CN1752066A - Synthesis method of glycollate - Google Patents
Synthesis method of glycollate Download PDFInfo
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- CN1752066A CN1752066A CN 200510030740 CN200510030740A CN1752066A CN 1752066 A CN1752066 A CN 1752066A CN 200510030740 CN200510030740 CN 200510030740 CN 200510030740 A CN200510030740 A CN 200510030740A CN 1752066 A CN1752066 A CN 1752066A
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- alcohol
- ethyl glycolate
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Abstract
A process for preparing the ethanolate includes such steps as mixing ethanolic acid with alcohol, adding benzene and perfluorosulfonate resin, thermal reflux, and vacuum distillation. Its advantages are high selectivity, low output of by-product (ether), and less environmental pollution.
Description
Technical field
The present invention relates to a kind of synthetic method of ethyl glycolate.
Background technology
Ethyl glycolate more and more is subjected to people's attention in recent years as a kind of important chemical material.Contain two kinds of functional groups of a-H and hydroxyl and ester group in the ethyl glycolate molecule, so it has the chemical property of pure and mild ester, as carbonylation, hydrolysis reaction, oxidizing reaction or the like, this just makes that the application of ethyl glycolate is also very extensive.
Its method for making has a lot, can obtain by carboxylic acid, acyl chlorides or acid anhydrides and alcohol reaction, also can be obtained by carboxylate salt and halohydrocarbons reaction, and carboxylic acid and diazomethane reaction produce carboxylate methyl ester; In addition, effect also generates carboxylicesters to cyanogen with alcohol under acidic conditions.
It is as follows that the method for preparing ethyl glycolate of present report is enumerated part:
(1) with boric acid as catalyzer, specifically react as follows:
(2) be raw material system carboxylic ester with carbon monoxide and alcohol, see U.S. Pat 2211625, specifically react as follows:
(3) chloracetic acid and alcohol synthesizing alcohol acid esters under alkaline condition, specifically react as follows:
(4) oxyacetic acid and haloalkane synthesizing alcohol acid esters, specifically react as follows:
(5) by amino acid synthol acid esters, specifically react as follows:
In sum, the method for preparing carboxylic ester has a lot, but some cost of material is more expensive, also uses carbon monoxide sometimes, the very big operation inconvenience of toxicity.In the esterification, the alcohol generation ether that often dewaters causes productive rate to reduce.Sulphuric acid catalysis is used in some reaction, and transformation efficiency is lower, and side reaction is many, and equipment corrosion is serious, pass through aftertreatments such as neutralization, washing, waste liquor contamination environment.
Summary of the invention:
One of purpose of the present invention is to provide a kind of synthetic method of ethyl glycolate.
For achieving the above object, the reaction mechanism that the inventive method has adopted is:
Wherein, R is C
1-C
4The straight or branched alkyl, or benzyl.
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A kind of synthetic method of ethyl glycolate, it is characterized in that, this method has following steps: in reaction vessel, with oxyacetic acid and pure mixed in molar ratio of pressing 1: 3, as the band aqua, perfluorinated sulfonic resin is as catalyzer with benzene, in the water trap that reflux is connect to reaction vessel during anhydrous telling, reaction finishes, and can obtain purified ethyl glycolate through normal pressure or underpressure distillation.Above-mentioned alcohol is C
1-C
4Primary alconol or the secondary alcohol or the tertiary alcohol, or benzyl alcohol.
The inventive method is a raw material with the oxyacetic acid that is easy to get and basic alcohol, selects for use perfluorinated sulfonic resin to make catalyzer, excellent catalytic effect, and by product ether significantly reduces, and improves selectivity, reduced atmospheric pollution, so present method is the important method of synthol acid esters.
Embodiment
Example one: the preparation of ethyl glycollate: in 10 liter of two neck bottle, add oxyacetic acid (760g, 10mol), (1.74 liters of dehydrated alcohols, 30mol), water liquid benzene (3.5 liters), perfluorinated sulfonic resin (1000g) and magnetic stick, load onto water trap, reflux condensing tube, oil bath and magnetic stirring apparatus, under stirring state, reflux 22 hours does not have moisture to go out in water trap, then cold filtration, with Rotary Evaporators remaining dehydrated alcohol in the filtrate and solvent benzol are steamed under reduced pressure, remaining filtrate is distilled in condition of normal pressure, collects 155 ℃ cut, perhaps collects the cut of 68 ℃/25mmHg under reduced pressure, obtain ethyl glycollate 898g, productive rate is 86%.
Example two: the preparation of methyl glycolate
In 10 liter of two neck bottle, add oxyacetic acid (760g, 10mol), (1.21 liters of anhydrous methanols, 30mol), water liquid benzene (3.5 liters), perfluorinated sulfonic resin (1000g) and magnetic stick are loaded onto water trap, reflux condensing tube, oil bath and magnetic stirring apparatus, under stirring state, reflux 22 hours does not have moisture to go out in water trap, then cold filtration, with Rotary Evaporators the anhydrous methanol in the filtrate and two kinds of solvents of benzene are steamed under reduced pressure, remaining filtrate is distilled in condition of normal pressure, collects 151 ℃ cut, perhaps collects the cut of 66 ℃/25mmHg under reduced pressure, obtain methyl glycolate 756g, productive rate is 84%.
