106131-20-8

Basic information

• Product Name: Diazene, bis(3-chlorophenyl)-, (Z)-
• CAS NO: 106131-20-8
• Molecular Formula: C12H8Cl2N2
• Molecular Weight: 251.115
• Mol File: 106131-20-8.mol
• Article Data: 87

Chemical Properties

• CAS DataBase Reference: Diazene, bis(3-chlorophenyl)-, (Z)-(CAS DataBase Reference)
• NIST Chemistry Reference: Diazene, bis(3-chlorophenyl)-, (Z)-(106131-20-8)
• EPA Substance Registry System: Diazene, bis(3-chlorophenyl)-, (Z)-(106131-20-8)

Safety Data

• Hazardous Substances Data: 106131-20-8(Hazardous Substances Data)

Upstream product

• 88-73-3 2-Chloronitrobenzene 
• 953-01-5 3,3'-dichlorohydrazobenzene 
• 108-42-9 3-chloro-aniline 
• 371-40-4 4-fluoroaniline 
• 29682-39-1 1-bromo-2-chloro-4-nitrobenzene 
• 121-73-3 3-Nitrochlorobenzene 
• 17099-19-3 3-chloro-N-(3-chloro-benzyliden)-aniline 
• 17064-65-2 3-chloro-N-(4-chloro-benzyliden)-aniline 
• 10480-27-0 3-chloro-N-(3-nitro-benzyliden)-aniline 
• 7705-08-0 iron(III) chloride 
• 156-87-6 propan-1-ol-3-amine 
• 932-78-5 1-chloro-3-nitrosobenzene 
• 139-24-2 (Z)-1,2-bis(3-chlorophenyl)diazene 1-oxide 
• 456-39-3 3-chlorobenzenediazonium tetrafluoroborate 

Downstream Products

• 953-01-5 3,3'-dichlorohydrazobenzene 
• 6004-21-3 3'-chloro-benzanilide 
• 84-68-4 2,2'-dichlorobenzidine 

Relevant articles and documents

Facile synthesis of azo compounds from aromatic nitro compounds using magnesium and triethylammonium formate

Magnesium/triethylammonium formate is a convenient reagent for the reduction of aromatic nitro compounds to corresponding symmetrically substituted azo compounds. Various azo compounds containing additional reducible substituents, including halogen, nitrile, acid, phenol, ester, and methoxy functions, have been synthesized in a single step by the use of this reagent. The conversion is reasonably fast, clean, high yielding, and occurs at room temperature in methanol.

Modulating the catalytic behavior of non-noble metal nanoparticles by inter-particle interaction for chemoselective hydrogenation of nitroarenes into corresponding azoxy or azo compounds

Aromatic azoxy compounds have wide applications and they can be prepared by stoichiometric or catalytic reactions with H2O2 or N2H4 starting from anilines or nitroarenes. In this work, we will present the direct chemoselective hydrogenation of nitroarenes with H2 to give aromatic azoxy compounds under base-free mild conditions, with a bifunctional catalytic system formed by Ni nanoparticles covered by a few layers of carbon (Ni@C NPs) and CeO2 nanoparticles. The catalytic performance of Ni@C-CeO2 catalyst surpasses the state-of-art Au/CeO2 catalyst for the direct production of azoxybenzene from nitrobenzene. By means of kinetic and spectroscopic results, a bifunctional mechanism is proposed in which, the hydrogenation of nitrobenzene can be stopped at the formation of azoxybenzene with >95% conversion and >93% selectivity, or can be further driven to the formation of azobenzene with >85% selectivity. By making a bifunctional catalyst with a non-noble metal, one can achieve chemoselective hydrogenation of nitroarenes not only to anilines, but also to corresponding azoxy and azo compounds.

The preparation of symmetrical azobenzenes from anilines by phase transfer catalyzed method

Used Galvinoxyl as catalyst, the phase transfer catalyzed method of oxidation of primary amines to symmetrical azobenzenes with a saturated solution of potassium ferricyanide in 2N aqueous potassium hydroxide and dichloromethane is described for the first time in this paper. The reaction has intimate relation with Hammett substituent constants. This report offers an efficient and rapid method to prepare azobenzenes and a possible mechanism is also suggested.

