Method for preparing 4-phosphoryl-1,4,5-tri-substituted 1,2,3-triazole in water phase or biomedium

A biological medium and phosphoryl technology, applied in chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, organic chemistry, etc., can solve the problems of preparation technology that have not been reported publicly, and achieve high reaction efficiency and reaction The effect of mild conditions

Active Publication Date: 2018-09-21
DALIAN UNIV OF TECH
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  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although some methods for modifying the regioselectivity of internal alkyne-azido cycloaddition reactions have been reported, for 4-phosphoryl-1,4,5-trisubstituted 1,2,3-triazole The preparation technology has not yet been publicly reported

Method used

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  • Method for preparing 4-phosphoryl-1,4,5-tri-substituted 1,2,3-triazole in water phase or biomedium
  • Method for preparing 4-phosphoryl-1,4,5-tri-substituted 1,2,3-triazole in water phase or biomedium
  • Method for preparing 4-phosphoryl-1,4,5-tri-substituted 1,2,3-triazole in water phase or biomedium

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Example 1: Preparation of 4-phosphodimethyl-(1-benzyl)-5-phenyl-1H-1,2,3-triazole

[0021] Dissolve dimethyl phenylethynyl phosphate (0.2mmol, 42mg) in water (2mL) under air, then add benzyl azide (0.3mmol, 40.2mg) and [Rh(CO) 2 Cl] 2 (0.005mmol, 1.9mg), the reaction mixture was stirred at 40°C and reacted for 12h. After the reaction was completed, it was extracted with ethyl acetate, the solvent was selected to be dry, and the product was separated by column chromatography to obtain 54.9mg of a yellow oily product with a yield of 80%.

[0022]

[0023] 1 H NMR (500MHz, CDCl 3 ,TMS):δ7.50-7.43(m,3H),7.28-7.26(m,5H), 7.03-7.01(m,2H),5.45(s,2H),3.75(s,3H),3.73(s ,3H). 13 C NMR (125MHz, CDCl 3 ):δ143.4(d,J C-P =33.8Hz), 135.0(d, J C-P =241.3Hz), 134.6, 130.3, 129.8, 128.8, 128.7, 128.5, 127.6, 125.4, 53.3 (d, J C-P =6.3Hz), 52.1. 31 P NMR (200MHz, CDCl 3 ): δ9.9. HRMS (ESI) m / z calcdfor C 17 h 18 N 3 o 3 P(M+Na) + 366.0978,found 366.0984.

Embodiment 2

[0024] Example 2: Preparation of 4-diisopropyl phosphate-(1-benzyl)-5-phenyl-1H-1,2,3-triazole

[0025] Under air, diisopropyl phenylethynyl phosphate (0.2mmol, 53.2mg) was dissolved in water (2mL), and benzyl azide (0.3mmol, 40.2mg) and [Rh(CO) 2 Cl] 2 (0.005mmol, 1.9mg), the reaction mixture was stirred at 40°C and reacted for 12h. After the reaction was completed, it was extracted with ethyl acetate, the solvent was selected to be dry, and the product was separated by column chromatography to obtain 67mg of a yellow oily product with a yield of 84%.

[0026]

[0027] 1 H NMR (500MHz, CDCl 3 ,TMS):δ7.47-7.40(m,3H),7.28-7.24(m,5H), 7.02-7.00(m,2H),5.43(s,2H),4.77-4.71(m,2H),1.26 (d,J=10.0Hz,6H),1.16(d,J=10.0Hz,6H). 13 C NMR (125MHz, CDCl 3 ):δ142.6(d,J C-P =32.5Hz), 137.0(d, J C-P =241.3Hz), 134.8, 130.0, 130.0, 128.8, 128.5, 128.3, 127.5, 126.1, 71.6 (d, J C-P =5.0Hz),52.0,24.0(d,J C-P =3.8Hz), 23.6(d, J C-P =3.8Hz). 31 P NMR (200MHz, CDCl 3 ): δ5.5. HRMS (ESI...

Embodiment 3

[0028] Example 3: Preparation of 4-di-n-butyl phosphate-(1-benzyl)-5-phenyl-1H-1,2,3-triazole

[0029] Under air, di-n-butyl phenylethynyl phosphate (0.2mmol, 58.8mg) was dissolved in water (2mL), and benzyl azide (0.3mmol, 40.2mg) and [Rh(CO) 2 Cl] 2 (0.005mmol, 1.9mg), the reaction mixture was stirred at 40°C, and reacted for 12h. After the reaction, it was extracted with ethyl acetate, the solvent was selected to be dry, and the product was separated by column chromatography to obtain 60.6mg of a yellow oily product with a yield of 71%.

[0030]

[0031] 1 H NMR (500MHz, CDCl 3 ,TMS):δ7.48-7.41(m,3H),7.27-7.26(m,5H), 7.03-7.01(m,2H),5.44(s,2H),4.08-4.00(m,4H),1.55 -1.49(m,4H),1.29-1.24(m,4H),0.84(t,J=10.0Hz,6H). 13 C NMR (125MHz, CDCl 3 ):δ142.9(d,J C-P =32.5 Hz), 136.1(d, J C-P=241.3Hz), 134.7, 130.1, 130.0, 128.9, 128.6, 128.4, 127.5, 125.8, 66.5 (d, J C-P =6.3Hz), 52.0, 32.2(d, J C-P =6.3Hz), 18.6, 13.5. 31 P NMR (160MHz, CDCl 3 ): δ7.5. HRMS (ESI) m / z calc...

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Abstract

The invention belongs to the technical field of organic synthesis, and provides a method for preparing 4-phosphoryl-1,4,5-tri-substituted 1,2,3-triazole in a water phase or biomedium. In the water phase or biomedium, under the action of a catalyst tetracarbonyl dichloride rhodium dimer [Rh(CO)2Cl]2, an alkynyl phosphate compound and nitrine are catalyzed to prepare the 4-phosphoryl-1,4,5-tri-substituted 1,2,3-triazole. The preparation method of the 4-phosphoryl-1,4,5-tri-substituted 1,2,3-triazole is mild in reaction conditions, and the product yield is not less than 71 percent. The reaction conditions of the preparation method are mild; water is used as a solvent, so that the method is environmentally friendly, high in reaction efficiency and more suitable for large-scale production requirements; the prepared 4-phosphoryl-1,4,5-tri-substituted 1,2,3-triazole compound has potential physiological activity.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis and relates to a method for preparing 4-phosphoryl-1,4,5-trisubstituted 1,2,3-triazole in aqueous phase or biological medium. Background technique [0002] The alkyne-azido cycloaddition reaction is one of the most important methods for the preparation of 1,2,3-triazoles. In recent years, a series of documents or patents have reported the preparation methods of 1,2,3-triazole compounds. [0003] Since the copper-catalyzed terminal alkyne-azido cycloaddition reaction was reported by the Medal research group and the Sharpless research group in 2001 (J.Org.Chem., 2002, 67, 3057 and Angew.Chem.Int.Ed., 2002,41, 2596), this reaction has received extensive research and attention. However, for copper-catalyzed alkyne-azido cycloaddition reactions, 4-phosphoryl-1,4,5-trisubstituted 1,2,3-triazoles and 5-phosphoryl-1 , a mixture of 4,5-trisubstituted 1,2,3-triazoles (ARKIVOC, 2012, 252). How ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/6518
Inventor 宋汪泽郑楠郑玉斌
Owner DALIAN UNIV OF TECH
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