CN110483563B - Preparation method and application of novel ionic beta-naphthoic aldehyde Schiff base zirconium complex - Google Patents

Preparation method and application of novel ionic beta-naphthoic aldehyde Schiff base zirconium complex Download PDF

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CN110483563B
CN110483563B CN201910843557.4A CN201910843557A CN110483563B CN 110483563 B CN110483563 B CN 110483563B CN 201910843557 A CN201910843557 A CN 201910843557A CN 110483563 B CN110483563 B CN 110483563B
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李宁波
王灵晓
王静
靳朝晖
郝英健
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Shanxi Jiaxiangrui Technology Co ltd
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Abstract

The invention belongs to the technical field of catalytic organic synthesis, and particularly relates to a preparation method and application of a novel ionic beta-naphthoic aldehyde Schiff base zirconium complex. The zirconium atom, the beta-naphthoic aldehyde Schiff base ligand and the water molecule are coordinated, and two perfluoroalkyl (aryl) sulfonic acid groups are respectively combined with the central atom zirconium by a covalent bond and an ionic bond. Dissolving beta-naphthoic aldehyde Schiff base zirconium dichloride in a solvent and dissolving in N2Under protection, adding silver salt, reacting at room temperature in a dark place for 1-4h, filtering, adding n-hexane into the filtrate until layering, and freezing in a refrigerator for 24h to separate out the beta-naphthoic aldehyde Schiff base zirconium complex. The beta-naphthoic aldehyde Schiff base zirconium complex has high air stability and strong Lewis acidity, and can efficiently catalyze Hantzsch reaction of aldehyde, beta-keto ester and ammonium acetate to synthesize the 1, 4-dihydropyridine derivative.

Description

Preparation method and application of novel ionic beta-naphthoic aldehyde Schiff base zirconium complex
Technical Field
The invention belongs to the technical field of catalytic organic synthesis, and particularly relates to a preparation method and application of a novel ionic beta-naphthoic aldehyde Schiff base zirconium complex.
Background
The 1, 4-dihydropyridine compounds are nitrogen-containing heterocyclic compounds and have a wide range of biological and pharmaceutical values. Especially, the calcium ion channel blocker can be clinically used for treating cardiovascular and cerebrovascular diseases, hypertension and other diseases, and also plays an important role in the aspects of platelet aggregation resistance, neuroprotection and ischemia resistance. The classical method for the synthesis of 1, 4-dihydropyridines is by the Hantzsch reaction: i.e. by condensation of one molecule of aldehyde, two molecules of beta-ketoester and one molecule of ammonia. In recent years, the search for a simple and efficient synthesis method for 1, 4-dihydropyridine compounds has become a hotspot in the field of organic synthesis.
At present, the reported catalysts mainly include: (1) protonic acid catalyst: HClO4-SiO2Phenylboronic acid, PTSA, Alumina Sulfuric Acid (ASA), Silica Sulfuric Acid (SSA), HAc, etc.; (2) lewis acid catalyst: cu (OTf)2、AlCl3·6H2O、RuCl3、CeCl3·7H2O、La2O3Etc.; (3) ionic liquid catalyst: TMGT, [ EMIM ]]OAc, etc.; however, the above catalysts still have some problems, such as easy deliquescence, low catalytic activity, poor selectivity, inability of catalyst recycling, environmental pollution, etc., so that it is still worth intensive research to find a new catalyst capable of efficiently catalyzing the synthesis of the above nitrogen heterocyclic compounds.
Zirconium metal has received attention from scientists because of its high coordination capacity and catalytic activity. In recent years, organozirconium compounds have been used in many applications in the fields of organic synthesis and catalysis, particularly in the catalysis of olefin polymerization. However, zirconium complexes containing schiff base ligands have been reported rarely as lewis acid catalysts. The possible reason is that the heteroatom (N, O) of the ligand coordinates to the zirconium metal, reducing the lewis acidity of the zirconium central atom. Based on the concept that the stability and acidity of the complex to air can be increased by introducing long-chain perfluoroalkyl (aryl) sulfonic acid groups, in the invention, beta-naphthoic aldehyde Schiff base zirconium dichloride (a preparation method is shown in the literature of Analytica Chimica Acta,2005,551 and 37) is used as a starting material, and chlorine atoms of the Schiff base zirconium dichloride are replaced by strong electron-withdrawing long-chain perfluoroalkyl (benzene) sulfonate anions to synthesize the beta-naphthoic aldehyde Schiff base zirconium complex. And the introduction of long-chain perfluoroalkyl (aryl) increases the stability and Lewis acidity of the coordination compound. Further, the beta-naphthoic aldehyde Schiff base zirconium complex can be used for efficiently catalyzing and synthesizing the 1, 4-dihydropyridine derivative. At present, the preparation method of the beta-naphthoic aldehyde Schiff base zirconium complex and the published documents and patent applications for catalytically synthesizing the 1, 4-dihydropyridine derivatives are not available at home and abroad.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method and application of a novel ionic beta-naphthoic aldehyde Schiff base zirconium complex.
