Competitive homolytic and heterolytic decomposition pathways of gas‐phase negative ions generated from aminobenzoate esters
An alkyl‐radical loss and an alkene loss are two competitive fragmentation pathways that deprotonated aminobenzoate esters undergo upon activation under mass spectrometric conditions. For the meta and para isomers, the alkyl‐radical loss by a homolytic cleavage of the alkyl‐oxygen bond of the ester...
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| Autor*in: |
Xia, Hanxue [verfasserIn] |
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| Format: |
Artikel |
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| Sprache: |
Englisch |
| Erschienen: |
2016 |
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Nutzungsrecht: Copyright © 2016 John Wiley & Sons, Ltd. |
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Enthalten in: Journal of mass spectrometry - Chichester [u.a.] : Wiley, 1995, 51(2016), 3, Seite 245-253 |
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| Übergeordnetes Werk: |
volume:51 ; year:2016 ; number:3 ; pages:245-253 |
| Links: |
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| DOI / URN: |
10.1002/jms.3740 |
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| 520 | |a An alkyl‐radical loss and an alkene loss are two competitive fragmentation pathways that deprotonated aminobenzoate esters undergo upon activation under mass spectrometric conditions. For the meta and para isomers, the alkyl‐radical loss by a homolytic cleavage of the alkyl‐oxygen bond of the ester moiety is the predominant fragmentation pathway, while the contribution from the alkene elimination by a heterolytic pathway is less significant. In contrast, owing to a pronounced charge‐mediated ortho effect, the alkene loss becomes the predominant pathway for the ortho isomers of ethyl and higher esters. Results from isotope‐labeled compounds confirmed that the alkene loss proceeds by a specific γ ‐hydrogen transfer mechanism that resembles the McLafferty rearrangement for radical cations. Even for the para compounds, if the alkoxide moiety bears structural motifs required for the elimination of a more stable alkene molecule, the heterolytic pathway becomes the predominant pathway. For example, in the spectrum of deprotonated 2‐phenylethyl 4‐aminobenzoate, m/z 136 peak is the base peak because the alkene eliminated is styrene. Owing to the fact that all deprotonated aminobenzoate esters, irrespective of the size of the alkoxy group, upon activation fragment to form an m/z 135 ion, aminobenzoate esters in mixtures can be quantified by precursor ion discovery mass spectrometric experiments. Copyright © 2016 John Wiley & Sons, Ltd. | ||
| 540 | |a Nutzungsrecht: Copyright © 2016 John Wiley & Sons, Ltd. | ||
| 650 | 4 | |a even‐electron negative ions | |
| 650 | 4 | |a aminobenzoate esters | |
| 650 | 4 | |a procaine, benzocaine, collision‐induced dissociation | |
| 650 | 4 | |a even‐electron rule | |
| 650 | 4 | |a McLafferty rearrangement | |
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| 700 | 1 | |a Pavlov, Julius |4 oth | |
| 700 | 1 | |a Jariwala, Freneil B |4 oth | |
| 700 | 1 | |a Attygalle, Athula B |4 oth | |
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10.1002/jms.3740 doi PQ20160430 (DE-627)OLC1972830783 (DE-599)GBVOLC1972830783 (PRQ)p1780-bceaedbd483aa4534a7b9570a426068d005882377c69730a5effc0257d66d9843 (KEY)0065495720160000051000300245competitivehomolyticandheterolyticdecompositionpat DE-627 ger DE-627 rakwb eng 570 540 530 DNB BIODIV fid Xia, Hanxue verfasserin aut Competitive homolytic and heterolytic decomposition pathways of gas‐phase negative ions generated from aminobenzoate esters 2016 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier An alkyl‐radical loss and an alkene loss are two competitive fragmentation pathways that