3-Methoxy-13-methyl-17-oxo-16-(phenylthio)-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopentaphenanthrene | 57707-93-4

• 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: 3-Methoxy-13-methyl-17-oxo-16-(phenylthio)-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopentaphenanthrene
• 英文别名: 3-Methoxy-13-methyl-17-oxo-16-(phenylthio)-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthrene
• CAS: 57707-93-4
• 化学式: C₂₅H₂₈O₂S
• 分子量: 392.562
• InChiKey: MRNCAIJFGSHNOU-ZZDGKJOTSA-N

物化性质

• 沸点：
  554.7±50.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.89
• 重原子数：
  28.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  3.0

上下游信息

反应信息

• 作为反应物：
  描述：

  3-Methoxy-13-methyl-17-oxo-16-(phenylthio)-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopentaphenanthrene 在 咪唑 、 sodium tetrahydroborate 、 mercury(II) perchlorate 、 sodium hydride 作用下， 以 甲醇 为溶剂， 反应 4.5h， 生成 Dithiocarbonic acid S-methyl ester O-((8R,9S,13S,14S)-3,16,16-trimethoxy-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-yl) ester
  参考文献：
  名称：

  A new 1,2-carbonyl transposition method via phenylselenenylation. High yield transformation of O-methylestrone to O-methylisoestrone.

  摘要：

  O-甲基雌酮与PhSeCl和BF3.Et2O的酸性苯基硒化反应生成α-苯基硒酮和α-氯-α-苯基硒酮，二者在甲醇中与高氯酸汞（II）反应生成相同的α,α-二甲氧基酮。该产物经氢化还原、二硫代羰基化、酸水解和三丁基氢化锡处理后，得到O-甲基异雌酮，即1,2-羰基转位产物，总收率为75%。

  DOI：

  10.1248/cpb.33.1745
• 作为产物：
  描述：

  3-甲氧基雌酮 、 二苯二硫醚 生成 3-Methoxy-13-methyl-17-oxo-16-(phenylthio)-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopentaphenanthrene
  参考文献：
  名称：

  New synthetic methods. 1,2-(Alkylative) carbonyl transpositions

  摘要：

  DOI：

  10.1021/ja00835a045

文献信息

• New synthetic methods. 1,2-(Alkylative) carbonyl transpositions
  作者：Barry M. Trost、Kunio Hiroi、Seizi Kurozumi

  DOI：10.1021/ja00835a045

  日期：1975.1
• Electroinitiated oxygenation of alkenyl sulfides and alkynes in the presence of thiophenol
  作者：Junichi Yoshida、Shogo Nakatani、Sachihiko Isoe

  DOI：10.1021/jo00070a021

  日期：1993.8

  Electrolysis of alkenyl sulfides in the presence of thiophenol with bubbling of molecular oxygen gave the corresponding alpha-(phenylthio) carbonyl compounds with the consumption of a catalytic amount of electricity. An electroinitiated radical chain mechanism has been proposed. The reaction also took place without electrochemical initiation, but much (5-50 times) longer reaction time was required for the completion of the reaction. The potential utility of the present reaction in organic synthesis is demonstrated by the net 1,2-transposition of a phenylthio group and a carbonyl group. The electroinitiated oxygenation of ketene dithioacetals also proceeded smoothly to give the corresponding alpha-(phenylthio) thiol esters. It was also found that the electroinitiated oxygenation of alkynes in the presence of thiophenol gave alpha-(phenylthio) carbonyl compounds. A mechanism involving the initial formation of alkenyl sulfides has been proposed.
• New synthetic reactions. Sulfenylations and dehydrosulfenylations of esters and ketones
  作者：Barry M. Trost、Thomas N. Salzmann、Kunio Hiroi

  DOI：10.1021/ja00432a034

  日期：1976.8
• A new 1,2-carbonyl transposition method via phenylselenenylation. High yield transformation of O-methylestrone to O-methylisoestrone.
  作者：Yoshisuke Tsuda、Shinzo Hosoi

  DOI：10.1248/cpb.33.1745

  日期：——

  Acidic phenylselenenylation of O-methylestrone with PhSeCl and BF3.Et2O gave an α-phenylselenenylketone and an α-chloro-α-phenylselenenylketone, both of which were converted to the same α, α-dimethoxyketone on treatment with mercury (II) perchlorate in methanol. Hydride reduction of this, dithiocarbonylation of the resulting product followed by acid hydrolysis, and treatment with tributyltin hydride gave O-methylisoestrone, the 1, 2-carbonyl transposed product, in overall yield of 75%.

  O-甲基雌酮与PhSeCl和BF3.Et2O的酸性苯基硒化反应生成α-苯基硒酮和α-氯-α-苯基硒酮，二者在甲醇中与高氯酸汞（II）反应生成相同的α,α-二甲氧基酮。该产物经氢化还原、二硫代羰基化、酸水解和三丁基氢化锡处理后，得到O-甲基异雌酮，即1,2-羰基转位产物，总收率为75%。