Nitramine structure

Secondary amines give only a monosubstituted product. Both of these reactions are thermally reversible. The product with ammonia (3,3, 3"-nitrilotrispropionamide [2664-61-1] C9HlgN403) (5) is frequently found in crystalline acrylamide as a minor impurity and affects the free-radical polymerization. An extensive study (8) has determined the structural requirements of the amines to form thermally reversible products. Unsymmetrical dialkyl hydrazines add through the unsubstituted nitrogen in basic medium and through the substituted nitrogen in acidic medium (9)). AlonoalkyHiydroxylamine hydrochlorides react with preservation of the hydroxylamine structure (10). Primary nitramines combine in such a way as to keep the nitramine structure intact. 

Monoalkylhydroxylamine hydrochlorides react with preservation of the hydroxyl amine structure (10). Primary nitramines combine in such a way as to keep the nitramine structure intact. 

Scholl et al (Refs 3 4) prepared the same compds by treating ketoximes (such as pina-colone) with nitrogen tetroxide, but he assigned them the structure R2C=N-N02 and called them nitrimines. One of the compds described by him in Ref 4, p 27 is a weak expl. It is the Ag salt of pinacolone-nitraminic acid which puffs off on rapid heating (this compd described below under List of Nitrimines ). Further work on... 

Delpeyroux and coworkers16 have developed a set of molecular mechanics parameters for nitramines (R—N—NO2) for the EMO program and used it in conjunction with MM2-85 parameters to calculate the structures of 1,4-dinitro-glycoluryl (8), 1,3-dinitro-4,6-diacetylglycoluryl (9) and 2,5,7,9-tetranitro-tetraazabicyclo(4.3.0)nonanone (10). The complete parameter list for the nitramine functionality is provided in Reference 16 but the parameterization procedure is not discussed. 

The crystalline structure of 2-nitroguanidine had already been previously studied by Bryden and coworkers1 (Ref. 29 therein). They there report the existence, but not the position, of hydrogen bonds, which was instead rendered possible through the use of the neutron powder diffraction method5. The skeleton backbone of this molecule consisting of a central C atom and four N atoms is almost coplanar. Both nitramine groups are essentially on the plane of the molecular skeleton. 

Four nitrosamines, seven nitramines, three nitroesters and the explosives Semtex 10 and Composition B have been investigated by TGA. Linear dependence was confirmed between the position of the TGA onsets, as defined in the sense of Perkin-Elmer s TGA-7 standard program, and the samples weights. The slope of this dependence is closely related to the thermal reactivity and molecular structure. The intercept values of the dependence correlate with the autoignition temperatures and with the critical temperatures of the studied compounds, without any clear influence from molecular structure. Results show that Semtex 10 exhibits approximately the same thermostability as its active component pentaerythrityl tetranitrate (PETN, 274). Results also show that TGA data for Composition B do not correlate with analogous data for pure nitramines564. 

The chemical structures of some common mifttary explosives are shown in Figure 1. These include the nitrate esters such as nitrocellulose (NC), NG, EGDN, and (PETN) nitroarenes such as trinitrotoluene (TNT, CH3—C6H2(N02)3), picric acid (HO—C5H2(N02)3), and 2,4,6-trinitrophenylmethylnitramine (tetryl) and nitramines such as RDX (C3H6N6O6), HMX (C4H8N8O8), and hexanitrohexa-azaisowurtzitane (CL— 20). Of these, only CL— 20 is new , that is, less than 50 years old [3]. Mixtures of oxidizers and fuels, such as AN and FO (called ANFO), are also secondary explosives. 

The A-nitration of the furazan-based heterocycle (29) has been reported. The corresponding tetranitramine (30) is an unstable substance, but obtained on treating (29) with either trifluoroacetic anhydride (TFAA) in nitric acid or dinitrogen pentoxide in nitric acid. In this case the furazan rings stabilize the 1,4,5,8-tetraazadecalin structure and further reduce the basicity of the amidine amino groups. A number of other furazan and nitrogen-rich nitramines... 

Nitramine-nitrates of general structure (133) are known as NENAs and are conveniently prepared from the nitrative cleavage of A-alkylaziridines " with dinitrogen pentoxide or from the direct nitration of the corresponding aminoalcohols. These compounds find use as energetic plastisizers in explosive and propellant formulations Bu-NENA (R = n-Bu) is a component of some LOVA (low vulnerability ammunition) propellants. ... 

Zhitomirskaya, N. G., N.T. Erernko, N.l. Golovina, and L. O. Atovmyan. 1987. Structural and electronic parameters of some cyclic nitramines. Bull. Academy Science USSR, Division Chemical Science 36 525-29. 

Nitroguanidine (NQ) is a nitramine compound containing one N-NOj group in its molecular structure. In contrast to cyclic nitramines such as HMX and RDX, its density is low and its heat of explosion is also comparatively low. However, the Mg of its combustion products is low because of the high mass fraction of hydrogen contained within the molecule. Incorporating NQ particles into a double-base propellant forms a composite propellant termed a triple-base propellant, as used in guns. 

Triple-base propellants are made by the addition of crystalUne nitroguanidine (NQ) to double-base propellants, similar to the way in which nitramine is added to CMDB propellants as described in the preceding section. Since NQ has a relatively high mole fraction of hydrogen within its molecular structure, the molecular mass of the combustion products becomes low even though the flame temperature is reduced. Table 4.13 shows the chemical composition, adiabatic flame temperature, and thermodynamic energy,/ as defined in Eq. (1.84), of a triple-base propellant at 10 MPa (NC 12.6% N). 

The combustion wave structure of RDX composite propellants is homogeneous and the temperature in the solid phase and in the gas phase increases relatively smoothly as compared with AP composite propellants. The temperature increases rapidly on and just above the burning surface (in the dark zone near the burning surface) and so the temperature gradient at the burning surface is high. The temperature in the dark zone increases slowly. However, the temperature increases rapidly once more at the luminous flame front. The combustion wave structure of RDX and HMX composite propellants composed of nitramines and hydrocarbon polymers is thus very similar to that of double-base propellants composed of nitrate esters.[1 1... 

The burning surface of an HMX propellant only becomes covered with carbonaceous materials when the propellant is catalyzed with both LiF and C. This surface structure is similar to the burning surface of an HMX propellant catalyzed with a lead compound and C. The results indicate that the combushon mode and the action of LiF are the same as those resulting from the use of lead compounds to produce super-rate and plateau burning of nitramine propellants. 

HMX and RDX are energetic materials that produce high-temperature combustion products at about 3000 K. If one assumes that the combustion products at high temperature are HjO, Nj, and CO, rather than COj, both nitramines are considered to be stoichiometricaUy balanced materials and no excess oxidizer or fuel fragments are formed. When HMX or RDX particles are mixed with a polymeric hydrocarbon, a nitramine pyrolant is formed. Each nitramine particle is surrounded by the polymer and hence the physical structure is heterogeneous, similar to that of an AP composite pyrolant... 

Nitroxyethyl Nitramine Plasticizers Nitroxy ethyl nitramine (NENA) plasticizers are a new family of energetic plasticizers which have emerged recently. These are effective plasticizers in energetic formulations, particularly in nitrocellulosic systems. NENAs contain both nitrate ester and nitramine functionalities and possess the general structure RN (N02).CH2.CH2.0N02 where R is methyl, ethyl, propyl, isopropyl, butyl and pentyl. 

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