CN103360349A - Green synthesis process of alpha-acetyl-gamma-butyrolactone - Google Patents
Green synthesis process of alpha-acetyl-gamma-butyrolactone Download PDFInfo
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- CN103360349A CN103360349A CN201310302084XA CN201310302084A CN103360349A CN 103360349 A CN103360349 A CN 103360349A CN 201310302084X A CN201310302084X A CN 201310302084XA CN 201310302084 A CN201310302084 A CN 201310302084A CN 103360349 A CN103360349 A CN 103360349A
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- butyrolactone
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Abstract
The invention relates to a preparation method of a compound alpha-acetyl-gamma-butyrolactone represented by a formula (I). According to the invention, the compound of the formula (II) and ethyl acetate are subjected to condensation, acidification, and rectification under the existence of calcium oxide, such that the compound represented by the formula (I) is obtained. The compound is an important intermediate used for preparing vitamin and chlorophyll raw materials.
Description
Technical field
The present invention relates to the preparation method of formula (I) compound α-ethanoyl-gamma-butyrolactone, is the important intermediate of preparation VITAMIN and chlorophyll class raw material.Belong to chemosynthesis technical field.
Background technology
α-ethanoyl-gamma-butyrolactone (2-Acetylbutyrolactone, ABL) is preparation VITAMIN, chlorophyllous important intermediate
[1-2]Synthetic 3, the disubstituted pyridine of 4-, 5-(beta-hydroxyethyl)-important source material of 4-methylthiazol, 4-methyl-5-thiazole ethanol, also be synthetic antischizophrenic drugs of Risperidone, anticonvulsion and sedative hypnotic drug Wy-1485, prolong the medicine intermediate of the medicines such as pained and chloroquine
[3-5], be an irreplaceable product of long line that amount is large, wide.At present, the method for preparing α-ethanoyl-gamma-butyrolactone mainly contains two kinds: method one take oxyethane as starting raw material, prepares α-ethanoyl-gamma-butyrolactone (Scheme 1) with methyl aceto acetate condensation closed loop; Method two, take gamma-butyrolactone as raw material, and ethyl acetate condensation, acidolysis prepare α-ethanoyl-gamma-butyrolactone (Scheme 2).
Scheme 1
Scheme 2
A lot of patent literatures the improvement in synthesis of α-ethanoyl-gamma-butyrolactone, in Chinese patent 02138773.5, make the solvent of sodium Metal 99.5 with toluene, the catalyzed reaction of lowering the temperature after forming sodium sand under the higher temperature adds mixed ester in the dropping mode, and has increased surge tank, but because toluene and sodium Metal 99.5 are inflammable explosive article, still can't solve the safety problem of reaction, and the gamma-butyrolactone transformation efficiency is lower, friendly not to environment; Zhang Li replaces sodium Metal 99.5 with sodium alkoxide in the Chinese Journal of Pharmaceuticals, but this reaction yield is lower, can't reduce production costs; US Patent No. 5789603 is also take sodium alkoxide as catalyzer, high-temperature high-voltage reaction, and operational requirement is high, has security risk; United States Patent (USP) 2443827
[12]Method two is reported, it is take oxyethane as starting raw material, and oxyethane is the inflammable and explosive chemical substance of one-level, and storage condition is harsh, exists serious potential safety hazard in reaction, and preparation section is complicated, and products therefrom purity, yield are lower.
By the comparison to the synthesis technique of existing α-ethanoyl-gamma-butyrolactone, the pros and cons of the various synthesis techniques of integrated survey, the production technique of seeking a kind of α-ethanoyl of safe green-gamma-butyrolactone is imperative.
Summary of the invention
The purpose of this invention is to provide that security is good, the preparation method of the α-ethanoyl of environmental contamination reduction-gamma-butyrolactone.
The invention provides the preparation method of compound shown in the formula (I).May further comprise the steps:
I
II
(a) gamma-butyrolactone (formula II compound) mixes with ethyl acetate;
(b) grind calcium oxide, join in the mixed ester, the heated and stirred reaction;
(c) add hydrochloric acid and stir ethyl acetate extraction;
(d) underpressure distillation is spin-dried for ethyl acetate, and rectifying obtains formula (I) compound.
The invention provides the preparation method of formula (I) compound, step (a) Chinese style (II) compound and ethyl acetate mix, and mol ratio is 1:1-2, preferred 1:1.7.
The present invention also further provides the preparation method of formula (I) compound, and calcium oxide fully grinds in the step (b), prevents that its top layer is rotten, and impact is active.
The present invention also further provides the preparation method of formula (I) compound, and the control temperature is 60-90 ℃ in the step (b), preferred 80 ℃.
The present invention also further provides the preparation method of formula (I) compound, and the molar weight of adding hydrochloric acid and the mol ratio of gamma-butyrolactone are 0.5-1:1 in the step (c), preferred 0.57:1.
