2-((fluoromethyl)thio)pyridine

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2-((fluoromethyl)thio)pyridine
• 英文别名: Pyridine,2-[(fluoromethyl)thio]-(9CI)；2-(fluoromethylsulfanyl)pyridine
• 化学式: C₆H₆FNS
• 分子量: 143.185
• InChiKey: AQIIBYBJBDIOSC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  38.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-((fluoromethyl)thio)pyridine 在 sodium periodate 、 N-氯代丁二酰亚胺 、 rhodium(III) chloride hydrate 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 四氯化碳 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 1.0h， 生成 2-((chlorofluoromethyl)sulfonyl)pyridine
  参考文献：
  名称：

  从烯烃化到烷基化：Julia-Kocienski 中间体的原位卤化导致羰基化合物的正式亲核碘和溴二氟甲基化

  摘要：

  碘和溴二氟甲基化化合物是重要的合成中间体和卤素键受体。然而，通过亲核加成直接引入 -CF(2)I 和 -CF(2)Br 基团特别具有挑战性，因为 CF(2)Br(-) 和 CF(2)I(-) 的分解趋势很高到二氟卡宾。在这项工作中，我们开发了羰基化合物的正式亲核碘和溴二氟甲基化。该方法的关键策略是将 Julia-Kocienski 反应中原位生成的亚磺酸盐中间体卤化，将反应途径从传统的烯化转变为烷基化。在产物的晶体结构中观察到卤烃和芳族供体之间有趣的卤素-π 相互作用。

  DOI：

  10.1021/ja301601b
• 作为产物：
  描述：

  2-甲硫基吡啶 在 triethylamine tris(hydrogen fluoride) 作用下， 以 乙腈 为溶剂， 生成 2-((fluoromethyl)thio)pyridine
  参考文献：
  名称：

  Electrolytic Partial Fluorination of Organic Compounds. 19. A Novel Synthesis of Fluorothieno[2,3-b]pyridines Using Anodic Fluorination of Heterocyclic Sulfides as a Key Step

  摘要：

  Highly regioselective anodic monofluorination of 2-pyridyl and C-pyrimidinyl sulfides bearing various electron-withdrawing groups were successfully carried out. The fluorinated sulfides were easily converted into 2-fluorothieno[2,3-b]pyridines in good yields.

  DOI：

  10.1021/jo00128a044

文献信息

• Direct monofluoromethylation of O-, S-, N-, and P-nucleophiles with PhSO(NTs)CH₂F: the accelerating effect of α-fluorine substitution
  作者：Xiao Shen、Min Zhou、Chuanfa Ni、Wei Zhang、Jinbo Hu

  DOI：10.1039/c3sc51831k

  日期：——

  An efficient and direct monofluoromethylation of O-, S-, N-, and P-nucleophiles with PhSO(NTs)CH2F 1 has been developed. In contrast to the previously known detrimental effect of α-fluorine substitution on SN2 reactions, the current monofluoromethylation is accelerated by the α-fluorine substitution. Based on a mechanistic study, a new reactivity of sulfoximine (as a radical monofluoromethylation reagent) is disclosed.

  一种高效且直接的单氟甲基化反应已被开发，用于O、S、N和P亲核试剂和PhSO(NTs)CH2F 1。与之前已知的α-氟取代对SN2反应的负面影响不同，目前的单氟甲基化反应因α-氟取代而加速。基于机制研究，揭示了亚磺酰胺作为自由基单氟甲基化试剂的新反应性。
• Electrolytic partial fluorination of organic compounds. 13
  作者：Ayman W. Erian、Akinori Konno、Toshio Fuchigami

  DOI：10.1016/0040-4039(94)85372-x

  日期：1994.9

  Highly regioselective anodic monofluorination of 2-pyridyl and 6-pyrimidinyl sulfides was successfully carried out and fluorinated fused heterocycles were readily prepared in good yields using an anodically fluorinated sulfide.

  成功地进行了2-吡啶基和6-嘧啶基硫化物的高度区域选择性阳极单氟化，并且使用阳极氟化的硫化物可以高收率容易地制备氟化的稠合杂环。
• Electrolytic Partial Fluorination of Organic Compounds. 35.¹ Anodic Fluorination of 2-Pyrimidyl, 2-Pyridyl, and 2-Quinazolinonyl Sulfides
  作者：Kamal M. Dawood、Seiichiro Higashiya、Yankun Hou、Toshio Fuchigami

  DOI：10.1021/jo9909857

  日期：1999.10.1

  Highly regioselective electrochemical fluorination of 2-pyrimidyl sulfides having an electron(EWG) withdrawing group at the position alpha to the sulfur atom was successfully carried out using Et4NF . nHF (n = 3, 4) or Et3N . 3HF as a supporting electrolyte and a fluoride ion source in 1,2-dimethoxyethane (DME) in an undivided cell. 2-Methylthiopyrimidine devoid of an EWG was also selectively fluorinated in DME to provide 2-(fluoromethylthio)pyrimidine in a moderate yield as 63%, while corresponding 2-methylthiopyridine was less selectively fluorinated in lower yield along with alpha,alpha-difluorinated product. In contrast, the corresponding 2-quinazolinonyl sulfides underwent similarly alpha-fluorination along with unexpected ipso-fluorination through anodic desulfurization.
• Carbonyl olefination of diaryl ketones with heteroaryl sulfoxides
  作者：Bing Gao、Jingyu Hu、Yanchuan Zhao、Jinbo Hu

  DOI：10.1016/j.tetlet.2015.05.034

  日期：2015.7

  Heteroaryl sulfones are capable of converting the carbonyl functionalities to alkenyl motifs, which is well-known as Julia-Kocienski olefination reaction. However, their sulfoxide analogues have failed in such an olefination reaction for over twenty years. In this Letter, we demonstrate that the heteroaryl sulfoxide-participated carbonyl olefination reaction can be realized under certain conditions. Furthermore, a novel defluorinative olefination of diaryl ketones has been achieved with 2-pyridyl sulfoxides. (C) 2015 Elsevier Ltd. All rights reserved.