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Microwave synthesis method for diarylamine compound

A diarylamine and microwave synthesis technology, applied in the chemical industry, can solve the problems of harsh reaction conditions, high price, instability, etc., and achieve the effects of convenient post-processing, short reaction time, and clean reaction

Inactive Publication Date: 2013-07-24
GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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AI Technical Summary

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

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Example 1: Preparation of methyl 3-anilino-4-hydroxybenzoate

[0021] Methyl 3-dehydroshikimate (1.02 g, 5.5 mmol), aniline (0.46 ml, 5.0 mmol), p-toluenesulfonic acid (0.01 g, 0.05 mmol), 5 ml N,N-dimethylformamide in one pass into the microwave reaction vial. The reaction system was reacted in a microwave reactor at 130 °C for 8 min. 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 a solid was precipitated, which was filtered off with suction. The solid was recrystallized from dichloromethane-petroleum ether to obtain white crystals 3-anilino-4-hydroxyl Methyl benzoate 1.14 g, 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=8.0Hz, 1H, 5...

Embodiment 2

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

[0023] 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 were added to the microwave reaction flask at one time middle. The reaction system was reacted in a microwave reactor at 140 °C for 8 min. The reaction was monitored by TLC. After the reaction was completed, after cooling, the reaction solution was poured into 80 ml of saturated brine, stirred continuously, a solid was precipitated, filtered with suction, and the solid was recrystallized from ethyl acetate-petroleum ether to obtain 1.03 g of a white solid. Yield: 80%. m.p.152~153℃. 1 H NMR (DMSO-d 6 , 400M Hz) δ: 10.45 (s, 1H, 4-OH), 7.66 (d, J=2.0 Hz, 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 (1.11 g, 6.0 mmol), p-methoxyaniline (0.62 g, 5.0 mmol), p-toluenesulfonic acid (0.05 g, 0.25 mmol), and 5 ml of diethylene glycol were added at one time in a microwave reaction vial. The reaction system was reacted in a microwave reactor at 170 °C for 5 min. The reaction was monitored by TLC. After the reaction was completed, after cooling, the reaction solution was poured into 80 ml of saturated brine, stirred continuously, a solid was precipitated, suction filtered, and dried. : 87%. m.p.153~154℃. 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 3 ); MS(EI): m / z=273 [M] + , 258[M-CH 3 ] + , 170, 156, 141, 129.

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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 structural types are widely found in biologically active molecules and pharmaceutical products. For example: Nitrothiocyanate (Amoscanate) is an isothiocyanate broad-spectrum helminth drug, which has obvious killing effect on schistosomiasis, and is one of the current treatment drugs for domestic animal schistosomiasis (Central South Pharmacy, 2003, 1 (5): 268-271). Carbamazepine is the first marketed benzodiazepine antiepileptic drug, which produces antiepileptic effects by activating peripheral benzodiazepine receptors and blocking sodium channels. It is mainly used for phenytoin, etc. It can also be used to relieve trigeminal neuralgia and glossopharyngeal neuralgia for grand mal and complex partial seizures that ar...

Claims

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Application Information

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Patent Type & Authority Applications(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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