CN103387556A - Synthetic method for alpha-acetyl-gamma-butyrolactone - Google Patents
Synthetic method for alpha-acetyl-gamma-butyrolactone Download PDFInfo
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- CN103387556A CN103387556A CN2012101417817A CN201210141781A CN103387556A CN 103387556 A CN103387556 A CN 103387556A CN 2012101417817 A CN2012101417817 A CN 2012101417817A CN 201210141781 A CN201210141781 A CN 201210141781A CN 103387556 A CN103387556 A CN 103387556A
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- butyrolactone
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- ethanoyl
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Abstract
The invention relates to the technical field of chemical product preparation, and particularly relates to a synthetic method for alpha-acetyl-gamma-butyrolactone. The synthetic method comprises the steps of carrying out an aldol reaction on ketene dimer and 2-chloroethanol under the effect of a catalyst sodium alkoxide to obtain acetyl chloride ethanol acetate; preparing alpha-acetyl-gamma-butyrolactone: adding a solvent to acetyl chloride ethanol acetate, mixing with stirring, carrying out an intramolecular Claisen-Schmidt condensation reaction under the effect of an alkali catalyst, and directly generating alpha-acetyl-gamma-butyrolactone by cyclization. The synthetic method for alpha-acetyl-gamma-butyrolactone can prevent use of dangerous chemical products such as ethylene oxide, metallic sodium and the like and greatly reduce security risks. Besides, the synthetic yield is obviously higher than that of a conventional process, and production cost is significantly reduced.
Description
Technical field
The present invention relates to the preparing technical field of Chemicals, relate in particular to the synthetic method of a kind of α-ethanoyl-gamma-butyrolactone.
Background technology
The method of industrial synthetic α-ethanoyl-gamma-butyrolactone (ABL) mainly contains two kinds: 1, epoxy method: methyl aceto acetate and oxyethane are in aqueous phase system; be condensed into the butyrolactone sodium salt by breaking of liquid caustic soda; then repeatedly extract with hydrochloric acid neutralization, benzene; the lower aqueous layer discharging; the upper strata oil reservoir is through concentrating to obtain α-ethanoyl-gamma-butyrolactone crude product; α-ethanoyl-gamma-butyrolactone crude product stays to obtain finished product α-ethanoyl-gamma-butyrolactone through the high vacuum essence, and preferably yield is only 60%.This is the synthetic method that generally adopts during the nineties in last century.Because the oxyethane flash-point is low, vapour pressure is high, transport difficulty is large, and the benzene consumption is very big, the rate of recovery is lower, and operating environment is poor, and potential safety hazard is very big, and cost is high, and the later stage nineties is progressively replaced by the sodium method.2, sodium Metal 99.5 method: gamma-butyrolactone (GBL) in toluene system with active very high sodium Metal 99.5 as alkali source, be condensed into the butyrolactone sodium salt with vinyl acetic monomer, steam to obtain α-ethanoyl-gamma-butyrolactone through neutralization, concentrated, essence.This is the Industrialized synthesis method of present main flow, but, extremely strong activity due to sodium, produce a large amount of hydrogen in production process, reaction is violent, and potential safety hazard is very big, and big and small fire frequently occurs in manufacturer,, although cost is lower than epoxy method, be subjected to gamma-butyrolactone, sodium Metal 99.5 market value to affect larger.Therefore, study novel α-ethanoyl-gamma-butyrolactone synthetic technology and seem very necessary.
