CN112920223B - A kind of catalyst and preparation method for the siliconitrile reaction of aldehyde and trimethyl cyanosilane - Google Patents

Abstract

的氢氧化钠置于水中，经充分搅拌后转移到聚四氟乙烯内衬的反应釜中密封，并保持130‑150℃条件下加热两天到三天，随后关闭电源冷却到室温，将釜内混合物取出，用水洗涤，过滤、干燥后分离得到黄色块状晶体的催化剂。本发明具有合成方法简单、环保，可高效、多相催化醛与三甲基氰硅烷的硅氰化反应，并具有活性高、反应条件温和，催化剂用量低，结构稳定可循环使用以及底物适用范围广等特点。The invention discloses a catalyst for the siliconitrile reaction of aldehyde and trimethyl cyanosilane, a preparation method and application thereof. The catalyst of the present invention for the siliconitrile reaction of aldehyde and trimethyl cyanosilane, its structural formula is shown in formula 1, and its synthesis step is: manganese chloride, 5-(3-carboxy-phenyl) pyridine-2 ‑Carboxylic acid and 0.4‑1.2 mmol

The sodium hydroxide was placed in water, and after being fully stirred, it was transferred to a Teflon-lined reaction kettle for sealing, and heated at 130-150°C for two to three days. Then the power was turned off and cooled to room temperature. The inner mixture was taken out, washed with water, filtered and dried to obtain the catalyst as yellow block crystals. The invention has the advantages of simple synthesis method, environmental protection, high efficiency and heterogeneous catalysis of the silylcyanation reaction of aldehyde and trimethyl cyanosilane, high activity, mild reaction conditions, low catalyst dosage, stable structure, recyclable use and suitable substrate. Wide range and so on.

Description

A kind of catalyst and preparation for the siliconitrile reaction of aldehyde and trimethyl cyanosilane method

technical field

The present invention relates to a catalyst and its preparation method and application. Specifically speaking, the invention relates to a catalyst used for the siliconitrile reaction of aldehyde and trimethylsilyl cyanide, as well as its preparation method and application.

Background technique

The siliconitrile reaction is one of the basic reactions of carbon-carbon bond formation in organic chemistry, and is often used in the synthesis of cyanohydrin. Cyanohydrin is an important derivative for the synthesis of fine chemicals and pharmaceuticals [1]. Metal catalysts and metal complex catalysts were the earliest selected catalysts for the siliconitrile reaction. These traditional catalysts have disadvantages such as harsh synthesis conditions, high cost and environmental pollution [2,3]. Recently, metal-organic complexes have been used for the catalysis of siliconitrile reactions, which have the advantages of relatively simple synthesis conditions and designable structures. However, most of these complexes are homogeneous catalysts, and a certain amount of organic solvent is used in the synthesis [4].

references:

[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 asymmetriccyanohydrin synthesis. Chem. Rev., 2008, 108, 5146-5226.

[3] Mao Na. The progress of silicon cyanation reaction. "Value Engineering" 2011, 30 (13), 300-301.

[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.

SUMMARY OF THE INVENTION

The invention discloses a catalyst and a preparation method for the siliconitrile reaction of aldehyde and trimethyl cyanosilane, which can overcome the deficiencies of the prior art, and uses thereof.

The catalyst of the present invention for the siliconitrile reaction of aldehyde and trimethylsilane has the structural formula shown in formula 1,

The preparation method of the catalyst for the siliconitrile reaction of aldehyde and trimethyl cyanosilane of the present invention is shown in formula 2:

The specific synthesis steps are:

Place 0.2-0.6 mmol of manganese chloride, 0.2-0.6 mmol of 5-(3-carboxy-phenyl)pyridine-2-carboxylic acid and 0.4-1.2 mmol of sodium hydroxide in 10-30 ml of water and stir well After that, it was transferred to a polytetrafluoroethylene-lined reaction kettle and sealed, and heated at 130-150 °C for two to three days. Then, the power was turned off and cooled to room temperature. The mixture in the kettle was taken out, washed with water, filtered and dried. The catalyst was isolated as yellow bulk crystals.

Preferably, the preparation method of the catalyst for the siliconitrile reaction of aldehyde and trimethylcyanosilane of the present invention is characterized in that manganese chloride, 5-(3-carboxy-phenyl)pyridine-2-carboxylic acid and The substance ratio of sodium hydroxide is 1:1:2.

The catalyst of the present invention is used in the catalytic reaction of siliconitrile of aldehydes.

The invention has the advantages of simple synthesis method and environmental protection, and can efficiently and heterogeneously catalyze the silylation reaction of aldehyde and trimethylcyanosilane. The catalyst has the characteristics of high activity, mild reaction conditions, low catalyst dosage, stable structure, recyclable use, and wide application range of substrates.

