METHOD FOR PREPARING FORMAMIDE COMPOUNDS VIA HYDROGENATION OF CARBON DIOXIDE CATALYZED BY POROUS MATERIALS

Abstract

A method for preparing formamide compounds via hydrogenation of carbon dioxide catalyzed by porous materials includes the following steps: by taking porous organometallic polymers as catalysts, reacting amine compounds with carbon dioxide and hydrogen under an air atmosphere to prepare formamide compounds. The method has the advantages of high reaction efficiency, good selectivity, mild conditions, economy, environmental protection, and simple operation. The catalysts are solid organometallic polymers with large specific surface area, strong carbon dioxide adsorption, hierarchical pore distribution, and uniformly dispersed metal centers. They are designed and synthesized as the reaction catalysts by changing the proportion of the cross-linked comonomer. The catalysts can be especially used for catalytic synthesis of fine chemical N, N-dimethylformamide (DMF) without addition of any additional solvent, alkali, or other additives, which is convenient for separation and purification of DMF.

Claims

1. A method for preparing a formamide compound via hydrogenation of carbon dioxide catalyzed by porous materials, wherein by taking a porous organometallic polymer as shown in formula (V) as a catalyst (V), an organic amine compound (I), as shown in general formula (I), is reacted with carbon dioxide and hydrogen gas under an air atmosphere to form the formamide compound as shown in general formula (II); the method comprises the following steps: under the air atmosphere, adding the organic amine compound (I) and the catalyst (V) to a 125 mL autoclave, sealing the 125 mL autoclave, and charging the carbon dioxide and the hydrogen gas with a predetermined pressure to obtain a reaction system; placing the reaction system in an oil bath, and then stirring and heating the reaction system to perform a reaction at a predetermined reaction temperature for a predetermined reaction time; slowly releasing a pressure of the reaction system after cooling down, and obtaining the formamide compound by a distillation or a column separation; wherein a reaction formula is: ##STR00027## wherein: R.sub.1 is selected from the group consisting of hydrogen, optionally substituted C.sub.1-C.sub.20 alkyl, optionally substituted C.sub.4-C.sub.10 cycloalkyl, optionally substituted C.sub.6-C.sub.24 aryl, optionally substituted C.sub.6-C.sub.24 heteroaryl, optionally substituted C.sub.7-C.sub.25 aryl alkyl, optionally substituted C.sub.7-C.sub.25 heteroaryl alkyl, —(CH.sub.2).sub.n—OR.sub.3, and —(CH.sub.2).sub.n—NR.sub.4R.sub.5, wherein n=1-8; R.sub.2 is selected from the group consisting of optionally substituted C.sub.1-C.sub.20 alkyl, optionally substituted C.sub.4-C.sub.10 cycloalkyl, optionally substituted C.sub.6-C.sub.24 aryl, optionally substituted C.sub.6-C.sub.24 heteroaryl, optionally substituted C.sub.7-C.sub.25 aryl alkyl, optionally substituted C.sub.7-C.sub.25 heteroaryl alkyl, —(CH.sub.2).sub.n—OR.sub.3, and —(CH.sub.2).sub.n—NR.sub.4R.sub.5, wherein n=1-8, and R.sub.1 and R.sub.2 are connected into the optionally substituted C.sub.4-C.sub.10 cycloalkyl; wherein R.sub.3, R.sub.4 and R.sub.5 are separately selected from the group consisting of hydrogen, optionally substituted C.sub.1-C.sub.20 alkyl, optionally substituted C.sub.6-C.sub.24 aryl, optionally substituted C.sub.7-C.sub.25 aryl alkyl, and optionally substituted C.sub.7-C.sub.25 heteroaryl, wherein R.sub.4 and R.sub.5 are connected into optionally substituted C.sub.3-C.sub.10 cycloalkyl; wherein the “substituted” means that one or more hydrogen atoms in the group are substituted by a substituent selected from the group consisting of halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 halogenated alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy, hydroxyl, amino, and sulfhydryl; the porous organometallic polymer as shown in general formula (V) is: ##STR00028## wherein: ##STR00029## =(hetero)aryl and functional group substituted (hetero)aryl; N heterocyclic carbene ligands are benzimidazolylidene, phenanthromidazolylidene, acenaphthoimidazolylidene, pyrenoimidazolylidene, or bibenzimidazolylidene ligands; X is selected from the group consisting of halogen anion, tetrafluoroborate, hexafluorophosphate, and hexafluoroantimonate; L is an auxiliary ligand, and the auxiliary ligand is selected from the group consisting of halogen, carbonyl, benzene ring, cyclopentene ring, cyclooctadiene, hydroxyl, water, carbonate, acetate, acetylacetone anion, and phosphine ligand; R.sub.1 and R.sub.2 are separately selected from the group consisting of chain alkane groups with a carbon number of 1-12, a cyclic alkane group, benzyl, and aryl with a carbon number of 5-7; the organic amine compound (I) is an organic primary amine compound or an organic secondary amine compound.

