The venomous nature of the European salamander, Salamandra maculosa, has been known for years. Over a century ago the toxic substance was extracted from the skin glands of these salamanders.
2 Later it was found that this extract was a mixture of steroidal alkaloids.' One of the constituents of this mixture, samanine, was very recently found to have structure J.3ay4 This is one of the very few naturally occurring steroidal alkaloids in which the nitrogen is incorporated into the steroidal skeleton. Habermehl and Haaf also reoorted a synthesis of 1 from 166-hydroxy-56-cholestan-3-one (<) along with the original structural work. 4 The crucial step in this synthesis was the Beckmann rearrangement of the oximes from ketone < and the subsequent delicate chromatographic separation of the two resulting lactams. At about the same time, Oka and Hara reported a similar synthesis of i.5 HcJp-oH .J-Jp-OH H !, H F However, this synthesis required a chromatographic separation of the two oximes from ,? followed by a Beckmann rearrangement of one of the oximes to give only the desired 3-aza-A-homo compound. Since samanine was available in only small quantities from either the salamanders or synthesis, a detailed evaluation of its biological prooerties is not known.