- 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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- Nitrolysis of syn,syn-2,4,6-tris-(n-propyl)-hexahydro-1,3,5-tripropionyl-s-triazine
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Nitrolysis of syn,syn-2,4,6-tris-(n-propyl)-hexahydro-1,3,5-tripropionyl-s-triazine (3) with 1,1,1-trifluoroacetyl nitrate (TFAN) generated in situ from 1,1,1-trifluoroacetic anhydride and nitric acid in nitromethane gave mononitramine, dinitramine and trinitramine products depending on reaction duration and concentration of TFAN. Each of the three new nitramine products was purified and characterized by multi-nuclear magnetic resonance spectroscopy. An X-ray structure for syn,syn-2,4,6-tris-(n-propyl)-hexahydro-1,3,5-trinitro-s-triazine (syn,syn–10) is reported. The isomer syn,anti–3 did not yield analogous nitramine products by these nitrolysis conditions.
- Davis, Matthew C.,Imler, Gregory H.
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- 15N STUDIES OF THE MECHANISMS OF NITRATOIN OF HEXAMETHYLENETETRAMINE AND 3,7-DIACETYL-1,2,5,7-TETRAAZABICYCLONONANE
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Mechanistic studies of the nitration of hexamethylenetetramine (1) and some derivatives are reported and are compared with acetylation reactions.Nitration reactions, with nitric acid, were carried out using mixtures of - and -compounds and the destination of the nitrogen-isotopes in the products was determined mass spectrometrically.The results show that in nitration of (1) to give 3,7-dinitro-1,3,5,7-tetraazabicyclononane (DPT) extensive ring cleavage occurs to give species containing single amino-nitrogen fragments.Howover the nitration of 3,7-diacetyl- 1,3,5,7-tetraazabicyclononane to 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DADN) involves selective cleavage of the methylene bridge.A synthesis of DADN by acetolysis of DPT is reported.
- Crampton, Michael R.,Jones, Michael,Scranage, John K.,Golding, Peter
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- Reactions of amidosulfuric acid salts with formaldehyde
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Potassium amidosulfate reacts with formaldehyde at pH 7-12 to afford a mixture of dipotassium 4-hydroxy-1,3-diazabutane-1,3-disulfonate hydrate and tripotassium 6-hydroxy-1,3,5-triazahexane-1,3,5-trisulfonate HO(CH2NSO3K)n·H2O (n = 2, 3). The reaction of the same compounds at pH 1-3 gives diammonium 1,3,5,7-tetraazabicyclo[3.3.1]nonane-3,7-disulfonic acid sulfate dihydrate.
- Lyushnina,Bryukhanov,Turkina,Malakhov,Golod
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- An efficient and solvent-free method to synthesize HMX by nitrolysis of DPT catalyzed by reusable solid acid catalysts
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Direct nitrolysis of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane (DPT) is a feasible way to synthesize HMX, which is one of the most powerful explosives. A new nitrolysis process involving the use of nitric acid and various solid acid catalysts such as silica sulfuric acid, heteropoly acids, and metal nitrates was used as an effective and safe nitrating agents for the nitration of DPT to HMX under mild and heterogeneous conditions with good yields. In order to optimize the process, the reactions were carried out with a varying amount of catalysts and also the catalysts were efficiently recovered.
