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Preparation method of novel 4-phosphoryl-1, 4, 5-trisubstituted 1, 2, 3-triazole

A phosphoryl and tri-substituted technology, applied in the field of organic synthesis, can solve the problems such as no public reports on the preparation technology, and achieve the effects of high reaction efficiency and mild reaction conditions

Active Publication Date: 2018-09-21
DALIAN UNIV OF TECH
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  • Abstract
  • 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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  • Preparation method of novel 4-phosphoryl-1, 4, 5-trisubstituted 1, 2, 3-triazole
  • Preparation method of novel 4-phosphoryl-1, 4, 5-trisubstituted 1, 2, 3-triazole
  • Preparation method of novel 4-phosphoryl-1, 4, 5-trisubstituted 1, 2, 3-triazole

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

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

[0021] Under air, diethyl phenylethynyl phosphate (0.2mmol, 47.6mg) was dissolved in dichloromethane (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, 66mg of a yellow oily product was obtained by column chromatography, with a yield of 89%.

[0022]

[0023] 1 H NMR (500MHz, CDCl 3 ,TMS):δ7.48-7.47(m,1H),7.44-7.41(m,2H), 7.28-7.25(m,5H),7.03-7.01(m,2H),5.44(s,2H),4.16 -4.08(m,4H),1.21(t,J=7.5Hz,6H). 13 C NMR (125MHz, CDCl 3 ):δ143.0(d,J C-P =32.5Hz), 136.0(d, J C-P = 240.0Hz),134.7,130.0,129.9,128.8,128.6,128.4,127.6,125.7,62.8(d,J C-P =5.0 Hz), 52.0, 16.1(d, J C-P =6.3Hz). 31 P NMR (200MHz, CDCl 3 ):δ7.3.HRMS(ESI) m / z calcd for C 19 h 22 N 3 o 3 P(M+Na) + 394.1291,found 394.1297.

Embodiment 2

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

[0025] Under air, diethyl phenylethynyl phosphate (0.2mmol, 47.6mg) was dissolved in dichloromethane (2mL), then p-methylbenzyl azide (0.3mmol, 44.1mg) 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, 78mg of a yellow oily product was obtained by column chromatography, with a yield of 92%.

[0026]

[0027] 1 H NMR (500MHz, CDCl 3 ,TMS):δ7.49-7.42(m,3H),7.29-7.27(m,2H), 7.07(d,J=5.0Hz,2H),6.92(d,J=10.0Hz,2H),5.39( s,2H),4.13-4.06(m,4H), 2.30(s,3H),1.20(t,J=5.0Hz,6H). 13 C NMR (125MHz, CDCl 3 ):δ142.9(d,J C-P = 33.8Hz), 138.2, 135.9(d, J C-P =240.0Hz), 131.7, 130.1, 130.0, 129.5, 128.6, 127.6, 125.8, 62.8 (d, J C-P =5.0Hz), 51.8, 21.1, 16.1 (d, J C-P =6.3Hz). 31 P NMR (200MHz, CDCl 3 ): δ7.4. HRMS (ESI) m / z calcd for C 20 h 24 N 3 o 3 P(M+Na) + 408.1447, found 408.1454.

Embodiment 3

[0028] Example 3: Preparation of 4-diethyl phosphate-(1-p-chlorobenzyl)-5-phenyl-1H-1,2,3-triazole

[0029] Under air, diethyl phenylethynyl phosphate (0.2mmol, 47.6mg) was dissolved in dichloromethane (2mL), then p-chlorobenzyl azide (0.3mmol, 50.1mg) 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, 65.6mg of a yellow oily product was obtained by column chromatography, with a yield of 81%.

[0030]

[0031] 1 H NMR (400MHz, CDCl 3 ,TMS):δ7.51-7.44(m,3H),7.28-7.24(m,4H), 6.97(d,J=8.0Hz,2H),5.42(s,2H),4.15-4.08(m,4H ),1.22(t,J=8.0Hz,6H). 13 C NMR (125MHz, CDCl 3 ):δ143.0(d,J C-P =32.5Hz), 136.1(d, J C-P =240.0Hz), 134.5,133.1,130.3,129.8,129.1,128.7,125.5,115.4,63.0(d,J C-P =6.3Hz), 51.3, 16.1(d, J C-P =6.3Hz). 31P NMR (200MHz, CDCl 3 ):δ7.1.HRMS(ESI)m / z calcd for C 19 h 21 ClN 3 o 3 P(M+Na) + 408.1447,found408.1454.

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Abstract

The invention belongs to the technical field of organic synthesis, and provides a preparation method of novel 4-phosphoryl-1, 4, 5-trisubstituted 1, 2, 3-triazole. According to the preparation method,in an organic solvent, under the action of a tetracarbonyl rhodium dichloride dimer [Rh(CO)2Cl]2 catalyst, an alkynyl phosphate compound and azide are catalyzed to prepare the 4-phosphoryl-1, 4, 5-trisubstituted 1, 2, 3-triazole. By the preparation method of the 4-phosphoryl-1, 4, 5-trisubstituted 1, 2, 3-triazole product, provided by the invention, a reaction condition is mild and the product yield is not lower than 67%. With the preparation method, the reaction condition is mild and environmentally friendly, the reaction efficiency is high, a large-scale production requirement is met better, and the prepared 4-phosphoryl-1, 4, 5-trisubstituted 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 preparation method of a novel 4-phosphoryl-1,4,5-trisubstituted 1,2,3-triazole. 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 to change the regioselectivit...

Claims

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Application Information

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IPC IPC(8): C07F9/6518
Inventor 宋汪泽郑楠郑玉斌
Owner DALIAN UNIV OF TECH
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