ethyl 4-(2-(trifluoromethylthio)ethynyl)benzoate | 1388753-74-9

• 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 4-(2-(trifluoromethylthio)ethynyl)benzoate
• 英文别名: ethyl 4-(((trifluoromethyl)thio)ethynyl)benzoate；ethyl 4-{2-[(trifluoromethyl)sulfanyl]ethynyl}benzoate；Ethyl 4-[2-(trifluoromethylsulfanyl)ethynyl]benzoate
• CAS: 1388753-74-9
• 化学式: C₁₂H₉F₃O₂S
• 分子量: 274.263
• InChiKey: NWQBGTPNVQOWEJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  异戊醛 、 ethyl 4-(2-(trifluoromethylthio)ethynyl)benzoate 在 tetrakis(tetrabutylammonium)decatungstate(VI) 作用下， 以 水 、 乙腈 为溶剂， 以66 %的产率得到ethyl 4-(2,2-dimethyl-4-oxo-5-((trifluoromethyl)thio)cyclopentyl)benzoate
  参考文献：
  名称：

  Photocatalyzed Cascade Hydrogen Atom Transfers for Assembly of Multi‐Substituted α‐SCF3 and α‐SCF2H Cyclopentanones

  摘要：

  A photocatalyzed formal (3+2) cycloaddition has been developed to construct original polysubstituted α‐SCF3 cyclopentanones in a regio‐ and diastereoselective manner. This building block approach leverages trifluoromethylthio alkynes and branched / linear aldehydes, as readily available reaction partners, in consecutive hydrogen atom transfers and C–C bond formations. Difluoromethylthio alkynes are also compatible subtrates. Furthermore, the potential for telescoped reaction starting from alcohols instead of aldehydes was demonstrated, as well as process automatization and scale‐up under continuous microflow conditions. This prompted density functional theory calculations to support a free radical‐mediated cascade hydrogen atom transfer process.

  DOI：

  10.1002/anie.202407689
• 作为产物：
  描述：

  (三氟甲硫基)银(I) 、 4-乙炔苯甲酸乙酯 在 potassium phosphate 、 N-氯代丁二酰亚胺 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 以66 %的产率得到ethyl 4-(2-(trifluoromethylthio)ethynyl)benzoate
  参考文献：
  名称：

  Photocatalyzed Cascade Hydrogen Atom Transfers for Assembly of Multi‐Substituted α‐SCF3 and α‐SCF2H Cyclopentanones

  摘要：

  A photocatalyzed formal (3+2) cycloaddition has been developed to construct original polysubstituted α‐SCF3 cyclopentanones in a regio‐ and diastereoselective manner. This building block approach leverages trifluoromethylthio alkynes and branched / linear aldehydes, as readily available reaction partners, in consecutive hydrogen atom transfers and C–C bond formations. Difluoromethylthio alkynes are also compatible subtrates. Furthermore, the potential for telescoped reaction starting from alcohols instead of aldehydes was demonstrated, as well as process automatization and scale‐up under continuous microflow conditions. This prompted density functional theory calculations to support a free radical‐mediated cascade hydrogen atom transfer process.

  DOI：

  10.1002/anie.202407689

文献信息

• Metal-Free Oxidative Trifluoromethylthiolation of Terminal Alkynes with CF₃SiMe₃ and Elemental Sulfur
  作者：Chao Chen、Lingling Chu、Feng-Ling Qing

  DOI：10.1021/ja305801m

  日期：2012.8.1

  A metal-free oxidative trifluoromethyl-thiolation of terminal alkynes using readily available CF(3)SiMe(3) and elemental sulfur at room temperature has been developed. This reaction provides an efficient and convenient method for the preparation of alkynyl trifluoromethyl sulfides bearing a wide range of functional groups. Preliminary investigation revealed that elemental sulfur instead of air acted

  已经开发出在室温下使用现成的 CF(3)SiMe(3) 和元素硫对末端炔烃进行无金属氧化三氟甲基硫醇化。该反应为制备具有广泛官能团的炔基三氟甲基硫化物提供了一种高效便捷的方法。初步调查显示元素硫代替空气充当氧化剂。
• Difluorocarbene-based trifluoromethylthiolation of terminal alkynes
  作者：Guowen He、Yan-Hua Jiang、Xuan Xiao、Jin-Hong Lin、Xing Zheng、Ruo-Bing Du、Yu-Cai Cao、Ji-Chang Xiao

  DOI：10.1016/j.jfluchem.2019.109437

  日期：2020.2

  A large number of trifluoromethylthiolation methods have been developed, but a trifluoromethylthiolation reagent usually has to be used in these methods. Herein we describe a difluorocarbene-based trifluoromethylthiolation of terminal alkynes to construct a Csp-SCF3 bond catalysed by a copper complex. Ph3P+CF2CO2-/S8/F- was used as a reagent system to form the CF3S- anion, and the sequential formation

  已经开发了大量的三氟甲基硫醇化方法，但是在这些方法中通常必须使用三氟甲基硫醇化试剂。在本文中，我们描述了末端炔烃的基于二氟卡宾的三氟甲基硫醇化，以构建由铜配合物催化的Csp-SCF 3键。用Ph 3 P + CF 2 CO 2- / S 8 / F-作为试剂体系形成CF 3 S-阴离子，依次形成CF 2 = S，F-CF 2 S和C-SCF 3一步一步就可以实现纽带。
• A concise synthesis of (alkynyl)(trifluoromethyl)sulfanes via a bismuth(<scp>iii</scp>)-promoted reaction of trimethyl(alkynyl)silane with trifluoromethanesulfanylamide
  作者：Jie Sheng、Jie Wu

  DOI：10.1039/c4ob01451k

  日期：——

  A bismuth(III)-promoted reaction of trimethyl(alkynyl)silanes with trifluoromethanesulfanylamide is developed, giving rise to (alkynyl)(trifluoromethyl)sulfanes in good yields.

  开发了一种铋(III)促进的反应，将三甲基(炔基)硅烷与三氟甲烷磺酰胺反应，生成(炔基)(三氟甲基)硫醇，产率良好。