CN103450017B - Preparation method of methyl acetoacetate - Google Patents
Preparation method of methyl acetoacetate Download PDFInfo
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- CN103450017B CN103450017B CN201210562716.1A CN201210562716A CN103450017B CN 103450017 B CN103450017 B CN 103450017B CN 201210562716 A CN201210562716 A CN 201210562716A CN 103450017 B CN103450017 B CN 103450017B
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- methyl acetoacetate
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- ketene dimer
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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; there is special smell, 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)
Methyl acetoacetate purposes: (1) is that sterilant dislikes 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 in the organic syntheses such as agricultural chemicals, medicine, dyestuff, macromolecule stabilizer.
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 esterification at 20-150 DEG C, described esterification adopts tertiary amine, containing the one in the compound of ethyleneamines or basic cpd as catalyzer; By the product that esterification generates, carry out four tower negative pressure continuous rectifications, obtained methyl acetoacetate, content is greater than 99.7%.This processing disadvantages 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 DEG C of temperature, the different steps of esterification adds two kinds of different catalysts, before esterification, add catalyzer triethylene diamine, directly can drip ketene dimer, without the need to steam heating, after having reacted, generation liquid is cooled to 40 DEG C, add the catalyzer vitriol oil, be incubated half an hour, filter, filtrate is carried out continuous rectification, be separated the smart methyl acetoacetate that obtained content is greater than 99%.The shortcoming of this technique is that catalyzer must be removed, mother liquor purification still has residual, and rectification yield is low, and product content is low.
To sum up, in prior art, the shortcoming of the preparation method of methyl acetoacetate is that facility investment is large, and rectifying requires high, catalyzer must be removed, catalyzer is removed not thorough, and mother liquor is purified and still had catalyst residue to remain, and 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 solve the 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, improves the rectification yield of product, 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 fully being dissolved, heat up, drip ketene dimer, (2) dropwise, insulation, cooling, generates methyl acetoacetate crude product, (3) gained crude product is through rectifying, obtain 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 of condition difference, the present invention is directed to catalyst residue in product, destroy product stability, thus yield is declined, therefore have developed a kind of novel high-activity, amine type ion urges 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, amine is slowly added drop-wise to after in acid by the preparation method of described catalyzer, is heated to 50 ~ 80 DEG C, reaction times 2 ~ 4h, obtains amine type ionic-liquid catalyst.
According to the preparation method of methyl acetoacetate of the present invention, further preferably, amine is slowly added drop-wise to after in acid by the preparation method of described catalyzer, is heated to 60 ~ 70 DEG C, obtains amine type ionic-liquid catalyst.
According to the preparation method of methyl acetoacetate of the present invention, further preferably, amine is slowly added drop-wise to after in acid by the preparation method of described catalyzer, and reaction times 2.5 ~ 3.5h, obtains amine type ionic-liquid catalyst.
According to the preparation method of methyl acetoacetate of the present invention, preferably, described amine is selected from the one 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 the one 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) catalyst charge 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) catalyst charge 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 DEG C 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 DEG C 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, is heated to 50 ~ 80 DEG C, 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 drops 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, and drips ketene dimer in 60 ~ 120 DEG C, until the ketene dimer dropping end that proportioning is good, is incubated after 1 ~ 3 hour and cools, generate methyl acetoacetate crude product.Crude product, through rectifying, is removed height and is boiled, distillate 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, improve the rectification yield of product, ketene dimer transformation efficiency reaches 100%, and product yield is greater than 98%, obtain high-quality product, content reaches 99.7%; Present invention process is simple to operate simultaneously, and raw material consumption declines, 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 do not form any restriction to the present invention.
Embodiment 1:
A preparation technology for methyl acetoacetate, comprises 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 DEG C, 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 DEG C of temperature rising reflux, drip ketene dimer 50g, 3h dropwises, 120 DEG C of insulation 3h, detect without ketene dimer, reaction end, then after rectifying tower rectifying, distillate methyl acetoacetate finished product obtain methyl acetoacetate 68.1, product yield is 98.7%, product content 99.73%.
Embodiment 2:
Methyl alcohol 26.67g is added in the there-necked flask of 500ml, catalyzer nitric acid n-Butyl Amine 99 ionic liquid (catalyst preparing is with reference to embodiment 1) 0.077g, temperature rising reflux, drip ketene dimer 50g, 3h dropwises, 120 DEG C of insulation 3h, detect without ketene dimer, reaction end, then after rectifying tower rectifying, distillate methyl acetoacetate finished product obtain methyl acetoacetate 67.8g, product yield is 98.2%, product content 99.72%.
Embodiment 3:
Methyl alcohol 24.76g is added in the there-necked flask of 500ml, catalyst acetic acid ethamine ionic liquid (catalyst preparing is with reference to embodiment 1) 0.67g, temperature rising reflux, drip ketene dimer 50g, 3h dropwises, 120 DEG C of insulation 3h, detect without ketene dimer, reaction end, then after rectifying tower rectifying, distillate methyl acetoacetate finished product obtain methyl acetoacetate 67.9g, product yield is 98.3%, product content 99.76%.
