CN114177942B - Catalyst for condensation reaction of aldehyde and malononitrile Knoevenagel and preparation method thereof - Google Patents
Catalyst for condensation reaction of aldehyde and malononitrile Knoevenagel and preparation method thereof Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07F15/06—Cobalt compounds
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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Abstract
The invention discloses a catalyst for condensation reaction of aldehyde and malononitrile Knoevenagel, a preparation method and application thereof. The structural formula of the catalyst for the condensation reaction of aldehyde and malononitrile Knoevenagel is shown as formula 1, and the synthesis steps are as follows: cobalt chloride, 3,2',4' -biphenyl tricarboxylic acid, 4' -bipyridine and 0.6-1.8mmol sodium hydroxide are placed in water, and are transferred into a polytetrafluoroethylene lining reaction kettle after being fully stirred
Description
Technical Field
The invention relates to a catalyst and a preparation method and application thereof, in particular to a catalyst for the condensation reaction of aldehyde and malononitrile Knoevenagel 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 carbon-carbon double bonds, can directly synthesize a large number of useful compounds, and has wide application in various fields such as industry, agriculture, pharmaceutical industry, bioscience 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, or else ammonia, amines and salts thereof, etc. are used as catalysts, in homogeneous or heterogeneous phases, generally for longer times and in lower yields [1]. Recently, metal-organic complexes have begun to be used for catalysis of Knoevenagel condensation reactions, which have the advantages of relatively simple synthesis conditions and designable structures. However, such complex catalysts generally require heating and the use of organic solvents, and certain amounts of organic solvents [2,3] are used in the synthesis.
Reference is made to:
[1] bian Yanjiang, qin Ying, showy, li Jitai. New developments in Knoevenagel condensation reaction research, organic chemistry 2006,26 (9), 1165-1172.
[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 condensation reaction of aldehyde and malononitrile Knoevenagel, a preparation method and application thereof, which can overcome the defects of the prior art.
The structural formula of the catalyst for the condensation reaction of aldehyde and malononitrile Knoevenagel is shown as formula 1,
the preparation method of the catalyst for the condensation reaction of aldehyde and malononitrile of the invention is shown in
Formula 2:
the specific synthesis steps are as follows:
placing 0.3-0.9mmol of cobaltous chloride, 0.2-0.6mmol of 3,2',4' -biphenyl tricarboxylic acid, 0.3-0.9mmol of 4,4' -bipyridine and 0.6-1.8mmol of sodium hydroxide into 10-30ml of water, fully stirring, transferring into a reaction kettle, sealing, heating and keeping the temperature of 130-150 ℃ for fully reacting, cooling to room temperature, taking out the mixture in the kettle, washing with water, filtering, drying and separating to obtain the pink blocky crystal catalyst.
Preferably, the preparation method of the catalyst for the condensation reaction of aldehyde and malononitrile Knoevenagel is characterized in that the mass ratio of cobaltous chloride, 3,2',4' -biphenyltricarboxylic acid, 4' -bipyridine and sodium hydroxide is 1:0.67:1:2.
The catalyst of the invention is used for the condensation reaction of aldehyde and malononitrile Knoevenagel.
The method has the advantages of simplicity, environmental protection, high efficiency and heterogeneous catalysis of the condensation reaction of aldehyde and malononitrile Knoevenagel. The catalyst has the characteristics of high activity, environment-friendly reaction conditions (room temperature and water solvent), low catalyst consumption, stable structure, recycling, wide substrate application range and the like.
Drawings
FIG. 1 is an infrared spectrum of a cobalt complex of the present invention;
FIG. 2 is a thermogravimetric curve of a cobalt complex of the present invention;
FIG. 3 shows Knoevenagel condensation reaction product catalyzed by cobalt complex with benzaldehyde as substrate 1 H nuclear magnetic spectrum.
FIG. 4 is a schematic view of a conventional deviceO-nitrobenzaldehyde as substrate and cobalt complex catalyzed Knoevenagel condensation reaction product 1 H nuclear magnetic spectrum.
FIG. 5 shows the products of a cobalt complex catalyzed Knoevenagel condensation reaction with m-nitrobenzaldehyde as the substrate 1 H nuclear magnetic spectrum.
FIG. 6 shows the products of a cobalt complex catalyzed Knoevenagel condensation reaction with p-nitrobenzaldehyde as substrate 1 H nuclear magnetic spectrum.
FIG. 7 shows a cobalt complex catalyzed Knoevenagel condensation reaction product with p-chlorobenzaldehyde as substrate 1 H nuclear magnetic spectrogram; the-CH peak of the substrate (integral area 1.01) appeared at 9.98ppm and the-CH peak of the product (integral area 418.69) appeared at 7.73ppm, indicating that the substrate was largely converted to product. Yield= (418.69/419.7) ×100% = 99.8%.
