ethyl α,α-difluoro-α-(phenylseleno)acetate | 698378-63-1

• 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: ethyl α,α-difluoro-α-(phenylseleno)acetate
• 英文别名: Ethyl 2,2-difluoro-2-(phenylselanyl)acetate；ethyl 2,2-difluoro-2-phenylselanylacetate
• CAS: 698378-63-1
• 化学式: C₁₀H₁₀F₂O₂Se
• 分子量: 279.145
• InChiKey: WKOPMIMGVSPKRR-UHFFFAOYSA-N

物化性质

• 沸点：
  280.3±40.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.17
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 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：

  2,3-二氢呋喃 、 ethyl α,α-difluoro-α-(phenylseleno)acetate 在 2,4,6-三甲基吡啶 、 二苯基二硒醚 作用下， 以 二氯甲烷 为溶剂， 反应 16.5h， 以78%的产率得到3-(ethoxycarbonyldifluoromethyl)-2,3-dihydrofurane
  参考文献：
  名称：

  带有酯和膦酸酯基团的二氟甲基自由基对烯烃和芳族化合物的光化学取代

  摘要：

  在2,4,6-三甲基吡啶和二苯基二硒化物的存在下，成功地进行了光生的带有酯基和膦酸酯基团的二氟甲基基团对环状和无环乙烯基醚的高效选择性取代，从而选择性地提供了相应的区域选择性不饱和二氟亚甲基加合物。该反应涉及在早期阶段进行苯基硒烯基转移，随后一旦形成就选择性地提供不饱和二氟亚甲基加合物而从加合物中消除苯基硒醇。这种新颖的光化学方法已成功地扩展到芳族和杂芳族取代，从而以良好至中等的产率提供了相应的α-芳基-α，α-二氟乙酸酯和α-芳基-α，α-二氟甲基膦酸酯。

  DOI：

  10.1016/j.tet.2005.12.057
• 作为产物：
  描述：

  ethyl 2-fluoro-2-(phenylselanyl)acetate 在 triethylamine tris(hydrogen fluoride) 作用下， 以 二氯甲烷 为溶剂， 以84%的产率得到ethyl α,α-difluoro-α-(phenylseleno)acetate
  参考文献：
  名称：

  Electrosynthesis of ethyl α,α-difluoro-α-(phenylseleno)acetate and its photochemical synthetic application

  摘要：

  Anodic fluorination of ethyl alpha-fluoro-alpha-(phenylseleno)acetate was successfully carried out to give ethyl alpha,alpha-difluoro-alpha-(phenylseleno)acetate in high yield. Photolysis of the difluorinated product in the presence of various olefins provided regioselective difluorometylene adducts in good to moderate total yields. The reaction involves phenylselenyl transfer at the early stage followed by the elimination of a phenylselenyl group from the adducts once formed to provide the unsaturated and saturated difluoromethylene products. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2003.12.015

文献信息

• Acridine Orange Hemi(Zinc Chloride) Salt as a Lewis Acid‐Photoredox Hybrid Catalyst for the Generation of <i>α</i> ‐Carbonyl Radicals
  作者：Sanju Das、Tanumoy Mandal、Suman De Sarkar

  DOI：10.1002/adsc.202101053

  日期：2022.2.15

  A readily accessible organic-inorganic hybrid catalyst is reported for the reductive fragmentation of α-halocarbonyl compounds. The robust hybrid catalyst is a self-stabilizing combination of ZnCl2 Lewis acid and acridine orange as the photoactive organic dye. Mechanistic specifics of this hybrid catalyst have been studied in detail using both photophysical and electrochemical experiments. A systematic

