CN101085766A - Process for preparing citric anhydride - Google Patents
Process for preparing citric anhydride Download PDFInfo
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- CN101085766A CN101085766A CN 200710062336 CN200710062336A CN101085766A CN 101085766 A CN101085766 A CN 101085766A CN 200710062336 CN200710062336 CN 200710062336 CN 200710062336 A CN200710062336 A CN 200710062336A CN 101085766 A CN101085766 A CN 101085766A
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- anhydride
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- citric anhydride
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to a process of preparing citric acid anhydride. It comprises following steps: feeding organic acid anhydride, organic acid and waterless citrate into reactor according to molar ratio of 1- 3: 0- 4: 1, reacting at 40- 110 Deg. C for 15- 120 minutes; adding organic disslovant with the amount being 1- 5 times of that of reaction product in step one, getting crystal deposition, stewing for 2- 10 hours, filtering, washing with the same organic disslovant, drying at 40 -80 Deg. C, and getting crystal solid product. The invention is characterized by short reaction time, simple process, low cost, high product purity and suitability for industrial production.
Description
Technical field
The present invention relates to a kind of preparation technology of organic acid anhydride, relate in particular to a kind of preparation technology of Citric anhydride.
Technical background
Citric anhydride forms by dewatering between two carboxyls of citric acid, has strong acidylate ability, is a kind of important intermediate of synthetic pesticide, medicine, food, beverage, sanitising agent, makeup and resin; Simultaneously, Citric anhydride can react rapidly with airborne aqueous vapor, and readily biodegradable, therefore can be used as the siccative of food and medicine.
People such as A.J.REPTA are entitled as at one piece and have proposed in " Synthesis; Isolation; and SomeChemistry of citric acid anhydride " (Journal of Pharmaceuticalsciences.1969:1110-1115) paper with diacetyl oxide and citric acid 36 ~ 38 ℃ of reactions 19 hours down, generate Citric anhydride, utilization this method, the great people of grade of lunar history rolled up for the 1st phase at Anhui University of Science and Technology's journal (natural science edition) the 26th in 2006 3, open people such as beautiful beautiful woman in September, 2006 in the 22nd the 5th phase of volume of Qiqihar University's journal, delivered exercise question respectively and be " the synthetic and sign of Citric anhydride ", " the synthetic and infrared spectroscopic study of Citric anhydride ", reacted 16 ~ 18 hours down at 35 ~ 39 ℃, characterize by infrared spectra and the mass spectrum structure to product, the structure of having determined product is a cyclic acid anhydride.
But the long reaction time of these method synthesizing citric acid acid anhydrides; mainly be since citric acid in being dehydrated into anhydride process; improper as reaction conditions control; make hydroxyl and the esterification of carboxyl generation intramolecularly in the citric acid molecule easily; or hydroxyl in the citric acid and acid anhydrides generation acetylization reaction, cause the productive rate of Citric anhydride and purity to descend.
Summary of the invention
The present invention provides the technology of the high preparation Citric anhydride of a kind of processing ease, product yield height and purity.
Purpose of the present invention is achieved through the following technical solutions:
A certain amount of citric acid and a kind of organic acid anhydride are generated Citric anhydride, add certain amount of organic solvent then, crystallization at a certain temperature, filtration, washing, the dry product that gets.
The preparation method of Citric anhydride provided by the present invention is as follows:
1, be 1-3: 0-4 with organic acid anhydride, organic acid, Citric Acid, usp, Anhydrous Powder according to mol ratio: 1 material ratio drops in the reactor, is under 40-110 ℃ in temperature of reaction, reaction 15-120min;
2, after the reaction product in the step 1 cooling, in reaction product, add reaction product quality 1-5 organic solvent doubly, crystal precipitation appears, leave standstill 2-10 hour, filter, use with a kind of organic solvent washing, 40-80 ℃ dry down, the lenticular solid.
Aforesaid organic acid anhydride is the compound with following general formula
R
2, R
3Be that carbonatoms is the alkyl of 1-5;
Aforesaid organic acid is the compound with following general formula
R
4-COOH
R
4For carbonatoms is the alkyl of 1-5;
Aforesaid organic solvent is nonpolar or the low-pole organic compound, and nonpolar organic compound is chloroform, tetracol phenixin, sherwood oil.The low-pole organic compound is hexane, hexanaphthene, benzene or toluene etc.
The present invention compared with prior art has the following advantages:
The present invention has the reaction times weak point, and technical process is simple, and cost is low, and the product purity height is fit to suitability for industrialized production.
Embodiments of the invention are as follows:
Embodiment 1:
In having the 250ml four-hole boiling flask of thermometer, agitator, prolong, add the Citric Acid, usp, Anhydrous Powder of 0.2mol and the diacetyl oxide of 0.2mol, then at 40 ℃, reaction 120min.After the reaction product cooling, add 1 times in the reaction product, crystal precipitation occurs, left standstill 2 hours to the chloroform of reaction product amount, filter, with the chloroform washing of same amount, at 40 ℃, pressure 40-50mmHg is dry down, gets lenticular solid 24.5g, and product yield is 71%.
Embodiment 2:
In having the 250ml four-hole boiling flask of thermometer, agitator, prolong, the Citric Acid, usp, Anhydrous Powder and the acetate propionic anhydride of 0.6mol, the propionic acid of 0.1mol that add 0.2mol mix, under 110 ℃, and reaction 15-30min.After the reaction product cooling, add 3 times, crystal precipitation occurs, left standstill 5 hours to the tetracol phenixin of reaction product amount, filtration, dry under 80 ℃ with the tetracol phenixin washing of same amount, get white crystal shape solid 25.8g, product yield is 75%.
