WO2021147622A1 - 一种多孔材料催化二氧化碳氢化制备甲酰胺类化合物的方法 - Google Patents

一种多孔材料催化二氧化碳氢化制备甲酰胺类化合物的方法 Download PDF

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WO2021147622A1
WO2021147622A1 PCT/CN2020/140480 CN2020140480W WO2021147622A1 WO 2021147622 A1 WO2021147622 A1 WO 2021147622A1 CN 2020140480 W CN2020140480 W CN 2020140480W WO 2021147622 A1 WO2021147622 A1 WO 2021147622A1
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reaction
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carbon dioxide
substituted
catalyst
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涂涛
申雅靓
郑庆舒
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复旦大学
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Definitions

  • the invention belongs to the technical field of organic synthesis and heterogeneous catalysis, and specifically relates to a preparation method of formamide compounds.
  • Carbon dioxide is the most common greenhouse gas. About 800,000 years ago and at the beginning of the industrial revolution, its content in the atmosphere was about 280 ppm. With the over-exploitation and utilization of fossil fuels (coal, oil and natural gas) and forests The large area of vegetation is reduced, and the carbon dioxide content in the atmosphere is getting higher and higher. It is now about 400ppm (this figure means that there are 400 carbon dioxide molecules per million air molecules in the air). Carbon dioxide can radiate longer-wavelength long-wave radiation to the ground after intensively absorbing the ground long-wave radiation, which plays a role in insulating the ground. The increasing greenhouse effect has led to global warming, resulting in a series of scientifically unpredictable global climate problems.
  • CO 2 is also considered to be a rich, cheap, non-toxic, and renewable C1 resource.
  • the conversion of CO 2 into the chemicals we need through chemical conversion can not only improve the long-term dependence of humans on fossil energy. Difficulties, and it can effectively reduce the content of carbon dioxide in the air, which is beneficial to alleviate the greenhouse effect caused by CO 2.
  • replacing the toxic and volatile acylation reagents, phosgene and carbon monoxide used in the traditional chemical industry with carbon dioxide is more important.
  • Formamide is a kind of compound widely used in organic synthesis. It can be used to synthesize high-value heterocycles, biological intermediates and drugs. Formamide is also used as a Lewis base organic catalyst in hydrosilylation reactions and other transformations. In addition, the formyl group is a useful protecting group for the amine functional group in peptide synthesis.
  • the N-formylation reaction of amine and formic acid under the action of a catalyst is the most widely accepted method for preparing a variety of formamides, among which the synthesis of N,N-dimethylformamide (DMF) has attracted much attention. In addition to being an important "universal solvent", DMF is also widely used in industrial production as an important intermediate in organic synthesis, medicine and pesticide industries.
  • the industrial synthesis method of DMF is mainly through the direct reaction of dimethylamine and carbon monoxide catalyzed by sodium methoxide to generate DMF.
  • This production method has the advantages of wide sources of raw materials and is suitable for large-scale continuous production. Most large-scale enterprises in the United States, Japan and my country adopt this method. However, in the actual production of this method, some side reactions will occur, producing by-products monomethyl formamide (MMF), dimethyl acetamide (DMAC), formic acid and salt substances sodium hydroxide, sodium formate, sodium bicarbonate, carbonic acid Sodium, etc., so it is necessary to stop at regular intervals for the removal of solid deposits and equipment maintenance.
  • MMF monomethyl formamide
  • DMAC dimethyl acetamide
  • salt substances sodium hydroxide, sodium formate, sodium bicarbonate, carbonic acid Sodium, etc.
  • this method still relies on non-renewable coal resources, which consumes a lot in the large-scale production of DMF, which is not conducive to sustainable development.
  • CO 2 is a cheap, non-toxic and renewable C1 resource
  • hydrogen is the cleanest and most economical reducing agent.
  • a mixture of greenhouse gases CO 2 and H 2 is used as a formylation reagent and The direct reaction of amines to prepare various N-methylation reactions is undoubtedly a green and environmentally friendly way.
  • the purpose of the present invention is to provide a gentle, convenient and efficient method for preparing carboxamide compounds by using porous materials to catalyze the hydrogenation of carbon dioxide.
  • the method for preparing formamide compounds by using porous materials to catalyze the hydrogenation of carbon dioxide uses the porous organometallic polymer shown in (V) as a catalyst, and in an air atmosphere, the amine compound of the general formula (I) is combined with Carbon dioxide and hydrogen react to form a formamide compound of general formula II; the specific preparation steps are:
  • organic amine compound (I) and catalyst (V) In an air atmosphere, add organic amine compound (I) and catalyst (V) to a 125 ml autoclave, seal it, and fill it with carbon dioxide and hydrogen at a certain pressure; place the reaction system in an oil bath with stirring and heating for a certain period of time; Slowly release the pressure after cooling, and obtain formamide products through distillation or column separation;
  • reaction formula is:
  • R 1 and R 2 may be connected to form a substituted or unsubstituted C 4 -C 10 cycloalkyl group;
  • R 3 , R 4 , R 5 are each independently selected from: hydrogen, substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 6 -C 24 aryl, substituted or unsubstituted A substituted C 7 -C 25 arylalkyl or heteroaryl group, wherein R 4 and R 5 can be connected to form a substituted or unsubstituted C 3 -C 10 cycloalkyl group;
  • substituted means that one or more hydrogen atoms in the group are substituted by a substituent selected from the following group: halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxy, hydroxyl, amino, mercapto.
  • the porous organometallic polymer material with the structure represented by the general formula (V) is:
  • the nitrogen heterocyclic carbene ligands are benzimidazole carbene, phenanthrmidazole carbene, acenaphthoimidazole carbene, pyrenoimidazole carbene, and bibenzimidazole carbene ligand;
  • X is halogen anion, tetrafluoroborate, hexafluorophosphate or hexafluoroantimonate
  • L is an auxiliary ligand
  • the auxiliary ligand is a halogen, a carbonyl group, a benzene ring, a benzene ring, a cyclooctadiene, a hydroxyl group, a water, a carbonate group, an acetate group, an acetylacetone anion, or a phosphine ligand;
  • R 1 and R 2 are a chain alkane group having 1 to 12 carbons, a cyclic alkane group having 5 to 7 carbons, a benzyl group, or an aryl group.
  • the amine compound is a primary organic amine or a secondary organic amine compound.
  • the molar ratio of the organic amine compound to the catalyst is (1000-100000):1, preferably (5000-20000):1.
  • the reaction time is 2 to 160 hours, preferably 2 to 48 hours.
  • the hydrogen pressure is controlled to be 5-40 atmospheres, and the carbon dioxide pressure is 5-40 atmospheres.
  • the hydrogen pressure is 30 atmospheres and the carbon dioxide pressure is 30 atmospheres.
  • the reaction temperature is 80-150°C, preferably 80-120°C.
  • the reaction is carried out in an organic solvent, and the organic solvent is selected from: DMF, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, tert-butyl methyl ether, benzene, toluene, two Toluene, methanol, ethanol, isopropanol, tert-butanol; or a combination of several of them, preferably methanol and tetrahydrofuran.
  • the organic solvent is selected from: DMF, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, tert-butyl methyl ether, benzene, toluene, two Toluene, methanol, ethanol, isopropanol, tert-butanol; or a combination of several of them, preferably methanol and tetrahydrofuran
  • the specific operation steps are: add organic amine compounds, catalyst (V) and organic solvent to a 125 ml autoclave under air atmosphere, seal it, and fill it with carbon dioxide at a certain pressure And hydrogen; place the reaction system in an oil bath with stirring and heating for a certain period of time; slowly release the pressure after cooling, and obtain formamide products through distillation or column separation.
  • the reaction when the amine compound is dimethylamine or its equivalent dimethylamine carbon dioxide salt, the product is DMF. At this time, the reaction does not need to be carried out in an organic solvent, and does not require alkali and other additives; the reaction formula is:
  • the molar ratio of the dimethylamine equivalent, that is, the dimethylamine carbon dioxide salt to the catalyst is (1000-100000):1, preferably (10000-100000):1.
