9-t-butyl-1,2,3,4-tetrafluorotriptycene | 89657-23-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 9-t-butyl-1,2,3,4-tetrafluorotriptycene
• CAS: 89657-23-8
• 化学式: C₂₄H₁₈F₄
• 分子量: 382.401
• InChiKey: PJVIEOVDSWARKM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.43
• 重原子数：
  28.0
• 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

• 作为产物：
  描述：

  9-T-丁基蒽 、 2-氨基-3,4,5,6-四氟苯甲酸 在 亚硝酸异戊酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.0h， 以37%的产率得到9-t-butyl-1,2,3,4-tetrafluorotriptycene
  参考文献：
  名称：

  Dependence of through-space proton-fluorine-19 coupling on molecular geometry in 9-alkyl-1,2,3,4-tetrafluorotriptycene derivatives

  摘要：

  DOI：

  10.1021/jo00185a013

文献信息

• Reactivities of Stable Rotamers. XXXIX. Thermal Decomposition of<b><i>t</i></b>-Butyl 3-Methyl-3-(substituted 9-triptycyl)peroxybutanoate Rotamers
  作者：Michinori Oki、Ichiro Fujino、Daisuke Kawaguchi、Kazumasa Chuda、Yoko Moritaka、Yasunori Yamamoto、Shingo Tsuda、Tadashi Akinaga、Michihiko Aki、Hiroharu Kojima、Nobuhiro Morita、Makoto Sakurai、Shinji Toyota、Yasuhiro Tanaka、Toshihiro Tanuma、Gaku Yamamto

  DOI：10.1246/bcsj.70.457

  日期：1997.2

  The ap and sc rotamers of the title compound, where substituents are 1,4-dimethyl, 1,4-dimethoxy, 1,2,3,4-tetrafluoro, and 1,2,3,4-tetrachloro, were thermolyzed in toluene solutions to examine the effects of interactions between the radical center and the substituent. The rates of thermolyses were affected neither by the substituent nor by the rotameric positions, but the product distributions showed dependence on the substituent. In the ap-forms, the effectively bulkier the substituent at the 1-position, the higher the yields of the 5-membered ring compound. This was attributed to the degree of the tilting of the 9-substituent, which forces the radical center to be pushed into the triptycene skeleton. For the sc-forms, the chloro and the methyl substituents exhibited special effects, the former affording a colligation product between benzyl and 2-(1,2,3,4-tetrachloro-9-triptycyl)-2-methylpropyl radicals and the latter showing a tendency of radical migration to the benzylic position. Comparison of the results of thermolyses of the 1,4-dimethyl peroxyester with those of 2(1H)-thioxo-1-pyridyl 3-(1,4-dimethyl-9-triptycyl)-3-methylbutanoate indicates that, although it is believed that these precursors afford the same 2-(1,4-dimethyl-9-triptycyl)-2-methylpropyl radicals, the product distributions were significantly different from each other. These results were attributed to the stabilizing effects of the sulfur compound on the radical in the solvent cage in the latter.

  在甲苯溶液中对取代基为 1,4-二甲基、1,4-二甲氧基、1,2,3,4-四氟和 1,2,3,4-四氯的标题化合物的 ap 和 sc 转聚体进行热解，以考察自由基中心与取代基之间相互作用的影响。热解速率既不受取代基的影响，也不受转子位置的影响，但产物分布却与取代基有关。在 ap 型化合物中，1 位上的取代基越大，5 元环化合物的产量就越高。这是因为 9-取代基的倾斜程度迫使自由基中心挤入三庚烯骨架。对于 sc 形式，氯和甲基取代基显示出特殊效果，前者在苄基和 2-（1,2,3,4-四氯-9-三辛基）-2-甲基丙基自由基之间产生碰撞产物，后者则显示出自由基向苄基位置迁移的趋势。将 1,4-二甲基过氧化酯的热解结果与 2(1H)-硫酮-1-吡啶基 3-(1,4-二甲基-9-三甲苯基)-3-甲基丁酸酯的热解结果进行比较后发现，虽然认为这些前体产生的 2-(1,4-二甲基-9-三甲苯基)-2-甲基丙基自由基相同，但产物分布却明显不同。这些结果归因于硫化合物对后者溶剂笼中自由基的稳定作用。