[2-chloro-6-(trifluoromethyl)benzene]lithium | 380611-49-4

• 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: [2-chloro-6-(trifluoromethyl)benzene]lithium
• CAS: 380611-49-4
• 化学式: C₇H₃ClF₃Li
• 分子量: 186.49
• InChiKey: MGZCKVWGUVDZSI-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：

  [2-chloro-6-(trifluoromethyl)benzene]lithium 、 甲酸甲酯 在 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 0.5h， 生成 2-氯-6-(三氟甲基)苯甲醛
  参考文献：
  名称：

  [DE] VERFAHREN ZUR METALLORGANISCHEN HERSTELLUNG ORGANISCHER ZWISCHENPRODUKTE ÜBER ARYLLITHIUM-BASEN
  [EN] METHOD FOR METAL-ORGANIC PRODUCTION OF ORGANIC INTERMEDIATE PRODUCTS BY MEANS OF ARYL LITHIUM-BASES
  [FR] PROCEDE POUR LA PRODUCTION PAR VOIE ORGANOMETALLIQUE D'INTERMEDIAIRES ORGANIQUES AU MOYEN DE BASES ARYLLITHIUM

  摘要：

  该发明涉及一种通过生成锂芳基并将其与适当的亲电试剂反应来制备取代芳香化合物的方法，其中首先（步骤1）通过将卤代芳烃与锂金属反应生成芳基锂化合物（“辅助碱”），随后（步骤2）将其用于去质子化芳香底物以生成相应的锂芳烃，最后（步骤3）将其与相应的亲电试剂反应以形成所需的取代芳香化合物。请参见说明书第2页。

  公开号：

  WO2004024738A1
• 作为产物：
  描述：

  间氯三氟甲苯 在 二异丙胺 、 lithium diisopropyl amide 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

文献信息

• Lithium Diisopropylamide-Mediated Ortholithiations: Lithium Chloride Catalysis
  作者：Lekha Gupta、Alexander C. Hoepker、Kanwal J. Singh、David B. Collum

  DOI：10.1021/jo802713y

  日期：2009.3.6

  Ortholithiations of a range of arenes mediated by lithium dilsopropylamide (LDA) in THF at -78 degrees C reveal substantial accelerations by as little as 0.5 mol % of LiCl (relative to LDA). Substrate dependencies suggest a specific range of reactivity within which the LiCl catalysis is optimal. Standard protocols with unpurified commercial samples of n-butyllithium to prepare LDA or commercially available LDA show marked batch-dependent rates-up to 100-fold-that could prove significant to the unwary practitioner. Other lithium salts elicit more modest accelerations. The mechanism is not discussed.
• [DE] VERFAHREN ZUR METALLORGANISCHEN HERSTELLUNG ORGANISCHER ZWISCHENPRODUKTE ÜBER ARYLLITHIUM-BASEN<br/>[EN] METHOD FOR METAL-ORGANIC PRODUCTION OF ORGANIC INTERMEDIATE PRODUCTS BY MEANS OF ARYL LITHIUM-BASES<br/>[FR] PROCEDE POUR LA PRODUCTION PAR VOIE ORGANOMETALLIQUE D'INTERMEDIAIRES ORGANIQUES AU MOYEN DE BASES ARYLLITHIUM
  申请人：CLARIANT GMBH

  公开号：WO2004024738A1

  公开（公告）日：2004-03-25

  Die Erfindung betrifft ein Verfahren zur Herstellung von substituierten aromatischen Verbindungen durch Erzeugung von Lithiumarylen und deren Umsetzung mit geeigneten Elektrophilen, wobei zunächst (Schritt 1) durch Umsetzung eines Halogenaromaten mit Lithiummetall eine Aryllithiumverbindung („ Hilfsbase“) generiert wird, die anschliessend (Schritt 2) zur Deprotonierung des aromatischen Substrates unter Bildung des entsprechenden Lithiumaromaten umgesetzt wird, wobei dieser abschliessend (Schritt 3) mit einem entsprechenden Elektrophil unter Bildung der gewünschten substituierten aromatischen Verbindung zur Reaktion gebracht wird, siehe Seite 2 der Beschreibung.

  该发明涉及一种通过生成锂芳基并将其与适当的亲电试剂反应来制备取代芳香化合物的方法，其中首先（步骤1）通过将卤代芳烃与锂金属反应生成芳基锂化合物（“辅助碱”），随后（步骤2）将其用于去质子化芳香底物以生成相应的锂芳烃，最后（步骤3）将其与相应的亲电试剂反应以形成所需的取代芳香化合物。请参见说明书第2页。
• 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.