2,2,2-Trifluoroethyl bicyclo<3.3.1>non-2-ene-7-carboxylate | 144434-96-8

• 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: 2,2,2-Trifluoroethyl bicyclo<3.3.1>non-2-ene-7-carboxylate
• 英文别名: 2,2,2-Trifluoroethyl bicyclo[3.3.1]non-6-ene-3-carboxylate
• CAS: 144434-96-8
• 化学式: C₁₂H₁₅F₃O₂
• 分子量: 248.245
• InChiKey: UFDBSLLCZYTQCJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  4^a-hydroxyadamantan-2-one 在 吡啶 、 2,6-二甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 3.7h， 生成 2,2,2-Trifluoroethyl bicyclo<3.3.1>non-2-ene-7-carboxylate
  参考文献：
  名称：

  Solvolyses of 4-Oxo-2eq- and -2ax-adamantyl Triflates: Significant Through-Bond Interaction of the .beta.-Carbonyl Lone Pair with the Cationic p Orbital in Equatorial Solvolyses

  摘要：

  The rates of solvolysis in ethanol, methanol, 2,2,2-trifluoroethanol (TFE), and aqueous ethanols at 25 degrees C have been determined for 4-oxo-2(eq)- and -2(ax)-adamantyl trifluoromethanesulfonates (triflates) (1(eq)-OTF and 1(ax)-OTf, respectively). 1(eq)-OTf solvolyzed faster than 1(ax)-OTf by a factor of 15-24 in the solvents examined, supporting the idea of through-bond stabilization of the transition state in the ionization of 1(eq)-OTf. In trifluoroethanolysis, both 1(eq)-OTf and 1(ax)-OTf gave the equatorial substitution products 1(eq)-OTFE and 3-OTFE (by fragmentation) as major products, indicating that through-bond interaction is at work not only in the ionization step but also in the product-forming step. On the other hand, in methanolysis, both triflates afforded the corresponding inverted methyl ethers as major product. The intervention of a nucleophilically solvated ion pair intermediate has been suggested.

  DOI：

  10.1021/jo00100a059

文献信息

• Through-Bond Interaction in the Trifluoroethanolysis of 4-Oxo-2_eq-adamantyl Triflate and Its Essential Vanishing in the Corresponding 2-Phenyl Substituted Trifluoroacetate
  作者：Masayasu Yoshida、Koichi Mitsuhashi、Tsutomu Kimura、Ken’ichi Takeuchi、Emiko Fukuyo、Kazunori Yanagi

  DOI：10.1246/cl.1992.1771

  日期：1992.9

  Attachment of an oxo substituent on the 4-position of 2-adamantyl triflate alters the rate of trifluoroethanolysis at 25 °C by respective factors of 10−1.1 and 10−2.5 for 2eq- and 2ax-triflates, and 10−2.9 and 10−2.5 for the corresponding 2-phenyl-2eq- and -2ax-adamantyl trifluoroacetates, indicating the presence of through-bond interaction in the secondary equatorial and its essential vanishing in the 2-phenyl system. Product distributions agree with this notion.

  在 2-金刚烷基三氟甲磺酸酯的 4 位上连接氧代取代基可改变 25 °C 下三氟乙醇分解的速率，对于 2eq- 和 2ax-三氟甲磺酸酯，分别改变 10−1.1 和 10−2.5 因子，以及 10−2.9 和 10− 2.5对于相应的2-苯基-2eq-和-2ax-金刚烷基三氟乙酸酯，表明在次级赤道中存在通过键相互作用，并且其在2-苯基系统中基本消失。产品分布符合这一概念。
• Solvolyses of 4-Oxo-2eq- and -2ax-adamantyl Triflates: Significant Through-Bond Interaction of the .beta.-Carbonyl Lone Pair with the Cationic p Orbital in Equatorial Solvolyses
  作者：Ken'ichi Takeuchi、Masayasu Yoshida、Yumiko Kurihara、Tomomi Kinoshita、Toshikazu Kitagawa

  DOI：10.1021/jo00100a059

  日期：1994.10

  The rates of solvolysis in ethanol, methanol, 2,2,2-trifluoroethanol (TFE), and aqueous ethanols at 25 degrees C have been determined for 4-oxo-2(eq)- and -2(ax)-adamantyl trifluoromethanesulfonates (triflates) (1(eq)-OTF and 1(ax)-OTf, respectively). 1(eq)-OTf solvolyzed faster than 1(ax)-OTf by a factor of 15-24 in the solvents examined, supporting the idea of through-bond stabilization of the transition state in the ionization of 1(eq)-OTf. In trifluoroethanolysis, both 1(eq)-OTf and 1(ax)-OTf gave the equatorial substitution products 1(eq)-OTFE and 3-OTFE (by fragmentation) as major products, indicating that through-bond interaction is at work not only in the ionization step but also in the product-forming step. On the other hand, in methanolysis, both triflates afforded the corresponding inverted methyl ethers as major product. The intervention of a nucleophilically solvated ion pair intermediate has been suggested.