CN112920223B - Catalyst for silicon cyanation reaction of aldehyde and trimethylsilyl cyanide and preparation method thereof - Google Patents

Catalyst for silicon cyanation reaction of aldehyde and trimethylsilyl cyanide and preparation method thereof Download PDF

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CN112920223B
CN112920223B CN202110173146.6A CN202110173146A CN112920223B CN 112920223 B CN112920223 B CN 112920223B CN 202110173146 A CN202110173146 A CN 202110173146A CN 112920223 B CN112920223 B CN 112920223B
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顾金忠
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    • B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
    • B01J2231/343—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones to prepare cyanhydrines, e.g. by adding HCN or TMSCN
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Abstract

The invention discloses a catalyst for silicon cyanation reaction of aldehyde and trimethylsilyl cyanide, a preparation method and application thereof. The structural formula of the catalyst for silicon cyanation reaction of aldehyde and trimethylsilyl cyanide is shown as formula 1, and the synthesis steps are as follows: manganese chloride, 5- (3-carboxy-phenyl) pyridine-2-carboxylic acid and 0.4-1.2mmol

Description

Catalyst for silicon cyanation reaction of aldehyde and trimethylsilyl cyanide and preparation method thereof
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, in particular to a catalyst for silicon cyanation reaction of aldehyde and trimethylsilyl cyanide, and a preparation method and application thereof.
Background
The silicon cyanation reaction belongs to one of the basic reactions of carbon-carbon bond formation in organic chemistry, and is commonly used for synthesizing cyanohydrin. Cyanohydrins are an important class of derivatives for the synthesis of fine chemicals and drugs [1 ]. The catalysts for silicon cyanation reaction were selected from metal catalysts and metal complex catalysts, and these traditional catalysts have the disadvantages of harsh synthesis conditions, high cost, environmental pollution, etc. [2,3 ]. Recently, metal-organic complexes have begun to be used in the catalysis of silicon cyanation reactions, which have the advantages of relatively simple synthesis conditions and designable structure. However, most of these complexes are homogeneous catalysts, and a certain amount of organic solvent is used in the synthesis [4 ].
Reference documents:
[1]Mowry,D.T.The preparation of nitriles.Chem.Rev.,1948,42,189–283.
[2]North,M.；Usanov,D.L.；Young,C.Lewis acid catalyzed asymmetric cyanohydrin synthesis.Chem.Rev.,2008,108,5146-5226.
[3] maona. progress of the silicon cyanidation reaction [ value engineering ] 2011,30(13), 300-.
[4]Karmakar,A.；Paul,A.；Rúbio,G.M.D.M.；Guedes da Silva,M.F.C.；Pombeiro,A.J.L.Zinc(II)and copper(II)metal-organic frameworks constructed from a terphenyl-4,4”-dicarboxylic acid derivative:synthesis,structure,and catalytic application in the cyanosilylation of aldehydes.Eur.J.Inorg.Chem.,2016,5557-5567.。
Disclosure of Invention
The invention discloses a catalyst for silicon cyanation reaction of aldehyde and trimethylsilyl cyanide, a preparation method and application thereof, which can overcome the defects of the prior art.
The structural formula of the catalyst for silicon cyanation reaction of aldehyde and trimethylsilyl cyanide is shown as formula 1,
Figure BDA0002939479430000021
the preparation method of the catalyst for silicon cyanation of aldehyde and trimethylsilyl cyanide of the present invention is shown in formula 2:
Figure BDA0002939479430000022
the specific synthesis steps are as follows:
putting 0.2-0.6mmol of manganese chloride, 0.2-0.6mmol of 5- (3-carboxyl-phenyl) pyridine-2-carboxylic acid 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 days to three days under the condition of keeping the temperature of 130-150 ℃, 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 massive yellow crystal catalyst.
Preferably, the method for preparing a catalyst for the silicon cyanation reaction of aldehyde with trimethylsilyl cyanide of the present invention is characterized in that the mass ratio of manganese chloride, 5- (3-carboxy-phenyl) pyridine-2-carboxylic acid and sodium hydroxide is 1: 2.
The catalyst of the invention is used for the silicon cyanation catalytic reaction of aldehyde.
The method has the advantages of simple synthesis method, environmental protection, high efficiency and heterogeneous catalysis of the silicon cyanidation reaction of aldehyde and trimethylsilyl cyanide. The catalyst has the characteristics of high activity, mild reaction conditions, low catalyst consumption, 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 that manganese complex catalyzed cyanation reaction product with p-nitrobenzaldehyde as substrate 1 H nuclear magnetic spectrum;
FIG. 4 shows the reaction product of a manganese complex catalyzed cyanation reaction with benzaldehyde as a substrate 1 H nuclear magnetic spectrum;
FIG. 5 shows the reaction product of a manganese complex catalyzed cyanation reaction with o-nitrobenzaldehyde as a substrate 1 H nuclear magnetic spectrum;
FIG. 6 shows that the reaction product of the cyanation catalysis catalyzed by the manganese complex takes m-nitrobenzaldehyde as the substrate 1 H nuclear magnetic spectrum;