2. The method according to claim 1, wherein a molar ratio of the organic amine compound (I) to the catalyst (V) is (1,000-100,000):1; the predetermined reaction temperature is 80-150° C., and the predetermined reaction time is 2-160 hours.

3. The method according to claim 1, wherein the predetermined pressure of the hydrogen gas is controlled at 5-40 atm, and the predetermined pressure of the carbon dioxide is controlled at 5-40 atm.

4. The method according to claim 1, wherein the reaction is carried out in at least one organic solvent selected from the group consisting of: DMF, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, glycol dimethyl ether, tert-butyl methyl ether, benzene, methylbenzene, xylene, methanol, ethanol, isopropanol, and tert-butanol.

5. The method according to claim 1, wherein when the organic amine compound (I) is dimethylamine or an equivalent dimethylamine carbon dioxide salt of the dimethylamine, the formamide compound is DMF.

6. The method according to claim 1, wherein the catalyst (V) is recyclable and reusable.

7. The method according to claim 1, wherein the porous organometallic polymer is prepared by a method comprising the following steps: at a room temperature, obtaining a reaction mixture by dissolving in an organic solvent a bis-carbene iridium compound shown by general formula (III) and 3-9 equivalents of arene shown by general formula (IV), and slowly adding a cross-linking agent and a Lewis acid as catalysts under nitrogen conditions, and then sealing the reaction mixture; placing the reaction mixture in an oil bath at 30-80° C. to perform a synthetic reaction for 1-72 hours until the synthetic reaction stops; after cooling the reaction mixture, performing filtering, washing, Soxhlet extraction and vacuum drying to obtain the porous organometallic polymer shown by the general formula (V); wherein a reaction formula is: ##STR00030## wherein: ##STR00031## =(hetero)aryl and functional group substituted (hetero)aryl; the N-heterocyclic carbene ligands are benzimidazolylidene, phenanthromidazolylidene, acenaphthoimidazolylidene, pyrenoimidazolylidene, or bibenzimidazolylidene ligands; X is selected from the group consisting of halogen anion, tetrafluoroborate, hexafluorophosphate, and hexafluoroantimonate; L is the auxiliary ligand, and the auxiliary ligand is selected from the group consisting of halogen, carbonyl, benzene ring, cyclopentene ring, cyclooctadiene, hydroxyl, water, carbonate, acetate, acetylacetone anion, and phosphine ligand; R.sub.1 and R.sub.2 are separately selected from the group consisting of the chain alkane groups with the carbon number of 1-12, and the cyclic alkane groups, benzyl, and aryl with the carbon number of 5-7.

8. (canceled)

9. The method according to claim 7, wherein a mass ratio of the arene shown by the general formula (IV) to the bis-carbene iridium compound shown by the general formula (III) is (1-24):1; a mass ratio of the cross-linking agent to the bis-carbene iridium compound shown by the general formula (III) is (1-100):1.

