9-(o-tert-butylphenyl)fluorene | 62753-75-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9-(o-tert-butylphenyl)fluorene
• 英文别名: sp-9-(o-tert-butylphenyl)fluorene；9-(2-Tert-butylphenyl)-9H-fluorene
• CAS: 62753-75-7；78737-79-8；202755-78-0
• 化学式: C₂₃H₂₂
• 分子量: 298.428
• InChiKey: FDOTZFXSPPEGLG-UHFFFAOYSA-N

物化性质

• 沸点：
  418.0±30.0 °C(Predicted)
• 密度：
  1.068±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• 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

反应信息

• 作为反应物：
  描述：

  9-(o-tert-butylphenyl)fluorene 、 碘甲烷 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 6.08h， 以82%的产率得到ap-9-(o-tert-butylphenyl)-9-methylfluorene
  参考文献：
  名称：

  The surprising formation of structurally distorted ap-9-(o-tert-butylphenyl)-9-methylthiofluorene and its facile homolysis into sp-9-(o-tert-butylphenyl)-3-methylthiofluorene and sp-9-(o-tert-butylphenyl)fluorene

  摘要：

  对旋转限制的9-(o-叔丁基苯基)芴的持续研究提供了令人惊讶的结果。在酸性条件下，用乙醇或甲醇处理sp-9-(o-叔丁基苯基)-9-芴醇（1）可得到sp-9-(o-叔丁基苯基)-9-乙氧基芴（2b）和sp-9-(o-叔丁基苯基)-9-甲氧基芴（3b），但用甲硫醇进行类似处理会将1转化为旋转异构体相反的ap-9-(o-叔丁基苯基)-9-甲硫基芴（4a）。虽然所有三种产物反映了在C-9处的反转反应，但2b和3b反映了随后的旋转，而4a则不是这种情况。X射线衍射显示4a高度扭曲和变形，但显然在热力学上比其sp异构体更受青睐。在室温下观察到4a的自由基裂解，在升高温度时，形成sp-9-(o-叔丁基苯基)芴（6b）和sp-9-(o-叔丁基苯基)-3-甲硫基芴（7c）作为主要产物。X射线衍射显示6b和7c几乎没有扭曲。通过其负离子对6b进行甲基化也会进行反转而不旋转，形成ap-9-(o-叔丁基苯基)-9-甲基芴（4c）。动态核磁共振意外地显示，在这些ap构型中，4c的9-CH₃（甲基）比4a的9-CH₃S（甲硫基）对o-叔丁基团进入芴平面具有更大的体积效应。关键词：芴，旋转异构体，扭曲，自由基裂解，负离子，碳阳离子，自由基。

  DOI：

  10.1139/v99-088
• 作为产物：
  描述：

  sp-9-(o-tert-butylphenyl)-9-fluorenol 在 氢溴酸 、 二甲基亚砜 作用下， 反应 0.5h， 生成 9-(o-tert-butylphenyl)fluorene
  参考文献：
  名称：

  The surprising formation of structurally distorted ap-9-(o-tert-butylphenyl)-9-methylthiofluorene and its facile homolysis into sp-9-(o-tert-butylphenyl)-3-methylthiofluorene and sp-9-(o-tert-butylphenyl)fluorene

  摘要：

  对旋转限制的9-(o-叔丁基苯基)芴的持续研究提供了令人惊讶的结果。在酸性条件下，用乙醇或甲醇处理sp-9-(o-叔丁基苯基)-9-芴醇（1）可得到sp-9-(o-叔丁基苯基)-9-乙氧基芴（2b）和sp-9-(o-叔丁基苯基)-9-甲氧基芴（3b），但用甲硫醇进行类似处理会将1转化为旋转异构体相反的ap-9-(o-叔丁基苯基)-9-甲硫基芴（4a）。虽然所有三种产物反映了在C-9处的反转反应，但2b和3b反映了随后的旋转，而4a则不是这种情况。X射线衍射显示4a高度扭曲和变形，但显然在热力学上比其sp异构体更受青睐。在室温下观察到4a的自由基裂解，在升高温度时，形成sp-9-(o-叔丁基苯基)芴（6b）和sp-9-(o-叔丁基苯基)-3-甲硫基芴（7c）作为主要产物。X射线衍射显示6b和7c几乎没有扭曲。通过其负离子对6b进行甲基化也会进行反转而不旋转，形成ap-9-(o-叔丁基苯基)-9-甲基芴（4c）。动态核磁共振意外地显示，在这些ap构型中，4c的9-CH₃（甲基）比4a的9-CH₃S（甲硫基）对o-叔丁基团进入芴平面具有更大的体积效应。关键词：芴，旋转异构体，扭曲，自由基裂解，负离子，碳阳离子，自由基。

