ethyl bicyclo[2.2.2]octane-1-carboxylate | 31818-12-9

• 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: ethyl bicyclo[2.2.2]octane-1-carboxylate
• 英文别名: bicyclo[2.2.2]octane-1-carboxylic acid ethyl ester；Bicyclo[2.2.2]octan-1-carbonsaeure-aethylester
• CAS: 31818-12-9
• 化学式: C₁₁H₁₈O₂
• mdl: MFCD00829792
• 分子量: 182.263
• InChiKey: JHFICTMLQKMABC-UHFFFAOYSA-N

物化性质

• 沸点：
  75-76 °C(Press: 3 Torr)
• 密度：
  1.060±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.909
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl bicyclo[2.2.2]octane-1-carboxylate 在 氢氧化钾 作用下， 生成 双环[2.2.2]辛烷-1-甲酸甲酯
  参考文献：
  名称：

  Preparation of 4-substituted 1-methoxycarbonylbicyclo[2.2.2]octanes, 4-substituted 1-phenylbicyclo[2.2.2]octanes, 4-substituted 1-p-nitrophenylbicyclo[2.2.2]octanes and 1,4-disubstituted bicyclo[2.2.2]octanes

  摘要：

  DOI：

  10.1021/jo00829a010
• 作为产物：
  描述：

  ethyl 1,3-cyclohexadiene-1-carboxylate 在 吡啶 、 palladium on activated charcoal 、 氢气 、 lead(IV) tetraacetate 、 potassium carbonate 作用下， 以 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 12.0h， 生成 ethyl bicyclo[2.2.2]octane-1-carboxylate
  参考文献：
  名称：

  由鼠标嗅觉受体OR-I7碳链形状选择性†

  摘要：

  啮齿动物OR-I7是被脂族醛例如辛烷醛活化的嗅觉受体的例子。短于庚烷的正常链烷烃结合OR-1而不激活它，因此在体外起拮抗剂作用。我们报告了一系列醛，这些醛旨在探测对于太短的脂肪族配体链的结构要求，以致不能满足受体激活的最小约6.9Å长度的要求。使用异源细胞中表达的重组小鼠OR-I7进行的实验表明，在短醛拮抗剂的情况下，OR-I7更喜欢结合无分支的脂肪链，尽管允许碳3上有一个甲基。受体可以容纳出乎意料的大量碳（例如只要碳是构象约束环系统的一部分，则碳原子数为10）。与新拮抗剂对接的基于视紫红质的小鼠OR-I7同源模型表明，烷基链上的小烷基分支在空间上干扰结合位点上的疏水残基，但是当将碳原子绑回到紧凑的环系统中时，可以容纳分支碳原子像金刚烷基和双环[2.2.2]辛基系统。

  DOI：

  10.1039/c8ob00205c

文献信息

• Synthese und Reaktionen 1-substituierter Bicyclo-[2,2,2]-octane. Untersuchungen in der Bicyclo-[2,2,2]-octan-Reihe, 2. Mitteilung
  作者：C. A. Grob、M. Ohta、E. Renk、A. Weiss

  DOI：10.1002/hlca.19580410504

  日期：——

  Known procedures for the synthesis of the bridgehead-substituted bicyclo-[2,2,2]-octanes Ia, b, c, d and f have been modified and improved.

  桥头取代的双环[2,2,2]-辛烷Ia，b，c，d和f的合成方法已得到改进和改进。
• Abnormal Benzo Substituent Effect on Free Radical Formation Process. A Local Symmetry Effect
  作者：Iwao Tabushi、Zen-ichi Yoshida、Yasuhiro Aoyama

  DOI：10.1246/bcsj.47.3079

  日期：1974.12

  (9), 1-benzobicyclo[2.2.2]-octenyl (10), 1-dibenzobicyclo[2.2.2]octadienyl (11), and 1-tribenzobicyclo[2.2.2]octatrienyl(12) radicals were obtained by means of the relative rates of the free radical bromine abstraction from the corresponding bridgehead bromides by a silyl radical. It was found that 9 and 12 were more stable than expected. The observed order of stability 9>10>12>11 can not be explained

  1-双环[2.2.2]辛基(9)、1-苯并双环[2.2.2]-辛烯基(10)、1-二苯并双环[2.2.2]辛二烯基(11)和1-三苯并双环[2.2]的相对稳定性。 2]辛三烯基(12)自由基是通过甲硅烷基从相应桥头溴化物中提取自由基溴的相对速率获得的。发现9和12比预期的更稳定。观察到的稳定性顺序 9>10>12>11 不能仅用通常的概念来解释。9 或 12 的额外稳定（或 10 或 11 的不稳定）被解释为这些自由基的局部对称性（或局部不对称性）。
• Decomposition of bicyclo[2.2.2]-1-formyl and pivaloyl peroxides
  作者：J. E. Leffler、A. A. More

  DOI：10.1021/ja00762a048

  日期：1972.4
• Solvolyses of 2-Oxo Bridgehead Compounds:  A Critical Examination of π-Conjugative Stabilization of α-Carbonyl Carbocations
  作者：Ken'ichi Takeuchi、Yasushi Ohga、Masayasu Yoshida、Keizo Ikai、Tadashi Shibata、Midori Kato、Akio Tsugeno

  DOI：10.1021/jo970454n

  日期：1997.8.1

  The methodology of changing ring flexibility to detect the pi-conjugative stabilization of bridgehead carbocations has been applied to eight 2-oxo (X = O) bridgehead carbocations. On the basis of the solvolytic behavior observed in kinetics and product analyses, the eight 2-oxo bridgehead substrates were classified into three categories: three substrates solvolyzing without ion-pair return that leads to primary isomers (class A), three substrates that form primary isomers by ion-pair return during solvolysis (class B), and two substrates that undergo solvent addition to the carbonyl group to form hemiacetals during solvolysis (class C). It was concluded that the substrates of class C could not be used for the present purpose. Essentially constant ethanolysis rate ratios, k(X = O)/k(X = H-2), of 10(-8.2)-10(-8.7) at 25 degrees C were obtained between four 2-oxo substrates in classes A and B and the corresponding parent unsubstituted ones. The result was interpreted to suggest that the pi-conjugative stabilization of tertiary alpha-carbonyl carbocations is negligibly small, if present. Slightly more negative k(X = O)/k(X = H-2) values of 10(-9.7) and 10(-9.2) for highly flexible bicyclo[4.2.2]dec-1-yl and bicyclo[4.3.1]dec-l-yl systems, respectively, were attributed to complex conformations in the ground and incipient carbocations. PM3 calculations on some 2-methylene and 2-oxo bridgehead carbocations supported the experimental results. Comparison of the solvolysis rates of 1,1,3,3-tetramethyl-2-oxobutyl mesylate with those of 1,1,3,3-tetramethylbutyl mesylate estimated from the rates of the corresponding chloride also failed to support the pi-conjugative stabilization of alpha-carbonyl carbocations.
• Photochemical and mass spectral behavior of bridgehead acetone derivatives
  作者：R. R. Sauers、M. Gorodetsky、J. A. Whittle、C. K. Hu

  DOI：10.1021/ja00750a035

  日期：1971.10