19129-74-9

Upstream product

• 91-23-6 2-Nitroanisole 
• 90-04-0 2-methoxy-phenylamine 
• 787-77-9 N,N'-bis-(2-methoxy-phenyl)-hydrazine 
• 117359-11-2 2-<(2-Methoxyphenyl)amino>-1H-isoindol-1,3-(2H)-dion 
• 71-43-2 benzene 
• 3425-23-8 2-methoxybenzenediazonium chloride 
• 13620-57-0 2,2'-dimethoxyazoxybenzene 
• 88-73-3 2-Chloronitrobenzene 
• 3032-81-3 3,5-dichloroiodobenzene 
• 492-95-5 2-methoxyphenyldiazonium tetrafluoroborate 
• 77-78-1 dimethyl sulfate 
• 106-47-8 4-chloro-aniline 
• 62-53-3 aniline 
• 589-16-2 4-aminoethylbenzene 

Downstream Products

• 119-90-4 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine 
• 787-77-9 N,N'-bis-(2-methoxy-phenyl)-hydrazine 
• 90-04-0 2-methoxy-phenylamine 
• 1647096-99-8 (E)-1-(2-methoxy-6-nitrophenyl)-2-(2-methoxyphenyl)diazene 
• 13620-57-0 (Z)-1,2-bis(2-methoxyphenyl)diazene 1-oxide 

Relevant academic research and scientific papers

Copper-Manganese Spinel Oxide Catalyzed Synthesis of Amides and Azobenzenes via Aminyl Radical Cations

A highly efficient Cu-Mn-catalyzed process for the aminolysis of esters was developed. Also, the catalyst promoted the self- And cross-dehydrogenative coupling of anilines to generate symmetrical and unsymmetrical azobenzenes, respectively. The reactions were performed under neutral conditions with an inexpensive catalyst, gave high yields, and offered wide functional group tolerance. Spinel tap: A novel facet of aminyl radical cation reactivity with esters for the synthesis of amides is presented. The developed method also gives access to symmetrical and unsymmetrical azobenzenes. The reactions are performed under neutral conditions with an inexpensive catalyst, give high yields, and have a wide functional group tolerance.

Selective Oxidation of Anilines to Azobenzenes and Azoxybenzenes by a Molecular Mo Oxide Catalyst

Aromatic azo compounds, which play an important role in pharmaceutical and industrial applications, still face great challenges in synthesis. Herein, we report a molybdenum oxide compound, [N(C4H9)4]2[Mo6O19] (1), catalyzed selective oxidation of anilines with hydrogen peroxide as green oxidant. The oxidation of anilines can be realized in a fully selectively fashion to afford various symmetric/asymmetric azobenzene and azoxybenzene compounds, respectively, by changing additive and solvent, avoiding the use of stoichiometric metal oxidants. Preliminary mechanistic investigations suggest the intermediacy of highly active reactive and elusive Mo imido complexes.

Photocatalytic oxidative coupling of arylamines for the synthesis of azoaromatics and the role of O2 in the mechanism

The photocatalytic oxidative coupling of aryl amines to selectively synthesize azoaromatic compounds has been realized. Multiple different photocatalysts can be used to perform the general reaction; however, Ir(dF-CF3-ppy)2(dtbpy)+, where dF-CF3-ppy is 2-(2,4-difluorophenyl)-5-(trifluoromethyl)-pyridine and dtpby is 4,4′-tert-butyl-2,2′-bipyridine, showed the greatest range of reactivity with various amine substrates. Both electron-rich and -deficient amines can be coupled with yields up to 95% under an ambient air atmosphere. Oxygen was deemed to be essential for the reaction and is utilized in the regeneration of the photocatalyst. Fluorescence quenching and radical trap experiments indicate an amine radical coupling mechanism that proceeds through a hydrazoaromatic intermediate before further oxidation occurs to form the desired azoaromatic products.

Single crystal MnOOH nanotubes for selective oxidative coupling of anilines to aromatic azo compounds

Catalytic synthesis of aromatic azo compounds by oxidative coupling of anilines using molecular oxygen represents a facile, green and valuable process; however, such an economical process suffers from poor catalytic activity and selectivity. Herein, novel single crystal MnOOH nanotubes with abundant Mn3+sites and high oxygen defects were successfully synthesized. The catalyst exhibited high selectivity for oxidative coupling of anilines, achieving complete transformation into aromatic azo compounds under mild conditions, even at room temperature.

Chemoselective electrochemical reduction of nitroarenes with gaseous ammonia

Valuable aromatic nitrogen compounds can be synthesized by reduction of nitroarenes. Herein, we report electrochemical reduction of nitroarenes by a protocol that uses inert graphite felt as electrodes and ammonia as a reductant. Depending on the cell voltage and the solvent, the protocol can be used to obtain aromatic azoxy, azo, and hydrazo compounds, as well as aniline derivatives with high chemoselectivities. The protocol can be readily scaled up to >10 g with no decrease in yield, demonstrating its potential synthetic utility. A stepwise cathodic reduction pathway was proposed to account for the generations of products in turn.

