3,3-dimethyl-1-hydroxybicyclo[2.2.2]octan-2-one | 116760-06-6

• 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: 3,3-dimethyl-1-hydroxybicyclo[2.2.2]octan-2-one
• 英文别名: 1-Hydroxy-3,3-dimethylbicyclo[2.2.2]octan-2-one
• CAS: 116760-06-6
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: AUWSHPCMMFQELC-UHFFFAOYSA-N

物化性质

• 沸点：
  261.9±23.0 °C(Predicted)
• 密度：
  1.124±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,3-dimethyl-1-hydroxybicyclo[2.2.2]octan-2-one 在 2,6-二甲基吡啶 作用下， 反应 50.0h， 生成 bornan-10-oic acid methyl ester
  参考文献：
  名称：

  评估2-亚甲基和2-氧代取代基的π-共轭作用对双环桥头衍生物溶剂分解中碳正离子稳定性的影响

  摘要：

  与刚性较强的2-亚甲基双环[2.2.2]辛-1-基阳离子相比，初始的2-亚甲基双环[3.2.2]壬-1-基阳离子通过烯丙基结合稳定在4 kcal / mol。与此相反，在2-氧代双环[3.2.2]壬-1-基阳离子中未检测到由于羰基π-共轭引起的明显稳定，表明在叔α-酮基阳离子中π-共轭稳定的重要性不高。

  DOI：

  10.1016/s0040-4039(00)82470-3
• 作为产物：
  描述：

  1-hydroxy-3,3-dimethylbicyclo[2.2.2]oct-2-yl benzoate 在 甲醇 、 氢氧化钾 、 silver carbonate 、 Celite 作用下， 生成 3,3-dimethyl-1-hydroxybicyclo[2.2.2]octan-2-one
  参考文献：
  名称：

  评估2-亚甲基和2-氧代取代基的π-共轭作用对双环桥头衍生物溶剂分解中碳正离子稳定性的影响

  摘要：

  与刚性较强的2-亚甲基双环[2.2.2]辛-1-基阳离子相比，初始的2-亚甲基双环[3.2.2]壬-1-基阳离子通过烯丙基结合稳定在4 kcal / mol。与此相反，在2-氧代双环[3.2.2]壬-1-基阳离子中未检测到由于羰基π-共轭引起的明显稳定，表明在叔α-酮基阳离子中π-共轭稳定的重要性不高。

  DOI：

  10.1016/s0040-4039(00)82470-3

文献信息

• 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.
• TAKEUCHI, KENICHI;AKIYAMA, FUMIO;IKAI, KEIZO;SHIBATA, TADASHI;KATO, MIDOR+, TETRAHEDRON LETT., 29,(1988) N 8, 873-876
  作者：TAKEUCHI, KENICHI、AKIYAMA, FUMIO、IKAI, KEIZO、SHIBATA, TADASHI、KATO, MIDOR+

  DOI：——

  日期：——
• Solvolysis of 2-Thioxo Bicyclic Bridgehead Derivatives:  Evaluation of π-Conjugative Stabilization of α-Thiocarbonyl Carbocations
  作者：Kazuhiko Tokunaga、Takafumi Ohtsu、Yasushi Ohga、Ken'ichi Takeuchi

  DOI：10.1021/jo9719564

  日期：1998.4.1

  The ethanolysis rates of 3,3-dimethyl-2-thioxobicyclo[2.2.2]oct-1 triflate and 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl triflate relative to their corresponding parent compounds (3,3-dimethylbicyclo[2.2.2]oct-1-yl triflate and 3,3-dimethylbicyclo[3.2.2]non-1-yl triflate, respectively) at 25.0 degrees C increase from 10(-6.2) to 10(-2.5). The increase in the rate ratios with the flexibility of the ring system supports the applicability of the authors' methodology to change the conjugative ability of bridgehead carbocations. Formation of 3,3-dimethyl-1,2-epithio-2-ethoxybicyclo[3.2.2]nonane in the ethanolysis of 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl 2,2,2-trifluoroethanesulfonate indicates cyclization of the intermediate 3,3-dimethyl-2-thioxobicyclo[3.2.2]nonyl cation into an episulfide cation. Computational studies at the HF/6-31G* level indicate that the resonance interaction between the cationic center and the C=S pi system is greater in the 3,3-dimethyl-2-thioxobicyclo[3.2,2]nonyl cation than in the 3,3-dimethyl-2-thioxobicyclo[2.2.2]octyl cation.