2-Methylene-1-adamantyl mesylate | 144028-09-1

• 英文名称: 2-Methylene-1-adamantyl mesylate
• 英文别名: (2-Methylidene-1-adamantyl) methanesulfonate
• CAS: 144028-09-1
• 化学式: C₁₂H₁₈O₃S
• 分子量: 242.339
• InChiKey: BGSDVIBGWJSNNP-UHFFFAOYSA-N

物化性质

• 沸点：
  376.1±12.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.83
• 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-Methylene-1-adamantyl mesylate 、 乙醇 以 水 为溶剂， 生成 1-Ethoxy-2-methyleneadamantane
  参考文献：
  名称：

  γ-氰基取代基在烯丙基桥头溶剂中的作用：碳正离子中氰基π共轭的证据

  摘要：

  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。

  DOI：

  10.1016/s0040-4020(97)00505-x
• 作为产物：
  描述：

  2-Methylenadamantan-1-ol 、 甲基磺酰氯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以38%的产率得到2-Methylene-1-adamantyl mesylate
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo00094a012

文献信息

• Ohga Yasushi, Munakata Motohiro, Kitagawa Toshikazu, Kinoshita Tomomi, Ta+, J. Org. Chem, 59 (1994) N 15, S 4056-4067
  作者：Ohga Yasushi, Munakata Motohiro, Kitagawa Toshikazu, Kinoshita Tomomi, Ta+

  DOI：——

  日期：——