3-fluorobenzyne | 62209-91-0

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 3-fluorobenzyne
• 英文别名: 1-Fluorocyclohexa-1,3-dien-5-yne
• CAS: 62209-91-0
• 化学式: C₆H₃F
• 分子量: 94.0882
• InChiKey: LAFVYDIGFNJXFG-UHFFFAOYSA-N

物化性质

• 沸点：
  92.1±29.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• 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：
  1

反应信息

• 作为反应物：
  描述：

  3-fluorobenzyne 、 1,2,3-trimethylisoindole 生成 3-fluoro-1,8,15-trimethyl-15-azatetracyclo[6.6.1.02,7.09,14]pentadeca-2(7),3,5,9,11,13-hexaene
  参考文献：
  名称：

  GRIBBLE G. W.; ALLEN R. W.; ANDERSON P. S.; CHRISTY M. E.; COLTON C. D., TETRAHEDRON LETT., 1976, NO 41, 3673-3676

  摘要：

  DOI：
• 作为产物：
  描述：

  (2,6-difluorophenyl)lithium 以 四氢呋喃 、 甲苯 为溶剂， 生成 3-fluorobenzyne
  参考文献：
  名称：

  Structural and Rate Studies of the Formation of Substituted Benzynes

  摘要：

  The key elimination step for the formation of 3-substituted and 3,6-disubstituted benzynes from 2-haloaryllithiums displays a pronounced solvent-dependent regioselectivity. All 2-haloaryllithiums with electron withdrawing groups in the 6 position are shown by Li-6 and C-13 NMR spectroscopic studies to be monomers in THF. DFT computational studies implicate trisolvates. Rate studies reveal that LiF eliminates via monomer-based pathways requiring THF dissociation whereas LiCl eliminates via nondissociative pathways. Elimination to form 3-chloro- and 3-fluorobenzyne from 2-chloro-6-fluorophenyllithium displays a pronounced solvent-dependent regioselectivity that is traced to competing solvent-dissociative and nondissociative dissociative pathways for the elimination of LiCl and LiF, respectively.

  DOI：

  10.1021/ja0754655

文献信息

• Lewis Acid Triggered Reactivity of a Lewis Base Stabilized Scandium-Terminal Imido Complex: C–H Bond Activation, Cycloaddition, and Dehydrofluorination
  作者：Jiaxiang Chu、Xianghao Han、Christos E. Kefalidis、Jiliang Zhou、Laurent Maron、Xuebing Leng、Yaofeng Chen

  DOI：10.1021/ja5061559

  日期：2014.8.6

  A stable scandium-terminal imido complex is activated by borane to form an unsaturated terminal imido complex by removing the coordinated Lewis base, 4-(dimethylamino)pyridine, from the metal center. The ensuing terminal imido intermediate can exist as a THF adduct and/or undergo cycloaddition reaction with an internal alkyne, C-H activation of a terminal alkene, and dehydrofluorination of fluoro-substituted

  通过从金属中心去除配位的路易斯碱 4-（二甲氨基）吡啶，硼烷激活稳定的钪末端酰亚胺复合物，形成不饱和末端酰亚胺复合物。随后的末端亚氨基中间体可以作为 THF 加合物存在和/或与内部炔烃发生环加成反应、末端烯烃的 CH 活化以及氟取代的苯或烷烃在室温下脱氟化氢。DFT 研究进一步突出了末端烯烃和氟芳烃的 CH 活化的容易性。他们还阐明了这两种反应的机制方面。
• Formation of Benzynes from 2,6-Dihaloaryllithiums:  Mechanistic Basis of the Regioselectivity
  作者：Antonio Ramírez、John Candler、Crystal G. Bashore、Michael C. Wirtz、Jotham W. Coe、David B. Collum

  DOI：10.1021/ja044899m

  日期：2004.11.1

  The key elimination step for the formation of 3-chloro- and 3-fluorobenzyne from 2-chloro-6-fluorophenyllithium displays a pronounced solvent-dependent regioselectivity. 6Li and 13C NMR spectroscopic studies on 2-chloro-6-fluorophenyllithium reveal a single monomeric aryllithium, suggested by DFT computational studies to be a trisolvate. Rate studies indicate that the elimination of LiCl and LiF proceeds

  从 2-氯-6-氟苯基锂形成 3-氯-和 3-氟苄的关键消除步骤显示出明显的溶剂依赖性区域选择性。2-氯-6-氟苯基锂的 6Li 和 13C NMR 光谱研究揭示了单一单体芳基锂，DFT 计算研究表明它是一种三溶剂化物。速率研究表明 LiCl 和 LiF 的消除分别通过三溶剂化和二溶剂化单体进行。
• GRIBBLE, GORDON W.;KEAVY, DANIEL J.;BRANZ, STAPHEN E.;KELLY, WILLIAM J.;P+, TETRAHEDRON LETT., 29,(1988) N 48, C. 6227-6230
  作者：GRIBBLE, GORDON W.、KEAVY, DANIEL J.、BRANZ, STAPHEN E.、KELLY, WILLIAM J.、P+

  DOI：——

  日期：——
• Structural and Rate Studies of the Formation of Substituted Benzynes
  作者：Jason C. Riggs、Antonio Ramirez、Matthew E. Cremeens、Crystal G. Bashore、John Candler、Michael C. Wirtz、Jotham W. Coe、David B. Collum

  DOI：10.1021/ja0754655

  日期：2008.3.1

  The key elimination step for the formation of 3-substituted and 3,6-disubstituted benzynes from 2-haloaryllithiums displays a pronounced solvent-dependent regioselectivity. All 2-haloaryllithiums with electron withdrawing groups in the 6 position are shown by Li-6 and C-13 NMR spectroscopic studies to be monomers in THF. DFT computational studies implicate trisolvates. Rate studies reveal that LiF eliminates via monomer-based pathways requiring THF dissociation whereas LiCl eliminates via nondissociative pathways. Elimination to form 3-chloro- and 3-fluorobenzyne from 2-chloro-6-fluorophenyllithium displays a pronounced solvent-dependent regioselectivity that is traced to competing solvent-dissociative and nondissociative dissociative pathways for the elimination of LiCl and LiF, respectively.
• GRIBBLE G. W.; ALLEN R. W.; ANDERSON P. S.; CHRISTY M. E.; COLTON C. D., TETRAHEDRON LETT., 1976, NO 41, 3673-3676
  作者：GRIBBLE G. W.、 ALLEN R. W.、 ANDERSON P. S.、 CHRISTY M. E.、 COLTON C. D.

  DOI：——

  日期：——