110543-65-2Relevant academic research and scientific papers
Reactions of N-Phenyl α-Halogenophosphonamidates with Alkoxide: Migration of the Anilino Group from Phosphorus to the α Carbon Atom
Harger, Martin J. P.,Williams, Andrew
, p. 1681 - 1686 (2007/10/02)
When Me2CClP(O)(NHPh)OMe is treated with 0.5M NaOMe-MeOH the anilino group migrates from phosphorus to the α carbon atom.Reaction is complete within 2 min at 60 deg C and Me2C(NHPh)P(O)(OMe)2 is formed quantitatively.Similar behaviour is observed with MeCHClP(O)(NHPh)OMe but the reaction is ca. 50-times slower and in the later stages some of the resulting MeCH(NHPh)P(O)(OMe)2 becomes demethylated.For the still less reactive compounds XCH2P(O)(NHPh)OMe (X = Cl or I) demethylation of the substrate and/or product is extensive, but with ICH2P(O)(NHPh)OEt in 0.15M NaOEt-EtOH at 60 deg C the product PhNHCH2P(O)(OEt)2 can be obtained within 1 h in high yield.The relative rates of rearrangement of the various substrates are consistent with a mechanism involving a three-membered cyclic intermediate, the phosphorus analogue of an α-lactam.
