1-异亚丙基-3-苯基-2-环丁烯 | 116053-66-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1-异亚丙基-3-苯基-2-环丁烯
• 英文名称: 1-Isopropylidene-3-phenyl-2-cyclobutene
• 英文别名: (3-Propan-2-ylidenecyclobuten-1-yl)benzene
• CAS: 116053-66-8
• 化学式: C₁₃H₁₄
• 分子量: 170.254
• InChiKey: WAWFNXPTYHQDNI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-异亚丙基-3-苯基-2-环丁烯 在 polymer-based Rose Bengal 、 氧气 作用下， 以 氯仿 为溶剂， 反应 2.0h， 生成 (3-Hydroperoxy-3-prop-1-en-2-ylcyclobuten-1-yl)benzene
  参考文献：
  名称：

  环氧丁烯在环丁烯酮和环丁烯醇的合成和反应中的中介作用

  摘要：

  Vinylcyclobutenol 7，产生经由alkylidenecyclobutene的单氧合5，重排在室温下的异构体二烯酮的溶剂取决于混合物10和11。Alkylidenecyclobutene 5被依次制备经由逆维蒂希加入异丙基叶立德cyclobutenone的4 ; 在将酮通常加到叶立德中时，还得到乙烯基亚丙基12。最后，相应的4，4-二氯环丁烯酮3的Wittig反应仅产生2，4-二氯异构体13。当该反应在n的存在下进行时-丁氧化物生成二烯酮32。

  DOI：

  10.1016/s0040-4020(99)00695-x
• 作为产物：
  描述：

  Trimethyl-(2-phenyl-4-propan-2-ylidenecyclobut-2-en-1-yl)silane 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以99%的产率得到1-异亚丙基-3-苯基-2-环丁烯
  参考文献：
  名称：

  Murakami, Masahiro; Amii, Hideki; Itami, Kenichiro, Angewandte Chemie, 1995, vol. 107, # 13/14, p. 1649 - 1650

  摘要：

  DOI：

文献信息

• Surprising exocyclic regioselectivity in electrophilic additions to alkylidenecyclobutenes
  作者：Hillel Pizem、Ofer Sharon、Aryeh A. Frimer

  DOI：10.1016/s0040-4020(02)00267-3

  日期：2002.4

  alkylidenecyclobutenes shows a strong regioselectivity—in some cases regiospecificity—for the exocyclic double bond. Depending on the reagent, the endocyclic double bond will only undergo reaction upon the addition of a second equivalent of reagent. In the case of the first three reagents, this exocyclic regioselectivity is rationalized by invoking the formation of the more stabilized carbocation intermediate

  向亚烷基环丁烯中添加过酸，溴，TCNE和单线态氧显示出对环外双键的强烈区域选择性（在某些情况下为区域特异性）。取决于试剂，内环双键将仅在添加第二当量的试剂时发生反应。在前三种试剂的情况下，通过调用更稳定的碳正离子中间体或过渡态的形成来合理化这种环外区域选择性。关于1 O 2，其中极性机制很少，我们将此环外区域选择性归因于不适当的排列，因此缺乏环内烯丙基氢的反应性。
• Study of the substituted vinylallene-methylenecyclobutene electrocyclic equilibria. Comparison with the butadiene-cyclobutene and bisallene-bismethylenecyclobutene electrocyclic equilibria
  作者：Daniel J. Pasto、Wei Kong

  DOI：10.1021/jo00278a010

  日期：1989.8
• Preparation and Photosensitized Oxidation of Isopropylidenecyclobutanes and -cyclobutenes
  作者：Aryeh A. Frimer、Joseph Weiss、Hugo E. Gottlieb、Joel L. Wolk

  DOI：10.1021/jo00083a019

  日期：1994.2

  Isopropylidenecyclobutanes 2-5 underwent facile ene reaction with singlet dioxygen, yielding (upon Ph(3)P reduction) the corresponding pairs of epimeric allylic alcohols 9 and 10, 11 and 12, 13 and 14, and 15 and 16, respectively. A combination of spectral evidence and molecular modeling studies were utilized in the structural assignment of the epimers. The data clearly indicate that steric considerations play an important role in determining the face of the ring which O-1(2) approaches. Isopropylidenecyclobutenes 6 and 7 reacted with singlet oxygen more slowly than their monoolefinic analogs, yielding upon reduction allylic alcohols 21b and 22, respectively. Benzo analog 7 also generated a small and solvent-dependent amount of isomeric aldehydes 23 and 24, presumably via a free-radical mechanism. n-Butyl diene 8 underwent rapid photosensitized oxygenation producing allylic alcohol 35 (as the O-1(2) ene product) and dione 37 (the Hock-cleavage product of allylic hydroperoxide 39, formed in turn via a free-radical route) in a 1:9 ratio. Ah initio (STO-3G) calculations confirm that, in their lowest energy conformations, compounds 2-8 are planar with the methylene ring hydrogens displaced ca. 36 degrees from the perpendicular. As a result, only exocyclic ene product is formed, since O-1(2) strongly prefers axial or pseudoaxial allylic hydrogens. These calculations combined with the relative rate data suggest that the initial interaction between the electrophilic O-1(2) and alkylidenecyclobutenes involves both ends of the singlet dioxygen molecule, in which the ''front'' end attacks the reactive exocyclic double bond while the ''back'' end obtains stabilization by interacting with the more electron rich but unreactive endocyclic olefin linkage. Because of this added, and presumably substantial, stabilization, the relative rates within this system are determined in part by the orbital coefficients at the latter olefinic center.
• Cycloaddition reactions of 1,1-dimethylallene with substituted alkynes
  作者：Daniel J. Pasto、Wei Kong

  DOI：10.1021/jo00255a027

  日期：1988.9
• PASTO, DANIEL J.;KONG, WEI, J. ORG. CHEM., 54,(1989) N3, C. 3215-3216
  作者：PASTO, DANIEL J.、KONG, WEI

  DOI：——

  日期：——

表征谱图