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Hydride transfer reactions via ion-neutral complex: fragmentation of protonated N-benzylpiperidines and protonated N-benzylpiperazines in mass spectrometry.
J Mass Spectrom. 2010 May; 45(5):496-503.JM

Abstract

An ion-neutral complex (INC)-mediated hydride transfer reaction was observed in the fragmentation of protonated N-benzylpiperidines and protonated N-benzylpiperazines in electrospray ionization mass spectrometry. Upon protonation at the nitrogen atom, these compounds initially dissociated to an INC consisting of [RC(6)H(4)CH(2)](+) (R = substituent) and piperidine or piperazine. Although this INC was unstable, it did exist and was supported by both experiments and density functional theory (DFT) calculations. In the subsequent fragmentation, hydride transfer from the neutral partner to the cation species competed with the direct separation. The distribution of the two corresponding product ions was found to depend on the stabilization energy of this INC, and it was also approved by the study of substituent effects. For monosubstituted N-benzylpiperidines, strong electron-donating substituents favored the formation of [RC(6)H(4)CH(2)](+), whereas strong electron-withdrawing substituents favored the competing hydride transfer reaction leading to a loss of toluene. The logarithmic values of the abundance ratios of the two ions were well correlated with the nature of the substituents, or rather, the stabilization energy of this INC.

Authors+Show Affiliations

Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, China.No affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

20301171

Citation

Chai, Yunfeng, et al. "Hydride Transfer Reactions Via Ion-neutral Complex: Fragmentation of Protonated N-benzylpiperidines and Protonated N-benzylpiperazines in Mass Spectrometry." Journal of Mass Spectrometry : JMS, vol. 45, no. 5, 2010, pp. 496-503.
Chai Y, Jiang K, Pan Y. Hydride transfer reactions via ion-neutral complex: fragmentation of protonated N-benzylpiperidines and protonated N-benzylpiperazines in mass spectrometry. J Mass Spectrom. 2010;45(5):496-503.
Chai, Y., Jiang, K., & Pan, Y. (2010). Hydride transfer reactions via ion-neutral complex: fragmentation of protonated N-benzylpiperidines and protonated N-benzylpiperazines in mass spectrometry. Journal of Mass Spectrometry : JMS, 45(5), 496-503. https://doi.org/10.1002/jms.1731
Chai Y, Jiang K, Pan Y. Hydride Transfer Reactions Via Ion-neutral Complex: Fragmentation of Protonated N-benzylpiperidines and Protonated N-benzylpiperazines in Mass Spectrometry. J Mass Spectrom. 2010;45(5):496-503. PubMed PMID: 20301171.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Hydride transfer reactions via ion-neutral complex: fragmentation of protonated N-benzylpiperidines and protonated N-benzylpiperazines in mass spectrometry. AU - Chai,Yunfeng, AU - Jiang,Kezhi, AU - Pan,Yuanjiang, PY - 2010/3/20/entrez PY - 2010/3/20/pubmed PY - 2010/8/3/medline SP - 496 EP - 503 JF - Journal of mass spectrometry : JMS JO - J Mass Spectrom VL - 45 IS - 5 N2 - An ion-neutral complex (INC)-mediated hydride transfer reaction was observed in the fragmentation of protonated N-benzylpiperidines and protonated N-benzylpiperazines in electrospray ionization mass spectrometry. Upon protonation at the nitrogen atom, these compounds initially dissociated to an INC consisting of [RC(6)H(4)CH(2)](+) (R = substituent) and piperidine or piperazine. Although this INC was unstable, it did exist and was supported by both experiments and density functional theory (DFT) calculations. In the subsequent fragmentation, hydride transfer from the neutral partner to the cation species competed with the direct separation. The distribution of the two corresponding product ions was found to depend on the stabilization energy of this INC, and it was also approved by the study of substituent effects. For monosubstituted N-benzylpiperidines, strong electron-donating substituents favored the formation of [RC(6)H(4)CH(2)](+), whereas strong electron-withdrawing substituents favored the competing hydride transfer reaction leading to a loss of toluene. The logarithmic values of the abundance ratios of the two ions were well correlated with the nature of the substituents, or rather, the stabilization energy of this INC. SN - 1096-9888 UR - https://www.unboundmedicine.com/medline/citation/20301171/Hydride_transfer_reactions_via_ion_neutral_complex:_fragmentation_of_protonated_N_benzylpiperidines_and_protonated_N_benzylpiperazines_in_mass_spectrometry_ L2 - https://doi.org/10.1002/jms.1731 DB - PRIME DP - Unbound Medicine ER -