CN102189000B - Preparation method for bifunctional proline ionic liquid catalyst - Google Patents
Preparation method for bifunctional proline ionic liquid catalyst Download PDFInfo
- Publication number
- CN102189000B CN102189000B CN2011100845502A CN201110084550A CN102189000B CN 102189000 B CN102189000 B CN 102189000B CN 2011100845502 A CN2011100845502 A CN 2011100845502A CN 201110084550 A CN201110084550 A CN 201110084550A CN 102189000 B CN102189000 B CN 102189000B
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- proline
- liquid catalyst
- difunctional
- vacuum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method for a bifunctional proline ionic liquid catalyst, and belongs to the field of organic chemical synthesis. The method comprises the following steps: weighing L-proline and halogen acid according to a certain mol ratio, continuously stirring the mixture for reaction for 2 hours at room temperature, evaporating water and halogen acid by reducing pressure,putting the resultant in a vacuum drying oven, heating the resultant for 1 hour to 2 hours at a temperature of 80 DEG C in vacuum, respectively evenly mixing the product with CuI, ZnCl2, FeCl3, CuCl2, or MgCl2 according to a mol ratio of 1:2 to 2:1, and heating and drying the mixture at a temperature of 80 DEG C for 1.5 to 2 hours in vacuum so as to obtain an evenly dispersed bifunctional prolineionic liquid catalyst. The ionic liquid catalyst in the invention has high stability and activity, the reagents used are cheap, and the catalyst can be recovered and reused in a reaction while the properties of the catalyst maintain the same.
Description
Technical field:
The invention belongs to the synthetic field of organic chemistry, be specifically related to a kind of preparation method of difunctional proline ionic liquid catalyst.
Background technology:
Chemical industry also becomes the main source of environmental pollution when promoting the human society develop rapidly.In recent years, " Green Chemistry " causes the increasing concern of scientific circles, and the optimization of chemical reaction catalyst and solvent is become an of paramount importance ring in the Green Chemistry.The rise of Green Chemistry has directly promoted the appearance of ionic liquid research boom; Ionic liquid (ionic liquid) is as a kind of new chemical reaction solvent; Being described as 21 century cleans one of optimal reaction medium in the green industry; Because it has the characteristic that is different from molecular solvent; In chemical reaction, demonstrate unique advantage, have remarkable advantages improving the aspects such as recycle of reaction rate, be used for widely replacing traditional molecular solvent and become new reaction medium with selectivity and optimization catalyst.In recent years, ionic liquid demonstrates great potential at catalytic field again, and some reactions with alternative other organic catalysts of ionic-liquid catalyst have the reaction yield height, are easy to separate and recycle repeatedly and the still good characteristic of catalytic activity.Therefore, ionic liquid more and more receives people's attention as a kind of novel reaction media and catalyst.
Summary of the invention:
First aspect purpose of the present invention is to provide a kind of preparation method of difunctional proline ionic liquid catalyst.
The technical scheme that the present invention takes for the realization above-mentioned purpose is following,
A kind of preparation method of difunctional proline ionic liquid catalyst is characterized in that, may further comprise the steps: the L-proline and the halogen acids that take by weighing certain mol proportion; At room temperature continue stirring reaction 2 hours; Pressure reducing and steaming water and halogen acids are placed on vacuum drying chamber again, and vacuum heated 1-2 hour down for 80 ℃; Obtain the proline ionic liquid; Proline ionic liquid and lewis acid are mixed, at 80 ℃ of following heat drying 1.5～2h of vacuum, obtain finely dispersed difunctional proline ionic liquid catalyst again.
More excellent is:
Described lewis acid is selected from CuI, ZnCl
2, FeCl
3, CuCl
2Or MgCl
2
Described proline ionic liquid and lewis acid 1:2～2:1 in molar ratio mix.
Reaction scheme of the present invention is following:
The difunctional proline ionic liquid catalyst that adopts said method to make; Owing to have Br nsted and Lewis acid centre simultaneously; Have advantages of higher stability and activity, and the agents useful for same price is all very cheap, can in reaction, repeats reclaim to use and property retention is constant.
Another aspect of the present invention purpose is to provide a kind of difunctional proline ionic liquid catalyst of above-mentioned preparation; Sub-alkene and alkylamine carry out the application in the azepine Michael addition reaction by short of electricity in catalysis; It is characterized in that; The difunctional proline ionic liquid catalyst that uses method for preparing to obtain carries out catalysis, and the sub-alkene of described short of electricity is methyl acrylate, butyl acrylate or methyl methacrylate; Alkylamine is diethylamine, morphine quinoline, piperidines or isopropylamine.
The catalytic reaction equation is following:
。
Difunctional proline ionic liquid catalyst of the present invention; When the above-mentioned reaction of catalysis, have advantages of higher stability and activity, and after the catalytic reaction that repeatedly circulates; The catalytic activity of difunctional proline ionic liquid catalyst does not have obvious reduction, the advantage that have green, environmental protection, can be recycled.