10. The method according to claim 9, wherein the cross-linking agent is selected from the group consisting of: dimethoxymethane, trimethyl orthoformate, trimethyl orthoacetate, triethyl orthoformate, triisopropyl orthoformate, dichlorobenzene, dibromobenzene, 1,4-dibenzyl chloride, 1,4-dibenzyl bromide, and carbon tetrachloride; the organic solvent is selected from the group consisting of dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; and the Lewis acid is selected from iron chloride and aluminum chloride.

11. The method according to claim 2, wherein the reaction is carried out in at least one organic solvent selected from the group consisting of: DMF, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, glycol dimethyl ether, tert-butyl methyl ether, benzene, methylbenzene, xylene, methanol, ethanol, isopropanol, and tert-butanol.

12. The method according to claim 3, wherein the reaction is carried out in at least one organic solvent selected from the group consisting of: DMF, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, glycol dimethyl ether, tert-butyl methyl ether, benzene, methylbenzene, xylene, methanol, ethanol, isopropanol, and tert-butanol.

13. The method according to claim 2, wherein when the organic amine compound (I) is dimethylamine or an equivalent dimethylamine carbon dioxide salt of the dimethylamine, the formamide compound is DMF.

14. The method according to claim 3, wherein when the organic amine compound (I) is dimethylamine or an equivalent dimethylamine carbon dioxide salt of the dimethylamine, the formamide compound is DMF.

15. The method according to claim 4, wherein when the organic amine compound (I) is dimethylamine or an equivalent dimethylamine carbon dioxide salt of the dimethylamine, the formamide compound is DMF.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0058] FIG. 1 shows the carbon dioxide adsorption profile of a porous organometallic polymer material 1a prepared in Embodiment 1.

[0059] FIG. 2 shows the carbon dioxide adsorption profile of a porous organometallic polymer material 1b prepared in Embodiment 2.

[0060] FIG. 3 shows the carbon dioxide adsorption profile of a porous organometallic polymer material 1c prepared in Embodiment 3.

[0061] FIG. 4 shows the cyclic performance test of a catalyst 1b provided in Embodiment 11 in the dimethylamine formylation reaction.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0062] In order to make the objectives, technical solutions and advantages of the present invention clearer, the embodiments of the present invention will be described in detail as follows. However, those of ordinary skill in the art will understand that various technical details are proposed in the embodiments of the present invention for the readers to better understand the application. However, even without these technical details and various changes and modifications based on the following embodiments, the technical solutions to be protected by the claims of this application can be realized as well.

Embodiment 1: Synthesis of a Porous Organometallic Polymer Material 1a

[0063] ##STR00007##

[0064] 1 mmol of bisbenzimidazolylidene iridium compound (0.63 g) was added into a 50 mL Schlenk tube, vacuumized and purged three times with nitrogen; then 10 mL of 1,2-dichloroethane and 3 mmol of benzene (0.23 g) were added in sequence; the mixture was stirred for a period of time at a room temperature until the solid was completely dissolved; 20 mmol of dimethoxy methane (FDA, 1.52 g) and anhydrous ferric chloride (3.24 g) were added. After being sealed, the reaction system was placed in an 80° C. oil bath to react for 24 hours. After the reaction was completed, the solution was cooled to the room temperature, filtered and washed; the resulting solid was subjected to Soxhlet extraction for 24 hours, and vacuum dried at 60° C. for 24 hours to obtain a porous organometallic polymer POMP 1a. The carbon dioxide adsorption profile of the solid is as shown in FIG. 1. Yield: 0.99 g, 90%.

