332-07-0

Usage

Uses

Used in Organic Synthesis:
(E)-bis(4-fluorophenyl)diazene is used as a building block in organic synthesis for the creation of complex organic molecules. Its diazene linkage and fluorophenyl groups provide unique reactivity and selectivity in chemical reactions, facilitating the synthesis of novel compounds with specific properties.
Used in Coordination Chemistry:
In coordination chemistry, (E)-bis(4-fluorophenyl)diazene is used as a ligand to form coordination complexes with metal ions. The presence of the diazene group and fluorinated phenyl rings allows for the formation of stable complexes with interesting electronic and structural properties, which can be further explored for various applications.
Used in Organic Light-Emitting Diodes (OLEDs):
(E)-bis(4-fluorophenyl)diazene is used as a component in the development of organic light-emitting diodes (OLEDs) due to its potential electronic properties. (E)-bis(4-fluorophenyl)diazene's ability to emit light upon electrical stimulation makes it a candidate for improving the performance and efficiency of OLEDs in display and lighting technologies.
Used as Photoswitches:
(E)-bis(4-fluorophenyl)diazene is utilized as a photoswitch in various applications, such as molecular switches and sensors, due to its ability to undergo reversible photochemical reactions. (E)-bis(4-fluorophenyl)diazene's photoresponsive nature allows for the control of its properties and functions upon exposure to light, enabling its use in smart materials and devices.

Upstream product

• 352-15-8 4-fluoro-nitrosobenzene 
• 371-40-4 4-fluoroaniline 
• 108-42-9 3-chloro-aniline 
• 350-46-9 4-Fluoronitrobenzene 
• 58-27-5 menadione 
• 332-06-9 (4,4'-difluoro)-1,2-diphenylhydrazine 
• 3296-02-4 p-azidofluorobenzene 
• 108-88-3 toluene 
• 94-09-7 p-aminoethylbenzoate 
• 99-92-3 p-aminobenzophenone 
• 51789-00-5 4,4'-difluoroazobenzene 
• 3382-69-2 C₁₄H₁₂FNO₂ 
• 1545-83-1 4-fluoroazobenzene 
• 1073-69-4 N-4-chlorophenylhydrazine 

Downstream Products

• 332-06-9 (4,4'-difluoro)-1,2-diphenylhydrazine 
• 1440357-16-3 C₂₂H₂₆F₂N₂ 
• 1545-83-1 4-fluoroazobenzene 
• 326-04-5 1,2-bis(4-fluorophenyl)diazene oxide 
• 1601-98-5 (E)-bis(4-bromophenyl)diazene 
• 51789-00-5 4,4'-difluoroazobenzene 
• 1595026-04-2 2-(4-methylphenylsulfonamido)-4,4'-difluoroazobenzene 
• 1239969-18-6 C₁₉H₂₂F₂N₂Si 
• 1112075-74-7 bis(μ-acetato)bis(4,4'-difluoroazobenzene-C2,N)dipalladium(II) 
• 150207-14-0 η2-N,N-di(4-fluorophenyl)diazene-tris(trimethylphosphine)cobalt(0) 

Relevant academic research and scientific papers

The improved method of oxidation of 4-fluoroaniline to 4- fluoroazobenzene

The improved method of oxidation of 4-fluoroaniline to 4- fluoroazobenzene with K3Fe(CN)6/KOH and 2,4,6-tri-tert-butylphenol as catalyst is described for the first time in this paper. This report offers an efficient and rapid method to prepare azobenzene and a possible mechanism is also suggested.

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.

Rhodium(III)-catalyzed regioselective C–H nitrosation/annulation of unsymmetrical azobenzenes to synthesize benzotriazole N-oxides via a RhIII/RhIII redox-neutral pathway

A Rh(III)-catalyzed regioselective C–H nitrosation/annulation reaction of unsymmetrical azobenzenes with [NO][BF4] has been developed to achieve high-yielding syntheses of benzotriazole N-oxides with excellent functional group tolerance. Computational studies have revealed that this oxidative C–H functionalization reaction involves an interesting redox-neutral Rh(III)/Rh(III) pathway without the change of Rh oxidation state.

Electrosynthesis of Azobenzenes Directly from Nitrobenzenes

The electrochemical reduction strategy of nitrobenzenes is developed. The chemistry occurs under ambient conditions. The protocol uses inert electrodes and the solvent, DMSO, plays a dual role as a reducing agent. Its synthetic value has been demonstrated by the highly efficient synthesis of symmetric, unsymmetric and cyclic azo compounds.

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.

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.

Cu(OTf)2-Mediated Cross-Coupling of Nitriles and N-Heterocycles with Arylboronic Acids to Generate Nitrilium and Pyridinium Products**

Metal-catalyzed C–N cross-coupling generally forms C?N bonds by reductive elimination from metal complexes bearing covalent C- and N-ligands. We have identified a Cu-mediated C–N cross-coupling that uses a dative N-ligand in the bond-forming event, which, in contrast to conventional methods, generates reactive cationic products. Mechanistic studies suggest the process operates via transmetalation of an aryl organoboron to a CuII complex bearing neutral N-ligands, such as nitriles or N-heterocycles. Subsequent generation of a putative CuIII complex enables the oxidative C–N coupling to take place, delivering nitrilium intermediates and pyridinium products. The reaction is general for a range of N(sp) and N(sp2) precursors and can be applied to drug synthesis and late-stage N-arylation, and the limitations in the methodology are mechanistically evidenced.

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.

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.