CN105017132A - 1,4-dihydropyridine compound and preparation method thereof - Google Patents
1,4-dihydropyridine compound and preparation method thereof Download PDFInfo
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- CN105017132A CN105017132A CN201510349835.2A CN201510349835A CN105017132A CN 105017132 A CN105017132 A CN 105017132A CN 201510349835 A CN201510349835 A CN 201510349835A CN 105017132 A CN105017132 A CN 105017132A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen directly attached to ring carbon atoms
- C07D211/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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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
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- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a 1,4-dihydropyridine compound and a preparation method thereof. The 1,4-dihydropyridine compound is shown in the formula (I). In the formula, R1 represents aryl or alkyl and R2 represents alkyl. Methyl 3-aminocrotonate and aldehyde as raw materials undergo a reaction in water as a solvent in the presence of high-molecular solid acid as a catalyst to produce the 1,4-dihydropyridine compound with a high yield. The used raw materials are conventional organic reagents and have low prices. The catalysis system reaction conditions are mild and can be controlled easily. The catalyst can be recycled so that a synthesis cost is greatly reduced. The experiment process is environmentally friendly and has no pollution. The experiment process is simple and effective. The preparation method can produce products with multiple structures. Water is used as a solvent so that after-treatment is simple, environmental pollution is small, green synthesis is realized and industrial production is realized easily.
Description
Technical field:
The present invention relates to a kind of Isosorbide-5-Nitrae-dihydropyridine compound and preparation method thereof, what refer to a kind of solid acid catalysis especially prepares Isosorbide-5-Nitrae-dihydropyridine compound by heterogeneous catalysis, belongs to chemosynthesis technical field.
Technical background:
1,4-dihydropyridine compound (DHPs) belongs to hexa-atomic nitrogen-containing heterocycle compound, extensively be present in many natural products, there is much important pharmacologically active, as as business available ca channel blocker, calcium antagonist etc. can obviously improve biological tissue's availability, selectivity and stability etc.Along with Bay K 8644 is found, the calcium agonist that many Isosorbide-5-Nitrae-dihydropyridines derive is introduced and conduct treatment specifics in heart failure successively.In addition, the cerebrocrast that part Isosorbide-5-Nitrae-dihydropyridine derives also has neuroprotective, strengthens cognitive and to symptoms such as shortage neurones specificity calcium antagonism.Therefore, carrying out the study on the synthesis to having dihydropyridine framework compound, realizing the synthesis of polysubstituted dihydropyridine compound, for development methodology of organic synthesis and pharmaceutical chemistry significant undoubtedly.
In recent years, polysubstituted 1 is synthesized by building dihydropyridine skeleton, 4-dihydrogen pyridine derivative obtains significant progress, many effective synthetic methods are in the news, mainly contain following two schemes: 1. utilize methyl acetoacetate and analogue thereof and aldehyde and ammonium acetate Reactive Synthesis 1,4-dihydrogen pyridine derivative is the method that research is the most deep at present, existing a large amount of bibliographical information (Koukabi, N.; Kolvari, E.; Zolfigol, M.A.; Khazaei, A.; Shaghasemi, B.S.; Fasahati, B.Adv.Synth.Catal.2012,354,2001-2008; Koukabi, N.; Kolvari, E.; Khazaei, A.; Zolfigol, M.A.; Shaghasemi, B.S.; Khavasi H. R.Chem.Commun., 2011,47,9230-9232).2. utilize methyl acetoacetate and analogue thereof and METHYL 3 AMINO CROTONATE and aldehyde reaction synthesize Isosorbide-5-Nitrae-dihydrogen pyridine derivative (
m.;
m.; Cepanec, I.;
v.Molecules2007,12,2546-2558; Zhang, Y.W.; Shen, Z.X.; Pan, B.; Chan, M.H.Synth.Commu., 1995,25 (6), 857-62), also have more bibliographical information.In recent years, indivedual bibliographical information is only had to utilize METHYL 3 AMINO CROTONATE and aldehyde two component reaction to prepare Isosorbide-5-Nitrae-dihydrogen pyridine derivative (Mirza-Aghayan, M.; Langrodi, M.K.; Rahimifard, M.; Boukherroub, R.Appl.Organometal.Chem.2009,23,267 – 271; Filipan-Litvic ', M.; Litvic ', M.; Vinkovic ', V.Tetrahedron, 2008,64,5649 – 5656), but due to the precious metals such as the larger material of the toxicity such as methyl iodide and metal platinum will be used, greatly limit its range of application.In addition, often there is following problem in the experimental technique of existing bibliographical information: multi-component reaction by product is more, and overall yield is on the low side; Relate to comparatively violent experiment condition, be unfavorable for suitability for industrialized production; Catalyzer is expensive, and a lot of catalyzer can not be recycled.
