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.
• 4,5-Secoandrostanes by Eschenmoser's reaction
  作者：Alexander Kasal、Ladislav Kohout、Jiří Filip

  DOI：10.1135/cccc19851402

  日期：——

  17β-Benzoyloxy-4,5-secoandrost-3-yn-5-one (V), accessible from testosterone in three steps, can be converted both to Δ⁵-unsaturated alkynes of the type XXV (via axial hydroxy derivative XVII) and to alkynes of the type XXVI (by hydrogenolysis of equatorial methanesulfonate XXIII). These compounds were hydrated and hydrolysed to 17β-hydroxy-4,5-secoandrost-5-en-3-one and 17β-hydroxy-4,5-secoandrostan-3-one (XXX and I respectively). Catalytic hydrogenation of compound XXX with tritium afforded [5,6-³H₂]-derivative XXXI.

  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。