- Trinitromethane
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The structure of cubic trinitromethane, CHN3O6, has been determined at 200 K.Warning: a severe explosion has been reported during the preparation of a sodium trinitromethanide salt.
- Schoedel, Holger,Dienelt, Ruediger,Bock, Hans
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- THE MECHANISM OF AROMATIC NITRATION BY TETRANITROMETHANE
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Aromatic nitrations by tetranitromethane are shown to be photochemically initiated and are believed to proceed via trinitromethyl nitrite.
- Isaacs, Neil S.,Abed, Obaid Hassan
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- Formamidinium Nitroformate: An Insensitive RDX Alternative
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Five nitroformate (trinitromethanide) salts featuring nitrogen-containing cations were prepared. The salts were characterized by multinuclear NMR, IR, and Raman spectroscopy, single-crystal X-ray analysis, differential thermal analysis, and friction and impact sensitivity testing. These experimental data are supplemented with thermochemical calculations using the Gaussian-4 composite method, and the performance of these energetic materials was calculated based on the Chapman-Jouguet thermodynamic detonation theory. Out of the five compounds studied by us, the formamidinium salt, [CH(NH2)2]+[C(NO2)3]-, is most interesting. Its performance matches that of RDX (research department explosive, cyclotrimethylenetrinitramine), while it is much less sensitive to impact and friction and, therefore, might be an excellent, less sensitive replacement for RDX.
- Baxter, Amanda F.,Martin, Igor,Christe, Karl O.,Haiges, Ralf
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- Synthesis of Neutral and Charged Trinitromethyl Borohydrides and Their Complexes
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We propose several simple and effective methods for the synthesis of previously unknown trinitromethyl borohydrides and their complexes with simple cyclic ethers and aromatic nitrogen- containing heterocycles, whereas acyclic ethers did not form such complexes. The data from physicochemical investigations showed that these unique compounds contain directly linked oxidizing and reducing fragments. Some transformations of trinitromethylborane complexes were demonstrated, which can occur by cleavage of all types of bonds formed by boron atom in the starting compounds.
- Shitov,Tartakovskii,Ioffe
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p. 1647 - 1657
(2015/02/05)
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- Derivatives of 5-nitro-1,2,3-2H-triazole-high performance energetic materials
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The energetic derivatives of 5-nitro-1,2,3-2H-triazole, which include 2-(methyl or amino)-4-(nitramino, azido, or nitro)-5-nitro-1,2,3-2H-triazoles, were prepared in moderate yields, and confirmed with NMR and IR spectroscopy, and elemental analysis. Their key properties, viz., melting and decomposition temperatures, densities, detonation pressures and velocities, and impact sensitivities, were measured or calculated. Among the new derivatives, 2-amino-4,5-dinitro-1,2,3-2H-triazole exhibits properties (Tm, 94 °C; Td, 190 °C; ρ, 1.83 g cm-3; P, 36.2 Gpa, vD, 8843 m s-1, IS, 24 J), comparable with RDX (T m, 205 °C; Td, 230 °C; ρ, 1.80 g cm -3; P, 35.0 Gpa, vD, 8762 m s-1, IS, 7.5 J), and may have potential as a high-performance energetic material.
- Zhang, Yanqiang,Parrish, Damon A.,Shreeve, Jean'Ne M.
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p. 585 - 593
(2013/07/04)
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- α-nitration of ketones via enol silyl ethers. Radical cations as reactive intermediates in thermal and photochemical processes
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Highly colored (red) solutions of various enol silyl ethers and tetranitromethane (TNM) are readily bleached to afford good yields of α-nitro ketones in the dark at room temperature or below. Spectral analysis show the red colors to be associated with the intermolecular 1:1 electron donor-acceptor (EDA) complexes between the enol silyl ether and TNM. The formation of similar vividly colored EDA complexes with other electron acceptors (such as chloranil, tetracyanobenzene, tetracyanoquinodimethane, etc.) readily establish enol silyl ethers to be excellent electron donors. The deliberate irradiation of the diagnostic (red) charge-transfer absorption bands of the EDA complexes of enol silyl ethers and TNM at -40 °C affords directly the same α-nitro ketones, under conditions in which the thermal reaction is too slow to compete. A common pathway is discussed in which the electron transfer from the enol silyl ether (ESE) to TNM results in the radical ion triad [ESE?+, NO2?, C(NO2)3-]. A subsequent fast homolytic coupling of the cation radical of the enol silyl ether with NO2? leads to the α-nitro ketones. The use of time-resolved spectroscopy and the disparate behavior of theisomeric enol silyl ethers of α- and β-tetralones as well as of 2-methylcyclohexanone strongly support cation radicals (ESE?+) as the critical intermediate in thermal and photoinduced electron-transfer as described in Schemes 1 and 2, respectively.
