CN101492439A - Dihydromyricetin-3-carboxylic ester and preparation method thereof - Google Patents
Dihydromyricetin-3-carboxylic ester and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 9
- 229930195729 fatty acid Natural products 0.000 claims abstract description 9
- 239000000194 fatty acid Substances 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- DCYOADKBABEMIQ-FLCVNNLFSA-N myricitrin Natural products O([C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](C)O1)C1=C(c2cc(O)c(O)c(O)c2)Oc2c(c(O)cc(O)c2)C1=O DCYOADKBABEMIQ-FLCVNNLFSA-N 0.000 claims description 49
- DCYOADKBABEMIQ-OWMUPTOHSA-N myricitrin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC1=C(C=2C=C(O)C(O)=C(O)C=2)OC2=CC(O)=CC(O)=C2C1=O DCYOADKBABEMIQ-OWMUPTOHSA-N 0.000 claims description 42
- -1 butyryl radicals Chemical class 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 4
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229960003742 phenol Drugs 0.000 claims description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- KJXSIXMJHKAJOD-LSDHHAIUSA-N (+)-dihydromyricetin Chemical compound C1([C@@H]2[C@H](C(C3=C(O)C=C(O)C=C3O2)=O)O)=CC(O)=C(O)C(O)=C1 KJXSIXMJHKAJOD-LSDHHAIUSA-N 0.000 abstract description 12
- KQILIWXGGKGKNX-UHFFFAOYSA-N dihydromyricetin Natural products OC1C(=C(Oc2cc(O)cc(O)c12)c3cc(O)c(O)c(O)c3)O KQILIWXGGKGKNX-UHFFFAOYSA-N 0.000 abstract description 6
- 235000013305 food Nutrition 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 230000003078 antioxidant effect Effects 0.000 description 9
- 230000003026 anti-oxygenic effect Effects 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 235000006708 antioxidants Nutrition 0.000 description 7
- 229940074391 gallic acid Drugs 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000219099 Parthenocissus quinquefolia Species 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- 239000012675 alcoholic extract Substances 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YEDFEBOUHSBQBT-UHFFFAOYSA-N 2,3-dihydroflavon-3-ol Chemical compound O1C2=CC=CC=C2C(=O)C(O)C1C1=CC=CC=C1 YEDFEBOUHSBQBT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000009388 Parthenocissus quinquefolia Nutrition 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- ZONYXWQDUYMKFB-UHFFFAOYSA-N SJ000286395 Natural products O1C2=CC=CC=C2C(=O)CC1C1=CC=CC=C1 ZONYXWQDUYMKFB-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000001924 fatty-acyl group Chemical group 0.000 description 1
- 229930003949 flavanone Natural products 0.000 description 1
- 235000011981 flavanones Nutrition 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to dihydromyricetin-3-carboxylic ester with a structural general formula , wherein R is fatty acid acyl or aromatic acid acyl containing 1-7 carbon atoms. The dihydromyricetin-3-carboxylic ester has oxidation resistance obviously superior to that of dihydromyricetin, has good stability, can be used in the fields of food, medicine, feed and the like, and has wide market development prospect. The invention also relates to a preparation method of the dihydromyricetin-3-carboxylic ester, which has the advantages of simplicity, convenience, practicability, high yield, low cost and the like and is easy to realize industrial production.
Description
Technical field
The present invention relates to dibydro myricetrin-3-carboxylicesters and preparation method thereof.
Background technology
Dibydro myricetrin (3,5,7,3 ', 4 ', 5 '-hexahydroxy--2, the 3-flavanonol dihydromyricetin), has another name called two hydrogen ampelopsin, belongs to the flavanone alcohol compound, is present in the ampelopsis in a large number.This compound first by Kotake and Kubota in 1940 from Vitaceae ampelopsis fujian tea, promptly separate obtaining called after ampelopsin (ampelopsin) in the leaf of A. Meliaefolia (A.Meliaefolia).The dibydro myricetrin structural formula is as follows:
Dibydro myricetrin has tangible antioxygenation.Under the situation of equal addition, its antioxidant property can reach even surpass present chemosynthesis antioxidant TBHQ (see poplar book treasure etc., Chinese oil, 2003, (1): 44～46 and Zhang Yousheng etc., medicine journal, 2003,38 (4): 241～244).
Yet dihydromyricetin prime system polarity compounds is insoluble in grease compound system, if to joining in the grease after its emulsification, can constantly separate out from product along with the variation of time again, thereby has limited the application of dibydro myricetrin.Therefore need transform the dibydro myricetrin chemical structure and solve the problem that it is insoluble in oil, but reach both prolonged preservation, have better antioxidation again.
