CN103649037A - Hydrolysis and esterification with acid catalysts - Google Patents
Hydrolysis and esterification with acid catalysts Download PDFInfo
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- CN103649037A CN103649037A CN201280025615.9A CN201280025615A CN103649037A CN 103649037 A CN103649037 A CN 103649037A CN 201280025615 A CN201280025615 A CN 201280025615A CN 103649037 A CN103649037 A CN 103649037A
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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Abstract
Ionic liquids derived from a quaternary ammonium salt and a counter ion providing hydrogen donor compound are used as an acidic catalyst for a hydrolysis of an organic carboxylic acid esters and for an esterification of a carboxylic acid and an alcohol.
Description
Field
The present invention relates to a kind of technique that organic carboxyl acid and organic carboxylic ester transform mutually in acid catalyst and ionic liquid.
Background
For example, viscosity melting salt is exactly a kind of ionic liquid, is in a liquid state or lower than envrionment temperature.20 years in the past, ion liquid system, in the multinomial application as solvent, cosolvent and catalyzer, because having multiple noticeable and useful characteristic and purposes, obtained deep use.Synthetic, dyestuff, battery, fuel cell, photovoltaic apparatus, electrodeposition technology, semi-conductor at electrochemistry, compound are clean, pyrolysis, gasify and relate to the various fields such as cellulose dissolution application, and ion liquid system has successfully replaced traditional molecular solvent.
By the demand that ionic liquid replaces traditional molecule acid catalyst, result from an urgent demand of development feature of environmental protection technique.Ionic liquid shows low-down vapour pressure or zero vapour pressure, therefore, is different from traditional molecular solvent, and ionic liquid can not produce any steam.
Existing knowledge:
United States Patent (USP) 5892124 discloses quaternary ammonium or quaternary phosphonium base ionic liquid, and its general formula is Q
+a
-, A wherein
-represent various negatively charged ion, comprise tetrachloro aluminate and three chlorozincates, and for wearing A Deer (Dies-Alder) reaction, disclose the feasibility of ion liquid system.
United States Patent (USP) 6573405 discloses through type R
1r
2r
3r
4+n
+x
-the halogenide (or two or more mixtures wherein) of quaternary ammonium compound (or two or more mixtures wherein) and zinc, tin or iron react, form quaternary ammonium group ionic compound, and the first-selected ionic compound obtaining from Lipotril and zinc chloride is disclosed, be intended to be applied to dissolving, the battery of electrochemistry, galvanic deposit, electrochromism and metal oxide and wear A Deer reaction.
Another United States Patent (USP) 7183433 discloses from formula R
1r
2r
3r
4n
+x
-the quaternary ammonium group ionic compound that obtains of quaternary ammonium compound (or two or more mixtures wherein) and urea reaction, as Lipotril and urea reaction.Similarly, also attempt carrying out synthesis type R with concrete hydrogen donor compound (being selected from carboxylic acid, acid amides, ether, ester, aldehyde, ketone, alcohol and carbohydrate)
1r
2r
3r
4n
+x
-the ionic liquid of quaternary ammonium compound.Formula R
1r
2r
3r
4n
+x
-quaternary ammonium compound in negatively charged ion be muriate, nitrate and tetraboric acid.Above-mentioned United States Patent (USP) also discloses by change the negatively charged ion X of negatively charged ion with symmetrical amine salt
-effect.
Spent ion exchange resin is hydrolyzed alkyl ester, as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, is intended to produce methyl alcohol and acetic acid.This type of hydrolysis reaction is balanced reaction, if do not remove the alcohol forming in reaction, instead would not continue.Therefore, the alcohol forming in reaction will be with reactant, with the form of azeotrope, is removed continuously.This can cause the transformation efficiency of every batch of mixture not high.And, also need high temperature, could remove continuously the alcohol forming in reaction process.
