CN102010338A - Method for preparing epicatechol gallate and protocatechuic acid ester compounds from natural shikimic acid - Google Patents
Method for preparing epicatechol gallate and protocatechuic acid ester compounds from natural shikimic acid Download PDFInfo
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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
The present invention relates to the organic synthesis field, particularly a kind of method for preparing gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid.
Background technology
Gallic acid ester (3,4,5-trihydroxybenzoic acid ester) and Protocatechuic Acid ester (3,4-resorcylic acid ester) compounds are important Fine Organic Chemical product and medicine intermediates, are widely used in industries such as medicine, agricultural chemicals and food.As: Tenox PG has important biological such as excellent anti-oxidation characteristics, cancer resistance and antimutagenic, can be used as inhibitor of antiultraviolet in the antioxidant addn, makeup of grease and food etc. (applied chemistry, 2010,27,328-332); Methyl gallate energy platelet aggregation-against has therapeutic action to cardiovascular and cerebrovascularinfarction, transient ischemia, allergy and asthma etc.; Also have antivirus action, obvious to the simple scar rash of II-type effect.Methyl gallate also can be used as photochromics, plant-growth regulator, metallic material corrosion inhibitor, hair conditioner etc. (the Guizhou chemistry, 2002,27,12-13).The Protocatechuic Acid compounds is the effective active composition in salviamiltiorrhizabung, lotus, the Sharpleaf Galangal Fruit, have anti-oxidant, suppress growth of tumour cell and induce effect (biological chemistry and the biophysics progress of HL60 leukemia cell, HepG2 hepatoma cell apoptosis, 2008,35,1168-1174; Biosci.Biotechnol.Biochem., 2004,68,1221-1227), also can be used as medicine intermediate and foodstuff additive.
At present, the acquisition methods about gallic acid ester and Protocatechuic Acid ester compound mainly is to adopt plant extract (Chinese medicinal materials, 2006,29,1281-1282) or with the acid (being gallic acid and Protocatechuic Acid) of ready-made fragrant skeleton carry out esterification and make (Guizhou chemistry, 2002,27,12-13; Biosci.Biotechnol.Biochem., 2004,68,1221-1227).Still there is not at present the report for preparing gallic acid ester and Protocatechuic Acid ester compound by non-aromatic compounds.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, a kind of environmental friendliness, cost is low, technology is simply prepared gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid method are provided.
Purpose of the present invention is achieved through the following technical solutions:
A kind of method for preparing gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid; be to be raw material with natural shikimic acid; obtain shikimate through esterification; under the effect of 2-iodoxy phenylformic acid oxygenant, obtain 3-dehydrogenation shikimate then, under the effect of catalyzer, realize aromizing again, obtain gallic acid ester (3; 4; 5-trihydroxybenzoic acid ester) or Protocatechuic Acid ester (3,4-resorcylic acid ester) compounds, specifically comprise the steps:
(1) is raw material with shikimic acid (structural formula 1), under the effect of acylating reagent thionyl chloride,, obtains shikimate (structural formula 2) with alcohol generation esterification;
(2) described shikimate is dissolved in the organic solvent, under the oxygenant effect oxidative dehydrogenation takes place, and obtains 3-dehydrogenation shikimate (structural formula 3);
(3) described 3-dehydrogenation shikimate is dissolved in the reaction solvent, and under the effect of catalyzer, reacting by heating through separation and purification, obtains gallic acid ester or Protocatechuic Acid ester compound (structural formula 4).
In formula 2～formula 4, R
1Straight or branched alkane for C1～C6 is preferably CH
3, CH
2CH
3, CH
2CH
2CH
3, CH (CH
3)
2R
2, R
4Be H or OH, and R
2, R
4Be not H simultaneously; R
3Be OH.
