CN104262156A - Method for microwave-assisted fast and efficient preparation of phenethyl caffeate - Google Patents
Method for microwave-assisted fast and efficient preparation of phenethyl caffeate Download PDFInfo
- Publication number
- CN104262156A CN104262156A CN201410454887.1A CN201410454887A CN104262156A CN 104262156 A CN104262156 A CN 104262156A CN 201410454887 A CN201410454887 A CN 201410454887A CN 104262156 A CN104262156 A CN 104262156A
- Authority
- CN
- China
- Prior art keywords
- microwave
- reaction
- cape
- assisted
- rapidly
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of phenethyl caffeate. The preparation method is characterized by comprising the following steps: 1) putting reaction raw materials, namely adding caffeic acid, phenethyl alcohol, a reaction solvent and a molecular sieve into a reaction kettle, and uniformly stirring at normal temperatures to obtain a pre-mixture; introducing nitrogen to remove oxygen for 5 minutes to obtain the deoxidized pre-mixture, wherein the molar ratio of caffeic acid and phenethyl alcohol is (1:1)-(1:20), the mass ratio of caffeic acid and the reaction solvent is (1:1)-(1:20), and the addition amount of the molecular sieve is 50-80g/L; 2) carrying out microwave-assisted transesterification, namely adding 100-200ppm antioxidant into the deoxidized pre-mixture, controlling the temperature at 120-140 DEG C, stirring at an ordinary pressure for reaction for 5-20 minutes under a microwave-assisted condition, stopping microwave heating, and naturally cooling to 40 DEG C; and 3) carrying out post-treatment of a product to obtain phenethyl caffeate. The method has the characteristics of rapid reaction, simplicity in operation and mild reaction condition, the utilization ratio of raw materials can be effectively improved, and the prepared product phenethyl caffeate is high in purity and yield.
Description
Technical field
The present invention relates to a kind of preparation method of CAPE, being specifically related to a kind of is solvent and catalyzer with ionic liquid, and quick under microwave-assisted effect, efficiently to prepare CAPE method, belongs to natural product molecular modification and lipid field of deep.
Background technology
CAPE (CAPE), chemistry 3-(3 ', 4 '-dihydroxy phenyl)-2-vinylformic acid phenylglycollic ester by name, it is the principle active component in propolis, have anti-oxidant, antiviral, suppress DNA, cell death inducing, antibacterial, anti-inflammatory, arteriosclerosis and improve the multiple pharmacologically actives such as immunizing power, in antitumor, anti-oxidant, anti-inflammatory, immunomodulatory etc., show unique physiological and pharmacological effect.Wherein anti-tumor activity is the most remarkable, and receiving much concern, is the focus compound of current new drug development.It is reported, it is clinical that CAPE entered for III phase as antitumor drug abroad.
CAPE is mainly extracted from the natural matter such as propolis, Root of Kirilow Rhodiola; but the natural resource such as propolis are limited; and have that extraction and purification technique is loaded down with trivial details, cost is high; be difficult to problems such as accomplishing scale production, therefore the method for synthetic CAPE causes the concern of many experts and scholars.Synthetic method mainly contains biological synthesis process and chemical synthesis, biological synthesis process has that reaction conditions temperature is low, side reaction is few and the advantage such as environmentally friendly, but there is long reaction time, the suitableeest mol ratio of reaction of reaction substrate coffic acid and phenylethyl alcohol is low, solvent consumption is large, lipase usage quantity is large, and industrialization efficiency is low; The problems such as it is fast that chemical synthesis has speed of response, transformation efficiency advantages of higher, and be industrialized common method, but it is high to there is temperature of reaction, reaction yield is lower, and side reaction is many, the high and contaminate environment of energy consumption, have perplexed development prepared by CAPE mass-producing.At present, the synthesis report both at home and abroad about CAPE is more, and patent 201110302227.8 discloses caffeinic enzymatic synthesis method in ionic liquid, and this reaction times is longer, is 10-150h; Patent 201310066925.1 discloses in ionic liquid that coffic acid alkyl ester is by the method for transesterification enzyme' s catalysis CAPE, and wherein the reaction times longer (10-72h), the consumption of enzyme, phenylethyl alcohol and ionic liquid is all very big; Disclose the method for enzyme' s catalysis CAPE in a kind of complexation extraction agent/ionic liquid system in patent 201310391913.6, the method operation is comparatively complicated, and phenylethyl alcohol large usage quantity.