In order to achieve the above purpose, the present invention proposes the following technical solutions:
a novel ionic beta-naphthoic aldehyde Schiff base zirconium complex:
the cationic beta-naphthoic Schiff base zirconium complex (I) is formed by coordination of a zirconium atom, a naphthoic Schiff base ligand, a water molecule and an X, and the other anion X-Form an ionic bond with the cationic portion of the complex; the complex has the following structural formula (I):
Figure BDA0002194467950000021
x is perfluorooctyl sulfonic acid group OSO2C8F17Pentafluorophenyl sulfonic acid group OSO2C6F5Perfluorohexylsulfonic acid group OSO2C6F13Or perfluorobutylsulfonic acid group OSO2C4F9One of (1);
a preparation method of a novel ionic beta-naphthoic aldehyde Schiff base zirconium complex comprises the following steps:
dissolving beta-naphthoic aldehyde Schiff base zirconium dichloride in a solvent and dissolving in N2Under protection, adding silver salt, reacting at room temperature in a dark place for 1-4h, filtering, adding n-hexane into the filtrate until layering, placing the filtrate into a refrigerator for freezing for 24h, and separating out the complex which is the beta-naphthoic aldehyde Schiff base zirconium complex (I).
The solvent is as follows: tetrahydrofuran, acetone, acetonitrile, methanol or ethanol; the silver salt is: all-purposeSilver fluorooctyl sulfonate AgOSO2C8F17Silver pentafluorophenyl sulfonate AgOSO2C6F5Silver perfluorohexylsulfonate AgOSO2C6F13Or silver perfluorobutylsulfonate AgOSO2C4F9One kind of (1).
The application of the novel ionic beta-naphthoic aldehyde Schiff base zirconium complex comprises the following steps:
the beta-naphthoic aldehyde Schiff base zirconium complex (I) can catalyze: hantzsch reaction of aldehydes, beta-ketoesters and ammonium acetate produces 1, 4-dihydropyridine derivatives.
An application method of a novel ionic beta-naphthoic aldehyde Schiff base zirconium complex comprises the following steps:
beta-naphthoic aldehyde Schiff base zirconium complex (I) is used as a catalyst, aldehyde, beta-ketoester and ammonium acetate are used as raw materials, a common organic solvent is used as a reaction solvent, and the reaction is carried out for 1 to 12 hours at a temperature of between 50 and 120 ℃. After the reaction is finished, removing the solvent, adding dichloromethane for dilution, filtering, recovering the catalyst, spin-drying the filtrate, and separating by column chromatography to obtain the 1, 4-dihydropyridine derivative; the structural formula is as follows:
Figure BDA0002194467950000031
R1is one of phenyl, p-methylphenyl, p-methoxyphenyl, p-hydroxyphenyl, o-fluorophenyl, p-chlorophenyl, p-bromophenyl, o-nitrophenyl, m-nitrophenyl, 2-naphthyl, styryl, 2-furfuryl, ethyl or propyl; r2Is one of methyl or ethyl;
the aldehyde is one of benzaldehyde, p-tolualdehyde, p-methoxybenzaldehyde, p-hydroxybenzaldehyde, o-fluorobenzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, 2-naphthaldehyde, cinnamaldehyde, furfural, propionaldehyde or butyraldehyde;
the beta-ketoester is one of methyl acetoacetate or ethyl acetoacetate;
the solvent is one of tetrahydrofuran, acetonitrile, 1,2 dichloroethane, acetone, ethanol and toluene;
the dosage of the catalyst is 1.0-10 mol%; the catalyst can be reused for more than 5 times.