In the step 1, described alcohol is the straight or branched alcohol of C1～C6, and alcohol both had been that reaction substrate is also as reaction solvent.The mol ratio of shikimic acid, thionyl chloride and alcohol is 1: (1～2): (20～50), preferred molar ratio are 1: 1.5: 40.
In the step 2, the temperature of reaction of oxydehydrogenation is 0～65 ℃, and the reaction times is 0.5～15 hour.Described organic solvent is one or more mixtures in tetrahydrofuran (THF), ethyl acetate, acetone or the acetonitrile; Be preferably tetrahydrofuran (THF).
In the step 2, described oxygenant is 2-iodoxy phenylformic acid (being called for short IBX), and shikimate and the benzoic mol ratio of 2-iodoxy are 1: (1～3).
In the step 3, described catalyzer is neutralized verdigris, copper sulfate, cupric bromide, zinc acetate, zinc oxide or concentrated hydrochloric acid; The mol ratio of catalyzer and 3-dehydrogenation shikimate is (0.1～3): 1.Wherein, selecting the Lewis acid with oxidisability for use is the gallic acid ester compounds as the resulting product of catalyzer, and described Lewis acid with oxidisability comprises copper sulfate, neutralized verdigris, cupric bromide; Selecting Lewis acid or concentrated hydrochloric acid with oxidisability for use is the Protocatechuic Acid ester compound as the resulting product of catalyzer, and the described Lewis acid that does not have oxidisability is zinc acetate, zinc oxide.
In the step 3, described reaction solvent is the mixed solvent or the alcoholic solvent of Glacial acetic acid and water.When adopting Lewis acid as catalyzer, reaction solvent is the mixed solvent of Glacial acetic acid and water, and the volume ratio of Glacial acetic acid and water is 6: (1～3); When adopting concentrated hydrochloric acid as catalyzer, reaction solvent is an alcoholic solvent, particular methanol, ethanol or propyl alcohol.
In the step 3, described temperature of reaction is 20～80 ℃, is preferably 50 ℃; Reaction times is 5～30 hours, is preferably 12 hours.
Synthetic route of the present invention is as follows:
The present invention compared with prior art has following advantage and effect:
(1) raw material of the present invention's employing is natural shikimic acid, belongs to anistree water soluble ingredient, is a kind of non-aromatic compounds, belongs to the renewable non-grain biomass resource of China's characteristic, and output is big, steady sources, can be used as the ideal substitute of petrochemical materials.
(2) higher value application of shikimic acid helps increasing farmers' income, and helps the expansion and the protection of anistree resource, helps the comprehensive exploitation of anistree each component.
(3) reaction conditions gentleness of the present invention is simple to operate, and less demanding to equipment is easy to scale preparation.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
Step 1: in 250mL three neck round-bottomed flasks, add shikimic acid (17.4g, 0.1mol) and anhydrous methanol (150mL, 3.7mol), fully stir down in the control reaction solution temperature in the time of 10 ℃ gradually dripping thionyl chloride (15mL, 0.2mol).After dropwising, temperature is reacted 3h at 40 ℃ in the control.Concentrate, get viscous liquid, use re-crystallizing in ethyl acetate, get white powder solid methyl shikimate 14.76g, yield: 78.5%.m.p.112～113℃.
(c＝0.2，MeOH)；
1H?NMR(CD
3COCD
3，400MHz)δ6.73(m，1H，2-H)，4.38(m，1H，3-H)，4.02(s，1H，4-OH?D
2O?exchangeable)，4.00(brs，2H，3，5-OH?D
2O?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
2O)，157(M
+-OCH
3)，129(M
+-COOCH
3)。
Step 2: with methyl shikimate (0.94g, 5mmol), IBX (1.54g, 5.5mmol) and tetrahydrofuran (THF) 20mL put in the reaction flask, be heated to 20 ℃, stirring reaction 4h.Filter, concentrate, get faint yellow solid.With ethyl acetate-sherwood oil recrystallization, get white fine acicular crystal 3-dehydrogenation methyl shikimate 0.67g, yield: 72%.m.p.122～123℃.
