CN1384091A - Clean method of esterifying halide - Google Patents
Clean method of esterifying halide Download PDFInfo
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- CN1384091A CN1384091A CN 02119563 CN02119563A CN1384091A CN 1384091 A CN1384091 A CN 1384091A CN 02119563 CN02119563 CN 02119563 CN 02119563 A CN02119563 A CN 02119563A CN 1384091 A CN1384091 A CN 1384091A
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- ionic liquid
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Abstract
The present invention is characterized by that ionic liquid containing cationic azacyclic compound alkyl pyridine or 1,3-dimethyl imidazole and organic or inorganic anionic compound is used as catalyst and reaction medium for the reaction of halide and alkali metal salt of organic acid. Compared with conventional phase transferring catalytic process, the present invention has the features of no use of organic solvent and water, fast esterification speed, reliatively lower reaction temperature, good separation between the product and ionic liquid, high product purity, reuse of the ionic liquid and great industrial application foreground.
Description
Technical field
The ionic liquid that the present invention relates to a kind of high-efficiency cleaning is as reaction medium and catalyst halogenide and organic acid alkali metal salt esterification process.
Technical background
Halohydrocarbon is multiple ester class synthetic effective ways with the synthetic corresponding ester compound of organic carboxyl acid an alkali metal salt effect.Because most of organic acid salt has certain water-soluble, be insoluble to organic solvent, and halohydrocarbon is water insoluble, with multiple immiscible organic solvent, so be difficult to find a kind of molten the two solvent of effectively holding concurrently to carry out esterification.Become the effective ways of realizing this reaction by the phase-transfer catalysis process that water and organic solvent and phase-transfer catalyst constituted.But, in these class methods, tradition phase-transfer catalysis process ubiquity that temperature of reaction height, efficient are low, the product purity finite sum uses problems such as toxic organic solvent, the exploitation low toxicity, method of esterifying halide not only has important economic benefit efficiently, but also has good benefits in environment.
In recent years, eco-friendly catalyst system provided more wide space to ionic liquid at room temperature for people explore.Room-temperature ion liquid itself has excellent chemistry and thermodynamic stability, many materials is all had good solvency power, and at room temperature have vapour pressure hardly, and this makes to be applied in and has had the characteristic of being convenient to product separation and catalyst recovery in the catalyzed reaction concurrently.At present, various countries scholar and researchist have realized much having the catalyzed reaction of important economic worth effectively in ionic liquid.
Summary of the invention
The objective of the invention is to replace traditional phase-transfer catalysis method of esterifying halide, a kind of efficient and eco-friendly reaction medium and catalyzer are provided, under the reaction conditions of gentleness, the esterification of catalytic halogenation thing and organic acid alkali metal salt.
Method of the present invention, it is characterized in that using nitrogen-containing heterocycle compound positively charged ion and ionic liquid inorganic or that organic anion constitutes to be reaction medium and catalyzer, at normal pressure, 40 to 100 ℃ of temperature of reaction, in 1 to 3 hour reaction times, catalytic halogenation thing and organic acid alkali metal salt action are produced corresponding ester.
Nitrogen-containing heterocycle compound positively charged ion of the present invention and ionic liquid reaction medium and catalyzer inorganic or that organic anion constitutes is characterized in that the nitrogen-containing heterocycle compound positively charged ion is alkyl pyridine or 1, and 3-dialkylimidazolium positively charged ion, alkyl chain length are C
1To C
6
Nitrogen-containing heterocycle compound positively charged ion of the present invention and ionic liquid reaction medium and catalyzer inorganic or that organic anion constitutes is characterized in that inorganic or organic anion is that tetrafluoro closes borate, hexafluoro closes phosphate radical, chlorine aluminate, trifluoracetic acid root, acetate, nitrate radical, nitrite anions, tosic acid root, Phenylsulfonic acid root, trifluoromethanesulfonic acid root, sulfate radical, perchlorate, chlorion, bromide anion, iodide ion.
Method of the present invention is characterized in that employed halogenide is benzyl chloride, epoxy chloropropane, chlorallylene, chloracetate.
Method of the present invention is characterized in that employed organic acid alkali metal salt is sodium acetate trihydrate.
Method of the present invention is characterized in that organic acid alkali metal salt and halogenide mol ratio are 1: 2 to 5: 1, and ionic liquid and halid volume ratio are 2: 1 to 5: 1.
The present invention realizes by following measure:
Ion liquid typical production used in the present invention is: get equimolar bromination 1, after 3-dialkylimidazolium salt and sodium tetrafluoroborate mix, normal temperature stirred 24 hours down in proper amount of acetone, remove insoluble solid, steam and remove acetone, kept 1 to 3 hour under 80 ℃ of vacuum, promptly obtain a kind of limpid liquid that at room temperature is in a liquid state, be Tetrafluoroboric acid 1,3-dialkylimidazolium ionic liquid at room temperature.Ion liquid synthesizing of other kinds can be with reference to reference (Huddleston JG, Visser A E, Reichert W M, Willauer H D, Broker G A, RogersR D, Green Chem.2001,3,156).
