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

Oxime-based method for synthesis of pyridine derivative by [2+2+2] cycloaddition

A technology of cycloaddition and derivatives, which is applied in the field of addition synthesis of pyridine derivatives, to achieve the effects of novel synthetic routes, reduced toxicity, and good reaction effects

Inactive Publication Date: 2013-01-16
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
View PDF6 Cites 4 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] At present, there are many reports on the reaction of pyridine derivatives prepared by this [2+2+2] cycloaddition method, but there are no reports on the use of oxime as the starting material. The present invention is made on the starting substrate nitrile and the catalytic system Some improvements have been made, and this kind of reaction has been carried out by oxime instead of nitrile, and good results have been achieved.

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
  • Oxime-based method for synthesis of pyridine derivative by [2+2+2] cycloaddition
  • Oxime-based method for synthesis of pyridine derivative by [2+2+2] cycloaddition
  • Oxime-based method for synthesis of pyridine derivative by [2+2+2] cycloaddition

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] The novel reaction synthesis steps and product structural formula are as follows:

[0016]

[0017] The specific steps of this reaction are as follows:

[0018] Take three-necked reaction flask, add hydroxylamine hydrochloride (66mmol, 4.6g), add ethanol after inert gas replacement three times, add ethyl glyoxylate 6 (66mmol, 13.5g), add Et under stirring 3 N (66mmol, 9.3mL), react at room temperature. Adjust the pH value of the reaction solution to close to 7 with hydrochloric acid, extract the aqueous phase with ether (50mL×3), combine the organic phases, and wash the organic phase with anhydrous Na 2 SO 4 After drying, filtering and evaporating the solvent, compound 7 was obtained by column chromatography (yield: 62%).

[0019] Get the Schlenk reaction tube, weigh Rh(NBD) in the glove box 2 BF 4 (0.025mmol, 9.3mg) and BINAP (0.025mmol, 15.6mg) and molecular sieves (137.8mg), DCE (2mL) was added under the protection of an inert gas, and compound 7 (0.1ml) was ...

Embodiment 2

[0023] The novel reaction synthesis steps and product structural formula are as follows:

[0024]

[0025] The specific steps of this reaction are as follows:

[0026] Take three-necked reaction flask, add hydroxylamine hydrochloride (66mmol, 4.6g), add ethanol after inert gas replacement three times, add ethyl glyoxylate 6 (66mmol, 13.5g), add Et under stirring 3 N (66mmol, 9.3mL), react at room temperature. Adjust the pH value of the reaction solution to close to 7 with hydrochloric acid, extract the aqueous phase with ether (50mL×3), combine the organic phases, and wash the organic phase with anhydrous Na 2 SO 4 After drying, filtering and evaporating the solvent, compound 7 was obtained by column chromatography (yield: 62%).

[0027] Get the Schlenk reaction tube, weigh Rh(NBD) in the glove box 2 BF 4 (0.05mmol, 18.7mg) and BINAP (0.05mmol, 31.1mg) and molecular sieves (208.2mg), under the protection of inert gas, add DCE, after stirring for a while, add compound 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 relates to a new oxime-based method for synthesis of a pyridine derivative by [2+2+2] cycloaddition. According to the invention, corresponding oxime is synthesized from aldehyde, Rh(NBD)2BF4 is taken as a metal precursor, BINAP is adopted as a diphosphine ligand, DCE is employed as a solvent, a molecular sieve is used as an additive, and diyne is added to react with the materials for 48h at a temperature of 80DEG C, thus obtaining the corresponding pyridine derivative. Compared with previous nitrile raw materials, the starting material required by the method has the characteristics of simple synthesis, high yield, substantially reduced toxicity, stability in water and air, and strong operability.

Description

technical field [0001] The present invention relates to a new method for synthesizing pyridine derivatives through [2+2+2] cycloaddition based on oxime. Compared with the previous nitrile raw materials, the starting materials required by the method have the advantages of simple synthesis, high yield, greatly reduced toxicity and enhanced air stability. This reaction realizes the synthesis of pyridine derivatives by [2+2+2] cycloaddition by replacing nitriles with oximes. Background technique [0002] According to literature 1 [Chang H T.; Jeganmohan M.; Cheng C H. Org. Lett.2007, 9, 505-508], literature 2 [Cioni P,; Diversi P,; Ingrosso G, et al.J.Mol .Catal.1987,40,337-357], and document 3 [Diversi P,; Ingrosso G,; Catalyze the [2+2+2] cycloaddition reaction between diynes and nitriles, and then prepare multi-substituted pyridine derivatives. The previous synthesis often goes through the following routes: [0003] [0004] This synthetic route uses nitriles as startin...

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): C07D471/04C07D221/04
Inventor 万伯顺徐粉吴凡
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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