Microwave has a lot of advantage as hertzian wave in strengthening reaction: reaction solvent microwave energy absorbing, forms substrate, product solution system altogether, promotes the mass transfer between molecule; Compared with traditional heating, in reaction process, the stability of lipase of microwave treatment is stronger, and namely microwave treatment can significantly improve the stability of enzyme.Enzyme is electric dipole normally, and in microwave electric field, electric dipole can produce judder, increases mutual collision between molecule, thus produces more heat in lipase microenvironment, improves the speed of reaction.Microwave reinforced being applied in the esterification of CAPE can effectively be improved coffic acid solubleness, shorten reaction time of esterification, improve transformation efficiency and yield.The research report of CAPE enzyme' s catalysis is carried out seldom with microwave crop strengthening means about relating in the synthesis report of CAPE, one is disclosed in protic organic solvent by 3 in patent 201210209415.0,4-Dihydroxy benzaldehyde and Phenylethyl ethanoate pass through the method for microwave irradiation synthesis CAPE under organic base catalytic, this method catalysts and solvents is organism, is unfavorable for environmental protection.Under microwave-assisted condition, ionic liquid is simultaneously as catalysts and solvents, and the research of quick, efficient synthesis CAPE there is no report.
Summary of the invention
A kind of microwave-assisted is the object of the present invention is to provide rapidly and efficiently to prepare the method for CAPE, present method has and is swift in response, simple to operate, the feature of reaction conditions gentleness, effectively can improve raw material availability, the product CAPE purity of preparation and productive rate are all very high.
For achieving the above object, the technical solution used in the present invention is as follows: a kind of microwave-assisted rapidly and efficiently prepares the method for CAPE, it is characterized in that it comprises the steps:
1) pre-treatment of raw material: reaction solvent (ionic liquid), coffic acid are respectively at 60 DEG C-80 DEG C vacuum-drying 8-12h, and moisture content controls at below 1wt%; Phenylethyl alcohol adopts anhydrous sodium sulphate to dewater, and moisture content controls at below 0.2wt%;
2) input of reaction raw materials: coffic acid, phenylethyl alcohol, reaction solvent, molecular sieve are added in reactor, stirs under normal temperature, obtain pre-composition, logical nitrogen, except oxygen 5min, obtains the pre-composition after deoxygenation; Wherein, coffic acid and phenylethyl alcohol mol ratio are 1:1-1:20, and the mass ratio of coffic acid and reaction solvent is 1:1-1:20, and the add-on of molecular sieve is 50-80g/L (adding 50-80g molecular sieve in often liter of reaction solvent);
3) microwave-assisted transesterification reaction: add antioxidant 100-200ppm in the pre-composition after deoxygenation, temperature control is at 120-140 DEG C, and stirring reaction 5-20min under microwave-assisted normal pressure, stops microwave heating, naturally cool to 40 DEG C;
4) aftertreatment of product: after completion of the reaction, centrifugal removing molecular sieve, vacuum rotary steam removes excessive phenylethyl alcohol, obtains product; Adopt extraction agent (volume ratio of extraction agent and product is 1:1) to extract 3 times product CAPE to be extracted completely from reaction solvent (ionic liquid), vacuum rotary steam removing extraction agent, namely obtains CAPE.
By such scheme, the reaction solvent (i.e. the reaction solvent of esterification) described in step (1) is [Bmim] [Tf
2n], [Emim] PF
6, [Bmim] PF
6, [Omim] PF
6, [Bmim] [HSO
4], [Bmim] CF
3sO
3the mixture of any proportioning is pressed Deng a kind of or any two above (containing any two) ionic liquid.
By such scheme, in Microwave Assisted Process described in step (3), microwave power is 100-300W, corresponding overall treatment time is 5min-20min, each microwave treatment cycle is 1-6min, interval time between twice microwave treatment is 1min-3min, and temperature of reaction remains on 120-140 DEG C.
By such scheme, the antioxidant described in step (3) is the one in the fat-soluble antioxidants such as natural VE, fat-soluble tea polyphenol, Ascorbyl Palmitate, tertiarybutylhydroquinone (TBHQ); Preferred fat-soluble tea polyphenol, add-on is 100-200ppm.
