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

Method for preparing 2-iodo aryl ether under action of alkali metal hydride

A technology of alkali metal hydrides and aryl ethers, which is applied in the preparation of organic compounds, metal/metal oxide/metal hydroxide catalysts, ester reaction to prepare ethers, etc., to achieve cheap reagents, high compatibility, and simple reactions Effect

Active Publication Date: 2021-06-18
SUZHOU UNIV
View PDF2 Cites 9 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The prior art uses noble metal catalysts to catalyze the reaction of monohalogen substituted arenes and phenols, and there is no report on the reaction of double halogen substituted arenes with phenols

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 2-iodo aryl ether under action of alkali metal hydride
  • Method for preparing 2-iodo aryl ether under action of alkali metal hydride
  • Method for preparing 2-iodo aryl ether under action of alkali metal hydride

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027]

[0028] Sodium hydride (60% in oil, 36 mg, 0.9 mmol, 3 eq.) was suspended in THF (1 mL), and phenol 2a (36 mg, 0.3 mmol, 1 eq.) was added in DMA (0.3 mL ) solution, stirred at room temperature for 10 minutes after the addition was completed, then added a solution of 1a (148 mg, 0.45 mmol, 1.5 eq.) in THF (0.2 mL), reacted at room temperature for 2 hours, quenched with water, and then dissolved in ethyl acetate The ester was extracted three times, the organic layers were combined, dried with sodium sulfate, evaporated to dryness, and purified by column chromatography to obtain the product iodoaryl ether 3aa with a yield of 99%. figure 1 , LR-MS (ESI): m / z 322.1 [M+H] + .

[0029]

[0030] The above-mentioned sodium hydride was replaced with potassium hydride in an equimolar amount, and the rest remained unchanged to obtain the product iodoaryl ether 3aa with a yield of 39%.

[0031] Replace the above-mentioned sodium hydride with lithium hydride in an equimolar...

Embodiment 2

[0037]

[0038] Sodium hydride (60% in oil, 36 mg, 0.9 mmol, 3 eq.) was suspended in THF (1 mL), and phenol 2a (28 mg, 0.3 mmol, 1 eq.) was added in DMA (0.3 mL ) solution, stirred at room temperature for 10 minutes after the addition was complete, then added a solution of 1a (148 mg, 0.45 mmol, 1.5 eq.) in THF (0.2 mL), reacted at room temperature for 1 hour, quenched with water, washed with ethyl acetate The ester was extracted three times, the organic layers were combined, dried over sodium sulfate, evaporated to dryness, and purified by column chromatography to obtain the product iodoaryl ether 3ba with a yield of 35%.

Embodiment 3

[0040]

[0041] Sodium hydride (60% in oil, 36 mg, 0.9 mmol, 3 eq.) was suspended in THF (1 mL), and phenol 2b (42 mg, 0.3 mmol, 1 eq.) was added in DMA (0.3 mL ) solution, stirred at room temperature for 10 minutes after the addition was complete, then added a solution of 1a (148 mg, 0.45 mmol, 1.5 eq.) in THF (0.2 mL), reacted at room temperature for 0.5 hours, quenched with water, washed with ethyl acetate The ester was extracted three times, the organic layers were combined, dried over sodium sulfate, evaporated to dryness, and purified by column chromatography to obtain the product iodoaryl ether 3ab with a yield of 97%. 1 H NMR (400 MHz, CDCl 3 ) δ: 8.22 (d, J =7.8 Hz, 2H), 7.92 (d, J = 7.5 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H), 7.09 (d, J =7.5 Hz, 1H), 7.03 (t, J = 7.2 Hz, 1H), 6.96 (d, J = 7.8 Hz, 2H). LR-MS (ESI): m / z 342.1 [M+H] + .

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 discloses a method for preparing 2-iodo aryl ether under the action of alkali metal hydride, which comprises the following steps: adding alkali metal hydride and phenol into a solvent, then adding 1, 2-diiodo aromatic hydrocarbon, and reacting at 0-100 DEG C to obtain a 2-iodo aryl ether product. In the coupling process, no transition metal catalyst needs to be added, so that metal pollution to the product is avoided; the method provided by the invention can be carried out at room temperature, has high functional group compatibility, and solves the problem that the existing metal-catalyzed coupling aryl ether reaction needs to be carried out at a relatively high temperature.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to producing an aryne intermediate from an iodine halide under the action of an alkali metal hydride, and then reacting with a phenol coupling to generate 2-iodoaryl ether. Background technique [0002] 2-Iodoaryl ether is a very useful building block in organic synthesis, which can be used in the synthesis of various oxygen-containing heterocycles, and can also carry out various transformations of iodine to prepare ortho-substituted aryl ether derivatives. In the prior art, a carbon-carbon or carbon-heteroatom bond formation reaction requires a metal catalyst or a strong base as a promoter; or a complex precursor is used, such as compound 1 as a precursor, and reacted for 12 hours in the presence of cesium carbonate The iodoaryl ether is obtained. [0003] [0004] In the prior art, noble metal catalysts are used to catalyze the reaction of monohalogen sub...

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
Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/04C07C253/30C07C255/54C07C41/16C07C43/29C07C201/12C07C205/38B01J23/04
CPCC07B41/04C07C253/30C07C41/16C07C201/12B01J23/04C07C255/54C07C43/29C07C205/38
Inventor 张士磊祝文静方春辉胡延维陈鑫黄加文
Owner SUZHOU 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