CN113150040A - Preparation method of chemically synthesized whitening agent diglucosyl gallic acid - Google Patents
Preparation method of chemically synthesized whitening agent diglucosyl gallic acid Download PDFInfo
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- CN113150040A CN113150040A CN202110345896.7A CN202110345896A CN113150040A CN 113150040 A CN113150040 A CN 113150040A CN 202110345896 A CN202110345896 A CN 202110345896A CN 113150040 A CN113150040 A CN 113150040A
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229940074391 gallic acid Drugs 0.000 title claims abstract description 45
- 235000004515 gallic acid Nutrition 0.000 title claims abstract description 45
- 230000002087 whitening effect Effects 0.000 title claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 claims abstract description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 4
- IQZPSLFUPRAAFH-UHFFFAOYSA-N (5-acetamido-2,3,4-triacetyloxy-6-oxohexyl) acetate Chemical compound CC(=O)NC(C=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)COC(C)=O IQZPSLFUPRAAFH-UHFFFAOYSA-N 0.000 abstract description 3
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 229910015900 BF3 Inorganic materials 0.000 description 3
- 238000006418 Brown reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 238000006640 acetylation reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010010144 Completed suicide Diseases 0.000 description 1
- 102100024295 Maltase-glucoamylase Human genes 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- 108010028144 alpha-Glucosidases Proteins 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 230000013595 glycosylation Effects 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
- C07H15/203—Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a preparation method of chemical synthesis whitening agent diglucosyl gallic acid. The synthesis method comprises the steps of reacting methyl gallate and pentaacetylglucosamine serving as raw materials with boron trifluoride diethyl etherate serving as a catalyst to obtain methyl gallate-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside); the mixture is dissolved in absolute methanol after separation and purification, then 30-50% NaOH aqueous solution is dripped to react to obtain gallic acid methyl ester-diglucoside sodium salt (not dried), and diglucosyl gallic acid is obtained under the acidification of concentrated hydrochloric acid. The method has the advantages of simple and convenient operation, less discharge of three wastes, high yield and low cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of daily chemicals, and particularly relates to a preparation method of a chemical synthesis whitening agent diglucosyl gallic acid.
Background
The chemical name of the diglucosyl gallic acid is trihydroxybenzoic acid-3, 5-diglucoside, and the diglucosyl gallic acid is a very stable, efficient and safe whitening agent. The diglucosyl gallic acid can effectively permeate into the skin basal layer of a human body, and the alpha-glucosidase generated by the skin microbial layer cuts off the glucose bond of the diglucosyl gallic acid to generate the gallic acid, so that the defects of high instability and almost insolubility of the gallic acid in water are overcome, and the excellent antioxidant effect and the powerful tyrosinase inhibition effect of the gallic acid are fully exerted. The whitening principle of suicide attack has a very good application prospect through the cooperation of the diglucosyl gallic acid and the muscle bottom microorganisms, so that the diglucosyl gallic acid is widely applied to various whitening cosmetics. At present, the synthesis method of diglucosyl gallic acid comprises biological extraction, enzymatic synthesis, chemical synthesis and the like. The structural formula of the diglucosyl gallic acid is as follows:
the synthesis of diglucosyl gallic acid takes beta-pentaacetyl glucose and gallic acid methyl ester as raw materials. At present, the commonly used synthesis method is to react gallic acid with acetic anhydride in NaOH aqueous solution to prepare 3, 5-diacetyl gallic acid, then react the 3, 5-diacetyl gallic acid with acetyl bromide glucose to obtain gallic acid-1, 3, 5-tris (2,3,4, 6-tetra-O-acetyl glucoside), and finally react the acetylated product with Ba (OH)2After the reaction, the diglucosyl gallic acid is obtained by neutralization with sulfuric acid. In the preparation method, the 3, 5-diacetyl gallic acid is used as glycosyl receptor to react with acetyl bromide glucose to easily generate glycosylation byproducts, and the raw materials are extremely toxic, the steps and the cost are high, so that the preparation method is not suitable for industrial production. In addition, the preparation of 3, 5-diacetyl gallic acid requires a large excess of acetic anhydride, thereby increasing the production cost; the prepared gallic acid-1, 3, 5-tri (2,3,4, 6-tetra-O-acetyl glucoside) needs to be crystallized and purified, the yield of the purification is not more than 80 percent, and after the solvent is recovered from the crystallization mother liquor, the residual residue needs to be treated by three wastes.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention provides the preparation method for chemically synthesizing the diglucosyl gallic acid, which has the advantages of simple operation, high yield, less discharge of three wastes and low cost.
