1-ethoxy-1-(p-methoxyphenyl)-2,2-diphenylethene | 122127-42-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1-ethoxy-1-(p-methoxyphenyl)-2,2-diphenylethene
• 英文别名: 1-Anisyl-2,2-diphenylvinyl-1-aethylaether；1-(1-Ethoxy-2,2-diphenylethenyl)-4-methoxybenzene
• CAS: 122127-42-8
• 化学式: C₂₃H₂₂O₂
• 分子量: 330.426
• InChiKey: PMOIAWPPBIMWDT-UHFFFAOYSA-N

物化性质

• 熔点：
  108-109 °C
• 沸点：
  453.9±33.0 °C(Predicted)
• 密度：
  1.080±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 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：
  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-2,2-二苯基乙烯基)-4-甲氧基苯 以 乙腈 为溶剂， 生成 1-ethoxy-1-(p-methoxyphenyl)-2,2-diphenylethene
  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

• Drastic Base Dependence of Products in Photolysis of 1-(<i>p</i>-Methoxyphenyl)-2,2-diphenylvinyl Bromide. ipso Substitution by Alkoxide Ions
  作者：Tsugio Kitamura、Takashi Kabashima、Shinjiro Kobayashi、Hiroshi Taniguchi

  DOI：10.1246/cl.1988.1951

  日期：1988.12.5

  Addition of alkoxide ions resulted in ipso substitution in the photolysis of an alcohol solution of 1-(p-methoxyphenyl)-2,2-diphenylvinyl bromide, whereas addition of triethylamine, pyridine, or NaHCO3 led to vinylic substitution.

  醇盐离子的添加​​导致 1-(对甲氧基苯基)-2,2-二苯基溴乙烯醇溶液光解中的 ipso 取代，而三乙胺、吡啶或 NaHCO3 的添加导致乙烯基取代。
• Ipso substitution of triarylvinyl cations by alkoxide anions
  作者：Tsugio Kitamura、Takashi Kabashima、Ichizo Nakamura、Tetsuro Fukuda、Hiroshi Taniguchi

  DOI：10.1021/ja00019a025

  日期：1991.9

  Photolysis and solvolysis of triarylbromoethanes 1 in the presence of alkoxide anions in alcohols resulted in significant formation of products derived from ipso substitution by alkoxide anions. Photolysis of 1-aryl-1-bromo-2,2-diphenylethenes 1Aa and 1Ab with 10 mol equiv of alkoxide anions gave 1-alkoxy-1-aryl-2,2-diphenylethenes 2A and 3,3-dialkoxy-6-(2,2-diphenylvinylidene)-1,4-cyclohexadienes 3A (ipso adducts). However, the photolysis with weak bases such as TEA, pyridine, NaHCO3, and K2CO3 did not give ipso adducts 3A but only enol ethers 2A. Interestingly, photolysis of 2,2-bis(p-alkoxyphenyl)-1-bromo-1-phenylethenes 4a and 4b with NaOEt in ethanol afforded ipso adducts 6a and 6b, respectively, which had a 1,2-aryl-rearranged structure. Furthermore, solvolysis of 1-bromo-1-(p-methoxyphenyl)ethenes 1Aa, 1Ba, and 1Ca in ethanol containing 10 mol equiv of NaOEt at 120-130-degrees-C for 1-3 days provided p-ethoxyphenyl-substituted enol ethers 2bb, p-ethoxyphenyl-substituted bromoethenes 1b, and p-methoxyphenyl-substituted enol ethers 2ab, respectively. The major formation of p-ethoxyphenyl-substituted compounds (ipso-substituted products) suggests that there is no large difference in ipso substitution between vinyl cations generated by photolysis and solvolysis. On the basis of the results obtained above the factors affecting ipso attack on arylvinyl cations are discussed.
• 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.
• KITAMURA, TSUGIO;KABASHIMA, TAKASHI;KOBAYASHI, SHINJIRO;TANIGUCHI, HIROSH+, CHEM. LETT.,(1988) N 12, C. 1951-1954
  作者：KITAMURA, TSUGIO、KABASHIMA, TAKASHI、KOBAYASHI, SHINJIRO、TANIGUCHI, HIROSH+

  DOI：——

  日期：——
• Why Are Vinyl Cations Sluggish Electrophiles?
  作者：Peter A. Byrne、Shinjiro Kobayashi、Ernst-Ulrich Würthwein、Johannes Ammer、Herbert Mayr

  DOI：10.1021/jacs.6b10889

  日期：2017.2.1

  slowly with trifluoroethanol than the parent benzhydrylium ion (Ph)2CH+, even though in solvolysis reactions (80% aqueous ethanol at 25 °C) the vinyl bromides leading to 2 and 3 ionize much more slowly (half-lives 1.15 yrs and 33 days) than (Ph)2CH-Br (half-life 23 s). The origin of this counterintuitive phenomenon was investigated by high-level MO calculations. We report that vinyl cations are not

  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