sp-9-(o-tert-butylphenyl)-9-methoxyfluorene | 244128-21-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: sp-9-(o-tert-butylphenyl)-9-methoxyfluorene
• 英文别名: 9-(o-tert-butylphenyl)-9-methoxyfluorene；9-(o-tert-butylphenyl)-9-fluorenyl methyl ether；9-(2-Tert-butylphenyl)-9-methoxyfluorene
• CAS: 244128-21-0；259186-48-6
• 化学式: C₂₄H₂₄O
• 分子量: 328.454
• InChiKey: VCQUKZQNDLVMEV-UHFFFAOYSA-N

物化性质

• 沸点：
  437.9±44.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  sp-9-(o-tert-butylphenyl)-9-methoxyfluorene 在 氢溴酸 作用下， 以 氯仿 为溶剂， 反应 2.0h， 生成 9-(o-tert-butylphenyl)fluorene 、 9-[o-(β-bromo-α,α-dimethylethyl)phenyl]fluorene
  参考文献：
  名称：

  The First Reported Halogenation of a tert-Butyl Group with HCl or HBr in CHCl₃. Unexpected Differences in the Reactions of HCl, HBr, HI, and HF with sp-9-(o-tert-Butylphenyl)-9-fluorenol

  摘要：

  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.

  DOI：

  10.1021/jo9910280
• 作为产物：
  描述：

  甲醇 、 sp-9-(o-tert-butylphenyl)-9-fluorenol 在 硫酸 作用下， 反应 0.17h， 以97.6%的产率得到sp-9-(o-tert-butylphenyl)-9-methoxyfluorene
  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

• Stereochemistry of Reactions Involving Rotationally Restricted, Sterically Hindered Cations, Radicals, and Anions:  9-Fluorenyl Systems
  作者：Yuqing Hou、Cal Y. Meyers

  DOI：10.1021/jo0351015

  日期：2004.2.1

  the rotational restriction and extensive blockage to the original face of the sp2 nonaromatic 9-radical (4n + 1 π electrons) and aromatic (4n + 2 π electrons) 9-anion. The barrier to rotation in some of the ortho-substituted 9-arylfluorenes is great enough to allow their sp and ap rotamers to be detected coexisting in solution, although their crystals were composed exclusively of one. Rotational restriction

  利用手性9-（邻-叔丁基苯基）芴已对涉及旋转受限，空间受阻的阳离子，自由基和阴离子的反应的立体化学途径进行了研究。以前关于这些或相关非手性化合物的研究报告均包含错误或模棱两可的结论。这项研究表明，先用（Tf 2 O-CHCl 3）处理（+）- SP -9-（邻-叔丁基苯基）-9-甲氧基-2-甲基芴，形成100％的9-阳离子，然后再用NaOMe- MeOH提供了29％的重新形成的底物（构型保留）和71％的（-）- SP对映体（转化）。HI-CHCl 3处理过的相同底物将其转化为9自由基，该自由基迅速还原，提供了100％（-）- SP -9-（邻叔丁基苯基）-2-甲基芴的分离（反型）。用n- BuLi-THF处理后者，得到9-阴离子，其在酸化时产生100％的对映体（+）- SP -9-（邻-叔丁基苯基）-2-甲基芴（转化）。在这些反应中的底物是热力学有利的SP的旋转异构体。反转直接产生的较高能量nonenantiomeric