CN102180773A - Method for preparing resveratrol - Google Patents
Method for preparing resveratrol Download PDFInfo
- Publication number
- CN102180773A CN102180773A CN2011100769335A CN201110076933A CN102180773A CN 102180773 A CN102180773 A CN 102180773A CN 2011100769335 A CN2011100769335 A CN 2011100769335A CN 201110076933 A CN201110076933 A CN 201110076933A CN 102180773 A CN102180773 A CN 102180773A
- Authority
- CN
- China
- Prior art keywords
- resveratrol
- reaction
- dimethoxyphenyl
- phenyl
- methoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses a method for preparing resveratrol, which comprises the following steps of: (1) preparing an intermediate (E)-2-(4-methoxyphenyl)-3-(3,5-dimethoxyphenyl)-acrylic acid; (2) performing decarboxylation reaction on the intermediate to prepare Z-3,4',5-trimethoxystilbene; and (3) performing protecting group removal or isomerization on the Z-3,4',5-trimethoxystilbene to prepare E-3,4',5-trihydroxystilbene, namely trans-resveratrol. In the method for preparing the resveratrol, inorganic alkali or organic alkali is added into an organic solvent and copper salt with catalytic amount is taken as a catalyst in the step (2), so compared with a quinoline/Cu powder catalyst in the prior art, the copper salt catalyst ensures that reaction time is greatly shortened, the reaction temperature is obviously reduced and reactants are difficult to carbonize; and the obtained product is single and easy to separate and purify.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of method for preparing trans-resveratrol.
Background technology
(Resveratrol, Res), chemistry is by name for trans-resveratrol
E-3,4 ', 5-trihydroxy-toluylene, extensively be present in the various plants such as grape, giant knotweed, Cassia tora, peanut, be natural polyphenol class phytoalexin, have many important biological, as reducing blood-fat, platelet aggregation-against, anti-oxidant, Green Tea Extract, antisepsis and anti-inflammation, antitumor, osteoporosis, skin care is brightened and prolongs life etc., because of the physiological function of its multiple beneficial has been subjected to increasingly extensive attention.Pezzuto in 1997 etc. report trans-resveratrol that initial, hyperplasia and three main phase of expansion that cancer takes place are all had restraining effect at " Science " magazine.A countries and regions is at exploitation trans-resveratrol raw material and preparation surplus in the of ten in the world at present, and it is called the another new green cancer therapy drug after taxol.The near over thousands of kind of the high-end formulation products of trans-resveratrol (comprising medicine and healthcare products) of American-European approved listing, market value is at 1.8 ten thousand～2.0 ten thousand yuan/kg.
In the prior art, the method for preparing trans-resveratrol mainly contains 3 kinds of approach: (1) plant extract method; (2) biological fermentation process; (3) chemical synthesis.Wherein, the committed step in the chemical synthesis is the structure of toluylene skeleton, and construction process mainly contains at present: and (1) Witting reaction method (referring to: J Med. Chem. 2003,46:3546-3554; Chem. Pharm. Bull. 1992,40 (5): 1130-1136); (2) Witting-Horner reaction (referring to: the patent No. is 200610037059.3 Chinese invention patent); (3) the Heck reaction method (referring to Tetrahedron Letters, 2002,43:597-598); (4) Perkin reaction (referring to: Tetrahedron, 2003,59:3315-3321; The patent No. is 200510101900.6,200910037290.6 Chinese invention patent).
