CN101723771A - Novel method for preparing beta-aminoketone, ester, nitrile and amide derivatives through catalysis of functional ionic liquid - Google Patents
Novel method for preparing beta-aminoketone, ester, nitrile and amide derivatives through catalysis of functional ionic liquid Download PDFInfo
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- CN101723771A CN101723771A CN 200810167605 CN200810167605A CN101723771A CN 101723771 A CN101723771 A CN 101723771A CN 200810167605 CN200810167605 CN 200810167605 CN 200810167605 A CN200810167605 A CN 200810167605A CN 101723771 A CN101723771 A CN 101723771A
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Abstract
The invention relates to a method for generating beta-aminoketone, ester, nitrile and amide derivatives by performing aza-Michael addition on amine substances and electron-deficient alkenes through an efficient environment-friendly catalyst under solvent-free mild (room temperature) reaction conditions. The method comprises the steps of taking ionic liquid as the catalyst, subjecting amine substances and electron-deficient alkenes to aza-Michael addition at room temperature under normal pressure and obtaining corresponding beta-aminoketone, ester, nitrile and amide derivatives. The ionic liquid is repeatedly used five times, and reaction yield does not obviously drop. The method has the advantages of simple operation, high yield, good using repeatability of the catalytic reaction system, mild reaction conditions and good prospects for industrialization.
Description
Technical field
The present invention relates under a kind of efficient, green, condition of no solvent, is the method that the Michael addition of catalyzer prepares beta-amino ketones, ester, nitrile and amide derivatives with the new function ionic liquid.
Technical background
Beta-amino ketones, ester, nitrile and amide derivatives are widely used in fine chemistry industry and microbiotic field of medicaments as intermediate.General synthetic method comprises Mannich reaction and aza-Michael addition.By contrast, the Michael addition is more suitable in preparation beta-amino ketones, ester, nitrile and amide derivatives.For many years, emerged in large numbers a lot of catalyzer, as: SnCl
4/ FeCl
3, InCl
3, CeCl
37H
2O-NaI, Yb (OTf)
3, CAN, Bi (NO
3) and LiClO
4Deng, though these methods have all obtained certain success,, wherein there are some defectives in they, as: need excessive greatly reagent, long reaction times, the reaction conditions of harshness and the use of some noxious solvents such as methylene dichloride and acetonitrile.Therefore, develop efficient, green amine and grip altogether and add to electron deficiency olefin production beta-amino ketones, ester, nitrile and amide derivatives method and not only have important economic benefit, and also have good environment and social benefit.
In recent years, functional ion liquid had pointed out to explore the important directions of eco-friendly catalystic converter system for people.Ionic liquid itself has characteristics such as special physicochemical characteristic and thermodynamic stability, dissolving power are strong, low volatility, molecular structure adjustability, make it be successfully applied to catalyzed reaction (as solvent or catalyzer), aftertreatment is simple, ionic liquid can be repeatedly used, and shows very excellent characteristics.Therefore, it is necessary utilizing catalysis of functional ionic liquid carbonnitrogen bond Michael addition newly developed.
Summary of the invention
The objective of the invention is to replace the method for traditional catalysis aza-Michael addition amine and electron deficiency olefin production beta-amino ketones, ester, nitrile and amide derivatives, a kind of efficient, eco-friendly catalyzer is provided, and solvent-free gentleness (room temperature) reaction conditions is realized the aza-Michael addition down.
According to the present invention, the method that described aza-Michael addition by amine substance and electron deficiency alkene prepares beta-amino ketones, ester, nitrile and amide derivatives comprises: be catalyzer with the ionic liquid, under room temperature, the normal pressure, need not any solvent, amine substance and electron deficiency alkene carried out the aza-Michael addition reaction 1～24 hour, obtained corresponding beta-amino ketones, ester, nitrile and amide derivatives; Wherein, described ionic liquid is:
Wherein, the mol ratio of described amine substance and electron deficiency alkene is 1: 1～1: 2.
Wherein, described ion liquid molar weight is 0.01～1 times of amine substance.
