CN104311413A - Method for synthesis of ferulic acid ester by solid acid catalysis - Google Patents
Method for synthesis of ferulic acid ester by solid acid catalysis Download PDFInfo
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- CN104311413A CN104311413A CN201410463153.XA CN201410463153A CN104311413A CN 104311413 A CN104311413 A CN 104311413A CN 201410463153 A CN201410463153 A CN 201410463153A CN 104311413 A CN104311413 A CN 104311413A
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
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Abstract
The invention discloses a method for synthesis of ferulic acid ester by solid acid catalysis, and relates to a method for synthesis of the ferulic acid ester, and the method is as follows: a, preparation of silica powder, to be more specific, taking sodium metasilicate nonahydrate to prepare into aqueous solution, starting to stir, heating, adding dropwise ethyl acetate, after gel is formed, performing low temperature vacuum drying to obtain white silica powder; b, catalyst preparation, to be more specific, putting the silica powder prepared by the step a into a muffle furnace for activation, mixing into aqueous solution of sodium bisulfate, soaking, filtering by suction, washing with distilled water until the filtrate is colorless, processing by low-temperature vacuum drying for standby use; c, catalyzed synthesis of the ferulic acid ester, to be more specific, adding ferulic acid, alcohol and a catalyst into a three necked flask equipped with a stirrer, a thermometer, a reflux condenser and a water separator, stirring, heating for reflux until no water is separated out in the water separator; and d, drying and recovery. The process is simple, cheap, non-toxic, non-corrosive and environmentally friendly, catalytic activity is high, catalytic reaction products are easy to separate and can be repeatedly used.
Description
Technical field
The present invention relates to a kind of method of synthesizing ferulic acid ester, particularly relate to the method for a kind of solid acid catalysis synthesis ferulic acid ester.
Background technology
Forulic acid (Ferulic acid, Ferulic acid are called for short FA), as shown in the formula:
Find in the seed and leaf of plant at first, it is a kind of phenolic acid be present in the plants such as Radix Angelicae Sinensis, Ligusticum wallichii, asafoetide, there is anti-inflammatory, anti-oxidant, antithrombotic and multiple physiologically active, be widely used in the fields such as healthcare products, makeup, medicine, agricultural chemicals and foodstuff additive.But forulic acid molecular hydrophylic is strong, fat-soluble difference, more difficultly plays a role through microbial film lipid bilayer, makes it apply restricted greatly.Therefore, carry out modification to forulic acid molecule and prepare derivative and cause people's great interest to improve the fat-soluble research of molecule, wherein forulic acid and alcohol are reacted into ester is improve its fat-soluble and best approach that is result of use.
The synthesis of ferulic acid ester mainly contains acid catalyzed esterification method and lipase-catalyzed esterification method.The shortcoming such as acid catalyzed esterification method also exists that temperature of reaction is high, energy consumption is large, side reaction is many, product yield is low, poor product quality, environmental pollution are serious.Biological enzyme synthesis method also also exists the problems such as the control of water activity in catalyzer, the selection of reaction media and synthetic reaction process.Therefore, the new synthetic process studying ferulic acid ester becomes inexorable trend.But the catalysis of solid catalyst study on the synthesis of ferulic acid ester is less.Solid acid catalyst has the advantages such as high, environmentally friendly, the reusable and product separation of catalytic activity is easy, and the high absorption property load sodium pyrosulfate of the present invention's silicon-dioxide obtains solid acid catalyst NaHSO
4/ SiO
2, with it for catalyzer has synthesized ferulic acid ester, obtain comparatively satisfied effect.
Summary of the invention
The object of the present invention is to provide a kind of solid acid catalysis to synthesize the method for ferulic acid ester, in the present invention, catalyzing and synthesizing of ferulic acid ester is passed through: the preparation of silicon-dioxide powdery, the preparation of catalyzer, ferulic acid ester catalyze and synthesize three steps to realize.Solid catalyst NaHSO
4/ SiO
2can be used for catalytically synthesizing ferulic acid cyclohexyl, this catalyzer has the advantages such as preparation technology is simple, inexpensive, nontoxic, non-corrosiveness, environmentally friendly, catalytic activity is high, catalytic reaction products is easily separated and can reuse.
