21650-54-4

Upstream product

• 917-64-6 methyl magnesium iodide 
• 60-29-7 diethyl ether 
• 99-99-0 1-methyl-4-nitrobenzene 
• 623-11-0 1-methyl-4-nitrosobenzene 
• 925-90-6 ethylmagnesium bromide 
• 15182-74-8 2-Methylsulfinylanilin 
• 623-10-9 N-(4-methylphenyl)hydroxylamine 
• 540-23-8 p-toluidine hydrochloride 
• 2028-84-4 p-methylbenzenediazonium chloride 
• 67-66-3 chloroform 
• 112160-74-4 acetic acid-(2,4,N-trichloro-anilide) 
• 106-49-0 p-toluidine 
• 861367-03-5 3-p-tolyl-triazane-1,2-dicarboxylic acid diethyl ester 
• 108-88-3 toluene 

Downstream Products

• 91-62-3 6-methylquinoline 
• 637-47-8 1,2-di(p-tolyl)hydrazine 
• 13556-70-2 N-(4-methylphenyl)-5-methyl-1,2-phenylenediamine 
• 955-98-6 1,2-bis(4-methylphenyl)diazene oxide 
• 17082-75-6 1,2,4,5-Tetra-p-tolyl-3,3,6,6-tetramethyl-1,2,4,5-tetraaza-3,6-disila-cyclohexan 
• 17082-76-7 1.2.4.5-Tetra-p-tolyl-3.3.6.6-tetraphenyl-1.2.4.5-tetraaza-3.6-disila-cyclohexan 
• 22264-09-1 1,2,4,5-Tetrahydro-1,2-bis(4-methylphenyl)-3,6-pyridazindion 
• 111122-26-0 1,2-di-p-tolylhexahydropyridazine 
• 31935-68-9 1,1,1-Trimethyl-N-(4-methylphenyl)-N-(trimethylsilyl)silanamine 
• 144499-80-9 4,4'-dimethyl-3-heptafluoropropylazobenzene 
• 127388-15-2 N-((E)-Styryl)-N,N'-di-p-tolyl-hydrazine 
• 114854-78-3 4-(bromomethyl)-4'-methylazobenzene 
• 14618-59-8 N-(tert-butoxycarbonyl)-4-methylaniline 
• 106-49-0 p-toluidine 

Relevant academic research and scientific papers

Aryliminodimagnesium Reagents. V. The Reaction with Bifunctional Nitroarenes

The reactions of p-methylphenyliminodimagnesium reagent (p-MeC6H4N(MgBr)2) with p- and m-dinitrobenzenes, bis(p-nitrophenyl)methane, bis(p-nitrophenyl) sulfide and ether, p- and m-nitrobenzaldehydes as well as 4-nitro-4'-methylbenzophenone were investigated. p-Dinitrobenzene, which is the strongest electron-acceptor among the substrates used, gave ca. 30percent combined yield of bis(azoxy) and azoxy azo products.The oxidative coupling product, 4,4'-dimethylazobenzene, was isolated in 20-30percent yields.About 60percent combined yield of the bis(azoxy) and azoxy azo products was obtained in the same reaction with m-dinitrobenzene, which is less electron-accepting than the p-isomer.In the reaction of bis(p-nitrophenyl)methane, bis(p-nitrophenyl)sulfide and ether with five molar amounts of the reagent, ca. 70percent combined yields of bis(azoxy), azoxy azo, and bis(azo) products were obtained.On the treatment of the nitrobenzaldehydes and the nitrobenzophenone, in contrast, the reaction took place exclusively on the nitro group.The results are discussed in terms of the electron-accepting ability of substrates.

SYNTHESIS AND SOME PHYSICAL PROPERTIES OF UNSYMMETRICAL 4,4 prime -DIALKYLAZOXYBENZENES.

Two series of unsymmetrical 4,4 prime -dialkylazoxy compounds were obtained. The method of their synthesis and the results of measurements of the phase transition temperatures, dielectric constant, refractive indices and densities are presented. Compounds

Unraveling the surface properties of PMMA/azobenzene blends as coating films with photoreversible surface polarity

Various reports demonstrated that azobenzene derivatives are the chromophore of choice in photoresponsive surfaces showing reversible surface polarity. Hitherto the surface study of coating films based on polymer/azobenzene blends using contact angle meas

Guest-Induced Breathing Effect in a Flexible Molecular Crystal

By introducing a flexible component into a molecular building block, we present an unprecedented alkyl-decorated flexible crystalline material with a breathing behavior. Its selective adsorption is derived from the breathing effect induced by a guest trig

H2O2-mediated room temperature synthesis of 2-arylacetophenones from arylhydrazines and vinyl azides in water

An environmentally benign, cost-efficient and practical methodology for the room temperature synthesis of 2-arylacetophenones in water has been discovered. The facile and efficient transformation involves the oxidative radical addition of arylhydrazines with α-aryl vinyl azides in the presence of H2O2 (as a radical initiator) and PEG-800 (as a phase-transfer catalyst). From the viewpoint of green chemistry and organic synthesis, the present protocol is of great significance because of using cheap, non-toxic and readily available starting materials and reagents as well as amenability to gram-scale synthesis, which provides an attractive strategy to access 2-arylacetophenones.

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.

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.

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.

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.