##STR00008##

Embodiment 2: Synthesis of a Porous Organometallic Polymer Material 1b

[0065] 1 mmol of bisbenzimidazolylidene iridium compound (0.63 g) was added into a 50 mL Schlenk tube, vacuumized and purged three times with nitrogen; then 10 mL of 1,2-dichloroethane and 6 mmol of benzene (0.46 g) were added in sequence; the mixture was stirred for a period of time at a room temperature until the solid was completely dissolved; 20 mmol of dimethoxy methane (FDA, 1.52 g) and anhydrous ferric chloride (3.24 g) were added. After being sealed, the reaction system was placed in an 80° C. oil bath to react for 24 hours. After the reaction was completed, the solution was cooled to the room temperature, filtered and washed; the resulting solid was subjected to Soxhlet extraction for 24 hours, and vacuum dried at 60° C. for 24 hours to obtain a porous organometallic polymer POMP 1b. The carbon dioxide adsorption profile of the solid is as shown in FIG. 2. Yield: 1.17 g, 88%.

Embodiment 3: Synthesis of a Porous Organometallic Polymer Material 1c

[0066] ##STR00009##

[0067] 1 mmol of bisbenzimidazolylidene iridium compound (0.63 g) was added into a 50 mL Schlenk tube, vacuumized and purged three times with nitrogen; then 10 mL of 1,2-dichloroethane and 9 mmol of benzene (0.70 g) were added in sequence; the mixture was stirred for a period of time at a room temperature until the solid was completely dissolved; 20 mmol of dimethoxy methane (FDA, 1.52 g) and anhydrous ferric chloride (3.24 g) were added. After being sealed, the reaction system was placed in an 80° C. oil bath to react for 24 hours. After the reaction was completed, the solution was cooled to the room temperature, filtered and washed; the resulting solid was subjected to Soxhlet extraction for 24 hours, and vacuum dried at 60° C. for 24 hours to obtain a porous organometallic polymer POMP 1c. The carbon dioxide adsorption profile of the solid is as shown in FIG. 3. Yield: 1.37 g, 87%.

Embodiment 4: Effect of Different Temperatures on Catalyzing Dimethylamine Formylation Reaction with a Porous Organometallic Polymer Material 1b

[0068] ##STR00010##

[0069] Under an air atmosphere, the dimethylamine carbon dioxide salt (40 mmol, 5.36 g, 4 mL) and a solid catalyst POMP 1b (20 ppm, 38 mg) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan at a set temperature for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. 20 mL of methanol was added, and then mesitylene (240 mg, 2 mmol) was added into the reaction system as an internal standard for .sup.1H NMR analysis to determine the yield. (See Table 1 for the results).

TABLE-US-00001 TABLE 1 Effect of Different Temperatures on Catalyzing Dimethylamine Formylation Reaction with a Porous Organometallic Polymer Material 1b Temperature (° C.) 60 80 100 120 140 Yield (%) 0 23 59 99 99

[0070] In the above table, the yields of DMF are all determined by .sup.1H NMR with mesitylene as the internal standard.

[0071] It may be known from Table 1 that the changes in temperature had a significant effect on the results of the reaction. When the temperature was lower than 60° C., no reaction would occur. The yield increased significantly as the temperature rose. When the reaction temperature was 120° C., the yield could reach a quantitative level, and the quantitative yield could be obtained still by increasing the temperature. Considering energy consumption and practical industrial applications, the optimal reaction temperature is 120° C.

Embodiment 5: Effect of Carbon Dioxide and Hydrogen Pressures on Catalyzing Dimethylamine Formylation Reaction with a Porous Organometallic Polymer Material 1b

[0072] ##STR00011##

[0073] Under an air atmosphere, the dimethylamine carbon dioxide salt (40 mmol, 5.36 g, 4 mL) and a solid catalyst POMP 1b (20 ppm, 38 mg) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with carbon dioxide of a certain pressure, and then charged with hydrogen of a certain pressure. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. 20 mL of methanol was added, and then mesitylene (240 mg, 2 mmol) was added into the reaction system as an internal standard for .sup.1H NMR analysis to determine the yield. The results are shown in Table 2:

TABLE-US-00002 TABLE 2 Effect of Carbon Dioxide and Hydrogen Pressures on Catalyzing Dimethylamine Formylation Reaction with a Porous Organometallic Polymer Material 1b Carbon Dioxide Pressures (atm) 10 20 30 40 Hydrogen Pressures (atm) 10 20 30 40 .sup.1H NMR Yield (%) 10 56 99 99

[0074] In the above table, the yields of DMF are all determined by .sup.1H NMR with mesitylene as the internal standard.