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is described further.
Description of drawings:
Fig. 1 is the infared spectrum (FT-IR 5DX type infrared spectrometer (U.S. Nicolet company), attenuate total reflection (ATR)) of the difunctional proline ionic liquid of the embodiment of the invention 1;
Fig. 2 is the product gas chromatogram (Tianjin, island GC-14CPTF gas chromatograph, Rtx-1 30mx0.25mmX0.25um) of the difunctional ionic liquid catalyst reaction of CuI for lewis acid in the embodiment of the invention 3;
Fig. 3 is recycling the influence that Michael is reacted for the difunctional proline ionic liquid of the embodiment of the invention 1.
The specific embodiment:
Embodiment 1:
Take by weighing L-proline (Proline) 11.5g (0.1mol) and 40% hydrobromic acid 21g (0.11mol), slowly drip 40% hydrobromic acid under the stirring at room, dripped off in 30 minutes.At room temperature continued stirring reaction 2 hours; Pressure reducing and steaming water and hydrobromic acid obtain weak yellow liquid, are placed on vacuum drying chamber again, heating in vacuum (80 ℃) 1-2 hour; Proline ionic liquid that obtains and 9.5g CuI is even with the mixed in molar ratio of 2:1; Be the khaki viscous fluid, 80 ℃ of heat drying 1.5-2h of vacuum obtain finely dispersed difunctional proline ionic liquid (CuI/Proline (1:2) ionic liquid) again.The CuI/Proline that makes (1:2) ionic liquid is carried out the infared spectrum analysis, and the infared spectrum of CuI/Proline (1:2) ionic liquid shows as shown in Figure 1, among the figure: 1460 cm
-1Be that pyridine adsorption is in Lewis acid, and at 1630,1640 cm
-1The flexural vibrations absworption peak at place is to be adsorbed in the Br nsted acid, explains that to comprise Lewis acid in the structure of this catalyst sour with Br nsted.
Embodiment 2:
Take by weighing L-proline 11.5 g (0. 1mol) and hydroiodic acid 14 g (0.11mol), slowly drip hydroiodic acid under the stirring at room, dripped off in 10 minutes.At room temperature continued stirring reaction 2 hours; Pressure reducing and steaming water and hydroiodic acid obtain weak yellow liquid, are placed on vacuum drying chamber again, heating in vacuum (80 ℃) 1-2 hour; Proline ionic liquid that obtains and 19g CuI is even with the mixed in molar ratio of 1:1; Be the khaki viscous fluid, 80 ℃ of heat drying 1.5-2h of vacuum obtain finely dispersed difunctional proline ionic liquid again.
Embodiment 3:
With methyl acrylate (0.12 mol), diethylamine (0.1mol) and difunctional proline ionic liquid (1% mol) (proline ionic liquid and lewis acid mol ratio are 2:1); At room temperature stirring reaction 1-5 minute; Carry out azepine Michael addition reaction, its experimental data sees the following form.
The catalytic reaction effect of table 1 different catalysts under the differential responses time
It is as shown in Figure 2 that the ion liquid catalytic effect of CuI/Proline among the embodiment 3 (1:2) carries out gas chromatographic analysis, and among Fig. 2: the peak about 3.1 minutes is excessive methyl acrylate, and the peak about 5.9 minutes is the chromatographic peak of product.
Embodiment 4:
With the ionic liquid catalyst for preparing among the embodiment 1; After once using; Separate through centrifugal separatory, after reclaiming with acetone (5mL) washing back decompression distillation, the azepine Michael addition reaction of circulation catalysis diethylamine and methyl acrylate (1:1.2); Catalytic activity does not have obvious reduction, and its catalytic effect is as shown in Figure 3.
Claims (1)
1. the preparation method of a difunctional proline ionic liquid catalyst is characterized in that, may further comprise the steps: take by weighing the L-proline of 0.1mol and the halogen acids of 0.11mol; At room temperature continue stirring reaction 2 hours; Pressure reducing and steaming water and halogen acids are placed on vacuum drying chamber again, and vacuum heated 1-2 hour down for 80 ℃; Obtain the proline ionic liquid; Proline ionic liquid and lewis acid are mixed, and described proline ionic liquid and lewis acid 1:2～2:1 in molar ratio mix, and described lewis acid is CuI, ZnCl
2, FeCl
3, CuCl
2Or MgCl
2, at 80 ℃ of following heat drying 1.5～2h of vacuum, obtain finely dispersed difunctional proline ionic liquid catalyst again.
2
.Sub-alkene and alkylamine carry out the application in the azepine Michael addition reaction to the difunctional proline ionic liquid catalyst of the said method of a kind of claim 1 preparation by short of electricity in catalysis.
