CN113058653B - Catalyst for Knoevenagel condensation reaction of aldehyde and malononitrile and preparation method thereof - Google Patents

Catalyst for Knoevenagel condensation reaction of aldehyde and malononitrile and preparation method thereof Download PDF

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CN113058653B
CN113058653B CN202110323185.XA CN202110323185A CN113058653B CN 113058653 B CN113058653 B CN 113058653B CN 202110323185 A CN202110323185 A CN 202110323185A CN 113058653 B CN113058653 B CN 113058653B
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顾金忠
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Abstract

The invention discloses a catalyst for Knoevenagel condensation reaction of aldehyde and malononitrile, a preparation method and application thereof. The structural formula of the catalyst for the Knoevenagel condensation reaction of aldehyde and malononitrile is shown as a formula 1,

Description

Catalyst for Knoevenagel condensation reaction of aldehyde and malononitrile and preparation method thereof
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, in particular to a catalyst for Knoevenagel condensation reaction of aldehyde and malononitrile, and a preparation method and application thereof.
Background
The Knoevenagel condensation reaction is a dehydration condensation reaction of a carbonyl compound and an active methylene compound, is used for forming a carbon-carbon double bond, can directly synthesize a large amount of useful compounds, and has wide application in various fields such as industry, agriculture, pharmaceutical industry, biological science and the like. Such reactions are generally carried out by heating in the liquid phase, in particular in organic solvents, using Lewis acids or bases as catalysts, and also by reactions in homogeneous or heterogeneous phase, using ammonia, amines and their salts as catalysts, which generally take a relatively long time and give low yields [1 ]. Recently, metal-organic complexes have begun to be used in the catalysis of Knoevenagel condensation reactions, which have the advantages of relatively simple synthesis conditions and designable structure. However, the use of such complex catalysts generally requires heating and the use of organic solvents, and a certain amount of organic solvents are used in the synthesis [2,3 ].
Reference documents:
[1] the new development of condensation reaction research of Knoevenagel, organic chemistry 2006,26(9), 1165-one-wall 1172.
[2]Zhai,Z.W.；Yang,S.H.；Lv,Y.R.；Du,C.X.；Li,L.K.；Zang,S.Q.Amino functionalized Zn/Cd-metal-organic frameworks for selective CO 2 adsorption and Knoevenagel condensation reactions.Dalton.Trans.,2019,48,4007-4014.
[3]Yao,C.；Zhou,S.L；Kang,X.J.；Zhao,Y.；Yan,R.；Zhang,Y.；Wen,L.L.A cationic zinc-metal-organic framework with Lewis acidic and basic bifunctional sites as an efficient solvent-free catalyst:CO 2 fixation and Knoevenagel condensationreaction.Inorg.Chem.,2018,57,11157-11164.
Disclosure of Invention
The invention discloses a catalyst for Knoevenagel condensation reaction of aldehyde and malononitrile, a preparation method and application thereof, which can overcome the defects of the prior art.
The structural formula of the catalyst for Knoevenagel condensation reaction of aldehyde and malononitrile is shown as a formula 1,
Figure BDA0002993581620000021
the preparation of the catalyst for Knoevenagel condensation of aldehydes with malononitrile according to the invention is described in
Formula 2:
Figure BDA0002993581620000022
the specific synthesis steps are as follows:
putting 0.2-0.6mmol of manganese chloride, 0.2-0.6mmol of 2, 3-dihydroxy-terephthalic acid, 0.2-0.6mmol of 2, 2' -bipyridine and 0.4-1.2mmol of sodium hydroxide in 10-30ml of water, fully stirring, transferring to a reaction kettle with a polytetrafluoroethylene lining, sealing, heating for two to three days at the temperature of 130 ℃ and 150 ℃, then closing a power supply, cooling to room temperature, taking out the mixture in the kettle, washing with water, filtering, drying and separating to obtain the catalyst of yellow blocky crystals.
