CN102267898A - Method for preparing diethyl succinate by using pyridine ionic liquid as catalyst - Google Patents
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Abstract
The invention discloses a method for preparing diethyl succinate by using a pyridine ionic liquid as a catalyst, and the method comprises: mixing succinic acid with ethanol at a molar ratio of 1:3, adding a Bronsted acidic pyridine ionic liquid used as the catalyst which is 5-8wt% of succinic acid, reacting at the reaction temperature of 60-70 DEG C for 2-3 hours, and separating the catalyst and products by using an ethyl ether extraction method. The pyridine ionic liquid used in the method disclosed by the invention has the advantages of high catalytic activity, good selectivity, low cost and stable properties, and can be reused after being subjected to simple rotary distillation water removing treatment, thereby achieving green synthesis, reducing the manufacturing cost and improving economic benefits. The method disclosed by the invention can be used for synthesizing diethyl succinate and is suitable for industrial mass production.
Description
Technical field
The invention belongs to the synthetic field of compound, especially a kind of synthetic method of ester, specifically a kind of ionic liquid-catalyzed method for preparing diethyl succinate of pyridines of using.
Background technology
Diethyl succinate has another name called ethyl succinate, can be used as synthetic perfume and foodstuff additive, the solvent of preparation berry essence and fruit type spices, also can be used as organic synthesis and medicinal intermediates and gas phase chromatographic stationary liquid, obtained widespread use in industry such as food, spices, daily-use chemical industry, medicine, coating, rubber, plastics.In addition, diethyl succinate also has the effect of antibiotic, antiulcer agent, detoxifcation, inhibition maincenter.
The traditional synthesis of diethyl succinate is to be raw material with Succinic Acid and dehydrated alcohol, and the vitriol oil is made catalyzer, and this method is to the conversion unit seriously corroded, and side reaction is many, and yield is not high, and aftertreatment complexity and wastewater discharge are big, serious environment pollution.
In recent years, along with the broad research to catalyzer, multiple esterifying catalysts such as solid super-strong acid, heteropolyacid, tosic acid and storng-acid cation exchange resin have appearred, as:
1. consolidate to pass will etc. (catalytic esterification-adsorption dewatering synthesizing succinic acid diethyl ester [J]. " daily chemical industry ", 2008,38 (4): be catalyzer 245-248.) with Zeo-karb NKC-9,3A molecular sieve adsorbing and dewatering technology synthesizing succinic acid diethyl ester.Investigated the influence of factors such as proportioning raw materials, catalyst levels and reaction times to esterification, the transformation efficiency of Succinic Acid reaches 98.8% under optimum process condition; After catalyzer was reused 6 times, the transformation efficiency of Succinic Acid still can reach 98.5%, shows advantages of high catalytic activity.But macropore styrene type cation exchange resin poor heat stability, catalyzer are in the life-time service process, and the acid site number of catalyst surface reduces, and strength of acid weakens, and catalytic activity reduces.
2. Lin Jin etc. (research [J] of catalysis of phosphotungstic acid synthesizing succinic acid diethyl ester. " Guangdong chemical industry ", 1999(2): 4-5.) phospho-wolframic acid is used for catalysis synthesizing succinic acid diethyl ester, obtain good result: 0.1mol Succinic Acid, 0.6mol dehydrated alcohol, 10mL toluene are band aqua, 0.4 phospho-wolframic acid reflux water-dividing 4h, and Succinic Acid esterification rate reaches 92.8%; Simultaneously, the catalyzer of recovery is reused 4 times, and esterification yield still reaches 92.3%, does not almost change.But because the specific surface of heteropolyacid is less, be difficult to and product separation, reclaim difficulty.
3. Wang Lanzhi etc. (Catalyzed by p-Toluenesulfonic Acid synthesizing succinic acid diethyl ester [J]. " Hebei Normal University's journal ", 1999,23(4): 523-529.) with tosic acid as Succinic Acid and alcoholic acid esterifying catalyst, explored the optimum process condition of esterification, the ester yield is 85% ~ 87%.Under the same conditions, compare with the vitriol oil, the ester yield that sulfuric acid is made catalyzer is 72-75%, and it is good to make the catalyst prod color and luster with tosic acid, the purity height, and " three wastes " are handled simple, not etching apparatus.But make catalyzer with tosic acid, long reaction time, catalyzer can't recycle and reuse, and causes serious waste.
