20739-72-4

Upstream product

• 64-17-5 ethanol 
• 41381-50-4 N-(4-chloro-phenyl)-N'-p-tolyl-hydrazine 
• 106-49-0 p-toluidine 
• 106-47-8 4-chloro-aniline 
• 99-99-0 1-methyl-4-nitrobenzene 
• 100-00-5 4-chlorobenzonitrile 
• 3296-05-7 1-azido-4-chlorobenzene 
• 2101-86-2 p-methylazidobenzene 
• 108-95-2 phenol 
• 7647-01-0 hydrogenchloride 
• 2497-33-8 4-((4-methylphenyl)azo)phenol 

Downstream Products

• 41381-50-4 N-(4-chloro-phenyl)-N'-p-tolyl-hydrazine 
• 74769-84-9 N²-(4-chloro-phenyl)-4-methyl-o-phenylenediamine 
• 144499-81-0 4-chloro-3'-heptafluoropropyl-4'-methylazobenzene 
• 96295-23-7 N'-<4-Chlor-phenyl>-N-p-tolyl-diimid-N-oxid 
• 96294-55-2 1-(4-chlorophenyl)-2-(p-tolyl)diazene oxide 

Relevant academic research and scientific papers

Heterocoupling of Different Aryl Nitrenes to Produce Asymmetric Azoarenes Using Iron-Alkoxide Catalysis and Investigation of the Cis-Trans Isomerism of Selected Bulky Asymmetric Azoarenes

Heterocoupling of different aryl nitrenes (originating in organoazides) to produce asymmetric azoarenes using two different iron-alkoxide catalysts is reported. Fe(OCtBu2(3,5-Ph2C6H3))2(THF)2 was previously shown to catalyze the homocoupling of a variety of aryl nitrenes. While bulky nitrenes featuring ortho substituents were coupled more efficiently, coupling of the less bulky meta- and para-substituted aryl nitrenes was also demonstrated. In contrast, the iron(II) complex of a chelating bis(alkoxide) ligand, Fe[OO]Ph(THF)2, was previously shown to efficiently couple nonbulky aryl nitrenes lacking substituents in ortho positions. In the present work, we demonstrate that the combination of two different nitrenes (10 equiv overall, 5 equiv each) with Fe(OCtBu2(3,5-Ph2C6H3))2(THF)2 (10 mol %) produced a statistical or close to statistical distribution (25:25:50 for the two homocoupled products and the heterocoupled product, respectively) for various combinations containing one or two ortho alkyl substituents at one nitrene and a single ortho alkyl group at another. Surprisingly, the combination of Fe[OO]Ph(THF)2 with two different nonbulky organoazides was found to primarily catalyze the homocoupling of the resulting aryl nitrenes (21-49%), with a smaller proportion (～8-15%) of asymmetric product formation. Six different heterocoupled products featuring one or two alkyl groups in the ortho positions were isolated as a mixture of cis and trans isomers at room temperature and characterized by NMR spectroscopy, UV-vis spectroscopy, and high-resolution mass spectrometry. Following their isolation, cis-trans isomerism in these species was investigated. Heating the cis-trans mixture to 60 °C produced the trans isomer cleanly, while shining UV light on the cis-trans mixture significantly increased the amount of the cis isomer (up to 90%). The cis isomer was found to be relatively stable, exhibiting t1/2 values of approximately 10 days at room temperature.

Method for preparing azobenzene and azobenzene compound by electro-catalysis

The invention relates to a method for preparing azobenzene and azoxybenzene compounds through electrocatalysis. Under the conditions of room temperature and inert gas, an aromatic nitro compound is reduced and coupled with an aromatic amino compound to be oxidized through electro-catalysis, and an azoxybenzene compound is obtained. The method has the advantages of mild conditions, high efficiencyand selectivity, and high universality, and can realize the synthesis of asymmetric azobenzene and azoxybenzene compounds.