  • the reaction time is 2 to 160 hours, preferably 2 to 96 hours.
  • the hydrogen pressure is 5-40 atm
  • the carbon dioxide pressure is 5-40 atm
  • the hydrogen pressure is 25-30 atm
  • the carbon dioxide pressure is 25-30 atm.
  • the reaction temperature is in the range of 80-150°C, preferably 100-120°C.
  • the catalyst used in the reaction does not need to be dissolved in DMF or other solvents, and can be recovered by centrifugal filtration after the reaction is completed.
  • the recovered catalyst does not require any additional activation steps and can be directly used in the next cycle.
  • the catalyst recovered by centrifugal filtration and other methods can be recycled dozens of times and still maintain stable catalytic activity and selectivity.
  • the catalyst porous organometallic polymer material is prepared by the following method; the specific preparation steps are: at room temperature, the biscarbene iridium compound represented by the general formula III and 3-9 equivalents of the general formula
  • the aromatics and hydrocarbons shown in IV are dissolved in organic solvents, cross-linking agent and Lewis acid catalyst are slowly added under nitrogen, and sealed; the reaction system is placed in an oil bath at 30-80°C and reacted for 1-72 hours. Stop; after cooling, filter, wash, Soxhlet extraction, and vacuum drying to obtain a porous organometallic polymer material represented by general formula V.
  • the nitrogen heterocyclic carbene ligands are benzimidazole carbene, phenanthrmidazole carbene, acenaphthoimidazole carbene, pyrenoimidazole carbene, and bibenzimidazole carbene ligand.
  • X is halogen anion, tetrafluoroborate, hexafluorophosphate or hexafluoroantimonate
  • L is an auxiliary ligand
  • the auxiliary ligand is a halogen, a carbonyl group, a benzene ring, a benzene ring, a cyclooctadiene, a hydroxyl group, a water, a carbonate group, an acetate group, an acetylacetone anion, or a phosphine ligand;
  • R 1 and R 2 are a chain alkane group having 1 to 12 carbons, a cyclic alkane group having 5 to 7 carbons, a benzyl group, or an aryl group.
  • the types of homogeneous catalyst precursor and comonomer are selected, and the ratio of the two can be changed to realize the regulation and control of the activity of the solid catalytic material. Specifically:
  • the amount ratio (mass ratio) of the copolymerized aromatic hydrocarbon compound IV and the homogeneous catalyst precursor III is (1-24):1, preferably (3-9):1.
  • the amount ratio of the crosslinking agent to the homogeneous catalyst precursor III is (1-100):1, preferably (15-20):1.
  • the crosslinking agent is selected from: dimethanol formal, trimethyl orthoformate, trimethyl orthoacetate, triethyl orthoformate, triisopropyl orthoformate, dichlorobenzene, dibromobenzene, 1,4-p-dibenzyl chloride, 1,4-p-dibenzyl bromide, carbon tetrachloride;
  • the solvent is selected from dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, preferably dimethanol formal.
  • the Lewis acid is selected from ferric chloride and aluminum chloride; the solvent is dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane; preferably, the Lewis acid is ferric chloride, chlorinated aluminum.
  • the present invention adopts direct super-crosslinking method to prepare synthetic porous organometallic polymer material, which not only has the advantages of stable properties, large specific surface area, strong carbon dioxide adsorption, multi-level channel distribution, highly dispersed metal centers, etc., but also can be adjusted by adjusting the comonomer
  • the ratio realizes the regulation of the catalytic activity of the material.
  • the catalytic material is used in the catalytic conversion of the greenhouse gas carbon dioxide to prepare carboxamide compounds (including DMF).
  • the reaction is green and environmentally friendly, and does not involve the use of toxic gases.
  • the reaction selectivity is high. Water is the only one.
  • conversion efficiency refers to the percentage ratio of the amount of reactants consumed in a chemical reaction to the total amount of reactants initially added.
  • conversion efficiency of the present invention is calculated with dimethylamine.
  • conversion number refers to the ratio of the number of moles of reactants that have been converted to the number of moles of catalyst in a certain period of time.
  • conversion number of the present invention is calculated with dimethylamine.
  • the conversion efficiency and conversion number are calculated by 1 H NMR or separation method.
  • FIG. 1 is a carbon dioxide adsorption curve of the porous organometallic polymer material 1a prepared in Example 1.
  • Example 2 is a carbon dioxide adsorption curve of the porous organometallic polymer material 1b prepared in Example 2.
  • Example 3 is a carbon dioxide adsorption curve of the porous organometallic polymer material 1c prepared in Example 3.
  • Fig. 4 shows the cycle performance test of the catalyst 1b provided in Example 11 in the dimethylamine formylation reaction.
  • Example 4 The effect of different temperatures on the dimethylcarbamylation reaction catalyzed by porous organometallic polymer material 1b
  • dimethylamine carbon dioxide salt 40 mmol, 5.36 g, 4 mL
  • solid catalyst POMP 1b 20 ppm, 38 mg
  • the reaction system was stirred for 24 hours in an oil bath at a set temperature. After the reaction was completed, the autoclave was cooled to room temperature and the pressure was slowly released. 20 mL of methanol was added, and then mesitylene (240 mg, 2 mmol) was added to the reaction system as an internal standard for 1 H NMR analysis to determine the yield. (The results are shown in Table 1).
  • Example 5 The influence of CO 2 and H 2 pressure on the dimethylamine formylation reaction catalyzed by porous organometallic polymer material 1b
  • dimethylamine carbon dioxide salt 40 mmol, 5.36 g, 4 mL
  • solid catalyst POMP 1b 20 ppm, 38 mg
  • the reaction system was stirred in an oil bath at 120°C for 24 hours. After the reaction was completed, the autoclave was cooled to room temperature and the pressure was slowly released. 20 mL of methanol was added, and then mesitylene (240 mg, 2 mmol) was added to the reaction system as an internal standard for 1 H NMR analysis to determine the yield.
  • Table 2 The results are shown in Table 2:
  • Example 6 The effect of different reaction times on the dimethylcarbamylation reaction catalyzed by porous organometallic polymer material 1b
  • dimethylamine carbon dioxide salt 40 mmol, 5.36 g, 4 mL
  • solid catalyst POMP 1b 20 ppm, 38 mg
  • the reaction system was stirred for a certain period of time in an oil bath at 120°C. After the reaction was completed, the autoclave was cooled to room temperature and the pressure was slowly released. 20 mL of methanol was added, and then mesitylene (240 mg, 2 mmol) was added to the reaction system as an internal standard for 1 H NMR analysis to determine the yield.
  • Table 3 The results are shown in Table 3:
  • reaction time has a great influence on the reaction yield.
  • the reaction starts slowly, and there is almost no reaction in the first two hours.
  • the reaction yield increases with time.
  • the reaction time reaches 24 hours , DMF can be obtained in a quantitative yield, the reaction time will be further extended without by-products such as excessive hydrogenation, and the catalytic system exhibits good selectivity.
  • the optimal response time is 24 hours.
  • Example 7 The effect of different catalysts on the dimethylamine formylation reaction catalyzed by porous organometallic polymer material 1b
  • the solid porous organometallic polymer material formed by the direct super-crosslinking method exhibits the activity of the homogeneous catalyst precursor in this reaction.
  • the resulting catalytic material can more efficiently catalyze the conversion of carbon dioxide into DMF, reducing or increasing benzene
  • the equivalent weight of the obtained catalytic material will deteriorate the activity of the obtained catalytic material, so it is preferable that the porous organometallic polymer material POMP 1b is the catalyst.
