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
• acetofenony chemie   MeSH
• anionty chemie   MeSH
• cyklopropany chemie   MeSH
• epoxidové sloučeniny chemie   MeSH
• hmotnostní spektrometrie s elektrosprejovou ionizací MeSH
• molekulární struktura MeSH
• roztoky chemie   MeSH
• spirosloučeniny chemie   MeSH
• teoretické modely MeSH
• vzácné plyny chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Research Support, N.I.H., Extramural MeSH
• Názvy látek
• acetofenony MeSH
• anionty MeSH
• cyklopropany MeSH
• epoxidové sloučeniny MeSH
• roztoky MeSH
• spirosloučeniny MeSH
• vzácné plyny MeSH