bicyclo[12.2.2]octadeca-13,15,17-trien-2-one | 109318-90-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: bicyclo[12.2.2]octadeca-13,15,17-trien-2-one
• CAS: 109318-90-3
• 化学式: C₁₈H₂₆O
• 分子量: 258.404
• InChiKey: BXZLJDVMUKEEHR-YBEGLDIGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.14
• 重原子数：
  19.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.61
• 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：

  bicyclo[12.2.2]octadeca-13,15,17-trien-2-one 以98%的产率得到
  参考文献：
  名称：

  LEI XUEGONG; DOUBLEDAY CH. , JR.; TURRO N. J., TETRAHEDRON LETT., 27,(1986) N 39, 4675-4678

  摘要：

  DOI：
• 作为产物：
  描述：

  2-phenylcyclododecanone 以 甲醇 为溶剂， 生成 bicyclo[12.2.2]octadeca-13,15,17-trien-2-one
  参考文献：
  名称：

  2-苯基环酮的光化学。通过瓶中船和爬行策略形成环芳烃和封装

  摘要：

  五元和六元气旋酮的光化学在机械有机化学的发展和我们对双自由基的了解中发挥了重要作用。这些烷酮的主要主要光化学过程是 T/sub 1/ (n,..pi..*) 状态的均裂 ..cap α..-裂解（I 型过程），产生三重双自由基。后者通过歧化反应（生成烯酮和/或烯醛）和组合反应（生成起始结构或异构体）在系统间交叉为单线态双自由基后稳定。例如，2-苯基环戊酮和2-苯基环己酮的光解以良好的产率产生链烯醛。我们报告说较大环旋风酮 (10, 11, 12, 和 15 名成员）通过以前未曾预料和史无前例的双自由基稳定组合过程产生对环烷。我们还报告说，光化学旋风酮到环烷烃的转化过程中发生的尺寸/形状变化可以用作瓶中船和爬行策略的基础，以不可逆地将有机分子封装在沸石的超级笼状空隙中。

  DOI：

  10.1021/ja00269a051

文献信息

• Photochemistry of large ring 2-phenylcycloalkanones and 2,n-diphenylcycloalkanones
  作者：Xuegong Lei、Charles Doubleday、Nicholas J. Turro

  DOI：10.1016/s0040-4039(00)85035-2

  日期：1986.1
• Utilization of radical scavenging to develop nuclear spin polarization and magnetic isotope separation in long flexible biradicals
  作者：Nicholas J. Turro、Kuo Chu Hwang、V. Pushkara Rao、Charles Doubleday

  DOI：10.1021/j100158a002

  日期：1991.3

  Irradiation of argon-purged acetonitrile solutions of 2-phenylcyclododecanone (1) in the probe of a 250-MHz NMR spectrometer does not produce significant H-1 or C-13 chemically induced dynamic nuclear polarization (CIDNP). However, irradiation of 1 in oxygen-purged acetonitrile, argon-purged acetonitrile containing small amounts of bromotrichloromethane, or argon-purged carbon tetrachloride solutions, in the probe of a 250-MHz NMR spectrometer, produces intense H-1 and C-13 CIDNP. Irradiation of argon-purged acetonitrile solutions of 1 in the earth's field does not lead to measurable C-13 enrichment of the recovered starting material or in the products of photolysis. However, irradiation of 1 in carbon tetrachloride or in acetonitrile solutions purged with oxygen or containing small amounts of bromotrichloromethane results in significant enrichment of an isomeric product, 2. The development of CIDNP and of isotopic enrichment is proposed to result from a common feature of the systems containing oxygen, carbon tetrachloride, or bromotrichloromethane: the opening of a competitive chemical scavenging pathway (oxygen, carbon tetrachloride, or bromotrichloromethane as scavengers) for the triplet biradical (3BR) produced by homolytic cleavage of electronically excited 1. This competitive pathway, when its rate is within an appropriate "kinetic window", provides a mechanism for effective sorting of nuclear spins to develop CIDNP and the effective sorting of nuclear isotopes to develop isotopic separation.