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Author:

Chai, Yunfeng (Chai, Yunfeng.) | Shao, Yunlong (Shao, Yunlong.) | Wang, Lu (Wang, Lu.) | Wang, Lin (Wang, Lin.)

Indexed by:

Scopus SCIE PubMed

Abstract:

In electrospray ionization tandem mass spectrometry of protonated 1-benzoylamines (1benzoylpiperadine, 1-benzoylmorpholine, and 1-benzoyl-4-methylpiperazine), the dominant fragmentation pathway was amide bond cleavage to form benzoyl cation and neutral amine. Meanwhile, in their fragmentations, an interesting loss of benzaldehyde (106 Da) was observed and identified to derive from hydride transfer reaction between the benzoyl cation and amine. A stepwise mechanism for loss of 106 Da (benzene and CO) could be excluded with the aid of deuterium labeling experiment. Theoretical calculations indicated that hydride transfers from amines (piperadine, morpholine, and 1-methylpiperazine) to benzoyl cation were thermodynamically permitted, and 1-methylpiperazine was the best hydride donor among the 3 amines. The mass spectrometric experimental results were consistent with the computational results. The relative abundance of the iminium cation (relative to the benzoyl cation) in the fragmentation of protonated 1-benzoyl-4-methylpiperazine was higher than that in the fragmentation of the other 2 protonated 1-benzoylamines. By comparing the fragmentations of protonated 1-benzyl-4methylpiperazine and protonated 1-benzoyl-4-methylpiperazine and the energetics of their hydride transfer reactions, this study revealed that benzoyl cation was a hydride acceptor in the gas phase, but which was weaker than benzyl cation.

Keyword:

benzoyl cation hydride acceptor fragmentation mechanism hydride transfer loss of benzaldehyde

Author Community:

  • [ 1 ] [Chai, Yunfeng]Chinese Acad Agr Sci, Tea Res Inst, 9 South Meiling Rd, Hangzhou 310008, Zhejiang, Peoples R China
  • [ 2 ] [Shao, Yunlong]Beijing Univ Technol, Dept Chem & Chem Engn, Beijing 100124, Peoples R China
  • [ 3 ] [Wang, Lin]Beijing Univ Technol, Dept Chem & Chem Engn, Beijing 100124, Peoples R China
  • [ 4 ] [Wang, Lu]Zhejiang Univ, Coll Pharmaceut Sci, Hangzhou 310058, Zhejiang, Peoples R China
  • [ 5 ] [Chai, Yunfeng]Zhejiang Univ, Dept Chem, Hangzhou 310027, Zhejiang, Peoples R China

Reprint Author's Address:

  • [Chai, Yunfeng]Chinese Acad Agr Sci, Tea Res Inst, 9 South Meiling Rd, Hangzhou 310008, Zhejiang, Peoples R China;;[Wang, Lu]Beijing Univ Technol, Dept Chem & Chem Engn, Beijing 100124, Peoples R China

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Source :

JOURNAL OF MASS SPECTROMETRY

ISSN: 1076-5174

Year: 2017

Issue: 10

Volume: 52

Page: 664-671

2 . 3 0 0

JCR@2022

ESI Discipline: CHEMISTRY;

ESI HC Threshold:212

CAS Journal Grade:3

Cited Count:

WoS CC Cited Count: 3

SCOPUS Cited Count: 3

ESI Highly Cited Papers on the List: 0 Unfold All

WanFang Cited Count:

Chinese Cited Count:

30 Days PV: 2

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