594-70-7Relevant articles and documents
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Kornblum,Clutter
, p. 4494,4495 (1954)
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Comparison of Heterogeneous and Homogeneous Electron-Transfer Rates for Some Nitroalkanes and Diketones
Evans, Dennis H.,Gilicinski, Andrew G.
, p. 2528 - 2533 (1992)
Redox catalysis has been used to investigate the homogeneous electron-transfer reactions between the substrates (nitroalkane or diketone) and the reduced form of the catalyst, which was terephthalonitrile.The substrates were RNO2 (R=Me, Et, i-Pr, and t-Bu) and RC(O)C(O)R (R=Me, Et, and t-Bu).The experiments were conducted in acetonitrile solvent at 298 K with three different electrolytes, R4NClO4 (R=Et, n-Bu, and n-C7H15).The effect of added water and alcohols (methanol, ethanol, and s-butanol) was investigated.Formal potentials and standard heterogeneous electron-transfer rate constants, ks, were also determined.It was found that increasing the size of the cation of the electrolyte resulted in a decrease in ks but did not affect the rate of the homogeneous electron-transfer reactions.The result is interpreted as a decrease in electron-tunneling rate with increasing thickness of a compact layer of adsorbed cations, a double-layer effect that cannot influence the homogeneous reaction.Addition of the hydroxylic solutes, S, caused diminution of both ks and the rate constant of homogeneous electron transfer from the anion radical of the substrate to the catalyst.This result is discussed in terms of two models, viz., complexation or adduct formation between the anion radical and S or increasing solvation energy of the anion radical.
Copper(II) mediated phenol ring nitration by nitrogen dioxide
Kumar, Vikash,Ghosh, Somnath,Saini, Anoop Kumar,Mobin, Shaikh M.,Mondal, Biplab
, p. 19909 - 19917 (2015/12/01)
Cu(ii) complexes of N2O2 type ligands, L1H2 and L2H2 [L1H2 = 6,6′-(((pyridin-2-ylmethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol); L2H2 = 2,4-di-tert-butyl-6-(((3-(tert-butyl)-2-hydroxy-5-methylbenzyl)(pyridin-2-yl-methyl)amino)methyl)phenol], have been synthesized. Addition of nitrogen dioxide (NO2) in THF solutions of the complexes resulted in the nitration at the 4-position of a coordinated equatorial phenolate ring of the ligand frameworks. This nitration did not occur at the phenol ring which is axially coordinated to the metal center. Spectroscopic evidence suggests that the reaction proceeds through a phenoxyl radical complex formation.
HYDROCARBON FEED FLEXIBLE HIGH PRESSURE NITRATION PLANT DESIGN
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Page/Page column 21-26, (2011/07/09)
Disclosed is an apparatus for synthesizing nitroalkanes by reaction of a hydrocarbon feedstock with aqueous nitric acid. The apparatus may be designed such that it can synthesize more than one nitroalkane using the same equipment.
Spin trapping of Au-H intermediate in the alcohol oxidation by supportedand unsupported gold catalysts
Conte, Marco,Miyamura, Hiroyuki,Kobayashi, Shu,Chechik, Victor
supporting information; experimental part, p. 7189 - 7196 (2009/09/30)
Electron paramagnetic resonance (EPR) spectroscopy and spin trapping were used to explore the mechanism of alcohol oxidation over gold catalysts. Reaction of secondary alcohols with supported and unsupported gold catalysts (e.g., Au/CeO2, polymer-Incarcerated Au nanoparticles,PPh 3-protected Au nanoparticles) In the presence of spin tr aps led to the formation of a hydrogen spin adduct. Using Isotope labeling, we confirmed that the hydrogen In the spin adduct originates from the cleavage of the C-H bond In the alcohol molecule. The formation of thehydrogen spin adduct most likely results from the abstraction of hydrog en from the Au surface by a spin trap. These results thus strongly suggest Intermediate formation of Au-H species during alcohol oxidation. The role of oxygen In this mechanism Is to restore the catalytic activity rather than oxidize alcohol. This was further confirmed by carrying out gold-catalyzed alcohol oxidation In the absence of oxygen, with nitroxidesas hydrogen abstractors. The support (e.g., metal oxides) can activate oxygen and act as an H abstractor from the gold surface and hence lead t o a faster recovery of the activity. Peroxyl radicals were also observedduring alcohol oxidation, consistent with a free-radical autoxidation m echanism. However, this mechanism Is likely to be a minor side reaction,which does not lead to the formation of an appreciable amount of oxidat ion products.