Tandem selective reduction of nitroarenes catalyzed by palladium nanoclusters

We report a catalytic tandem reduction of nitroarenes by sodium borohydride (NaBH4) in aqueous solution under ambient conditions, which can selectively produce five categories of nitrogen-containing compounds: anilines, N-aryl hydroxylamines, azoxy-, azo- and hydrazo-compounds. The catalyst is in situ-generated ultrasmall palladium nanoclusters (Pd NCs, diameter of 1.3 ± 0.3 nm) from the reduction of Pd(OAc)2 by NaBH4. These highly active Pd NCs are stabilized by surface-coordinated nitroarenes, which inhibit the further growth and aggregation of Pd NCs. By controlling the concentration of Pd(OAc)2 (0.1-0.5 mol% of nitroarene) and NaBH4, the water/ethanol solvent ratio and the tandem reaction sequence, each of the five categories of N-containing compounds can be obtained with excellent yields (up to 98%) in less than 30 min at room temperature. This tunable catalytic tandem reaction works efficiently with a broad range of nitroarene substrates and offers a green and sustainable method for the rapid and large-scale production of valuable N-containing chemicals.

Conversion of anilines into azobenzenes in acetic acid with perborate and Mo(VI): correlation of reactivities

Azobenzenes are extensively used to dye textiles and leather and by tuning the substituent in the ring, vivid colours are obtained. Here, we report preparation of a large number of azobenzenes in good yield from commercially available anilines using sodium perborate (SPB) and catalytic amount of Na2MoO4 under mild conditions. Glacial acetic acid is the solvent of choice and the aniline to azobenzene conversion is zero, first and first orders with respect to SPB, Na2MoO4 and aniline, respectively. Based on the kinetic orders, UV–visible spectra and cyclic voltammograms, the conversion mechanism has been suggested. The reaction rates of about 50 anilines at 20–50?°C and their energy and entropy of activation conform to the isokinetic or Exner relationship and compensation effect, respectively. However, the reaction rates, deduced by the so far adopted method, fail to comply with the Hammett correlation. The specific reaction rates of molecular anilines, obtained through a modified calculation, conform to the Hammett relationship. Thus, this work presents a convenient inexpensive non-hazardous method of preparation of a larger number of azobenzenes, and shows the requirement of modification in obtaining the true reaction rates of anilines in acetic acid and the validity of Hammett relationship in the conversion process, indicating operation of a common mechanism.

Immobilized antimony species on magnetite: A novel and highly efficient magnetically reusable nanocatalyst for direct and gram-scale reductive-coupling of nitroarenes to azoarenes

In this study, magnetic nanoparticles of Fe3O4@SbFx from the immobilization of SbF3 on magnetite were synthesized. The prepared nanocomposite system was then characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, vibrating sample magnetometry and inductively coupled plasma optical emission spectroscopy. Next, the catalytic activity of Fe3O4@SbFx MNPs was highlighted by one-pot reductive-coupling of aromatic nitro compounds to the corresponding azoarene materials with NaBH4. The reactions were carried out in refluxing EtOH within 6-25 min to afford the products in high yields. The reusability of the Sb-magnetite system was also studied for 6 consecutive cycles without significant loss of catalytic activity. This synthetic protocol provided several advantages in terms of introducing a novel catalytic system based on antimony species for direct and gram-scale preparation of azoarenes from nitroarenes, low loading of the nanocatalyst, mild reaction conditions, using ethanol as a green and economic solvent and high yield of the products.

Synthesis of Azobenzene Dyes Mediated by CotA Laccase

An eco-friendly protocol for the synthesis of azobenzene dyes by oxidative coupling of primary aromatic amines is reported. As efficient biocatalytic systems, CotA laccase and CotA laccase/ABTS (2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid)) enable the oxidation of various substituted anilines, in aqueous medium, ambient atmosphere and under mild reaction conditions of pH and temperature. A series of azobenzene dyes were prepared in good to excellent yields in an one-pot reaction. A mechanistic proposal for the formation of the azo derivatives is presented. Our strategy offers an alternative approach for the direct synthesis of azobenzene dyes, avoiding the harsh conditions generally required for most of the traditional synthetic methods.

Preparation of carbon-based AuAg alloy nanoparticles by using the heterometallic [Au4Ag4] cluster for efficient oxidative coupling of anilines

We herein report the preparation of unique heteroatom-doped and carbon-based AuAg alloy nanoparticles (NPs) via the pyrolysis of a structurally defined octanuclear heterometallic Au(i)-Ag(i) cluster [Au4Ag4(Dppy)4(Tab)sub