  • Example 8 The effect of different catalyst dosages on POMP 1b catalyzed dimethylamino formylation reaction
  • Example 9 Dimethylamine formylation catalyzed by POMP 1b with a molar equivalent of 1.67 million
  • dimethylamine carbon dioxide salt 115 mmol, 15.08 g, 23 mL
  • solid catalyst POMP 1b 0.6 ppm, 3.2 mg
  • Example 10 Dimethylamine formylation catalyzed by four millionths of a molar equivalent of POMP 1b
  • dimethylamine carbon dioxide salt 110 mmol, 14.54 g, 23 mL
  • solid catalyst POMP 1b 0.25 ppm, 1.3 mg
  • Example 11 Dimethylamine formylation catalyzed by POMP 1b with a molar equivalent of one fifty thousandths and recycling of catalyst 1b
  • dimethylamine carbon dioxide salt 40 mmol, 5.36 g, 4 mL
  • solid catalyst POMP 1b 20 ppm, 38 mg
  • the catalyst can be recycled more than 12 times, while the catalytic activity and selectivity are still maintained at a quantitative level (see Figure 4).
  • Example 12 Morpholine formylation catalyzed by 1/10000 molar equivalent of POMP 1b
  • Example 13 N-Phenylpiperazine formylation reaction catalyzed by POMP 1b of one ten thousandth of a molar equivalent
  • N-phenylpiperazine (10 mmol, 1.62 g), solid catalyst POMP 1b (100 ppm, 24 mg), and methanol (2 mL) were added to a stainless steel autoclave equipped with a magnetic stir bar. Tighten the autoclave, purge it with carbon dioxide three times, and finally fill with 30atm of carbon dioxide, and then fill the autoclave with 30atm of hydrogen to a total pressure of 60atm. Then, the reaction system was stirred in an oil bath at 120°C for 24 hours. After the reaction was completed, the autoclave was cooled to room temperature and the pressure was slowly released.
  • N-phenyl-N-formyl Piperazine is a white solid (1.90 g) with a yield of 99%.
  • Example 14 Piperidine carboxylation reaction catalyzed by 1/10,000 molar equivalent of POMP 1b
  • Example 15 Diethylamine formylation catalyzed by POMP 1b of one ten thousandth of a molar equivalent
  • diethylamine (10 mmol, 0.73 g), solid catalyst POMP 1b (100 ppm, 24 mg), and methanol (2 mL) were added to a stainless steel autoclave equipped with a magnetic stir bar. Tighten the autoclave, purge it with carbon dioxide three times, and finally fill with 30 atm of carbon dioxide, and then fill the autoclave with 30 atm of hydrogen to a total pressure of 60 atm. Then, the reaction system was stirred in an oil bath at 120°C for 24 hours. After the reaction was completed, the autoclave was cooled to room temperature and the pressure was slowly released.
  • Example 16 Diethanolamine formylation catalyzed by POMP 1b of one ten thousandth of a molar equivalent
  • diethanolamine (10 mmol, 1.05 g), solid catalyst POMP 1b (100 ppm, 24 mg), and methanol (2 mL) were added to a stainless steel autoclave equipped with a magnetic stir bar. Tighten the autoclave, purge it with carbon dioxide three times, and finally fill with 30 atm of carbon dioxide, and then fill the autoclave with 30 atm of hydrogen to a total pressure of 60 atm. Then, the reaction system was stirred in an oil bath at 120°C for 24 hours. After the reaction was completed, the autoclave was cooled to room temperature and the pressure was slowly released.
  • Example 17 Cyclohexylcarbamylation catalyzed by POMP 1b of 1/10,000th molar equivalent
  • Example 18 Benzylcarbamylation reaction catalyzed by POMP 1b of one ten-thousandth molar equivalent
  • benzylamine (10 mmol, 1.07 g), solid catalyst POMP 1b (100 ppm, 24 mg), and methanol (2 mL) were added to a stainless steel autoclave equipped with a magnetic stir bar. Tighten the autoclave, purge it with carbon dioxide three times, and finally fill with 30atm of carbon dioxide, and then fill the autoclave with 30atm of hydrogen to a total pressure of 60atm. Then, the reaction system was stirred in an oil bath at 120°C for 24 hours. After the reaction was completed, the autoclave was cooled to room temperature and the pressure was slowly released.
  • the obtained mixture was filtered through a short silica gel column (about 2 cm), washed with ethyl acetate (5 mL x 3), and the filtrate obtained was dried with anhydrous sodium sulfate, and the solvent was removed by rotary evaporation to obtain N-formylbenzylamine colorless liquid (1.35g), the yield is 99%.
