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N2-substituted 1,2,3-triazole derivative for Cu (I) ligand as well as preparation method and application of N2-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, catalytic reactions, etc., can solve problems such as low reaction yield, difficult synthesis, and application limitations , to achieve the effects of high product yield, strong substrate adaptability, and small catalyst dosage

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

Problems solved by technology

[0003] (1) Solid catalyst system of Cu(I) salt: add Cu(I) to the resin-immobilized terminal alkyne, and react in the presence of a base such as DIPEA (N,N-diisopropylethylamine) to generate the desired 1 ,4-disubstituted-1,2,3-triazoles; this method is suitable for a variety of reaction conditions and resin types, but the reaction yield is low due to the self-coupling of excess alkynes.
[0004] (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 its application has certain limitations
[0005] (3) Ligand-assisted Cu(I)-formed complex catalytic system: Cu(I) forms complexes with different ligands, and catalyzes the reaction in the corresponding solvent system to generate the corresponding 1,4-disubstituted 1, 2,3-triazole; this method can stabilize Cu(I) and enhance the catalytic activity of Cu(I) because the ligand can form a relatively stable complex with Cu(I), thereby greatly improving the efficiency of the reaction , but the current research on ligands for Cu(I) catalysis is mainly based on ligands with complex structures such as polyamines and amines substituted with 1,2,3-triazoles. Such ligands are not easy to synthesize, so their applications are limited. certain restrictions

Method used

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  • N2-substituted 1,2,3-triazole derivative for Cu (I) ligand as well as preparation method and application of N2-substituted 1,2,3-triazole derivative
  • N2-substituted 1,2,3-triazole derivative for Cu (I) ligand as well as preparation method and application of N2-substituted 1,2,3-triazole derivative
  • N2-substituted 1,2,3-triazole derivative for Cu (I) ligand as well as preparation method and application of N2-substituted 1,2,3-triazole derivative

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Ligand 1 Synthesis:

[0028]

[0029] 4-(2-pyridine)-NH-1,2,3-triazole (0.84g, 10mmol), benzyl bromide (1.88g, 11mmol), potassium carbonate (99mg, 1mmol), Potassium iodide (0.23g, 2mmol), DMF (40mL) was used as the reaction solvent, stirred at room temperature for 1-2h, the reaction was complete, and the reaction process was monitored by TLC. After the reaction was completed, it was extracted with ethyl acetate, and the organic phase was washed with anhydrous Na 2 SO 4 Drying, filtration and concentration to obtain the crude product was separated and purified by thin-layer silica gel column chromatography to obtain N1 substituted product and N2 substituted product respectively, wherein the N2 substituted product was a white solid which was Ligand 1, with 2.13g and a yield of 60% . The structure of the compound is characterized as follows: 1H NMR (400MHz, CDCl3) δ8.53(s, 1H), 8.19(d, J=7.9Hz, 1H), 8.05(s, 1H), 7.78-7.75(m, 1H) ,7.37(s,1H),7.22–7.19(m,5H),5.58(s,2H...

Embodiment 2

[0031] Ligand 2 Synthesis:

[0032]

[0033] Add 5-phenyl-4-(2-pyridine)-NH-1,2,3-triazole (0.84g, 10mmol), benzyl bromide (1.88g, 11mmol), potassium carbonate ( 99mg, 1mmol), potassium iodide (0.23g, 2mmol), DMF (40mL) was used as the reaction solvent, stirred at room temperature for 1-2h, the reaction was complete, and the reaction process was monitored by TLC. After the reaction was completed, it was extracted with ethyl acetate, and the organic phase was washed with anhydrous Na 2 SO 4 Drying, filtration and concentration to obtain a crude product was separated and purified by thin-layer silica gel column chromatography to obtain a white solid which is Ligand 2, 2.00 g, with a yield of 74%. The structure of the compound is characterized as follows: 1H NMR (400MHz, CDCl3) δ8.45 (s, 1H), 7.75 (d, J=3.6Hz, 1H), 7.64-7.62 (m, 2H), 7.47-7.40 (m, 3H),7.33–7.15(m,4H),7.12(s,1H),7.03(s,2H),5.45(s,2H).

Embodiment 3

[0035] Ligand 3 Synthesis:

[0036]

[0037]Add 5-phenyl-4-(2-pyridine)-NH-1,2,3-triazole (1.00g, 10mmol), iodobenzene (1.02g, 11mmol), potassium carbonate ( 100mg, 1mmol), cuprous iodide (59mg, 0.1mmol), L-proline (50mg, 0.1mmol), with DMF (40mL) as the reaction solvent, heated to 80°C under the protection of argon and stirred for 1~2h The reaction was complete, and the reaction process was monitored by TLC. After the reaction was completed, it was extracted with ethyl acetate, and the organic phase was washed with anhydrous Na 2 SO 4 After drying, filtration and concentration, the crude product was separated and purified by thin-layer silica gel column chromatography to obtain a white solid which was Ligand 3, 1.76 g, with a yield of 87%. The structural characterization of the compound is as follows: 1H NMR (400MHz, CDCl3) δ8.69(s,1H),7.67–7.63(m,6H),7.38(s,4H),7.26(s,2H),6.88(s, 1H).

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Abstract

The invention relates to an N2-substituted 1,2,3-triazole derivative for a Cu (I) ligand as well as a preparation method and an application of the N2-substituted 1,2,3-triazole derivative. The derivative has the structural general formula as shown in the specification, wherein R is alkyl or aryl, R' is H atom, alkyl or aryl, and X is CH or N atom. The preparation method comprises the following steps: mixing NH-1,2,3-triazole, halogenated hydrocarbon and K2CO3, stirring, reacting, extracting and drying after the reaction is ended, and filtering and concentrating to obtain a coarse product; separating and purifying through thin-layer column chromatography on silica gel, thus obtaining the product; or mixing NH-1,2,3-triazole, halogenated aromatic hydrocarbon, CuX and K2CO3, by taking DMF as a solvent, heating, reacting, extracting and drying after the reaction is ended, filtering and concentrating to obtain a coarse product, separating and purifying through thin-layer column chromatography on silica gel, thus obtaining the product. The invention has the advantages that the N2-substituted 1,2,3-triazole derivative is simple in synthesis and stable in property and has the characteristics of small catalyst amount, mild reaction conditions, high product yield and high substrate adaptability.

Description

technical field [0001] The present invention relates to N2-substituted 1,2,3-triazole derivatives used as Cu(I) ligands and their preparation methods and applications. Background technique [0002] The early 1,3-dipolar Huisgen cycloaddition reaction of organic azides and terminal alkynes synthesized mixtures 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, The 4-disubstituted-1,2,3-triazole product, and the reaction conditions are mild, and the application range is w...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D401/04C07D249/06B01J31/22
CPCC07D401/04B01J31/1815B01J2231/34B01J2531/16C07D249/06
Inventor 刘文倩陈云峰马姗潘志权
Owner WUHAN INSTITUTE OF TECHNOLOGY
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