1,2-Nitramines

The nitramines, which have found practical application as explosives are multi-functional nitramines, usually cyclic (Fig. 7). Nitramines have been studied by many groups and multiple decomposition pathways 

N2o + CH2O + no2 + NH2CNO Fig. 8 Behren s Proposed Routes of RDX Decomposition (Ref. 61) 

We examined the thermal decomposition of a number of nitramines in dilute solution and in the melt phase. The nitramines included acyclic dialkyl mononitramines, where the dialkyls were methyl, ethyl, propyl and isopropyl cyclic mononitramines (N-nitro-pipeiidine and N-nitropyrrolidine) and cycle multifunctional nitramines (N-dinitropiperazhe l,3-dinitro-l,3-diazacyclo-pentane l,3-dinitro-l,3-diazacycbhexane RDX and HMX). For all nitramines, the predominant condensed-phase product was the nitrosamine though the amount formed depending on the nitramine and the phase of the thermolysis. The common trigger in the decompositions was N-N02 ho mo lysis, but the fate of the resultant amine radical depended on the phase. In solution the radical was stabilized sufficiently so that it resisted further decomposition and, instead, reacted with NO to form nitrosamine. In vapor or condensed phase, the amine radical underwent further reaction therefore, 

In general, compounds containing N-N02 have more positive heats of formation than those containing C-N02, and multi-cyclic compounds achieve higher density than mono-cyclic. For these reasons, the synthesis of caged nitramines is pursued, and in 1987 Nielsen patented the synthesis of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW or Cl-20) [64,65]. Like HMX, CL-20 exists in several solid polymorphs, four of which can be isolated at ambient conditions [66, 67]. CL-20 can be 

In addition to military uses, it should be noted that aromatic nitro compounds such as trifluralin (2,6-dinitro-A,A-dipropyl-4-(trifluoromethyl)aniline and dinoseb (2,4-dinitro-6-5 ec-butylphenol) 

Although the possibility of bioremediation of sites contaminated with nitrotoluene waste is clearly possible, important issues should be clearly appreciated. These include (a) additional carbon sources may be necessary to accomplish partial or complete reduction of nitro groups, (b) under aerobic conditions, dimeric azo compounds may be formed as terminal metabolites, and (c) aromatic amines may be incorporated into humic material by covalent bonding and thereby resist further degradation. 

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Nitramine, picrylmethylnitramine, 2,4,6-trinitrophenylmethyl nitramine (indicator) dissolve 0.1 g in 60 mL alcohol and dilute with water to 100 mL pH range colorless 10.8-13.0 red-brown the solution should be kept in the dark as nitramine is unstable on boiling with alkali it decomposes quickly. Fresh solutions should be prepared every few months. 

MonoalkyUiydroxylarnine hydrochlorides react with preservation of the hydroxylamine stmcture (10). Primary nitramines combine in such a way as to keep the nitramine stmcture intact. 

Polymer-based rocket propellants are generally referred to as composite propellants, and often identified by the elastomer used, eg, urethane propellants or carboxy- (CTPB) or hydroxy- (HTPB) terrninated polybutadiene propellants. The cross-linked polymers act as a viscoelastic matrix to provide mechanical strength, and as a fuel to react with the oxidizers present. Ammonium perchlorate and ammonium nitrate are the most common oxidizers used nitramines such as HMX or RDX may be added to react with the fuels and increase the impulse produced. Many other substances may be added including metallic fuels, plasticizers, stabilizers, catalysts, ballistic modifiers, and bonding agents. Typical components are Hsted in Table 1. 

Oxidizers. The characteristics of the oxidizer affect the baUistic and mechanical properties of a composite propellant as well as the processibihty. Oxidizers are selected to provide the best combination of available oxygen, high density, low heat of formation, and maximum gas volume in reaction with binders. Increases in oxidizer content increase the density, the adiabatic flame temperature, and the specific impulse of a propellant up to a maximum. The most commonly used inorganic oxidizer in both composite and nitroceUulose-based rocket propellant is ammonium perchlorate. The primary combustion products of an ammonium perchlorate propellant and a polymeric binder containing C, H, and O are CO2, H2, O2, and HCl. Ammonium nitrate has been used in slow burning propellants, and where a smokeless exhaust is requited. Nitramines such as RDX and HMX have also been used where maximum energy is essential. 

The anhydride of nitric acid, N20, reacts with 2-methyl aziridine to give the dinitrate (105). In the case of A/-substituted aziridines, the reaction stops at the stage of the nitramine nitrate prior to elimination of N2O (106). 

Nitration is defined in this article as the reaction between a nitration agent and an organic compound that results in one or more nitro (—NO2) groups becoming chemically bonded to an atom in this compound. Nitric acid is used as the nitrating agent to represent C-, 0-, and N-nitrations. O-nitrations result in esters. N-nitrations result in nitramines. 

Organic Solids A few organic compounds decompose before melting, mostly nitrogen compounds azides, diazo compounds, and nitramines. The processes are exothermic, classed as explosions, and may follow an autocatalytic law. Temperature ranges of decomposition are mostly 100 to 200°C (212 to 392°F). Only spotty results have been obtained, with no coherent pattern. The decomposition of malonic acid has been measured for both the solid and the supercooled liquid. The first-order specific rates at 126.3°C (259.3°F) were 0.00025/min for solid and 0.00207 for liquid, a ratio of 8 at II0.8°C (23I.4°F), the values were 0.000021 and 0.00047, a ratio of 39. The decomposition of oxalic acid (m.p. I89°C) obeyed a zero-order law at 130 to I70°C (266 to 338°F). 

Methyidichloroarsine Methylene glycol dinitrate Methyl ethyl ketone peroxide, >50% alpha-Methylglucoside tetranitrate alpha-Methylglycerol trinitrate Methyl nitramine (dry) metal salts of Methyl nitrate Methyl nitrite... 

Both the 4- (38) and 6-(31) nitrimines are reduced with sodium boro-hydride to the corresponding y5-nitramine derivatives, e.g., (41)], which are methylated with methyl iodide and potassium carbonate. The A -methyl derivative is reduced in modest yield to the 5a-fluoride (43) with lithium aluminum hydride. 

A rather simple derivative of imidazoimidazoline has been described as an antidepressant agent. Preparation of this compound starts with the displacement of the nitramine grouping in imidazoline derivative by phenyl ethanol amine The product of this reaction is then treated with thio-nyl chloride. The probable chloro intermediate ( ) cyclizes under the reaction conditions to afford imafen (5. ... 

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

S. Bulusu, Photochemical Studies of Secondary Nitramines. 1. Absorption Spectra of Nitramines and Photolysis of DimethyInitramine in Solution , PATR 4068 (1970) 45) S. 

The Na salt of MEDINA was fluorinated in w, the sain extd with methylene chloride, and the solv evapd to give a yellow oil whose IR spectrum showed absence of NH and the presence of NF absorption, and analysis indicated was a mixt (Ref 22). Nitramines in the presence of sulfuric acid are capable of nitrating reactive aromatic compds, but when acetanilide was treated with MEDINA in the presence of this acid, no nitroacetanilide was isolated. Instead compds indicating that the MEDINA had been fragmented and the fragments reacted with the acetanilide were isolated (Ref 12)... 

Analytical. The thin layer chromatog of MEDINA and the sepn from other expls and nitramines on thin layer plates (MEDINA spots tend to comet) are described in Ref 23... 

Goldhaven, Heats of Combustion of Some Simple Aliphatic Nitramines , NPF Memo Re-port88(Nov 1954), AD-49349 16) Anon,... 

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