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Method for synthesizing aryl monofluoromethylthio compound from Bunte salt

A technology of methylthio compounds, applied in the field of organic synthesis, can solve the problems of unfavorable industrial production and difficult accurate weighing, etc., and achieve the effects of convenient processing, less waste, simple and safe operation

Active Publication Date: 2019-05-31
NANJING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The raw materials used in the direct method need to be prepared by multi-step reactions, and the obtained reagents are liquid, which is difficult to weigh accurately, which is not conducive to industrial production

Method used

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  • Method for synthesizing aryl monofluoromethylthio compound from Bunte salt
  • Method for synthesizing aryl monofluoromethylthio compound from Bunte salt
  • Method for synthesizing aryl monofluoromethylthio compound from Bunte salt

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045]Add 100.5mg (0.5mmol) p-bromophenylboronic acid, 168.0mg (1.0mmol) Bunte salt (S-(one fluoromethyl) sodium thiosulfate), 47.5mg (0.25mmol) sulfide iodide to a 25mL pressure tube Copper, 45.0 mg (0.25 mmol) 1,10-phenanthroline, 138.0 mg (1.0 mmol) potassium carbonate, and 2 mL (50 mmol) methanol. The reaction was stirred at 90°C for 10h. After the reaction was completed, the reaction solution was diluted with 20 mL of ethyl acetate, washed three times with saturated brine, the organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (the eluent was a mixture of ethyl acetate and petroleum ether, the volume ratio of the two was 1:20) to obtain 83.6 mg of 4-fluoromethylthiobromobenzene with a yield of 76%, and NMR The characterization data are as follows:

[0046] 1 H NMR (500MHz, CDCl 3 )δ7.47(d, J=8.5Hz, 2H), 7.36(d, J=8.5Hz, 2H), 5.69(d, J=52.7H...

Embodiment 2

[0050] Add 73.5mg (0.5mmol) 4-cyanophenylboronic acid, 168.0mg (1.0mmol) Bunte salt (S-(one fluoromethyl) sodium thiosulfate), 47.5mg (0.25mmol) iodine to a 25mL pressure tube Cuprous chloride, 45.0 mg (0.25 mmol) 1,10-phenanthroline, 138.0 mg (1.0 mmol) potassium carbonate and 2 mL (50 mmol) methanol. The reaction was stirred at 90°C for 10h. After the reaction was completed, the reaction solution was diluted with 20 mL of ethyl acetate, washed three times with saturated brine, the organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (the eluent was a mixture of ethyl acetate and petroleum ether, the volume ratio of which was 1:20) to obtain 60.1 mg of 4-fluoromethylthiobenzonitrile with a yield of 72%. The NMR characterization data are as follows:

[0051] 1 H NMR (500MHz, CDCl 3 )δ7.61(d, J=8.5Hz, 2H), 7.53(d, J=8.5Hz, 2H), 5.80(d, J=52.3Hz, 2H...

Embodiment 3

[0055] Add 95.0mg (0.5mmol) 4-trifluoromethylphenylboronic acid, 168.0mg (1.0mmol) Bunte salt (S-(one fluoromethyl) sodium thiosulfate), 47.5mg (0.25mmol) to a 25mL pressure tube ) cuprous iodide, 45.0 mg (0.25 mmol) 1,10-phenanthroline, 138.0 mg (1.0 mmol) potassium carbonate and 2 mL (50 mmol) methanol. The reaction was stirred at 90°C for 10h. After the reaction was completed, the reaction solution was diluted with 20 mL of ethyl acetate, washed three times with saturated brine, the organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (the eluent was a mixture of ethyl acetate and petroleum ether, the volume ratio of the two was 1:20) to obtain 73.5 mg of 4-fluoromethylthiobenzotrifluoride, with a yield of 70%. The NMR characterization data are as follows:

[0056] 1 H NMR (500MHz, CDCl 3 )δ7.60–7.56(m,4H),5.78(d,J=52.5Hz,2H);

[0057] 13 C N...

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Abstract

The invention discloses a method for synthesizing an aryl monofluoromethylthio compound from a Bunte salt. With a phenylboronic acid derivative and S-(monofluoromethyl) sodium thiosulfate in the Buntesalt as raw materials, copper iodide as a catalyst, 1,10-phenanthroline as a ligand, potassium carbonate as alkali and methanol as a solvent, a reaction is fully carried out at the reaction temperature of 80-90 DEG C. After the reaction is finished, a reaction solution is separated and purified to obtain the aryl monofluoromethylthio compound. The method is reasonable in process condition and easy and safe to operate; the use of thiophenol and other substrates with unpleasant smell is avoided, less waste gas, waste water and industrial residue are generated, and the method is environmentallyfriendly; the reagent is simple in synthesis route and is an odorless solid, treatment is convenient, and the method is a new approach to synthesizing the aryl monofluoromethylthio compound.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for synthesizing aryl-fluoromethylthio compounds from Bunte salts. Background technique [0002] Organic sulfur-containing compounds widely exist in nature and organisms, and sulfur is also the most abundant mineral in the human body besides calcium and phosphorus. On the other hand, fluorine is the most active non-metallic element in the periodic table and has the strongest electronegativity. The introduction of fluorine atoms or fluorine-containing functional groups into organic molecules will affect the electron cloud distribution, dipole moment, acidity and alkalinity of the entire molecule, and change the physical, chemical and biological properties of the parent molecule, thus giving fluorine-containing organic compounds unique features. According to the theory of soft and hard acids and bases, the sulfur atom, as a softer atom, has good coordination properties w...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C319/14C07C323/09C07C323/03C07C323/62
Inventor 刘帆敏王潇颖易文斌仇晃耀
Owner NANJING UNIV OF SCI & TECH
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