AbstractDie Hydrolyse der Monoester (I) und (II), eine Reaktion pseudoerster Ordnung, wird im pH‐Bereich von 1‐10 untersucht.

Beim Umsetzen mit CH, N 2 werden die Pyridylphosphonsäureester (Ia) bzw. (Ib) zu den Derivaten (IIa) bzw. (IIb) N‐methyliert, wobei die direkte N‐Methylierung eher als eine O‐Methylierung gefolgt von Wanderung der O‐Methylgruppe zum N‐Atom verläuft.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTElimination-addition mechanisms of acyl group transfer: hydrolysis and aminolysis of aryl phenylmethanesulfonatesMichael B. Davy, Kenneth T. Douglas, John S. Loran, Alex Steltner, and Andrew WilliamsCite this: J. Am. Chem. Soc. 1977, 99, 4, 1196–1206Publication Date (Print):February 1, 1977Publication History Published online1 May 2002Published inissue 1 February 1977https://pubs.acs.org/doi/10.1021/ja00446a035https://doi.org/10.1021/ja00446a035research-articleACS PublicationsRequest reuse permissionsArticle Views290Altmetric-Citations27LEARN 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 InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

The hydrolysis of O-(4-nitrophenyl) 2-pyridylphosphonate possesses kinetic terms in hydroxide and hydrogen ion concentration and zwitterion and anion concentration. Comparison with suitable models where the proton is localised shows that the 'anion' term arises from hydroxide ion attack on the zwitterion rather than water attack on the monoanion; 'zwitterion' term involves attack of hydroxide ion on the cationic species. The hydrolysis of O-(4-nitrophenyl)(N-methyl-2-pyridinio)phosphonate possesses a 'neutral' term from hydroxide ion attack on the cationic species. 2-Pyridylphosphonate diesters hydrolyse via attack by water on the neutral form of the ester; there is no detectable anchimeric assistance by the pyridine nitrogen possibly due to the very low basicity of the base. The hydrolysis of O-(4-nitrophenyl) phenylphosphonate at neutral pH involves decomposition of the monoanion presumably by water attack rather than the equivalent reaction of hydroxide ion with the neutral form of the ester. O-(4-Nitrophenyl) 2-pyridyl)phosphonate is shown to complex with transition metal ions which also catalyse the hydrolysis of the ester possibly via electrophilic participation.

Chemischer InformationsdienstVolume 8, Issue 24 Organoelement Compounds ChemInform Abstract: INTRAMOLECULAR NUCLEOPHILIC CATALYSIS IN THE HYDROLYSIS OF 4-NITROPHENYL QUINOLIN-8-YL PHOSPHATE J. S. LORAN, J. S. LORANSearch for more papers by this authorA. WILLIAMS, A. WILLIAMSSearch for more papers by this author J. S. LORAN, J. S. LORANSearch for more papers by this authorA. WILLIAMS, A. WILLIAMSSearch for more papers by this author First published: June 14, 1977 https://doi.org/10.1002/chin.197724287AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume8, Issue24June 14, 1977 RelatedInformation

The hydrolysis of the title ester is shown to involve expulsion of 4-nitrophenol via intramolecular nucleophilic attack at phosphorus by the quinolinyl nitrogen. Strain in ring closure is proposed as the explanation for the less efficient action than carboxylate attack in the hydrolysis of 2-carboxyphenyl 4-nitrophenyl phosphate. The considerable mechanistic ambiguity due to the dibasic nature of the ester is resolved by comparison with appropriate models.

J. S. Loran, R. A. Naylor and A. Williams, J. Chem. Soc., Perkin Trans. 2, 1976, 1444 DOI: 10.1039/P29760001444

The hydrolysis and aminolysis of substituted phenyl toluene-α-sulphonates possess a stepwise elimination–addition mechanism (E1cB) involving a sulphene intermediate; the E1cB pathway for the hydrolysis of 5-nitro-2-hydroxytoluene-α-sulphonic acid sultone is sterically suppressed.