Reduction of nitrosobenzenes to azoarenes with SmI2

A novel method was developed to synthesise azoarenes from nitrosobenzenes under mild conditions. Samarium (II) iodine was used to achieve the N-N coupling. The method also provides evidence for the proposed mechanism involved in the reduction of nitro compounds to the amines with SmI2.

AlCl3·6H2O/KI/CH3CN/ H2O system: An efficient general system for deoxygenation of organic N-oxides in hydrated media

An efficient general system for deoxygenation of organic N-oxides such as N-aryl nitrones, azoxy benzenes and N-heteroarene N-oxides uses AlCl3·6H2O/KI/CH3CN/H2O system at room temperature in hydrated media. The deoxygenated products were found in good yields.

Visible-light-induced electron transport from small to large nanoparticles in bimodal gold nanoparticle-loaded Titanium(IV) oxide

A key to realizing the sustainable society is to develop highly active photocatalysts for selective organic synthesis effectively using sunlight as the energy source. Recently, metal-oxide-supported gold nanoparticles (NPs) have emerged as a new type of visible-light photocatalysts driven by the excitation of localized surface plasmon resonance of Au NPs. Here we show that visible-light irradiation (λ>430nm) of TiO2-supported Au NPs with a bimodal size distribution (BM-Au/TiO2) gives rise to the long-range (>40nm) electron transport from about 14 small (ca. 2nm) Au NPs to one large (ca. 9nm) Au NP through the conduction band of TiO2. As a result of the enhancement of charge separation, BM-Au/TiO2 exhibits a high level of visible-light activity for the one-step synthesis of azobenzenes from nitrobenzenes at 25C with a yield greater than 95 and a selectivity greater than 99, whereas unimodal Au/TiO2 (UM-Au/TiO2) is photocatalytically inactive. Visible-light-induced electron transport: Visible-light irradiation of TiO2-supported gold nanoparticles (NPs) with a bimodal size distribution (BM-Au/TiO2) gives rise to long-range electron transport from about 14 small NPs to one large Au NP through the conduction band of TiO2. As a result of the enhancement of the charge separation, BM-Au/TiO2 exhibits a high level of visible-light activity for the synthesis of azobenzenes (see picture) from nitrobenzenes.

Reduction of aromatic azo-,azoxy- and nitro-compounds by ultrasonically activated nickel

Substituted hydrazobenzenes were obtained in excellent yields from reduction of the corresponding azo- or azoxy- compounds by hydrazine hydrate under the catalysis of ultrasonically activated nickel (UAN). Reduction of nitroarenes by UAN produced azoxyarenes as the major products.

A general method for the deoxygenation of aromatic N-oxides using RuCl 3?xH2O

An efficient, simple and selective method for the deoxygenation of aromatic N-oxides, such as N-arylnitrones, azoxybenzenes, N-heteroarene N-oxides using ruthenium(III) chloride to afford deoxygenated products in excellent yields, is described.

An efficient catalyst-free and chemoselective synthesis of azobenzenes from nitrobenzenes

NaOH mediated reaction of nitrobenzenes in EtOH was performed at 80 °C temperature affording azobenzenes in excellent yield. This methodology presents an easy synthesis of a wide variety of azo compounds from readily available nitrobenzene derivatives. This journal is

Kinetics and mechanism of meso-tetraphenyl-porphyriniron (III) chloride catalyzed oxidation of aniline and its substituents by oxone in aqueous acetic acid medium

Metalloporphyrins are present naturally in cytochromes and hemoglobins. Perhaps the most interesting feature of heme-enzymes, such as cytochromes P450, is their ability to perform extremely difficult oxidations with high selectivity. The present work is undertaken with the aspiration of designing the mechanistic studies on meso-tetraphenylporphyriniron(III) chloride catalyzed oxidation of anilines by potassium peroxymonosulfate (oxone) in aqueous acetic acid medium. The study of oxidation with respect to the catalyst reveals that there is degradation of the catalyst. The concentration-protonated aniline (a less reactive species) increases due to the increase in [H+], which inhibits the rate of the reaction. The thermodynamic parameters for the oxidation have been determined and discussed. It confirms the Exner relationship and also the activation parameters to the isokinetic relationships. The oxone oxidation with 12 meta- and para-substituted anilines complies with the isokinetic relationship but not with any of the linear free energy relationships. The solvent interaction plays a major role in governing the reactivity. A suitable mechanism is proposed for this reaction.

