74763-66-9

Upstream product

• 74763-65-8 1,4-Bis(p-bromophenyl)-1,4-dimethyl-2-tetrazene 
• 19717-43-2 4,4'-dibromo-N,N'-diphenylhydrazine 
• 74-88-4 methyl iodide 
• 6911-87-1 4-bromo-N-methylaniline 
• 586-77-6 4-bromo-N,N-dimethylaniline 

Relevant academic research and scientific papers

PIFA-Promoted, Solvent-Controlled Selective Functionalization of C(sp2)-H or C(sp3)-H: Nitration via C-N Bond Cleavage of CH3NO2, Cyanation, or Oxygenation in Water

A novel nitration (via C(sp3)-N breaking/C(sp2)-N formation with CH3NO2) mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA) is described. The NO2 transfer from CH3NO2 to the aromatic group of the substrate is possible with careful selection of the solvent, NaX, and oxidant. In addition, the solvent-controlled C(sp2)-H functionalization can shift to an α-C(sp3)-H functionalization (cyanation or oxygenation) of the α-C(sp3)-H of cyclic amines.

Iodine-mediated oxidative N-N coupling of secondary amines to hydrazines

An I2-mediated N-N coupling reaction has been established for oxidative dimerization of N-aryl aminopyridines to a variety of novel hydrazine derivatives under mild conditions. This synthetic method does not require use of transition metals and

Transition-Metal-Free Dehydrogenative N–N Coupling of Secondary Amines with KI/KIO4

A transition-metal-free method for the dehydrogenative N–N coupling of secondary amines has been accomplished. This oxidative KI/KIO4 protocol is mild and operationally simple. A diverse range of diphenylamines, carbazoles, and N-alkylanilines readily undergo N–N homo-coupling effectively. Notably, the N–N cross-coupling of two different arylamines is also demonstrated, which provides a straightforward approach to the complex N–N structures.

Facile Cu(I)-catalyzed oxidative coupling of anilines to azo compounds and hydrazines with diaziridinone under mild conditions

A mild and highly efficient Cu(I)-catalyzed oxidative coupling of anilines is described. Various primary and secondary anilines can be efficiently coupled under mild conditions to the corresponding azo compounds and hydrazines in high yields. This method provides a direct and practical access to these compounds and is also amenable to gram scale with no special precautions to exclude air or moisture.

A dehydrogenative homocoupling reaction for the direct synthesis of hydrazines from N-alkylanilines in air

A copper-catalyzed N-N bond-forming reaction was performed by a dehydrogenative homocoupling of N-alkylanilines, affording N,N-dialkyl-N,N- diphenylhydrazines in 72-88% yields. This new strategy has the advantages of direct synthesis from N-alkylanilines,

Fast synthesis of hydrazine and Azo derivatives by oxidation of rare-earth-metal-nitrogen bonds

A novel N-N coupling reaction was developed through the oxidation of rare-earth-metal-nitrogen bonds produced by treatment of the easily available rare-earth-metal amides [(Me3Si)2N]3RE(μ-Cl) Li(THF)3 with aromatic primary or secondary amines. The reaction provides the symmetrical or unsymmetrical azo compounds and hydrazine derivatives in good to high yields within a very short time under mild conditions.

Photobenzidine Rearrangements. 7. Disproportionation and Recombination of N-Methylarylamino Radicals in the Photodecomposition of 1,4-Bis(p-cyanophenyl)-1,4-dimethyl-2-tetrazene and Other 2-Tetrazenes