Summary of the invention:
First aspect present invention object is to provide a kind of Isosorbide-5-Nitrae-dihydropyridine compound, its structural formula as shown in Equation 1:
In formula 1:
R
1for aryl or alkyl;
R
2for alkyl.
A second aspect of the present invention object is to provide a kind of 1, the preparation method of 4-dihydrogen pyridine derivative, it is characterized in that, comprise the following steps: with aldehyde and METHYL 3 AMINO CROTONATE and derivative thereof for raw material, spherical polymer solid acid is as catalyzer, in water, 60 DEG C are carried out reaction and prepare Isosorbide-5-Nitrae-dihydropyridine compound
The reaction formula that the present invention relates to is as follows:
Further setting is:
Described reaction raw materials, when selecting aldehyde and METHYL 3 AMINO CROTONATE and derivative mol ratio thereof to be 2.5:1, has optimal yield;
Described temperature of reaction is 60 DEG C, and the reaction times is 6-10 hour, and have optimum response effect, when temperature is too low, transformation efficiency is on the low side, and temperature is too high, has more by product to generate, and therefore, Comprehensive Control temperature of reaction and time, effectively can improve product yield.
The present invention take solid acid as catalyzer, and the reaction effects such as other catalyzer example hydrochloric acid, sulfuric acid, Glacial acetic acid are all poor, and catalyzer can not be recycled, and when especially solid acid catalyst consumption is 10mg, catalytic effect is best.
The present invention is preferably solvent with water, and found through experiments, select other solvent as methyl alcohol, ethanol, tetrahydrofuran (THF) or methylene dichloride etc., not only reaction effect is not good, and environmental pollution is larger.Take water as solvent, reaction yield is better, and water is green and environment-friendly solvent, can not bring side effect to environment.
Prioritizing selection of the present invention is heated to 60 DEG C and reacts in water, when reacting in water, and this reaction of solid acid catalyst heterogeneous catalysis of suspension, and experiment effect is relatively better, and catalyzer recycle can avoid the problems such as energy dissipation.This reaction subsequent operations is simple, can obtain purer target compound, have very strong operability by means of only laboratory facilities such as simple filtration, extraction and column chromatographys.
The present invention take spherical polymer solid acid as catalyzer, can realize catalyst recovery utilize by simple aftertreatment.We with embodiment 1 substrate for model substrates, detect catalyzer reusable edible, experimental result shows, by just realizing catalyst recycling to recovery solid acid simple process, after 4 recycles, Isosorbide-5-Nitrae-dihydropyridine compound yield still can reach 81%.
To sum up, the present invention with METHYL 3 AMINO CROTONATE compounds and aldehyde cpd for raw material, by solid acid catalysis, synthesis Isosorbide-5-Nitrae-dihydropyridine compound.Cheaper starting materials of the present invention is easy to get, and catalyzer can be recycled, and is controlled by solvent, temperature of reaction, reaction times, product yield is improved a lot, and present method is without the need to metal catalyst, and aftertreatment is simple, the gentle easily control of reaction conditions, has fine practicality and economic worth.
Further: the preparation method of a kind of Isosorbide-5-Nitrae-dihydrogen pyridine derivative of the present invention, is characterized in that, comprise the following steps:
(1) preparation of solid acid catalyst and character
Take furfural 10g respectively, hydroxyethylsulfonic acid 5g, put into the reactor filling 80mL deionized water, sealing is reacted 3-5 hours under being placed in the condition of 140 DEG C, after question response terminates, filter, use water and washed with methanol respectively, the baking oven subsequently gained solid being placed in 100 DEG C heats 3-5 hours, can obtain required solid acid catalyst.