Adopt the reaction of ion exchange resin hydrolysis alkyl ester in a plurality of patent documents, to have report, as Chinese patent 1343649, Chinese patent 1377873, Chinese patent 1380273, Chinese patent 2536587, Chinese patent 101130482, Chinese patent 1927792, Chinese patent 101012162, Chinese patent 101306981, Chinese patent 101348415, Chinese patent 101186575, Chinese patent 101209955, Chinese patent 101244982, Chinese patent 101704733, Chinese patent 101481293 and Korean Patent 100888065, Japanese Patent 53031608, Japanese Patent 56007739, Japanese Patent 59036631, Japanese Patent 10139716, Japanese Patent 2007210980, English Patent 687902, English Patent 826240, and United States Patent (USP) 2002/0183549, 2008/0128262 and 2010/0041919.In the application of all above-mentioned these type of patents/patent, adopt the reactor structure of ion exchange resin hydrolysis alkyl ester of all kinds, as fixed bed, reaction formula rectifying tower, range of reaction temperature is 50-150 ℃, be intended to by the rectifying of continuous backflow formula, reaction is continued.
As everyone knows, esterification alcohols and carboxylic-acid are to carry out in acid catalyst to generate the reaction of relevant alkyl ester.Adopt Zeo-karb to impel the report of esterification a lot.But seldom have technique to use mineral acid, and great majority are all used sulfuric acid and organic catalyst, as phosphoric acid, tosic acid etc.Sometimes also adopt acid organic catalyst.In prior art, the method for esterifying alcohol is to carry out in the temperature range of 50-150 ℃.Esterification is balanced reaction, therefore, wishes very much to remove wherein a kind of product, reaction is continued, thereby improve transformation efficiency.
At European patent 0087870, United States Patent (USP) 2719166, United States Patent (USP) 3014066, United States Patent (USP) 4435595, United States Patent (USP) 4481146, United States Patent (USP) 4939294, United States Patent (USP) 5430178, United States Patent (USP) 5518699, United States Patent (USP) 5998658, United States Patent (USP) 4939294, United States Patent (USP) 5430178, United States Patent (USP) 5518699, United States Patent (USP) 5998658, United States Patent (USP) 6028215, United States Patent (USP) 6458992, in United States Patent (USP) 6693123 and United States Patent (USP) 2006/0041162, the esterification of report comprises pyroreaction, be intended to obtain acceptable single transformation efficiency, result causes large reflux ratio.
But the reaction reported so far exists many shortcomings, comprise and need hot conditions and not environmental protection.
Therefore, sensation need to be developed a kind of new acid catalyst system, for being hydrolyzed organic carboxylic ester class and esterification alcohols and organic carboxyl acid class, not only cost efficient but also environmental protection.
Goal of the invention:
An object of the present invention is, a kind of technique that organic carboxyl acid and organic carboxylic ester transform mutually of carrying out in acid catalyst and ionic liquid is provided.
Another object of the present invention is that a kind of the have organic carboxyl acid of high conversion and the technique that organic carboxylic ester transforms are mutually provided
The present invention also has another one object, is just to provide the technique that a kind of organic carboxyl acid at low temperatures and organic carboxylic ester transform mutually
The present invention also has another one object, is just to provide the technique that organic carboxyl acid that a kind of cost benefit is good and organic carboxylic ester transform mutually
The present invention has an object again, is just to provide a kind of organic carboxyl acid of environmental protection and the technique that organic carboxylic ester transforms mutually
Definition:
While using in this manual, following word and phrase generally have the implication of elucidated hereinafter, unless separately had dated when it uses in the text.
The phrase " ion fluid " using herein refers to a kind of solvate of preparing, by the mixture of dissolved hydrogen compound donator and quaternary ammonium salt, and a kind of ionic compound forming in position.