Compared with the prior art, the invention has the following advantages:
the invention provides a method for preparing an ionic type beta-naphthoaldehyde alkali zirconium complex and a method for catalytically synthesizing a 1, 4-dihydropyridine derivative by using the ionic type beta-naphthoaldehyde alkali zirconium complex. A new effective and simple way is developed for preparing the 1, 4-dihydropyridine derivative, the catalyst has high stability and catalytic activity, the catalyst can be repeatedly utilized for more than 5 times, and the experimental operation is simple and convenient.
Drawings
FIG. 1 is a scheme for the preparation of zirconium beta-naphtholite Schiff base complexes;
FIG. 2 catalytic synthesis of 1, 4-dihydropyridine derivatives.
Detailed Description
The synthetic route of the beta-naphthoic aldehyde Schiff base zirconium complex provided by the invention is shown in figure 1: dissolving beta-naphthoic aldehyde Schiff base zirconium dichloride in one of tetrahydrofuran, acetone, acetonitrile, methanol, ethanol and dichloromethane, and adding N2Under protection, one of silver perfluoro alkyl (aryl) sulfonate is added into the mixture, and the mixture is reacted for l to 4 hours at room temperature in a dark place. Filtering, adding n-hexane into the filtrate until the layers are separated. And (3) putting the mixture into a refrigerator for freezing for 24 hours, separating out the complex, and performing suction filtration to obtain a yellow solid beta-naphthoic aldehyde Schiff base zirconium complex.
The beta-naphthoic aldehyde Schiff base zirconium complex is used as a catalyst for catalytic synthesis of 1, 4-dihydropyridine derivatives, and the 1, 4-dihydropyridine compound can be prepared according to the following steps: adding aldehyde, beta-ketoester, ammonium acetate and solvent into a reaction vessel, and reacting at 50-120 ℃ for 1-12 h. After the reaction is finished, dichloromethane is added, the catalyst is recovered by filtration, the filtrate is dried by spinning, and the crude product is separated by column chromatography to obtain the target compound.
Note: the solvent for the reaction is one of tetrahydrofuran, acetonitrile, 1,2 dichloroethane, ethanol and toluene; the dosage of the catalyst is 1.0-10 mol%; the catalyst can be reused for more than 5 times.
The invention is further illustrated below with reference to specific preparation examples:
synthesis of novel beta-naphthoic aldehyde Schiff base zirconium perfluoroalkyl (phenyl) sulfonic acid complex
Preparation example 1
Dissolving beta-naphthoic Schiff base zirconium dichloride (1.0mmol) in Tetrahydrofuran (THF), and adding N2Under protection, adding perfluorooctyl silver sulfonate (2.0mmol), and reacting for 1h at room temperature in a dark place. Filtering, adding n-hexane into the filtrate until the layers are separated. And (5) putting the mixture into a refrigerator for freezing for 24 hours, and precipitating yellow solid with the yield of 80%.
Preparation example 2
Dissolving beta-naphthoic aldehyde Schiff base zirconium dichloride (1.0mmol) in acetonitrile (CH)3CN) in N2Silver perfluorophenylsulfonate (2.0mmol) was added under protection and reacted at room temperature for 3h in the absence of light. Filtering, adding n-hexane into the filtrate until the layers are separated. The mixture was frozen in a refrigerator for 24 hours to precipitate a yellow solid with a yield of 70%.
Preparation example 3
Dissolving beta-naphthoic aldehyde Schiff base zirconium dichloride (1.0mmol) in acetone, and adding N2Under protection, adding silver perfluorohexyl sulfonate (2.0mmol), and reacting for 2h at room temperature in a dark place. Filtering, adding n-hexane into the filtrate until the layers are separated. And (5) putting the mixture into a refrigerator for freezing for 24h, and precipitating yellow solid with the yield of 74%.
Preparation example 4
Dissolving beta-naphthoic aldehyde Schiff base zirconium dichloride (1.0mmol) in dichloromethane, and adding N2Under protection, adding silver perfluorobutylsulfonate (2.0mmol), and reacting at room temperature in the dark for 4 h. Filtering, adding n-hexane into the filtrate until the layers are separated. The mixture was put into a refrigerator to be frozen for 24 hours, and a yellow solid was precipitated, with the yield of 67%.