(c＝0.2，MeOH)；
1HNMR(CD
3COCD
3，400MHz)δ6.45(d，J＝2.8Hz，1H，2-H)，4.57(d，J＝3.6Hz，1H，4-OH?D
2O?exchangeable)，4.47(d，J＝3.6Hz，1H，5-OH?D
2Oexchangeable)，4.57(dd，J
1＝10.4Hz，J
2＝3.6Hz，1H，4-H)，3.85(m，1H，5-H)，3.81(s，3H，OCH
3)，3.06(dd，J
1＝18.4Hz，J
2＝5.2Hz，1H，6α-H)，2.18(ddd，J
1＝18.4Hz，J
2＝8.8Hz，J
3＝3.2Hz，1H，6β-H).MS，m/z(％)：186(M+)，155(M
+-OCH
3)，127(M
+-COOCH
3).
Step 3: with 3-dehydrogenation methyl shikimate (0.744g, 4mmol), Cu (OAc)
2H
2O (1.76g, 8.8mmol) and AcOH/H
2(3: 1, V/V) 50mL put in the middle of the reaction flask O, is heated to 50 ℃ of reactions, stirring reaction 26h.Filter, concentrate, ethyl acetate extraction merges organic layer, with anhydrous magnesium sulfate drying, concentrates, and the water recrystallization gets white solid methyl gallate 0.62g, yield: 81.5%.m.p.198～199℃.
1H?NMR(CD
3COCD
3，400MHz)δ8.25(s，2H，3，5-OH)，8.10(brs，1H，4-OH)，7.10(s，2H，Ar-H)，3.77(s，3H，OCH
3).MS(EI)，m/z(％)：184(M
+)，153(M
+-OCH
3)，125(M
+-COOCH
3).
Embodiment 2
Step 1: with embodiment 1.
Step 2: with methyl shikimate (7.52g, 40mmol), IBX (13.44g, 48mmol) and tetrahydrofuran (THF) 160mL put in the reaction flask, be heated to 67 ℃, stirring reaction 1h.Filter, concentrate, get faint yellow solid.With ethyl acetate-sherwood oil recrystallization, get white fine acicular crystal 3-dehydrogenation methyl shikimate 3.84g, yield: 51.6%.
Step 3: with 3-dehydrogenation methyl shikimate (0.744g, 4mmol), Cu (OAc)
2H
2O (1.60g, 8mmol) and AcOH/H
2(2: 1, V/V) 50mL put in the middle of the reaction flask O, is heated to 50 ℃, stirring reaction 26h.Filter, concentrate, ethyl acetate extraction merges organic layer with anhydrous magnesium sulfate drying, concentrates, and the water recrystallization gets white solid methyl gallate 0.58g, yield: 78% then.
Embodiment 3:
Step 1: with embodiment 1.
Step 2: with methyl shikimate (7.52g, 40mmol), IBX (13.44g, 48mmol) and tetrahydrofuran (THF) 160mL put in the reaction flask, be heated to 50 ℃, stirring reaction 6h.Filter, concentrate, get faint yellow solid.With ethyl acetate-sherwood oil recrystallization, obtain white fine acicular crystal 3-dehydrogenation methyl shikimate 4.17g, yield: 56.0%.
Step 3: with 3-dehydrogenation methyl shikimate (0.744g, 4mmol), ZnO (0.163g, 0.8mmol) and AcOH/H
2(6: 1, V/V) 50mL put in the middle of the reaction flask O, is heated to 50 ℃ of reaction 16h.Concentrate, ethyl acetate extraction merges organic layer, with anhydrous magnesium sulfate drying, concentrates, and the water recrystallization gets white solid Protocatechuic Acid methyl esters 0.61g, yield: 90.5%.m.p.134～135℃.