Wherein, described amine substance is morpholine, Tri N-Propyl Amine, pyrroles, N methyl piperazine, N-ethyl piperazidine, imidazoles, 2 isopropyl imidazole, piperidines, diethylamine, hexahydroaniline or para-totuidine.
Wherein, it is characterized in that described electron deficiency alkene is methyl acrylate, ethyl propenoate, n-butyl acrylate, Methyl Methacrylate, vinyl cyanide, methylene acetone, α, β-unsaturated cyclonene or acrylic acid amides.
Wherein, after reaction finishes, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation obtain product (after substrate surpasses 1 mole, direct rectifying separation reaction solution, obtain high purity product), extracting phase (raffinate in the rectifying tower still) 60 ℃ of vacuum-dryings of ionic liquid are used for the next batch reaction after 5 hours, ionic liquid is reused 5 times, does not find that reaction yield obviously descends.
Provided by the inventionly utilize novel ion liquid catalysis to grip the addition amine substance altogether, generate the method for beta-amino ketones, ester, nitrile and amide derivatives, realize by following approach to electron deficiency alkene:
The ion liquid preparation process of new function used in the present invention (applying for a patent separately):
Carboxylic acid (lactic acid, acetate, n Propanoic acid and butanic acid) is added drop-wise among the DBU of equimolar amount, temperature of reaction is controlled at below 10 ℃ during dropping, drips off in 0.5-2 hour, and room temperature mechanical stirred 24 hours, 60-80 ℃ vacuum-drying 5-10 hour, obtain light yellow transparent liquid.The ionic liquid of preparation is used
1H NMR,
13C NMR structural confirmation.Four kinds of ionic liquids are respectively described ionic liquid and are:
Abbreviate [DBU] [Ac] as,
Aza-Michael adduct preparation process is:
In the there-necked flask of magnetic stirring apparatus is housed, add Ammonia material, electron deficiency alkene and ionic liquid successively.Wherein the mol ratio of Ammonia material and electron deficiency alkene is 1: 1-1: 2, and the mol ratio of ionic liquid and Ammonia material is 0.01: 1-1: 1, need not any solvent compartment normal temperature and pressure reaction 1-24 hour, thin-layer chromatography (TLC) is followed the tracks of extent of reaction.After reaction finishes, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product (after substrate surpasses 1 mole, directly the rectifying separation reaction solution obtains high purity product), 60 ℃ of vacuum-dryings of extracting phase (bottom product) ionic liquid are used for the next batch reaction after 5 hours, ionic liquid is reused 5 times, does not find that reaction yield obviously descends.
Embodiment
The present invention will be further described below with reference to embodiment, and embodiments of the invention only are used to technical scheme of the present invention is described, and non-limiting the present invention.
Embodiment 1
Morpholine (5mmol), methyl acrylate (5.5mmol), 1mmol lactic acid ion liquid [DBU] [Lac] are joined in the 50mL single port bottle successively, stirring at room 2 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 95%, content 98%.3-(1-Morpholinyl)-propionic?acid?methylester：
1H?NMR(400MHz，CDCl
3)(ppm)：3.66(s，3H，OCH
3)，3.67-3.65(m，4H，morpholinyl)，2.65(t，2H，J＝6Hz，CH
2)，2.48(t，2H，J＝6Hz，CH
2)，2.43-2.41(m，4H，morpholinyl)；
13C?NMR(100MHz，CDCl
3)(ppm)：172.8，66.8，53.8，53.3，51.6，31.7.
Embodiment 2
Tri N-Propyl Amine (5mmol), methyl acrylate (5.5mmol), 1mmol n Propanoic acid ionic liquid [DBU] [Pr] are joined in the 50mL single port bottle successively, stirring at room 2 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 86%, content 95%.3-(1-Propylamine)-propionic?acidmethyl?ester：
1H?NMR(400MHz，CDCl
3)(ppm)：3.63(s，3H，OCH
3)，2.62(t，2H，J＝6.4Hz，CH
2)，2.45(t，2H，J＝6.4Hz，CH
2)，2.58(m，2H，CH
2)，1.41(m，2H，CH
2)，0.90(m，3H，CH
3)；
13C?NMR(100MHz，CDCl
3)(ppm)：170.5，66.8，52.8，52.1，44.9，28.1，12.3.
