2810-74-4

Upstream product

• 1665-83-4 2-(diphenylmethylene)-1-methyl-1-phenylhydrazine 
• 930-68-7 cyclohexenone 
• 100-61-8 N-methylaniline 
• 121-69-7 N,N-dimethyl-aniline 

Downstream Products

• 191601-42-0 N⁴,N^4'-Dimethyl-N⁴-(4'-methyl-[2,2']bipyridinyl-4-ylmethyl)-biphenyl-4,4'-diamine 

Relevant academic research and scientific papers

Cu-Catalyzed Intermolecular-Site C-H Amination of Cyclohexenone Derivatives: The Benefit of Bifunctional Ligands

Utilizing 1,10-phenanthroline-Type bifunctional ligands, an efficient Cu-catalyzed intermolecular site-selective remote C-H amination using cyclohexenone derivatives and anilines was realized. The amide group installed on the bifunctional ligand played a

Scandium ion-enhanced oxidative dimerization and N -demethylation of N, N -dimethylanilines by a non-heme iron(IV)-oxo complex

Oxidative dimerization of N,N-dimethylaniline (DMA) occurs with a nonheme iron(IV)-oxo complex, [FeIV(O)(N4Py)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), to yield the corresponding dimer, tetramethylbenzidine (TMB), in acetonitrile. The rate of the oxidative dimerization of DMA by [FeIV(O)(N4Py)]2+ is markedly enhanced by the presence of scandium triflate, Sc(OTf)3 (OTf = CF3SO3-), when TMB is further oxidized to the radical cation (TMB?+). In contrast, we have observed the oxidative N-demethylation with para-substituted DMA substrates, since the position of the C-C bond formation to yield the dimer is blocked. The rate of the oxidative N-demethylation of para-substituted DMA by [FeIV(O) (N4Py)]2+ is also markedly enhanced by the presence of Sc(OTf) 3. In the case of para-substituted DMA derivatives with electron-donating substituents, radical cations of DMA derivatives are initially formed by Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+, giving demethylated products. Binding of Sc3+ to [FeIV(O)(N4Py)]2+ enhances the Sc3+ ion-coupled electron transfer from DMA derivatives to [Fe IV(O)(N4Py)]2+, whereas binding of Sc3+ to DMA derivatives retards the electron-transfer reaction. The complicated kinetics of the Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+ are analyzed by competition between binding of Sc3+ to DMA derivatives and to [FeIV(O)(N4Py)] 2+. The binding constants of Sc3+ to DMA derivatives increase with the increase of the electron-donating ability of the para-substituent. The rate constants of Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+, which are estimated from the binding constants of Sc3+ to DMA derivatives, agree well with those predicted from the driving force dependence of the rate constants of Sc3+ ion-coupled electron transfer from one-electron reductants to [FeIV(O)(N4Py)]2+. Thus, oxidative dimerization of DMA and N-demethylation of para-substituted DMA derivatives proceed via Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+.

Electron Spin Resonance, Electron Spin Echo Modulation, and Electron Nuclear Double Resonance Studies on the Photoionization of N-Alkyl-N,N',N'-trimethylbenzidine in Anionic and Cationic Micelles

N-Alkyl-N,N',N'-trimethylbenzidines (CnTMB, n = 1-6, 8) were synthesized and photoionized in rapidly frozen anionic and cationic micelles.The photoyields of the cation radicals were investigated by electron spin resonance spectroscopy.Electron spin echo modulation spectroscopy and proton matrix electron nuclear double resonance were used to determine the relative location of the photoproduced cation radical with respect to the deuterated aqueous interface.No dependence on the photoyield as a function of the electron donor alkyl chain length is observed, although increasing the alkyl chain length on the benzidine moiety moves its location toward the aqueous interface.The lack of a photoyield trend is interpreted in terms of the solubilization geometry, which determines the paths of electron escape to form charge-separated products.An electron escape cone defined as the solid angle formed from the center of the electron donor moiety through the width of the spin distribution that intersects the interface changes only slowly as a function of radical location over a limited range.Hence, the photoyield is little changed.

REARRANGEMENTS OF AROMATIC CARBONYL ARYLHYDRAZONES OF BENZENE, NAPHTHALENE, AND AZULENE

Aromatic carbonyl arylhydrazones have been shown to undergo two kinds of rearrangement in polyphosphoric acid both involving nitrogen-nitrogen bond cleavage.The first proceeds via insertion of the imine portion in the position ortho to the second nitrogen atom to give o-phenylenediamine intermediates: their evolution depends on the nature of the starting substrate.This reaction has been employed for synthesizing the quinoxalines (5) and the phenanthridines (11), and was demonstrated to be intramolecular.The second reaction path is a sigmatropic rearrangment exclusive to electron-rich aromatic carbonyl hydrazones.