2-溴-2,2-二氟乙酸烯丙酯 | 155820-76-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 2-溴-2,2-二氟乙酸烯丙酯
• 中文别名: 溴二氟苯乙酸2-丙烯基酯
• 英文名称: allyl bromodifluoroacetate
• 英文别名: prop-2-enyl 2-bromo-2,2-difluoroacetate
• CAS: 155820-76-1
• 化学式: C₅H₅BrF₂O₂
• 分子量: 214.994
• InChiKey: YHYZVEQMOASHNH-UHFFFAOYSA-N

物化性质

• 沸点：
  150℃
• 密度：
  1.607
• 闪点：
  45℃

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险品标志：
  Xi
• 海关编码：
  2915900090

反应信息

• 作为反应物：
  描述：

  2-溴-2,2-二氟乙酸烯丙酯 在 potassium fluoride 、 copper(l) iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 8.0h， 以89%的产率得到1,1,1-三氟丁烯-3
  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
• 作为产物：
  描述：

  二氟溴乙酰氟 、 烯丙醇 在 吡啶 作用下， 反应 0.17h， 以75%的产率得到2-溴-2,2-二氟乙酸烯丙酯
  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

• Gold-Catalyzed Highly Selective Photoredox C(sp² )−H Difluoroalkylation and Perfluoroalkylation of Hydrazones
  作者：Jin Xie、Tuo Zhang、Fei Chen、Nina Mehrkens、Frank Rominger、Matthias Rudolph、A. Stephen K. Hashmi

  DOI：10.1002/anie.201508622

  日期：2016.2.18

  hydrazones are highly functionalized, versatile molecules. A mild reduction of the coupling products can efficiently produce gem‐difluoromethylated β‐amino phosphonic acids and β‐amino acid derivatives. In mechanistic studies, a difluoroalkyl radical intermediate was detected by an EPR spin‐trapping experiment, indicating that a gold‐catalyzed radical pathway is operating.

  据报道，使用容易获得的R F -Br试剂，gold的金催化光氧化还原C（sp 2）-H二氟烷基化和hydr的全氟烷基化。所得的宝石二氟甲基化和全氟烷基化的azo是高度官能化的多用途分子。偶合产物的轻度减少可以有效地生产出宝石-二氟甲基化的β-氨基膦酸和β-氨基酸衍生物。在机理研究中，通过EPR自旋捕获实验检测到二氟烷基自由基中间体，表明金催化的自由基途径正在起作用。
• 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。
• Synthesis of Alkoxycarbonyldifluoromethyl-Substituted Semisquarates and Their Transformations
  作者：Yoshihiko Yamamoto、Takashi Kurohara、Jiang Jiyue、Masatoshi Shibuya

  DOI：10.1055/s-0036-1591887

  日期：2018.4

  rearrangement. The compatibility of the highly reactive EtO2CCF2 group in ring transformations of the obtained semisquarate is investigated. Various EtO2CCF2-substituted, highly functionalized compounds, such as quinones, tetronates, cyclopentenones and a bicyclo-[3.2.0]heptenone, are successfully synthesized by ring transformations of the EtO2CCF2-substituted semisquarate. Also, an allylO2CCF2-substituted

  摘要 一种新的EtO 2 CCF 2取代的半方酸酯是由二异丙基方酸酯通过选择性地1,2加成源自BrCF 2 CO 2 Et的Reformatsky试剂并随后进行-催化的烯丙基醇重排而合成的。研究了高反应性的EtO 2 CCF 2基团在所得半方形的环转化中的相容性。各种环氧乙烷2 CCF 2 -取代的，高功能的化合物，如醌，tetronates，环戊烯酮和二环- [3.2.0]庚烯酮，成功地由环氧乙烷的环转化合成2 CCF 2取代的半方形。同样，制备烯丙基O 2 CCF 2取代的半方酸酯，并将其转化为相应的tetronate。随后的钯催化的脱铝反应，然后在温和的条件下将所得的羧酸与几种胺进行缩合，可以以良好的收率得到相应的α，α-二氟酰胺。 一种新的EtO 2 CCF 2取代的半方酸酯是由二异丙基方酸酯通过选择性地1,2加成源自BrCF 2 CO 2 Et的Reformatsky试剂并随后进
• Synthesis of new α,α-difluoro-γ-lactones through intramolecular radical cyclization as a key reaction
  作者：Toshiyuki Itoh、Hiroyuki Ohara、Sachie Emoto

  DOI：10.1016/0040-4039(95)00518-h

  日期：1995.5

  Carbon radicals from allyl o-trimethylsilyl-alpha-bromo-alpha,alpha-difluoroacetals can cyclize onto olefines regiospecifically to give gamma-lactols in good yield. These lactols have been converted to the corresponding alpha,alpha-difluoro-gamma-lactones. The first synthesis of three new alpha,alpha-difluoro-gamma-lactones has been accomplished.
• 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.