Synthesis of 4‐[2‐(N,N‐dimethylamino)ethylaminosulfonyl]‐7‐N‐methylhydrazino‐2,1,3‐benzoxadiazole (DAABD‐MHz) as a derivatization reagent for aldehydes in liquid chromatography/electrospray ionization–tandem mass spectrometry

Abstract

Benzofurazan derivatization reagent, 4-[2-(N,N-dimethylamino)ethylaminosulfonyl]-7-N-methylhydrazino-2,1,3-benzoxadiazole (DAABD-MHz), for aldehydes in liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS), was synthesized. DAABD-MHz reacted with aliphatic aldehydes under mild conditions. The generated derivatives were separated on a reversed-phase column and detected by ESI-MS/MS with detection limits of 30-60 fmol on-column. Upon collision-induced dissociation, a single and intense fragment ion at m/z 151 was observed. These results suggested that DAABD-MHz was suitable as a derivatization reagent in LC/ESI-MS/MS.

Enhancement of the capabilities of liquid chromatography–mass spectrometry with derivatization: General principles and applications

“…4). Benzofurazan reagents with R 2 ¼ -NHNH 2 could be used to label a ketone (>C=O), aldehyde (-COH) or carboxylic acid (-COOH) (Santa et al, 2008a). Reagents with R 2 ¼ F react with amine-containing compounds (Song et al, 2004;Song, Liang, & Liu, 2007), whereas those with R 2 ¼ -NH 2 , >NH are mainly used for carboxylic acids analysis (Santa et al, 1998(Santa et al, , 2007(Santa et al, , 2008b(Santa et al, , 2009.…”

Derivatization reagents in liquid chromatography/electrospray ionization tandem mass spectrometry

“…The generated derivatives gave a predominant product ion at m/z 151 by CID, derived from the protonated ( N , N ‐dimethylamino)ethylaminosulfonyl moiety of the reagent (Fig. 1c; Santa et al ., 2008). 4‐[2‐(Trimethylammonio)ethoxy]benzenaminium halide (4‐APC) reacted with aldehydes and generated amines in the presence of NaBH 3 CN.…”

Recent progress in the development of derivatization reagents having a benzofurazan structure

“…As a result, benzofurazan compounds having -SO 2 NHCH 2 CH 2 N(CH 3 ) 2 group and an amino group at 4-and 7-positions produced an intense fragment ion at m/z 151 corresponding to -SO 2 NHCH 2 CH 2 N(CH 3 ) 2 moiety by CID. These included DAABD-AE, DAABDApy for carboxylic acids (Santa et al, 2007a) and DAABD-MHz for aldehydes (Santa et al, 2007b). DAABD-AE was applied to the determination of marker metabolites for several inherited metabolic disorders such as glutaric acidemia.…”