1-(1-Ethoxy-2-methyl-propenyl)-4-methoxy-benzene | 40811-09-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-(1-Ethoxy-2-methyl-propenyl)-4-methoxy-benzene
• 英文别名: 1-(1-Ethoxy-2-methylprop-1-enyl)-4-methoxybenzene
• CAS: 40811-09-4
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: ZFYLQQCXCHBLKQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  乙醇 、 1-(1-溴-2-甲基丙-1-烯基)-4-甲氧基苯 以 乙腈 为溶剂， 生成 1-(1-Ethoxy-2-methyl-propenyl)-4-methoxy-benzene
  参考文献：
  名称：

  为什么乙烯基阳离子是缓慢的亲电试剂？

  摘要：

  乙烯基阳离子 2 [Ph2C=C+-(4-MeO-C6H4)] 和 3 [Me2C=C+-(4-MeO-C6H4)]（由激光闪光光解产生）与多种亲核试剂（例如、吡咯、卤化物离子和含有不同量水或醇的溶剂）已通过光度法测定。发现亲核试剂对这些乙烯基阳离子的反应顺序与对二芳基碳鎓离子（二苯甲基鎓离子）的反应顺序相同。然而，乙烯基阳离子的反应速率受亲核试剂变化的影响仅是二苯甲基离子的反应速率的一半。因此，乙烯基阳离子和二苯甲基离子的相对反应性在很大程度上取决于亲核试剂的性质。结果表明，乙烯基阳离子 2 和 3 分别反应，使用三氟乙醇比母体二苯鎓离子 (Ph)2CH+ 慢 227 和 14 倍，即使在溶剂分解反应（25°C 时为 80% 乙醇水溶液）中，导致 2 和 3 的乙烯基溴离子化得更慢（半衰期 1.15年和 33 天）比 (Ph)2CH-Br（半衰期 23 秒）。通过高级 MO 计算研究了这

  DOI：

  10.1021/jacs.6b10889

文献信息

• Rappoport,Z.; Gal,A., Journal of the Chemical Society. Perkin transactions II, 1973, p. 301 - 310
  作者：Rappoport,Z.、Gal,A.

  DOI：——

  日期：——
• Stability−Reactivity Relation on the Reaction of β,β-Disubstituted Vinyl Cations with Ethanol
  作者：Shinjiro Kobayashi、Yuji Hori、Toshinori Hasako、Ken-ichi Koga、Hiroshi Yamataka

  DOI：10.1021/jo9603441

  日期：1996.1.1

  A family of beta,beta-disubstituted alpha-(p-methoxyphenyl)vinyl cations has been generated by the laser flash photolysis of the corresponding vinyl bromides, and the rates of reactions of the cations with ethanol in acetonitrile have been measured at 25 degrees C. The observed rate constants differ greatly depending on the substituents, ranging from 3.05 x 10(5) L mol(-1) s(-1) to 8.18 x 10(7) L mol(-1) s(-1). The thermodynamic stabilities of the vinyl cations have been estimated by means of ab initio MO calculations for model compounds, which reveals that their stability is almost unaffected by beta,beta-dialkyl substituents. In the present system, therefore, the stability-reactivity relation, in which a less stable cation is expected to show higher reactivity, breaks down. Several model transition structures have been considered in the MO calculations, and the results indicate that the beta substituents can move away from the incoming nucleophile to avoid steric congestion but that there still exists a large steric repulsion in the transition state; The calculations indicate that the reactivity of the vinyl cations is primarily controlled by this steric effect, which is the reason for the breakdown of the stability-reactivity relationship.