3-[(trifluoromethyl)thio]thiophene | 86369-94-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 3-[(trifluoromethyl)thio]thiophene
• 英文别名: 3-(Trifluoromethylsulfanyl)thiophene
• CAS: 86369-94-0
• 化学式: C₅H₃F₃S₂
• 分子量: 184.206
• InChiKey: YSDZKPHHRJMDAH-UHFFFAOYSA-N

物化性质

• 沸点：
  111.6±40.0 °C(Predicted)
• 密度：
  1.45±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  53.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-[(trifluoromethyl)thio]thiophene 在 硫酸 、 双氧水 、 potassium nitrate 作用下， 以 溶剂黄146 为溶剂， 反应 6.0h， 生成 2-nitro-4-(trifluoromethylsulfonyl)thiophene
  参考文献：
  名称：

  Hurtel, Patrice; Decroix, Bernard; Morel, Jean, Journal of Chemical Research, Miniprint, 1983, # 3, p. 725 - 754

  摘要：

  DOI：
• 作为产物：
  描述：

  3-Thiocyanato-thiophen 、 (三氟甲基)三甲基硅烷 在 caesium carbonate 作用下， 以 乙腈 为溶剂， 反应 12.0h， 生成 3-[(trifluoromethyl)thio]thiophene
  参考文献：
  名称：

  通过C 3合成芳基三和二氟甲基硫醚。H-硫氰化/氟烷基化级联

  摘要：

  发现了一种由AlCl 3催化的CH硫氰化，并与Langlois型三氟甲基化结合，直接从芳烃，N-硫氰基琥珀酰亚胺（NTS）和Ruppert-Prakash试剂中得到芳基三氟甲基硫醚。与铜介导的二氟甲基化的类似组合可使用芳基二氟甲基硫醚。对于芳烃的电子最多，空间受阻最小的位置，这两个过程都具有出色的区域选择性。硫和氟代烷基基团来自不同的来源，因此避免了使用昂贵的预先形成的氟代烷基硫代化试剂。

  DOI：

  10.1002/chem.201502914

文献信息

• Oxidative Trifluoromethylthiolations of Aryl Boronic Acids Using a Copper/O ₂ ‐Based Protocol
  作者：Cheng‐Pan Zhang、David A. Vicic

  DOI：10.1002/asia.201200347

  日期：2012.8

  All you need is air: A new protocol has been developed which can mediate the coupling of aryl and vinyl boronic acids at room temperature in high yields (see scheme, dtbpy=4,4′‐di‐tert‐butyl‐2,2′‐bipyridine). The reactions take place using simple copper(II) salts under aerobic conditions and do not require the use of expensive silver oxidants.

  您所需要的只是空气：已开发出一种新的协议，可以在室温下以高收率介导芳基和乙烯基硼酸的偶联（请参阅方案，dtbpy = 4,4'-二叔丁基-2,2' -联吡啶）。反应在有氧条件下使用简单的铜（II）盐进行，不需要使用昂贵的银氧化剂。
• Triphenylphosphine-Mediated Deoxygenative Reduction of CF₃ SO₂ Na and Its Application for Trifluoromethylthiolation of Aryl Iodides
  作者：Yi Yang、Long Xu、Siqi Yu、Xiaoqiang Liu、Yu Zhang、David A. Vicic

  DOI：10.1002/chem.201504790

  日期：2016.1.18

  several air‐stable [LCu(SCF3)] complexes as valuable trifluoromethylthiolating agents. In addition, the CuSCF3 intermediate can be directly employed for the trifluoromethylthiolation of (hetero)aryl iodides with operational simplicity and atomic efficiency.

  我们在此报告了一种通过三苯基膦介导的脱氧还原过程来驯服Langlois试剂CF 3 SO 2 Na生成CuSCF 3的实用方法。这种化学反应突出了Langlois试剂固有的CF 3 S骨架在温和条件下作为CF 3 S原料的新用途。通过该协议生成的CuSCF 3中间体可以与各种各样的支持配体反应，从而提供几种空气稳定的[LCu（SCF 3）]络合物作为有价值的三氟甲基硫醇化剂。此外，CuSCF 3 该中间体可以直接用于操作（操作简便）和原子效率高的（杂）芳基碘化物的三氟甲基硫醇化反应。
• Fundamental Studies and Development of Nickel-Catalyzed Trifluoromethylthiolation of Aryl Chlorides: Active Catalytic Species and Key Roles of Ligand and Traceless MeCN Additive Revealed
  作者：Guoyin Yin、Indrek Kalvet、Ulli Englert、Franziska Schoenebeck

  DOI：10.1021/jacs.5b00538

  日期：2015.4.1

  A catalytic protocol to convert aryl and heteroaryl chlorides to the corresponding trifluoromethyl sulfides is reported herein. It relies on a relatively inexpensive Ni(cod)(2)/dppf (cod = 1,5-cyclooctadiene; dppf = 1,1'-bis(diphenylphosphino)ferrocene) catalyst system and the readily accessible coupling reagent (Me4N)SCF3. Our computational and experimental mechanistic data are consistent with a Ni-(0)/Ni-(II) cycle and inconsistent with Ni-(I) as the reactive species. The relevant intermediates were prepared, characterized by X-ray crystallography, and tested for their catalytic competence. This revealed that a monomeric tricoordinate Ni-(I) complex is favored for dppf and Cl whose role was unambiguously assigned as being an off-cycle catalyst deactivation product. Only bidentate ligands with wide bite angles (e.g., dppf) are effective. These bulky ligands render the catalyst resting state as [(P-P)Ni(cod)]. The latter is more reactive than Ni(P-P)(2), which was found to be the resting state for ligands with smaller bite angles and suffers from an initial high-energy dissociation of one ligand prior to oxidative addition, rendering the system unreactive. The key to effective catalysis is hence the presence of a labile auxiliary ligand in the catalyst resting state. For more challenging substrates, high conversions were achieved via the employment of MeCN as a traceless additive. Mechanistic data suggest that its beneficial role lies in decreasing the energetic span, therefore accelerating product formation. Finally, the methodology has been applied to synthetic targets of pharmaceutical relevance.
• CN116102507
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  公开号：——

  公开（公告）日：——