The acidity of solid acid catalyst is comparatively strong, records its acidity and is about 2.4mmol/g, by ammonia adsorption desorption (NH by acid base titration
3-TPD) experiment show, this solid acid catalyst has good adsorption when 400-600 DEG C to ammonia.
(2) synthesis of solid acid catalysis Isosorbide-5-Nitrae-dihydrogen pyridine derivative
Respectively 0.75mmol METHYL 3 AMINO CROTONATE compounds, 0.3mmol aldehyde and 10mg solid acid are put in 3ml water, be heated to 60 DEG C, reaction 6-10 hour, TLC follows the tracks of reaction process, after question response completes, be cooled to room temperature, filter out solid matter, purified by column chromatography after ethyl acetate extraction and obtain corresponding product.
(3) recycling of solid acid catalyst
Solid acid catalyst is filtered out from reaction system, uses deionized water and washed with methanol respectively, solid acid is placed in 120 DEG C of baking ovens subsequently, heating 4-6 hour, can obtain and original active close solid acid catalyst.
Accompanying drawing illustrates:
fig. 1isosorbide-5-Nitrae-the dihydropyridine compound derived for p-tolyl aldehyde in the present invention
1h NMR, 400M compose
figure.
Embodiment:
Following examples will contribute to understanding the present invention, but be not limited to content of the present invention:
Embodiment 1:
Taking 0.75mmol METHYL 3 AMINO CROTONATE, 0.3mmol phenyl aldehyde and 10mg solid acid successively adds in the reaction tubes filling 3mL water respectively, 60 DEG C are heated in oil bath, TLC tracking test process, react about 6 hours, be cooled to room temperature after question response completes, leach solid matter, ethyl acetate is extracted, concentrate and pass through post layer chromatography separating-purifying (ethyl acetate: sherwood oil=1:10-1:4) and carry out column chromatography for separation, obtain white solid matter, productive rate is 86%.
Product confirms:
Mp:198-200℃,
1H NMR(400 MHz,CDCl
3):δ＝7.11-7.29(m,5H,ArH),5.69(br,s,1H,NH),5.01(s,1H,CH),3.66(s,6H,OCH
3),2.35(s,6H,CH
3).IR(KBr):ν＝3344,3253,3077,2953,1701,1650,1491cm
-1.
Embodiment 2:
Taking 0.75mmol METHYL 3 AMINO CROTONATE, 0.3mmol 4-chloro-benzaldehyde and 10mg solid acid successively adds in the reaction tubes filling 3mL water respectively, 60 DEG C are heated in oil bath, TLC tracking test process, react about 6 hours, be cooled to room temperature after question response completes, leach solid matter, ethyl acetate is extracted, concentrate and pass through post layer chromatography separating-purifying (ethyl acetate: sherwood oil=1:10-1:4) and carry out column chromatography for separation, obtain white solid matter, productive rate is 81%.
Product confirms:
Mp:196-198℃,
1H NMR(400 MHz,CDCl
3):δ＝7.32(d,2H,J＝8.0Hz,ArH),7.25(d,2H,J＝8.4Hz,ArH),5.71(br,s,1H,NH),5.00(s,1H,CH),3.64(s,6H,OCH
3),2.35(s,6H,CH
3).IR(KBr):ν＝3341,3250,3073,2954,1693,1648,1487cm
-1.
Embodiment 3:
Taking 0.75mmol METHYL 3 AMINO CROTONATE, 0.3mmol p-bromobenzaldehyde and 10mg solid acid successively adds in the reaction tubes filling 3mL water respectively, 60 DEG C are heated in oil bath, TLC tracking test process, react about 6 hours, be cooled to room temperature after question response completes, leach solid matter, ethyl acetate is extracted, concentrate and pass through post layer chromatography separating-purifying (ethyl acetate: sherwood oil=1:10-1:4) and carry out column chromatography for separation, obtain yellow solid matter, productive rate is 83%.
Product confirms:
Mp:199-201℃,
1H NMR(400 MHz,CDCl
3):δ＝7.68(d,2H,J＝8.4Hz,ArH),7.36(d,2H,J＝8.4Hz,ArH),5.71(br,s,1H,NH),5.01(s,1H,CH),3.66(s,6H,OCH
3),2.35(s,6H,CH
3).IR(KBr):ν＝3314,3248,3100,2955,1695,1643,1488cm
-1.
