1,1,7,10-Tetramethyl-1,2,6,10b-tetrahydro-6,10b-o-benzenoaceanthrylene | 128787-14-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 1,1,7,10-Tetramethyl-1,2,6,10b-tetrahydro-6,10b-o-benzenoaceanthrylene
• 英文别名: 1,1,7,10-tetramethyl-1,2,6,10b-tetrahydro-6,10b-o-benzoacenanthrene；1,1,7,10-tetramethyl-1,2,6,10b-o-benzenoaceanthrylene；2,2,11,14-Tetramethylhexacyclo[7.6.6.11,4.010,15.016,21.08,22]docosa-4(22),5,7,10,12,14,16,18,20-nonaene
• CAS: 128787-14-4
• 化学式: C₂₆H₂₄
• 分子量: 336.477
• InChiKey: TZFDLESDAMXFRG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  3-(1,4-dimethyl-9-triptycyl)-3-methylbutanoyl chloride 在 盐酸 、 sodium azide 、 potassium tert-butylate 、 亚硝酸异戊酯 作用下， 以 水 、 丙酮 、 苯 为溶剂， 反应 13.25h， 生成 1,1,7,10-Tetramethyl-1,2,6,10b-tetrahydro-6,10b-o-benzenoaceanthrylene
  参考文献：
  名称：

  稳定旋转异构体的反应性。三十五。2-(1,4-二甲基-9-三苯甲基)-2-甲基丙胺旋转异构体的重氮化

  摘要：

  标题胺旋转异构体由相应的羧酸制备，并在苯中的乙酸存在下用亚硝酸异戊酯重氮化。该适体提供作为主要产物的烯烃，其在中间碳阳离子重排后通过去质子化衍生，以及少量相应乙酸酯和环化产物中的每一种，两者均衍生自未重排的阳离子。相比之下，烯烃是次要产物，环化产物在形式上是通过在重排之前将插入的阳离子插入 1-甲基的 C-H 键而衍生出来的，在 sc 异构体的情况下是主要的。该环状产物是独立合成的。在sc相对于ap的情况下，相应乙酸盐的产率增加到相当大的程度。

  DOI：

  10.1246/bcsj.68.1485

文献信息

• Reactivities of Stable Rotamers. XXXII. Chlorodecarboxylation of 3-(1,4-Dimethyl-9-triptycyl)-3-methylbutanoic Acid Rotamers
  作者：Michinori Oki、Yasushi Taguchi、Toshiyuki Okamoto、Tsutomu Miyasaka、Koji Hamada、Shinji Toyota、Katsumi Yonemoto、Gaku Yamamoto

  DOI：10.1246/bcsj.66.3790

  日期：1993.12

  carboxylic acid were treated with lead(IV) acetate in the presence of lithium chloride or benzyltriethylammonium chloride in benzene. The ap-isomer afforded a chloride, which was expected from normal chlorodecarboxylation, in addition to a cyclized compound, which was produced by radical addition to a near-by benzene ring. By contrast, the sc-isomer afforded no normal chloride, but a benzylic chloride, which

  在氯化锂或苄基三乙基氯化铵的苯中，用乙酸铅(IV)处理标题羧酸的旋转异构体。除了通过自由基加成到附近的苯环产生的环化化合物之外，对映异构体还提供氯化物，这是正常的氯代脱羧反应所预期的。相比之下，sc-异构体不提供正常氯化物，但主要产物是苄基氯化物，它是通过氢转移到苄基位置的 9-取代基中的自由基位点形成的。此外，获得原始sc-羧酸的丙酮酯和少量的1-乙酰氧基甲基化合物和烯烃。
• Syntheses and Structures of 1,1-Dimethyl-1,2,6,10b-tetrahydro-6,10b-<i>o</i>-benzenoaceanthrylenes: Sterically Congested Triptycenes Carrying Five-Membered Ring
  作者：Shinji Toyota、Masahiko Endo、Mitsuru Teruhi、Yoshiyuki Noda、Michinori Oki、Mikio Yamasaki、Takashi Shibahara

  DOI：10.1246/bcsj.66.2088

  日期：1993.7

  compounds which carry a five-membered ring condensed to the triptycene skeleton were synthesized by the Diels-Alder reaction of 1,1-dimethyl-1,2-dihydroaceanthrylene with a benzyne. The structures of three compounds were determined by X-ray crystallography. The molecules have several abnormal bond lengths and angles in addition to significant deformation of the benzene rings as well as the triptycene

  通过 1,1-二甲基-1,2-二氢乙酰蒽与苄的 Diels-Alder 反应合成了带有稠合到三苯乙烯骨架的五元环的空间压缩的标题化合物。三种化合物的结构通过 X 射线晶体学确定。除了苯环和三苯乙烯骨架的显着变形外，分子还有几个异常的键长和角度，以避免关于 C(1)–C(10b) 和 C(1)–C(2) 键的重叠构象. 7-10 位取代基的影响相当小，但在比较 C(10a)-C(10)-取代基键角时发现了一个有趣的键角变形。对二甲氧基化合物进行分子力学计算，以将计算结构与 X 射线结构进行比较。
• 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。
• Reactivities of Stable Rotamers XXXVII : Thermolyses and Photolyses of 2(1<i>H</i>)-Thioxo-1-pyridyl 3-(1,4-Dimethyl-9-triptycyl)-3-methylbutanoate Rotamers
  作者：Shinji Toyota、Michinori Oki

  DOI：10.1246/bcsj.69.177

  日期：1996.1

  dimers of radicals. The results are attributed to formation of high concentration of the radicals in photolyses. The product distributions are also affected by the phase, i. e. solution, melts, or solid, as well as temperature. Solid state photolyses afforded 2-pyridyl thioethers as almost exclusive products, suggesting that recombination of radicals in the cage is important under the conditions where

  通过标题化合物的分解，产生2-(1,4-二甲基-9-三苯甲基)-2-甲基丙基自由基旋转异构体。在热解过程中，α-异构体作为主要产物产生环状化合物，该化合物是由邻近苯环上的自由基攻击而形成的，而在 sc 的情况下，发生了广泛的重排以产生 1-取代的甲基衍生物。在光解中，从包括自由基二聚体在内的两种旋转异构体中发现了各种笼外产物。结果归因于在光解中形成高浓度的自由基。产物分布也受相（即溶液、熔体或固体）以及温度的影响。固态光解提供 2-吡啶基硫醚作为几乎独特的产品，
• Substantial differences in the product distributions between thermolyses and photolyses of 2-thiono-1-pyridyl 3-(1,4-dimethyl-9-triptycyl)-3-butanoate ester and the effects of rotational isomerism
  作者：Shinji Toyota、Michinori Ōki

  DOI：10.1016/0040-4039(94)02333-7

  日期：1995.2

  The product distribution in the thermolysis of the title compound was found to be substantially different from that in the photolysis. The product distribution was also affected by the rotational isomerism of the compound.

  发现标题化合物在热解中的产物分布与光解中的产物分布基本上不同。产物的分布也受该化合物的旋转异构性影响。