4. old offer peach etc. (the four water Catalyzed by Ceric Sulfate synthesizing succinic acid diethyl esters and the catalyst deactivation analysis of causes [J]. " Hunan Technology College's journal ", 2005,18(4): 54-55.) reported that four water Catalyzed by Ceric Sulfate have synthesized diethyl succinate, its optimum process condition is acid alcohol mol ratio 1:6, catalyzer Ce (SO
4)
24H
2O 0.8g, temperature of reaction is 130 ℃, reaction times 1.5h, the esterification yield of Succinic Acid reaches 93.4%.But four water cerous sulfate poor heat stability, catalyst levels is more and recycle and reuse difficulty.Lewis acid (as iron trichloride, tin tetrachloride) is because inexpensive, acidity a little less than, lower to equipment corrosion, environmental pollution is little, side reaction also once caused people's attention less.
5. happy growing tall waits that [pleasure is grown tall, Ding Jianhua. Anhydrous Ferric Chloride catalysis synthesizing succinic acid diethyl ester [J]. " printing during chemical industry ", 1999,13(8): 34-35.] reported FERRIC CHLORIDE ANHYDROUS catalysis synthesizing succinic acid diethyl ester: with 0.1mol Succinic Acid, 0.24mol dehydrated alcohol, 0.0003mol FERRIC CHLORIDE ANHYDROUS back flow reaction 3h, the Succinic Acid transformation efficiency reaches 73.4%; If add 10mL hexanaphthene reflux water-dividing, transformation efficiency is 73.4%; And transformation efficiency only reaches 47.8% when adopting 0.0030mol BiCl3.
The preparation method of the diethyl succinate that above-mentioned document is reported, make some shortcoming in the Preparation of catalysts method though overcome tradition to a certain extent with the vitriol oil, but also all ubiquity preparation process complexity, catalytic activity and poor stability, acidic site density low, reclaim problems such as difficulty, spent acid contaminate environment, its industrial applications is restricted.
Ionic liquid (Ionic Liquids, write a Chinese character in simplified form: ILs), claim that again (Room or Ambient Temperature Ionic Liquids RTILs), is meant the salt that is in a liquid state, be made up of zwitterion fully to ionic liquid at room temperature under room temperature or the condition near room temperature.Ionic liquid is as a kind of novel environmental friendliness liquid catalyst, the high-density reaction active site that has liquid acid catalyst, its volatility is lower, good stability, structure and acid adjustable, be used for catalytic process and have advantages such as catalytic activity height, environmental friendliness, selectivity height, product are easily separated, reusable edible, have the potentiality that replace the traditional industry acid catalyst.
Summary of the invention
The technical problem to be solved in the present invention, provide a kind of ionic liquid-catalyzed method for preparing diethyl succinate of pyridines of using, it is with Br φ nsted(Chinese translation: bronsted) acidic pyridinium class ionic liquid is as catalyzer, overcome that catalyst system therefor exists in the prior art etching apparatus, severe reaction conditions, esterification yield are low, side reaction is many, catalyzer is difficult for recovery, aftertreatment is loaded down with trivial details and problem such as environmental pollution, realized the green high-efficient acid alcohol esterification under the mild conditions, preparation is simple, with low cost, the recyclable recycling of catalyzer.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is:
A kind of ionic liquid-catalyzed method for preparing diethyl succinate of pyridines of using, carry out according to the following steps order:
1. get material
Get Succinic Acid, ethanol with mol ratio 1:3, mix, add Br φ nsted acidic pyridinium class ionic-liquid catalyst, described catalyst consumption is 5-8% of a Succinic Acid quality;
2. heat, react
Be heated to 60-70 ℃, stir in the time of heating, react 2-3h, room temperature leaves standstill;
3. extraction
Add the extraction agent ether, extraction diethyl succinate and surplus ethanol, extraction liquid through revolve steam the diethyl succinate crude product;
Extraction liquid lower floor ionic liquid removes water treatment through revolving to steam, and can directly enter next round-robin reaction as catalyzer;
4. purifying
Extraction gained crude product is removed the Succinic Acid crystal through crystallisation by cooling, can make purified diethyl succinate.
