101-54-2Relevant articles and documents
Synthesis and properties of 4-[(E)-(4'-R-phenyl)diazenyl]phthalonitriles and cobalt phthalocyanines obtained therefrom
Tikhomirova,Gruzdeva,Shaposhnikov
, p. 2778 - 2785 (2015)
The diazotization-azocoupling method has been utilized to prepare a series of previously unknown 4-[(E)-(4'-R-phenyl)diazenyl]phthalonitriles, which were further transformed into the corresponding cobalt phthalocyanines. The effect of the peripheral substitution of the phthalocyanine ligand on the spectral properties of the prepared compounds has been demonstrated.
Industrial-scale palladium-catalyzed coupling of aryl halides and amines - A personal account
Buchwald, Stephen L.,Mauger, Christelle,Mignani, Gerard,Scholz, Ulrich
, p. 23 - 39 (2006)
The palladium-catalyzed coupling of amines and aryl halides or aryl alcohol derivatives has matured from an exotic small-scale transformation into a very general, efficient and robust reaction during the last ten years. This article reports several applications of this method from an industrial vantage point, including ligand synthesis, synthesis of arylpiperazines, arylhydrazines and diarylamines. Much emphasis in placed on issues of scale-up and safety to underline the potential of C-N couplings as solutions for industrial-scale synthetic problems.
Preparation of N-phenyl-p-phenylenediamine by coupling of aniline and nitrobenzene in KOH–poly(ethylene glycol) medium
Babkin, Alexander V.,Asachenko, Andrey F.,Uborsky, Dmitry V.,Kononovich, Dmitry S.,Izmer, Vyatcheslav V.,Kudakina, Vera A.,Shnaider, Viktoriya A.,Shevchenko, Nikolay E.,Voskoboynikov, Alexander Z.
, p. 555 - 557 (2016)
A novel protocol for efficient coupling of nitrobenzene and aniline in poly(ethylene glycol) medium in the presence of KOH giving diphenylamine derivatives has been developed, to enable the exclusion of the toxic tetramethylammonium hydroxide catalyst commonly used in the rubber antidegradant industry.
Surface-Enhanced Raman Spectroscopy as a Probe of Electroorganic Reaction Pathways. 2. Ring-Coupling Mechanisms during Aniline Oxidation
Gao, Ping,Gosztola, David,Weaver, Michael J.
, p. 3753 - 3760 (1989)
The adsorbed ring-coupling products formed during aniline electrooxidation at gold-aqueous interfaces have been identified by means of real-time surface-enhanced Raman-spectroscopy (SERS) in conjunction with linear sweep voltammetry.In the absence of solution species, the electrooxidation of irreversibly adsorbed aniline yields predominantly adsorbed benzidine.In the presence of solution aniline, however, the "head-to-tail" dimer N-phenyl-1,4-phenylenediamine (PPDA) as well as benzidine is formed at the interface, the proportion of the former adsorbate increasing toward higher pH and larger aniline concentrations.A distinction between these interfacial reaction products can readily be made from the characteristic and intense SER spectra of the two-electron oxidation products formed from PPDA and benzidine.Markedly different ring-coupling product distributions were formed in solution (i.e., within the diffusion layer) as deduced voltammetrically, PPDA predominating except in strong acidic media.Possible reasons for these observed differences are discussed.In alkaline media, azobenzene is observed to be the major ring-coupling product in both adsorbed and solution-phase environments.
2,6-Bis(diphenylphosphino)pyridine: A simple ligand showing high performance in palladium-catalyzed CN coupling reactions
Nadri, Shirin,Rafiee, Ezzat,Jamali, Sirous,Joshaghani, Mohammad
, p. 4098 - 4101 (2014)
The use of commercially available 2,6-bis(diphenylphosphino)pyridine as a ligand in conjunction with K2CO3, DMAc and TBAB is an effective method for the palladium-catalyzed CN coupling of a variety of aryl halides with anilines, N-heterocyclic aromatic amines, and a cyclic secondary amine. The reactions proceed in good to excellent yield (up to 98%) while the loading of Pd(OAc)2 was as low as 0.025 mol %.
