CN101121657A - Method for catalyzing acetylization reaction - Google Patents
Method for catalyzing acetylization reaction Download PDFInfo
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- CN101121657A CN101121657A CNA2007100463376A CN200710046337A CN101121657A CN 101121657 A CN101121657 A CN 101121657A CN A2007100463376 A CNA2007100463376 A CN A2007100463376A CN 200710046337 A CN200710046337 A CN 200710046337A CN 101121657 A CN101121657 A CN 101121657A
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- reaction
- morbsa
- hso
- room temperature
- ionic liquid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method of catalytic acetylation reaction. The method is: in the process of the acetylation reaction with the alcohol or phenol and acetic anhydride, the [MORBSA][HSO4] ionic liquid is used as the catalyst; the catalyst quantity is 0.5 to 1.0 percent of the total mol number of the reaction materials; after the reaction, the catalyst is separated, and the rate of reaction conversion is test. The invention has the following advantages: first, the rate of transformation is high and reaches above 95 percent; secondly, the catalytic activity is high and the used quantity is little; thirdly, the reaction conditions are mild and the reaction time is short; fourthly, the catalyst can be reused several times and still maintain a high activity; fifthly, the invention is friendly to the environment.
Description
Technical field
The present invention relates to the organic chemistry synthesis technical field, specifically a kind of method of catalyzing acetylization reaction.
Background technology
The reaction of phenolic compound and carboxylic acid halides or acid anhydrides is called acylation reaction.Comprising the hydrogen atom of hydroxyl in alcohol or the phenol molecule by the process of acyl substituted or alkynes and acid-respons.The present invention mainly is a kind of novel method at this type of reaction.Often use the research of catalyzer to comprise some protonic acids for acylation reaction; Lewis acid and some acidic resins, but these an acidic catalysts have the corrodibility height, the spent acid solution contaminate environment; product be difficult to separate with catalyzer and also catalyzer not easy to be recycled, product is coloured wait not enough.Up-to-date acylation reaction catalyst comprises iodine, NaHSO
4SiO
2, La (NO
3)
36H
2O etc., and these catalyzer generally have and cost an arm and a leg, toxicity is big, characteristics such as unstable properties.Therefore, background technology can't realize yield height, low, the eco-friendly target of cost simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of method of eco-friendly, highly active catalyzing acetylization reaction, is that catalyzer solves the existing problem of background technology with ionic liquid.
The object of the present invention is achieved like this:
A kind of method of catalyzing acetylization reaction, characteristics are: in the acetylization reaction process that alcohol or phenol and diacetyl oxide carried out, with [MORBSA] [HSO
4] ionic liquid makes catalyzer, catalyst levels accounts for 0.5～1.0% of reaction raw materials total mole number, after reaction finishes, and separating catalyst, assaying reaction transformation efficiency; Concrete steps are as follows:
The 1st step [MORBSA] [HSO
4] ion liquid preparation
It with mol ratio 1.1: 1 morphine quinoline and 1, the 4-butane sultone places container, under 50 ℃ of conditions, add with reactant molar ratio be that 1: 0.8～1.2 ethanol is made solvent, mix and stir 4～5h, reaction obtains white solid 1-alkyl-3-(butyl-4-sulfonic group) alkylbenzyldimethylasaltsum saltsum after finishing, this salt is washed 2～4 times with ether, and carry out vacuum-drying; At room temperature, will dropwise add in this salt, under 70～90 ℃, stir 4～6h, obtain [MORBSA] [HSO with above-mentioned 1-alkyl-3-(butyl-4-sulfonic group) equimolar vitriol oil of alkylbenzyldimethylasaltsum saltsum
4] ionic liquid; The gained ionic liquid is with ether washing 2～4 times, removes to revolve to steam behind the nonionic resistates and removes ether;
The 2nd step acetylization reaction
At room temperature, in alcohol or phenol and diacetyl oxide mol ratio are 1: 1.0～4.0 solution, add 0.5～1.0mol%[MORBSA] [HSO
4] ionic liquid, room temperature reaction 1～10min, reaction finishes, and gets product.
Reaction expression is as follows:
Catalyzer of the present invention is reusable, after reaction finishes each time, removes ion liquid upper strata product, and then revolve and steam the solvent remove wherein, unreacted reactant and product are thrown the raw material of same ratio once more, repeat reaction under identical condition.
Compared with prior art, the present invention has following tangible advantage:
1, the reaction times is short.
2, the yield height reaches as high as more than 95%.
3, little to equipment corrosion.
4, environmental friendliness can realize that cleaning is green synthetic.
5, catalyzer can be recycled and reused for down secondary response.
Embodiment
Below all embodiment all carry out according to operation steps of the present invention.
Embodiment 1
The 1st step [MORBSA] [HSO
4] ion liquid preparation
25mL ethanol is made solvent, 0.22mol morpholine and 0.2mol 1, the 4-butane sultone stirs 4h under 50 ℃ of conditions, after reaction finishes, obtain 1-alkyl-3-(butyl-4-sulfonic group) alkylbenzyldimethylasaltsum saltsum of 36.9g, with this salt with ether washing 3 times and carry out vacuum-drying.
