Mass Spectrometry and Gas‐Phase Chemistry of Anilines

Eberlin, Marcos N.; Augusti, Daniella Vasconcellos; Augusti, Rodinei

doi:10.1002/9780470682531.pat0387

Cited by 4 publications

(5 citation statements)

References 123 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This mechanism of molecular fragmentation is analogous to CO loss from phenols . Our measured mass spectrum of molecular PhNH 2 shows a good agreement with published data …”

Section: Resultssupporting

confidence: 90%

“…[13,28] Our measured mass spectrum of molecular PhNH 2 shows a good agreement with published data. [28,29] For production of small (PhNH 2 ) N clusters, coexpansion with helium buffer gas was used. Under these conditions, only small (PhNH 2 ) n + cluster ions (n ≤ 3) were observed as can be seen in Fig.…”

Section: Resultssupporting

confidence: 86%

“…The metastable decay of the aniline parent ion, m/z = 93, is well known and has been described in detail previously. [28,29] The ion decays by the loss of HNC to yield the [C 5 H 6 ] + ion, m/z = 66, with the subsequent secondary fragmentation. This mechanism of molecular fragmentation is analogous to CO loss from phenols.…”

Section: Resultssupporting

confidence: 85%

“…(a), the typical fragmentation pattern was observed, where the major fragment ions at m / z = 39, 65 and 66 appeared. The metastable decay of the aniline parent ion, m / z = 93, is well known and has been described in detail previously . The ion decays by the loss of HNC to yield the [C 5 H 6 ] + ion, m / z = 66, with the subsequent secondary fragmentation.…”

Section: Resultsmentioning

confidence: 93%

See 3 more Smart Citations

Proton transfer and isotope-induced reaction in aniline cluster ions

2015

View full text Add to dashboard Cite

The proton transfer (PT) and other intraclusters reactions occurring after electron ionization of aniline clusters (PhNH2)N are investigated by the time-of-flight mass spectrometry. The mass spectra are recorded for different expansion conditions leading to the generation of different cluster sizes. Several fragment ions are shown to originate from intracluster reactions, namely, [Ph](+), [PhNH3](+) and [Ph-N-Ph](+). Reaction schemes are proposed for these ions starting with the PT process. The mass region beyond the monomer mass is dominated by cluster ions (PhNH2)n(+) accompanied by satellites with ±H and +2H. In experiments with deuterated species, new fragment ions are identified. The aniline isotopomer d5-PhNH2 yields the fragment ions (PhNH2)n⋅(N-Ph-NH2)(+). Analogical series is observed in experiments with d7-PhND2, and additional fragments occur corresponding to (PhND2)n⋅(D2N-ND-Ph-ND-ND2)(+) ions. The possible reaction pathways to these ions and the unusual isotope effects are discussed.

show abstract

“…This mechanism of molecular fragmentation is analogous to CO loss from phenols . Our measured mass spectrum of molecular PhNH 2 shows a good agreement with published data …”

Section: Resultssupporting

confidence: 90%

Section: Resultssupporting

confidence: 86%

Section: Resultssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 93%

See 2 more Smart Citations

Proton transfer and isotope-induced reaction in aniline cluster ions

2015

View full text Add to dashboard Cite

show abstract

“…For example, no textbook on mass spectral interpretation uses spectra of N-substituted haloanilines as typical examples for demonstrating the ortho effect. Even a recent review on mass spectrometry and gas-phase chemistry of anilines failed to mention this strong ortho effect of acylanilines [21]. Hopefully, results presented here will encourage wider acknowledgment and practical usage of this dramatic effect.…”

Section: Resultsmentioning

confidence: 74%

Ortho effect in electron ionization mass spectrometry of N-acylanilines bearing a proximal halo substituent

Jariwala

Figus

Attygalle

2008

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

Electron ionization (EI) mass spectra are not very helpful for characterizing ortho, meta, and para isomers of underivatized haloanilines since their spectra are virtually identical. In contrast, when the amino group of chloro-, bromo-, or iodoanilines is transformed to an N-formyl, N-acetyl, or N-benzoyl derivative, the spectra of the derivatives reveal a highly dramatic loss of a halogen radical, instead of an HX elimination usually expected from an "ortho effect." For example, the spectra of N-formyl, N-acetyl, and N-benzoyl derivatives of ortho isomers of chloro-, bromo-, and iodoanilines show a very prominent peak at m/z 120, 134, and 196, respectively, for the loss of the corresponding halogen atom.

show abstract

Assessment of the molecular structure and spectroscopic properties of CF3-substituted sulfinylaniline derivatives

Chemes

Lezama

Cutin

et al. 2021

Journal of Molecular Structure

View full text Add to dashboard Cite

The presence of a perfluorinated functional group as a substituent of the aromatic ring in m -and otrifluoromethylsulfinylaniline may provide conformational and vibrational properties of interest for the synthesis of compounds of pharmacological relevance, as it was observed for other N-sulfinylaniline derivatives previously reported. The air sensitive and highly reactive compounds under study were prepared by the reaction of the corresponding aniline derivatives and thionyl chloride. The liquid samples were characterized by FT IR, Raman and NMR ( 1 H and 13 C) spectroscopies and GC/MS spectrometry. The experimental spectra indicate the presence of a single conformer of syn geometry ( syn of the C-N bond with respect to the S = O bond), in good agreement with results obtained by quantum chemical calculations derived from the Functional Density Theory. The stable conformation found as the global minimum of the potential energy surface was rationalized by considering intramolecular orbital interactions evinced by a Natural Bond Orbital (NBO) analysis and the quantum theory of Atoms In Molecules (AIM). Through this last approach, an intramolecular C-H O interaction meeting the characteristics of an anti -hydrogen bond was found.

show abstract

Mass Spectrometry and Gas‐Phase Chemistry of Anilines

Abstract: 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 … Show more

Cited by 4 publications

References 123 publications

Proton transfer and isotope-induced reaction in aniline cluster ions

Proton transfer and isotope-induced reaction in aniline cluster ions

Ortho effect in electron ionization mass spectrometry of N-acylanilines bearing a proximal halo substituent

Assessment of the molecular structure and spectroscopic properties of CF3-substituted sulfinylaniline derivatives

Contact Info

Product

Resources

About