1122-60-7Relevant articles and documents
Zeolite (H-ZSM 5)-catalysed reduction of conjugated nitroalkenes with sodium cyanoborohydride
Gupta, Anuradha,Haque, Azizul,Vankar, Yashwant D.
, p. 1653 - 1654 (1996)
Conjugated nitroalkenes are readily reduced to the corresponding nitroalkanes with sodium cyanoborohydride in the presence of the zeolite H-ZSM 5 in methanol.
Direct and Efficient Preparation of gem-Chloronitro Compounds or Nitro Compounds from gem-Bromonitro Compounds
Amrollah-Madjdabadi, A.,Beugelmans, R.,Lechevallier, A.
, p. 826 - 828 (1986)
Sodiumethanethiolate in methanol is an efficient reducing agent for gem-bromonitro compounds; treatment of the resultant nitronates with a protic acid or with N-chlorosuccinimide gives high yields of the corresponding nitro or gem-chloronitro compounds, respectively.
Fast cleavage reactions following electron transfer. Reduction of 1,1-dinitrocyclohexane
Rühl, Janet C.,Evans, Dennis H.,Hapiot, Philippe,Neta, Pedatsur
, p. 5188 - 5194 (1991)
One-electron reduction of 1,1-dinitrocyclohexane is followed by rapid cleavage of a C-N bond, giving nitrite and 1-nitrocyclohexyl radical. The rate constant has been determined in dimethylformamide by homogeneous redox catalysis (1.6 × 106 s-1) and in aqueous solution by pulse radiolysis (1.1 × 106 s-1). These values are of the order of 106 larger than the rate constant for cleavage of mononitroalkane radical anions. In the case of electrochemical reduction, the electron transfer and bond cleavage are followed by further reduction of the nitroalkyl radical to give the nitronate anion of nitrocyclohexane. For scan rates exceeding about 0.1 V/s in cyclic voltammetry, the 1-nitrocyclohexyl radical is reduced by the anion radical of 1,1-dinitrocyclohexane rather than at the electrode. Controlled potential electrolysis and product analysis showed that about 1.2 electrons were required per molecule of 1,1-dinitrocyclohexane; essentially no nitronate was found, but instead some nitrocyclohexane and substantial amounts of 1,1′-dinitrobicyclohexyl (5) were produced. This latter product arises from the radical chain reaction of nitronate with starting material. A key chain-carrying step in this reaction scheme is the reaction of 1-nitrocyclohexyl radical with the nitronate to give the anion radical of 5. The rate constant for this step was found to be 2.6 × 106 L mol-1 in water by pulse radiolysis. Fitting of fast-scan cyclic voltammograms by digital simulation showed that this rate constant must be about 5 × 108 L mol-11 s-1 in dimethylformamide with a termination reaction (kt = 2 × 104 s-1) of hydrogen atom abstraction by 1-nitrocyclohexyl to produce the nitrocyclohexane found in the electrolyzed solutions.
From azides to nitro compounds in a few seconds using HOF·CH3CN
Rozen, Shlomo,Carmeli, Mira
, p. 8118 - 8119 (2003)
HOF·CH3CN, a very efficient oxygen-transfer agent, was reacted with various azides to form the corresponding nitro compounds in excellent yields and in very short reaction times. The respective nitroso derivatives were found to be intermediates in this reaction. When the azides were reacted with MCPBA or DMDO, no reaction took place, and the starting materials were fully recovered. Copyright
Highly selective co-production of nitrocyclohexane and adipic acid from vapor phase catalytic nitration-oxidation of cyclohexane with NO2
You, Kuiyi,Jian, Jian,Xiao, Haijun,Liu, Pingle,Ai, Qiuhong,Luo, He'An
, p. 174 - 178 (2012)
A simple and efficient approach for highly selectivity co-production of nitrocyclohexane and adipic acid from vapor phase nitration-oxidation of cyclohexane with NO2 at atmospheric pressure has been successfully developed in this work. This finding provides a novel strategy for co-production of nitroalkanes and dicarboxylic acids from vapor phase nitration-oxidation of low-carbon cycloalkanes. This method may be very significant to establish such a synthesis process for aliphatic nitro-compounds and dicarboxylic acids in organic fields.
Structure, Synthesis, and Properties of Some Persubstituted 1,2-Dinitroethanes. In Quest of Nitrocyclopropyl-Anion Derivatives
Kai, Yasushi,Knochel,Paul,Kwiatkowski, Stefan,Dunitz, Jack D.,Oth, Jean F. M.,et al.
, p. 137 - 161 (1982)
Attempts to deprotonate nitrocyclopropane led to solutions which showed strong ESR. signals (Fig. 1) and from which 1-nitro-1'-nitroso-bicyclopropyl (3) and 1,1'-dinitro-bicyclopropyl (2) were isolated.The activation energy for rotation about the central C,C-bond of 2 is estimated to be about 12 kcal/mol (1H-NMR. spectra in Fig. 2).In contrast, the open-chain analoque 2,3-dimethyl-2,3-dinitrobutane (1) shows a metyl singlet down to -70 deg C.Low-temperature X-ray analyses of 1, 2, 3, and also of 1,1'-dinitro-bicyclobutyl (4) show that all four molecules have gauche-conformations but reveal striking structural differences between the open-chain and the cyclic derivatives (Fig. 4-6): the central C,C-bond is long in 1 (1.575 Angstroem), short in 2 (1.479 Angstroem); the C,N-bonds are long in 1 (1.549 Angstroem), short in 2 (1.488 Angstroem); the orientation of the nitro groups is bisected in 2 and perpendicular in 1.The crystal structure of the nitro-nitroso compound 3 is isimorphous with that of the dinitro compound 2 and thus disordered (Fig. 15-16).The effect of the nitro group as ?-electron acceptor on the molecular conformations and bond lengths is discussed.From analysis of the anisotropic vibrational parameters of 2 the root-mean-square librational amplitude of the nitro groups about their C,N-bonds is estimated to be about 5.8 deg at 95 K, corresponding to a rotational barrier of about 9 kcal/mol, i. e. the same order of magnitude as the NMR. estimate of about 12 kcal/mol for C,C-rotation.
SELECTIVE C-C BOND HYDROGENATION IN UNSATURATED NITRO COMPOUNDS IN THE PRESENCE OF THE RhCl3-ALIQUAT 336 CATALYST SYSTEM
Amer, Ibrahim,Bravdo, Tamar,Blum, Jochanan,Vollhardt, K. Peter C.
, p. 1321 - 1322 (1987)
The ion pair formed from aqueous rhodium trichloride and Aliquat 336 catalyzes the selective hydrogenation of olefinic bonds of a variety of unsaturated nitro compounds in a two liquid phase system at 30 deg C.Nitrobenzene gives, under these conditions, a mixture of aniline and nitrocyclohexane.
New Method for the Facile Reduction of α-Nitro Sulfones to Nitroalkanes via an Electron-Transfer-Hydrogen Atom Abstraction Mechanism
Chen, Jian,Tanner, Dennis D.
, p. 3897 - 3900 (1988)
The mechanism for the reduction of several α-nitro sulfones with 1,3-dimethyl-2-phenylbenzimidazoline (DMBI) was investigated.The reduction proceeds by a free-radical chain process where the initiation step and one of the propagation steps involve single electron transfer reactions.The synthetic utility of the reduction was investigated.
Structural insights into the ene-reductase synthesis of profens
Waller,Toogood,Karuppiah,Rattray,Mansell,Leys,Gardiner,Fryszkowska,Ahmed,Bandichhor,Reddy,Scrutton
, p. 4440 - 4448 (2017)
Reduction of double bonds of α,β-unsaturated carboxylic acids and esters by ene-reductases remains challenging and it typically requires activation by a second electron-withdrawing moiety, such as a halide or second carboxylate group. We showed that profen precursors, 2-arylpropenoic acids and their esters, were efficiently reduced by Old Yellow Enzymes (OYEs). The XenA and GYE enzymes showed activity towards acids, while a wider range of enzymes were active towards the equivalent methyl esters. Comparative co-crystal structural analysis of profen-bound OYEs highlighted key interactions important in determining substrate binding in a catalytically active conformation. The general utility of ene reductases for the synthesis of (R)-profens was established and this work will now drive future mutagenesis studies to screen for the production of pharmaceutically-active (S)-profens.
Method for co-producing adipic acid and cyclohexanone-oxime from cyclohexane
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Paragraph 0100-0107, (2021/06/13)
The invention relates to a method for co-producing adipic acid and cyclohexanone-oxime from cyclohexane. The method comprises the following steps: (1) carrying out oxidation nitration on cyclohexane and NOx to generate adipic acid, nitrocyclohexane, nitrogen oxides and a byproduct-A, and separating to obtain crude adipic acid and nitrocyclohexane; (2) carrying out catalytic hydrogenation on the obtained nitrocyclohexane and hydrogen to generate cyclohexanone-oxime and a small amount of cyclohexylamine, separating to obtain crude cyclohexanone-oxime and cyclohexylamine, and enabling cyclohexylamine to be directly used as a byproduct or to be continuously converted into cyclohexanone-oxime. and (3) partially oxidizing the cyclohexylamine obtained in the previous step with molecular oxygen to obtain an oxidation reaction product consisting of cyclohexanone-oxime, a byproduct B and possibly unconverted cyclohexylamine, and then separating the oxidation reaction product without separation, or firstly separating part or all of water in the oxidation reaction product, carrying out hydrogenation amination reaction under the action of a catalyst, or carrying out hydrogenation and amination reaction, or only carrying out hydrogenation reaction, and then separating to obtain the cyclohexanone-oxime. The method can realize high-selectivity co-production of adipic acid and cyclohexanone-oxime, and is short in process flow, low in equipment investment and low in material consumption, energy consumption and cost.