Summary of the invention:
According to the present invention, the technique that provides a kind of organic carboxyl acid and organic carboxylic ester mutually to transform, described technique comprises:
A kind of hydrogen donor compound of dissolving equimolar amount and a kind of quaternary ammonium salt are in a kind of medium, and this medium contains at least one being selected from the one group of liquid that comprises the first alcohol and water, are intended to obtain the ion fluid of the ionic compound that contains a kind of original position generation; And execution is selected from least one reactions steps comprising with in next group step:
A adds a kind of organic carboxylic ester in this ion fluid to and is hydrolyzed, and in the temperature range of 20-100 ℃, continues to stir; And
B adds a kind of organic carboxyl acid and the second alcohol in this ion fluid, to carry out esterification to, and in the temperature range of 20-50 ℃, continues to stir.
Conventionally, the first alcohol is identical with the second alcohol.
Conventionally, in method steps b, can not add the second alcohol in ion fluid.
But the first alcohol can be identical with the second alcohol.
Conventionally, hydrogen donor compound is selected from and comprises tosic acid, oxalic acid, toxilic acid, methylsulfonic acid and tartaric one group of compound.
Conventionally, quaternary ammonium salt is Lipotril.
Conventionally, alcohol is selected from least one in the one group of alcohol that comprises methyl alcohol, ethanol, Virahol and propyl carbinol.
Conventionally, organic carboxyl acid is selected from least one in the one group of carboxylic acid that comprises acetic acid, propionic acid and butyric acid.
Conventionally, organic carboxylic ester is selected from least one in the one group of ester that comprises methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, pentyl acetate and hexyl acetate.
Conventionally, the ratio of organic carboxylic ester and water in molar ratio Range Representation be 1:1-1:10.
Conventionally, the ratio of organic carboxyl acid and alcohol in molar ratio Range Representation be 0.1:2-2:0.1.
Conventionally, in method steps a, the hydrolysis of organic carboxylic ester is to carry out under the azeotropic temperature of organic carboxylic ester.
Conventionally, in method steps b, esterification first-selection is carried out in the temperature range of 20-50 ℃.
Detailed Description Of The Invention:
The present invention has imagined a kind of organic carboxyl acid and organic carboxylic ester mutual technique transforming in acid catalyst, and this acid catalyst exists with the form of ion fluid.
By hydrogen bond, connect the ionic compound with zwitterion, according to report, having supramolecular structure tissue (consults: Oliver-Bourbigou, H. wait people to be reported in < < Applied Catalysis > > A volume: total the 373rd phase, 1-56 page, 2010; Deetlefs, the people such as m. are reported in < < Physical Chemistry > > periodical B the 110th phase of volume, 12055-12061 page; Canongia Lopez, J.N. and Padua, A.A.H. be reported in < < Physical Chemistry > > periodical B the 110th phase of volume, 3330-3335 page, 2006).By the formed continuous micro scale structure of hydrogen bond network, seem to be conducive to acid catalyzed reaction.
In the prior art, find that the method for preparing degree of depth eutectic ionic compound makes us dull relatively largely.The ion combination properties generating is extremely sticky, and the technique that generates ionic compound is not only consuming time, and needs high temperature.
The present invention obtains from quaternary ammonium salt and hydrogen donor compound for the preparation of the ionic compound of ion fluid.
According to an aspect of the present invention, such ionic compound is used as acid catalyst.Conventionally, adopt the method that heats hydrogen donor compound together with quaternary ammonium compound to synthesize the ionic compound of degree of depth eutectic mixture form.
According to another aspect of the present invention, the technique that provides a kind of organic carboxyl acid and organic carboxylic ester mutually to transform, wherein adopts ion fluid as acid catalyst.
According to the present invention, the ion fluid that is used as acid catalyst is to adopt a kind of simple technique to prepare at low temperatures, thereby overcome in prior art report, prepares the defect that ionic compound is relevant.
Conventionally, preparation ion fluid and organic carboxyl acid and organic carboxylic ester transform mutually in the ion fluid of preparation technique are carried out in the following manner:
In first aspect, the invention provides a kind of hydrolysis reaction, a kind of organic carboxylic ester is hydrolyzed into relevant alkyl alcohol and carboxylic acid; And
In second aspect, the invention provides a kind of esterification, a kind of organic carboxyl acid is become to relevant organic carboxylic ester with a kind of alkyl alcohol esterification.