A New Route to 4-Aminodiphenylamine via Nucleophilic Aromatic Substitution for Hydrogen: Reaction of Aniline and Azobenzene
Stern, Michael K.,Cheng, Brian K.,Hileman, Frederick D.,Allman, James M.
, p. 5627 - 5632 (1994)
A new example of nucleophilic aromatic substitution for hydrogen is described which encompasses reacting aniline and azobenzene (1) in the presence of base under aerobic conditions to generate 4-(phenylazo)diphenylamine (2) in high yield.Monitoring the time course of the reaction under anaerobic conditions revealed that hydrazobenzene (9) was formed as an intermediate in the reaction in equal molar amounts as 2.However, under aerobic conditions 9 was shown not to persist in the reaction mixture.The kinetic effect of isotopic substitution on this reaction was probed by competition experiments utilizing equal molar mixtures azobenzene-d10 and undeuterated material which gave a kH/kD of 4.6 +/- 0.1.It was concluded from these studies that azobenzene was functioning as both the electrophile and oxidant in this reaction.Catalytic hydrogenation of 2 generates 4-aminodiphenylamine (4-ADPA) (10) and aniline.These reactions form the basis of a novel synthetic route to 4-ADPA which does not utilize halogenated intermediates or reagents and ultimately relies on O2 as the terminal oxidant in the system.
Gold(I)-mediated rearrangement of 1,2-diphenylhydrazine to semidines
Xia, Aibing,James, Alan J.,Sharp, Paul R.
, p. 451 - 453 (1999)
Reaction of 1,2-diphenylhydrazine with the gold oxo complex [(PPh3Au)3(μ-O)]BF4 gives a mixture of [(Ph3PAu)3(μ-N-1,4-C6H 4-NHPh)]BF4 (1; 82%) and [(Ph3PAu)3(μ-N-1,2-C6H 4-NHPh)]BF4 (2; 18%) in CH2-Cl2 at ambient temperature, A crossover experiment using a 1:1 mixture of 1,2-diphenylhydrazine and 1,2-diphenylhydrazine-d10 indicates that the rearrangement process is intramolecular.
Reduction of 4-nitrosodiphenylamine with sodium hydroxy- and aminoalkanesulfinates
Polenov,Egorova,Ryazantseva
, p. 1787 - 1791 (2003)
The kinetics of reduction of 4-nitrosodiphenylamine with sodium alkanesulfinates were studied, and the reaction mechanism was suggested.
Heterogeneous Catalytic Transfer Hydrogenation of 4-Nitrodiphenylamine to p-Phenylenediamines
Banerjee, Ankur A.,Mukesh, Doble
, p. 1275 - 1276 (1988)
p-Phenylenediamine analogues have been prepared from 4-nitrodophenylamine (1) by catalytic transfer hydrogenation in one stage; the process can be extended to the general condensation of a nitro compound with an alcohol (with Raney nickel as catalyst) or a ketone (with palladium as catalyst).
Superoxide-Promoted Oxidation Reactions of Aniline and N-Methylaniline in Dimethyl Sulfoxide
Stuehr, Dennis J.,Marletta, Michael A.
, p. 694 - 696 (1985)
The chemistry of superoxide was investigated in reference to its reactions with primary and secondary aromatic amines.Two aromatic amines (aniline and N-methylaniline) reacted extensively in aprotic solutions containing potassium superoxide.In the case of aniline, trans-azobenzene and 4-nitrodiphenylamine were the major products, with smaller amounts of 4-aminodiphenylamine, 4-nitrosodiphenylamine, and p-(phenylazo)diphenylamine also being produced.With N-methylaniline, both oxidation and demethylation occurred, leading to the isolation of N-phenylformamide, aniline,and smaller amounts of azobenzene and 4-nitrodiphenylamine.Both superoxide and hydrogen peroxide alone were unable to convert either 4-aminodiphenylamine to its nitro and nitroso derivatives or N-phenylformamide to aniline.Solutions containing potassium tert-butoxide in place of superoxide produced the same products and oxygen was required for the reaction.Taken together, these results indicated that primary and secondary reducing aromatic amines are readily ionized by superoxide in aprotic solutions and then oxidized in a process involving molecular oxygen, leading to products whose structures suggest that processes such as radical recombination, N-oxidation, and N-demethylation have taken place.