Synthesis of 1, 4-dihydropyridine compound by catalysis of bis, beta-naphthoic aldehyde Schiff base zirconium complex
Preparation example 1
In a 50mL round bottom flask was added benzaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent THF (2mL) and β -naphtholite schiff base zirconium perfluorooctylsulfonic acid complex (X ═ OSO)2C8F17) (0.05mmol) and stirred at 80 ℃ for 12 h. Spin-drying the solvent after the reaction is finishedThe remainder being CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was rotary-distilled, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4-phenyl-3, 5-diethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in a yield of 94%.
Preparation example 2
A50 mL round-bottomed flask was charged with p-chlorobenzaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), acetonitrile (2mL) as a solvent, and a beta-naphtholite Schiff base zirconium perfluorophenylsulfonic acid complex (X ═ OSO)2C6F5) (0.05mmol) and stirred at 100 ℃ for 2 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was evaporated by rotary evaporation, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4- (p-chlorophenyl) -3, 5-diethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in a yield of 95%.
Preparation example 3
To a 50mL round bottom flask were added p-bromobenzaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent THF (2mL) and β -naphtholite schiff base zirconium perfluorobutanesulfonic acid complex (X ═ OSO)2C4F9) (0.05mmol) and stirred at 80 ℃ for 12 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was evaporated by rotary evaporation, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4- (p-chlorophenyl) -3, 5-diethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in 93% yield.
Preparation example 4
To a 50mL round bottom flask were added m-nitrobenzaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), acetone (2mL) as a solvent, and zirconium perfluorooctylsulfonate complex (X ═ OSO) as a β -naphthoic schiff base2C8F17) (0.05mmol) and stirred at 50 ℃ for 12 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalystReceiving and utilizing combined CH2Cl2The filtrate was evaporated, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4- (m-nitrophenyl) -3, 5-diethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in 78% yield.
Preparation example 5
A50 mL round bottom flask was charged with p-tolualdehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), ethanol (2mL) as a solvent, and zirconium perfluorooctyl sulfonate complex (X ═ OSO) as a beta-naphthoic Schiff base2C8F17) (0.05mmol) and stirred at 80 ℃ for 8 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was evaporated by rotary evaporation, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4- (p-methylphenyl) -3, 5-diethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in 84% yield.
Preparation example 6
A50 mL round bottom flask was charged with p-methoxybenzaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), THF (2mL) as a solvent, and zirconium perfluorohexylsulfonic acid complex (X ═ OSO) as a beta-naphthoic Schiff base2C6F13) (0.05mmol) and stirred at 100 ℃ for 6 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was evaporated by rotary evaporation, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4- (p-methoxyphenyl) -3, 5-diethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in 82% yield.
Preparation example 7
To a 50mL round bottom flask was added p-hydroxybenzaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent 1, 2-dichloroethane (2mL) and beta-naphtholite schiff base zirconium perfluorooctylsulfonic acid complex (X ═ OSO)2C8F17) (0.10mmol) and stirred at 80 ℃ for 8 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was evaporated by rotary evaporation, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4- (p-hydroxyphenyl) -3, 5-diethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in 87% yield.
Preparation example 8
To a 50mL round bottom flask was added propionaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent THF (2mL) and β -naphtholite schiff base zirconium perfluorooctylsulfonic acid complex (X ═ OSO)2C8F17) (0.05mmol) and stirred at 100 ℃ for 12 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was rotary-distilled, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4-ethyl-3, 5-diethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in a yield of 94%.
Preparation example 9
In a 50mL round bottom flask was added trans-cinnamaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent 1, 2-dichloromethane (2mL), and beta-naphtholite schiff base zirconium perfluorobutanesulfonic acid complex (X ═ OSO)2C4F9) (0.05mmol) and stirred at 80 ℃ for 10 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was rotary-distilled, and the residue was separated by silica gel column chromatography to give a pale yellow solid, (E)2, 6-dimethyl-4-styryl-3, 5-diethoxycarbonyl-1, 4-dihydropyridine, in 90% yield.
Preparation example 10
In a 50mL round bottom flask was added furfural (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent THF (2mL) and beta-naphtholite schiff base zirconium perfluorooctylsulfonic acid complex (X ═ OSO)2C8F17) (0.05mmol) and stirred at 80 ℃ for 9 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2Filtrate is evaporated in a rotary way, and the remainder is separated by silica gel column chromatography to obtain light yellow solid 2, 6-diMethyl-4- (2-furfuryl) -3, 5-diethoxycarbonyl-1, 4-dihydropyridine, yield 87%.
