di-1-bicyclo<2.2.2>octyl ketone | 93754-95-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: di-1-bicyclo<2.2.2>octyl ketone
• 英文别名: Bis(1-bicyclo<2.2.2>octyl) ketone；Bis(1-bicyclo[2.2.2]octanyl)methanone
• CAS: 93754-95-1
• 化学式: C₁₇H₂₆O
• 分子量: 246.393
• InChiKey: CPHGQCZQXOJOQB-UHFFFAOYSA-N

物化性质

• 沸点：
  337.8±10.0 °C(Predicted)
• 密度：
  1.106±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  di-1-bicyclo<2.2.2>octyl ketone 在 叔丁基锂 作用下， 以 乙醚 为溶剂， 生成 1,1-Bis-bicyclo[2.2.2]oct-1-yl-2,2-dimethyl-propan-1-ol
  参考文献：
  名称：

  Formation of alkyl carbanions by alkoxide fragmentation in HMPT

  摘要：

  DOI：

  10.1021/jo00185a064
• 作为产物：
  描述：

  1,1-Bis-bicyclo[2.2.2]oct-1-yl-2,2-dimethyl-propan-1-ol 以 十二烷 为溶剂， 生成 di-1-bicyclo<2.2.2>octyl ketone 、 Bis-bicyclo[2.2.2]oct-1-yl-methanol
  参考文献：
  名称：

  Thermolysis of highly congested tri-tert-alkylmethanols: strain energies of bridgehead alkyl radicals

  摘要：

  DOI：

  10.1021/jo00222a019

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

  DOI：——

  日期：——