Electron-impact-induced 3,3-sigmatropic rearrangement and cyclization in phenyl allenylmethyl ethers

Abstract

A 3,3-sigmatropic rearrangement in the M(+·) of phenyl allenylmethyl ether is proposed for the observed losses of CO, C2H4, and CH3. Direct cyclization in the M(+·) also leads to the [M-CH3] ion. The presence of sulfur as the heteroatom in phenyl allenylmethyl sulfide does not significantly influence the occurrence of Claisen rearrangement. Ortho interaction of the nitro group with the allenyl double bond in the side chain leads to characteristic fragment ions in 2-nitrophenyl allenylmethyl ether. Linked scans, high-resolution mass spectrometry, collision-activated dissociation-B/E linked-scan spectra, and D-labeling have been employed to support the proposed mechanisms and ion structures.

Evidence for an aryl migration during the electron impact induced fragmentation of substituted aryloxymethylquinoxalines

“…The methoxy group is known to be a good hydrogen donor in ortho ‐disubstituted aromatic compounds 28. If there is a nitro group in the ortho position, it interacts strongly in aromatic compounds during the mass spectral decomposition.…”