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Preparation method of 2-aryl-ethenylsulfonyl chloride compound

A technology of sulfonyl fluoride compounds and vinyl sulfonyl fluorides, which is applied in the field of synthesis of 2-aryl-vinyl sulfonyl fluoride compounds, can solve the problem of unstable aryl diazonium salts, poor functional group tolerance, and limited applications and other problems, to achieve the effect of low load, low requirements for equipment and simple operation

Inactive Publication Date: 2017-09-22
WUHAN UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The third is to use aryl diazonium salt (Angew.Chem.Int.Ed., 2016, 14155) and vinylsulfonyl fluoride as starting materials to realize the synthesis of 2-aryl-vinylsulfonyl fluoride, and aromatic The base diazonium salt is unstable and explosive, and the functional group tolerance is poor when preparing the diazonium salt, which greatly limits its application
The lack of good synthetic methods greatly limits the application of this series of compounds in related fields

Method used

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  • Preparation method of 2-aryl-ethenylsulfonyl chloride compound
  • Preparation method of 2-aryl-ethenylsulfonyl chloride compound
  • Preparation method of 2-aryl-ethenylsulfonyl chloride compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036]

[0037] In a 250mL reaction flask, add phenylboronic acid (2.44g, 20mmol), vinylsulfonyl fluoride (13.20g, 120mmol), Pd(OAc) 2 (0.22g, 1.0mmol, 5mol%), DDQ (6.80g, 30mmol), AcOH (100mL), heated to 80°C with stirring for 12h, the reaction solution was distilled under reduced pressure to recover glacial acetic acid and vinylsulfonyl fluoride, the residual The product was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain 2-phenyl-vinylsulfonyl fluoride (3.46 g, 93% yield). The reaction solution can also be filtered with silica gel, and the filtrate can be concentrated to dryness and then crystallized by adding ether to obtain this product. Mp 99–100°C. 1 H NMR (400MHz, CDCl 3 )δ7.81(d,J=15.6Hz,1H),7.58–7.44(m,5H,),6.87(dd,J=15.2,1.6Hz,1H,). 13 C NMR (101MHz, CDCl 3 )δ149.0, 132.8, 131.0, 129.5, 129.2, 118.0 (d, J=30.3Hz). 19FNMR (376MHz, CDCl 3 )δ62.1.EI-quadrupole MS calculated for C 8 h 7 FO 2 S[M] ...

Embodiment 2

[0039]

[0040] In a 250mL reaction flask, add potassium phenyltrifluoroborate (3.68g, 20mmol), vinylsulfonyl fluoride (13.20g, 120mmol), Pd(OAc) 2 (0.22g, 1.0mmol, 5mol%), DDQ (6.80g, 30mmol), AcOH (100mL), heated to 80°C with stirring for 12h, the reaction solution was distilled under reduced pressure to recover glacial acetic acid and vinylsulfonyl fluoride, the residual The product was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain 2-phenyl-vinylsulfonyl fluoride (3.20 g, 86% yield). The reaction solution can also be filtered with silica gel, and the filtrate can be concentrated to dryness and then crystallized by adding ether to obtain this product. Characterization data is the same as embodiment 1.

Embodiment 3

[0042]

[0043] In a 250mL reaction flask, add phenylboronic acid (2.44g, 20mmol), vinylsulfonyl fluoride (13.20g, 120mmol), Pd(OAc) 2 (0.22g, 1.0mmol, 5mol%), TEMPO (0.31g, 2mmol, 10mol%), AcOH (100mL), oxygen was passed through an oxygen balloon, heated to 80°C for 12h under stirring, and the reaction liquid was recovered by distillation under reduced pressure Glacial acetic acid and vinylsulfonyl fluoride, and the residue was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 20:1 (v / v)) to obtain 2-phenyl-vinylsulfonyl Fluorine (1.82 g, 49% yield). The reaction solution can also be filtered with silica gel, and the filtrate can be concentrated to dryness and then crystallized by adding ether to obtain this product. Characterization data is the same as embodiment 1.

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Abstract

The invention discloses a preparation method of 2-aryl-ethenylsulfonyl chloride compound, comprising the steps of using arylboronic acid, arylboronic acid ester or arylboronic acid salt as a raw material, mixing with ESF (ethenylsulfonyl chloride), palladium catalyst, an oxidant and a solvent, allowing reacting at 20-120 DEG C for 2 h and longer, separating and purifying to obtain an ethenylsulfonyl chloride product. A molar ratio of arylboronic acid (ester) and its salt, ethenylsulfonyl chloride, the palladium catalyst and the oxidant is 1:(1-10):(0.000001-0.2):(0.5-5). The preparation method has the advantages that raw materials are simple and easy to obtain, large-scale commercial supply is available for both arylboronic acid (ester) and its salt, the arylboronic acid (ester) and its salt are tolerant to most functional groups and good in reaction selectivity (both bromine and chlorine substituent on aryl are not involved in the reaction under same reaction conditions), and the preparation method has good technical potential in large-scale preparation in labs and industrial amplified production.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a synthesis method of 2-aryl-vinylsulfonyl fluoride compounds. Background technique [0002] Hexavalent sulfur-fluoride exchange chemistry (Sulfur(VI) Fluoride Exchange, SuFEx, Angew.Chem.Int.Ed., 2014, 9430) is a new generation of clicks proposed by Nobel Prize winner K.B.Sharpless in 2014 Chemistry (Click Chemistry). While sulfonyl fluoride (SO 2 F), vinyl sulfonyl fluoride (ESF) is a well-studied fluorine-containing hexavalent sulfur building block, and is currently used in polymer synthesis (Angew.Chem.Int.Ed., 2014, 9466), chemical biology (J. Am.Chem.Soc., 2016, 7353), covalent drug research (Chem.Sci., 2015, 2650) and other fields have shown great application value. 2-Aryl-vinylsulfonyl fluoride is a derivative of vinylsulfonyl fluoride. It has two nucleophilic reaction sites at the same time, and many substituents can be introduced in the aromati...

Claims

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Application Information

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IPC IPC(8): C07C303/02C07C309/81C07C309/82C07C309/84C07D307/79C07D213/61C07D333/76
CPCC07C303/02C07D213/61C07D307/79C07D333/76C07C309/81C07C309/82C07C309/84
Inventor 秦华利查高峰冷静尚振鹏
Owner WUHAN UNIV OF TECH
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