  • Example 19 2-Methylaminopyridinecarboxylation reaction catalyzed by POMP 1b of one ten thousandth of a molar equivalent
  • Example 20 Amlodipine base formylation reaction catalyzed by POMP 1b of one ten-thousandth molar equivalent
  • the amlodipine base (1 mmol, 0.41 g), the solid catalyst POMP 1b (100 ppm, 2.4 mg), and methanol (2 mL) were added to a stainless steel autoclave equipped with a magnetic stirrer. Tighten the autoclave, purge it with carbon dioxide three times, and finally fill with 30 atm of carbon dioxide, and then fill the autoclave with 30 atm of hydrogen to a total pressure of 60 atm. Then, the reaction system was stirred in an oil bath at 120°C for 24 hours. After the reaction was completed, the autoclave was cooled to room temperature and the pressure was slowly released. The obtained mixture was separated through a silica gel column (about 5 cm) to obtain the formamide product, a white solid (0.35 g), with a yield of 81%.

Abstract

本发明属于有机合成和非均相催化技术领域，具体为一种多孔材料催化二氧化碳氢化制备甲酰胺类化合物的方法。本发明以多孔有机金属聚合物为催化剂，在空气气氛下，胺类化合物与二氧化碳和氢气进行反应，制备得到甲酰胺类化合物；具有反应效率高、选择性好、条件温和、经济环保和操作简便等优点；其中，通过改变交联共聚物的比例，设计合成了比表面积大、二氧化碳吸附强、多级孔道分布、金属中心高度分散的固体金属聚合物材料作为反应催化剂；尤其用于催化合成精细化工品N,N-二甲基甲酰胺(DMF)反应中，不需要任何外加溶剂、碱或者其他添加剂，方便DMF的分离提纯；催化剂可回收循环使用；反应无需特殊设备，反应操作简便，更有利于进一步的工业应用。

Description

一种多孔材料催化二氧化碳氢化制备甲酰胺类化合物的方法 技术领域
本发明属于有机合成和非均相催化技术领域，具体涉及甲酰胺类化合物的制备方法。
背景技术
二氧化碳是最常见的温室气体，大约在80万年前和工业革命开始的时候，它在大气中的含量大约是280ppm，随着人类对化石燃料(煤、石油及天然气)的过度开发利用和森林植被的大面积减少，大气中的二氧化碳含量越来越高，发展到如今大约是400ppm(这个数字意味着每百万空气分子的空气中有400个二氧化碳分子)。二氧化碳在强烈吸收地面长波辐射后能向地面辐射出波长更长的长波辐射，对地面起到了保温作用，温室效应不断加剧导致全球气候变暖，产生一系列当今科学不可预测的全球性气候问题，例如“厄尔尼诺现象”和“拉尼娜现象”，均被认为与二氧化碳的过量排放有关。而另一方面，CO 2也被认为是一种丰富的廉价、无毒、可再生C1资源，通过化学转化的途径将CO 2转化为我们需要的化学品，不仅能改善人类长期依赖化石能源的困境，而且可以有效地减少空气中二氧化碳的含量，有利于缓解CO 2带来的温室效应，除此之外，以二氧化碳代替传统化学工业使用的有毒且易挥发酰基化试剂、光气和一氧化碳更符合绿色化学的理念[Carbon Dioxide as Chemical Feedst℃k,Ed.:Aresta,M.；Wiley-VCH,Weinheim,2010.]。因此化学家们一直致力于开发更为绿色高效的方法实现二氧化碳的资源化和能源化。但是二氧化碳是一种热力学和动力学都非常稳定的气体分子，其碳处于最高的氧化态，因此对CO 2的转化非常具有挑战性，目前为止90％以上的CO 2都是用于生产尿素、无机碳酸盐、碳酸酯、聚碳酸酯和水杨酸等，而被固定和转化为其它高附加值化学品的二氧化碳则相对较少。
甲酰胺是一类广泛用于有机合成的化合物，可以用于合成高价值的杂环，生物中间体和药物。甲酰胺还用作氢化硅烷化反应和其他转化中的路易斯碱有机催化剂。此外，甲酰基是肽合成中胺基官能团有用的保护基团。胺与甲酸在催化剂作用下发生N-甲酰化反应是制备多种甲酰胺最被广泛接受的方法，在这其中备受关注的N,N-二甲基甲酰胺(DMF)的合成。DMF除作为一种重要的“万能溶剂”外，还作为有机合成、医药和农药工业的重要中间体被广泛应用于工业生产。工业上DMF的合成方法主要是通过甲醇钠催化二甲胺和一氧化碳直接反应生成DMF。此生产方法具有原料来源广，适合大规模连续生产等优点，美国、日本以及我国上规模企业等大多采用此法。但是此方法在实际生产中，会发生一些副反应，产生副产品一甲基甲酰胺(MMF)、二甲基乙酰胺(DMAC)、甲酸以及盐类物质氢氧化钠、甲酸钠、碳酸氢钠、碳酸钠等，因此每隔一段时间就需要停车进行固体沉积物的清除及设备保养。而且这种方法仍然依赖于不可再生的煤炭资源，在DMF的大规模生产中消耗量大，不利于可持续发展。基于CO 2是一种廉价无毒可再生的C1资源，氢气是最清洁，最经济的还原剂，从可持续发展的角度考虑，利用温室气体CO 2和H 2的混合物作为甲酰化试剂与胺直接反应制备各种N-甲基化反应无疑是一条绿色环保的途径。
二氧化碳在氢气和二甲胺存在下通过N-甲酰化反应制备DMF这种重要的工业原料 和化工试剂具有很重要的经济价值，虽然已有一些相关的报道研究，但是这些方法都面临着一下一些劣势：(1)需要极高的压力(高至210atm)，早期发展的均相催化体系虽然可以达到42万的转化数(TON)[Jessop,P.G.；Hsiao,Y.；Ikariya,T.；Noyori,R.J.Am.Chem.s℃.1994,116,8851-8852.Jessop.P G；Hsiao,Y；Ikariya.T；Noyori.R.J.Am.Chem.S℃.1996,118,344-355.]，但是需要引入超临界反应体系，总压力需达到210atm，对反应设备要求高，不利于DMF的工业生产；(2)需要外加碱、溶剂、还原剂等；(3)催化剂难以回收，DMF分离困难；(4)催化效率低，不利于工业生产。除此之外，这些均相催化体系多涉及到对空气、水十分敏感、价格昂贵的膦配体的使用，催化剂的造价高、合成复杂，使实际操作变得困难。即使已有一些稳定的非均相氮杂环卡宾铱聚合物材料用于此反应，催化剂用量仍然较高(0.1mol％)，催化效率不高，转化数只能达到730[Zhang,Y.；Wang,J.；Zhu,H.；Tu,T.Chem.Asian J.2018,13,3018–3021.]，远远达不到工业生产的要求。
因此本领域亟需一种结构稳定、合成方便、催化效率高、选择性好、底物适用性广的催化材料，并将其应用于温和条件下二氧化碳转化为甲酰胺类化合物，尤其是大宗精细化工品DMF的反应中，为此体系进一步的工业应用奠定基础。
发明内容
本发明的目的是提供一种温和、便利、高效的利用多孔材料催化二氧化碳氢化制备甲酰胺类化合物的方法。
本发明提供的利用多孔材料催化二氧化碳氢化制备甲酰胺类化合物的方法，是以(V)所示的多孔有机金属聚合物为催化剂，在空气气氛下，通式为(I)的胺类化合物与二氧化碳和氢气进行反应，形成通式为II的甲酰胺类化合物；制备的具体步骤为：
在空气气氛下，向125毫升高压釜中加入有机胺类化合物(I)、催化剂(V)，密闭，充入一定压力的二氧化碳和氢气；将反应体系置于油浴中搅拌加热反应一定时间；冷却后缓慢释放压力，通过蒸馏或者过柱分离得到甲酰胺类产物；
其反应式为：
Figure PCTCN2020140480-appb-000001
式中：
R 1为氢、取代的或未取代的C 1-C 20烷基、取代的或未取代的C 4-C 10环烷基、取代的或未取代的C 6-C 24芳基或杂芳基、取代的或未取代的C 7-C 25的芳基烷基或杂芳基烷基、-(CH 2) n-OR 3或-(CH 2) n-NR 4R 5,其中，n＝1-8；
R 2为取代的或未取代的C 1-C 20烷基、取代的或未取代的C 4-C 10环烷基、取代的或未取代的C 6-C 24芳基或杂芳基、取代的或未取代的C 7-C 25芳基烷基或杂芳基烷基、-(CH 2) n-OR 3或-(CH 2) n-NR 4R 5,其中，n＝1-8,R 1与R 2可以连接成取代的或未取代的C 4-C 10环烷基；
其中，R 3、R 4、R 5各自独立地选自：氢、取代的或未取代的C 1-C 20烷基、取代的或未取代的C 6-C 24芳基、取代的或未取代的C 7-C 25芳基烷基或杂芳基，其中R 4与R 5可以连接成取代的或未取代的C 3-C 10环烷基；
其中，所述“取代的”是指基团中一个或多个氢原子被选自下组的取代基所取代：卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 2-C 6烯基、C 2-C 6炔基、C 1-C 6烷氧基、羟基、胺基、巯基。
所述通式(V)所示结构的多孔有机金属聚合物材料为：
Figure PCTCN2020140480-appb-000002
式中：