Summary of the invention
The present invention is directed to the deficiency that present α-ethanoyl-gamma-butyrolactone synthesis technique exists; a kind of α-ethanoyl-gamma-butyrolactone synthetic method is provided; can avoid using the hazardous chemicals such as oxyethane, sodium Metal 99.5; potential safety hazard greatly reduces; and synthesis yield is apparently higher than existing technique, and production cost significantly descends.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
The synthetic method of a kind of α-ethanoyl-gamma-butyrolactone, comprise the steps:
(1) preparation of etheric acid chloroethene alcohol ester: ketene dimer under the effect of catalyzer sodium alkoxide with ethylene chlorhydrin generation aldol reaction, make ethyl acetoacetic acid chloroethene alcohol ester;
(2) preparation of α-ethanoyl-gamma-butyrolactone: to adding solvent in etheric acid chloroethene alcohol ester, be uniformly mixed, claisen-Si Mite (Claisen-Schmidt) condensation reaction in the basic catalyst effect issues son estranged, directly cyclization generates α-ethanoyl-gamma-butyrolactone.
The reactive chemistry formula of synthetic method of the present invention is as follows:
Further, described etheric acid chloroethene alcohol ester can substitute with etheric acid bromoethanol ester.
Further, the temperature of described aldol reaction is 75 ℃.
Further, described alkaline catalyst is sodium alkoxide, sodium carbonate, solid caustic soda etc.
Further, the described temperature that is uniformly mixed is controlled at 15～30 ℃.
Further, described solvent is toluene, water, methyl alcohol, glycol dimethyl ether, Virahol etc.
Compared with prior art, the present invention can avoid using the hazardous chemicals such as oxyethane, sodium Metal 99.5, and potential safety hazard greatly reduces, and synthesizes the associating yield more than 85%, and apparently higher than existing technique, production cost significantly descends.
Embodiment
Describe the present invention below in conjunction with embodiment, the description of this part is only exemplary and indicative, should any restriction not arranged to protection scope of the present invention.
Embodiment 1
(1) preparation of etheric acid chloroethene alcohol ester:
Add 100g ketene dimer, 105g ethylene chlorhydrin, 20g sodium ethylate in the 500ml round-bottom reaction flask, start and stir, be heated to 75 ℃ of back flow reaction and be cooled to room temperature after 8 hours, reaction finishes, and obtains 187.09g etheric acid chloroethene alcohol ester mixing solutions (ketene dimer transformation efficiency 95%).
(2) preparation of α-ethanoyl-gamma-butyrolactone:
Add 80ml toluene in the flask that holds etheric acid chloroethene alcohol ester mixing solutions, be uniformly mixed to control between 15 ~ 30 ℃ of temperature and drip 32% liquid caustic soda 175g, the strict temperature of reaction (15 ~ 30 ℃) of controlling, dropwise insulation reaction 2h, then be neutralized to PH7.5 with hydrochloric acid, continue to stir 1h, standing and demixing 1h, concentrated solution is emitted in upper strata vacuum concentration to cooling after 120 ℃ of liquid temperatures, weigh: 130g concentrated solution (crude product), content 90%(efficient liquid phase chromatographic analysis), etheric acid chloroethanol transformation efficiency 81%.
Embodiment 2
(1) preparation of etheric acid bromoethanol ester:
Add 100g ketene dimer, 160g2-bromoethanol, 20g sodium ethylate in the 500ml round-bottom reaction flask, start and stir, be heated to 75 ℃ of back flow reaction and be cooled to room temperature after 8 hours, reaction finishes, and obtains 236.27g etheric acid bromoethanol ester mixing solutions (ketene dimer transformation efficiency 95%).
(2) preparation of α-ethanoyl-gamma-butyrolactone:
Add 80ml toluene in the flask that holds etheric acid chlorine bromoethanol ester mixing solutions, be uniformly mixed to control between 15 ~ 30 ℃ of temperature and drip 32% liquid caustic soda (175g), the strict temperature of reaction of controlling, dropwise insulation reaction 2h, then with hydrochloric acid, is neutralized to PH7.5, continue to stir 1h, standing and demixing 1h, after upper strata is evaporated to 120 ℃, concentrated solution is emitted in cooling, weighs: 142g concentrated solution (crude product), content 92%(efficient liquid phase chromatographic analysis), etheric acid bromoethanol transformation efficiency 90%.
