5-氯-5H-二苯并[b,d]硼杂环戊二烯 | 13059-59-1

• 分子结构分类: 有机化合物 - 苯类化合物
• 中文名称: 5-氯-5H-二苯并[b,d]硼杂环戊二烯
• 英文名称: 9-chloro-9-borafluorene
• 英文别名: 9-Chlor-9-bora-fluoren；9-chloroborafluorene；5-chlorobenzo[b][1]benzoborole
• CAS: 13059-59-1
• 化学式: C₁₂H₈BCl
• 分子量: 198.46
• InChiKey: CWLYMXHRDXEBBF-UHFFFAOYSA-N

物化性质

• 熔点：
  52°C(lit.)
• 沸点：
  110°C/0.1mmHg(lit.)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.01
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  5-氯-5H-二苯并[b,d]硼杂环戊二烯 在 air 作用下， 以 二氯甲烷 为溶剂， 生成 tris(2-biphenylyl)boroxine
  参考文献：
  名称：

  Synthesis and Structural Characterization of 9-Azido-9-Borafluorene: Monomer and Cyclotrimer of a Borole Azide

  摘要：

  The reaction of 2,2'-dilithiobiphenyl, generated from 2,2'-dibromobiphenyl and n-BuLi, with BCl3 using n-hexane as solvent provides a high-yielding, simple preparative route to 9-chloro-9-borafluorene la. This in turn can be reacted with trimethylsilyl azide to yield 9-azido-9-borafluorene 2. Compound 2 exists as a cyclic trimer in the solid state, but in dichloromethane solution the monomer can coexist with the trimer. Azide 2 is rather unstable both in the solid state and in solution, and it transforms with trace amounts of water and oxygen to the 1,3,5-tris(2-biphenylyl)cyclotriboroxane that was characterized by X-ray diffraction analysis. Addition of pyridine and t-butyl pyridine to azide 2 afford the corresponding pyridine adducts. Compound la as well as the Lewis base adducts of 2 have been characterized by multinuclear NMR spectroscopy, and the structures were confirmed by X-ray diffraction analysis. The structural features of azide 2 and the strong Lewis acidity of its boron center have also been investigated by computational chemistry techniques at the MP2 level of theory.

  DOI：

  10.1021/ic902436s
• 作为产物：
  描述：

  dibutylchloroborane 生成 5-氯-5H-二苯并[b,d]硼杂环戊二烯
  参考文献：
  名称：

  Koester; Benedikt, Angewandte Chemie, 1963, vol. 75, p. 419

  摘要：

  DOI：

文献信息

• Photo electron transfer induced desilylation of <i>N</i>,<i>N</i>-bis(trimethylsilyl)aminodibenzoborole to aminodibenzoborole
  作者：Constanze Keck、Cäcilia Maichle-Mössmer、Holger F. Bettinger

  DOI：10.1039/c9cc03415c

  日期：——

  The synthesis of 9-amino-9-borafluorene is described using a photoinduced twofold desilylation of the N,N-bis(trimethylsilyl) derivative 2. The mechanistic analysis suggests an initial single electron transfer step from 2 to the halogen containing solvent. 9-Amino-9-borafluorene undergoes a photoinduced cyclooligomerization, most reasonably to the dimer.

  使用光诱导的N，N-双（三甲基甲硅烷基）衍生物2的两倍去甲硅烷基化反应，描述了9-氨基-9-硼芴的合成。机理分析表明初始的单电子转移步骤是从2到含卤素的溶剂。9-氨基-9-硼芴经历了光诱导的环寡聚，最合理地是二聚体。
• Rearrangement from the heteroantiaromatic borole to the heteroaromatic azaborine motif
  作者：Sunanda Biswas、Cäcilia Maichle-Mössmer、Holger F. Bettinger

  DOI：10.1039/c2cc30914a

  日期：——

  Treatment of 9-chloro-9-borafluorene with N,O-bis(trimethylsilyl)hydroxylamine results in 10-trimethylsilyloxy-9-aza-10-boraphenanthrene 6b. NMR spectroscopy shows that the expected antiaromatic 9-(trimethylsilyloxyamino)-9-borafluorene 5b rearranges to the formally aromatic phenanthrene 6b at room temperature.