- Rathore, Rajendra,Kochi, Jay K.
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p. 627 - 639
(2007/10/03)
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- Photochemical Nitration by Tetranitromethane. VIII. Isolation, X-Ray Structural Analysis and Chemical Properties of a Vicinal Nitro/trinitromethyl Adduct from Fluoranthene
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The photolysis of a dichloromethane solution of fluoranthene and tetranitromethane by light with cut-off at λ less than 435 nm gave a mixture of nitro/trinitromethyl adducts (ca. 10percent) and nitrofluoranthenes (ca. 60percent).One of the adducts could be isolated and proved to be a vicinal one trans-2-nitro-3-trinitromethyl-2,3-dihydrofluoranthene (1), as demonstrated by in X-ray crystallographic analysis.Adducts were formed in acetonitrile too, but the adduct yield was smaller.Adduct 1 was stable for many days in dichloromethane but slowly (τ1/2 about 19 h) eliminated nitroform to give 2-nitrofluoranthene in acetonitrile, whereas added hindered or unhindered bases strongly accelerated the reaction in both dichloromethane and acetonitrile.Under GLC condition 1 analyzed as 2-nitrofluoranthene.The spin adduct of trinitromethyl radical and α-phenyl-N-tert-butylnitrone (PBN) was formed and detected by EPR spectroscopy in low concentration and persisted for a long time when 1 and PBN were kept in dichloromethane solution.
- Eberson, Lennart,Hartshorn, Michael P.,Radner, Finn,Robinson, Ward
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p. 410 - 415
(2007/10/02)
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- The Addition-Elimination Mechanism in the Photonitration of Naphthalene by Tetranitromethane
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By the isolation and kinetic studies of an adduct (cis-1,4-dihydro-1-nitro-4-trinitromethylnaphthalene) from the photolysis of naphthalene-tetranitromethane in dichloromethane or acetonitrile, it is shown that the route to nitro substitution products proceeds via addition-elimination, the latter step being either thermal or base-catalysed.
- Eberson, Lennart,Hartshorn, Michael P.,Radner, Finn,Robinson, Ward T.
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p. 566 - 567
(2007/10/02)
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- REACTION OF α-POLYNITROALKYL DERIVATIVES OF SULFUR AND SELENUM WITH HYDROGEN HALIDES AND HALIDE IONS
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Hydrogen halides ( HCl and HF) react with α-polynitroalkylsulfides and α-polynitroalkylselenides as elctrophilic or as nucleophilic reagents depending on the conditions, forming accordingly products of electrophilic or nucleophilic substitution at the α-carbon atom.In contrast to this, halogen ions (Cl-, F-) always bond to the α-carbon.The use of dipolar aprotic solvents ad activators ( Lewis acids or strong mineral acids) facilitates the formation of products of nucleophilic substitution at the α-carbon.
- Erashko, V. I.,Baryshnikov, A. T.,Zubanova, N. I.,Tishaninova, A. A.
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p. 1939 - 1944
(2007/10/02)
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- CHEMICAL GENERATION OF TRINITROMETHYL RADICALS IN THE REACTION OF XENON DIFLUORIDE WITH THE NITROFORM ANION
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In the reaction between the trinitromethane potassium salt and xenon difluoride in acetonitrile in the presence of benzene and THF the trinitromethyl derivatives of benzene and THF are formed in addition to the fluorination products.This indicates that the reaction takes place through the formation of trinitromethyl radicals.