FIG. 7 shows the reaction product of a manganese complex catalyzed cyanation reaction with p-chlorobenzaldehyde as a substrate 1 H nuclear magnetic spectrum;
FIG. 8 shows the reaction product of a manganese complex catalyzed cyanation reaction with p-hydroxybenzaldehyde as a substrate 1 H nuclear magnetic spectrum;
FIG. 9 of catalytic reaction product of cyanation catalyzed by manganese complex with p-tolualdehyde as substrate 1 H nuclear magnetic spectrum;
FIG. 10 shows that the reaction product of the catalytic cyanation reaction is catalyzed by manganese complex with p-methoxybenzaldehyde as a substrate 1 H nuclear magnetic spectrum.
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
A mixture of manganese chloride (0.2mmol, 39.6mg), 5- (3-carboxy-phenyl) pyridine-2-carboxylic acid (0.2mmol, 48.6mg), and sodium hydroxide (0.4mmol, 16.0mg) was stirred in a beaker with water (10mL) as a solvent for 15min, transferred to a 25mL polytetrafluoroethylene-lined reaction vessel, 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: 65% (based on manganese chloride). Elemental analysis C 13 H 11 MnNO 6 The theoretical value is as follows: c47.01, H3.34, N4.22%. Measured value: c47.31, H3.36, N4.20%. Infrared spectroscopic analysis (KBr, cm) -1 )：3420m，3171m，1616w，1564s，1487w，1434w，1399s，1365s，1288w，1248w，1169w，1128w，1094w，1032w，978w，916w，881w，850w，804w，771m，704w，655w，548w。
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 through Mo K α Ray (C)
Figure BDA0002939479430000042
) The crystal structure was determined. The diffraction data were absorption corrected using the program SADABS to solve the single crystal structure directly, while for all the coordinates of the non-hydrogen atoms in the structure F was corrected by means of 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 complex are shown in table 1 below.
TABLE 1 crystallographic data of manganese complexes
Figure BDA0002939479430000041
Figure BDA0002939479430000051
And (3) measuring the thermal stability:
in order to investigate the thermal stability of the manganese complex, the thermogravimetric curve of the complex was determined at a temperature range of 25-800 ℃ under nitrogen protection with a temperature rise rate of 10 ℃/min (see fig. 2). The complex loses 11.3 percent of weight between 123 ℃ and 167 ℃, and correspondingly loses two coordinated water molecules (theoretical value is 11.4 percent). The remaining framework began to collapse at 418 ℃.
(II) catalytic Properties of manganese Complex of the present invention in silicon cyanation of aldehyde
After adding aromatic aldehyde (0.5mmol, using 4-nitrobenzaldehyde as a substrate), trimethylsilyl cyanide (1.0mmol) and manganese complex (3%) to 2.5mL of dichloromethane, respectively, and stirring at 35 ℃ for a certain period of time, the catalyst was removed by centrifugation, and the solvent was removed by rotary evaporation to obtain a yellow liquid 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 BDA0002939479430000061
Formula 3 silicon cyanation reaction catalyzed by manganese complex with p-nitrobenzaldehyde as substrate
TABLE 2 data of the manganese complex catalyzed silicocyanation reaction using p-nitrobenzaldehyde as substrate
Figure BDA0002939479430000062
Reaction conditions are as follows: catalyst (3 mol%), substrate p-nitrobenzaldehyde (0.5mmol), trimethylsilyl cyanide (1.0mmol), solvent (2.5mL), temperature 35 ℃. b The yield was calculated from the nuclear magnetic data as: [ moles of product/moles of p-nitrobenzaldehyde]×100％。
2.1 Synthesis of 2- (4-nitrophenyl) -2- [ (trimethylsilyl) oxy ] acetonitrile from p-nitrobenzaldehyde as raw Material under catalysis of manganese Complex
P-nitrobenzaldehyde (0.5mmol), trimethylsilyl cyanide (1.0mmol) and manganese complex (3.0 mol%) were added to 2.5mL of methylene chloride, and the mixture was stirred at 35 ℃ for 10 hours, after which the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation, a yellow liquid 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, see fig. 3: at 10.15ppm, no substrate-CH peak was present and at 5.60ppm, a product-CH peak was present, indicating complete conversion of substrate to product and thus a yield of 100%.
The present inventors have also investigated the silicocyanation reaction yield of manganese complexes as catalysts on other substrates (formula 4 and Table 3)
Figure BDA0002939479430000071
Formula 4 silicon cyanation reaction catalyzed by manganese complex with other aldehydes as substrate
Table 3 data for catalytic silicocyanation reactions with other aldehydes as substrates.
Figure BDA0002939479430000072
Reaction conditions are as follows: catalyst (3.0 mol.%), benzaldehyde substrate (0.5mmol), trimethylsilyl cyanide (1.0mmol), solvent dichloromethane (2.5mL), 35 ℃. b The yield was calculated using nuclear magnetic data as follows: [ moles of product/moles of substrate [ ]]×100％。
2.2 Synthesis of 2-phenyl-2- [ (trimethylsilyl) oxy ] acetonitrile from benzaldehyde as raw Material under catalysis of manganese Complex
Benzaldehyde (0.5mmol), trimethylsilyl cyanide (1.0mmol) and a manganese complex (3.0 mol%) were added to 2.5mL of methylene chloride, respectively, and the mixture was stirred at 35 ℃ for 10 hours, and then centrifuged to remove the catalyst, and the solvent was removed by rotary evaporation to obtain a yellow liquid 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 97% from the hydrogen spectrum, see fig. 4: the-CH peak of the substrate (integrated area 1) appeared at 10.06ppm and the-CH peak of the product (integrated area 35.68) appeared at 5.52ppm, indicating partial conversion of the substrate to the product. The yield was (35.68/36.68) × 100% ═ 97.3%.