There is limitation separately in above-mentioned various chemical synthesis process, and is relatively poor as Witting, Witting-Horner reaction and Heck reaction of atomic economy, and the condition harshness needs anhydrous, strong basicity and cold condition.The Perkin reaction scheme is brief, but decarboxylation reaction conditions harshness, need high temperature, for example: the patent No. is that 200510101900.6 Chinese invention patent discloses a kind of method for preparing trans-resveratrol: by 3, condensation reaction takes place in 5-dimethoxy benzaldehyde and PARA METHOXY PHENYL ACETONITRILE under sodium catalysis, form the toluylene skeleton structure, through high-temperature hydrolysis and decarboxylic reaction, obtain genial trans-3,4 ', 5-trimethoxy toluylene mixture, separation or isomerization obtain trans 3 then, 4 ', 5-trimethoxy toluylene obtains trans-resveratrol by demethylating reaction at last; Wherein, decarboxylic reaction need be with 4～6 times of normal copper powders as catalyzer, and the reaction times is 2～5 hours, and temperature of reaction is 160～240 ℃.The contriver repeats this experiment according to the technical scheme of this patent disclosure record, and reaction below 220 ℃ 4 hours, productive rate was 68%; 190 ℃ of reactions 2 hours, decarboxylize was less, reacts 4 hours, and productive rate is 40.9%.Owing to used a large amount of copper powder catalysts in this method, therefore at a large amount of operational difficultys when synthetic, and the reaction times is longer, and temperature of reaction is higher, and product is
Z/EMixture need carry out column chromatography for separation, separation difficulty.Therefore the total recovery that obtains trans-resveratrol is not high, less than 30%.
The patent No. be the disclosed method for preparing trans-resveratrol of 200910037290.6 Chinese invention patents (
E)-2-(4-hydroxy phenyl)-3-(3, the 5-dihydroxy phenyl)-vinylformic acid need react 2～4 hours 200～220 ℃ of decarboxylations, obtained 54.8%～60.1% productive rate.If 180 ℃ of decarboxylations, need 8 hours, productive rate has only 50%.
Summary of the invention
Goal of the invention of the present invention provides the method that a kind of Perkin reaction method prepares trans-resveratrol, when improving total recovery, reduces catalyst consumption, shortens the reaction times, cuts down the consumption of energy, and simplifies the separation and purification process.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of method for preparing trans-resveratrol may further comprise the steps:
(1) preparation intermediate (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-vinylformic acid;
Also comprise: (2) carry out the decarboxylic reaction preparation to intermediate
Z-3,4 ', 5-trimethoxy toluylene;
(3) right at last
Z-3,4 ', 5-trimethoxy toluylene carries out deprotection base/isomerization, prepares
E-3,4 ', 5-trihydroxy-toluylene is trans-resveratrol;
Wherein, step (2) specifically comprises: will (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-vinylformic acid, alkali, catalyzer add in the high boiling solvent, and more than 20 minutes, separation and purification obtains then at 160～200 ℃ of following stirring reactions
Z-3,4 ', 5-trimethoxy toluylene; Described alkali is selected from: potassium hydroxide KOH, sodium hydroxide NaOH, lithium hydroxide LiOH, salt of wormwood K
2CO
3, yellow soda ash Na
2CO
3, cesium carbonate CsCO
3, 8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU); Described catalyzer is selected from: cuprous bromide CuBr, cuprous chloride CuCl, copper sulfate CuSO
4Described high boiling solvent is selected from: N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or quinoline; Described alkali, catalyzer and (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-acrylic acid mol ratio is 0.5～1.5: 0.1～1.5: 1.
In the technique scheme, in the step (2), described alkali is preferably KOH or NaOH.
In the technique scheme, in the step (2), described catalyzer is a mantoquita, rather than the copper powder that uses in the prior art.Copper powder is heavier, and in the prior art, the copper powder consumption is big, operational difficulty during big quantitative response; Described catalyzer is preferably cuprous bromide CuBr, and catalyst consumption be intermediate (
E0.2～0.5 times of)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-acrylic acid mole number.
In the technique scheme, in the step (2), described high boiling solvent is preferably quinoline.
In the technique scheme, in the step (2), temperature of reaction is preferably 180～195 ℃, and the reaction times is preferably 20 minutes～and 1.0 hours; The too high reaction times of temperature is long, when for example being higher than 220 ℃, if the reaction times reaches 2～5 hours, just causes the reaction system carbonization easily, and is unfavorable to the purifies and separates of product.
In the technique scheme, in the step (2), alkali, catalyzer and (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-acrylic acid mol ratio is preferably 1: 0.2～and 0.3: 1.
In the technique scheme, the preparation intermediate (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-acrylic acid carries out according to following steps: 3, and 5-dimethoxy benzaldehyde and homoanisic acid are at K
2CO
3Exist down, in diacetyl oxide, be heated to 100～160 ℃, carry out pul gold (Perkin) reaction 1～12h, separate and purify, obtain (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-vinylformic acid.
