Fragmentation of protonated O, O-diethyl O-aryl phosphorothionates in tandem mass spectral analysis

Tuula Kuivalainen, Risto Kostiainen, Rolf Uggla, Markku Sundberg, Heikki Björk

Research output: Contribution to journalArticleScientificpeer-review

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Abstract

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.
Original languageEnglish
Pages (from-to)189-197
Number of pages9
JournalJournal of the American Society for Mass Spectrometry
Volume7
Issue number2
DOIs
Publication statusPublished - 1996
MoE publication typeA1 Journal article-refereed

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Spectrum analysis
Ions
Butanes
Protons
Gases
Oxygen
Sulfur
Orbital calculations
Protein Subunits
Mass spectrometers
Molecular orbitals
Benzene
Ionization
Pressure
Experiments

Cite this

Kuivalainen, Tuula ; Kostiainen, Risto ; Uggla, Rolf ; Sundberg, Markku ; Björk, Heikki. / Fragmentation of protonated O, O-diethyl O-aryl phosphorothionates in tandem mass spectral analysis. In: Journal of the American Society for Mass Spectrometry. 1996 ; Vol. 7, No. 2. pp. 189-197.
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title = "Fragmentation of protonated O, O-diethyl O-aryl phosphorothionates in tandem mass spectral analysis",
abstract = "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.",
author = "Tuula Kuivalainen and Risto Kostiainen and Rolf Uggla and Markku Sundberg and Heikki Bj{\"o}rk",
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volume = "7",
pages = "189--197",
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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 journalArticleScientificpeer-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 -