The technique that in the present invention, organic carboxyl acid and organic carboxylic ester transform is mutually to carry out in a kind of acid catalyst, and this acid catalyst is the ion fluid that original position produces.
The hydrogen donor compound of equimolar amount and quaternary ammonium salt are dissolved in a kind of medium, and continue to stir, obtain a kind of ion fluid of the ionic compound that contains original position generation.
This medium according to the present invention contains at least one being selected from the one group of liquid that comprises the first alcohol and water.
The present invention is in hydrolysis during organic carboxylic ester, for the medium of dissolved hydrogen compound donator and quaternary ammonium salt, can be alcohol or water, first-selected water.
A kind of organic carboxylic ester is added in the ion fluid obtaining from quaternary ammonium salt and hydrogen donor compound, be intended to obtain a kind of reaction mixture.
According to the present invention, organic carboxylic ester is selected from least one in the one group of ester that comprises methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, pentyl acetate and hexyl acetate.
The ratio of organic carboxylic ester and water in molar ratio Range Representation is 1:1-1:10.
The present inventor has studied the impact of the speed that is hydrolyzed in the ion fluid that temperature produces in position on organic carboxylic ester.
According to the present invention, the temperature range being hydrolyzed in the ion fluid that organic carboxylic ester produces is in position 20-100 ℃.
The hydrolysising experiment of one group of organic carboxylic ester is to carry out in the temperature range of 20-30 ℃, and another group experiment is to carry out under the azeotropic temperature of relevant organic carboxylic ester.
According to one embodiment of present invention, hydrolysis organic carboxylic ester is to carry out in the temperature range of 20-50 ℃.
According to another embodiment of the invention, hydrolysis organic carboxylic ester is to carry out under the azeotropic temperature of organic carboxylic ester.
Methyl acetate and the formation of methanol azeotrope, the boiling point of methyl acetate/methanol is 53.4 ℃.Therefore, the hydrolysising experiment of one group of methyl acetate relates to hydrolysis at 26 ℃, and another group experiment relates in the ion fluid producing in position and in 55 ℃ (azeotropic temperatures of methyl acetate) lower hydrolysis.
Be similar to the hydrolysis of methyl acetate, the hydrolysis of ethyl acetate, isopropyl acetate and n-butyl acetate is also to carry out at two kinds of different temperature.One group of experiment is under room temperature (first-selected 25-27 ℃), and another group experiment is to carry out under the azeotropic temperature of relevant organic carboxylic ester and in the ion fluid producing in position.
Conventionally, the azeotropic temperature that ethyl acetate, isopropyl acetate and n-butyl acetate are hydrolyzed is respectively 70 ℃, 80 ℃ and 100 ℃.
The hydrolysis of propyl carbinol can only be carried out under its azeotropic temperature, because at room temperature, the compatibility of propyl carbinol in water is negligible, but at 100 ℃ of temperature, can increase a lot.
After having reacted, reaction mixture has pending product to resolve.
The data that organic carboxylic ester is hydrolyzed under room temperature (first-selected 25-27 ℃) and the azeotropic temperature at organic carboxylic ester are listed in the table 1 – table 11 of this specification sheets.
The comparative data providing from table 1, table 2 and the table 3 of this specification sheets clearly illustrates, the speed of the reaction that is hydrolyzed in the ion fluid that methyl acetate produces is in position faster than the hydrolysis reaction carrying out in only there is sour medium (consulting: table 3).
Organic carboxylic ester is hydrolyzed the speed of reaction faster than the hydrolysis reaction carrying out in only there is sour medium in ion fluid lower and that produce in position in room temperature (first-selected 25-27 ℃).But sometimes, in the previous case, find that final transformation efficiency reduces.At room temperature, reactant and product are present in liquid phase simultaneously, and having of strongly-acid ionic liquid is beneficial to reversible reaction, thereby have reduced final transformation efficiency (consulting table 1 and the table 3 of this specification sheets).
