9-azido-9H-fluorene | 24040-37-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9-azido-9H-fluorene
• CAS: 24040-37-7
• 化学式: C₁₃H₉N₃
• mdl: MFCD14652833
• 分子量: 207.235
• InChiKey: POJUGTQVVISLBM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.076
• 拓扑面积：
  14.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  9-azido-9H-fluorene 生成 9-芴酮
  参考文献：
  名称：

  35.在硫酸存在下，三苯甲醇，芴-9-醇和二苯甲醇与酸的相互作用

  摘要：

  DOI：

  10.1039/jr9530000178
• 作为产物：
  描述：

  9-羟基芴 在 [Bmim]Cl-ZnCl2 、 叠氮基三甲基硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 0.42h， 以85%的产率得到9-azido-9H-fluorene
  参考文献：
  名称：

  Recyclable zinc (II) ionic liquid catalyzed synthesis of azides by direct azidation of alcohols using trimethylsilylazide at room temperature

  摘要：

  A new efficient method has been reported for the synthesis of azides by direct azidation of alcohols with TMSN3 in presence of recyclable task specific ionic liquid (TSIL) [bmim]ZnCl3 as a catalyst in DCM at room temperature. Ionic liquid [[bmim]ZnCl3 was synthesized under solvent free conditions and characterized by IR, H-1 NMR, C-13 NMR and HRMS. The Lewis acidity of catalyst was also examined using IR spectroscopy. The main features of this new methodology are high yields of products, recyclability of catalyst, scalability of reaction to gram scale and short reaction time. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2017.05.046

文献信息

• Experiments and calculations for determination of the stabilities of benzyl, benzhydryl, and fluorenyl carbocations: antiaromaticity revisited
  作者：Tina L. Amyes、John P. Richard、Michael Novak

  DOI：10.1021/ja00047a010

  日期：1992.10

  formation of benzyl, benzhydryl, and fluorenyl carbocations in 50:50 (v:v) trifluoroethanol/water at I=0.50 (NaClO 4 ) were determined as pK R =-log (k HOH [H 2 O]/k H ), where k H is the second-order rate constant for acid-catalyzed reaction of the alcohol to form the carbocation and k HOH is the second-order rate constant for capture of the carbocation by water

  在 I=0.50 (NaClO 4 ) 的 50:50 (v:v) 三氟乙醇/水中形成苄基、二苯甲基和芴基碳正离子的以下 pK R 值确定为 pK R =-log (k HOH [H 2 O]/k H )，其中 k H 是醇酸催化反应形成碳阳离子的二级速率常数，k HOH 是水捕获碳阳离子的二级速率常数
• PREPARATION OF DIAZO AND DIAZONIUM COMPOUNDS
  申请人：Raines Ronald Thaddeus

  公开号：US20100125132A1

  公开（公告）日：2010-05-20

  A method for making diazo-compounds, diazonium salts thereof and other protected forms of these compounds. Diaz-compounds are prepared by reaction of a tertiary phosphine reagent carrying a reactive carbonyl group with an azide. The reaction can also generate an acyl triazene which can be converted thermally or by addition of base to form the diazo-compound or the acyl triazene can be isolated. The method is particularly useful for conversion of azides carrying one or more electron withdrawing groups to diazo-compounds. The method can be carried out in aqueous medium under mild conditions and is particularly useful for conversion of azido sugars to diazo-compound and diazonium salts thereof under physiological conditions. Tertiary phosphine reagents, particularly those that are water-soluble, and precursors for preparation of the reagents are provided.

  一种制备重氮化合物、其重氮盐和这些化合物的其他保护形式的方法。通过将携带反应性羰基基团的三级膦试剂与偶氮化物反应来制备重氮化合物。该反应还可以生成酰基三氮烯，可以通过热转化或加入碱来形成重氮化合物，或者可以分离出酰基三氮烯。该方法特别适用于将携带一个或多个电子吸引基团的偶氮化物转化为重氮化合物。该方法可以在温和条件下在水性介质中进行，并且特别适用于在生理条件下将偶氮糖转化为重氮化合物和其重氮盐。提供了三级膦试剂，特别是那些水溶性的试剂，以及用于制备这些试剂的前体。
• Fluorogenic Strain‐Promoted Alkyne–Diazo Cycloadditions
  作者：Frédéric Friscourt、Christoph J. Fahrni、Geert‐Jan Boons

