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

A method for synthesizing 2,5-dicarbonylpiperazines

A technology for dicarbonylpiperazine and compounds, applied in the field of organic synthesis, can solve the problems of harsh reaction conditions, failure to obtain products and the like, and achieve the effect of mild reaction conditions

Active Publication Date: 2017-04-12
TIANJIN UNIV OF SCI & TECH
View PDF1 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the reaction requires microwave-assisted heating and the reaction conditions are relatively harsh (300W, 200°C, and 18bar); when isonitriles with large steric hindrance substituents (such as tert-butylisonitrile) are used as reactants, the expected products cannot be obtained

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
  • A method for synthesizing 2,5-dicarbonylpiperazines
  • A method for synthesizing 2,5-dicarbonylpiperazines
  • A method for synthesizing 2,5-dicarbonylpiperazines

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Add 2.0mL of methanol to a round bottom flask, and add in sequence, 22.6mg (0.20mmol) of thiazole-2-aldehyde, 21.4mg (0.20mmol) of p-toluidine, 26.0mg (0.20mmol) of monomethyl maleate and tert-butyl iso Nitrile 16.6mg (0.24mmol), and then heated to 45 ° C reaction, 10-20h after the point plate detection reaction is complete, with ethyl acetate: dichloromethane: petroleum ether = 1:1:10 to 1:1:5 as Mobile phase, column chromatography yielded 172.2 mg of compound, yield: 87%.

[0030] Synthesis of compound 1 (structure shown in the figure below).

[0031]

[0032] The synthetic method of embodiment 1 is the same as above-mentioned synthetic general method.

[0033] White solid; Yield: 87%.

[0034] 1 H NMR (400MHz, DMSO-d 6 ):δ8.87(s,0.5H,H a ),8.59(s,0.5H,H a ), 7.90(t, J=3.2Hz, 1H, thiazole), 7.83(t, J=3.6Hz, 1H, thiazole), 7.21~6.92(m, 4H, aryl), 4.12(dd, J=5.2, 10.8 Hz,0.5H,H b ),3.87(dd,J=6.8,8.8Hz,0.5H,H b ),3.60(s,1.5H,-OC H 3 ),3.51(s,1.5H,-OC H 3 ...

Embodiment 2

[0036] Add 2.0mL methanol to the round bottom flask, add in sequence, imidazole-2-carboxaldehyde 19.2mg (0.20mmol), p-toluidine 21.4mg (0.20mmol), monomethyl maleate 26.0mg (0.20mmol) and tert-butyl iso Nitrile 16.6mg (0.24mmol), and then heated to 45 ° C reaction, 10-20h after the point plate detection reaction is complete, with ethyl acetate: dichloromethane: petroleum ether = 1:1:10 to 1:1:5 as Mobile phase, column chromatography yielded 253.4 mg of compound, yield: 67%.

[0037] Synthesis of compound 2 (structure shown in the figure below).

[0038]

[0039] The synthetic method of embodiment 2 is the same as above-mentioned synthetic general method.

[0040] White solid; Yield: 67%.

[0041] 1 H NMR (400MHz, DMSO-d 6 ):δ12.64(s,0.3H,N H ),12.51(s,0.7H,N H ),10.50(s,0.3H,H a ),10.37(s,0.7H,H a ),7.21~6.92(m,6H,imidazol and aryl overlap),3.87~3.79(m,1H,H b ),3.55(s,1H,-OC H 3 ),3.47(s,2H,-OC H 3 ),2.87~2.69(m,1.3H,H c ),2.21(s,1H,-C H 3 ),2.20(s,2H,-C H ...

Embodiment 3

[0043] Add 2.0mmL of methanol to the round bottom flask, add successively, pyridine-2-carbaldehyde 21.4mg (0.20mmol), p-toluidine 21.4mg (0.20mmol), monomethyl maleate 26.0mg (0.20mmol) and tert-butyl iso Nitrile 16.6mg (0.24mmol), and then heated to 45 ° C reaction, 10-20h after the point plate detection reaction is complete, with ethyl acetate: dichloromethane: petroleum ether = 1:1:10 to 1:1:5 as Mobile phase, column chromatography obtained 350.7 mg of compound, yield: 62%.

[0044] Synthesis of compound 3 (structure shown in the figure below).

[0045]

[0046] The synthetic method of embodiment 3 is the same as above-mentioned synthetic general method.

[0047] White solid; Yield: 62%.

[0048] 1 H NMR (400MHz, DMSO-d 6 ):δ9.33(s,0.2H,H a ),9.08(s,0.8H,H a ), 8.47(t, J=4.4Hz, 1H, Py), 7.91~7.86(m, 1H, Py), 7.50~7.42(m, 1H, Py), 7.34(d, J=8.8Hz, 0.8H, Py),7.13~7.05(m,4H,aryl),4.00(dd,J=5.2,10.8Hz,0.8H,H b ),3.89(t,J=7.6Hz,0.2H,H b ),3.61(s,0.6H,-OC H 3 ),3.49(s...

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 synthesizing 2,5-dicarbonyl piperazine compounds. In the reaction, the solvent is methyl alcohol, the reaction temperature is 45 DEG C, reaction time is 10-20 hours, the R1 is 4-methyl phenyl, n-propyl or benzyl, the R2 is methoxy acyl or ethoxy acyl, the aldehyde is heteroaromatic aldehyde with heteroatom at alpha site. The aldehyde used in the Ugi reaction is heteroaromatic aldehyde with heteroatom at alpha site, so that the heteroatom at the aromatic ring and the amide in the Ugi product can form intramolecular hydrogen bond, Micheal reaction is promoted to be carried out smoothly, the purpose of mild reaction condition is realized, all the reactions are finished once and are convenient and rapid.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for synthesizing 2,5-dicarbonylpiperazine compounds, which involves synthesizing 2,5-dicarbonylpiperazine compounds by combining Ugi reaction and Micheal reaction. Background technique [0002] 2,5-dicarbonylpiperazines (2,5-DKPs) are an important class of heterocyclic compounds, which widely exist in natural products and food and medicine, have good biological activity and high medicinal value, and are widely attention of scientists from all over the world. Various methods for synthesizing such compounds were reported in the early days, such as desepeptide synthesis, Ugi synthesis, intramolecular Wittig synthesis, etc., and gradually developed a series of effective synthesis of 2,5-dicarbonylpiperazine compounds Methods. [0003] Recently, two scientists, Santra and Andreana, reported that a series of 2,5-dicarbonylpiperazines were rapidly and efficiently synthesized ...

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 Patents(China)
IPC IPC(8): C07D417/04C07D403/04C07D401/04C07D413/04
CPCC07D401/04C07D403/04C07D413/04C07D417/04
Inventor 郁彭刘琰全德武商天奕徐传明芦逵
Owner TIANJIN UNIV OF SCI & TECH
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