CN103649037B - Acid catalyst is adopted to be hydrolyzed and esterification - Google Patents
Acid catalyst is adopted to be hydrolyzed and esterification Download PDFInfo
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- CN103649037B CN103649037B CN201280025615.9A CN201280025615A CN103649037B CN 103649037 B CN103649037 B CN 103649037B CN 201280025615 A CN201280025615 A CN 201280025615A CN 103649037 B CN103649037 B CN 103649037B
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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
- 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
- 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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- 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
From a kind of quaternary ammonium salt and provide the ionic liquid obtained the gegenion of hydrogen donor compound to be used as a kind of acid catalyst, for being hydrolyzed a kind of organic carboxylic ester and a kind of carboxylic acid of esterification and a kind of 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
Such as, viscous molten salt is exactly a kind of ionic liquid, is in a liquid state or lower than envrionment temperature.Two decades years in the past, ion liquid system, as in the multinomial application of solvent, cosolvent and catalyzer, because having multiple noticeable and useful characteristic and purposes, has obtained deep use., pyrolysis clean at the synthesis of electrochemistry, compound, dyestuff, battery, fuel cell, photovoltaic apparatus, electrodeposition technology, semi-conductor, gasify and relate to the various fields such as cellulose dissolution application, ion liquid system successfully instead of traditional molecular solvent.
An urgent demand of development feature of environmental protection technique is resulted from by the demand that ionic liquid replaces traditional molecule acid catalyst.Ionic liquid shows low-down vapour pressure or zero vapour pressure, and therefore, be different from traditional molecular solvent, 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
-, wherein A
-represent various negatively charged ion, comprise four chloro-aluminates 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 disclose the first-selected ionic compound obtained from Lipotril and zinc chloride, be intended to be applied to electrochemistry, galvanic deposit, electrochromism and metal oxide dissolving, battery 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 the negatively charged ion X by changing 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 formed in reaction, reaction can not continue.Therefore, the alcohol formed in reaction with reactant, will be removed continuously with the form of azeotrope.This can cause the transformation efficiency often criticizing mixture not high.And, also need high temperature, the alcohol formed in reaction process could be removed continuously.
The reaction of ion exchange resin hydrolysis alkyl ester is adopted in multiple patent document, 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 all this type of patents above-mentioned/patent application, 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 DEG C, be intended to, by the rectifying of continuous backflow formula, reaction be continued.
As everyone knows, esterification alcohols and carboxylic-acid are 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 all use sulfuric acid and organic catalyst, as phosphoric acid, tosic acid etc.Sometimes also acid mineral catalyzer is adopted.In prior art, the method for esterifying alcohol is carried out in the temperature range of 50-150 DEG C.Esterification is balanced reaction, therefore, wishes very much to remove wherein a kind of product, reaction is continued, thus improves 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 rate, result causes large reflux ratio.
But reaction reported so far exists many shortcomings, comprise and need hot conditions and not environmentally.
Therefore, feel to need to develop 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 of carrying out organic carboxyl acid and organic carboxylic ester and mutually transforming in acid catalyst and ionic liquid is provided.
Another object of the present invention is, provide a kind of there is high conversion organic carboxyl acid and the technique that mutually transforms of organic carboxylic ester
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 the good organic carboxyl acid of a kind of cost benefit and organic carboxylic ester transform mutually
The present invention has an object again, is just to provide the technique that a kind of organic carboxyl acid of environmental protection and organic carboxylic ester transform mutually
Definition:
When using in this manual, following word and phrase generally have the implication illustrated below, unless separately had dated when it uses in the text.
Phrase used herein " ion fluid " refers to a kind of solvate prepared, by the mixture of dissolved hydrogen compound donator and quaternary ammonium salt, and a kind of ionic compound formed in position.
Summary of the invention:
According to the present invention, provide the technique that a kind of 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 and comprising in one group of liquid of the first alcohol and water, are intended to the ion fluid obtaining the ionic compound produced containing a kind of original position; And perform at least one reactions steps being selected from and comprising with in next group step:
A kind of organic carboxylic ester adds in this ion fluid and is hydrolyzed by a, and in the temperature range of 20-100 DEG C Keep agitation; And
A kind of organic carboxyl acid and the second alcohol add in this ion fluid and carry out esterification by b, and in the temperature range of 20-50 DEG C Keep agitation.
