10,10-dimethyl-9-phenylethynyl-9,10-dihydrophenanthren-9-ol | 1447767-19-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 10,10-dimethyl-9-phenylethynyl-9,10-dihydrophenanthren-9-ol
• 英文别名: 10,10-Dimethyl-9-phenylethynyl-9,10-dihydro-phenanthren-9-ol；10,10-dimethyl-9-(2-phenylethynyl)phenanthren-9-ol
• CAS: 1447767-19-2
• 化学式: C₂₄H₂₀O
• 分子量: 324.422
• InChiKey: BQCBCWALKUJQBN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  10,10-dimethyl-9-phenylethynyl-9,10-dihydrophenanthren-9-ol 在 antimony pentafluoride 、 氯氟磺酰 、 氟磺酸 作用下， 以 二氯甲烷-D2 为溶剂， 反应 0.2h， 生成 5a,6-dimethyl-4-phenyl-4,5,5a,6-tetrahydroacephenanthrylene-4,6-bis(ylium)
  参考文献：
  名称：

  Cyclization reactions of long-lived 10,10-dimethyl-9-phenylethynyl-9,10-dihydrophenanthren-9-yl cation

  摘要：

  According to the NMR data, long-lived 10,10-dimethyl-9-phenylethynyl-9,10-dihydrophenanthren-9-ylium in acid medium undergoes cyclization whose direction is determined by the acidity of the medium. The cyclization in HSO3F-SbF5 superacid involves the aromatic ring in the phenanthrene core as nucleophilic component and yields 5a,6-dimethyl-4-phenyl-4,5,5a,6-tetrahydroacephenantrylene-4,6-bis(ylium). In trifluoroacetic acid the nucleophilic component is the side-chain phenyl group, and the cyclization product is neutral 8b,14b-dimethyl-8b,14b-dihydrobenzo[g]chrysen-10-yl trifluoroacetate. Both cyclization directions are observed in moderate-strength trifluoromethanesulfonic acid.

  DOI：

  10.1134/s1070428013090121
• 作为产物：
  描述：

  10,10-二甲基菲-9-酮 、 lithium phenylacetylide 在 水 、 氯化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.42h， 以100%的产率得到10,10-dimethyl-9-phenylethynyl-9,10-dihydrophenanthren-9-ol
  参考文献：
  名称：

  Structure of long-lived alkynyl-substituted carbocations of the phenanthrene series and their precursors

  摘要：

  According to the NMR data, 9-(R-ethynyl)-9-hydroxy-10,10-dimethyl-9,10-dihydrophenanthrenes (R = H, Me, Ph) in superacid medium (HSO3F-SO2ClF) at low temperature undergo dehydroxylation with formation of the corresponding long-lived 10,10-dimethyl-9-(R-ethynyl)-9,10-dihydrophenanthren-9-yl cations which do not isomerize to 10-(R-ethynyl)-9,10-dimethyl-9,10-dihydrophenanthren-9-ylium. In contrast, longlived 10,10-dimethyl-9-(3,3,3-trifluoroprop-1-yn-1-yl)-9,10-dihydrophenanthren-9-yl cation derived from 9-(3,3,3-trifluoroprop-1-yn-1-yl)-10,10-dimethyl-9,10-dihydrophenanthren-9-ol undergoes partial isomerization to 10-(3,3,3-trifluoroprop-1-yn-1-yl)-9,10-dimethyl-9,10-dihydrophenanthren-9-yl cation.

  DOI：

  10.1134/s1070428013060092

文献信息

• Formation of dications bearing a S(OH)₂⁺ group from long-lived 9,9-dimethyl-10 R-phenanthrenium cations in FSO₃H–SbF₅/SO₂ClF/SO₂: a mechanistic study
  作者：George E. Salnikov、Alexander M. Genaev、Vladimir A. Bushmelev、Andrey A. Nefedov、Vyacheslav G. Shubin

  DOI：10.1039/c4ra11673a

  日期：——

  A key step in the reaction mechanism is addition of SO₂ to the superelectrophilic intermediates – protonated phenanthrenium cations.

  反应机理的关键步骤是将SO2加到超电子亲电中间体上 - 质子化的菲咯啉阳离子。