Figure PCTCN2020140480-appb-000003
氮杂环卡宾配体为苯并咪唑卡宾、菲并咪唑卡宾、苊并咪唑卡宾、芘并咪唑卡宾、联苯并咪唑卡宾配体；
X为卤素负离子、四氟硼酸根、六氟磷酸根或六氟锑酸根；
L为辅助配体，所述辅助配体为卤素、羰基、苯环、茂环、环辛二烯、羟基、水、碳酸根、醋酸根、乙酰丙酮负离子或膦配体；
R 1,R 2为碳数为1～12的链状烷烃基、碳数为5～7的环状烷烃基、苄基或芳基。
本发明的制备甲酰胺类化合物的方法，实验操作无需诸如手套箱等特殊设备，反应无需碱及其他添加剂。
本发明中，所述胺类化合物为有机伯胺或有机仲胺类化合物。
本发明中，所述有机胺类化合物与催化剂的摩尔比为(1000-100000):1，优选的为(5000-20000)：1。
本发明中，反应时间为2-160小时，优选的为2-48小时。
本发明中，控制氢气压力为5-40大气压，二氧化碳气压力为5-40大气压，优选的为氢气压力为30大气压，二氧化碳压力为30大气压。
本发明中，反应温度为80-150℃，优选的为80-120℃。
本发明中，反应在有机溶剂中进行，所述有机溶剂选自：DMF、四氢呋喃、2-甲基四氢呋喃、二氧六环、乙二醇二甲醚、叔丁基甲基醚、苯、甲苯、二甲苯、甲醇、乙醇、异丙醇、叔丁醇；或其中几种的组合，优选的为甲醇和四氢呋喃。
本发明提出的制备甲酰胺类化合物的方法，具体操作步骤为：在空气气氛下，向125毫升高压釜中加入有机胺类化合物、催化剂(V)和有机溶剂，密闭，充入一定压力的二氧 化碳和氢气；将反应体系置于油浴中搅拌加热反应一定时间；冷却后缓慢释放压力，通过蒸馏或者过柱分离得到甲酰胺类产物。
本发明中，当所述胺类化合物为二甲胺或其等价物二甲胺二氧化碳盐时，其产物为DMF。这时，反应不需要在有机溶剂中进行，也不需要碱及其他添加剂；反应式为：
Figure PCTCN2020140480-appb-000004
其中：
二甲胺等价物即二甲胺二氧化碳盐与催化剂的摩尔比为(1000-100000):1，优选(10000-100000):1。
反应时间为2-160小时，优选的为2-96小时。
氢气压力为5-40大气压，二氧化碳气压力为5-40大气压，优选的为氢气压力为25-30大气压，二氧化碳压力为25-30大气压。
反应温度范围为80-150℃，优选为100-120℃。
反应所用催化剂不需要溶于DMF或者其他溶剂，反应完成之后可以通过离心过滤等方式回收。
回收后的催化剂无需任何额外的活化步骤，可以直接用于下一轮循环。
通过离心过滤等方式回收后的催化剂可以循环使用数十次仍然保持稳定的催化活性和选择性。
循环时，只需将回收得到的催化剂再次加入到高压釜中，重复上述步骤进行反应和后处理。这样催化剂可以循环是有数十次仍保持稳定的活性和选择性。
本发明中，所述催化剂多孔有机金属聚合物材料由如下方法制备得到；制备的具体步骤为：在室温下，将通式III所示的双卡宾铱化合物和3-9个当量的通式IV所示的芳，烃溶解于有机溶剂中，在氮气条件下缓慢加入交联剂和路易斯酸催化剂，密封；将反应体系置于30-80℃的油浴锅中反应1-72小时，反应停止；冷却后，经过过滤、洗涤、索氏提取、真空干燥，得到通式V所示的多孔有机金属聚合物材料。
其化学反应式为：
Figure PCTCN2020140480-appb-000005
式中：
Figure PCTCN2020140480-appb-000006
氮杂环卡宾配体为苯并咪唑卡宾、菲并咪唑卡宾、苊并咪唑卡宾、芘并咪唑卡宾、联苯并咪唑卡宾配体。
X为卤素负离子、四氟硼酸根、六氟磷酸根或六氟锑酸根；
L为辅助配体，所述辅助配体为卤素、羰基、苯环、茂环、环辛二烯、羟基、水、碳酸根、醋酸根、乙酰丙酮负离子或膦配体；
R 1,R 2为碳数为1～12的链状烷烃基、碳数为5～7的环状烷烃基、苄基或芳基。
本发明中，选定均相催化剂前体和共聚单体的类型，改变二者的比例可以实现固体催化材料的活性调控。具体来说：
共聚芳烃化合物IV与均相催化剂前体III的用量比(质量比)为(1-24)：1，优选的为(3-9):1。
交联剂与均相催化剂前体III的用量比为(1-100)：1，优选的为(15-20):1。
本发明中，所述交联剂选自：二甲醇缩甲醛、原甲酸三甲酯、原乙酸三甲酯、原甲酸三乙酯、原甲酸三异丙酯、二氯苯、二溴苯、1,4-对二苄氯、1,4-对二苄溴、四氯化碳；
所述溶剂选自二氯甲烷、三氯甲烷、四氯化碳、1,2-二氯乙烷，优选为二甲醇缩甲醛。
所述路易斯酸选自氯化铁、氯化铝；所述溶剂为二氯甲烷、三氯甲烷、四氯化碳、1,2-二氯乙烷；优选路易斯酸为氯化铁、氯化铝。
本发明采用直接超交联手段制备合成的多孔有机金属聚合物材料，不仅具有性质稳定、比表面积大、二氧化碳吸附强、多级孔道分布、金属中心高度分散等优点，还可以通过调节共聚单体的比例实现材料催化活性的调控，将此催化材料应用于温室气体二氧化碳催化转化制备甲酰胺类化合物(包括DMF)中，反应绿色环保，不涉及有毒气体的使用，反应选择性高，水是唯一的副产物，反应条件温和，无需特殊设备，操作简便，符合绿色经济可持续发展的理念。尤其是在大宗化学品DMF的制备中，即使在催化剂用量<0.0001mol％的条件下，也可实现二氧化碳到DMF的高效转化，转化数(TON)最高可达1581588。除此之外，反应无需任何外加溶剂、碱及其他添加剂，不仅降低了甲酰胺类化合物(包括DMF)的生产成本，而且得益于固体多孔有机金属聚合物材料在DMF和其他溶剂中的不溶性，有利于最终产物DMF的分离提纯。通过简单的离心过滤等方式回收的催化剂无需额外的活化步骤便可直接用于下一轮循环中，催化剂可以循环使用数十次仍然保持高活性和高选择性。
本文所用的术语“转化效率”(或称效率)是指在化学反应中已消耗掉的反应物的量与初始加入的该反应物总量的百分比率。本发明的转化效率以二甲胺来计算。
本文所用的术语“转化数”是指某一时间段内,已经转化的反应物的摩尔数与催化剂的摩尔数的比值。本发明的转化数以二甲胺来计算。
在本发明中,转化效率和转化数的计算是通过 1H NMR或者分离法两种方式进行。
附图说明
图1为实施例1所制备的多孔有机金属聚合物材料1a的二氧化碳吸附曲线。
图2为实施例2所制备的多孔有机金属聚合物材料1b的二氧化碳吸附曲线。
图3为实施例3所制备的多孔有机金属聚合物材料1c的二氧化碳吸附曲线。
图4为实施例11所提供的催化剂1b在二甲胺甲酰化反应中的循环性能测试。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将对本发明的各实施方式进行详细的阐述。然而，本领域的普通技术人员可以理解，在本发明各实施方式中，为了使读者更好地理解本申请而提出了许多技术细节。但是，即使没有这些技术细节和基于以下各实施方式的种种变化和修改，也可以实现本申请各权利要求所要求保护的技术方案。
实施例1：多孔有机金属聚合物材料1a的合成
Figure PCTCN2020140480-appb-000007
于50mL Schlenk管中加入1mmol双苯并咪唑氮杂环卡宾铱化合物(0.63g)，抽真空换氮气三次，然后依次加入10mL 1,2-二氯乙烷和3mmol苯(0.23g)，室温搅拌一段时间直至固体完全溶解之后，再加入20mmol二甲醇缩甲醛(FDA，1.52g)和无水氯化铁(3.24g)。密封之后将反应体系放入80度的油浴中反应24小时。反应完全之后，冷却至室温，过滤，洗涤，得到的固体索氏提取24小时，在60度下真空干燥24小时得到多孔有机金属聚合物POMP 1d。固体的二氧化碳吸附曲线如附图1所示。产率：0.99g，90％。
实施例2：多孔有机金属聚合物材料1b的合成
Figure PCTCN2020140480-appb-000008
于50mL Schlenk管中加入1mmol双苯并咪唑氮杂环卡宾铱化合物(0.63g)，抽真空换氮气三次，然后依次加入10mL 1,2-二氯乙烷和6mmol苯(0.46g)，室温搅拌一段时间直至固体完全溶解之后，再加入20mmol二甲醇缩甲醛(FDA，1.52g)和无水氯化铁(3.24g)。密封之后将反应体系放入80度的油浴中反应24小时。反应完全之后，冷却至室温，过滤，洗涤，得到的固体索氏提取24小时，在60度下真空干燥24小时得到多孔有机金属聚合物POMP 1b。固体的二氧化碳吸附曲线如附图2所示。产率：1.17g，88％。
实施例3：多孔有机金属聚合物材料1c的合成
Figure PCTCN2020140480-appb-000009
于50mL Schlenk管中加入1mmol双苯并咪唑氮杂环卡宾铱化合物(0.63g)，抽真空换氮气三次，然后依次加入10mL 1,2-二氯乙烷和9mmol苯(0.70g)，室温搅拌一段时间直至固体完全溶解之后，再加入20mmol二甲醇缩甲醛(FDA，1.52g)和无水氯化铁(3.24g)。密封之后将反应体系放入80度的油浴中反应24小时。反应完全之后，冷却至室温，过滤，洗涤，得到的固体索氏提取24小时，在60度下真空干燥24小时得到多孔有机金属聚合物POMP 1c。固体的二氧化碳吸附曲线如附图3所示。产率：1.37g，87％。
实施例4:不同温度对多孔有机金属聚合物材料1b催化二甲胺甲酰化反应的影响
Figure PCTCN2020140480-appb-000010
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入二甲胺二氧化碳盐(40mmol，5.36g，4mL)，固体催化剂POMP 1b(20ppm，38mg)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在设定温度的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。加入20mL甲醇，之后在反应体系中加入均三甲苯(240mg，2mmol)作为 1H NMR分析的内标以确定产率。(结果见表1)。
表1不同温度对多孔有机金属聚合物材料1b催化二甲胺甲酰化反应的影响