1HNMR(CD
3COCD
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(％)：168(M
+)，137(M
+-OCH
3)，109(M
+-COOCH
3).
Embodiment 4:
Step 1: with embodiment 1.
Step 2: with methyl shikimate (0.94g, 5mmol), IBX (2.8g, 10mmol) and tetrahydrofuran (THF) 50mL put in the reaction flask, be heated to 10 ℃, stirring reaction 15h.Filter, concentrate, get faint yellow solid.With ethyl acetate-sherwood oil recrystallization, get white fine acicular crystal 3-dehydrogenation methyl shikimate 0.45g, yield: 48%.
Step 3: with 3-dehydrogenation methyl shikimate (0.744g, 4mmol), ZnO (0.326g, 4mmol) and AcOH/H
2O (6: 1, V/V) 50mL puts in the middle of the reaction flask, and nitrogen protection is heated to 50 ℃ of reaction 16h.Concentrate, ethyl acetate extraction merges organic layer, with anhydrous magnesium sulfate drying, concentrates, and the water recrystallization obtains white solid Protocatechuic Acid methyl esters 0.62g, yield: 92.3%.
Embodiment 5:
Step 1: with embodiment 1.
Step 2: with methyl shikimate (7.52g, 40mmol), IBX (13.44g, 48mmol) and tetrahydrofuran (THF) 160mL put in the reaction flask, be heated to 20 ℃, stirring reaction 8h.Filter, concentrate, get faint yellow solid.With ethyl acetate-sherwood oil recrystallization, obtain white fine acicular crystal 3-dehydrogenation methyl shikimate 5.2g, yield: 70.5%.
Step 3: with 3-dehydrogenation methyl shikimate (0.372g, 2mmol), Zn (OAc)
22H
2O (0.438g, 2mmol) and AcOH/H
2O (3: 1, V/V) 25mL puts in the middle of the reaction flask, and nitrogen protection is heated to 60 ℃ of reactions, stirring reaction 7h.Concentrate, ethyl acetate extraction merges organic layer with anhydrous magnesium sulfate drying, concentrates, and the water recrystallization obtains white solid Protocatechuic Acid methyl esters 0.27g, yield: 80.3%.
Embodiment 6:
Step 1: with embodiment 1.
Step 2: with embodiment 1.
Step 3: with 3-dehydrogenation methyl shikimate (0.744g, 2mmol), concentrated hydrochloric acid (0.2mL, 0.24mmol) and 20mL methyl alcohol put in the middle of the reaction flask, nitrogen protection is heated to 60 ℃, the reaction 16h.Concentrate, the water recrystallization obtains white solid Protocatechuic Acid methyl esters 0.35g, yield: 52.1%.
Embodiment 7:
Step 1: in 250mL three neck round-bottomed flasks, add shikimic acid (17.4g, 0.1mol) and dehydrated alcohol (150mL, 2.6mol), fully stir down in the control reaction solution temperature in the time of 10 ℃ gradually dripping thionyl chloride (11.25mL, 0.15mol).After dropwising, temperature is reacted 3h at 40 ℃ in the control.Concentrate, get viscous liquid, use re-crystallizing in ethyl acetate, obtain white powder solid shikimic acid ethyl ester 16.16g, productive rate is 85.0%.m.p.96～97℃.
(c＝0.2，MeOH)；
1H?NMR(d
6-DMSO，400MHz)δ1.22(t，J＝7.1，3H，CH
3)，2.05，2.42(2dm，J＝17.8，2H，6-H)，3.58(m，1H，4-H)，3.85(m，1H，5-H)，4.12(q，J＝7.1，2H，CH
2)，4.22(m，1H，3-H)，4.64(d，J＝4.2，1H，OH)，4.83(d，J＝4.2，1H，OH)，4.85(s，1H，OH)，6.62(s，1H，2-H)；MS(EI)，m/z(％)：202(M
+)，185(M
+-OH)，173，156，143，138，110，97.