Preferably, the process for the preparation of the catalyst for the Knoevenagel condensation reaction of an aldehyde with malononitrile according to the invention is characterized in that the mass ratio of manganese chloride, 2, 3-dihydroxy-terephthalic acid, 2' -bipyridine and sodium hydroxide is 1:1:1: 2.
The catalyst of the invention is used for Knoevenagel condensation reaction of aldehyde and malononitrile.
The method has the advantages of simple synthesis method, environmental protection, and high efficiency and heterogeneous catalysis of the Knoevenagel condensation reaction of aldehyde and malononitrile. The catalyst has the characteristics of high activity, green and environment-friendly reaction conditions (room temperature and hydrosolvent), low catalyst dosage, stable structure, recycling, wide substrate application range and the like.
Drawings
FIG. 1 is an infrared spectrum of a manganese complex of the present invention;
FIG. 2 thermogravimetric curves of manganese complexes of the present invention;
FIG. 3 shows the reaction product of Knoevenagel condensation catalyzed by manganese complex with benzaldehyde as substrate 1 H nuclear magnetic spectrum.
FIG. 4 shows the Knoevenagel condensation reaction product catalyzed by manganese complex with o-nitrobenzaldehyde as the substrate 1 H nuclear magnetic spectrum.
FIG. 5 shows the Knoevenagel condensation reaction product catalyzed by manganese complex with m-nitrobenzaldehyde as the substrate 1 H nuclear magnetic spectrum.
FIG. 6 shows the Knoevenagel condensation reaction product catalyzed by manganese complex with p-nitrobenzaldehyde as the substrate 1 H nuclear magnetic spectrum.
FIG. 7 shows the Knoevenagel condensation reaction product catalyzed by manganese complex with p-chlorobenzaldehyde as substrate 1 H nuclear magnetic spectrum.
FIG. 8 shows the reaction product of Knoevenagel condensation catalyzed by manganese complex using p-hydroxybenzaldehyde as a substrate 1 H nuclear magnetic spectrum.
FIG. 9 shows the reaction product of Knoevenagel condensation reaction catalyzed by manganese complex using p-tolualdehyde as a substrate 1 H nuclear magnetic spectrum.
FIG. 10 production of Knoevenagel condensation reaction product catalyzed by manganese complex using p-methoxybenzaldehyde as substrate 1 H nuclear magnetic spectrum; the-CH peak of the substrate (integrated area 1) appeared at 9.89ppm and the-CH peak of the product (integrated area 2.43) appeared at 7.65ppm, indicating partial conversion of the substrate to the product. The yield was (2.43/3.43) × 100% ═ 70.8%.
FIG. 11 powder diffraction patterns before and after the catalytic reaction of the manganese complex of the present invention.
Detailed Description
The invention is illustrated below with reference to examples.
(one) catalyst preparation
The preparation method of the catalyst disclosed by the invention is shown in formula 2:
Figure BDA0002993581620000041
the specific synthesis steps are as follows:
putting 0.2-0.6mmol of manganese chloride, 0.2-0.6mmol of 2, 3-dihydroxy-terephthalic acid, 0.2-0.6mmol of 2, 2' -bipyridine and 0.4-1.2mmol of sodium hydroxide in 10-30ml of water, fully stirring, transferring to a reaction kettle with a polytetrafluoroethylene lining, sealing, heating for two to three days at the temperature of 130 ℃ and 150 ℃, then closing a power supply, cooling to room temperature, taking out the mixture in the kettle, washing with water, filtering, drying and separating to obtain the catalyst of yellow blocky crystals.
