20, 21‐Azirdin‐Steroide: Reaktion von Derivaten der Oxime von 5‐Pregnen‐20‐on,9β,10α‐5‐Pregnen‐20‐on und 9β,10α‐5,7‐Pregnadien‐20‐on mit Lithiumaluminiumhydrid und von 3β‐Hydroxy‐5‐pregnen‐20‐on‐oxim mit Grignard ‐Verbindungen

20, 21‐Aziridine Steroids: Reaction of Derivatives of the Oximes of 5‐Pregnen‐20‐one, 9β, 10α‐5‐Pregnen‐20‐one and 9β, 10α‐5,7‐Pregnadiene‐20‐one with Lithium Aluminium Hydride, and of 3β‐Hydroxy‐5‐pregnen‐20‐one Oxime with Grignard Reagents. Reduction of 3β‐hydroxy‐5‐pregnen‐20‐one oxime ( 2 ) with LiAlH 4 in tetrahydrofuran yielded 20α‐amino‐5‐pregnen‐3β‐ol ( 1 ), 20β‐amino‐5‐pregnen‐3β‐ol ( 3 ), 20β, 21‐imino‐5‐pregnen‐3β‐ol ( 6 ) and 20β, 21‐imino‐5‐pregnen‐3β‐ol ( 9 ). The aziridines 6 and 9 were separated via the acetyl derivatives 7 and 10 . The reaction of 6 and 9 with CS 2 gave 5‐(3β‐hydroxy‐5‐androsten‐17β‐yl)‐thiazolidine‐2‐thione ( 8 ). Treatment of the 20‐oximes 12 and 15 of the corresponding 9β,10α(retro)‐pregnane derivatives with LiAlH 4 gave the aziridines 13 and 16 , respectively. Their deamination led to the diene 14 and triene 17 , respectively. Reduction of isobutyl methyl ketone‐oxime with LiAlH 4 in tetrahydrofuran yielded 2‐amino‐4‐methyl‐pentane ( 19 ) as main product, 1, 2‐imino‐4‐methyl‐pentane ( 22 ) as second product and the epimeric 2,3‐imino‐4‐methyl‐pentanes 20 and 21 as minor products. – 3β‐Hydroxy‐5‐pregnen‐20‐one oxime ( 2 ) was transformed by methylmagnesium iodide in toluene to 20α, 21‐imino‐20‐methyl‐5‐pregnen‐3β‐ol ( 23 ) and 20β, 21‐imino‐20‐methyl‐5‐pregnen‐3β‐ol ( 26 ). Acetylation of these aziridines was accompanied by elimination reactions leading to 3β‐acetoxy‐20‐methylidene‐21‐N‐acetylamino‐5‐pregnene ( 30 ) and 3β‐acetoxy‐20‐methyl‐21‐N‐acetylamino‐5,17‐pregnadiene ( 32 ). The reaction of oxime 2 with ethylmagnesium bromide in toluene gave 20α, 21‐imino‐20‐ethyl‐5‐pregnen‐3β‐ol ( 24 ) and 20α,21‐imino‐20‐ethyl‐5‐pregnen‐3β‐ol ( 27 ). Acetylation of 24 and 27 led to 3β‐acetoxy‐20‐ethylidene‐21‐N‐acetylamino‐5‐pregnene ( 31 ), 3β‐acetoxy‐20‐ethyl‐21‐N‐acetylamino‐5,17‐pregnadiene 33 and 3β, 20‐diacetoxy‐20‐ethyl‐21‐N‐acetylamino‐5‐pregnene ( 37 ). With phenylmagnesium bromide in toluene the oxime 2 was transformed to 20β, 21‐imino‐20‐phenyl‐5‐pregnen‐3β‐ol ( 25 ) and 20β,21‐imino‐20‐phenyl‐5‐pregnen‐3β‐ol ( 28 ). Acetylation of 25 and 28 yielded 3β‐acetoxy‐20‐phenyl‐21‐N‐acetylamino‐5, 17‐pregnadiene ( 34 ) and 3β,20‐diacetoxy‐20‐phenyl‐21‐N‐acetylamino‐5‐pregnene ( 39 ). LiAlH 4 ‐reduction of 39 gave 3β, 20‐dihydroxy‐20‐phenyl‐21‐N‐ethylamino‐5‐pregnene ( 41 ). – The 20, 21‐aziridines are stable to LiAlH 4 . Consequently they are no intermediates in the formation of the 20‐amino derivatives obtained from the oxime 2 .