9-methylphenenthrene-9,10-oxide | 80641-44-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 9-methylphenenthrene-9,10-oxide
• 英文别名: 9b-methyl-1aH-phenanthro[9,10-b]oxirene
• CAS: 80641-44-7
• 化学式: C₁₅H₁₂O
• 分子量: 208.26
• InChiKey: PWAZUEJOWDHZTC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.65
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  12.53
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  9-methylphenenthrene-9,10-oxide 、 磷酸二乙酯 以72%的产率得到
  参考文献：
  名称：

  DI, RADDO, P.;CHAN, T. H., J. ORG. CHEM., 1982, 47, N 8, 1427-1431

  摘要：

  DOI：
• 作为产物：
  描述：

  9-甲基菲 在 sodium hypochlorite 、 水 、 四丁基硫酸氢铵 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以75%的产率得到9-methylphenenthrene-9,10-oxide
  参考文献：
  名称：

  Manganese Catalysts for C−H Activation: An Experimental/Theoretical Study Identifies the Stereoelectronic Factor That Controls the Switch between Hydroxylation and Desaturation Pathways

  摘要：

  We describe competitive C-H bond activation chemistry of two types, desaturation and hydroxylation, using synthetic manganese catalysts with several substrates. 9,10-Dihydrophenanthrene (DHP) gives the highest desaturation activity, the final products being phenanthrene (P1) and phenanthrene 9,10-oxide (P3), the latter being thought to arise from epoxidation of some of the phenanthrene. The hydroxylase pathway also occurs as suggested by the presence of the dione product, phenanthrene-9,10-dione (P2), thought to arise from further oxidation of hydroxylation intermediate 9-hydroxy-9,10-dihydrophenanthrene. The experimental work together with the density functional theory (DFT) calculations shows that the postulated Mn oxo active species, [Mn(O)(tpp)(Cl)] (tpp = tetraphenylporphyrin), can promote the oxidation of dihydrophenanthrene by either desaturation or hydroxylation pathways. The calculations show that these two competing reactions have a common initial step, radical H abstraction from one of the DHP sp(3) C-H bonds. The resulting Mn hydroxo intermediate is capable of promoting not only OH rebound (hydroxylation) but also a second H abstraction adjacent to the first (desaturation). Like the active Mn-V=O species, this Mn-IV-OH species also has radical character on oxygen and can thus give H abstraction. Both steps have very low and therefore very similar energy barriers, leading to a product mixture. Since the radical character of the catalyst is located on the oxygen p orbital perpendicular to the Mn-IV-OH plane, the orientation of the organic radical with respect to this plane determines which reaction, desaturation or hydroxylation, will occur. Stereoelectronic factors such as the rotational orientation of the OH group in the enzyme active site are thus likely to constitute the switch between hydroxylase and desaturase behavior.

  DOI：

  10.1021/ja908744w

文献信息

• Reactions of the K-region epoxides of polycyclic aromatic hydrocarbons with phosphodiesters. A potential detoxification reaction
  作者：P. Di Raddo、T. H. Chan

  DOI：10.1021/jo00347a009

  日期：1982.4