CN103450017A - Preparation method of methyl acetoacetate - Google Patents
Preparation method of methyl acetoacetate Download PDFInfo
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- CN103450017A CN103450017A CN2012105627161A CN201210562716A CN103450017A CN 103450017 A CN103450017 A CN 103450017A CN 2012105627161 A CN2012105627161 A CN 2012105627161A CN 201210562716 A CN201210562716 A CN 201210562716A CN 103450017 A CN103450017 A CN 103450017A
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- methyl acetoacetate
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Abstract
The invention provides a preparation method of methyl acetoacetate. The preparation method sequentially comprises the following steps of: (1) fully dissolving methanol and a catalyst, then adding the mixture into an esterification reaction kettle, heating up, and dropwise adding ketene dimer; (2) after completing dropwise addition, insulating, and cooling to produce crude methyl acetoacetate; (3) rectifying the crude product to obtain the finished methyl acetoacetate. The preparation method is characterized in that the catalyst in the step (1) is an amine type ionic liquid catalyst which is selected from one or more of n-butylamine nitrate, n-butylamine acetate, ethylamine nitrate, ethylamine acetate, propylamine nitrate and propylamine acetate. According to the preparation method of methyl acetoacetate, the amine type ionic liquid catalyst is researched and is good in stability, the stability of methyl acetoacetate is enhanced under the action of the catalyst, the rectification yield of a product can be improved, the technological operations are simple, the raw material consumption is reduced, and the catalyst has obvious advantages and a positive effect.
Description
Technical field
The invention belongs to chemical production field, be specifically related to a kind of preparation method of methyl acetoacetate.
Background technology
Methyl acetoacetate; colourless liquid; special smell is arranged, soluble in water, fusing point :-28 ° of C; boiling point: 169-170 ° C70mmHg (lit.); density: 1.077, specific refractory power: n20/D1.419 (lit.), flash-point: 158 °F; solubleness: 460g/L (20 ° of C), water-soluble: 460g/L (20& Ordm; C)
The methyl acetoacetate purposes: (1) is that sterilant is disliked mould spirit, dimethirimol, the phonetic phenol of second for medicine industry (2) methyl acetoacetate, sterilant diazinon, Coumaphos, pirimioxyphos, herbicide imazethapyr, the intermediate of rodenticide coumatetralyl, warfarin etc.(3) as the solvent of ether of cellulose and the composition of celluosic resin mixed solvent, also for organic syntheses such as agricultural chemicals, medicine, dyestuff, macromolecule stabilizers.
The prior art synthesis technique:
The patent of invention of our company's application: CN102276464A, a kind of production method of methyl acetoacetate.It is characterized in that, step is as follows: thick ketene dimer and methyl alcohol are carried out to esterification under 20-150 ℃, and described esterification adopts tertiary amine, a kind of as catalyzer containing in the compound of ethyleneamines or basic cpd; The product that esterification is generated, carry out four tower negative pressure continuous rectifications, makes methyl acetoacetate, and content is greater than 99.7%.This technique shortcoming is: facility investment is large, and rectifying requires high.
Chinese invention patent, CN101337890A, a kind of method of preparing methyl acetoacetate by using novel composite catalyst, methyl alcohol and ketene dimer generation esterification generate thick methyl acetoacetate at lower than 120 ℃ of temperature, the different steps of esterification adds two kinds of different catalysts, before esterification, add the catalyzer triethylene diamine, can directly drip ketene dimer, without steam heating, to generate liquid after having reacted and be cooled to 40 ℃, add the catalyzer vitriol oil, be incubated half an hour, filter, filtrate is carried out to continuous rectification, separate and make the smart methyl acetoacetate that content is greater than 99%.It is residual that to be that catalyzer must be removed, mother liquor is purified still have the shortcoming of this technique, and rectification yield is low, and product content is low.
To sum up, in prior art, the preparation method's of methyl acetoacetate shortcoming is that facility investment is large, and rectifying requires high, catalyzer must be removed, the catalyzer removal is not thorough, and mother liquor is purified and still had catalyst residue residual, affects the stability of product, feed stock conversion is low, and rectification yield is low, and product content is low.
Summary of the invention
In order to address the above problem, the object of the present invention is to provide a kind of preparation method of methyl acetoacetate, this preparation method develops a kind of amine type ionic-liquid catalyst, and this catalyst stability is good, aobvious neutral, under this catalyst action, in the preparation of methyl acetoacetate, catalyzer need not be removed, and the stability of product is increased, and has improved the rectification yield of product, the ketene dimer transformation efficiency reaches 100%, product yield is greater than 98%, obtains high-quality product, and content reaches 99.7%.