Meso-tetraphenylironporphyrin(III) chloride catalyzed oxidation of aniline and its substituents by m-chloroperbenzoic acid

The most fascinating feature of heme-enzymes such as cytochromes P450 is their ability to carry out oxidations with high selectivity. Metalloporphyrin complexes are used as replicate compounds for cytochrome P450. A kinetic analysis has been carried out with the aim of understanding the mechanistic studies on oxidation of anilines by m-chloroperbenzoic acid catalyzed by meso-tetraphenylironporphyrin(III) chloride in aqueous acetic acid medium. The order of the reaction is found to be second order with respect to the substrate and first order with respect to the catalyst and oxidant. Product analysis proves that azobenzene is the sole product in the catalytic oxidation. The increase of [H+] in this oxidation retards the rate of the reaction. The effects of substituents on the oxidation rate are studied with 19 ortho-, meta- and para- substituted anilines at five different temperatures. The thermodynamic parameters for the oxidation have been determined and discussed. The catalysed m-chloroperbenzoic acid oxidation with substituted anilines fulfills the isokinetic relationship and Exner correlation but not to any of the linear free energy relationships. The solvent interaction also plays a major role in leading the reactivity. Based on the kinetic results and product analysis a probable mechanism is proposed.

Kinetics and thermodynamics of oxidation of some meta-substituted anilines by tetrabutylammonium bromochromate in aqueous acetic acid medium

The tetrabutylammonium bromochromate (TBABC) oxidation of anilines, in an aqueous acetic acid medium in the presence of perchloric acid is described. The reaction is first order with respect to aniline, TBABC and acid. The reaction rate has been determined at different temperatures and activation parameters calculated. The TBABC oxidation of meta-substituted anilines obeys Hammett relationships.

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Structure-reactivity correlation of anilines in acetic acid

The oxidation of aniline in glacial acetic acid with percarbonate, a dry carrier of hydrogen peroxide, is a second-order reaction conforming to the isokinetic relationship. The hitherto followed method of correlation of the reaction rates in terms of the structure-reactivity relationships is unsatisfactory and erroneous. But the reaction rates of molecular anilines, obtained for the first time, conform to the structure-reactivity relationships.

Iron(III)-salen-H2O2 as a peroxidase model: Electron transfer reactions with anilines

Iron(III)-salen complexes catalyze the H2O2 oxidation of various ring-substituted anilines in MeCN have been studied, and [O=Fe IV(salen)]+? is proposed as the active species. Study of the kinetics of the reaction by spectrophotometry shows the emergence of a new peak at 445 nm in the spectrum which corresponds to azobenzene. Further oxidation of azobenzene by H2O2 leads to the formation of azoxybenzene. ESI-MS studies also support the formation of these products. The rate constants for the oxidation of meta- and para-substituted anilines were determined from the rate of decay of oxidant as well as the rate of formation of azobenzene, and the reaction follows Michaelis-Menten kinetics. The rate data show a linear relationship with the Hammett σ constants and yield a ρ value of -1.1 to -2.4 for substituent variation in the anilines. A reaction mechanism involving electron transfer from aniline to [O=Fe(salen)] +? is proposed. The presence of axial ligands modulates the activity of the complex. Graphical Abstract: [Figure not available: see fulltext.]

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.

Synthesis of novel 1,2-diarylpyrazolidin-3-one–based compounds and their evaluation as broad spectrum antibacterial agents

There is a continuous need to develop new antibacterial agents with non-traditional mechanisms to combat the nonstop emerging resistance to most of the antibiotics used in clinical settings. We identified novel pyrazolidinone derivatives as antibacterial hits in an in-house library screening and synthesized several derivatives in order to improve the potency and increase the polarity of the discovered hit compounds. The oxime derivative 24 exhibited promising antibacterial activity against E. coli TolC, B. subtilis and S. aureus with MIC values of 4, 10 and 20 μg/mL, respectively. The new lead compound 24 was found to exhibit a weak dual inhibitory activity against both the E. coli MurA and MurB enzymes with IC50 values of 88.1 and 79.5 μM, respectively, which could partially explain its antibacterial effect. A comparison with the previously reported, structurally related pyrazolidinediones suggested that the oxime functionality at position 4 enhanced the activity against MurA and recovered the activity against the MurB enzyme. Compound 24 can serve as a lead for further development of novel and safe antibiotics with potential broad spectrum activity.