CN101811917A - Application of L-arginine used as catalyst in Knoevenagel reaction adopting ionic liquid as medium - Google Patents
Application of L-arginine used as catalyst in Knoevenagel reaction adopting ionic liquid as medium Download PDFInfo
- Publication number
- CN101811917A CN101811917A CN200910191236A CN200910191236A CN101811917A CN 101811917 A CN101811917 A CN 101811917A CN 200910191236 A CN200910191236 A CN 200910191236A CN 200910191236 A CN200910191236 A CN 200910191236A CN 101811917 A CN101811917 A CN 101811917A
- Authority
- CN
- China
- Prior art keywords
- reaction
- aldehyde
- ionic liquid
- application
- arginine
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the application of L-arginine used as a catalyst in a Knoevenagel reaction adopting ionic liquid as a medium. The L-arginine has the advantages of good catalytic activity, moderate reaction condition, simple operation, short reaction time, no environmental pollution, recycling use, low reaction cost, wide range of application of substrate, and the like.
Description
Technical field
The present invention relates to a kind of new application of compound, particularly the L-arginine in Knoevenagel (Borneo camphor Wen Gaier) reaction that with the ionic liquid is medium as Application of Catalyst.
Background technology
Ionic liquid has caused people's extensive concern as the novel green solvent of alternative existing volatile organic solvent.Because ionic liquid is non-volatile, not flammable, electroconductibility is strong, viscosity is low, thermal capacitance is big, vapour pressure is little, stable in properties, and many inorganic salt and organism are had good solubility, demonstrates good prospects for application in sepn process and chemical reaction field.The Knoevenagel of aldehyde and active methylene compound reaction is the important method that forms carbon-carbon double bond in the organic synthesis, is subjected to people's great attention for a long time, is widely used in synthetic fields such as fine chemistry industry such as spices, medicine, prepolymers.Research is the Knoevenagel reaction of medium with the ionic liquid, meets the requirement of current Green Chemistry, has important science and using value.
Knoevenagel reaction catalyzer commonly used has alkali, zeolite, clay, double-deck oxyhydroxide (LDHs), hydrotalcite, Lewis acid as TiCl
4, ZnCl
2, CeCl
37H
2O/NaI and HClO
4-SiO
2Deng.The Knoevenagel reaction report that with amino acid is catalyzer is less, rarely seen two seed amino acids (being respectively L-proline(Pro) and L-glycine) are reported as Application of Catalyst in the Knoevenagel reaction that with the ionic liquid is medium at present, but report shows simultaneously, L-proline(Pro) catalysis Knoevenagel reaction needed is carried out under hot conditions, and there are deficiencies such as long reaction time in the catalysis of L-glycine.
Summary of the invention
In view of this, for overcoming the deficiencies in the prior art, the object of the present invention is to provide the L-arginine in the Knoevenagel reaction that with the ionic liquid is medium as Application of Catalyst, have that catalytic activity is good, reaction conditions is gentle, advantages such as simple to operate, reaction times weak point, environmentally safe, recyclable repeated use, reaction cost are low, wide application range of substrates.
For reaching this purpose, the invention provides the L-arginine in the Knoevenagel reaction that with the ionic liquid is medium as Application of Catalyst.
Further, described Knoevenagel reaction is aromatic aldehyde, heteroaromatic aldehyde or α, the reaction between beta-unsaturated aldehyde and propane dinitrile or the methyl ethyl diketone, and reaction product is α, alpha, beta-unsaturated nitriles or alpha, beta-unsaturated esters;
Further, described ionic liquid is 1-ethyl-3-Methylimidazole sulfovinic acid;
Further, described L-arginine and aromatic aldehyde, heteroaromatic aldehyde or α, the mol ratio of beta-unsaturated aldehyde is 0.2～0.3: 1;
Further, the described temperature that is reflected at is to carry out under 15～35 ℃ of conditions.
