Sequential methyl elimination from ionized dimethyl[2.n]paracyclophane-enes (n=3, 4, 5, 6): Interaction of ionized aromatic rings in strained cyclophane conformations?

Zoric S, Wellbrock C, Grützmacher H-F (1997)
EUROPEAN MASS SPECTROMETRY 3(1): 127-140.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
The fragmentations of the molecular ions of a series of dimethyl[2.n]paracyclophane-enes (n = 3, 4, 5, 6) have been studied by mass-analyzed ion kinetic energy (MIKE) spectrometry and deuterium labeling, The characteristic fragmentation sequence of the molecular ions of all dimethyl[2.n]paracyclophane-enes is the sequential elimination of three methyl radicals, The first methyl radical originates predominantly from the methyl substituent of the ethylene bridge and this process is accompanied by a large kinetic energy release (KER) indicative of a preceding rearrangement, The kinetic energy release distribution (KERD) observed is independent of the size of the polymethylene bridge of the dimethyl[2.n]paracyclophane-enes and even of the source of the methyl radical, Abundant loss of a second methyl radical is observed from metastable [M - CH3](+) ions in spite of a violation of the ''even-electron-rule''. Again, the methyl radical lost is chiefly a methyl substituent at the ethylene bridge, although methyl loss from the inner methylene groups of the polymethylene bridge occurs also, A small KER is observed for this fragmentation, which is again independent of the source of the methyl radical, These observations are rationalized by a rearrangement of the molecular ions by bond formation between the aromatic rings and subsequent hydrogen migrations either before or after a benzylic cleavage of the saturated bridge.
Erscheinungsjahr
Zeitschriftentitel
EUROPEAN MASS SPECTROMETRY
Band
3
Zeitschriftennummer
1
Seite
127-140
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Zoric S, Wellbrock C, Grützmacher H-F. Sequential methyl elimination from ionized dimethyl[2.n]paracyclophane-enes (n=3, 4, 5, 6): Interaction of ionized aromatic rings in strained cyclophane conformations? EUROPEAN MASS SPECTROMETRY. 1997;3(1):127-140.
Zoric, S., Wellbrock, C., & Grützmacher, H. - F. (1997). Sequential methyl elimination from ionized dimethyl[2.n]paracyclophane-enes (n=3, 4, 5, 6): Interaction of ionized aromatic rings in strained cyclophane conformations? EUROPEAN MASS SPECTROMETRY, 3(1), 127-140. doi:10.1255/ejms.31
Zoric, S., Wellbrock, C., and Grützmacher, H. - F. (1997). Sequential methyl elimination from ionized dimethyl[2.n]paracyclophane-enes (n=3, 4, 5, 6): Interaction of ionized aromatic rings in strained cyclophane conformations? EUROPEAN MASS SPECTROMETRY 3, 127-140.
Zoric, S., Wellbrock, C., & Grützmacher, H.-F., 1997. Sequential methyl elimination from ionized dimethyl[2.n]paracyclophane-enes (n=3, 4, 5, 6): Interaction of ionized aromatic rings in strained cyclophane conformations? EUROPEAN MASS SPECTROMETRY, 3(1), p 127-140.
S. Zoric, C. Wellbrock, and H.-F. Grützmacher, “Sequential methyl elimination from ionized dimethyl[2.n]paracyclophane-enes (n=3, 4, 5, 6): Interaction of ionized aromatic rings in strained cyclophane conformations?”, EUROPEAN MASS SPECTROMETRY, vol. 3, 1997, pp. 127-140.
Zoric, S., Wellbrock, C., Grützmacher, H.-F.: Sequential methyl elimination from ionized dimethyl[2.n]paracyclophane-enes (n=3, 4, 5, 6): Interaction of ionized aromatic rings in strained cyclophane conformations? EUROPEAN MASS SPECTROMETRY. 3, 127-140 (1997).
Zoric, Sandra, Wellbrock, Christoph, and Grützmacher, Hans-Friedrich. “Sequential methyl elimination from ionized dimethyl[2.n]paracyclophane-enes (n=3, 4, 5, 6): Interaction of ionized aromatic rings in strained cyclophane conformations?”. EUROPEAN MASS SPECTROMETRY 3.1 (1997): 127-140.