The object of the invention is to be achieved through the following technical solutions:
The method of solid acid catalysis synthesis ferulic acid ester, described method comprises the steps:
A) preparation of silicon-dioxide powdery: get 56.8 g (0.2 mol) non-hydrate sodium metasilicate and be made into the aqueous solution, start stirring, heating, drip 18 mL (0.18 mol) ethyl acetate, after gel formation, stir lower to about dilute hydrochloric acid adjust pH to 4, stop stirring; Suction filtration, filter cake distilled water is washed till in filtrate not containing Cl
-till, low-temperature vacuum drying, namely obtains 11.2 g white silicon-dioxide powderies;
B) preparation of catalyzer: silicon-dioxide powdery prepared by a step is placed in retort furnace 200 DEG C activation 2 h, the silicon-dioxide getting 10 g activation is mixed in 30 mL sodium bisulphate solution, soak suction filtration after 24 h, be washed with distilled water to filtrate colourless, again after low-temperature vacuum drying, be placed in retort furnace 200 DEG C activation 3 h, cool in moisture eliminator, for subsequent use;
C) the catalyzing and synthesizing of ferulic acid ester: in the 500mL three-necked flask that agitator, thermometer, reflux condensing tube and water trap (filling saturated aqueous common salt) are housed, add 38.8 g (0.20mol) forulic acid, alcohol and catalyzer, stir, reflux in water trap almost anhydrous separate till; Filtered while hot removing catalyzer, reclaiming catalyzer can reuse, and resistates with saturated aqueous sodium carbonate neutralization, saturated common salt water washing and anhydrous magnesium sulfate drying 24 h, obtains ferulic acid ester, calculated yield of weighing after reclaiming unreacted alcohol successively.
The method of described solid acid catalysis synthesis ferulic acid ester, the preparation of described a step and silicon-dioxide powdery, non-hydrate sodium metasilicate concentration of aqueous solution is 3 mass percent to 10 mass percents, Heating temperature to 50 ~ 55 DEG C, the speed dripping ethyl acetate is 10 ~ 30 droplets/minute, is 0.2 ~ 2 molL by dilute hydrochloric acid concentration
-1, reconcile about pH to 4 and can be pH=3 ~ 5; Not containing Cl in filtrate
-can detect with Silver Nitrate reagent.
The method of described solid acid catalysis synthesis ferulic acid ester, the preparation of described b step and catalyzer, activates silicon-dioxide powdery prepared by a step, and activation temperature can be 190 ~ 210 DEG C, and soak time can be 1 ~ 8 h; The concentration of sodium pyrosulfate is 4 quality % to 16 quality %; Soak time is 24 h, or is 25 h, 26 h, 27 h; Then, activate 3 h with 200 DEG C of retort furnaces, activation temperature can be 190 ~ 210 DEG C, and soak time can be 1 ~ 8 h.
The method of described solid acid catalysis synthesis ferulic acid ester, catalyzing and synthesizing of described step c and ferulic acid ester, alcohol is hexalin or Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol etc.;
The method of described solid acid catalysis synthesis ferulic acid ester, catalyzing and synthesizing of described step c and ferulic acid ester, reflux temperature is not fixed, and according to the difference of acid-alcohol ratio charging capacity, the difference of alcohol kind, backflow temperature changes to some extent; Catalyzing and synthesizing of step c and ferulic acid ester, acid-alcohol ratio is 5:1 to 15:1; The consumption of catalyzer is 3 quality % to 10 quality % of alkyd total mass.
The method of described solid acid catalysis synthesis ferulic acid ester, catalyzing and synthesizing of described step c and ferulic acid ester, the reaction times is as the criterion with anhydrous separating in water trap, and the reaction times is 2 ~ 5 h; Catalyzing and synthesizing of step c and ferulic acid ester, the catalyzer of recovery does not need to activate direct recycling.
Advantage of the present invention and effect are:
In the present invention, catalyzing and synthesizing of ferulic acid ester is passed through: the preparation of silicon-dioxide powdery, the preparation of catalyzer, ferulic acid ester catalyze and synthesize three steps to realize.Solid catalyst NaHSO
4/ SiO
2can be used for catalytically synthesizing ferulic acid cyclohexyl, this catalyzer has the advantages such as preparation technology is simple, inexpensive, nontoxic, non-corrosiveness, environmentally friendly, catalytic activity is high, catalytic reaction products is easily separated and can reuse.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1:
(preparation of forulic acid cyclohexyl)
Get the aqueous solution that 56.8g (0.2 mol) non-hydrate sodium metasilicate is made into 5.0%, start stirring, be heated to 55 DEG C, drip 18mL (0.18mol) ethyl acetate, after gel formation, stir lower to about dilute hydrochloric acid adjust pH to 4, stop stirring.Suction filtration, filter cake distilled water is washed till in filtrate not containing Cl
-till, low-temperature vacuum drying, namely obtains 11.2g white silicon-dioxide powdery.
The silicon-dioxide powdery of above-mentioned preparation is placed in retort furnace 200 DEG C activation 2h, the silicon-dioxide getting 10g activation is mixed in 30mL 10% sodium bisulphate solution, suction filtration after immersion 24h, be washed with distilled water to filtrate colourless, again after low-temperature vacuum drying, be placed in retort furnace 200 DEG C activation 3h, cool in moisture eliminator, for subsequent use.
