CN104496768A - Highly-efficient synthetic method for 2, 6-dimethoxy-4-vinylphenol - Google Patents
Highly-efficient synthetic method for 2, 6-dimethoxy-4-vinylphenol Download PDFInfo
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Abstract
The invention provides a highly-efficient synthetic method for 2, 6-dimethoxy-4-vinylphenol. The method comprises the following steps: with sinapic acid as a raw material and alumina as a solid-phase carrier, carrying out thermal decarboxylation in the presence of an alkaline catalyst under a microwave-assisted condition, adding a polymerization inhibitor to reduce and prevent polymerization of synthetic products, neutralizing the alkaline catalyst in the reaction system when the reaction is completed, extracting the synthetic products with an organic solvent, carrying out washing and drying, then carrying out purifying by using preparative liquid chromatography, and carrying out vacuum drying to obtain high-purity 2, 6-dimethoxy-4-vinylphenol. The highly-efficient synthetic method for 2, 6-dimethoxy-4-vinylphenol provided by the invention has the characteristics of significant improvement of reaction rate, fast temperature rise, convenient operation, high conversion rate, easy purification of the products, etc.; and the synthesized 2, 6-dimethoxy-4-vinylphenol has the properties of high purity, strong oxidation resistance, etc.
Description
Technical field
The present invention relates to food chemistry synthesis technical field, be specifically related to a kind of high-efficiency synthesis method of 2,6-dimethoxy-4 '-vinylphenol.
Background technology
Polyphenolic compound is the class secondary metabolite be extensively present in plant, plays and prevent the damage of plant ultraviolet radiation, anti-insect, virus and the infringement of bacterium and the regulating effect of plant hormone in the process of growth of plant.Rape is one of most important oil crops of China, long-term cultivated area about 1.2 hundred million mu, and total product 1100-1200 ten thousand tons, accounts for 25% of the world.Polyphenol content in Semen Brassicae campestris, far above other oil crops, reaches 2-4%, and containing about 3% in dregs of rapeseed cake after degreasing, is approximately 30 times of dregs of beans.Polyphenol from rapeseed is divided into phenolic acid and tannin, and wherein phenolic acid is divided into again the esterification of free phenolic acid, solubility or glucoside phenolic acid and insoluble phenolic acid, and tannin is divided into again solubility and soluble tannin.Sinapinic acid (3,5-dimethoxy-4 '-hydroxy-cinnamic acid) is topmost phenolic acid in Semen Brassicae campestris, accounts for 80% of free phenolic acid.Large quantity research shows, plant polyphenol has superior antioxidant property, in anticancer, Antiradiation injury, resisting pathogenic microbes, reducing blood-fat, prevents and treats all many-sides such as cardiovascular system diseases and has good action.The phenolic hydroxyl structure of polyphenol from rapeseed makes it to have stronger Scavenging ability and antioxidant property, can develop delay senility, the healthcare products of prophylaxis of tumours and cardio-cerebrovascular diseases and natural antioxidants.
There are some researches show, heat-treated oil vegetable seed can make wherein naturally occurring sinapinic acid decarboxylation change into novel polyphenol from rapeseed 2,6-dimethoxy-4 's-vinylphenol (2,6-dimethoxy-4-vinylphenol).Compared with sinapinic acid, the anti-oxidant activity of 2,6-dimethoxy-4 '-vinylphenol is higher, and has antimutagenic characteristic, and therefore, this compound has very important using value and potentiality.2,6-dimethoxy-4 '-vinylphenol has stronger fat-soluble, about has transferring in oil of 50-80%, thus significantly improve oil oxidation stability after liquefaction.In general rapeseed oil 2,6-dimethoxy-4 '-vinylphenol content is 0-2000 μ g/g, along with the increase of rapeseed oil processing degree, in oil 2,6-dimethoxy-4 '-vinylphenol almost complete loss, therefore, can't detect the existence of 2,6-dimethoxy-4 '-vinylphenol in full refining rapeseed oil.