deprotonated aminobenzoate esters undergo upon activation under mass spectrometric conditions. For the meta and para isomers, the alkyl‐radical loss by a homolytic cleavage of the alkyl‐oxygen bond of the ester moiety is the predominant fragmentation pathway, while the contribution from the alkene elimination by a heterolytic pathway is less significant. In contrast, owing to a pronounced charge‐mediated ortho effect, the alkene loss becomes the predominant pathway for the ortho isomers of ethyl and higher esters. Results from isotope‐labeled compounds confirmed that the alkene loss proceeds by a specific γ ‐hydrogen transfer mechanism that resembles the McLafferty rearrangement for radical cations. Even for the para compounds, if the alkoxide moiety bears structural motifs required for the elimination of a more stable alkene molecule, the heterolytic pathway becomes the predominant pathway. For example, in the spectrum of deprotonated 2‐phenylethyl 4‐aminobenzoate, m/z 136 peak is the base peak because the alkene eliminated is styrene. Owing to the fact that all deprotonated aminobenzoate esters, irrespective of the size of the alkoxy group, upon activation fragment to form an m/z 135 ion, aminobenzoate esters in mixtures can be quantified by precursor ion discovery mass spectrometric experiments. Copyright © 2016 John Wiley & Sons, Ltd. Nutzungsrecht: Copyright © 2016 John Wiley & Sons, Ltd. even‐electron negative ions aminobenzoate esters procaine, benzocaine, collision‐induced dissociation even‐electron rule McLafferty rearrangement Zhang, Yong oth Pavlov, Julius oth Jariwala, Freneil B oth Attygalle, Athula B oth Enthalten in Journal of mass spectrometry Chichester [u.a.] : Wiley, 1995 51(2016), 3, Seite 245-253 (DE-627)182631915 (DE-600)1221763-3 (DE-576)04390775X 1076-5174 nnns volume:51 year:2016 number:3 pages:245-253 http://dx.doi.org/10.1002/jms.3740 Volltext http://onlinelibrary.wiley.com/doi/10.1002/jms.3740/abstract http://www.ncbi.nlm.nih.gov/pubmed/26956391 http://search.proquest.com/docview/1771393184 GBV_USEFLAG_A SYSFLAG_A GBV_OLC FID-BIODIV SSG-OLC-PHY SSG-OLC-CHE SSG-OLC-PHA SSG-OLC-DE-84 GBV_ILN_70 AR 51 2016 3 245-253 |
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10.1002/jms.3740 doi PQ20160430 (DE-627)OLC1972830783 (DE-599)GBVOLC1972830783 (PRQ)p1780-bceaedbd483aa4534a7b9570a426068d005882377c69730a5effc0257d66d9843 (KEY)0065495720160000051000300245competitivehomolyticandheterolyticdecompositionpat DE-627 ger DE-627 rakwb eng 570 540 530 DNB BIODIV fid Xia, Hanxue verfasserin aut Competitive homolytic and heterolytic decomposition pathways of gas‐phase negative ions generated from aminobenzoate esters 2016 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier An alkyl‐radical loss and an alkene loss are two competitive fragmentation pathways that deprotonated aminobenzoate esters undergo upon activation under mass spectrometric conditions. For the meta and para isomers, the alkyl‐radical loss by a homolytic cleavage of the alkyl‐oxygen bond of the ester moiety is the predominant fragmentation pathway, while the contribution from the alkene elimination by a heterolytic pathway is less significant. In contrast, owing to a pronounced charge‐mediated ortho effect, the alkene loss becomes the predominant pathway for the ortho isomers of ethyl and higher esters. Results from isotope‐labeled compounds confirmed that the alkene loss proceeds by a specific γ ‐hydrogen transfer mechanism that resembles the McLafferty rearrangement for radical cations. Even for the para compounds, if the alkoxide moiety bears structural motifs required for the elimination of a more stable alkene molecule, the heterolytic pathway becomes the predominant pathway. For example, in the spectrum of deprotonated 2‐phenylethyl 4‐aminobenzoate, m/z 136 peak is the base peak because the alkene