  DOI：

  10.1139/v99-088

文献信息

• Exclusivity of the<i>sp</i>Rotamers of 9-(<i>o</i>-<i>tert</i>-Butylphenyl)fluorene and 9-(<i>o</i>-<i>tert</i>-Butylphenyl)-9-fluorenol in Solution and the Crystalline State
  作者：P. D. Robinson、Y. Hou、H. G. Lutfi、C. Y. Meyers

  DOI：10.1107/s0108270197012638

  日期：1998.1.15

  Both 9-(o-tert-butylphenyl)fluorene (C23H22) and 9-(o-tert-butylphenyl)-9-fluorenol (C23H22O) maintained sp rotameric structures exclusively in crystalline form as well as in solution. This result is in contrast to that obtained for the corresponding 9-(o-isopropylphenyl)fluorene and 9-(o-isopropylphenyl)-9-fluorenol. In-plane sterically imposed distortion of the tert-butyl group is exhibited in sp-9-(o-tert-butylphenyl)-fluorene and to a much larger extent in sp-9-(o-tert-butylphenyl)-9-fluorenol. The asymmetric unit of the latter contains two crystallographically distinct, but nearly identical, molecules which are hydrogen bonded to each other via their respective OH groups; hydrogen bonding between the crystallographically equivalent molecules is not observed.
• The surprising formation of structurally distorted <i>ap</i>-9-(<i>o-tert-</i>butylphenyl)-9-methylthiofluorene and its facile homolysis into <i>sp-</i>9-(<i>o-tert-</i>butylphenyl)-3-methylthiofluorene and <i>sp-</i>9-(<i>o-tert-</i>butylphenyl)fluorene
  作者：Yuqing Hou、Cal Y Meyers

  DOI：10.1139/v99-088

  日期：1999.6.1

  The continued study of rotationally restricted 9-(o-tert-butylphenyl)fluorenes has provided surprising results. Treatment of sp-9-(o-tert-butylphenyl)-9-fluorenol (1) with ethanol or methanol under acidic conditions affords sp-9-(o-tert-butylphenyl)-9-ethoxyfluorene (2b) and sp-9-(o-tert-butylphenyl)-9-methoxyfluorene (3b), respectively, but similar treatment with methanethiol converts 1 into the rotamerically opposite ap-9-(o-tert-butylphenyl)-9-methylthiofluorene (4a). While all three products reflect reaction with inversion at C-9, 2b and 3b reflect subsequent rotation, which is not the case with 4a. X-ray diffraction shows 4a to be highly distorted and strained, but apparently favored thermodynamically over its sp rotamer. Homolysis of 4a is observed at room temperature, and at elevated temperatures accounts for the formation of sp-9-(o-tert-butylphenyl)fluorene (6b) and sp-9-(o-tert-butylphenyl)-3-methylthiofluorene (7c) as major products. X-ray diffraction shows 6b and 7c to be virtually devoid of distortion. Methylation of 6b via its anion also proceeds with inversion without rotation to form ap-9-(o-tert-butylphenyl)-9-methylfluorene (4c). Dynamic NMR unexpectedly showed that in these ap configurations 9-CH₃ (of 4c) has a greater bulk effect than 9-CH₃S (of 4a) in forcing the o-tert-butyl group into the fluorene plane.Key words: fluorene, rotamer, distortion, homolysis, carbanion, carbocation, radical.