Although Semen Brassicae campestris is liquefaction after Overheating Treatment, in oil 2, the content of 6-dimethoxy-4 '-vinylphenol significantly improves, but from oil, there is two problems during this material of extraction purification: one is do not possess economy (overall content is on the low side), and two is also there is no need (can improve oil oxidation stability in oil).Therefore, efficiently synthesizing 2,6-dimethoxy-4 '-vinylphenol is a practicable approach.
Through retrieval, the domestic patent about extraction purification polyphenol from rapeseed from Semen Brassicae campestris or rapeseed oil, rapeseed meal has 2: the Chinese Academy of Forestry applies for and discloses " one Semen Brassicae campestris is soaked slag (dregs of rice) and extracted the method (ZL 201110000781.0) preparing phenolic acid ", and Hua Zhong Agriculture University applies for and discloses " from rapeseed cake dregs or rapeseed hull extraction agent extracting polyphenol and preparation method thereof (ZL 200410012980.3) ".The main bibliographical information about " polyphenol from rapeseed " has the novel technology for extracting research of polyphenol from rapeseed " in the dregs of rapeseed cake ", " extraction of polyphenol from rapeseed, purifying, Structural Identification and functionally active are commented ", " Preliminary Purification of Rapeseed Polyphenol by Column Chromatography of Macroreticular Resin ", " extraction of tannin in Semen Brassicae campestris, composition and property Quality Research " etc.
ZL 201110000781.0 discloses one Semen Brassicae campestris and soaks slag (dregs of rice) and extract and prepare the method for phenolic acid.This patent is with the dish dregs of rice for raw material, and with 70% methanol/ethanol solution for extraction solvent, extracting solution sodium hydroxide solution is hydrolyzed, and then uses hydrochloric acid conditioning solution pH value, is finally extracted with ethyl acetate, and obtains vegetable seed phenolic acid after lyophilize.The phenolic acid crude product yield 1.61%-2.57% (with charging capacity ratio) of this patent, phenolic acid fine work yield 0.9%-1.5%.
ZL 200410012980.3 discloses extraction agent extracting polyphenol and preparation method thereof from rapeseed cake dregs or rapeseed hull.Extraction agent described in this patent is neutral calcium salt or some components such as analogue and ethanol, adopt this extraction agent, with the dish dregs of rice or degreasing vegetable seed skin for raw material, obtain refining polyphenol from rapeseed through operations such as lixiviate, vacuum distilling, purification by column chromatography, vacuum concentration and dryings, refining polyphenol from rapeseed can obtain the more much higher phenol fraction of purity with the purifying such as resin or dextrane gel further.The polyphenol yield of this patent is 1.7%-2.3%, and purity is respectively 40%-70% and more than 98%.
At present both at home and abroad also not about the patent of novel polyphenol from rapeseed 2,6-dimethoxy-4 's-vinylphenol synthetic method aspect, representative to publish document as follows:
It is raw material that the people such as Sinha report with syringic aldehyde, Microwave synthesize 2, the method of 6-dimethoxy-4 '-vinylphenol, main process is as follows: take a certain amount of syringic aldehyde, add propanedioic acid, piperidines and acetic acid, after mixing under 150W power and 130 DEG C of conditions, microwave auxiliary reflux reaction 8min, frozen water is poured into after cooling, be extracted with ethyl acetate 3 times again, organic phase saturated common salt water washing also uses dried over sodium sulfate, solvent evaporation under reduced pressure, then silica column purification is used, normal hexane and ethyl acetate mixed solvent wash-out, obtain 2, 6-dimethoxy-4 '-vinylphenol purity reaches 86%.(literature reference: Sinha, A.K.; Sharma, A.; Joshi, B.P.One-pot two-step synthesis of 4-vinylphenols from 4-hydroxysubstituted benzaldehydes under microwave irradiation:A new perspective on theclassical Knoevenagel-Doebner reaction.Tetrahedron 2007,63 (4), 960-965.)
