CN1280122A - Method for producing acetylacetic ester - Google Patents
Method for producing acetylacetic ester Download PDFInfo
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- CN1280122A CN1280122A CN 99114312 CN99114312A CN1280122A CN 1280122 A CN1280122 A CN 1280122A CN 99114312 CN99114312 CN 99114312 CN 99114312 A CN99114312 A CN 99114312A CN 1280122 A CN1280122 A CN 1280122A
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- acetylacetic ester
- ethyleneamines
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Abstract
An acetylacetic ester production method produces acetylacetic aster through esterification of divinyl ketone with alcoholin the presence of catalyst containing ethylidene amine compound with the product being rectified. The present invention is easy to obtain the catalyst, has mild reaction conditions and high yield of high-purity product, and is suitable for large scale industrial production.
Description
The present invention relates to a kind of carboxylicesters, is a kind of acetylacetic ester.
Utilize ketene dimer and alcohol reaction to generate acetylacetic ester in the prior art, for fast reaction speed must add catalyzer, relatively classic methods is to make catalyzer with the vitriol oil, but it is bigger to the conversion unit corrosion to make catalyzer with the vitriol oil, and the acetylacetic ester that generates easily makes product generation oxidation when rectification and purification, the easy coking of material in reactor, thus in product, form a kind of high boiling material, influenced the purity of product, content is low.German Patent No.717652 and U.S. Patent No. 2351366 have been introduced low-grade amine such as Trimethylamine or triethylamine and have been made catalyzer, but for used lower alcohol such as methyl alcohol, when ethanol and ketene dimer reaction, methyl alcohol or ethanol reflux with Trimethylamine or triethylamine, so just reduced the Liquid Phase by Catalytic agent concentration in the reactant, be unfavorable for safety operation, and the commodity aqueous solution content of the Trimethylamine 99 of being sold on the market can only reach about 36%, therefore in reaction medium, increased moisture content again, easily cause the hydrolysis of ketene dimer, generate by products such as acetone, can use triethylamine during for higher alcohols and ketene dimer reaction, but the amount of triethylamine must increase, otherwise ketene dimer gathers in the reaction solution, also is unfavorable for safety.
The object of the present invention is to provide a kind of catalyzer to be easy to get, to react the production method of safety, acetylacetic ester that product content is high.
The object of the present invention is achieved like this:
A kind of production method of acetylacetic ester adopts ketene dimer and alcohol to carry out esterification for reactant, and its difference with prior art is: the esterification employing be the catalyzer that contains the ethyleneamines compounds, rectifying goes out product after the esterification.
The production method of above-mentioned acetylacetic ester, concrete steps comprise successively:
1. with alcohol and ketene dimer under the condition that the catalyzer that contains the ethyleneamines compounds exists, under 0～140 ℃, carry out esterification;
2. will be put in the rectifying device through the reaction mixture of 1. reaction,, promptly get the acetylacetic ester product in 70～200 ℃ of following rectifying.
The catalyzer that contains the ethyleneamines compounds is the mixture of mixture, pyridine and ethyleneamines vitriol that contains mixture, ethylene amines and the sodium-acetate of the compound of ethyleneamines or pyridine and ethyleneamines.
The compound that contains ethyleneamines is diethylenetriamine or triethylene diamine, tetrem alkene diamines.Alcohol with the mole proportioning of ketene dimer is: 1: 1.3.Alcohol with the mole proportioning of ketene dimer is: 1: 1.05.Catalyst consumption is 0.05%～3% of a reactant gross weight.Catalyst consumption is 0.1%～1.5% of a reactant gross weight.Rectification temperature is 90～180 ℃.During rectifying, vacuum tightness is 500～750mmHg, is good with 650～740mmHg.
Catalyzer of the present invention is easy to get, reaction conditions is gentle easily grasps, and reaction safety and product purity height, yield height are suitable for industrialized production.
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
The methyl alcohol that in the 1000L reactor, adds 4.3～5.9Kmol, 0.001Kmol～0.01Kmol (routine 0.001Kmol, 0.003Kmol, 0.006Kmol, 0.008Kmol, 0.01Kmol) catalyzer, catalyzer adopts the mixture of diethylenetriamine or diethylenetriamine and sodium-acetate, stir, in normal temperature is that starting temperature begins to drip ketene dimer 3.5Kmol, after rising to 60 ℃ naturally, temperature continues to drip ketene dimer 2Kmol, temperature slowly rises to 115 ℃, (starting temperature to the outlet temperature interval that drips ketene dimer can be 0 ℃～140 ℃, 20 ℃～130 ℃ of examples, 30 ℃～110 ℃) to drip off follow-up continuation of insurance temperature (can be 0.1 in 0.1～5 hour, 1,2,3,4,5 hours), being put into behind the filtering residue in the smart filter equipment in 400～600mmHg (can be 400,500, remove low-boiling point materials such as methyl alcohol 600mmHg), it (can be 700 that vacuum tightness is raised to 700～760mmHg, 720,740,760mmHg), reflux ratio is 3～8 (can be 3,4,5,6,7,8), temperature (can be 70 for 70～200 ℃, 90,130,160,180,200 ℃) condition under reclaim product, get water white methyl acetoacetate, purity 99.3%, yield 96.6%.
