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Selective production method of N-1-oxyalkyl-substituted 1,2,3-triazole compound and N2-oxyalkyl-substituted 1,2,3-triazole compound

A compound and selective technology, applied in organic chemistry and other directions, can solve the problems of no commercialization, cannot be selectively obtained at the same time, and single reaction product structure, and achieve the effects of simple operation, excellent selectivity, and easy availability of raw materials.

Active Publication Date: 2019-10-25
QUFU NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] Although the above methods can effectively synthesize N-1 and N-2 oxoalkyl substituted 1,2,3-triazole compounds, most of the 1H-1,2,3-triazoles in these methods are not commercialized, Most of them need to be pre-prepared through relatively complex synthetic procedures
Moreover, the reaction product has a single structure and cannot simultaneously selectively obtain 1,2,3-triazole compounds substituted by N-1 and N-2 oxoalkyl groups

Method used

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  • Selective production method of N-1-oxyalkyl-substituted 1,2,3-triazole compound and N2-oxyalkyl-substituted 1,2,3-triazole compound
  • Selective production method of N-1-oxyalkyl-substituted 1,2,3-triazole compound and N2-oxyalkyl-substituted 1,2,3-triazole compound
  • Selective production method of N-1-oxyalkyl-substituted 1,2,3-triazole compound and N2-oxyalkyl-substituted 1,2,3-triazole compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028]

[0029] At room temperature, CuCl (5mol%), phenylacetylene (0.2mmol), TMSN 3 (0.4mmol), tetrahydrofuran (THF, 1mL, 12mmol), and tert-butanol peroxide (TBHP, 0.5mmol), mix well. Close the reaction tube, stir and react at 80°C for 16h. After the reaction is completed, concentrate under reduced pressure in a vacuum (0.08Mpa) to no solvent to obtain a crude product, which is then washed with a mixture of petroleum ether and ethyl acetate with a volume ratio of 5:1. After washing with deagent, flash silica gel column chromatography, 36.6 mg of the N-1 oxoalkyl-substituted 1,2,3-triazole product 4a of this example was obtained, with a yield of 85%.

[0030] 1 H NMR (500MHz, DMSO-d 6 ):δ8.70(s,1H),7.93–7.87(m,2H),7.46(t,J=4.7Hz,2H),7.35(t,J=4.3Hz,1H),6.39–6.27(m, 1H),4.11–4.07(m,1H),3.99–3.95(m,1H),2.51–2.44(m,2H),2.25–2.15(m,1H),2.10–2.01(m,1H); 13 C NMR (125MHz, DMSO-d 6 ): δ147.0, 131.1, 129.3, 128.4, 125.7, 120.3, 89.3, 69.4, 32.1, 24.3

Embodiment 2

[0032]

[0033] At room temperature, CuCl (5mol%), p-tolueneacetylene (0.2mmol), TMSN 3 (0.4mmol), tetrahydrofuran (THF, 1mL, 12mmol), and tert-butanol peroxide (TBHP, 0.5mmol), mix well. Close the reaction tube, stir and react at 80°C for 16h. After the reaction is completed, concentrate under reduced pressure in a vacuum (0.08Mpa) to no solvent to obtain a crude product, which is then washed with a mixture of petroleum ether and ethyl acetate with a volume ratio of 5:1. Washing with deagent, silica gel column flash column chromatography, obtained 30.2 mg of the N-1 oxoalkyl-substituted 1,2,3-triazole product 4b of this example, with a yield of 66%.

