bicyclo<3.3.1>non-1-yl mesylate | 130829-60-6

• 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: bicyclo<3.3.1>non-1-yl mesylate
• 英文别名: 1-Bicyclo[3.3.1]nonanyl methanesulfonate
• CAS: 130829-60-6
• 化学式: C₁₀H₁₈O₃S
• 分子量: 218.317
• InChiKey: BOTBGTRTFUDCBZ-UHFFFAOYSA-N

物化性质

• 沸点：
  346.9±9.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  14
• 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：
  3

反应信息

• 作为反应物：
  描述：

  甲醇 、 bicyclo<3.3.1>non-1-yl mesylate 在 2,6-二甲基吡啶 作用下， 生成 1-Methoxybicyclo<3.3.1>nonane
  参考文献：
  名称：

  Foiled Conjugation in α-Oximino Carbocations

  摘要：

  The 4-CHNOCH3 group is a cation-stabilizing group when placed in the para-position of a cumyl cation. The effect of this group on cumyl cations when flanked by adjacent methyl groups has now been determined. Solvolysis rates of 3,5-(CH3)(2)-4-(CHNOCH3)cumyl trifluoroacetates are somewhat slower than that of 3,5-dimethylcumyl trifluoroacetate. This is attributed to steric inhibition of the cation-stabilizing resonance effect of the p-oximino group. In a l-adamantyl system, where an alpha-oximino group has been placed directly adjacent to a developing cationic center, solvolysis rates relative to l-adamantyl mesylate are slowed by a factor of 10(8). This is attributed a cation-destabilizing inductive effect where geometric constraints prevent stabilizing orbital overlap of the cationic center with the adjacent alpha-oximino group. This cation-destabilizing effect fades in the homoadamantyl and the bicyclo[3.3.1]nonyl systems, where rate-retarding effects are 1.6 x 10(4) and 1.5 x 10(2), respectively. The behavior of geometrically constrained alpha-oximino cations parallels that of analogously constrained allylic cations. Computational studies at the HF/6-31G* level indicate that twisting the alpha-oximino group out of planarity with a tertiary cationic center into a perpendicular arrangement decreases stabilization by 21 kcal/mol. These studies suggest that conjugative interactions, and not ground state destabilization, are the most important factors in controlling rates of formation of alpha-oximino cations from mesylates and trifluoroacetates.

  DOI：

  10.1021/jo960073u
• 作为产物：
  描述：

  1-bromobicyclo<3.3.1>nonane 在 水 、 碳酸氢钠 、 三乙胺 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 2.33h， 生成 bicyclo<3.3.1>non-1-yl mesylate
  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

• TAKEUCHI, KENICHI;YOSHIDA, MASAYASU;OHGA, YASUSHI;TSUGENO, AKIO;KITAGAWA,+, J. ORG. CHEM., 55,(1990) N5, C. 6063-6065
  作者：TAKEUCHI, KENICHI、YOSHIDA, MASAYASU、OHGA, YASUSHI、TSUGENO, AKIO、KITAGAWA,+

  DOI：——

  日期：——