According to the present invention, in the ion fluid that methyl acetate original position lower 55 ℃ (azeotropic temperatures of methyl acetate) and that obtaining from tosic acid and Lipotril produces, can in 30 minutes, reach inversion equilibrium, and the hydrolysis reaction that methyl acetate carries out in tosic acid can reach inversion equilibrium in 60 minutes.
The hydrolysis reaction that the speed ratio of reaction of being hydrolyzed in the ion fluid that organic carboxylic ester produces under its relevant azeotropic temperature and in position carries out in only there is organic acid medium is high a lot.Under azeotropic temperature, compared with lower boiling product, by forming a kind of azeotrope with organic carboxylic ester, remain vapor phase, therefore, the product that removes continuously steam form is conducive to reaction to be continued.
Ethyl acetate, isopropyl acetate and n-butyl acetate at ion fluid acid catalyst with in only there is sour medium and under room temperature (first-selected 25-27 ℃) and azeotropic temperature, be hydrolyzed reaction data list in the table 4-table 11 of this specification sheets.
According to a second aspect of the invention, provide in ion fluid acid catalyst the esterification of organic carboxyl acid and alcohol.
Be similar to the Fang Fa Bu Sudden in the hydrolytic process intermediate ion fluid generation of organic carboxylic ester, by dissolve hydrogen donor compound and the quaternary ammonium salt of equimolar amount in a kind of medium, produce in position the ion fluid acid catalyst for esterification organic carboxyl acid and alcohol.
This medium according to the present invention contains at least one being selected from the one group of liquid that comprises water and the first alcohol.
According to the present invention, the first-selected the first alcohol of medium in the Fang of esterification Fa Bu Sudden.
Organic carboxyl acid compound and the second alcohol are added in the ion fluid of acquisition, and continue to stir in the temperature range of 20-30 ℃ and under normal atmosphere.
According to one embodiment of present invention, the first alcohol is identical with the second alcohol.
According to another embodiment of the invention, the first alcohol can be different from the second alcohol.
According to the present invention, if the second alcohol using in the Fang Fa Bu Sudden of the first alcohol using in the Fang Fa Bu Sudden dissolving and esterification is identical, so, in the Fang of esterification Fa Bu Sudden, the second alcohol can not added in ion fluid.
According to the present invention, alcohol is selected from least one in the one group of alcohol that comprises methyl alcohol, ethanol, Virahol and propyl carbinol.
According to the present invention, organic carboxyl acid is selected from least one in the one group of carboxylic acid that comprises acetic acid, propionic acid and butyric acid.
Add after organic carboxylic acid cpd, obtained reaction mixture is maintained to predetermined temperature and continues to stir, until the condition that averages out.
According to one embodiment of present invention, the Fang Fa Bu Sudden first-selection of esterification is carried out in the temperature range of 25-27 ℃.
According to the present invention, the ratio of organic carboxyl acid and alcohol in molar ratio Range Representation is 0.1:2-2:0.1.
It is to carry out in only there is organic acid medium that organic carboxyl acid and alcohol ester are changed into relevant organic carboxylic ester, and its pressure and temperature condition is identical with the condition that esterification organic carboxyl acid and alcohol maintain in ion fluid.
The ion fluid producing in position and in only there is organic acid medium the analytical data of esterification organic carboxyl acid and alcohol list in the table 12 – table 19 of this specification sheets.
The data that provide from table 12 – table 19 clearly illustrate, the equilibrium conversion of two kinds of situations (in the ion fluid producing in position and carry out in only there is organic acid medium esterification) is all higher.
But the speed of sometimes carrying out esterification in ion fluid acid catalyst can be faster, as carried out the situation (consulting: the table 14 of this specification sheets and table 15) of ethyl esterification reaction in the ion fluid obtaining from oxalic acid, toxilic acid and tartrate.
For the situation of Virahol, the esterification that in the ion fluid producing in position, contrast is carried out in only there is acid compound, its transformation efficiency can height a lot (consulting: the table 16 of this specification sheets and table 17).