  对旋转限制的9-(o-叔丁基苯基)芴的持续研究提供了令人惊讶的结果。在酸性条件下，用乙醇或甲醇处理sp-9-(o-叔丁基苯基)-9-芴醇（1）可得到sp-9-(o-叔丁基苯基)-9-乙氧基芴（2b）和sp-9-(o-叔丁基苯基)-9-甲氧基芴（3b），但用甲硫醇进行类似处理会将1转化为旋转异构体相反的ap-9-(o-叔丁基苯基)-9-甲硫基芴（4a）。虽然所有三种产物反映了在C-9处的反转反应，但2b和3b反映了随后的旋转，而4a则不是这种情况。X射线衍射显示4a高度扭曲和变形，但显然在热力学上比其sp异构体更受青睐。在室温下观察到4a的自由基裂解，在升高温度时，形成sp-9-(o-叔丁基苯基)芴（6b）和sp-9-(o-叔丁基苯基)-3-甲硫基芴（7c）作为主要产物。X射线衍射显示6b和7c几乎没有扭曲。通过其负离子对6b进行甲基化也会进行反转而不旋转，形成ap-9-(o-叔丁基苯基)-9-甲基芴（4c）。动态核磁共振意外地显示，在这些ap构型中，4c的9-CH₃（甲基）比4a的9-CH₃S（甲硫基）对o-叔丁基团进入芴平面具有更大的体积效应。关键词：芴，旋转异构体，扭曲，自由基裂解，负离子，碳阳离子，自由基。
• The First Reported Halogenation of a <i>tert-</i>Butyl Group with HCl or HBr in CHCl₃. Unexpected Differences in the Reactions of HCl, HBr, HI, and HF with <i>sp-</i>9-(<i>o</i><i>-tert-</i>Butylphenyl)-9-fluorenol
  作者：Cal Y. Meyers、Yuqing Hou、Hisham G. Lutfi、Howard L. Saft

  DOI：10.1021/jo9910280

  日期：1999.12.1

  The reactions of sp-9-(o-tert-butylphenyl)-9-fluorenol (1) with HCl, HBr, HI, and HF, respectively, were found to follow diverse pathways. Most unexpected is the unprecedented monohalogenation of a tert-butyl group, sp-9-[o-(beta-chloro-alpha,alpha-dimethylethyl)phenyl]fluorene (2) being formed quantitatively from 1 treated with HCl-CHCl3 and sp-9-[o-(beta-bromo-alpha,alpha-dimethylethyl)phenyl]fluorene (3) (>90%), along with a very small amount of sp-9-(o-tert-butylphenyl)fluorene (4), being formed from 1 treated with HBr-CHCl3. The absolute structure of 2 was ascertained by X-ray crystal analysis. Likewise, the expected 9-chloro- and 9-bromofluorenes from the usual substitution of OH by halogen in reactions of alcohols with SOCl4 and SOBr2 were not obtained from treatment of 1 with these reagents; the only products were 2 and 3, respectively. These products are formed by nucleophilic attack of halide ion on a tert-butyl methyl group of the 9-cation (1a) with concerted intramolecular displacement of hydride to 9-C+, while 4 results from the slower electron transfer from Br- to 1a to form free radical 1b, which captures an H atom from HBr. The high redox potential of I- and weak HI bond ensures the rapid conversions 1a --> 1b --> 4, making 4 the exclusive product from treatment of 1 with HI-CHCl3. In contrast to the other halides, fluoride is a poor nucleophile in displacement reactions and poor electron-transfer agent. Consequently, strongly electrophilic la reacts with F- to provide sp-9-(o-tert-butylphenyl)-9-fluorofluorene (5) as the only product from the reaction of 1 with pyridine(HF)(x). Dynamic NMR provided strong evidence that the reaction with HI occurs with inversion, the ap rotamer (4a) of 9-(o-tert-butylphenyl)fluorene being formed initially, followed by rotation to the isolated sp rotamer, 4. The largely planar configuration of C-9 of the unsymmetrically hindered cation intermediate 1a, responsible for this inversion and the related inversions, was supported by NMR.