2.3 Synthesis of 2- (2-nitrophenyl) -2- [ (trimethylsilyl) oxy ] acetonitrile from o-nitrobenzaldehyde as raw Material under catalysis of manganese Complex
To 2.5mL of methylene chloride were added o-nitrobenzaldehyde (0.5mmol), trimethylsilyl cyanide (1.0mmol) and manganese complex (3.0 mol-%), respectively, and after stirring at 35 ℃ for 10 hours, the catalyst was removed by centrifugation, and the solvent was removed by rotary evaporation to give a yellow liquid 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 97% from the hydrogen spectrum, see fig. 5: the-CH peak of the substrate (integrated area 1) appeared at 10.40ppm and the-CH peak of the product (integrated area 38.57) appeared at 6.20ppm, indicating partial conversion of the substrate to the product. The yield was (38.57/39.57) × 100% ═ 97.5%.
2.4 Synthesis of 2- (3-nitrophenyl) -2- [ (trimethylsilyl) oxy ] acetonitrile from m-nitrobenzaldehyde as raw Material under catalysis of manganese Complex
After m-nitrobenzaldehyde (0.5mmol), trimethylsilyl cyanide (1.0mmol) and manganese complex (3.0 mol%) were added to 2.5mL of methylene chloride, respectively, and stirred at 35 ℃ for 10 hours, the catalyst was removed by centrifugation, and the solvent was removed by rotary evaporation to obtain a yellow liquid 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, see fig. 6: the-CH peak of the substrate (integrated area 1) appeared at 10.03ppm and the-CH peak of the product (integrated area 37.59) appeared at 5.50ppm, indicating partial conversion of the substrate to the product. The yield was (37.59/38.59) × 100% ═ 97.4%.
2.5 Synthesis of 2- (4-chlorophenyl) -2- [ (trimethylsilyl) oxy ] acetonitrile from p-chlorobenzaldehyde as raw material under catalysis of manganese Complex
P-chlorobenzaldehyde (0.5mmol), trimethylsilyl cyanide (1.0mmol) and manganese complex (3.0 mol%) were added to 2.5mL of methylene chloride, respectively, and after stirring at 35 ℃ for 10 hours, the catalyst was removed by centrifugation, and the solvent was removed by rotary evaporation to obtain a yellow liquid 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 68% from the hydrogen spectrum, see fig. 7: the-CH peak for the substrate (integrated area 1) appeared at 9.97ppm and the-CH peak for the product (integrated area 2.15) appeared at 5.45ppm, indicating partial conversion of substrate to product. The yield was (2.15/3.15) × 100% ═ 68.3%.
2.6 Synthesis of 2- (4-hydroxyphenyl) -2- [ (trimethylsilyl) oxy ] acetonitrile from p-hydroxybenzaldehyde as raw material under catalysis of manganese Complex
P-hydroxybenzaldehyde (0.5mmol), trimethylsilyl cyanide (1.0mmol) and manganese complex (3.0 mol-%) were added to 2.5mL of dichloromethane, respectively, and after stirring for 10 hours at 35 ℃, the catalyst was removed by centrifugation and the solvent was removed by rotary evaporation to give a yellow liquid 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 17% from the hydrogen spectrum, see fig. 8: the-CH peak of the substrate (integrated area 1) appeared at 9.89ppm and the-CH peak of the product (integrated area 0.21) appeared at 5.43ppm, indicating partial conversion of the substrate to the product. The yield was (0.21/1.21) × 100% ═ 17.4%.
2.7 Synthesis of 2- (4-methylphenyl) -2- [ (trimethylsilyl) oxy ] acetonitrile from p-tolualdehyde as raw material under catalysis of manganese Complex
P-tolualdehyde (0.5mmol), trimethylsilyl cyanide (1.0mmol) and manganese complex (3.0 mol%) were added to 2.5mL of methylene chloride, respectively, and after stirring at 35 ℃ for 10 hours, the catalyst was removed by centrifugation, and the solvent was removed by rotary evaporation to obtain a yellow liquid 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 60% from the hydrogen spectrum, see fig. 9: the-CH peak of the substrate (integrated area 1) appeared at 9.97ppm and the-CH peak of the product (integrated area 1.50) appeared at 5.45ppm, indicating partial conversion of the substrate to the product. The yield was (1.50/2.50) × 100% ═ 60.0%.
2.8 Synthesis of 2- (4-methoxyphenyl) -2- [ (trimethylsilyl) oxy ] acetonitrile from p-methoxybenzaldehyde under catalysis of manganese complex
P-methoxybenzaldehyde (0.5mmol), trimethylsilyl cyanide (1.0mmol) and manganese complex (3.0 mol%) were added to 2.5mL of methylene chloride, respectively, and after stirring at 35 ℃ for 10 hours, the catalyst was removed by centrifugation, and the solvent was removed by rotary evaporation to obtain a yellow liquid 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 14% from the hydrogen spectrum, see fig. 10: the-CH peak of the substrate (integrated area 1) appeared at 9.89ppm and the-CH peak of the product (integrated area 0.46) appeared at 5.44ppm, indicating partial conversion of the substrate to the product. The yield was (0.16/1.16) × 100% ═ 13.8%.
In order to test the stability and the recycling availability of the manganese complex as a catalyst in the silicon cyanation catalytic reaction, 5 times of cyclic catalysis experiments are carried out in the research process of the invention, and the yield is 100, 99, 98, 97 and 95 percent respectively. The powder diffraction pattern shows (fig. 11) that the structure of the manganese complex is still stable after 5 catalytic reactions.

