ethyl fluoro(methylthio)acetate | 109705-26-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl fluoro(methylthio)acetate
• 英文别名: Ethyl fluoro(methylsulfanyl)acetate；ethyl 2-fluoro-2-methylsulfanylacetate
• CAS: 109705-26-2
• 化学式: C₅H₉FO₂S
• 分子量: 152.19
• InChiKey: KRLSPGMUNGCSTO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl fluoro(methylthio)acetate 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 ethyl 2-fluoro-2-(methanesulfonyl)acetate
  参考文献：
  名称：

  Site-selective fluorination of organic compounds using 1-alkyl-4-fluoro-1,4-diazabicyclo[2.2.2]octane salts (selectfluor reagents)

  摘要：

  The new ''N-F''-type electrophilic reagent family of 1-alkyl-4-fluoro-1,4-diazabicyclo[2.2.2]octane salts8d (derived from elemental fluorine (F2) and 1-alkyl-1,4-diazabicyclo[2.2.2]octane salts) has been found to be very effective for the fluorination of a wide variety of organic substrates. These include steroidal enol acetates and silyl enol ethers, phenyl-substituted olefins, sulfides bearing alpha-H atoms, certain carbanions, and mildly activated aromatic compounds. The products were obtained with good yields and regioselectivity under very mild reaction conditions.

  DOI：

  10.1021/jo00062a023
• 作为产物：
  描述：

  (甲硫基)乙酸乙酯 在 1,3-二溴-5,5-二甲基海因 、 tetrabutylammonium bifluoride 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以65%的产率得到ethyl fluoro(methylthio)acetate
  参考文献：
  名称：

  氧化脱硫-氟化条件下α-氟烷基硫化物的简便合成

  摘要：

  用 n-Bu4NH2F3 和 1,3-二溴-5,5-二甲基乙内酰脲处理后，各种有机硫化物发生普默勒型重排，然后氟化，得到 α-氟硫化物。当应用于 RCH(SMe)CF2SMe 时，氟-Pummerer 重排得到三氟硫化物 RCF(SMe)CF2SMe。当使用 HF-吡啶试剂作为氟化剂时，根据底物的结构发生氧化脱硫-氟化反应。

  DOI：

  10.1246/bcsj.71.2687

文献信息

• α-Fluorination of Sulfides with<i>N</i>-Fluoropyridinium Triflates
  作者：Teruo Umemoto、Ginjiro Tomizawa

  DOI：10.1246/bcsj.59.3625

  日期：1986.11

  The reaction of sulfides possessing α-hydrogen with various N-fluoropyridinium salts was examined. While the fluorinating power increased in the order of N-fluoro-2,4,6-trimethylpyridinium triflate 12, and 3 no longer produced the α-fluoro sulfide. Triflate 1 was more reactive than the corresponding tetrafluoroborate 4. Thus, it was shown that 1 satisfactorily fluorinated various kinds of sulfides under very mild conditions, giving α-fluoro sulfides. A two-step mechanism, oxidative fluorination of sulfur and Pummerer-type rearrangement, was proposed for the fluorination. The corresponding α-fluoro sulfoxide or sulfones were easily prepared from the sulfides by successive fluorination–oxidation procedure.

  我们研究了具有α-氢的硫化物与各种N-氟吡啶盐的反应。氟化能力按以下顺序增加：N-氟-2,4,6-三甲基吡啶三氟甲磺酸盐1 < N-氟吡啶三氟甲磺酸盐2 < N-氟-3,5-二氯吡啶三氟甲磺酸盐3，而α-氟硫化物的产率则按以下顺序递减：1 > 2，3不再产生α-氟硫化物。三氟甲磺酸盐1的反应性优于相应的四氟硼酸盐4。因此，研究表明，1在非常温和的条件下能有效氟化各种硫化物，生成α-氟硫化物。我们提出了一种两步机制，即硫的氧化氟化和Pummerer型重排，用于氟化反应。相应的α-氟亚磺酸盐或磺酮可通过连续的氟化-氧化过程轻松从硫化物中制备。
• Fluoro-pummerer rearrangement under oxidative desulfurization fluorination conditions. facile synthesis of oligofluoroalkyl sulfides
  作者：Satoru Furuta、Manabu Kuroboshi、Tamejiro Hiyama

  DOI：10.1016/0040-4039(95)01768-d

  日期：1995.11

  Upon treatment with n-Bu4NH2F3 and 1,3-dibromo-5,5-dimethylhydantoin, various organic sulfides were readily fluorinated to give α-fluoro sulfides. When (HF)9-Py was used as the fluorinating agent, normal oxidative desulfurization fluorination occurred depending on the structure of the substrates.

  用n- Bu 4 NH 2 F 3和1，3-二溴-5，5-二甲基乙内酰脲处理后，各种有机硫化物易于氟化，得到α-氟硫化物。当使用（HF）9 -Py作为氟化剂时，取决于基板的结构，发生正常的氧化脱硫氟化。
• UMEMOTO TERUO; TOMIZAWA GINJIRO, BULL. CHEM. SOC. JAP., 59,(1986) N 11, 3625-3629
  作者：UMEMOTO TERUO、 TOMIZAWA GINJIRO

  DOI：——

  日期：——
• Site-selective fluorination of organic compounds using 1-alkyl-4-fluoro-1,4-diazabicyclo[2.2.2]octane salts (selectfluor reagents)
  作者：G. Sankar Lal

  DOI：10.1021/jo00062a023

  日期：1993.5

  The new ''N-F''-type electrophilic reagent family of 1-alkyl-4-fluoro-1,4-diazabicyclo[2.2.2]octane salts8d (derived from elemental fluorine (F2) and 1-alkyl-1,4-diazabicyclo[2.2.2]octane salts) has been found to be very effective for the fluorination of a wide variety of organic substrates. These include steroidal enol acetates and silyl enol ethers, phenyl-substituted olefins, sulfides bearing alpha-H atoms, certain carbanions, and mildly activated aromatic compounds. The products were obtained with good yields and regioselectivity under very mild reaction conditions.
• Facile Synthesis of<b><i>α</i></b>-Fluoroalkyl Sulfides under the Oxidative Desulfurization–Fluorination Conditions
  作者：Satoru Furuta、Manabu Kuroboshi、Tamejiro Hiyama

  DOI：10.1246/bcsj.71.2687

  日期：1998.11

  sulfides. The fluoro-Pummerer rearrangement, when applied to RCH(SMe)CF2SMe, gave trifluoro sulfides RCF(SMe)CF2SMe. When an HF-pyridine reagent was used as the fluorinating agent, an oxidative desulfurization–fluorination reaction occurred depending on the structure of the substrates.

  用 n-Bu4NH2F3 和 1,3-二溴-5,5-二甲基乙内酰脲处理后，各种有机硫化物发生普默勒型重排，然后氟化，得到 α-氟硫化物。当应用于 RCH(SMe)CF2SMe 时，氟-Pummerer 重排得到三氟硫化物 RCF(SMe)CF2SMe。当使用 HF-吡啶试剂作为氟化剂时，根据底物的结构发生氧化脱硫-氟化反应。