(difluoromethyl)(naphthalen-1-yl)sulfane | 1454765-37-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (difluoromethyl)(naphthalen-1-yl)sulfane
• 英文别名: 1-Difluoromethylthionaphthalene；1-(difluoromethylsulfanyl)naphthalene
• CAS: 1454765-37-7
• 化学式: C₁₁H₈F₂S
• 分子量: 210.247
• InChiKey: PICFSFQLCHCRGQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-叠氮丙二酸二甲酯 、 (difluoromethyl)(naphthalen-1-yl)sulfane 在 bis{rhodium[3,3'-(1,3-phenylene)bis(2,2-dimethylpropanoic acid)]} 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 以83%的产率得到difluoromethyl(naphthalen-1-yl) bis(carbomethoxy)methylide sulfonium ylide
  参考文献：
  名称：

  用亲电子的二氟甲基化Y叶立德直接对醇进行二氟甲基化

  摘要：

  开发了在温和的反应条件下且具有良好的官能团耐受性的烷基二氟甲基醚形成的通用方法。该方法的发展是基于一种稳定的，亲电子的二氟甲基化试剂二氟甲基-（4-硝基苯基）-双（羰甲氧基）亚甲基叶立德的发明，它是通过容易获得的4-硝基苯基（二氟甲基）的反应合成的铑催化剂存在下，硫醚和重氮丙二酸二甲酯。

  DOI：

  10.1002/anie.201603166
• 作为产物：
  描述：

  1-奈硫酚 在 lithium tetrafluoroborate 、 lithium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.42h， 生成 (difluoromethyl)(naphthalen-1-yl)sulfane
  参考文献：
  名称：

  Direct S-difluoromethylation of thiols using the Ruppert–Prakash reagent

  摘要：

  Direct S-difluoromethylation of aryl and aliphatic thiols using the Ruppert-Prakash reagent is demonstrated. The reaction produces trimethylsilyldifluoromethyl sulfides, which upon cleavage with fluoride produces the difluoromethyl sulfides. The key reaction features are the use of relatively inexpensive and commercially available starting materials, shorter reaction times, ambient temperatures, easy reaction procedure, and selective S-difluoromethylation in the presence of-OH, -NH2 and -CO2H functional groups. Furthermore, one-pot arylthiodifluoromethyl transfer to PhCHO is also demonstrated. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2015.09.011

文献信息

• Copper-Promoted Sandmeyer Difluoromethylthiolation of Aryl and Heteroaryl Diazonium Salts
  作者：Jiang Wu、Yang Gu、Xuebing Leng、Qilong Shen

  DOI：10.1002/anie.201502113

  日期：2015.6.22

  An efficient copper‐promoted difluoromethylthiolation of aryl and heteroaryl diazonium salts is described. The reaction is conducted under mild reaction conditions and various functional groups were compatible. In addition, reactions of heteroaryl diazonium salts such as pyridyl, quinolinyl, benzothiazolyl, thiophenyl, carbazolyl, and pyrazolyl diazonium salts occurred smoothly to afford the medicinally

  描述了一种有效的铜促进的芳基和杂芳基重氮盐的二氟甲基硫醇化反应。该反应在温和的反应条件下进行，并且各种官能团是相容的。另外，杂芳基重氮盐如吡啶基，喹啉基，苯并噻唑基，噻吩基，咔唑基和吡唑基重氮盐的反应平稳地进行，以提供具有医学重要性的二氟甲基硫代杂芳基。此外，还开发了一种更实用的单锅直接重氮化和二氟甲基硫醇化方案，并将苯胺衍生物转化为二氟甲基硫醇化的芳烃。该方法的实用性通过许多天然产物和药物分子的二氟甲基硫醇化得到证明。
• Pd-Catalyzed Difluoromethylthiolation of Aryl Chlorides, Bromides and Triflates
  作者：Jiang Wu、Changhui Lu、Long Lu、Qilong Shen

  DOI：10.1002/cjoc.201800306

  日期：2018.11

  A highly efficient Pd‐catalyzed difluoromethylthiolation of aryl chlorides, bromides and triflates is described. A variety of aryl halides with common functional groups were difluoromethylthiolated in moderate to excellent yields. Furthermore, several natural, drug and material molecules containing an aryl chloride, bromide, and phenol unit were successfully difluoromethylthiolated, thus providing

