endo-6-Carbomethoxybicyclo<2.2.1>heptan-2-one | 70680-88-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: endo-6-Carbomethoxybicyclo<2.2.1>heptan-2-one
• 英文别名: endo-2-carbomethoxybicyclo[2.2.1]heptan-2-one；methyl 6-oxonorbornane-2-endo-carboxylate；Norbornanon-(6)-carbonsaeure-(2endo)；methyl (1S,2R,4R)-6-oxobicyclo[2.2.1]heptane-2-carboxylate
• CAS: 70680-88-5
• 化学式: C₉H₁₂O₃
• 分子量: 168.192
• InChiKey: XHNOTHJTHRGVSI-DSYKOEDSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  endo-6-Carbomethoxybicyclo<2.2.1>heptan-2-one 在 盐酸 、 氯化铵 作用下， 以 甲醇 、 水 为溶剂， 反应 20.0h， 生成 (1S,3R,6S,7R)-5-oxo-4-azatricyclo[4.2.1.03,7]nonane-3-carboxylic acid
  参考文献：
  名称：

  Strecker 合成和 Bucherer - Bergs 反应的一些立体化学方面

  摘要：

  Strecker 和 Bucherer-Bergs 反应均将降冰片烷酮酯甲酯双环[2.2.1]hept-6-one-2-endo-carboxylate 转化为内酰胺 6-endo-aminobicyclo[2.2.1]heptane-2-endo-carboxylate羧酸-γ-内酰胺-6-外-羧酸。这种内酰胺异常稳定，不能水解成相应的氨基酸。Strecker 反应中的立体化学（其中氨基为内基）与文献先例所预期的相反。Bucherer-Bergs 反应中的立体化学，其中氨基也是 endo，已通过中间体螺乙内酰脲 (±)-bicyclo[2.2.1]heptane-2-endo-carboxy acid- 的 X 射线晶体学分析得到证实。 6-螺-5'-乙内酰脲。

  DOI：

  10.1071/ch03202
• 作为产物：
  描述：

  5-norbornene-2-carboxylic acid 在 sodium hydroxide 、 溴 、 碳酸氢钠 作用下， 以 甲醇 、 水 为溶剂， 反应 3.5h， 生成 endo-6-Carbomethoxybicyclo<2.2.1>heptan-2-one
  参考文献：
  名称：

  Monoamine oxidase-catalyzed oxidation of endo,endo -2-amino-6-[( Z )-2′-phenyl]ethenylbicyclo[2.2.1]heptane, a potential probe for a radical cation intermediate

  摘要：

  An 11-step synthesis of endo,endo-2-amino-6-[(E)-2'-phenyl]ethenylbicyclo[2.2.1]heptane (6) and the corresponding (Z)-isomer (7) was carried out in an attempt to make a compound that could trap the purported amine radical cation intermediate during monoamine oxidase (MAO)-catalyzed oxidation of amines. The E-isomer was not a substrate for MAO, and the Z-isomer was a very poor substrate. No trapping product was observed. Possible explanations for the inability of these compounds to trap a potential radical cation intermediate are discussed. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(00)00094-8

文献信息

• Photochemistry of alkyl halides. 8. Formation of a bridgehead alkene
  作者：Paul J. Kropp、Paul R. Worsham、Robert I. Davidson、Tappey H. Jones

  DOI：10.1021/ja00378a033

  日期：1982.7
• Chemical Consequences of Long-Range Orbital Interactions in Norbornane-Based 1,4-Diol Monosulfonate Esters
  作者：Petrus M. F. M. Bastiaansen、Joannes B. P. A. Wijnberg、Aede de Groot

  DOI：10.1021/jo00118a046

  日期：1995.6

  Seven monotosylated 1,4-diols with the rigid norbornane skeleton were treated with a strong base in refluxing benzene to find out whether these compounds react by initial heterolysis of the tosylate ester bond induced by long-range orbital interactions. The tosylates 1-7 were designed to investigate the influence of the sigma-relay (U-, sickle-, or W-shaped) between the donor and acceptor end of the system, to check whether primary carbocationic ion pairs could act as intermediates, and to study conformational influences on reactivity and product formation. Tosylate 1 with a U-like arrangement of the sigma-relay reacted relatively slowly and followed reaction pathways in which no long-range orbital interactions are involved. The reaction outcome of tosylate 2 which possesses a sickle-like arrangement of the sigma-relay indicates two competitive processes with and without the involvement of long-range orbital interactions. The secondary tosylates 3, 6, and 7 which all possess a W-like arrangement reacted relatively fast and showed predominantly homofragmentation. Although an ideal W-like arrangement is present in the primary tosylates 4 and 5, no reactions in which long-range orbital interactions are involved were observed. The tosylates 6 and 7 in which the tosylate group is conformationally mobile can give rise to mixtures of products. The ratio in which these products are formed can be rationalized by using the Curtin-Hammett principle.
• Beckmann,S. et al., Chemische Berichte, 1969, vol. 102, p. 815 - 819
  作者：Beckmann,S. et al.

  DOI：——

  日期：——
• NAKAZAKI M.; NAEMURA K.; KONDO Y., J. ORG. CHEM. <JOCE-AH>, 1976, 41, NO 7, 1229-1233
  作者：NAKAZAKI M.、 NAEMURA K.、 KONDO Y.

  DOI：——

  日期：——