The technical scheme of the invention is as follows: the synthetic route of the invention is as follows:
the synthesis preparation method of the diglucosyl gallic acid comprises the following steps:
(1.1) dissolving gallic acid methyl ester and pentaacetylglucosamine as raw materials in dimethylbenzene, reacting for 4-8 hours at 30-60 ℃ by using boron trifluoride ether solution as a catalyst to obtain gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside);
(1.2) separating and purifying the obtained gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-O-acetyl glucoside), dissolving in a mixed solvent of anhydrous methanol and water, then dropwise adding a 30-50% NaOH aqueous solution into the mixed solution, and reacting at 40-80 ℃ for 2-5 hours to obtain undried gallic acid methyl ester-diglucoside sodium salt;
(1.3) acidifying the obtained undried gallic acid methyl ester-diglucoside sodium salt at 30-60 ℃ by concentrated hydrochloric acid to remove acetyl on a sugar ring and methyl of an ester group on a benzene ring, and finally obtaining the diglucosyl gallic acid.
Further, in the step (1.1), the molar ratio of the gallic acid methyl ester to the pentaacetylglucose is 1:2 to 3, and the molar ratio of the boron trifluoride diethyl etherate solution to the pentaacetylglucose is 1.5 to 1: 1.
Further, in the step (1.1), the dosage of the xylene is 2-4 ml/g of pentaacetylglucose.
Further, in the step (1.2), the molar ratio of the 30-50% NaOH aqueous solution to the gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-acetyl glucoside) is 12-8: 1.
further, in the step (1.2), the amount of the anhydrous methanol is 3 to 6 ml/g of gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-acetylglucoside), the amount of the water is 1.5 to 3 ml/g of gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-acetylglucoside), and the volume ratio of the anhydrous methanol to the water is 2: 1.
further, in the step (1.3), the gallic acid methyl ester-diglucoside sodium salt is acidified by concentrated hydrochloric acid and then the pH value is adjusted to 1-2.
The invention has the beneficial effects that: compared with the prior art, the gallic acid methyl ester and the beta-pentaacetyl glucose are dissolved by adding dimethylbenzene and then are put into BF3And (3) reacting the gallic acid methyl ester with diethyl ether solution in a one-pot method to obtain gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-O-acetyl glucoside) (yield is over 85 percent), and then removing acetyl on a sugar ring and methyl on an ester group on a benzene ring in sodium hydroxide, methanol and water to obtain the diglucosyl gallic acid (the reaction yield in the step is over 50 percent). Therefore, the total yield of the diglucosyl gallic acid synthesized by the method is over 40 percent. Therefore, the invention has convenient operation, less three-waste discharge and low cost.
Drawings
FIG. 1 is a flow chart of the architecture of the present invention;
FIG. 2 is a mass spectrum of diglucosyl gallic acid prepared in the example of the present invention; wherein m/z is 493 and 494, and is a product peak.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following detailed description is made with reference to the accompanying drawings:
a preparation method of a chemical synthesis whitening agent diglucosyl gallic acid comprises the following specific operation steps:
(1.1) dissolving gallic acid methyl ester and pentaacetylglucosamine as raw materials in dimethylbenzene, reacting for 3-8 hours at 30-60 ℃ by using boron trifluoride ether solution as a catalyst to obtain gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside);
(1.2) separating and purifying the obtained gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-O-acetyl glucoside), dissolving the gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-O-acetyl glucoside) in a mixed solvent of anhydrous methanol and water, dropwise adding a 30-50% NaOH aqueous solution into the mixed solution, and reacting at the temperature of 40-80 ℃ for 2-5 hours to obtain undried gallic acid methyl ester-diglucoside sodium salt;
(1.3) acidifying the obtained undried gallic acid methyl ester-diglucoside sodium salt at 30-60 ℃ by concentrated hydrochloric acid to remove acetyl on a sugar ring and methyl of an ester group on a benzene ring, and finally obtaining the diglucosyl gallic acid.
Further, in the step (1.1), the molar ratio of the gallic acid methyl ester to the pentaacetylglucose is 1:2 to 3, and the molar ratio of the boron trifluoride diethyl etherate solution to the pentaacetylglucose is 1.5 to 1: 1.
Further, the optimal molar ratio of the gallic acid methyl ester to the beta-pentaacetylglucosamine is 1: 2.9.
Further, in the step (1.1), the dosage of the xylene is 2-4 ml/g of pentaacetylglucose.
Further, in the step (1.2), the molar ratio of the 30-50% NaOH aqueous solution to the gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-acetyl glucoside) is 12-8: 1.
further, in the step (1.2), the amount of the anhydrous methanol is 3 to 6 ml/g of gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-acetylglucoside), and the amount of the water is 1.5 to 3 ml/g of gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-acetylglucoside); the volume ratio of the anhydrous methanol to the water is 2: 1.
further, in the step (1.3), the gallic acid methyl ester-diglucoside sodium salt is acidified by concentrated hydrochloric acid and then the pH value is adjusted to 1-2.
