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

Method for oxidizing N-pyridine indoline compound by air

A pyridine indoline, air oxidation technology, applied in the direction of organic chemistry, etc., can solve the problems of harsh reaction conditions, expensive transition metal catalysts, low applicability, etc.

Inactive Publication Date: 2021-01-12
NINGBO UNIV
View PDF0 Cites 2 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are still many problems in these methods: for example, the transition metal catalyst is expensive, the reaction conditions are relatively harsh, and the applicability is low.
[0004] The oxidation process of N-pyridine indoline is an important step in the preparation of many C7 functional group modified indole derivatives with high biological activity, but currently, the known oxidation process of N-pyridine indoline can only Realized in the presence of 2,3-dichloro-5,6-dicyano-p-benzoquinone, this method needs to be carried out under high temperature conditions and generates a large amount of by-products

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 oxidizing N-pyridine indoline compound by air
  • Method for oxidizing N-pyridine indoline compound by air
  • Method for oxidizing N-pyridine indoline compound by air

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-8

[0027] Embodiment 1-8 reaction condition optimization

[0028] Taking N-pyridine indoline as example, in order to determine the best reaction conditions, at first take N-pyridine indoline as template substrate, take the consumption of N-pyridine indoline as benchmark (39.3mg, 0.2mmol), to Reaction condition is optimized, and the consumption of catalyst, organic solvent used in reaction and reaction yield are as shown in table 1

[0029]

[0030] Wherein the typical test operation of embodiment 1 is as follows:

[0031] In the reactor, N-pyridine indoline (39.3mg, 0.2mmol), Cu(OAc) shown in formula 1a were added successively. 2 ·H 2 O (2.0 mg, 0.01 mmol), N-hydroxyphthalimide (6.5 mg, 0.04 mmol) and acetonitrile (3.0 mL), then the reaction mixture was stirred at room temperature under an oxygen atmosphere for 12 hours, monitored by TLC The reaction is complete, then the reaction mixture is filtered and concentrated under reduced pressure, and the resulting residue is sepa...

Embodiment 9

[0035] Example 9 Synthesis of 5-methoxy-N-pyridindole (2b)

[0036]

[0037] In the reactor, 5-methoxy-N-pyridindoline (45.3mg, 0.2mmol), Cu(OAc) shown in formula 1b were added successively. 2 ·H 2 O (2.0 mg, 0.01 mmol), N-hydroxyphthalimide (6.5 mg, 0.04 mmol) and acetonitrile (3.0 mL), then the reaction mixture was stirred at room temperature under air atmosphere for 12 hours, monitored by TLC The reaction is complete, then the reaction mixture is filtered and concentrated under reduced pressure, and the resulting residue is separated by column chromatography (ethyl acetate / petroleum ether is the elution solvent, volume ratio 1: 15) and purified to obtain the target compound shown in formula 2b. Product 5-methoxy-N-pyridindole (37.2 mg, 81% yield %). 1 HNMR (400MHz, CDCl 3 )δ8.55(d, J=4.8Hz, 1H), 8.17(d, J=9.0Hz, 1H), 7.82-7.78(m, 1H), 7.70(d, J=3.4Hz, 1H), 7.46( d, J=8.2Hz, 1H), 7.16-7.11(m, 2H), 6.95-6.93(m, 1H), 6.64(d, J=3.4Hz, 1H), 3.88(s, 3H)ppm; 13 C NMR (101M...

Embodiment 10

[0038] Example 10 Synthesis of 5-benzyloxy-N-pyridindole (2c)

[0039]

[0040] In the reactor, 5-benzyloxy-N-pyridindoline (60.5mg, 0.2mmol), Cu(OAc) shown in formula 1c were added successively. 2 ·H 2 O (2.0 mg, 0.01 mmol), N-hydroxyphthalimide (6.5 mg, 0.04 mmol) and acetonitrile (3.0 mL), then the reaction mixture was stirred at room temperature under air atmosphere for 12 hours, monitored by TLC The reaction is complete, then the reaction mixture is filtered and concentrated under reduced pressure, and the resulting residue is separated by column chromatography (ethyl acetate / petroleum ether is the elution solvent, volume ratio 1:15) and purified to obtain the target compound shown in formula 2c. Product 5-Benzyloxy-N-pyridindole (48.7 mg, 81% yield). 1 HNMR (400MHz, CDCl 3 )δ8.55-8.54(m, 1H), 8.17(d, J=9.0Hz, 1H), 7.82-7.79(m, 1H), 7.69(d, J=3.5Hz, 1H), 7.50-7.45(m , 3H), 7.40(t, J=7.5Hz, 2H), 7.34(d, J=7.1Hz, 1H), 7.19(d, J=2.6Hz, 1H), 7.16-7.14(m, 1H), 7.04 -7....

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 oxidizing an N-pyridine indoline compound by air. According to the method, a copper salt and N-hydroxyphthalimide are used as a common catalyst, air is used as anoxidizing agent, C2 and C3 sites of the N-pyridine indoline compound are dehydrogenated and oxidized in an organic solvent, and the N-pyridine indoline derivative is obtained. The method is simple inreaction operation and mild in condition, and has the advantages of low reaction cost, high yield and the like.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for air oxidation of N-pyridine indoline compounds. Background technique [0002] The indole skeleton is one of the most common heterocycles in nature, and its wide range of biological activities has been widely used in medicine, pesticides, and material science, so the synthesis of indole derivatives has attracted much attention. Among them, the oxidation of indoline is one of the important methods for preparing indole derivatives. Traditional indoline oxidation usually uses equivalent or excess strong oxidants, such as 2,3-dichloro-5,6-dicyano-p-benzoquinone, manganese dioxide, etc., but such methods are usually accompanied by a large number of toxic by-products generated, causing serious environmental pollution. [0003] In recent years, transition metal-catalyzed dehydrogenation of indoline has provided a new way for the preparation of indole ...

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): C07D401/04C07D403/04
CPCC07D401/04C07D403/04
Inventor 骆钧飞王威霖
Owner NINGBO 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