- Tselinskii, I. V.,Mel'nikov, A. A.,Trubitsin, A. E.
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p. 619 - 622
(2007/10/02)
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- REACTION OF DINITROMETHYL COMPOUNDS WITH XENON DIFLUORIDE IN VARIOUS SOLVENTS
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The products from the reaction of xenon difluoride with the potassium salts of a series of dinitromethyl compounds ( dinitromethane, trinitromethane, 1,1-dinitroethane, phenyldinitromethane) in methylene chloride, carbon tetrachloride, and acetonitrile were investigated.On the basis of the data from analysis by GLC and UV spectroscopy it was found that in most cases the reaction takes place with the participation of solvent molecules.The proposed reaction mechanism includes a stage of one-electron oxidation of the anion of the dinitromethyl compound by the XeF2 molecule to a dinitromethyl radical.
- Tselinskii, I. V.,Mel'nikov, A. A.,Trubitsin, A. E.
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p. 1485 - 1487
(2007/10/02)
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- I. Photochemical nitration of methoxybenzenes from charge-transfer complexes with tetranitromethane
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The direct irradiation of the charge-transfer (CT) absorption band of the 1/1 electron donor-acceptor complexes of dimethoxybenzenes with tetranitromethane leads to aromatic nitration with a high quantum yield.The analogous methoxytoluenes under the same photochemical conditions are converted in equally high yields to products of aromatic trinitromethylation.This dichotomy with different methoxybenzenes (ArH) is discussed within the context of the common reactive intermediates derived from the CT excitation of the complex.The subsequent interactions of the geminate fragments, i.e., +., C(NO2)3-, .NO2>, by radical-pair and ion-pair annihilation represent a unifying mechanism for the CT photochemistry leading to aromatic nitration and trinitromethylation.
- Sankararaman, S.,Kochi, J. K.
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p. 278 - 285
(2007/10/02)
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- Mechanism of the Hydrolysis of Xenon Difluoride
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The hydrolysis of XeF2 has been studied, and it has been shown that two intermediate species are formed.The first (XeO) is an oxidising agent which interacts with H2O to form the second intermediate (H2O2).The reactivity of XeO has been studied.The oxidation of H2O2 by xenon difluoride has been shown to involve a radical chain mechanism in which the interaction between XeO and H2O2 provides the initiation stage.Mechanisms for the oxidation of H2O2 and for hydrolysis of XeF2 are proposed, and the rate constants of the suggested reactions are determined.
- Goncharov, A. A.,Kozlov, Yu. N.,Purmal', A. P.
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p. 927 - 936
(2007/10/02)
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- KINETICS AND MECHANISM OF THE REACTION OF TETRANITROMETHANE WITH NITROETHANE IN AN ALKALINE MEDIUM
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The kinetics of the reaction of tetranitromethane with nitroethane in alkaline aqueous buffer media were investigated by a spectrophotometric method.The process has radical-ion chain character, but there is a small contribution from a nonchain component.The kinetics of both reactions are described by equations of overall second order, i.e., first in the tetranitromethane and first in the nitrocarbanion.The proposed radical-anion chain mechanism involves electron transfer from the nitrocarbanion to tetranitromethane, addition of the NO2. radical which forms to the nitroalkane radical anion to tetranitromethane.A possible mechanism for the nonchain process is discussed.
- Kuznetsova, I. I.,Bazanov, A. G.,Tselinskii, I. V.
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p. 619 - 625
(2007/10/02)
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- Process for nitroform isolation
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A method of isolating nitroform from a solution of nitric acid, nitroform, and water by adding sulfuric acid and preferentially extracting the nitroform with methylene chloride. The nitroform is then extracted from the methylene chloride solution into water. It is a particular advantage of the present method that no distillations involving nitroform are required.
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- Production of trinitromethane
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A method of producing trinitromethane comprising reacting isopropyl alcohol with nitric acid, wherein the reaction is maintained within a temperature range of from about 25° to about 85° C to produce said trinitromethane and recovering the trinitromethane so produced. It is a particular advantage of the present method that no catalyst is required.
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