At room temperature, take by weighing 1-alkyl-3-(butyl-4-sulfonic group) alkylbenzyldimethylasaltsum saltsum of 0.1mol, dropwise add the vitriol oil of 0.1mol, 80 ℃ of following stirring reactions 4 hours can obtain [MORBSA] [HSO
4] ionic liquid; The gained ionic liquid is with ether washing 3 times, remove the nonionic resistates after, revolve to steam and remove ether.
The 2nd step acetylization reaction
At room temperature, [the MORBSA] [HSO that in the solution of 0.1mol phenylcarbinol and 0.11mol diacetyl oxide, adds 0.002mol
4] ionic-liquid catalyst, stirring at room, the 1min afterreaction finishes, and gets product, and reaction conversion ratio reaches 99%.
Embodiment 2
Except for the following differences, all the other are identical with embodiment 1.
At room temperature, [the MORBSA] [HSO that in the solution of 0.1mol propyl carbinol and 0.11mol diacetyl oxide, adds 0.002mol
4] ionic-liquid catalyst, stirring at room, the 4min afterreaction finishes, and gets product, and reaction conversion ratio reaches 99%.
Embodiment 3
Except for the following differences, all the other are identical with embodiment 1.
At room temperature, [the MORBSA] [HSO that in the solution of 0.1mol ethylene glycol monomethyl ether and 0.11mol diacetyl oxide, adds 0.002mol
4] ionic-liquid catalyst, stirring at room, the 1min afterreaction finishes, and gets product, and reaction conversion ratio reaches 98%.
Embodiment 4
Except for the following differences, all the other are identical with embodiment 1.
At room temperature, [the MORBSA] [HSO that in the solution of 0.1mol hexalin and 0.11mol diacetyl oxide, adds 0.002mol
4] ionic-liquid catalyst, stirring at room, the 5min afterreaction finishes, and gets product, and reaction conversion ratio reaches 99%.
Embodiment 5
Except for the following differences, all the other are identical with embodiment 1.
At room temperature, [the MORBSA] [HSO that in the solution of 0.1mol phenol and 0.11mol diacetyl oxide, adds 0.002mol
4] ionic-liquid catalyst, stirring at room, the 1min afterreaction finishes, and gets product, and reaction conversion ratio reaches 99%.
Embodiment 6
Except for the following differences, all the other are identical with embodiment 1.
At room temperature, [the MORBSA] [HSO that in the solution of 0.1mol butyleneglycol and 0.22mol diacetyl oxide, adds 0.002mol
4] ionic-liquid catalyst, room temperature reaction 4min, reaction finishes, and gets product, and reaction conversion ratio reaches 98%.
Embodiment 7
Except for the following differences, all the other are identical with embodiment 1.
At room temperature, [the MORBSA] [HSO that in the solution of 0.1mol isooctyl alcohol and 0.11mol diacetyl oxide, adds 0.0015mol
4] ionic-liquid catalyst, room temperature reaction 10min, reaction finishes, and gets product, and reaction conversion ratio reaches 98%.
Embodiment 8
Except for the following differences, all the other are identical with embodiment 1.
At room temperature, [the MORBSA] [HSO that in the solution of 0.1mol Resorcinol and 0.4mol diacetyl oxide, adds 0.003mol
4] ionic-liquid catalyst, room temperature reaction 5min, reaction finishes, and gets product, and reaction conversion ratio reaches 97%.
Embodiment 9
Except for the following differences, all the other are identical with embodiment 1, the active repeated experiment of catalysts:
| Embodiment | Multiplicity/T | Transformation efficiency/% |
| 9 10 11 12 13 | 1 2 3 4 5 | 99 99 98 98 97 |
Claims (1)
1. the method for a catalyzing acetylization reaction is characterized in that: in the acetylization reaction process that alcohol or phenol and diacetyl oxide carried out, with [MORBSA] [HSO
4] ionic liquid makes catalyzer, catalyst levels accounts for 0.5～1.0% of reaction raw materials total mole number, after reaction finishes, and separating catalyst, assaying reaction transformation efficiency; Its concrete steps are as follows:
The 1st step [MORBSA] [HSO
4] ion liquid preparation
It with mol ratio 1.1: 1 morphine quinoline and 1, the 4-butane sultone places container, under 50 ℃ of conditions, add with reactant molar ratio be that 1: 0.8～1.2 ethanol is made solvent, mix and stir 4～5h, reaction obtains white solid 1-alkyl-3-(butyl-4-sulfonic group) alkylbenzyldimethylasaltsum saltsum after finishing, this salt is washed 2～4 times with ether, and carry out vacuum-drying; At room temperature, will dropwise add in this salt, under 70～90 ℃, stir 4～6h, obtain [MORBSA] [HSO with above-mentioned 1-alkyl-3-(butyl-4-sulfonic group) equimolar vitriol oil of alkylbenzyldimethylasaltsum saltsum
4] ionic liquid; The gained ionic liquid is with ether washing 2～4 times, removes to revolve to steam behind the nonionic resistates and removes ether;
