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.

• MeSH
• Acetophenones chemistry   MeSH
• Anions chemistry   MeSH
• Cyclopropanes chemistry   MeSH
• Epoxy Compounds chemistry   MeSH
• Spectrometry, Mass, Electrospray Ionization MeSH
• Molecular Structure MeSH
• Solutions chemistry   MeSH
• Spiro Compounds chemistry   MeSH
• Models, Theoretical MeSH
• Noble Gases chemistry   MeSH
• Publication type
• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH
• Research Support, N.I.H., Extramural MeSH
• Names of Substances
• Acetophenones MeSH
• Anions MeSH
• Cyclopropanes MeSH
• Epoxy Compounds MeSH
• Solutions MeSH
• Spiro Compounds MeSH
• Noble Gases MeSH