Example 1:
mixing methyl gallate (3g, 0.0163mol) and beta-pentaacetylglucosamine (18.45g, 0.0473mol), adding mixed xylene 40 ml, adding boron trifluoride diethyl etherate (0.00245mol, 0.308ml), stirring at 43 deg.C for reaction for 3 hr to obtain brown transparent viscous liquid (indicating complete acetylation reaction), quantitatively obtaining methyl gallate-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside), distilling the brown reaction liquid under reduced pressure to obtain crude product, washing the crude product with 20 ml of xylene and 100 ml of water respectively, concentrating, drying to obtain light yellow solid 13 g, recrystallizing methyl gallate-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside) (white solid) with 100 ml of anhydrous ethanol 12.3 g, the yield thereof was found to be 89.4%.
Dissolving the obtained gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-O-acetyl glucoside) (8.44g, 0.01mol) in a mixed solution of 26 ml of anhydrous methanol and 13ml of water, starting stirring, slowly dropwise adding 8.16g of 49% NaOH (wt%) aqueous solution, and reacting for 2 hours at 40 ℃; acidifying the reaction mixed solution at 30 ℃ by using concentrated hydrochloric acid until the pH value is 1-2, then carrying out vacuum concentration, drying to obtain solid diglucosyl gallic acid and sodium chloride, adding methanol to dissolve the diglucosyl gallic acid and the sodium chloride, filtering the sodium chloride, carrying out vacuum concentration on the filtrate, drying to obtain 2.6 g of diglucosyl gallic acid solid, and recrystallizing ethyl acetate to obtain 2.5 g of white needle crystals with the yield of 50.6%.
Example 2:
mixing gallic acid methyl ester (5g, 0.0271mol) with beta-pentaacetylglucose (31g, 0.0787mol), adding mixed xylene 65 ml, adding boron trifluoride diethyl ether (0.00407mol, 0.513ml), stirring at 47 deg.C for 5 hr to obtain brown transparent viscous liquid (indicating complete acetylation), quantitatively obtaining gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside), distilling the brown reaction liquid under reduced pressure to obtain crude product, washing the crude product with 40 ml of xylene and 200 ml of water respectively, concentrating, drying to obtain pale yellow solid 22 g, recrystallizing gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside) (white solid) with 100 ml of anhydrous ethanol 20.8 g, the yield thereof was found to be 90.9%.
Dissolving the obtained methyl gallate-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside) (16.88g, 0.02mol) in a mixed solution of 32 ml of anhydrous methanol and 26 ml of water, stirring, slowly dropwise adding 16.32g of 49% NaOH (wt%) aqueous solution, reacting at 60 ℃ for 3.5 hours, acidifying the reaction mixed solution at 45 ℃ with concentrated hydrochloric acid to pH 1-2, then carrying out vacuum concentration, drying to obtain diglucosyl gallic acid and sodium chloride solid, adding methanol for dissolving, filtering sodium chloride, carrying out vacuum concentration on the filtrate, drying to obtain 5.5 g of diglucosyl gallic acid solid, recrystallizing ethyl acetate to obtain 5.1 g of white needle crystal, wherein the yield is 51.6%.
Example 3:
mixing methyl gallate (3g, 0.0163mol) and beta-pentaacetylglucosamine (18.45g, 0.0473mol), adding mixed xylene 40 ml, adding boron trifluoride diethyl etherate (0.00326mol, 0.538ml), stirring at 45 deg.C for 8 hr to obtain brown transparent viscous liquid (indicating complete acetylation), quantitatively obtaining methyl gallate-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside), distilling the brown reaction liquid under reduced pressure to obtain crude product, washing the crude product with 20 ml of xylene and 100 ml of water, concentrating, drying to obtain light yellow solid 13.8 g, recrystallizing methyl gallate-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside) (white solid) with 100 ml of anhydrous ethanol 12.7 g, the yield thereof was found to be 92.3%.
Dissolving the obtained methyl gallate-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside) (8.44g, 0.01mol) in a mixed solution of 26 ml of anhydrous methanol and 13ml of water, stirring, slowly dropwise adding 8.16g of 49% NaOH (wt%) aqueous solution, reacting at 80 ℃ for 5 hours, acidifying the reaction mixed solution at 60 ℃ with concentrated hydrochloric acid until the pH value is 1-2, then carrying out vacuum concentration, drying to obtain diglucosyl gallic acid and sodium chloride solid, adding methanol for dissolving, filtering sodium chloride, carrying out vacuum concentration on the filtrate, drying to obtain 2.7 g of diglucosyl gallic acid solid, recrystallizing ethyl acetate to obtain 2.6 g of white needle-like crystals, and obtaining the yield of 52.6%.