Embodiment 3:
In having the 500ml four-hole boiling flask of thermometer, agitator, prolong, add the Citric Acid, usp, Anhydrous Powder of 0.5mol, the butyryl oxide of 1.2mol and the butyric acid of 0.25mol mix, and under 100 ℃, react 100min then.Reaction product adds 3 times to the hexane of reaction product amount after cooling off, and crystal precipitation occurs, leaves standstill 7 hours, filters, and with the hexane wash of same amount, at 50 ℃, pressure 40-50mmHg is dry down, gets white crystal shape solid 67.1g, and product yield is 78%.
Embodiment 4:
In having the 500ml four-hole boiling flask of thermometer, agitator, prolong, add the Citric Acid, usp, Anhydrous Powder of 0.5mol and the butyric acid valeric anhydride of 1.0mol, the valeric acid of 2.0mol, under 105 ℃, react 100min then.After the reaction product cooling, add 4 times, crystal precipitation occurs, left standstill 10 hours to the sherwood oil of reaction product amount, filter, with the tetracol phenixin washing of same amount, at 40 ℃, pressure 30-40mmHg is dry down, gets white crystal shape solid 67.9g, and product yield is 79%.
Embodiment 5:
In having the 500ml four-hole boiling flask of thermometer, agitator, prolong, add the Citric Acid, usp, Anhydrous Powder of 0.5mol, the butyryl oxide of 1.2mol and the butyric acid of 0.25mol mix, and under 100 ℃, react 100min then.Reaction product adds 3 times to the hexanaphthene of reaction product amount after cooling off, and crystal precipitation occurs, leaves standstill 7 hours, filters, and with the hexane wash of same amount, at 60 ℃, pressure 55-60mmHg is dry down, gets white crystal shape solid 67.1g, and product yield is 78%.
Embodiment 6:
In having the 500ml four-hole boiling flask of thermometer, agitator, prolong, add the Citric Acid, usp, Anhydrous Powder of 0.5mol and the propionic anhydride of 1.0mol, the valeric acid of 2.0mol, under 105 ℃, react 100min then.After the reaction product cooling, add 5 times, crystal precipitation occurs, left standstill 10 hours to the toluene of reaction product amount, filter, with the tetracol phenixin washing of same amount, at 70 ℃, pressure 25-30mmHg is dry down, gets white crystal shape solid 67.9g, and product yield is 79%.
Claims (6)
1, a kind of technology for preparing Citric anhydride is characterized in that comprising the steps:
(1), be 1-3: 0-4 with organic acid anhydride, organic acid, Citric Acid, usp, Anhydrous Powder according to mol ratio: 1 material ratio drops in the reactor, is under 40-110 ℃ in temperature of reaction, reaction 15-120min;
(2), add reaction product quality 1-5 organic solvent doubly in the reaction product in step (1), crystal precipitation appears, leave standstill 2-10 hour, filter, use with a kind of organic solvent washing, 40-80 ℃ dry down, the lenticular solid.
2, a kind of technology for preparing Citric anhydride as claimed in claim 1 is characterized in that described organic acid anhydride is the compound with following general formula
R
2, R
3Be that carbonatoms is the alkyl of 1-5
3, a kind of technology for preparing Citric anhydride as claimed in claim 1 is characterized in that described organic acid is the compound with following general formula
R
4-COOH
R
4For carbonatoms is the alkyl of 1-5
4, a kind of technology for preparing Citric anhydride as claimed in claim 1 is characterized in that described organic solvent is nonpolar or the low-pole organic compound.
5, a kind of technology for preparing Citric anhydride as claimed in claim 4 is characterized in that described nonpolar organic compound is chloroform, tetracol phenixin or sherwood oil.
6 a kind of technologies that prepare Citric anhydride as claimed in claim 4 is characterized in that described low-pole organic compound is hexane, hexanaphthene, benzene or toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710062336 CN101085766A (en) | 2007-07-17 | 2007-07-17 | Process for preparing citric anhydride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710062336 CN101085766A (en) | 2007-07-17 | 2007-07-17 | Process for preparing citric anhydride |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503991A (en) * | 2011-10-08 | 2012-06-20 | 中国日用化学工业研究院 | Process of preparing alcohol ether glucoside citrate monoester salts |
| CN103214440A (en) * | 2013-04-26 | 2013-07-24 | 江苏理工学院 | Method for synthesizing citric acid anhydride through microwave assistance |
| CN109810288A (en) * | 2018-12-28 | 2019-05-28 | 东莞建泰生物科技有限公司 | A kind of crosslinking agent, preparation method and application |
-
2007
- 2007-07-17 CN CN 200710062336 patent/CN101085766A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503991A (en) * | 2011-10-08 | 2012-06-20 | 中国日用化学工业研究院 | Process of preparing alcohol ether glucoside citrate monoester salts |
| CN103214440A (en) * | 2013-04-26 | 2013-07-24 | 江苏理工学院 | Method for synthesizing citric acid anhydride through microwave assistance |
| CN109810288A (en) * | 2018-12-28 | 2019-05-28 | 东莞建泰生物科技有限公司 | A kind of crosslinking agent, preparation method and application |
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