3-Methyl-cholesta-3,5-dien | 1249-79-2

• 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: 3-Methyl-cholesta-3,5-dien
• 英文别名: (8S,9S,10R,13R,14S,17R)-3,10,13-trimethyl-17-[(2R)-6-methylheptan-2-yl]-2,7,8,9,11,12,14,15,16,17-decahydro-1H-cyclopenta[a]phenanthrene
• CAS: 1249-79-2
• 化学式: C₂₈H₄₆
• 分子量: 382.673
• InChiKey: AZUUAEYWJRSEKQ-OKPKYCIKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.7
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  3-Methyl-cholesta-3,5-dien 在 palladium on activated charcoal 氢气 、 四氯苯醌 、 苯甲醚 、 菲醌 作用下， 以 乙醇 为溶剂， 反应 48.5h， 生成 3,17-dimethyl-18,19-dinor-17α-cholesta-1,3,5,7,9,11,13-heptaene
  参考文献：
  名称：

  Synthesis of triaromatic steroid hydrocarbons methylated at position 2, 3 or 6: molecular fossils of yet unknown biological origin

  摘要：

  C-21-29 triaromatic steroid hydrocarbons bearing a methyl group at unusual positions 2, 3 or 6 have been synthesized from pregnenolone, cholesterol or stigmasterol via stera-3,5-dienes. Their occurrence in various sedimentary rocks and petroleums suggests the presence of yet unknown biological precursors.

  DOI：

  10.1016/s0040-4020(01)80848-6
• 作为产物：
  描述：

  4-胆甾烯-3-酮 在 对甲苯磺酸 作用下， 以 乙醚 、 正己烷 、 甲苯 为溶剂， 反应 2.0h， 生成 3-Methyl-cholesta-3,5-dien
  参考文献：
  名称：

  Synthesis of triaromatic steroid hydrocarbons methylated at position 2, 3 or 6: molecular fossils of yet unknown biological origin

  摘要：

  C-21-29 triaromatic steroid hydrocarbons bearing a methyl group at unusual positions 2, 3 or 6 have been synthesized from pregnenolone, cholesterol or stigmasterol via stera-3,5-dienes. Their occurrence in various sedimentary rocks and petroleums suggests the presence of yet unknown biological precursors.

  DOI：

  10.1016/s0040-4020(01)80848-6

文献信息

• Role of Sterically Demanding Chiral Dirhodium Catalysts in Site-Selective C–H Functionalization of Activated Primary C–H Bonds
  作者：Changming Qin、Huw M. L. Davies

  DOI：10.1021/ja504797x

  日期：2014.7.9

  sterically demanding dirhodium tetracarboxylate catalysts on the site selectivity of C-H functionalization by means of rhodium carbene-induced C-H insertion is described. The established dirhodium tetraprolinate-catalyzed reactions of aryldiazoacetates cause preferential C-H functionalization of secondary C-H bonds as a result of competing steric and electronic effects. The sterically more demanding dirhodium

  描述了空间要求严格的四羧酸二铑催化剂通过铑卡宾诱导的 CH 插入对 CH 官能化的位点选择性的影响。由于竞争性空间和电子效应，已建立的四脯氨酸二铑催化芳基重氮乙酸酯反应导致二级 CH 键的优先 CH 官能化。空间上要求更高的四（三芳基环丙烷羧酸）二铑催化剂，例如四[（R）-（1-（联苯）-2,2-二苯基环丙烷羧酸）] [Rh2（R-BPCP）4]，有利于活化伯的 CH 官能化CH 债券。使用该催化剂实现了对包含伯苄基、烯丙基和甲氧基 CH 键的各种简单底物的高度位点选择性和对映选择性 CH 官能化。
• PHOTOCHEMICAL TRANSFORMATIONS OF DIENES: VII. STEREOCHEMISTRY OF ADDITION OF ALCOHOL, AND EFFECT OF SUBSTITUENTS AND ACIDS ON THE PHOTOCHEMISTRY OF CHOLESTA-3,5-DIENES
  作者：G. Bauslaugh、G. Just、E. Lee-Ruff