Technical solution of the present invention is as follows:
A kind of preparation method of methyl acetoacetate, in turn include the following steps: (1) joins reaction kettle of the esterification after methyl alcohol and catalyzer are fully dissolved, and heats up, and drips ketene dimer, (2) dropwise, insulation, cooling, generate the methyl acetoacetate crude product, (3) the gained crude product is through rectifying, obtain the methyl acetoacetate finished product, it is characterized in that, the catalyzer in described step (1) is amine type ionic-liquid catalyst.
According to the preparation method of methyl acetoacetate of the present invention, preferably, described amine type ionic-liquid catalyst is selected from one or more in nitric acid n-Butyl Amine 99, acetic acid n-Butyl Amine 99, nitric acid ethamine, acetate triethylamine, nitric acid propylamine, acetic acid propylamine.
Methyl acetoacetate easily decomposes because condition is different, the present invention is directed to catalyst residue in product, destroy product stability, thereby yield is descended, therefore developed a kind of novel high-activity, amine type ion is urged the liquid agent, catalyst type is as follows: the amine type ionic liquids such as nitric acid n-Butyl Amine 99, acetic acid n-Butyl Amine 99, nitric acid ethamine, acetate triethylamine, nitric acid propylamine, acetic acid propylamine.
According to the preparation method of methyl acetoacetate of the present invention, preferably, the preparation method of described catalyzer, after slowly being added drop-wise in acid by amine, is heated to 50～80 ℃, and reaction times 2～4h, obtain amine type ionic-liquid catalyst.
According to the preparation method of methyl acetoacetate of the present invention, further preferably, the preparation method of described catalyzer, after slowly being added drop-wise in acid by amine, is heated to 60～70 ℃, obtains amine type ionic-liquid catalyst.
According to the preparation method of methyl acetoacetate of the present invention, further preferably, the preparation method of described catalyzer is that after slowly being added drop-wise in acid by amine, reaction times 2.5～3.5h, obtain amine type ionic-liquid catalyst.
According to the preparation method of methyl acetoacetate of the present invention, preferably, described amine is selected from a kind of in ethamine, propylamine and n-Butyl Amine 99.
According to the preparation method of methyl acetoacetate of the present invention, preferably, described acid is selected from a kind of in nitric acid and acetic acid.
According to the preparation method of methyl acetoacetate of the present invention, preferably, in described step (1), ketene dimer with the amount of substance ratio of methyl alcohol add-on is: 1:1～1:1.5.
According to the preparation method of methyl acetoacetate of the present invention, further preferably, in described step (1), ketene dimer with the amount of substance ratio of methyl alcohol add-on is: 1:1.18～1:1.38.
According to the preparation method of methyl acetoacetate of the present invention, preferably, in described step (1) the catalyzer add-on be ketene dimer be by percentage to the quality: 0.04%～4%.
According to the preparation method of methyl acetoacetate of the present invention, further preferably, in described step (1) the catalyzer add-on be ketene dimer be by percentage to the quality: 0.14%～0.7%.
According to the preparation method of methyl acetoacetate of the present invention, preferably, after being warming up to 60～120 ℃ in described step (1), drip ketene dimer.
According to the preparation method of methyl acetoacetate of the present invention, further preferably, after being warming up to 80～100 ℃ in described step (1), drip ketene dimer.
According to the preparation method of methyl acetoacetate of the present invention, preferably, in described step (2), the time of insulation is 1～3 hour.
The preparation method of methyl acetoacetate provided by the invention is as follows:
The preparation of catalyzer: appropriate n-Butyl Amine 99 slowly drips Glacial acetic acid, dropwises, and is heated to 50～80 ℃, continues reaction 2～4h, obtains catalyst body acetic acid n-Butyl Amine 99 ionic liquid.
Esterification: appropriate methyl alcohol and catalyzer are fully dissolved and drop into reaction kettle of the esterification (ketene dimer: the amount of substance ratio of methyl alcohol is: 1:1～1:1.5; The mass ratio of catalyzer and ketene dimer is: 0.04%～4%), heats up, drips ketene dimers in 60～120 ℃, finish until the good ketene dimer of proportioning drips, and cooling after being incubated 1～3 hour, generate the methyl acetoacetate crude product.Crude product, through rectifying, is removed height and is boiled, and distillates the methyl acetoacetate finished product.
The invention has the beneficial effects as follows: the preparation method of a kind of methyl acetoacetate provided by the invention, this preparation method develops a kind of amine type ionic-liquid catalyst, this catalyst stability is good, aobvious neutral, and under this catalyst action, in the preparation of methyl acetoacetate, catalyzer need not be removed, the stability of product is increased, improved the rectification yield of product, the ketene dimer transformation efficiency reaches 100%, and product yield is greater than 98%, obtain high-quality product, content reaches 99.7%; Technological operation of the present invention simultaneously is simple, and raw material consumption descends, and has obvious advantage and positively effect.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated, it will be appreciated by those skilled in the art that described embodiment is only for example, and the present invention is not formed to any restriction.
