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Method for preparing aryl alkyl amine compounds with 3-dehydrogenation methyl shikimate

A technology of arylalkylamine and acid methyl ester, which is applied in the field of preparation of arylalkylamine compounds, can solve the problems of low reactivity of alcohols and harsh reaction conditions, and achieve stable sources, mild reaction conditions, The effect of high yield

Inactive Publication Date: 2012-03-21
GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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  • Abstract
  • Description
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Problems solved by technology

Although the raw materials of this method are easy to obtain and can embody 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 Lu , Zou Jianping, Study on C-N Bond Formation Reaction Promoted by LPNM[J], Journal of Soochow University (Natural Science Edition), 2010, 26(2): 84-86)
There is no report on the preparation of arylalkylamines by non-aromatic compounds

Method used

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  • Method for preparing aryl alkyl amine compounds with 3-dehydrogenation methyl shikimate
  • Method for preparing aryl alkyl amine compounds with 3-dehydrogenation methyl shikimate
  • Method for preparing aryl alkyl amine compounds with 3-dehydrogenation methyl shikimate

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Experimental program
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Effect test

Embodiment 1

[0028] 3, Preparation of methyl 4-dihydroxy-5-methylaminobenzoate:

[0029] 3-Dehydroshikimate methyl ester (0.93g, 5.0mmol), methylamine (0.75ml, 5.0mmol), formic acid (9.36μl, 0.25mmol) in the reaction flask, add 20ml CH 3 OH, stirred and reacted at 20°C for 3h, and the reaction was complete as detected by TLC. After completion of the reaction, concentrate (remove CH 3 OH) to dryness, extracted with ethyl acetate, combined the organic layers, and added anhydrous MgSO 4 After drying and filtering, the filtrate was concentrated, and then recrystallized from ethyl acetate-petroleum ether to obtain 0.55 g of methyl 3,4-dihydroxy-5-methylaminobenzoate as a yellow solid, yield: 56%. m.p.163-164°C. 1 H NMR (DMSO-d 6 , 400MHz) δ: 6.84 (d, J = 2.0Hz, 1H, 2-ArH), 6.60 (d, J = 2.0Hz, 1H, 6-ArH), 3.74 (s, 3H, OCH 3 ), 2.69 (s, 3H, CH 3 ); MS(EI): m / z=197[M] + , 182[M-CH 3 ] + , 166, 154.

Embodiment 2

[0031] 3, Preparation of methyl 4-dihydroxy-5-ethylaminobenzoate:

[0032] Methyl 3-dehydroshikimate (0.93g, 5.0mmol), ethylamine (0.38ml, 6.0mmol), acetic acid (14.30μl, 0.25mmol) were added to a reaction flask, 20ml DMSO was added, and the reaction was stirred at 50°C for 2h. TLC detects that the reaction is complete. After the reaction is complete, cool to 25°C, concentrate (remove DMSO) to dryness, extract with ethyl acetate, combine the organic layers, add anhydrous MgSO to the organic layer 4 After drying and filtering, the filtrate was concentrated, and then recrystallized from ethyl acetate-petroleum ether to obtain 0.77 g of methyl 3,4-dihydroxy-5-ethylaminobenzoate as a white solid, yield: 73%. m.p.180~182℃. 1 H NMR (DMSO-d 6 , 400MHz) δ: 6.84 (d, J=1.6Hz, 1H, 2-ArH), 6.66 (d, J=1.6Hz, 1H, 6-ArH), 3.73 (s, 3H, OCH 3 ), 3.07 (q, 2H, CH 2 ), 1.15(t,J 1 =7.2Hz,J 2 =6.8Hz, 3H, CH 3 ); MS(EI): m / z=211[M] + , 196[M-CH 3 ] + , 180, 164.

Embodiment 3

[0034] 3, the preparation of 4-dihydroxy-5-n-propylaminobenzoic acid methyl ester:

[0035] 3-Dehydroshikimate methyl ester (0.93g, 5.0mmol), n-propylamine (0.45ml, 5.5mmol), p-toluenesulfonic acid (0.01g, 0.05mmol) in a reaction flask, add 20ml t-BuOH, 30 ℃ The reaction was stirred for 4 h, and the reaction was complete as detected by TLC. After the reaction is complete, cool to 25°C, concentrate (remove t-BuOH) to dryness, extract with ethyl acetate, combine the organic layers, add anhydrous MgSO to the organic layer 4 After drying and filtering, the filtrate was concentrated, and then recrystallized from ethyl acetate-petroleum ether to obtain 0.71 g of gray-green solid methyl 3,4-dihydroxy-5-n-propylaminobenzoate, yield: 63%. m.p.159~160℃. 1 H NMR (DMSO-d 6 , 400MHz) δ: 9.34(s, 1H, OH), 6.83(d, J=1.6Hz, 1H, 2-ArH), 6.65(d, J=1.6Hz, 1H, 6-ArH), 3.73(s, 3H, OCH 3 ), 2.99(t,J 1 =6.8Hz,J 2 =7.2Hz, 2H, CH 2 ), 1.56 (m, 2H, CH 2 ), 0.91(t,J 1 =7.6Hz,J 2 =7.2Hz, 3H, CH...

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Abstract

The invention relates to a method for preparing aryl alkyl amine compounds with 3-dehydrogenation methyl shikimate, in particular to a method for preparing 3,4-dyhydroxy-5-alkyl amino methyl benzoate compounds. The method includes steps of enabling 3-dehydrogenation methyl shikimate and aryl primary amine compounds to give a condensation-dehydrogenation reaction by means of catalysis of acid catalyst under the normal pressure and mixing conditions so that a six-membered ring framework gives an aromatization reaction, and then obtaining the 3,4-dyhydroxy-5-alkyl amino methyl benzoate compounds after the reacted mixture is concentrated, extracted, dried, filtered and recrystallized. The reaction is carried out for two to six hours at the temperature ranging from 20 DEG C to 50 DEG C. The method utilizes 3-dehydrogenation shikimic acid compounds which are renewable resources as raw materials, thereby having the advantages of fine atom economy, simplicity in operation, mild condition, high yield, low cost, less pollution and the like and being capable of realizing sustainable development.

Description

technical field [0001] The invention relates to the field of chemical industry, and relates to a method for preparing arylalkylamine compounds, in particular to preparing 3,4-dihydroxy-5-alkylaminobenzoic acid methyl esters from 3-dehydroshikimate methyl esters synthetic method. Background technique [0002] Arylalkylamines are important intermediates in organic synthesis and are widely used in the fields of medicine, pesticides, dyes and functional materials. For example: Bumetanide (Bumetanide) is a powerful loop diuretic, and its diuretic effect is 40 to 60 times that of furosemide (furosemide). Clinically, it is mainly used for various cardiogenic, hepatic, renal and nutritional edema, and also for patients with drug poisoning requiring forced diuresis and edema (including venous obstructive edema) and effusion in chest, abdomen, pericardium and other body cavities (Tang Weigao, Peng Chongying, Synthesis of Bumetanide [J], West China Pharmaceutical Journal, 1994, 9(1):...

Claims

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Application Information

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IPC IPC(8): C07C229/64C07C227/08
Inventor 邹永吴伟陈煜魏文黄桐堃吕泽良
Owner GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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