methyl 2-fluoro-2-phenylsulfanylacetate | 109705-27-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: methyl 2-fluoro-2-phenylsulfanylacetate
• 英文别名: methyl 2-fluoro-2-(phenylthio)acetate；methyl-2-fluoro-2-(phenylthio)acetate
• CAS: 109705-27-3
• 化学式: C₉H₉FO₂S
• 分子量: 200.234
• InChiKey: SJDWTTBVGHLNPX-UHFFFAOYSA-N

物化性质

• 沸点：
  250.1±30.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  methyl 2-fluoro-2-phenylsulfanylacetate 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 生成 Benzenesulfinyl-fluoro-acetic acid methyl ester
  参考文献：
  名称：

  苯基亚磺酰基氟乙酸乙酯，一种用于制备α-氟-α，β-不饱和羧酸酯的新型多功能试剂

  摘要：

  标题化合物2可以用多种烷基卤化物和迈克尔受体烷基化。随后热消除苯基亚磺酸3会导致α-氟代-α，β-不饱和羧酸乙酯5和10，这是含氟生物活性化合物的重要中间体。

  DOI：

  10.1016/s0040-4020(01)80956-x
• 作为产物：
  描述：

  methyl 2-chloro-2-(phenylsulfanyl)acetate 在 triethylamine tris(hydrogen fluoride) 、 zinc dibromide 作用下， 以 乙腈 为溶剂， 反应 18.0h， 以66%的产率得到methyl 2-fluoro-2-phenylsulfanylacetate
  参考文献：
  名称：

  Synthesis of α-fluoro-β-hydroxy alkylsulfanyl esters via a nucleophilic fluorination of sulfides

  摘要：

  By halogen-exchange reaction using NEt3-3HF as fluoride source, methyl 2-fluoro-2-alkylsulfanyl acetate 3a-d could be obtained in good yields. Their ester enolates reacted with aromatic or aliphatic aldehydes, to lead to methyl alpha-alkylsulfanyl-alpha-fluoro-beta-hydroxy esters 4-8. By using benzaldehyde as electrophile, the retro-aldol reaction could be favorised by a temperature effect. The selective formation of the syn or the anti diastereoisomers has been controled. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00639-5

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。
• Sulfur Assisted Tandem Electrophilic Fluorinative Deacylation: Synthesis of α-Fluoro β-Ketosulfides
  作者：Begur Vasanthkumar Varun、Kandikere Ramaiah Prabhu

  DOI：10.1021/acs.joc.7b01547

  日期：2017.9.15

  A successful synthesis of α-fluoro-β-ketosulfides using an electrophilic fluorination method has been reported for the first time. The reaction proceeds via an electrophilic fluorination of α-sulfenyl-β-diketones followed by an unexpected tandem deacylation. The resulting products, α-fluoro-β-ketosulfides, are easily oxidized to the corresponding α-fluoro-β-ketosulfones, which can be used for further

  首次报道了使用亲电氟化方法成功合成α-氟-β-酮硫醚。该反应通过α-亚磺酰基-β-二酮的亲电氟化反应进行，然后发生意外的串联脱酰反应。所得产物，α-氟-β-酮基硫醚，很容易被氧化成相应的α-氟-β-酮基砜，可用于进一步有用的烯化反应。
• Effect of solvents on the selective electrofluorination of aromatic compounds containing active methylene groups
  作者：V. Suryanarayanan、M. Noel

  DOI：10.1016/s0022-1139(98)00267-x

  日期：1998.11

  Voltammetry and constant current electrolysis was used to study the oxidative fluorination of PhSCH2COOMe, PhSCH2CONH2, PhSCH2COOPh and PhCH2CN in solvent-free Et3N·3HF and Et3N·3HF dissolved in CH3CN, THF, DME and sulfolane. Sulfolane, DME and THF containing Et3N·3HF show much lower oxidation limits when compared to CH3CN/Et3N·3HF. These compounds undergo simultaneous oxidation along with background