Example three: the preparation of ethanol acid benzyl ester
In 10 liter of two neck bottle, add oxyacetic acid (760g, 10mol), (3.10 liters of anhydrous benzylalcohols, 30mol), water liquid benzene (3.5 liters), perfluorinated sulfonic resin (1000g) and magnetic stick, load onto water trap, reflux condensing tube, oil bath and magnetic stirring apparatus, under stirring state, reflux 23 hours, in water trap, there is not moisture to go out, cold filtration steams the anhydrous benzylalcohol in the filtrate and two kinds of solvents of benzene with Rotary Evaporators under reduced pressure then, and remaining filtrate is collected the cut of 136 ℃/14mmHg under reduced pressure, obtain ethanol acid benzyl ester 1329g, productive rate is 80%.
Example four: the preparation of Glycolic acid n butyl ester
In 10 liter of two neck bottle, add oxyacetic acid (760g, 10mol), (2.74 liters of anhydrous normal butyl alcohol, 30mol), water liquid benzene (3.5 liters), perfluorinated sulfonic resin (1000g) and magnetic stick are loaded onto water trap, reflux condensing tube, oil bath and magnetic stirring apparatus, under stirring state, reflux 25 hours does not have moisture to go out in water trap, then cold filtration, with Rotary Evaporators the anhydrous normal butyl alcohol in the filtrate and two kinds of solvents of benzene are steamed under reduced pressure, remaining filtrate is distilled in condition of normal pressure, collects 193 ℃ cut, perhaps collects the cut of 92 ℃/25mmHg under reduced pressure, obtain Glycolic acid n butyl ester 911g, productive rate is 69%.
Example five: the preparation of the oxyacetic acid tert-butyl ester
In 10 liter of two neck bottle, add oxyacetic acid (760g, 10mol), (2.74 liters of anhydrous tertiary butanols, 30mol), water liquid benzene (3.5 liters), perfluorinated sulfonic resin (1000g) and magnetic stick, load onto water trap, reflux condensing tube, oil bath and magnetic stirring apparatus, under stirring state, reflux 28 hours, in water trap, there is not moisture to go out, cold filtration steams the anhydrous tertiary butanol in the filtrate and two kinds of solvents of benzene with Rotary Evaporators under reduced pressure then, and remaining filtrate is collected the cut of 71 ℃/25mmHg under reduced pressure, obtain oxyacetic acid tert-butyl ester 686g, productive rate is 52%.
Claims (2)
1. the synthetic method of an ethyl glycolate, it is characterized in that, this method has following steps: in reaction vessel, with oxyacetic acid and pure mixed in molar ratio of pressing 1: 3, as the band aqua, perfluorinated sulfonic resin is as catalyzer with benzene, in the water trap that reflux is connect to reaction vessel during anhydrous telling, reaction finishes, and can obtain purified ethyl glycolate through normal pressure or underpressure distillation.
2. the synthetic method of ethyl glycolate according to claim 1 is characterized in that described alcohol is C
1-C
4Primary alconol or the secondary alcohol or the tertiary alcohol, or benzyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100307400A CN100408544C (en) | 2005-10-27 | 2005-10-27 | Synthesis method of glycollate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100307400A CN100408544C (en) | 2005-10-27 | 2005-10-27 | Synthesis method of glycollate |
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| Publication Number | Publication Date |
|---|---|
| CN1752066A true CN1752066A (en) | 2006-03-29 |
| CN100408544C CN100408544C (en) | 2008-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100307400A Active CN100408544C (en) | 2005-10-27 | 2005-10-27 | Synthesis method of glycollate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400503C (en) * | 2006-09-21 | 2008-07-09 | 上海大学 | 5,5,5 trifluorin 4 (4 methox phenyl amido) methyl valerate, and synthetic method |
| WO2016066071A1 (en) * | 2014-10-28 | 2016-05-06 | 中国科学院大连化学物理研究所 | Method for preparing glycolate from carbohydrate |
| CN108084021A (en) * | 2017-12-27 | 2018-05-29 | 上海应用技术大学 | A kind of preparation method of isobutyl palmitate |
| CN112169835A (en) * | 2020-10-27 | 2021-01-05 | 山东益丰生化环保股份有限公司 | Catalyst for synthesizing mercaptocarboxylic ester compound and preparation method and application thereof |
| CN112705265A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Supported solid acid catalyst for synthesizing methyl glycolate and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044457A (en) * | 1989-01-24 | 1990-08-08 | 尹厚毅 | A kind of industrial process of ethyl glycollate |
-
2005
- 2005-10-27 CN CNB2005100307400A patent/CN100408544C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400503C (en) * | 2006-09-21 | 2008-07-09 | 上海大学 | 5,5,5 trifluorin 4 (4 methox phenyl amido) methyl valerate, and synthetic method |
| WO2016066071A1 (en) * | 2014-10-28 | 2016-05-06 | 中国科学院大连化学物理研究所 | Method for preparing glycolate from carbohydrate |
| CN108084021A (en) * | 2017-12-27 | 2018-05-29 | 上海应用技术大学 | A kind of preparation method of isobutyl palmitate |
| CN112705265A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Supported solid acid catalyst for synthesizing methyl glycolate and preparation method and application thereof |
| CN112705265B (en) * | 2019-10-25 | 2023-04-07 | 中国石油化工股份有限公司 | Supported solid acid catalyst for synthesizing methyl glycolate and preparation method and application thereof |
| CN112169835A (en) * | 2020-10-27 | 2021-01-05 | 山东益丰生化环保股份有限公司 | Catalyst for synthesizing mercaptocarboxylic ester compound and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100408544C (en) | 2008-08-06 |
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Effective date of registration: 20130902 Address after: 226600 Haian City, Jiangsu Province Town Industrial Park Patentee after: Nantong Hongyu Chemical Co.,Ltd. Address before: 200444 Baoshan District Road, Shanghai, No. 99 Patentee before: Shanghai University |