Zur lokalisierung funktioneller gruppen mit hilfe der massenspektrometrie—VIII : 6-hydroxy-androstan-3,17-dione und 6,17β-dihydroxy-androstan-3-one |
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Authors: | FJ Hammerschmidt G Spiteller |
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Institution: | Organisch-Chemisches Institut der Universität Göttingen Germany |
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Abstract: | 5β-androstan-3-ones carrying a 6α-OH group show in their mass spectra a key-ion indicating the loss of water and C-1 to C-4 as C4H5O? particle. 6β-OH isomers lose instead C-1 to C-4 in form of C4H7O?.In 6α-hydroxy-androstan-3-ones differentiation between the connection of the A/B-ring system is possible, because in 5α-isomers the loss of C-3 to C-7 occurs as a C5H6O2 particle, while the 5β-isomers lose the same C atoms as a C5H7O? unit.Compounds with a 6β-OH group in an A/B trans connected ring system show a tendency for thermal water elimination. After rearrangement of the double bond in 4,5 position the typical fragments for 3-keto-Δ4-steroids are obtained.Occasionally a strong influence of a 6-OH group on fragmentation reactions in the D-ring system is observed: The presence of a 6α-OH group in an androstan-3,17-dione enhances the loss of C-16 and C-17 in the form of acetaldehydenol. Also the connection of the A/B-ring system may have a considerable influence on this type of reaction: In 6,17β-dihydroxy-androstan-3-ones only by trans connection of the A/B-ring system, C-16 and C-17 are lost with high probability after water elimination. |
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