It is raw material that the people such as Bernini report with sinapinic acid, Microwave synthesize 2, the method of 6-dimethoxy-4 '-vinylphenol, main process is as follows: take a certain amount of sinapinic acid, add 1, 8-diazabicyclo [5.4.0]-7-undecylene, Resorcinol and aluminum oxide, first by the solvent evaporation under reduced pressure in system, then microwave heating 15min under 650w power, neutralize with hydrochloric acid soln after being cooled to room temperature, be extracted with ethyl acetate three times again, organic phase saturated common salt water washing also uses anhydrous sodium sulfate drying, 2, the productive rate of 6-dimethoxy-4 '-vinylphenol is 84%.(literature reference: Bernini, R.; Mincione, E.; Barontini, M.; Provenzano, G.; Setti, L.Obtaining 4-vinylphenols by decarboxylation of natural4-hydroxycinnamic acids under microwave irradiation.Tetrahedron 2007,63,9663-9667.)
The people such as Harbaum-Piayda report with 4-acetoxy-3,5-dimethoxy styrene is that raw material is hydrolyzed preparation 2, the method of 6-dimethoxy-4 '-vinylphenol, key step is as follows: potassium hydroxide is dissolved in methyl alcohol, add 4-acetoxy-3,5-dimethoxy styrene methanol solution, suspension is placed in overnight at room temperature (15h).Then with glacial acetic acid by suspension acidifying, then be extracted with ethyl acetate three times, organic phase washed with water and the washing of 5% sodium hydrogen carbonate solution, then vacuum-drying is except desolventizing, obtains 2,6-dimethoxy-4 '-vinylphenol.(literature reference: Harbaum-Piayda B, Oehlke K, S nichsen F, D, Zacchi P, Eggers R, Schwarz K.New polyphenolic compounds in commercial deodistillateand rapeseed oils.Food Chemistry, 2010,123:607-615.)
To sum up, also do not have special in 2 at present both at home and abroad, the patented technology that 6-dimethoxy-4 '-vinylphenol efficiently synthesizes, although there is foreign literature to report with syringic aldehyde, the sinapinic acid microwave synthesis method that is raw material and with 4-acetoxy-3,5-dimethoxy styrene is the hydrolysis method of raw material, but combined coefficient is not high, the synthetic method therefore developing a kind of 2,6-efficient, simple and direct dimethoxy-4 's-vinylphenol also just becomes one of study hotspot.
Summary of the invention
The object of this invention is to provide a kind of take sinapinic acid as the synthetic method of 2, the 6-dimethoxy-4 's-vinylphenol of raw material, and it has, and speed of reaction is fast, heat up quick, easy to operate, the characteristic such as transformation efficiency is high, product purity is high, oxidation-resistance is strong.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of high-efficiency synthesis method of 2,6-dimethoxy-4 '-vinylphenol, comprises the steps:
(1) preparation of solid-phase reaction system: take a certain amount of sinapinic acid and be placed in round-bottomed flask, after adding dissolve with methanol, add a certain amount of basic catalyst, stopper and solid phase carrier aluminum oxide, then make methyl alcohol evaporation under reduced pressure, obtain the equally distributed solid-phase reaction system of sinapinic acid;
(2) Microwave synthesize: round-bottomed flask is placed in microwave oven, arranges microwave parameters (power and time), solid-phase reaction system is reacted under microwave condition;
(3) neutralize: round-bottomed flask is taken out from microwave oven, is cooled to room temperature, add a certain amount of acid solution, in and solid-phase reaction system in basic catalyst;
(4) extract: with the synthetic product in organic solvent extraction solid-phase reaction system, carry out washing after collecting organic phase with dry;
(5) purifying: extraction liquid is injected preparative liquid chromatography instrument, on-line ultraviolet detects, and when appearance 2,6-dimethoxy-4 's-vinylphenol chromatographic peak, collects elutriant;
(6) dry: preparative liquid chromatography to be separated the elutriant obtained and to be placed in freeze drier, obtained 2,6-dimethoxy-4 '-vinylphenol white powder.
According to above scheme, the sinapinic acid in described step (1) and the mol ratio of basic catalyst be 1:3 ~ 1:9, be 1:0.05 ~ 1:0.3 with the mol ratio of stopper, be 1:10 ~ 1:30 with the mol ratio of aluminum oxide.
According to above scheme, basic catalyst in described step (1) comprises 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (1,8-Diazabicyclo [5.4.0] undec-7-ene, DBU), 1,5-diazabicyclo [4.3.0]-5-in ninth of the ten Heavenly Stems alkene (DBN), 2-Dimethylamino pyridine, DMAP (DMAP), DIPEA.