FIG. 8 shows a cobalt complex catalyzed Knoevenagel condensation reaction product with p-hydroxybenzaldehyde as substrate 1 H nuclear magnetic spectrogram; the-CH peak of the substrate (integral area 1) appeared at 9.86ppm and the-CH peak of the product (integral area 0.28) appeared at 7.64ppm, indicating partial conversion of the substrate to product. Yield= (0.28/1.28) ×100% = 21.9%.
FIG. 9 shows a cobalt complex catalyzed Knoevenagel condensation reaction product with p-tolualdehyde as substrate 1 H nuclear magnetic spectrum.
FIG. 10 shows a cobalt complex catalyzed Knoevenagel condensation reaction product with p-methoxybenzaldehyde as substrate 1 H nuclear magnetic spectrum.
FIG. 11 is a powder diffraction pattern of a cobalt complex of the present invention before and after catalytic reaction.
Detailed Description
The invention is illustrated below with reference to examples.
(one) catalyst preparation
The catalyst preparation method of the invention is shown in formula 2:
the specific synthesis steps are as follows:
placing 0.3-0.9mmol of cobaltous chloride, 0.2-0.6mmol of 3,2',4' -biphenyl tricarboxylic acid, 0.3-0.9mmol of 4,4' -bipyridine and 0.6-1.8mmol of sodium hydroxide into 10-30ml of water, fully stirring, transferring into a polytetrafluoroethylene lining reaction kettle, sealing, heating for two to three days at 130-150 ℃, then turning off a power supply, cooling to room temperature, taking out the mixture in the kettle, washing with water, filtering, drying, and separating to obtain the pink blocky crystal catalyst.
The following is a preferred embodiment of the catalyst prepared according to the present invention:
a mixture of cobalt chloride (0.3 mmol,71.4 mg), 3,2',4' -biphenyltricarboxylic acid (0.2 mmol,57.2 mg), 4' -bipyridine (0.3 mmol,46.8 mg) and sodium hydroxide (0.6 mmol,24.0 mg) was placed in a beaker and stirred for 15min, then transferred to a 25mL polytetrafluoroethylene-lined reactor for sealing, and heated at 150℃for three days. And then the power supply is turned off, the mixture in the kettle is taken out, distilled water is used for washing, filtering and drying are carried out, and then the cobalt complex catalyst with pink blocky crystals is obtained through manual separation. Yield: 57% (based on cobalt chloride). Elemental analysis C 60 H 46 Co 3 N 6 O 16 Theoretical value: C56.13,H 3.61,N 6.55%. Actual measurement value: C56.37,H 3.59,N 6.53%. Infrared spectroscopic analysis (KBr, cm) –1 )：3672w，3404w，3065w，1624m，1597s，1579m，1540m，1490w，1438m，1380s，1273w，1223w，1170w，1072w，1001w，938w，859w，814m，792w，766m，735w，699w，668w，654w。
Determination of catalyst structure:
firstly, selecting transparent crystal with regular form, proper size, no crack and no impurity attached on the surface, then placing on graphite monochromator of X-ray single crystal diffractometer, using Mo-K alpha ray
The crystal structure was measured. Absorption correction of diffraction data using the program SADABS, single crystal structure was resolved using direct method, and junction was correctedThe coordinates of all non-hydrogen atoms in the structure are calculated by the programs SHELXS-2014 and SHELXL-2014 for F 2 And carrying out fine correction by using a full matrix least square method, and finally obtaining the coordinates of the hydrogen atoms through theoretical calculation. The main crystallographic data of the cobalt complex are shown in table 1 below.
TABLE 1 crystallographic data of cobalt complexes
Thermal stability determination:
to investigate the thermal stability of the cobalt complex, the thermogravimetric profile of the complex was determined at a temperature rise rate of 10 ℃/min under nitrogen protection in the range 33-800 ℃. The complex loses four water molecules at 47-161 ℃ and the framework begins to collapse at 237 ℃.
(II) catalytic Properties of cobalt Complex of the invention in the condensation reaction of aldehyde with malononitrile Knoevenagel
Aromatic aldehyde (0.5 mmol, using benzaldehyde as substrate) and malononitrile (1.0 mmol) and cobalt complex (2%) were added to 1.0mL of water, respectively, and after stirring at 25deg.C for a certain period of time, the catalyst was removed by centrifugation, and the solvent was removed by rotary evaporation to give a yellow solid product. After the product was dissolved in deuterated chloroform, nuclear magnetic resonance hydrogen spectrum was measured. The conversion of the catalytic reaction was calculated from the hydrogen spectrum.
