Gas-phase fragmentation of deprotonated p-hydroxyphenacyl derivatives |
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Authors: | Remeš Marek Roithová Jana Schröder Detlef Cope Elizabeth D Perera Chamani Senadheera Sanjeewa N Stensrud Kenneth Ma Chi-cheng Givens Richard S |
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Institution: | Department of Organic Chemistry, Faculty of Sciences, Charles University in Prague, Hlavova 8, 12083 Prague 2, Czech Republic. |
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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. |
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