Modern scientific research finds that the oxidation-resistance of flavonoid compound depends on hydroxy position and degree of hydroxylation, and a lot of equal hydroxyls of material show different oxidation-resistances with hydroxyl number and position difference.Studies show that in a large number 3 ', 4 ', 5 ' hydroxyl on the dibydro myricetrin is main reactive site anti-oxidant, that remove free radical, wherein 4 ' hydroxyl is the strong anti-oxidation base, and promptly strong active group is the strong and weak primary factor of decision oxidation-resistance; 5 hydroxyls, 7 hydroxyls help antioxygenic activity, to anti-oxidant synergism; And 3 hydroxyls should (be seen Zhang Hongyu, Chinese science (B), 1999,29 (1): 91～96) to oxidation-resistance is invalid.
The chemically modified of dibydro myricetrin is by carboxylic acid halides and dibydro myricetrin direct esterification at present, change its fat-soluble relatively poor weakness, but in the reaction process often in conjunction with or shielded dibydro myricetrin main anti-oxidant functional group--phenolic hydroxyl group (is seen Guo Qingquan etc., Food science, 2006,27 (5): 21～23).
The Chinese patent publication number is CN200410026610.5, open day is on September 28th, 2005, the name of innovation and creation is called the preparation method of dibydro myricetrin fatty acid ester, it is raw material that this application discloses with the dibydro myricetrin, under alkaline condition,, prepare the method for dibydro myricetrin fatty acid ester with the effect of lipid acid carboxylic acid halides.Use this synthetic method, the dibydro myricetrin phenolic hydroxyl group is than the preferential formation ester of alcoholic extract hydroxyl group, and promptly 5,7,3 ', 4 ', 5 ' hydroxyl easily forms ester than 3 hydroxyls.When dibydro myricetrin and lipid acid carboxylic acid halides ratio were less than or equal to 1: 5, fatty acyl group formed mono fatty acid ester or many fatty acid ester at 5,7,3 ', 4 ', 5 '; When dibydro myricetrin and lipid acid carboxylic acid halides ratio during, then form ester simultaneously at 5,7,3 ', 4 ', 5 ' and 3 more than or equal to 1: 6.
Dibydro myricetrin after chemically modified though increased fat-solublely, helps antioxidant effect; But because esterification, combine the antioxygenic activity group, thereby reduced the resistance of oxidation of material itself, therefore the essentially no variation of antioxygenic activity of the dibydro myricetrin before and after the modification (is seen Zhang Yousheng etc., research and development of natural products, 2006, (18): 260～262 and Li Wei etc., Food science, 2005,26 (9): 73～76).
Summary of the invention
The objective of the invention is in order to overcome deficiency of the prior art, providing a kind of had both had good fat-solublely, had dibydro myricetrin-3-carboxylicesters of strong antioxygenic activity and preparation method thereof again.
The invention provides a kind of dibydro myricetrin-3-carboxylicesters, have general structure (I):
Wherein, R is fatty acid acyl or the aromatic acid acyl group that contains 1～7 carbon atom.
Dibydro myricetrin of the present invention-3-carboxylicesters, the preferred formyl radical of described fatty acid acyl, ethanoyl, propionyl, butyryl radicals, pentanoyl, caproyl or oenanthyl.
Dibydro myricetrin of the present invention-3-carboxylicesters, the preferred galloyl of described aromatic acid acyl group, salicyloyl, benzoyl, para hydroxybenzene formyl radical, protocatechuoyl, vanilloyl, coffee acyl, cinnamoyl, to hydroxyl cinnamoyl, asafoetide acyl group, different asafoetide acyl group or green former acyl group.
The preparation method of dibydro myricetrin of the present invention-3-carboxylicesters may further comprise the steps:
Dibydro myricetrin is mixed than 1: 1～3 by amount with complexing agent; be dissolved in the inert organic solvents at 60～80 ℃; the aliphatic or aromatic acid that adds 1.2～1.8 times of dibydro myricetrin amounts then adds catalyzer again, reacts under nitrogen protection; temperature of reaction is 80～120 ℃; reaction times is 4～12h, and the pressure reducing and steaming solvent is used ethyl alcohol recrystallization; drying makes dibydro myricetrin-3-carboxylicesters.This method preparation dibydro myricetrin-3-carboxylicesters productive rate can be up to 60～82%.
The preparation method of dibydro myricetrin of the present invention-3-carboxylicesters, described complexing agent preferred boric acid.