Beneficial effect of the present invention is: in the Knoevenagel reaction that with the ionic liquid is medium, adopt the L-arginine as catalyzer, have cheap and easy to get, safety non-toxic, catalytic activity is good, reaction conditions is gentle, simple to operate, the reaction times short, the product yield advantages of higher; And L-arginine and ionic liquid only need simple extraction, can reclaim repeated use repeatedly except that water treatment, and catalytic activity does not have obvious reduction, thereby reduce reaction cost, minimizing environmental pollution greatly; In addition, the catalytic wide application range of substrates of L-arginine, when aldehyde is aromatic aldehyde, heteroaromatic aldehyde or α, beta-unsaturated aldehyde, when active methylene compound is active stronger propane dinitrile or active more weak methyl ethyl diketone, all can obtain reaction result preferably, products therefrom α, alpha, beta-unsaturated nitriles or alpha, beta-unsaturated esters are important intermediate or the finished product in the field of fine chemical; Therefore, the L-arginine is very wide as the Application of Catalyst prospect in the Knoevenagel reaction that with the ionic liquid is medium.
Embodiment
In order to make the purpose, technical solutions and advantages of the present invention clearer, below the preferred embodiments of the present invention are described in detail.
In a preferred embodiment, raw material and reagent are commercially available product and without being further purified, adopt tlc (GF254 silica-gel plate) monitoring reaction process in the reaction, flash column chromatography (200～300 order silica gel) purification of target product, gained target product employing Bruker AV-300 type nmr determination proton nmr spectra (1HNMR) and carbon-13 nmr spectra (
13CNMR), Varian 7.0T type electro-spray ionization fourier transform ion cyclotron resonance mass spectrometer (ICR) (ESI-FTICR-MS) is measured high resolution mass spectrum (HRMS).Compare for ease of the result, in the preferred embodiment " room temperature " all be controlled at 25 ± 1 ℃.
In research work, be model substrates at first with p-met hoxycinnamic aldehyde and methyl ethyl diketone, be medium with ionic liquid 1-ethyl-3-Methylimidazole sulfovinic acid, investigated 20 kinds of catalytic activitys that natural amino acid reacts Knoevenagel.The results are shown in Table 1.
Table 1 different aminoacids is to the catalytic activity of the Knoevenagel reaction of p-met hoxycinnamic aldehyde and methyl ethyl diketone
A: the product yield behind the flash column chromatography purifying.
As shown in Table 1, when adding amino acid in the reaction, partial amino-acid demonstrates good catalytic activity, and wherein the catalytic activity of L-proline(Pro) is best, product yield the highest (85%); L-tryptophane, L-Methionin are close with the arginic catalytic activity of L-, product yield higher (77～78%); The very approaching altheine of structure has extremely different catalytic activitys with L-glutaminate, and product yield is respectively 31% and 0; Other amino acid whose poor catalytic activity, product yield low (≤31%).As if because of L-Methionin and L-arginine are basic aminoacids, above-mentioned reaction result points out amino acid whose alkalescence that catalytic activity is had considerable influence, but the L-Histidine that is similarly basic aminoacids does not provide analog result, and its product yield is 0; And the product yield that contains the L-tryptophane of indole ring in the structure is higher than the L-Histidine that contains imidazole ring in the structure far away, and well-known, the alkalescence of indole ring is weaker than imidazole ring, therefore, in general, amino acid whose alkalescence is not the principal element that influences catalytic activity.
According to above-mentioned result of study, with the L-arginine is catalyzer, with ionic liquid 1-ethyl-3-Methylimidazole sulfovinic acid is medium, select different aromatic aldehydes, heteroaromatic aldehyde or α, beta-unsaturated aldehyde and propane dinitrile or methyl ethyl diketone carry out the Knoevenagel reaction, with the versatility of verification method.
