bicyclo<3.2.2>nonane-1,2-diol | 110977-44-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: bicyclo<3.2.2>nonane-1,2-diol
• 英文别名: 1,2-bicyclo[3.2.2]nonanediol；Bicyclo[3.2.2]nonane-1,2-diol
• CAS: 110977-44-1
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: OLSLAHICSVJRNQ-UHFFFAOYSA-N

物化性质

• 沸点：
  284.1±8.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bicyclo<3.2.2>nonane-1,2-diol 生成 (Z)-2-ethylidenebicyclo<3.2.2>non-1-yl mesylate
  参考文献：
  名称：

  Takeuchi, K.; Ohga, Y.; Kitagawa, T., Journal de Chimie Physique et de Physico-Chimie Biologique, 1992, vol. 89, # 7, p. 1631 - 1638

  摘要：

  DOI：
• 作为产物：
  描述：

  双环[2.2.2]辛烷-1-甲醇 在 氢氧化钾 、 2,6-二叔丁基-4-甲基吡啶 、 三氟甲磺酸 、 pyridinium chlorochromate 作用下， 以 甲醇 、 四氯化碳 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 bicyclo<3.2.2>nonane-1,2-diol
  参考文献：
  名称：

  Ring-Expansion of Bridgehead Aldehydes with 1-Adamantanecarbonyl Cation or Benzoyl Trifluoromethanesulfonate: A New Route to Bicyclic and Tricyclic 1,2-Diols

  摘要：

  在三氟甲磺酸存在下，桥头醛与由 1-金刚烷阳离子和一氧化碳生成的 1-金刚烷羰基阳离子或与三氟甲磺酸苯甲酰酯发生酰化反应，会使醛环扩张一个碳原子。将反应混合物加水处理后，可得到在邻接碳上含有酰氧基的桥头醇，皂化后可得到邻接二醇，总产率很高。例如，双环[2.2.1]庚烷-1-甲醛可生成双环[2.2.2]辛烷-1,2-二醇，而其他方法很难获得这种物质。

  DOI：

  10.1055/s-1987-28022

文献信息

• Evaluation of the π-conjugative effect of the 2-methylene and the 2-oxo substituent on the stability of carbocations in the solvolysis of bicyclic bridgehead derivatives
  作者：Ken'ichi Takeuchi、Fumio Akiyama、Keizo Ikai、Tadashi Shibata、Midori Kato

  DOI：10.1016/s0040-4039(00)82470-3

  日期：1988.1

  The incipient 2-methylenebicyclo[3.2.2]non-1-yl cation is stabilized by allylic conjugation by 4 kcal/mol compared with the more rigid 2-methylenebicyclo[2.2.2]oct-1-yl cation. In contrast to this, no appreciable stabilization due to carbonyl π-conjugation was detected in the 2-oxobicyclo[3.2.2]non-1-yl cation, indicating unimportance of π-conjugative stabilization in tertiary α-keto cations.

  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。
• Solvolysis of 2-Bicyclo[3.2.2]nonyl <i>p</i>-Toluenesulfonate. Evidence for the Formation of Classical Carbocation Intermediates
  作者：Takao Okazaki、Eiichi Terakawa、Toshikazu Kitagawa、Ken'ichi Takeuchi

  DOI：10.1021/jo9914061

  日期：2000.3.1

  2-bicyclo[3.2.2]nonyl cation is classical and that 10 is formed at a former ionization stage than 2-substituted bicyclo[3.2.2]nonane. The (13)C redistributions for both exo-2-substituted bicyclo[3.3.1]nonane and 11, which are yielded via 1,3-hydride shift, were similar to that of 2-substituted bicyclo[3.2.2]nonane, suggesting that 1,3-hydride shift occurs mainly at the solvent-separated ion pair.

  2-双环[3.2.2]壬基对甲苯磺酸盐（6-OTs）的溶剂分解速率几乎与2,2,2-三氟乙醇（TFE）中环庚基对甲苯磺酸盐的溶解速率相同。这表明6-OTs中的乙烯桥不会显着提高该速率，并且6-OTs在没有嵌合助剂的情况下电离。[1-（13）C] -2-双环[3.2.2]壬基对甲苯磺酸盐在甲醇或TFE中的溶剂分解得到2-取代的双环[3.2.2]壬烷，外-2-取代的双环[3.3.1] ]壬烷，2-双环[3.2.2]壬烯（10）和2-双环[3.3.1]壬烯（11），其（13）C标记的分布是通过定量（13）C NMR分析使用松弛剂。（13）C标签仅放置在两个位置，它们的比率不统一，并且10个标签中的标签混乱程度不及其他产品。这些结果表明2-双环[3.2.2]壬基阳离子是经典的，并且在2-取代的双环[3.2.2]壬烷之前的电离阶段形成了10。通过1，3-氢化物移位获得的exo-2-取代的双环[3.3
• Solvolysis of 2-methylene bicyclic bridgehead derivatives: a model for gradual variation of .pi.-conjugation in carbocations
  作者：Kenichi Takeuchi、Toshikazu Kitagawa、Yasushi Ohga、Masayasu Yoshida、Fumio Akiyama、Akio Tsugeno

  DOI：10.1021/jo00027a050

  日期：1992.1

  The rates of solvolysis in ethanol or 80% ethanol at 25-degrees-C have been determined on 2-methylenebicyclo[2.2.2]oct-1-yl triflate (4a), 2-methylenebicyclo[3.2.1]oct-1-yl triflate (5a), 2-methylenebicyclo[3.2.2]non-1-yl mesylate (6a), 2-methylenebicyclo[3.3.1]non-1-yl mesylate (7a-OMs) and heptafluorobutyrate (7a-OHFB), 1-chloro-2-methylenebicyclo[4.2.2]decane (8a), 2-methylenebicyclo[4.3.1]dec-1-yl trifluoroacetate (9a), and 4-methylene-3-homoadamantyl heptafluorobutyrate (10a) and on their corresponding parent 1-bicycloalkyl and 3-homoadamantyl derivatives 4b-10b containing the respective leaving group. The rate ratios for 4a/4b, 5a/5b, 10a/10b, 6a/6b, 7a/7b, 8a/8b, and 9a/9b are 10(-3.9), 10(-1.9), 10(-1.1), 10(0.8), 10(0.9) (for mesylate), 10(-0.2), and 10(0.7), respectively. A plot of the logarithms of the rate ratios against olefinic strain energies of their corresponding unsubstituted bridgehead olefins shows that the smaller the olefinic strain energy, the greater the rate ratio, providing a methodology to gradually change the conjugative ability of bridgehead carbocations. The enhancement of allylic conjugation with increasing skeletal flexibility has been further verified by the enhanced solvolysis rate of (E)-2-ethylidenebicyclo[3.2.2]non-1-yl mesylate ((E)-6e) relative to 6a by a factor of 259. A similar study on much more rigid (E)-2-ethylidenebicyclo[2.2.2]oct-1-yl triflate ((E)-4e) gave a (E)-4e/4a rate ratio of 6.3. AM1 semiempirical molecular orbital calculations on pertinent 2-methylene and (E)-2-ethylidene bridgehead carbocations and corresponding hydrocarbons (L = hydrogen) also supported the increase in the conjugation with increasing skeletal flexibility. The solvolysis products were solely bridgehead substitution products, no indication for the formation of bridgehead olefin via an S(N)1' mechanism having been obtained.
• 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：——