4,12,15-tribromo<2.2>paracyclophane | 146304-47-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 4,12,15-tribromo<2.2>paracyclophane
• 英文别名: 4,7,12-tribromo<2.2>paracyclophane；5,11,13-tribromotricyclo[8.2.2.24,7]hexadeca-1(13),4,6,10(14),11,15-hexaene
• CAS: 146304-47-4
• 化学式: C₁₆H₁₃Br₃
• 分子量: 444.991
• InChiKey: GKZYMDNXSZDLQM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.86
• 重原子数：
  19.0
• 可旋转键数：
  0.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  苯乙烯 、 4,12,15-tribromo<2.2>paracyclophane 在 palladium diacetate 、 四丁基溴化铵 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 72.0h， 以27%的产率得到4,7,12-tristyryl<2.2>paracyclophane
  参考文献：
  名称：

  Koenig, Burkhard; Knieriem, Burkhard; Meijere, Armin de, Chemische Berichte, 1993, vol. 126, # 7, p. 1643 - 1650

  摘要：

  DOI：
• 作为产物：
  描述：

  对二甲苯二聚体 在 溴 、 铁粉 作用下， 以 四氯化碳 为溶剂， 反应 3.0h， 生成 4,12,15-tribromo<2.2>paracyclophane
  参考文献：
  名称：

  The first three aromatic tribromides of the [2.2]paracyclophane series

  摘要：

  From the reaction mixtures in the uncatalyzed polybromination of [2.2]paracyclophane by the action of excess Br2 in CCl4, there have been found along with the known products - 4,15- and 4,16-dibromo[2.2]paracyclophanes - two new aromatic tribromides of this series, which have been isolated in pure form: 4,12,15- and 4,15,16-tribromo[2.2]paracyclophanes. Special experiments demonstrated that the mixtures of these tribromides are formed as a result of competitive monobromination of 4,15-dibromo[2.2]paracyclophane; the 4,15,16-tribromo[2.2]paracyclophane, together with still another newly isolated isomer of this series - 4,8,12-tribromo[2.2]paracyclophane - is formed as a result of competitive monobromination of 4,16-dibromo[2.2]paracyclophane. As an explanation of the features of the orienting effect of substituents in these competing reactions, a rule was proposed: On the conventional orientation (from the electronic point of view) of entry of the bromine atom into the substituted ring (para > ortho > meta), a steric limitation is imposed on its attack in the pseudo-gem-position, owing to the bulky bromine atom that is transannularly positioned above it in the neighboring aromatic ring. The structures of all of the tribromides were established on the basis of elemental analyses, mass spectrometry, and H-1 NMR spectrometry (including PMR using the homonuclear Overhauser effect). The data obtained in this work indicate that the 4,12,15-tribromo[2.2]paracyclophane and 4,15,16-tribromo[2.2]paracyclophane are predecessors of the two tetrabromides previously obtained by Cram - 4,7,12,15- and 4,5,15,16-tetrabromo[2.2]paracyclophanes; and the 4,8,12-tribromo[2.2]paracyclophane is a possible predecessor of 4,8,12,16-tetrabromo[2.2]paracyclophane, which is unknown up to the present time.

  DOI：

  10.1007/bf00864341

文献信息

• Koenig, Burkhard; Knieriem, Burkhard; Meijere, Armin de, Chemische Berichte, 1993, vol. 126, # 7, p. 1643 - 1650
  作者：Koenig, Burkhard、Knieriem, Burkhard、Meijere, Armin de

  DOI：——

  日期：——
• The first three aromatic tribromides of the [2.2]paracyclophane series
  作者：V. A. Nikanorov、V. G. Kharitonov、E. V. Yatsenko、D. P. Krut'ko、M. V. Galakhov、S. O. Yakushin、V. V. Mikul'shina、V. I. Rozenberg、V. N. Guryshev、V. P. Yur'ev、O. A. Reutov

  DOI：10.1007/bf00864341

  日期：1992.8

  From the reaction mixtures in the uncatalyzed polybromination of [2.2]paracyclophane by the action of excess Br2 in CCl4, there have been found along with the known products - 4,15- and 4,16-dibromo[2.2]paracyclophanes - two new aromatic tribromides of this series, which have been isolated in pure form: 4,12,15- and 4,15,16-tribromo[2.2]paracyclophanes. Special experiments demonstrated that the mixtures of these tribromides are formed as a result of competitive monobromination of 4,15-dibromo[2.2]paracyclophane; the 4,15,16-tribromo[2.2]paracyclophane, together with still another newly isolated isomer of this series - 4,8,12-tribromo[2.2]paracyclophane - is formed as a result of competitive monobromination of 4,16-dibromo[2.2]paracyclophane. As an explanation of the features of the orienting effect of substituents in these competing reactions, a rule was proposed: On the conventional orientation (from the electronic point of view) of entry of the bromine atom into the substituted ring (para > ortho > meta), a steric limitation is imposed on its attack in the pseudo-gem-position, owing to the bulky bromine atom that is transannularly positioned above it in the neighboring aromatic ring. The structures of all of the tribromides were established on the basis of elemental analyses, mass spectrometry, and H-1 NMR spectrometry (including PMR using the homonuclear Overhauser effect). The data obtained in this work indicate that the 4,12,15-tribromo[2.2]paracyclophane and 4,15,16-tribromo[2.2]paracyclophane are predecessors of the two tetrabromides previously obtained by Cram - 4,7,12,15- and 4,5,15,16-tetrabromo[2.2]paracyclophanes; and the 4,8,12-tribromo[2.2]paracyclophane is a possible predecessor of 4,8,12,16-tetrabromo[2.2]paracyclophane, which is unknown up to the present time.