Embodiment 1～13, the catalysis of L-arginine are the Knoevenagel reaction of medium with the ionic liquid
To containing aldehyde (1mmol), propane dinitrile or methyl ethyl diketone (1～2mmol) with the reaction system of ionic liquid 1-ethyl-3-Methylimidazole sulfovinic acid (0.32g) in add L-arginine (0.2～0.3mmol), stirring reaction under the room temperature, adopt the tlc monitoring reaction to finishing, add methylene dichloride (10mL) dilute reaction solution, water (5ml) washing, water is used dichloromethane extraction (10mL * 2) again, merge organic phase, underpressure distillation removes and desolvates, promptly get target product, optionally available flash column chromatography (moving phase is the mixed solution of ethyl acetate and sherwood oil) carries out purifying.Reaction substrate, reaction times and product yield see table 2 for details.Products therefrom is used
1HNMR,
13CNMR and HRMS identify.
The catalysis of table 2L-arginine is the Knoevenagel reaction of medium with the ionic liquid
M among a: the embodiment 1～10: n: L-arginine (mol ratio)=1: 1: 0.2, m among the embodiment 11～13: n: L-arginine (mol ratio)=1: 2: 0.3;
B: embodiment 1～6 is without the flash column chromatography purifying but NMR shows the product yield of purity＞95%, and embodiment 7～13 is the product yield behind the flash column chromatography purifying.
As shown in Table 2: 1. aromatic aldehyde, heteroaromatic aldehyde or α, the Knoevenagel reaction of beta-unsaturated aldehyde and propane dinitrile or methyl ethyl diketone all can be carried out smoothly and obtain α, and alpha, beta-unsaturated nitriles or alpha, beta-unsaturated esters, yield are 45%～100%; 2. compare with the Knoevenagel reaction (embodiment 7～13) of methyl ethyl diketone and aldehyde, propane dinitrile reacts very fast (embodiment 1～6) with the Knoevenagel of identical aldehyde, its reason is: the electron-withdrawing power of cyano group is better than carbonyl, so the methylene radical in the propane dinitrile is active than the methylene radical in the methyl ethyl diketone, easier and aldehyde reacts; In the present invention, the Knoevenagel of propane dinitrile and aldehyde is reflected in 2～5 minutes and can finishes (embodiment 1～6), and according to nearest bibliographical information, glycine is catalytic to be the longer reaction times (2～100 minutes) of similar Knoevenagel reaction needed of medium with the ionic liquid; 3. when aldehyde is aromatic aldehyde or heteroaromatic aldehyde, the Knoevenagel reaction times of itself and propane dinitrile or methyl ethyl diketone is grown (embodiment 4～6,10～13), and work as aldehyde is α, during beta-unsaturated aldehyde, reaction times is lacked (embodiment 1～3,7～9), infer that its reason is the influence of steric effect, aldehyde radical carbon atom in aromatic aldehyde or the heteroaromatic aldehyde is than α, β-unsaturated aromatic aldehyde exists bigger sterically hindered, so the nucleophilic attack that is unfavorable for active methylene compound is the long time of reaction needed.
In research work, also investigated L-arginine and the ionic liquid repeat performance in the Knoevenagel reaction: with the L-arginine is catalyzer, with ionic liquid 1-ethyl-3-Methylimidazole sulfovinic acid is medium, after the Knoevenagel of p-met hoxycinnamic aldehyde and propane dinitrile reaction finishes, add the methylene dichloride dilute reaction solution, wash with water, water is used dichloromethane extraction again, collect water, underpressure distillation dewaters, resistates is L-arginine and ionic liquid, is directly used in next round Knoevenagel reaction.The results are shown in Table 3.
Table 3L-arginine and the ionic liquid repeat performance in the Knoevenagel of p-met hoxycinnamic aldehyde and methyl ethyl diketone reaction
A: without the flash column chromatography purifying but NMR shows the product yield of purity＞95%.
As shown in Table 3, L-arginine and ionic liquid are reused 5 times after simple extraction, removing water treatment, and its catalytic activity is not seen obvious reduction.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and the spirit and scope of the present invention that do not depart from appended claims and limited.
