6-氟-3-甲氧基苯炔 | 1017576-52-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 中文名称: 6-氟-3-甲氧基苯炔
• 英文名称: 6-fluoro-3-methoxybenzyne
• CAS: 1017576-52-1
• 化学式: C₇H₅FO
• 分子量: 124.115
• InChiKey: SZYLMUJYOHHRQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-氟-3-甲氧基苯炔 、 螺[2.4]庚-4,6-二烯 以 四氢呋喃 为溶剂， 生成 5-fluoro-8-methoxy-9,9-spirocyclopropyl-1,4-dihydro-1,4-methano-naphthalene
  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
• 作为产物：
  描述：

  2,3-difluoro-6-methoxyphenyllithium 以 四氢呋喃 、 甲苯 为溶剂， 生成 6-氟-3-甲氧基苯炔
  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

• METHODS FOR STABILIZING LITHIATED HALOGEN-SUBSTITUTED AROMATIC COMPOUNDS
  申请人：Ji Yaohui

  公开号：US20090118546A1

  公开（公告）日：2009-05-07

  The present invention provides novel methods for stabilizing lithiated halogen-substituted aromatic compounds. In particular, the method is useful for the preparation of 2-methoxy-5, 6-difluorobenzaldehyde, an important intermediate for the preparation of [4-amino-2-(1-methanesulfonylpiperidin-4-ylamino) pyrimidin-5-yl](2,3-difluoro-6methoxyphenyl)methanone, a potent and selective inhibitor of CDK4/Cyclin D1, CDK2/Cyclin E and CDK1/Cyclin B. The method is also useful for stabilizing other lithiated halogen-substituted aromatic compounds and is particularly useful for scale up reactions where the exothermic nature of the reaction can lead to reaction runway.

  本发明提供了一种稳定锂化卤代芳香化合物的新方法。特别是，该方法对于制备2-甲氧基-5,6-二氟苯甲醛非常有用，该化合物是制备[4-氨基-2-(1-甲磺酰基哌啶-4-基氨基)嘧啶-5-基](2,3-二氟-6-甲氧基苯基)甲酮的重要中间体，后者是CDK4 / Cyclin D1，CDK2 / Cyclin E和CDK1 / Cyclin B的有效选择性抑制剂。该方法还对于稳定其他锂化卤代芳香化合物非常有用，尤其适用于规模化反应，其中反应的放热性质可能导致反应失控。
• US7619123B2
  申请人：——

  公开号：US7619123B2

  公开（公告）日：2009-11-17
• [EN] METHODS FOR STABILIZING LITHIATED HALOGEN-SUBSTITUTED AROMATIC COMPOUNDS<br/>[FR] PROCÉDÉS DE STABILISATION DE COMPOSÉS AROMATIQUES LITHIÉS À SUBSTITUTION HALOGÈNE
  申请人：HOFFMANN LA ROCHE

  公开号：WO2009056487A1

  公开（公告）日：2009-05-07

  The present invention provides novel methods for stabilizing lithiated halogen-substituted aromatic compounds. In particular, the method is useful for the preparation of 2-methoxy-5, 6-difluorobenzaldehyde, an important intermediate for the preparation of [4-amino-2-(1-methanesuifonyrpiperidin-4-ylamino) pyrimidin-5-yl](2,3-difluoro- 6methoxyphenyl)methanone, a potent and selective inhibitor of CDK4/Cyclin D1, CDK2/Cyclin E and CDK1/Cyclin B. The method is also useful for stabilizing other lithiated halogen-substituted aromatic compounds and is particularly useful for scale up reactions where the exothermic nature of the reaction can lead to reaction runway. The reaction runaway hazard can be eliminated by using anhydrous MgCl2 as an additive to complex with and stabilize the reactive species and slow down the rate of decomposition.
• 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.