1. Gas-phase fragmentation of deprotonated p-hydroxyphenacyl derivatives.
- Author
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Remeš M, Roithová J, Schröder D, Cope ED, Perera C, Senadheera SN, Stensrud K, Ma CC, and Givens RS
- Subjects
- Models, Theoretical, Molecular Structure, Solutions chemistry, Spectrometry, Mass, Electrospray Ionization, Acetophenones chemistry, Anions chemistry, Cyclopropanes chemistry, Epoxy Compounds chemistry, Noble Gases chemistry, Spiro Compounds chemistry
- Abstract
Electrospray ionization of methanolic solutions of p-hydroxyphenacyl derivatives HO-C(6)H(4)-C(O)-CH(2)-X (X = leaving group) provides abundant signals for the deprotonated species which are assigned to the corresponding phenolate anions (-)O-C(6)H(4)-C(O)-CH(2)-X. Upon collisional activation in the gas phase, these anions inter alia undergo loss of a neutral "C(8)H(6)O(2)" species concomitant with formation of the corresponding anions X(-). The energies required for the loss of the neutral roughly correlate with the gas phase acidities of the conjugate acids (HX). Extensive theoretical studies performed for X = CF(3)COO in order to reveal the energetically most favorable pathway for the formation of neutral "C(8)H(6)O(2)" suggest three different routes of similar energy demands, involving a spirocyclopropanone, epoxide formation, and a diradical, respectively.
- Published
- 2011
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