3β-chlorocholest-4-ene | 13901-09-2

• 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: 3β-chlorocholest-4-ene
• 英文别名: 3β-chloro-cholest-4-ene；3β-Chlor-cholest-4-en；3β-Chlor-cholesten-(4)；3β-Chlor-cholesten-4
• CAS: 13901-09-2
• 化学式: C₂₇H₄₅Cl
• 分子量: 405.107
• InChiKey: QKOWLIHHJYBRRJ-DPAQBDIFSA-N

物化性质

• 熔点：
  116-120 °C(Solv: ethyl ether (60-29-7))
• 沸点：
  477.5±14.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.64
• 重原子数：
  28.0
• 可旋转键数：
  5.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  3β-chlorocholest-4-ene 在 palladium on activated charcoal 硼氘化钠 、 氘代甲醇-d 、 氢气 、 sodium methylate 、 nickel dichloride 作用下， 以 四氢呋喃 、 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.25h， 生成 3α-deuteriocholestane
  参考文献：
  名称：

  Desulfurization with nickel and cobalt boride: scope, selectivity, stereochemistry, and deuterium-labeling studies

  摘要：

  A variety of organosulfur compounds containing alkylthio and arylthio groups underwent reductive desulfurization under notably mild conditions when treated with nickel boride, generated in situ from nickel chloride hexahydrate and sodium borohydride in methanol-THF(3:1). Phenyl,chloro, and ester groups are not reduced under these conditions, while iodo, bromo, nitrile, aldehyde, ketone, cyclopropane, and olefinic functions are reduced either completely or partially. Deuterium-labeling studies indicate that the hydrogen that is incorporated into the product originates from both the sodium borohydride and the protic solvent, suggesting the intermediacy of dihydrogen. The epimers 3alpha- and 3beta-(phenylthio)cholestane afforded 3alpha- and 3beta-deuteriocholestane, respectively, demonstrating that the reaction proceeds with retention of configuration. The method may thus be employed for the stereospecific preparation of deuterated products from organosulfur compounds. Arguments are presented in support of a tentative mechanism involving an oxidative addition-reductive elimination sequence via a nickel hydride intermediate.

  DOI：

  10.1021/jo00061a011
• 作为产物：
  描述：

  5α-Chlor-cholestan-3β-ol 在 四氯化碳 、 五氯化磷 、 potassium acetate 作用下， 生成 3β-chlorocholest-4-ene
  参考文献：
  名称：

  Wasizu, Yakugaku Zasshi/Journal of the Pharmaceutical Society of Japan, 1940, vol. 60, p. 616,618

  摘要：

  DOI：

文献信息

• Steroids and walden inversion—LVII
  作者：C.W. Shoppee、J.K. Hummer、R.E. Lack、P. Ram、S.K. Roy

  DOI：10.1016/s0040-4020(01)99119-7

  日期：1966.1

  Solvolysis of 3β-chlorocholest-4-ene (C1, quasiequatorial) or of 3α-chlorocholest-4-ene (C1, quasiaxial) gave the same mixture of cholest-4-en-3β-ol (48%) and cholest-4-en-3α-ol (52%); these proportions are taken to give a measure of stereochemical partition at C-3 of the mesomeric cholest-4-enyl cation.

  3β-chlorocholest-4-ene（C1，quaquaiequaqua）或3α-chlorocholest-4-ene（C1，quasiaxial）的溶剂分解得到cholest-4-en-3β-ol（48％）和cholest-4的相同混合物-en-3α-ol（52％）；采取这些比例以给出介孔的胆甾-4-烯基阳离子在C-3处的立体化学分配的量度。
• Shoppee et al., Journal of the Chemical Society, 1957, p. 3107,3108, 3110
  作者：Shoppee et al.

  DOI：——

  日期：——
• Allylic Rearrangements. XLII. The Preparation and Some Reactions of 3β-Chlorocholest-4-ene and 3α-Chlorocholest-4-ene¹
  作者：W. G. Young、R. E. Ireland、T. I. Wrigley、C. W. Shoppee、B. D. Agashe、G. H. R. Summers

  DOI：10.1021/ja01515a042

  日期：1959.3