It is only below the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. the synthetic method of α-ethanoyl-gamma-butyrolactone, is characterized in that comprising the steps:
(1) preparation of etheric acid chloroethene alcohol ester: ketene dimer under the effect of catalyzer sodium alkoxide with ethylene chlorhydrin generation aldol reaction, make ethyl acetoacetic acid chloroethene alcohol ester;
(2) preparation of α-ethanoyl-gamma-butyrolactone: to adding solvent in etheric acid chloroethene alcohol ester, be uniformly mixed, claisen-Si Mite condensation reaction in the basic catalyst effect issues son estranged, directly cyclization generates α-ethanoyl-gamma-butyrolactone.
2. the synthetic method of a kind of α-ethanoyl according to claim 1-gamma-butyrolactone; it is characterized in that: a kind of brand-new synthesis route; take ketene dimer as starting raw material; synthesis of acetyl acetic acid chlorine (or bromine) ethanol ester, then by the ester condensation of etheric acid chlorine (or bromine) ethanol, produce α-ethanoyl-gamma-butyrolactone.
3. the synthetic method of a kind of α-ethanoyl according to claim 1-gamma-butyrolactone, it is characterized in that: the temperature of described aldol reaction is 75 ℃.
4. the synthetic method of a kind of α-ethanoyl according to claim 1-gamma-butyrolactone, it is characterized in that: described alkaline catalyst is sodium alkoxide, sodium carbonate, solid caustic soda.
5. the synthetic method of a kind of α-ethanoyl according to claim 1-gamma-butyrolactone, it is characterized in that: the described temperature that is uniformly mixed is 15～30 ℃.
6. the synthetic method of a kind of α-ethanoyl according to claim 1-gamma-butyrolactone, it is characterized in that: described solvent is toluene, water, methyl alcohol, glycol dimethyl ether, Virahol.
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| CN2012101417817A CN103387556A (en) | 2012-05-08 | 2012-05-08 | Synthetic method for alpha-acetyl-gamma-butyrolactone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118183A (en) * | 2017-05-17 | 2017-09-01 | 成都化润药业有限公司 | A kind of synthetic method of the furancarbinol of tetrahydrochysene 3 |
| CN108299345A (en) * | 2018-02-09 | 2018-07-20 | 东北制药集团股份有限公司 | A kind of preparation method of α-acetyl-gamma-butyrolacton |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4254282A (en) * | 1979-01-03 | 1981-03-03 | Fmc Corporation | Process for preparing cis-3-(2,2-dihalovinyl)-2,2-dimethylcyclopropanecarboxylic acid |
| CN102212062A (en) * | 2010-04-02 | 2011-10-12 | 东莞市长安东阳光新药研发有限公司 | Derivative of amino ester, salt thereof and using method |
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2012
- 2012-05-08 CN CN2012101417817A patent/CN103387556A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4254282A (en) * | 1979-01-03 | 1981-03-03 | Fmc Corporation | Process for preparing cis-3-(2,2-dihalovinyl)-2,2-dimethylcyclopropanecarboxylic acid |
| CN102212062A (en) * | 2010-04-02 | 2011-10-12 | 东莞市长安东阳光新药研发有限公司 | Derivative of amino ester, salt thereof and using method |
Non-Patent Citations (1)
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| 陈国华 等.: "新型二氢吡啶类钙拮抗剂化合物的合成与生物活性", 《有机化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118183A (en) * | 2017-05-17 | 2017-09-01 | 成都化润药业有限公司 | A kind of synthetic method of the furancarbinol of tetrahydrochysene 3 |
| CN107118183B (en) * | 2017-05-17 | 2021-02-02 | 成都化润药业有限公司 | Synthesis method of tetrahydro-3-furanmethanol |
| CN108299345A (en) * | 2018-02-09 | 2018-07-20 | 东北制药集团股份有限公司 | A kind of preparation method of α-acetyl-gamma-butyrolacton |
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Application publication date: 20131113 |