According to above scheme, the stopper in described step (1) comprises Resorcinol, para benzoquinone, phenothiazine, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone (TBHQ).
According to above scheme, during reduction vaporization in described step (1), vacuum tightness is-0.05 ~-0.1MPa, and temperature is 35 ~ 45 DEG C.
According to above scheme, the microwave power in described step (2) is 400 ~ 1200W, and the microwave time is 5 ~ 30min.
According to above scheme, the acid solution in described step (3) is hydrochloric acid soln, and its volumetric molar concentration is 0.5 ~ 1.5M, and add-on and the added basic catalyst equivalent of described step (1), by pH detection paper reaction system in neutral.
According to above scheme, the organic solvent in described step (4) is ethyl acetate, and the consumption of extraction solvent is 10 ~ 30mL, and extraction times is 3 times, has extracted rear merging organic phase; Washing in described step (4) comprises pure water or saturated common salt water washing, its objective is in order to catalyzer, stopper etc. residual in washing system; Drying in described step (4) is for using anhydrous sodium sulfate drying
According to above scheme, the preparative liquid chromatography condition in described step (5) is: chromatographic column is anti-phase C18 post, and mobile phase A is 100% ultrapure water, and Mobile phase B is 100% Chromatographic Pure Methanol, with 60 ~ 90% mobile phase A isocratic elutions.
According to above scheme, the lyophilize condition in described step (6) is: vacuum tightness 0.3 ~ 1.0mbar, condenser temperature-48 DEG C, shelf temperature 0 ~ 5 DEG C.
The present invention adopts high performance liquid chromatography to detect products obtained therefrom purity, weighs byproduct of reaction with 2,6-dimethoxy-4 '-vinylphenol dimer content, and the content of dipolymer adopts high performance liquid chromatography to detect.
Transformation efficiency of the present invention and productive rate calculate respectively as follows: amount × 100% of transformation efficiency (%)=(1-remains the amount of sinapinic acid)/initial sinapinic acid; Productive rate (%)=2,6-dimethoxy-4 's-vinylphenol growing amount/(1-remains the amount of sinapinic acid) × 100%.
The invention has the beneficial effects as follows:
(1) the present invention adopts the mode ancillary synthetic reaction of microwave radiation, have significantly improve speed of reaction, be rapidly heated, easy to operate, transformation efficiency is high and the feature such as easy purification of products.
(2) basic catalyst selectivity of the present invention is high, excellent catalytic effect; The stopper adopted can control the polymerization of synthetic product very well, dipolymer do not detected in final product, and stopper also can control the oxidation of target product in building-up process simultaneously.
(3) the present invention adopts preparative liquid chromatography purification of target product, have product purity high, pollute little advantage.
(4) the present invention adopts cryodesiccated mode to carry out the product after chromatogram purification, is conducive to the biological activity of containment objective product.
(5) integrated artistic of the present invention is simple and direct, simple to operate.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described.
Example 1:
A kind of high-efficiency synthesis method of 2,6-dimethoxy-4 '-vinylphenol, comprises the steps:
(1) preparation of solid-phase reaction system: take 1mmol sinapinic acid in 20mL round-bottomed flask, add 2mL dissolve with methanol, then add 6mmolDBU, 0.1mmol Resorcinol and 1g aluminum oxide; Round-bottomed flask is connected to Rotary Evaporators, arranges that bath temperature is 40 DEG C, vacuum tightness is-0.05MPa, the methyl alcohol in underpressure distillation removing reaction system;
(2) Microwave synthesize: round-bottomed flask is placed in microwave oven, arranges that microwave power is 800W, the microwave time is 20min, and question response terminates rear taking-up flask and is cooled to room temperature;
(3) neutralize: add the hydrochloric acid soln that concentration is 1M, vibration makes hydrochloric acid and DBU fully contact the system of being neutralized in neutral, uses pH detection paper;
(4) extract: add 10mL ethyl acetate oscillation extraction, after layering, shift ethyl acetate phase, then add 10mL ethyl acetate and extract 2 times respectively, combined ethyl acetate phase; Ethyl acetate uses saturated common salt water washing mutually to system in neutral, then uses anhydrous sodium sulfate drying, and collect washing and dried ethyl acetate phase, with this understanding, transformation efficiency is 40%, and productive rate is 63%;
(5) purifying: extraction liquid is injected preparative liquid chromatography instrument, 70% mobile phase A isocratic elution, UV-detector on-line checkingi, determined wavelength is 280nm, collects 2,6-dimethoxy-4 '-vinylphenol component;
(6) dry: to be placed in container by the elutriant collected, setting lyophilize condition is: vacuum tightness 0.95mbar, cold hydrazine temperature-48 DEG C, baffle temperature 0 DEG C, obtains 2,6-dimethoxy-4 '-vinylphenol white powder after freeze-drying.
