov et al, Khim.prirod. Soedin., 1981, 623 Z. Osmanov et al, ibid, 1982, 126),... 

A recent synthesis of (+)-nitramine (275) and (-)-isonitramine (276) has been reported [611]. Resolution of an a-substituted p-ketoester with pig liver esterase was the key improvement to provide the required chiral quaternary carbon. Subsequent cyclization of the piperidine ring gave 275 and 276. In a recent synthesis of sibirine (277), a-deprotonation/alkylation of an imine gave an intermediate having the required quaternary carbon,... 

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