Dealkylation Of Amines Research Articles

A cyclic divalent N(I) species isoelectronic to carbodiphosphoranes.

The formation of a rare type of diphosphazenium cation is described. Its synthesis features a unique oxidative dealkylation of an iminophosphorane-phosphole by a silver(I) salt. DFT study of this compound reveals the low valent character of the N(I) center.

Electrocatalytic Dealkylation of Amines Mediated by Ferrocene

The homogeneous catalytic oxidation of dicyclohexylamine (DCHA), N,N-dimethylcyclohexylamine (DMCHA) and N,N-dicyclohexylmethylamine (DCHMA) has been investigated in the presence of electrochemically generated ferrocenium ions as the catalyst. Mechanistic details for this electrocatalytic process have been scrutinized with the use of cyclic voltammetry, bulk electrolysis, and digital simulations techniques. A one-electron catalytic process between ferrocene and the respective amines was observed. The products obtained from bulk electrolysis were isolated and identified by FTIR, 1H and 13C NMR spectroscopy, and mass spectrometry. Both DCHMA and DMCHA proceed to yield a secondary amine product by the elimination of one methyl group. In the absence of this group, as in the case of DCHA, the cycloalkyl group is then eliminated. The catalytic efficiency and the second-order rate constants were estimated and found to follow the order DCHA ≪ DMCHA < DCHMA. The results presented in this work should open up a new avenue to achieve simple, low-cost, and efficient amine oxidation, which could be useful in several areas of chemistry.

Atom-Economical Synthesis of the Versatile Ruthenium Precursor [TpRuCl(COD)] (Tp = Hydrotris(pyrazol-1-yl)borate) Discloses a Diamine Ligand Dealkylation Process

An atom-economical, more environmentally friendly alternative method of synthesis of the versatile complex [TpRuCl(COD)] (1) (Tp = hydrotris(pyrazol-1-yl)borate; COD = 1,5-cyclooctadiene) has been developed. Instead of starting from [RuHCl(COD)(NH2NMe2)3]+, 1 can be conveniently prepared by reaction of the derivative trans-[RuCl2(COD)(Me2NCH2CH2NHMe)] (2) with KTp in acetone at 55 °C. Compound 2, which has been structurally characterized by X-ray crystallography, results from an unexpected diamine dealkylation process which takes place in the course of the reaction of [{RuCl2(COD)}n] with tmeda (tmeda = Me2NCH2CH2NMe2) in toluene at 80 °C. This process had been overlooked in the literature, as compound 2 had been misidentified as cis-[RuCl2(COD)(tmeda)], and suggests that amine dealkylation might occur more commonly than previously anticipated.

A formal method for the de-N,N-dialkylation of Sommelet–Hauser rearrangement products

Selective amine de-alkylation enables the conversion of Sommelet–Hauser rearrangement products into 2-aryl-2-bromoacetic acid derivatives. These compounds are valuable synthetic intermediates in the synthesis of α-aryl-α-amino or α-aryl-β-amino acid derivatives. The method presented herein is a formal de-N,N-dialkylation of Sommelet–Hauser rearrangement products.

1,2-Dimethoxy-4,5-dimethylene: a new protecting group for acyclic amino acid derivatives prepared by Stevens rearrangement

A new protecting group, 1,2-dimethoxy-4,5-dimethylene, for acyclic amino acid derivatives could be introduced by N,N-dialkylation with 1,2-bis(bromomethyl)-4,5-dimethoxybenzene (1) and removed via amine de-alkylation with acyl chlorides. The method can be used with base-induced [2,3] and [1,2] Stevens rearrangement products.

Oxidative dealkylation of aromatic amines by "bare" FeO+ in the gas phase

The gas-phase oxidations of aniline, N-methylaniline, and N,N-dimethylaniline by FeO+ cation are examined by using mass spectrometric techniques. Although bare FeO+ is capable of hydroxylating aromatic C—H bonds, the fate of the oxidation of arylamines is determined by docking of the FeO+ unit at nitrogen. The major reactions of the metastable aniline/FeO+ complex are losses of molecular hydrogen, ammonia, and water, all involving at least one N-H proton. N-alkylation results in a complete shift of the course of the reaction. The unimolecular processes observed can be regarded as initial steps of an oxidative dealkylation of the amines mediated by FeO+. More detailed mechanistic insight is obtained by examining the C—H(D) bond activation of N-methyl-N-([D3]-methyl)aniline by bare and ligated FeO+ species. The gas-phase reactions of FeO+ with methylanilines show some similarities to the enzymatic dealkylation of amines by cytochrome P-450. The kinetic isotope effects observed experimentally suggest an electron transfer mechanism for the gas-phase reaction.Key words: mass spectrometry, gas-phase chemistry, iron, dealkylation, N,N-dimethylaniline.

