Wölfling János, Hackler László, Mernyák Erzsébet, Schneider Gyula, Tóth István, Szécsi Mihály, Julesz János, Sohár Pál, Csámpai Antal
Department of Organic Chemistry, University of Szeged, Dóm tér 8, H-6720, Hungary.
Steroids. 2004 Jul;69(7):451-60. doi: 10.1016/j.steroids.2004.04.003.
During the alkaline methanolysis of 3beta-acetoxy-21-chloromethyl-pregn-5-ene-20beta-N-phenylurethane, and its p-substituted phenyl derivatives, cyclization occurs, in the course of which 17beta-[3-(N-phenyl)tetrahydrooxazin-2-on-6-yl]androst-5-en-3beta-ol and its p-substituted phenyl derivatives are formed. The cyclization takes place with (N(-)-6) neighboring group participation. Oppenauer oxidation of the 3beta-hydroxy-exo-heterocyclic steroids yielded the corresponding delta4-3-ketosteroids. The structures of the new compounds were proved by IR, 1H and 13C NMR spectroscopy, using up-to-date measuring techniques such as 2D-COSY, HMQC, and HMBC. The inhibitory effects (CI50) of the delta4-3-ketosteroids on 5alpha-reductase were studied.
在3β-乙酰氧基-21-氯甲基-孕甾-5-烯-20β-N-苯基脲及其对取代苯基衍生物的碱性甲醇解过程中发生环化反应，在此过程中形成了17β-[3-(N-苯基)四氢恶嗪-2-酮-6-基]雄甾-5-烯-3β-醇及其对取代苯基衍生物。环化反应是通过（N(-)-6）邻基参与进行的。3β-羟基-外型-杂环甾体的欧芬脑尔氧化反应生成了相应的Δ4-3-酮甾体。利用二维COSY、HMQC和HMBC等最新测量技术，通过红外光谱、1H和13C核磁共振光谱对新化合物的结构进行了确证。研究了Δ4-3-酮甾体对5α-还原酶的抑制作用（CI50）。