The process of this esterification process is: in three neck round-bottomed flasks of mechanical stirring, reflux condensing tube and thermometer are housed, add halogenide, organic acid alkali metal salt and ionic liquid successively.Wherein, organic metal salt and halogenide mol ratio are 1: 2 to 5: 1, and ionic liquid and halid volume ratio are 2: 1 to 5: 1.At normal pressure, vigorous stirring is 1 to 3 hour under 40 ℃ to the 100 ℃ conditions then.Stop heating, cool to below 25 ℃, left standstill 20 to 30 minutes.Because formed ester is insoluble with ionic liquid, with the ionic liquid natural layering, remove the esterification products on upper strata and the solid that bottom is separated out, behind the 30 minutes purifying of finding time under in 80 to 100 ℃ of the remaining ionic liquids, can reuse.
The present invention compares its substantial characteristics with the synthetic ester of traditional phase-transfer catalysis esterification process:
1. not making water and other organic solvent, is an eco-friendly reaction process;
2. it is lower to have higher esterification ability and temperature of reaction, has reduced energy consumption;
3. esterification products and ionic liquid AUTOMATIC ZONING make sepn process become more easy;
4. the ionic liquid that reacted through 80 to 100 ℃ of following evacuation processes numbers minute, can reuse.
In the embodiment embodiment 1:. ionic liquid synthetic (the comparing) of Benzyl Acetate with the phase-transfer catalysis method
Get Tetrafluoroboric acid 1-methyl-3-ethyl imidazol(e) ([EMIm] BF
4) ionic liquid 50ml, add 0.22mol benzyl chloride and 0.31mol sodium-acetate, after 2 hours, be cooled to room temperature in 60 ℃ of following stirring reactions, use the HP1790 gas chromatograph to carry out qualitative and quantitative analysis.
Simultaneously, replace ionic liquid with isopyknic water, add 0.005mol Tetrabutylammonium bromide (TBAB) and benzyl trimethyl ammonium chloride (BTMAC) respectively as catalyzer, reaction is 4 hours under 60 ℃ of conditions, analyzes after the cooling.Concrete reaction result is listed in table 1.
In table 1. ionic liquid synthetic (the comparing) of Benzyl Acetate with the phase-transfer catalysis method
Embodiment 2: in the ionic liquid synthetic (the comparing with the phase-transfer catalysis method) of acetic acid allyl ester
| Catalyst system | Reaction times (h) | Benzyl chloride transformation efficiency (%) | Benzyl Acetate selectivity (%) |
| ????[EMIm]BF 4 | ????2 | ????100 | ????99 |
| TBAB/ water | ????4 | ????49 | ????85 |
| BTMAC/ water | ????4 | ????18 | ????88 |
Replace the 0.22mol benzyl chloride with the 0.22mol propenyl chloride, all the other are with embodiment 1.Reaction result is listed in table 2.
In table 2. ionic liquid synthetic (the comparing) of acetic acid allyl ester with the phase-transfer catalysis method
Embodiment 3: the esterification of different ionic liquid catalysis benzyl chloride prepares the Benzyl Acetate reactivity worth relatively
| Catalyst system | Reaction times (h) | Benzyl chloride transformation efficiency (%) | Benzyl Acetate selectivity (%) |
| ????[EMIm]BF 4 | ????2 | ????100 | ????99 |
| TBAB/ water | ????8 | ????34 | ????88 |
| BTMAC/ water | ????12 | ????17 | ????88 |
Use Tetrafluoroboric acid 1-methyl-3-butyl imidazole ([BMIm] BF respectively
4), nitric acid 1-methyl-3-ethyl imidazol(e) ([EMIm] NO
3), phosphofluoric acid 1-methyl-3-butyl imidazole ([BMIm] PF
6), Tetrafluoroboric acid 1-methyl-3-hexyl imidazoles ([HMIm] BF
4), Tetrafluoroboric acid 1-butyl-pyridinium ([BPy] BF
4) replacement Tetrafluoroboric acid 1-methyl-3-ethyl imidazol(e) ([EMIm] BF
4), all the other are with embodiment 1.Reaction result is listed in table 3.