Oxidative dealkylation of aromatic amines by "bare" FeO&lt;sup&gt;+&lt;/sup&gt; in the gas phase

The gas-phase oxidations of aniline, N-methylaniline, and N,N-dimethylaniline by FeO+ cation are examined by using mass spectrometric techniques. Although bare FeO+ is capable of hydroxylating aromatic C—H bonds, the fate of the oxidation of arylamines is determined by docking of the FeO+ unit at nitrogen. The major reactions of the metastable aniline/FeO+ complex are losses of molecular hydrogen, ammonia, and water, all involving at least one N-H proton. N-alkylation results in a complete shift of the course of the reaction. The unimolecular processes observed can be regarded as initial steps of an oxidative dealkylation of the amines mediated by FeO+. More detailed mechanistic insight is obtained by examining the C—H(D) bond activation of N-methyl-N-([D3]-methyl)aniline by bare and ligated FeO+ species. The gas-phase reactions of FeO+ with methylanilines show some similarities to the enzymatic dealkylation of amines by cytochrome P-450. The kinetic isotope effects observed experimentally suggest an electron transfer mechanism for the gas-phase reaction.Key words: mass spectrometry, gas-phase chemistry, iron, dealkylation, N,N-dimethylaniline.

Net Amine Dealkylation at a Diruthenium Center: Dehydrogenation of a Secondary Amine and Hydrolysis of a Coordinated Imine

Net Amine Dealkylation at a Diruthenium Center: Dehydrogenation of a Secondary Amine and Hydrolysis of a Coordinated Imine

Mechanism of Oxidative Amine Dealkylation of Substituted N,N-Dimethylanilines by Cytochrome P-450: Application of Isotope Effect Profiles

Mechanism of Oxidative Amine Dealkylation of Substituted N,N-Dimethylanilines by Cytochrome P-450: Application of Isotope Effect Profiles

On the mechanism of amine oxidations by P450.

1. Experimental data previously used to support an electron/proton transfer mechanism for oxidative dealkylation of amines by P450 are critically analysed with the conclusion that the mechanistic evidence is indecisive. 2. A new mechanistic criterion recently proposed to distinguish between electron/proton transfer and hydrogen atom transfer mechanisms is discussed. It is based on isotope effect profiles determined for the deprotonation of a series of para-substituted N-methyl-N-trideuteriomethyl)aniline cation radicals by pyridine and for hydrogen atom abstraction from the corresponding neutral amines by the tert-butoxyl radical. These reactions model the steps proposed in the two P450 mechanisms. 3. Isotope effect profiles measured for the demethylation of substituted NN-bis(dideuteriomethyl)anilines by four different forms of P450 were found to be experimentally indistinguishable from the hydrogen atom transfer profile, and distinctly different from the cation radical deprotonation profile. This provides strong evidence that P450 oxidatively dealkylates the amines by a hydrogen atom transfer mechanism and not by an electron/proton transfer mechanism.

Organoselenium chemistry. Dealkylation of amines with benzeneselenol

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTOrganoselenium chemistry. Dealkylation of amines with benzeneselenolHans J. Reich and Martin L. CohenCite this: J. Org. Chem. 1979, 44, 18, 3148–3151Publication Date (Print):August 1, 1979Publication History Published online1 May 2002Published inissue 1 August 1979https://doi.org/10.1021/jo01332a012RIGHTS & PERMISSIONSArticle Views507Altmetric-Citations37LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (544 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Kinetics of photoreduction of benzophenones by amines. Deamination and dealkylation of amines

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTKinetics of photoreduction of benzophenones by amines. Deamination and dealkylation of aminesSaul G. Cohen and Nina M. SteinCite this: J. Am. Chem. Soc. 1971, 93, 24, 6542–6551Publication Date (Print):December 1, 1971Publication History Published online1 May 2002Published inissue 1 December 1971https://doi.org/10.1021/ja00753a036RIGHTS & PERMISSIONSArticle Views402Altmetric-Citations56LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts