3β-chloro-5,6α-epoxy-5α-cholestane | 13095-30-2

• 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-chloro-5,6α-epoxy-5α-cholestane
• 英文别名: 3β-chloro-5,6-α-epoxy-5α-cholestane；3β-chloro-5α,6α-epoxycholestane；3β-Chlor-5,6α-epoxy-5α-cholestan；(1S,2R,5S,7R,9S,11S,12S,15R,16R)-5-chloro-2,16-dimethyl-15-[(2R)-6-methylheptan-2-yl]-8-oxapentacyclo[9.7.0.02,7.07,9.012,16]octadecane
• CAS: 13095-30-2
• 化学式: C₂₇H₄₅ClO
• 分子量: 421.107
• InChiKey: STUMUGIDOYWJQH-ZEQHCUNVSA-N

物化性质

• 熔点：
  89.5-90.5 °C(Solv: acetone (67-64-1))
• 沸点：
  492.8±28.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3β-chloro-5,6α-epoxy-5α-cholestane 在 硫酸 、 溶剂黄146 作用下， 生成 3β-chloro-5α-hydroxycholest-6β-acetate
  参考文献：
  名称：

  用硼氢化钠/三氟乙酸还原吡啶基甲醇

  摘要：

  1977 年，Gribble 和同事报告说，可以用硼氢化钠/三氟乙酸有效地还原二芳基甲醇和三芳基甲醇，得到相应的二芳基甲烷和三芳基甲烷。1991 年，Nutaitis 和同事 2 将这种方法扩展到从具有噻吩、呋喃、苯并噻吩、苯并呋喃或苯基取代基的甲醇合成二和三杂芳基甲烷，并在 1997 年减少了提供的 1,3-唑和 1,3-苯并唑甲醇有一个额外的芳基或π-过量杂芳基（噻吩基、苯并[b] 噻吩基、呋喃基或苯并[b]呋喃基）取代基。3 具有 1,3-唑或 1,3-苯并唑配体的甲醇和仅一个额外的芳基或杂芳基取代基对还原呈惰性。以此类推，预计具有吡啶基取代基取代 1,3-唑/l 的化合物，3-苯并唑配体的行为类似。这种转化将证明是有用的，因为相应的 α-取代的吡啶基甲烷已被证明是有价值的杀真菌剂、“肝微粒体血红素加氧酶和细胞色素 P450 的诱导剂”、多种金属的提取剂，包括铬、6”金?h 锌、和钴、6d

  DOI：

  10.1080/00304940209356774
• 作为产物：
  描述：

  氯化胆固醇 在 间氯过氧苯甲酸 作用下， 以 氯仿 为溶剂， 反应 27.5h， 以92%的产率得到3β-chloro-5,6α-epoxy-5α-cholestane
  参考文献：
  名称：

  Interaction of 3-β-chloro-Δ5-steroids with trifluoroperacetic acid

  摘要：

  It has been established that the reaction of 3 beta-chloro-Delta(5)-steroids with trifluoroperacetic acid forms not only the 5 alpha,6-peroxides (3a,d), but also the 5 alpha,6 beta-diols (5a,b,d) and their 6-trifluoroacetates.

  DOI：

  10.1007/bf02238215

文献信息

• Dichlororuthenium(IV) Complex ofmeso-Tetrakis(2,6-dichlorophenyl)porphyrin: Active and Robust Catalyst for Highly Selective Oxidation of Arenes, Unsaturated Steroids, and Electron-Deficient Alkenes by Using 2,6-DichloropyridineN-Oxide
  作者：Jun-Long Zhang、Chi-Ming Che

  DOI：10.1002/chem.200401008

  日期：2005.6.20

  under acid-free conditions, a wide variety of hydrocarbons including 1) cycloalkenes, conjugated enynes, electron-deficient alkenes (to afford epoxides), 2) arenes (to afford quinones), and 3) Delta5-unsaturated steroids, Delta4-3-ketosteroids, and estratetraene derivatives (to afford epoxide/ketone derivatives of steroids) in up to 99 % product yield within several hours with up to 100 % substrate conversion

  由[Ru（VI）（2,6-Cl2tpp）O2]与Me3SiCl的反应以90％的收率制备的[Ru（IV）（2,6-Cl2tpp）Cl2]是通过X射线晶体学表征的结构明显优于[Ru（IV）（tmp）Cl2]，[Ru（IV）（ttp）Cl2]和[Ru（II）（por）（CO）]（por = 2,6-Cl2tpp，F20-tpp ，F28-tpp）作为烯烃与2,6-Cl2pyNO（2,6-Cl2tpp = meso-tetrakis（2,6-dichlorophenyl）porphyrinato dianion; tmp = meso-tetramesitylporphyrinato dianion; ttp = meso-tetrakis（对甲苯基）卟啉二价阴离子; F20-tpp =间四（五氟苯基）卟啉二价阴离子; F28-tpp = 2,3,7,8,12,13,17,18-八氟-5,10,15
• A Selenium Catalyzed Epoxidation in Perfluorinated Solvents with Hydrogen Peroxide
  作者：Bodo Betzemeier、Frédéric Lhermitte、Paul Knochel