  DOI：10.1002/chem.201502242

  日期：2015.9.28

  Fluorogenic reactions, in which non‐ or weakly fluorescent reagents produce highly fluorescent products, are attractive for detecting a broad range of compounds in the fields of bioconjugation and material sciences. Herein, we report that a dibenzocyclooctyne derivative modified with a cyclopropenone moiety (Fl‐DIBO) can undergo fast strain‐promoted cycloaddition reactions under catalyst‐free conditions

  荧光反应，其中非荧光或弱荧光试剂产生高荧光产物，对于生物缀合和材料科学领域中的多种化合物的检测非常有吸引力。在本文中，我们报道了在无催化剂的条件下，与叠氮化物，硝酮，腈氧化物以及单取代和二取代的重氮衍生物一起，用环丙烯酮部分（F1-DIBO）改性的二苯并环辛炔衍生物可以进行快速的应变促进的环加成反应。尽管与腈氧化物，硝酮和二取代的重氮化合物反应生成的环加合物的量子产率较低，但单取代的重氮试剂可产生1 H吡唑衍生物比Fl-DIBO的荧光增强约160倍，亮度增加超过10000倍。从量子化学计算中得出结论，可能是由于存在能量较低的（n，π*）状态，因此与双取代的重氮衍生物反应形成的3 H-吡唑类化合物发生了荧光猝灭。荧光探针Fl-DIBO已成功用于标记重氮标记的蛋白质，而没有可检测到的背景信号。重氮衍生物正在成为生物分子标记的有吸引力的报道者，本文介绍的研究表明，Fl-DIBO可用于可视化此类生物分子，而无需进行探针冲洗。
• Optimal Destabilization of DNA Double Strands by Single-Nucleobase Caging
  作者：Patrick Seyfried、Marcel Heinz、György Pintér、Dean-Paulos Klötzner、Yvonne Becker、Michael Bolte、Hendrik R. A. Jonker、Lukas S. Stelzl、Gerhard Hummer、Harald Schwalbe、Alexander Heckel

  DOI：10.1002/chem.201804040

  日期：2018.11.27

  developed to identify protecting group derivatives with superior caging properties. Bulky rests are attached to the cage moiety via Cu‐catalyzed azide–alkyne cycloaddition post‐synthetically on DNA. Interestingly, the decrease in melting temperature upon introducing o‐nitrobenzyl‐caged (NPBY‐) and diethylaminocoumarin‐cages (DEACM‐) in DNA duplexes reaches a limiting value. NMR spectroscopy was used to

  光不稳定的保护基被广泛用于触发寡核苷酸活性。开/关幅度是一个关键参数。已经开发出实验装置以鉴定具有优异笼蔽性质的保护基衍生物。大块的残基通过铜催化的叠氮化物-炔烃环加成反应，在DNA上合成后附着在笼子部分。有趣的是，引入o后熔融温度降低DNA双链体中的‐硝基苄基笼（NPBY‐）和二乙基氨基香豆素笼（DEACM‐）达到极限值。NMR光谱用于表征各个碱基对的稳定性，并确定选定数量的光笼DNA分子的实验结构。实验结构与MD模拟预测的结构吻合良好。综合起来，结构数据表明，一旦添加空间要求基团以生成三取代碳，空间要求较低的笼部分就指向相邻的核苷，而较大的取代基仍保留在主凹槽中。
• Regioselective Synthesis of Fluorosulfonyl 1,2,3-Triazoles from Bromovinylsulfonyl Fluoride
  作者：Joice Thomas、Valery V. Fokin

  DOI：10.1021/acs.orglett.8b01309

  日期：2018.7.6

  A regioselective metal-free preparation of 4-fluorosulfonyl 1,2,3-triazoles from organic azides and a hitherto underexplored bromovinylsulfonyl fluoride building block is described. This reaction is very general and was extended to the synthesis of various sulfonates, sulfonamides, and sulfonic acid derivatives of triazoles and other azole heterocycles which would otherwise be difficult to access by

  描述了由有机叠氮化物和迄今未充分研究的溴movinyl磺酰氟结构单元的区域选择性无金属制备4-氟磺酰基1,2,3-三唑的方法。该反应非常普遍，并且扩展到三唑和其他唑杂环的各种磺酸盐，磺酰胺和磺酸衍生物的合成，否则将难以通过现有方法来获得。