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Electrospray‐Ionization Mass Spectrometry. Part 2. Neighboring‐Group Participation in the Mass‐Spectral Decomposition of 4‐Hydroxycinnamoyl‐spermidines
Author(s) -
Hu Wenqing,
Reder Elke,
Hesse Manfred
Publication year - 1996
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19960790809
Subject(s) - chemistry , electrospray ionization , dissociation (chemistry) , mass spectrometry , tandem mass spectrometry , amide , collision induced dissociation , ion , electrospray , analytical chemistry (journal) , ionization , decomposition , medicinal chemistry , chromatography , organic chemistry
The three mono substituted N ‐[( E )‐3‐(4‐hydroxyphenyl)prop‐2‐enoyl]spermidines 1–3 have been studied by positive‐ion electrospray‐ionization tandem mass spectrometry (ESI‐MS/MS). Because of the neighboring‐group participation, the MS/MS of [ 1 + H] + and [ 2 + H] + are essentially similar, while compound 3 can be easily distinguished from 1 and 2 because of the characteristic ions at m/z 218. However, with the source collision‐induced dissociation (source‐CID) MS/MS technique, the compounds 1 and 2 can be unambiguously distinguished by the signal of the pyrrolidinium ion ( m/z 72) from their daughter ion ( m/z 275). The source‐CID MS/MS of the labeled compound N ‐(4‐aminobutyl)‐ N ‐(3‐aminopropyl)‐ N ‐[3‐(4‐ hydroxyphenyl)prop‐2‐en[ 15 N]amide] ([ 15 N(4)]‐ 2 ) provide more information on the decomposition mechanisms and proved the occurrence of a partial transamidation reaction 2→1 during the measurement.