Embodiment 4:
Taking 0.75mmol METHYL 3 AMINO CROTONATE, 0.3mmol paranitrobenzaldehyde and 10mg solid acid successively adds in the reaction tubes filling 3mL water respectively, 60 DEG C are heated in oil bath, TLC tracking test process, react about 8 hours, be cooled to room temperature after question response completes, leach solid matter, ethyl acetate is extracted, concentrate and pass through post layer chromatography separating-purifying (ethyl acetate: sherwood oil=1:10-1:4) and carry out column chromatography for separation, obtain yellow solid matter, productive rate is 78%.
Product confirms:
Mp:210-21℃,
1H NMR(400 MHz,CDCl
3):δ＝8.10(d,2H,J＝8.4Hz,ArH),7.48(d,2H,J＝8.8Hz,ArH),5.76(br,s,1H,NH),5.11(s,1H, CH),3.66(s,6H,OCH
3),2.37(s,6H,CH
3).IR(KBr):ν＝3314,3244,3077,2999,2954,1708,1645,1591cm
-1.
Embodiment 5:
Taking 0.75mmol METHYL 3 AMINO CROTONATE, 0.3mmol p-tolyl aldehyde and 10mg solid acid successively adds in the reaction tubes filling 3mL water respectively, 60 DEG C are heated in oil bath, TLC tracking test process, react about 6 hours, be cooled to room temperature after question response completes, leach solid matter, ethyl acetate is extracted, concentrate and pass through post layer chromatography separating-purifying (ethyl acetate: sherwood oil=1:10-1:4) and carry out column chromatography for separation, obtain white solid matter, productive rate is 85%.
Product confirms:
Mp:210-212℃,
1H NMR(400 MHz,CDCl
3):δ＝7.12(d,2H,J＝8.0Hz,ArH),6.99(d,2H,J＝8.0Hz,ArH),5.68(br,s,1H,NH),4.93(s,1H,CH),3.61(s,6H,OCH
3),2.30(s,6H,CH
3),2.24(s,3H,CH
3).IR(KBr):ν＝3319,3243,3097,2989,1697,1659,1648,1496cm
-1.
Embodiment 6:
Taking 0.75mmol METHYL 3 AMINO CROTONATE, 0.3mmol aubepine and 10mg solid acid successively adds in the reaction tubes filling 3mL water respectively, 60 DEG C are heated in oil bath, TLC tracking test process, react about 6 hours, be cooled to room temperature after question response completes, leach solid matter, ethyl acetate is extracted, concentrate and pass through post layer chromatography separating-purifying (ethyl acetate: sherwood oil=1:10-1:4) and carry out column chromatography for separation, obtain white solid matter, productive rate is 89%.
Product confirms:
Mp:188-190℃,
1H NMR(400 MHz,CDCl
3):δ＝7.20(d,2H,J＝8.4Hz,ArH),6.79(d,2H,J＝8.4Hz,ArH),5.68(br,s,1H,NH),4.98(s,1H,CH),3.77(s,3H,OCH
3),3.68(s,6H,OCH
3),2.36(s,6H,CH
3),2.24(s,3H,CH
3).IR(KBr):ν＝3341,3249,2994,1697,1649,1628cm
-1.
Embodiment 7:
Taking 0.75mmol METHYL 3 AMINO CROTONATE, 0.3mmol isovaleric aldehyde and 10mg solid acid successively adds in the reaction tubes filling 3mL water respectively, 60 DEG C are heated in oil bath, TLC tracking test process, react about 10 hours, be cooled to room temperature after question response completes, leach solid matter, ethyl acetate is extracted, concentrate and pass through post layer chromatography separating-purifying (ethyl acetate: sherwood oil=1:10-1:4) and carry out column chromatography for separation, obtain white solid matter, productive rate is 73%.
Product confirms:
Mp:122-124℃,
1H NMR(400 MHz,CDCl
3):δ＝5.66(br,s,1H,NH),3.86(s,1H,CH),3.62(s,6H,OCH
3),2.20(s,6H,CH
3),1.34(m,1H,CH),1.02(t,J＝6.8Hz,CH
2),0.76(d,6H,J＝6.0Hz,CH
3).IR(KBr):ν＝3355,3235,2955,1698,1662,1645,1489cm
-1。
Claims (8)
1. Isosorbide-5-Nitrae-dihydropyridine compound, its structure as shown in Equation 1:
In formula 1:
R
1for aryl or alkyl,
R
2for alkyl.