Esterification organic carboxyl acid and alcohol, without hot conditions, just can be obtained high conversion.The compatibility of two kinds of reactants together with catalyzer time is to obtain one of reason of high equilibrium conversion at 26 ℃.
Sometimes, either way there is equilibrium conversion faster, and no matter whether have ion fluid, because a kind of acid catalyst system has been eliminated the defect of using traditional acid catalyst system.
For the situation of esterification organic carboxyl acid and alcohol in the ion fluid acid catalyst producing in position, obtained equilibrium conversion has been eliminated the demand to complex reaction rectifying tower, thereby has reduced fund and operation input.
According to the present invention, hydrogen donor compound is selected from and comprises methylsulfonic acid, tosic acid, oxalic acid, toxilic acid and tartaric one group of compound.
Quaternary ammonium salt used in the present invention is Lipotril.
According to the present invention, at suitable medium intermediate ion fluid, form in position this fact, the solvability raising by hydrogen donor compound in a kind of suitable medium is confirmed.For example, oxalic acid solubleness in water in the time of 25 ℃ is 14%, and can bring up to 30% in Lipotril.This phenomenon clearly illustrates that, in the time of 25 ℃, the ionic compound forming by hydrogen bond has improved the solubleness of oxalic acid.Otherwise, water temperature need to be brought up to about 40-45 ℃, could in water, dissolve 30% oxalic acid.
The present inventor surprisingly finds, the product obtaining by technique of the present invention is completely containing any residual acid.This has just eliminated the demand of neutralization reaction mixture before separating out product, as existing technique requires.
Now consult following indefiniteness example, the present invention will be further described:
example 1:
The monohydrate of tosic acid (PTSA), a kind of hydrogen donor compound (5.7 grams) and Lipotril (4.2 grams) are added in 17 ml waters by equimolar ratio, and continue to stir with preparation ion fluid.In the ion fluid of preparation, add 15 milliliters of methyl acetates, be intended to obtain reaction mixture, reaction is carried out at 26 ℃.After having reacted, in reaction mixture, parse reaction product.Methyl acetate changes into acetic acid and methyl alcohol, and obtained transformation efficiency is 53.4%.
example 2-5:
With different hydrogen donors, replace after PTSA, follow the step of example 1.Details are provided in table 1.
Table 1: be hydrolyzed methyl acetate with ionic compound at 26 ℃
example 6-10: except maintaining the temperature of reaction of 55 ℃, follow the step of example 2.Details are provided in table 2.
Table 2: be hydrolyzed methyl acetate with ionic compound at 55 ℃
example 11-20: adopt different acid and follow the step (not using any ionic compound) of above example (routine 1-example 10).Details are provided in table 3.
Table 3: be only hydrolyzed methyl acetate with acid catalyst
example 21: except replacing methyl acetate by ethyl acetate and reacting and carry out, follow the step of example 1 at 26 ℃.Ethyl acetate is converted to acetic acid and ethanol, and obtained transformation efficiency is 24.4%.
example 22-25: with different hydrogen donor, replace after PTSA the reaction that is hydrolyzed of the step of following example 21.Details are provided in table 4.
Table 4: be hydrolyzed ethyl acetate with ionic compound at 26 ℃.
example 26-30: except maintaining the temperature of reaction of 70 ℃, follow the step of example 22.Details are provided in table 5.
Table 5: be hydrolyzed ethyl acetate with ionic compound at 70 ℃
example 31-40: only adopt different acid and follow the step (without any ionic compound) of above routine 21-example 30.Table 6 provides the details of reaction.
Table 6: only adopt acid catalyst hydrolysis ethyl acetate
example 41: except replacing methyl acetate with isopropyl acetate and reacting and carry out, follow the step of example 1 at 26 ℃.Isopropyl acetate changes into acetic acid and Virahol, and obtained transformation efficiency is 21%.
example 42-45: with different hydrogen donor, replace after PTSA the reaction that is hydrolyzed of the step of following example 41.Details are provided in table 7.