Formula 3 Knoevenagel condensation reaction catalyzed by cobalt complex with benzaldehyde as substrate
TABLE 2 data of Knoevenagel condensation reaction catalyzed by cobalt complex with benzaldehyde as substrate
Reaction conditions were catalyst (2 mol%), substrate benzaldehyde (0.5 mmol), malononitrile (1.0 mmol), solvent (1.0 mL), temperature 25 ℃. The yield is calculated according to the nuclear magnetic data and is [ product mole number/(product mole number+benzaldehyde mole number) ]multipliedby 100%.
2.1 Synthesis of Benzallyl dinitrile with Benzaldehyde as raw material under the catalysis of cobalt Complex
To 1.0mL of water, benzaldehyde (0.5 mmol), malononitrile (1.0 mmol) and cobalt complex (2.0 mol-%) were added, respectively, and after stirring at 25℃for 55 minutes, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give a yellow solid product. After the product was dissolved in deuterated chloroform, nuclear magnetic resonance hydrogen spectrum was measured. The conversion of the catalytic reaction was calculated to be 100% based on the hydrogen spectrum. As in fig. 3: no-CH peak of the substrate appears at 10.02ppm and a-CH peak of the product appears at 7.79ppm, indicating that the substrate has been completely converted to product, so the yield is 100%.
The present invention also investigated the Knoevenagel condensation reaction yields of cobalt complexes as catalysts for other substrates (formula 4 and Table 3)
Formula 4 Knoevenagel condensation reaction catalyzed by cobalt complex with other aldehyde as substrate
Table 3 data on Knoevenagel condensation catalyzed reactions with other aldehydes as substrates.
Reaction conditions were catalyst (2.0 mol.%), benzaldehyde substrate (0.5 mmol), malononitrile (1.0 mmol), solvent water (1.0 mL), 25 ℃. The yield was calculated using nuclear magnetic data [ product moles/(substrate moles + product moles) ]. Times.100%.
2.2 Synthesis of 1, 1-dicyano-2- (-o-nitrophenyl) -ethylene by using o-nitrobenzaldehyde as raw material under the catalysis of cobalt complex
O-nitrobenzaldehyde (0.5 mmol), malononitrile (1.0 mmol) and cobalt complex (2.0 mol-%) were added to 1.0mL of water, respectively, and after stirring at 25℃for 55 minutes, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give a yellow solid product. After the product was dissolved in deuterated chloroform, nuclear magnetic resonance hydrogen spectrum was measured. The conversion of the catalytic reaction was calculated to be 100% based on the hydrogen spectrum. As in fig. 4: no-CH peak of the substrate appears at 10.40ppm and a-CH peak of the product appears at 8.45ppm, indicating that the substrate has been completely converted to product, so the yield is 100%.
2.3 Synthesis of 1, 1-dicyano-2- (-m-nitrophenyl) -ethylene by using m-nitrobenzaldehyde as raw material under the catalysis of cobalt complex
M-nitrobenzaldehyde (0.5 mmol), malononitrile (1.0 mmol) and cobalt complex (2.0 mol-%) were added to 1.0mL of water, respectively, and after stirring at 25℃for 55 min, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give a yellow solid product. After the product was dissolved in deuterated chloroform, nuclear magnetic resonance hydrogen spectrum was measured. The conversion of the catalytic reaction was calculated to be 100% based on the hydrogen spectrum. As in fig. 5: no-CH peak of the substrate occurred at 10.03ppm and the-CH peak of the product occurred at 7.88ppm, indicating complete conversion of the substrate to product. The yield was 100%.
2.4 Synthesis of 1, 1-dicyano-2- (-p-nitrophenyl) -ethylene by using p-nitrobenzaldehyde as raw material under the catalysis of cobalt complex
To 1.0mL of water were added p-nitrobenzaldehyde (0.5 mmol), malononitrile (1.0 mmol) and cobalt complex (2.0 mol-%) respectively, and after stirring at 25℃for 55 minutes, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give a yellow solid product. After the product was dissolved in deuterated chloroform, nuclear magnetic resonance hydrogen spectrum was measured. The conversion of the catalytic reaction was calculated to be 100% based on the hydrogen spectrum. As in fig. 6: no-CH peak of the substrate occurred at 10.15ppm and a-CH peak of the product occurred at 7.88ppm, indicating that the substrate had been completely converted to product. The yield was 100%.
