N1 substituted 1,2,3-triazole derivative for ligand of Cu(I) as well as preparation method and application of N1 substituted 1,2,3-triazole derivative

A technology of triazole derivatives and ligands, applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, chemical/physical processes, etc., can solve the problem of low reaction yield, difficult synthesis, easy salt Disproportionation and other problems, to achieve the effect of high product yield, strong substrate adaptability and stable properties

Inactive Publication Date: 2014-09-03
WUHAN INSTITUTE OF TECHNOLOGY
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  • Abstract
  • Description
  • Claims
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AI Technical Summary

Problems solved by technology

[0004] The reaction was carried out in the presence of (N,N-diisopropylethylamine) to generate the desired 1,4-disubstituted-1,2,3-triazole; this method is suitable for a variety of reaction conditions and resin types, but due to the Self-coupling results in lower reaction yields.
[0005] (2) Liquid-phase catalytic system of Cu(I) salts: CuI, CuBr, CuCl, CuCN, CuOAc and other monovalent copper salts are added to a certain solvent system to catalyze the reaction to obtain the corresponding 1,4-disubstituted 1,2,3-triazole; this method can achieve good yields, but Cu(I) salts are easily disproportionated or oxidized, and the reaction system catalyzed by Cu(I) salts requires the use of specific solvents and even the addition of bases , so that

Method used

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  • N1 substituted 1,2,3-triazole derivative for ligand of Cu(I) as well as preparation method and application of N1 substituted 1,2,3-triazole derivative
  • N1 substituted 1,2,3-triazole derivative for ligand of Cu(I) as well as preparation method and application of N1 substituted 1,2,3-triazole derivative
  • N1 substituted 1,2,3-triazole derivative for ligand of Cu(I) as well as preparation method and application of N1 substituted 1,2,3-triazole derivative

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Synthesis of Ligand 1

[0029]

[0030] In a 250mL round bottom flask, add pyridylacetylene (14.5g, 100mmol), benzyl azide (15.7g, 110mmol), CuSO 4 ·5H 2 O (1.25g, 5mmol), sodium ascorbate (1.98g, 10mmol), using anhydrous methanol (180mL) as the reaction solvent, stirred at room temperature for 30min to 1h to complete the reaction. After the reaction, use a rotary evaporator to remove absolute ethanol, concentrate to obtain a crude product, and separate and purify by thin-layer silica gel column chromatography to obtain a white solid, 12.3 g, with a yield of 52%. The structure of the compound is characterized as follows: 1H NMR (400MHz, CDCl3) δ8.64(s, 1H), 8.18(s, 1H), 7.91(d, J=7.2Hz, 1H), 7.74(t, J=7.2Hz ,1H),7.35-7.22(m,6H),5.65(s,2H).

Embodiment 2

[0032] Synthesis of Ligand 2

[0033]

[0034] In a 250mL round bottom flask, add pyridylacetylene (14.5g, 100mmol), 2-pyridine azido (17.4g, 110mmol), CuSO 4 ·5H 2 O (1.25g, 5mmol), sodium ascorbate (1.98g, 10mmol), using anhydrous methanol (180mL) as the reaction solvent, stirred at room temperature for 30min to 1h to complete the reaction. After the reaction, the absolute ethanol was removed by a rotary evaporator, concentrated to obtain a crude product, separated and purified by thin-layer silica gel column chromatography to obtain a white solid, 13.5 g, with a yield of 61%. The structure of the compound is characterized as follows: 1H NMR (400MHz, CDCl3) δ9.18 (s, 1H), 8.66 (d, J = 4.4Hz, 1H), 8.55 (d, J = 4.4Hz, 1H), 8.26-8.23 (m,2H),7.94(t,J=7.6Hz,1H),7.82(t,J=7.6Hz,1H),7.40-7.35(m,1H),7.29(d,J=8.8Hz,1H) .

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Abstract

The invention relates to an N1 substituted 1,2,3-triazole derivative for a ligand of Cu(I) as well as a preparation method and application of the N1 substituted 1,2,3-triazole derivative. The structural general formula I of the N1 substituted 1,2,3-triazole derivative is as shown in the specification: R is alkyl or aryl; R' is an H atom, alkyl or aryl; X is a CH or N atom. The preparation method comprises the steps of mixing nitrogen-containing heterocyclic ring substituted terminal alkyne with azide, CuSO4 and sodium ascorbate, stirring based on absolute methanol as a solvent in the air under room temperature, reacting for 0.5-1 hour, and then directly generating a solid namely the N1 substituted 1,2,3-triazole derivative. Compared with the prior art, the N1 substituted 1,2,3-triazole derivative disclosed by the invention has the advantages that compared with other ligands, the ligand is simple in synthesis and stable in property. In a cycloaddition reaction between mono-valent copper ion catalytic terminal alkyne and azide, the ligand is small in catalyst dose, mild in reaction condition, high in product yield and strong in substrate adaptability.

Description

technical field [0001] The present invention relates to N1 substituted 1,2,3-triazole derivatives as ligands for Cu(I) and their use. Background technique [0002] The earliest 1,3-dipolar Huisgen cycloaddition reaction of organic azides and terminal alkynes synthesized a mixture of 1,4-disubstituted and 1,5-disubstituted triazoles. This reaction requires a strong electron-withdrawing group attached to the azide compound or the alkynyl group as an activation group, and requires high temperature and pressure and a long reaction time. Therefore, the application of synthesizing 1,4-disubstituted-1,2,3-triazole compounds is greatly limited. In 2002, Sharpless and Meldal discovered Cu(I)-catalyzed 1,3-dipolar Huisgen cycloaddition reaction between organic azides and terminal alkynes on this basis. This method not only obtains specific 1, 4-disubstituted-1,2,3-triazole products, and the reaction conditions are mild, and the application range is wide, so that the synthesis and ap...

Claims

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Application Information

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IPC IPC(8): C07D401/04C07D401/14C07D249/06C07D249/04B01J31/22
CPCC07D401/04B01J31/181B01J31/1815C07D249/04C07D249/06C07D401/14
Inventor 陈云峰刘文倩马姗潘志权
Owner WUHAN INSTITUTE OF TECHNOLOGY
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