[0075] It may be known from Table 2 that carbon dioxide and hydrogen pressures had a great effect on the results of the reaction. The increases in carbon dioxide and hydrogen pressures were favorable for the conversion of carbon dioxide into DMF. In the selected pressure, when the partial pressures of carbon dioxide and hydrogen were both 30 atm, the quantitative preparation of DMF could be achieved. Further increases in the pressures could still achieve the high-selectivity preparation of DMF without excessive hydrogenation and other by-products. Considering safety and practical industrial applications, the optimal carbon dioxide and hydrogen pressures are 30 atm/30 atm.

Embodiment 6: Effect of Different Reaction Times on Catalyzing Dimethylamine Formylation Reaction with a Porous Organometallic Polymer Material 1b

[0076] ##STR00012##

[0077] Under an air atmosphere, dimethylamine carbon dioxide salt (40 mmol, 5.36 g, 4 mL) and a solid catalyst POMP 1b (20 ppm, 38 mg) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for a certain period of time. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. 20 mL of methanol was added, and then mesitylene (240 mg, 2 mmol) was added into the reaction system as an internal standard for .sup.1H NMR analysis to determine the yield. The results are shown in Table 3:

TABLE-US-00003 TABLE 3 Effect of Different Reaction Times on Catalyzing Dimethylamine Formylation Reaction with a Porous Organometallic Polymer Material 1b Time (h) 2 6 12 24 48 Yield (%) 5 18 49 99 99

[0078] In the above table, the yields of DMF are all determined by .sup.1H NMR with mesitylene as the internal standard.

[0079] It may be known from Table 3 that the reaction time had a great effect on the results of the reaction. The reaction started slowly, and almost no reaction occurred in the first two hours. The reaction yield increased over time. When the reaction time reached 24 hours, DMF could be obtained in a quantitative yield, no excessive hydrogenation by-products would occur by further extending the reaction time, and the catalytic system exhibited a good selectivity. Considering energy consumption and actual industrial applications, the optimal reaction time is 24 hours.

Embodiment 7: Effect of Different Catalysts on Catalyzing Dimethylamine Formylation Reaction with a Porous Organometallic Polymer Material 1b

[0080] ##STR00013##

[0081] Under an air atmosphere, the dimethylamine carbon dioxide salt (40 mmol, 5.36 g, 4 mL) and a catalyst (20 ppm) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. 20 mL of methanol was added, and then mesitylene (240 mg, 2 mmol) was added into the reaction system as an internal standard for .sup.1H NMR analysis to determine the yield. The results are shown in Table 4:

TABLE-US-00004 TABLE 4 Effect of Different Catalysts on Dimethylamine Formylation Reaction Catalyst Homogeneous Catalyst 1 POMP 1a POMP 1b POMP 1c Yield (%) 20 53 99 42

[0082] In the above table, the yields of DMF are all determined by .sup.1H NMR with mesitylene as the internal standard.

[0083] It may be known from Table 4 that among the catalysts investigated, the solid porous organometallic polymer materials formed by the direct super-crosslinking method exhibited a activity better than that of the homogeneous catalyst precursor in this reaction. In the solid catalysts formed at several different copolymer ratios, when the ratio of homogeneous catalyst precursor 1 to benzene was 1:6, the resulting catalytic material could catalyze the conversion of carbon dioxide into DMF more efficiently, the activity of the resulting catalytic material would become worse by reducing or increasing equivalent weight of benzene, and thus the porous organometallic polymer material POMP 1b was preferred as the catalyst.