Description of drawings

The infrared spectrum of Fig. 1 manganese complex of the present invention;

Fig. 2 thermogravimetric curve of manganese complex of the present invention;

Fig. 3 takes p-nitrobenzaldehyde as substrate manganese complex-catalyzed nitrification catalytic reaction product of ¹ H NMR spectrum;

Fig. 4 uses benzaldehyde as substrate, the ¹ H NMR spectrum of the nitrification catalytic reaction product catalyzed by manganese complex;

Fig. 5 takes o-nitrobenzaldehyde as a substrate, the ¹ H nuclear magnetic spectrum of the nitrification catalytic reaction product catalyzed by manganese complex;

Fig. 6 uses m-nitrobenzaldehyde as substrate, the ¹ H NMR spectrum of the nitrification catalytic reaction product catalyzed by manganese complex;

Fig. 7 takes p-chlorobenzaldehyde as substrate, the ¹ H NMR spectrum of the nitrification catalytic reaction product catalyzed by manganese complex;

Fig. 8 takes p-hydroxybenzaldehyde as a substrate, the ¹ H NMR spectrum of the nitrification catalytic reaction product catalyzed by manganese complex;

Fig. 9 takes p-methylbenzaldehyde as a substrate, the ¹ H nuclear magnetic spectrum of the nitrification catalytic reaction product catalyzed by manganese complex;

Figure 10 ¹ H NMR spectrum of the catalytic reaction product of nitrification catalyzed by manganese complexes using p-methoxybenzaldehyde as a substrate.

Fig. 11 Powder diffractograms of the manganese complex of the present invention before and after the catalytic reaction.

Detailed ways

The present invention is explained below with reference to the embodiments.

(1) Catalyst preparation

Using water (10 mL) as solvent, combine manganese chloride (0.2 mmol, 39.6 mg), 5-(3-carboxy-phenyl)pyridine-2-carboxylic acid (0.2 mmol, 48.6 mg) and sodium hydroxide (0.4 mmol) , 16.0 mg) mixture was placed in a beaker and stirred for 15 min, then transferred to a 25 mL polytetrafluoroethylene-lined reaction kettle, sealed, and heated at 150° C. for three days. Then, the power was turned off and cooled to room temperature, and the mixture in the kettle was taken out, washed with distilled water, filtered, dried, and manually separated to obtain a manganese complex catalyst with yellow bulk crystals. Yield: 65% (based on manganese chloride). Elemental analysis C ₁₃ H ₁₁ MnNO ₆ , theoretical: C 47.01, H 3.34, N 4.22%. Found: C 47.31, H 3.36, N 4.20%. Infrared spectroscopy (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:

)测定其晶体结构。使用程序SADABS对衍射数据进行吸收矫正，采用直接法解出单晶结构，而对于结构中所有非氢原子的坐标，借助程序SHELXS-2014和SHELXL-2014对F²以全矩阵最小二乘法进行精细修正，最后通过理论计算得出氢原子的坐标。锰配合物的主要晶体学数据如下表1所示。First, select transparent crystals with regular morphology, proper size, no cracks, and no impurities attached to the surface, and then placed on the graphite monochromator of the X-ray single crystal diffractometer, through Mo K _α rays (

) to determine its crystal structure. The diffraction data were subjected to absorption correction using the program SADABS, the single crystal structure was solved by the direct method, and for the coordinates of all non-hydrogen atoms in the structure, F ² was refined by the full-matrix least squares method with the aid of the programs SHELXS-2014 and SHELXL-2014 Correction, and finally obtain the coordinates of the hydrogen atom through theoretical calculation. The main crystallographic data of the manganese complexes are shown in Table 1 below.

Table 1 Crystallographic data of manganese complexes

Thermal Stability Determination:

In order to study the thermal stability of the manganese complex, the thermogravimetric curve of the complex was measured in the range of 25-800 °C under nitrogen protection, and the heating rate was controlled at 10 °C/min (see Figure 2). The complex lost 11.3% weight between 123-167°C, corresponding to the loss of two coordinated water molecules (theoretical value 11.4%). The remaining skeleton begins to collapse at 418 °C.

(2) catalytic properties of manganese complex of the present invention in the siliconitrile reaction of aldehyde

In 2.5 mL of dichloromethane, aromatic aldehyde (0.5 mmol, using 4-nitrobenzaldehyde as substrate), trimethylsilyl cyanide (1.0 mmol) and manganese complex (3%) were added respectively and stirred at 35 °C After 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 was dissolved in deuterated chloroform, the H NMR spectrum was measured. The conversion of the catalytic reaction was calculated from the hydrogen spectrum.