Obtained 2,6-dimethoxy-4 's-vinylphenol dissolve with methanol, through liquid chromatography calculated by peak area, its purity is 98.5%.
Embodiment 2:
A kind of high-efficiency synthesis method of 2,6-dimethoxy-4 '-vinylphenol, comprises the steps:
(1) preparation of solid-phase reaction system: take 0.2mmol sinapinic acid in 100mL round-bottomed flask, add 2mL dissolve with methanol, then add 1.2mmolDBU, 0.02mmol phenothiazine and 4mmol aluminum oxide; Round-bottomed flask is connected to Rotary Evaporators, arranges that bath temperature is 40 DEG C, vacuum tightness is-0.08MPa, the methyl alcohol in underpressure distillation removing reaction system;
(2) Microwave synthesize: round-bottomed flask is placed in microwave oven, arranges that microwave power is 800W, the microwave time is 5min, and question response terminates rear taking-up flask and is cooled to room temperature;
(3) neutralize: add the hydrochloric acid soln that concentration is 1M, vibration makes hydrochloric acid and DBU fully contact the system of being neutralized in neutral, uses pH detection paper;
(4) extract: add 10mL ethyl acetate oscillation extraction, after layering, shift ethyl acetate phase, then add 10mL ethyl acetate and extract 2 times respectively, combined ethyl acetate phase; Ethyl acetate uses saturated common salt water washing mutually to system in neutral, then uses anhydrous sodium sulfate drying, collects washing and dried ethyl acetate phase.With this understanding, transformation efficiency is 55%, and productive rate is 65%;
(5) purifying: extraction liquid is injected preparative liquid chromatography instrument, 70% mobile phase A isocratic elution, UV-detector on-line checkingi, determined wavelength is 280nm, collects 2,6-dimethoxy-4 '-vinylphenol component;
(6) dry: to be placed in container by the elutriant collected, setting lyophilize condition is: vacuum tightness 0.65mbar, cold hydrazine temperature-48 DEG C, baffle temperature 5 DEG C, obtains 2,6-dimethoxy-4 '-vinylphenol white powder after freeze-drying.
Obtained 2,6-dimethoxy-4 's-vinylphenol dissolve with methanol, through liquid chromatography calculated by peak area, its purity is 99%.
Embodiment 3:
A kind of high-efficiency synthesis method of 2,6-dimethoxy-4 '-vinylphenol, comprises the steps:
(1) preparation of solid-phase reaction system: take 0.2mmol sinapinic acid in 100mL round-bottomed flask, add 2mL dissolve with methanol, then add 1.8mmolDBN, 0.06mmol Resorcinol and 6mmol aluminum oxide; Round-bottomed flask is connected to Rotary Evaporators, arranges that bath temperature is 35 DEG C, vacuum tightness is-0.06MPa, the methyl alcohol in underpressure distillation removing reaction system;
(2) Microwave synthesize: round-bottomed flask is placed in microwave oven, arranges that microwave power is 1200W, the microwave time is 10min, and question response terminates rear taking-up flask and is cooled to room temperature;
(3) neutralize: add the hydrochloric acid soln that concentration is 1.5M, vibration makes hydrochloric acid and DBU fully contact the system of being neutralized in neutral, uses pH detection paper;
(4) extract: add 10mL ethyl acetate oscillation extraction, after layering, shift ethyl acetate phase, then add 10mL ethyl acetate and extract 2 times respectively, combined ethyl acetate phase; Ethyl acetate uses saturated common salt water washing mutually to system in neutral, then uses anhydrous sodium sulfate drying, collects washing and dried ethyl acetate phase; With this understanding, transformation efficiency is 62%, and productive rate is 76%;
(5) purifying: extraction liquid is injected preparative liquid chromatography instrument, 70% mobile phase A isocratic elution, UV-detector on-line checkingi, determined wavelength is 280nm, collects 2,6-dimethoxy-4 '-vinylphenol component;
(6) dry: to be placed in container by the elutriant collected, setting lyophilize condition is: vacuum tightness 0.3mbar, cold hydrazine temperature-48 DEG C, baffle temperature 3 DEG C, obtains 2,6-dimethoxy-4 '-vinylphenol white powder after freeze-drying.
