Fragmentation of Protonated <i>N</i>-(3-Aminophenyl)Benzamide and Its Derivatives in Gas Phase

Zu, Chengli; Mukhopadhyay, Shayok; Hanley, Patrick S.; Xia, Shijing; Bell, Bruce M.; Grigg, David; Gilbert, J.; O’Brien, John P.

doi:10.1007/s13361-016-1342-z

Cited by 6 publications

(3 citation statements)

References 39 publications

(40 reference statements)

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“…In some cases, even the structural class of the molecule was different from what was claimed on the bottle. A recent paper describing a mislabeled synthetic compound shows nicely how mass spectrometry can be used to detect such a problem (Zu et al, 2016). Thus, it is possible that some of the reference standards used to produce spectra of abietic/neoabietic acid were mislabeled.…”

Section: Resultsmentioning

confidence: 99%

CASMI 2016: A manual approach for dereplication of natural products using tandem mass spectrometry

Nikolić

2017

Phytochemistry Letters

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The Critical Assessment of Small Molecule Identification (CASMI) contest is an initiative designed as an unbiased test of manual and automated strategies for the identification of small molecules from raw mass spectrometric data. In this contest, the participants are provided a set of high resolution MS and MS/MS data and asked to identify the unknown structure. CASMI 2016 is the fourth round of this contest in which the author participated in Category 1: Best Identification of Natural Products using a manual approach. The provided high resolution mass spectrometric data were interpreted manually using a combination of fragment and neutral loss analysis, literature consultation, manual database searches, deductive logic and experience. Out of 18 challenges, the author submitted correct structures as lead candidates for 14 challenges and 2nd ranked candidate for four challenges and was declared the winner of this category Pitfalls and challenges encountered during data interpretation are discussed.

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Section: Resultsmentioning

confidence: 99%

CASMI 2016: A manual approach for dereplication of natural products using tandem mass spectrometry

Nikolić

2017

Phytochemistry Letters

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“…Although this pathway was minor (~ 2% of the base peak) it is mechanistically interesting considering that loss of water in tandem mass spectra is typically associated with the presence of a hydroxyl group. Loss of water from N ‐(3‐aminophenyl) benzamide was reported recently by Zu et al and has been shown to involve a water‐nitrilium ion complex . While this mechanism might be operational for our compounds, we propose another mechanism that involves electrophilic attack of the protonated amideonto the aromatic ring as shown in Scheme .…”

Section: Resultsmentioning

confidence: 54%

Collision‐induced dissociation of phenethylamides: role of ion‐neutral complexes

Nikolić

Macias

Lankin

et al. 2017

Rapid Comm Mass Spectrometry

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RATIONALE Phenethylamides are a large group of naturally occurring molecules found both in the plant and animal kingdoms. In addition, they are used as intermediates for the synthesis of pharmaceutically important dihydro- and tetrahydroisoquinolines. To enable efficient characterization of this class of molecules, a detailed mass spectrometric fragmentation study of a broad series of analogs was carried out. METHODS The test compounds were synthesized using standard methods for amide bond formation. Low energy high resolution tandem mass spectra were acquired on a hybrid quadrupole/time-of-flight mass spectrometer using positive ion electrospray ionization. RESULTS A total of 26 analogs were investigated in the study. Fragmentation of phenethylamides was found to proceed via intermediate ion-neutral complexes. The complexes can break down via multiple pathways including dissociation, proton transfer, Friedel-Crafts acylation, and single electron transfer. The relative contribution of each of these pathways strongly depends on the structure of the coupling amine and acid. CONCLUSIONS A general scheme for the fragmentation of phenethylamides was developed. This study further extends the knowledge base of the ion-neutral complex by discovering Friedel-Crafts acylation as a novel reaction. The strong influence of minor structural modifications on the fragmentation patterns highlights the importance of testing many analogs in order to fully predict a fragmentation pattern of a particular class of molecules.

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“…Jiang and co-workers reported a novel oxygen transfer pathway in the dissociation of protonated N -phenyl p -toluenesulfonamides, whereby an oxygen atom of sulfonyl group is transferred to the ortho, meta, or para position of the aniline ring in the CID process. Zu reported an unprecedented reaction via N–O exchange in the CID experiments of protonated N -(3-aminophenyl)benzamide. The carbonyl oxygen was transferred to the aniline ring by a water molecule migration rearrangement.…”

Section: Introductionmentioning

confidence: 99%

CID Fragmentation of Deprotonated N-Acyl Aromatic Sulfonamides. Smiles-Type and Nitrogen–Oxygen Rearrangements

Liang

Simón‐Manso

Neta

et al. 2021

J. Am. Soc. Mass Spectrom.

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The NIST tandem mass spectral library (2020 version) includes over 800 aromatic sulfonamides. In negative mode, upon collisional activation most benzenesulfonamides lose a neutral SO 2 molecule leading to an anilide anion (C 6 H 5 NH − , m/z 92). However, for deprotonated N-benzoyl aromatic sulfonamides, the phenoxide ion (C 6 H 5 O − , m/z 93.0343) is the principal product ion. A variety of N-acylbenzenesulfonamide derivatives were also found to overwhelmingly produce the phenoxide ion as the most intense product ion. A mechanism is proposed in which, at low energy, a carbonyl oxygen atom (CO) is transferred to a benzene ring, known as a Smiles-type rearrangement (the amide oxygen atom attacks the arylsulfonyl group at the ipso position), in parallel and determining the reaction at high energy a nitrogen−oxygen rearrangement mechanism leads to the formation of the phenoxide ion. Tandem mass spectra of deprotonated N-benzoyl-18 O-benzenesulfonamide and N-thiobenzoyl-p-toluenesulfonamide confirmed the rearrangement since base peaks at m/z 95.0384 and 123.0270 which correspond to an 18 O phenoxide ion ([C 6 H 518 O] − ) and a 4-methylbenzenethiolate anion ([CH 3 C 6 H 4 S] − ) were observed, respectively. The parallel mechanism is supported by the strong correlation between the observed product ion intensities and the corresponding activation energies obtained by Density Functional Theory calculations. This is an example of a relatively simple ion with a complex path to fragmentation, being a cautionary tale for indiscriminate use of in silico spectra in place of actual measurement.

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Fragmentation of Protonated N-(3-Aminophenyl)Benzamide and Its Derivatives in Gas Phase

Cited by 6 publications

References 39 publications

CASMI 2016: A manual approach for dereplication of natural products using tandem mass spectrometry

CASMI 2016: A manual approach for dereplication of natural products using tandem mass spectrometry

Collision‐induced dissociation of phenethylamides: role of ion‐neutral complexes

CID Fragmentation of Deprotonated N-Acyl Aromatic Sulfonamides. Smiles-Type and Nitrogen–Oxygen Rearrangements

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