Formula 3 Siliconitrile catalyzed by manganese complexes using p-nitrobenzaldehyde as substrate

Table 2 takes p-nitrobenzaldehyde as the substrate, the siliconitrile reaction data catalyzed by manganese complex

Reaction conditions: catalyst (3 mol%), substrate p-nitrobenzaldehyde (0.5 mmol), trimethylsilyl cyanide (1.0 mmol), solvent (2.5 mL), temperature 35°C. ^b Yield calculated from NMR data: [moles of product/moles of p-nitrobenzaldehyde]×100%.

2.1 Synthesis of 2-(4-nitrophenyl)-2-[(trimethylsilyl)oxy]acetonitrile with p-nitrobenzaldehyde as raw material under the catalysis of manganese complex

In 2.5 mL of dichloromethane, p-nitrobenzaldehyde (0.5 mmol), trimethylsilyl cyanide (1.0 mmol) and manganese complex (3.0 mol-%) were added respectively, and after stirring at 35 °C for 10 hours, centrifugation The catalyst was removed and the solvent was removed by rotary evaporation to obtain a yellow liquid product. After the product was dissolved in deuterated chloroform, the H NMR spectrum was measured. The conversion rate of the catalytic reaction was calculated as 100% according to the hydrogen spectrum, see Figure 3: the -CH peak of the substrate does not appear at 10.15 ppm, and the -CH peak of the product appears at 5.60 ppm, indicating that the substrate has been completely converted to the product , so the yield is 100%.

The present invention also studies the siliconitrile reaction yield of manganese complex as a catalyst for other substrates (Formula 4 and Table 3)

Formula 4 Siliconitrile catalyzed by manganese complexes with other aldehydes as substrates

Table 3. Data on the catalytic reaction of siliconitrile with other aldehydes as substrates.

Reaction conditions: catalyst (3.0 mol.%), benzaldehyde-based substrate (0.5 mmol), trimethylsilyl cyanide (1.0 mmol), solvent dichloromethane (2.5 mL), 35°C. ^b Yields were calculated from NMR data: [moles of product/moles of substrate]×100%.

2.2 Synthesis of 2-phenyl-2-[(trimethylsilyl)oxy]acetonitrile with benzaldehyde as raw material under the catalysis of manganese complex

In 2.5 mL of dichloromethane, benzaldehyde (0.5 mmol), trimethylsilyl cyanide (1.0 mmol) and manganese complex (3.0 mol-%) were added, and after stirring at 35 °C for 10 hours, the catalyst was removed by centrifugation. After rotary evaporation to remove the solvent, a yellow liquid product was obtained. After the product was dissolved in deuterated chloroform, the H NMR spectrum was measured. The conversion of the catalytic reaction was calculated to be 97% according to the hydrogen spectrum, see Figure 4: the -CH peak of the substrate appeared at 10.06 ppm (integrated area 1), and the -CH peak of the product appeared at 5.52 ppm (integrated area 35.68) , indicating that the substrate is partially converted to the product. Yield=(35.68/36.68)×100%=97.3%.

2.3 Synthesis of 2-(2-nitrophenyl)-2-[(trimethylsilyl)oxy]acetonitrile with o-nitrobenzaldehyde as raw material under the catalysis of manganese complex

In 2.5 mL of dichloromethane, o-nitrobenzaldehyde (0.5 mmol), trimethylsilyl cyanide (1.0 mmol) and manganese complex (3.0 mol-%) were added respectively, and after stirring at 35°C for 10 hours, centrifugation The catalyst was removed and the solvent was removed by rotary evaporation to obtain a yellow liquid product. After the product was dissolved in deuterated chloroform, the H NMR spectrum was measured. The conversion of the catalytic reaction was calculated to be 97% according to the hydrogen spectrum, see Figure 5: the -CH peak of the substrate appeared at 10.40 ppm (integrated area 1), and the -CH peak of the product appeared at 6.20 ppm (integrated area 38.57) , indicating that the substrate is partially converted to the product. Yield=(38.57/39.57)×100%=97.5%.

2.4 Synthesis of 2-(3-nitrophenyl)-2-[(trimethylsilyl)oxy]acetonitrile with m-nitrobenzaldehyde as raw material under the catalysis of manganese complex

In 2.5 mL of dichloromethane, m-nitrobenzaldehyde (0.5 mmol), trimethylsilyl cyanide (1.0 mmol) and manganese complex (3.0 mol-%) were added respectively, and after stirring at 35 °C for 10 hours, centrifugation The catalyst was removed and the solvent was removed by rotary evaporation to obtain a yellow liquid product. After the product was dissolved in deuterated chloroform, the H NMR spectrum was measured. The conversion rate of the catalytic reaction was calculated to be 100% according to the hydrogen spectrum, see Figure 6: the -CH peak of the substrate appeared at 10.03 ppm (integrated area 1), and the -CH peak of the product appeared at 5.50 ppm (integrated area 37.59) , indicating that the substrate is partially converted to the product. Yield=(37.59/38.59)×100%=97.4%.