Usually, the first alcohol is identical with the second alcohol.
Usually, in method steps b, the second alcohol can not be added in ion fluid.
But the first alcohol can be identical with the second alcohol.
Usually, hydrogen donor compound is selected from and comprises tosic acid, oxalic acid, toxilic acid, methylsulfonic acid and tartaric one group of compound.
Usually, quaternary ammonium salt is Lipotril.
Usually, alcohol is selected from least one comprised in one group of alcohol of methyl alcohol, ethanol, Virahol and propyl carbinol.
Usually, organic carboxyl acid is selected from least one comprised in one group of carboxylic acid of acetic acid, propionic acid and butyric acid.
Usually, organic carboxylic ester is selected from least one comprised in one group of ester of methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, pentyl acetate and hexyl acetate.
Usually, the ratio of organic carboxylic ester and water in molar ratio Range Representation be 1:1-1:10.
Usually, the ratio of organic carboxyl acid and alcohol in molar ratio Range Representation be 0.1:2-2:0.1.
Usually, in method steps a, organic carboxyl acid ester hydrolysis carries out under the azeotropic temperature of organic carboxylic ester.
Usually, in method steps b, esterification first-selection is carried out in the temperature range of 20-50 DEG C.
Detailed Description Of The Invention:
Present invention contemplates a kind of organic carboxyl acid and organic carboxylic ester mutual technique transformed in acid catalyst, this acid catalyst exists with the form of ion fluid.
Connect the ionic compound with zwitterion by hydrogen bond, according to report, there is supramolecular structure tissue and (consult: the people such as Oliver-Bourbigou, H. are reported in " AppliedCatalysis " A and roll up: total 373rd phase, 1-56 page, 2010 years; The people such as Deetlefs, m. are reported in " PhysicalChemistry " periodical B and rolled up for the 110th phase, 12055-12061 page; CanongiaLopez, J.N. and Padua, A.A.H. is reported in " PhysicalChemistry ", and periodical B rolled up for the 110th phase, 3330-3335 page, 2006 years).The continuous micro scale structure formed by hydrogen bond network seems to be conducive to acid catalyzed reaction.
In the prior art, find that the method preparing deep eutectic ionic compound makes us dull relatively largely.The ion combination properties generated is extremely sticky, and the technique generating 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.Usually, adopt the method heating hydrogen donor compound together with quaternary ammonium compound to synthesize the ionic compound of deep eutectic form of mixtures.
According to another aspect of the present invention, provide the technique that a kind of organic carboxyl acid and organic carboxylic ester transform mutually, wherein adopt ion fluid as acid catalyst.
According to the present invention, the ion fluid as acid catalyst adopts a kind of simple technique to prepare at low temperatures, thus overcome in prior art report the defect prepared ionic compound and be correlated with.
Usually, ion fluid is prepared and organic carboxyl acid and organic carboxylic ester transform mutually in the ion fluid of preparation technique is 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, by the organic carboxylic ester that a kind of organic carboxyl acid becomes to be correlated with a kind of alkyl alcohol esterification.
The technique that in the present invention, organic carboxyl acid and organic carboxylic ester transform mutually is carried 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 Keep agitation, obtain a kind of ion fluid of the ionic compound containing original position generation.
This medium according to the present invention contains at least one being selected from and comprising in one group of liquid of the first alcohol and water.
The present invention is when being hydrolyzed organic carboxylic ester, and the medium for 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 obtained from quaternary ammonium salt and hydrogen donor compound, is intended to obtain a kind of reaction mixture.
According to the present invention, organic carboxylic ester is selected from least one comprised in one group of ester of 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 have studied in the ion fluid that temperature produces in position on organic carboxylic ester the impact of the speed that is hydrolyzed.
According to the present invention, the temperature range be hydrolyzed in the ion fluid that organic carboxylic ester produces in position is 20-100 DEG C.
The hydrolysising experiment of one group of organic carboxylic ester carries out in the temperature range of 20-30 DEG C, and another group experiment carries out under the azeotropic temperature of relevant organic carboxylic ester.
According to one embodiment of present invention, being hydrolyzed organic carboxylic ester is carry out in the temperature range of 20-50 DEG C.