温度(℃) 60 80 100 120 140
产率(％) 0 23 59 99 99
上表中：DMF的产率都是通过 1H NMR以对均三甲苯为内标测定。
从表1可知，温度的变化对反应结果有显著的影响。低于60℃时，反应无法发生，随着温度的升高，产率有明显提升，当反应温度为120℃时，产率可以达到定量，继续升高温度仍然可以得到定量的产率。考虑到能耗和实际的工业应用，最优的反应温度为120℃。
实施例5:CO 2和H 2压力对多孔有机金属聚合物材料1b催化二甲胺甲酰化反应的影响
Figure PCTCN2020140480-appb-000011
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入二甲胺二氧化碳盐(40mmol，5.36g，4mL)，固体催化剂POMP 1b(20ppm，38mg)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入一定压力的二氧化碳，然后在高压釜内充入一定压力的氢气。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。 加入20mL甲醇，之后在反应体系中加入均三甲苯(240mg，2mmol)作为 1H NMR分析的内标以确定产率。结果如表2所示：
表2CO 2和H 2压力对多孔有机金属聚合物材料1b催化二甲胺甲酰化反应的影响
Figure PCTCN2020140480-appb-000012
上表中：DMF的产率都是通过 1H NMR以对均三甲苯为内标测定。
从表2可知，二氧化碳和氢气的压力对反应的影响很大。二氧化碳和氢气压力上升有利于二氧化碳转化为DMF。在所选压力中，当CO 2和H 2的分压均为30atm时可以实现DMF的定量制备。进一步升高压力仍然可以实现DMF高选择性制备，不会出现过度氢化等副产物。考虑到安全性和实际的工业应用，最优的CO 2和H 2压力为30atm/30atm。
实施例6:不同反应时间对多孔有机金属聚合物材料1b催化二甲胺甲酰化反应的影响
Figure PCTCN2020140480-appb-000013
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入二甲胺二氧化碳盐(40mmol，5.36g，4mL)，固体催化剂POMP 1b(20ppm，38mg)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌一定的时间。反应完成后，将高压釜冷却至室温并缓慢释放压力。加入20mL甲醇，之后在反应体系中加入均三甲苯(240mg，2mmol)作为 1H NMR分析的内标以确定产率。结果如表3所示：
表3不同反应时间对多孔有机金属聚合物材料1b催化二甲胺甲酰化反应的影响
时间(h) 2 6 12 24 48
产率(％) 5 18 49 99 99
上表中：DMF的产率都是通过 1H NMR以对均三甲苯为内标测定。
从表3可知，反应时间对反应产率的影响很大，此反应启动较慢，在最初的两个小时几乎没有反应，反应产率随着时间的延长而提高，当反应时间达到24小时时，可以以定量的产率得到DMF，进一步延长反应时间不会出现过度氢化等副产物，催化体系表现出良好的选择性。考虑到能耗和实际的工业应用，最优的反应时间为24小时。
实施例7:不同催化剂对多孔有机金属聚合物材料1b催化二甲胺甲酰化反应的影响
Figure PCTCN2020140480-appb-000014
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入二甲胺二氧化碳盐(40mmol，5.36g，4mL)，催化剂(20ppm)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。加入20mL甲醇，之后在反应体系中加入均三甲苯(240mg，2mmol)作为 1H NMR分析的内标以确定产率。结果如表4所示：
表4不同催化剂对二甲胺甲酰化反应的影响
催化剂 均相催化剂1 POMP 1a POMP 1b POMP 1c
产率(％) 20 53 99 42
上表中：DMF的产率都是通过 1H NMR以对均三甲苯为内标测定。
从表4可知，在所考察的几种催化剂中，通过直接超交联手段形成的固体多孔有机金属聚合物材料在此反应中表现出由于其均相催化剂前体的活性。而在几种不同共聚体比例条件下形成的固体催化剂中，当均相催化剂前体1与苯的比例为1:6时，所得催化材料能更高效的催化二氧化碳转化为DMF，降低或者增加苯的当量都会使所得催化材料活性变差，因此优选多孔有机金属聚合物材料POMP 1b为催化剂。
实施例8:不同催化剂用量对POMP 1b催化二甲胺甲酰化反应的影响
Figure PCTCN2020140480-appb-000015
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入二甲胺二氧化碳盐(40mmol，5.36g，4mL)，一定量的固体催化剂POMP 1b。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。加入20mL甲醇，之后在反应体系中加入均三甲苯(240mg，2mmol)作为 1H NMR分析的内标以确定产率。结果如表5所示：
表5不同催化剂用量对POMP 1b催化二甲胺甲酰化反应的影响
POMP 1b(mol％) 0.005 0.002 0.001 0.0005
产率(％) 99 99 99 68
TON 20000 50000 100000 136000
TOF(h -1) 833 2083 4167 5667
上表中：DMF的产率都是通过 1H NMR以对均三甲苯为内标测定。
从表5可知，POMP 1b在二氧化碳催化转化制备DMF的反应中表现出非常高的催化活性，即使催化量低至0.001mol％(十万分之一摩尔当量)，DMF的产率仍然可以达到定量。进一步降低催化量至0.0005mol％(百万分之五摩尔当量)，反应24小时后，虽然产率降至68％，但是转化数提高到136000，TOF也提升至5667h -1。因此降低催化剂的用量有利于提高POMP 1b的催化效率。
实施例9：一百六十七万分之一摩尔当量POMP 1b催化的二甲胺甲酰化
Figure PCTCN2020140480-appb-000016
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入二甲胺二氧化碳盐(115mmol，15.08g，23mL)，固体催化剂POMP 1b(0.6ppm，3.2mg)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入40atm的二氧化碳，然后在高压釜内充入40atm的氢气至总压力为80atm。之后将反应体系在140℃的油浴锅中下搅拌96小时。反应过程中无需再进行二氧化碳或者氢气的补充。反应结束后，将高压釜冷却至室温并缓慢释放压力。将体系中的液体转移至圆底烧瓶中，通过减压蒸馏(80℃,3.1torr)的手段得到DMF和水的混和物无色液体19.5克( 1H NMR分析显示含水量通常介于7％-16％，计算产率时按含水量20％计算)，反应产率为95％，相对应的转化数(TON)为1581588。
实施例10：四百万分之一摩尔当量POMP 1b催化的二甲胺甲酰化
Figure PCTCN2020140480-appb-000017
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入二甲胺二氧化碳盐(110mmol，14.54g，23mL)，固体催化剂POMP 1b(0.25ppm，1.3mg)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入40atm的二氧化碳，然后在高压釜内充入40atm的氢气至总压力为80atm。之后将反应体系在120℃的油浴锅中下搅拌168小时。反应过程中无需再进行二氧化碳或者氢气的补充。反应结束后，将高压釜冷却至室温并缓慢释放压力。将体系中的液体转移至圆底烧瓶中，通过减压蒸馏(80℃,3.1torr)的手段得到DMF和水的混和物无色液体4.2克( 1H NMR分析显示含水量通常介于7％-16％，计算产率时按含水量20％计算)，反应产率为21％，相对应的转化数(TON)为840000。
实施例11：五万分之一摩尔当量的POMP 1b催化的二甲胺甲酰化反应及催化剂1b的循环利用
Figure PCTCN2020140480-appb-000018
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入二甲胺二氧化碳盐(40mmol，5.36g，4mL)，固体催化剂POMP 1b(20ppm，38mg)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。
之后将所得液体转移至离心管中，经过简单的离心分离之后，将上清液倾倒至圆底烧瓶中，催化剂留在离心管中。重复步骤3-4次，将DMF彻底分离至圆底烧瓶中。通过减压蒸馏(80℃,3.1torr)的手段得到DMF和水的混和物无色液体3.7克( 1H NMR分析显示含水量通常介于7％-16％，计算产率时按含水量20％计算)，反应产率为99％。离心管中的催化剂干燥之后再次将入到125mL的高压釜中，重复上述步骤进行下一轮次二甲胺甲酰化反应。催化剂不需要额外的活化步骤。
通过简单的离心分离操作，催化剂可以循环使用12次以上，而催化活性和选择性仍然保持在定量(见附图4)。
实施例12：万分之一摩尔当量的POMP 1b催化的吗啉甲酰化反应
Figure PCTCN2020140480-appb-000019