2.5 Synthesis of 2-(4-chlorophenyl)-2-[(trimethylsilyl)oxy]acetonitrile with p-chlorobenzaldehyde as raw material under the catalysis of manganese complex

In 2.5 mL of dichloromethane, were added p-chlorobenzaldehyde (0.5 mmol), trimethylsilyl cyanide (1.0 mmol) and manganese complex (3.0 mol-%), stirred at 35°C for 10 hours, and removed by centrifugation After the catalyst was evaporated to remove the solvent, a yellow liquid product was obtained. After the product was dissolved in deuterated chloroform, the H NMR spectrum was measured. The conversion of the catalytic reaction was calculated to be 68% according to the hydrogen spectrum, see Figure 7: the -CH peak of the substrate appeared at 9.97 ppm (integrated area 1), and the -CH peak of the product appeared at 5.45 ppm (integrated area 2.15) , indicating that the substrate is partially converted to the product. Yield=(2.15/3.15)×100%=68.3%.

2.6 Synthesis of 2-(4-hydroxyphenyl)-2-[(trimethylsilyl)oxy]acetonitrile using p-hydroxybenzaldehyde as raw material under the catalysis of manganese complex

In 2.5 mL of dichloromethane, were added p-hydroxybenzaldehyde (0.5 mmol), trimethylsilyl cyanide (1.0 mmol) and manganese complex (3.0 mol-%), stirred at 35°C for 10 hours, and removed by centrifugation After the catalyst was evaporated to remove the solvent, a yellow liquid product was obtained. After the product was dissolved in deuterated chloroform, the H NMR spectrum was measured. The conversion of the catalytic reaction was calculated to be 17% according to the hydrogen spectrum, see Figure 8: the -CH peak of the substrate appeared at 9.89 ppm (integrated area 1), and the -CH peak of the product appeared at 5.43 ppm (integrated area 0.21) , indicating that the substrate is partially converted to the product. Yield=(0.21/1.21)×100%=17.4%.

2.7 Synthesis of 2-(4-methylphenyl)-2-[(trimethylsilyl)oxy]acetonitrile with p-methylbenzaldehyde as raw material under the catalysis of manganese complex

In 2.5 mL of dichloromethane, p-methylbenzaldehyde (0.5 mmol), trimethylsilyl cyanide (1.0 mmol) and manganese complex (3.0 mol-%) were added respectively, and after stirring at 35°C for 10 hours, centrifugation The catalyst was removed and the solvent was removed by rotary evaporation to obtain a yellow liquid product. After the product was dissolved in deuterated chloroform, the H NMR spectrum was measured. The conversion of the catalytic reaction was calculated to be 60% according to the hydrogen spectrum, see Figure 9: the -CH peak of the substrate appeared at 9.97 ppm (integrated area 1), and the -CH peak of the product appeared at 5.45 ppm (integrated area 1.50) , indicating that the substrate is partially converted to the product. Yield=(1.50/2.50)×100%=60.0%.

2.8 Synthesis of 2-(4-methoxyphenyl)-2-[(trimethylsilyl)oxy]acetonitrile with p-methoxybenzaldehyde as raw material under the catalysis of manganese complex

In 2.5 mL of dichloromethane, p-methoxybenzaldehyde (0.5 mmol), trimethylsilyl cyanide (1.0 mmol) and manganese complex (3.0 mol-%) were respectively added, and after stirring at 35°C 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 was dissolved in deuterated chloroform, the H NMR spectrum was measured. The conversion of the catalytic reaction was calculated to be 14% according to the hydrogen spectrum, see Figure 10: the -CH peak of the substrate appeared at 9.89 ppm (integrated area 1) and the -CH peak of the product appeared at 5.44 ppm (integrated area 0.46) , indicating that the substrate is partially converted to the product. Yield=(0.16/1.16)×100%=13.8%.

In order to test the stability and cyclic availability of manganese complexes as catalysts in the siliconitrile catalytic reaction, 5 cyclic catalysis experiments were performed during the research process of the present invention, and the yields were 100, 99, 98, 97 and 95 respectively. %. The powder diffractogram showed (Fig. 11) that the structure of the manganese complex remained 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,

space group, unit cell parameter a =12.1926(13)

，b=10.4695(6)

，c=11.4659(12)

，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:

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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