The photochemical decomposition of 1,4-bis(p-cyanophenyl)-1,4-dimethyl-2-tetrazene (1c) in 1,2-dimethoxyethane (DME) was studied in detail.It was deduced that N-methyl-p-cyanoanilino radicals are formed and undergo three reactions: recombination into 1,2-bis(p-cyanophenyl)-1,2-dimethylhydrazine (2c, 21 percent), disproportionation (70 percent) into N-methyl-p-cyanoaniline (3c) and N-methylene-p-cyanoaniline (4c), and hydrogen atom abstraction (7 percent).A small amount of a p-semidine is thought to be formed also.These deductions were made from quantitative high-pressure LC measurements of yields of 2c, 3c, p-cyanoaniline (5c), and formaldehyde, the last two products arising from hydrolysis of 4c.Quantitative measurement of the conversion of 4c into 3c by hydrogenation and by trapping of radicals with butyl mercaptan was also used.Approximately 10 percent of 2e is formed in a solvent cage.Disproportionation also appears to occur within the cage.Less detailed studies were carried out with 1,4-diphenyl-1,4-dimethyl-2-tetrazene (1d) and 1,4-bis(p-bromophenyl)-1,4-dimethyl-2-tetrazene (1e).Decomposition of 1d led to 40 percent of N,N'-dimethyldiphenylhydrazine (2d, 10 percent in cage) and 40 percent of disproportionation products.The remaining 20 percent of the 1d is thought to form a p-semidine (N,N'-dimethyl-N-phenyl-1,4-benzenediamine) and the dibenzocarbazole related to it.Radicals from the decomposition of 1e led to 37 percent of 1,2-bis(p-bromophenyl)-1,2-dimethylhydrazine (2e, 10 percent in cage), 47 percent of disproportionation, and 16 percent of hydrogen abstraction.

Photobenzidine Rearrangements. 6. Mechanism of the Photodecomposition of 1,4-Diaryl-1,4-dialkyl-2-tetrazenes

The photodecomposition of the tetrazene p-XC6H4N(Me)N=N(Me)NC6H4Y-p (1e,X=Y=Me) in dimethoxyethane (DME) gave 47.4percent of p-XC6H4(Me)NN(Me)C6H4Y-p (2e,X=Y=Me) and 39.6 percent of N-methyl-p-toluidine. When irradiation was carried out in the presence of increasing initial concentrations of n-BuSH, the yield of 2e fell and levelled off at 6percent.Similar experiments in cyclohexane showed that the yield of 2e fell from 45.1percent and leveled off at 10percent.The data indicate that 1e decomposes by a radical pathway and that the 2e is formed partly within and partly outside of a solvent cage. Similar studies with 1d(X=Me, Y=CO2Et) in DME gave three hydrazines: 2d(X=Me,Y=CO2Et) in 13percent and 14.7percent yield, 2e in 7.3percent and 8.0percent yield,and 2f(X=Y=CO2Et) in 14.9percent and 21.2percent yield. The formation of three hydrazines again indicates the formation and intermolecular recombination of methylarylamino radicals. Irradiation of 1d in DME solutions containing n-BuSH caused a fall in the yield of 2e to zero and a leveling off in the yield of 2d to 6percent. The yield of 2f also fell but could not be monitored at high concentrations of n-BuSH because of overlapping high-pressure LC peaks. The results with 1d are also consistent with a cage-recombination process (for 2d) and an intermolecular recombination of radicals (for 2d-f). The methylarylamines p-XC6H4NHMe and p-YC6H4NHMe (X=Me; Y=CO2Et) were also formed from 1d. A sixth product was the bis(arylamino)methane p-YC6H4NHCH2NHC6H4Y-p(4f, Y=CO2Et) in 14-32percent yield (three runs). The origin of 4f is believed to be the disproportionation of radicals p-YC6H4NMe, giving p-YC6H4NHMe and p-YC6H4N=CH2(7f). Hydrolysis of 7f (by small amounts of water in the solvent) to p-YC6H4NH2 (6f) and HCHO followed by addition of 6f to 7f would give 4f. HCHO was found as a volatile product after irradiation. The formation of 4f is further evidence for the formation and intermolecular reaction of arylamino radicals in the photodecomposition of 1,4-dialkyl-1,4-diaryl-2-tetrazenes.