Embodiment 1:
A kind of preparation technology of methyl acetoacetate, comprise the following steps:
The preparation of amine type ionic-liquid catalyst: add 15.4g(0.21mol in there-necked flask) n-Butyl Amine 99, slowly drip 12.0g(0.2mol) Glacial acetic acid, dropwise, be heated to 60 ℃, continue reaction 2h, obtain weak yellow liquid acetic acid n-Butyl Amine 99, productive rate is 96%.
Esterification process: add methyl alcohol 28.57g in the there-necked flask of 500ml, catalyst acetic acid n-Butyl Amine 99 ionic liquid 0.071g, 80 ℃ of temperature rising reflux, drip ketene dimer 50g, and 3h dropwises, 120 ℃ of insulation 3h, detection is without ketene dimer, and reaction finishes, then distillates the methyl acetoacetate finished product obtain methyl acetoacetate 68.1 after rectifying tower rectifying, product yield is 98.7%, product content 99.73%.
Embodiment 2:
Add methyl alcohol 26.67g in the there-necked flask of 500ml, catalyzer nitric acid n-Butyl Amine 99 ionic liquid (prepared with reference to embodiment 1 by catalyzer) 0.077g, temperature rising reflux, drip ketene dimer 50g, and 3h dropwises, 120 ℃ of insulation 3h, detection is without ketene dimer, and reaction finishes, then distillates the methyl acetoacetate finished product obtain methyl acetoacetate 67.8g after rectifying tower rectifying, product yield is 98.2%, product content 99.72%.
Embodiment 3:
Add methyl alcohol 24.76g in the there-necked flask of 500ml, catalyst acetic acid ethamine ionic liquid (prepared with reference to embodiment 1 by catalyzer) 0.67g, temperature rising reflux, drip ketene dimer 50g, and 3h dropwises, 120 ℃ of insulation 3h, detection is without ketene dimer, and reaction finishes, then distillates the methyl acetoacetate finished product obtain methyl acetoacetate 67.9g after rectifying tower rectifying, product yield is 98.3%, product content 99.76%.
Embodiment 4:
Add methyl alcohol 22.86g in the there-necked flask of 500ml, catalyzer nitric acid ethamine ionic liquid (prepared with reference to embodiment 1 by catalyzer) 0.73g, temperature rising reflux, drip ketene dimer 50g, and 3h dropwises, 120 ℃ of insulation 3h, detection is without ketene dimer, and reaction finishes, then distillates the methyl acetoacetate finished product obtain methyl acetoacetate 67.9g after rectifying tower rectifying, product yield is 98.3%, product content 99.75%.
Embodiment 5:
Add methyl alcohol 20.95g in the there-necked flask of 500ml, catalyst acetic acid propylamine ionic liquid (prepared with reference to embodiment 1 by catalyzer) 0.35g, temperature rising reflux, drip ketene dimer 50g, and 3h dropwises, 120 ℃ of insulation 3h, detection is without ketene dimer, and reaction finishes, then distillates the methyl acetoacetate finished product obtain methyl acetoacetate 67.9g after rectifying tower rectifying, product yield is 98.4%, product content 99.73%.
Embodiment 6:
Add methyl alcohol 19.05g in the there-necked flask of 500ml, catalyst acetic acid propylamine ionic liquid (prepared with reference to embodiment 1 by catalyzer) 0.35g, temperature rising reflux, drip ketene dimer 50g, and 3h dropwises, 120 ℃ of insulation 3h, detection is without ketene dimer, and reaction finishes, then distillates the methyl acetoacetate finished product obtain methyl acetoacetate 67.6g after rectifying tower rectifying, product yield is 98.0%, product content 99.78%.
The comparative example 1:
Method with reference to Chinese patent CN101337890A, in the there-necked flask of 500ml, the methyl alcohol that adds 20g, the triethylene diamine that adds 0.025g under stirring, drip the ketene dimer of 50g, 110-120 ℃ is incubated 1 hour, cool to 40 ℃, add the vitriol oil of 0.05g to make catalyzer, insulation generates half an hour filters to obtain two second methyl esters slightly, thick two second methyl esters enters in the low tower that boils, take off low-boiling-point substance, in low-boiling-point substance, 70% methyl acetoacetate reclaims and enters rectifying tower, obtains the finished product methyl acetoacetate, product yield 96.5%, content reaches 99.12%.
Below with preferred embodiment, disclose the present invention, so it is not intended to limiting the invention, and all employings are equal to replaces or technical scheme that the equivalent transformation mode obtains, within all dropping on protection scope of the present invention.
