Aliphatic nitramino alcohols and their derivatives

Abstract

The methods of preparation and reactivity of aliphatic nitramino alcohols as well as their ethers and esters, which are promising intermediates in the synthesis of aliphatic nitramines used as the components of gunpowder and fuel compositions, are considered.

New Takes on Nitrate Ester Chemistry: Salts with Oxygen‐Rich Ammonium Cations

“…In the TGA studies, N-(2-nitroxyethyl)-N,N,N-trimethyl-ammonium (1) nitrate and N,Nbis(2-nitroxyethyl)-N,N-dimethylammonium (3) nitrate were very stable, losing less than 0.1 % mass per day in isother-mal heating experiments at both 75 8C and 100 8C (see Table 1). N-(2,3-dinitroxypropyl)-N-(2-nitroxyethyl)-N,N-dimethylammonium (7) nitrate and N,N,N-tris(2-nitroxyethyl)-Nmethyl ammonium (5) nitrate, on the other hand, exhibited high mass losses at 75 8C. Initial small scale safety testing yielded impact and friction values for the salts that were between those of PETN and RDX.…”

“…N-(2-Nitroxyethyl)-N,N,N-trimethylammonium (1) nitrate, whose DG r (298) was determined to be À38 kJ mol À1 , did not exhibit significant mass loss after 24 h at 100 8C and had a DSC decomposition onset > 150 8C. The positive DG r (298) values calculated for N,N-bis(2-nitroxyethyl)-N,N-dimethylammonium (3), N,N,N-tris(2-nitroxyethyl)-N-methylammonium (5), and N-(2,3-dinitroxypropyl)-N-(2-nitroxyethyl)-N,N-dimethylammonium (7) indicate that they are endothermic compounds. However, neither N,N-bis(2-nitroxyethyl)-N,N-dimethylammonium (3) nitrate nor N-(2,3-dinitroxypropyl)-N-(2nitroxyethyl)-N,N-dimethylammonium (7) were observed to decompose after many months of storage at ambient temperature.…”

“…The positive DG r (298) values calculated for N,N-bis(2-nitroxyethyl)-N,N-dimethylammonium (3), N,N,N-tris(2-nitroxyethyl)-N-methylammonium (5), and N-(2,3-dinitroxypropyl)-N-(2-nitroxyethyl)-N,N-dimethylammonium (7) indicate that they are endothermic compounds. However, neither N,N-bis(2-nitroxyethyl)-N,N-dimethylammonium (3) nitrate nor N-(2,3-dinitroxypropyl)-N-(2nitroxyethyl)-N,N-dimethylammonium (7) were observed to decompose after many months of storage at ambient temperature. This suggests that there are kinetic barriers to their decomposition that, in contrast to salts with acidic protons, are not readily surmounted at temperatures near 25 8C.…”

“…In the last decade, there has been a resurgence of interest in energetic salts/ionic liquids as ingredients for propellants and explosives. New materials have been created from a wide variety of platforms, with charge delocalized, asymmetric cations paired with oxygen rich nitrate, dinitramide, perchlorate, 3-nitro-1,2,4-triazol-5-one, nitroformate, 3,5-dinitro-1,2,4-triazolate, and even nitrotetrazole N-oxide anions being among those synthesized [1][2][3][4][5][6][7][8][9][10]. Most efforts have focused on designing and constructing cations with aza-heterocycles because they tend to have high densities, stabilizing charge delocalization, endothermic properties, and resistance to oxidation [11][12][13][14][15][16][17][18][19][20].…”

“…The study reported herein provides property information for N-(2-nitroxyethyl)-N,N,N-trimethylammonium (1) nitrate, N,N-bis(2-nitroxyethyl)-N,N-dimethylammonium (3) nitrate, N,N,N-tris(2-nitroxyethyl)-N-methylammonium (5) nitrate, and N-(2,3-dinitroxypropyl)-N-(2-nitroxyethyl)-N,N-dimethylammonium (7) nitrate. Compared to similar neutral nitrate esters, they are more hydrolytically and thermally stable, and have reduced sensitivities to impact and friction.…”