2. according to claim 1 a kind of 1, the preparation method of 4-dihydropyridine compound, is characterized in that comprising the following steps: with METHYL 3 AMINO CROTONATE and aldehyde for raw material, spherical polymer solid acid is catalyzer, Reactive Synthesis Isosorbide-5-Nitrae-dihydropyridine compound is carried out in water.
3. the preparation method of a kind of Isosorbide-5-Nitrae-dihydropyridine compound according to claim 2, is characterized in that: described METHYL 3 AMINO CROTONATE amount of substance and aldehyde amount of substance are than being 2.5:1.
4. the preparation method of a kind of Isosorbide-5-Nitrae-dihydropyridine compound according to claim 2, is characterized in that: described temperature of reaction is 60 DEG C.
5. the preparation method of a kind of Isosorbide-5-Nitrae-dihydropyridine compound according to claim 2, is characterized in that: the time of described reaction is 6-10 hour.
6. the preparation method of a kind of Isosorbide-5-Nitrae-dihydropyridine compound according to claim 2, is characterized in that: the consumption of described solid acid catalyst is 10mg.
7. the preparation method of a kind of Isosorbide-5-Nitrae-dihydropyridine compound according to claim 2, is characterized in that: adopt two component reaction height yields to synthesize polysubstituted Isosorbide-5-Nitrae-dihydropyridine compound.
8. the preparation method of a kind of Isosorbide-5-Nitrae-dihydropyridine compound according to claim 2, is characterized in that: comprise the following steps:
(1) preparation of solid acid catalyst
Take furfural 10g respectively, hydroxyethylsulfonic acid 5g puts into the reactor filling 80mL deionized water, sealing is reacted 3-5 hours under being placed in the condition of 140 DEG C, after question response terminates, filter, use water and washed with methanol respectively, the baking oven subsequently gained solid being placed in 100 DEG C heats 3-5 hours, can obtain required solid acid catalyst;
(2) synthesis of the Isosorbide-5-Nitrae-dihydrogen pyridine derivative of solid acid catalysis
Respectively the aldehyde of 0.75mmol METHYL 3 AMINO CROTONATE compounds, 0.3mmol and 10mg solid acid are placed in the water of 3ml, be heated to 60 DEG C, TLC follows the tracks of reaction process, reaction 6-10 hour, after question response completes, be cooled to room temperature, filter out solid catalyst, purified by column chromatography after ethyl acetate purification and obtain white or yellow solid matter.
(3) recycling of solid acid catalyst
Solid acid catalyst is filtered out from reaction system, uses deionized water and washed with methanol respectively, subsequently solid acid is placed in the baking oven of 120 DEG C, heating 4-6 hour, can obtain and original active close solid acid catalyst.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989072A (en) * | 2022-05-27 | 2022-09-02 | 四川大学 | Method for asymmetric catalytic synthesis of chiral 1, 4-dihydropyridine compound and application thereof |
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| CN101773860A (en) * | 2010-02-05 | 2010-07-14 | 绍兴文理学院 | Carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process |
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2015
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101773860A (en) * | 2010-02-05 | 2010-07-14 | 绍兴文理学院 | Carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process |
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| Title |
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| BALOGH, MARIA; GERSTMANS, ANDRE; HERMECZ, ISTVAN: "Solid acid catalyzed reaction of aminals with methyl 3-aminocrotonate", 《HETEROCYCLIC COMMUNICATIONS》 * |
| KARIMI, BABAK等: "Improving the Selectivity toward Three-Component Biginelli versus Hantzsch Reactions by Controlling the Catalyst Hydrophobic/Hydrophilic Surface Balance", 《CHEMCATCHEM》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989072A (en) * | 2022-05-27 | 2022-09-02 | 四川大学 | Method for asymmetric catalytic synthesis of chiral 1, 4-dihydropyridine compound and application thereof |
| CN114989072B (en) * | 2022-05-27 | 2023-07-21 | 四川大学 | Method for asymmetric catalytic synthesis of chiral 1, 4-dihydropyridine compound and application thereof |
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