1,3,5,7-Tetra-tert-butyl-2,6,9-trioxabicyclo<3.3.1>nona-3,7-diene-4,8-dicarboxylic acid diethyl ester | 169213-39-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,3,5,7-Tetra-tert-butyl-2,6,9-trioxabicyclo<3.3.1>nona-3,7-diene-4,8-dicarboxylic acid diethyl ester
• 英文别名: Diethyl 1,3,5,7-tetratert-butyl-2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene-4,8-dicarboxylate
• CAS: 169213-39-2
• 化学式: C₂₈H₄₆O₇
• 分子量: 494.669
• InChiKey: ACGVLRHQSNEIGM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  35
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1,3,5,7-Tetra-tert-butyl-2,6,9-trioxabicyclo<3.3.1>nona-3,7-diene-4,8-dicarboxylic acid diethyl ester 在 氢气 作用下， 以 水 为溶剂， 以80%的产率得到1,3,5,7-Tetra-tert-butyl-2,4,6,8-tetraoxa-tricyclo[3.3.1.1^3,7]decane-9,10-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  A convenient de novo synthesis of functionalised 2,4,6,8-tetraoxaadamantanes

  摘要：

  通过在稳定的 α-oxoketene 1 上添加亲核剂，可轻松获得三氧杂双环己二烯 2 和 4，并通过酸催化水解作用，高产率地将其转化为相应的 2,4,6,8-四氧杂金刚烷 3 和 5。

  DOI：

  10.1039/c39950000797
• 作为产物：
  描述：

  2-[2,6-Di-tert-butyl-5-(2,2-dimethyl-propionyl)-4-oxo-4H-[1,3]dioxin-2-yl]-4,4-dimethyl-pent-1-ene-1,3-dione 在 氯化亚砜 、 对甲苯磺酸 作用下， 生成 1,3,5,7-Tetra-tert-butyl-2,6,9-trioxabicyclo<3.3.1>nona-3,7-diene-4,8-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  A convenient de novo synthesis of functionalised 2,4,6,8-tetraoxaadamantanes

  摘要：

  通过在稳定的 α-oxoketene 1 上添加亲核剂，可轻松获得三氧杂双环己二烯 2 和 4，并通过酸催化水解作用，高产率地将其转化为相应的 2,4,6,8-四氧杂金刚烷 3 和 5。

  DOI：

  10.1039/c39950000797

文献信息

• Reactions of dipivaloylketene dimer with nucleophiles: new access to the 2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene ring system (bridged bis-dioxines)
  作者：C. Oliver Kappe、Gert Kollenz、Walter M. F. Fabian、Curt Wentrup、Gerald Faerber

  DOI：10.1021/jo00064a024

  日期：1993.6

  Novel and convenient methods to prepare several functionalized 2,6,9-trioxabicyclo[3.3.1]nonadienes (''bridged bis-dioxines'') 6, 10, 11, and 12 are described. In general, these are obtained by addition of nucleophiles to alpha-oxoketene 5 in a multistep reaction sequence, where the specific reaction pathway depends strongly on the type of nucleophile employed: Aromatic amines with electron-donating substituents afford the trioxabicyclononadienes 6, while with aliphatic amines or thiolates, 2 equiv of the corresponding dipivaloylacetamides 13 or thioesters 14, respectively, are formed. In the case of OH nucleophiles, the primary 1:1 adducts 8 are isolable, characterized by an X-ray analysis of 8a. Under acidic conditions, 8 can be cyclized to the bifunctionalized bis-dioxines 10. The bis-carboxylic acid 10c serves as a valuable intermediate to synthesize other derivatives, e.g. the bis-acid chloride 11 and the bis-ester 12. Mechanistic pathways leading to the various reaction products are discussed in detail and supported by semiempirical molecular orbital calculations using the AM1 method. The spontaneous formation of the bis-dioxine skeleton in the reaction 5 --> 6 is likely to proceed via an unusual [4 + 4] type tandem cyclization reaction.
• Kappe C. Oliver, Kollenz Gert, Fabian Walter M. F., Wentrup Curt, Faerber+, J. Org. Chem., 58 (1993) N 12, S 3361- 3367
  作者：Kappe C. Oliver, Kollenz Gert, Fabian Walter M. F., Wentrup Curt, Faerber+

  DOI：——

  日期：——
• A convenient de novo synthesis of functionalised 2,4,6,8-tetraoxaadamantanes
  作者：Werner Heilmayer、Turkaram S. Dalvi、C. Oliver Kappe、Curt Wentrup、Karl Gruber、Heinz Sterk、Gert Kollenz

  DOI：10.1039/c39950000797

  日期：——

  Trioxabicyclononadienes 2 and 4, easily obtained by addition of nucleophiles to the stable α-oxoketene 1, are transformed into the corresponding 2,4,6,8-tetraoxaadamantanes 3 and 5 in high yields by acid-catalysed hydrolysis.

  通过在稳定的 α-oxoketene 1 上添加亲核剂，可轻松获得三氧杂双环己二烯 2 和 4，并通过酸催化水解作用，高产率地将其转化为相应的 2,4,6,8-四氧杂金刚烷 3 和 5。