α,α'-dibromo-2-trifluoromethyl-m-xylene | 238074-65-2

• 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: α,α'-dibromo-2-trifluoromethyl-m-xylene
• 英文别名: 2,6-bis(bromomethyl)trifluoromethylbenzene
• CAS: 238074-65-2
• 化学式: C₉H₇Br₂F₃
• 分子量: 331.958
• InChiKey: JZYGHKMBLUFPQY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  二-叔丁基膦 、 α,α'-dibromo-2-trifluoromethyl-m-xylene 以 丙酮 为溶剂， 反应 2.0h， 以76%的产率得到Ditert-butyl-[[3-(ditert-butylphosphanylmethyl)-2-(trifluoromethyl)phenyl]methyl]phosphane
  参考文献：
  名称：

  Formation of Difluoromethylene−Arenium Complexes by Consecutive Aryl−CF₃ C−C Bond Activation and C−F Bond Cleavage

  摘要：

  Oxidative addition of one of the strongest C-C bonds, Aryl-CF3, to Rh(I) takes place upon Creating 1-CF3-2,6-((CH2PBu2)-Bu-t)(2)-C6H3 (1, PCP) with [RhClL2](2) (L = C2H4 or C8H14) in dioxane or toluene at elevated temperatures leading to quantitative formation of Rh(CF3)(2,6-((CH2PBu2)-Bu-t)(2)-C6H3)Cl (2-Cl). The iodide analogue 2-I was prepared by reacting Rh(eta(1)-N-2)(2,6-((CH2PBu2)-Bu-t)(2)-C6H3) (3) with CF3I at room temperature. ArCF2-F bond cleavage was not observed in parallel to the C-C bond activation. Treating a dioxane solution of the thermally stable Rh-III-CF3 complexes 2-Cl,I with excess trifluoromethanesulfonic acid (HOTf) at room temperature resulted in C-F bond cleavage and selective formation of the unique difluoromethylene-arenium complexes [Rh(1-CF2-2,6-((CH2PBu2)-Bu-t)(2)-C6H3)X][OTf] (4; X = Cl, I) which were characterized spectroscopically by NMR, UV/vis, and ED-MS. No reaction was observed with HCl. Reaction of 2-Cl with BF3 or Ph3CBF4 (trityl cation) also resulted in C-F bond cleavage to give [Rh(1-CF2-2,6-((CH2PBu2)-Bu-t)(2)-C6H3)Cl]BF4 (10).

  DOI：

  10.1021/ja990779g
• 作为产物：
  描述：

  2,6-二甲基溴苯 在 1-甲基吡咯烷 、 N-溴代丁二酰亚胺(NBS) 、 copper(l) iodide 、 偶氮二异丁腈 作用下， 以 四氯化碳 为溶剂， 反应 62.0h， 生成 α,α'-dibromo-2-trifluoromethyl-m-xylene
  参考文献：
  名称：

  Formation of Difluoromethylene−Arenium Complexes by Consecutive Aryl−CF₃ C−C Bond Activation and C−F Bond Cleavage

  摘要：

  Oxidative addition of one of the strongest C-C bonds, Aryl-CF3, to Rh(I) takes place upon Creating 1-CF3-2,6-((CH2PBu2)-Bu-t)(2)-C6H3 (1, PCP) with [RhClL2](2) (L = C2H4 or C8H14) in dioxane or toluene at elevated temperatures leading to quantitative formation of Rh(CF3)(2,6-((CH2PBu2)-Bu-t)(2)-C6H3)Cl (2-Cl). The iodide analogue 2-I was prepared by reacting Rh(eta(1)-N-2)(2,6-((CH2PBu2)-Bu-t)(2)-C6H3) (3) with CF3I at room temperature. ArCF2-F bond cleavage was not observed in parallel to the C-C bond activation. Treating a dioxane solution of the thermally stable Rh-III-CF3 complexes 2-Cl,I with excess trifluoromethanesulfonic acid (HOTf) at room temperature resulted in C-F bond cleavage and selective formation of the unique difluoromethylene-arenium complexes [Rh(1-CF2-2,6-((CH2PBu2)-Bu-t)(2)-C6H3)X][OTf] (4; X = Cl, I) which were characterized spectroscopically by NMR, UV/vis, and ED-MS. No reaction was observed with HCl. Reaction of 2-Cl with BF3 or Ph3CBF4 (trityl cation) also resulted in C-F bond cleavage to give [Rh(1-CF2-2,6-((CH2PBu2)-Bu-t)(2)-C6H3)Cl]BF4 (10).

  DOI：

  10.1021/ja990779g

文献信息

• Synthesis of Substituted Diazoniapentaphene Salts by an Unexpected Rearrangement-Cyclodehydration Sequence
  作者：Anton Granzhan、Heiko Ihmels、Katya Mikhlina、Hans-Jörg Deiseroth、Holger Mikus

  DOI：10.1002/ejoc.200500463

  日期：2005.10

  intramolecular ipso-addition to the substituted benzene moiety, followed by an [1,2]-methyl shift in case of 4a–b or HBr elimination in case of 4d. The proposed mechanism was confirmed by the isolation of the intermediate hydroxy derivative 10b from the cyclization of 3a in refluxing HBr and conversion of 10b to the final product 4a by dehydration in polyphosphoric acid. Electronic absorption and fluorescence

  双（吡啶鎓甲基）甲基苯 3a-b 在多磷酸中的环脱水生成甲基取代的重氮五苯盐 4a-b，而不是线性重氮并五苯衍生物，而 1,3-双（吡啶鎓甲基）溴苯 3d 形成半甜菜碱 4a,12a -diazoniapentaphen-14-olate 4d 在这些条件下。这种重排-环化脱水序列的机制细节可以通过分子内同位加成到取代的苯部分，然后在 4a-b 的情况下发生 [1,2]-甲基转移或在 4d 的情况下消除 HBr 来解释。通过在回流 HBr 中从 3a 的环化中分离中间体羟基衍生物 10b 并通过在多磷酸中脱水将 10b 转化为最终产物 4a，证实了所提出的机制。已经研究了以前未知的重氮五苯盐的电子吸收和荧光特性。4a-b 的光物理性质类似于母体重氮五苯盐的光物理性质，而半甜菜碱 4d 具有红移吸收和荧光最大值，以及关于吸收性质的显着溶剂化变色。(© Wiley-VCH Verlag GmbH