Embodiment 3
Piperidines (5mmol), methyl acrylate (5.5mmol), 1mmol acetato-liquid [DBU] [Ac] are joined in the 50mL single port bottle successively, stirring at room 1.5 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 96%, content 98%.3-(1-Piperidinyl)-propionic?acidmethyl?ester：
1H?NMR(400MHz，CDCl
3)(ppm)：3.86(s，3H，OCH
3)，2.86(t，2H，J＝6Hz，CH
2)，2.68(t，2H，J＝6Hz，CH
2)，1.80-1.75(m，4H，piperidinyl)，1.61-1.44(m，4H，piperidiny)，1.42-1.26(m，2H，piperidinyl)；
13C?NMR(100MHz，CDCl
3)(ppm)：173.8，54.2，53.8，52.9，31.8，29.3，25.8，24.6，23.1.
Embodiment 4
2 isopropyl imidazole (5mmol), methyl acrylate (5.5mmol), 1mmol butanic acid ionic liquid [DBU] [n-Bu] are joined in the 50mL single port bottle successively, stirring at room 10 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 87%, content 98%.3-(2-Isopropyl-1-imidazole)-propionic?acid?methyl?ester：
1H?NMR(400MHz，CDCl
3)(ppm)：6.94(d，1H，J＝1.2Hz，imidazole)，6.81(d，1H，J＝1.2Hz，imidazole)，4.20(t，2H，J＝7.2Hz，CH
2)，3.71(s，3H，OCH
3)，3.03(q，1H，J＝7.2Hz，CH)2.76(t，2H，J＝7.2Hz，CH
2)，1.33(d，6H，2CH
3)；
13C?NMR(100MHz，CDCl
3)(ppm)：170.9，152.4，127.4，118.3，52.0，40.6，35.6，25.7，21.8.
Embodiment 5
Morpholine (5mmol), ethyl propenoate (5.5mmol), 1mmol lactic acid ion liquid [DBU] [Lac] are joined in the 50mL single port bottle successively, stirring at room 3 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 90%, content 96%.3-(1-Morpholinyl)-propionic?acid?ethylester：
1H?NMR(400MHz，CDCl
3)(ppm)：4.15(q，2H，J＝7.2Hz，OCH
2)，3.7(m，4H，J＝4.4Hz，morpholinyl)，2.69(t，2H，J＝7.6Hz，CH
2)，2.50(t，2H，J＝7.6Hz，CH
2)，2.47(q，4H，J＝4.4Hz，morpholinyl)，1.27(t，3H，J＝7.2Hz，CH
3)；
13C?NMR(100MHz，CDCl
3)(ppm)：175.4，66.9，60.4，53.9，53.4，32.1，14.2.
Embodiment 6
Morpholine (5mmol), n-butyl acrylate (5.5mmol), 1mmol lactic acid ion liquid [DBU] [Lac] are joined in the 50mL single port bottle successively, stirring at room 4 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 90%, content 96%.3-(1-Morpholinyl)-propionic?acid?butylester：
1H?NMR(400MHz，CDCl
3)(ppm)：4.09(t，2H，J＝8.4Hz，OCH
2)，3.69(t，4H，J＝4.4Hz，morpholinyl)，2.68(t，2H，J＝7.6Hz，CH
2)，2.49(t，2H，J＝7.6Hz，CH
2)，1.65-1.58(m，2H，CH
2)，0.94(t，3H，J＝7.2Hz，CH
3)；
13C?NMR(100MHz，CDCl
3)(ppm)：172.5，66.9，64.3，53.9，53.3，32.1，30.6，19.1，13.7.
Embodiment 7
Morpholine (5mmol), Methyl Methacrylate (5.5mmol), 1mmol acetato-liquid [DBU] [Ac] are joined in the 50mL single port bottle successively, stirring at room 4 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 90%, content 96%.2-Methyl-3-(1-morpholinyl)-propionic?acid?methyl?ester：
1H?NMR(400MHz，CDCl
3)(ppm)：3.69(s，3H，OCH
3)，3.68-3.64(m，4H，morpholinyl)，2.74-2.62(m，2H，morpholinyl)，2.50-2.41(m，2H，morpholinyl)，2.41-2.36(m，2H，CH
2)，2.33-2.28(m，1H，CH)，1.15(d，3H，J＝6.8Hz，CH
3)；
13C?NMR(100MHz，CDCl
3)(ppm)：176.4，67.0，62.0，53.7，51.6，37.5，15.5.
