Dimethyl nitramine

Wright illustrated the effectiveness of chloride-catalyzed nitration for a number of amines of different basicity. Wright showed that weakly basic amines like iminodiacetonitrile and its dimethyl and tetramethyl derivatives are all nitrated in high yield with nitric acid-acetic anhydride mixtures in the absence of chloride ion. In contrast, the slightly more basic 3,3 -iminodipropionitrile is not appreciably nitrated with acetic anhydride-nitric acid, but the inclusion of a catalytic amount of the hydrochloride salt of the amine base generates the corresponding nitramine in 71 % yield. ... 

Mannich condensations involving polyamines or polynitramines are more complex, and in the case of linear dinitramines, leads to very interesting and diverse chemistry, enabling the synthesis of many cyclic nitramine products. The reaction of methylenedinitramine (168) with various primary amines in the presence of formaldehyde leads to l,5-dinitro-l,3,5,7-tetraazacyclooctanes the 3,7-dimethyl analogue (186) is isolated when methylamine is used. ... 

Je nach den Bedingungen bei der Nitramin-Umlagerung laBt sich z.B. in konz. Schwe-felsaure/Eisessig bzw. konz. Salzsaure/Eisessig ein Verhaltnis von 2,3-Dimethyl-1-nitro-zu 3,4-Dimethyl-1-nitro-benzol von 49/51 bzw. 17/83 einstellen1. 

It was applied by Bamberger and Kirpal [35] in the preparation of dimethyl-nitramine and nitropiperidine with a rather poor yield. They used acetic anhydride as a dehydrating medium. 

Dimethyl-1,3-dinitroaminopropane, (H3C)2C(CH2NHN02)2 mw 192.18, N 29.16%. Synthesis was undertaken but not completed because of diffc in obtg 2,2"dimethyl-l,3 diaminopropane in good yields Refs 1) Beil — not found 2) A.T. Blom-quist, Certain Aliphatic Nitramines and Related Compounds , OSRD 4134(1944), 21... 

Dinitro-3/6-dimethyl-nitraniline 4,6-Dinitro-2,5-dimethylphenyl-nitramine,... 

J.M. Flournoy, Thermal Decomposition of Gaseous Dimethyl Nitramine, J. Phys. Chem., 36 (1962) 1106-1107 ibid, 1107-1108. 

N-Ethyl-N-nitro-3,5-dimethyl-2,4,6-trinitro-aniline [Ethyl-(trinitrodimethylphenyl)nitramine], (CH8)2C6(N02)3.N(N02).C2Hb mw 329.24,... 

Ethenolat 2,2-Dicyan-l-(2-dimethyl-sulfoniono-ethoxy)- Ell, 451 [(NC)2C=C(OR)2 +R2S] Nitramin, Methyl-(phenylthio-... 

Mass spectral fragmentation pattern of dimethyl-nitramine, CH3N(N02)CH3, mw 90 Instrument, CEC 21-104 Ionization Voltage 70 eV... 

Mass spectra of the important explosives RDX, HMX, TNT, TNB and Tetryl were first briefly reported by Meyer (Ref 34) and later investigated in greater detail with high resolution and labeling techniques by Bulusu et al (Ref 45). Mass spectrometric studies of the photodecomposition of labeled dimethyl-nitramine (Ref 56) and the thermal decomposition of HMX and RDX (Refs 27 31) illustrate the application of these techniques to studies of reaction mechanism and bond dissociation processes. Nitroguanidines have only recently been investigated by Beynon (Ref 35)... 

Methylnitramine decomposes explodvely in contact with concentrated sulfuric acid. If the substance is dissolved in water, and if concentrated sulfuric acid is added little by little until a considerable concentration is built up, then the decomposition proceeds more moderately, nitrous oxide is given off, and dimethyl ether (from the methyl alcohol first formed) remains dissolved in the sulfuric acid. The same production of nitrous made occurs even in the nitrometer in the presence of mercury. If methyl-nitramine and a small amoimt of phenol are dissolved together in water, and if concentrated sulfuric acid is then added little by little, a distinct yellow color shows that a trace of nitric acid has been formed. The fact that methylnitramine gives a blue color witii the diphenylamine reagent shows the same thing. 

Pyrolytic sources are trimethylamine (22), dimethylnitrosamine (16), dimethyl-nitramine (14), and tetramethyltetrazene (25, 31, 33), the pyrolyses proceeding according to the thermal analogs of Reactions 11, 12, and 13. A further probable source of these radicals is provided by the reaction between dimethylchloramine and copper-bronze in ether at 40° (19). 

We see from the experiments which have been described and from the figures that tropeolin 0, phenolphthalein, thymolphthal-ein, thymol blue, and bromphenol blue become more sensitive towards strong acids when present in alcohol-water mixtures. Nitramine, curcumin, methyl orange, dimethyl yellow, tropeolin 00, and methyl violet, on the other hand, become more alkali sensitive. 

FIGURE 6 The global minimum structure of the dimethyl-nitramine complex with methyl alcohol. The carbon atoms are gray, hydrogens—white, nitrogens—blue, and oxygens—red. (From Bukowski etal., 1999.)... 

A presentation of direct experimental evidence for the initial fast decompositions of the more powerful mihtary explosives, HMX, RDX and TNAZ, as well as of a non-explosive molecule, dimethyl nitramine (DMNA), is a topic of paper [55]. Experimental data indicate that electronic excitation, in the gas phase, of all the nitramines studied, with 248 mn, 15 nanosecond pulses from the excimer laser leads to the formation of electronically excited NO2 ( 62), resulting from the primary N - N bond scission in the electronically... 

Chardin, A., Laurence, C., Berthelot, M. and Morris, D.G. (1996) pAThb scale of dimethyl-nitramine, nitramine vinylogs and nitramidates. Bidl. Soc. Chim. Fr, 133, 389-393. 

---