Table 7: be hydrolyzed isopropyl acetate with ionic compound at 26 ℃.
example 46-50: except maintaining the temperature of reaction of 80 ℃, follow the step of example 42.Details are provided in table 8.
Table 8: be hydrolyzed isopropyl acetate with ionic compound at 80 ℃
example 51-60: only adopt different acid and follow the step (without any ionic compound) of above routine 41-example 50.Details are provided in table 9.
Table 9: only adopt acid catalyst hydrolysis isopropyl acetate
example 61: except replacing methyl acetate with n-butyl acetate and reacting and carry out, follow the step of example 1 at 100 ℃.N-butyl acetate changes into acetic acid and propyl carbinol, and obtained transformation efficiency is 49.3%.
example 62-65: with different hydrogen donor, replace after PTSA the reaction that is hydrolyzed of the step of following example 61.Details are provided in table 10.
Table 10: be hydrolyzed n-butyl acetate with ionic compound at 100 ℃.
example 66-70: only adopt different acid and follow the step (without any ionic compound) of above routine 61-example 65.Details are provided in table 11.
Table 11: adopt acid catalyst hydrolysis n-butyl acetate at 100 ℃
example 71: the monohydrate of tosic acid (PTSA), a kind of hydrogen donor compound (5.7 grams) and Lipotril (4.2 grams) are added in 15 ml methanol by equimolar ratio, and continue to stir to obtain ion fluid.In the ion fluid of preparation, add 21.5 milliliters of acetic acid.Reaction is carried out at 26 ℃.The esterified one-tenth methyl acetate of methyl alcohol and water, obtained equilibrium conversion is 78%,
example 72-75: with different hydrogen donors, replace after PTSA, follow the step of example 71 and carry out esterification.Details are provided in table 12.
Table 12: with ionic compound esterification methyl alcohol at 26 ℃
example 76-80: only adopt different acid and follow the step (without any ionic compound) of above example 71.Details are provided in table 13.
Table 13: with acid catalyst esterification methyl alcohol at 26 ℃
example 81-85: except replacing methyl alcohol with ethanol, follow the step of example 71.The esterified one-tenth ethyl acetate of ethanol and water.Details are provided in table 14.
Table 14: with ionic compound esterification ethanol at 26 ℃
example 86-90: only adopt different acid and follow the step (without any ionic compound) of above example 81.Details are provided in table 15.
Table 15: with acid catalyst esterification ethanol at 26 ℃
example 91-96: except replacing methyl alcohol with Virahol, follow the step of example 71.The esterified one-tenth propyl acetate of Virahol and water.Details are provided in table 16.
Table 16: with ionic compound esterification Virahol at 26 ℃
example 96-100: only adopt different acid and follow the step (without any ionic compound) of above example 91.Details are provided in table 17.
Table 17: with acid catalyst esterification Virahol at 26 ℃
example 101-105: except replacing methyl alcohol with propyl carbinol, follow the step of example 91.The esterified one-tenth acetic acid of propyl carbinol fourth alcohol and water.Details are provided in table 18.
Table 18: with ionic compound esterification propyl carbinol at 26 ℃
example 106-110: only adopt different acid and follow the step (without any ionic compound) of above example 101.Details are provided in table 19.
Table 19: with acid catalyst esterification propyl carbinol at 26 ℃
Technical advance:
The invention has the advantages that, a kind of novel method that organic carboxyl acid and organic carboxylic ester transform mutually in ion fluid acid catalyst is provided, comprising:
1. original position produces a kind of ion fluid, thereby has omitted the processing step of relevant synthetic degree of depth eutectic compound;
2. this technique is more saved time than traditional technique and is more energy-conservation;
3. this technique is than more cost efficient, the more environmental protection and safer of traditional technique.
" as long as stipulated the scope of value, the arbitrary value in 10% numerical value (in specialized range) bound all comprises within the scope of the invention ".