In the 500mL three-necked flask that agitator, thermometer, reflux condensing tube and water trap (filling saturated aqueous common salt) are housed, add 38.8g (0.20mol) forulic acid, hexalin (acid-alcohol ratio 10:1) and catalyzer (5% of alkyd quality), stir, straight 3.5 h of reflux in water trap almost anhydrous separate.Filtered while hot removing catalyzer, resistates with saturated aqueous sodium carbonate neutralization, saturated common salt water washing and anhydrous magnesium sulfate drying 24h, obtains forulic acid cyclohexyl, yield 80% after reclaiming unreacted hexalin successively.
Embodiment 2:
(preparation of forulic acid n-pentyl ester)
Get the aqueous solution that 56.8g (0.2 mol) non-hydrate sodium metasilicate is made into 5.0%, start stirring, be heated to 50 DEG C, drip 18mL (0.18mol) ethyl acetate, after gel formation, stir lower to about dilute hydrochloric acid adjust pH to 4, stop stirring.Suction filtration, filter cake distilled water is washed till in filtrate not containing Cl
-till, low-temperature vacuum drying, namely obtains 11.2g white silicon-dioxide powdery.
The silicon-dioxide powdery of above-mentioned preparation is placed in retort furnace 200 DEG C activation 2h, the silicon-dioxide getting 10g activation is mixed in 30mL 10% sodium bisulphate solution, suction filtration after immersion 24h, be washed with distilled water to filtrate colourless, again after low-temperature vacuum drying, be placed in retort furnace 200 DEG C activation 3h, cool in moisture eliminator, for subsequent use.
Agitator is being housed, thermometer, in the 250mL three-necked flask of reflux condensing tube and water trap (filling saturated aqueous common salt), add 38.8g (0.20mol) forulic acid, Pentyl alcohol (acid-alcohol ratio 2:1), catalyzer (6% of alkyd quality) and hexanaphthene (0.06 mol), stir, straight 3 h of reflux in water trap almost anhydrous separate, hexanaphthene distillation is removed, filtered while hot removing catalyzer, resistates neutralizes with saturated aqueous sodium carbonate successively, saturated common salt water washing and anhydrous magnesium sulfate drying, forulic acid n-pentyl ester is obtained after reclaiming unreacted hexalin, yield 97%.
Embodiment 3:
(preparation of forulic acid n-pentyl ester, catalyzer recycling experiment)
On the basis that experiment condition and embodiment 2 are consistent, carry out the investigation of the repeat performance of catalyzer, the results are shown in Table 1.
The impact on esterification reused by table 1 catalyzer
Can be analyzed by the data in form, the NaHSO of preparation
4/ SiO
2catalyzer, in the esterification of forulic acid and Pentyl alcohol, when recycling 5 times, still can ensure that yield is greater than 80%.
Claims (6)
1. the method for solid acid catalysis synthesis ferulic acid ester, it is characterized in that, described method comprises the steps:
A) preparation of silicon-dioxide powdery: get 56.8 g (0.2 mol) non-hydrate sodium metasilicate and be made into the aqueous solution, start stirring, heating, drip 18 mL (0.18 mol) ethyl acetate, after gel formation, stir lower to about dilute hydrochloric acid adjust pH to 4, stop stirring; Suction filtration, filter cake distilled water is washed till in filtrate not containing Cl
-till, low-temperature vacuum drying, namely obtains 11.2 g white silicon-dioxide powderies;
B) preparation of catalyzer: silicon-dioxide powdery prepared by a step is placed in retort furnace 200 DEG C activation 2 h, the silicon-dioxide getting 10 g activation is mixed in 30 mL sodium bisulphate solution, soak suction filtration after 24 h, be washed with distilled water to filtrate colourless, again after low-temperature vacuum drying, be placed in retort furnace 200 DEG C activation 3 h, cool in moisture eliminator, for subsequent use;
C) the catalyzing and synthesizing of ferulic acid ester: in the 500mL three-necked flask that agitator, thermometer, reflux condensing tube and water trap (filling saturated aqueous common salt) are housed, add 38.8 g (0.20mol) forulic acid, alcohol and catalyzer, stir, reflux in water trap almost anhydrous separate till; Filtered while hot removing catalyzer, reclaiming catalyzer can reuse, and resistates with saturated aqueous sodium carbonate neutralization, saturated common salt water washing and anhydrous magnesium sulfate drying 24 h, obtains ferulic acid ester, calculated yield of weighing after reclaiming unreacted alcohol successively.