  用伏安法和恒流电解法研究了在无溶剂的Et 3 N·3HF和Et 3 N·3HF溶于CH 3 CN中的PhSCH 2 COOMe，PhSCH 2 CONH 2，PhSCH 2 COOPh和PhCH 2 CN的氧化氟化， THF，DME和环丁砜。与CH 3 CN / Et 3 N·3HF相比，含Et 3 N·3HF的环丁砜，DME和THF的氧化极限低得多。这些化合物与背景氧化过程同时进行氧化。无溶剂Et 3N·3HF具有更大的阳极电位范围，可用于氧化有机化合物。PhSCH 2 COOMe和PhSCH 2 COOPh的选择性电氟化没有显示出明显的溶剂作用。已发现，与CH 3 CN相比，THF和DME对PhSCH 2 CONH 2和PhCH 2 CN的选择性氟化更有效。
• tert-Butylsulfinyl-fluoroacetate: versatile reagent for the preparation of fluoroethylidenoate derivatives
  作者：David Chevrie、Thierry Lequeux、Jean-Claude Pommelet

  DOI：10.1016/s0040-4020(02)00456-8

  日期：2002.6

  The preparation of (Z)-α-fluoroalkenoates from readily available methyl-tert-butylsulfanyl- or tert-butylsulfinylfluoroacetate 1 or 5 is described. This short synthesis, based on a direct extrusion of SO2 from β-hydroxysulfoxides, presents a moderate to high selectivity and affords (Z)-α-fluoroalkenoates in 40–81% overall yields without purifications of the intermediates. This procedure was applied

  描述了由容易获得的甲基-叔丁基硫烷基甲基或叔丁基亚磺酰基氟乙酸酯1或5制备（Z）-α-氟代链烯酸酯。这种短暂的合成基于从β-羟基亚砜直接挤出SO 2，具有中等至高的选择性，无需纯化中间体即可以40-81％的总收率获得（Z）-α-氟代链烯酸酯。该程序应用于官能化的醛和酮。还讨论了反应的机理。
• Electrochemical Fluorination and Radiofluorination of Methyl(phenylthio)acetate Using Tetrabutylammonium Fluoride (TBAF)
  作者：Mehrdad Balandeh、Christopher Waldmann、Daniela Shirazi、Adrian Gomez、Alejandra Rios、Nathanael Allison、Asad Khan、Saman Sadeghi

  DOI：10.1149/2.0941709jes

  日期：——

  efficiency. Electrochemical fluorination resulted in formation of mono-fluorinated methyl 2-fluoro-2-(phenylthio)acetate verified by gas chromatography–mass spectrometry (GC-MS) and nuclear magnetic resonance (NMR) Spectroscopy. Under optimum conditions 44 ± 3% mono fluorination yield was obtained after a 30 min electrolysis. Electrochemical radiofluorination for the synthesis of methyl 2-[18F]fluoro-2-(phenothio)

  使用四丁基氟化铵 (TBAF) 实现了（苯硫基）乙酸甲酯的电化学氟化。电化学氟化是在恒电位阳极氧化下使用未分开的电池在含有 TBAF 和三氟甲磺酸的乙腈中进行的。研究了氧化电位、时间、温度、超声处理、TBAF浓度和三氟甲磺酸浓度等几个参数对氟化效率的影响。发现三氟甲磺酸与 TBAF 的浓度比对氟化效率起关键作用。电化学氟化导致形成单氟化的 2-氟-2-（苯硫基）乙酸甲酯，经气相色谱-质谱 (GC-MS) 和核磁共振 (NMR) 光谱验证。在最佳条件下，电解 30 分钟后获得 44 ± 3% 的单氟化产率。用于合成 2-[18F] 氟-2-(苯硫基) 乙酸甲酯的电化学放射性氟化也使用相同的优化电化学电池参数实现，其中 TBAF 首先通过含有氟 18 的阴离子交换树脂。电解 30 分钟后，放射化学氟化效率达到 7±1%。