Synthetic vinegar acid benzyl ester reactivity worth relatively in table 3. different ionic liquid
Embodiment 4: ionic liquid synthetic vinegar acid benzyl ester repeat performance
| Ionic liquid | Benzyl chloride transformation efficiency (%) | Benzyl Acetate selectivity (%) |
| ????[BMIm]BF 4 | ????99 | ????99 |
| ????[EMIm]NO 3 | ????99 | ????99 |
| ????[BMIm]PF 6 | ????61 | ????96 |
| ????[HMIm]BF 4 | ????98 | ????99 |
| ????[BPy]BF 4 | ????65 | ????99 |
Ionic liquid reaction back among the embodiment 1 was 100 ℃ of following underpressure distillation 15 minutes, and the reinforced once more esterification that repeats circulates nine times, the results are shown in table 4.
The synthetic vinegar acid benzyl ester is reused the result in table 4. ionic liquid
| Cycle index | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ????9 |
| Benzyl chloride transformation efficiency (%) | ????99 | ????99 | ????98 | ????99 | ????97 | ????98 | ????99 | ????98 | ????97 |
| Benzyl Acetate selectivity (%) | ????99 | ???100 | ???100 | ????98 | ????99 | ????97 | ????98 | ????98 | ????97 |
Claims (6)
1. the halogenide of a cleaning and organic acid alkali metal salt esterification process, it is characterized in that using nitrogen-containing heterocycle compound positively charged ion and ionic liquid inorganic or that organic anion constitutes to be catalyzer and reaction medium, at normal pressure, 40 to 100 ℃ of temperature of reaction, in 1 to 3 hour reaction times, catalytic halogenation thing and organic acid alkali metal salt action are produced corresponding ester.
2. the method for claim 1 is characterized in that the nitrogen-containing heterocycle compound positively charged ion is alkyl pyridine or 1, the 3-dialkylimidazolium, and alkyl chain length is C
1To C
6
3. the method for claim 1 is characterized in that inorganic or organic anion is that tetrafluoro closes borate, hexafluoro closes phosphate radical, chlorine aluminate, trifluoracetic acid root, acetate, nitrate radical, nitrite anions, tosic acid root, Phenylsulfonic acid root, trifluoromethanesulfonic acid root, sulfate radical, perchlorate, chlorion, bromide anion, iodide ion.
4. the method for claim 1 is characterized in that employed halogenide is benzyl chloride, epoxy chloropropane, chlorallylene, chloracetate.
5. the method for claim 1 is characterized in that employed organic acid alkali metal salt is sodium acetate trihydrate.
6. the method for claim 1 is characterized in that organic metal salt and halogenide mol ratio are 1: 2 to 5: 1, and ionic liquid and halid volume ratio are 2: 1 to 5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02119563 CN1384091A (en) | 2002-05-25 | 2002-05-25 | Clean method of esterifying halide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02119563 CN1384091A (en) | 2002-05-25 | 2002-05-25 | Clean method of esterifying halide |
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|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006219477A (en) * | 2005-01-17 | 2006-08-24 | Sumitomo Chemical Co Ltd | Method for producing carboxylic ester |
| CN100427568C (en) * | 2003-12-18 | 2008-10-22 | 石油大学(北京) | Ion liquid solvent for dissolving and removing asphaltene deposit and preparing method thereof, and method for removing asphaltene and regeneration method of the ion liquid solvent |
| GB2482525A (en) * | 2010-08-05 | 2012-02-08 | Phoenix Chemicals Ltd | A process for the production of acyloxymethyldioxanylacetic derivatives |
| CN103242139A (en) * | 2013-05-22 | 2013-08-14 | 南京工业大学 | Method for preparing 2-methyl allyl alcohol by esterification and hydrolysis |
| CN108409964A (en) * | 2018-05-18 | 2018-08-17 | 东华大学 | Using ionic liquid as poly ion liquid of skeleton and preparation method thereof |
-
2002
- 2002-05-25 CN CN 02119563 patent/CN1384091A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427568C (en) * | 2003-12-18 | 2008-10-22 | 石油大学(北京) | Ion liquid solvent for dissolving and removing asphaltene deposit and preparing method thereof, and method for removing asphaltene and regeneration method of the ion liquid solvent |
| JP2006219477A (en) * | 2005-01-17 | 2006-08-24 | Sumitomo Chemical Co Ltd | Method for producing carboxylic ester |
| GB2482525A (en) * | 2010-08-05 | 2012-02-08 | Phoenix Chemicals Ltd | A process for the production of acyloxymethyldioxanylacetic derivatives |
| CN103242139A (en) * | 2013-05-22 | 2013-08-14 | 南京工业大学 | Method for preparing 2-methyl allyl alcohol by esterification and hydrolysis |
| CN103242139B (en) * | 2013-05-22 | 2015-07-01 | 南京工业大学 | Method for preparing 2-methyl allyl alcohol by esterification and hydrolysis |
| CN108409964A (en) * | 2018-05-18 | 2018-08-17 | 东华大学 | Using ionic liquid as poly ion liquid of skeleton and preparation method thereof |
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