- Bicentral oxidation of nitrosolic acids: Synthesis of 1,1-dinitroalkanes
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gem-Dinitrozo compounds are cleanly oxidized into the gem-dinitro analogues on treatment with formic acid/hydrogen peroxide system.
- Sheremetev, Aleksei B.,Aleksandrova, Natal'Ya S.,Suponitsky, Kyrill Yu.
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- Oxidative nitration of mononitroalkanes in a system sodium nitrite-polyhaloalkane
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In reaction of nitroethane lithium salt with sodium nitrite in DMSO, DMF or HMPA involving polyhaloalkanes 1,1-dinitroethane formed in a high yield. The highest yield was obtained with bromo-and iododerivatives. The reaction fits to a kinetic equation of over all second order: the first with respect to the nitroethane anion, and the first in polyhaloalkane. The rate constants of the process are linearly dependent on the electron affinities of the perhaloalkanes molecules. Nauka/Interperiodica 2007.
- Petrova,Shcherbinin,Bazanov,Tselinskii
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p. 646 - 651
(2008/02/08)
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- Electrooxidative coupling of salts of nitro compounds with halide, nitrite, cyanide, and phenylsulfinate anions
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Electrolysis of salts of primary and secondary nitro compounds (nitroethane, 1- and 2-nitropropanes, nitrocyclohexane, and nitrocycloheptane) in the presence of excess halide, nitrite, cyanide, and phenylsulfinate anions under undivided and divided amperostatic electrolysis conditions in a two-phase medium (CH2Cl2/H2O) produces geminal nitrohalides (35-85% yields), dinitro compounds (15-51%), nitronitriles (6-27%), and nitrosulfones (50-70%). The salts of secondary nitro compounds form the products of oxidative coupling with halide and phenylsulfinate anions under the undivided electrolysis conditions. In all other cases, divided electrolysis is required.
- Ilovaisky,Merkulova,Ogibin,Nikishin
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p. 1585 - 1592
(2007/10/03)
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- PARTICIPATION OF ACTIVE OXYGEN IN THE REACTION OF 1-CHLORO-1-NITROETHANE WITH THE NITRITE ION (ter MEER REACTION)
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Reaction of 1-halo-1-nitroalkanes with the nitrite ion (ter Meer reaction) is accompanied by generation of active oxygen forms, in particular, superoxide radical anion, which participates in the subsequent elementary stages of the chain process.The formation of the main reaction product, 1,1-dinitroalkane, is inhibited by the enzyme superoxidedismutase.Possible reaction pathways of active oxygen forms that arise in the course of the process with components of the system 1-halo-1-nitroalkane-nitrite ion are discussed.
- Shugalei, I. V.,Tselinskii, I. V.
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p. 279 - 282
(2007/10/02)
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- INTERPHASE ANALYSIS IN THE CHEMISTRY OF ALIPHATIC NITRO COMPOUNDS. 1. ALKYLATION OF ALKALI METAL SALTS OF TRINITROMETHANE UNDER INTERPHASE CATALYSIS CONDITIONS IN SOLID PHASE-LIQUID SYSTEMS
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Methylation of trinitromethane salts was studied under interphase catalysis conditions in a solid phase (a trinitromethane salt)-liquid (methyl iodide) system in the presence of interphase transfer catalysts - onium salts, cyclic and acyclic polyethers.The dependence of the yield of the methylation product - 1,1,1-trinitroethane - on the nature of the catalyst was also investigated, and based on this, catalysts were found, in whose presence the methylation process is realized more effectively than under homogeneous conditions.
- Shevelev, S. A.,Dalinger, L. I.,Vinogradov, V. M.,Fainzil'berg, A. A.
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p. 1647 - 1650
(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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- 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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- Synthesis of geminal dinitro compounds
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Geminal dinitro compounds are prepared by reacting an organic nitro compound having a replaceable hydrogen on the carbon to which the nitro group is attached with a source of nitrite ions in the presence of an oxidizing agent and a catalytic amount of an alkali metal ferricyanide.
