Microsynthesis and mass spectral study of Chemical Weapons Convention related 2‐alkyl‐1,3,6,2‐dioxathiaphosphocane‐2‐oxides

Chemical Weapons Convention (CWC)‐related compounds where the phosphorus atom is part of a ring have very limited representation in mass spectral libraries and the open literature. Here we report electron ionization (EI), chemical ionization (CI) and electrospray ionization tandem mass spectrometry (ESI‐MSⁿ) spectra and retention indices for 2‐alkyl‐1,3,6,2‐dioxathiaphosphocane‐2‐oxides (alkyl C₁ to C₃) which are new cyclic chemicals covered under the CWC. The EI mass spectra show a pattern of ion fragmentation that is similar to that of other cyclic phosphonates in that loss of the alkylphosphonic acid as a neutral loss is more important than the presence of the protonated alkylphosphonic acid. In contrast to other cyclic phosphonates, the 2‐alkyl‐1,3,6,2‐dioxathiaphosphocane‐2‐oxides show almost no protonated alkylphosphonic acid and as a result the spectra do not carry the same distinctive signature of the phosphorus–carbon bond that is required for the chemical to be covered under the CWC. Copyright © 2008 John Wiley & Sons, Ltd.