The following is a preferred embodiment of the catalyst of the present invention:
a mixture of manganese chloride (0.2mmol, 39.6mg), 2, 3-dihydroxy-terephthalic acid (0.2mmol, 40.0mg), 2, 2' -bipyridine (0.2mmol, 31.2mg) and sodium hydroxide (0.4mmol, 16.0mg) was stirred in a beaker with water (10mL) as a solvent, transferred to a 25mL Teflon-lined reactor and sealed and heated at 150 ℃ for three days. And then, turning off the power supply, cooling to room temperature, taking out the mixture in the kettle, washing with distilled water, filtering, drying, and manually separating to obtain the yellow blocky crystal manganese complex catalyst. Yield: 55% (based on manganese chloride). Elemental analysis C 18 H 12 MnN 2 O 6 The theoretical value is as follows: c53.09, H2.97, N6.88 percent. Measured value: c53.01, H2.99, N6.83%. Infrared spectroscopic analysis (KBr, cm) –1 )：1640w，1592s，1476m，1441m，1384s，1332m，1260m，1222w，1132w，1062w，1013w，852w，835w，810m，764m，736w，646w。
Determination of catalyst Structure:
firstly, selecting transparent crystal with regular shape, proper size, no crack and no impurity attached on the surface, then placing on graphite monochromator of X-ray single crystal diffractometer, passing Cu-K alpha ray
Figure BDA0002993581620000052
The crystal structure was determined. The diffraction data were absorption corrected using the program SADABS, the single crystal structure was solved directly, and F was corrected for the coordinates of all non-hydrogen atoms in the structure by the programs SHELXS-2014 and SHELXL-2014 2 And performing fine correction by using a full matrix least square method, and finally obtaining the coordinates of hydrogen atoms through theoretical calculation. The main crystallographic data of the manganese complexes are shown in table 1 below.
TABLE 1 crystallographic data for manganese complexes
Figure BDA0002993581620000051
Figure BDA0002993581620000061
And (3) measuring the thermal stability:
to investigate the thermal stability of the manganese complex, the thermogravimetric curve of the complex was determined in the range of 25-800 ℃ under nitrogen with a controlled ramp rate of 10 ℃/min (see fig. 2). The backbone of the complex began to collapse at 298 ℃.
(II) catalytic property of manganese complex in Knoevenagel condensation reaction of aldehyde and malononitrile
After aromatic aldehyde (0.5mmol, using benzaldehyde as a substrate), malononitrile (1.0mmol) and manganese complex (2%) are respectively added into 1.0mL of water and stirred for a certain time at 25 ℃, the catalyst is removed by centrifugation, and the solvent is removed by rotary evaporation to obtain a yellow solid product. After the product is dissolved in deuterated chloroform, the hydrogen spectrum of nuclear magnetic resonance is measured. The conversion of the catalytic reaction was calculated from the hydrogen spectrum.
Figure BDA0002993581620000062
TABLE 2 data of Knoevenagel condensation reactions catalyzed by manganese complexes using benzaldehyde as substrate
Figure BDA0002993581620000071
Reaction conditions catalyst (2 mol%), substrate benzaldehyde (0.5mmol), malononitrile (1.0mmol), solvent (1.0mL), temperature 25 ℃. The yield is calculated according to nuclear magnetic data and is [ the mol number of the product/(the mol number of the product + the mol number of the benzaldehyde) ]. times.100%.
2.1 Synthesis of Benzallyldinitrile with benzaldehyde as raw Material under catalysis of manganese Complex
Benzaldehyde (0.5mmol), malononitrile (1.0mmol) and manganese complex (2.0 mol-%) were added to 1.0mL of water, respectively, and after stirring at 25 ℃ for 1 hour, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation, a yellow solid product was obtained. After the product is dissolved in deuterated chloroform, the hydrogen spectrum of nuclear magnetic resonance is measured. The conversion of the catalytic reaction was calculated to be 100% from the hydrogen spectrum. As shown in fig. 3: the-CH peak of the substrate did not appear at 10.02ppm and the-CH peak of the product appeared at 7.79ppm, indicating that the substrate had been completely converted to the product, so the yield was 100%.
The present inventors also investigated the Knoevenagel condensation reaction yield of manganese complexes as catalysts for other substrates (formula 4 and Table 3)
Figure BDA0002993581620000072
Table 3 Knoevenagel condensation catalytic reaction data with other aldehydes as substrates.