It more than is basic step of the present invention, select for use ether as extraction agent, be because the only molten target product of ether and insoluble ionic-liquid catalyst (in fact the also available benzene of extraction agent, hexanaphthene, ethyl acetate, they all have the characteristics of the insoluble ionic-liquid catalyst of only molten target product); Various compositions in the reaction process do not have corrosion to equipment, the reaction conditions gentleness, and esterification yield height, catalyzer are easy to reclaim, and postorder is handled simple, environment is not polluted, and realizes the green high-efficient of acid alcohol esterification.
As qualification of the present invention, described Br φ nsted acidic pyridinium class ionic liquid general structure is as follows:
N in the formula=1,2,3,4;
Negatively charged ion X
-Be bisulfate ion HSO
4 -, hexafluoro-phosphate radical PF
6 -, tetrafluoroborate BF
4 -, thiocyanate ion SCN
-, tosic acid root CH
3PhSO
3 -In a kind of.
The preferred n of the present invention=1,2,3,4 is because along with n increases, positive charge on the pyridine ring is more concentrated, strengthens the interaction between zwitterion, and the ionic liquid fusing point is raise, and at n=1,2,3,4 o'clock, the ionic liquid fusing point was lower, under agitation condition, was fit to homogeneous reaction;
Negatively charged ion X
-Preferably from one of above-mentioned negatively charged ion, purpose is to make ionic liquid to be acid, and acidic ion liquid is higher to acid alcohol esterification catalytic effect.
As optimization of the present invention, the reaction of described step in 2. is to carry out under the reflux condensation mode state.
Because the alcoholic acid boiling point is lower, in order to reduce the loss that its heating evaporation causes, the special preferred reflux condensation mode restriction that increases.
As another kind of optimization of the present invention, the crystallisation by cooling of described step in 4. is meant at 0-15 ℃ to keep 1-5h.
In fact because the Succinic Acid amount that is slightly soluble in the ester is very little, and it at room temperature also can separate out in crystallization, but needs the long time, therefore to the above-mentioned optimization of carrying out of Tc and time, the Succinic Acid crystallization quickly and efficiently that more helps being slightly soluble in ester is separated out, and further guarantees the purity of product.
Owing to adopted above-mentioned technical scheme, the present invention compared with prior art, obtained technical progress is:
(1) Preparation of Catalyst of the present invention's use is simple, avoided the use of a large amount of organic solvents in synthesizing, and this catalyzer is cheap, compliance with environmental protection requirements;
(2) catalyst of the present invention's use is active high, and consumption is few, the product selectivity height, and the recyclable back of catalyzer is reused repeatedly, and catalytic activity does not have obvious reduction;
(3) temperature of reaction of esterification of the present invention is low, and the reaction times is short, and (selectivity 100%) takes place in no side reaction, reduced cost, improved economic benefit;
(4) catalyst stability of the present invention's use is good, and it is simple to reclaim technology;
(5) method provided by the invention is simple to operate, is easy to control, and esterification yield is suitable for suitability for industrialized production more than 90%.
The present invention can be used for synthetic fourth diester diethyl ester, is fit to large-scale industrialization production.
Annotate: esterification yield of the present invention is according to the GB/T1668-2008 method, and the acid number by solution before and after the assaying reaction is calculated as follows again:
E?=?(1-X
2/X
1)×100%
In the formula: E is an esterification yield, and unit is %; X
1, X
2Be respectively the forward and backward acid number of mixture reaction (acid number promptly refer in and the milligram number of residue Succinic Acid required potassium hydroxide in the 1g reaction solution, unit: mgKOH/g).
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment
Following examples only are used to illustrate the present invention, are not qualification of the present invention.
