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

Preparation method of polysubstituted azatricycloazine derivative

An azatricyclic azine and multi-substitution technology is applied in the field of preparation of multi-substituted azatricyclic azine derivatives, and can solve the problems of incompatibility with green chemistry, poor substrate applicability, complex starting materials and the like, and achieves The effect of post-processing green, short reaction time and easy post-processing

Active Publication Date: 2018-09-04
HUAQIAO UNIVERSITY
View PDF0 Cites 1 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are many problems in these methods: 1) the use of noble metal catalysts does not conform to green chemistry; 2) the starting materials are complex and need to be prepared in advance; 3) the reaction steps are complicated and require multi-step processing; 4) the substrates of these methods are suitable not wide

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
  • Preparation method of polysubstituted azatricycloazine derivative
  • Preparation method of polysubstituted azatricycloazine derivative
  • Preparation method of polysubstituted azatricycloazine derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Preparation of ethyl 1-benzyl-7-methyl-2-carbonyl-1,2-dihydroimidazo[5,1,2-cd]indazine-3,4-dibutyrate

[0023]

[0024] 0.1mmol of N-benzyl-3-methyl-2-aminopyridine, 0.5mmol of dibutyne diethyl ester, 0.002mmol of manganese (III) acetate dihydrate, 0.002mmol of 2,2'-bipyridine, di Add 0.2 mmol of tert-butyl peroxide to an open reaction tube, add 2 mL of acetonitrile, place in an oil bath at 70° C., and react for 16 h. Remove the heat source from the reaction and cool to room temperature. The reaction solution was concentrated and purified by column chromatography to obtain 34.6 mg of the target product with a yield of 85%. The NMR characterization of this compound is as follows: 1 H NMR (400MHz, CDCl 3 )δ7.85(d, J=8.7Hz, 1H), 7.40(d, J=8.7Hz, 1H), 7.34-7.27(m, 3H), 7.20(d, J=6.9Hz, 2H), 5.46( s, 2H), 4.54(q, J=7.1Hz, 2H), 4.44(q, J=7.1Hz, 2H), 2.44(s, 3H), 1.48(t, J=7.1Hz, 3H), 1.44( t, J=7.1Hz, 3H).13C NMR (100MHz, CDCl 3 )δ 163.2 (double), 155.9, 136.8, 133.0,...

Embodiment 2

[0026] 1-(4-Methylbenzyl)-7-methyl-2-carbonyl-1,2-dihydroimidazo[5,1,2-cd]indazine-3,4-dibutyric acid ethyl ester preparation

[0027]

[0028] 0.1mmol of N-(4-methylbenzyl)-3-methyl-2-aminopyridine, 0.5mmol of dibutyne diethyl ester, 0.002mmol of manganese (III) acetate dihydrate, 2,2'-di Add 0.002 mmol of bipyridine and 0.2 mmol of di-tert-butyl peroxide to an open reaction tube, add 2 mL of acetonitrile, place in an oil bath at 70°C, and react for 16 hours. Remove the heat source from the reaction and cool to room temperature. The reaction solution was concentrated and purified by column chromatography to obtain 29.9 mg of the target product with a yield of 71%. The NMR characterization of this compound is as follows: 1 HNMR (400MHz, CDCl 3 )δ7.83(d, J=8.7Hz, 1H), 7.39(d, J=8.7Hz, 1H), 7.13-7.06(m, 4H), 5.41(s, 2H), 4.54(q, J=7.0 Hz, 2H), 4.43(q, J=7.1Hz, 2H), 2.45(s, 3H), 2.30(s, 3H), 1.48(t, J=6.9Hz, 3H), 1.43(t, J=7.0 Hz, 3H). 13 C NMR (100MHz, CDCl 3 )δ 163.2 ...

Embodiment 3

[0030] 1-(4-Methoxybenzyl)-7-methyl-2-carbonyl-1,2-dihydroimidazo[5,1,2-cd]indazine-3,4-dibutyric acid ethyl ester preparation of

[0031]

[0032] 0.1mmol of N-(4-methoxybenzyl)-3-methyl-2-aminopyridine, 0.5mmol of dibutyldiacetylene, 0.002mmol of manganese (III) acetate dihydrate, 2,2'- Add 0.002 mmol of bipyridine and 0.2 mmol of di-tert-butyl peroxide to an open reaction tube, add 2 mL of acetonitrile, place in an oil bath at 70°C, and react for 16 hours. Remove the heat source from the reaction and cool to room temperature. The reaction solution was concentrated and purified by column chromatography to obtain 36.2 mg of the target product with a yield of 83%. The NMR characterization of this compound is as follows: 1 H NMR (400MHz, CDCl 3 )δ7.82(d, J=8.7Hz, 1H), 7.39(d, J=8.7Hz, 1H), 7.14(d, J=8.5Hz, 2H), 6.83(d, J=8.6Hz, 2H) , 5.38(s, 2H), 4.54(q, J=7.1Hz, 2H), 4.43(q, J=7.1Hz, 2H), 3.76(s, 3H), 2.47(s, 3H), 1.48(t, J=7.1Hz, 3H), 1.43(t, J=7.1Hz, 3H). 13 C NMR (...

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 preparation method of a polysubstituted azatricycloazine derivative. The preparation method comprises the following steps: after uniformly mixing substituted aminopyridine, acetylene dicarboxylate, a catalyst, a ligand, an oxidant and an organic solvent, heating under an air atmosphere and carrying out cyclization reaction; after the reaction is finished, cooling to roomtemprature to obtain the polysubstituted azatricycloazine derivative. According to the preparation method, the azatricycloazine derivative with various substituent groups, which cannot be synthesizedby other methods, can be synthesized. The cheap metal catalyst is adopted; the preparation method has the advantages of easiness for obtaining the raw materials, high yield, moderate reaction conditions, short reaction time, wide substrate range, strong reaction specificity, simplicity and convenience for post-treatment and greenness.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of multi-substituted azatricyclazine derivatives. Background technique [0002] Multi-substituted azatricyclazine derivatives are a class of organic synthesis intermediates with a wide range of uses, and have important application values ​​in natural products, pharmaceutical production, and organic synthesis. Therefore, the research on new synthesis methods of multi-substituted azatricyclazines has important application value and has attracted the attention of researchers in related fields. [0003] Traditional methods for the synthesis of azatricyclazine derivatives include transition metal-catalyzed cyclization of imidazo[1,2-a]pyridines with 1,2-disubstituted alkynes or benzynes, and 2-amino-6-alkynyl Multi-step cyclization of pyridine itself. However, there are many problems in these methods: 1) the use of noble metal catalysts doe...

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): C07D471/16
CPCC07D471/16
Inventor 崔秀灵喻云亮
Owner HUAQIAO UNIVERSITY
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