Claims (5)
1.L-arginine in the Knoevenagel reaction that with the ionic liquid is medium as Application of Catalyst.
2. the arginic application of L-according to claim 1, it is characterized in that: described Knoevenagel reaction is aromatic aldehyde, heteroaromatic aldehyde or α, the reaction between beta-unsaturated aldehyde and propane dinitrile or the methyl ethyl diketone, and reaction product is α, alpha, beta-unsaturated nitriles or alpha, beta-unsaturated esters.
3. the arginic application of L-according to claim 2 is characterized in that: described ionic liquid is 1-ethyl-3-Methylimidazole sulfovinic acid.
4. the arginic application of L-according to claim 3 is characterized in that: described L-arginine and aromatic aldehyde, heteroaromatic aldehyde or α, the mol ratio of beta-unsaturated aldehyde is 0.2～0.3: 1.
5. the arginic application of L-according to claim 4 is characterized in that: the described temperature that is reflected at is to carry out under 15～35 ℃ of conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910191236 CN101811917B (en) | 2009-10-27 | 2009-10-27 | Application of L-arginine used as catalyst in Knoevenagel reaction adopting ionic liquid as medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910191236 CN101811917B (en) | 2009-10-27 | 2009-10-27 | Application of L-arginine used as catalyst in Knoevenagel reaction adopting ionic liquid as medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101811917A true CN101811917A (en) | 2010-08-25 |
| CN101811917B CN101811917B (en) | 2013-08-21 |
Family
ID=42619308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910191236 Expired - Fee Related CN101811917B (en) | 2009-10-27 | 2009-10-27 | Application of L-arginine used as catalyst in Knoevenagel reaction adopting ionic liquid as medium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101811917B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728403A (en) * | 2012-07-17 | 2012-10-17 | 石家庄学院 | Organic solid base catalyst for synthesizing alpha-cyanoethyl cinnamate, and preparation method and application thereof |
| CN103204845A (en) * | 2013-03-12 | 2013-07-17 | 西北大学 | Imidazolyl ionic liquid, and synthesizing method and application thereof |
| CN104356045A (en) * | 2014-09-29 | 2015-02-18 | 西南大学 | Application and method of L-prolone in catalyzing multiple components to generate 3-substituted indole derivative |
| CN113861202A (en) * | 2021-10-14 | 2021-12-31 | 暨南大学 | Large-scale preparation process of pterosin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948264A (en) * | 2006-09-08 | 2007-04-18 | 浙江工业大学 | Preparation method of alpha-acetyl substituted alpha, beta-unsaturated ester |
-
2009
- 2009-10-27 CN CN 200910191236 patent/CN101811917B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948264A (en) * | 2006-09-08 | 2007-04-18 | 浙江工业大学 | Preparation method of alpha-acetyl substituted alpha, beta-unsaturated ester |
Non-Patent Citations (2)
| Title |
|---|
| KARADE, NANDKISHOR. N. ET AL: "L-Proline Catalyzed Solvent-Free Knoevenagel Condensation for the Synthesis of 3-Substituted Coumarins", 《CHINESE JOURNAL OF CHEMISTRY》 * |
| SHAO GUO-QIANG: "The Knoevenagel Condensation Induced by Microwave Irradiation in Ionic Liquid Solvents", 《CHINESE JOURNAL OF SYNTHETIC CHEMISTRY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728403A (en) * | 2012-07-17 | 2012-10-17 | 石家庄学院 | Organic solid base catalyst for synthesizing alpha-cyanoethyl cinnamate, and preparation method and application thereof |
| CN103204845A (en) * | 2013-03-12 | 2013-07-17 | 西北大学 | Imidazolyl ionic liquid, and synthesizing method and application thereof |
| CN103204845B (en) * | 2013-03-12 | 2014-12-24 | 西北大学 | Imidazolyl ionic liquid, and synthesizing method and application thereof |
