4-chloro(bromo)-5-alkylthio-3-pyrrolidone derivative and synthesis thereof

A technology of alkylthio and pyrrolidone, which is applied in the field of 4-chloro(bromo)-5-alkylthio-3-pyrrolone derivatives and synthesis thereof, and achieves the effects of low cost, easy industrial production and high yield

Inactive Publication Date: 2015-11-25
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

One-step synthesis of 4- The method of chloro(bromo)-3-pyrrolone derivatives has not been reported in the literature

Method used

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  • 4-chloro(bromo)-5-alkylthio-3-pyrrolidone derivative and synthesis thereof
  • 4-chloro(bromo)-5-alkylthio-3-pyrrolidone derivative and synthesis thereof
  • 4-chloro(bromo)-5-alkylthio-3-pyrrolidone derivative and synthesis thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0029]

[0030] In the glove box, weigh 1-thiomethyl-1-anilino-5-phenyl-1,4-pentadien-3-one 2a (0.5mmol), copper chloride (2.0mmol), carbonic acid Potassium (2.0mmol), lithium chloride (1.5mmol) in a 25mL Schlenk reaction flask, under argon, add N,N-dimethylformamide (DMF) solvent 5mL, stir at room temperature for 2 minutes, put in 100 °C in an oil bath for 12 hours. After the reaction, the mixture was cooled to room temperature, filtered with diatomaceous earth, extracted with ethyl acetate and 10% ammonia water in mass concentration, collected the organic phase, dried over anhydrous magnesium sulfate, filtered, removed volatile components under reduced pressure, and then used a silica gel column to Chromatographic separation (eluent: petroleum ether (60-90°C) / ethyl acetate, v / v=20:1) gave the target product 1a as a red solid (115 mg, yield 70%). The target product was confirmed by NMR and high-resolution mass spectrometry.

Embodiment 2

[0032]

[0033] In the glove box, weigh 1-thiomethyl-1-p-methoxyanilino-5-phenyl-1,4-pentadien-3-one 2b (0.5 mmol), copper chloride (1.5 mmol), potassium phosphate (1.5mmol), and lithium chloride (1.5mmol) in a 25mL Schlenk reaction flask, under argon, add 5mL of DMF solvent, stir at room temperature for 2 minutes, and put it into an oil bath at 120°C for reaction 6 Hour. After the reaction, the mixture was cooled to room temperature, filtered with celite, extracted with ethyl acetate and 10% ammonia water, the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the volatile components were removed under reduced pressure, followed by silica gel column chromatography Separation (eluent: petroleum ether (60-90°C) / ethyl acetate, v / v=20:1) gave the target product 1b (166 mg, yield 93%) as a red solid. The target product was confirmed by NMR and high-resolution mass spectrometry.

Embodiment 3

[0035]

[0036]In the glove box, successively weigh 1-thiomethyl-1-m-fluoroanilino-5-phenyl-1,4-pentadien-3-one 2c (0.5mmol), copper chloride (2.0mmol) , potassium phosphate (2.0mmol), and lithium chloride (1.5mmol) were placed in a 25mL Schlenk reaction flask, under argon, 5mL of DMF solvent was added, stirred at room temperature for 2 minutes, and placed in an oil bath at 80°C for 2 hours. After the reaction, the mixture was cooled to room temperature, filtered with celite, extracted with ethyl acetate and 10% ammonia water, the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the volatile components were removed under reduced pressure, followed by silica gel column chromatography Separation (eluent: petroleum ether (60-90°C) / ethyl acetate, v / v=20:1) gave the target product 1c (159 mg, yield 92%) as a red solid. The target product was confirmed by NMR and high-resolution mass spectrometry.

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Abstract

The invention discloses a 4-chloro(bromo)-5-alkylthio-3-pyrrolidone derivative and its synthesis. By using 1-alkylthio-1-amino-5- aromatic (heterocyclic) ring-1,4-pentadiene-3-ketone as a starting material, using CuCl2 or CuBr2 as a promoter and using LiCl or LiBr as an auxiliary agent, intramolecular cycloamination and halogenating reaction are carried out under the heading condition so as to generate the 4-chloro(bromo)-5-alkylthio-3-pyrrolidone derivative by one step. The obtained 3-pyrrolidone derivative can undergo further conversation to generate a functional product. The method has the following advantages: raw materials are easily available; synthesis reaction conditions are mild; reaction efficiency is high; and stereoselectivity of the product is good, and its functional group has diversity.

Description

technical field [0001] The invention relates to an unsaturated nitrogen-containing heterocyclic compound 4-chloro(bromo)-5-alkylthio-3-pyrrolone derivative and a synthesis method thereof. Starting from 1-alkylthio-1-amino-5-aryl(hetero)cyclo-1,4-pentadien-3-one, CuCl 2 or CuBr 2 As a promoter, LiCl or LiBr as an auxiliary agent, under heating conditions, through intramolecular ring amination and halogenation reactions, one-step generation of 4-chloro(bromo)-5-alkylthio-3-pyrrolone derivatives. [0002] Compared with the reported synthetic method of 3-pyrrolidone derivatives, the present invention has easy-to-obtain raw materials, simple operation, mild synthetic reaction conditions, high efficiency, yield of 51%-94%, and the product has good stereoselectivity properties and functional group diversity. The 4-chloro(bromo)-5-alkylthio-3-pyrrolidone skeleton synthesized by the present invention is a brand-new skeleton structure, and in this structure, the 4-position halogen an...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D207/44C07D409/06C07D405/06
CPCC07D207/44C07D405/06C07D409/06
Inventor 余正坤黄菲王连弟
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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