eliminated is styrene. Owing to the fact that all deprotonated aminobenzoate esters, irrespective of the size of the alkoxy group, upon activation fragment to form an m/z 135 ion, aminobenzoate esters in mixtures can be quantified by precursor ion discovery mass spectrometric experiments. Copyright © 2016 John Wiley & Sons, Ltd. Nutzungsrecht: Copyright © 2016 John Wiley & Sons, Ltd. even‐electron negative ions aminobenzoate esters procaine, benzocaine, collision‐induced dissociation even‐electron rule McLafferty rearrangement Zhang, Yong oth Pavlov, Julius oth Jariwala, Freneil B oth Attygalle, Athula B oth Enthalten in Journal of mass spectrometry Chichester [u.a.] : Wiley, 1995 51(2016), 3, Seite 245-253 (DE-627)182631915 (DE-600)1221763-3 (DE-576)04390775X 1076-5174 nnns volume:51 year:2016 number:3 pages:245-253 http://dx.doi.org/10.1002/jms.3740 Volltext http://onlinelibrary.wiley.com/doi/10.1002/jms.3740/abstract http://www.ncbi.nlm.nih.gov/pubmed/26956391 http://search.proquest.com/docview/1771393184 GBV_USEFLAG_A SYSFLAG_A GBV_OLC FID-BIODIV SSG-OLC-PHY SSG-OLC-CHE SSG-OLC-PHA SSG-OLC-DE-84 GBV_ILN_70 AR 51 2016 3 245-253 |
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10.1002/jms.3740 doi PQ20160430 (DE-627)OLC1972830783 (DE-599)GBVOLC1972830783 (PRQ)p1780-bceaedbd483aa4534a7b9570a426068d005882377c69730a5effc0257d66d9843 (KEY)0065495720160000051000300245competitivehomolyticandheterolyticdecompositionpat DE-627 ger DE-627 rakwb eng 570 540 530 DNB BIODIV fid Xia, Hanxue verfasserin aut Competitive homolytic and heterolytic decomposition pathways of gas‐phase negative ions generated from aminobenzoate esters 2016 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier An alkyl‐radical loss and an alkene loss are two competitive fragmentation pathways that deprotonated aminobenzoate esters undergo upon activation under mass spectrometric conditions. For the meta and para isomers, the alkyl‐radical loss by a homolytic cleavage of the alkyl‐oxygen bond of the ester moiety is the predominant fragmentation pathway, while the contribution from the alkene elimination by a heterolytic pathway is less significant. In contrast, owing to a pronounced charge‐mediated ortho effect, the alkene loss becomes the predominant pathway for the ortho isomers of ethyl and higher esters. Results from isotope‐labeled compounds confirmed that the alkene loss proceeds by a specific γ ‐hydrogen transfer mechanism that resembles the McLafferty rearrangement for radical cations. Even for the para compounds, if the alkoxide moiety bears structural motifs required for the elimination of a more stable alkene molecule, the heterolytic pathway becomes the predominant pathway. For example, in the spectrum of deprotonated 2‐phenylethyl 4‐aminobenzoate, m/z 136 peak is the base peak because the alkene eliminated is styrene. Owing to the fact that all deprotonated aminobenzoate esters, irrespective of the size of the alkoxy group, upon activation fragment to form an m/z 135 ion, aminobenzoate esters in mixtures can be quantified by precursor ion discovery mass spectrometric experiments. Copyright © 2016 John Wiley & Sons, Ltd. Nutzungsrecht: Copyright © 2016 John Wiley & Sons, Ltd. even‐electron negative ions aminobenzoate esters procaine, benzocaine, collision‐induced dissociation even‐electron rule McLafferty rearrangement Zhang, Yong oth Pavlov, Julius oth Jariwala, Freneil B oth Attygalle, Athula B oth Enthalten in Journal of mass spectrometry Chichester [u.a.] : Wiley, 1995 51(2016), 3, Seite 245-253 (DE-627)182631915 (DE-600)1221763-3 (DE-576)04390775X 1076-5174 nnns volume:51 year:2016 number:3 pages:245-253 http://dx.doi.org/10.1002/jms.3740 Volltext http://onlinelibrary.wiley.com/doi/10.1002/jms.3740/abstract http://www.ncbi.nlm.nih.gov/pubmed/26956391 http://search.proquest.com/docview/1771393184 GBV_USEFLAG_A SYSFLAG_A GBV_OLC FID-BIODIV SSG-OLC-PHY SSG-OLC-CHE SSG-OLC-PHA SSG-OLC-DE-84 GBV_ILN_70 AR 51 2016 3 245-253 |