In the technique scheme, deprotection base in the step (3)/isomerized method is: will
Z-3,4 ', a kind of reaction in 5-trimethoxy toluylene and boron tribromide, boron trichloride or the aluminum chloride added water after 1～20 hour, extraction, and drying, evaporate to dryness, recrystallization prepares
E-3,4 ', 5-trihydroxy-toluylene is trans-resveratrol.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
In the method for preparing trans-resveratrol of the present invention, in the step (2), in organic solvent, add mineral alkali or organic bases, and the mantoquita (about 0.25 equivalent) with catalytic amount is a catalyzer, compares with quinoline in the prior art/Cu powder catalysis, and the reaction times shortens dramatically (from 2～5 hours, shorten to 20 minutes～2.0 hours), temperature of reaction obviously reduces (being reduced to 180～195 ℃ from 220 ℃), and reactant is difficult for carbonization, the easily separated purifying of product; And products therefrom is comparatively single (to be mainly
Z-3,4 ', 5-trimethoxy toluylene, rather than
Z/EMixture), therefore, the productive rate of decarboxylic reaction is higher among the present invention, and more than 68%, catalyst levels is few, and temperature of reaction is lower, and the reaction times is short, and energy consumption reduces, and product is single easily separated.And the reaction scheme of preparation trans-resveratrol of the present invention is short, so the overall yield height, is up to 62.7%.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-acrylic acid preparation
With 3,5-dimethoxy benzaldehyde 8.50g (51.15mmol), 4-methoxyphenylacetic acid 9.35g (56.27mmol), anhydrous K
2CO
33.53g (25.54mmol) drop in the 50mL round-bottomed flask, add 20mL and heavily steam diacetyl oxide, back flow reaction 2h.Add water after the cooling, separate out red oil, discard water layer, oily matter adds 2mol.L
-1NaOH solution 30mL, backflow 1h filters.Filtrate is used the concentrated hydrochloric acid acidifying, separates out precipitation.Filter, filter residue 80% ethyl alcohol recrystallization gets faint yellow solid 14.50g, productive rate 90.2%.mp：294～295℃。
Embodiment two:
Z-3,4 ', the preparation of 5-trimethoxy toluylene
Will (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-vinylformic acid 5.00g (15.90mmol), CuBr 0.65g (4.53mmol) and KOH0.89g (15.90mmol) add in the 50mL quinoline, reaction 0.5h in the time of 190 ℃.After reaction finishes, add the dilution of 20mL ethyl acetate, use 1mol.L successively
-1Hydrochloric acid, saturated common salt water washing, anhydrous MgSO
4Dry.Solvent evaporated, the alcohol-water recrystallization gets white crystal 3.49g, productive rate 81.2%.mp：57～58℃。
Embodiment three:
Z-3,4 ', the preparation of 5-trimethoxy toluylene
Will (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-vinylformic acid 5.00g (15.90mmol), CuBr 0.65g (4.53mmol) and NaOH 0.64g (16.0mmol) add in the 50mL quinoline, reaction 0.5h in the time of 190 ℃.After reaction finishes, add the dilution of 20mL ethyl acetate, use 1mol.L successively
-1Hydrochloric acid, saturated common salt water washing, anhydrous MgSO
4Dry.Solvent evaporated, the alcohol-water recrystallization gets white crystal 3.47g, productive rate 80.7%.mp：57～58℃。
Embodiment four:
Z-3,4 ', the preparation of 5-trimethoxy toluylene
Will (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-vinylformic acid 5.00g (15.90mmol), CuBr 0.65g (4.53mmol) and DBU2.42g (15.90mmol) add in the 50mL quinoline, reaction 1h in the time of 190 ℃.After reaction finishes, add the dilution of 20mL ethyl acetate, use 1mol.L successively
-1Hydrochloric acid, saturated common salt water washing, anhydrous MgSO
4Dry.Solvent evaporated, the alcohol-water recrystallization gets white crystal 3.01g, productive rate 70.1%.mp：57～58℃。
Embodiment five:
Z-3,4 ', the preparation of 5-trimethoxy toluylene
Will (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-vinylformic acid 5.00g (15.92mmol), CuBr 0.65g (4.53mmol) and NaOH 0.64g (16.0mmol) add among the 50mL DMSO, at 180 ℃ of reaction 2h.After reaction finishes, add the dilution of 20mL ethyl acetate, use 1mol.L successively
-1Hydrochloric acid, saturated common salt water washing, anhydrous MgSO
4Dry.Solvent evaporated, the alcohol-water recrystallization gets white crystal 2.94g, productive rate 68.4%.mp：57～58℃。
Embodiment six (comparative example):
Will (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-vinylformic acid 5.00g (15.90mmol), Cu powder 6.06g (95.4mmol) adds in the 50mL quinoline, reaction 4h in the time of 190 ℃.After reaction finishes, add the dilution of 20mL ethyl acetate, use 1mol.L successively
-1Hydrochloric acid, saturated common salt water washing, anhydrous MgSO
4Dry.Solvent evaporated, the alcohol-water recrystallization gets white crystal 1.76g, productive rate 40.9%.mp：57～58℃。
Embodiment two～six products therefroms are analyzed, are got following data:
1H-NMR(CDCl
3,?400M?Hz):?7.23(d,?2H,?