Embodiment 8
Morpholine (5mmol), vinyl cyanide (5.5mmol), 1mmol n Propanoic acid ionic liquid [DBU] [Pr] are joined in the 50mL single port bottle successively, stirring at room 3 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 92%, content 98%.3-(1-Morpholinyl)-propionitrile：
1H?NMR(400MHz，CDCl
3)(ppm)：3.72(t，4H，J＝4.4Hz，morpholinyl)，2.68(t，2H，J＝7.2Hz，CH
2)，2.53(t，2H，J＝7.2Hz，CH
2)，2.51(t，4H，J＝4.4Hz，morpholinyl)；
13C?NMR(100MHz，CDCl
3)(ppm)：118.5，66.5，53.4，52.9，15.6.
Embodiment 9
Morpholine (5mmol), acrylic acid amides (5.5mmol), 1mmol butanic acid ionic liquid [DBU] [n-Bu] are joined in the 50mL single port bottle successively, stirring at room 3 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 93%, content 98%.3-(1-Morpholinyl)-propanamide：
1HNMR(400MHz，CDCl
3)(ppm)：7.84(br，1H，NH)，6.06(br，1H，NH)，3.73(s，4H，morpholinyl)，2.64(t，2H，J＝6Hz，CH
2)，2.51(s，4H，morpholinyl)，2.41(t，2H，J＝6Hz，CH
2)；
13C?NMR(100MHz，CDCl
3)(ppm)：175.0，66.7，54.1，52.9，31.6.
Embodiment 10
Imidazoles (5mmol), methyl acrylate (5.5mmol), 1mmol lactic acid ion liquid [DBU] [Lac] are joined in the 50mL single port bottle successively, stirring at room 2 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 92%, content 96%.3-Imidazol-1-yl-propionic?acid?methylester：
1H?NMR(400MHz，CDCl
3)(ppm)：7.54(s，1H，imidazole)，7.05(s，1H，imidazole)，6.93(s，1H，imidazole)，4.27(t，2H，J＝6.6Hz，CH
2)，3.70(s，3H，OCH
3)，2.78(t，2H，J＝6.6Hz，CH
2)；
13C?NMR(100MHz，CDCl
3)(ppm)：172.8，66.8，53.8，53.3，51.6，31.7.
Embodiment 11
Diethylamine (5mmol), methylene acetone (5.5mmol), 1mmol lactic acid ion liquid [DBU] [Lac] are joined in the 50mL single port bottle successively, stirring at room 2 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 88%, content 96%.4-Diethyamino-1-yl-butan-2-one：
1H?NMR(400MHz，CDCl
3)(ppm)：2.76(m，4H，2CH
2)，2.52(q，4H，J＝7.2Hz，2CH
2)，2.14(s，3H，CH
3)，1.03(t，6H，J＝7.2Hz，2CH
3)；
13C?NMR(100MHz，CDCl
3)(ppm)：207.3，52.4，47.1，40.0，30.3，12.2.
Embodiment 12
With miaow N methyl piperazine (5mmol), α, β-unsaturated cyclonene (5.5mmol), 1mmol lactic acid ion liquid [DBU] [Lac] join in the 50mL single port bottle successively, stirring at room 2 hours, TLC detects, and raw material disappears, and uses the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 95%, content 98%.3-(1-Methylpiperazine)-6-yl-cyclohexan-1-one：
1H?NMR(400MHz，CDCl
3)(ppm)：2.88(m，4H)，2.70(m，1H，CH)，2.27(s，3H，CH
3)，2.13(m，2H，CH
2)，1.72(m，2H，CH
2)，1.55(m，2H，CH
2)，1.42(m，2H，CH
2)；
13C?NMR(100MHz，CDCl
3)(ppm)：207.0，55.9，49.1，47.9，45.8，40.8，32.8，27.8，22.2.