3
.Sub-alkene and alkylamine carry out the application in the azepine Michael addition reaction to the difunctional proline ionic liquid catalyst of the said method of a kind of claim 1 preparation by short of electricity in catalysis, and it is characterized in that: the sub-alkene of described short of electricity is methyl acrylate, butyl acrylate or methyl methacrylate; Alkylamine is diethylamine, morphine quinoline, piperidines or isopropylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100845502A CN102189000B (en) | 2011-04-06 | 2011-04-06 | Preparation method for bifunctional proline ionic liquid catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100845502A CN102189000B (en) | 2011-04-06 | 2011-04-06 | Preparation method for bifunctional proline ionic liquid catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102189000A CN102189000A (en) | 2011-09-21 |
| CN102189000B true CN102189000B (en) | 2012-11-07 |
Family
ID=44598400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100845502A Expired - Fee Related CN102189000B (en) | 2011-04-06 | 2011-04-06 | Preparation method for bifunctional proline ionic liquid catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102189000B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621152A (en) * | 2004-10-11 | 2005-06-01 | 北京大学 | Ion liquid of amino acid ester cation and its preparation method |
| CN1631539A (en) * | 2004-12-03 | 2005-06-29 | 北京大学 | Amino acid salt ion liquid and its preparation |
| CN101050195A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Compound of containing cation radical of L - proline, preparation method, and application |
| CN101050196A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Bronsted acidic compound of containing L- proline radical, preparation method, and application |
-
2011
- 2011-04-06 CN CN2011100845502A patent/CN102189000B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621152A (en) * | 2004-10-11 | 2005-06-01 | 北京大学 | Ion liquid of amino acid ester cation and its preparation method |
| CN1631539A (en) * | 2004-12-03 | 2005-06-29 | 北京大学 | Amino acid salt ion liquid and its preparation |
| CN101050195A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Compound of containing cation radical of L - proline, preparation method, and application |
| CN101050196A (en) * | 2007-05-15 | 2007-10-10 | 武汉大学 | Bronsted acidic compound of containing L- proline radical, preparation method, and application |
Non-Patent Citations (2)
| Title |
|---|
| 柳文敏 等，."L_脯氨酸离子液催化苹果酯的合成".《南阳师范学院学报》.2010,第9卷(第9期),第27-30页. |
| 柳文敏 等,."L_脯氨酸离子液催化苹果酯的合成".《南阳师范学院学报》.2010,第9卷(第9期),第27-30页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102189000A (en) | 2011-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Karami et al. | Novel silica tungstic acid (STA): Preparation, characterization and its first catalytic application in synthesis of new benzimidazoles | |
| Barroso-Bogeat et al. | FT-IR analysis of pyrone and chromene structures in activated carbon | |
| van Kalkeren et al. | In situ phosphine oxide reduction: a catalytic Appel reaction | |
| CN104974750B (en) | Method for preparing carbon quantum dots by virtue of polyethyleneimine decomposition | |
| CN106631649A (en) | Method for preparing deuterated chemicals and deuterated chemicals | |
| CN101168493B (en) | Preparation method for fluorochlorobenzene | |
| CN104549495A (en) | Activated carbon immobilized ionic liquid catalyst and application thereof | |
| CN104479134B (en) | Block polysiloxane polymer and pigment dispersant containing same | |
| CN106492754A (en) | A kind of preparation method of adsorbent, method of modifying and application | |
| CN102189000B (en) | Preparation method for bifunctional proline ionic liquid catalyst | |
| CN108314671B (en) | Porous zirconium pyrophosphate catalyst and its application in pepper aldehyde hydrogenation reaction | |
| CN103214328B (en) | Synthesis method for alpha-bromo-aromatic ketone compounds | |
| CN104262227B (en) | A method of preparing (S) -1- (2- chloracetyls) pyrrolidines -2- formonitrile HCNs | |
| CN109438409A (en) | A kind of method of synthesizing annular carbonate | |
| CN105859761B (en) | A kind of aromatic boronic acid ester composite synthetic method | |
| Ambler et al. | Copper-catalyzed decarboxylative trifluoromethylation of propargyl bromodifluoroacetates | |
| CN103897753A (en) | Method for preparing biological aircraft fuel by using mesoporous molecular sieve | |
| CN104356176A (en) | Preparation method of tannins ether stearate | |
| CN106008309B (en) | A kind of method that visible light catalytic prepares Isatine derivatives | |
| CN106242947B (en) | A kind of method using cerium modified zirconium-silicon molecular sieve catalyst preparation dichlorohydrin | |
| Fairlamb et al. | Suzuki-Miyaura cross-couplings mediated by trans-PdBr (N-succ)(PPh3) 2: A convenient synthetic method for diarylmethanes and aryl (heteroaryl) methanes | |
| CN102134320B (en) | Preparation method of organic silicon methoxy/ethoxy high boiling silicone oil | |
| CN105646134B (en) | A kind of method of high selectivity iodine benzene-like compounds | |
| CN109456160A (en) | A kind of method of photochemical catalytic oxidation fracture lignin model compound | |
| CN103387592B (en) | A kind of preparation method of ruthenium complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121107 Termination date: 20150406 |
|
| EXPY | Termination of patent right or utility model |