(E)-2-ethylidene-1-adamantyl mesylate | 138968-97-5

• 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: (E)-2-ethylidene-1-adamantyl mesylate
• 英文别名: [(2E)-2-ethylidene-1-adamantyl] methanesulfonate
• CAS: 138968-97-5
• 化学式: C₁₃H₂₀O₃S
• 分子量: 256.366
• InChiKey: WIQKKCKEWLTMBI-KGVSQERTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.85
• 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：

  2,2,2-三氟乙醇 、 (E)-2-ethylidene-1-adamantyl mesylate 在 2,6-二甲基吡啶 作用下， 生成 1-(2,2,2-Trifluoroethoxy)-(E)-2-ethyledeneadamantane
  参考文献：
  名称：

  (Z)- 和 (E)-2-Ethylidene-1-adamantyl Chlorides 和 Mesylates 的溶剂分解。一个独特的例子显示氯化物比甲磺酸盐的 F 应变效应更大

  摘要：

  标题氯化物和甲磺酸盐在 25°C 下三氟乙醇分解中的 Z/E 速率比分别为 1023 和 126，表明 (Z)-氯化物比 (Z) 中的前应变（F 应变）效应更大-甲磺酸盐。结果得到了 MM2 和 AM1 计算的支持。

  DOI：

  10.1246/cl.1991.2209
• 作为产物：
  描述：

  1-hydroxy-2-adamantanone t-butyldimethylsilyl ether 在 吡啶 、 正丁基锂 、 氯化亚砜 作用下， 以 正戊烷 、 苯 为溶剂， 生成 (E)-2-ethylidene-1-adamantyl mesylate
  参考文献：
  名称：

  (Z)- 和 (E)-2-Ethylidene-1-adamantyl Chlorides 和 Mesylates 的溶剂分解。一个独特的例子显示氯化物比甲磺酸盐的 F 应变效应更大

  摘要：

  标题氯化物和甲磺酸盐在 25°C 下三氟乙醇分解中的 Z/E 速率比分别为 1023 和 126，表明 (Z)-氯化物比 (Z) 中的前应变（F 应变）效应更大-甲磺酸盐。结果得到了 MM2 和 AM1 计算的支持。

  DOI：

  10.1246/cl.1991.2209

文献信息

• Effects of γ-cyano substituent in allylic bridgehead solvolyses: evidence for cyano π conjugation in carbocations
  作者：Ken'ichi Takeuchi、Toshikazu Kitagawa、Yasushi Ohga、Akitoshi Nakakimura、Motohiro Munakata

  DOI：10.1016/s0040-4020(97)00505-x

  日期：1997.6

  solvolyzes 2 × 105 times faster than rigid 2-methylene-1-adamantyl mesylate. Placement of a cyano substituent on the (E) position of the vinylic carbon of these systems hardly alter the rate ratio (6 × 105). The result suggests fortuitous cancellation of the inductive destabilizing effect of the cyano substituent by its mesomeric stabilizing effect toward the partially conjugated allylic cation. PM3 calculations

  略带挠性的甲磺酸4-亚甲基-3-高金刚烷基酯的溶剂分解速度比刚性的甲磺酸2-亚甲基-1-金刚烷基酯快2×10 5倍。在这些体系的乙烯基碳的（E）位置上放置氰基取代基几乎不会改变速率比（6×10 5）。该结果表明，通过氰基取代基对部分共轭的烯丙基阳离子的介观稳定作用，偶然消除了氰基取代基的感应去稳定作用。作为模型的简单烯丙基阳离子的PM3计算支持了实验结果。
• Solvolyses of Bicyclo[2.2.2]oct-1-yl and 1-Adamantyl Systems Containing an Ethylidene Substituent on the 2-Position: Typical Examples of Rate Enhancements Ascribed to Relief of F-Strain
  作者：Yasushi Ohga、Motohiro Munakata、Toshikazu Kitagawa、Tomomi Kinoshita、Ken'ichi Takeuchi、Yasuo Oishi、Hiroshi Fujimoto

  DOI：10.1021/jo00094a012

  日期：1994.7

  The first typical examples are described on the solvolysis rate enhancements ascribed to the relief of F-strain between an alkyl group and the leaving group atom directly attached to the reaction center. The rates and products of solvolyses in ethanol were studied for 2-methylene- and (Z)- and (E)-2-ethylidenebicyclo[2.2.2]oct-1-yl triflates. Solvolyses were also conducted in ethanol and 2,2,2-trifluoroethanol (TFE) on 2-methylene- and (Z)- and (E)-2-ethylidene-1-adamantyl compounds having OMs, F, Cl, Br, or I asa leaving group. Ah the substrates gave the corresponding bridgehead substitution products as kinetic control products. The Z:E rate ratios at 25 degrees C were 217 +/- 6 for 2-ethylidenebicyclo[2.2.2]oct-1-yl triflates (ethanol) and 109 +/- Il(ethanol) and 117 fl(TFE)for 2-ethylidene-1-adamantyl mesylates. O-18 scrambling studies on the ethanolyses of(Z)- and (E)2-ethylidene-1-adamantyl mesylates showed that the titrimetrically determined Z:E rate ratios can be used as a measure of the rate ratios for the ionization step. The Z:E rate ratio in TFE at 25 degrees C for 2-ethylidene-1-adamantyl halides varied in the sequence F (ca. 70), Cl(1020 +/- 160), Br (2230 +/- 90), and I (9500 +/- 280). The significant increases in the rate ratio with the increase in the atomic size of halogen were explained in terms of the presence of F-strain in the Z substrates and its essential absence in the E substrates. Linear correlations were found in a plot of 1.36 x log[k(Z)/k(E)] against the MM2 steric energy difference between the Z and E isomers (slope 1.0) and against Hansch's Es, demonstrating the significance of F-strain effect in the enhanced rates of the (Z)-2-ethylidene-1-adamantyl system. These correlations showed an intercept of 0.8 kcal mol(-1), which suggested the greater stability of the (Z)-2-ethylidene-1-adamantyl cation than the corresponding E cation by this amount. Ab initio calculations (RHF/G-31G**) showed that the Z cation is more stable than the E cation by 1.0 kcal mol(-1), and that the large Z:E rate ratios are in part ascribed to the difference in the cation stability.
• Takeuchi, K.; Ohga, Y.; Kitagawa, T., Journal de Chimie Physique et de Physico-Chimie Biologique, 1992, vol. 89, # 7, p. 1631 - 1638
  作者：Takeuchi, K.、Ohga, Y.、Kitagawa, T.

  DOI：——

  日期：——