Catalytic hydrogenation of optically active 2-pyridyl ethylcarbinol (1) formed the alkaloid conliydrine (2) stereospecifically. Application of the von Braun reaction gave conversion of (+)-conliydrine into R-(-)-3-octyl benzoate and of (-)-conliydrine into tlie S-(+)-antimer. Both the relative and absolute configuration of the two asymmetric centers in natural (+)-conhydrine have been determined by the combined use of optical rotatory dispersion (0.r.d.) and circular dicliroism (c.d.). The results are in agreement with other physical and clieniical evidence.Canadian Journal of Chemistry, 47, 4393 (1969) The alkaloid conhydrine was isolated from Coniunz maculatum and natural (+)-conhydrine was oxidized to L-(-)-pipecolic acid (1). The relative configuration of the two asymmetric centres in conhydrine is regarded as erythro on the basis of chemical evidence (2, 3) identifying the octan-3,4-diol obtained from (+)-conhydrine by Hofmann degradation and hydrogenation of the methine base (4) with racemic erythro-octan-3,4-diol.Since this work was done on the racemic alkaloid, and the conclusions are based on assumptions regarding the stereochemistry of the intermediate steps, it was desirable to obtain further evidence concerning the configuration of the carbiiiol carbon. This has now been achieved both by chemical means and by the 0.r.d.-c.d. method previously applied (5) to the configuration of tlie sedridine and allosedridine alkaloids.The catalytic hydrogenation of optically active (+)-2-pyridyl ethylcarbinol(1) under conditions identical to those used (6a) for tlie reaction forming sedridine gave, by asymmetric induction, (+)-conhydrine (2) as the major product (66).
Z U S AMMENF AS SU N G :Polylithiumacenaphthylen wurde rnit Aldehyden, Nitrilcn, Schwefel, Phenylisocyanat und Dimethylformamid umgesetzt. Polyacenaphthylen konnte bromiert und hydroxynitriert werden. Die Darstellung einer Polyacenaphthylencarbonsaure gelang dnrch Oxydation des acetylierten Polyacenaphthylens mit Hypochlorit.
S U M M A R Y :Polylithioacenaphthylene was reacted with aldehydes, nitriles, sulfur, phenylisocyanate and dimethylformamide. Polyacenaphthylene was brominated and hydroxynitrated. polyacenaphthylene-carboxylic acid was prepared by oxidation of an acetylated polyacenaphthylene with hypochlorite.
3,4′‐Dimethoxy‐3′,5,7‐trihydroxyflavon (I) und Centaureidin (VI) wurden als cytotoxische Flavonole aus den Blättern und Zweigen von Baccharis sarothroides isoliert.
(+)‐Conhydrin (II), dargestellt durch katalytische Hydrierung des (+)‐Pyridylcarbinols (I), besitzt aufgrund chemischer Reaktionen und der ORD‐Kurven von (II) und (II)‐Hydrochlorid sowie des positiven CD die angegebene absolute Konfiguration.
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