9-hydroxy-9-vinylfluorene | 92496-21-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9-hydroxy-9-vinylfluorene
• 英文别名: 9-vinyl-9H-fluoren-9-ol；9-vinyl-9Hfluoren-9-ol；9-ethenyl-9H-fluoren-9-ol；9-Vinyl-fluorenol-(9)；9-Vinyl-9-fluorenol；9-Ethenylfluoren-9-ol
• CAS: 92496-21-4
• 化学式: C₁₅H₁₂O
• 分子量: 208.26
• InChiKey: SLEDONQBEBNSAW-UHFFFAOYSA-N

物化性质

• 熔点：
  91 °C(Solv: ligroine (8032-32-4))
• 沸点：
  70-80 °C
• 密度：
  1.265±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  9-hydroxy-9-vinylfluorene 在 臭氧 作用下， 以 甲醇 为溶剂， 生成 9-formyl-9-hydroxyfluorene
  参考文献：
  名称：

  Effect of oxime substituents on 9-fluorenyl carbocations

  摘要：

  9-Fluorenyl carbocations substituted with the oxime functional groups CH=NOCH3, CH3C=NOCH3, and i-PrC=NOCH3 were generated by solvolyses of the corresponding chlorides in methanol, These cations form at rates which greatly exceed those of formation of the parent 9-fluorenyl cation. Relative rate data suggest that stabilization of 9-fluorenyl cations by CH=NOCH3 is greater than stabilization by CH3C=NOCH3, which is in turn greater than that by i-PrC=NOCH3. Computational studies on these cations show that the oxime group is progressively rotated out of conjugation with the cationic center as the oxime group becomes larger. These rate and computational studies also suggest that 9-fluorenyl cations are not antiaromatic. They are essentially delocalized 'nonatetraenyl' cations, where formally antiaromatic resonance forms contribute little to the overall structure. Copyright (C) 2000 John Wiley & Sons, Ltd.

  DOI：

  10.1002/1099-1395(200006)13:6<337::aid-poc249>3.0.co;2-t
• 作为产物：
  描述：

  9-乙炔-9-芴醇 在 Pd(SIPr)(PCy3) 、 氢气 作用下， 以 甲醇 为溶剂， 20.0 ℃ 、100.0 kPa 条件下， 反应 24.0h， 以95%的产率得到9-hydroxy-9-vinylfluorene
  参考文献：
  名称：

  的C加氢？在轻度反应条件下[Pd（NHC）（PCy3）]（NHC = N-杂环碳烯）介导的C多键

  摘要：

  N-杂环卡宾又做一次！[Pd（SIPr）（PCy 3）]（1 ; SIPr = N，N '-（双（2,6-二异丙基苯基）咪唑烷）在H 2下稳定，被证明是高活性的加氢催化剂即使使用空间位阻烯烃（三取代和四取代），反应也会在温和的条件下（相对较低的Pd负载，RT，H 2低压）进行。

  DOI：

  10.1002/chem.200802412

文献信息

• Carboxylate-directed C–H allylation with allyl alcohols or ethers
  作者：Xiao-Qiang Hu、Zhiyong Hu、A. Stefania Trita、Guodong Zhang、Lukas J. Gooßen

  DOI：10.1039/c8sc01741g

  日期：——

  A [Ru(p-cymene)Cl2]2 catalyst activates allyl alcohols and ethers for the regioselective ortho-C–H allylation of aromatic and heteroaromatic carboxylates. The reaction is orthogonal to most C–H functionalisations with allyl alcohols in that allyl arenes rather than carbonyl compounds are obtained. A wide range of substrates are thus smoothly transformed to allylarenes at 50 °C in phosphate-buffered

  [Ru（p- Cymene）Cl 2 ] 2催化剂可活化烯丙醇和醚，用于芳族和杂芳族羧酸酯的区域选择性邻位-C-H烯丙基化。该反应与用烯丙醇进行的大多数C–H官能化正交，因为可得到烯丙基芳烃而不是羰基化合物。因此，在磷酸盐缓冲的2,2,2-三氯乙醇中，各种各样的底物可在50°C的条件下平稳转化为烯丙基芳烃。反应概念结合了丰富的试剂和导向基团的使用，以一种可持续的，废物最少的方法形成C-C键。
• Graphene Oxide Promotes Site-Selective Allylic Alkylation of Thiophenes with Alcohols
  作者：Laura Favaretto、Juzeng An、Marco Sambo、Assunta De Nisi、Cristian Bettini、Manuela Melucci、Alessandro Kovtun、Andrea Liscio、Vincenzo Palermo、Andrea Bottoni、Francesco Zerbetto、Matteo Calvaresi、Marco Bandini

