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Type: Artigo de periódico
Title: Mechanisms of nucleophilic substitution reactions of methylated Hydroxylamines with bis(2,4-dinitrophenyl)phosphate. Mass spectrometric identification of key intermediates
Author: Domingos, JB
Longhinotti, E
Brandao, TAS
Bunton, CA
Santos, LS
Eberlin, MN
Nome, F
Abstract: Mono- and dimethylation of hydroxylamine on nitrogen does not significantly affect rates of initial attack of NHMeOH and NMe2OH on bis(2,4-dinitrophenyl)phosphate (BDNPP), which is largely by oxygen phosphorylation. O-Methylation, however, blocks this reaction and NH2OMe then slowly reacts with BDNPP via N-attack at phosphorus and at the aryl group. With NHMeOH, the initial product of O-attack at phosphorus reacts further, either by reaction with a second NHMeOH or by a spontaneous shift of NHMe to the aryl group via a transient cyclic intermediate. There is a minor N-attack of NHMeOH on BDNPP in an S(N)2(Ar) reaction. Reactions occurring via N-attack are blocked by N-dimethylation, and reaction of NMe2OH with BDNPP occurs via O-attack, generating a long-lived product. Reaction mechanisms have been probed, and intermediates identified, by using both NMR and MS spectroscopy, with the novel interception of key reaction intermediates in the course of reaction by electrospray ionization mass and tandem mass spectrometry.
Country: EUA
Editor: Amer Chemical Soc
Citation: Journal Of Organic Chemistry. Amer Chemical Soc, v. 69, n. 18, n. 6024, n. 6033, 2004.
Rights: fechado
Identifier DOI: 10.1021/jo0494735
Date Issue: 2004
Appears in Collections:Unicamp - Artigos e Outros Documentos

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