Microwave synthesis method for diarylamine compound

A technology for diarylamine and microwave synthesis is applied in the chemical industry, which can solve the problems of harsh reaction conditions, high price, instability and the like, and achieves the effects of convenient post-processing, short reaction time and simple operation.

Inactive Publication Date: 2015-05-13
GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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Problems solved by technology

[0004] At present, the preparation methods of diarylamine compounds mainly contain the following: (1) cross-coupling reaction (Buchwald-Hartwig reaction) between palladium-catalyzed arylamine and aryl halide, but this type of method exists Catalysts are highly toxic, expensive, difficult to obtain some aryl halides, and need to use highly toxic and unstable organic phosphine ligands, etc. (Chemical Reagents, 2008, 30(10): 781-783)
(2) Copper-catalyzed Ullmann cross-coupling reaction between arylamine and aryl halide, but the reaction conditions of this type of method are relatively harsh, requiring higher reaction temperature (100-200°C), excessive Cu powder, Participation of strong bases and highly polar and toxic solvents (Organic Chemistry, 2010, 30(2): 181-199)

Method used

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  • Microwave synthesis method for diarylamine compound
  • Microwave synthesis method for diarylamine compound

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Experimental program
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Effect test

Embodiment 1

[0020] Embodiment 1: Preparation of 3-anilino-4-hydroxybenzoic acid methyl ester

[0021] Methyl 3-dehydroshikimate (1.02g, 5.5mmol), aniline (0.46ml, 5.0mmol), p-toluenesulfonic acid (0.01g, 0.05mmol), and 5ml N,N-dimethylformamide were used in one go Add to microwave reaction vial. The reaction system was reacted at 130° C. for 8 min in a microwave reactor. The reaction was monitored by TLC. After the reaction was completed, after cooling, the reaction solution was poured into 80ml of saturated saline solution, stirred continuously, and a solid was precipitated, filtered by suction, and the solid was recrystallized with dichloromethane-petroleum ether to obtain a white crystal 3-anilino-4-hydroxyl Methyl benzoate 1.14g, yield: 94%. m.p.160~162℃. 1 H NMR (DMSO-d 6 , 400MHz) δ: 10.48 (s, 1H, 4-OH), 7.74 (d, J=2.0Hz, 1H, 2-ArH), 7.40 (dd, J 1 =8.0Hz,J 2 =2.0Hz, 1H, 6-ArH), 7.37(s, 1H, NH), 7.22(t, J=7.6Hz, 2H, 3', 5'-ArH), 7.04(d, J=7.6Hz, 2H , 2′, 6′-ArH), 6.91 (d, J=8....

Embodiment 2

[0022] Example 2: Methyl 3-(4'-methylanilino)-4-hydroxybenzoate

[0023] Add methyl 3-dehydroshikimate (0.93g, 5.0mmol), p-toluidine (0.54g, 5.0mmol), p-toluenesulfonic acid (0.05g, 0.25mmol), and 5ml of ethylene glycol into the microwave reaction flask at one time middle. The reaction system was reacted at 140° C. for 8 minutes in a microwave reactor. The reaction was monitored by TLC. After the reaction was completed, after cooling, the reaction solution was poured into 80 ml of saturated brine, and stirred continuously, and a solid was precipitated, filtered by suction, and the solid was recrystallized with ethyl acetate-petroleum ether to obtain 1.03 g of a white solid. Yield: 80%. m.p.152-153°C. 1 H NMR (DMSO-d 6 , 400M Hz) δ: 10.45 (s, 1H, 4-OH), 7.66 (d, J=2.0Hz, 1H, 2-ArH), 7.34 (dd, J 1 =8.4Hz,J 2 =2.0Hz, 1H, 6-ArH), 7.18(s, 1H, NH), 7.05(d, J=8.4Hz, 2H, 2', 6'-ArH), 6.98(d, J=8.4Hz, 2H , 3′, 5′-ArH), 6.88 (d, J=8.4Hz, 1H, 5-ArH), 3.73 (s, 3H, OCH 3 ), 2.22 (s...

Embodiment 3

[0024] Example 3: Methyl 3-(4'-methoxyanilino)-4-hydroxybenzoate

[0025] Methyl 3-dehydroshikimate (1.11g, 6.0mmol), p-methoxyaniline (0.62g, 5.0mmol), p-toluenesulfonic acid (0.05g, 0.25mmol), and 5ml of diethylene glycol were added all at once microwave reaction vial. The reaction system was reacted at 170° C. for 5 min in a microwave reactor. The reaction was monitored by TLC. After the reaction was completed, after cooling, the reaction solution was poured into 80ml of saturated brine, stirred continuously, and the solid was precipitated, filtered by suction, and dried. The solid was recrystallized with ethyl acetate-petroleum ether to obtain 1.19g of a gray-green solid. The yield : 87%. m.p.153-154°C. 1 H NMR (DMSO-d 6 , 400MHz) δ: 10.42 (s, 1H, 4-OH), 7.51 (d, J=2.0Hz, 1H, 2-ArH), 7.28 (dd, J 1 =8.0Hz,J 2 =2.0Hz, 1H, 6-ArH), 7.06(d, J=6.8Hz, 2H, 3', 5'-ArH), 6.88(d, J=8.0Hz, 1H, 5-ArH), 6.85(d , J=6.8Hz, 2H, 2', 6'-ArH), 3.72(s, 3H, COOCH 3 ), 3.71 (s, 3H, OCH ...

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Abstract

The invention discloses a microwave synthesis method for a diarylamine compound. The method comprises the following steps of: subjecting 3-methyl dehydroshikimic acid and a primary arylamine compound to a condensation reaction, an isomerization reaction and a dehydration reaction under the action of an organic solvent, a catalyst and microwaves to enable a hexatomic ring framework to be aromatized; and then, cooling a reaction liquid, pouring the reaction liquid into saturated brine, rapidly stirring the solution, separating out a solid, and carrying out suction filtration, drying and recrystallization to obtain a 3-amido-4-hydroxybenzoic acid methyl ester compound. The raw material 3-methyl dehydroshikimic acid adopted in the method is a non-aromatic compound and can be prepared from shikimic acid by using a simple and convenient method without depending on fossil resources; sustainable exploitation and utilization can be realized; in addition, the microwave synthesis method adopts a microwave method which is short in reaction time, simple and convenient in operation, convenient in after-treatment and high in yield; and the microwave synthesis method is clean in reaction, friendly to the environment and low in energy consumption.

Description

technical field [0001] The invention relates to the field of chemical industry, in particular to a method for synthesizing diarylamine compounds by microwave. Background technique [0002] Diarylamines are an important class of organic compounds, and related structures are widely found in bioactive molecules and pharmaceutical products. For example: nitrate cyanamide (Amoscanate) is a kind of isothiocyanate broad-spectrum helminth medicine, and it has obvious killing effect to schistosomiasis, is one of the treatment medicine of domestic animal schistosomiasis at present (Zhongnan Pharmacy, 2003, 1 (5): 268-271). Carbamazepine is the first listed benzodiazepine antiepileptic drug, which produces antiepileptic effect by activating peripheral benzodiazepine receptors and blocking sodium channels. Grand mal seizures and complex partial seizures that are difficult to control with other drugs can also be used to relieve trigeminal neuralgia and glossopharyngeal neuralgia (Journ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C229/64C07C227/00
Inventor 邹永张恩生徐田龙魏文黄桐堃黄琦
Owner GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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