Figure BDA0002993581620000081
Reaction conditions catalyst (2.0 mol.%), benzaldehyde substrate (0.5mmol), malononitrile (1.0mmol), solvent water (1.0mL),25 ℃. The yield was calculated from nuclear magnetic data as [ moles of product/(moles of substrate + moles of product) ]. times.100%.
2.2 Synthesis of 1, 1-dicyano-2- (-o-nitrophenyl) -ethene from o-nitrobenzaldehyde as raw Material under catalysis of manganese Complex
To 1.0mL of water were added o-nitrobenzaldehyde (0.5mmol), malononitrile (1.0mmol) and manganese complex (2.0 mol-%), respectively, and after stirring at 25 ℃ for 1 hour, the catalyst was removed by centrifugation, and the solvent was removed by rotary evaporation to give a yellow solid product. After the product is dissolved in deuterated chloroform, the hydrogen spectrum of nuclear magnetic resonance is measured. The conversion of the catalytic reaction was calculated to be 100% from the hydrogen spectrum. As shown in FIG. 4: at 10.40ppm, no substrate-CH peak was present, and at 8.45ppm, a product-CH peak was present, indicating complete conversion of substrate to product, resulting in a 100% yield.
2.3 Synthesis of 1, 1-dicyano-2- (-m-nitrophenyl) -ethene from m-nitrobenzaldehyde as starting Material under catalysis of manganese Complex
After m-nitrobenzaldehyde (0.5mmol), malononitrile (1.0mmol) and manganese complex (2.0 mol-%) were added to 1.0mL of water, respectively, and stirred at 25 ℃ for 1 hour, the catalyst was removed by centrifugation, and the solvent was removed by rotary evaporation to give a yellow solid product. After the product is dissolved in deuterated chloroform, the hydrogen spectrum of nuclear magnetic resonance is measured. The conversion of the catalytic reaction was calculated to be 100% from the hydrogen spectrum. As shown in fig. 5: at 10.03ppm, no substrate-CH peak was present, and at 7.88ppm, a product-CH peak was present, indicating complete conversion of substrate to product. Therefore, the yield was 100%.
2.4 Synthesis of 1, 1-dicyano-2- (-p-nitrophenyl) -ethene from p-nitrobenzaldehyde as raw Material under catalysis of manganese Complex
P-nitrobenzaldehyde (0.5mmol), malononitrile (1.0mmol) and manganese complex (2.0 mol-%) were added to 1.0mL of water, respectively, and after stirring for 1 hour at 25 ℃, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give a yellow solid product. After the product is dissolved in deuterated chloroform, the hydrogen spectrum of nuclear magnetic resonance is measured. The conversion of the catalytic reaction was calculated to be 100% from the hydrogen spectrum. As shown in fig. 6: at 10.15ppm, no substrate-CH peak was present and at 7.88ppm, a product-CH peak was present, indicating complete conversion of substrate to product. Therefore, the yield was 100%.
2.5 Synthesis of 1, 1-dicyano-2- (-p-chlorophenyl) -ethene by using p-chlorobenzaldehyde as raw material under catalysis of manganese Complex
P-chlorobenzaldehyde (0.5mmol), malononitrile (1.0mmol) and manganese complex (2.0 mol-%) were added to 1.0mL of water, respectively, and after stirring for 1 hour at 25 ℃, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give a yellow solid product. After the product is dissolved in deuterated chloroform, the hydrogen spectrum of nuclear magnetic resonance is measured. The conversion of the catalytic reaction was calculated to be 100% from the hydrogen spectrum. As shown in fig. 7: A-CH peak for the substrate at 9.97ppm and a-CH peak for the product at 7.73ppm were not present, indicating complete conversion of the substrate to the product. Therefore, the yield was 100%.
