- Electrical and optical properties of the nitramine group and molecular structure of some N-nitramines
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The electrical and optical properties (dipole moment, electrooptical and optical Kerr constants, molecular polarizability anisotropy, polarizability tensor, molecular refraction) of N,N-dimethylnitramine as the simplest N-NO2 derivative were studied by a set of experimental and theoretical methods with the aim to determine the components of the polarizability ellipsoid of the N-NO2 group and develop a valence-optical scheme for calculating the optical and electrooptical parameters of N-NO2 compounds. Conjugation of the p electrons of the imide nitrogen atom with the π electrons of the nitro group results in deviation of the properties of N,N-dimethylnitramine from the additive values. Comparative evaluation of the parameters of the Csp3-NO2, Csp2-NO2, and N-NO2 groups was made.
- Prezhdo,Bykova,Daszkiewicz,Halas,Iwaszkiewicz-Kostka,Prezhdo,Kyziol,Blaszczak
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- Process for Synthesizing Nitramine Compounds
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There is disclosed a process for synthesizing nitrosamine compounds. Specifically, there is disclosed a process for synthesizing N-nitropyrrolidine.
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Page/Page column 3
(2009/12/05)
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- Formation of N-nitrosamines and N-nitramines by the reaction of secondary amines peroxynitrite and other reactive nitrogen species: Comparison with nitrotyrosine formation
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Reactive nitrogen species, including nitrogen oxides (N2O3 and N2O4), peroxynitrite (ONOO-), and nitryl chloride (NO2Cl), have been implicated as causes of inflammation and cancer. We studied reactions of secondary amines with peroxynitrite and found that both N-nitrosamines and N- nitramines were formed. Morpholine was more easily nitrosated by peroxynitrite at alkaline pH than at neutral pH, whereas its nitration by peroxynitrite was optimal at pH 8.5. The yield of nitrosomorpholine in this reaction was 3 times higher than that of nitromorpholine at alkaline pH, whereas 2 times more nitromorpholine than nitrosomorpholine was formed at pH 2N·), which react with nitric oxide (·NO) or nitrogen dioxide (·NO2) to yield nitroso and nitro secondary amines, respectively. Reaction of morpholine with NO· and superoxide anion (O2·-), which were concomitantly produced from spermine NONOate and by the xanthine oxidase systems, respectively, also yielded nitromorpholine, but its yield was 2·- inhibited its formation. Reactions of morpholine with nitrite plus HOCl or nitrite plus H2O2, with or without addition of myeloperoxidase or horseradish peroxidase, also yielded nitration and nitrosation products, in yields that depended on the reactants. Tyrosine was nitrated easily by synthetic peroxynitrite, by NaNO2 plus H2O2 with myeloperoxidase, and by NaNO2 plus H2O2 under acidic conditions. Nitrated secondary amines, e.g., N-nitroproline, could be identified as specific markers for endogenous nitration mediated by reactive nitrogen species.
- Masuda, Mitsuharu,Mower, Howard F.,Pignatelli, Brigitte,Celan, Irena,Friesen, Marlin D.,Nishino, Hoyoku,Ohshima, Hiroshi
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p. 301 - 308
(2007/10/03)
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- Clean nitrations: Novel syntheses of nitramines and nitrate esters by nitrodesilylation reactions using dinitrogen pentoxide (N2O5)
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In this novel nitration method dinitrogen pentoxide (N2O5) in an inert solvent is used as the nitrating agent, thereby removing the need for strong acids as the reaction medium. The N2O5 cleaves heteroatom-silicon bonds, in silylamines and silyl ethers respectively, to yield the desired energetic groupings (nitramines or nitrate esters respectively) without liberation of acids which would occur with conventional substrates (amines or alcohols). These nitrodesilylation reactions proceed cleanly and in good yield, and the scope of the reaction is illustrated by 29 examples, some of which produce high energy compounds, notably plasticisers and an energetic polymer precursor. These reactions are therefore potentially clean nitrations for the manufacture of energetic compounds which will minimise the impact of this activity on the environment in the future.
