Fragmentation mechanisms from electron-impact of complex cyclic ethers formed in combustion

Chemical kinetics of cyclic ethers in combustion

“…Herbinet et al [427] also proposed rules for the fragmentation of CEs in electron impact mass spectrometry to allow their identification when their mass spectra are not available. More recently, Koritzke et al [428] performed a similar work and reported mass spectra for 10 CEs. The authors considered four conventional mechanisms to analyze fragmentation patterns in the mass spectra: -cleavage, inductive effect, hydrogen rearrangement and transannular cleavage.…”

“…The authors considered four conventional mechanisms to analyze fragmentation patterns in the mass spectra: -cleavage, inductive effect, hydrogen rearrangement and transannular cleavage. Rules were proposed to explain the main fragments observed in the CE mass spectra [427,428]. The analysis of mass spectra for a series of 5-and 6-membered ring cyclic ethers that are formed in n-alkane oxidation (with one alkyl group in position 2 or two alkyl groups in positions 2 and 5) showed that the molecular ions are quite unstable and likely decompose through the loss of one of the alkyl chains.…”

“…The peak at m/z 57 in the mass spectrum of 2-ethyloxetane likely results from the loss of the ethyl group. The mass spectra obtained by Koritze et al [428] showed that the fragmentation of oxirane type cyclic ethers is even more complex.…”