2.6 Synthesis of 1, 1-dicyano-2- (-p-hydroxyphenyl) -ethene from p-hydroxybenzaldehyde as raw Material under catalysis of manganese Complex
P-hydroxybenzaldehyde (0.5mmol), malononitrile (1.0mmol) and manganese complex (2.0 mol-%) were added to 1.0mL of water, respectively, and after stirring for 1 hour at 25 ℃, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give the product as a yellow solid. After the product is dissolved in deuterated chloroform, the hydrogen spectrum of nuclear magnetic resonance is measured. The conversion of the catalytic reaction was calculated to be 16% from the hydrogen spectrum. As shown in fig. 8: the-CH peak of the substrate (integrated area 1) appeared at 9.85ppm and the-CH peak of the product (integrated area 0.19) appeared at 7.64ppm, indicating partial conversion of the substrate into the product. The yield was (0.19/1.19) × 100% ═ 16.0%.
2.7 Synthesis of 1, 1-dicyano-2- (-p-methylphenyl) -ethene with p-tolualdehyde as raw Material under catalysis of manganese Complex
P-tolualdehyde (0.5mmol), malononitrile (1.0mmol) and manganese complex (2.0 mol-%) were added to 1.0mL of water, respectively, and after stirring for 1 hour at 25 ℃, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give the product as a yellow solid. After the product is dissolved in deuterated chloroform, the hydrogen spectrum of nuclear magnetic resonance is measured. The conversion of the catalytic reaction was calculated to be 98% from the hydrogen spectrum. As shown in fig. 9: the-CH peak of the substrate (integrated area 1) appeared at 9.96ppm and the-CH peak of the product (integrated area 64.54) appeared at 7.73ppm, indicating partial conversion of the substrate to the product. The yield was (64.54/65.54) × 100% ═ 98.5%.
2.8 Synthesis of (4-methoxybenzene) malononitrile from p-methoxybenzaldehyde as raw material under catalysis of manganese complex
P-methoxybenzaldehyde (0.5mmol), malononitrile (1.0mmol) and manganese complex (2.0 mol-%) were added to 1.0mL of water, respectively, and after stirring for 1 hour at 25 ℃, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give the product as a yellow solid. After the product is dissolved in deuterated chloroform, the hydrogen spectrum of nuclear magnetic resonance is measured. The conversion of the catalytic reaction was calculated to be 71% from the hydrogen spectrum. As shown in fig. 10: the-CH peak for the substrate (integrated area 1) appeared at 9.89ppm and the-CH peak for the product (integrated area 2.43) appeared at 7.65ppm, indicating partial conversion of the substrate to the product. The yield was (2.43/3.43) × 100% ═ 70.8%.
In order to test the stability and the recycling availability of the manganese complex serving as a catalyst in the Knoevenagel condensation catalytic reaction, 5 times of cyclic catalytic experiments are carried out in the research process of the invention, and the yield is 100, 99 and 98 percent respectively. The powder diffraction pattern shows that, referring to fig. 11, the structure of the manganese complex is still stable after 5 catalytic reactions.

Claims (4)

1. The catalyst for the condensation reaction of aldehyde and malononitrile has a structural formula shown as a formula 1,
Figure DEST_PATH_IMAGE001
。
2. the process for preparing a catalyst for Knoevenagel condensation reaction of aldehyde with malononitrile according to claim 1, characterized in that the synthesis process is as shown in formula 2:
Figure DEST_PATH_IMAGE002
the specific synthesis steps are as follows:
0.2-0.6mmol of manganese chloride, 0.2-0.6mmol of 2, 3-dihydroxy-terephthalic acid, 0.2-0.6mmol of 2, 2' -bipyridyl and 0.4-1.2mmol of sodium hydroxide are placed in 10-30ml of water, are fully stirred and then are transferred into a reaction kettle with a polytetrafluoroethylene lining for sealing, are heated for two to three days under the condition of keeping the temperature of 130 ℃ and 150 ℃, then are closed to cool to room temperature, and the mixture in the kettle is taken out, washed by water, filtered and dried to separate the catalyst which is yellow blocky crystals.
3. The method of claim 2, wherein the mass ratio of manganese chloride, 2, 3-dihydroxy-terephthalic acid, 2' -bipyridine and sodium hydroxide is 1:1:1: 2.
4. The catalyst of claim 1 for use in Knoevenagel condensation reactions of aldehydes with malononitrile.
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