17β-hydroxy-4,5-secoandrost-3-yn-5-one benzoate | 99463-59-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 17β-hydroxy-4,5-secoandrost-3-yn-5-one benzoate
• 英文别名: 17β-Benzoyloxy-4,5-secoandrost-3-yn-5-one；[(3S,3aS,5aS,6R,9aS,9bS)-6-but-3-ynyl-3a,6-dimethyl-7-oxo-1,2,3,4,5,5a,8,9,9a,9b-decahydrocyclopenta[a]naphthalen-3-yl] benzoate
• CAS: 99463-59-9
• 化学式: C₂₆H₃₂O₃
• 分子量: 392.538
• InChiKey: UPVGLFUHNVHUAA-JYAKILMVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  17β-hydroxy-4,5-secoandrost-3-yn-5-one benzoate 在 mercury(II) diacetate 盐酸 、 氢氧化钾 、 氯化亚砜 、 溶剂黄146 、 lithium tri-t-butoxyaluminum hydride 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 为溶剂， 反应 25.5h， 生成 17β-Hydroxy-4,5-secoandrost-5-en-3-one
  参考文献：
  名称：

  4,5-Secoandrostanes by Eschenmoser's reaction

  摘要：

  17β-苯甲氧基-4,5-去氢雄甾-3-炔-5-酮（V）可从睾酮经过三步反应制备，可以转化为Δ⁵-不饱和炔类化合物XXV（通过轴向羟基衍生物XVII）和炔类化合物XXVI（通过赤道甲磺酸酯XXIII的氢解）。这些化合物被水合和水解成17β-羟基-4,5-去氢雄甾-5-烯-3-酮和17β-羟基-4,5-去氢雄甾烷-3-酮（分别为XXX和I）。将化合物XXX与氚进行催化氢化，得到[5,6-³H₂]-衍生物XXXI。

  DOI：

  10.1135/cccc19851402
• 作为产物：
  描述：

  Benzoic acid (8S,9S,10R,13S,14S,17S)-10,13-dimethyl-3-oxo-hexadecahydro-20-oxa-cyclopropa[4,5]cyclopenta[a]phenanthren-17-yl ester 在 对甲苯磺酰肼 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 反应 1.0h， 以10.5 g的产率得到17β-hydroxy-4,5-secoandrost-3-yn-5-one benzoate
  参考文献：
  名称：

  4,5-Secoandrostanes by Eschenmoser's reaction

  摘要：

  17β-苯甲氧基-4,5-去氢雄甾-3-炔-5-酮（V）可从睾酮经过三步反应制备，可以转化为Δ⁵-不饱和炔类化合物XXV（通过轴向羟基衍生物XVII）和炔类化合物XXVI（通过赤道甲磺酸酯XXIII的氢解）。这些化合物被水合和水解成17β-羟基-4,5-去氢雄甾-5-烯-3-酮和17β-羟基-4,5-去氢雄甾烷-3-酮（分别为XXX和I）。将化合物XXX与氚进行催化氢化，得到[5,6-³H₂]-衍生物XXXI。

  DOI：

  10.1135/cccc19851402

文献信息

• A novel stereospecific rearrangement of 3-substituted B-homo-5-azasteroids to their A-nor analogs. Preparation, stereochemistry, and conformational studies
  作者：Thomas G. Back、Joseph H. L. Chau、Penelope W. Codding、Patricia L. Gladstone、David H. Jones、Jacek W. Morzycki、Aleksander W. Roszak

  DOI：10.1021/jo00041a013

  日期：1992.7

  The novel 3-alpha- and 3-beta-hydroxy-B-homo-5-azasteroid lactams 4 and 5 were prepared from testosterone. When the hydroxyl group in these compounds is converted into a leaving group, rearrangement to the corresponding A-nor azasteroids occurs under a variety of conditions, along with competing substitution with inversion of configuration at C-3. The rearrangements proceed with complete stereospecificity and are faster and more efficient in the 3-alpha-series. The observed stereochemistry, as well as the results of molecular modeling, low-temperature NMR, and X-ray crystallographic studies support a mechanism involving neighboring-group participation by the nitrogen atom in the departure of the nucleofuge from C-3 via the formation of aziridinium ion intermediates. Compounds in the 3-alpha-series require prior ring-flipping to the A-boat conformation, while those in the 3-beta-series react through the corresponding A-chairs. The differences in the free energies of the A-boat and A-chair forms are greater in the 3-beta-compounds (1.6-3.4 kcal/mol) than in the corresponding 3-alpha-isomers (0.1-1.3 kcal/mol). The 3-alpha-chloro derivative 19 exists mainly as the A-chair in solution (DELTA-G = 0.3 kcal/mole; DELTA-G* = 12.2 kcal/mol), but crystallizes in the A-boat conformation. Molecular modeling studies of several 3-substituted derivatives and X-ray investigations of 19 and its 3-beta-isomer 20 also reveal separate flip forms of the B-rings associated with the A-chair and A-boat conformations in each case. Relief of steric hindrance between one of the hydrogen atoms at C-19 and the beta-hydrogen at C-7 (this H-H contact is only 1.98 angstrom in the crystal structure of 19) in the A-boat conformations of the 3-alpha-series enhances anchimeric assistance to the departure of the leaving group and facilitates the rearrangements of these compounds relative to their 3-beta-counterparts.