J?=?8.7?Hz,?ArH),?6.77(d,?2H,?
J?=?8.7?Hz,?ArH),?6.53(d,?1H,?
J?=?12.5?Hz,?CH=CH),?6.45~6.43(m,?3H,?CH=CH?&?ArH),?6.32(t,?1H,?
J?=?2.0?Hz,?ArH),?3.78(s,?3H,?OCH
3),?3.67(s,?6H,?OCH
3)。
Above digital proof gained compound really is a target product.
Embodiment seven: trans-resveratrol synthetic
With 1.80g (6.70mmol) 3,4 ', 5-trimethoxy toluylene is dissolved in the 15mL exsiccant methylene dichloride, and ice bath stirs and drips BBr down
3(5.7mL, dichloromethane solution 5mL 60.30mmol) slowly rise to room temperature behind the 0.5h, continue stirring reaction 5h.Add water 20mL then, and ethyl acetate extraction (3 * 20mL), merge organic phase, anhydrous MgSO
4Dry.Filter, evaporate to dryness, the alcohol-water recrystallization,
E-3,4 ', 5-trihydroxy-toluylene 1.31g, productive rate 85.7%.
Above-claimed cpd is analyzed, is got following data:
mp：263～264℃；
IR(KBr,?cm
-1):?3292,?3020,?1587,?1511,?1444,?1608,?964；
1H-NMR(DMSO-d
6,?400M?Hz):?9.58(s,?1H,?OH-4’),?9.24(s,?2H,?OH-3,5),?7.40(d,?2H,?
J?=?8.2?Hz,?ArH),?6.95(d,?1H,?
J?=?16.5?Hz,?CH=CH),?6.85~6.70(m,?3H,?CH=CH?&?ArH),?6.42(d,?2H,?
J?=?3.2?Hz,?ArH),?6.15(t,?1H,?
J?=?2.0?Hz,?ArH)；
13C-NMR(DMSO-d
6,?400MHz):159.1(C-3,5),?157.8(C-4’),?139.9(C-1),?128.7?(C-1’),?128.5?(C-β),?126.3(C-2’,6’),?116.2(C-3’,5’),?105.0(C-2,6),?102.4?(C-4).
Above digital proof gained compound really is a target product.
Claims (8)
1. method for preparing trans-resveratrol may further comprise the steps:
(1) preparation intermediate (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-vinylformic acid;
It is characterized in that, further comprising the steps of:
(2) step (1) gained intermediate is carried out the decarboxylic reaction preparation
Z-3,4 ', 5-trimethoxy toluylene;
(3) right
Z-3,4 ', 5-trimethoxy toluylene carries out deprotection base/isomerization, prepares
E-3,4 ', 5-trihydroxy-toluylene is trans-resveratrol;
Wherein, the described decarboxylic reaction of step (2) comprises: will (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-vinylformic acid, alkali, catalyzer add in the high boiling solvent, and more than 20 minutes, separation and purification obtains then at 160～200 ℃ of following stirring reactions
Z-3,4 ', 5-trimethoxy toluylene; Described alkali is selected from: potassium hydroxide, sodium hydroxide, lithium hydroxide, salt of wormwood, yellow soda ash, cesium carbonate, 8-diazabicyclo [5.4.0] 11 carbon-7-alkene; Described catalyzer is selected from: cuprous bromide, cuprous chloride, copper sulfate; Described high boiling solvent is selected from: N, dinethylformamide, dimethyl sulfoxide (DMSO) or quinoline; Described alkali, catalyzer and (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-acrylic acid mol ratio is 0.5～1.5: 0.1～1.5: 1.
