N-(4-aminophenyl)-1,3,5,7-tetratert-butyl-2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene-4-carboxamide | 143948-91-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(4-aminophenyl)-1,3,5,7-tetratert-butyl-2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene-4-carboxamide
• CAS: 143948-91-8
• 化学式: C₂₉H₄₄N₂O₄
• 分子量: 484.679
• InChiKey: FCAQUQMGMSTDMX-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：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  82.8
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  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 、 N-(4-aminophenyl)-1,3,5,7-tetratert-butyl-2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene-4-carboxamide 生成 N,N'-(1,4-phenylene)bis(1,3,5,7-tetra-tert-butyl-2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene-4-carboxamide)
  参考文献：
  名称：

  一种新颖且方便的方法来官能化2,6,9-三氧杂双环[3.3.1] nona-3,7-二烯（桥连双二恶英）。

  摘要：

  描述了通过二新戊酰基烯酮二聚体1与芳族胺反应合成N-芳基-2,6,9-三氧杂双环[3.3.1] nona-3,7-二烯-4-羧酰胺2。双-衍生物5，6 RESP。由1和芳族二胺形成。N-苯基羧酰胺2a的结构通过X射线晶体学证明，这些化合物（例如2b）的手性通过NMR研究确定。还讨论了异常转化1 → 2的合理反应途径。

  DOI：

  10.1016/s0040-4039(00)61310-2
• 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 、 对苯二胺 以 二氯甲烷 为溶剂， 反应 1.0h， 以78%的产率得到N-(4-aminophenyl)-1,3,5,7-tetratert-butyl-2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene-4-carboxamide
  参考文献：
  名称：

  一种新颖且方便的方法来官能化2,6,9-三氧杂双环[3.3.1] nona-3,7-二烯（桥连双二恶英）。

  摘要：

  描述了通过二新戊酰基烯酮二聚体1与芳族胺反应合成N-芳基-2,6,9-三氧杂双环[3.3.1] nona-3,7-二烯-4-羧酰胺2。双-衍生物5，6 RESP。由1和芳族二胺形成。N-苯基羧酰胺2a的结构通过X射线晶体学证明，这些化合物（例如2b）的手性通过NMR研究确定。还讨论了异常转化1 → 2的合理反应途径。

  DOI：

  10.1016/s0040-4039(00)61310-2

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.
• A novel and convenient approach to functionalized 2,6,9-trioxabicyclo[3.3.1]nona-3,7-dienes (bridged bis-dioxines).
  作者：C.Oliver Kappe、Gereld Färber、Curt Wentrup、Gert Kollenz

  DOI：10.1016/s0040-4039(00)61310-2

  日期：1992.8

  The synthesis of N-aryl-2,6,9-trioxabicyclo[3.3.1]nona-3,7-diene-4-carboxamides 2 by reaction of dipivaloylketene-dimer 1 with aromatic amines is described. Bis-derivatives 5, 6 resp. are formed from 1 and aromatic diamines. The structure of N-phenylcarboxamide 2a was proved by X-ray crystallography, the chirality of these compounds (e.g. 2b) established by NMR studies. A reasonable reaction pathway

  描述了通过二新戊酰基烯酮二聚体1与芳族胺反应合成N-芳基-2,6,9-三氧杂双环[3.3.1] nona-3,7-二烯-4-羧酰胺2。双-衍生物5，6 RESP。由1和芳族二胺形成。N-苯基羧酰胺2a的结构通过X射线晶体学证明，这些化合物（例如2b）的手性通过NMR研究确定。还讨论了异常转化1 → 2的合理反应途径。