5,13-di-tert-butyl-8,16-difluoro<2.2>metacyclophane-1,9-diene | 92661-23-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 5,13-di-tert-butyl-8,16-difluoro<2.2>metacyclophane-1,9-diene
• 英文别名: 5,13-di-tert-butyl-8,16-difluoro[2.2]metacyclophane-1,9-diene
• CAS: 92661-23-9
• 化学式: C₂₄H₂₆F₂
• 分子量: 352.467
• InChiKey: YIILGJFJBAGHHG-XOHWUJONSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.43
• 重原子数：
  26.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  5,13-di-tert-butyl-8,16-difluoro<2.2>metacyclophane-1,9-diene 在 溴 作用下， 以 四氯化碳 为溶剂， 反应 0.25h， 以90%的产率得到1,2,9,10-tetrabromo-5,13-di-tert-butyl-8,16-difluoro<2.2>metacyclophane
  参考文献：
  名称：

  Metacyclophanes and related compounds. 22. Medium-sized cyclophanes. Preparation and valence tautomerism of 8,16-disubstituted [2.2]metacyclophane-1,9-dienes

  摘要：

  Introduction of functional groups other than hydrogen or alkyl groups into the internal positions of [2.2]metacyclophane-1,9-dienes was attempted. [2.2]Metacyclophane-1,9-dienes 6a-6g, bearing variously halogen, methoxy, and methyl substituents in the 8 and 16 positions, were prepared from the corresponding bis(halomethyl)benzenes 1 and bis(mercaptomethyl)benzenes 2 involving use of Wittig rearrangement of 2,11-dithia-[3.3]metacyclophanes followed by Hofmann elimination. Although 6a-6c, 6f, and 6g were isolated as thermally stable crystals, isolation of 6d failed since this compound was thermally labile and transformed spontaneously into 2,7-di-tert-butyl-1-chloropyrene (7). The photochemical and thermal valence tautomerizations of [2.2]metacyclophanes which were prepared in the present work are described. Attempts to convert 8,16-disubstituted [2.2]metacyclophane-1,9-dienes 6 to 4,5,9,10-tetrabromo-10b,10c-disubstituted 10b,10c-dihydropyrenes by treatment of these compounds with bromine in carbon tetrachloride failed but instead gave addition products 13 and transannular reaction products 14. The reaction pathways of the bromination are also discussed.

  DOI：

  10.1021/jo00027a047
• 作为产物：
  描述：

  dimethoxymethylium tetrafluoroborate 、 syn/anti-6,15-di-tert-butyl-9,18-difluoro-2,11-dithia<3.3>metacyclophane 、 碘甲烷 生成 5,13-di-tert-butyl-8,16-difluoro<2.2>metacyclophane-1,9-diene
  参考文献：
  名称：

  Metacyclophanes and related compounds. 22. Medium-sized cyclophanes. Preparation and valence tautomerism of 8,16-disubstituted [2.2]metacyclophane-1,9-dienes

  摘要：

  Introduction of functional groups other than hydrogen or alkyl groups into the internal positions of [2.2]metacyclophane-1,9-dienes was attempted. [2.2]Metacyclophane-1,9-dienes 6a-6g, bearing variously halogen, methoxy, and methyl substituents in the 8 and 16 positions, were prepared from the corresponding bis(halomethyl)benzenes 1 and bis(mercaptomethyl)benzenes 2 involving use of Wittig rearrangement of 2,11-dithia-[3.3]metacyclophanes followed by Hofmann elimination. Although 6a-6c, 6f, and 6g were isolated as thermally stable crystals, isolation of 6d failed since this compound was thermally labile and transformed spontaneously into 2,7-di-tert-butyl-1-chloropyrene (7). The photochemical and thermal valence tautomerizations of [2.2]metacyclophanes which were prepared in the present work are described. Attempts to convert 8,16-disubstituted [2.2]metacyclophane-1,9-dienes 6 to 4,5,9,10-tetrabromo-10b,10c-disubstituted 10b,10c-dihydropyrenes by treatment of these compounds with bromine in carbon tetrachloride failed but instead gave addition products 13 and transannular reaction products 14. The reaction pathways of the bromination are also discussed.

  DOI：

  10.1021/jo00027a047