Ortho-position dihalogen substitution compound of aryl pyrimidine and preparing method thereof

A technology for arylpyrimidines and compounds, which is applied to the ortho-dihalogenated compounds of arylpyrimidines and their preparation fields, can solve the problems of harshness, large limitations, and low reaction yields, and achieves mild conditions, environment-friendly reaction, and operation. simple effect

Inactive Publication Date: 2010-02-24
SHANGHAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0015] In summary, there are many methods for preparing aryl ortho-dihalides, but the regioselectivity of these reactions is not easy to control, and it is difficult to obtain a single ortho-dihalide product
In some reactions, the reaction raw materials are limited, the reaction yield is low, the reaction reagents are expensive, and the reaction conditions are relatively harsh, etc.

Method used

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  • Ortho-position dihalogen substitution compound of aryl pyrimidine and preparing method thereof
  • Ortho-position dihalogen substitution compound of aryl pyrimidine and preparing method thereof
  • Ortho-position dihalogen substitution compound of aryl pyrimidine and preparing method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Example 1: Preparation of 2-(2,6-dichlorophenyl)pyrimidine

[0041] 2-(2,6-dichlorophenyl)pyrimidine adopts the following steps: 1. add 10 grams of 2-phenylpyrimidine, 250 milligrams of palladium acetate, 22 grams of additive copper trifluoroacetate, and 35 grams of Calcium chloride, 150ml acetic acid, heated to 80°C. Use thin layer chromatography to track the reaction until the reaction raw material 2-phenylpyrimidine disappears; ② After the reaction, remove the solvent with a rotary evaporator, add saturated sodium bicarbonate solution to the system, extract the product with ethyl acetate, and dry Remove the solvent with a rotary evaporator to obtain a crude product; ③ the crude product is purified by column chromatography (petroleum ether: ethyl acetate=20: 1) to obtain 14.4 grams of 2-(2,6-dichlorophenyl) pyrimidine, producing The rate is 96%. Melting point: 130-132°C.

[0042] IR (KBr, cm -1 ): 3044, 1587, 1562, 1466, 1430, 1406, 780.

[0043] 1 H NMR (CDCl ...

Embodiment 2

[0045] Example 2: Preparation of 2-(2,6-dichloro-4-methylphenyl)pyrimidine

[0046] 2-(2,6-dichloro-4-methylphenyl) pyrimidine adopts the following steps: 1. add 10 grams of 2-(4-methylphenyl) pyrimidine, 370 mg of palladium acetate in a 250 ml round bottom flask , 17 grams of additive copper trifluoroacetate, 30 grams of calcium chloride, 150 milliliters of acetic acid, heated to 80 ° C. Track the reaction with thin-layer chromatography until the reaction raw material 2-(4-methylphenyl)pyrimidine disappears; 2. After the reaction is finished, remove the solvent with a rotary evaporator, add saturated sodium bicarbonate solution to the system, and use ethyl acetate Ester extraction product, after drying, remove the solvent with a rotary evaporator to obtain a crude product; ③The crude product is purified by column chromatography (petroleum ether:ethyl acetate=20:1) to obtain 13.6 grams of 2-(2,6-dichloro -4-methylphenyl)pyrimidine, the yield was 97%. Melting point: 117-119°C...

Embodiment 3

[0050] Example Three: Preparation of 2-(2,6-dibromo-4-methylphenyl)pyrimidine

[0051] 2-(2,6-dibromo-4-methylphenyl) pyrimidine adopts the following steps: 1. add 10 grams of 2-(4-methylphenyl) pyrimidine, 500 mg of palladium acetate in a 250 ml round bottom flask , 50 grams of additive copper trifluoroacetate, 70 grams of calcium bromide, 150 milliliters of acetic acid, heated to 80 ° C, followed the reaction with thin-layer chromatography until the reaction raw material 2-(4-methylphenyl) pyrimidine disappeared; ② After the reaction was finished, remove the solvent with a rotary evaporator, add saturated sodium bicarbonate solution in the system, extract the product with ethyl acetate, remove the solvent with a rotary evaporator after drying, and obtain the crude product; ③ the crude product was analyzed by column chromatography (petroleum ether:ethyl acetate=20:1) to obtain 18.3 g of 2-(2,6-dibromo-4-methylphenyl)pyrimidine with a yield of 95%. Melting point: 142-144°C. ...

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Abstract

The invention relates to an ortho-position dihalogen substitution compound of aryl pyrimidine and a preparing method thereof. The compound has the following structural formula I: R1=H, p-Me, p-Cl, p-COOEt, p-CF3, m-Me, m-OMe, R2=H, 4-Ph, 5-Ph, X=Cl, Br. The invention comprises the following steps: dissolving aryl pyrimidine, palladium acetate, additive and halogenation calcium into acetic acid, stirring, and reacting until reaction raw material disappears; removing solvent, adding saturation sodium bicarbonate solution into a system, and extracting a product with ethyl acetate; obtaining a crude product by drying the organic phase and removing the solvent; purifying the product to obtain the corresponding ortho-position dihalogen substitution compound of aryl pyrimidine. The compound of the invention is a kind of important organic synthesis intermediate. The invention has easily obtained raw material, high reaction selectivity, and adopts calcium chloride and calcium bromide with low price as a halogen source, uses common solvent in reaction, and has simple operation, moderate reaction condition and environmentally friendly reaction, maximum reaction yield can reach 95%, so that the invention is very suitable for industrial production.

Description

technical field [0001] The invention relates to an aryl pyrimidine derivative and a preparation method thereof, in particular to an ortho-position dihalogen substituted compound of an aryl pyrimidine and a preparation method thereof. Background technique [0002] Halides widely exist in nature, especially in the ocean, where the chlorine content reaches 0.5M, the bromine content is about 0.1M, and the iodine content can reach 1μM. Due to their special biological activity, organic halides are also one of the sources of a wide range of drugs. For example, many halides are good antibacterial drugs, anti-inflammatory drugs and anti-tumor drugs. The metabolite Aeroplysinin-1 of the sponge body is an antibacterial drug; the 14-debromoprearaplysillin extracted from the sponge body Druinella purpurea, and the polybrominated phenol extracted from the sponge body Dysidea also have bactericidal effects; the diterpene extracted from the gorgonian coral Solenolide E has anti-inflammator...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D239/26
Inventor 许斌宋炳瑞郑晓建
Owner SHANGHAI UNIV
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