3-(4'-methoxyphenyl)-4,4-dimethylpentanoic acid | 103427-27-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 苯丙酸
• 英文名称: 3-(4'-methoxyphenyl)-4,4-dimethylpentanoic acid
• 英文别名: 3-(4-Methoxyphenyl)-4,4-dimethylpentanoic acid
• CAS: 103427-27-6
• 化学式: C₁₄H₂₀O₃
• 分子量: 236.311
• InChiKey: RKARGQRUGMQVSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(4'-methoxyphenyl)-4,4-dimethylpentanoic acid 在 氯化亚砜 作用下， 以 乙醚 为溶剂， 反应 3.0h， 生成 2-diazo-5-(4'-methoxyphenyl)-6,6-dimethylheptan-3-one
  参考文献：
  名称：

  Dynamic Equilibria in the Products of Intramolecular Buchner Additions of Diazoketones to Aryl Rings Bearing Methoxy Substituents

  摘要：

  Rhodium carboxylate catalyzed aromatic addition reactions of a range of diazoketones bearing methoxy-substituted aryl rings have been explored. While the existence of norcaradiene-cycloheptatriene equilibria in related compounds is well established, the aromatic addition products in this study display more complex dynamic equilibria due to conjugation with the methoxy group; the experimental evidence for this is discussed in detail. In the azulenone products 21-26 derived from p-methoxy-substituted diazoketones 14-16, the diastereomers interconvert via a spiro intermediate 39. A related mechanistic process in the azulenones 43-46 derived from the o-methoxy-substituted diazoketones 17, 18 interconverts regioisomers, explaining the conflicting reports for the regioselectivity of the cyclization of diazoketone 1. With the m-methoxy-substituted diazoketone 19, involvement of the methoxy group through a different pathway results in fragmentation of the azulenone to form the tetralone 47. With the azulenones 21-26 exclusive trapping of the norcaradiene associated with the less thermodynamically stable diastereomers in a cycloadduct with N-phenylmaleimide is observed. Due to the presence of the activating methoxy substituent on the aromatic ring, the aromatic addition reactions of the diazoketones studied were not very sensitive to the nature of the rhodium catalyst.

  DOI：

  10.1021/jo015750l
• 作为产物：
  描述：

  叔丁基氯化镁 、 4-甲氧基肉桂酸 以 乙醚 为溶剂， 反应 3.0h， 以86%的产率得到3-(4'-methoxyphenyl)-4,4-dimethylpentanoic acid
  参考文献：
  名称：

  Dynamic Equilibria in the Products of Intramolecular Buchner Additions of Diazoketones to Aryl Rings Bearing Methoxy Substituents

  摘要：

  Rhodium carboxylate catalyzed aromatic addition reactions of a range of diazoketones bearing methoxy-substituted aryl rings have been explored. While the existence of norcaradiene-cycloheptatriene equilibria in related compounds is well established, the aromatic addition products in this study display more complex dynamic equilibria due to conjugation with the methoxy group; the experimental evidence for this is discussed in detail. In the azulenone products 21-26 derived from p-methoxy-substituted diazoketones 14-16, the diastereomers interconvert via a spiro intermediate 39. A related mechanistic process in the azulenones 43-46 derived from the o-methoxy-substituted diazoketones 17, 18 interconverts regioisomers, explaining the conflicting reports for the regioselectivity of the cyclization of diazoketone 1. With the m-methoxy-substituted diazoketone 19, involvement of the methoxy group through a different pathway results in fragmentation of the azulenone to form the tetralone 47. With the azulenones 21-26 exclusive trapping of the norcaradiene associated with the less thermodynamically stable diastereomers in a cycloadduct with N-phenylmaleimide is observed. Due to the presence of the activating methoxy substituent on the aromatic ring, the aromatic addition reactions of the diazoketones studied were not very sensitive to the nature of the rhodium catalyst.

  DOI：

  10.1021/jo015750l

文献信息

• On the mechanism of the addition of organolithium reagents to cinnamic acids
  作者：Marı́a José Aurell、Marı́a José Bañuls、Ramon Mestres、Elena Muñoz

  DOI：10.1016/s0040-4020(00)01096-6

  日期：2001.2

  regioselectivity of the addition of tert-butyllithium to cinnamic acid is subject to reaction conditions and to substituent electronic effects. Significant effects are observed in the presence of several additives including a radical trap such as α-methylstyrene. Competition experiments by addition of the organolithium reagent to mixtures of substituted cinnamic acids show that the relative rates of both

  向肉桂酸添加叔丁基锂的区域选择性受反应条件和取代基电子效应的影响。在几种添加剂的存在下观察到了显着的效果，其中包括自由基陷阱，例如α-甲基苯乙烯。通过向取代的肉桂酸混合物中添加有机锂试剂进行竞争实验表明，起始酸的转化率和1,3-加合物的形成的相对速率均受电子效应的影响，而1,4-加成的速率则受到电子效应的影响。不依赖于取代基。这些特征与极性加成机理相一致，但是也可以实现快速SET平衡，然后进行缓慢的自由基结合。
• Addition of organolithium reagents to cinnamic acids
  作者：María José Aurell、María José Bañuls、Ramon Mestres、Elena Muñoz

  DOI：10.1016/s0040-4020(98)01074-6

  日期：1999.1

  Reaction of tert-butyllithium with p- and m-substituted cinnamic acids at low temperature affords mixtures of 1,4- and 1,3-addition products, whose composition depend on the nature of the substituents. Electron-donating and electron-withdrawing groups favour 1,4- and 1,3-additions, respectively. Linear correlations are obtained with electronic effect and with radical substituent constants.

  的反应叔与丁基锂p -和米处的1,4-和1,3-加成产物，其组成依赖于取代基的性质低温，得到的混合物取代的肉桂酸。给电子基团和吸电子基团分别有利于1，4-和1，3-加成。线性相关通过电子效应和自由基取代基常数获得。
• Dynamic Equilibria in the Products of Intramolecular Buchner Additions of Diazoketones to Aryl Rings Bearing Methoxy Substituents
  作者：Anita R. Maguire、Patrick O'Leary、Francis Harrington、Simon E. Lawrence、Alexander J. Blake

  DOI：10.1021/jo015750l

  日期：2001.10.1

  Rhodium carboxylate catalyzed aromatic addition reactions of a range of diazoketones bearing methoxy-substituted aryl rings have been explored. While the existence of norcaradiene-cycloheptatriene equilibria in related compounds is well established, the aromatic addition products in this study display more complex dynamic equilibria due to conjugation with the methoxy group; the experimental evidence for this is discussed in detail. In the azulenone products 21-26 derived from p-methoxy-substituted diazoketones 14-16, the diastereomers interconvert via a spiro intermediate 39. A related mechanistic process in the azulenones 43-46 derived from the o-methoxy-substituted diazoketones 17, 18 interconverts regioisomers, explaining the conflicting reports for the regioselectivity of the cyclization of diazoketone 1. With the m-methoxy-substituted diazoketone 19, involvement of the methoxy group through a different pathway results in fragmentation of the azulenone to form the tetralone 47. With the azulenones 21-26 exclusive trapping of the norcaradiene associated with the less thermodynamically stable diastereomers in a cycloadduct with N-phenylmaleimide is observed. Due to the presence of the activating methoxy substituent on the aromatic ring, the aromatic addition reactions of the diazoketones studied were not very sensitive to the nature of the rhodium catalyst.