Embodiment 8: Effect of Different Catalyst Dosages on Catalyzing Dimethylamine Formylation Reaction with POMP 1b

[0084] ##STR00014##

[0085] Under an air atmosphere, the dimethylamine carbon dioxide salt (40 mmol, 5.36 g, 4 mL) and a certain amount of a solid catalyst POMP 1b were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. 20 mL of methanol was added, and then mesitylene (240 mg, 2 mmol) was added into the reaction system as an internal standard for .sup.1H NMR analysis to determine the yield. The results are shown in Table 5:

TABLE-US-00005 TABLE 5 Effect of Different Catalyst Dosages on Catalyzing Dimethylamine Formylation Reaction with POMP 1b POMP 1b (mol %) 005 002 001 0005 Yield (%) 99 99 99 68 TON 20000 50000 100000 136000 TOF(h.sup.−1) 833 2083 4167 5667

[0086] In the above table, the yields of DMF are all determined by .sup.1H NMR with mesitylene as the internal standard.

[0087] It may be known from Table 5 that POMP 1b exhibited a very high catalytic activity in the reaction of the catalytic conversion of carbon dioxide into DMF. Even if the catalytic amount was as low as 0.001 mol % (1/100,000 molar equivalent), the yield of DMF could still reach the quantitative amount. When the catalytic amount was further reduced to 0.0005 mol % (5% molar equivalent), after 24 hours of reaction, although the yield decreased to 68%, the turnover number increased to 136,000 and the TOF also increased to 5667 h.sup.−1. Therefore, reducing the catalyst dosage is favorable for improving the catalytic efficiency of POMP 1b.

Embodiment 9: Dimethylamine Formylation Reaction Catalyzed with a POMP 1b of 1/1,670,000 Molar Equivalent

[0088] ##STR00015##

[0089] Under an air atmosphere, the dimethylamine carbon dioxide salt (115 mmol, 15.08 g, 23 mL) and the solid catalyst POMP 1b (0.6 ppm, 3.2 mg) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 40 atm of carbon dioxide, and then charged with 40 atm hydrogen until a total pressure reaches 80 atm. Afterwards, the reaction system was stirred in an oil bath pan of 140° C. for 96 hours. It was unnecessary to supplement carbon dioxide or hydrogen during the reaction. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. The liquid in the system was transferred to a round-bottomed flask, and 19.5 g of colorless liquid, a mixture of DMF and water, was obtained by means of vacuum distillation (80° C., 3.1 torr) NMR analysis showed that the water content was usually 7%-16%, and the yield was calculated based on a water content of 20%). The reaction yield was 95%, and the corresponding turnover number (TON) was 1,581,588.

Embodiment 10: Dimethylamine Formylation Reaction Catalyzed with a POMP 1b of 1/4,000,000 Molar Equivalent

[0090] ##STR00016##

[0091] Under an air atmosphere, the dimethylamine carbon dioxide salt (110 mmol, 14.54 g, 23 mL) and a solid catalyst POMP 1b (0.25 ppm, 1.3 mg) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 40 atm of carbon dioxide, and then charged with 40 atm hydrogen until a total pressure reaches 80 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 168 hours. It was unnecessary to supplement carbon dioxide or hydrogen during the reaction. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. The liquid in the system was transferred to a round-bottomed flask, and 4.2 g of colorless liquid, a mixture of DMF and water, was obtained by means of vacuum distillation (80° C., 3.1 torr) NMR analysis showed that the water content was usually 7%-16%, and the yield was calculated based on a water content of 20%). The reaction yield was 21%, and the corresponding turnover number (TON) was 840,000.

Embodiment 11: Dimethylamine Formylation Reaction Catalyzed with a POMP 1b of 1/50,000 Molar Equivalent and the Recycling of Catalyst 1b

[0092] ##STR00017##

[0093] Under an air atmosphere, the dimethylamine carbon dioxide salt (40 mmol, 5.36 g, 4 mL) and a solid catalyst POMP 1b (20 ppm, 38 mg) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly.

