332-07-0

Basic information

• Product Name: (E)-bis(4-fluorophenyl)diazene
• Synonyms: Azobenzene, 4,4'-difluoro-
• CAS NO: 332-07-0
• Molecular Formula: C₁₂H₈F₂N₂
• Molecular Weight: 218.2021
• Mol File: 332-07-0.mol

Chemical Properties

• Boiling Point: 314.6°C at 760 mmHg
• Flash Point: 144.1°C
• Density: 1.18g/cm³
• Vapor Pressure: 0.000851mmHg at 25°C
• Refractive Index: 1.549
• CAS DataBase Reference: (E)-bis(4-fluorophenyl)diazene(CAS DataBase Reference)
• NIST Chemistry Reference: (E)-bis(4-fluorophenyl)diazene(332-07-0)
• EPA Substance Registry System: (E)-bis(4-fluorophenyl)diazene(332-07-0)

Safety Data

• Hazardous Substances Data: 332-07-0(Hazardous Substances Data)

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 
• 106-49-0 p-toluidine 
• 106-47-8 4-chloro-aniline 
• 108-42-9 3-chloro-aniline 
• 350-46-9 4-Fluoronitrobenzene 
• 108-44-1 1-amino-3-methylbenzene 
• 326-04-5 N,N'-Bis-(4-fluoro-phenyl)-diazene N-oxide 
• 58-27-5 menadione 
• 332-06-9 (4,4'-difluoro)-1,2-diphenylhydrazine 
• 101906-10-9 N-butyl-4-fluoroaniline 
• 201230-82-2 carbon monoxide 
• 1073-69-4 N-4-chlorophenylhydrazine 
• 62-53-3 aniline 

Downstream Products

• 332-06-9 (4,4'-difluoro)-1,2-diphenylhydrazine 
• 326-04-5 1,2-bis(4-fluorophenyl)diazene oxide 
• 150207-14-0 η2-N,N-di(4-fluorophenyl)diazene-tris(trimethylphosphine)cobalt(0) 
• 1112075-74-7 bis(μ-acetato)bis(4,4'-difluoroazobenzene-C2,N)dipalladium(II) 
• 1239969-18-6 C₁₉H₂₂F₂N₂Si 
• 1440357-16-3 C₂₂H₂₆F₂N₂ 
• 1595026-04-2 2-(4-methylphenylsulfonamido)-4,4'-difluoroazobenzene 
• 81701-86-2 5-fluoro-2-(4-fluorophenylazo)phenol 
• 326-04-5 N,N'-Bis-(4-fluoro-phenyl)-diazene N-oxide 
• 371-40-4 4-fluoroaniline 
• 1128-61-6 6-fluoro-2-methyl-quinoline 
• 366-75-6 N-(4-fluorophenyl)benzamide 

Relevant articles and documents

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.

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.

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.).

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.

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.

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.

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.

Bifunctional Cs?Au/Co3O4 (Basic and Redox)-Catalyzed Oxidative Synthesis of Aromatic Azo Compounds from Anilines

An eco-friendly alkali-promoted (Cs?Au/Co3O4) catalyst, with redox and basic properties for the oxidative dehydrogenative coupling of anilines to symmetrical and unsymmetrical aromatic azo compounds, was developed. We realized a base additive- and molecular O2 oxidant-free process (using air), with reasonable reusability of the catalyst achieved under milder reaction conditions. Notably, the enhanced catalytic activity was also linked to the increased basic site concentration, low reduction temperatures, and the effect of lattice oxygen on the nanomaterials. The increased basic strength of the cation-promoted catalyst improved the electron density of the active Au species, resulting in higher yields of the desired aromatic azo compounds.