Claims (4)

1. Catalyst for the silicon cyanation of aldehydes with trimethylsilyl cyanide of the formula C 13 H 11 MnNO 6 Molecular weight 332.17, monoclinic system,
Figure DEST_PATH_IMAGE001
space group, unit cell parameter a =12.1926(13)
Figure 271962DEST_PATH_IMAGE002
，b=10.4695(6)
Figure 995068DEST_PATH_IMAGE002
，c=11.4659(12)
Figure 278282DEST_PATH_IMAGE002
，α=90º，β=116.769(14)º，γ=90º。
2. The method for preparing a catalyst for the silicon cyanation of aldehyde with trimethylcyanosilane as set forth in claim 1, characterized in that the synthesis method is shown in formula 2:
Figure DEST_PATH_IMAGE003
formula 2
The specific synthesis steps are as follows:
putting 0.2-0.6mmol of manganese chloride, 0.2-0.6mmol of 5- (3-carboxyl-phenyl) pyridine-2-carboxylic acid and 0.4-1.2mmol of sodium hydroxide into 10-30ml of water, fully stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining, sealing, heating for two days to three days under the condition of keeping 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.
3. The method of claim 2, wherein the mass ratio of manganese chloride, 5- (3-carboxy-phenyl) pyridine-2-carboxylic acid and sodium hydroxide is 1:1: 2.
4. The catalyst of claim 1 for use in the silicocyanation of aldehydes.
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