Method for preparing formamide compound by catalyzing carbon dioxide hydrogenation with porous material

Abstract

The invention belongs to the technical field of organic synthesis and heterogeneous catalysis, and particularly relates to a method for preparing a formamide compound by catalyzing carbon dioxide hydrogenation through a porous material. The method comprises the following steps: by taking a porous organic metal polymer as a catalyst, reacting an amine compound with carbon dioxide and hydrogen in anair atmosphere to prepare the formamide compound. The method has the advantages of high reaction efficiency, good selectivity, mild conditions, economy, environmental protection, simple operation andthe like; wherein a solid metal polymer material with large specific surface area, strong carbon dioxide adsorption, hierarchical pore channel distribution and highly dispersed metal centers is designed and synthesized as a reaction catalyst by changing a cross-linked copolymer proportion; the catalyst is especially used for catalytic synthesis of fine chemical N, N-dimethylformamide (DMF), doesnot need any additional solvent, alkali or other additives, and is convenient for separation and purification of DMF. The catalyst can be recycled; no special equipment is needed in the reaction, thereaction operation is simple, and further industrial application is facilitated.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis and heterogeneous catalysis, and specifically relates to a preparation method of formamide compounds. Background technique [0002] Carbon dioxide is the most common greenhouse gas. About 800,000 years ago and when the industrial revolution began, its content in the atmosphere was about 280ppm. The large area of ​​vegetation is reduced, and the carbon dioxide content in the atmosphere is getting higher and higher, which is about 400ppm today (this figure means that there are 400 carbon dioxide molecules in the air per million air molecules). After strongly absorbing ground long-wave radiation, carbon dioxide can radiate longer-wavelength long-wave radiation to the ground, which plays a role in insulating the ground. The increasing greenhouse effect leads to global warming, resulting in a series of global climate problems that cannot be predicted by today's science. For example, "El Niño...

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Problems solved by technology

[0004] The preparation of DMF, an important industrial raw material and chemical reagent, by N-formylation reaction of carbon dioxide in the presence of hydrogen and dimethylamine has very important economic value. Although there have been some related reports and researches, these methods are faced with the following Some disadvantages: (1) It requires extremely high pressure (up to 210atm), although the homogeneous catalytic system developed in the early stage can reach a conversion number (TON) of 420,000 [Jessop, P.G.; Hsiao, Y.; Ikariya, T.; Noyori, R.J.Am.Chem.s℃.1994,116,8851-8852.Jessop.P G; Hsiao,Y; Introducing a supercritical reaction system, the total pressure needs to reach 210atm, which requires high reaction equipment, which is unfavorable for the industrial production of DMF; (2) needs to add alkali, solvent, reducing agent, etc.; (3) catalyst is difficult to recycle, and DMF is difficult to separate; ( 4) The catalytic efficiency is low, which is not conducive to industrial production

In addition, most of these homogeneous catalytic systems involve the use of expensive phosphine ligands that are sensitive to air and water. The high cost of catalysts and complex synthesis make practical operation difficult.

Even if some stable heterogeneous nitrogen heterocyclic carbene iridium polymer materials have been used for this reaction, the amount of catalyst is still high (0.1mol%), the catalytic efficiency is not high, and the conversion number can only reach 730 [Zhang, Y.; Wang, J.; Zhu, H.; Tu, T. Chem. Asian J. 2018, 13, 3018–3021.], far below the requirements of industrial production

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