1-Isopropylidene-3-n-butylcyclobutane | 155189-49-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1-Isopropylidene-3-n-butylcyclobutane
• 英文别名: 1-Butyl-3-propan-2-ylidenecyclobutane
• CAS: 155189-49-4
• 化学式: C₁₁H₂₀
• 分子量: 152.28
• InChiKey: ADLXTFHSOZBNHU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 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-Isopropylidene-3-n-butylcyclobutane 在 polymer-based Rose Bengal 、 氧气 、 三苯基膦 作用下， 生成 3-Butyl-1-isopropenyl-cyclobutanol 、 3-Butyl-1-isopropenyl-cyclobutanol
  参考文献：
  名称：

  Preparation and Photosensitized Oxidation of Isopropylidenecyclobutanes and -cyclobutenes

  摘要：

  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.

  DOI：

  10.1021/jo00083a019
• 作为产物：
  描述：

  2,2-dichloro-3-butylcyclobutanone 在 正丁基锂 、 溶剂黄146 、 锌 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.75h， 生成 1-Isopropylidene-3-n-butylcyclobutane
  参考文献：
  名称：

  Preparation and Photosensitized Oxidation of Isopropylidenecyclobutanes and -cyclobutenes

  摘要：

  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.

  DOI：

  10.1021/jo00083a019

文献信息

• 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.

表征谱图