TY - JOUR
T1 - Gas-phase fragmentations of anions derived from N-phenyl benzenesulfonamides
AU - Hibbs, John A.
AU - Jariwala, Freneil B.
AU - Weisbecker, Carl S.
AU - Attygalle, Athula B.
PY - 2013/8
Y1 - 2013/8
N2 - In addition to the well-known SO2 loss, there are several additional fragmentation pathways that gas-phase anions derived from N-phenyl benzenesulfonamides and its derivatives undergo upon collisional activation. For example, N-phenyl benzenesulfonamide fragments to form an anilide anion (m/z 92) by a mechanism in which a hydrogen atom from the ortho position of the benzenesulfonamide moiety is specifically transferred to the charge center. Moreover, after the initial SO2 elimination, the product ion formed undergoes primarily, an inter-annular H2 loss to form a carbazolide anion (m/z 166) because the competing intra-annular H2 loss is significantly less energetically favorable. Results from tandem mass spectrometric experiments conducted with deuterium-labeled compounds confirmed that the inter-ring mechanism is the preferred pathway. Furthermore, N-phenyl benzenesulfonamide and its derivatives also undergo a phenyl radical loss to form a radical ion with a mass-to-charge ratio of 155, which is in violation of the so-called "even-electron rule." [Figure not available: see fulltext.]
AB - In addition to the well-known SO2 loss, there are several additional fragmentation pathways that gas-phase anions derived from N-phenyl benzenesulfonamides and its derivatives undergo upon collisional activation. For example, N-phenyl benzenesulfonamide fragments to form an anilide anion (m/z 92) by a mechanism in which a hydrogen atom from the ortho position of the benzenesulfonamide moiety is specifically transferred to the charge center. Moreover, after the initial SO2 elimination, the product ion formed undergoes primarily, an inter-annular H2 loss to form a carbazolide anion (m/z 166) because the competing intra-annular H2 loss is significantly less energetically favorable. Results from tandem mass spectrometric experiments conducted with deuterium-labeled compounds confirmed that the inter-ring mechanism is the preferred pathway. Furthermore, N-phenyl benzenesulfonamide and its derivatives also undergo a phenyl radical loss to form a radical ion with a mass-to-charge ratio of 155, which is in violation of the so-called "even-electron rule." [Figure not available: see fulltext.]
KW - ESI-MS/MS
KW - Even-electron rule
KW - Fragmentation
KW - Substituent effects
KW - Sulfonamides
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U2 - 10.1007/s13361-013-0671-4
DO - 10.1007/s13361-013-0671-4
M3 - Article
C2 - 23780491
AN - SCOPUS:84880831884
SN - 1044-0305
VL - 24
SP - 1280
EP - 1287
JO - Journal of the American Society for Mass Spectrometry
JF - Journal of the American Society for Mass Spectrometry
IS - 8
ER -