  DOI：10.1139/v66-423

  日期：1966.12.1

  Results for the photolysis of 6-methylcholesta-3,5-diene are described. The photolysis of these and other dienes proceeds by a unimolecular process, giving bicyclobutanes, or a bimolecular process, giving carbonium ions. Reaction of the bicyclobutane with a protic solvent results in stereospecific incorporation of a proton (4β), whereas direct abstraction of a proton by a photo-excited species results

  描述了 6-methylcholesta-3,5-diene 的光解结果。这些和其他二烯的光解通过单分子过程进行，产生双环丁烷，或双分子过程，产生碳正离子。双环丁烷与质子溶剂的反应导致质子 (4β) 的立体定向结合，而光激发物质直接提取质子导致非立体定向提取。在少量酸的存在下，获得更多或部分源自双分子途径的新产物。 注意到当薄层色谱（硅胶）时差向异构醇的正常色谱洗脱顺序（氧化铝）被颠倒) 被使用。
• Reactions of iron pentacarbonyl with some steroid dienes
  作者：Howard Alper、John T. Edward

  DOI：10.1016/s0022-328x(00)87681-0

  日期：1968.10

  Tricarbonyliron complexes of steroidal Δ2,4- and Δ5,7-dienes have been prepared. The transoid Δ3,5- and Δ4,6-dienes, when heated with iron pentacarbonyl, rearrange to form the cisoid Δ2,4-diene complexes. Complex formation, followed by liberation of the diene ligand, thus offers a means of converting heteroannular steroidal dienes into their thermodynamically less stable homoannular isomers.

  甾体Δ的Tricarbonyliron络合物2,4 -和Δ 5,7 -dienes已经制备。所述transoidΔ 3,5 -和Δ 4,6 -dienes，当与五羰基铁加热，重新排列以形成cisoidΔ 2,4 -二烯配合物。形成复合物，随后释放二烯配体，因此提供了将异环类固醇二烯转化为其热力学上较不稳定的均环异构体的方法。
• PHOTOCHEMICAL TRANSFORMATIONS OF DIENES: II. THE PHOTOLYSIS OF 3-METHYLCHOLESTA-3,5-DIENE (V)
  作者：G. Just、V. Di Tullio

  DOI：10.1139/v64-321

  日期：1964.10.1

  Photolysis of 3-methylcholesta-3,5-diene (V) in ethanol gave 3-methylenecholest-5-ene (VI), 6β-ethoxy-3α-methyl-3β,5-cyclo-5β-cholestane (VII), 3β-ethoxy-3α-methylcholest-5-ene (VIII), and 3α-methylcholesterol (VIIIa) as well as a number of unidentified hydrocarbons and alcohols. A similar photolysis in pentane, followed by reaction of the resulting 3β,5;4α,6α-bicyclo-5β-cholestane (IIa) with ethanol

  3-methylcholesta-3,5-diene (V) 在乙醇中的光解得到 3-methylenecholest-5-ene (VI), 6β-ethoxy-3α-methyl-3β,5-cyclo-5β-cholestane (VII), 3β -ethoxy-3α-methylcholest-5-ene (VIII) 和 3α-methylcholesterol (VIIIa) 以及一些不明的碳氢化合物和醇。在戊烷中进行类似的光解，随后生成的 3β,5;4α,6α-双环-5β-胆甾烷 (IIa) 与乙醇反应，得到环醚 VII 作为唯一可分离的产物。
• STEROIDS: VIII. SOME REACTIONS OF THE 3-METHYLCHOLEST-5-EN-3-OLS AND THEIR DERIVATIVES
  作者：G. Just、V. Di Tullio

  DOI：10.1139/v64-397

  日期：1964.12.1

  The preparation and ethanolysis of 3-methylcholesteryl derivatives is described. It was noticed that Δ5-3-methyl-3-oxygenated steroids undergo hydrogenolysis, which can be suppressed by addition of sodium nitrite.

  描述了 3-甲基胆固醇衍生物的制备和乙醇分解。注意到 Δ5-3-methyl-3-oxygenated steroids 发生氢解, 这可以通过添加亚硝酸钠来抑制。