By such scheme, in step (4), the extraction agent described in last handling process of product can be one or two or more kinds mixture by any proportioning such as tertiary amyl alcohol, the trimethyl carbinol, ethyl acetate.
By such scheme, the reaction solvent (ionic liquid) after step (4) extraction treatment can recycle after passing through underpressure distillation again.
In the present invention, microwave-assisted is introduced in the building-up reactions of CAPE, adopt ionic liquid simultaneously as catalyzer and reaction solvent, provide a kind of method that microwave-assisted prepares CAPE.The present invention, by the method for microwave-assisted esterification, greatly can improve speed and the transformation efficiency of CAPE Enzymatic transformation.Present method has reaction conditions gentleness; speed of response is fast; product yield is high; and the features such as environmental protection; solve traditional method prepare CAPE method exist speed low; the bottleneck difficult problems such as productive rate is low, yield poorly, may be used for the safe, clean, efficient of CAPE and mass-producing preparation.
Beneficial outcomes of the present invention is:
1., compared to traditional CAPE preparation method, in the present invention, microwave-assisted reacts to have and carries out at ambient pressure, and equipment is simple, easy and simple to handle, reaction times is short, efficiency advantages of higher, overall yield of reaction be greater than 80% (can in 10 minutes transformation efficiency can reach 90% with) on;
2., compared to traditional CAPE preparation method, in the present invention, microwave-assisted reaction Raw coffic acid concentration improves decades of times, can increase substantially the output of single reaction; Coffic acid and phenylethyl alcohol mol ratio significantly reduce, and can significantly improve the utilization ratio of raw material (phenylethyl alcohol), and reduce following purification steps.
3. the method provided in the present invention utilizes microwave-assisted esterification, the ionic liquid that employing is described as " 21 century cleans optimal reaction medium in green industry " is simultaneously as reaction solvent and catalyzer, whole reaction has environmental protection, convenient product separation, the features such as solvent is recyclable.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
CAPE prepared by microwave-assisted detects mainly through high performance liquid chromatography, testing conditions is as follows: chromatographic column is (5 μm, RP-C18 post, 250mm × 4.6mm), column temperature is 30 DEG C, moving phase is that acetonitrile (A) and water are (containing the Glacial acetic acid of 0.5%, B), take the method for gradient elution, namely after 70% (v/v) B keeps 7min, B is down to 30% (v/v) and keeps 11min, and B is again increased to after 70% (v/v) keeps 7min and stops subsequently.The flow velocity of moving phase is 1mL/min, and sample size is 20 μ L, and determined wavelength is 325nm.
Embodiment 1:
Microwave-assisted rapidly and efficiently prepares a method for CAPE, and it comprises the steps:
(1) pre-treatment of raw material: reaction solvent [Bmim] [PF
6], coffic acid respectively at 60 DEG C of vacuum-drying 8h, moisture content controls respectively at below 1wt%; Phenylethyl alcohol adopts anhydrous sodium sulphate to dewater, and moisture content controls at below 0.2wt%;
(2) input (coffic acid and phenylethyl alcohol mol ratio are 1:1) of reaction raw materials: by 72g coffic acid, 49g phenylethyl alcohol, 72g [Bmim] [PF
6] and 4.8g molecular sieve add (add-on of molecular sieve is 50g/L, adds 50g molecular sieve in often liter of reaction solvent) in reactor, stir under normal temperature, obtain pre-composition, logical nitrogen, except oxygen 5min, obtains the pre-composition after deoxygenation;
(3) microwave-assisted transesterification reaction: add antioxidant L-ascorbic acid palmitate 100ppm in the pre-composition after deoxygenation, temperature control is at 120 DEG C, under microwave-assisted normal pressure, (microwave power is 100W to stirring reaction 5min, overall treatment time is 5min, treatment cycle is 2min, co-processing 2 times, and interval time is 1min), microwave heating, naturally cools to 40 DEG C;
(4) aftertreatment of product: after completion of the reaction, centrifugal removing molecular sieve, vacuum rotary steam removes excessive phenylethyl alcohol, adopt extraction agent tertiary amyl alcohol (with bulk product than 1:1), product CAPE can be extracted from ionic liquid, re-extract 3 times, vacuum rotary steam removing tertiary amyl alcohol, obtain CAPE sterling purity and reach more than 95% (quality), overall yield of reaction is greater than 90%.
