sp-9-(o-tert-butylphenyl)-9-fluorenol | 65213-15-2

• 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-fluorenol
• 英文别名: 9-(o-tert-butylphenyl)-9-fluorenol；9-(2-Tert-butylphenyl)-9H-fluoren-9-OL；9-(2-tert-butylphenyl)fluoren-9-ol
• CAS: 65213-15-2
• 化学式: C₂₃H₂₂O
• 分子量: 314.427
• InChiKey: LDEUWBSSGDPGGS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  24
• 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：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  9-(o-tert-butylphenyl)-9-fluorofluorene 在 silica gel 作用下， 生成 sp-9-(o-tert-butylphenyl)-9-fluorenol
  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

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.
• <i>sp</i>-9-[<i>o</i>-(β-Chloro-α,α-dimethylethyl)phenyl]fluorene: an Unanticipated Exclusive Product from the Reaction of<i>sp</i>-9-(<i>o</i>-<i>tert</i>-Butylphenyl)-9-fluorenol with Thionyl Chloride
  作者：P. D. Robinson、Y. Hou、C. Y. Meyers

  DOI：10.1107/s0108270198002911

  日期：1998.8.15

  The reaction of sp-9-(o-tert-butylphenyl)-9-fluorenol, (1), with thionyl chloride in CHCl3 at room temperature quantitatively provided the title compound [(2), C23H21Cl], instead of the expected 9-(o-tert-butylphenyl)-9-chlorofluorene. Chlorination of an alkyl group under the conditions in which (1) was converted into (2) is apparently unprecedented, While the unexpected structure of (2) was suggested by H-1 and C-13 NMR, unequivocal characterization required X-ray crystallographic analysis. Surprisingly, introduction of the Cl atom in (2) imposes only a few minor changes in the bonding parameters compared with its non-chlorinated counterpart, sp-9-(o-tert-butylphenyl)fluorene.