1-chloro-2-hydroxyadamantane | 81315-92-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-chloro-2-hydroxyadamantane
• 英文别名: 1-Chloro-2-adamantanol；1-chloroadamantan-2-ol
• CAS: 81315-92-6
• 化学式: C₁₀H₁₅ClO
• 分子量: 186.681
• InChiKey: UCGDCXCUDALBTI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.16
• 重原子数：
  12.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-chloro-2-hydroxyadamantane 在 jones reagent 、 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 、 丙酮 为溶剂， 反应 18.0h， 生成 1-chloro-2-adamantanone tosylhydrazone sodium salt
  参考文献：
  名称：

  Substituent effects on the regioselectivity of intramolecular carbene carbon-hydrogen insertion. Cyclizations of 1- and 5-substituted 2-adamantylidenes

  摘要：

  DOI：

  10.1021/jo00134a005
• 作为产物：
  描述：

  4-protoadamantanone 在 lithium aluminium tetrahydride 、 五氯化磷 、 硫酸 作用下， 以 四氯化碳 、 乙醚 为溶剂， 反应 16.03h， 生成 1-chloro-2-hydroxyadamantane
  参考文献：
  名称：

  Substituent effects on the regioselectivity of intramolecular carbene carbon-hydrogen insertion. Cyclizations of 1- and 5-substituted 2-adamantylidenes

  摘要：

  DOI：

  10.1021/jo00134a005

文献信息

• 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.
• HIRSL-STARCEVIC, S.;MAJERSKI, Z., J. ORG. CHEM., 1982, 47, N 13, 2520-2525
  作者：HIRSL-STARCEVIC, S.、MAJERSKI, Z.

  DOI：——

  日期：——
• Substituent effects on the regioselectivity of intramolecular carbene carbon-hydrogen insertion. Cyclizations of 1- and 5-substituted 2-adamantylidenes
  作者：Sanja Hirsl-Starcevic、Zdenko Majerski

  DOI：10.1021/jo00134a005

  日期：1982.6