Preparation example 11
A50 mL round bottom flask was charged with 2-naphthaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), THF (2mL) as solvent, and zirconium perfluorooctylsulfonate complex (X ═ OSO) as β -naphthoic Schiff base2C8F17) (0.05mmol) and stirred at 70 ℃ for 12 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was evaporated by rotary evaporation, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4- (2-naphthyl) -3, 5-diethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in a yield of 90%.
Preparation example 12
In a 50mL round bottom flask was added benzaldehyde (1mmol), methyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent THF (2mL) and β -naphtholite schiff base zirconium perfluorobutanesulfonic acid complex (X ═ OSO)2C4F9) (0.05mmol) and stirred at 90 ℃ for 12 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was rotary-distilled, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4-phenyl-3, 5-dimethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in a yield of 91%.
Preparation example 13
To a 50mL round bottom flask were added p-chlorobenzaldehyde (1mmol), methyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent THF (2mL) and β -naphtholite schiff base zirconium perfluorobutanesulfonic acid complex (X ═ OSO)2C6F13) (0.05mmol) and stirred at 80 ℃ for 10 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was rotary-distilled, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4- (p-chlorophenyl) -3, 5-dimethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in a yield of 94%.
Preparation example 14
A50 mL round bottom flask was charged with p-tolualdehyde (1mmol), methyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), THF (2mL) as solvent, and zirconium perfluorobutanesulfonic acid complex (X ═ OSO) as β -naphthoic Schiff base2C4F9) (0.01mmol) and stirred at 100 ℃ for 1 h. After the reaction is finished, the solvent is dried in a spinning mode, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was rotary-distilled, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4- (p-methylphenyl) -3, 5-dimethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in 86% yield.
Preparation example 15
A50 mL round bottom flask was charged with o-nitrobenzaldehyde (1mmol), methyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), toluene (2mL) as solvent, and beta-naphtholite Schiff base zirconium perfluorooctylsulfonate complex (X ═ OSO)2C8F17) (0.05mmol) and stirred at 120 ℃ for 1 h. After the reaction is finished, the solvent is dried in a rotary manner, and the residue is added with CH2Cl2Extracting for 3 times, collecting solid catalyst for recycling, and mixing CH2Cl2The filtrate was rotary-distilled, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4- (2-nitrophenyl) -3, 5-dimethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in 92% yield.
In order to further embody the superiority of the method, the following catalytic systems were selected as comparative examples:
comparative example 1
A50 mL round-bottom flask was charged with benzaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent THF (2mL) and zirconium tetrachloride (0.05mmol) and stirred at 80 ℃ for 12 h. After the reaction is finished, the solvent is dried by spinning, and the remainder is separated by silica gel column chromatography to obtain light yellow solid, 2, 6-dimethyl-4-phenyl-3, 5-diethoxycarbonyl-1, 4-dihydropyridine with the yield of 23%. The catalyst cannot be recycled.
Comparative example 2
A50 mL round bottom flask was charged with benzaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent THF (2mL) and zirconocene dichloride (0.05mmol) and stirred at 80 ℃ for 12 h. After the reaction is finished, the solvent is dried by spinning, and the remainder is separated by silica gel column chromatography to obtain light yellow solid, 2, 6-dimethyl-4-phenyl-3, 5-diethoxycarbonyl-1, 4-dihydropyridine with the yield of 41%. The catalyst cannot be recycled.
Comparative example 3
A50 mL round-bottom flask was charged with benzaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent THF (2mL) and scandium triflate (0.05mmol) and stirred at 80 ℃ for 12 h. After the reaction is finished, the solvent is dried by spinning, and the remainder is separated by silica gel column chromatography to obtain light yellow solid, 2, 6-dimethyl-4-phenyl-3, 5-diethoxycarbonyl-1, 4-dihydropyridine with the yield of 65%. The catalyst cannot be recycled.
Comparative example 4
A50 mL round bottom flask was charged with benzaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), solvent THF (2mL) and perfluorooctylsulfonic acid (0.05mmol) and stirred at 80 ℃ for 12 h. After the reaction, the solvent was dried by spinning, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4-phenyl-3, 5-diethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in 27% yield. The catalyst cannot be recycled.
