2-methyl-1,3-diphenyl-2-(phenylmethyl)-1,3-propandione

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 2-methyl-1,3-diphenyl-2-(phenylmethyl)-1,3-propandione
• 英文别名: 2-Benzyl-2-methyl-1,3-diphenylpropane-1,3-dione
• 化学式: C₂₃H₂₀O₂
• 分子量: 328.411
• InChiKey: DQQGIZNULRZOOC-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：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-甲基-1,3-二苯基丙烷-1,3-二酮 、 溴甲苯 在 苯并-15-冠醚-5 sodium hydride 作用下， 以 甲苯 为溶剂， 反应 15.0h， 以100%的产率得到2-methyl-1,3-diphenyl-2-(phenylmethyl)-1,3-propandione
  参考文献：
  名称：

  Influence of phase transfer catalyst structure on the E:Z ratio in the O-alkylation of an enolate

  摘要：

  由 2-甲基-1,3-二苯基丙烷-1,3-二酮（1）产生的 C-s.O-烷基化反应和 Z-s.E-烯醇醚生成反应都会受到相转移催化剂结构的影响。在 1 与硫酸二甲酯的 PTC 反应中，O-甲基化是主要过程。通过使用不同的催化剂，E:Z 产物比可在大约 1:1 到 4:96 之间变化。这只是催化剂结构能产生决定性影响的第五种转化类型。

  DOI：

  10.1039/b100880n

文献信息

• Systematic Ranking of Nucleophiles as Electron Donors.
  作者：Kim Daasbjerg、Stig R. Knudsen、Katrine N. Sonnichsen、Adalgisa R. Andrade、Steen U. Pedersen、Hiroaki Murase、Tatsuya Shono、H. Toftlund

  DOI：10.3891/acta.chem.scand.53-0938

  日期：——

  A systematic ranking of different nucleophiles (including enolates, phenolates, thiophenolates, hydroxide, cyanide) with respect to their ability to stabilise the transition state of substitution reactions has been carried out in acetonitrile and dimethyl sulfoxide. The method is based on a comparison of the rate constant, k(SUB), for the substitution reaction between a given nucleophile and benzyl chloride with the rate constant, ka(ET), for the corresponding electron transfer from an aromatic radical anion to benzyl chloride. The ratio k(SUB)/k(ET) expresses the rate enhancement due to electronic interaction in the transition state, Delta G(sta), of the substitution reaction. In this study, k(SUB)/k(ET) ratios between 5 and 10(31) were determined corresponding to Delta G(Sta)-values of 4-175 kJ mol(-1). These values cover substitution reactions going from outer-sphere electron transfer to S(N)2 with partial bond formation in the transition state. The k(SUB)/k(ET) values are round to be largest for nucleophiles such as OH- and CN- with very poor electron-donating abilities thigh oxidation potentials). When different. types of nucleophile with similar oxidation potentials are compared, a decrease in k(SUB)/k(ET) is observed going from sulfur- to carbon- and further to oxygen-centred nucleophiles. The ranking of nucleophiles in reactions involving electrophiles other than benzyl chloride is discussed with emphasis on steric hindrance and electronic effects.
• Components and catalysts for the polymerization of olefins
  申请人：MONTELL NORTH AMERICA INC.

  公开号：EP0646605B1

  公开（公告）日：1999-06-02
• Facile <i>n</i>Bu₄ NF Mediated Benzylation Of Congested 1,3-Diketones
  作者：Jens Christoffers

  DOI：10.1080/00397919908085742

  日期：1999.1.1

  Facile benzylation of 1,3-diketones is mediated by nBu(4)NF in THF-water. The reaction conditions are mild, the performance is simple, and the yields are high. Importantly, no O-alkylation side reactions or subsequent retro-Claisen C-C-bond cleavage are observed even in sterically congested systems.
• US5468704A
  申请人：——

  公开号：US5468704A

  公开（公告）日：1995-11-21
• Influence of phase transfer catalyst structure on the E:Z ratio in the O-alkylation of an enolate
  作者：Eckehard Volker Dehmlow、Michael Kaiser、Jörg Bollhöfer

  DOI：10.1039/b100880n

  日期：——

  Both C-  s. O-alkylations and Z s. E enol ether formation from 2-methyl-1,3-diphenylpropane-1,3-dione (1) can be influenced by the structure of the phase transfer catalyst. O-Methylation is the major process in the PTC reaction of 1 with dimethyl sulfate. The E:Z product ratio can be varied between roughly 1:1 and 4:96 by use of different catalysts. This is only the fifth type of conversion in which the catalyst structure can exert a decisive influence.

  由 2-甲基-1,3-二苯基丙烷-1,3-二酮（1）产生的 C-s.O-烷基化反应和 Z-s.E-烯醇醚生成反应都会受到相转移催化剂结构的影响。在 1 与硫酸二甲酯的 PTC 反应中，O-甲基化是主要过程。通过使用不同的催化剂，E:Z 产物比可在大约 1:1 到 4:96 之间变化。这只是催化剂结构能产生决定性影响的第五种转化类型。