According to another embodiment of the invention, being hydrolyzed organic carboxylic ester is 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 DEG C.Therefore, the hydrolysising experiment of one group of methyl acetate relates to hydrolysis at 26 DEG C, and another group experiment relates in the ion fluid produced in position and hydrolysis under 55 DEG C (azeotropic temperature of methyl acetate).
Be similar to the hydrolysis of methyl acetate, the hydrolysis of ethyl acetate, isopropyl acetate and n-butyl acetate is also carry out at two kinds of different temperature.One group of experiment is under room temperature (first-selected 25-27 DEG C), and another group experiment carries out under the azeotropic temperature of relevant organic carboxylic ester and in the ion fluid produced in position.
Usually, the azeotropic temperature that ethyl acetate, isopropyl acetate and n-butyl acetate are hydrolyzed is respectively 70 DEG C, 80 DEG C and 100 DEG C.
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 can increase a lot at 100 DEG C of temperature.
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 DEG C) and the azeotropic temperature at organic carboxylic ester are listed in the table 1 – table 11 of this specification sheets.
The comparative data provided from the table 1 of this specification sheets, table 2 and table 3 clearly illustrates, the speed of the reaction that is hydrolyzed in the ion fluid that methyl acetate produces in position is faster than only there is the hydrolysis reaction (consulting: table 3) carried out in the medium of acid.
Organic carboxylic ester is hydrolyzed the speed of reaction faster than the hydrolysis reaction that carries out in the medium that only there is acid under room temperature (first-selected 25-27 DEG C) and in the ion fluid produced in position.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 strong acidic ion liquid is beneficial to reversible reaction, thus decrease final transformation efficiency (consulting table 1 and the table 3 of this specification sheets).
According to the present invention, methyl acetate is under 55 DEG C (azeotropic temperature of methyl acetate) and in the ion fluid of the original position generation obtained from tosic acid and Lipotril, can reach inversion equilibrium in 30 minutes, and the hydrolysis reaction that methyl acetate carries out in tosic acid can reach inversion equilibrium in 60 minutes.
Organic carboxylic ester is hydrolyzed the speed ratio of reaction only to there is the hydrolysis reaction carried out in organic acid medium high a lot of under azeotropic temperature that it is relevant and in the ion fluid produced in position.Under azeotropic temperature, more lower boiling product remains vapor phase by forming a kind of azeotrope with organic carboxylic ester, and therefore, the product removing vaporous form is continuously conducive to reaction to be continued.
Ethyl acetate, isopropyl acetate and n-butyl acetate ion fluid acid catalyst and only exist acid medium in and be hydrolyzed under room temperature (first-selected 25-27 DEG C) and azeotropic temperature react 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.
Being similar to the Fang Fa Bu Sudden produced at the hydrolytic process intermediate ion fluid of organic carboxylic ester, by dissolving hydrogen donor compound and the quaternary ammonium salt of equimolar amount in a kind of medium, producing the ion fluid acid catalyst being used for esterification organic carboxyl acid and alcohol in position.
This medium according to the present invention contains at least one be selected from the one group of liquid comprising water and the first alcohol.
According to the present invention, the first alcohol first-selected of the medium in the Fang Fa Bu Sudden of esterification.
Organic carboxylic acid compounds and the second alcohol are added in the ion fluid of acquisition, and Keep agitation in the temperature range of 20-30 DEG C 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 first alcohol used in the Fang Fa Bu Sudden dissolved is identical with the second alcohol used in the Fang Fa Bu Sudden of esterification, so, in the Fang Fa Bu Sudden of esterification, the second alcohol can not be added in ion fluid.
According to the present invention, alcohol is selected from least one comprised in one group of alcohol of methyl alcohol, ethanol, Virahol and propyl carbinol.
According to the present invention, organic carboxyl acid is selected from least one comprised in one group of carboxylic acid of acetic acid, propionic acid and butyric acid.
After adding organic carboxylic acid compounds, obtained reaction mixture is maintained predetermined temperature and Keep agitation, 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 DEG C.
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.
Organic carboxyl acid and alcohol ester being changed into relevant organic carboxylic ester is carry out only existing in organic acid medium, and its pressure and temperature condition is identical with the condition that alcohol maintains with esterification organic carboxyl acid in ion fluid.
