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Method for preparing epicatechol gallate and protocatechuic acid ester compounds from natural shikimic acid

A technology of gallate and shikimate, applied in the preparation of organic compounds, preparation of carboxylate, chemical instruments and methods, etc., to achieve the effects of low requirements for equipment, mild reaction conditions and simple operation

Inactive Publication Date: 2013-05-22
GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

There is no report on the preparation of gallate and protocatechuate compounds by non-aromatic compounds

Method used

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  • Method for preparing epicatechol gallate and protocatechuic acid ester compounds from natural shikimic acid
  • Method for preparing epicatechol gallate and protocatechuic acid ester compounds from natural shikimic acid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Step 1: Add shikimic acid (17.4g, 0.1mol) and anhydrous methanol (150mL, 3.7mol) in a 250mL three-necked round-bottomed flask, and gradually add chlorinated oxychloride dropwise under sufficient stirring to control the internal temperature of the reaction solution at 10°C Sulfone (15 mL, 0.2 mol). After the dropwise addition was completed, the internal temperature was controlled at 40° C., and the reaction was carried out for 3 hours. Concentrate to obtain a viscous liquid, which is recrystallized from ethyl acetate to obtain 14.76 g of white powdery solid methyl shikimate, yield: 78.5%. m.p.112~113℃. (c=0.2, MeOH); 1 H NMR (CD 3 COCD 3 , 400MHz) δ6.73(m, 1H, 2-H), 4.38(m, 1H, 3-H), 4.02(s, 1H, 4-OH D 2 O exchangeable), 4.00 (brs, 2H, 3, 5-OH D 2 O exchangeable), 3.69 (s, 3H, OCH 3 ), 3.85(m, 1H, 5-H), 3.68(m, 1H, 4-H), 2.64(dd, J 1 =17.6Hz,J 2 = 4.4Hz, 1H, 6α-H), 2.18(dd, J 1 =17.6Hz,J 2 =6.8Hz, 1H, 6β-H).MS(EI), m / z(%): 188(M + ), 170(M + -H 2 O), 157 (...

Embodiment 2

[0030] Step 1: Same as Example 1.

[0031] Step 2: Put methyl shikimate (7.52g, 40mmol), IBX (13.44g, 48mmol) and 160mL tetrahydrofuran into a reaction flask, heat to 67°C, and stir for 1h. Filtration and concentration gave a light yellow solid. Recrystallized from ethyl acetate-petroleum ether to obtain 3.84 g of white fine needle crystals of methyl 3-dehydroshikimate, yield: 51.6%.

[0032] Step 3: Methyl 3-dehydroshikimate (0.744 g, 4 mmol), Cu(OAc) 2 ·H 2 O (1.60g, 8mmol) and AcOH / H 2 O (2:1, V / V) 50mL was put into the reaction flask, heated to 50°C, and stirred for 26h. Filtration, concentration, extraction with ethyl acetate, combined organic layers were dried over anhydrous magnesium sulfate, concentrated, and then recrystallized with water to obtain 0.58 g of white solid methyl gallate, yield: 78%.

Embodiment 3

[0034] Step 1: Same as Example 1.

[0035] Step 2: Put methyl shikimate (7.52g, 40mmol), IBX (13.44g, 48mmol) and 160mL tetrahydrofuran into a reaction flask, heat to 50°C, and stir for 6h. Filtration and concentration gave a light yellow solid. Recrystallized from ethyl acetate-petroleum ether to obtain 4.17 g of white fine needle crystals of methyl 3-dehydroshikimate, yield: 56.0%.

[0036] Step 3: Methyl 3-dehydroshikimate (0.744g, 4mmol), ZnO (0.163g, 0.8mmol) and AcOH / H 2 50 mL of O (6:1, V / V) was put into the reaction flask, and heated to 50° C. for 16 h. Concentrate, extract with ethyl acetate, combine the organic layers, dry over anhydrous magnesium sulfate, concentrate, and recrystallize with water to obtain 0.61 g of methyl protocatechuate as a white solid, yield: 90.5%. m.p.134~135℃. 1 HNMR (CD 3 COCD 3 , 400MHz) δ8.50 (brs, 2H, 3, 4-OH), 7.48 (d, J=2.0, 1H, 2-H), 7.43 (dd, J 1 =8.0Hz,J 2 =2.0Hz, 1H, 6-ArH), 6.89(d, J 1 =8.4Hz, 1H, 5-ArH).MS(EI), m / z(%): 16...

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Abstract

The invention discloses a method for preparing epicatechol gallate and protocatechuic acid ester compounds from a natural shikimic acid. The method comprises the following steps of: performing an esterification reaction of the shikimic acid serving as a raw material to obtain shikimic acid ester; obtaining 3-dehydro-shikimic acid ester under the action of 2-iodyl benzoic acid; and realizing aromatization under the action of a catalyst to obtain epicatechol gallate or protocatechuic acid ester compound. A renewable raw material serves as a starting material and a polyhydroxy substituted benzoic acid is formed by a brand new method, so the method has the advantages of simpleness in operation, mild reaction condition, high yield, capacity of realizing sustainable development and the like.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for preparing gallate and protocatechin compounds from natural shikimic acid. Background technique [0002] Gallate (3,4,5-trihydroxybenzoate) and protocatechin (3,4-dihydroxybenzoate) compounds are important fine organic chemicals and pharmaceutical intermediates, widely Used in pharmaceutical, pesticide and food industries. For example: Propyl gallate has important biological activities such as excellent antioxidant, anticancer and antimutagenic properties, and can be used as an antioxidant additive for oils and foods, and an inhibitor of UV protection in cosmetics (Applied Chemistry, 2010 , 27, 328-332); methyl gallate can resist platelet aggregation, and has therapeutic effects on cardiovascular and cerebrovascular infarction, transient ischemia, allergy and asthma; The effect is obvious. Methyl gallate can also be used as photosensitive material, plant growth reg...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C69/84C07C67/31C07C67/30
Inventor 邹永陈煜魏文刘新伟杨少凡陈爱民吕泽良
Owner GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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