Embodiment 13
With miaow N-hexyl piperazine (5mmol), α, β-unsaturated cyclonene (5.5mmol), 1mmol lactic acid ion liquid [DBU] [Lac] join in the 50mL single port bottle successively, stirring at room 2 hours, TLC detects, and raw material disappears, and uses the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 96%, content 98%.3-(1-ethylpiperazine)-6-yl-cyclohexan-1-one：
1H?NMR(400MHz，CDCl
3)(ppm)：3.25(q，2H，J＝7.2Hz，CH
2)，2.85(m，4H)，2.65(m，1H，CH)，2.35(m，2H，CH
2)，2.15(q，3H，J＝7.2Hz，CH
3)，2.08(m，2H，CH
2)，1.69(m，2H，CH
2)，1.52(m，2H，CH
2)，1.40(m，2H，CH
2)；
13C?NMR(100MHz，CDCl
3)(ppm)：206.8，56.7，50.2，48.7，40.3，32.5，21.8，11.5.
Embodiment 14
Hexahydroaniline (5mmol), methylene acetone (5.5mmol), 1mmol lactic acid ion liquid [DBU] [Lac] are joined in the 50mL single port bottle successively, stirring at room 2 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 85%, content 96%.4-Cyclohexylamine-1-yl-butan-2-one：
1HNMR(400MHz，CDCl
3)(ppm)：2.73(m，4H，2CH
2)，2.30(m，1H)，2.12(s，3H，CH
3)，1.90(m，1H)，2.30(m，1H)，1.73(m，1H)，1.62(m，1H)，1.14(m，1H)，1.02(m，1H)，；
13C?NMR(100MHz，CDCl
3)(ppm)：207.5，53.1，51.1，41.2，37.5，30.9，27.2，25.4.
Embodiment 15
4-monomethylaniline (5mmol), methyl acrylate (5.5mmol), 1mmol lactic acid ion liquid [DBU] [Lac] are joined in the 50mL single port bottle successively, stirring at room 3 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 94%, content 98%.3-(4-Methlphenyl)-propionic?acidmethyl?ester：
1H?NMR(400MHz，CDCl
3)(ppm)：6.79-6.73(m，2H，ArH)，6.59-6.56(m，2H，ArH)，1.73(s，3H，CH
3)，3.73(s，3H，OCH
3)，3.37(t，2H，J＝6.4Hz，CH
2)，2.58(t，2H，J＝6.4Hz，CH
2)；
13C?NMR(100MHz，CDCl
3)(ppm)：168.9，149.4，139.5，112.9，112.4，53.6，49.7，38.8，32.1.
Embodiment 16
Extracting phase among morpholine (5mmol), methyl acrylate (5.5mmol), the embodiment 1 is joined in the 50mL single port bottle successively through the ionic liquid of 60 ℃ of vacuum-dryings after 5 hours, stirring at room 2 hours, TLC detects, raw material disappears, use the extracted with diethyl ether reaction solution, merge organic phase, lean on chromatographic separation and obtain product, yield 93%, content 98%.Ionic liquid is reused 5 times, does not find that yield obviously descends, and specifically sees Table 1.NMR data embodiment 1.
Table 1
Need to prove that foregoing invention content and embodiment are intended to prove the practical application of technical scheme provided by the present invention, should not be construed as qualification protection domain of the present invention.Those skilled in the art are in spirit of the present invention and principle, when doing various modifications, being equal to and replacing or improve.Protection scope of the present invention is as the criterion with appended claims.
Claims (10)
1. the aza-Michael addition by amine substance and electron deficiency alkene prepares the method for beta-amino ketones, ester, nitrile and amide derivatives, it is characterized in that, described method comprises with the ionic liquid being catalyzer, amine substance and electron deficiency alkene carry out the aza-Michael addition reaction under room temperature, the normal pressure, obtain corresponding beta-amino ketones, ester, nitrile and amide derivatives; Wherein, described ionic liquid is:
2. the method for claim 1 is characterized in that, the mol ratio of described amine substance and electron deficiency alkene is 1: 1～1: 2.