  描述了芳基氯化物，溴化物和三氟甲磺酸酯的高效钯催化二氟甲基硫醇化反应。各种具有常见官能团的芳基卤化物被二氟甲基硫醇化，产率中等至优异。此外，几个含有芳基氯，溴化物和苯酚单元的天然，药物和物质分子已成功地被二氟甲基硫醇化，从而为药物化学家提供了领先的晚期二氟甲基硫醇化的通用方法。
• [EN] SYNTHESIS OF DIFLUOROMETHYL ETHERS AND SULFIDES<br/>[FR] SYNTHÈSE DE DIFLUOROMÉTHYLÉTHERS ET DE DIFLUOROMÉTHYLSULFURES
  申请人：UNIV CALIFORNIA

  公开号：WO2014107380A1

  公开（公告）日：2014-07-10

  The synthesis of difluoromethyl ethers and sulfides with a simple, non-ozone- depleting reagent is described. The difluoromethylation of phenols with this reagent occurs at room temperature within minutes with exceptional functional group tolerance. The mild conditions makes possible tandem processes for the conversion of aryl boronic acids, aryl halides and arenes to difluoromethyl ethers. Mechanistic studies support a reaction pathway involving nucleophilic attack of the phenolate to difluorocarbene.

  描述了使用一种简单、无臭氧破坏剂的方法合成二氟甲基醚和硫醚。使用这种试剂对酚进行二氟甲基化反应在室温下几分钟内就能完成，并且具有异常的官能团容忍性。温和的条件使得可能进行串联过程，将芳基硼酸、芳基卤代烃和芳烃转化为二氟甲基醚。机理研究支持一个涉及酚酚根攻击二氟卡宾的反应途径。
• Palladium-catalyzed difluoromethylthiolation of heteroaryl bromides, iodides, triflates and aryl iodides
  作者：Jiang Wu、Yafei Liu、Changhui Lu、Qilong Shen

  DOI：10.1039/c6sc00082g

  日期：——

  A palladium-catalyzed difluoromethylthiolation of heteroaryl halides and triflates under mild conditions was described. A vast range of heteroaryl halides such as pyridyl, quinolinyl, benzothiazolyl, thiophenyl, carbazolyl and pyazolyl halides could be difluoromethylthiolated efficiently, thus providing medicinal chemists with new tools for their search of new lead compounds for drug discovery. Likewise

  描述了在温和条件下钯催化的杂芳基卤化物和三氟甲磺酸二氟甲基硫醇化反应。各种杂芳基卤化物（例如吡啶基，喹啉基，苯并噻唑基，硫代苯基，咔唑基和吡唑基卤化物）可以有效地被二氟甲基硫醇化，从而为药物化学家提供了寻找新的先导化合物以发现药物的新工具。同样，在改良的反应条件下，高产率地将芳基碘化物二氟甲基硫醇化。
• PhSO₂SCF₂H: A Shelf-Stable, Easily Scalable Reagent for Radical Difluoromethylthiolation
  作者：Dianhu Zhu、Xinxin Shao、Xin Hong、Long Lu、Qilong Shen

  DOI：10.1002/anie.201609468

  日期：2016.12.19

  A new shelf‐stable and easily scalable difluoromethylthiolating reagent S‐(difluoromethyl) benzenesulfonothioate (PhSO2SCF2H) was developed. PhSO2SCF2H is a powerful reagent for radical difluoromethylthiolation of aryl and alkyl boronic acids, decarboxylative difluoromethylthiolation of aliphatic acids, and a phenylsulfonyl‐difluoromethylthio difunctionalization of alkenes under mild reaction conditions

  开发了一种新的货架稳定且易于扩展的二氟甲基硫醇化试剂S-（二氟甲基）苯磺酸硫（PhSO 2 SCF 2 H）。PhSO 2 SCF 2 H是用于在温和的反应条件下进行芳基和烷基硼酸的自由基二氟甲硫基化，脂肪酸的脱羧二氟甲硫基化以及烯烃的苯磺酰基-二氟甲硫基二官能化的强大试剂。