Abstract
| Original language | English |
|---|---|
| Pages (from-to) | 189-197 |
| Number of pages | 9 |
| Journal | Journal of the American Society for Mass Spectrometry |
| Volume | 7 |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - 1996 |
| MoE publication type | A1 Journal article-refereed |
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Fragmentation of protonated O, O-diethyl O-aryl phosphorothionates in tandem mass spectral analysis. / Kuivalainen, Tuula; Kostiainen, Risto; Uggla, Rolf; Sundberg, Markku; Björk, Heikki.
In: Journal of the American Society for Mass Spectrometry, Vol. 7, No. 2, 1996, p. 189-197.Research output: Contribution to journal › Article › Scientific › peer-review
TY - JOUR
T1 - Fragmentation of protonated O, O-diethyl O-aryl phosphorothionates in tandem mass spectral analysis
AU - Kuivalainen, Tuula
AU - Kostiainen, Risto
AU - Uggla, Rolf
AU - Sundberg, Markku
AU - Björk, Heikki
PY - 1996
Y1 - 1996
N2 - The gas-phase ion chemistry of protonated O,O-diethyl O-aryl phosphorothionates was studied with tandem mass spectrometric and ab initio theoretical methods. Collision-activated dissociation (CAD) experiments were performed for the [M+H]+ ions on a triple quadrupole mass spectrometer. Various amounts of internal energy were deposited into the ions upon CAD by variation of the collision energy and collision gas pressure. In addition to isobutane, deuterated isobutane C4D10 also was used as reagent gas in chemical ionization. The daughter ions [M+H−C2H4]+ and [M+H−2C2H4]+ dominate the CAD spectra. These fragments arise via various pathways, each of which involves γ-proton migration. Formation of the terminal ions [M+H−2C2H4−H2O]+, [M+H−2C2H4−H2S]+, [ZPhOH2]+, [ZPhSH2]+, and [ZPhS]+ [Z = substituent(s) on the benzene ring] suggests that (1) the fragmenting [M+H]+ ions of O,O-diethyl O-aryl phosphorothionates have protons attached on the oxygen of an ethoxy group and on the oxygen of the phenoxy group; (2) thiono-thiolo rearrangement by aryl migration to sulfur occurs; (3) the fragmenting rear-ranged [M+H]+ ions have protons attached on the oxygen of an ethoxy group and on the sulfur of the thiophenoxy group. To get additional support for our interpretation of the mass spectrometric results, some characteristics of three protomers of O,O-diethyl O-phenyl phosphorothionate were investigated by carrying out ab initio molecular orbital calculations at the RHF/3–21G* level of theory.
AB - The gas-phase ion chemistry of protonated O,O-diethyl O-aryl phosphorothionates was studied with tandem mass spectrometric and ab initio theoretical methods. Collision-activated dissociation (CAD) experiments were performed for the [M+H]+ ions on a triple quadrupole mass spectrometer. Various amounts of internal energy were deposited into the ions upon CAD by variation of the collision energy and collision gas pressure. In addition to isobutane, deuterated isobutane C4D10 also was used as reagent gas in chemical ionization. The daughter ions [M+H−C2H4]+ and [M+H−2C2H4]+ dominate the CAD spectra. These fragments arise via various pathways, each of which involves γ-proton migration. Formation of the terminal ions [M+H−2C2H4−H2O]+, [M+H−2C2H4−H2S]+, [ZPhOH2]+, [ZPhSH2]+, and [ZPhS]+ [Z = substituent(s) on the benzene ring] suggests that (1) the fragmenting [M+H]+ ions of O,O-diethyl O-aryl phosphorothionates have protons attached on the oxygen of an ethoxy group and on the oxygen of the phenoxy group; (2) thiono-thiolo rearrangement by aryl migration to sulfur occurs; (3) the fragmenting rear-ranged [M+H]+ ions have protons attached on the oxygen of an ethoxy group and on the sulfur of the thiophenoxy group. To get additional support for our interpretation of the mass spectrometric results, some characteristics of three protomers of O,O-diethyl O-phenyl phosphorothionate were investigated by carrying out ab initio molecular orbital calculations at the RHF/3–21G* level of theory.
U2 - 10.1016%2F1044-0305%2895%2900634-6
DO - 10.1016%2F1044-0305%2895%2900634-6
M3 - Article
VL - 7
SP - 189
EP - 197
JO - Journal of the American Society for Mass Spectrometry
JF - Journal of the American Society for Mass Spectrometry
SN - 1044-0305
IS - 2
ER -