Embodiment 1 uses the ionic liquid-catalyzed method for preparing the pyridines diethyl succinate of pyridines
0.05mol Succinic Acid, 0.15mol ethanol, 0.295g N-picoline hydrosulfate are added in the there-necked flask that reflux condensation mode is housed (the adding order of three kinds of materials is unrestricted), magnetic agitation (stirs in the time of heating, purpose is in order to make reaction more even, while augmenting response speed, reduce the reaction times, the mode that stirs is not limited to magnetic agitation, can adopt other alr mode);
React 2h under 60 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make the diethyl succinate crude product;
0 ℃ of crystallisation by cooling 1h, centrifugation removes the solid Succinic Acid that decrystallizes out, can obtain purified diethyl succinate product.Esterification yield reaches 93.72%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 2 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.31g N-ethylpyridine hydrosulfate are equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2h under 65 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
5 ℃ of crystallisation by cooling 1.5h, centrifugation removes the solid Succinic Acid that decrystallizes out, can obtain purified product.Esterification yield reaches 94.32%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 3 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.325g N-propyl group pyridinium tetrafluoroborate salt are equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2.5h under 60 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams remove ether and excess ethyl alcohol makes product diethyl succinate crude product;
10 ℃ of crystallisation by cooling 4h remove the solid Succinic Acid that decrystallizes out, can obtain purified product.Esterification yield reaches 93.16%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 4 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
With the 0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.34g N-butyl-pyridinium hydrosulfate is equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2h under 60 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
8 ℃ of crystallisation by cooling 3.5h remove the solid Succinic Acid that decrystallizes and separate out, and can obtain purified product.Esterification yield reaches 96.63%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 5 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
With the 0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.365g N-butyl-pyridinium thiocyanate-is equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2.5h under 65 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
15 ℃ of crystallisation by cooling 5h remove the solid Succinic Acid that decrystallizes and separate out, and can obtain purified product.Esterification yield reaches 94.71%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 6 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
With the 0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.38g N-ethylpyridine hexafluorophosphate is equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2.0h under 65 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
12 ℃ of crystallisation by cooling 4h remove the solid Succinic Acid that decrystallizes and separate out, and can obtain purified product.Esterification yield reaches 92.15%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 7 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
With the 0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.395g N-ethylpyridine a tetrafluoro borate is equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2.5h under 70 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
Crystallisation by cooling 5h under the room temperature removes the solid Succinic Acid that decrystallizes and separate out, and can obtain purified product.Esterification yield reaches 94.78%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 8 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.41g N-butyl-pyridinium tosilate are equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2.0h under 60 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams remove ether and excess ethyl alcohol makes product diethyl succinate crude product;
15 ℃ of crystallisation by cooling 5h remove the small amount of solid Succinic Acid, can obtain purified product.Esterification yield reaches 96.89%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 9 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.42 g N-ethylpyridine tosilate are equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2.0h under 65 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
2 ℃ of crystallisation by cooling 4.5h remove the small amount of solid Succinic Acid, can obtain purified product.Esterification yield reaches 95.33%, selectivity 100%.
Extraction liquid lower floor ionic liquid is reused after steaming is handled through simply revolving.
Embodiment 10 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
With the 0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.43g N-picoline thiocyanate-is equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 3.0h under 65 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
6 ℃ of crystallisation by cooling 2h remove the small amount of solid Succinic Acid, can obtain purified product.Esterification yield reaches 94.12%, selectivity 100%.
Ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 11 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.44g N-propyl group pyridine hydrosulfate are equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2.5h under 60 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
11 ℃ of crystallisation by cooling 3h remove the small amount of solid Succinic Acid, can obtain purified product.Esterification yield reaches 92.79%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 12 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.45g N-picoline a tetrafluoro borate are equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2.5h under 65 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
13 ℃ of crystallisation by cooling 4h remove the small amount of solid Succinic Acid, can obtain purified product.Esterification yield reaches 93.16%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 13 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.46g N-butyl-pyridinium hexafluorophosphate are equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2.5h under 60 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
14 ℃ of crystallisation by cooling 4.5h, crystallisation by cooling is removed the small amount of solid Succinic Acid, can obtain purified product.Esterification yield reaches 92.63%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 14 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.47g N-ethylpyridine thiocyanate-are equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2.5h under 65 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
15 ℃ of crystallisation by cooling 5h remove the small amount of solid Succinic Acid, can obtain purified product.Esterification yield reaches 94.02%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Embodiment 15 uses the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines
0.05mol Succinic Acid, 0.15mol ethanol, the adding of 0.472 g N-propyl group pyridine tosilate are equipped with in the there-necked flask of reflux condensation mode, magnetic agitation,
React 2.0h under 60 ℃ of conditions; Then
Add the extraction agent ether, inclining the upper strata mixing solutions, and 40-55 ℃ of vacuum rotary steams are removed ether and excess ethyl alcohol, make product diethyl succinate crude product;
0 ℃ of crystallisation by cooling 1h removes the small amount of solid Succinic Acid, can obtain purified product.Esterification yield reaches 95.78%, selectivity 100%.