[0094] Afterwards, the resulting liquid was transferred to a centrifuge tube, and the supernatant subjected to simple centrifugal separation was poured into a round bottom flask, with the catalyst remaining in the centrifuge tube. The steps were repeated 3-4 times until DMF was completely separated into the round-bottomed flask. 3.7 g of colorless liquid, a mixture of DMF and water, was obtained by vacuum distillation (80° C., 3.1 torr) NMR analysis showed that the water content was usually 7%-16%, and the yield was calculated based on a water content of 20%). The reaction yield was 99%. After being dried, the catalyst in the centrifuge tube was put into a 125 mL autoclave, and the above steps were repeated for the next round of dimethylamine formylation reaction. No additional activation steps were required for the catalyst.

[0095] Through the simple centrifugal separation operation, the catalyst could be recycled for more than 12 times, while the catalytic activity and selectivity were still maintained at a quantitative level (see FIG. 4).

Embodiment 12: Morpholine Formylation Reaction Catalyzed with a POMP 1b of 1/10,000 Molar Equivalent

[0096] ##STR00018##

[0097] Under an air atmosphere, the morpholine (10 mmol, 0.87 g), a solid catalyst POMP 1b (100 ppm, 24 mg) and methanol (2 mL) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. The resulting mixture was filtered by a short silica gel column (about 2 cm), and washed with ethyl acetate (5 mL×3); the resulting filtrate was dried with anhydrous sodium sulfate; and the solvent was removed by rotary evaporation to obtain a colorless liquid (1.15 g) of N-formylmorpholine, with a yield of up to 99%.

[0098] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.97 (s, 1H), 3.12 (t, J=6.0, 4H), 1.64 (s, 4H) ppm; .sup.13C NMR (100 MHz, DMSO) δ 161.4, 67.2, 66.2, 45.5, 40.3 ppm.

Embodiment 13: N-Phenylpiperazine Formylation Reaction Catalyzed with a POMP 1b of 1/10,000 Molar Equivalent

[0099] ##STR00019##

[0100] Under an air atmosphere, the N-phenylpiperazine (10 mmol, 1.62 g), a solid catalyst POMP 1b (100 ppm, 24 mg) and methanol (2 mL) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. The resulting mixture was filtered by a short silica gel column (about 2 cm), and washed with ethyl acetate (5 mL×3); the resulting filtrate was dried with anhydrous sodium sulfate; and the solvent was removed by rotary evaporation to obtain a white solid (1.90 g) of N-phenyl-N-formylpiperazine, with a yield of up to 99%.

[0101] .sup.1H NMR (400 MHz, DMSO) δ 8.08 (s, 1H), 7.23 (t, J=7.8 Hz, 2H), 6.97 (d, J=8.4 Hz, 2H), 6.83 (d, J=7.2 Hz, 1H), 3.50 (q, J=4.5 Hz, 4H), 3.14 (t, J=5.2 Hz, 2H), 3.08 (t, J=5.2 Hz, 2H) ppm;

[0102] .sup.13C NMR (100 MHz, DMSO) δ 161.3, 151.3, 129.4, 120.0, 116.7, 49.9, 48.7, 45.0 ppm.

Embodiment 14: Piperidine Formylation Reaction Catalyzed with a POMP 1b of 1/10,000 Molar Equivalent

[0103] ##STR00020##

[0104] Under an air atmosphere, the piperidine (10 mmol, 0.85 g), a solid catalyst POMP 1b (100 ppm, 24 mg) and methanol (2 mL) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. The resulting mixture was filtered by a short silica gel column (about 2 cm), and washed with ethyl acetate (5 mL×3); the resulting filtrate was dried with anhydrous sodium sulfate; and the solvent was removed by rotary evaporation to obtain a colorless liquid (1.04 g) of N-formylpiperidine, with a yield of up to 92%.

[0105] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.62 (major isomer, s, 0.84H), 8.00 (minor isomer, s, 0.25H), 3.02 (t, J=6.0 Hz, 4H), 1.78 (d, J=5.6 Hz, 4H), 1.643-1.629 (m, 2H) ppm.

