(phenylethynyl)(trifluoromethyl)sulfane | 2002-89-3

• 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: (phenylethynyl)(trifluoromethyl)sulfane
• 英文别名: {2-[(trifluoromethyl)sulfanyl]ethynyl}benzene；(trifluoromethylthio)ethynylbenzene；{[(Trifluoromethyl)thio]ethynyl}benzene；2-(trifluoromethylsulfanyl)ethynylbenzene
• CAS: 2002-89-3
• 化学式: C₉H₅F₃S
• 分子量: 202.2
• InChiKey: XMGKHJYSXPUKNW-UHFFFAOYSA-N

物化性质

• 沸点：
  162.4±50.0 °C(Predicted)
• 密度：
  1.32±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (phenylethynyl)(trifluoromethyl)sulfane 在 tetrakis(tetrabutylammonium)decatungstate(VI) 、 溶剂黄146 作用下， 以 甲醇 、 水 、 乙腈 为溶剂， 反应 30.0h， 生成 1-(4,4-dimethyl-3-phenyl-2-((trifluoromethyl)thio)cyclopentylidene)-2-(4-methoxyphenyl)hydrazine
  参考文献：
  名称：

  10.1002/anie.202407689

  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：

  在 bis(1,5-cyclooctadiene)iridium(I) tetrafluoroborate 、 2-叠氮丙二酸二甲酯 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 12.0h， 以62%的产率得到(phenylethynyl)(trifluoromethyl)sulfane
  参考文献：
  名称：

  铱 (I) 催化的氟烷基亚砜与重氮丙二酸二甲酯脱氧得到氟烷基硫醚

  摘要：

  研究了铱(I)催化重氮丙二酸二甲酯脱氧氟代烷基亚砜制备三氟甲基硫醚和二氟甲基硫醚的新方法。在反应体系中，以重氮丙二酸二甲酯为还原剂，通过氧原子从氟烷基亚砜转移到重氮丙二酸，生成相应的氟烷基硫醚。该方案具有有效的氧原子转移、温和的反应条件和良好的官能团耐受性，为氟烷基硫醚的合成提供了另一种策略。

  DOI：

  10.1016/j.cclet.2022.02.061
• 作为试剂：
  描述：

  异戊醛 、 2,2,6,6-四甲基哌啶氧化物 在 tetrakis(tetrabutylammonium)decatungstate(VI) 、 (phenylethynyl)(trifluoromethyl)sulfane 作用下， 以 水 、 乙腈 为溶剂， 生成
  参考文献：
  名称：

  10.1002/anie.202407689

  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

• Structure–Reactivity Relationship of Trifluoromethanesulfenates: Discovery of an Electrophilic Trifluoromethylthiolating Reagent
  作者：Xinxin Shao、Chunfa Xu、Long Lu、Qilong Shen

  DOI：10.1021/jo502645m

  日期：2015.3.20

  A family of electrophilic trifluoromethanesulfenates was prepared. Structure–reactivity relationship studies showed that the substituted groups on the aryl ring of the trifluoromethylthiolating reagent did not have an obvious influence on their reactivities. A simplified electrophilic trifluoromethylthiolating reagent 1c was then identified that can react with a wide range of nucleophiles such as Grignard

  制备了亲电三氟甲烷亚磺酸盐家族。结构反应关系研究表明，三氟甲基硫醇化试剂的芳基环上的取代基对其反应活性没有明显影响。然后鉴定出一种简化的亲电子三氟甲基硫醇化试剂1c，它可以在温和的反应条件下与格氏试剂，芳基硼酸，炔烃，吲哚，β-酮酸酯，羟吲哚和亚磺酸钠等多种亲核试剂反应。在这些条件下可以耐受多种官能团。
• Copper-Catalyzed, Stereoselective Bis-trifluoromethylthiolation of Propiolic Acid Derivatives with AgSCF₃
  作者：Shen Pan、Huan Li、Yangen Huang、Xiu-Hua Xu、Feng-Ling Qing

  DOI：10.1021/acs.orglett.7b01366

  日期：2017.6.16

  A copper-catalyzed chemo- and stereoselective oxidative bis-trifluoromethylthiolation of propiolic acid derivatives was achieved by using carboxylic acid as the activating group and formic acid as a cosolvent. The reaction of propiolic acid derivatives and AgSCF3 in the presence of (NH4)2S2O8 and catalytic Cu(OAc)2 in MeCN/HCO2H afforded bis-trifluoromethylthiolated acrylic acids in moderate to excellent

  通过使用羧酸作为活化基团和甲酸作为助溶剂，实现了丙酸衍生物的铜催化的化学和立体选择性氧化双三氟甲基硫醇化。丙酸衍生物和AgSCF 3在（NH 4）2 S 2 O 8和催化性Cu（OAc）2存在下于MeCN / HCO 2 H中反应，可得到中等收率至优异收率的双三氟甲基硫代丙烯酸，并具有E选择性。所得产物的进一步衍生得到一系列含多取代的SCF 3的烯烃。
• Base-Catalyzed Electrophilic Trifluoromethylthiolation of Terminal Alkynes
  作者：Sébastien Alazet、Luc Zimmer、Thierry Billard

  DOI：10.1002/anie.201305179

  日期：2013.10.4

  Pin the tail on the alkyne: CF3S‐ or CF3CF2S‐alkynes can be simply and quickly obtained by mixing terminal alkynes with a trifluoromethanesulfenamide reagent. The reaction uses easy‐to‐handle reagents, and functions under mild conditions without activation by transition metals.

  将尾巴钉在炔烃上：通过将末端炔烃与三氟甲亚磺酰胺试剂混合，可以轻松快速地获得CF 3 S-或CF 3 CF 2 S-炔烃。该反应使用易于处理的试剂，可在温和条件下运行，而不会被过渡金属激活。
• Copper-Catalyzed Perfluoroalkylthiolation of Alkynes with Perfluoroalkanesulfenamides
  作者：Anis Tlili、Sébastien Alazet、Quentin Glenadel、Thierry Billard

  DOI：10.1002/chem.201601338

  日期：2016.7.11

  Copper‐catalyzed direct perfluoroalkylthiolation of alkynes by using the corresponding perfluoroalkanesulfenamide reagent is reported. The selective mono‐ and bis‐perfluoroalkylthiolation of alkynes can be conducted under very mild conditions (no base, room temperature) in very good to excellent yields. This approach, which uses a low toxicity, inexpensive copper catalyst that incorporates a commercially

  据报道，使用相应的全氟烷烃亚磺酰胺试剂进行铜催化的炔烃全氟烷基硫醇化反应。炔烃的选择性单-和双-全氟烷基硫醇化反应可以在非常温和的条件下（无碱，室温）进行，并且收率非常好。这种方法使用了一种低毒，廉价的铜催化剂，该催化剂结合了市售的配体，可在没有任何其他碱的情况下使用。初步的机械研究为观察到的前所未有的反应性提供了一些启示。
• 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。

表征谱图