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Preparation method for N-arylazoles compounds

A technology of azole compounds and compounds, applied in the field of compound preparation, can solve the problems of only 69% yield, low yield, and narrow scope of substrate application, and achieve the effects of low price, simple operation, and easy industrial production

Inactive Publication Date: 2008-09-10
ZHEJIANG UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

People use 0.1 equiv of [Cu(OH)TMEDA] 2 Cl 2 As a catalyst, the N-phenylation reaction of benzopyrazole was carried out at 50°C in DMF, but the yield was only 69% (Lam, P.Y.S.; Deudon, S.; Averill, K.M.; Li, R.; He , M.Y.; DeShong, P.; Clark, C.G.J.Am.Chem.Soc.2000, 122, 7600)
Recently it was reported that a catalytic amount of Cu / FeCl 3 As a co-catalyst, the reaction of silicon reagent and nitrogen-containing heterocyclic compound is not high, but the yield of most of the reactions is not high, and the scope of application of the substrate is also very narrow (Song, R.-J.; Deng, C.-L. ; Xie, Y.-X; Li, J.-H. Tetrahedron Lett., 2007, 48, 7845.)

Method used

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  • Preparation method for N-arylazoles compounds

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Cu was added sequentially to a 25mL single-neck round bottom flask 2 O (4 mg, 5 mol%), 2,2'-bipyridine (8 mg, 10 mol%), methanol (3 mL), TBAF (1.0 mmol) in THF (1 M, 1 mL), phenyltrimethoxysilane (1 mmol) and Benzimidazole (0.5mmol), connected to a condensing reflux tube at the bottle mouth, placed the device in a 50°C oil bath, stirred magnetically, reacted for 12h, removed the solvent under reduced pressure, and carried out column separation with petroleum ether / ethyl acetate to obtain the product , NMR to determine the structure. Yield was 99%.

[0020] 1 H NMR (400MHz, CDCl 3 , TMS)δ8.04(s, 1H), 7.86-7.88(d, 1H, J=7.2Hz), 7.44-7.49(m, 3H), 7.35-7.39(m, 3H), 7.23-7.31(m, 2H). MS (EI): m / z (%): 194(100) [M + ], 193(24)[M + -1].

Embodiment 2

[0022] Cu was added sequentially to a 25mL single-neck round bottom flask 2 O (4 mg, 5 mol%), 2,2'-bipyridine (8 mg, 10 mol%), methanol (4 mL), TBAF (1.0 mmol) in THF (1 M, 1 mL), phenyltrimethoxysilane (1 mmol) and 5,6-Dimethylbenzimidazole (0.5mmol), connect the condensing reflux tube to the bottle mouth, place the device in a 50°C oil bath, stir magnetically, react for 24h, remove the solvent under reduced pressure, use petroleum ether / ethyl acetate The ester was subjected to column separation to obtain the product, and the structure was determined by NMR. Yield was 89%.

[0023] 1 H NMR (400MHz, CDCl 3 , TMS)δ8.00(s, 1H), 7.63(s, 1H), 7.53-7.57(t, 2H), 7.41-7.49(m, 3H), 7.31(s, 1H), 2.39(s, 3H) , 2.37 (s, 3H). MS (EI): m / z (%): 222 (100) [M + ], 221(51)[M + -1], 207(55), 77(7).

Embodiment 3

[0025] Cu was added sequentially to a 25mL single-neck round bottom flask 2 O (7 mg, 5 mol%), 2,2'-bipyridine (16 mg, 10 mol%), methanol (6 mL), TBAF (2.0 mmol) in THF (1 M, 2 mL), phenyltrimethoxysilane (2 mmol) and Imidazole (1.0 mmol), connected to a condensing reflux tube at the bottle mouth, placed the device in a 50°C oil bath, stirred magnetically, reacted for 12 h, removed the solvent under reduced pressure, and carried out column separation with petroleum ether / ethyl acetate to obtain the product. NMR Determine the structure. Yield was 98%.

[0026] 1 H NMR (400MHz, CDCl 3 , TMS)δ7.86(s, 1H), 7.46-7.49(t, 2H), 7.36-7.39(t, 3H), 7.27(s, 1H), 7.21(s, 1H). MS(EI): m / z(%): 144(100)[M + ], 117(43), 90(31), 77(23), 51(10).

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Abstract

The invention discloses a preparation method for an N-aryl azole compound. 0.5 mmol of azole compound, 1 to 2 mmol of aryl siloxane, 1 to 2ml of tetrahydrofuran solution (1M) of tetrabutylammonium fluoride (TBAF), 5 to 10 mol percent of cuprous oxide, and 10 to 20 mol percent of 2, 2-bipyridyl are added with 3 to 6 ml of methanol in a reactor, are made a magnetic stirring, and are reacted for 12 to 48 hours in the air with the temperature of 25 to 50 DEG C, the solvent is dried, and the product is obtained through the silica gel column chromatography. The preparation method has the advantages that: 1) the reaction conditions are mild, the reaction can be finished within 12 to 48 hours in the methanol with the temperature of 25 to 50 DEG C, and the yield is high. 2) the reaction is made in the air, is steady to the water and the air, and does not need the water-free oxygen-free operation; the methanol is taken as the solvent, has low boiling point, is easy to handle and has simple and convenient operation. 3) catalyst and ligand are economic and easily obtained. 4) reaction raw material, aryl siloxane, has low cost, and the industrial production is easily realized.

Description

technical field [0001] The present invention relates to a preparation method of a compound, in particular to a preparation method of an N-arylazole compound. Background technique [0002] N-arylazole compounds are one of the most common structural components in natural products, have a variety of important physiological activities, are widely used, and have great development and utilization value in medicine and pesticides. [0003] Copper-catalyzed N-arylation of nitrogen-containing heterocyclic compounds is a very efficient method for the synthesis of such compounds (Ley, S.V.; Thomas, A.W. Angew. Chem., Int. Ed. 2003, 42, 5400.). Halogenated hydrocarbons and organometallic reagents (including lead reagents, bismuth reagents, iodonium salts, tin reagents, boron reagents, silicon reagents, etc.) can be used for C-N coupling. The conditions of the halogenated hydrocarbon reaction usually require the participation of a strong base, the reaction temperature is high (80-160 ° ...

Claims

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Application Information

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IPC IPC(8): C07D235/04C07D233/58C07D233/68C07D249/08C07D231/12C07B37/04
Inventor 时圣银张玉红赵金龙
Owner ZHEJIANG UNIV
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