Finally, it should be understood that the embodiments described herein are merely illustrative of the principles of embodiments of the present invention; other variations are possible within the scope of the invention; thus, by way of example, and not limitation, alternative configurations of embodiments of the invention may be considered consistent with the teachings of the present invention; accordingly, the embodiments of the invention are not limited to the embodiments explicitly described and depicted.
Claims (6)
1. A preparation method of a chemically synthesized whitening agent diglucosyl gallic acid is characterized by comprising the following specific operation steps:
(1.1) dissolving gallic acid methyl ester and pentaacetylglucose as raw materials in dimethylbenzene, and using boron trifluoride ethyl ether solution as a catalyst in a reaction condition of 30-60%OReacting for 4-8 hours under C to obtain gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O O-acetyl glucoside);
(1.2) separating and purifying the obtained gallic acid methyl ester-3, 5-bis (2,3,4, 6-tetra-O-O-acetyl glucoside), dissolving in a mixed solvent of anhydrous methanol and water, then dropwise adding a 30-50% NaOH aqueous solution into the mixed solution, and carrying out reaction in a reaction condition of 40-80%OReacting for 2-5 hours under C to obtain undried gallic acid methyl ester-diglucoside sodium salt;
(1.3) adding the obtained undried gallic acid methyl ester-diglucoside sodium salt at 30-60%OAnd acidifying the solution C by concentrated hydrochloric acid to remove acetyl on a sugar ring and methyl of an ester group on a benzene ring, and finally obtaining the diglucosyl gallic acid.
2. The method for preparing diglucosyl gallic acid as a chemical synthesis whitening agent according to claim 1, wherein in step (1.1), the molar ratio of the gallic acid methyl ester to the pentaacetylglucose is 1:2 to 3, and the molar ratio of the boron trifluoride ethyl ether solution to the pentaacetylglucose is 1.5 to 1: 1.
3. The method for preparing diglucosyl gallic acid as a chemical synthesis whitening agent according to claim 1, wherein in step (1.1), the amount of xylene is 2-4 ml/g pentaacetylglucose.
4. The method for preparing diglucosyl gallic acid as a chemical synthesis whitening agent according to claim 1, wherein in step (1.2), the molar ratio of the 30-50% NaOH aqueous solution to methyl gallate-3, 5-bis (2,3,4, 6-tetra-O-acetyl glucoside) is 12-8: 1.
5. the method for preparing diglucosyl gallic acid as a chemical synthesis whitening agent according to claim 1, wherein in step (1.2), the amount of the anhydrous methanol is 3 to 6 ml/g of methyl gallate-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside), the amount of the water is 1.5 to 3 ml/g of methyl gallate-3, 5-bis (2,3,4, 6-tetra-O-O-acetylglucoside), and the volume ratio of the anhydrous methanol to the water is 2: 1.
6. the method for preparing diglucosyl gallic acid as a chemical synthesis whitening agent according to claim 1, wherein in step (1.3), the pH value of the gallic acid methyl ester-diglucoside sodium salt is adjusted to 1-2 after being acidified by concentrated hydrochloric acid.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000319116A (en) * | 1999-04-30 | 2000-11-21 | Lion Corp | Stabilized gallic acid derivative and external preparation composition containing the same |
| JP2004123699A (en) * | 2002-08-01 | 2004-04-22 | Mitsubishi Chemicals Corp | Method for producing diglycosylated gallic acid derivative |
| JP2004175694A (en) * | 2002-11-26 | 2004-06-24 | Mitsubishi Chemicals Corp | Method for producing gallic acid glycoside |
| JP2004217540A (en) * | 2003-01-10 | 2004-08-05 | Mitsubishi Chemicals Corp | Method for producing gallic acid glycoside |
| CN1668627A (en) * | 2002-07-11 | 2005-09-14 | 三井化学株式会社 | Process for producing glycoside |
-
2021
- 2021-03-31 CN CN202110345896.7A patent/CN113150040A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000319116A (en) * | 1999-04-30 | 2000-11-21 | Lion Corp | Stabilized gallic acid derivative and external preparation composition containing the same |
| CN1668627A (en) * | 2002-07-11 | 2005-09-14 | 三井化学株式会社 | Process for producing glycoside |
| JP2004123699A (en) * | 2002-08-01 | 2004-04-22 | Mitsubishi Chemicals Corp | Method for producing diglycosylated gallic acid derivative |
| JP2004175694A (en) * | 2002-11-26 | 2004-06-24 | Mitsubishi Chemicals Corp | Method for producing gallic acid glycoside |
| JP2004217540A (en) * | 2003-01-10 | 2004-08-05 | Mitsubishi Chemicals Corp | Method for producing gallic acid glycoside |
Non-Patent Citations (1)
| Title |
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| 广西农学院编: "《有机化学》", 31 December 1983 * |
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