The present invention passes through the comparison to the synthesis technique of existing α-ethanoyl-gamma-butyrolactone; the pros and cons of the various synthesis techniques of integrated survey; and on the advantage basis that is easy to get in conjunction with local raw material; select the synthetic α-ethanoyl of raw material gamma-butyrolactone and ethyl acetate-gamma-butyrolactone; in building-up process; replace sodium Metal 99.5 with the basic oxide calcium oxide; well avoid the potential safety hazard in the production process; effectively reduce production costs; minimizing is the novel environment-friendly process of a kind of α of production-ethanoyl-gamma-butyrolactone to the pollution of environment.
Embodiment
Following example is to describe in detail the present invention, and unrestricted the present invention.
Embodiment:Synthesizing of α-ethanoyl-gamma-butyrolactone
Take by weighing 108 g gamma-butyrolactones and 188 g ethyl acetate mix.Take by weighing the 40g calcium oxide and grind evenly, join in the reaction flask.The 100g mixed ester joins in the reaction flask fast, and 77 ℃ of temperature controls slowly drip the residue mixed ester.77 ℃ of insulation reaction 20h, the gas phase monitoring reaction is complete, revolves the steaming solvent, adds 18% hydrochloric acid 52g, and 82 ℃ are stirred 1h, and ethyl acetate extraction concentrates and obtains red liquid, and rectifying obtains colourless α-ethanoyl-gamma-butyrolactone 104.48 g, yield 65%.
1H NMR(CDCl
3): d4.40-4.29(m, 2H), 3.80-3.76(m, 1H) and, 2.77-2.74(m, 1H), 2.43(s, 3H) and, 2.36-2.33 (m, 1H), MS:m/e(129, M+1), ultimate analysis C
6H
8O
3, calculated value: C 56.24, H 6.29.Experimental value: C56.21, H6.28.
Claims (6)
1. method for preparing α-ethanoyl-gamma-butyrolactone (formula I compound) is characterized in that may further comprise the steps:
I II
(a) gamma-butyrolactone (formula II compound) mixes with ethyl acetate;
(b) grind calcium oxide, join in the mixed ester, the heated and stirred reaction;
(c) add hydrochloric acid and stir ethyl acetate extraction;
(d) underpressure distillation is spin-dried for ethyl acetate, and rectifying obtains formula (I) compound.
2. a kind of method for preparing α-ethanoyl-gamma-butyrolactone (formula I compound) according to claim 1 is characterized in that step (a) Chinese style (II) compound and ethyl acetate mix, and mol ratio 1:1-2, preferred 1:1.7.
3. a kind of method for preparing α-ethanoyl-gamma-butyrolactone (formula I compound) according to claim 1 is characterized in that the calcium oxide in the step (b) is wanted the grind into fine powder solid.
4. a kind of method for preparing α-ethanoyl-gamma-butyrolactone (formula I compound) according to claim 1 is characterized in that the control temperature is 60-90 ℃ in the step (b), preferred 80 ℃.
5. a kind of method for preparing α-ethanoyl-gamma-butyrolactone (formula I compound) according to claim 1 is characterized in that the reaction times in the step (b) is controlled at 18-25h, preferred 25h.
6. a kind of method for preparing α-ethanoyl-gamma-butyrolactone (formula I compound) according to claim 1 is characterized in that the molar weight of adding hydrochloric acid in the step (c) and the mol ratio of gamma-butyrolactone are 0.5-1:1, preferred 0.57:1.
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| CN201310302084XA CN103360349A (en) | 2013-07-18 | 2013-07-18 | Green synthesis process of alpha-acetyl-gamma-butyrolactone |
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| CN201310302084XA CN103360349A (en) | 2013-07-18 | 2013-07-18 | Green synthesis process of alpha-acetyl-gamma-butyrolactone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018810A (en) * | 2019-12-13 | 2020-04-17 | 浙江联盛化学股份有限公司 | Device and method for continuously producing α -acetyl-gamma-butyrolactone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5789603A (en) * | 1996-02-24 | 1998-08-04 | Huels Aktiengesellschaft | Method for preparing 2-acetyl-γ-butyrolactone |
| CN102030729A (en) * | 2010-11-04 | 2011-04-27 | 山西大学 | Preparation method of alpha-acetyl-gamma-butyrolactone |
-
2013
- 2013-07-18 CN CN201310302084XA patent/CN103360349A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5789603A (en) * | 1996-02-24 | 1998-08-04 | Huels Aktiengesellschaft | Method for preparing 2-acetyl-γ-butyrolactone |
| CN102030729A (en) * | 2010-11-04 | 2011-04-27 | 山西大学 | Preparation method of alpha-acetyl-gamma-butyrolactone |
Non-Patent Citations (1)
| Title |
|---|
| 濮存恬等: "α-乙酰基-γ-丁内酯合成工艺优化", 《江苏化工》, vol. 23, no. 1, 3 December 1995 (1995-12-03) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111018810A (en) * | 2019-12-13 | 2020-04-17 | 浙江联盛化学股份有限公司 | Device and method for continuously producing α -acetyl-gamma-butyrolactone |
| CN111018810B (en) * | 2019-12-13 | 2021-09-14 | 浙江联盛化学股份有限公司 | Device and method for continuously producing alpha-acetyl-gamma-butyrolactone |
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Application publication date: 20131023 |