Method for immobilizing carbon dioxide

Abstract

The invention belongs to the technical field of organic catalysis, and particularly discloses a method for immobilizing carbon dioxide, which adopts epoxide shown as a formula II and carbon dioxide togenerate a cyclic carbonate compound under the catalysis of a catalyst shown as a formula I under the condition of 60-120 DEG C. The method has the advantages of high conversion rate of carbon dioxide, no metal residue in the reaction, mild reaction conditions and easier preparation of the catalyst, and can be widely applied to industrial production.

Description

technical field

[0001] The invention belongs to the technical field of organic catalysis, in particular to a method for fixing carbon dioxide. Background technique

[0002] With the progress of the industrial revolution, the concentration of carbon dioxide in the atmosphere has increased dramatically, causing many environmental problems, such as global warming, sea level rise and frequent extreme weather, etc. The main causes of these problems are the burning of fossil fuels and human production activities. Therefore, the development of chemical processes for efficient fixation and utilization of carbon dioxide has become a current research hotspot. Among them, the chemical fixation of carbon dioxide into chemicals with higher added value is the most popular, because carbon dioxide can be used as a renewable and cheap carbon source in the chemical industry. Among many methods for fixing carbon dioxide, the method of combining carbon dioxide with epoxides to form cyclic car...

Examples

Embodiment 1

[0047] The reaction flask was dehydrated and deoxygenated, and catalyst 1 (24.1 mg, 0.1 mmol, 0.01 equiv) and epoxide J (1.2 mL, 10 mmol, 1.0 equiv) were added under the condition of inert gas. Evacuate the inert gas in the reaction bottle, fill it with carbon dioxide, and repeat it three times. Insert a balloon filled with carbon dioxide and put it into an oil bath at 100°C to react for 5 hours. After the reaction, cooling, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a rotary evaporator to obtain a yellow solid, which was dried to constant weight. The conversion rate is 58%, and the hydrogen spectrogram of the product is as follows figure 1 Shown, (Proton NMR spectrum, 400Hz, CDCl 3 ). The spectrogram data is: 1 H NMR (400MHz, Chloroform-d) δ7.49–7.39(m,3H),7.43–7.31(m,2H),5.68(t,J=8.0Hz,1H),4.80(t,J=8.4Hz, 1H),4.34(t,J=8.3Hz, 1H).

[0048] Catalyst...

Embodiment 2

[0050] The reaction flask was dehydrated and deoxygenated, and catalyst 2 (28.4 mg, 0.1 mmol, 0.01 equiv) and epoxide J (1.2 mL, 10 mmol, 1.0 equiv) were added under the condition of inert gas. Evacuate the inert gas in the reaction bottle, fill it with carbon dioxide, and repeat it three times. Insert a balloon filled with carbon dioxide and put it into an oil bath at 100°C to react for 5 hours. After the reaction, cooling, after column chromatography (petroleum ether: ethyl acetate=5:1), obtain the mixed solution that dissolves the product, the solution is spin-dried on the rotary evaporator, obtains yellow solid, is dried to constant weight, The conversion rate is 80%.

[0051] Catalyst 2 was prepared as follows: 4-dimethylaminopyridine (1.221 g, 10 mmol, 1.0 equiv) was dissolved in 5 mL of dichloromethane. Iodine chloride (0.50 mL, 10 mol, 1 equiv) was dissolved in 20 mL of dichloromethane. At 0°C, add the iodine chloride solution in dichloromethane dropwise into the 4-...

Embodiment 3

[0053] The reaction flask was dehydrated and deoxygenated, and catalyst 3 (25.5 mg, 0.1 mmol, 0.01 equiv) and epoxide J (0.6 mL, 5 mmol, 0.5 equiv) were added under the condition of inert gas. Evacuate the inert gas in the reaction bottle, fill it with carbon dioxide, and repeat it three times. Insert a balloon filled with carbon dioxide and put it into an oil bath at 100°C to react for 5 hours. After the reaction, cooling, after column chromatography (petroleum ether: ethyl acetate=5:1), obtain the mixed solution that dissolves the product, the solution is spin-dried on the rotary evaporator, obtains yellow solid, is dried to constant weight, The conversion rate was 83%.