2. according to the described method for preparing trans-resveratrol of claim 1, it is characterized in that in the step (2), described alkali is potassium hydroxide or sodium hydroxide.
3. according to the described method for preparing trans-resveratrol of claim 1, it is characterized in that in the step (2), described catalyzer is a cuprous bromide, and catalyst consumption be intermediate (
E0.2～0.5 times of)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-acrylic acid mole number.
4. according to the described method for preparing trans-resveratrol of claim 1, it is characterized in that in the step (2), described high boiling solvent is a quinoline.
5. according to the described method for preparing trans-resveratrol of claim 1, it is characterized in that in the step (2), temperature of reaction is 180～195 ℃, the reaction times is 20 minutes～2 hours.
6. according to the described method for preparing trans-resveratrol of claim 1, it is characterized in that, in the step (2), alkali, catalyzer and (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-acrylic acid mol ratio is 1: 0.2～0.3: 1.
7. according to the described method for preparing trans-resveratrol of claim 1, it is characterized in that, preparation intermediate in the step (1) (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-acrylic acid is: 3, and 5-dimethoxy benzaldehyde and homoanisic acid are in the presence of salt of wormwood, in diacetyl oxide, be heated to 100～160 ℃, carry out pul gold reaction 1～12h, separate and purify, obtain (
E)-2-(4-p-methoxy-phenyl)-3-(3, the 5-Dimethoxyphenyl)-vinylformic acid.
8. according to the described method for preparing trans-resveratrol of claim 1, it is characterized in that deprotection base in the step (3)/isomerized method is: will
Z-3,4 ', a kind of reaction in 5-trimethoxy toluylene and boron tribromide, boron trichloride or the aluminum chloride added water after 1～20 hour, extraction, and drying, evaporate to dryness, recrystallization prepares
E-3,4 ', 5-trihydroxy-toluylene is trans-resveratrol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100769335A CN102180773B (en) | 2011-03-29 | 2011-03-29 | Method for preparing resveratrol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100769335A CN102180773B (en) | 2011-03-29 | 2011-03-29 | Method for preparing resveratrol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102180773A true CN102180773A (en) | 2011-09-14 |
| CN102180773B CN102180773B (en) | 2013-06-05 |
Family
ID=44567090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100769335A Expired - Fee Related CN102180773B (en) | 2011-03-29 | 2011-03-29 | Method for preparing resveratrol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102180773B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554266A (en) * | 2015-09-06 | 2017-04-05 | 联化科技(盐城)有限公司 | A kind of preparation method of methoxyphenylacetic acid, its intermediate and its salt |
| CN109689603A (en) * | 2016-10-04 | 2019-04-26 | Dic株式会社 | The manufacturing method of E- olefin(e) compound |
| CN110041173A (en) * | 2019-05-10 | 2019-07-23 | 贵州医科大学 | A kind of new resveratrol and its derivative synthesizing process and application |
| CN110172373A (en) * | 2019-06-14 | 2019-08-27 | 中国农业科学院农产品加工研究所 | Application of the resveratrol in peanut oil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481300A (en) * | 2009-02-20 | 2009-07-15 | 中国科学院广州化学研究所 | Preparation of trans-polyhydroxy diphenyl ethylene |
-
2011
- 2011-03-29 CN CN2011100769335A patent/CN102180773B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481300A (en) * | 2009-02-20 | 2009-07-15 | 中国科学院广州化学研究所 | Preparation of trans-polyhydroxy diphenyl ethylene |
Non-Patent Citations (1)
| Title |
|---|