Step 2: with the shikimic acid ethyl ester (1.01g, 5mmol), IBX (1.54g, 5.5mmol) and tetrahydrofuran (THF) 20mL put in the reaction flask, be heated to 25 ℃, the reaction 4h.Filter, concentrate,, get white plates crystal 3-dehydrogenation shikimic acid ethyl ester 0.70g, yield: 70% with ethyl acetate-sherwood oil recrystallization.m.p.116～117℃.MS(EI)，m/z(％)：200(M
+)。m.p.112～113℃。
(c＝0.2，MeOH)；
1H?NMR(CDCl
3，400MHz)δ6.60(d，J＝2.4Hz，1H，2-H)，4.29(q，J＝7.2，2H，CH
2)，4.10(d，J＝11.2Hz，1H，4-H)，3.93(m，1H，5-H)，3.219(dd，J
1＝18.8Hz，J
2＝5.6Hz，1H，6β-H)，2.59(ddd，J
1＝18.8Hz，J
2＝10.4Hz，J
3＝3.2Hz，1H，6α-H)，2.23(brs，2-H，OH)，1.32(t，J＝6.8，3H，CH
3)；MS(EI)m/z：182(M
+-H
2O)，155，154，136，113.
Step 3: with 3-dehydrogenation shikimic acid ethyl ester (0.80g, 4mmol), Cu (OAc)
2H
2O (1.76g, 8.8mmol) and AcOH/H
2(3: 1, V/V) 50mL put in the middle of the reaction flask O, is heated to 40 ℃, reaction 30h.Filter, concentrate, ethyl acetate extraction merges organic layer with anhydrous magnesium sulfate drying, concentrates, and the water recrystallization gets white solid Progallin A 0.66g, yield: 83.1%.m.p.153～154℃.MS，m/z(％)：198(M
+).170，153.
Embodiment 8:
Step 1: with embodiment 7.
Step 2: with the shikimic acid ethyl ester (1.01g, 5mmol), IBX (1.54g, 5.5mmol) and tetrahydrofuran (THF) 20mL put in the reaction flask, be cooled to 10 ℃, the reaction 15h.Filter, concentrate,, get white fine acicular crystal 3-dehydrogenation shikimic acid ethyl ester 0.69g, yield: 69% with ethyl acetate-sherwood oil recrystallization.
Step 3: with 3-dehydrogenation shikimic acid ethyl ester (0.80g, 4mmol), ZnO (0.326g, 4mmol) and AcOH/H
2O (85: 15, V/V) 50mL puts in the middle of the reaction flask, and nitrogen protection is heated to 55 ℃, reaction 16h.Filter, concentrate, ethyl acetate extraction merges organic layer with anhydrous magnesium sulfate drying, concentrates, and the water recrystallization gets white solid ethyl protocatechuate 0.667g, yield: 91.6%.m.p.133℃.
1H?NMR(CDCl
3，400MHz)δ9.80(brs，1H，4-OH)，9.40(brs，1H，5-OH)，7.40(d，J
1＝2.0Hz，1H，2-ArH)，7.34(dd，J
1＝8.0Hz，J
2＝2.0Hz，1H，6-ArH)，6.84(d，J
1＝8.4Hz，1H，5-ArH).MS，m/z(％)：182(M
+)，137(M
+-OCH
2CH
3).
Embodiment 9:
Step 1: with embodiment 7.
Step 2: with embodiment 7.
Step 3: with 3-dehydrogenation shikimic acid ethyl ester (0.80g, 4mmol), concentrated hydrochloric acid (.3.3mL, 4mmol) and 20mL ethanol put in the middle of the reaction flask nitrogen protection, heating reflux reaction, stirring reaction 1h.Concentrate, get viscous liquid.The water recrystallization obtains white solid ethyl protocatechuate 0.44g, yield: 61%.