Embodiment 2:
Microwave-assisted rapidly and efficiently prepares a method for CAPE, and it comprises the steps:
(1) pre-treatment of raw material: reaction solvent [Bmim] [Tf
2n] and coffic acid vacuum-drying 12h at 70 DEG C respectively, moisture content controls respectively at below 1wt%; Phenylethyl alcohol adopts anhydrous sodium sulphate to dewater, and moisture content controls at below 0.2wt%;
(2) input (coffic acid and phenylethyl alcohol mol ratio are 1:10) of reaction raw materials: by 36g coffic acid, 245g phenylethyl alcohol, 360g [Bmim] [Tf
2n] and 28.6g molecular sieve add (now, the add-on of molecular sieve is 60g/L, adds 60g molecular sieve in often liter of reaction solvent) in reactor, stir under normal temperature, obtain pre-composition, logical nitrogen, except oxygen 5min, obtains the pre-composition after deoxygenation;
(3) microwave-assisted transesterification reaction: add antioxidant natural VE 150ppm in the pre-composition after deoxygenation, temperature control is at 130 DEG C, under microwave-assisted normal pressure, (microwave power is 200W to stirring reaction 9 min, overall treatment time is 9min, treatment cycle is 1min, co-processing 5 times, and interval time is 1min), stop microwave heating, naturally cool to 40 DEG C;
(4) aftertreatment of product: after completion of the reaction, centrifugal removing molecular sieve, vacuum rotary steam removes excessive phenylethyl alcohol, adopt extraction agent ethyl acetate (with bulk product than 1:1) product CAPE can be extracted from ionic liquid, re-extract 3 times, vacuum rotary steam removing ethyl acetate, obtain CAPE sterling purity and reach more than 97% (quality), overall yield of reaction is greater than 95%.
Embodiment 3:
Microwave-assisted rapidly and efficiently prepares a method for CAPE, and it comprises the steps:
(1) pre-treatment of raw material: reaction solvent [Emim] PF
6vacuum-drying 12h at 80 DEG C; Coffic acid 80 DEG C of vacuum-drying 12h, moisture content controls at below 1wt%; Phenylethyl alcohol adopts anhydrous sodium sulphate to dewater, and moisture content controls at below 0.2wt%;
(2) input (coffic acid and phenylethyl alcohol mol ratio are 1:20) of reaction raw materials: by 14.4g coffic acid, 195.5g phenylethyl alcohol, 288g [Emim] PF
6add in reactor with 30.5g molecular sieve (now, the add-on of molecular sieve is 80g/L, adds 80g molecular sieve in often liter of reaction solvent), stir, obtain pre-composition under normal temperature, logical nitrogen, except oxygen 5min, obtains the pre-composition after deoxygenation;
(3) microwave-assisted transesterification reaction: add antioxidant fat-soluble tea polyphenol 200ppm in the pre-composition after deoxygenation, temperature control is at 140 DEG C, under microwave-assisted normal pressure, (microwave power is 300W to stirring reaction 20 min, overall treatment time is 20min, treatment cycle is 2min, co-processing 7 times, and interval time is 1min), stop microwave heating, naturally cool to 40 DEG C;
(4) aftertreatment of product: after completion of the reaction, centrifugal removing molecular sieve, vacuum rotary steam removes excessive phenylethyl alcohol, adopt the extraction agent trimethyl carbinol (with bulk product than 1:1) product CAPE can be extracted from ionic liquid, re-extract 3 times, the vacuum rotary steam removing trimethyl carbinol, obtains CAPE sterling, purity reaches more than 98% (quality), and overall yield of reaction is greater than 94%.
