J. Fischer et al.
in anhydrous diethoxymethan) was added dropwise at room taint in pig back fat samples. Details of ongoing investigations in
temperature. The orange‐colored reaction mixture was stirred our laboratory will be reported in due course.
further for 5 h, then cooled to 0 °C and subsequently quenched by
the addition of water (10 mL). The reaction mixture was transferred
into a separatory funnel and extracted with a mixture of petroleum
Acknowledgements
ether and EtOAc (3:1; 2 × 100 mL). The organic layers were The authors thank M. Gütschow, Pharmaceutical Institute,
University of Bonn, for his general advice and synthetic support.
The technical assistance by S. Kehraus for the recording of NMR
spectra, as well as the measurement of UPLC–MS spectra by B.
Zimmermann is very much appreciated. This work was
financially supported by the Ministry for Climate Protection,
Environment, Agriculture, Nature Conservation and Consumer
Protection of North Rhine‐Westphalia, Germany.
combined, dried using anhydrous sodium sulfate, and evaporated
to dryness in vacuo. For further purification, the crude white residue
was redissolved in hot MeOH (20 mL, 65 °C) and mixed with water
until the solution turned slightly cloudy. After cooling to −20°C, a
precipitate was separated by centrifugation to give 6 as a white
solid (1.52 g, 78%), m.p. 121–123 °C,34 123–124 °C. 1H NMR (CDCl3)
δ: 0.74 (s, 3H, 19‐CH3), 0.83 (s, 3H, 18‐CH3), 3.59 (m, 1H, 3‐H), 5.68 (m,
1H, 16‐H), 5.83 (m, 1H, 17‐H); 13C NMR (CDCl3) δ: 13.72 (19‐CH3),
18.48 (18‐CH3), 22.62 (CH2), 29.50 (t, 1C, 1J (C,D) =19.2 Hz, C‐6), 32.88
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Conclusion
Aside from the synthesis of d3‐skatole in high isotopic purity, a
concise four‐step procedure to afford d3‐androstenone has been
developed. The improved procedure presented allows for the
selective reduction of Δ5,6‐double bonds in hydrophobic
steroids in aqueous solvent systems without affecting present
carbonyl functions. As D2O is utilized as a cheap and convenient
deuterium source when compared with gaseous D2, the method
presented provides a highly valuable and convenient alternative
where the deuteration of double bonds in hydrophobic systems
is required. All synthesized compounds were characterized in
detail by NMR and MS techniques. As calculated from GC–MS
spectra of unlabeled and labeled androstenone, 81% were either
d2‐labeled or d3‐labeled of which 60% were the d3‐isotopomer.
Both labeled androstenone and skatole were found suitable for
the use as internal standards in SIDA–GC–MS analysis of boar
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Copyright © 2011 John Wiley & Sons, Ltd.