Abstract
Functional group interaction occurs in the loss of a phenoxy radical from the molecular ions of ω‐phenylthio alkylphenylethers ØO(CH2)nSØ (n= 2–6). Labelling data provide evidence for the S‐phenyl thietanium, S‐phenyl tetrahydrothiophenium and S‐phenyl tetrahydrothiopyranium structures of the decomposing (lifetimes between 10−6and 10−5s) [M ‐ ØO]+ions in the case ofn= 3, 4 and 5, respectively.