Embodiment 4:
Methyl alcohol 22.86g is added in the there-necked flask of 500ml, catalyzer nitric acid ethamine ionic liquid (catalyst preparing is with reference to embodiment 1) 0.73g, temperature rising reflux, drip ketene dimer 50g, 3h dropwises, 120 DEG C of insulation 3h, detect without ketene dimer, reaction end, then after rectifying tower rectifying, distillate methyl acetoacetate finished product obtain methyl acetoacetate 67.9g, product yield is 98.3%, product content 99.75%.
Embodiment 5:
Methyl alcohol 20.95g is added in the there-necked flask of 500ml, catalyst acetic acid propylamine ionic liquid (catalyst preparing is with reference to embodiment 1) 0.35g, temperature rising reflux, drip ketene dimer 50g, 3h dropwises, 120 DEG C of insulation 3h, detect without ketene dimer, reaction end, then after rectifying tower rectifying, distillate methyl acetoacetate finished product obtain methyl acetoacetate 67.9g, product yield is 98.4%, product content 99.73%.
Embodiment 6:
Methyl alcohol 19.05g is added in the there-necked flask of 500ml, catalyst acetic acid propylamine ionic liquid (catalyst preparing is with reference to embodiment 1) 0.35g, temperature rising reflux, drip ketene dimer 50g, 3h dropwises, 120 DEG C of insulation 3h, detect without ketene dimer, reaction end, then after rectifying tower rectifying, distillate methyl acetoacetate finished product obtain methyl acetoacetate 67.6g, product yield is 98.0%, product content 99.78%.
Comparative example 1:
With reference to the method for Chinese patent CN101337890A, in the there-necked flask of 500ml, add the methyl alcohol of 20g, the triethylene diamine of 0.025g is added under stirring, drip the ketene dimer of 50g, 110-120 DEG C is incubated 1 hour, cool to 40 DEG C, the vitriol oil adding 0.05g makees catalyzer, and insulation generates half an hour filters to obtain slightly two second methyl esters, thick two second methyl esters enters and lowly boils in tower, take off low-boiling-point substance, in low-boiling-point substance, the methyl acetoacetate of 70% reclaims and enters rectifying tower, obtains finished product methyl acetoacetate, product yield 96.5%, content reaches 99.12%.
Below disclose the present invention with preferred embodiment, so it is not intended to limiting the invention, and all employings are equal to replacement or the technical scheme that obtains of equivalent transformation mode, all drop within 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, improve the rectification yield of product, ketene dimer transformation efficiency reaches 100%, and product yield is greater than 98%, obtain high-quality product, content reaches 99.7%; Present invention process is simple to operate simultaneously, and raw material consumption declines, and has obvious advantage and positively effect.
Claims (8)
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 fully being dissolved, heat up, drip ketene dimer, (2) dropwise, insulation, cooling, generates methyl acetoacetate crude product, (3) gained crude product is through rectifying, obtain methyl acetoacetate finished product, it is characterized in that, the catalyzer in described step (1) is amine type ionic-liquid catalyst;
Described amine type ionic-liquid catalyst be selected from nitric acid n-Butyl Amine 99, acetic acid n-Butyl Amine 99, nitric acid ethamine, acetate triethylamine, nitric acid propylamine, acetic acid propylamine one or more.
2. the preparation method of methyl acetoacetate according to claim 1, is characterized in that, in described step (1), ketene dimer and the amount of substance of methyl alcohol add-on are than being 1:1 ~ 1:1.5.
3. the preparation method of methyl acetoacetate according to claim 1, is characterized in that, in described step (1) catalyst charge be ketene dimer be 0.04% ~ 4% by percentage to the quality.
4. the preparation method of methyl acetoacetate according to claim 1, is characterized in that, after being warming up to 60 ~ 120 DEG C, drips ketene dimer in described step (1).
5. 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.
6. the preparation method of methyl acetoacetate according to claim 1, it is characterized in that, described catalyzer is amine type ionic-liquid catalyst, it is prepared by following preparation method: be slowly added drop-wise to by amine after in acid, be heated to 50 ~ 80 DEG C, reaction times 2 ~ 4h, obtains amine type ionic-liquid catalyst.
7. the preparation method of methyl acetoacetate according to claim 6, is characterized in that, described amine is selected from the one in ethamine, propylamine and n-Butyl Amine 99.
8. the preparation method of methyl acetoacetate according to claim 6, is characterized in that, described acid is selected from the one in nitric acid and acetic acid.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| CN111470968B (en) * | 2020-04-16 | 2022-04-22 | 南通柏盛药业有限公司 | Method for synthesizing methyl acetoacetate |
| 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 |
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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 乙酰乙酸甲酯合成工艺条件的优化;陆亚平等;《江苏化工》;20040430;第32卷(第2期);47-48 * |
| 胺型离子液体催化合成乙酸己酯;叶庆华等;《精细与专用化学品》;20111031;第19卷(第10期);19-21 * |
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