Metastable ion study of fluorinated organic compounds. Part 3. α, α, α-trifluoroanisole and α, α, α-trifluorocresols

Yanagisawa, Tamae; Tajima, Susumu; Iizuka, Masaki; Tobita, Seiji; Mitani, Makoto; Matsumotο, Takeo

doi:10.1016/0168-1176(93)80016-8

Cited by 14 publications

(8 citation statements)

References 20 publications

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“…16,17 It is seen from ) from 1 . 3 Hence, although this was not confirmed in 2, it can be supposed that the m/z 112 ions were generated in one step from 1 and 2 . The difference between the mass of this fragment ion and that of the molecular ion is 50 u, indicating that the neutral species lost is difluorocarbene (CF 2 ).…”

Section: Resultsmentioning

confidence: 99%

“…1 We have reported the unimolecular fragmentation processes of some ionized fluorinated organic compounds. [2][3][4][5][6] It has been shown that many skeletal rearrangement reactions, such as trifluoromethyl (CF 3 ), 3 fluorine (F) atom, 2,3,5,6 double fluorine atom migrations 6 or F-ring walk, 4 are observed during their fragmentations.…”

mentioning

confidence: 99%

“…[8][9][10] However, we could not clucidate the structure of the resultant ion at m/z 112 from 1 by using unimolecular MIKE spectrometry. 3 In this paper, we used energy-resolved mass spectra (collision-induced dissociation (CID) spectra versus collision energy) [11][12][13] to elucidate CF 2 elimination from 1 and 2 (hereafter, these spectra are termed 'CID-curves'). The CID-curves of the molecular ions (m/z 112) of 3-5 were used as reference.…”

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confidence: 99%

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Elimination of difluorocarbene from the molecular ions of α,α,α-Trifluorocresols with a fluorine atom migration in an ion trap mass spectrometer

Tajima

Takahashi

Sekiguchi

1999

Rapid Commun. Mass Spectrom.

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The elimination of difluorocarbene (CF(2)) from the molecular ions of m-alpha,alpha,alpha-trifluorocresol (MW 162, 1) and p-alpha, alpha, alpha-trifluorocresol (MW 162, 2) upon electron impact have been investigated using a quadrupole ion trap mass spectrometer. This reaction involves a fluorine (F) atom migration from the trifluoromethyl group to the benzene ring. In the case of 1, an F atom migrates via a four-membered ring transition state to give rise to the molecular ion of p-fluorophenol (MW 112, 5) and a small amount of o-fluorophenol (MW 112, 3). On the other hand, in the case of 2, an F atom migrates to the ipso position of the benzene ring via a three-membered ring transition state to give rise to 5(+). These conclusions were confirmed by the comparison of the energy-resolved mass spectra (collision-induced dissociation (CID) spectra versus collision energy) of the m/z 112 ions from 1(+) and 2(+) with those of reference compounds, o-, m- and p-fluorophenol (3-5).

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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Elimination of difluorocarbene from the molecular ions of α,α,α-Trifluorocresols with a fluorine atom migration in an ion trap mass spectrometer

Tajima

Takahashi

Sekiguchi

1999

Rapid Commun. Mass Spectrom.

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“…As noted above, the second loss of a neutral species with 48 Da frequently occurs from organic ions containing F and O atoms. 16), 17) However, it is not clear whether the 48 Da is the single neutral species CHFO or two species HF and CO. In order to clarify this ambiguity, the energy dependence of CID spectra 18)῎22) for the m/z 113 ions from 1 ῌῌ and 2 ῌῌ have been measured.…”

Section: ) 27)mentioning

confidence: 99%

“…One of the issues to be addressed is the observed loss of neutral species with mass 48 Da, which frequently occurs from organic ions containing both F and O atoms, 16 pathways, as will be discussed below.…”

Section: )῎15)mentioning

confidence: 99%

Unimolecular Metastable Decomposition of Bis(2,2,2-trifluoroethyl) Ether, CF3CH2OCH2CF3, and Ethyl 2,2,2-Trifluoroethyl Ether, CH3CH2OCH2CF3, upon Electron Ionization.

Tajima

Sekiguchi

Nakajima

et al. 2002

J. Mass Spectrom. Soc. Jpn.

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The unimolecular metastable decompositions of bis(2,2,2-trifluoroethyl) ether, CF3CH2OCH2CF3 (1), and ethyl 2,2,2-trifluoroethyl ether, CH3CH2OCH2CF3 (2), induced by electron ionization, have been investigated by mass-analyzed ion kinetic energy (MIKE) spectrometry and energy-dependent collision-induced dissociation (CID) spectra in conjunction with thermochemical data. In the metastable time window, the molecular ions of 1 decompose into the ions at m/z 113 by the loss of CF ῌῌ and 2 ῌῌ decompose in a variety of ways: in addition to the fragment ion m/z 65, which is generated by the elimination of CHFO, four other fragment ions with m/z 83, 63, 61, and 31 are observed , which correspond to the competitive losses of CH2O, (CH2OῌHF), CH2F2, and C2HF3 (or C2H4F2O), respectively.

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Mass Spectrometry and Gas‐Phase Ion Chemistry of Phenols

Kuck

2009

Patai's Chemistry of Functional Groups

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Introduction Gaseous Radical Cations Derived from Phenols: Thermochemistry of Some Typical Species and Reactions Unimolecular Fragmentation Reactions of Phenol Radical Cations The Effect of the Hydroxyl Group on the Reversible Intramolecular Hydrogen Transfer in Ionized Phenols Ortho Effects in Substituted Phenols Secondary Fragmentation Reactions of Phenol Radical Cations Miscellaneous Fragmentations of Phenol Radical Cations Chemical Ionization Mass Spectrometry of Phenols Ionized Phenol and Cyclohexa‐1,3‐Dien‐5‐One ( ortho ‐Isophenol) Generated by Fragmentation of Precursor Ions Ion/Molecule Reactions of Phenols in the Gas Phase Gaseous Phenol Anions Miscellaneous Analytical Examples Mass Spectrometry of Calixarenes Phenolic Compounds as Maldi Matrices Acknowledgements

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Metastable ion study of fluorinated organic compounds. Part 3. α, α, α-trifluoroanisole and α, α, α-trifluorocresols

Cited by 14 publications

References 20 publications

Elimination of difluorocarbene from the molecular ions of α,α,α-Trifluorocresols with a fluorine atom migration in an ion trap mass spectrometer

Elimination of difluorocarbene from the molecular ions of α,α,α-Trifluorocresols with a fluorine atom migration in an ion trap mass spectrometer

Unimolecular Metastable Decomposition of Bis(2,2,2-trifluoroethyl) Ether, CF3CH2OCH2CF3, and Ethyl 2,2,2-Trifluoroethyl Ether, CH3CH2OCH2CF3, upon Electron Ionization.

Mass Spectrometry and Gas‐Phase Ion Chemistry of Phenols

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