9-T-丁基蒽 | 13719-97-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 中文名称: 9-T-丁基蒽
• 英文名称: 9-tert-butylanthracene
• 英文别名: 9-t-butylanthracene
• CAS: 13719-97-6
• 化学式: C₁₈H₁₈
• 分子量: 234.341
• InChiKey: GWJJSVKKSBCHJD-UHFFFAOYSA-N

物化性质

• 熔点：
  105 °C
• 沸点：
  376.4±9.0 °C(Predicted)
• 密度：
  1.044±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 海关编码：
  2902909090

反应信息

• 作为反应物：
  描述：

  9-T-丁基蒽 在 臭氧 作用下， 以 丙酮 为溶剂， 以55%的产率得到Molozonide
  参考文献：
  名称：

  Palladium(II)-mediated oxidation of olefins using the transannular ozonides of 9-tert-butylanthracenes as an oxygen atom source

  摘要：

  DOI：

  10.1021/jo00224a081
• 作为产物：
  描述：

  9-t-butyl-9,10-dihydroanthracen-9-ol 在 四磷十氧化物 作用下， 以 四氯化碳 为溶剂， 反应 6.0h， 以70%的产率得到9-T-丁基蒽
  参考文献：
  名称：

  三并茂衍生物中不对称扭曲的苯的亲电取代

  摘要：

  在本文中，我们公开了9-取代的三联烯在亲电取代中的独特导向作用，以实现三联烯核的区域选择性功能化。Hirshfeld人口分析被用来预测亲电取代的选择性。发现TMS和t- Bu基团大大促进了在C 2位置的反应以产生C 3对称异构体。系统地研究了畸变与苯环内电荷分布之间的相关性。

  DOI：

  10.1021/acs.orglett.1c00970

文献信息

• Reactions of cupric halides with organic compounds—III
  作者：D. Mosnaim、D.C. Nonhebel、J.A. Russell

  DOI：10.1016/s0040-4020(01)82883-0

  日期：1969.1

  9-Alkyl and 9-arylanthracenes have been shown to undergo halogenation with cupric halides to give good yields of their 10-halogenated derivatives. Electron-donating groups in 9-arylanthracenes were shown to increase the rate of reaction. The results are interpreted in terms of a ligand-transfer mechanism.

  已显示9-烷基和9-芳基蒽通过卤化铜进行卤化以使其10-卤代衍生物具有良好的产率。显示9-芳基蒽中的给电子基团可增加反应速率。结果是根据配体转移机理来解释的。
• Substituent-Dependent Nitration of 9-Substituted 9,10-Dihydro-9,10-ethanoanthracenes
  作者：MC Harsanyi、RK Norris、G Sze、PK Witting

  DOI：10.1071/ch9951949

  日期：——

  Mononitration of 9-substituted ethanoanthracenes, bearing Me, But, F, Br, I, OMe , NO2, CN, CHO or CO2Me substituents at the bridgehead carbon, was found to occur exclusively at the β-positions of the aromatic ring. The mononitro products were isolated, identified by 1H n.m.r. spectroscopy, and their relative proportions were estimated by quantitative g.l.c . and/or by 1H n.m.r. spectroscopy. For all the above substrates the proportion of nitration at the β-position meta to the bridgehead carbon bearing the substituent [to give compounds of the general form (4)] was greater than the proportion of nitration at the corresponding β-position para to the bridgehead substituent [to give compounds of the general form (3)]. Whilst the preferential nitration at the β-positions of the aromatic rings is consistent with the previously reported nitration of 9,10-dihydro-9,10-ethanoanthracene (2a) itself, no observations of this preferential meta attack have been made previously. No correlation could be made of this behaviour with available substituent parameters for the widely sterically and electronically disparate set of substituents used in this study, and the origin of this preferential attack remains unclear. Dinitration in this system was studied only superficially. The influence of the bridgehead substituent together with that of the nitro group already present on one aromatic ring appear to combine with quite unpredictable results in orienting the position of attack of the incoming nitro group onto the other (non-nitrated) aromatic ring.