2. the method for solid acid catalysis synthesis ferulic acid ester according to claim 1, it is characterized in that, the preparation of described a step and silicon-dioxide powdery, non-hydrate sodium metasilicate concentration of aqueous solution is 3 mass percent to 10 mass percents, Heating temperature to 50 ~ 55 DEG C, the speed dripping ethyl acetate is 10 ~ 30 droplets/minute, is 0.2 ~ 2 molL by dilute hydrochloric acid concentration
-1, reconcile about pH to 4 and can be pH=3 ~ 5; Not containing Cl in filtrate
-can detect with Silver Nitrate reagent.
3. the method for solid acid catalysis synthesis ferulic acid ester according to claim 1, it is characterized in that silicon-dioxide powdery prepared by a step activates by the preparation of described b step and catalyzer, activation temperature can be 190 ~ 210 DEG C, and soak time can be 1 ~ 8 h; The concentration of sodium pyrosulfate is 4 quality % to 16 quality %; Soak time is 24 h, or is 25 h, 26 h, 27 h; Then, activate 3 h with 200 DEG C of retort furnaces, activation temperature can be 190 ~ 210 DEG C, and soak time can be 1 ~ 8 h.
4. the method for solid acid catalysis according to claim 1 synthesis ferulic acid ester, is characterized in that, catalyzing and synthesizing of described step c and ferulic acid ester, alcohol is hexalin or Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol etc.
5. the method for solid acid catalysis synthesis ferulic acid ester according to claim 1, it is characterized in that, catalyzing and synthesizing of described step c and ferulic acid ester, reflux temperature is not fixed, according to the difference of acid-alcohol ratio charging capacity, the difference of alcohol kind, backflow temperature changes to some extent; Catalyzing and synthesizing of step c and ferulic acid ester, acid-alcohol ratio is 5:1 to 15:1; The consumption of catalyzer is 3 quality % to 10 quality % of alkyd total mass.
6. the method for solid acid catalysis according to claim 1 synthesis ferulic acid ester, is characterized in that, catalyzing and synthesizing of described step c and ferulic acid ester, and the reaction times is as the criterion with anhydrous separating in water trap, and the reaction times is 2 ~ 5 h; Catalyzing and synthesizing of step c and ferulic acid ester, the catalyzer of recovery does not need to activate direct recycling.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622403A (en) * | 2015-12-31 | 2016-06-01 | 镇江高鹏药业有限公司 | Method for synthesizing and preparing high-quality methyl salicylate |
| CN105618148A (en) * | 2015-12-31 | 2016-06-01 | 镇江高鹏药业有限公司 | Efficient solid catalyst used for methyl salicylate synthesis |
| CN107540721A (en) * | 2017-09-11 | 2018-01-05 | 南京林业大学 | A kind of ferulic acid ester preparation method based on recessed soil matrix catalyst cellulignin |
| CN111217703A (en) * | 2020-02-21 | 2020-06-02 | 上海仰世实业有限公司 | Preparation method of hexafluorobutyl acrylate |
| CN111747852A (en) * | 2020-07-31 | 2020-10-09 | 济南大学 | Cis-ferulic acid amyl ester compound and preparation method and application thereof |
-
2014
- 2014-09-12 CN CN201410463153.XA patent/CN104311413A/en active Pending
Non-Patent Citations (2)
| Title |
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| 孔祥文等: "二氧化硅负载硫酸氢钠催化合成对羟基苯甲酸正丁酯", 《食品科技》 * |
| 龚盛昭等: "硫酸氢钠催化合成阿魏酸戊酯的研究", 《化学研究与应用》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622403A (en) * | 2015-12-31 | 2016-06-01 | 镇江高鹏药业有限公司 | Method for synthesizing and preparing high-quality methyl salicylate |
| CN105618148A (en) * | 2015-12-31 | 2016-06-01 | 镇江高鹏药业有限公司 | Efficient solid catalyst used for methyl salicylate synthesis |
| CN107540721A (en) * | 2017-09-11 | 2018-01-05 | 南京林业大学 | A kind of ferulic acid ester preparation method based on recessed soil matrix catalyst cellulignin |
| CN107540721B (en) * | 2017-09-11 | 2020-04-28 | 南京林业大学 | Method for preparing ferulic acid ester based on catalysis of cellolignin by attapulgite-based catalyst |
| CN111217703A (en) * | 2020-02-21 | 2020-06-02 | 上海仰世实业有限公司 | Preparation method of hexafluorobutyl acrylate |
| CN111747852A (en) * | 2020-07-31 | 2020-10-09 | 济南大学 | Cis-ferulic acid amyl ester compound and preparation method and application thereof |
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Application publication date: 20150128 |