The preparation method of dibydro myricetrin of the present invention-3-carboxylicesters, described inert organic solvents is preferred 1,4-dioxane, methyl-sulphoxide, N, one or more arbitrary proportions in dinethylformamide, the hexanaphthene mix.
The preparation method of dibydro myricetrin of the present invention-3-carboxylicesters, one or more arbitrary proportions in the preferred sulfonic compound of described catalyzer mix.
The preparation method of dibydro myricetrin of the present invention-3-carboxylicesters, the preferred tosic acid of described sulfonic compound, Phenylsulfonic acid or thionamic acid.
Dibydro myricetrin of the present invention-3-carboxylicesters is on the one hand because esterification obtains good fat-soluble, on the other hand because the carboxylic acid bonded is to invalid 3 alcoholic extract hydroxyl groups of answering of oxidation-resistance on the dibydro myricetrin, the phenolic hydroxyl group that antioxygenic activity is stronger has been retained, thereby improved antioxygenic activity, the resistance of oxidation that obviously is better than dibydro myricetrin, and have satisfactory stability, can be used for fields such as food, medicine and feed, have brilliant market developing prospect.
The preparation method of dibydro myricetrin of the present invention-3-carboxylicesters, have easy, practical, productive rate is high, low cost and other advantages, is easy to realize suitability for industrialized production.
Embodiment
Below by embodiment the present invention is done further specific descriptions, but embodiments of the present invention are not limited thereto.
The preparation of embodiment 1. dibydro myricetrins-3-gallic acid ester
Get dibydro myricetrin 3.20g (10mmol), boric acid 1.24g (20mmol) is dissolved in 100mL 1 under 70 ℃; in the 4-dioxane, add gallic acid 2.40g (14mmol) then, tosic acid 0.50g (3mmol); under nitrogen protection, react; temperature is 105 ℃, insulation backflow 8h, pressure reducing and steaming solvent; use ethyl alcohol recrystallization; drying gets solid dibydro myricetrin-3-gallic acid ester 3.86g, and productive rate is 81.86%.
The preparation of embodiment 2. dibydro myricetrins-3-gallic acid ester
Get dibydro myricetrin 3.20g (10mmol), boric acid 1.24g (20mmol) is dissolved under 70 ℃ in the 100mL hexanaphthene; add gallic acid 2.40g (14mmol) then, tosic acid 0.50g (3mmol), assembling water trap; nitrogen protection is fully stirred, and temperature is 95 ℃; insulation backflow 6h; cooled and filtered is used ethyl alcohol recrystallization, drying; get solid dibydro myricetrin-3-gallic acid ester 3.31g, productive rate is 70.20%.
The preparation of embodiment 3. dibydro myricetrins-3-acetic ester
Get dibydro myricetrin 3.20g (10mmol), boric acid 1.24g (20mmol) is dissolved in 100mL 1 under 70 ℃; in the 4-dioxane, add glacial acetic acid 0.84g (14mmol) then, tosic acid 0.50g (3mmol); under nitrogen protection, react; temperature is 105 ℃, insulation backflow 6h, pressure reducing and steaming solvent; use ethyl alcohol recrystallization; drying gets solid dibydro myricetrin-3-acetic ester 2.25g, and productive rate is 62.15%.
Comparative Examples 1. dibydro myricetrins-3-carboxylicesters and the anti-oxidant test of dibydro myricetrin carboxylicesters
Be that the described method of patent application of CN200410026610.5 prepares dibydro myricetrin-3-carboxylicesters, the dibydro myricetrin carboxylicesters is to be measured by the present invention and Chinese patent publication number respectively, in the dibydro myricetrin carboxylicesters preparation process ratio of dibydro myricetrin and carboxylic acid halides be divided into 1: 1 and 1: 6 two kinds.With blank sample, 2,6 ditertiary butyl p cresol (BHT), dibydro myricetrin is control sample, carries out anti-oxidant test according to the following steps respectively:
Take by weighing lard 25g, add the sample of 0.01g, fully mixing is placed in 70 ℃ of constant temperature vibrating bins heat tracing in the water-bath.Accurately take by weighing 2g lard every 48h, place the iodine flask of 250mL, add 25mL trichloromethane-glacial acetic acid (V
Glacial acetic acid: V
Chloroform=3: 2) mixed solution dissolves lard fully.Add the 1.00mL saturated solution of potassium iodide, closely filled in bottle cap, and jolting 0.5min gently, 5min in the dark placed then.Taking-up adds 100mL water, shakes up, and uses 2 * 10 at once
-3MolL
-1The sodium thiosulfate standard solution titration adds the 1mL Starch Indicator to faint yellow, continues titration to blue the disappearance and is terminal point.Experimental result sees Table 1.
