Jump to main content
Jump to site search

Issue 19, 2003
Previous Article Next Article

Competing sulfonylation and phosphonylation following rearrangement of an O-sulfonyl-N-phosphinoylhydroxylamine with tert-butylamine: demonstration of a phosphonamidic-sulfonic anhydride intermediate and 18O-labelling evidence on how it may be formed1

Author affiliations

Abstract

Reaction of R(Ph)P(O)NHOSO2Bn (R = PhMeCH) with ButNH2 in CH2Cl2 gives a mixture of RP(O)(NHPh)NHBut and ButNHSO2Bn, the proportion of the sulfonamide increasing steadily (14.6% to 32.9%) as the concentration of amine is reduced (8.0 to 0.2 mol dm−3). Apparently the phenyl and sulfonate groups in the substrate become transposed, giving a phosphonamidic-sulfonic anhydride RP(O)(NHPh)OSO2Bn which then reacts at the phosphorus or sulfur atom to give the final products; an authentic sample of the anhydride gives similar mixtures of products. Substrate labelled with 18O in the sulfonyl position (57 mol% one 18O atom) gives sulfonamide containing most but not all of the label (43.7 mol% one 18O atom with 2.0 mol dm−3 amine). This implies partial equilibration of the three sulfonate oxygen atoms during rearrangement, or after the anhydride intermediate has been formed.

Graphical abstract: Competing sulfonylation and phosphonylation following rearrangement of an O-sulfonyl-N-phosphinoylhydroxylamine with tert-butylamine: demonstration of a phosphonamidic-sulfonic anhydride intermediate and 18O-labelling evidence on how it may be formed1

Back to tab navigation

Article information


Submitted
16 May 2003
Accepted
05 Aug 2003
First published
28 Aug 2003

Org. Biomol. Chem., 2003,1, 3390-3395
Article type
Paper

Competing sulfonylation and phosphonylation following rearrangement of an O-sulfonyl-N-phosphinoylhydroxylamine with tert-butylamine: demonstration of a phosphonamidic-sulfonic anhydride intermediate and 18O-labelling evidence on how it may be formed

M. J. P. Harger, Org. Biomol. Chem., 2003, 1, 3390
DOI: 10.1039/B305510H

Social activity

Search articles by author

Spotlight

Advertisements