Determination of the site of protonation of substituted benzenes in water chemical ionization mass spectrometry

Martinsen, D. P.; Buttrill, S. E.

doi:10.1002/oms.1210110710

Cited by 72 publications

(47 citation statements)

References 12 publications

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“…The site of protonation on anilines as well as other substituted benzenes has also been estimated by CI mass spectrometry employing labeled protonating reagents 85 . For instance, using H 2 O and D 2 O as the CI gases, hence H 3 O + and D 3 O + as the major protonating species, extensive exchange of the ring hydrogens with deuteriums was correlated with protonation on the aromatic ring 85,86 .…”

Section: B Site Of Protonation Of Anilinesmentioning

confidence: 99%

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Mass Spectrometry and Gas‐Phase Chemistry of Anilines

Eberlin

Augusti

2009

Patai's Chemistry of Functional Groups

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Introduction Ionization Energies ( IE ) and Proton Affinities ( PA ) of Anilines: The Influence of the Substituents 70 e V EI Mass Spectrometry of Anilines: The Influence of the Nature of Substituents on Unimolecular Dissociation Ortho Effects in Substituted Anilines Miscellaneous Dissociations of Ionized Anilines Chemical Ionization and Electrospray Ionization Mass Spectrometry of Anilines Gas‐Phase Reactivity of Anilines Acknowledgments

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Section: B Site Of Protonation Of Anilinesmentioning

confidence: 99%

“…For instance, using H 2 O and D 2 O as the CI gases, hence H 3 O + and D 3 O + as the major protonating species, extensive exchange of the ring hydrogens with deuteriums was correlated with protonation on the aromatic ring 85,86 .…”

Section: B Site Of Protonation Of Anilinesmentioning

confidence: 99%

Mass Spectrometry and Gas‐Phase Chemistry of Anilines

Eberlin

Augusti

2009

Patai's Chemistry of Functional Groups

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“…It also has been shown that protonated aromatic hydrocarbons exchange the aromatic hydrogens when D,O, CH,OD, or C,H,OD are used as chemical ionization reagents (15)(16)(17)(18)(19) and such exchange reactions have been developed into a method for identifying alkyl aromatic isomers (18,19).…”

mentioning

confidence: 99%

Reactive collisions in quadrupole cells. 6. H/D exchange reactions of protonated alkylbenzenes with D₂O, CH₃OD, and C₂H₅OD

Ni¹,

Harrison²

1995

Can. J. Chem.

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The H/D exchange reactions occurring on collision of protonated alkylbenzenes with C2H5OD, CH3OD, and D2O at low collision energies in the quadrupole collision cell of a hybrid tandem mass spectrometer have been studied for 22 alkylbenzenes. The exchange reactions with D2O are much less efficient than the exchange reactions with C2H5OD or CH3OD; this difference is rationalized on energetics grounds. The H/D exchange of the protonated alkylbenzenes with C2H5OD or CH3OD leads, typically, to 40–70% deuterium incorporation in the protonated alkylbenzene and, for most cases, to significant ion signals corresponding to exchange of the added hydrogen and the aromatic hydrogens. Thus, the method is a feasible approach to counting the number of aromatic hydrogens in alkylbenzenes. The extent of exchange decreases with increasing size of the alkyl group in monoalkylbenzenes for reasons that are not readily understood. Keywords: protonated alkylbenzenes, H/D exchange, reactive collisions.

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“…The calculations of De Frees et al [6] employing the idea of isodesmic reactions gave the same result (14.9 kcal/mol). The only experimental finding that contradicts preference of ring over oxygen protonation for related bases is that of Martinson and Butrill [23]. They concluded from nonequilibrium H2O chemical ionization mass spectrometry studies that protonation of phenol occurs at the oxygen rather than in the ring, presumably due to the additional stabilization of oxonium ion provided by hydrogen bonding of the highly positive hydrogen atoms bound to oxygen in this ion.…”

Section: H H> a Bmentioning

confidence: 98%

MINDO/3 Study of the Protonation of Phenol and Methylphenols

Eckert‐Maksić

1982

Zeitschrift Für Naturforschung A

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The electronic and molecular structures of phenol and its ortho-meta-, and para-methyl derivates as well as their conjugate acids were studied by the semiempirical MINDO/3 method. The calculations predict substantial structural changes upon protonation. Theoretically predicted protonation sites are in very good agreement with experimentally observed modes of protonation under superacidic conditions.

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Determination of the site of protonation of substituted benzenes in water chemical ionization mass spectrometry

Abstract: The site of protonation of a substituted benzene may be determined using chemical onization mass spectrometry with D20 as a reagent gas. The observation of extensive exchange

Cited by 72 publications

References 12 publications

Mass Spectrometry and Gas‐Phase Chemistry of Anilines

Mass Spectrometry and Gas‐Phase Chemistry of Anilines

Reactive collisions in quadrupole cells. 6. H/D exchange reactions of protonated alkylbenzenes with D₂O, CH₃OD, and C₂H₅OD

MINDO/3 Study of the Protonation of Phenol and Methylphenols

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Determination of the site of protonation of substituted benzenes in water chemical ionization mass spectrometry

Abstract: The site of protonation of a substituted benzene may be determined using chemical onization mass spectrometry with D20 as a reagent gas. The observation of extensive exchange

Cited by 72 publications

References 12 publications

Mass Spectrometry and Gas‐Phase Chemistry of Anilines

Mass Spectrometry and Gas‐Phase Chemistry of Anilines

Reactive collisions in quadrupole cells. 6. H/D exchange reactions of protonated alkylbenzenes with D2O, CH3OD, and C2H5OD

MINDO/3 Study of the Protonation of Phenol and Methylphenols

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Reactive collisions in quadrupole cells. 6. H/D exchange reactions of protonated alkylbenzenes with D₂O, CH₃OD, and C₂H₅OD