Embodiment 4:
Microwave-assisted rapidly and efficiently prepares a method for CAPE, and it comprises the steps:
(1) pre-treatment of raw material: the reaction solvent (ionic liquid namely reclaimed---[Bmim] [PF
6]) vacuum-drying 8h at 70 DEG C; Coffic acid 80 DEG C of vacuum-drying 12h, moisture content controls at below 1wt%; Phenylethyl alcohol adopts anhydrous sodium sulphate to dewater, and moisture content controls at below 0.2wt%;
(2) input of reaction raw materials: (add-on of molecular sieve is 50g/L by 72g coffic acid, 49g phenylethyl alcohol and 4.8g molecular sieve, 4.8g molecular sieve is added in often liter of reaction solvent) add in reactor, then by ionic liquid [the Bmim] [PF in the step (4) of embodiment 1 after extraction treatment
6] 72g (moisture content controls at below 1wt%) recycle puts in reactor, stirs, obtain pre-composition under normal temperature, logical nitrogen, except oxygen 5min, obtains the pre-composition after deoxygenation;
(3) microwave-assisted transesterification reaction: add antioxidant L-ascorbic acid palmitate 200ppm in the pre-composition after deoxygenation, temperature control is at 120 DEG C, under microwave-assisted normal pressure, (microwave power is 100W to stirring reaction 5min, overall treatment time is 5min, treatment cycle is 2min, co-processing 2 times, and interval time is 1min), stop microwave heating, naturally cool to 40 DEG C;
(4) aftertreatment of product: after completion of the reaction, centrifugal removing molecular sieve, vacuum rotary steam removes excessive phenylethyl alcohol, adopt extraction agent tertiary amyl alcohol (with bulk product than 1:1) product CAPE can be extracted from ionic liquid, re-extract 3 times, vacuum rotary steam removing tertiary amyl alcohol, obtains CAPE sterling, purity reaches more than 92% (quality), and overall yield of reaction is greater than 88%.
Embodiment 5:
Substantially the same manner as Example 1, difference is in step (1): reaction solvent [Bmim] [PF
6] by [Omim] [PF
6] substitute; In step (4): extraction agent tertiary amyl alcohol is replaced by the trimethyl carbinol; The CAPE sterling purity obtained reaches more than 96% (quality), and overall yield of reaction is greater than 88%.
Embodiment 6:
Substantially the same manner as Example 1, difference is in step (1): reaction solvent [Bmim] [PF
6] by [Emim] PF
6substitute; In step (3): microwave power is 300w, antioxidant is replaced by tertiarybutylhydroquinone (TBHQ); The CAPE sterling purity obtained reaches more than 92% (quality), and overall yield of reaction is greater than 84%.
Embodiment 7:
Substantially the same manner as Example 1, difference is in step (1): reaction solvent [Bmim] [PF
6] by [Bmim] [HSO
4] substitute; Microwave power is 200w; In step (4): extraction agent tertiary amyl alcohol is by the trimethyl carbinol and tertiary amyl alcohol, or the trimethyl carbinol and ethyl acetate replace by the mixture of any proportioning; The CAPE sterling purity obtained reaches more than 91% (quality), and overall yield of reaction is greater than 83%.
Embodiment 8:
Substantially the same manner as Example 1, difference is in step (1): reaction solvent [Bmim] [PF
6] by [Bmim] CF
3sO
3substitute; Microwave power is 200w; The CAPE sterling purity obtained reaches more than 90% (quality), and overall yield of reaction is greater than 82%.
Embodiment 9:
Substantially the same manner as Example 1, difference is in step (1): reaction solvent [Bmim] [PF
6] by [Bmim] [Tf
2n], [Emim] PF
6, [Bmim] PF
6, [Omim] PF
6, [Bmim] [HSO
4], [Bmim] CF
3sO
3in any two kinds of ionic liquids substitute; Microwave power is 300w; The CAPE sterling obtained, purity reaches more than 90% (quality), and overall yield of reaction is greater than 80%.
Each raw material cited by the present invention, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
Claims (8)
1. microwave-assisted rapidly and efficiently prepares a method for CAPE, it is characterized in that it comprises the steps:
1) input of reaction raw materials: coffic acid, phenylethyl alcohol, reaction solvent, molecular sieve are added in reactor, stirs under normal temperature, obtain pre-composition, logical nitrogen, except oxygen 5min, obtains the pre-composition after deoxygenation; Wherein, coffic acid and phenylethyl alcohol mol ratio are 1:1-1:20, and the mass ratio of coffic acid and reaction solvent is 1:1-1:20, and the add-on of molecular sieve is 50-80g/L;
2) microwave-assisted transesterification reaction: add antioxidant 100-200ppm in the pre-composition after deoxygenation, temperature control is at 120-140 DEG C, and stirring reaction 5-20 min under microwave-assisted normal pressure, stops microwave heating, naturally cool to 40 DEG C;
3) aftertreatment of product: after completion of the reaction, centrifugal removing molecular sieve, vacuum rotary steam removes excessive phenylethyl alcohol, obtains product; Adopt extraction agent to extract 3 times, vacuum rotary steam removing extraction agent, namely obtains CAPE.
