Aryl pyrimidine ortho-single halogen substituted compound and synthetic method thereof

A technology for arylpyrimidines and compounds, which is applied in the field of arylpyrimidine ortho-halogen substitution compounds and their synthesis, can solve the problems of harsh reaction conditions, large limitations, and high toxicity of halogenated reagents, and achieve high reaction selectivity, The effect of environmental protection and simple operation

Inactive Publication Date: 2009-11-25
SHANGHAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0022] In summary, there are many methods for preparing aryl halides, but the regioselectivity of these reactions is not easy to control, and it is difficult to obtain monohalogenated products with high regioselectivity.
In some reactions, the reaction raw materials are relatively limited, the halogenation reagents are more toxic and easy to cause environmental pollution, and the yield of some reactions is relatively low or the reaction conditions are relatively harsh, etc.

Method used

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  • Aryl pyrimidine ortho-single halogen substituted compound and synthetic method thereof
  • Aryl pyrimidine ortho-single halogen substituted compound and synthetic method thereof
  • Aryl pyrimidine ortho-single halogen substituted compound and synthetic method thereof

Examples

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Embodiment 1

[0046] Example 1: Preparation of 2-(2-chloro-4-ethoxycarbonylphenyl)pyrimidine

[0047] 2-(2-chloro-4-ethoxycarbonylphenyl) pyrimidine adopts the following steps: 1. add 1 gram of 2-(4-ethoxycarbonylphenyl) pyrimidine, 500 mg of palladium acetate in a 250 ml round bottom flask, 16 grams of additive copper trifluoroacetate, 30 grams of calcium chloride, 100 milliliters of acetic acid, heated to 80 ° C. Track the reaction with thin-layer chromatography until the reaction raw material 2-(4-ethoxycarbonylphenyl)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 acetic acid Extract the product with ethyl ester, and remove the solvent with a rotary evaporator after drying to obtain a crude product; ③The crude product is purified by column chromatography (petroleum ether:ethyl acetate=15:1) to obtain 10.2 grams of 2-(2-chloro-4 -ethoxycarbonylphenyl)pyrimidine in 89% ...

Embodiment 2

[0053] Embodiment two: the method of 2-(2-chloro-4-trifluoromethylphenyl) pyrimidine

[0054] 2-(2-chloro-4-trifluoromethylphenyl) pyrimidine adopts the following steps: 1. add 1 gram of 2-(-4-trifluoromethylphenyl) pyrimidine in a 250 ml round bottom flask, 500 mg Palladium acetate, 15 grams of additive copper trifluoroacetate, 32 grams of calcium chloride, 100 milliliters of acetic acid, heated to 80 ° C, follow the reaction with thin layer chromatography, to the reaction raw material 2-(-4-trifluoromethylphenyl ) pyrimidine disappears; 2. After the reaction is finished, remove the solvent with a rotary evaporator, add saturated sodium bicarbonate solution to the system, extract the product with ethyl acetate, remove the solvent with a rotary evaporator after drying, and obtain a crude product; 3. Use a rotary evaporator for the crude product Purification by column chromatography (petroleum ether: ethyl acetate = 10:1) gave 10.3 g of 2-(2-chloro-4-trifluoromethylphenyl)pyrim...

Embodiment 3

[0061] Embodiment three: the preparation of 2-(2,4-dichlorophenyl) pyrimidine

[0062] 2-(2,4-dichlorophenyl) pyrimidine adopts the following steps: 1. add 10 grams of 2-(4-chlorophenyl) pyrimidine, 300 mg of palladium acetate, 15 grams of additive trifluoro Copper acetate, 26 grams of calcium chloride, 100 milliliters of acetic acid, heated to 80 ° C, followed by thin-layer chromatography until the reaction raw material 2-(4-chlorophenyl) pyrimidine disappeared; ② after the reaction, use rotary evaporation Remove the solvent with an instrument, add saturated sodium bicarbonate solution to the system, extract the product with ethyl acetate, and remove the solvent with a rotary evaporator after drying to obtain a crude product; ③The crude product is subjected to column chromatography (petroleum ether: ethyl acetate=20 : 1) purification to obtain 11.4 g of 2-(2,4-dichlorophenyl)pyrimidine with a yield of 96%.

[0063] IR (KBr, cm -1 ): 3059, 3038, 1587, 1566, 1479, 1438, 1415,...

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Abstract

The invention relates to an aryl pyrimidine ortho-single halogen substituted compound and a synthetic method thereof. The structural formula of the compound is R1=o-Me, m-Me, m-OMe, p-Me, p-Cl, p-COOEt, p-CF3R2=H, 4-Ph, 5-PhX=Cl, Br. The method has specific steps of dissolving aryl pyrimidine, palladium acetate, additive and calcium halide in acetic acid or mixture of acetic acid and acetic anhydride, stirring to react until the raw materials disappear; removing the solvent, adding in saturated sodium bicarbonate solution, extracting the product with ethyl acetate, drying organic phase, obtaining crude product after removing the solvent; and passivating the crude product, thus obtaining the corresponding aryl pyrimidine ortho-single halogen substituted compound. The aryl pyrimidine ortho-single halogen substituted compound is an important organically synthesized intermediate. The invention has easily obtained raw materials, high reaction selectivity, and cheap calcium chloride and calcium bromide as halogen sources. During reaction, the invention uses routine solvent, has simple operation, mild condition, environment-friendly reaction, and reaction yield up to 95%, and is very suitable for industrial production.

Description

technical field [0001] The invention relates to an aryl pyrimidine and a synthesis method thereof, in particular to an ortho-position monohalogen substitution compound of an aryl pyrimidine and a synthesis 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-l of the sponge body is an antibacterial drug; 14-debromoprearaplysillin extracted from the sponge body Druinella purpurea and polybrominated phenols extracted from the sponge body Dysidea also have bactericidal effects; The terpene Solenolide E has anti-inflammatory and antiviral effects. The chlorinated compounds Teico...

Claims

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Application Information

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IPC IPC(8): C07D239/26B01J31/04
Inventor 许斌宋炳瑞郑晓建
Owner SHANGHAI UNIV
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