- Shaghayeghi Toosi, Foad,Jadidoleslami, Mahdi
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- Investigation of the effect of metallic lewis acid on the nitrolysis of [3,7-diacetyl-1,3,5,7-tetraazabicyclo(3.3.1)-nonane] and hexamine
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The effect of metallic ions on the nitrolysis of DAPT [3,7-diacetyl-1,3,5, 7-tetraazabicyclo(3.3.1)nonane] and HA (hexamine) was investigated by experimental and theoretical approaches. The combinatorial reagent, M(NO -3)n/Ac2/NH4NO 3 (M=Mg2+, Cu2+, Pb2+, Bi 3+, Fe3+ and Zr4+), was found to be efficient in the experiment of the nitrolysis of DAPT. A key intermediate during the nitrolysis of DAPT was detected by 1H NMR. The formation mechanism of the intermediate was proposed and analyzed. Some discrepant results for the nitrolysis of DAPT and HA catalyzed by different metallic nitrates were explained based on hard-soft and acid-base principle and stabilized energy of ion-complex. From the latter point of view, some cations with high polarizable ligands, e.g., OSO2CF3-, (CF3SO 2)2N-, and (C4F9SO 2)2N-, can increase the yields. Two newly designed catalysts, Cu[(CF3SO2)2N]2 and Cu[(C4F9SO2)2N]2, were tested to be highly efficient. Copyright
- Shi, Liangwei,Yu, Menglong,Zhang, Yazhu,Qin, Guangming,Lue, Jian,Zhao, Gang
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- Synthesis and characterization of guanidinium difluoroiodate, [C(NH 2)3]+[IF2O2]- and its evaluation as an ingredient in agent defeat weapons
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Ammonium and guanidinium difluoroiodate(V), [NH4] +[IF2O2]- (1a) and [C(NH 2)3]+[IF2O2]- (1b), and diazidoglyoxime, [N3C=N-OH]2 (2) were synthesized and the molecular structures in the solid state of 1b and 2 were elucidated by single-crystal X-ray diffraction. 1b: P1, a = 6.6890(5), b = 10.2880(6), c = 10.30.92(8) A, α = 105.447(6), β = 108.568(7), γ = 91.051(5)°, V = 644.08(8) A3, P = 2.650 g·cm-3; 2: P21/n, a = 4.4211(3), b = 13.7797(9), c = 4.9750(3) A, β = 98.735(6), V = 299.57(3) A3, P = 1.886 g·cm-3. The suitability of compounds 1a and 1b as active ingredients for agent defeat weapons (ADW) with biocidal activity has been shown in detonation tests using geobacillus stearothermophilus spores. In addition, a complete energetic characterization of the promising primary explosive 2 is given.
- Fischer, Dennis,Klapoetke, Thomas M.,Stierstorfer, Joerg
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- Application of [PVI-SO3H]NO3as a novel polymeric nitrating agent with ionic tags in preparation of high-energetic materials
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In this paper, poly(vinyl imidazole) sulfonic acid nitrate [PVI-SO3H]NO3was synthesized and fully characterized. Then, [PVI-SO3H]NO3was applied for the preparation of energetic materials such as 1,1-diamino-2,2-dinitroethene (FOX-7), pentaerythritol tetranitrate (PETN), 1,3,5-trinitro-1,3,5-triazinane (RDX) and trinitrotoluene (TNT). The major advantages of the presented methodology are mild, facile workup, high yields and short reaction times. [PVI-SO3H]NO3is a suitable nitrating agent forin situgeneration of NO2and without using any co-catalysts of the described nitrating reagent.
- Sepehrmansourie, Hassan,Zarei, Mahmoud,Zolfigol, Mohammad Ali,Mehrzad, Amin,Hafizi-Atabak, Hamid Reza
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p. 8367 - 8374
(2021/03/03)
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- Novel Method for Directly Nitration of OH-, SH-and NHR-Functions in Organic Molecules by Means of in Situ Generated Carbonic Acid Dinitrate
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The invention relates to a nitration method having the following principles: a phosgene species is converted with two equivalent silver nitrates into a double-mixed anhydride of carbonic acid and nitric acid, known here as carbonic acid dinitrate (I). Said operation is carried out in situ, and the formed dinitrate decomposes spontaneously. In addition to carbon dioxide, nitrate ions and nitronium ions are formed, said ions comprising electrophiles which are necessary for nitration. The solution which is used is acetonitrile, and is insignificant if the alcohol species is dissolved or suspended. The necessary equivalent silver nitrates are introduced into the system and optionally heated or cooled to the desired temperature. Subsequently, the acid chloride is introduced slowly, drop by drop or slowly little by little. Phosgene, diphosgene, triphosgene and chloroformic acid ester can be used as carbonic acid dichloride and monochloride, and their thiocarbonic acid analogues. A brown colouration and precipitated silver chloride display the formation of the carbonic acid reactants, said brown colouration rapidly discolouring due to an immediate reaction of the nitronium ions with the substrate with is to be nitrated. Towards the end of the addition of phosgene, the brown colouration remains for longer and longer until it no longer disappears. Then, it is stirred for another hour at room temperature. In the event of high acid-sensitive educts, non-nucleophilic nitrogen bases such as DBU can be added to the system in order to intercept the formation of nitric acid.
