(E)-2-Bromo-5-phenyladamantane | 132317-56-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-2-Bromo-5-phenyladamantane
• CAS: 132317-56-7；132435-79-1
• 化学式: C₁₆H₁₉Br
• 分子量: 291.231
• InChiKey: ICUHYOYWNRNGIP-DLQDSKHDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.53
• 重原子数：
  17.0
• 可旋转键数：
  1.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  (E/Z)-5-phenyladamantan-2-ol 在 磷酸 、 phosphorus pentoxide 、 potassium bromide 作用下， 反应 1.5h， 生成 (E)-2-Bromo-5-phenyladamantane 、 (Z)-2-Bromo-5-phenyladamantane
  参考文献：
  名称：

  Face Selection in the Capture of Anionic Carbon

  摘要：

  Several reactions of 2-(5-phenyladamantyl) derivatives have been examined with the objective of determining the stereochemistry of addition of electrophiles to a trigonal center Ct carrying a full or partial negative charge. These reactions included the carbonation and bromination of the 2-lithioadamantane(s) attack at the zu face was found to be predominant. Methylation of 5-phenyl-2-adamantanone with either methyllithium or lithium dimethylcuprate gave mixtures of the methyl alcohols in which the E-isomer is the main product. Attempts to study the reactions of the enolate anion derived from the (E)- and (Z)-phenyl 2-(5-phenyladamantyl) ketones 7-Ph were not successful: bromination could not be forced at all, and methylation and protonation occur at oxygen. The enol ether and enol were studied also; brominations of these neutral species occur at the zu face. It is concluded that even the imposition of negative charge upon the trigonal center does not engender the type of hyperconjugation envisioned by Anh in the capture of electrophiles. Protonation of the enol ether led to an equilibrium mixture of ketones 7-Ph; protonation of the enol itself gave an excess of the E-isomer. Possible reasons for this unexpected outcome are discussed.

  DOI：

  10.1021/jo00091a009

文献信息

• Electronic control of face selection in the capture of radicals
  作者：Vani R. Bodepudi、William J. Le Noble

  DOI：10.1021/jo00006a009

  日期：1991.3

  A simple procedure is described which leads to the pure epimeric 2-(5-phenyl)adamantanecarboxylic acids E-1 and Z-1. Both acids upon treatment with bromine and mercuric oxide in carbon tetrachloride undergo the Hunsdiecker reaction to give the same mixture of E- and Z- 2-bromo-5-phenyladamantanes 4. 5-Phenyl-2-methyleneadamantane 6 undergoes reaction with bromotrichloromethane to give two diastereomeric adducts. In both instances, the major isomer results from the abstraction of a bromine atom by the zu face of the intermediate 5-phenyl-2-adamantyl radicals. The results mesh with other examples of face selection which we have previously ascribed to transition-state hyperconjugation. An additional case (hydride shift in a carbocation) was encountered in this work, as well as one apparent exception: the oxirane formation from adamantanone and sulfonium ylids. That result is attributed to thermodynamic control of the initial addition step.