Obtained 2,6-dimethoxy-4 's-vinylphenol dissolve with methanol, through liquid chromatography calculated by peak area, its purity is 98%.
Embodiment 4:
A kind of high-efficiency synthesis method of 2,6-dimethoxy-4 '-vinylphenol, comprises the steps:
(1) preparation of solid-phase reaction system: take 0.2mmol sinapinic acid in 100mL round-bottomed flask, add 2mL dissolve with methanol, then add 0.6mmolDBU, 0.01mmolTBHQ and 2mmol aluminum oxide; Round-bottomed flask is connected to Rotary Evaporators, arranges that bath temperature is 45 DEG C, vacuum tightness is-0.1MPa, the methyl alcohol in underpressure distillation removing reaction system;
(2) Microwave synthesize: round-bottomed flask is placed in microwave oven, arranges that microwave power is 400W, the microwave time is 30min, and question response terminates rear taking-up flask and is cooled to room temperature;
(3) neutralize: add the hydrochloric acid soln that concentration is 0.5M, vibration makes hydrochloric acid and DBU fully contact the system of being neutralized in neutral, uses pH detection paper;
(4) extract: add 10mL ethyl acetate oscillation extraction, after layering, shift ethyl acetate phase, then add 10mL ethyl acetate and extract 2 times respectively, combined ethyl acetate phase; Ethyl acetate uses saturated common salt water washing mutually to system in neutral, then uses anhydrous sodium sulfate drying, collects washing and dried ethyl acetate phase.With this understanding, transformation efficiency is 55%, and productive rate is 78%;
(5) purifying: extraction liquid is injected preparative liquid chromatography instrument, 70% mobile phase A isocratic elution, UV-detector on-line checkingi, determined wavelength is 280nm, collects 2,6-dimethoxy-4 '-vinylphenol component;
(6) dry: to be placed in container by the elutriant collected, setting lyophilize condition is: vacuum tightness 1.0mbar, cold hydrazine temperature-48 DEG C, baffle temperature 2 DEG C, obtains 2,6-dimethoxy-4 '-vinylphenol white powder after freeze-drying.
Obtained 2,6-dimethoxy-4 's-vinylphenol dissolve with methanol, through liquid chromatography calculated by peak area, its purity is 98%.
Above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although above-described embodiment is to invention has been detailed description, the person skilled of this area is to be understood that: can modify to the present invention or replace on an equal basis, but any amendment not departing from spirit and scope of the invention all should be encompassed in right of the present invention with local replacement.
Claims (10)
1. the high-efficiency synthesis method of 2,6-dimethoxy-4 's-vinylphenol, is characterized in that comprising the steps:
(1) preparation of solid-phase reaction system: take a certain amount of sinapinic acid and be placed in round-bottomed flask, after adding dissolve with methanol, add a certain amount of basic catalyst, stopper and solid phase carrier aluminum oxide, then make methyl alcohol evaporation under reduced pressure, obtain the equally distributed solid-phase reaction system of sinapinic acid;
(2) Microwave synthesize: round-bottomed flask is placed in microwave oven, arranges microwave parameters, and solid-phase reaction system is reacted under microwave condition;
(3) neutralize: round-bottomed flask is taken out from microwave oven, is cooled to room temperature, add a certain amount of acid solution, in and solid-phase reaction system in basic catalyst;
(4) extract: with the synthetic product in organic solvent extraction solid-phase reaction system, carry out washing after collecting organic phase with dry;
(5) purifying: extraction liquid is injected preparative liquid chromatography instrument, on-line ultraviolet detects, and when appearance 2,6-dimethoxy-4 's-vinylphenol chromatographic peak, collects elutriant;
(6) dry: preparative liquid chromatography to be separated the elutriant obtained and to be placed in freeze drier, obtained 2,6-dimethoxy-4 '-vinylphenol white powder.
