97860-68-9Relevant articles and documents
Highly Efficient Binuclear Copper-catalyzed Oxidation of N,N-Dimethylanilines with O2
Liu, Yuxia,Yan, Yonggang,Xue, Dong,Wang, Zhongfu,Xiao, Jianliang,Wang, Chao
, p. 2221 - 2225 (2020/03/23)
A binuclear copper-salicylate complex, [Cu(Sal)2(NCMe)]2 (Sal=salicylate), was found to be an active catalyst for the oxidation of N,N-dimethylanilines by O2, affording the corresponding N-methyl-N-phenylformamides as major products. The reactions were carried out with a O2 balloon and the S/C (substrate/catalyst ratio) of the model reaction could be up to 1×105, providing a practical and highly efficient catalytic protocol for accessing N-methyl-N-phenylformamides.
Catalytic and stoichiometric oxidation of N,N-dimethylanilines mediated by nonheme oxoiron(IV) complex with tetrapyridyl ligand
Lakk-Bogáth, Dóra,Kripli, Balázs,Meena, Bashdar I.,Speier, Gábor,Kaizer, József
, p. 169 - 175 (2019/05/29)
Nonheme iron(II) complex, [(N4Py*)FeII(CH3CN)](ClO4)2 (1) with pentadentate tetrapyridyl ligand (N4Py* = N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine) has been shown to catalyze the oxidation of N,N-dimethylaniline (DMA) with H2O2, tert-butyl hydroperoxide (TBHP), peracetic acid (PAA), meta-chloroperoxybenzoic acid (mCPBA) and PhIO resulting N-methylaniline (MA) as the predominant product with N-methylformanilide (MFA) as a result of a free-radical chain process. The product composition (MA/MFA) is remarkably influenced by the electron density on the substrate, especially in the 1/mCPBA system, and by the co-oxidants used. No formation of MFA occurred when the oxidation of DMA was carried out in the presence of 1 with PhIO as co-oxidants under argon. Based on spectral investigation (UV–Vis) of reaction systems above, oxoiron(IV) intermediate, [FeIV(N4Py*)(O)]2+ (2) has been suggested to be the key active species of the N-dealkylation reaction in all catalytic systems. The shift in the λmax value of the oxoiron(IV) species in the presence of DMA from 705 to 750 nm, and the new intense absorption in the range of 5–600 nm indicates a complexation and charge-transfer (CT) type interactions between the oxidant and substrate. The stoichiometric oxidation of various N,N-dimethylaniline derivatives with 2 provided clear evidence (Hammett correlation with ρ = ?1.99, and the large negative slope (?4.1) from the logkobs versus Eoox (DMAs) plot) for the rate-determining electron transfer (ET) followed by a proton transfer (PT) process.
Copper-Catalyzed N-Formylation of Amines through Tandem Amination/Hydrolysis/Decarboxylation Reaction of Ethyl Bromodifluoroacetate
Li, Xiao-Fang,Zhang, Xing-Guo,Chen, Fan,Zhang, Xiao-Hong
, p. 12815 - 12821 (2018/10/20)
Ethyl bromodifluoroacetate (BrCF2COOEt) was first used as the N-formylating reagent in the copper-catalyzed N-formylation of amines. A range of primary, secondary, cyclic arylamines, and aliphatic amines underwent the N-formylation smoothly to furnish the N-formamides in moderate-to-excellent yields.