| GUOXING LI, ET AL.: "An efficient synthesis of resveratrol and a hydroxyl derivative via the Perkin reaction cis to trans isomerisation in a demethylation process", 《JOURNAL OF CHEMICAL RESEARCH》, 30 November 2007 (2007-11-30), pages 657 - 659, XP008177037, DOI: doi:10.3184/030823407X266234 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554266A (en) * | 2015-09-06 | 2017-04-05 | 联化科技(盐城)有限公司 | A kind of preparation method of methoxyphenylacetic acid, its intermediate and its salt |
| CN106554266B (en) * | 2015-09-06 | 2020-02-11 | 联化科技(盐城)有限公司 | Preparation method of methoxyphenylacetic acid, intermediate thereof and salt thereof |
| CN109689603A (en) * | 2016-10-04 | 2019-04-26 | Dic株式会社 | The manufacturing method of E- olefin(e) compound |
| CN110041173A (en) * | 2019-05-10 | 2019-07-23 | 贵州医科大学 | A kind of new resveratrol and its derivative synthesizing process and application |
| CN110172373A (en) * | 2019-06-14 | 2019-08-27 | 中国农业科学院农产品加工研究所 | Application of the resveratrol in peanut oil |
| CN110172373B (en) * | 2019-06-14 | 2022-08-05 | 中国农业科学院农产品加工研究所 | Application of resveratrol in peanut oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102180773B (en) | 2013-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108689968B (en) | Two compounds, preparation method thereof and application thereof in synthesis of brivaracetam | |
| CN102180773B (en) | Method for preparing resveratrol | |
| CN102503805B (en) | Method for preparing 4-felbinac through rearrangement reaction | |
| CN102617302B (en) | Process for synthesizing trimethoxyphenyl stilbene | |
| CN106365986A (en) | Compounds and preparation methods thereof, and uses of compounds in synthesis of brivaracetam | |
| CN101066912B (en) | Process of preparing trans-polyhydroxy diphenyl ethylene | |
| CN101607971A (en) | 9-[2-(diethoxy phosphonium mesitoyl methoxyl group) ethyl] synthetic method of VITAMIN B4 | |
| CN102320984B (en) | Preparation method of (R)-3-(3-methoxy phenyl)-N,N,2-trimethylpent-3-ene-1-amine | |
| CN1923801A (en) | Preparation method of phenyl (S)-N-ethyl-N-methyl-3-[1-(dimethyamino)ethyl]-amidoformate (I) and tartrate thereof (II) | |
| CN101481300B (en) | Preparation of trans-polyhydroxy diphenyl ethylene | |
| CN103012268B (en) | Novel preparation method for ivabradine | |
| CN103450130A (en) | Toluylene compound and preparation method thereof | |
| CN110128439A (en) | It a kind of oxa-spiro compound and its efficiently synthesizes and method for splitting | |
| CN102126931B (en) | Preparation method of resveratrol | |
| CN101343214B (en) | Preparation method for E-diarylethene derivant containing phenolic hydroxyl group or acetoxy group | |
| CN103319356A (en) | One-step green synthesis process of antimalarial raw material benflumetol | |
| CN1150160C (en) | Process for synthesizing Tuoteluodin L-tartrate | |
| CN102557902A (en) | Preparation method for 5-fluorosalicylaldehyde | |
| CN103880740A (en) | Synthesis of 4-nitro-3-hydroxy-2-picolinic acid | |
| CN101812071A (en) | Method for processing mother liquor obtained by splitting clopidogrel hydrogen sulfate intermediate | |
| CN106946828A (en) | Scopolactone phenol ether derivative and its preparation method and application | |
| CN103193679B (en) | The preparation method of rivastigmine intermediate (R)-N-ethyl-N-methylamino formic acid-3-(1-hydroxyethyl) phenyl ester | |
| CN107915715A (en) | A kind of synthetic method of rosuvastatin calcium side chain key intermediate | |
| CN102381995A (en) | Preparation method of metoprolol | |
| CN100432035C (en) | Technical method for synthesizing beta p-hydroxy phenethyl alcohol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: Suzhou City, Jiangsu province 215137 Xiangcheng District Ji Road No. 8 Patentee after: Soochow University Address before: 215123 Suzhou City, Suzhou Province Industrial Park, No. love road, No. 199 Patentee before: Soochow University |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130605 Termination date: 20160329 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |