Method for preparing diaryl amine compound from 3-methyl dehydroshikimate

A technology of diarylamine and methyl acid is applied in the preparation of organic compounds, preparation of sulfonic acid amides, chemical instruments and methods, etc., and can solve the problems of increased cost and operational difficulty, harsh reaction conditions, and low reactivity, etc. To achieve the effect of stable source, mild reaction conditions and high yield

Inactive Publication Date: 2014-07-02
GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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  • Abstract
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Problems solved by technology

Although the raw materials used in this method are easy to get and can reflect the concept of green chemistry, because the reactivity of alcohols is not high and the reaction conditions are relatively harsh, complexes of transition metals such as Ru, Ir, and Re are often required to catalyze (Mao Haifeng, Wang et al. Lu, Zou Jianping, Research on C-N bond formation reaction promoted by LPNM [J], Journal of Soochow University (Natural Science Edition), 2010, 26(2): 84-86), which increases the cost and operation difficulty
At present, there is no report on the preparation of diarylamines from non-aromatic natural compounds.

Method used

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  • Method for preparing diaryl amine compound from 3-methyl dehydroshikimate
  • Method for preparing diaryl amine compound from 3-methyl dehydroshikimate
  • Method for preparing diaryl amine compound from 3-methyl dehydroshikimate

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Experimental program
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Effect test

Embodiment 1

[0028] Preparation of 3-anilino-4-hydroxybenzoic acid methyl ester:

[0029] 3-Dehydroshikimate methyl ester (0.93g, 5.0mmol), aniline (0.50ml, 5.5mmol), p-toluenesulfonic acid (0.05g, 0.25mmol) in the reaction flask, add 20ml CH 3 OH, the oil bath was heated to 60° C. and stirred for 6 h, and the reaction was complete as detected by TLC. After completion of the reaction, cool to 25°C, concentrate (remove CH 3 OH) to dryness, extracted with ethyl acetate to obtain an organic layer, anhydrous MgSO was added to the organic layer 4 After drying, after filtration, the filtrate was concentrated, and then recrystallized from ethyl acetate-petroleum ether to obtain 1.12 g of white needle-like crystals of methyl 3-anilino-4-hydroxybenzoate, yield: 92%. 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....

Embodiment 2

[0031] Preparation of 3-(4'-methylanilino)-4-hydroxybenzoic acid methyl ester:

[0032]Methyl 3-dehydroshikimate (0.93g, 5.0mmol), p-toluidine (0.59g, 5.5mmol), and formic acid (9.36μl, 0.25mmol) were placed in a reaction flask, and 20ml of DMSO was added. The oil bath was heated to 80° C. and stirred for 6 h, and TLC detected that the reaction was complete. After the reaction is complete, cool to 25°C, concentrate (remove DMSO) to dryness, extract with ethyl acetate to obtain an organic layer, add anhydrous MgSO to the organic layer 4 After drying, after filtration, the filtrate was concentrated, and then recrystallized with ethanol-chloroform to obtain 1.14 g of white solid 3-(4'-methylanilino)-4-hydroxybenzoic acid methyl ester, yield: 89%. m.p.152-153°C. 1 H NMR (DMSO-d 6 , 400MHz) 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), 6.8...

Embodiment 3

[0034] Preparation of 3-(4'-methoxyanilino)-4-hydroxybenzoic acid methyl ester:

[0035] Methyl 3-dehydroshikimate (0.93g, 5.0mmol), p-methoxyaniline (0.62g, 5.0mmol), and acetic acid (14.30μl, 0.25mmol) were placed in a reaction flask, and 20ml of DMF was added. The oil bath was heated to 70° C. and the reaction was stirred for 6 h, and the reaction was complete as detected by TLC. After the reaction is complete, cool to 25°C, concentrate (remove DMF) to dryness, extract with ethyl acetate to obtain an organic layer, add anhydrous MgSO to the organic layer 4 After drying, after filtering, the filtrate was concentrated, and then recrystallized with ethyl acetate-chloroform to obtain 1.16 g of gray-green solid 3-(4'-methoxyanilino)-4-hydroxybenzoic acid methyl ester, yield: 85 %. 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...

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Abstract

The invention relates to a method for preparing diaryl amine compound, in particular 3-arylamine-4-hydroxyl methyl benzoate compound, from 3-methyl dehydroshikimate, which comprises the following steps: carrying out a condensation-dehydration reaction on the 3-methyl dehydroshikimate and aryl primary amine compound under the catalysis of a Lewis acid catalyst in normal pressure and agitation conditions, so that a hexatomic ring skeleton generates aromatization, wherein the reaction temperature is 20-80 DEG C, and the reaction time is 6-18 hours; and concentrating, extracting, drying, filtering and recrystallizing a reaction mixture to obtain the 3-arylamine-4-hydroxyl methyl benzoate compound. By using the method, renewable resource 3-dehydroshikimic acid compound is used as a raw material; the method has the advantages of good atom economy, simpleness in operation, moderate condition, high yield, low cost, less pollution and the like; and the sustainable development can be achieved.

Description

technical field [0001] The invention belongs to the field of chemical industry, and relates to a method for preparing diarylamine compounds, in particular to a method for preparing 3-arylamino-4-hydroxybenzoic acid methyl ester compounds from 3-dehydroshikimate methyl ester . Background technique [0002] Diarylamine compounds are important intermediates in organic synthesis and are widely used in the fields of medicine, pesticides, dyes and functional materials. For example: Diclofenac (Diclofenac) is a non-steroidal anti-inflammatory drug, which has strong anti-rheumatic, anti-inflammatory, analgesic and antipyretic effects, and is often used in the treatment of acute or chronic rheumatoid arthritis, osteoarthritis, trauma and Postoperative inflammatory pain, etc. (Benchi, Research Progress of Diclofenac Preparations [J], Modern Journal of Integrated Traditional Chinese and Western Medicine, 2010, 19(23): 2983-2985). Mefenamic acid is also a non-steroidal antipyretic ana...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B43/04C07C227/06C07C229/64C07C303/40C07C311/39
Inventor 邹永吴伟魏文陈煜吕泽良黄桐堃
Owner GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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