4316-50-1Relevant articles and documents
Oxidative activation in aromatic substitutions. Reactions of N,N- dimethylanilines with secondary anilines promoted by thallium triacetate
Ciminale,Ciardo,Francioso,Nacci
, p. 2459 - 2464 (1999)
The reactions of N,N-dimethyl-p-anisidine (1a), N,N-dimethylaniline (1b), and N,N-dimethyl-p-fluoroaniline (1c) toward secondary anilines 2(a- d)-H in the presence of thallium triacetate sesquihydrate have been studied as representative of a novel oxidatively activated aromatic substitution affording 1,4-benzenediamine derivatives 3a-d. All of the substrates considered gave substitution with diphenylamine (2d-H). However, with anilines 2b,c-H, only 1a underwent substitution, and substrates 1b,c were practically unreactive. The observed differences in reactivity are well accounted for within a mechanistic framework wherein oxidative activation of both the substrate and the secondary aniline is regarded as alternatively (or simultaneously) possible, depending on the redox characteristics of the reactants. For instance, it can be stated, beyond any reasonable doubt, that reactions of 1a with 2b,c-H proceed via nucleophilic attack of the latter on 1a+., and that the reaction of 1a-c with 2d-H must involve the diphenylamino radical 2d·.
Biaryl Phosphine Based Pd(II) Amido Complexes: The Effect of Ligand Structure on Reductive Elimination
Arrechea, Pedro Luis,Buchwald, Stephen L.
supporting information, p. 12486 - 12493 (2016/10/07)
Kinetic studies conducted under both catalytic and stoichiometric conditions were employed to investigate the reductive elimination of RuPhos (2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl) based palladium amido complexes. These complexes were found to be the resting state in Pd-catalyzed cross-coupling reactions for a range of aryl halides and diarylamines. Hammett plots demonstrated that Pd(II) amido complexes derived from electron-deficient aryl halides or electron-rich diarylamines undergo faster rates of reductive elimination. A Hammett study employing SPhos (2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl) and analogues of SPhos demonstrated that electron donation of the lower aryl group is key to the stability of the amido complex with respect to reductive elimination. The rate of reductive elimination of an amido complex based on a BrettPhos-RuPhos hybrid ligand (2-(dicyclohexylphosphino)-3,6-dimethoxy-2′,6′-diisopropoxybiphenyl) demonstrated that the presence of the 3-methoxy substituent on the "upper" ring of the ligand slows the rate of reductive elimination. These studies indicate that reductive elimination occurs readily for more nucleophilic amines such as N-alkyl anilines, N,N-dialkyl amines, and primary aliphatic amines using this class of ligands.
Method for producing hydroxytriarylamine (by machine translation)
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Paragraph 0038, (2018/02/24)
PROBLEM TO BE SOLVED: To economically provide arylamines such as triarylamine. SOLUTION: An arylamine compound represented by formula (1) and an aryl compound having a leaving group represented by formula (2): X-Ar2-X1, are subjected to an arylamination reaction in the presence of a basic group, an alkaline metal salt and/or an alkaline earth metal salt, and an iron catalyst to thereby obtain arylamines such as triarylamines. In formula (1), Ar and Ar1are identical or different, and denote a substituted or non-substituted aryl group, and may be ring-condensed; and a denotes 1 or 2. In formula (2), X and X1are identical or different, and denote at least one leaving group selected from the group consisting of H or Br, I, CMs (mesylate), OTf (triflate) and OTs (tosylate), provided that X and X1are not simultaneously H, and have at least one leaving group; and Ar2denotes a substituted or non-substituted aryl group. COPYRIGHT: (C)2012,JPO&INPIT