  对9-氯-9-硼氟烯与N,O-双(三甲基硅基)羟胺的处理生成10-三甲基硅氧基-9-氮-10-硼芴烯6b。核磁共振光谱显示，预期中的反芳香性化合物9-(三甲基硅氧基氨基)-9-硼氟烯5b在室温下重排为正式的芳香性化合物芴烯6b。
• Small Molecule Activation with Intramolecular “Inverse” Frustrated Lewis Pairs
  作者：Chamila Manankandayalage、Daniel K. Unruh、Clemens Krempner

  DOI：10.1002/chem.202005143

  日期：2021.4.7

  Si−H, B−H and C=O bonds. 4 and 5 deprotonated terminal alkynes and acetylene to form the zwitterionic borates 1‐(RC≡C‐BR2)‐2‐[(Me2N)2C=NH]‐C6H4 (R=Ph, H) and reacted with ammonia, BnNH2 and pyrrolidine, to generate the FLP adducts 1‐(R2HN→BR2)‐2‐[(Me2N)2C=NH]‐C6H4, where the N‐H functionality is activated by intramolecular H‐bond interactions. In addition, 5 was found to rapidly add across the double

  分子内“逆”沮丧通式路易斯双（FLP信号）1-BR 2 -2 - [（ME 2 N）2 C = N] -C 6 H ^ 4（3 - 6）[BR 2 = BMES 2（3），BC 12 H 8，（4），BBN（5），BBNO（6）]的合成，并通过多核NMR光谱和X射线分析对其结构进行了表征。这些新型的预组织FLP，具有强碱性胍基单元，可通过邻位与弱Lewis酸性硼基部分刚性连接-亚苯基连接基，能够激活H，CH，NH，OH，SiH，BH和C = O键。4和5使末端炔烃和乙炔去质子化，形成两性离子硼酸盐1–（RC≡C‐BR 2）‐2 ‐ [（Me 2 N）2 C = NH] ‐C 6 H 4（R = Ph，H）和与氨，BnNH 2和吡咯烷反应生成FLP加合物1-（R 2 HN→BR 2）-2-[（Me 2 N）2 C = NH] -C 6 H 4，其中NH功能被分子内的H键相互作用激活。另外5据发现，H
• Heavy-Atom Free <i>spiro</i> Organoboron Complexes As Triplet Excited States Photosensitizers for Singlet Oxygen Activation
  作者：Paulina H. Marek-Urban、Mateusz Urban、Magdalena Wiklińska、Klaudia Paplińska、Krzysztof Woźniak、Agata Blacha-Grzechnik、Krzysztof Durka

  DOI：10.1021/acs.joc.1c01254

  日期：2021.9.17

  new strategy for the development of efficient heavy-atom free singlet oxygen photosensitizers based on rigid borafluorene scaffolds. Physicochemical properties of borafluorene complexes can be easily tuned through the choice of ligand, thus allowing exploration of numerous organoboron structures as potent 1O2 sensitizers. The singlet oxygen generation quantum yields of studied complexes vary in the range

  在此，我们提出了一种开发基于刚性硼芴支架的高效无重原子单线态氧光敏剂的新策略。硼芴配合物的物理化学性质可以通过配体的选择轻松调整，从而允许探索许多有机硼结构作为有效的1 O 2敏化剂。研究的复合物的单线态氧产生量子产率在 0.55-0.78 的范围内变化。理论计算表明，硼芴部分的引入对于单线态电荷转移态的稳定至关重要，而正交供体-受体分子结构促进了系统间跨越到局部三线态。我们的研究表明，只需 0.05 mol% 的光催化剂负载量，就可以在 20-120 分钟的照射时间内实现对选定有机底物的定量氧化。
• Intermolecular insertion reactions of azides into 9-borafluorenes to generate 9,10-B,N-phenanthrenes
  作者：Sam Yruegas、Jesse J. Martinez、Caleb D. Martin

  DOI：10.1039/c8cc01529e

  日期：——

  The reactions of 9-borafluorenes with organic azides result in either the insertion of the α-nitrogen and elimination of N2 or the insertion of the γ-nitrogen to generate the corresponding phenanthrene analogues with boron and nitrogen in the 9- and 10-positions, respectively.

  9-硼芴与有机叠氮化物的反应导致α-氮的插入和N 2的消除或γ-氮的插入，从而生成相应的菲类似物，其中9和10位的硼和氮， 分别。