2. according to claim 12, the high-efficiency synthesis method of 6-dimethoxy-4 '-vinylphenol, it is characterized in that, the sinapinic acid in described step (1) and the mol ratio of basic catalyst be 1:3 ~ 1:9, be 1:0.05 ~ 1:0.3 with the mol ratio of stopper, be 1:10 ~ 1:30 with the mol ratio of aluminum oxide.
3. according to claim 12, the high-efficiency synthesis method of 6-dimethoxy-4 '-vinylphenol, it is characterized in that, basic catalyst in described step (1) comprises 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1,5-diazabicyclo [4.3.0]-5-in ninth of the ten Heavenly Stems alkene, 2-Dimethylamino pyridine, DMAP, DIPEA.
4. according to claim 12, the high-efficiency synthesis method of 6-dimethoxy-4 '-vinylphenol, it is characterized in that, the stopper in described step (1) comprises Resorcinol, para benzoquinone, phenothiazine, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone.
5. the high-efficiency synthesis method of 2,6-dimethoxy-4 's according to claim 1-vinylphenol, is characterized in that, during reduction vaporization in described step (1), vacuum tightness is-0.05 ~-0.1MPa, and temperature is 35 ~ 45 DEG C.
6. the high-efficiency synthesis method of 2,6-dimethoxy-4 's according to claim 1-vinylphenol, is characterized in that, the microwave power in described step (2) is 400 ~ 1200W, and the microwave time is 5 ~ 30min.
7. according to claim 12, the high-efficiency synthesis method of 6-dimethoxy-4 '-vinylphenol, it is characterized in that, acid solution in described step (3) is hydrochloric acid soln, its volumetric molar concentration is 0.5 ~ 1.5M, add-on and the added basic catalyst equivalent of described step (1), by pH detection paper reaction system in neutral.
8. the high-efficiency synthesis method of 2,6-dimethoxy-4 's according to claim 1-vinylphenol, is characterized in that, organic solvent in described step (4) is ethyl acetate, the consumption of extraction solvent is 10 ~ 30mL, and extraction times is 3 times, has extracted rear merging organic phase; Washing in described step (4) comprises pure water or saturated common salt water washing, its objective is in order to catalyzer, stopper etc. residual in washing system; Drying in described step (4) is for using anhydrous sodium sulfate drying.
9. according to claim 12, the high-efficiency synthesis method of 6-dimethoxy-4 '-vinylphenol, it is characterized in that, preparative liquid chromatography condition in described step (5) is: chromatographic column is anti-phase C18 post, mobile phase A is 100% ultrapure water, Mobile phase B is 100% Chromatographic Pure Methanol, with 60 ~ 90% mobile phase A isocratic elutions.
10. according to claim 12, the high-efficiency synthesis method of 6-dimethoxy-4 '-vinylphenol, is characterized in that, the lyophilize condition in described step (6) is: vacuum tightness 0.3 ~ 1.0mbar, condenser temperature-48 DEG C, shelf temperature 0 ~ 5 DEG C.
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| CN110615731A (en) * | 2019-09-16 | 2019-12-27 | 中国农业科学院油料作物研究所 | Method for preparing 2, 6-dimethoxy-4-vinylphenol |
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| CN110615731A (en) * | 2019-09-16 | 2019-12-27 | 中国农业科学院油料作物研究所 | Method for preparing 2, 6-dimethoxy-4-vinylphenol |
| CN110615731B (en) * | 2019-09-16 | 2022-10-14 | 中国农业科学院油料作物研究所 | Method for preparing 2, 6-dimethoxy-4-vinylphenol |
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