- Formation of Organic Nitro-compounds in Flowing H2O2+NO2+N2+Organic Vapour Systems. Part 2.-H2O2+NO2+N2+Alkane System
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The principal products from the surface-initiated reactions in flowing mixtures of H2O2, NO2,N2 and RH, where RH=ethane, propane, n-butane and n-pentane, have been identified as the nitroalkane, alkyl nitrite and alkyl nitrate.The product yields have been measured; in the case of propane the variation of the yields with total gas pressure has also been studied.Values have been obtained for the relative rates of primary and secondary H-atom abstraction from each alkane by OH and for the rate-constant ratios k3/k4 and k5/k6 at 298 K:.The trends in the product yields with the variation of pressure and change of R indicate that RO radicals are produced via reactions (4)-(6) rather than by a single-step reaction of R with NO2.
- Baulch, Donald L.,Campbell, Ian M.,Chappel, Jonathan M.
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- Formation of Organic Nitro-compounds in Flowing H2O2+NO2+N2+Organic Vapour Systems. Part 3.-Effects of O2 Addition on H2O2+NO2+N2+Alkane Systems
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The effects of oxygen on the product distribution from the surface-initiated reactions in flowing mixtures of H2O2, NO2, N2 and RH, where RH=ethane, propane, n-butane and n-pentane, at 298 K have been studied.In the absence of O2, the principal products are the corresponding nitroalkane, alkyl nitrite and alkyl nitrate.In the presence of sufficiently large concentrations of O2, the predominant product is the alkyl nitrate and the only other products of significance, in some cases, are the corresponding carbonyl compounds.The variation of the product yields with / gives values for the rate-constant ratios k8/(k3+k4) for reaction at both primary and secondary radical sites:.Possible mechanisms by which the products are formed are discussed.
- Baulch, Donald L.,Campbell, Ian M.,Chappel, Jonathan M.
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- Synthesis of nitroalkanes from alkylhalides under mild and nonaqueous conditions by using polymer supported nitrites
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Alkyl halides are efficiently converted to their corresponding nitroalkanes under mild and nonaqueous conditions by using polymer supported nitrites. The polymeric reagent is regenerable.
- Zarchi, Mohammad Ali Karimi,Zarei, Amin
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- Kinetics and mechanisms of the gas-phase elimination of 2-substituted primary, secondary and tertiary hydroxy groups in nitroalkanes
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The kinetics of the gas-phase elimination of several 2-substituted primary, secondary and tertiary hydroxy groups in nitroalkanes were determined in a static reaction system over the temperature range 220-400°C and pressure range of 29-235 Torr. The reactions, in seasoned vessels, are homogeneous and unimolecular and obey a first-order rate law. The presence of secondary and tertiary hydroxy substituent at the 2-position of the nitro group in nitroalkanes leads to a retro-aldol type of decomposition. The mechanism may be rationalized in terms of a six-membered cyclic transition state to give the corresponding aldehyde or ketone and the nitroalkane, respectively. However, some of the primary 2-hydroxy groups in nitroalkanes undergo a dehydration process with very limited isomerization to the corresponding alkyl nitrate. The mechanism of dehydration is believed to proceed through a six-membered rather than the already reported four-membered cyclic transition state to give the nitroalkene and water. In the case of the primary hydroxy substituent in 2-methyl-2-nitro-1-pentanol, the products of elimination are HNO2 gas and 3-hydroxy-2-methyl-1-propene. This reaction is rationalized in terms of a four-membered cyclic transition state type of mechanism. The kinetic and thermodynamic parameters of the hydroxynitroalkane substrates are presented and discussed. Copyright 2004 John Wiley & Sons, Ltd.
- Dominguez, Rosa Maria,Herize, Armando,Rotinov, Alexandra,Alvarez-Aular, Alvaro,Visbal, Gonzalo,Chuchani, Gabriel
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- Green synthesis of low-carbon chain nitroalkanes via a novel tandem reaction of ketones catalyzed by TS-1
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A green and efficient one-pot method has been developed for the synthesis of low-carbon chain nitroalkanes via a novel TS-1 catalyzed tandem oxidation of ketones with H2O2 and NH3. The tandem reaction including ammoxidation, oximation and oxidation of oximes, afforded up to 88% yield and 98% chemo-selectivity requiring only 90 min, at 70 °C and atmospheric pressure. Moreover, this method was even amenable to 100-fold scale-up without loss of chemical efficiency with 87% yield, represents a significant advance towards industrial production of nitroalkanes. Furthermore, the plausible mechanism of TS-1 catalyzed tandem oxidation of ketones to prepare nitroalkanes was proposed.
- Chu, Qingyan,He, Guangke,Xi, Yang,Wang, Ping,Yu, Haoxuan,Liu, Rui,Zhu, Hongjun
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- Green synthesis method for preparing nitroalkanes by oxime oxidation
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The invention belongs to the field of organic chemical industries, and provides a green synthesis method for preparing nitroalkanes by oxime oxidation. At the temperature of 55 to 120 DEG C and under the pressure of 0 to 1.0 MPa, oxime, a solvent and hydrogen peroxide are reacted for 20 to 200min in the presence of certain amounts of nanoporous skeleton metal hybrid catalysts and cocatalysts, a reaction liquid is subjected to membrane separation, the catalysts can be repeatedly used for more than 7 times, and distilled to obtain nitroalkane products, the purity of the products is not less than 99%, and the yield of the products is not less than 95%. Furthermore, the green synthesis method for preparing nitroalkanes by the oxime oxidation disclosed by the invention is a green synthesis method of nitroalkanes, and suitable for large-scale industrialized production.
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Paragraph 0051; 0052
(2017/08/29)
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- PROCESS FOR NITROALKANE RECOVERY BY AQUEOUS PHASE RECYCLE TO NITRATION REACTOR
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Disclosed are a process and an apparatus for synthesizing nitroalkanes by reaction of a hydrocarbon feedstock with aqueous nitric acid. Energy and capital costs may be reduced by recycling a majority of the aqueous phase back to the reactor.
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Page/Page column 16-17
(2011/05/06)
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- PROCESS FOR THE MANUFACTURE OF NITRATED HYDROCARBONS
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Provided is a process for making nitrated hydrocarbons by reacting aqueous nitric acid with a hydrocarbon feedstock and a carboxylic acid under specific reaction conditions.
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Page/Page column 7
(2011/05/03)
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- Process For Nitroalkane Recovery By Aqueous Phase Recycle To Nitration Reactor
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Disclosed are a process and an apparatus for synthesizing nitroalkanes by reaction of a hydrocarbon feedstock with aqueous nitric acid. Energy and capital costs may be reduced by recycling a majority of the aqueous phase back to the reactor.
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Page/Page column 5
(2011/05/03)
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- ISOTHERMAL REACTOR FOR HYDROCARBON NITRATION
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Disclosed are a process and an apparatus for synthesizing nitroalkanes by reaction of a hydrocarbon feedstock with aqueous nitric acid. By using an isothermal reactor with multiple input ports for aqueous nitric acid, a hydrocarbon feedstock may be sequentially exposed to a plurality of flows of aqueous nitric acid as it flows through the reactor.
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Page/Page column 5
(2011/05/03)
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- PROCESS FOR THE MANUFACTURE OF NITROPROPANES
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Provided is a process for the formation of 2-nitropropane and/or 2,2-dinitropropane by the nitration of propane with dilute nitric acid.
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Page/Page column 15-16
(2009/12/02)
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- Separation of methylene chloride from tetrahydrofuran by extractive distillation
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Methylene chloride is difficult to separate from tetrahydrofuran by conventional distillation or rectification because of the proximity of their vapor pressures. Methylene chloride can be readily separated from tetrahydrofuran by extractive distillation. Effective agents are 1-pentanol, 1,2-butanediol and 3-nitrotoluene.
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- Process for preparing 7-substituted-amino-3-hydroxy-3-cephem-4-protected carboxy-sulfoxide esters
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A process for the conversion of a 4-chlorosulfonyl azetidinone (a) to a 3-hydroxy-3-cephem-sulfoxide ester (d) by subjecting an intermediate comprising a tin containing Lewis acid-type Fiedel-Crafts catalyst and 3-exomethylene cepham to ozonolysis.
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- SYNTHESIS OF LOW-MOLECULAR NITROPARAFFINS IN IONIC MELTS
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It was shown that pure low-molecular nitroparaffins can be synthesized by the reaction between alkyl sodium sulfates and nitrite ion in ionic melts.The yield of the product is temperature controlled.Because of the ambident nature of nitrite ion, the main side product is alkyl nitrite, subsequent decomposition of which results in formation of a series of organic oxygen-containing compounds.The formal kinetics of the alkylation of nitrite ion by alkyl sodium sulfates was found to be described by the first-order equation.
- Belobrzhetskaya, M. K.,Laskin, B. M.,Malin, A. S.
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p. 105 - 108
(2007/10/02)
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- Spectrochemical analysis of the laser-induced nitration of three cycloalkanes
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The tunable continuous wave carbon dioxide laser-induced reactions of cyclopropane, cyclobutane and cyclopentane with NO2 have been carried out under a variety of reaction conditions.Presented herein is our qualitative Fourier transform infrared spectroscopy and gas chromatography - mass spectroscopy spectrochemical analysis of the product mixtures.Optimal conditions were found for producing nitrocycloalkanes while reducing or eliminating the production of undesirable products.The array of products was found to be highly sensitive to the specific reaction conditions.
- Stanley, Ann E.,Godbey, Susan E.,Bonicamp, Judith M.,Ludwick, Larry M.
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p. 1987 - 1998
(2007/10/02)
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- Process for manufacturing 5-hydroxymethylfurfural
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The invention relates to a process for manufacturing 5-hydroxymethylfurfural. This process comprises decomposition of a hexose in a reaction medium constituted by water and an organic solvent, by heating to a temperature below 100° C., situated especially in the range from 70° to 95° C., in the presence of a solid catalytic support, especially an exchange resin with a cationic function. 5-hydroxymethylfurfural is applied in numerous syntheses.
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