Nitrate promoted mild and versatile Pd-catalysed C(sp2)-H oxidation with carboxylic acids

A nitrate-promoted Pd-catalysed mild cross-dehydrogenative C(sp2)-H bond oxidation of oximes or azobenzenes with diverse carboxylic acids has been developed. In contrast to the previous catalytic systems, this protocol features mild conditions (close to room temperature for most cases) and a broad substrate scope (up to 64 examples), thus constituting a versatile method to directly prepare diverse O-aryl esters. Moreover, the superiority of the nitrate additive in this mild transformation was further determined by experimental and computational evidence.

A metal-catalyst-free oxidative coupling of anilines to aromatic azo compounds in water using bleach

A simple route toward the synthesis of symmetrical and unsymmetrical aromatic azo compounds through oxidative coupling of anilines using widely available NaOCl is presented. This metal catalyst-free protocol is performed in water and affords the desired products in high yields.

Aromatic amine oxidation process for preparing aromatic azobenzene method

The invention relates to a method for preparing an aromatic azo compound by utilizing aromatic amine oxidation. In the method, air or oxygen serves as an oxygen source, and under the effect of a catalyst, aromatic amine is oxidized into the aromatic azo compound. The method is high in oxidization efficiency and product yield; the air or the oxygen serves as the oxygen source, and the method is economical and environmentally friendly. The product and the catalyst can be separated easily, and the aftertreatment is simple. The catalyst is easy to reuse, and the method has very good application prospect.

Oxidative coupling of anilines to azobenzenes using heterogeneous manganese oxide catalysts

We herein report the transition metal oxide-catalyzed synthesis of azobenzenes through the oxidative coupling of anilines. An octahedral molecular sieve of manganese oxide, OMS-2, exhibited the best activity and selectivity. Nine examples of symmetric azobenzenes and twenty unsymmetric ones were synthesized with 62-99% conversion and 64-99% selectivity. In the aniline cross-coupling reactions, the difference of the Hammett constants of two substituted groups (Δσ) determines the selectivity to unsymmetric azobenzenes, which are the major products at Δσ 0.32. In-depth studies reveal that the surface defect sites of the mixed-valence manganese oxide play a key role in facilitating electron transfer and activating molecular oxygen. The single-electron transfer (SET) reaction mechanism is proposed based on electron paramagnetic resonance and X-ray powder diffraction characterization.

Deoxygenative coupling of nitroarenes for the synthesis of aromatic azo compounds with CO using supported gold catalysts

A facile and efficient catalytic system based on a mesostructured ceria-supported gold (Au/meso-CeO2) catalyst was developed for the synthesis of various aromatic azo compounds by the reductive coupling of the corresponding nitroaromatics, using CO as the sole deoxygenative reagent, under additive-free and mild reaction conditions.

Phenyliodine(III) diacetate (PIDA) mediated synthesis of aromatic azo compounds through oxidative dehydrogenative coupling of anilines: Scope and mechanism

An efficient and environmentally benign method has been developed for the synthesis of symmetrical and unsymmetrical aromatic azo compounds through phenyliodine(III) diacetate (PIDA) mediated oxidative dehydrogenative coupling of anilines in high yields.

Phenyliodine(III) diacetate (PIDA) mediated synthesis of aromatic azo compounds through oxidative dehydrogenative coupling of anilines: Scope and mechanism

An efficient and environmentally benign method has been developed for the synthesis of symmetrical and unsymmetrical aromatic azo compounds through phenyliodine(III) diacetate (PIDA) mediated oxidative dehydrogenative coupling of anilines in high yields.

Highly efficient synthesis of azos catalyzed by the common metal copper (0) through oxidative coupling reactions

A facile and efficient approach to synthesize symmetric, asymmetric and bridged aromatic azo compounds (AAzos) from aromatic amines was developed by using red copper as catalyst. Despite numerous efforts towards the catalytic synthesis of symmetric and asymmetric AAzos derivatives, most reactions present certain drawbacks inhibiting their industrial applications, such as laborious multi-step processes, harsh reaction conditions and expensive reagents. And the synthesis of bridged azos had low yields before. With the presence of ammonium bromide as co-catalyst, pyridine as a ligand and molecular dioxygen as a sole oxidative reagent, red copper, a common and abundant metal in nature, exhibited unexpected catalytic activity towards the preparation of AAzos in high yields via one-step reaction, making this catalyst an attractive candidate for industrial and synthetic applications.