34913-29-6

Upstream product

• 5586-13-0 1-azido-4-(trifluoromethyl)benzene 
• 103-71-9 phenyl isocyanate 
• 34913-34-3 p,p'-bis-(trifluoromethyl)azoxybenzene 
• 455-14-1 4-trifluoromethylphenylamine 
• 402-54-0 p-nitrobenzotrifluoride 
• 2101-86-2 p-methylazidobenzene 
• 740-69-2 1,2-bis(4-(trifluoromethyl)phenyl)hydrazine 
• 214360-65-3 4-trifluoromethylphenylboronic acid pinacol ester 
• 121-69-7 N,N-dimethyl-aniline 
• 34913-26-3 4-nitroso-1-(trifluoromethyl)benzene 
• 67-56-1 methanol 
• 201230-82-2 carbon monoxide 
• 591-19-5 m-Bromoaniline 
• 63213-03-6 1,2-bis(3-bromophenyl)diazene 

Downstream Products

• 91266-44-3 1,2,3,4-tetrakis<4-(trifluoromethyl)phenyl>-5-isopropylidenetetrahydrotetrazole 
• 740-69-2 1,2-bis(4-(trifluoromethyl)phenyl)hydrazine 
• 69409-98-9 2-fluoro-4-(trifluoromethyl)aniline 
• 2805-84-7 6-(trifluoromethyl)-2,3,4,9,-tetrahydro-1H-carbazole 
• 691-24-7 1,3-di-tert-butylcarbodiimide 
• 150207-15-1 η2-N,N-di(4-trifluoromethylphenyl)diazene-tris(trimethylphosphine)cobalt(0) 

Relevant academic research and scientific papers

TEMPO catalyzed oxidative dehydrogenation of hydrazobenzenes to azobenzenes

A metal-free direct oxidative dehydrogenation approach for the synthesis of azobenzenes from hydrazobenzenes has been developed by using TEMPO as an organocatalyst for the first time. The reaction proceeded in open air under mild reaction conditions. A wide range of hydrazobenzenes readily undergo dehydrogenation to give the corresponding azobenzenes in excellent yields.

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.

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.

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.

In vitro biological, catalytic, and DFT studies of some iron(III) N-ligated complexes

Fe(III) complexes, [Fe(CH3CN)6][X]3 and [Fe(CH3CH2CN)6][X]3 (where X: counter anion = B{C6H3(m-CF3)2}4)? and B(C

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.

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.

Photocatalyzed oxidative dehydrogenation of hydrazobenzenes to azobenzenes

Visible light mediated oxidative dehydrogenation of hydrazobenzenes under an ambient atmosphere using an organic dye as a photocatalyst was reported for the first time. The reaction provides an environmentally benign method for the preparation of azobenzenes in excellent yields with good functional group tolerance.

T BuOK-triggered bond formation reactions

Recently, inexpensive and readily available tBuOK has seen widespread use in transition-metal-free reactions. Herein, we report the use of tBuOK for S-S, S-Se, NN and CN bond formations, which significantly extends the scope of tBuOK in chemical synthesis. Compared with traditional methods, we have realized mild and general methods for disulfide, azobenzenes imine etc. synthesis.

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.