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10.1002/jms.3740 doi PQ20160430 (DE-627)OLC1972830783 (DE-599)GBVOLC1972830783 (PRQ)p1780-bceaedbd483aa4534a7b9570a426068d005882377c69730a5effc0257d66d9843 (KEY)0065495720160000051000300245competitivehomolyticandheterolyticdecompositionpat DE-627 ger DE-627 rakwb eng 570 540 530 DNB BIODIV fid Xia, Hanxue verfasserin aut Competitive homolytic and heterolytic decomposition pathways of gas‐phase negative ions generated from aminobenzoate esters 2016 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier An alkyl‐radical loss and an alkene loss are two competitive fragmentation pathways that deprotonated aminobenzoate esters undergo upon activation under mass spectrometric conditions. For the meta and para isomers, the alkyl‐radical loss by a homolytic cleavage of the alkyl‐oxygen bond of the ester moiety is the predominant fragmentation pathway, while the contribution from the alkene elimination by a heterolytic pathway is less significant. In contrast, owing to a pronounced charge‐mediated ortho effect, the alkene loss becomes the predominant pathway for the ortho isomers of ethyl and higher esters. Results from isotope‐labeled compounds confirmed that the alkene loss proceeds by a specific γ ‐hydrogen transfer mechanism that resembles the McLafferty rearrangement for radical cations. Even for the para compounds, if the alkoxide moiety bears structural motifs required for the elimination of a more stable alkene molecule, the heterolytic pathway becomes the predominant pathway. For example, in the spectrum of deprotonated 2‐phenylethyl 4‐aminobenzoate, m/z 136 peak is the base peak because the alkene eliminated is styrene. Owing to the fact that all deprotonated aminobenzoate esters, irrespective of the size of the alkoxy group, upon activation fragment to form an m/z 135 ion, aminobenzoate esters in mixtures can be quantified by precursor ion discovery mass spectrometric experiments. Copyright © 2016 John Wiley & Sons, Ltd. Nutzungsrecht: Copyright © 2016 John Wiley & Sons, Ltd. even‐electron negative ions aminobenzoate esters procaine, benzocaine, collision‐induced dissociation even‐electron rule McLafferty rearrangement Zhang, Yong oth Pavlov, Julius oth Jariwala, Freneil B oth Attygalle, Athula B oth Enthalten in Journal of mass spectrometry Chichester [u.a.] : Wiley, 1995 51(2016), 3, Seite 245-253 (DE-627)182631915 (DE-600)1221763-3 (DE-576)04390775X 1076-5174 nnns volume:51 year:2016 number:3 pages:245-253 http://dx.doi.org/10.1002/jms.3740 Volltext http://onlinelibrary.wiley.com/doi/10.1002/jms.3740/abstract http://www.ncbi.nlm.nih.gov/pubmed/26956391 http://search.proquest.com/docview/1771393184 GBV_USEFLAG_A SYSFLAG_A GBV_OLC FID-BIODIV SSG-OLC-PHY SSG-OLC-CHE SSG-OLC-PHA SSG-OLC-DE-84 GBV_ILN_70 AR 51 2016 3 245-253 |
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10.1002/jms.3740 doi PQ20160430 (DE-627)OLC1972830783 (DE-599)GBVOLC1972830783 (PRQ)p1780-bceaedbd483aa4534a7b9570a426068d005882377c69730a5effc0257d66d9843 (KEY)0065495720160000051000300245competitivehomolyticandheterolyticdecompositionpat DE-627 ger DE-627 rakwb eng 570 540 530 DNB BIODIV fid Xia, Hanxue verfasserin aut Competitive homolytic and heterolytic decomposition pathways of gas‐phase negative ions generated from aminobenzoate esters 2016 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier An alkyl‐radical loss and an alkene loss are two competitive fragmentation pathways that deprotonated aminobenzoate esters undergo upon activation under mass spectrometric conditions. For the meta and para isomers, the alkyl‐radical loss by a homolytic cleavage of the alkyl‐oxygen bond of the ester moiety is the predominant fragmentation