1-lithio-2-chloro-5-(trifluoromethyl)benzene | 135227-01-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-lithio-2-chloro-5-(trifluoromethyl)benzene
• 英文别名: [2-chloro-4-(trifluoromethyl)benzene]lithium
• CAS: 135227-01-9
• 化学式: C₇H₃ClF₃Li
• 分子量: 186.49
• InChiKey: DORDWZUQKRHWKK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.78
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-lithio-2-chloro-5-(trifluoromethyl)benzene 在 二异丙胺 作用下， 以 四氢呋喃 为溶剂， 生成 [2-chloro-6-(trifluoromethyl)benzene]lithium
  参考文献：
  名称：

  Regioselective Lithium Diisopropylamide-Mediated Ortholithiation of 1-Chloro-3-(trifluoromethyl)benzene: Role of Autocatalysis, Lithium Chloride Catalysis, and Reversibility

  摘要：

  Ortholithiation of 1-chloro-3-(trifluoromethyl) benzene with lithium diisopropylamide (LDA) in tetrahydrofuran at -78 degrees C displays characteristics of reactions in which aggregation events are rate limiting. Metalation with lithium-chloride-free LDA involves a rate-limiting deaggregation via dimer-based transition structures. The post-rate-limiting proton transfers are suggested to involve highly solvated triple ions. Autocatalysis by the resulting aryllithiums or catalysis by traces (<100 ppm) of LiCl diverts the reaction through di- and trisolvated monomer-based pathways for metalation at the 2 and 6 positions, respectively. The regiochemistry is dictated by a combination of kinetically controlled metalations overlaid by an equilibration involving diisopropylamine that is shown to occur by the microscopic reverse of the monomer-based metalations.

  DOI：

  10.1021/ja200906z
• 作为产物：
  描述：

  间氯三氟甲苯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 [2-chloro-6-(trifluoromethyl)benzene]lithium 、 1-lithio-2-chloro-5-(trifluoromethyl)benzene
  参考文献：
  名称：

  Regioselective Lithium Diisopropylamide-Mediated Ortholithiation of 1-Chloro-3-(trifluoromethyl)benzene: Role of Autocatalysis, Lithium Chloride Catalysis, and Reversibility

  摘要：

  Ortholithiation of 1-chloro-3-(trifluoromethyl) benzene with lithium diisopropylamide (LDA) in tetrahydrofuran at -78 degrees C displays characteristics of reactions in which aggregation events are rate limiting. Metalation with lithium-chloride-free LDA involves a rate-limiting deaggregation via dimer-based transition structures. The post-rate-limiting proton transfers are suggested to involve highly solvated triple ions. Autocatalysis by the resulting aryllithiums or catalysis by traces (<100 ppm) of LiCl diverts the reaction through di- and trisolvated monomer-based pathways for metalation at the 2 and 6 positions, respectively. The regiochemistry is dictated by a combination of kinetically controlled metalations overlaid by an equilibration involving diisopropylamine that is shown to occur by the microscopic reverse of the monomer-based metalations.

  DOI：

  10.1021/ja200906z

文献信息

• Synthesis of unsymmetrical biaryls via kinetic higher order cyanocuprates: scope, limitations, and spectroscopic insights
  作者：Bruce H. Lipshutz、Konstantin Siegmann、Emiliano Garcia、Frank Kayser

  DOI：10.1021/ja00073a051

  日期：1993.10

  Treatment of lower order arylcyanocuprates ArCu(CN)Li with 1 equiv of an aryllithium (Ar'Li) at temperatures around -125 o C leads to higher order reagents Ar(Ar')Cu(CN)Li 2 . Upon exposure of such reagents at this temperature to ground-state molecular oxygen, good yields of the unsymmetrical biaryl Ar-Ar' can be realized. Several different types of aryl ligands have been examined, including naphthalenes

  在 -125 o C 左右的温度下，用 1 当量的芳基锂 (Ar'Li) 处理低级芳基氰铜酸盐 ArCu(CN)Li 会产生高级试剂 Ar(Ar')Cu(CN)Li 2 。在该温度下将此类试剂暴露于基态分子氧后，可以实现不对称联芳基 Ar-Ar' 的良好产率。已经检查了几种不同类型的芳基配体，包括萘，以评估该方法的通用性。已经在 -130 o C 和更高温度下获得了三种不同铜酸盐的光谱数据（ 13 C NMR），以确定它们的动力学性质（如合成化学所示）是否可以通过物理方法证实
• "Kinetic" higher order cyanocuprates: applications to biaryl synthesis
  作者：Bruce H. Lipshutz、Konstantin Siegmann、Emiliano Garcia

  DOI：10.1021/ja00021a049

  日期：1991.10
• Regioselective Lithium Diisopropylamide-Mediated Ortholithiation of 1-Chloro-3-(trifluoromethyl)benzene: Role of Autocatalysis, Lithium Chloride Catalysis, and Reversibility
  作者：Alexander C. Hoepker、Lekha Gupta、Yun Ma、Marc F. Faggin、David B. Collum

  DOI：10.1021/ja200906z

  日期：2011.5.11

  Ortholithiation of 1-chloro-3-(trifluoromethyl) benzene with lithium diisopropylamide (LDA) in tetrahydrofuran at -78 degrees C displays characteristics of reactions in which aggregation events are rate limiting. Metalation with lithium-chloride-free LDA involves a rate-limiting deaggregation via dimer-based transition structures. The post-rate-limiting proton transfers are suggested to involve highly solvated triple ions. Autocatalysis by the resulting aryllithiums or catalysis by traces (<100 ppm) of LiCl diverts the reaction through di- and trisolvated monomer-based pathways for metalation at the 2 and 6 positions, respectively. The regiochemistry is dictated by a combination of kinetically controlled metalations overlaid by an equilibration involving diisopropylamine that is shown to occur by the microscopic reverse of the monomer-based metalations.