(5Ξ)-5-(3β-hydroxy-androst-5-en-17β-yl)-thiazolidine-2-thione | 60534-29-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: (5Ξ)-5-(3β-hydroxy-androst-5-en-17β-yl)-thiazolidine-2-thione
• CAS: 60534-29-4；60534-50-1
• 化学式: C₂₂H₃₃NOS₂
• 分子量: 391.642
• InChiKey: XPIMQKAMFWHFTC-RNMSGCPLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.92
• 重原子数：
  26.0
• 可旋转键数：
  1.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  32.26
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  二硫化碳 、 δ⁵-pregnen-3β-ol-20-one oxime 生成 (5Ξ)-5-(3β-hydroxy-androst-5-en-17β-yl)-thiazolidine-2-thione
  参考文献：
  名称：

  [20,21-氮丙啶类固醇：5-孕20-，9beta，10alpha-5-孕20和9beta，10alpha-5,7-孕二烯-20-肟的衍生物与氢化铝锂的反应，以及带有Grignard试剂的3beta-hydroxy-5-pregnen-20-one肟（作者的翻译）]。

  摘要：

  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 LiAlH4 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 CS2 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 LiAlH4 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 LiAlH4 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). LiAlH4‐reduction of 39 gave 3β, 20‐dihydroxy‐20‐phenyl‐21‐N‐ethylamino‐5‐pregnene (41). – The 20, 21‐aziridines are stable to LiAlH4. Consequently they are no intermediates in the formation of the 20‐amino derivatives obtained from the oxime 2.

  DOI：

  10.1002/hlca.19760590542