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入吗啡啉(10mmol，0.87g)，固体催化剂POMP 1b(100ppm，24mg)，甲醇(2mL)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。所得混和物经过短硅胶柱(约2厘米)过滤，用乙酸乙酯洗涤(5mL x 3)后所得滤液以无水硫酸钠干燥，旋蒸除掉溶剂,得到N-甲酰吗啉无色液体(1.15g)，产率99％。
1H NMR(400MHz,CDCl 3)δ7.97(s,1H),3.12(t,J＝6.0,4H),1.64(s,4H)ppm； 13C NMR(100MHz,DMSO)δ161.4,67.2,66.2,45.5,40.3ppm.。
实施例13：万分之一摩尔当量的POMP 1b催化的N-苯基哌嗪甲酰化反应
Figure PCTCN2020140480-appb-000020
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入N-苯基哌嗪(10mmol， 1.62g)，固体催化剂POMP 1b(100ppm，24mg)，甲醇(2mL)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。所得混和物经过短硅胶柱(约2厘米)过滤，用乙酸乙酯洗涤(5mL x 3)后所得滤液以无水硫酸钠干燥，旋蒸除掉溶剂,得到N-苯基-N-甲酰哌嗪白色固体(1.90g)，产率99％。
1H NMR(400MHz,DMSO)δ8.08(s,1H),7.23(t,J＝7.8Hz,2H),6.97(d,J＝8.4Hz,2H),6.83(d,J＝7.2Hz,1H),3.50(q,J＝4.5Hz,4H),3.14(t,J＝5.2Hz,2H),3.08(t,J＝5.2Hz,2H)ppm；
13C NMR(100MHz,DMSO)δ161.3,151.3,129.4,120.0,116.7,49.9,48.7,45.0ppm.。
实施例14：万分之一摩尔当量的POMP 1b催化的哌啶甲酰化反应
Figure PCTCN2020140480-appb-000021
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入哌啶(10mmol，0.85g)，固体催化剂POMP 1b(100ppm，24mg)，甲醇(2mL)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。所得混和物经过短硅胶柱(约2厘米)过滤，用乙酸乙酯洗涤(5mL x 3)后所得滤液以无水硫酸钠干燥，旋蒸除掉溶剂,得到N-甲酰哌啶无色液体(1.04g)，产率92％。
1H NMR(400MHz,CDCl 3)δ8.62(major isomer,s,0.84H),8.00(minor isomer,s,0.25H),3.02(t,J＝6.0Hz,4H),1.78(d,J＝5.6Hz,4H),1.643-1.629(m,2H)ppm.。
实施例15：万分之一摩尔当量的POMP 1b催化的二乙胺甲酰化反应
Figure PCTCN2020140480-appb-000022
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入二乙胺(10mmol，0.73g)，固体催化剂POMP 1b(100ppm，24mg)，甲醇(2mL)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。所得混和物经过短硅胶柱(约2厘米)过滤，用乙酸乙酯洗涤(5mL x 3)后所得滤液以无水硫酸钠干燥，旋蒸除掉溶剂,得到N,N-二乙基甲酰胺无色液体(0.84g)，产率83％。
1H NMR(400MHz,CDCl 3)δ7.77(s,1H),3.09-3.03(m,4H),0.94-0.85(m,6H)ppm； 13C NMR(100MHz,CDCl 3)δ162.0,41.6,36.3,14.7,12.5ppm.。
实施例16：万分之一摩尔当量的POMP 1b催化的二乙醇胺甲酰化反应
Figure PCTCN2020140480-appb-000023
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入二乙醇胺(10mmol，1.05g)，固体催化剂POMP 1b(100ppm，24mg)，甲醇(2mL)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。所得混和物经过短硅胶柱(约2厘米)过滤，用乙酸乙酯洗涤(5mL x 3)后所得滤液以无水硫酸钠干燥，旋蒸除掉溶剂,得到N,N-二(2-羟基乙基)甲酰胺无色液体(1.21g)，产率91％。
1H NMR(400MHz,CDCl 3)δ8.15(s,1H)3.91(t,J＝4.8Hz,2H),3.78(t,J＝4.8Hz,2H),3.53(t,J＝4.8Hz,2H),3.44(t,J＝4.8,2H)ppm.。
实施例17：万分之一摩尔当量的POMP 1b催化的环己基胺甲酰化反应
Figure PCTCN2020140480-appb-000024
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入环己基胺(10mmol，0.99g)，固体催化剂POMP 1b(100ppm，24mg)，甲醇(2mL)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。所得混和物经过短硅胶柱(约2厘米)过滤，用乙酸乙酯洗涤(5mL x 3)后所得滤液以无水硫酸钠干燥，旋蒸除掉溶剂,得到N-甲酰环己基胺无色液体(1.02g)，产率80％。
1H NMR(400MHz,DMSO)δ7.91(s,1H),3.59(d,J＝8.0Hz,1H),1.70(t,J＝9.6Hz,4H),1.53(q,J＝3.2Hz,1H),1.28-1.13(m,5H)ppm； 13C NMR(100MHz,DMSO)δ160.4,46.5,32.7,25.6,24.8ppm.。
实施例18：万分之一摩尔当量的POMP 1b催化的苄胺甲酰化反应
Figure PCTCN2020140480-appb-000025
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入苄胺(10mmol，1.07g)，固体催化剂POMP 1b(100ppm，24mg)，甲醇(2mL)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。所得混和物经过短硅胶柱(约2厘米)过滤，用乙酸乙酯洗涤(5mL x 3)后所得滤液以无水硫酸钠干燥，旋蒸除掉溶剂,得到N-甲酰苄胺无色液体(1.35g)，产率99％。
H NMR(400MHz,DMSO)δ8.51(br,1H),8.14(s,1H),7.33-7.25(m,5H),4.30(s,2H)ppm； 13C NMR(100MHz,CDCl 3)δ165.0(minorisomer),161.6(majorisomer),137.7,128.9,128.7,127.7,127.5,127.0,42.0ppm.。
实施例19：万分之一摩尔当量的POMP 1b催化的2-甲氨基吡啶甲酰化反应
Figure PCTCN2020140480-appb-000026
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入2-甲氨基吡啶(10mmol，1.08g)，固体催化剂POMP 1b(100ppm，24mg)，甲醇(2mL)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。所得混和物经过短硅胶柱(约2厘米)过滤，用乙酸乙酯洗涤(5mL x 3)后所得滤液以无水硫酸钠干燥，旋蒸除掉溶剂,得到N-吡啶-2-甲基甲酰胺黄色液体(1.13g)，产率83％。
1H NMR(400MHz,DMSO)δ8.60(br,1H),8.50(d,J＝4.8Hz,0.86H),8.17(s,1H),7.76(d,J＝4.8Hz,1H),7.30(m,2H),4.41(s,1H)ppm； 13C NMR(100MHz,CDCl 3)δ165.5(minor isomer),161.1(major isomer),156.1,148.9,137.0,122.5,122.1,47.1(minor isomer),43.0(major isomer)ppm.。
实施例20：万分之一摩尔当量的POMP 1b催化的氨氯地平碱甲酰化反应
Figure PCTCN2020140480-appb-000027
在空气气氛中，向配备有磁力搅拌子的不锈钢高压釜中加入氨氯地平碱(1mmol，0.41g)，固体催化剂POMP 1b(100ppm，2.4mg)，甲醇(2mL)。将高压釜拧紧，用二氧化碳吹扫三次，最后充入30atm的二氧化碳，然后在高压釜内充入30atm的氢气至总压力为60atm。之后将反应体系在120℃的油浴锅中下搅拌24小时。反应完成后，将高压釜冷却至室温并缓慢释放压力。所得混和物经过硅胶柱(约5厘米)进行分离，得到甲酰胺产物，白色固体(0.35g)，产率81％。
1H NMR(400MHz,CDCl3)δ8.27(s,1H),7.37(d,J＝7.7Hz,1H),7.22(d,J＝7.9Hz,1H),7.14(dd,J＝16.3,8.9Hz,2H),7.04(t,J＝7.6Hz,1H),5.88(s,1H),5.40(s,1H),4.72(dd,J＝36.6,15.7Hz,2H),4.04(ddt,J＝10.2,6.8,3.6Hz,2H),3.73–3.50(m,8H),2.37(s,3H),1.18(t,J＝7.1Hz,3H).