  DOI：10.1021/acs.orglett.8b01531

  日期：2018.6.15

  The graphene oxide (GO) assisted allylic alkylation of thiophenes with alcohols is presented. Mild reaction conditions and a low GO loading enabled the isolation of a range of densely functionalized thienyl and bithienyl compounds in moderate to high yields (up to 90%). The cooperative action of the Brønsted acidity, epoxide moieties, and π-surface of the 2D-promoter is highlighted as crucial in the

  提出了石墨烯氧化物（GO）辅助噻吩与醇的烯丙基烷基化。温和的反应条件和低的GO负载量可以中等至高产率（高达90％）分离出一系列稠密官能化的噻吩基和二噻吩基化合物。布朗斯台德酸度，环氧化物部分和2D启动子的π表面的协同作用在当前Friedel-Crafts型实验方案的反应过程中被认为是至关重要的。
• One‐Pot Synthesis of Allylic Sulfones, Ketosulfones, and Triflyl Allylic Alcohols from Domino Reactions of Allylic Alcohols with Sulfinic Acid under Metal‐Free Conditions
  作者：Xue‐Qiang Chu、Hua Meng、Xiao‐Ping Xu、Shun‐Jun Ji

  DOI：10.1002/chem.201500469

  日期：2015.8.3

  A metal‐free tandem procedure by using a sulfonylation reaction of aryl allylic alcohols followed by an iodobenzenediacetate (PIDA)‐promoted oxidative functionalization has been established. Allylic sulfones, γ‐ketosulfones, and triflyl allylic alcohols have been constructed in a single operation. The methodology incorporates the sulfonyl (both aryl and triflyl) functionality with a simple work‐up

  通过建立芳基烯丙醇的磺酰化反应，然后由碘代苯二乙酸酯（PIDA）促进氧化功能化，建立了无金属串联程序。烯丙基砜，γ-酮砜和三氟烯丙基烯丙醇可通过一次操作构建。该方法结合了磺酰基（芳基和triflyl）功能，并具有简单的后处理步骤。
• TBAI-Catalyzed/Water-Assisted Double C−S Bond Formations: An Efficient Approach to Sulfides through Metal-Free Three-Component Reactions
  作者：Xue-Qiang Chu、Xiao-Ping Xu、Shun-Jun Ji

  DOI：10.1002/chem.201603099

  日期：2016.9.26

  been developed. A diverse range of functionalized sulfides, including pharmaceutical and biological derivatives, can be obtained in an efficient and eco‐friendly manner under air. The mechanistic studies revealed that this tetrabutylammonium‐iodide‐catalyzed/water‐assisted reaction generated a mercaptan species as the key intermediate.

  已经开发出一种用于双C键形成的水催化方法，该方法涉及醇衍生物，有机卤化物和硫代硫酸钠。在空气中可以高效，环保的方式获得各种功能化的硫化物，包括药物和生物衍生物。机理研究表明，这种四丁基碘化铵催化/水辅助反应生成了硫醇作为主要中间体。
• Anionic Dimerization in Reductive Cleavage of an Allyl Ether with Sodium-Potassium Alloy
  作者：D. H. Hunter、D. W. Moore

  DOI：10.1139/v71-271

  日期：1971.5.15

  The reaction of 9-methoxy-9-vinylfluorene (2a) with sodium–potassium alloy does not yield the expected 9-vinylfluorenylanion (1). The anions derived from the reaction were characterized by carbonation and subsequent methylation. Four esters (5, 6, 7, and 8) accounting for about two-thirds of the starting material were isolated and characterized. Structures were assigned on the basis of mass spectra

  9-甲氧基-9-乙烯基芴（2a）与钠钾合金的反应不会产生预期的9-乙烯基芴阴离子（1）。源自反应的阴离子的特征在于碳酸化和随后的甲基化。分离并表征了约占起始材料三分之二的四种酯（5、6、7 和 8）。在质谱和核磁共振谱的基础上分配结构，特别是使用去偶联实验。介绍了一个简要的机械方案。

表征谱图