501-58-6

Usage

Purification Methods

Chromatograph it on basic alumina and elute with *benzene. Then crystallise the residue from 2:2:1 (v/v) methanol/ethanol/*benzene or Me2CO. [Beilstein 16 H 112, 16 I 237, 16 II 43, 16 III 93, 16 IV 172.]

InChI:InChI=1/C14H14N2O2/c1-17-13-7-3-11(4-8-13)15-16-12-5-9-14(18-2)10-6-12/h3-10H,1-2H3/b16-15+

Upstream product

• 60-29-7 diethyl ether 
• 1516-21-8 4-methoxynitrosobenzene 
• 100-17-4 para-methoxynitrobenzene 
• 82570-64-7 cis-4,4'-dimethoxyazobenzene 
• 71-43-2 benzene 
• 1128-65-0 [1,1']bicyclohexyl-1,1'-diene 
• 118622-95-0 N-(4-methoxyphenylaminothio)phthalimide 
• 2942-05-4 7-nitrobenzothiazole 
• 2942-07-6 5-nitrobenzothiazole 
• 2942-08-7 4-nitrobenzothiazole 
• 107940-72-7 2-<(4-Methoxyphenyl)amino>-1H-isoindol-1,3-(2H)-dion 
• 3315-32-0 2,4,6-tri-tert-butylphenoxyl 
• 17333-79-8 p-methoxybenzenediazonium 
• 5194-50-3 (E,Z)-2,4-hexadiene 

Downstream Products

• 20841-05-8 N--hexamethyldisilazan 
• 1027-40-3 bis(4-methoxyphenyl)hydrazine 
• 104-94-9 4-methoxy-aniline 
• 1562-94-3 4,4'-dimethoxyazoxybenzene 
• 107820-83-7 Ru₃(NC₆H₅)(NC₆H₄OCH₃)(CO)9 
• 227310-24-9 [(4,4'-bis(methoxy)C6H3NNC6H4)Pt(μ-Cl)]2 
• 227310-27-2 (4,4'-bis(methoxy)C₆H₃NNC₆H₄)Pt(acac) 
• 1440356-76-2 C₂₄H₃₂N₂O₂ 
• 1421276-36-9 C₂₁H₁₈N₂O₃ 
• 17377-95-6 benzyl(4-methoxyphenyl)amine 
• 5263-87-6 6-methoxy quinoline 
• 1619236-41-7 (E)-5-methoxy-2-((4-methoxyphenyl)diazenyl)phenyl benzoate 
• 2396-60-3 4-methoxyazobenzene 

Relevant academic research and scientific papers

Well-defined vanadium organoazide complexes and their conversion to terminal vanadium imides: Structural snapshots and evidence for a nitrene capture mechanism

We report the synthesis and structural characterization of a family of well-defined organoazide complexes supported by a three-fold-symmetric pyrrolide scaffold and their conversion to the corresponding terminal imido congeners. Kinetic measurements on a

Correlation studies in the oxidation of Vanillin Schiff bases by acid bromate - A kinetic and semi-empirical approach

Kinetics and mechanistic aspects of oxidation of Vanillin Schiff bases (obtained from Vanillin and p-substituted anilines) by bromate in acid medium has been studied at 313 ?K. The reaction exhibited first order in [bromate] and less than unity order each in [Vanillin Schiff base] and [acid]. The increase in the rate of reaction with decrease in dielectric constant of the medium is observed with all the studied substrates. The reaction failed to induce the polymerization of acrylonitrile. Electron withdrawing substituents in the aniline ring moiety of Vanillin Schiff base accelerate the rate of oxidation to a large extent and electron releasing substituents retard the rate. The order of reactivity is found to be p-nitro ?> ?p-bromo ?> ?p-chloro ?> ?–H ?> ?p-fluoro ?> ?p-methyl ?> ?p-methoxy ?> ?p-ethoxy and the sensitivity of the substrates towards the reaction rate is further supported by the semi-empirical calculation of electronic properties and global descriptors of the substrates (Vanillin Schiff bases) with different substituents in the aniline ring moiety. The observed trend in the reactivity of the substrates was correlated with the calculated descriptors like electronegativity, chemical potential, electrophilicity index, chemical hardness and frontier molecular orbitals. The linear free-energy relationship is characterized by a straight line in the Hammett's plot of log k versus σ. The ρ values are positive and increase with increase in temperature. From the Exner and Arrhenius plots, the isokinetic relationship is discussed. Oxidation products identified are p-substituted azobenzene and vanillic acid. Based on the experimental observations, a plausible mechanism is proposed and rate law is derived.

Hydrogen peroxide based oxidation of hydrazines using HBr catalyst

Azo compounds (RN = NR′) are an important class of organic molecules that find wide application in organic synthesis. Herein, we report an efficient, practical and metal-free oxidation of hydrazines (RNH-NHR’) to azo compounds using 5 mol% HBr and hydrogen peroxide as terminal oxidant. This new method has been demonstrated by 40 examples with excellent yields. In addition, we showcased two examples of the one-pot sequential reactions involving our hydrazine oxidation/hydrolysis/Heck reaction or Cu-catalyzed N-arylation with aryl boronic acid. The distinct advantages of this protocol include metal-free catalysis, waste prevention, and easy operation.

Azo synthesis meets molecular iodine catalysis

A metal-free synthetic protocol for azo compound formation by the direct oxidation of hydrazine HN-NH bonds to azo group functionality catalyzed by molecular iodine is disclosed. The strengths of this reactivity include rapid reaction times, low catalyst loadings, use of ambient dioxygen as a stoichiometric oxidant, and ease of experimental set-up and azo product isolation. Mechanistic studies and density functional theory computations offering insight into this reactivity, as well as the events leading to azo group formation are presented. Collectively, this study expands the potential of main-group element iodine as an inexpensive catalyst, while delivering a useful transformation for forming azo compounds.

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.

Manganese Catalyzed Hydrogenation of Azo (N=N) Bonds to Amines

We report the first example of homogeneously catalyzed hydrogenation of the N=N bond of azo compounds using a complex of an earth-abundant-metal. The hydrogenation reaction is catalyzed by a manganese pincer complex, proceeds under mild conditions, and yields amines, which makes this methodology a sustainable alternative route for the conversion of azo compounds. A plausible mechanism involving metal-ligand cooperation and hydrazine intermediacy is proposed based on mechanistic studies. (Figure presented.).

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.

A synthetic method of aromatic azo compounds

The present invention belongs to the field of azo compound technology, discloses a method of synthesis of an aromatic azo compound. The present invention is an aromatic amine and a catalyst massager ratio 1: 0.05 ~ 0.06 mixed, at 95 ~ 110 ° C reaction 22

Light-Promoted C–N Coupling of Aryl Halides with Nitroarenes

A photochemical C–N coupling of aryl halides with nitroarenes is demonstrated for the first time. Catalyzed by a NiII complex in the absence of any external photosensitizer, readily available nitroarenes undergo coupling with a variety of aryl halides, providing a step-economic extension to the widely used Buchwald–Hartwig C–N coupling reaction. The method tolerates coupling partners with steric-congestion and functional groups sensitive to bases and nucleophiles. Mechanistic studies suggest that the reaction proceeds via the addition of an aryl radical, generated from a NiI/NiIII cycle, to a nitrosoarene intermediate.

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.