Method for synthesizing aromatic monofluoromethylthio compounds by one-pot method

A monofluoromethylthio and aromatic technology, applied in organic chemistry, thioether preparation, etc., can solve the problems of low substrate expansion ability, few types of S-containing substrates, difficult operation and treatment, etc., and achieve high conversion rate , environment-friendly, and easy conditions

Active Publication Date: 2022-06-07
NANJING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0010] (1) The first type of indirect synthesis method is limited by the small number of S-containing substrates, which makes its substrate expansion ability low;
[0011] (2) The second type of direct fluorothiomethyl reagent needs to be prepared in advance, which is difficult to handle;
[0012] (3) Some raw materials have a pungent smell, and will cause serious pollution to the environment, and there will also be safety problems

Method used

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  • Method for synthesizing aromatic monofluoromethylthio compounds by one-pot method
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  • Method for synthesizing aromatic monofluoromethylthio compounds by one-pot method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Add a magnetic stir bar, 4-bromoaniline (0.5 mmol), HBF to the dry pressure. 4 (1 mmol), tert-butyl nitrite (1 mmol) and anhydrous acetonitrile (2 ml), the reaction was placed in an ice bath for 2 h. After the reaction was completed, CuCl (0.05 mmol) was added, CuCl 2 (0.05 mmol), 1,10-phenanthroline (0.05 mmol) and KSCN (0.75 mmol), and stirred in an ice bath for 3 h. After the reaction is over, add KOH (5mmol) and ICFH to the system 2 (1 mmol) in an ice bath to continue the reaction for 7 h. After the reaction was finished, the reaction solution was filtered after returning to room temperature, the filtrate was dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure, and the crude product was through column chromatography (eluent was ethyl acetate and petroleum ether mixed solution, the two The volume ratio is 1:19) to obtain 98.35 mg of 1-monofluorothiomethyl-4-bromobenzene with a yield of 89%.

[0050] 1-Monofluorothiomethyl-4-brom...

Embodiment 2

[0053] Add a magnetic stir bar, 4-nitroaniline (0.5 mmol), HBF to the dry pressure. 4 (1 mmol), tert-butyl nitrite (1 mmol) and anhydrous acetonitrile (2 ml), and the reaction was placed in an ice bath for 2 h. After the reaction was completed, CuCl (0.05 mmol) was added, CuCl 2 (0.05 mmol), 1,10-phenanthroline (0.05 mmol) and KSCN (0.75 mmol), and stirred in an ice bath for 3 h. After the reaction is over, add KOH (5mmol) and ICFH to the system 2 (1 mmol) in an ice bath to continue the reaction for 7 h. After the reaction is finished, the reaction solution is filtered after returning to room temperature, the filtrate is dried over anhydrous sodium sulfate and the solvent is removed under reduced pressure, and the crude product is through column chromatography (eluent is ethyl acetate and petroleum ether mixed solution, the two The volume ratio is 1:19) to isolate 86.02 mg of 1-monofluorothiomethyl-4-nitrobenzene with a yield of 92%.

[0054] 1-Monofluorothiomethyl-4-nitro...

Embodiment 3

[0057] Add a magnetic stir bar, 4-cyanoaniline (0.5 mmol), HBF to the dry pressure. 4 (1 mmol), tert-butyl nitrite (1 mmol) and anhydrous acetonitrile (2 ml), and the reaction was placed in an ice bath for 2 h. After the reaction was completed, CuCl (0.05 mmol) was added, CuCl 2 (0.05 mmol), 1,10-phenanthroline (0.05 mmol) and KSCN (0.75 mmol), and stirred in an ice bath for 3 h. After the reaction is over, add KOH (5mmol) and ICFH to the system 2 (1 mmol) in an ice bath to continue the reaction for 7 h. After the reaction is finished, the reaction solution is filtered after returning to room temperature, the filtrate is dried over anhydrous sodium sulfate and the solvent is removed under reduced pressure, and the crude product is through column chromatography (eluent is ethyl acetate and petroleum ether mixed solution, the two The volume ratio is 1:19) to isolate 76.82 mg of 1-monofluorothiomethyl-4-cyanobenzene with a yield of 92%.

[0058] 1-Monofluorothiomethyl-4-cyano...

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Abstract

The invention discloses a method for synthesizing aromatic fluoromethylthio compounds through a one-pot method. The method uses aromatic amines as raw materials, under the action of tert-butyl nitrite and tetrafluoroboric acid, with anhydrous acetonitrile as a solvent, first reacts in an ice bath to generate the corresponding diazonium salt; then reacts in copper chloride, chlorine Under the action of cuprous chloride and 1,10-phenanthroline, potassium thiocyanate was used as a sulfur source to react and introduce sulfur atoms in an ice bath; finally, under the action of potassium hydroxide, through a fluoroiodomethane, in an ice bath Introducing a fluoromethyl group in the reaction to obtain an aromatic fluoromethylthio compound. The method of the invention has simple and safe steps, high reaction conversion rate, less waste, and is environmentally friendly.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and relates to a method for synthesizing aromatic monofluoromethylthio compounds by a one-pot method. Background technique [0002] Among the fluorine-containing functional groups, CFH 2 The group has unique physical and chemical properties, and has huge potential application value in the fields of medicine and pesticides. Contains monofluoromethylthio SCFH 2 In the organic molecules of , due to the effect of F atoms, the two hydrogen atoms on the carbon connected with fluorine have a certain acidity, which is easy to produce secondary interactions such as intermolecular and intramolecular hydrogen bonds. will SCFH 2 The introduction of the group into the active molecule may increase the metabolic stability of the molecule in vivo. In addition, contains SCFH 2 of organic molecules have between -SCF 3 with-sch 3 The moderate Hansch lipophilic coefficient between them also provides a possibi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C319/14C07C323/09C07C323/62
CPCC07C319/14C07C323/09C07C323/62
Inventor 易文斌曹原刘帆敏蒋绿齐赫五卷
Owner NANJING UNIV OF SCI & TECH
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