Embodiment 2: catalyzer adopts the mixture of tetrem alkene diamines or triethylene diamine or triethylene diamine and pyridine, catalyst levels be the reactant gross weight 0.05%～3% (can be 0.05%, 0.1%, 0.5%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%) all the other all with embodiment 1, product purity 99.7%, yield 98%.
Embodiment 3:
With the methyl alcohol among the ethanol replacement embodiment 1, all the other get water white methyl acetoacetate, purity 99.2%, yield 96.2% all with embodiment 1.
Embodiment 4:
With the methyl alcohol among the Virahol replacement embodiment 1, all the other get water white methyl acetoacetate, purity 99.0%, yield 97% all with embodiment 1.
Embodiment 5:
With the methyl alcohol among the benzylalcohol replacement embodiment 1, all the other get benzyl acetoacetate, purity 96%, yield 84% all with embodiment 1.
Embodiment 6:
With the methyl alcohol among the trimethyl carbinol replacement embodiment 1, all the other get tert-butyl acetoacetate, purity 98.2%, yield 86% all with embodiment 1.
Claims (10)
1, a kind of production method of acetylacetic ester adopts ketene dimer and alcohol to carry out esterification for reactant, and it is characterized in that: what esterification adopted is the catalyzer that contains the ethyleneamines compounds, and rectifying goes out product behind the alcoholization reaction.
2, the production method of acetylacetic ester according to claim 1, it is characterized in that: concrete steps comprise successively:
1. with alcohol and ketene dimer under the condition that the catalyzer that contains the ethyleneamines compounds exists, under 0～140 ℃, carry out esterification;
2. will be put in the rectifying device through the reaction mixture of 1. reaction,, promptly get the acetylacetic ester product in 70～200 ℃ of following rectifying.
3, the production method of acetylacetic ester according to claim 1 and 2 is characterized in that: the catalyzer that contains the ethyleneamines compounds is the mixture of mixture, pyridine and ethyleneamines vitriol that contains mixture, ethylene amines and the sodium-acetate of the compound of ethyleneamines or pyridine and ethyleneamines.
4, the production method of acetylacetic ester according to claim 3 is characterized in that: the compound that contains ethyleneamines is diethylenetriamine or triethylene diamine, tetrem alkene diamines.
5, the production method of acetylacetic ester according to claim 1 and 2 is characterized in that: alcohol with the mole proportioning of ketene dimer is: 1: 1.3.
6, the production method of acetylacetic ester according to claim 5 is characterized in that: alcohol with the mole proportioning of ketene dimer is: 1: 1.05.
7, the production method of acetylacetic ester according to claim 1 and 2 is characterized in that: catalyst consumption is 0.05%～3% of a reactant gross weight.
8, the production method of acetylacetic ester according to claim 7 is characterized in that: catalyst consumption is 0.1%～1.5% of a reactant gross weight.
9, the production method of acetylacetic ester according to claim 2 is characterized in that: rectification temperature is 90～180 ℃.