- Millar, Ross W.,Philbin, Simon P.
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p. 4371 - 4386
(2007/10/03)
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- Reactions of Secondary Nitramines with Tributyltin Hydride and Tris(trimethylsilyl)silane
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The reactions of secondary nitramines (N-nitroamines) with tributyltin hydride or tris(trimethylsilyl)silane have been investigated under free radical conditions.Reactions of nitramines with tributyltin radicals gave mostly the denitration products (secondary amines) whilst reactions with tris(trimethylsilyl)silyl radicals afforded almost exclusively nitrosamines (N-nitrosoamines).
- Imrie, Christopher
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p. 328 - 329
(2007/10/03)
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- ELECTROPHILIC TETRAALKYLAMMONIUM NITRATE NITRATION. I. CONVENIENT NEW ANHYDROUS NITRONIUM TRIFLATE SYNTHESIS AND IN-SITU HETEROCYCLIC N-NITRATION
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Keywords: Anhydrous Nitration, Nitronium Triflate, Tetrabutylammonium Nitrate, Triflic Anhydride Reaction of tetra-n-butylammonium nitrate and triflic anhydride, CF3SO2OSO2CF3 (Tf2O), in dichloromethane (CH2Cl2) solvent at 0 degrees C, produces anhydrous nitronium nitrate, NO2OSO2CF3 (NO2OTf).Subsequent introduction of various heterocycles and their N-acetylated analogs yield N-nitrated products in 20-76 percent yield with an overall one-pot procedure.
- Adams, Christopher M.,Sharts, Clay M.,Shackelford, Scott A.
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p. 6669 - 6672
(2007/10/02)
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- A Convenient Method For N-Nitration Using Ammonium Nitrate/Trifluoroacetic Anhydride
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A mixture of ammonium nitrate and trifluoroacetic anhydride is found to be a convenient reagent for N-nitration in the synthesis of nitramines, nitramides, and nitrimides.Yields are comparable to those from conventional, but less convenient or safe, nitrating reagents.
- Suri, Suresh Chander,Chapman, Robert D.
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p. 743 - 745
(2007/10/02)
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- On the Nitro Group Transfer from 2-Nitro-4,5,6,7-tetrachloro-2H-benzotriazole and 2-Nitro-2H-phenanthrotriazole to Secondary Amines
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The synthesis of 2-nitro-4,5,6,7-tetrachloro-2H-benzotriazole 1 and of 2-nitro-2H-phenanthrotriazole 2 and their transfer of the nitro group to give 2-nitropyrrolidine 4a and 1-nitromorpholine 4b in high yields when reacted with pyrrolidine or morpholine are reported.The reaction of 1 also gives the pyrrolidinium and morpholinium salts 5a-b of 1.
- Cohen-Fernandes, Pauline,Habraken, Clarisse L.
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p. 1653 - 1656
(2007/10/02)
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- EFFECT OF THE STRUCTURE OF DIALKYLAMINES ON THE KINETICS OF THEIR REACTION WITH METHYL-N,N-DINITROAMINE
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The rate of the reaction of methyl-N,N-dinitroamine with a series of dialkylamines, which occurs through a stage of electron transfer with the formation of dialkyl-N-nitroamines and salts of methyl-N-nitroamine, was measured by a spectrophotometric method in acetonitrile at 15-45 deg C.The reaction has first order in each of the reagents.An isokinetic relationship is observed in the reaction series, β=38819 deg K.The effect of the structure of the amine on the rate of the process is described by the Swain-Scott and Taft equations.The low value of the reaction constant ρ* in the last equation (0.99-1.60) shows that the transition state of the reaction has low polarity.
- Shcherbinin, M. B.,Bazanov, A. G.,Tselinskii, I. V.,Dudyrev, A. S.
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p. 964 - 967
(2007/10/02)
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