Claims (9)
1. one kind prepares the method for gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid, it is characterized in that comprising the steps:
(1) is raw material with the shikimic acid, under the effect of acylating reagent thionyl chloride,, obtains shikimate with alcohol generation esterification;
(2) described shikimate is dissolved in the organic solvent, under the oxygenant effect oxidative dehydrogenation takes place, and obtains 3-dehydrogenation shikimate;
(3) described 3-dehydrogenation shikimate is dissolved in the reaction solvent, and under the effect of catalyzer, reacting by heating through separation and purification, obtains gallic acid ester or Protocatechuic Acid ester compound.
2. according to claim 1ly prepare the method for gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid, it is characterized in that: in the step 1, described alcohol is the straight or branched alcohol of C1～C6.
3. according to claim 1ly prepare the method for gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid, it is characterized in that: in the step 1, the mol ratio of shikimic acid, thionyl chloride and alcohol is 1: (1～2): (20～50).
4. according to claim 1ly prepare the method for gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid, it is characterized in that: in the step 2, the temperature of reaction of oxydehydrogenation is 0～65 ℃, and the reaction times is 0.5～15 hour.
5. the method for preparing gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid according to claim 1; it is characterized in that: in the step 2; described oxygenant is a 2-iodoxy phenylformic acid, and shikimate and the benzoic mol ratio of 2-iodoxy are 1: (1～3).
6. the method for preparing gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid according to claim 1, it is characterized in that: in the step 2, described organic solvent is one or more mixtures in tetrahydrofuran (THF), ethyl acetate, acetone or the acetonitrile.
7. according to claim 1ly prepare the method for gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid, it is characterized in that: in the step 3, described catalyzer is neutralized verdigris, copper sulfate, cupric bromide, zinc acetate, zinc oxide or concentrated hydrochloric acid.
8. according to claim 1ly prepare the method for gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid, it is characterized in that: in the step 3, the mol ratio of catalyzer and 3-dehydrogenation shikimate is (0.1～3): 1.
9. according to claim 1ly prepare the method for gallic acid ester and Protocatechuic Acid ester compound by natural shikimic acid, it is characterized in that: in the step 3, described temperature of reaction is 20～80 ℃, and the reaction times is 5～30 hours.
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| CN105503606A (en) * | 2015-12-30 | 2016-04-20 | 贵阳单宁科技有限公司 | Stable crystal form of gallicin and preparing method thereof |
| CN112047828A (en) * | 2020-09-04 | 2020-12-08 | 宜昌东阳光生化制药有限公司 | Method for preparing protocatechuic acid by biochemical method |
| CN113321581A (en) * | 2021-06-29 | 2021-08-31 | 浙江得乐康食品股份有限公司 | Shikimate compound, shikimate compound and preparation method thereof |
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| CN103709039A (en) * | 2013-12-25 | 2014-04-09 | 南京龙源天然多酚合成厂 | Method for synthesizing methyl (ethyl) gallate through catalysis of Cu-mordenite |
| CN103709039B (en) * | 2013-12-25 | 2015-04-22 | 南京龙源天然多酚合成厂 | Method for synthesizing methyl (ethyl) gallate through catalysis of Cu-mordenite |
| CN105503606A (en) * | 2015-12-30 | 2016-04-20 | 贵阳单宁科技有限公司 | Stable crystal form of gallicin and preparing method thereof |
| CN112047828A (en) * | 2020-09-04 | 2020-12-08 | 宜昌东阳光生化制药有限公司 | Method for preparing protocatechuic acid by biochemical method |
| CN112047828B (en) * | 2020-09-04 | 2023-02-07 | 宜昌东阳光生化制药有限公司 | Method for preparing protocatechuic acid by biochemical method |
| CN113321581A (en) * | 2021-06-29 | 2021-08-31 | 浙江得乐康食品股份有限公司 | Shikimate compound, shikimate compound and preparation method thereof |
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