2.5 Synthesis of 1, 1-dicyano-2- (-p-chlorophenyl) -ethylene by using p-chlorobenzaldehyde as raw material under the catalysis of cobalt complex
To 1.0mL of water, p-chlorobenzaldehyde (0.5 mmol), malononitrile (1.0 mmol) and cobalt complex (2.0 mol-%) were added, respectively, and after stirring at 25℃for 55 minutes, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give a yellow solid product. After the product was dissolved in deuterated chloroform, nuclear magnetic resonance hydrogen spectrum was measured. The conversion of the catalytic reaction was calculated to be 100% based on the hydrogen spectrum. As in fig. 7: the-CH peak of the substrate (integral area 1.01) appeared at 9.97ppm and the-CH peak of the product (integral area 418.69) appeared at 7.73ppm, indicating that the substrate had been largely converted to the product. Yield= (418.69/419.7) ×100% = 99.8%.
2.6 Synthesis of 1, 1-dicyano-2- (-p-hydroxyphenyl) -ethylene by using Paraformaldehyde as raw material under the catalysis of cobalt Complex
To 1.0mL of water, parahydroxybenzaldehyde (0.5 mmol), malononitrile (1.0 mmol) and cobalt complex (2.0 mol-%) were added, respectively, and after stirring at 25℃for 55 minutes, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give a yellow solid product. After the product was dissolved in deuterated chloroform, nuclear magnetic resonance hydrogen spectrum was measured. The conversion of the catalytic reaction was calculated to be 16% based on the hydrogen spectrum. As in fig. 8: the-CH peak of the substrate (integral area 1) appeared at 9.86ppm and the-CH peak of the product (integral area 0.28) appeared at 7.64ppm, indicating partial conversion of the substrate to product. Yield= (0.28/1.28) ×100% = 21.9%.
2.7 Synthesis of 1, 1-dicyano-2- (-p-methylphenyl) -ethylene by using Paraformaldehyde as raw material under the catalysis of cobalt Complex
To 1.0mL of water, p-methylbenzaldehyde (0.5 mmol), malononitrile (1.0 mmol) and cobalt complex (2.0 mol-%) were added, respectively, and after stirring at 25℃for 55 minutes, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give a yellow solid product. After the product was dissolved in deuterated chloroform, nuclear magnetic resonance hydrogen spectrum was measured. The conversion of the catalytic reaction was calculated to be 98% based on the hydrogen spectrum. As in fig. 9: no-CH peak of the substrate occurred at 9.96ppm and a-CH peak of the product occurred at 7.73ppm, indicating that the substrate had been completely converted to product. The yield was 100%.
2.8 Synthesis of (4-methoxybenzyl) malononitrile with Paraformaldehyde as raw material under the catalysis of cobalt Complex
To 1.0mL of water, p-methoxybenzaldehyde (0.5 mmol), malononitrile (1.0 mmol) and cobalt complex (2.0 mol-%) were added, respectively, and after stirring at 25℃for 55 minutes, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give a yellow solid product. After the product was dissolved in deuterated chloroform, nuclear magnetic resonance hydrogen spectrum was measured. The conversion of the catalytic reaction was calculated to be 71% based on the hydrogen spectrum. As in fig. 10: no-CH peak of the substrate occurred at 9.89ppm and a-CH peak of the product occurred at 7.65ppm, indicating that the substrate had been completely converted to product. The yield was 100%.
In order to examine the stability and cyclic availability of cobalt complexes as catalysts in Knoevenagel condensation catalysis, 5 cyclic catalysis experiments were performed during the course of the present study, with yields of 100, 100 and 99%, respectively. The powder diffraction pattern shows that, referring to fig. 11, the cobalt complex is stable in structure after 5 catalytic reactions.
Claims (4)
1. The structural formula of the catalyst for the condensation reaction of aldehyde and malononitrile is shown as formula 1,
2. a process for the preparation of a catalyst for the condensation reaction of an aldehyde with malononitrile Knoevenagel according to claim 1, characterized in that the synthesis is described by formula 2:
the specific synthesis steps are as follows:
placing 0.3-0.9mmol of cobaltous chloride, 0.2-0.6mmol of 3,2',4' -biphenyl tricarboxylic acid, 0.3-0.9mmol of 4,4' -bipyridine and 0.6-1.8mmol of sodium hydroxide into 10-30ml of water, fully stirring, transferring into a reaction kettle, sealing, heating and keeping the reaction at 130-150 ℃ fully, cooling to room temperature, taking out the mixture from the kettle, washing with water, filtering, drying and separating to obtain the pink blocky crystal catalyst.
3. The method for preparing the catalyst for the condensation reaction of aldehyde and malononitrile Knoevenagel according to claim 2, characterized in that the mass ratio of cobaltous chloride, 3,2',4' -biphenyltricarboxylic acid, 4' -bipyridine and sodium hydroxide is 1:0.67:1:2.
4. The catalyst of claim 1 for use in the condensation reaction of an aldehyde with malononitrile Knoevenagel.
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