  研究发现，桥头碳上含有 Me、But、F、Br、I、OMe、NO2、CN、CHO 或 CO2Me 取代基的 9-取代乙蒽的单硝化作用只发生在芳香环的β位。单硝基产物被分离出来，并通过 1H n.m.r. 光谱进行鉴定，其相对比例则通过定量 g.l.c .和/或 1H n.m.r. 光谱进行估算。对于上述所有底物，在含有取代基的桥头碳的β-元位置上的硝化比例[得到一般形式 (4) 的化合物]大于在桥头取代基的相应β-对位位置上的硝化比例[得到一般形式 (3) 的化合物]。虽然芳香环 β 位的优先硝化与之前报道的 9,10-二氢-9,10-乙桥蒽 (2a) 本身的硝化一致，但之前并没有观察到这种优先元攻击。由于本研究中使用的取代基在立体和电子方面存在很大差异，因此无法将这种行为与现有的取代基参数联系起来，而且这种优先偏置的起源仍不清楚。 对该体系中的二硝化作用仅进行了表面研究。桥头取代基和一个芳香环上已经存在的硝基的影响，似乎在确定进入的硝基对另一个（未硝化的）芳香环的攻击位置时，产生了难以预测的结果。
• 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. VI. Manifestation of Differential Reactivities of the Methyls in a<i>t</i>-Butyl Group in Radical Halogenations
  作者：Shigetaka Seki、Tsutou Morinaga、Hiromi Kikuchi、Tsutomu Mitsuhashi、Gaku Yamamoto、Michinori Oki

  DOI：10.1246/bcsj.54.1465

  日期：1981.5

  The methyls in a t-butyl group are shown to exhibit different reactivities in radical halogenations, if rotation about a (CH3)3C–CXY2 bond is frozen. Barriers to rotation of halogenated 9-t-butyl-1,2,3,4-tetrachlorotriptycenes are obtained as ΔH\eweq ca. 32 kcal/mol. The cause of the selectivity in chlorination with sulfuryl chloride was discussed by obtaining reactivity data with a variety of compounds

  如果围绕 (CH3)3C-CXY2 键的旋转被冻结，则叔丁基中的甲基在自由基卤化中表现出不同的反应性。卤化 9-t-丁基-1,2,3,4-四氯三苯环的旋转障碍作为 ΔH\eweq ca 获得。32 大卡/摩尔。通过获得与多种化合物和卤化试剂的反应数据，讨论了磺酰氯氯化选择性的原因。得出的结论是，周围卤素取代基的相邻基团参与是造成观察到的选择性的原因。
• Restricted Rotation Involving the Tetrahedral Carbon. I. Some Diels-Alder Adducts Derived from 9-Substituted Anthracenes
  作者：Michinori Oki、Minoru Suda

  DOI：10.1246/bcsj.44.1876

  日期：1971.7

  9-t-Butylanthracene was treated with dimethyl acetylenedicarboxylate and benzoquinone to give Diels-Alder adducts. The NMR spectra of these adducts suggest that the internal rotation about the C1–CBu bond is not taking place on the NMR time scale. On the other hand, a Diels-Alder adduct prepared from 9-isopropylanthracene and dimethyl acetylenedicarboxylate shows the coalescence phenomenon of the NMR

  9-叔丁基蒽用乙炔二羧酸二甲酯和苯醌处理，得到狄尔斯-阿尔德加合物。这些加合物的 NMR 谱表明 C1-CBu 键的内旋没有发生在 NMR 时间尺度上。另一方面，由 9-异丙基蒽和乙炔二甲酸二甲酯制备的 Diels-Alder 加合物在温度升高时显示出 NMR 信号的聚结现象。指出了由于围绕 sp3-sp3 碳键的受阻旋转而导致光学分辨率的可能性。