Tertiary N-acyl phosphoramidates : a mechanistic study of their formation and collapse in reactions with nucleophiles
type: CreativeWork
description: Different synthetic approaches to tertiary mixed phosphoric-carboxylic imides(III) are discussed. The preparation of (III) via the N-acylation of phosphoramidates was investigated. The reaction of PhC(O)X (X = Br, Cl, F) with the conjugate base of (EtO)₂P(O)NHMe (IX) yields three products: PhCO₂Et (4), PhC(O)NHMe (5) and (PhCO)₂NMe (6). (5) and (6) are formed via the initial rapid formation of (EtO)₂P(O)-NMe-C(O)Ph (IIIe), while (4) results from the E1cB related reaction of (EtO)₂P(O)NMe involving electrophilic assistance by PhC(O)X. The attack of various nucleophilic species at the mixed-imide (IIIe) was studied, and the possible mechanisms of the P-N bond cleavage, followed by the N-methyl transfer from the phosphoryl to the carbonyl centre are discussed.
abstract: Different synthetic approaches to tertiary mixed phosphoric-carboxylic imides(III) are discussed. The preparation of (III) via the N-acylation of phosphoramidates was investigated. The reaction of PhC(O)X (X = Br, Cl, F) with the conjugate base of (EtO)₂P(O)NHMe (IX) yields three products: PhCO₂Et (4), PhC(O)NHMe (5) and (PhCO)₂NMe (6). (5) and (6) are formed via the initial rapid formation of (EtO)₂P(O)-NMe-C(O)Ph (IIIe), while (4) results from the E1cB related reaction of (EtO)₂P(O)NMe involving electrophilic assistance by PhC(O)X. The attack of various nucleophilic species at the mixed-imide (IIIe) was studied, and the possible mechanisms of the P-N bond cleavage, followed by the N-methyl transfer from the phosphoryl to the carbonyl centre are discussed.
author: Hendrickse, Theodore Franklin
language: eng
date published: 1983
date modified: 2026-07-22T22:23:46Z
provider: University of Cape Town
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: Department of Chemistry

PropertyValue
property ID: Handle
value: http://hdl.handle.net/11427/17035