The 2nd step acetylization reaction
At room temperature, [the MORBSA] [HSO that in alcohol or phenol and diacetyl oxide mol ratio are 1: 1.0～4.0 solution, adds 0.5～1.0mol%
4] ionic liquid, room temperature reaction 1～10min, reaction finishes, and gets product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100463376A CN101121657A (en) | 2007-09-25 | 2007-09-25 | Method for catalyzing acetylization reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100463376A CN101121657A (en) | 2007-09-25 | 2007-09-25 | Method for catalyzing acetylization reaction |
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|---|---|
| CN101121657A true CN101121657A (en) | 2008-02-13 |
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|---|---|---|---|
| CNA2007100463376A Pending CN101121657A (en) | 2007-09-25 | 2007-09-25 | Method for catalyzing acetylization reaction |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391060A (en) * | 2011-09-20 | 2012-03-28 | 浙江大学 | Method for acetylating catalytic hydroxyl |
| CN102942478A (en) * | 2012-12-13 | 2013-02-27 | 河南省科学院高新技术研究中心 | Method for preparing phenylacetate by using ionic liquid |
| CN102952014A (en) * | 2011-08-24 | 2013-03-06 | 岳阳蓬诚科技发展有限公司 | Method for preparing ethylene glycol monomethyl ether acetate |
| CN105363492A (en) * | 2014-08-27 | 2016-03-02 | 湖南中创化工股份有限公司 | Catalyst used for synthesizing acetic ester through anhydride method and method for preparing acetic ester through catalyst |
| CN107376967A (en) * | 2017-06-27 | 2017-11-24 | 常州大学 | A kind of preparation method of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst |
| CN107603554A (en) * | 2017-09-08 | 2018-01-19 | 芜湖市创源新材料有限公司 | Cellulose modified polyurethane adhesive of a kind of rice straw and preparation method thereof |
| CN107619504A (en) * | 2017-09-08 | 2018-01-23 | 芜湖市创源新材料有限公司 | A kind of starch film of caprolactone grafting rice straw cellulose enhancing and preparation method thereof |
| CN107629316A (en) * | 2017-09-08 | 2018-01-26 | 芜湖市创源新材料有限公司 | Cellulose modified polypropylene expanded acoustic material of a kind of acetylation rice straw and preparation method thereof |
| CN111036298A (en) * | 2019-12-17 | 2020-04-21 | 华侨大学 | Preparation method and application of natural walnut shell powder sulfonic acid catalyst |
| CN112426374A (en) * | 2020-12-11 | 2021-03-02 | 黄科 | Biological fermentation face cream and preparation method thereof |
-
2007
- 2007-09-25 CN CNA2007100463376A patent/CN101121657A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952014A (en) * | 2011-08-24 | 2013-03-06 | 岳阳蓬诚科技发展有限公司 | Method for preparing ethylene glycol monomethyl ether acetate |
| CN102952014B (en) * | 2011-08-24 | 2015-09-09 | 北京北科博源科技有限公司 | A kind of method preparing ethylene glycol monomethyl ether acetate |
| CN102391060A (en) * | 2011-09-20 | 2012-03-28 | 浙江大学 | Method for acetylating catalytic hydroxyl |
| CN102391060B (en) * | 2011-09-20 | 2013-10-23 | 浙江大学 | Method for acetylating catalytic hydroxyl |
| CN102942478A (en) * | 2012-12-13 | 2013-02-27 | 河南省科学院高新技术研究中心 | Method for preparing phenylacetate by using ionic liquid |
| CN105363492A (en) * | 2014-08-27 | 2016-03-02 | 湖南中创化工股份有限公司 | Catalyst used for synthesizing acetic ester through anhydride method and method for preparing acetic ester through catalyst |
| CN107376967A (en) * | 2017-06-27 | 2017-11-24 | 常州大学 | A kind of preparation method of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst |
| CN107376967B (en) * | 2017-06-27 | 2019-11-12 | 常州大学 | A kind of preparation method of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst |
| CN107603554A (en) * | 2017-09-08 | 2018-01-19 | 芜湖市创源新材料有限公司 | Cellulose modified polyurethane adhesive of a kind of rice straw and preparation method thereof |
| CN107619504A (en) * | 2017-09-08 | 2018-01-23 | 芜湖市创源新材料有限公司 | A kind of starch film of caprolactone grafting rice straw cellulose enhancing and preparation method thereof |
| CN107629316A (en) * | 2017-09-08 | 2018-01-26 | 芜湖市创源新材料有限公司 | Cellulose modified polypropylene expanded acoustic material of a kind of acetylation rice straw and preparation method thereof |
| CN111036298A (en) * | 2019-12-17 | 2020-04-21 | 华侨大学 | Preparation method and application of natural walnut shell powder sulfonic acid catalyst |
| CN112426374A (en) * | 2020-12-11 | 2021-03-02 | 黄科 | Biological fermentation face cream and preparation method thereof |
| CN112426374B (en) * | 2020-12-11 | 2023-11-28 | 苍南老中医化妆品有限公司 | Biological fermentation face cream and preparation method thereof |
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Open date: 20080213 |