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 
• 861367-03-5 3-p-tolyl-triazane-1,2-dicarboxylic acid diethyl ester 
• 108-88-3 toluene 
• 622-57-1 N-ethyl-p-tolylamine 
• 15795-42-3 N-sulfinyl-4-methylaniline 
• 67-56-1 methanol 
• 201230-82-2 carbon monoxide 
• 100-25-4 para-dinitrobenzene 

Downstream Products

• 17082-75-6 1,2,4,5-Tetra-p-tolyl-3,3,6,6-tetramethyl-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 
• 13556-70-2 N-(4-methylphenyl)-5-methyl-1,2-phenylenediamine 
• 97654-99-4 (1E)-1,2-bis[4-(bromomethyl)phenyl]diazene 
• 637-47-8 1,2-di(p-tolyl)hydrazine 
• 14618-59-8 N-(tert-butoxycarbonyl)-4-methylaniline 
• 2759-55-9 N-p-tolylpropionamide 
• 582-78-5 N-(4-methylphenyl)benzamide 
• 103-89-9 4-Methylacetanilide 
• 20172-29-6 N-(p-tolyl)butyramide 
• 20172-33-2 N-(4-methylphenyl)hexanamide 
• 496-72-0 4-methyl-1,2-diaminobenzene 
• 1239969-16-4 C₂₁H₂₈N₂Si 
• 1421276-54-1 2-(4-methylphenyl)-3-phenyl-5-methyl-2H-indazole 

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.

Selective Reduction of Nitroarenes to Arylamines by the Cooperative Action of Methylhydrazine and a Tris(N-heterocyclic thioamidate) Cobalt(III) Complex

We report an efficient catalytic protocol that chemoselectively reduces nitroarenes to arylamines, by using methylhydrazine as a reducing agent in combination with the easily synthesized and robust catalyst tris(N-heterocyclic thioamidate) Co(III) complex [Co(κS,N-tfmp2S)3], tfmp2S = 4-(trifluoromethyl)-pyrimidine-2-thiolate. A series of arylamines and heterocyclic amines were formed in excellent yields and chemoselectivity. High conversion yields of nitroarenes into the corresponding amines were observed by using polar protic solvents, such as MeOH and iPrOH. Among several hydrogen donors that were examined, methylhydrazine demonstrated the best performance. Preliminary mechanistic investigations, supported by UV-vis and NMR spectroscopy, cyclic voltammetry, and high-resolution mass spectrometry, suggest a cooperative action of methylhydrazine and [Co(κS,N-tfmp2S)3] via a coordination activation pathway that leads to the formation of a reduced cobalt species, responsible for the catalytic transformation. In general, the corresponding N-arylhydroxylamines were identified as the sole intermediates. Nevertheless, the corresponding nitrosoarenes can also be formed as intermediates, which, however, are rapidly transformed into the desired arylamines in the presence of methylhydrazine through a noncatalytic path. On the basis of the observed high chemoselectivity and yields, and the fast and clean reaction processes, the present catalytic system [Co(κS,N-tfmp2S)3]/MeNHNH2 shows promise for the efficient synthesis of aromatic amines that could find various industrial applications.

Invisible Silver Guests Boost Order in a Framework That Cyclizes and Deposits Ag3Sb Nanodots

The infusion of metal guests into (i.e., metalating) the porous medium of metal-organic frameworks (MOFs) is a topical approach to wide-ranging functionalization purposes. We report the notable interactions of AgSbF6 guests with the designer MOF host ZrL1 [Zr6O4(OH)7(L1)4.5(H2O)4]. (1) The heavy-atom guests of AgSbF6 induce order in the MOF host to allow the movable alkyne side arm to be fully located by X-ray diffraction, but they themselves curiously remain highly disordered and absent in the strucutral model. The enhanced order of the framework can be generally ascribed to interaction of the silver guests with the host alkyne and thioether functions, while the invisible heavy-atom guest represents a new phenomenon in the metalation of open framework materials. (2) The AgSbF6 guests also participate in the thermocyclization of the vicinal alkyne units of the L1 linker (at 450 °C) and form the rare nanoparticle of Ag3Sb supported on the concomitantly formed nanographene network. The resulted composite exhibits high electrical conductivity (1.0 S/cm) as well as useful, mitigated catalytic activity for selectively converting nitroarenes into the industrially important azo compounds, i.e., without overshooting to form the amine side products. The heterogeneous/cyclable catalysis entails only the cheap reducing reagents of NaBH4, ethanol, and water, with yields being generally close to 90%.

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.

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.