Perfluoro-3-allylcyclobutene | 161117-00-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: Perfluoro-3-allylcyclobutene
• 英文别名: 1,2,3,3,4-Pentafluoro-4-(1,1,2,3,3-pentafluoroprop-2-enyl)cyclobutene
• CAS: 161117-00-6
• 化学式: C₇F₁₀
• 分子量: 274.061
• InChiKey: KVJURHHEUIMMAJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  Perfluoro-3-allylcyclobutene 以11%的产率得到
  参考文献：
  名称：

  Jing Naiyong, Lemal David M., J. Org. Chem, 60 (1995) N 1, S 89-96

  摘要：

  DOI：
• 作为产物：
  描述：

  cis-Perfluoro-1,3,6-heptatriene 反应 18.0h， 以95%的产率得到Perfluoro-3-allylcyclobutene
  参考文献：
  名称：

  Thermal and Photochemistry of Perfluoro-1,6-heptadiene and the Perfluoro-1,3,6-heptatrienes

  摘要：

  Pyrolysis transformed the title diene (1) into a 9:1 mixture of perfluorobicyclo[3.1.1]heptane (2) and cis-perfluorobicyclo[3.2.0]heptane (3) at 300 degrees C and at > 450 degrees C principally into perfluarocyclopentene (11). Mercury-sensitized vapor phase photolysis of 1 also yielded 2 and 3, but the latter now dominated and its trans isomer 13 was formed as well. In the presence of nitrogen as a bath gas, the product was further enriched in the [3.2.0] isomers. Radical bromination of 1, a model reaction for the triplet photocyclization, gave cis- and trans-perfluoro-1,2-bis(bromomethyl)cyclopentane (IB). Configurations were assigned to the cis and trans isomers of perfluoro-1,3,6-heptatriene (19 and 20), and they were equilibrated with iodine/visible light (K-t-->c = 1.6(7) in CDCl3, 14 degrees C). The cis triene underwent electrocyclization at 133 degrees C to perfluoro-3-allylcyclobutene (27); thermal ring opening of this cyclobutene yielded exclusively the cis isomer. At 250 degrees C both the cis triene and the allylcyclobutene were transformed quantitatively into perfluorobicyclo[3.1.1]hept-2-ene (28). Trans triene gave no detectable cyclobutene over a range of temperatures, but yielded the [3.1.1] compound at 250 degrees C. Ultraviolet irradiation of cis triene produced the allylcyclobutene, and mercury photosensitization of either compound (or the trans triene) proceeded a step farther to give tricycloheptane valence isomers (31 and 32). The internal [2 + 2] cycloadditions described here contribute to our knowledge of the ground rules for reactions of this type in unsaturated fluorocarbons.

  DOI：

  10.1021/jo00106a019

文献信息

• Jing Naiyong, Lemal David M., J. Org. Chem, 60 (1995) N 1, S 89-96
  作者：Jing Naiyong, Lemal David M.

  DOI：——

  日期：——
• Thermal and Photochemistry of Perfluoro-1,6-heptadiene and the Perfluoro-1,3,6-heptatrienes
  作者：Naiyong Jing、David M. Lemal

  DOI：10.1021/jo00106a019

  日期：1995.1

  Pyrolysis transformed the title diene (1) into a 9:1 mixture of perfluorobicyclo[3.1.1]heptane (2) and cis-perfluorobicyclo[3.2.0]heptane (3) at 300 degrees C and at > 450 degrees C principally into perfluarocyclopentene (11). Mercury-sensitized vapor phase photolysis of 1 also yielded 2 and 3, but the latter now dominated and its trans isomer 13 was formed as well. In the presence of nitrogen as a bath gas, the product was further enriched in the [3.2.0] isomers. Radical bromination of 1, a model reaction for the triplet photocyclization, gave cis- and trans-perfluoro-1,2-bis(bromomethyl)cyclopentane (IB). Configurations were assigned to the cis and trans isomers of perfluoro-1,3,6-heptatriene (19 and 20), and they were equilibrated with iodine/visible light (K-t-->c = 1.6(7) in CDCl3, 14 degrees C). The cis triene underwent electrocyclization at 133 degrees C to perfluoro-3-allylcyclobutene (27); thermal ring opening of this cyclobutene yielded exclusively the cis isomer. At 250 degrees C both the cis triene and the allylcyclobutene were transformed quantitatively into perfluorobicyclo[3.1.1]hept-2-ene (28). Trans triene gave no detectable cyclobutene over a range of temperatures, but yielded the [3.1.1] compound at 250 degrees C. Ultraviolet irradiation of cis triene produced the allylcyclobutene, and mercury photosensitization of either compound (or the trans triene) proceeded a step farther to give tricycloheptane valence isomers (31 and 32). The internal [2 + 2] cycloadditions described here contribute to our knowledge of the ground rules for reactions of this type in unsaturated fluorocarbons.