77611-71-3

Upstream product

• 142068-90-4 1,2-bis(3,5-dimethylphenyl)hydrazine 
• 24586-65-0 mercury(II) acetamide 
• 108-69-0 3,5-dimethylaminoaniline 
• 70334-59-7 1-azido-3,5-dimethylbenzene 
• 62-53-3 aniline 
• 811-98-3 d⁽⁴⁾-methanol 
• 99-12-7 5-nitro-m-xylene 
• 2101-86-2 p-methylazidobenzene 
• 67083-40-3 1,3-dimethyl-5-nitrosobenzene 
• 108-88-3 toluene 

Downstream Products

• 20150-89-4 5,7-dimethylquinoline 
• 6479-89-6 1,3-dimethylphenazine 
• 1447966-71-3 (E)-1-(3,5-dimethylphenyl)-2-(2-iodo-3,5-dimethylphenyl)diazene 
• 1447966-65-5 (E)-1-(2-bromo-3,5-dimethylphenyl)-2-(3,5-dimethylphenyl)diazene 
• 1647096-96-5 (E)-1-(3,5-dimethyl-2-nitrophenyl)-2-(3,5-dimethylphenyl)diazene 
• 142068-90-4 1,2-bis(3,5-dimethylphenyl)hydrazine 

Relevant academic research and scientific papers

London Dispersion in Alkane Solvents

The importance of London dispersion interactions in solution is an ongoing debate. Although the significance of dispersion for structure and stability is widely accepted, the degree of its attenuation in solution is still not properly understood. Quantita

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.

Visible-light-promoted oxidative dehydrogenation of hydrazobenzenes and transfer hydrogenation of azobenzenes

Azo compounds are widely used in the pharmaceutical and chemical industries. Here, we report the use of a non-metal photo-redox catalyst, Eosin Y, to synthesize azo compounds from hydrazine derivatives. The use of visible-light with air as the oxidant makes this process sustainable and practical. Moreover, the visible-light-driven, photo-redox-catalyzed transfer hydrogenation of azobenzenes is compatible with a series of hydrogen donors such as phenyl hydrazine and cyclic amines. Compared with traditional (thermal/transition-metal) methods, our process avoids the issue of over-reduction to aniline, which extends the applicability of photo-redox catalysis and confirms it as a useful tool for synthetic organic chemistry.

Transition Metal-Free Oxidative Coupling of Primary Amines in Polyethylene Glycol at Room Temperature: Synthesis of Imines, Azobenzenes, Benzothiazoles, and Disulfides

A transition metal-free protocol has been developed for the oxidative coupling of primary amines to imines and azobenzenes, thiols to disulfides, and 2-aminothiophenols to benzothiazoles, offering excellent yields. The advantageous features of the present environmentally benign methodology include the usage of biocompatible and green reaction conditions such as, solvent, room temperature reactions and transition metal-free approach. Moreover, it offers a broader substrate scope.

Rhodium-Catalyzed Reaction of Azobenzenes and Nitrosoarenes toward Phenazines

A rhodium-catalyzed annulative reaction between azobenzenes and nitrosoarenes has been developed, leading to a series of phenazines in moderate to good yields. This procedure proceeds with sequential chelation-assisted addition of aryl C-H to nitrosoarenes and ring closure by electrophilic attack of azo group to aryl. During this transformation, the azo group served as not only a traceless directing group but also a building block in the final products.

Exploring London Dispersion and Solvent Interactions at Alkyl–Alkyl Interfaces Using Azobenzene Switches

Interactions on the molecular level control structure as well as function. Especially interfaces between innocent alkyl groups are hardly studied although they are of great importance in larger systems. Herein, London dispersion in conjunction with solvent interactions between linear alkyl chains was examined with an azobenzene-based experimental setup. Alkyl chains in all meta positions of the azobenzene core were systematically elongated, and the change in rate for the thermally induced Z→E isomerization in n-decane was determined. The stability of the Z-isomer increased with longer chains and reached a maximum for n-butyl groups. Further elongation led to faster isomerization. The origin of the intramolecular interactions was elaborated by various techniques, including 1H NOESY NMR spectroscopy. The results indicate that there are additional long-range interactions between n-alkyl chains with the opposite phenyl core in the Z-state. These interactions are most likely dominated by attractive London dispersion. This work provides rare insight into the stabilizing contributions of highly flexible groups in an intra- as well as an intermolecular setting.

Tying the alkoxides together: An iron complex of a new chelating bulky bis(alkoxide) demonstrates selectivity for coupling of non-bulky aryl nitrenes

New chelating bis(alkoxide) ligand H2[OO]Ph and its iron(ii) complex Fe[OO]Ph(THF)2 are described. The coordination of the ligand to the metal center is reminiscent of the coordination of two monodentate alkoxides in previously reported Fe(OR)2(THF)2 species. Fe[OO]Ph(THF)2 catalyzes selective and efficient dimerization of non-bulky aryl nitrenes to yield the corresponding azoarenes.

Palladium-Catalyzed Methylation of Nitroarenes with Methanol

A procedure for the synthesis of N-methyl-arylamines directly from nitroarenes using methanol as green methylating agent was developed. The key to success is the use of a specific catalyst system consisting of palladium acetate and the ligand 1-[2,6-bis(isopropyl)phenyl]-2-[tert-butyl(2-pyridinyl)phosphino]-1H-Imidazole (L1). The generality of this protocol is demonstrated in the synthesis of more than 20 N-methyl-arylamines under comparably mild conditions. Combining this novel methodology with subsequent coupling processes using the same catalyst allows for efficient diversification of aromatic nitro compounds to a broad variety of amines including drug molecules.

Catalytic Nitrene Homocoupling by an Iron(II) Bis(alkoxide) Complex: Bulking Up the Alkoxide Enables a Wider Range of Substrates and Provides Insight into the Reaction Mechanism

The reaction of HOR′ (OR′ = di-t-butyl-(3,5-diphenylphenyl)methoxide) with an iron(II) amide precursor forms the iron(II) bis(alkoxide) complex Fe(OR′)2(THF)2 (2). 2 (5-10 mol %) serves as a catalyst for the conversion of aryl azides

Palladium-catalyzed cyclizative carbonylation of azobenzenes toward 3H-Indazol-3-ones using formic acid as CO source

A palladium-catalyzed cyclizative carbonylation of azobenzenes has been developed to access 1-acyl 2-aryl 3H-indazol-3-ones in moderate to good yields with good functional compatibility. This procedure proceeded with the sequential ortho-C–H carbonylation and cyclization, where formic acid served as the CO source. The practicability of this transformation was further increased by the employment of facilely available azobenzenes derivatives as one-handled starting materials.