1-Adamantyl 1-bicyclo<2.2.2>octyl ketone | 93754-97-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Adamantyl 1-bicyclo<2.2.2>octyl ketone
• 英文别名: 1-adamantyl(1-bicyclo[2.2.2]octanyl)methanone
• CAS: 93754-97-3
• 化学式: C₁₉H₂₈O
• 分子量: 272.431
• InChiKey: CEVXJQOHDWJABU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.74
• 重原子数：
  20.0
• 可旋转键数：
  2.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-Adamantyl 1-bicyclo<2.2.2>octyl ketone 、 溴甲苯 在 lithium 作用下， 以 乙醚 为溶剂， 生成 1-(1-adamantyl)-1-(1-bicyclo[2.2.2]octanyl)-2-phenylethanol
  参考文献：
  名称：

  Reactions of thermally generated tert-butyl and di(tert-alkyl) ketyl radicals in toluene: cage effects and hydrogen transfer

  摘要：

  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.

  DOI：

  10.1021/jo00001a034
• 作为产物：
  描述：

  1-(1-Adamantyl)-1-(1-bicyclo[2.2.2]octanyl)-2,2-dimethylpropan-1-ol 、 甲苯 以27%的产率得到
  参考文献：
  名称：

  LOMAS, JOHN S.;BRIAND, SYLVETTE;FAIN, DOMINIQUE, J. ORG. CHEM., 56,(1991) N, C. 166-175

  摘要：

  DOI：

文献信息

• 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