Cleavage of phosphorus-carbon (P-C) bonds of α-amino phosphonates with intramolecular hydrogen migration in the gas phase using electrospray ionization tandem mass spectrometry

Abstract

An interesting intramolecular hydrogen atom migration between the amino and phosphoryl groups was observed with cleavage of the P-C bond in the molecule through a five-membered-ring intermediate. This characteristic fragmentation pathway not only provides some insights into the basic chemistry of compounds with P-C bonds, but could also have some applications in the structural determination of the α-amino phosphonate analogues.

GC-MS Study of Mono- and Bishaloethylphosphonates Related to Schedule 2.B.04 of the Chemical Weapons Convention: The Discovery of a New Intramolecular Halogen Transfer

“…The molecular masses of these compounds were confirmed by GC/ MS(CI) (SF 41-43). Furthermore, fragments from the cleavage of the P-C bond were also absent from the spectra, whereas this dissociation was detected in the mass spectra of α-amino phosphonates [41] and spiro alkylphosphonates [42]. Again, the nature of the halogen atom (X) plays a crucial role in the fragmentation pathway of compounds 13-24.…”