2. a kind of microwave-assisted according to claim 1 rapidly and efficiently prepares the method for CAPE, it is characterized in that: step 1) in raw material need through pre-treatment: reaction solvent, coffic acid are respectively at 60 DEG C-80 DEG C vacuum-drying 8-12 h, and moisture content controls at below 1wt%; Phenylethyl alcohol adopts anhydrous sodium sulphate to dewater, and moisture content controls at below 0.2wt%.
3. a kind of microwave-assisted according to claim 1 and 2 rapidly and efficiently prepares the method for CAPE, it is characterized in that: step 1) described in reaction solvent be [Bmim] [Tf
2n], [Emim] PF
6, [Bmim] PF
6, [Omim] PF
6, [Bmim] [HSO
4], [Bmim] CF
3sO
3middle a kind of or any two above mixture by any proportioning.
4. a kind of microwave-assisted according to claim 1 rapidly and efficiently prepares the method for CAPE, it is characterized in that: step 2) described in Microwave Assisted Process in microwave power be 100-300W, corresponding overall treatment time is 5min-20min, each microwave treatment cycle is 1-6min, twice microwave treatment intermittent time is 1min-3min, and temperature of reaction remains on 120-140 DEG C.
5. a kind of microwave-assisted according to claim 1 rapidly and efficiently prepares the method for CAPE, it is characterized in that: step 2) described in antioxidant be one in natural VE, fat-soluble tea polyphenol, Ascorbyl Palmitate, tertiarybutylhydroquinone.
6. a kind of microwave-assisted according to claim 1 rapidly and efficiently prepares the method for CAPE, it is characterized in that: step 3) in the extraction agent described in last handling process of product can be in tertiary amyl alcohol, the trimethyl carbinol, ethyl acetate one or two or more kinds by the mixture of any proportioning.
7. a kind of microwave-assisted according to claim 1 rapidly and efficiently prepares the method for CAPE, it is characterized in that: step 3) in the volume ratio of extraction agent and product be 1:1.
8. a kind of microwave-assisted according to claim 1 rapidly and efficiently prepares the method for CAPE, it is characterized in that: through step 3) reaction solvent after extraction treatment is again by can recycle after underpressure distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410454887.1A CN104262156B (en) | 2014-09-06 | 2014-09-06 | A kind of microwave-assisted rapidly and efficiently prepares the method for CAPE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410454887.1A CN104262156B (en) | 2014-09-06 | 2014-09-06 | A kind of microwave-assisted rapidly and efficiently prepares the method for CAPE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104262156A true CN104262156A (en) | 2015-01-07 |
| CN104262156B CN104262156B (en) | 2016-02-17 |
Family
ID=52153776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410454887.1A Active CN104262156B (en) | 2014-09-06 | 2014-09-06 | A kind of microwave-assisted rapidly and efficiently prepares the method for CAPE |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104262156B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107034251A (en) * | 2017-03-17 | 2017-08-11 | 浙江工商大学 | A kind of method of lipase-catalyzed synthesis L ascorbyl palmitates in ionic liquid |
| CN108863783A (en) * | 2018-07-11 | 2018-11-23 | 广东轻工职业技术学院 | A kind of method of microwave cooperating H-ZSM-5 type Zeolite synthesis tri-n-butyl citrate |
| CN108911984A (en) * | 2018-07-11 | 2018-11-30 | 广东轻工职业技术学院 | A kind of method of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate |
| WO2018230702A1 (en) * | 2017-06-15 | 2018-12-20 | 国立大学法人東北大学 | Method for producing cinnamic acid ester compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321692A (en) * | 2011-09-27 | 2012-01-18 | 江苏科技大学 | Preparation method for catalytic synthesis of caffeic acid phenethyl ester by using lipase in ionic liquid |
-
2014