Comparative example 5
A50 mL round bottom flask was charged with benzaldehyde (1mmol), ethyl acetoacetate (2.0mmol), ammonium acetate (1.2mmol), THF (2mL) as solvent and zirconium dichloride as beta-naphtholite Schiff base (0.05mmol) and stirred at 80 ℃ for 12 h. After the reaction, the solvent was dried by spinning, and the residue was separated by silica gel column chromatography to give 2, 6-dimethyl-4-phenyl-3, 5-diethoxycarbonyl-1, 4-dihydropyridine as a pale yellow solid in a yield of 46%. The catalyst cannot be recycled.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (5)

1. An ionic beta-naphthoic aldehyde Schiff base zirconium complex is characterized in that:
the cationic beta-naphthoic Schiff base zirconium complex (I) is characterized in that a zirconium atom, a naphthoic Schiff base ligand, a water molecule and an X are coordinated to form a cation, and the other anion X-Form an ionic bond with the cationic portion of the complex; the complex has the following structural formula (I):
Figure FDA0003333699440000011
x is perfluorooctyl sulfonic acid group OSO2C8F17Pentafluorophenyl sulfonic acid group OSO2C6F5Perfluorohexylsulfonic acid group OSO2C6F13Or perfluorobutylsulfonic acid group OSO2C4F9One kind of (1).
2. A method of preparing the ionic beta-naphthoic aldehyde schiff base zirconium complex of claim 1, wherein:
dissolving beta-naphthoic aldehyde Schiff base zirconium dichloride in a solvent and dissolving in N2Under protection, adding silver salt, reacting at room temperature in a dark place for 1-4h, filtering, adding n-hexane into the filtrate until layering, placing the filtrate into a refrigerator for freezing for 24h, and separating out the complex which is the beta-naphthoic aldehyde Schiff base zirconium complex (I).
3. The method for preparing the ionic beta-naphthoic aldehyde Schiff base zirconium complex according to claim 2, wherein the ionic beta-naphthoic aldehyde Schiff base zirconium complex comprises the following steps: the solvent is as follows: tetrahydrofuran, acetone, acetonitrile, methanol or ethanol; the silver salt is: silver perfluorooctyl sulfonate AgOSO2C8F17Silver pentafluorophenyl sulfonate AgOSO2C6F5Silver perfluorohexylsulfonate AgOSO2C6F13Or silver perfluorobutylsulfonate AgOSO2C4F9One kind of (1).
4. Use of an ionic beta-naphthoic schiff base zirconium complex according to claim 1, wherein:
the beta-naphthoic aldehyde Schiff base zirconium complex (I) can catalyze: hantzsch reaction of aldehydes, beta-ketoesters and ammonium acetate produces 1, 4-dihydropyridine derivatives.
5. A method of using the ionic beta-naphthoic schiff base zirconium complex of claim 1, wherein:
reacting beta-naphthoic aldehyde Schiff base zirconium complex (I) serving as a catalyst for 1-12h at 50-120 ℃ by taking aldehyde, beta-ketoester and ammonium acetate as raw materials and a common organic solvent as a reaction solvent; after the reaction is finished, removing the solvent, adding dichloromethane for dilution, filtering, recovering the catalyst, spin-drying the filtrate, and separating by column chromatography to obtain the 1, 4-dihydropyridine derivative; the structural formula is as follows:
Figure FDA0003333699440000021
R1is one of phenyl, p-methylphenyl, p-methoxyphenyl, p-hydroxyphenyl, o-fluorophenyl, p-chlorophenyl, p-bromophenyl, o-nitrophenyl, m-nitrophenyl, 2-naphthyl, styryl, 2-furfuryl, ethyl or propyl; r2Is one of methyl or ethyl;
the aldehyde is one of benzaldehyde, p-tolualdehyde, p-methoxybenzaldehyde, p-hydroxybenzaldehyde, o-fluorobenzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, 2-naphthaldehyde, cinnamaldehyde, furfural, propionaldehyde or butyraldehyde;
the beta-ketoester is one of methyl acetoacetate or ethyl acetoacetate;
the solvent is one of tetrahydrofuran, acetonitrile, 1,2 dichloroethane, acetone, ethanol and toluene;
the dosage of the catalyst is 1.0-10 mol%; the catalyst can be reused for more than 5 times.
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