Although the first-selected embodiment of Special attention will be given to, is not departing under principle of the present invention herein, allow and make many embodiment, allow first-selected embodiment is carried out to many changes.For those skilled in the art, can, according to content disclosed herein, to first-selected embodiment of the present invention, carry out such and such change obviously, should be expressly understood for this reason, embodiment described above, is only to explanation of the present invention, rather than limitation of the invention.
Claims (13)
1. the technique that organic carboxyl acid and organic carboxylic ester transform mutually, described technique comprises:
A kind of hydrogen donor compound of dissolving equimolar amount and a kind of quaternary ammonium salt are in a kind of medium, and this medium contains at least one being selected from the one group of liquid that comprises the first alcohol and water, are intended to obtain the ion fluid of the ionic compound that contains a kind of original position generation; And execution is selected from least one reactions steps comprising with in next group step:
A adds a kind of organic carboxylic ester in this ion fluid to and is hydrolyzed, and in the temperature range of 20-100 ℃, continues to stir; And
B adds a kind of organic carboxyl acid and the second alcohol in this ion fluid, to carry out esterification to, and under the temperature range of 20-50 ℃, continues to stir.
2. in technique claimed in claim 1, the first alcohol is identical with the second alcohol.
3. in technique claimed in claim 1, the first alcohol is not identical with the second alcohol.
4. in the technique described in claim 1 and 2, the second alcohol is not in the ion fluid in the Fang of adding to Fa Bu Sudden b.
5. in technique claimed in claim 1, hydrogen donor compound is selected from and comprises tosic acid, oxalic acid, toxilic acid, methylsulfonic acid and tartaric one group of compound.
6. in technique claimed in claim 1, quaternary ammonium salt is Lipotril.
7. in the technique described in claim 2 and 3, alcohol is selected from least one in the one group of alcohol that comprises methyl alcohol, ethanol, Virahol and propyl carbinol.
8. in technique claimed in claim 1, organic carboxyl acid is selected from least one in the one group of carboxylic acid that comprises acetic acid, propionic acid and butyric acid.
9. in technique claimed in claim 1, organic carboxylic ester is selected from least one in the one group of ester that comprises methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, pentyl acetate and hexyl acetate.
10. in technique claimed in claim 1, the ratio of organic carboxylic ester and water in molar ratio Range Representation is 1:1-1:10.
11. in technique claimed in claim 1, and the ratio of organic carboxyl acid and alcohol in molar ratio Range Representation is 0.1:2-2:0.1.
12. in technique claimed in claim 1, and in method steps a, the hydrolysis of organic carboxylic ester is to carry out under the azeotropic temperature of organic carboxylic ester.
13. in technique claimed in claim 1, and in method steps b, esterification first-selection is carried out in the temperature range of 25-27 ℃.
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| PCT/IN2012/000264 WO2012164573A2 (en) | 2011-05-27 | 2012-05-12 | Hydrolysis and esterification with acid catalysts |
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| CN111138277A (en) * | 2019-12-21 | 2020-05-12 | 华东理工大学 | Method for synthesizing ethyl laurate by using eutectic solvent catalyst based on cetyl trimethyl ammonium bromide |
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| CN112812008A (en) * | 2021-01-11 | 2021-05-18 | 大连理工大学 | Method for preparing diacid diester compound under catalysis of deep eutectic solvent |
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|---|---|---|---|---|
| CN111138277A (en) * | 2019-12-21 | 2020-05-12 | 华东理工大学 | Method for synthesizing ethyl laurate by using eutectic solvent catalyst based on cetyl trimethyl ammonium bromide |
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| PT107888B (en) | 2015-06-24 |
| CN105330538A (en) | 2016-02-17 |
| BR122015009423A2 (en) | 2019-01-22 |
| WO2012164573A3 (en) | 2013-03-28 |
| PT2012164573W (en) | 2014-10-08 |
| BR112013030031A2 (en) | 2016-09-13 |
| WO2012164573A2 (en) | 2012-12-06 |
| PT107888A (en) | 2014-11-11 |
| CN103649037B (en) | 2015-11-25 |
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