10, the production method of acetylacetic ester according to claim 2 is characterized in that: during rectifying, vacuum tightness is 500～750mmHg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99114312A CN1091762C (en) | 1999-07-08 | 1999-07-08 | Method for producing acetylacetic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99114312A CN1091762C (en) | 1999-07-08 | 1999-07-08 | Method for producing acetylacetic ester |
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| Publication Number | Publication Date |
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| CN1280122A true CN1280122A (en) | 2001-01-17 |
| CN1091762C CN1091762C (en) | 2002-10-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN99114312A Expired - Fee Related CN1091762C (en) | 1999-07-08 | 1999-07-08 | Method for producing acetylacetic ester |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333029C (en) * | 2004-11-17 | 2007-08-22 | 上海市涂料研究所 | Acetacetic acid alkyl ester metal chelate coating drier and production thereof |
| CN102101829A (en) * | 2009-12-22 | 2011-06-22 | 上海吴泾化工有限公司 | Process for preparing acetoacetic ester |
| CN102276464A (en) * | 2011-09-09 | 2011-12-14 | 南通醋酸化工股份有限公司 | Method for producing methyl acetoacetate |
| CN101337890B (en) * | 2008-08-01 | 2012-02-29 | 江苏天成生化制品有限公司 | Method for preparing methyl acetoacetate by using novel composite catalyst |
| CN102442907A (en) * | 2010-10-12 | 2012-05-09 | 上海吴泾化工有限公司 | Method for removing organic amine catalyst and acetic anhydride in acetoacetic ester reaction solution |
| CN102103363B (en) * | 2009-12-22 | 2012-12-26 | 上海吴泾化工有限公司 | Method and device for detecting and controlling acetoacetic ester continuous reaction system on line |
| CN103450018A (en) * | 2012-12-21 | 2013-12-18 | 南通醋酸化工股份有限公司 | Preparation method of ethyl acetoacetate |
| CN104045558A (en) * | 2013-03-15 | 2014-09-17 | 江苏天成生化制品有限公司 | Methyl acetoacetate production mass transfer process |
| CN104262153A (en) * | 2014-08-27 | 2015-01-07 | 江苏天成生化制品有限公司 | Technology method capable of continuously carrying out methyl acetoacetate production |
| CN105384631A (en) * | 2015-11-24 | 2016-03-09 | 江苏天成生化制品有限公司 | Process of continuously producing methyl acetoacetate |
| CN106748789A (en) * | 2016-12-07 | 2017-05-31 | 南通醋酸化工股份有限公司 | The production method that a kind of methyl acetoacetate low boiling is reclaimed |
| CN106748788A (en) * | 2016-12-07 | 2017-05-31 | 南通醋酸化工股份有限公司 | The production method that a kind of ethyl acetoacetate low boiling is reclaimed |
| CN107827749A (en) * | 2017-10-31 | 2018-03-23 | 南通醋酸化工股份有限公司 | A kind of synthetic method of tert-butyl acetoacetate |
| CN107840802A (en) * | 2017-10-31 | 2018-03-27 | 南通醋酸化工股份有限公司 | A kind of preparation technology of isopropyl acetoacetate |
| WO2019179144A1 (en) * | 2018-03-21 | 2019-09-26 | 南通醋酸化工股份有限公司 | Method and system for preparing methyl acetoacetate or ethyl acetoacetate by using tubular continuous flow reactor |
| CN110292894A (en) * | 2018-03-21 | 2019-10-01 | 南通醋酸化工股份有限公司 | A kind of tubular type continuous flow reaction unit and the method for preparing tert-butyl acetoacetate |
| CN110294676A (en) * | 2018-03-21 | 2019-10-01 | 南通醋酸化工股份有限公司 | A kind of method and system preparing ethyl acetoacetate using tubular type continuous flow reactor |
| CN110294674A (en) * | 2018-03-21 | 2019-10-01 | 南通醋酸化工股份有限公司 | A kind of tubular type continuous flow reaction unit and the method for preparing isopropyl acetoacetate |
| CN111825553A (en) * | 2019-04-17 | 2020-10-27 | 青岛海湾精细化工有限公司 | Preparation method of methyl acetoacetate |
| CN113045417A (en) * | 2019-12-29 | 2021-06-29 | 南通醋酸化工股份有限公司 | Process for producing acetoacetic ester by green catalytic method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL146786B (en) * | Hoechst Ag | PROCESS FOR PREPARING ACETYLAIC ACID ESTERS. | ||
| JPH01230547A (en) * | 1988-01-14 | 1989-09-14 | Takeda Chem Ind Ltd | Production of tertiary butyl 3-oxobutyrate and use thereof |
| JPH0469362A (en) * | 1990-07-11 | 1992-03-04 | Mitsui Toatsu Chem Inc | Preparation of acetoacetic acid l-menthyl ester |