  DOI：10.1055/s-1999-2630

  日期：1999.4

  The readily prepared 2,4-bisperfluorooctylphenyl butylselenide catalyzes the epoxidation of various olefins with hydrogen peroxide in a fluorous biphasic system. The catalyst is selectively soluble in perfluorinated solvents and can easily be recovered simply by phase separation. Furthermore, the catalyst can be reused several times without a decrease of yield and an increase of reaction time.

  readily prepared 2,4-bisperfluorooctylphenyl butylselenide 催化了在氟相双相体系中用过氧化氢对各种烯烃进行的环氧化反应。该催化剂在全氟化溶剂中具有选择性的溶解性，并且通过相分离可以轻松回收。此外，该催化剂可以重复使用多次，而不会降低产率或延长反应时间。
• Synthesis of 1,3-oxathiolane-2-thiones by the reaction of steroidal oxiranes with carbon disulfide
  作者：Shamsuzzaman、Anwar Salim

  DOI：10.1016/s0040-4039(97)01251-3

  日期：1997.8

  The reaction of 5, 6α-epoxy-5α-cholestane (1), its 3β-acetoxy-(2) and 3β- chloro-(3) analogues with carbon disulfide in THF at room temperature in the presence of Li Br as catalyst afford selectively the corresponding 1,3-oxathiolane-2-thiones (steroidal cyclic cis-dithiocarbonates) (4–6) in high yields.

  5、6α-环氧-5α-胆甾烷（1），其3β-乙酰氧基-（2）和3β-氯-（3）类似物与二硫化碳在室温下，在Li Br作为催化剂的条件下在THF中反应得到以高收率选择性地选择相应的1,3-氧杂硫杂环戊烷-2-硫酮（甾体环状顺式-二硫代碳酸酯）（4–6）。
• Regioselective formation of chlorohydrins from ring-opening of steroidal epoxides using silica-supported BiCl 3 : A spectral and X-ray crystallographic study
  作者：Mahboob Alam、Soonheum Park

  DOI：10.1016/j.tetlet.2017.06.035

  日期：2017.7

  The ring opening of steroidal epoxides are carried out in a regioselective manner using bismuth chloride, ferric chloride, indium chloride, silica supported BiCl3, FeCl3 and InCl3 under mild condition in variable yields. The products obtained were identified by various spectroscopic techniques. The structure of one of the compound has been determined by X-ray diffraction using the direct method and

  使用氯化铋，氯化铁，氯化铟，二氧化硅负载的BiCl 3，FeCl 3和InCl 3以区域选择性方式在温和条件下以可变收率进行甾族环氧化物的开环。通过各种光谱技术鉴定获得的产物。已使用直接方法通过X射线衍射确定了一种化合物的结构，并在F2上进行了精制通过全矩阵最小二乘法。根据当前和以前的结果以及环氧化物的开环方式，提出了一种一般的反应机理。为了探索可能的分子间相互作用，还绘制了3D Hirshfeld表面和相关的2D指纹图。指纹图谱证明了独立分子在分子间接触中的细微区别。
• Atypical regioselective biohydrolysis on steroidal oxiranes by Aspergillus niger whole cells: Some stereochemical features
  作者：Fabricio R. Bisogno、Alejandro A. Orden、Celeste Aguirre Pranzoni、Diego A. Cifuente、Oscar S. Giordano、Marcela Kurina Sanz

  DOI：10.1016/j.steroids.2007.04.003

  日期：2007.7

  5,6-Epoxycholestan-3 beta-ol derivatives were hydrolyzed in a diastereoconvergent manner by growing and resting cells of several strains of Aspergillus niger, particularly A. niger ATCC 11394. These strains displayed opposite regioselectivity toward each isomer in an a and P epoxide mixture, thus, the nucleophilic attack took place at the less substituted and the most substituted carbon atom on each diasteromer, respectively These biocatalysts opened trisubstituted oxiranes but were unable to hydrolyze the disubstituted oxiranes in the tested sterol derivatives. These findings suggest that A. niger strains possess another hydrolytic ability different from the commercial A. niger epoxide hydrolase (EH) that did not accept this kind of steroidal oxiranes as substrates. (c) 2007 Elsevier Inc. All rights reserved.

表征谱图