bis(adamantyl)methanol | 54821-21-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: bis(adamantyl)methanol
• 英文别名: Bis(1-adamantyl)methanol
• CAS: 54821-21-5
• 化学式: C₂₁H₃₂O
• 分子量: 300.484
• InChiKey: JWSQQRYJPVTHDE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  8.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bis(adamantyl)methanol 在 吡啶 、 二溴亚砜 作用下， 生成 1,1'-diadamantylmethyl bromide
  参考文献：
  名称：

  Lomas, John S., Journal of the Chemical Society. Perkin transactions II, 1995, # 3, p. 519 - 528

  摘要：

  DOI：
• 作为产物：
  描述：

  1,1'-diadamantyl ketimine 在 盐酸 、 lithium aluminium tetrahydride 、 水 作用下， 以 乙醚 为溶剂， 生成 bis(adamantyl)methanol
  参考文献：
  名称：

  金刚烷衍生物与四甲基硅烷的完全一步桥头甲基化

  摘要：

  研究了 AlCl 3和四甲基硅烷的组合用于金刚烷衍生物的桥头甲基化。重排的影响用各种例子说明，合成效用通过反应的放大来证明。机理研究表明，形成了由四甲基硅烷和 AlCl 3形成的反应甲基化复合物。

  DOI：

  10.1002/ejoc.202101004

文献信息

• Reactions of thermally generated tert-butyl and di(tert-alkyl) ketyl radicals in toluene: cage effects and hydrogen transfer
  作者：John S. Lomas、Sylvette Briand、Dominique Fain

  DOI：10.1021/jo00001a034

  日期：1991.1

  Thermolysis of di(1-adamantyl)-tert-butylmethanol (2a) in toluene at 145-185-degrees-C gives mainly bibenzyl, di(1-adamantyl) ketone, di(1-adamantyl)methanol, and the cross-product, 1,1-di(1-adamantyl)-2-phenylethanol. In the presence of benzophenone (BP) or benzenethiols as hydrogen-accepting and hydrogen-donating radical scavengers, respectively, the di(1-adamantyl)methanol/di(1-adamantyl) ketone ratio tends to steady values as the scavenger/2a ratio is increased, while the cross-product disappears. At 165-degrees-C the secondary alcohol minimum is 8% (BP) and the ketone minimum 11% (thiol). These represent the contributions of geminate hydrogen atom transfer reactions to the overall yields, i.e., the cage effects. With BP the major cross-product is 1,1,2-triphenylethanol. Products from the self- and cross-reactions of benzyl and thiyl radicals are found when thiol is present, the diaryl disulfide predominating at high thiol concentration. In both cases, cross-products resulting from reaction of the tert-butyl radical with the scavenger-derived radical are detected in small amounts, being of greater importance in deuteriated toluene. The tert-butyl radical is considered, therefore, to be less reactive in hydrogen atom abstraction than the 1-adamantyl radical. Cage effects for other di(tert-alkyl)-tert-butylmethanols that thermolyze with exclusive t-Bu-C bond fission have also been measured and the product composition of the scavenger-free reaction interpreted by kinetic simulation based on the steady state approximation. Rate constants for hydrogen abstraction by the tert-butyl radical from toluene are not accurately determined by this procedure but seem, nevertheless, to indicate that the literature value (14.4 M-1 s-1 at 48-degrees-C) is an overestimate. Solvent hydrogen abstraction by the ketyl radical shows a small but well-defined steric effect.
• Yurchenko, A. G.; Fedorenko, T. V., Journal of Organic Chemistry USSR (English Translation), 1987, vol. 23, # 5, p. 875 - 880
  作者：Yurchenko, A. G.、Fedorenko, T. V.

  DOI：——

  日期：——
• Thermolysis of highly congested tri-tert-alkylmethanols: strain energies of bridgehead alkyl radicals
  作者：John S. Lomas

  DOI：10.1021/jo00222a019

  日期：1985.11
• Reactions of thermally generated 1-adamantyl and di(1-adamantyl) ketyl radicals in toluene
  作者：John S. Lomas、Dominique Fain、Sylvette Briand

  DOI：10.1021/jo00290a044

  日期：1990.2
• Stable carbocations. Part 235. Solvolytic and stable ion studies of 1,1'-diadamantylmethyl cations
  作者：George A. Olah、G. K. Surya Prakash、Gao Liang、Paul V. R. Schleyer、W. David Graham

  DOI：10.1021/jo00345a029

  日期：1982.3