9-Methyl-7,8,12-trioxa-spiro[5.6]dodecane-9-carbaldehyde | 918902-01-9

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: 9-Methyl-7,8,12-trioxa-spiro[5.6]dodecane-9-carbaldehyde
• 英文别名: 9-Methyl-7,8,12-trioxaspiro[5.6]dodecane-9-carbaldehyde；9-methyl-7,8,12-trioxaspiro[5.6]dodecane-9-carbaldehyde
• CAS: 918902-01-9
• 化学式: C₁₁H₁₈O₄
• 分子量: 214.262
• InChiKey: MKBJSYZFTGXSJB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  9-Methyl-7,8,12-trioxa-spiro[5.6]dodecane-9-carbaldehyde 、 甲氧羰基亚甲基三苯基正膦 以 二氯甲烷 为溶剂， 反应 3.0h， 以62%的产率得到(E)-3-(9-Methyl-7,8,12-trioxa-spiro[5.6]dodec-9-yl)-acrylic acid methyl ester
  参考文献：
  名称：

  1,2,4-Trioxanes and 1,2,4-trioxepanes

  摘要：

  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。

  公开号：

  US20050256184A1
• 作为产物：
  描述：

  9-[(4-Chlorophenyl)sulfanylmethyl]-9-methyl-7,8,12-trioxaspiro[5.6]dodecane 在 2,6-二甲基吡啶 、 间氯过氧苯甲酸 、 三氟乙酸酐 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 6.0h， 生成 9-Methyl-7,8,12-trioxa-spiro[5.6]dodecane-9-carbaldehyde
  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。
• Synthesis of 1,2,4-trioxepanes via application of thiol-olefin Co-oxygenation methodology
  作者：Richard Amewu、Andrew V. Stachulski、Neil G. Berry、Stephen A. Ward、Jill Davies、Gael Labat、Jean-Francois Rossignol、Paul M. O’Neill

  DOI：10.1016/j.bmcl.2006.08.098

  日期：2006.12

  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.