Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Method for preparing bromoaryl azide

A technology of aryl azide and compound, which is applied in the field of preparation of bromoaryl azide compound, can solve the problems of small application range and achieve the effects of low cost, mild reaction conditions and simple operation

Inactive Publication Date: 2011-01-19
TONGJI UNIV
View PDF0 Cites 4 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 1962, Smith reported the method of brominating phenyl azide to p-bromophenyl azide with liquid bromine, and the yield was only 54% (Smith G.E.Phys. Rev. Lett.1962, 9, 487); Latyshev et al. Using 1,4-dioxane dibromide as the brominating agent, brominating 1,3-diazide-2-toluene to obtain 1,3-diazide-4-bromo-2-toluene, but this method Limited to the bromination of aryl azides containing donating groups, thus the application range is small (Latyshev, G.V.Synthesis, 2009, 2605)

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Method for preparing bromoaryl azide
  • Method for preparing bromoaryl azide
  • Method for preparing bromoaryl azide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Example 1: Preparation of 2,4-dibromophenylazide

[0017]

[0018] 3 mL of 1,2-dichloroethane, 16 mg (0.1 mmol) of anhydrous ferric chloride, 89 mg (0.5 mmol) of NBS, and 99 mg (0.5 mmol) of p-bromoazide were added to a 60 mL sealed tube, and the mixture was stirred at 80°C. The reaction was carried out for 24 hours, and 2 mL of water was added to the reaction solution, followed by extraction with ethyl acetate. After the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate, the solvent was removed by distillation under reduced pressure to obtain a crude product. The crude product was separated by column chromatography (petroleum ether as the eluent) to obtain 2,4-dibromophenyl stack. Nitrogen 84 mg, pale yellow liquid, yield 61%.

[0019] Its NMR data are as follows:

[0020] 1 H NMR (500MHz, CDCl 3 ): δ=7.04 (1H, d, J=8.5Hz), 7.46 (1H, dd, J=8.5, 2.1Hz), 7.70 (1H, d, J=2.1Hz).

Embodiment 2

[0021] Example 2: Preparation of 2,4-dibromophenylazide

[0022]

[0023] 3 mL of 1,2-dichloroethane, 32 mg (0.2 mmol) of anhydrous ferric chloride, 98 mg (0.55 mmol) of NBS, and 99 mg (0.5 mmol) of p-bromoazide were added to a 60 mL sealed tube, and the reaction was stirred at 80°C. After 24 hours, 2 mL of water was added to the reaction solution, followed by extraction with ethyl acetate. After the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate, the solvent was removed by distillation under reduced pressure to obtain a crude product. The crude product was separated by column chromatography (petroleum ether as the eluent) to obtain 2,4-dibromophenyl stack. Nitrogen 108 mg, pale yellow liquid, yield 78%.

[0024] Its NMR data are as follows:

[0025] 1 H NMR (500MHz, CDCl 3 ): δ=7.04 (1H, d, J=8.5Hz), 7.46 (1H, dd, J=8.5, 2.1Hz), 7.70 (1H, d, J=2.1Hz).

Embodiment 3

[0026] Example 3: Preparation of ethyl 3-bromo-4-azidobenzoate

[0027]

[0028] 3 mL of 1,2-dichloroethane, 32 mg (0.2 mmol) of anhydrous ferric chloride, 98 mg (0.55 mmol) of NBS, 96 mg (0.5 mmol) of ethyl 4-azidobenzoate were added to a 60 mL sealed tube, and the mixture was heated to 80 The reaction was stirred at °C for 24 hours, and 2 mL of water was added to the reaction solution, followed by extraction with ethyl acetate. After the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate, the solvent was removed by distillation under reduced pressure to obtain a crude product. The crude product was separated by column chromatography (petroleum ether as eluent) to obtain 3-bromo-4-azidobenzene Ethyl formate, 109 mg, was a pale yellow liquid, and the yield was 81%.

[0029] Its NMR data are as follows:

[0030] 1 H NMR (500MHz, CDCl 3 ): δ=1.40 (3H, t, J=7Hz), 4.38 (2H, q, J=7Hz), 7.21 (1H, d, J=8.5Hz), 8.02 (1H, dd, J=8.5, 1.5Hz) ), ...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention relates to a method for preparing bromoaryl azide. Aryl azide is used as a raw material; and the aryl azide and N-bromosuccinimide undergo bromination reaction in a 1,2-dichloroethane solvent in the presence of anhydrous ferric trichloride to efficiently synthesize the bromoaryl azide. The bromoaryl azide synthesized by the method can be used for synthesis of medicaments, pesticide, functional materials and the like. The method of the invention has the advantages of easily obtained raw material, low cost, simple operation, mild reaction condition and the like, is easy for industrialized production, and has broad application prospect.

Description

technical field [0001] The present invention relates to a preparation method of a bromoaryl azide compound. Background technique [0002] Aryl azides are an important class of organic compounds, which can be used in the synthesis of drugs, pesticides and functional materials due to their special structural and physicochemical properties (Brase S.Angew.Chem.Int.Ed., 2005, 44, 5188). Aryl azides can be reduced to corresponding aryl amines by reducing agents (Reddy P.G. Tetrahedron Lett. 2002, 43, 1919), which are widely used in the pharmaceutical industry. The 1,3-dipolar cycloaddition reaction of aryl azide compounds with alkynes, imines, nitrile groups, alkenes and other functional groups to synthesize five-membered heterocycles containing three or four nitrogens (Yadav J.S.Synlett.2002, 3 , 513), especially the synthesis of 1,2,3-triazole compounds through click chemistry, which have been widely used in antibacterial, immune, antitumor, treatment of arthritis, osteomalaci...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
IPC IPC(8): C07C247/16C07C247/18C07D277/50
Inventor 匡春香金辉王晓昆
Owner TONGJI UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com