3. the method for claim 1 is characterized in that, described ion liquid molar weight is 0.01～1 times of amine substance.
4. as claim 1,2 or 3 described methods, it is characterized in that described amine substance is morpholine, Tri N-Propyl Amine, pyrroles, N methyl piperazine, N-ethyl piperazidine, imidazoles, 2 isopropyl imidazole, piperidines, diethylamine, hexahydroaniline or para-totuidine.
5. method as claimed in claim 1 or 2, it is characterized in that, described electron deficiency alkene is methyl acrylate, ethyl propenoate, n-butyl acrylate, Methyl Methacrylate, vinyl cyanide, methylene acetone, α, β-unsaturated cyclonene or acrylic acid amides.
6. the method for claim 1 is characterized in that, reaction process need not any solvent.
7. as claim 1 or 6 described methods, it is characterized in that the reaction times is 1～24 hour.
8. method as claimed in claim 7 is characterized in that, reaction is used the extracted with diethyl ether reaction solution after finishing, and merges organic phase, and column chromatography for separation obtains product.
9. method as claimed in claim 8 is characterized in that, after reaction finished, behind the extracted with diethyl ether reaction solution, extracting phase repeated repeatedly to use through 60 ℃ of vacuum-dryings in 5 hours, and wherein, extracting phase is an ionic liquid.
10. method as claimed in claim 7 is characterized in that, after reaction finished, if when described amine substance surpasses 1 mole, directly rectifying, separating reaction liquid obtained high purity product.
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| GB0500028D0 (en) * | 2005-01-04 | 2005-02-09 | Univ Belfast | Base stable ionic liquids |
| WO2008043837A1 (en) * | 2006-10-13 | 2008-04-17 | Basf Se | Ionic liquids for solubilizing polymers |
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| CN103073454A (en) * | 2011-10-25 | 2013-05-01 | 中国科学院兰州化学物理研究所 | Synthetic method for beta-aminocarbonyl compound, beta-mercapto ketone and beta-alkoxy ketone |
| CN103304516A (en) * | 2013-05-15 | 2013-09-18 | 台州学院 | Method for preparing beta-aminoketone, ester and nitrile amide derivatives |
| CN103880575B (en) * | 2014-03-21 | 2015-06-03 | 台州学院 | Method for preparing beta-amino amide derivatives |
| CN103880575A (en) * | 2014-03-21 | 2014-06-25 | 台州学院 | Method for preparing beta-amino amide derivatives |
| CN103980079B (en) * | 2014-05-28 | 2016-01-13 | 台州学院 | Ionic liquid-catalyzed amine and unsaturated acyl amine aza-Michael addition method |
| CN103980204A (en) * | 2014-05-28 | 2014-08-13 | 台州学院 | Method for catalyzing amines and alpha, beta-unsaturated electron-deficient acceptors by ionic liquid |
| CN103980079A (en) * | 2014-05-28 | 2014-08-13 | 台州学院 | Ionic liquid catalyzed amine and unsaturated amide aza-Michael addition method |
| CN103980204B (en) * | 2014-05-28 | 2016-03-30 | 台州学院 | Ionic liquid-catalyzed amine and α, β-unsaturated electron deficiency receptor method |
| CN107827764A (en) * | 2017-11-27 | 2018-03-23 | 上海应用技术大学 | A kind of preparation method of double β amino ketones or double β amino esters |
| CN113372281A (en) * | 2020-03-09 | 2021-09-10 | 河北中科金辉药业有限公司 | Synthetic method of metronidazole |
| ES2904628A1 (en) * | 2020-10-05 | 2022-04-05 | Univ Extremadura | Assisting method Aza-Michael of Ansinas and unsaturated alpha-beta compounds (Machine-translation by Google Translate, not legally binding) |
| CN114907304A (en) * | 2022-05-27 | 2022-08-16 | 上海克琴科技有限公司 | Preparation method of tocopherol retinoic acid ester |
| CN114907304B (en) * | 2022-05-27 | 2024-02-13 | 上海克琴科技有限公司 | Preparation method of tocopherol retinoic acid ester |
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