13C NMR(101MHz,CDCl3)δ168.11,167.16,161.88,145.70,144.90,144.42,132.18,131.38,129.16,127.38,126.88,103.69,101.54,70.24,67.94,59.83,50.77,37.87,37.04,19.22,14.21.。
本领域的普通技术人员可以理解，上述各实施方式是实现本发明的具体实施例，而在实际应用中，可以在形式上和细节上对其作各种改变，而不偏离本发明的精神和范围。

Claims (10)

  1. 一种多孔材料催化二氧化碳氢化制备甲酰胺类化合物的方法，其特征在于，以(V)所示的多孔有机金属聚合物为催化剂，在空气气氛下，通式为(I)的胺类化合物与二氧化碳和氢气进行反应，形成通式为II的甲酰胺类化合物；制备的具体步骤为：
    在空气气氛下，向125毫升高压釜中加入有机胺类化合物(I)、催化剂(V)，密闭，充入一定压力的二氧化碳和氢气；将反应体系置于油浴中搅拌加热反应一定时间；冷却后缓慢释放压力，通过蒸馏或者过柱分离得到甲酰胺类产物；
    其反应式为：
    Figure PCTCN2020140480-appb-100001
    反应式中：
    R 1为氢、取代的或未取代的C 1-C 20烷基、取代的或未取代的C 4-C 10环烷基、取代的或未取代的C 6-C 24芳基或杂芳基、取代的或未取代的C 7-C 25的芳基烷基或杂芳基烷基、-(CH 2) n-OR 3或-(CH 2) n-NR 4R 5,其中，n＝1-8；
    R 2为取代的或未取代的C 1-C 20烷基、取代的或未取代的C 4-C 10环烷基、取代的或未取代的C 6-C 24芳基或杂芳基、取代的或未取代的C 7-C 25芳基烷基或杂芳基烷基、-(CH 2) n-OR 3或-(CH 2) n-NR 4R 5,其中，n＝1-8,R 1与R 2可以连接成取代的或未取代的C 4-C 10环烷基；
    其中，R 3、R 4、R 5各自独立地选自：氢、取代的或未取代的C 1-C 20烷基、取代的或未取代的C 6-C 24芳基、取代的或未取代的C 7-C 25芳基烷基或杂芳基，其中R 4与R 5可以连接成取代的或未取代的C 3-C 10环烷基；
    其中，所述“取代的”是指基团中一个或多个氢原子被选自下组的取代基所取代：卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 2-C 6烯基、C 2-C 6炔基、C 1-C 6烷氧基、羟基、胺基、巯基；
    所述通式(V)所示结构的多孔有机金属聚合物材料为：
    Figure PCTCN2020140480-appb-100002
    式中：
    Figure PCTCN2020140480-appb-100003
    氮杂环卡宾配体为苯并咪唑卡宾、菲并咪唑卡宾、苊并咪唑卡宾、芘并咪唑卡宾、联苯并咪唑卡宾配体；
    X为卤素负离子、四氟硼酸根、六氟磷酸根或六氟锑酸根；
    L为辅助配体，所述辅助配体为卤素、羰基、苯环、茂环、环辛二烯、羟基、水、碳酸根、醋酸根、乙酰丙酮负离子或膦配体；
    R 1,R 2为碳数为1～12的链状烷烃基、碳数为5～7的环状烷烃基、苄基或芳基；
    所述胺类化合物为有机伯胺或有机仲胺类化合物。
  2. 根据权利要求1所述的制备甲酰胺类化合物的方法，其特征在于，所述有机胺类化合物与催化剂的摩尔比为1000-100000:1；
    根据权利要求1所述的制备甲酰胺类化合物的方法，其特征在于，反应温度为80-150℃，反应时间为2-160小时。
  3. 根据权利要求1所述的制备甲酰胺类化合物的方法，其特征在于，控制氢气压力为5-40大气压，二氧化碳气压力为5-40大气压。
  4. 根据权利要求1-4之一所述的制备甲酰胺类化合物的方法，其特征在于，反应在有机溶剂中进行，所述有机溶剂选自：DMF、四氢呋喃、2-甲基四氢呋喃、二氧六环、乙二醇二甲醚、叔丁基甲基醚、苯、甲苯、二甲苯、甲醇、乙醇、异丙醇、叔丁醇；或其中几种的组合。
  5. 根据权利要求1-4之一所述的制备甲酰胺类化合物的方法，其特征在于，当所述胺类化合物为二甲胺或其等价物二甲胺二氧化碳盐时，其产物为DMF。
  6. 根据权利要求6所述的制备甲酰胺类化合物的方法，其特征在于，所述催化剂可以回收，循环使用。
  7. 根据权利要求1所述的制备甲酰胺类化合物的方法，其特征在于，所述催化剂多孔有机金属聚合物材料由如下方法制备得到；制备的具体步骤为：在室温下，将通式III所示的双卡宾铱化合物和3-9个当量的通式IV所示的芳，烃溶解于有机溶剂中，在氮气条件下缓慢加入交联剂和路易斯酸催化剂，密封；将反应体系置于30-80℃的油浴锅中反应1-72小时，反应停止；冷却后，经过过滤、洗涤、索氏提取、真空干燥，得到通式(V)所示的多孔有机金属聚合物材料；
    其化学反应式为：
    Figure PCTCN2020140480-appb-100004
    式中：
    Figure PCTCN2020140480-appb-100005
    氮杂环卡宾配体为苯并咪唑卡宾、菲并咪唑卡宾、苊并咪唑卡宾、芘并咪唑卡宾、联苯并咪唑卡宾配体。
  8. X为卤素负离子、四氟硼酸根、六氟磷酸根或六氟锑酸根；
    L为辅助配体，所述辅助配体为卤素、羰基、苯环、茂环、环辛二烯、羟基、水、碳酸根、醋酸根、乙酰丙酮负离子或膦配体；
    R 1,R 2为碳数为1～12的链状烷烃基、碳数为5～7的环状烷烃基、苄基或芳基。
  9. 根据权利要求8所述的制备甲酰胺类化合物的方法，其特征在于，所制备的催化剂中，选定均相催化剂前体和共聚单体的类型，改变二者的比例，以实现固体催化材料的活性调控，具体为：
    共聚芳烃化合物IV与均相催化剂前体III的质量比为(1-24)：1；
    交联剂与均相催化剂前体III的质量比为(1-100)：1。
  10. 根据权利要求9所述的制备甲酰胺类化合物的方法，其特征在于，所述交联剂选自：二甲醇缩甲醛、原甲酸三甲酯、原乙酸三甲酯、原甲酸三乙酯、原甲酸三异丙酯、二氯苯、二溴苯、1,4-对二苄氯、1,4-对二苄溴、四氯化碳；
    所述溶剂选自二氯甲烷、三氯甲烷、四氯化碳、1,2-二氯乙烷；
    所述路易斯酸选自氯化铁、氯化铝；所述溶剂为二氯甲烷、三氯甲烷、四氯化碳、1,2-二氯乙烷。
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