  据报道，一种易于获得的有机-无机杂化催化剂用于α-卤代羰基化合物的还原断裂。稳健的杂化催化剂是 ZnCl 2 Lewis 酸和吖啶橙作为光活性有机染料的自稳定组合。已经使用光物理和电化学实验详细研究了这种混合催化剂的机械特性。一项系统的研究使我们能够发现合适的路易斯酸以有效地稳定α-卤代羰基化合物，从而降低标准有机染料范围内的还原电位。该策略通过引导光氧化还原循环通过氧化猝灭途径解决了脱卤氢化或烷基自由基同源偶联等问题。光活性有机染料和路易斯酸对应物之间的协同作用通过有效和受控地生成烷基自由基，使功能化与广泛的偶联伙伴成为可能，并作为昂贵的后过渡金属基光催化剂的合适替代品。为了证明这种协同催化体系的应用潜力，研究了四种不同的α-羰基溴的合成转化，具有广泛的底物范围。
• Aromatic Substitution with Photochemically Generated Difluoromethyl ­Radicals Bearing Electron-Withdrawing Group
  作者：Toshio Fuchigami、Satoru Murakami、Shokaku Kim、Hideki Ishii

  DOI：10.1055/s-2004-820026

  日期：——

  Novel and facile aromatic and heteroaromatic substitutions with difluoromethyl radicals bearing electron-withdrawing group generated by the photo-initiated Se-CF 2 bond cleavage of ethyl α,α-difluoro-α-(phenylseleno)acetate and diethyl α,α-difluoromethyl-α-(phenylseleno)phosphonate were successfully carried out to provide the corresponding a-aryl-α,α-difluoroacetates and α-aryl-α,α-difluoromethylphosphonates

  通过光引发 Se-CF 2 键裂解 α,α-二氟-α-（苯基硒基）乙酸乙酯和二乙基 α,α-二氟甲基-α 产生带有吸电子基团的二氟甲基自由基的新型和简便的芳族和杂芳族取代-(苯基硒基)膦酸酯被成功地进行以良好到中等的产率提供相应的α-芳基-α,α-二氟乙酸酯和α-芳基-α,α-二氟甲基膦酸酯。
• Electrosynthesis of ethyl α,α-difluoro-α-(phenylseleno)acetate and its photochemical synthetic application
  作者：Satoru Murakami、Hideki Ishii、Toshio Fuchigami

  DOI：10.1016/j.jfluchem.2003.12.015

  日期：2004.4

  Anodic fluorination of ethyl alpha-fluoro-alpha-(phenylseleno)acetate was successfully carried out to give ethyl alpha,alpha-difluoro-alpha-(phenylseleno)acetate in high yield. Photolysis of the difluorinated product in the presence of various olefins provided regioselective difluorometylene adducts in good to moderate total yields. The reaction involves phenylselenyl transfer at the early stage followed by the elimination of a phenylselenyl group from the adducts once formed to provide the unsaturated and saturated difluoromethylene products. (C) 2004 Elsevier B.V. All rights reserved.
• Photochemical substitution of olefins and aromatic compounds with difluoromethyl radicals bearing ester and phosphonate groups
  作者：Satoru Murakami、Hideki Ishii、Toshiki Tajima、Toshio Fuchigami

  DOI：10.1016/j.tet.2005.12.057

  日期：2006.4

  transfer at an early stage followed by elimination of phenylselenol from the adducts once formed to provide the unsaturated difluoromethylene adducts selectively. This novel photochemical method was successfully extended to aromatic and heteroaromatic substitutions to provide the corresponding α-aryl-α,α-difluoroacetates and α-aryl-α,α-difluoromethylphosphonates in good to moderate yields.

  在2,4,6-三甲基吡啶和二苯基二硒化物的存在下，成功地进行了光生的带有酯基和膦酸酯基团的二氟甲基基团对环状和无环乙烯基醚的高效选择性取代，从而选择性地提供了相应的区域选择性不饱和二氟亚甲基加合物。该反应涉及在早期阶段进行苯基硒烯基转移，随后一旦形成就选择性地提供不饱和二氟亚甲基加合物而从加合物中消除苯基硒醇。这种新颖的光化学方法已成功地扩展到芳族和杂芳族取代，从而以良好至中等的产率提供了相应的α-芳基-α，α-二氟乙酸酯和α-芳基-α，α-二氟甲基膦酸酯。