The ion fluid produced in position and listing in the table 12 – table 19 of this specification sheets at the analytical data that only there is esterification organic carboxyl acid and alcohol in organic acid medium.
The data provided from table 12 – table 19 clearly illustrate, the equilibrium conversion of two kinds of situations (in the ion fluid namely produced in position and only exist in organic acid medium carry out 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 obtained from oxalic acid, toxilic acid and tartrate.
For the situation of Virahol, contrast and only there is the esterification of carrying out in acid compound in the ion fluid produced in position, 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 the need to hot conditions, just can obtain high conversion.Compatibility when two kinds of reactants are together with catalyzer is one of reason obtaining high equilibrium conversion at 26 DEG C.
Sometimes, either way there is equilibrium conversion faster, and no matter whether there is ion fluid, because a kind of acid catalyst system eliminates the defect using traditional acid catalyst system.
For the situation of esterification organic carboxyl acid and alcohol in the ion fluid acid catalyst produced in position, acquired equilibrium conversion eliminates the demand to complex reaction rectifying tower, thus decreases 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, form this fact in position at suitable medium intermediate ion fluid, improved by the solvability of hydrogen donor compound in a kind of suitable medium and be confirmed.Such as, the solubleness of oxalic acid 25 DEG C time in water is 14%, and can bring up to 30% in Lipotril.This phenomenon clearly illustrates that, 25 DEG C time, the ionic compound formed by hydrogen bond improves the solubleness of oxalic acid.Otherwise, need water temperature to bring up to about 40-45 DEG C, the oxalic acid of 30% could be dissolved in water.
The present inventor surprisingly finds, the product obtained by technique of the present invention is not completely containing any residual acid.This obviates the demand of neutralization reaction mixture before separating out product, required by existing technique.
Now consult following indefiniteness example, the present invention will be further described:
example 1:
The monohydrate (PTSA) of tosic acid, a kind of hydrogen donor compound (5.7 grams) and Lipotril (4.2 grams) are added in 17 ml waters by equimolar ratio, and Keep agitation is to prepare ion fluid.In the ion fluid of preparation, add 15 milliliters of methyl acetates, be intended to obtain reaction mixture, react and carry out at 26 DEG C.After having reacted, in reaction mixture, parse reaction product.Methyl acetate changes into acetic acid and methyl alcohol, and acquired transformation efficiency is 53.4%.
example 2-5:
After replacing PTSA with different hydrogen donors, follow the step of example 1.Details are provided in table 1.
Table 1: be hydrolyzed methyl acetate with ionic compound at 26 DEG C
example 6-10: except maintaining the temperature of reaction of 55 DEG C, follow the step of example 2.Details are provided in table 2.
Table 2: be hydrolyzed methyl acetate with ionic compound at 55 DEG C
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: carry out at 26 DEG C except replacing methyl acetate by ethyl acetate and reacting, follow the step of example 1.Ethyl acetate is converted to acetic acid and ethanol, and acquired transformation efficiency is 24.4%.
example 22-25: replace after PTSA with different hydrogen donors, the step following example 21 is hydrolyzed reaction.Details are provided in table 4.
Table 4: be hydrolyzed ethyl acetate with ionic compound at 26 DEG C.
example 26-30: except maintaining the temperature of reaction of 70 DEG C, follow the step of example 22.Details are provided in table 5.
Table 5: be hydrolyzed ethyl acetate with ionic compound at 70 DEG C
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: carry out at 26 DEG C except replacing methyl acetate with isopropyl acetate and reacting, follow the step of example 1.Isopropyl acetate changes into acetic acid and Virahol, and acquired transformation efficiency is 21%.
example 42-45: replace after PTSA with different hydrogen donors, the step following example 41 is hydrolyzed reaction.Details are provided in table 7.
Table 7: be hydrolyzed isopropyl acetate with ionic compound at 26 DEG C.
example 46-50: except maintaining the temperature of reaction of 80 DEG C, follow the step of example 42.Details are provided in table 8.
Table 8: be hydrolyzed isopropyl acetate with ionic compound at 80 DEG C
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: carry out at 100 DEG C except replacing methyl acetate with n-butyl acetate and reacting, follow the step of example 1.N-butyl acetate changes into acetic acid and propyl carbinol, and acquired transformation efficiency is 49.3%.
example 62-65: replace after PTSA with different hydrogen donors, the step following example 61 is hydrolyzed reaction.Details are provided in table 10.
