6-Bromo-tricyclo[11.3.1.1^5,9]octadeca-1(16),5,7,9(18),13(17),14-hexaene | 144194-77-4

• 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: 6-Bromo-tricyclo[11.3.1.1^5,9]octadeca-1(16),5,7,9(18),13(17),14-hexaene
• 英文别名: 6-Bromotricyclo[11.3.1.15,9]octadeca-1(16),5,7,9(18),13(17),14-hexaene
• CAS: 144194-77-4
• 化学式: C₁₈H₁₉Br
• 分子量: 315.253
• InChiKey: GZJRTVMWGHNSRA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  6-Bromo-tricyclo[11.3.1.1^5,9]octadeca-1(16),5,7,9(18),13(17),14-hexaene 在 正丁基锂 、 硫酸 作用下， 反应 17.42h， 生成 5-(methoxycarbonyl)<3.3>metacyclophane
  参考文献：
  名称：

  Conformational analysis of [3.3]cyclophanes. 4. A conformational study of [3.3]metacyclophanes through variable-temperature proton NMR and optical rotation

  摘要：

  Conformational behavior of 2,2,11,11-tetradeuterio[3.3]metacyclophanes 1-d4 and 2-d4 has been studied by a variable-temperature (VT) H-1 NMR method. In order to simplify the interpretation of the H-1 NMR spectrum, four deuteriums were introduced at C-2 and C-11 positions of the trimethylene bridges of [3.3]metacyclophanes by reductive desulfurization of 2,11-bis(1,4-dithiabutane-1,4-diyl)[3.3]metacyclophanes 4 and 5 with tri-n-butyltin deuteride. Our previous conformational study of tetradeuterio-1,4-dioxa[4.3.3]cyclophane (3-d4) revealed that the temperature-dependent phenomenon in the H-1 NMR spectrum of 1 was ascribed to the inversion the trimethylene bridges. The work also suggested the presence of benzene ring inversion. To confirm this, optically active [3.3]metacyclophanechromium tricarbonyl complexes (-)- and (+)-17 were prepared by means of the HPLC separation of racemic complex (+/-)-17 using a chiral stationary phase. Racemization occurred when (-)- and (+)-17 were decomplexed at 20-degrees-C. This result as well as the fact that the energy barrier (DELTAG(double dagger)) for the benzene ring inversion could not be detected by the VT NMR method indicated that the barrier is much lower than that of trimethylene bridge inversion (DELTAG(double dagger) = 11-12 kcal/mol). The most stable conformer of 1-d4 and 2-d4 is a syn(chair-chair), and the less stable conformer is estimated to be a syn(chair-boat) on the basis of the H-1 NMR data.

  DOI：

  10.1021/jo00050a031
• 作为产物：
  描述：

  6-Bromo-tricyclo[11.3.1.1^5,9]octadeca-1(16),5,7,9(18),13(17),14-hexaene-3,11-dione 在 氢氧化钾 、 一水合肼 作用下， 以 various solvent(s) 为溶剂， 以92%的产率得到6-Bromo-tricyclo[11.3.1.1^5,9]octadeca-1(16),5,7,9(18),13(17),14-hexaene
  参考文献：
  名称：

  Conformational analysis of [3.3]cyclophanes. 4. A conformational study of [3.3]metacyclophanes through variable-temperature proton NMR and optical rotation

  摘要：

  Conformational behavior of 2,2,11,11-tetradeuterio[3.3]metacyclophanes 1-d4 and 2-d4 has been studied by a variable-temperature (VT) H-1 NMR method. In order to simplify the interpretation of the H-1 NMR spectrum, four deuteriums were introduced at C-2 and C-11 positions of the trimethylene bridges of [3.3]metacyclophanes by reductive desulfurization of 2,11-bis(1,4-dithiabutane-1,4-diyl)[3.3]metacyclophanes 4 and 5 with tri-n-butyltin deuteride. Our previous conformational study of tetradeuterio-1,4-dioxa[4.3.3]cyclophane (3-d4) revealed that the temperature-dependent phenomenon in the H-1 NMR spectrum of 1 was ascribed to the inversion the trimethylene bridges. The work also suggested the presence of benzene ring inversion. To confirm this, optically active [3.3]metacyclophanechromium tricarbonyl complexes (-)- and (+)-17 were prepared by means of the HPLC separation of racemic complex (+/-)-17 using a chiral stationary phase. Racemization occurred when (-)- and (+)-17 were decomplexed at 20-degrees-C. This result as well as the fact that the energy barrier (DELTAG(double dagger)) for the benzene ring inversion could not be detected by the VT NMR method indicated that the barrier is much lower than that of trimethylene bridge inversion (DELTAG(double dagger) = 11-12 kcal/mol). The most stable conformer of 1-d4 and 2-d4 is a syn(chair-chair), and the less stable conformer is estimated to be a syn(chair-boat) on the basis of the H-1 NMR data.

  DOI：

  10.1021/jo00050a031

文献信息

• Conformational analysis of [3.3]cyclophanes. 4. A conformational study of [3.3]metacyclophanes through variable-temperature proton NMR and optical rotation
  作者：Katsuya Sako、Teruo Shinmyozu、Hiroyuki Takemura、Masahiko Suenaga、Takahiko Inazu

  DOI：10.1021/jo00050a031

  日期：1992.11

  Conformational behavior of 2,2,11,11-tetradeuterio[3.3]metacyclophanes 1-d4 and 2-d4 has been studied by a variable-temperature (VT) H-1 NMR method. In order to simplify the interpretation of the H-1 NMR spectrum, four deuteriums were introduced at C-2 and C-11 positions of the trimethylene bridges of [3.3]metacyclophanes by reductive desulfurization of 2,11-bis(1,4-dithiabutane-1,4-diyl)[3.3]metacyclophanes 4 and 5 with tri-n-butyltin deuteride. Our previous conformational study of tetradeuterio-1,4-dioxa[4.3.3]cyclophane (3-d4) revealed that the temperature-dependent phenomenon in the H-1 NMR spectrum of 1 was ascribed to the inversion the trimethylene bridges. The work also suggested the presence of benzene ring inversion. To confirm this, optically active [3.3]metacyclophanechromium tricarbonyl complexes (-)- and (+)-17 were prepared by means of the HPLC separation of racemic complex (+/-)-17 using a chiral stationary phase. Racemization occurred when (-)- and (+)-17 were decomplexed at 20-degrees-C. This result as well as the fact that the energy barrier (DELTAG(double dagger)) for the benzene ring inversion could not be detected by the VT NMR method indicated that the barrier is much lower than that of trimethylene bridge inversion (DELTAG(double dagger) = 11-12 kcal/mol). The most stable conformer of 1-d4 and 2-d4 is a syn(chair-chair), and the less stable conformer is estimated to be a syn(chair-boat) on the basis of the H-1 NMR data.