Synthesis of trans‐4,5‐epoxy‐(E)‐2‐decenal and its deuterated analog used for the development of a sensitive and selective quantification method based on isotope dilution assay with negative chemical ionization

• Published in: Lipids 1999-10, Vol.34 (10), p.1117-1126
• Main Authors: Lin, Jianming, Fay, Laurent B., Welti, Dieter H., Blank, Imre
• Format: Article
• Language: English
• Subjects: Aldehydes - chemical synthesis; Aldehydes - chemistry; Aluminum; Chemistry - methods; Epoxy Compounds - chemical synthesis; Epoxy Compounds - chemistry; Gas chromatography; Hydrogen peroxide; Ionization; Lithium; Manganese; Manganese oxides; Mass spectrometry
• ISSN: 0024-4201; 1558-9307
• DOI: 10.1007/s11745-999-0463-8

The volatile compound trans‐4,5‐epoxy‐(E)‐2‐decenal (1) was synthesized in two steps with good overall yields. The newly developed method is based on trans‐epoxidation of (F)‐2‐octenal with alkaline hydrogen peroxide followed by a Wittig‐type chain elongation with the ylide formylmethylene triphenylphosphorane. For the synthesis of [4,5‐2H2]‐trans‐4,5‐epoxy‐(E)‐2‐decenal (d‐1), [2,3‐2H2]‐(E)‐2‐octenal was prepared by reduction of 2‐octyn‐1‐ol with lithium aluminum deuteride and subsequent oxidation of [2,3‐2H2]‐(E)‐2‐octen‐1‐ol with manganese oxide. Compound d‐1 was used as internal standard for the quantification of 1 by isotope dilution assay. Among various mass spectrometry (MS) ionization techniques tested, negative chemical ionization with ammonia as reagent gas gave best results with respect to both sensitivity and selectivity. The detection limit was found to be at about 1 pg of the analyte introduced into the gas chromatography‐MS system.