[0034] 1 H NMR (500MHz, DMSO-d 6 ):δ8.61(s,1H),7.76(d,J=8.1Hz,2H),7.24(d,J=7.9Hz,2H),6.38–6.30(m,1H),4.08–4.04(m, 1H),3.97–3.92(m,1H),2.47–2.38(m,2H),2.32(s,3H),2.22–2.13(m,1H),2.07–2.00(m,1H); 13 C NMR (125MHz, DMSO-d 6 ): δ147.0, 137.7, 129.9, 128.4, 125.6, 119.8, 89.2, 69.4, 32.1, 24.3, 21.3

Embodiment 3

[0036]

[0037] At room temperature, CuCl (5mol%), p-chlorophenylacetylene (0.2mmol), TMSN 3 (0.4mmol), tetrahydrofuran (THF, 1mL, 12mmol), and tert-butanol peroxide (TBHP, 0.5mmol), mix well. Close the reaction tube, stir and react at 80°C for 16h. After the reaction is completed, concentrate under reduced pressure in a vacuum (0.08Mpa) to no solvent to obtain a crude product, which is then washed with a mixture of petroleum ether and ethyl acetate with a volume ratio of 5:1. After washing with deagent, flash column chromatography on silica gel column, 35.4 mg of the N-1 oxoalkyl-substituted 1,2,3-triazole product 4c of this example was obtained, with a yield of 71%.

[0038] 1 H NMR (500MHz, DMSO-d 6):δ8.75(s,1H),7.94–7.90(m,2H),7.54–7.51(m,2H),6.37(t,J=4.7Hz,1H),4.11–4.07(m,1H), 3.99–3.95(m,1H),2.49–2.43(m,2H),2.23–2.14(m,1H),2.09–2.03(m,1H); 13 C NMR (125MHz, DMSO-d 6 ): δ145.9, 132.8, 130.1, 129.4, 127.4, 120.6, 89.4, 69.5, 32.1, 24.2; HRMS calc.for C12H13ClN3O(M+...

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Abstract

The invention discloses a selective production method of a N-1-oxyalkyl-substituted 1,2,3-triazole compound and a N2-oxyalkyl-substituted 1,2,3-triazole compound. The selective production method of the N-1-oxyalkyl-substituted 1,2,3-triazole compound and the N2-oxyalkyl-substituted 1,2,3-triazole compound comprises the steps of mixing alkyne, azidotrimethylsilane and an ether solvent, then addinga copper catalyst and a tert-butyl hydroperoxide oxidizing agent, and carrying out a reaction at 70-90 DEG C; when the dosage of the copper catalyst is 5 mol%, the N-1-oxyalkyl-substituted 1,2,3-triazole compound is obtained from the reaction; and when the dosage of the copper catalyst is 20 mol%, the N2-oxyalkyl-substituted 1,2,3-triazole compound is obtained from the reaction. The selective production method of the N-1-oxyalkyl-substituted 1,2,3-triazole compound and the N2-oxyalkyl-substituted 1,2,3-triazole compound has the advantages that the simple commercial raw materials are adopted, by changing the dosage of the copper catalyst, the N-1-oxyalkyl-substituted 1,2,3-triazole compound and the N2-oxyalkyl-substituted 1,2,3-triazole compound can be selectively synthesized, and the reaction has high application values.

Description

technical field [0001] The invention belongs to the field of organic synthetic chemistry, and relates to a selective preparation method of N-1 and N2-oxoalkyl substituted 1,2,3-triazole compounds, in particular to a copper-catalyzed alkyne, alkene A method for selectively synthesizing N-1 and N2-oxoalkyl substituted 1,2,3-triazole compounds by three-component reaction of nitrogen trimethylsilane and ether. Background technique [0002] 1,2,3-Triazole derivatives are widely used in biomedicine, pesticides, materials and other fields. In particular, N-substituted-1,2,3-triazole derivatives are particularly prominent in the development of anti-cancer, anti-AIDS, antibacterial and other pharmaceutical compounds and in the field of organic synthesis. Oxyalkyl structural units often exist as key skeletons in a variety of biologically active drug molecules and natural products. In recent years, organic synthesis workers have been trying to introduce oxane gene into 1,2,3-triazole...

Claims

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Application Information

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IPC IPC(8): C07D405/04C07D409/14C07D405/14C07D249/06
CPCC07D405/04C07D409/14C07D405/14C07D249/06
Inventor 魏伟鲍鹏丽吕玉芬
Owner QUFU NORMAL UNIV
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