pathway, while the contribution from the alkene elimination by a heterolytic pathway is less significant. In contrast, owing to a pronounced charge‐mediated ortho effect, the alkene loss becomes the predominant pathway for the ortho isomers of ethyl and higher esters. Results from isotope‐labeled compounds confirmed that the alkene loss proceeds by a specific γ ‐hydrogen transfer mechanism that resembles the McLafferty rearrangement for radical cations. Even for the para compounds, if the alkoxide moiety bears structural motifs required for the elimination of a more stable alkene molecule, the heterolytic pathway becomes the predominant pathway. For example, in the spectrum of deprotonated 2‐phenylethyl 4‐aminobenzoate, m/z 136 peak is the base peak because the alkene eliminated is styrene. Owing to the fact that all deprotonated aminobenzoate esters, irrespective of the size of the alkoxy group, upon activation fragment to form an m/z 135 ion, aminobenzoate esters in mixtures can be quantified by precursor ion discovery mass spectrometric experiments. Copyright © 2016 John Wiley & Sons, Ltd. Nutzungsrecht: Copyright © 2016 John Wiley & Sons, Ltd. even‐electron negative ions aminobenzoate esters procaine, benzocaine, collision‐induced dissociation even‐electron rule McLafferty rearrangement Zhang, Yong oth Pavlov, Julius oth Jariwala, Freneil B oth Attygalle, Athula B oth Enthalten in Journal of mass spectrometry Chichester [u.a.] : Wiley, 1995 51(2016), 3, Seite 245-253 (DE-627)182631915 (DE-600)1221763-3 (DE-576)04390775X 1076-5174 nnns volume:51 year:2016 number:3 pages:245-253 http://dx.doi.org/10.1002/jms.3740 Volltext http://onlinelibrary.wiley.com/doi/10.1002/jms.3740/abstract http://www.ncbi.nlm.nih.gov/pubmed/26956391 http://search.proquest.com/docview/1771393184 GBV_USEFLAG_A SYSFLAG_A GBV_OLC FID-BIODIV SSG-OLC-PHY SSG-OLC-CHE SSG-OLC-PHA SSG-OLC-DE-84 GBV_ILN_70 AR 51 2016 3 245-253 |
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Owing to the fact that all deprotonated aminobenzoate esters, irrespective of the size of the alkoxy group, upon activation fragment to form an m/z 135 ion, aminobenzoate esters in mixtures can be quantified by precursor ion discovery mass spectrometric experiments. 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Competitive homolytic and heterolytic decomposition pathways of gas‐phase negative ions generated from aminobenzoate esters |
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Competitive homolytic and heterolytic decomposition pathways of gas‐phase negative ions generated from aminobenzoate esters |
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competitive homolytic and heterolytic decomposition pathways of gas‐phase negative ions generated from aminobenzoate esters |
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Competitive homolytic and heterolytic decomposition pathways of gas‐phase negative ions generated from aminobenzoate esters |
| abstract |
An alkyl‐radical loss and an alkene loss are two competitive fragmentation pathways that deprotonated aminobenzoate esters undergo upon activation under mass spectrometric conditions. For the meta and para isomers, the alkyl‐radical loss by a homolytic cleavage of the alkyl‐oxygen bond of the ester moiety is the predominant fragmentation pathway, while the contribution from the alkene elimination by a heterolytic pathway is less significant. In contrast, owing to a pronounced charge‐mediated ortho effect, the alkene loss becomes the predominant pathway for the ortho isomers of ethyl and higher esters. Results from isotope‐labeled compounds confirmed that the alkene loss proceeds by a specific γ ‐hydrogen transfer mechanism that resembles the McLafferty rearrangement for radical cations. Even for the para compounds, if the alkoxide moiety bears structural motifs required for the elimination of a more stable alkene molecule, the heterolytic pathway becomes the predominant pathway. For example, in the spectrum of deprotonated 2‐phenylethyl 4‐aminobenzoate, m/z 136 peak is the base peak because the alkene eliminated is styrene. Owing to the fact that all deprotonated aminobenzoate esters, irrespective of the size of the alkoxy group, upon activation fragment to form an m/z 135 ion, aminobenzoate esters in mixtures can be quantified by precursor ion discovery mass spectrometric experiments. Copyright © 2016 John Wiley & Sons, Ltd. |
