bicyclo<3.2.1>oct-1-yl triflate | 137494-90-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: bicyclo<3.2.1>oct-1-yl triflate
• 英文别名: 1-Bicyclo[3.2.1]octanyl trifluoromethanesulfonate；1-bicyclo[3.2.1]octanyl trifluoromethanesulfonate
• CAS: 137494-90-7
• 化学式: C₉H₁₃F₃O₃S
• 分子量: 258.262
• InChiKey: VPYANTPNMRGDGN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  双环[3.2.1]辛烷-1-羧酸 在 吡啶 、 硫酸 、 双氧水 作用下， 以 二氯甲烷 为溶剂， 反应 5.25h， 生成 bicyclo<3.2.1>oct-1-yl triflate
  参考文献：
  名称：

  Solvolysis of 2-methylene bicyclic bridgehead derivatives: a model for gradual variation of .pi.-conjugation in carbocations

  摘要：

  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.

  DOI：

  10.1021/jo00027a050

文献信息

• 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.