10437-90-8

Upstream product

• 1165952-91-9 cyclohexa-1,3-diene 
• 100-65-2 N-Phenylhydroxylamine 
• 98-95-3 nitrobenzene 
• 62-53-3 aniline 
• 586-96-9 Nitrosobenzene 
• 64-17-5 ethanol 
• 60-29-7 diethyl ether 

Downstream Products

• 68234-27-5 1′,2′,3′,6′-tetrahydro-[1,1′-biphenyl]-2-amine 

Relevant academic research and scientific papers

Super electron donor-mediated reductive transformation of nitrobenzenes: A novel strategy to synthesize azobenzenes and phenazines

The transformation of nitrobenzenes into azobenzenes by pyridine-derived super electron donor 2 is described. This method provides an efficient synthesis of azobenzenes because of not requiring the use of expensive transition-metals, toxic or flammable reagents, or harsh conditions. Moreover, when using 2-fluoronitrobenzenes as substrates, phenazines were found to be obtained. The process affords a novel synthesis of phenazines.

Enhancement in facial selectivity of a plane nonsymmetric double bond induced by a conjugating methoxycarbonyl group

Introduction of a methoxycarbonyl group on the plane nonsymmetric double bond of 2,3-dioxa and 2,3-oxaza bicyclo[2.2.2]oct-5-enes brought about a clear-cut increase in syn selectivity of their reactions with 1,3-dipoles.

Titania-Supported Gold Nanoparticles Catalyze the Selective Oxidation of Amines into Nitroso Compounds in the Presence of Hydrogen Peroxide

In this article, the catalytic activity of titania-supported gold nanoparticles (Au/TiO2) was studied for the selective oxidation of amines into nitroso compounds using hydrogen peroxide (H2O2). Gold nanoparticles deposited on Degussa P25 polymorphs of titania (TiO2) have been found to promote the selective formation of a variety of nitroso arenes in high yields and selectivities, even in a large-scale synthesis. In contrast, alkyl amines are oxidized to the corresponding oximes under the examined conditions. Kinetic studies indicated that aryl amines substituted with electron-donating groups are oxidized faster than the corresponding amines bearing an electron-withdrawing functionality. A Hammett-type kinetic analysis of a range of para-X-substituted aryl amines implicates an electron transfer (ET) mechanism (ρ=-1.15) for oxidation reactions with concomitant formation of the corresponding N-aryl hydroxylamine as possible intermediate. We also show that the oxidation protocol of aryl amines in the presence of 1,3-cyclohexadiene leads in excellent yields to the corresponding hetero Diels-Alder adducts between the diene and the in situ formed nitrosoarenes.

Copper-catalyzed aerobic oxidation of N-substituted hydroxylamines: Efficient and practical access to nitroso compounds

A general and efficient aerobic oxidation of N-substituted hydroxylamines is described. The mild reaction conditions employed provide a catalytic and sustainable alternative to stoichiometric oxidation methods to gain access to a range of nitroso compound

X-ray structural analysis for the prediction on the nature of the retro DielsAlder pathway: Concerted or stepwise. structural studies on nitrosobenzene cycloadducts

Crystal structures of nitrosobenzene cycloadducts 57 reveal structural effects consistent with the early stages of the retro DielsAlder fragmentation. There is a clear differentiation between the structure parameters of cycloadduct 5, which reacts by a co

In situ generation of nitroso compounds from catalytic hydrogen peroxide oxidation of primary aromatic amines and their one-pot use in hetero-Diels-Alder reactions

A method for in situ generation of nitroso compounds from organoselenium-catalyzed oxidation of anilines by hydrogen peroxide was developed. The generated nitroso compounds were subsequently used in hetero-Diels-Alder reactions. A variety of oxazines were synthesized in reasonable to good yields by this one-pot procedure using primary aromatic amines with different substituents and various conjugated dienes. This strategy might facilitate the current methodologies for nitroso chemistry since no isolation or purification of the nitroso compounds is required. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

A molybdenum-catalyzed oxidative system forming oxazines (hetero-Diels-Alder adducts) from primary aromatic amines, hydrogen peroxide, and conjugated dienes

The development of a new molybdenum-catalyzed procedure for the formation of oxazines-hetero-Diels-Alder adducts - from primary aromatic amines, hydrogen peroxide, and conjugated dienes is presented. The method is based on a molybdenum-peroxo complex, which in the presence of hydrogen peroxide as the terminal oxidant selectively catalyzes the oxidation of primary aromatic amines to the corresponding dienophilic nitroso compounds. The molybdenum-peroxo catalyst is under the present reaction conditions not reactive toward conjugated dienes and substituents attached to the aromatic nuclei of the primary aromatic amines. Several oxazines are synthezised following this new procedure using primary aromatic amines having either electron-withdrawing or electron-donating substituents and 1,3-cyclohexadiene as the standard diene. The scope of the new procedure is also demonstrated by the preparation of several oxazines using different alkyland phenyl-substituted conjugated dienes and 4-chloroaniline as precursor for the dienophile. Moderate diastereomeric excesses are found when the reaction is carried out with 1-(2-aminophenyl)-ethanol and 1,3-cyclohexadiene or (E)-1-phenyl-1,3-butadiene. The stereochemical and electronic factors governing the reaction course are briefly discussed.

Diels-Adler Reactions in Nonaqueous Polar Solvents. Kinetic Effects of Chaotropic and Antichaotropic Agents and of β-Cyclodextrin

The Diels-Adler addition reactions of nitrosobenzene with 1,3-cyclohexadiene and of methyl vinyl ketone with 1,3-cyclopentadiene are faster in formamide or in ethylene glycol than in other organic solvents, but not as fast as in water solution.The reactions in these organic solvents are also accelerated by β-cyclodextrin.The kinetic results indicate that there is solvophobic binding reactants to each other, or into the cyclodextrin cavity, in these polar solvents.In spite of this, there is no striking increase in endo/exo selectivity, as there is in water.We detect two classes of chaotropic agents.Urea and guanidinium ion, which are normally chaotropic in water and thus decrease the hydrophobic effect and the rate of our Diels-Adler reactions, show no such effect in the organic solvents.These solutes also decrease the solubility of benzene in ethylene glycol or in formamide, in contrast to their effects in water.The contrasts indicate that "waterlike" organic solvents still do not share some of the most striking properties of water itself.The results also indicate that the chaotropic effects of urea and guanidinium ion in water reflect primarily the interaction of the chaotropes with the water, not with the hydrocarbon solutes.By contrast, tetramethylammonium bromide, and even more so tetrabutylammonium bromide, belong to a second class of salting agents.They decrease the rate of the Diels-Adler addition of cyclopentadiene to methyl vinyl ketone, and tetramethylammonium bromide increases the solubility of benzene in ethylene glycol and formamide (as it does in water).These tetraalkylammonium cations probably act as pseudodetergents and interact primarily with the solutes, not the solvents.