| CN104356045A (en) * | 2014-09-29 | 2015-02-18 | 西南大学 | Application and method of L-prolone in catalyzing multiple components to generate 3-substituted indole derivative |
| CN104356045B (en) * | 2014-09-29 | 2016-08-03 | 西南大学 | L-PROLINE generates the application in 3-substituted indole derivant and method at catalysis multicomponent |
| CN113861202A (en) * | 2021-10-14 | 2021-12-31 | 暨南大学 | Large-scale preparation process of pterosin |
| CN113861202B (en) * | 2021-10-14 | 2022-11-08 | 暨南大学 | Large-scale preparation process of pterosin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101811917B (en) | 2013-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cheng et al. | Effect of hydrogen bond of hydroxyl-functionalized ammonium ionic liquids on cycloaddition of CO2 | |
| CN101811917B (en) | Application of L-arginine used as catalyst in Knoevenagel reaction adopting ionic liquid as medium | |
| CN110560170A (en) | Novel Pd @ MOF material, preparation method thereof and application thereof in biphenyl preparation | |
| CN101723771B (en) | Novel method for preparing beta-aminoketone, ester, nitrile and amide derivatives through catalysis of functional ionic liquid | |
| CN105061385A (en) | Method for catalytic synthesis of 4H-benzo[b]pyran derivative with basic ionic liquid | |
| Rashinkar et al. | An expeditious synthesis of homoallylic alcohols using Brønsted acidic supported ionic liquid phase catalyst with pendant ferrocenyl group | |
| Hou et al. | DABCO-based ionic liquids: Green and efficient catalysts with a dual catalytic role for aza-Michael addition | |
| CN105037381A (en) | Green catalytic preparation method of pyrano[4,3-b]pyran derivative | |
| CN101440025A (en) | Method for preparing ethylidene ether or ketal by N-methyl glyoxaline bisulphate ion liquid catalysis | |
| Wu et al. | Efficient synthesis of sec-butanol from sec-butyl acetate under mild conditions with the basic ionic liquid catalysts | |
| CN104892480B (en) | Method of preparing N-(2-hydroxy-1-naphthyl)(aryl)methyl-pyrrolidine-2-one derivatives via catalysis of di-sulfonate ionic liquid | |
| CN111875493B (en) | Method for synthesizing borneol by using imidazole acidic ionic liquid | |
| CN101463011B (en) | Process for synthesizing 3,4-dihydropyrimidine-2-keto | |
| CN101602681B (en) | Method for preparing derivatives of beta-enaminone and ester | |
| CN107892654A (en) | A kind of isolonglifolane base fluorescent type acid-base indicator and its synthetic method and application | |
| CN101642717A (en) | Application of L-tryptophane being taken as catalyst of Knoevenagel reaction | |
| CN109746042B (en) | Catalyst for synthesizing 3-methoxy methyl acrylate and solid-supported and using method | |
| CN108191814B (en) | Method for synthesizing cyclohexanone ethylene ketal under catalysis of titanium ammonium phosphotungstate composite salt | |
| CN104311484B (en) | A kind of method that catalyzes and synthesizes quinoline derivatives | |
| CN105170180A (en) | Application of 4,5-methylene-L-proline as catalyst in direct asymmetric Aldol reaction | |
| CN107540520B (en) | Method for preparing pyromellitic acid or trimellitic acid from pinacol | |
| CN102617260B (en) | Method for removing boric acid group by using aryl boric acid compound | |
| CN109824585B (en) | Method for preparing 1-aryl-2-quinolyl ethanol compound under catalysis of acidic ionic liquid | |
| CN103304443B (en) | Method for catalyzing and condensing aromatic aldehyde and active methylene compound by using multi-amino ionic liquid | |
| CN102911073B (en) | N-(4-acetylenyl phenyl carbonyl)-L-phenylglycine ethyl ester and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130821 Termination date: 20161027 |