| CH690035A5 (en) * | 1995-12-13 | 2000-03-31 | Lonza Ag | Process for the preparation of acetoacetates. |
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1999
- 1999-07-08 CN CN99114312A patent/CN1091762C/en not_active Expired - Fee Related
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333029C (en) * | 2004-11-17 | 2007-08-22 | 上海市涂料研究所 | Acetacetic acid alkyl ester metal chelate coating drier and production thereof |
| CN101337890B (en) * | 2008-08-01 | 2012-02-29 | 江苏天成生化制品有限公司 | Method for preparing methyl acetoacetate by using novel composite catalyst |
| CN102101829A (en) * | 2009-12-22 | 2011-06-22 | 上海吴泾化工有限公司 | Process for preparing acetoacetic ester |
| CN102103363B (en) * | 2009-12-22 | 2012-12-26 | 上海吴泾化工有限公司 | Method and device for detecting and controlling acetoacetic ester continuous reaction system on line |
| CN102101829B (en) * | 2009-12-22 | 2014-03-19 | 上海华谊（集团）公司 | Process for preparing acetoacetic ester |
| CN102442907B (en) * | 2010-10-12 | 2015-04-08 | 上海华谊工程技术有限公司 | Method for removing organic amine catalyst and acetic anhydride in acetoacetic ester reaction solution |
| CN102442907A (en) * | 2010-10-12 | 2012-05-09 | 上海吴泾化工有限公司 | Method for removing organic amine catalyst and acetic anhydride in acetoacetic ester reaction solution |
| CN102276464A (en) * | 2011-09-09 | 2011-12-14 | 南通醋酸化工股份有限公司 | Method for producing methyl acetoacetate |
| CN102276464B (en) * | 2011-09-09 | 2014-06-25 | 南通醋酸化工股份有限公司 | Method for producing methyl acetoacetate |
| CN103450018B (en) * | 2012-12-21 | 2015-06-17 | 南通醋酸化工股份有限公司 | Preparation method of ethyl acetoacetate |
| CN103450018A (en) * | 2012-12-21 | 2013-12-18 | 南通醋酸化工股份有限公司 | Preparation method of ethyl acetoacetate |
| CN104045558A (en) * | 2013-03-15 | 2014-09-17 | 江苏天成生化制品有限公司 | Methyl acetoacetate production mass transfer process |
| CN104262153A (en) * | 2014-08-27 | 2015-01-07 | 江苏天成生化制品有限公司 | Technology method capable of continuously carrying out methyl acetoacetate production |
| CN105384631A (en) * | 2015-11-24 | 2016-03-09 | 江苏天成生化制品有限公司 | Process of continuously producing methyl acetoacetate |
| CN106748788B (en) * | 2016-12-07 | 2020-03-06 | 南通醋酸化工股份有限公司 | Production method for recycling ethyl acetoacetate at low boiling point |
| CN106748788A (en) * | 2016-12-07 | 2017-05-31 | 南通醋酸化工股份有限公司 | The production method that a kind of ethyl acetoacetate low boiling is reclaimed |
| CN106748789A (en) * | 2016-12-07 | 2017-05-31 | 南通醋酸化工股份有限公司 | The production method that a kind of methyl acetoacetate low boiling is reclaimed |
| CN106748789B (en) * | 2016-12-07 | 2020-03-06 | 南通醋酸化工股份有限公司 | Production method for recycling methyl acetoacetate at low boiling point |
| CN107827749A (en) * | 2017-10-31 | 2018-03-23 | 南通醋酸化工股份有限公司 | A kind of synthetic method of tert-butyl acetoacetate |
| CN107840802A (en) * | 2017-10-31 | 2018-03-27 | 南通醋酸化工股份有限公司 | A kind of preparation technology of isopropyl acetoacetate |
| WO2019179144A1 (en) * | 2018-03-21 | 2019-09-26 | 南通醋酸化工股份有限公司 | Method and system for preparing methyl acetoacetate or ethyl acetoacetate by using tubular continuous flow reactor |
| CN110292894A (en) * | 2018-03-21 | 2019-10-01 | 南通醋酸化工股份有限公司 | A kind of tubular type continuous flow reaction unit and the method for preparing tert-butyl acetoacetate |
| CN110294676A (en) * | 2018-03-21 | 2019-10-01 | 南通醋酸化工股份有限公司 | A kind of method and system preparing ethyl acetoacetate using tubular type continuous flow reactor |
| CN110294674A (en) * | 2018-03-21 | 2019-10-01 | 南通醋酸化工股份有限公司 | A kind of tubular type continuous flow reaction unit and the method for preparing isopropyl acetoacetate |
| CN111825553A (en) * | 2019-04-17 | 2020-10-27 | 青岛海湾精细化工有限公司 | Preparation method of methyl acetoacetate |
| CN113045417A (en) * | 2019-12-29 | 2021-06-29 | 南通醋酸化工股份有限公司 | Process for producing acetoacetic ester by green catalytic method |
| CN113045417B (en) * | 2019-12-29 | 2023-04-07 | 南通醋酸化工股份有限公司 | Process for producing acetoacetic ester by catalytic method |
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| CN1091762C (en) | 2002-10-02 |
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