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Page/Page column 3
(2012/09/22)
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- Synthesis and nitration of condensation products of sulfamates with aliphatic amines and formaldehyde
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A method for the synthesis of 5-alkyl-1,3-dinitro-1,3,5-triazacyclohexanes and linear polynitramines was proposed. It includes the reaction of aliphatic amines with sulfamates and formaldehyde and nitration of the reaction products. The yield and composition of nitramino derivatives depend on the conditions of the condensation and nitration.
- Tartakovsky,Ermakov,Sigai,Vinogradov
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p. 1082 - 1085
(2007/10/03)
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- Kinetic Studies of the pH Dependence of the Decomposition of 3,7-Dinitro-1,3,5,7-tetra-azabicyclononane (DPT) and Related Compounds
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Kinetic studies are reported of the pH-dependence of the decompostition of 3,7-dinitro-1,3,5,7-tetra-azabicyclononane (DPT) in aqueous media.For comparison, data were also obtained for reaction of methylenedinitroamine (MDNA) and nitramide (NH2NO2) which are potential intermediates on the reaction pathway of DPT.Our results, while not providing a complete description of the decomposition of DPT, show that at all acidities two stages are observed.The first stage, k1, involves catalysis by protons and hydroxide ions and it is suggested that reaction occours via a low-concentration, ring-opened structure which is in equilibrium with DPT.In acidic solution an intermediate, (A), is observed which is identified as nitramide while in basic solution a different intermediate (B) is formed.MDNA is shown not to be an intermediate in the DPT reaction since its rate of decomposition is too slow.
- Cooney, Aidan P.,Crampton, Michael R.,Scranage, John K.,Golding, Peter
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- Nitration of the products from condensation of monoethanolamine and formaldehyde in the presence of ammonium nitrate
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The nitration of the products from the condensation of monoethanolamine with formaldehyde by nitric and acetic anhydride in the presence of ammonium nitrate was investigated.In both cases the main nitration product is 1-acetoxy-8-nitroxy-2,4,6-trinitro-2,4,6-triazaoctane.The same compound is formed during the nitration of a mixture of urotropine with monoethanolamine or its dinitrate by nitric acid and acetic anhydride.
- Gafarov, A. M.,Punegova, L. N.,Marchenko, G. A.,Novikov, S. S.
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p. 623 - 625
(2007/10/02)
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- NEW METHOD FOR THE PREPARATION & PURIFICATION OF CYCLOTRIMETHYLENE TRINITRAMINE (RDX).
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A simple three-feed four-stage method has been developed for the preparation of cyclotrimethylene trinitramine at 46 plus or minus 3C. Hexamine is nitrated in the presence of acetic acid-acetic anhydride using ammonium nitrate-nitric acid (10:10) mixture at 46 plus or minus 3C with 15% boron trifluoride as the catalyst. The effect of composition of the ammonium nitrate-nitric acid mixtures used and of varying the duration of addition of the reactants on the yield has also been studied.
- Singh,Kujur,Bhatia,Gadhikar
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p. 260 - 261
(2007/10/05)
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