| abstractGer |
An alkyl‐radical loss and an alkene loss are two competitive fragmentation pathways that deprotonated aminobenzoate esters undergo upon activation under mass spectrometric conditions. For the meta and para isomers, the alkyl‐radical loss by a homolytic cleavage of the alkyl‐oxygen bond of the ester moiety is the predominant fragmentation pathway, while the contribution from the alkene elimination by a heterolytic pathway is less significant. In contrast, owing to a pronounced charge‐mediated ortho effect, the alkene loss becomes the predominant pathway for the ortho isomers of ethyl and higher esters. Results from isotope‐labeled compounds confirmed that the alkene loss proceeds by a specific γ ‐hydrogen transfer mechanism that resembles the McLafferty rearrangement for radical cations. Even for the para compounds, if the alkoxide moiety bears structural motifs required for the elimination of a more stable alkene molecule, the heterolytic pathway becomes the predominant pathway. For example, in the spectrum of deprotonated 2‐phenylethyl 4‐aminobenzoate, m/z 136 peak is the base peak because the alkene eliminated is styrene. Owing to the fact that all deprotonated aminobenzoate esters, irrespective of the size of the alkoxy group, upon activation fragment to form an m/z 135 ion, aminobenzoate esters in mixtures can be quantified by precursor ion discovery mass spectrometric experiments. Copyright © 2016 John Wiley & Sons, Ltd. |
| abstract_unstemmed |
An alkyl‐radical loss and an alkene loss are two competitive fragmentation pathways that deprotonated aminobenzoate esters undergo upon activation under mass spectrometric conditions. For the meta and para isomers, the alkyl‐radical loss by a homolytic cleavage of the alkyl‐oxygen bond of the ester moiety is the predominant fragmentation pathway, while the contribution from the alkene elimination by a heterolytic pathway is less significant. In contrast, owing to a pronounced charge‐mediated ortho effect, the alkene loss becomes the predominant pathway for the ortho isomers of ethyl and higher esters. Results from isotope‐labeled compounds confirmed that the alkene loss proceeds by a specific γ ‐hydrogen transfer mechanism that resembles the McLafferty rearrangement for radical cations. Even for the para compounds, if the alkoxide moiety bears structural motifs required for the elimination of a more stable alkene molecule, the heterolytic pathway becomes the predominant pathway. For example, in the spectrum of deprotonated 2‐phenylethyl 4‐aminobenzoate, m/z 136 peak is the base peak because the alkene eliminated is styrene. Owing to the fact that all deprotonated aminobenzoate esters, irrespective of the size of the alkoxy group, upon activation fragment to form an m/z 135 ion, aminobenzoate esters in mixtures can be quantified by precursor ion discovery mass spectrometric experiments. Copyright © 2016 John Wiley & Sons, Ltd. |
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Competitive homolytic and heterolytic decomposition pathways of gas‐phase negative ions generated from aminobenzoate esters |
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Zhang, Yong Pavlov, Julius Jariwala, Freneil B Attygalle, Athula B |
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