[0054] 4-Methylpyridine (1.0 mL, 10 mmol, 1.0 equiv) was dissolved in 5 mL of dichloromethane. Iodine chloride (0.50 mL, 10 mol, 1 equiv) was dissolved in 20 mL of dichloromethane. At room temperature, the dichloromethane solution of iodine chloride was added dropwise to the dichloromethane solution of 4...

technical field

[0001] The invention belongs to the technical field of organic catalysis, in particular to a method for fixing carbon dioxide. Background technique

[0002] With the progress of the industrial revolution, the concentration of carbon dioxide in the atmosphere has increased dramatically, causing many environmental problems, such as global warming, sea level rise and frequent extreme weather, etc. The main causes of these problems are the burning of fossil fuels and human production activities. Therefore, the development of chemical processes for efficient fixation and utilization of carbon dioxide has become a current research hotspot. Among them, the chemical fixation of carbon dioxide into chemicals with higher added value is the most popular, because carbon dioxide can be used as a renewable and cheap carbon source in the chemical industry. Among many methods for fixing carbon dioxide, the method of combining carbon dioxide with epoxides to form cyclic car...

Examples

Embodiment 1

[0047] The reaction flask was dehydrated and deoxygenated, and catalyst 1 (24.1 mg, 0.1 mmol, 0.01 equiv) and epoxide J (1.2 mL, 10 mmol, 1.0 equiv) were added under the condition of inert gas. Evacuate the inert gas in the reaction bottle, fill it with carbon dioxide, and repeat it three times. Insert a balloon filled with carbon dioxide and put it into an oil bath at 100°C to react for 5 hours. After the reaction, cooling, after column chromatography (petroleum ether: ethyl acetate=5:1), a mixed solution in which the product was dissolved was obtained, and the solution was spin-dried on a rotary evaporator to obtain a yellow solid, which was dried to constant weight. The conversion rate is 58%, and the hydrogen spectrogram of the product is as follows figure 1 Shown, (Proton NMR spectrum, 400Hz, CDCl 3 ). The spectrogram data is: 1 H NMR (400MHz, Chloroform-d) δ7.49–7.39(m,3H),7.43–7.31(m,2H),5.68(t,J=8.0Hz,1H),4.80(t,J=8.4Hz, 1H),4.34(t,J=8.3Hz, 1H).

[0048] Catalyst...

Embodiment 2

[0050] The reaction flask was dehydrated and deoxygenated, and catalyst 2 (28.4 mg, 0.1 mmol, 0.01 equiv) and epoxide J (1.2 mL, 10 mmol, 1.0 equiv) were added under the condition of inert gas. Evacuate the inert gas in the reaction bottle, fill it with carbon dioxide, and repeat it three times. Insert a balloon filled with carbon dioxide and put it into an oil bath at 100°C to react for 5 hours. After the reaction, cooling, after column chromatography (petroleum ether: ethyl acetate=5:1), obtain the mixed solution that dissolves the product, the solution is spin-dried on the rotary evaporator, obtains yellow solid, is dried to constant weight, The conversion rate is 80%.

[0051] Catalyst 2 was prepared as follows: 4-dimethylaminopyridine (1.221 g, 10 mmol, 1.0 equiv) was dissolved in 5 mL of dichloromethane. Iodine chloride (0.50 mL, 10 mol, 1 equiv) was dissolved in 20 mL of dichloromethane. At 0°C, add the iodine chloride solution in dichloromethane dropwise into the 4-...

Embodiment 3

[0053] The reaction flask was dehydrated and deoxygenated, and catalyst 3 (25.5 mg, 0.1 mmol, 0.01 equiv) and epoxide J (0.6 mL, 5 mmol, 0.5 equiv) were added under the condition of inert gas. Evacuate the inert gas in the reaction bottle, fill it with carbon dioxide, and repeat it three times. Insert a balloon filled with carbon dioxide and put it into an oil bath at 100°C to react for 5 hours. After the reaction, cooling, after column chromatography (petroleum ether: ethyl acetate=5:1), obtain the mixed solution that dissolves the product, the solution is spin-dried on the rotary evaporator, obtains yellow solid, is dried to constant weight, The conversion rate was 83%.

[0054] 4-Methylpyridine (1.0 mL, 10 mmol, 1.0 equiv) was dissolved in 5 mL of dichloromethane. Iodine chloride (0.50 mL, 10 mol, 1 equiv) was dissolved in 20 mL of dichloromethane. At room temperature, the dichloromethane solution of iodine chloride was added dropwise to the dichloromethane solution of 4...

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