Table 10: be hydrolyzed n-butyl acetate with ionic compound at 100 DEG C.
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 to be hydrolyzed n-butyl acetate at 100 DEG C
example 71: the monohydrate (PTSA) of tosic acid, a kind of hydrogen donor compound (5.7 grams) and Lipotril (4.2 grams) are added in 15 ml methanol by equimolar ratio, and Keep agitation is to obtain ion fluid.21.5 milliliters of acetic acid are added in the ion fluid of preparation.Reaction is carried out at 26 DEG C.The esterified one-tenth methyl acetate of methyl alcohol and water, acquired equilibrium conversion is 78%,
example 72-75: after replacing PTSA with different hydrogen donors, the step following example 71 carries out esterification.Details are provided in table 12.
Table 12: with ionic compound esterification methyl alcohol at 26 DEG C
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 DEG C
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 DEG C
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 DEG C
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 DEG C
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 DEG C
example 101-105: except replacing methyl alcohol with propyl carbinol, follow the step of example 91.Propyl carbinol esterified one-tenth acetic acid fourth alcohol and water.Details are provided in table 18.
Table 18: with ionic compound esterification propyl carbinol at 26 DEG C
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 DEG C
Technical advance:
The invention has the advantages that, provide a kind of novel method that organic carboxyl acid and organic carboxylic ester transform mutually in ion fluid acid catalyst, comprising:
1. original position produces a kind of ion fluid, thus eliminates the processing step of relevant synthesis deep eutectic compound;
2. this technique is more saved time with more energy-conservation than traditional technique;
3. this technique is than more cost efficient, the more environmental protection and safer of traditional technique.
" as long as define 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, is allowing and make many embodiments, allow and carry out many changes to first-selected embodiment herein.For those skilled in the art, according to content disclosed herein, such and such change can be carried out to first-selected embodiment of the present invention obviously, should be expressly understood for this reason, embodiment described above is only to explanation of the present invention, instead of limitation of the invention.
Claims (4)
1. prepared a technique for organic carboxyl acid by organic carboxylic ester, described organic carboxyl acid is selected from the one group of carboxylic acid comprising acetic acid, propionic acid and butyric acid, and described technique comprises:
A. a kind of hydrogen donor compound of equimolar amount and Lipotril is dissolved in a kind of medium, this medium contains at least one solvent be selected from one group of liquid of the mixture comprising water and a kind of alcohol and water, is intended to the ion fluid obtaining the ionic compound produced containing a kind of original position; Wherein hydrogen donor compound is selected from and comprises tosic acid, oxalic acid, toxilic acid, methylsulfonic acid and tartaric one group of compound, and alcohol is selected from least one comprised in one group of alcohol of methyl alcohol, ethanol, Virahol and propyl carbinol; And
B. a kind of organic carboxylic ester is added in this ion fluid, and in the temperature range of 20-100 DEG C Keep agitation, be hydrolyzed this organic carboxylic ester, to obtain described organic carboxyl acid.
2. technique according to claim 1, wherein, organic carboxylic ester is selected from least one comprised in one group of ester of methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, pentyl acetate and hexyl acetate.
3. technique according to claim 1, wherein, the ratio of organic carboxylic ester and water is expressed as 1:5 in molar ratio.
4. technique according to claim 1, wherein, step b carries out under the boiling temperature of the mixture comprising this organic carboxylic ester and this solvent.
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| IN1585MU2011 | 2011-05-27 | ||
| IN1585/MUM/2011 | 2011-05-27 | ||
| 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 |
| 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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| Publication number | Publication date |
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| CN105330538A (en) | 2016-02-17 |
| PT107888B (en) | 2015-06-24 |
| CN103649037A (en) | 2014-03-19 |
| WO2012164573A2 (en) | 2012-12-06 |
| BR112013030031A2 (en) | 2016-09-13 |
| PT107888A (en) | 2014-11-11 |
| WO2012164573A3 (en) | 2013-03-28 |
| BR122015009423A2 (en) | 2019-01-22 |
| PT2012164573W (en) | 2014-10-08 |
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