9-[(4-Chlorophenyl)sulfanylmethyl]-9-methyl-7,8,12-trioxaspiro[5.6]dodecane | 869661-31-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 9-[(4-Chlorophenyl)sulfanylmethyl]-9-methyl-7,8,12-trioxaspiro[5.6]dodecane
• CAS: 869661-31-4
• 化学式: C₁₇H₂₃ClO₃S
• 分子量: 342.887
• InChiKey: PCTCJICPLUTPQU-UHFFFAOYSA-N

物化性质

• 沸点：
  442.0±40.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  53
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  9-[(4-Chlorophenyl)sulfanylmethyl]-9-methyl-7,8,12-trioxaspiro[5.6]dodecane 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以83%的产率得到9-(4-Chloro-benzenesulfinylmethyl)-9-methyl-7,8,12-trioxa-spiro[5.6]dodecane
  参考文献：
  名称：

  Synthesis of 1,2,4-trioxepanes via application of thiol-olefin Co-oxygenation methodology

  摘要：

  Thiol-olefin co-oxygenation (TOCO) of substituted allylic alcohols generates beta-hydroxy peroxides that can be condensed in situ with various ketones, to afford a series of functionalised 1,2,4-trioxepanes in good yields. Manipulation of the phenylsulfenyl group in 8a-8c allows for convenient modification to the spiro-trioxepane substituents. Surprisingly, and in contrast to the 1,2,4-trioxanes examined, 1,2,4-trioxepanes are inactive as antimalarials up to 1000 nM and we rationalize this observation based on the inherent stability of these systems to ferrous mediated degradation. FMO calculations clearly show that the sigma* orbital of the peroxide moiety of 1,2,4-trioxane derivatives 4a and 14b are lower in energy and more accessible to attack by Fe(II) compared to their trioxepane analogues 8b and 9b.

  DOI：

  10.1016/j.bmcl.2006.08.098
• 作为产物：
  描述：

  4-(4'-chlorophenyl)-3-hydroperoxy-3-methylbutanol 、 环己酮 在 对甲苯磺酸 作用下， 以 乙腈 为溶剂， 生成 9-[(4-Chlorophenyl)sulfanylmethyl]-9-methyl-7,8,12-trioxaspiro[5.6]dodecane
  参考文献：
  名称：

  Synthesis of 1,2,4-trioxepanes via application of thiol-olefin Co-oxygenation methodology

  摘要：

  Thiol-olefin co-oxygenation (TOCO) of substituted allylic alcohols generates beta-hydroxy peroxides that can be condensed in situ with various ketones, to afford a series of functionalised 1,2,4-trioxepanes in good yields. Manipulation of the phenylsulfenyl group in 8a-8c allows for convenient modification to the spiro-trioxepane substituents. Surprisingly, and in contrast to the 1,2,4-trioxanes examined, 1,2,4-trioxepanes are inactive as antimalarials up to 1000 nM and we rationalize this observation based on the inherent stability of these systems to ferrous mediated degradation. FMO calculations clearly show that the sigma* orbital of the peroxide moiety of 1,2,4-trioxane derivatives 4a and 14b are lower in energy and more accessible to attack by Fe(II) compared to their trioxepane analogues 8b and 9b.

  DOI：

  10.1016/j.bmcl.2006.08.098

文献信息

• 1,2,4-Trioxanes and 1,2,4-trioxepanes
  申请人：O'Neill M. Paul

  公开号：US20050256184A1

  公开（公告）日：2005-11-17

  Novel substituted 1,2,4-trioxanes and 1,2,4-trioxepanes useful as anti-malarial and/or anticancer agents, and an improved method for their preparation, preferably involving a thiol-olefin co-oxygenation (TOCO) reaction between an allylic alcohol and a ketone.

  新型替代品1,2,4-三氧杂环戊烷和1,2,4-三氧杂环庚烷可用作抗疟疾和/或抗癌药物，并提供了一种改进的制备方法，最好涉及烯基醇和酮之间的硫醇-烯烃共氧化（TOCO）反应。