Extraction liquid lower floor ionic liquid can be used as next round-robin catalyzer once more after simply revolving the steaming processing, thereby obtains reusing.
Claims (4)
1. one kind is used the ionic liquid-catalyzed method for preparing diethyl succinate of pyridines,
It is characterized in that:This method is carried out according to the following steps order:
1. get material
Get Succinic Acid, ethanol with mol ratio 1:3, mix, add Br φ nsted acidic pyridinium class ionic-liquid catalyst, described catalyst consumption is 5-8% of a Succinic Acid quality;
2. heat, react
Be heated to 60-70 ℃, stir in the time of heating, react 2-3h, room temperature leaves standstill;
3. extraction
Add the extraction agent ether, extraction diethyl succinate and surplus ethanol, extraction liquid through revolve steam the diethyl succinate crude product;
Extraction liquid lower floor ionic liquid removes water treatment through revolving to steam, and can directly enter next round-robin reaction as catalyzer;
4. purifying
Extraction gained crude product is removed a small amount of unreacted Succinic Acid crystal through crystallisation by cooling, can make purified diethyl succinate.
2. the ionic liquid-catalyzed method for preparing diethyl succinate of use pyridines according to claim 1,
It is characterized in thatDescribed Br φ nsted acidic pyridinium class ionic liquid general structure is as follows:
N in the formula=1,2,3,4;
Negatively charged ion X
-Be bisulfate ion HSO
4 -, hexafluoro-phosphate radical PF
6 -, tetrafluoroborate BF
4 -, thiocyanate ion SCN
-, tosic acid root CH
3PhSO
3 -In a kind of.
3. the ionic liquid-catalyzed method for preparing diethyl succinate of use pyridines according to claim 1,
It is characterized in that:The reaction of described step in 2. is to carry out under the reflux condensation mode state.
4. the ionic liquid-catalyzed method for preparing diethyl succinate of use pyridines according to claim 1,
It is characterized in that:The crystallisation by cooling of described step in 4. is meant at 0-15 ℃ to keep 1-5h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102757344A (en) * | 2012-07-19 | 2012-10-31 | 北京旭阳化工技术研究院有限公司 | Method for preparing methyl succinate from ionic liquid catalyst |
| CN103467382A (en) * | 2013-09-16 | 2013-12-25 | 浙江丽晶化学有限公司 | Method for preparing thiocyanate-containing ionic liquid and application of ionic liquid in polyacrylonitrile spinning processing |
| CN103819336A (en) * | 2014-03-19 | 2014-05-28 | 南京工业大学 | Method for preparing disuccinate |
| CN105688993A (en) * | 2016-03-04 | 2016-06-22 | 河北科技大学 | Load type polymeric acidic ionic liquid catalyst and preparation method and application thereof |
| CN112174876A (en) * | 2020-10-14 | 2021-01-05 | 江苏高科石化股份有限公司 | Preparation method and application of pyridine ionic liquid acidic catalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757344A (en) * | 2012-07-19 | 2012-10-31 | 北京旭阳化工技术研究院有限公司 | Method for preparing methyl succinate from ionic liquid catalyst |
| CN103467382A (en) * | 2013-09-16 | 2013-12-25 | 浙江丽晶化学有限公司 | Method for preparing thiocyanate-containing ionic liquid and application of ionic liquid in polyacrylonitrile spinning processing |
| CN103819336A (en) * | 2014-03-19 | 2014-05-28 | 南京工业大学 | Method for preparing disuccinate |
| CN105688993A (en) * | 2016-03-04 | 2016-06-22 | 河北科技大学 | Load type polymeric acidic ionic liquid catalyst and preparation method and application thereof |
| CN105688993B (en) * | 2016-03-04 | 2018-02-06 | 河北科技大学 | A kind of load type polymerization acidic ionic liquid catalysts and its preparation method and application |
| CN112174876A (en) * | 2020-10-14 | 2021-01-05 | 江苏高科石化股份有限公司 | Preparation method and application of pyridine ionic liquid acidic catalyst |
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Application publication date: 20111207 |