5-methoxycarbonylbicyclo<3.1.1>heptane-1-carboxylic acid | 110371-28-3

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 5-methoxycarbonylbicyclo<3.1.1>heptane-1-carboxylic acid
• 英文别名: 5-carbomethoxybicyclo<3.1.1>heptane-1-carboxylic acid；bicyclo[3.1.1]heptane-1,5-dicarboxylic acid monomethyl ester；5-(Methoxycarbonyl)bicyclo[3.1.1]heptane-1-carboxylic acid；5-methoxycarbonylbicyclo[3.1.1]heptane-1-carboxylic acid
• CAS: 110371-28-3
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: XBHAKHGDPDKVAY-UHFFFAOYSA-N

物化性质

• 熔点：
  76.5-78 °C
• 沸点：
  305.7±35.0 °C(Predicted)
• 密度：
  1.370±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-methoxycarbonylbicyclo<3.1.1>heptane-1-carboxylic acid 在 4-二甲氨基吡啶 、 氯化亚砜 、 2-碘-1,1,1-三氟乙烷 、 2-mercaptopyridine-1-oxide sodium salt 作用下， 以 苯 为溶剂， 反应 3.0h， 生成 methyl 5-iodobicyclo<3.1.1>heptane-1-carboxylate
  参考文献：
  名称：

  Synthesis of bridgehead fluorides by fluorodeiodination

  摘要：

  Fluorodeiodination is found to be an attractive procedure for the synthesis of bridgehead fluorides. Thus, treatment of the corresponding iodide with xenon difluoride in dichloromethane at ambient temperature generally leads to high yields of the fluoride. Evidence suggests the intermediacy of the bridgehead cation in this reaction, and accordingly the substrates which are unfavorably disposed to fluorodeiodination are the bicyclo[n.1.1]alkyl iodides. In this context the isolation of a small quantity of methyl 4-fluorobicyclo[2.1.1]hexane-1-carboxylate (46, R = COOMe) is significant because it represents the first occasion on which the elusive 1-bicyclo[2.1.1]hexyl cation has been trapped. We have also demonstrated that synthesis of the iodides themselves can be accomplished efficiently both by Barton halodecarboxylation and by treatment of the carboxylic acid with lead tetraacetate and iodine.

  DOI：

  10.1021/jo00036a018
• 作为产物：
  描述：

  二环己基[3.1.1]庚烷-1,5-二羧酸二甲酯 在 barium dihydroxide 、 水 、 盐酸 作用下， 以 甲醇 、 水 、 正戊烷 为溶剂， 以66%的产率得到5-methoxycarbonylbicyclo<3.1.1>heptane-1-carboxylic acid
  参考文献：
  名称：

  WO2008/75196

  摘要：

  公开号：

文献信息

• Bridgehead Carbocations: Solvolysis of a Series of 5-Substituted Bicycle [3.1.1]heptyl Bromides. Nucleophilic Solvent Assistance to Ionization of 1-Bromobicyclo[3.1.1]heptane
  作者：EW Della、GM Elsey

  DOI：10.1071/ch9950967

  日期：——

  The synthesis of a range of 5-substituted bicyclo [3.1.1] heptyl bromides for solvolytic studies is described. It is found that the substituent has a profound effect on the rate of solvolysis of the system and acts principally in accordance with the magnitude of its inductive/field constant σI. The most spectacular example of the effect of the substituent is provided by the COOMe group which leads to a retardation in the rate of methanolysis by a factor of 6.5°105. While a linear relationship in the plot of log k and σI is generally obeyed, as expected for a mechanism mediated by the bicyclo [3.1.1] heptyl bridgehead cation, two of the bromides, 1-bromobicyclo[3.1.1] heptane and its 5-methoxy derivative, show deviant behaviour and react more rapidly than predicted on the basis of the Hammett plot. Evidence is presented to show that the enhanced rate of the parent is the result of nucleophilic assistance by the solvent. Anchimeric assistance in the solvolysis of 5-methoxybicyclo[3.1.1] heptyl bromide is attributed to the powerful p-donor property of the methoxy substituent which stabilizes the transition state in a unique concerted ring-opening and ionization step.

  本文介绍了一系列 5 取代双环 [3.1.1] 庚基溴化物的合成方法，用于溶解研究。研究发现，取代基对体系的溶解速率有着深远的影响，其作用主要取决于其感应/场常数 σI 的大小。取代基影响最明显的例子是 COOMe 基团，它导致甲烷分解速率减慢 6.5°105 倍。虽然 log k 与 σI 的关系图一般符合由双环[3.1.1]庚桥头阳离子介导的机制的预期，但其中两种溴化物、1-溴双环[3.1.1]庚烷及其 5-甲氧基衍生物表现出偏离行为，其反应速度比根据 Hammett 图预测的要快。有证据表明，母体反应速率的提高是溶剂亲核作用的结果。 在 5-甲氧基双环[3.1.1]庚基溴的溶解过程中出现的嵌合体辅助作用归因于甲氧基取代基强大的对供体特性，它在独特的协同开环和电离步骤中稳定了过渡态。
• BENZIMIDAZOLE DERIVATIVES
  申请人：Munchhof Michael John

  公开号：US20100029615A1

  公开（公告）日：2010-02-04

  The present invention relates to a compound of the formula (I) or a pharmaceutically acceptable salt thereof, wherein R 1, R 2 , R 3 , R 4 , R 5 , A, X, n, and are as defined herein. Such novel benzamidazole derivatives are useful in trv treatment of abnormal cell growth, such as cancer, in mammals. This invention ate relates to a method of using such compounds in the treatment of abnormal cell growth in mammals, especially humans, and to pharmaceutical compositions containing sue compounds.

  本发明涉及式(I)的化合物或其药学上可接受的盐，其中R1、R2、R3、R4、R5、A、X、n和如此定义的。这些新型苯并咪唑衍生物在哺乳动物中治疗异常细胞生长，如癌症方面具有用途。本发明还涉及使用这些化合物治疗哺乳动物，特别是人类的异常细胞生长的方法，以及含有这些化合物的制药组合物。
• Della, Ernest W.; Tsanaktsidis, John, Australian Journal of Chemistry, 1986, vol. 39, p. 2061 - 2066
  作者：Della, Ernest W.、Tsanaktsidis, John

  DOI：——

  日期：——
• Della, Ernest W.; Tsanaktsidis, John, Australian Journal of Chemistry, 1989, vol. 42, # 1, p. 61 - 69
  作者：Della, Ernest W.、Tsanaktsidis, John

  DOI：——

  日期：——
• Reaction pathways of 3-(3'-methylenecyclobutyl)propyl and 2-(3'-methylenecyclobutyl)ethyl radicals
  作者：Paul E. Pigou

  DOI：10.1021/jo00281a043

  日期：1989.9