N
X
C
O
N
S
Hal
Solvents
Natural
Products
P Si
C
C
C C
C
C
378
8 Mass Spectrometry
Polyenes and Polyynes
Fragmentation: The spectra of aliphatic compounds with several triple and/or
double bonds are similar to those of aromatic hydrocarbons.
Ion series: Very similar to those of aromatic hydrocarbons, but fragments with
higher hydrogen contents than in aromatics (m/z 54, 55; 66, 67; 79, 80) are usually
found in polyenes and polyynes.
Intensities: Very similar distribution of peak intensities as for aromatic hydrocarbons.
Molecular ion: Usually strong, as in aromatic hydrocarbons.
References
[1] A.G. Loudon, A. Maccoll, The mass spectrometry of the double bond. In: The
Chemistry of Alkenes, Vol. 2; J. Zabicky, Ed.; Interscience: London, 1970; p
327.
[2] J.T. Bursey, M.M. Bursey, D.G. Kingston, Intramolecular hydrogen transfer in
mass spectra. 1. Rearrangements in aliphatic hydrocarbons and aromatic compounds, Chem. Rev. 1973, 73, 191.
[3] N.J. Jensen, M.L. Gross, Localization of double bonds. Mass Spectrom. Rev.
1987, 6, 497.
[4] C. Dass, Ion–molecule reactions of [ketene] +· as a diagnostic probe for distinguishing isomeric alkenes, alkynes, and dienes: A study of the C 4 H 8 and C 5 H 8
isomeric hydrocarbons, Org. Mass Spectrom. 1993, 28, 940.