1,2-oxygen azetidines compound and preparation method and application thereof

A technology of heterocyclobutanes and compounds, which is applied in the field of 1,2-oxazetidine compounds and their preparation, can solve the problems of poor functional group tolerance, poor chemoselectivity, poor atom economy, etc., and achieve high yield , good regioselectivity and mild reaction conditions

Active Publication Date: 2019-04-26
NANJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, all three types of reactions have certain limitations
For example, the substrate range of Mannich reaction is limited to aromatic compounds containing electron-donating groups, and the chemoselectivity is poor; the preparation of aryl organometallic reagents requires strict anhydrous and oxygen-free operations, and the functional group tolerance of the substrate is poor; The cross-coupling reaction catalyzed by transition metals needs to prepare aryl halides, and the waste of halides will be generated after the reaction is completed, and the atom economy is poor
[0004] Therefore, there is still a lack of a selective aminomethylation and hydroxymethylation reagent for aromatic compounds with high efficiency, atom economy, mild conditions, and a wide range of substrate applications.

Method used

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  • 1,2-oxygen azetidines compound and preparation method and application thereof
  • 1,2-oxygen azetidines compound and preparation method and application thereof
  • 1,2-oxygen azetidines compound and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 11

[0055] Example 1 Preparation of 1,2-oxazetidine compounds

[0056] (1) Add 120mmol 1,2-dibromoethane and 120mmol triethylamine to 80mL N,N-dimethylformamide solution containing 60mmol N-hydroxyphthalimide, and stir at room temperature until the reaction solution Become colorless, collect the precipitated solid in the reaction solution, dilute the filtrate with ice water and filter out the precipitated solid, combine the precipitated solid and recrystallize the precipitate with ethanol, which is compound III;

[0057] (2) Add 15 mL of hydrobromic acid with a mass concentration of 48% to 120 mmol of compound III in 10 mL of glacial acetic acid, stir and react at 130° C. for 5 minutes, cool, filter, and concentrate the filtrate to obtain yellow compound IV;

[0058] (3) Add 5 mL of pyridine to 8.7 mmol of compound IV, stir and react at room temperature for 5 minutes, then add 20.9 mmol of 4-methylbenzenesulfonyl chloride to the reaction solution, stir at room temperature for 5 ho...

Embodiment 2

[0062] (1) Add 120mmol 1,2-dibromoethane and 120mmol triethylamine to 80mL N,N-dimethylformamide solution containing 60mmol N-hydroxyphthalimide, and stir at room temperature until the reaction The liquid becomes colorless, collect the precipitated solid in the reaction solution, dilute the filtrate with ice water and filter out the precipitated solid, combine the precipitated solid and recrystallize the precipitate with ethanol, which is compound III;

[0063] (2) Add 15 mL of hydrobromic acid with a mass concentration of 48% to 120 mmol of compound III in 10 mL of glacial acetic acid, stir and react at 130° C. for 5 minutes, cool, filter, and concentrate the filtrate to obtain yellow compound IV;

[0064] (3) Add 5 mL of pyridine to 8.7 mmol of compound IV, stir and react at room temperature for 5 minutes, add 20.9 mmol of benzenesulfonyl chloride to the reaction solution, stir at room temperature for 5 hours, then add 1.0 M hydrochloric acid dropwise to the reaction solution...

Embodiment 3

[0067] (1) Add 120mmol 1,2-dibromoethane and 120mmol triethylamine to 80mL N,N-dimethylformamide solution containing 60mmol N-hydroxyphthalimide, and stir at room temperature until the reaction The liquid becomes colorless, collect the precipitated solid in the reaction solution, dilute the filtrate with ice water and filter out the precipitated solid, combine the precipitated solid and recrystallize the precipitate with ethanol, which is compound III;

[0068] (2) Add 15 mL of hydrobromic acid with a mass concentration of 48% to 120 mmol of compound III in 10 mL of glacial acetic acid, stir and react at 130° C. for 5 minutes, cool, filter, and concentrate the filtrate to obtain yellow compound IV;

[0069] (3) Add 5 mL of pyridine to 8.7 mmol of compound IV, stir and react at room temperature for 5 minutes, add 20.9 mmol of p-fluorobenzenesulfonyl to the reaction solution, stir at room temperature for 5 hours, then add 1.0 M hydrochloric acid solution to neutrality, extracted...

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Abstract

The invention discloses a 1,2-oxygen azetidines compound and preparation method and application thereof. The N-hydroxyphthalimide is reacted with 1,2-dibromoethane and triethylamine to obtain compoundIII; the compound III is reacted with hydrobromic acid to obtain yellow compound IV; the compound IV, the pyridine and halide R1X are reacted to obtain the compound V; the compound V is reacted withsodium hydride to obtain 1,2-oxygen azetidines compound. The 1,2-oxygen azetidines compound can be used for aminomethylation or hydroxymethylation of the 1-pyrimidyl indole compound; and the reactionprocess has the advantages of being good in region selectivity, high in yield, simple in process condition, mild in reaction condition, green, high in atom economy, and wide in substrate applicable range.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis methodology, and in particular relates to a 1,2-oxazetidine compound and its preparation method and application. Background technique [0002] Aminomethyl and hydroxymethyl fragment aromatic compounds widely exist in biologically active natural products, drug molecules and functional materials. In the field of organic synthesis, it is necessary to find a method for efficiently and accurately introducing aminomethyl and hydroxymethyl into aromatic systems. [0003] The current methods for introducing aminomethyl and hydroxymethyl groups into aromatic compounds include: (1) Mannich reaction; (2) nucleophilic addition reaction of highly active aryl organometallic reagents to imines or aldehydes; (3) transition Metal-catalyzed cross-coupling reactions of aryl halides with activated amines or aldehydes. However, all three types of reactions have certain limitations. For example, the substra...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D261/02C07D403/04
CPCC07D261/02C07D403/04
Inventor 胡绪红李松
Owner NANJING UNIV OF TECH
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