3,3-dimethyl-2,3-dihydro-[1,1'-biphenyl]-4(1H)-one | 1447969-36-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,3-dimethyl-2,3-dihydro-[1,1'-biphenyl]-4(1H)-one
• 英文别名: 6,6-Dimethyl-4-phenylcyclohex-2-en-1-one；6,6-dimethyl-4-phenylcyclohex-2-en-1-one
• CAS: 1447969-36-9
• 化学式: C₁₄H₁₆O
• 分子量: 200.28
• InChiKey: LCXPNSYHKKXERH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2,2-dimethyl-4-phenylpent-4-enoic acid 在 草酰氯 、 rhodium chloride 5,10,15,20-tetrakis(α-diethylphosphonate ester-m-tolyl)porphyrin 、 tert-butylammonium hexafluorophosphate(V) 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 37.0h， 生成 3,3-dimethyl-5-phenylbicyclo[3.1.0]hexan-2-one 、 3,3-dimethyl-2,3-dihydro-[1,1'-biphenyl]-4(1H)-one
  参考文献：
  名称：

  Interfacial Electric Field Effects on a Carbene Reaction Catalyzed by Rh Porphyrins

  摘要：

  An intramolecular reaction catalyzed by Rh porphyrins was studied in the presence of interfacial electric fields. 1-Diazo-3,3-dimethyl-5-phenylhex-5-en-2-one (2) reacts with Rh porphyrins via a putative carbenoid intermediate to form cyclopropanation product 3,3-dimethyl-5-phenylbicyclo[3.1.0]hexan-2-one (3) and insertion product 3,3-dimethyl-2,3-dihydro-[1,1'-biphenyl]-4(1H)-one (4). To study this reaction in the presence of an interfacial electric field, Si electrodes coated with thin films of insulating dielectric layers were used as the opposing walls of a reaction vessel, and Rh porphyrin catalysts were localized to the dielectric electrolyte-interface. The charge density was varied at the interface by changing the voltage across the two electrodes. The product ratio was analyzed as a function of the applied voltage and the surface chemistry of the dielectric layer. In the absence of an applied voltage, the ratio of 3:4 was approximately 10:1. With a TiO2 surface, application of a voltage induced a Rh porphyrin-TiO2 interaction that resulted in an increase in the 3:4 ratio to a maximum in which 4 was nearly completely suppressed (>100:1). With an Al2O3 surface or an alkylphosphonate-coated surface, the voltage caused a decrease in the 3:4 ratio, with a maximum effect of lowering the ratio to 1:2. The voltage-induced decrease in the 3:4 ratio in the absence of TiO2 was consistent with a field-dipole effect that changed the difference in activation energies for the product-determining step to favor product 4. Effects were observed for porphyrin catalysts localized to the electrode-electrolyte interface either through covalent attachment or surface adsorption, enabling the selectivity to be controlled with unfunctionalized Rh porphyrins. The magnitude of the selectivity change was limited by the maximum interfacial charge density that could be attained before dielectric breakdown.

  DOI：

  10.1021/ja404394z

文献信息

• Molecular catalysis at polarized interfaces created by ferroelectric BaTiO₃
  作者：Eugene S. Beh、Sergey A. Basun、Xiaofeng Feng、Ighodalo U. Idehenre、Dean R. Evans、Matthew W. Kanan

  DOI：10.1039/c6sc05032h

  日期：——

  densities that arise from the dipole moments of ferroelectric domains and can be used to create polarized solid–liquid interfaces without applying a voltage. We studied the effects of ferroelectric oxides on the selectivity of a Rh porphyrin-catalyzed carbene rearrangement. The addition of ferroelectric BaTiO3 nanoparticles to the reaction solution changed the product ratio in the same direction and by

  极化的固液界面处的局部环境为化学反应提供了独特的介质，可以利用该介质来控制非法拉第反应的选择性。极化界面通常是通过在电解质溶液中的电极上施加电压来制备的，但是在抑制法拉第反应的同时实现高表面电荷密度是一项挑战。铁电材料具有永久性的表面电荷密度，该密度由铁电畴的偶极矩产生，可用于产生极化的固液界面，而无需施加电压。我们研究了铁电氧化物对Rh卟啉催化的卡宾重排选择性的影响。铁电体BaTiO 3的添加与在电压极化的电极-电解质界面进行反应时，纳米粒子向反应溶液中的转化率在相同的方向和相似的大小上发生变化。结果表明，BaTiO 3纳米粒子的胶体悬浮液充当可分散的极化界面，可影响非法拉第反应的选择性。
• Interfacial Electric Field Effects on a Carbene Reaction Catalyzed by Rh Porphyrins
  作者：Craig F. Gorin、Eugene S. Beh、Quan M. Bui、Graham R. Dick、Matthew W. Kanan

  DOI：10.1021/ja404394z

  日期：2013.7.31

  An intramolecular reaction catalyzed by Rh porphyrins was studied in the presence of interfacial electric fields. 1-Diazo-3,3-dimethyl-5-phenylhex-5-en-2-one (2) reacts with Rh porphyrins via a putative carbenoid intermediate to form cyclopropanation product 3,3-dimethyl-5-phenylbicyclo[3.1.0]hexan-2-one (3) and insertion product 3,3-dimethyl-2,3-dihydro-[1,1'-biphenyl]-4(1H)-one (4). To study this reaction in the presence of an interfacial electric field, Si electrodes coated with thin films of insulating dielectric layers were used as the opposing walls of a reaction vessel, and Rh porphyrin catalysts were localized to the dielectric electrolyte-interface. The charge density was varied at the interface by changing the voltage across the two electrodes. The product ratio was analyzed as a function of the applied voltage and the surface chemistry of the dielectric layer. In the absence of an applied voltage, the ratio of 3:4 was approximately 10:1. With a TiO2 surface, application of a voltage induced a Rh porphyrin-TiO2 interaction that resulted in an increase in the 3:4 ratio to a maximum in which 4 was nearly completely suppressed (>100:1). With an Al2O3 surface or an alkylphosphonate-coated surface, the voltage caused a decrease in the 3:4 ratio, with a maximum effect of lowering the ratio to 1:2. The voltage-induced decrease in the 3:4 ratio in the absence of TiO2 was consistent with a field-dipole effect that changed the difference in activation energies for the product-determining step to favor product 4. Effects were observed for porphyrin catalysts localized to the electrode-electrolyte interface either through covalent attachment or surface adsorption, enabling the selectivity to be controlled with unfunctionalized Rh porphyrins. The magnitude of the selectivity change was limited by the maximum interfacial charge density that could be attained before dielectric breakdown.