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- SIDE PATHS IN THE REACTION OF 1-CHLORO-1-NITROETHANE WITH NITRITE ION
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The main side reactions which accompany the formation of 1,1-dinitroalkanes in the reactions of 1-chloro-1-nitroalkanes with the nitrite ion were studied by UV spectroscopy.The side products are formed as a result of the reaction of nucleophilic particles competing with the nitrite ion (hydroxide ion, 1-halogeno-1-nitroalkane anion, and molecular oxygen) for the chloronitroalkyl radical.The ratios of the rate constants for some of the competing reactions were calculated from the variation in the yield of the main reaction product (1,1-dinitroalkane) in relation to the reaction conditions.
- Shugalei, I. V.,Tselinskii, I. V.,Bazanov, A. G.
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p. 2242 - 2246
(2007/10/02)
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- EFFECT OF THE IONIC STRENGTH OF THE SOLUTION AND THE NATURE OF THE CATION ON THE KINETICS OF THE REACTION OF 1-CHLORO-1-NITROETHANE WITH NITRITE ION; INITIATED BY THE PERSULFATE DIANION, IN AN ALKALINE MEDIUM
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The effect of the ionic strength of the solution and the nature of the cation on the ter Meer reaction of 1-chloro-1-nitroethane with the nitrite ion, initiated by the persulfate dianion, was studied by a spectrophotometric method.Measurement of the dependence of the chain initiation rate on the ionic strength of the solution shows that the singly charged MS2O8(1-) anion (M = K, Na) takes part in one-electron oxidation of the 1-chloro-1-nitroethane anion.The nature of the effect of the ionic strength of the solution and of the nature of the cation on the rate of the chain process is consistent with the previously established quadratic chain termination.
- Shugalei, I. V.,Tselinskii, I. V.,Bazanov, A. V.
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p. 823 - 826
(2007/10/02)
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- REACTION OF 1,1-DINITROETHANE POTASSIUM SALT WITH XENON DIFLUORIDE
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The potassium salt of 1,1-dinitroethane reacts with xenon difluoride in methylene chloride to form a mixture of products, i.e., acetic acid, 1-fluoro-1,1-dinitroethane, 1-chloro-1,1-dinitroethane, 1,1,1-trinitroethane, and 1,1-dinitroethane.The ratios of the yields depend on the reaction conditions.The proposed mechanism for the formation of the reaction products involves one-electron oxidation of the dinitroethane radical, which enters into reaction with the methylene chloride molecules and intermediate radical particles.
- Tselinskii, I. V.,Mel'nikov, A. A.,Varyagina, L. G.,Trubitsin, A. E.
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p. 2276 - 2279
(2007/10/02)
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- Catalyzed Oxidative Nitration of Nitronate Salts
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Nitronate salts are converted to gem-dinitro compounds with nitrite ion and persulfate, in the presence of a catalytic amount of ferricyanide.The use of cyanide or sulfinate salts in place of nitrile gave gem-cyanonitro compounds and α-nitro sulfones, respectively.
- Garver, Lee C.,Grakauskas, V.,Baum, Kurt
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p. 1699 - 1702
(2007/10/02)
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- REACTIVITY OF α-HALOGENONITROALKANES. XIII.* EFFECT OF THE NATURE OF THE α-HALOGEN ON THE KINETICS OF THE TER MEER REACTION INITIATED BY THE PERSULFATE DIANION
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The kinetics of the radical-anion chain reaction of 1-bromo- and 1-iodo-1-nitroethanes with sodium nitrite, initiated by the persulfate dianion in an alkaline medium, were investigated by a spetrophotometric method.It was shown that, unlike the autocatalytic process, the mechanism of the initiated ter Meer reaction remains unchanged in the series of α-chloro-, α-bromo- and α-iodonitroalkanes.The effect of the α-halogen substituent on the kinetic parameters of the chain process is discussed.
- Shugalei, I. V.,Bazanov, A. G.,Tselinskii, I. V.
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p. 1641 - 1645
(2007/10/02)
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- REACTIONS OF THIOLATE ANIONS WITH 2-SUBSTITUTED-2-NITROPROPANES
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Thiolates undergo substitution reactions with 2-substituted-2-nitropropanes by an SRN1 mechanism or are oxidised to disulphides by an ionic mechanism.
- Bowman, W. Russel,Richardson, Geoffrey D.
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p. 1551 - 1554
(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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