The Veratrum Alkamines 300 



of this work the prime objective was to gain insight into the nature 

 of the underlying carbon-nitrogen skeleton by means of soda-lime 

 distillation and selenium dehydrogenation. This approach proved to 

 be immediately fruitful at least as far as the nitrogenous portion of 

 the molecule was concerned. Particularly informative in this respect 

 was the finding that 3-methyl-6-ethylpyridine (I) was formed on 

 selenium dehydrogenation from all the alkamines then so investigated, 

 and that the corresponding piperidine base was formed from cevine 

 on soda-lime distillation. There could be no doubt then that the 

 nitrogenous moiety was a substituted piperidine ring, joined, as it 

 turned out later, to the rest of the molecule through the a-carbon of 

 the ethyl group and, in the tertiary bases, also through the nitrogen 

 atom. The structural significance of three other basic dehydrogenation 

 products, 3-methyl-5-hydroxypyridine (II), from veratramine, a base 

 which in all probability is 3-methyl-5-hydroxy-6-ethylpyridine (III), 

 from jervine, and an isomer of jervine recently 1 assigned structure IV, 

 from cevine, will become evident later. 



It will be noted that the carbon skeleton of I is that of the cholesterol 

 side chain. It was then not unreasonable to adopt the working hy- 

 pothesis that the remainder of the molecule was made up of the 

 androstane skeleton. Strength was added to this supposition when it 

 was found (Prelog and Szpilvogel, 1942; Craig and Jacobs, 1943) that 

 solanidine, C07H43O, the main alkaloid of the potato plant (Solatium 

 tuberosum) , then already known to be a steroid, likewise contained 

 its nitrogen atom in a 3-methyl-6-ethylpiperidine moiety. Against it, 

 however, stood the fact that painstaking fractionation of the neutral 

 dehydrogenation products from jervine and cevine (up till then the 

 only alkamine so investigated), had failed to disclose the presence of 

 any phenanthrene derivatives. In fact, with the exception of a tricyclic 

 compound from cevine, 1,2-cyclopentenonapthalene (V), none of the 

 numerous physically and analytically well-characterized hydrocarbons 

 obtained from these alkamines could be identified structurally, and 

 some of the tetra- and pentacyclic members of the series exhibited 

 ultraviolet characteristics which indicated a relationship to fluorene 

 (VI) and 1,2-benzofluorene (VII) rather than to phenanthrene. For 

 this reason Jacobs and Craig for a time gave consideration to a modi- 

 fied steroidal nucleus with a five-membered ring B and a methyl group 

 at C5. However, when in 1943 they shifted their attention to rubi- 

 jervine, and later to its newly isolated isomer isorubijervine, it became 

 increasingly evident that these two alkamines, at any event, must be 

 normal steroids. Thus, rubijervine yielded on selenium dehydrogena- 



