401-44-5

Upstream product

• 348-54-9 2-Fluoroaniline 
• 454-21-7 1,2-bis(2-fluorophenyl)hydrazine 
• 497-87-0 (Z)-1,2-bis(2-fluorophenyl)diazene 1-oxide 
• 1493-27-2 ortho-nitrofluorobenzene 
• 76-05-1 trifluoroacetic acid 
• 62-53-3 aniline 
• 1227476-15-4 Azobenzene 
• 3296-04-6 1-azido-2-fluorobenzene 
• 108-88-3 toluene 

Downstream Products

• 454-21-7 1,2-bis(2-fluorophenyl)hydrazine 
• 497-87-0 (Z)-1,2-bis(2-fluorophenyl)diazene 1-oxide 
• 5509-65-9 2,6-difluoroaniline 
• 1647097-06-0 (E)-1-(2-fluoro-6-nitrophenyl)-2-(2-fluorophenyl)diazene 
• 1447966-67-7 (E)-1-(2-bromo-6-fluorophenyl)-2-(2-fluorophenyl)diazene 
• 1440357-04-9 C₂₂H₂₆F₂N₂ 
• 448-97-5 3,3'-difluorobiphenyl-4,4'-diamine 

Relevant academic research and scientific papers

A laser flash photolysis and quantum chemical study of the fluorinated derivatives of singlet phenylnitrene

Laser flash photolysis (LFP, Nd:YAG laser, 35 ps, 266 nm, 10 mJ or KrF excimer laser, 10 ns, 249 nm, 50 mJ) of 2-fluoro, 4-fluoro, 3,5-difluoro, 2,6-difluoro, and 2,3,4,5,6-pentafluorophenyl azides produces the corresponding singlet nitrenes. The singlet

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.

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.

Selective Propargylation of Diaryl Azo Compounds Using Metallic Barium

The Barbier-type propargylation of azo compounds with α,γ-disubstituted propargylic tosylates was achieved by using metallic barium as the promoter. Various propargylated hydrazines (α-adducts) were exclusively synthesized from the corresponding propargylic tosylates and azobenzenes (diaryldiazenes). The thus-obtained propargylic hydrazines were further efficiently converted into propargylic amines by reductive N-N bond cleavage. Benzidine rearrangement of the propargylic hydrazines was also attempted.

Synthesis of 2 - fluoro aniline compounds of the method

The invention discloses a method for synthesizing 2 - fluoro aniline compounds of the method, the method is: shown in formula Ia aniline compound of formula Ib α and β shown aniline compound as raw materials, through coupling reaction shown [...] azobenzene compound II, then the type II shown azobenzene compound with a palladium catalyst, fluorination reagent, additive, organic solvent, in the 30 - 150 °C temperature closed agitating the fluorination reaction, [...] compound of formula III, type III compounds are shown in the reaction under the action of a reducing [...] shown IV 2 - fluoro aniline compounds; this invention synthetic 2 - fluoro aniline compounds substrate wide adaptability, mild reaction conditions, the operation is simple, fluorinated and good selectivity, [...] aniline compounds is prepared by many drug molecule is an important intermediate and starting material, wide application prospects.

Anion ligand promoted selective C-F bond reductive elimination enables C(sp2)-H fluorination

A detailed mechanism study on the anion ligand promoted selective C-H bond fluorination is reported. The role of the anion ligand has been clarified by experimental evidence and DFT calculations. Moreover, the nitrate promoted C-F bond reductive elimination enabled a selective C-H bond fluorination of various symmetric and asymmetric azobenzenes to access diverse o-fluoroanilines.

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.

Convenient Electrocatalytic Synthesis of Azobenzenes from Nitroaromatic Derivatives Using SmI2

The synthesis of azobenzenes has been a long-standing challenge. Their current preparation at a preparative or industrial scale requires stoichiometric amounts of environmentally unfriendly reactants. Herein, we demonstrate that the catalytic use of electrogenerated samarium diiodide (SmI2) could promote, in one-step synthesis, the reduction of nitrobenzenes into azobenzenes in high yields under mild reaction conditions. This catalytic procedure contains many elements satisfying a sustainable chemical process for the preparation of one of the most widely wanted family of chemical compounds. The easy synthetic procedure, and the absence of precious metals, bases, and nonhazardous substances, already makes our catalytic procedure a serious alternative to currently available methods. This is a promising method for the efficient synthesis of both symmetrical and asymmetrical azo compounds with a high functional group tolerance.

Electrocatalytic Z → E Isomerization of Azobenzenes

A variety of azobenzenes were synthesized to study the behavior of their E and Z isomers upon electrochemical reduction. Our results show that the radical anion of the Z isomer is able to rapidly isomerize to the corresponding E configured counterpart with a dramatically enhanced rate as compared to the neutral species. Due to a subsequent electron transfer from the formed E radical anion to the neutral Z starting material the overall transformation is catalytic in electrons; i.e., a substoichiometric amount of reduced species can isomerize the entire mixture. This pathway greatly increases the efficiency of (photo) switching while also allowing one to reach photostationary state compositions that are not restricted to the spectral separation of the individual azobenzene isomers and their quantum yields. In addition, activating this radical isomerization pathway with photoelectron transfer agents allows us to override the intrinsic properties of an azobenzene species by triggering the reverse isomerization direction (Z → E) by the same wavelength of light, which normally triggers E → Z isomerization. The behavior we report appears to be general, implying that the metastable isomer of a photoswitch can be isomerized to the more stable one catalytically upon reduction, permitting the optimization of azobenzene switching in new as well as indirect ways.

The palladium and copper contrast: A twist to products of different chemotypes and altered mechanistic pathways

A novel contrast in palladium and copper catalysis is revealed to form products of different chemotypes resulting in a phenazine to azoarene twist through an altered mechanistic pathway (from non-radical C-H activation mode of C-N coupling to radical N-N coupling) during the oxidative self-coupling of anilines catalysed by Pd-Ag and Cu-Ag nanoclusters.