cinnamyl bromodifluoroacetate | 155820-77-2

• 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: cinnamyl bromodifluoroacetate
• 英文别名: 3-Phenylprop-2-enyl 2-bromo-2,2-difluoroacetate；3-phenylprop-2-enyl 2-bromo-2,2-difluoroacetate
• CAS: 155820-77-2
• 化学式: C₁₁H₉BrF₂O₂
• 分子量: 291.092
• InChiKey: GJJCHXACUSUCBA-UHFFFAOYSA-N

物化性质

• 沸点：
  331.1±42.0 °C(predicted)
• 密度：
  1.523±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  cinnamyl bromodifluoroacetate 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 1.75h， 生成 1,1,1-trifluoro-4-phenylbut-3-ene
  参考文献：
  名称：

  BBDFA：用于制备规模的烯丙醇和苄醇三氟甲基化的实用试剂

  摘要：

  我们报告了一种安全易用的试剂[1,1'-联苯] -4-基2-溴-2,2-二氟乙酸酯（BBDFA），用于铜催化的烯丙基或苄基醇的三氟甲基化。开发了制备BBDFA的操作简单且无需柱色谱的方法，并已证明其> 100 g规模。使用肉桂醇作为模型底物进行了详细的反应量热和脱氧三氟甲基化的热分析，表明该反应可以在制备规模上安全地进行。

  DOI：

  10.1021/acs.oprd.9b00201
• 作为产物：
  描述：

  肉桂醇 、 二氟溴乙酰氟 在 吡啶 作用下， 反应 0.17h， 以77%的产率得到cinnamyl bromodifluoroacetate
  参考文献：
  名称：

  Novel synthesis of 2,2,2-trifluoroethyl compounds from homoallylic alcohols: a copper(I) iodide-initiated trifluoromethyl–dehydroxylation process

  摘要：

  Benzyl, prop-2-ynyl and allyl chlorodifluoroacetates 3a, bromodifluoroacetates 3b or fluorosulfonyl-difluoroacetates 3c, when decomposed in the presence of 1 equivalent of copper(I) iodide at an appropriate temperature in dimethylformamide, gave the corresponding trifluoromethyl derivatives in good to excellent yields. The products can also be obtained directly by ester exchange of XCF2CO2Et (X = FSO2, Cl, Br) 6 and the corresponding alcohols in the presence of KF and Cul. A trifluoromethylation-dehydroxylation mechanism, initiated by Cul, is proposed.

  DOI：

  10.1039/p19940000725

文献信息

• Systematic Synthesis of Multifluorinated α,α-Difluoro-γ-lactones through Intramolecular Radical Cyclization
  作者：Toshiyuki Itoh、Kohei Sakabe、Kazutoshi Kudo、Hiroyuki Ohara、Yumiko Takagi、Hiroshi Kihara、Pierre Zagatti、Michel Renou

  DOI：10.1021/jo982035b

  日期：1999.1.1

  orbital of alpha,alpha-difluoroacetyl radical occurred; this caused unsuccessful cyclization. To apply the present radical reaction, the first synthesis of both enantiomers of difluoroeldanolide, analogues of the sex pheromone of the male African sugarcane borer, has been demonstrated. Electrophysiological tests revealed that the difluorinated analogues were as active as the natural eldanolide on the

  来自烯丙基O-（三甲基甲硅烷基）-α-溴-α，α-二氟乙缩醛的碳自由基可以区域特异性地环化到烯烃部分上，从而以高收率得到γ-内酯。然后将内酯转化为相应的α，α-二氟-γ-内酯。因此，通过分子内自由基环化作为关键反应，完成了多氟化α，α-二氟-γ-内酯的系统合成。半经验MO计算研究表明，α，α-二氟乙酸酯具有独特的性质，即电子在α，α-二氟乙酰基的SOMO轨道上发生了完全的离域化；这导致环化失败。为了应用目前的自由基反应，首先合成了二氟乙酰胺的两种对映体，即非洲雄性甘蔗蛀虫性信息素的类似物，已经证明。电生理学测试表明，二氟类似物在嗅觉受体上的活性与天然的艾德诺德同等。
• Novel synthesis of 2,2,2-trifluoroethyl compounds from homoallylic alcohols: a copper(<scp>I</scp>) iodide-initiated trifluoromethyl–dehydroxylation process
  作者：Jian-Xing Duan、Qing-Yun Chen

  DOI：10.1039/p19940000725

  日期：——

  Benzyl, prop-2-ynyl and allyl chlorodifluoroacetates 3a, bromodifluoroacetates 3b or fluorosulfonyl-difluoroacetates 3c, when decomposed in the presence of 1 equivalent of copper(I) iodide at an appropriate temperature in dimethylformamide, gave the corresponding trifluoromethyl derivatives in good to excellent yields. The products can also be obtained directly by ester exchange of XCF2CO2Et (X = FSO2, Cl, Br) 6 and the corresponding alcohols in the presence of KF and Cul. A trifluoromethylation-dehydroxylation mechanism, initiated by Cul, is proposed.
• BBDFA: A Practical Reagent for Trifluoromethylation of Allylic and Benzylic Alcohols on Preparative Scale
  作者：Chong Han、Lady Mae Alabanza、Sean M. Kelly、Douglas L. Orsi、Francis Gosselin、Ryan A. Altman

  DOI：10.1021/acs.oprd.9b00201

  日期：2019.8.16

  We report a safe and readily prepared reagent [1,1′-biphenyl]-4-yl 2-bromo-2,2-difluoroacetate (BBDFA) for Cu-catalyzed trifluoromethylation of allylic or benzylic alcohols. An operationally simple and column-chromatography-free process to prepare BBDFA was developed and demonstrated on >100 g scale. Detailed reaction calorimetry and thermal analysis of the deoxytrifluoromethylation were performed

  我们报告了一种安全易用的试剂[1,1'-联苯] -4-基2-溴-2,2-二氟乙酸酯（BBDFA），用于铜催化的烯丙基或苄基醇的三氟甲基化。开发了制备BBDFA的操作简单且无需柱色谱的方法，并已证明其> 100 g规模。使用肉桂醇作为模型底物进行了详细的反应量热和脱氧三氟甲基化的热分析，表明该反应可以在制备规模上安全地进行。