- 2014-09-06 CN CN201410454887.1A patent/CN104262156B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321692A (en) * | 2011-09-27 | 2012-01-18 | 江苏科技大学 | Preparation method for catalytic synthesis of caffeic acid phenethyl ester by using lipase in ionic liquid |
Non-Patent Citations (1)
| Title |
|---|
| 黎彧等: "微波协同离子液体催化酯化反应研究进展", 《粮食与油脂》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107034251A (en) * | 2017-03-17 | 2017-08-11 | 浙江工商大学 | A kind of method of lipase-catalyzed synthesis L ascorbyl palmitates in ionic liquid |
| WO2018230702A1 (en) * | 2017-06-15 | 2018-12-20 | 国立大学法人東北大学 | Method for producing cinnamic acid ester compound |
| JPWO2018230702A1 (en) * | 2017-06-15 | 2020-04-23 | 国立大学法人東北大学 | Method for producing cinnamic acid ester compound |
| US11021431B2 (en) | 2017-06-15 | 2021-06-01 | Tohoku University | Method for producing cinnamic acid ester compound |
| JP7197172B2 (en) | 2017-06-15 | 2022-12-27 | 国立大学法人東北大学 | Method for producing cinnamic acid ester compound |
| CN108863783A (en) * | 2018-07-11 | 2018-11-23 | 广东轻工职业技术学院 | A kind of method of microwave cooperating H-ZSM-5 type Zeolite synthesis tri-n-butyl citrate |
| CN108911984A (en) * | 2018-07-11 | 2018-11-30 | 广东轻工职业技术学院 | A kind of method of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104262156B (en) | 2016-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104262156B (en) | A kind of microwave-assisted rapidly and efficiently prepares the method for CAPE | |
| CN108484545A (en) | A kind of method and system of continuous synthesis furandicarboxylic acid | |
| CN103613501A (en) | Method for preparing tributyl citrate by taking macroporous strong-acid cation exchange resin as catalyst | |
| CN103396303B (en) | Method for separating and purifying eicosapentaenoic acid and docosahexaenoic acid from micro-algal oil or fish oil | |
| CN103012110A (en) | Production method of dimer acid | |
| CN103088078B (en) | Lipase synthesis-promoting method of propyl caffeate | |
| CN111875493A (en) | Method for synthesizing borneol by using imidazole acidic ionic liquid | |
| CN103846103A (en) | Silica gel loaded type catalyst and application of catalyst in Baeyer-Villiger reaction | |
| CN102267898A (en) | Method for preparing diethyl succinate by using pyridine ionic liquid as catalyst | |
| CN103159625A (en) | Method of producing trimethylolpropane oleate with single kettle | |
| CN101676252A (en) | Method for preparing acetal by using glyoxal | |
| CN103898176A (en) | Method for ultrasonic assisted enzymatic synthesis of D-ascorbic acid palmitate | |
| CN107365250B (en) | A kind of method that levulic acid is converted into using lignocellulose biomass by hydrolyzation | |
| CN103265429A (en) | Technical method for synthesizing methyl acetate | |
| CN102174633B (en) | Method for splitting ibuprofen | |
| CN102775311B (en) | Preparation method of isooctyl salicylate | |
| CN104193610B (en) | The synthetic method of hypericin | |
| CN104098469B (en) | Device for synthesizing tricyclodecenyl propionate by adopting loaded solid acid catalyst | |
| CN102285882B (en) | Method for synthesizing acetyl tributyl citrate (ATBC) by adopting composite ionic liquid catalyst | |
| CN101973873A (en) | Method for synthesizing carboxylic ester by microwave radiation catalysis | |
| CN103664853B (en) | Method for synthesizing lactone compound through catalyzing and oxidizing ring ketone by modified silicon | |
| CN103191781A (en) | Technology for preparing phenol by one-step catalytic oxidation of benzene through coordination of molecular sieve immobilized Schiff base and metal salt | |
| CN104151283A (en) | Method for catalytically synthesizing 12-aryl-8,9,10,12-tetrahydrobenzo[alpha]xanthenes-11-one derivative | |
| CN102584588A (en) | Method using catalysis transesterification to prepare n-amyl acetate cinnamate | |
| CN102584587B (en) | Method using catalysis transesterification to prepare n-butyl acetate cinnamate |
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 |