N-(benzyldipivaloyl)acetamide | 149381-89-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N-(benzyldipivaloyl)acetamide
• 英文别名: N-benzyl-2-(2,2-dimethylpropanoyl)-4,4-dimethyl-3-oxopentanamide
• CAS: 149381-89-5
• 化学式: C₁₉H₂₇NO₃
• 分子量: 317.428
• InChiKey: RDRVYCFHDRNDLF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  63.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  6-tert-butyl-2-(dipivaloylmethylene)-5-pivaloyl-1,3-dioxin-4(2H)-one 以 乙腈 为溶剂， 反应 1.5h， 生成 N-(benzyldipivaloyl)acetamide
  参考文献：
  名称：

  意外稳定的 α-Oxoketene-Pyridine 两性离子，2,2-双（叔丁基羰基）-1-[4-（二甲氨基）吡啶并]ethen-1-olate 的制备和化学

  摘要：

  在乙腈中用 4-(二甲氨基)吡啶 (DMAP) 处理二戊酰基乙烯酮 1 及其二聚体 2 和 3 得到 α-氧代烯酮-吡啶两性离子 4，为淡黄色固体。这是从真正的 alpha-oxoketene 获得的稳定两性离子的第一个例子。在室温下的无水溶液中，化合物 4 大部分裂解为反应物 1 和 DMAP。在 -60 摄氏度，平衡完全向两性离子 4 移动，如 C-13 NMR 测量所示。使用密度泛函理论 (B3LYP/6-311+G**) 的计算与 4 的形成和相对稳定性非常吻合。 N-15 标记实验表明 DMAP 的环氮原子参与生成新的两性离子 CN键。

  DOI：

  10.1002/1099-0690(200104)2001:7<1315::aid-ejoc1315>3.0.co;2-2

文献信息

• 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。
• 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：——