The experimental result of table 1 shows that the antioxygenic activity of dibydro myricetrin-3-carboxylicesters is better than dibydro myricetrin, 2,6-ditertbutylparacresol (BHT), also being better than by the Chinese patent publication number is the described method synthetic of the patent application dibydro myricetrin carboxylicesters of CN200410026610.5.
The POV value (peroxide value) of the anti-oxidant test of table 1 sample
Claims (8)
1, dibydro myricetrin-3-carboxylicesters has general structure (I):
Wherein, R is fatty acid acyl or the aromatic acid acyl group that contains 1～7 carbon atom.
2, the described dibydro myricetrin of claim 1-3-carboxylicesters is characterized in that, described fatty acid acyl is formyl radical, ethanoyl, propionyl, butyryl radicals, pentanoyl, caproyl or oenanthyl.
3, the described dibydro myricetrin of claim 1-3-carboxylicesters; it is characterized in that described aromatic acid acyl group is galloyl, salicyloyl, benzoyl, para hydroxybenzene formyl radical, protocatechuoyl, vanilloyl, coffee acyl, cinnamoyl, to hydroxyl cinnamoyl, asafoetide acyl group, different asafoetide acyl group or green former acyl group.
4, the preparation method of the described dibydro myricetrin of claim 1-3-carboxylicesters is characterized in that, may further comprise the steps:
Dibydro myricetrin is mixed than 1: 1～3 by amount with complexing agent; be dissolved in the inert organic solvents at 60～80 ℃; the aliphatic or aromatic acid that adds 1.2～1.8 times of dibydro myricetrin amounts then adds catalyzer again, reacts under nitrogen protection; temperature of reaction is 80～120 ℃; reaction times is 4～12h, and the pressure reducing and steaming solvent is used ethyl alcohol recrystallization; drying makes dibydro myricetrin-3-carboxylicesters.
5, the preparation method of the described dibydro myricetrin of claim 4-3-carboxylicesters is characterized in that described complexing agent is a boric acid.
6, the preparation method of the described dibydro myricetrin of claim 4-3-carboxylicesters is characterized in that described inert solvent is 1,4-dioxane, methyl-sulphoxide, N, and one or more arbitrary proportions in dinethylformamide, the hexanaphthene mix.
7, the preparation method of the described dibydro myricetrin of claim 4-3-carboxylicesters is characterized in that, described catalyzer is that one or more arbitrary proportions in the sulfonic compound mix.
8, the preparation method of the described dibydro myricetrin of claim 7-3-carboxylicesters is characterized in that, described sulfonic compound is tosic acid, Phenylsulfonic acid or thionamic acid.
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| CN 200910037329 CN101492439A (en) | 2009-02-18 | 2009-02-18 | Dihydromyricetin-3-carboxylic ester and preparation method thereof |
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| CN 200910037329 CN101492439A (en) | 2009-02-18 | 2009-02-18 | Dihydromyricetin-3-carboxylic ester and preparation method thereof |
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| CN101492439A true CN101492439A (en) | 2009-07-29 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103549154A (en) * | 2013-11-11 | 2014-02-05 | 天津盛康源生物科技发展有限公司 | Application of dihydromyricetin laurate as feed additive |
| CN110693872A (en) * | 2019-10-24 | 2020-01-17 | 贵州省生物研究所 | Dihydromyricetin with broad-spectrum anti-tumor activity, derivative and application thereof |
| CN114807262A (en) * | 2022-05-25 | 2022-07-29 | 江南大学 | Dihydromyricetin acylated derivative and preparation method thereof |
-
2009
- 2009-02-18 CN CN 200910037329 patent/CN101492439A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103549154A (en) * | 2013-11-11 | 2014-02-05 | 天津盛康源生物科技发展有限公司 | Application of dihydromyricetin laurate as feed additive |
| CN103549154B (en) * | 2013-11-11 | 2015-02-18 | 天津盛康源生物科技发展有限公司 | Application of dihydromyricetin laurate as feed additive |
| CN110693872A (en) * | 2019-10-24 | 2020-01-17 | 贵州省生物研究所 | Dihydromyricetin with broad-spectrum anti-tumor activity, derivative and application thereof |
| CN114807262A (en) * | 2022-05-25 | 2022-07-29 | 江南大学 | Dihydromyricetin acylated derivative and preparation method thereof |
| CN114807262B (en) * | 2022-05-25 | 2023-07-25 | 江南大学 | Dihydromyricetin acylated derivative and preparation method thereof |
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