Photoionization of 2,3-dimethyl-2-butanol (thexyl alcohol): interaction between the charged and expelled fragments

Journal of the American Society for Mass Spectrometry
John C Traeger, Thomas Hellman Morton

Abstract

Photoionization studies of (CH(3))(2)CHC(CH(3))(2)OH (tert-hexyl alcohol, also called thexyl alcohol) exhibit four fragmentations below 10 eV. As with other tertiary alcohols, no molecular ion is detected. The only ion observed at threshold corresponds to propane loss. Examination of a deuterated analogue, (CH(3))(2)CHC(CD(3))(2)OH, shows only loss of C(3)H(7)D, implying that the fragment ion has the structure of ionized acetone enol. There is no evidence for reversible deuterium transposition, as has been reported for isotopomers of the homologous secondary alcohol (CH(3))(2)CHCH(CH(3))OH. Propane loss from thexyl alcohol is attributed to intermediacy of ion-neutral complexes containing isopropyl radical and O-protonated acetone. Simple cleavage to give O-protonated acetone has an appearance energy 18 kJ mol(-1) higher than that of propane loss. Thermochemical estimates and ab initio calculations both predict that methyl loss should have a lower threshold than the fragmentation leading to isopropyl loss, but experiments show the appearance energy to be 6 kJ mol(-1) higher. This is consistent with previous reports of reverse activation barriers for methyl cleavages. Finally, formation of tert-hexyl cation, (CH(3))(2)CHC(CH(3))(...Continue Reading

References

Apr 16, 2002·Science·J L MargotD B Campbell
Jun 21, 2003·Science·J L Margot, M E Brown
Aug 1, 1991·Journal of the American Society for Mass Spectrometry·D J McAdooL L Griffin

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Citations

Oct 17, 2015·The Journal of Physical Chemistry. a·Hanyu FanFabien Goulay
May 10, 2005·Journal of Mass Spectrometry : JMS
Mar 20, 2010·Rapid Communications in Mass Spectrometry : RCM·Basem Kanawati, Philippe Schmitt-Kopplin
Apr 22, 2015·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Jos OomensThomas Hellman Morton
Jul 13, 2006·The Journal of Physical Chemistry. a·John C Traeger, Thomas Hellman Morton
Dec 22, 2005·The Journal of Physical Chemistry. a·Steen Hammerum, Christian B Nielsen
Oct 4, 2008·The Journal of Physical Chemistry. a·Jos OomensThomas Hellman Morton

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