The preparation method of a kind of methyl acetoacetate provided by the invention, this preparation method develops a kind of amine type ionic-liquid catalyst, this catalyst stability is good, aobvious neutral, and under this catalyst action, in the preparation of methyl acetoacetate, catalyzer need not be removed, the stability of product is increased, improved the rectification yield of product, the ketene dimer transformation efficiency reaches 100%, and product yield is greater than 98%, obtain high-quality product, content reaches 99.7%; Technological operation of the present invention simultaneously is simple, and raw material consumption descends, and has obvious advantage and positively effect.
Claims (9)
1. the preparation method of a methyl acetoacetate, in turn include the following steps: (1) joins reaction kettle of the esterification after methyl alcohol and catalyzer are fully dissolved, and heats up, and drips ketene dimer, (2) dropwise, insulation, cooling, generate the methyl acetoacetate crude product, (3) the gained crude product is through rectifying, obtain the methyl acetoacetate finished product, it is characterized in that, the catalyzer in described step (1) is amine type ionic-liquid catalyst.
2. the preparation method of methyl acetoacetate according to claim 1, it is characterized in that, described amine type ionic-liquid catalyst is selected from one or more in nitric acid n-Butyl Amine 99, acetic acid n-Butyl Amine 99, nitric acid ethamine, acetate triethylamine, nitric acid propylamine, acetic acid propylamine.
3. the preparation method of methyl acetoacetate according to claim 1, is characterized in that, in described step (1), ketene dimer is 1:1～1:1.5 with the amount of substance ratio of methyl alcohol add-on.
4. the preparation method of methyl acetoacetate according to claim 1, is characterized in that, in described step (1) the catalyzer add-on be ketene dimer be 0.04%～4% by percentage to the quality.
5. the preparation method of methyl acetoacetate according to claim 1, is characterized in that, after being warming up to 60～120 ℃ in described step (1), drips ketene dimer.
6. the preparation method of methyl acetoacetate according to claim 1, is characterized in that, in described step (2), the time of insulation is 1～3 hour.
7. the preparation method of methyl acetoacetate according to claim 1 and 2, it is characterized in that, described catalyzer is amine type ionic-liquid catalyst, it is by being prepared as follows the method preparation: after slowly being added drop-wise in acid by amine, be heated to 50～80 ℃, reaction times 2～4h, obtain amine type ionic-liquid catalyst.
8. the preparation method of methyl acetoacetate according to claim 7, is characterized in that, described amine is selected from a kind of in ethamine, propylamine and n-Butyl Amine 99.
9. the preparation method of methyl acetoacetate according to claim 7, is characterized in that, described acid is selected from a kind of in nitric acid and acetic acid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107986966A (en) * | 2017-12-14 | 2018-05-04 | 山东汇海医药化工有限公司 | A kind of preparation method 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 |
| CN111470968A (en) * | 2020-04-16 | 2020-07-31 | 南通柏盛化工有限公司 | Method for synthesizing methyl acetoacetate |
| CN112062680A (en) * | 2020-08-25 | 2020-12-11 | 南京工业大学 | Organic matter type ionic liquid, two-dimensional perovskite pure-phase quantum well structure film, preparation method and application thereof |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337890A (en) * | 2008-08-01 | 2009-01-07 | 江苏天成生化制品有限公司 | Method for preparing methyl acetoacetate by using novel composite catalyst |
-
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- 2012-12-21 CN CN201210562716.1A patent/CN103450017B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337890A (en) * | 2008-08-01 | 2009-01-07 | 江苏天成生化制品有限公司 | Method for preparing methyl acetoacetate by using novel composite catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 叶庆华等: "胺型离子液体催化合成乙酸己酯", 《精细与专用化学品》 * |
| 陆亚平等: "乙酰乙酸甲酯合成工艺条件的优化", 《江苏化工》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107986966A (en) * | 2017-12-14 | 2018-05-04 | 山东汇海医药化工有限公司 | A kind of preparation method 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 |
| 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 |
| CN111470968A (en) * | 2020-04-16 | 2020-07-31 | 南通柏盛化工有限公司 | Method for synthesizing methyl acetoacetate |
| CN111470968B (en) * | 2020-04-16 | 2022-04-22 | 南通柏盛药业有限公司 | Method for synthesizing methyl acetoacetate |
| CN112062680A (en) * | 2020-08-25 | 2020-12-11 | 南京工业大学 | Organic matter type ionic liquid, two-dimensional perovskite pure-phase quantum well structure film, preparation method and application thereof |
| CN112062680B (en) * | 2020-08-25 | 2021-06-22 | 南京工业大学 | Organic matter type ionic liquid, two-dimensional perovskite pure-phase quantum well structure film, preparation method and application thereof |
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