3-acetyl-5-tert-butyl-2-methyl-5-phenyl-4,5-dihydrofuran | 134391-09-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-acetyl-5-tert-butyl-2-methyl-5-phenyl-4,5-dihydrofuran
• 英文别名: 1-(2-tert-butyl-5-methyl-2-phenyl-3H-furan-4-yl)ethanone
• CAS: 134391-09-6
• 化学式: C₁₇H₂₂O₂
• 分子量: 258.36
• InChiKey: OQYHHDFAZCQSJU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (1-叔丁基乙烯基)苯 、 乙酰丙酮 在 CeONO₂ (CAN) 作用下， 以 乙腈 为溶剂， 反应 0.08h， 以84%的产率得到3-acetyl-5-tert-butyl-2-methyl-5-phenyl-4,5-dihydrofuran
  参考文献：
  名称：

  Electronic and steric effects in the addition of electrophilic 1,3-dicarbonylalkyl radicals to styrenes

  摘要：

  The addition reactions of 1,3-dicarbonylalkyl radicals to ring-substituted styrenes have been kinetically investigated in MeOH and/or MeCN. It has been observed that the rate effect of ring substituents is nearly identical in the reactions of MeCOCHCOMe (1), MeOCOCHCOMe (2) and MeOCOCHCOOMe (4), the rho-value, in MeOH being -0.96, -1.01 and -1.06, respectively. Since the three radicals are relatively strong oxidants and have similar reduction potentials, an important contribution of the charge transfer structure RCOCHCORCH2CHAr.+ to the addition transition state is suggested. It has also be found that in the reactions of 1 and 4 with alpha-alkyl-substituted styrenes the rate of addition is strongly influenced by the nature of the alkyl group, decreasing in the order: Me > Et > (i)Pr > (t)Bu. The observed effects are much larger than those reported for the corresponding reactions of the nucleophilic cyclohexyl radical. It is suggested that the alpha-alkyl substituents exert an effect of steric inhibition of resonance thereby ring delocalization of the charge and/or unpaired electron in the transition state is significantly reduced. Delocalization may be more important in the reactions of 1 and 4 than in those of the cyclohexyl radical since it is possible that the former utilizes a transition state occurring later along the reaction coordinate and/or characterized by a larger extent of charge transfer.

  DOI：

  10.1021/jo00015a037

文献信息

• Electronic and steric effects in the addition of electrophilic 1,3-dicarbonylalkyl radicals to styrenes
  作者：Enrico Baciocchi、Renzo Ruzziconi

  DOI：10.1021/jo00015a037

  日期：1991.7

  The addition reactions of 1,3-dicarbonylalkyl radicals to ring-substituted styrenes have been kinetically investigated in MeOH and/or MeCN. It has been observed that the rate effect of ring substituents is nearly identical in the reactions of MeCOCHCOMe (1), MeOCOCHCOMe (2) and MeOCOCHCOOMe (4), the rho-value, in MeOH being -0.96, -1.01 and -1.06, respectively. Since the three radicals are relatively strong oxidants and have similar reduction potentials, an important contribution of the charge transfer structure RCOCHCORCH2CHAr.+ to the addition transition state is suggested. It has also be found that in the reactions of 1 and 4 with alpha-alkyl-substituted styrenes the rate of addition is strongly influenced by the nature of the alkyl group, decreasing in the order: Me > Et > (i)Pr > (t)Bu. The observed effects are much larger than those reported for the corresponding reactions of the nucleophilic cyclohexyl radical. It is suggested that the alpha-alkyl substituents exert an effect of steric inhibition of resonance thereby ring delocalization of the charge and/or unpaired electron in the transition state is significantly reduced. Delocalization may be more important in the reactions of 1 and 4 than in those of the cyclohexyl radical since it is possible that the former utilizes a transition state occurring later along the reaction coordinate and/or characterized by a larger extent of charge transfer.