Method for synthesizing aromatic trifluoromethylthio compound

A technology for synthesizing aromatic hydrocarbons based on trifluoromethylthio group, which can be used in organic chemistry, thioether preparation and other directions, and can solve the problems of environmental problems of fluorine-containing reagents, high price, and limited substrate scope.

Active Publication Date: 2020-10-27
NANJING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] (1) Some fluorine-containing reagents will cause serious environmental problems, are expensive, and also have safety problems;
[0012] (2) The starting materials need to be prepared in advance, and the process is complicated. Such a synthesis method does not meet the expected simple and efficient synthesis
[0013] (3) The range of substrates used in the method is limited, focusing on electron-rich aromatics, which limits the applicability of the method

Method used

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  • Method for synthesizing aromatic trifluoromethylthio compound
  • Method for synthesizing aromatic trifluoromethylthio compound
  • Method for synthesizing aromatic trifluoromethylthio compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] in N 2 Under protection, add diphenyl phosphorus chloride (2.20g, 10mmol) and sodium trifluoromethanesulfinate (1.56g, 10mmol), add 20mLMeCN, stir at room temperature under airtight condition for 30min, then in N 2 4-Phenylaniline (1.69g, 10mmol), tert-butyl nitrite (1.54g, 15mmol) and anhydrous CuSO were sequentially added under protection. 4 (0.32g, 2mmol), heated to 70°C under airtight conditions, stirred at constant temperature for 12h, cooled to room temperature after fully reacting, the reaction solution was extracted 3 times with a mixture of dichloromethane and water, the organic layer was separated and dried over anhydrous sodium sulfate Then 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) to obtain the 4-phenyl-1-trifluoromethylthiobenzene product with a yield of 58%.

[0039] 4-Phenyl-1-trifluoromethylthiobenzene 1 H NMR see figur...

Embodiment 2

[0043] in N 2 Under protection, add diphenyl phosphorus chloride (2.20g, 10mmol) and sodium trifluoromethanesulfinate (1.56g, 10mmol), add 20mLMeCN, stir at room temperature under airtight condition for 30min, then in N 2 Under protection, 4-cyclohexylaniline (1.69g, 10mmol), tert-butyl nitrite (1.54g, 15mmol) and anhydrous CuSO were added successively. 4(0.32g, 2mmol), heated to 70°C under airtight condition, stirred at constant temperature for 12h, fully reacted and cooled to room temperature, the reaction solution was extracted 3 times with a mixture of dichloromethane and water, the organic layer was separated and dried over anhydrous sodium sulfate Then 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) to obtain the 4-cyclohexyl-1-trifluoromethylthiobenzene product with a yield of 65%.

[0044] 4-Cyclohexyl-1-trifluoromethylthiobenzene 1 H NMR se...

Embodiment 3

[0048] in N 2 Under protection, add diphenyl phosphorus chloride (2.20g, 10mmol) and sodium trifluoromethanesulfinate (1.56g, 10mmol), add 20mLMeCN, stir at room temperature under airtight condition for 30min, then in N 2 Under protection, 4-cyanoaniline (1.69g, 10mmol), tert-butyl nitrite (1.54g, 15mmol) and anhydrous CuSO were added successively. 4 (0.32g, 2mmol), heated to 70°C under airtight condition, stirred at constant temperature for 12h, fully reacted and cooled to room temperature, the reaction solution was extracted 3 times with a mixture of dichloromethane and water, the organic layer was separated and dried over anhydrous sodium sulfate Then 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) to obtain the 4-cyano-1-trifluoromethylthiobenzene product with a yield of 55%.

[0049] 4-cyano-1-trifluoromethylthio 1 H NMR see Figure 5 , 4-cyan...

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Abstract

The invention discloses a method for synthesizing an aromatic trifluoromethylthio compound. The method comprises the following steps: reacting sodium trifluoromethanesulfinate with Chlorodiphenyl phosphine at room temperature; after reacting for a period of time, sequentially adding an aniline compound and tert-butyl nitrite, fully reacting at 70 +/-5 DEG C by taking CuSO4 as a catalyst and acetonitrile as a solvent, cooling to room temperature after the reaction is finished, extracting, carrying out reduced pressure distillation, and carrying out column chromatography separation and purification on the reaction mixture to obtain the aromatic trifluoromethylthio compound. The method is simple and safe in process operation and high in reaction conversion rate, the used raw materials are economical and practical, few three wastes are generated, and no extra organic solvent needs to be treated.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for synthesizing aromatic ring trifluoromethylthio compounds. [0002] technical background [0003] Compounds containing trifluoromethylthio have been widely used in the fields of medicine, pesticides and materials. For example, the anticoccidial veterinary drug Toltrazuril, the insecticide Vaniliprole and the stimulant Tiflorex all contain trifluoromethylthio. Trifluoromethylthio (SCF 3 ) group incorporation into aromatic molecules is of interest to the pharmaceutical and agrochemical industries, where the high lipophilicity and high electron-withdrawing ability of this group are of great importance. Current industrial methods for the formation of trifluoromethyl aryl sulfides generally involve multi-stage processes requiring harsh conditions, properties limited by other substituents on the ring, and environmental hazards. A simple, direct method to form these compou...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C319/14C07C323/09C07C323/62
CPCC07C319/14C07C2601/14C07C323/09C07C323/62
Inventor 亚斯刘杰易文斌
Owner NANJING UNIV OF SCI & TECH
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