Embodiment 15: Diethylamine Formylation Reaction Catalyzed with a POMP 1b of 1/10,000 Molar Equivalent

[0106] ##STR00021##

[0107] Under an air atmosphere, the diethylamine (10 mmol, 0.73 g), a solid catalyst POMP 1b (100 ppm, 24 mg) and methanol (2 mL) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. The resulting mixture was filtered by a short silica gel column (about 2 cm), and washed with ethyl acetate (5 mL×3); the resulting filtrate was dried with anhydrous sodium sulfate; and the solvent was removed by rotary evaporation to obtain a colorless liquid (0.84 g) of N-diethylformamide, with a yield of up to 83%.

[0108] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.77 (s, 1H), 3.09-3.03 (m, 4H), 0.94-0.85 (m, 6H) ppm; .sup.13C NMR (100 MHz, CDCl.sub.3) δ 162.0, 41.6, 36.3, 14.7, 12.5 ppm.

Embodiment 16: Diethanolamine Formylation Reaction Catalyzed with a POMP 1b of 1/10,000 Molar Equivalent

[0109] ##STR00022##

[0110] Under an air atmosphere, the diethanolamine (10 mmol, 1.05 g), a solid catalyst POMP 1b (100 ppm, 24 mg) and methanol (2 mL) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. The resulting mixture was filtered by a short silica gel column (about 2 cm), and washed with ethyl acetate (5 mL×3); the resulting filtrate was dried with anhydrous sodium sulfate; and the solvent was removed by rotary evaporation to obtain a colorless liquid (1.21 g) of N-di(2-hydroxyethyl)formamide, with a yield of up to 91%.

[0111] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.15 (s, 1H) 3.91 (t, J=4.8 Hz, 2H), 3.78 (t, J=4.8 Hz, 2H), 3.53 (t, J=4.8 Hz, 2H), 3.44 (t, J=4.8, 2H) ppm.

Embodiment 17: Cyclohexylamine Formylation Reaction Catalyzed with a POMP 1b of 1/10,000 Molar Equivalent

[0112] ##STR00023##

[0113] Under an air atmosphere, the cyclohexylamine (10 mmol, 0.99 g), a solid catalyst POMP 1b (100 ppm, 24 mg) and methanol (2 mL) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. The resulting mixture was filtered by a short silica gel column (about 2 cm), and washed with ethyl acetate (5 mL×3); the resulting filtrate was dried with anhydrous sodium sulfate; and the solvent was removed by rotary evaporation to obtain a colorless liquid (1.02 g) of N-formyl-cyclohexylamine, with a yield of up to 80%.

[0114] .sup.1H NMR (400 MHz, DMSO) δ 7.91 (s, 1H), 3.59 (d, J=8.0 Hz, 1H), 1.70 (t, J=9.6 Hz, 4H), 1.53 (q, J=3.2 Hz, 1H), 1.28-1.13 (m, 5H) ppm; .sup.13C NMR (100 MHz, DMSO) δ 160.4, 46.5, 32.7, 25.6, 24.8 ppm.

Embodiment 18: Benzylamine Formylation Reaction Catalyzed with a POMP 1b of 1/10,000 Molar Equivalent

[0115] ##STR00024##

[0116] Under an air atmosphere, the benzylamine (10 mmol, 1.07 g), a solid catalyst POMP 1b (100 ppm, 24 mg) and methanol (2 mL) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. The resulting mixture was filtered by a short silica gel column (about 2 cm), and washed with ethyl acetate (5 mL×3); the resulting filtrate was dried with anhydrous sodium sulfate; and the solvent was removed by rotary evaporation to obtain a colorless liquid (1.35 g) of N-formyl benzylamine, with a yield of up to 99%.

[0117] .sup.1H NMR (400 MHz, DMSO) δ 8.51 (br, 1H), 8.14 (s, 1H), 7.33-7.25 (m, 5H), 4.30 (s, 2H) Ppm; .sup.13C NMR (100 MHz, CDCl.sub.3) δ 165.0 (minor isomer), 161.6 (major isomer), 137.7, 128.9, 128.7, 127.7, 127.5, 127.0, 42.0 ppm.

Embodiment 19: 2-Methylaminopyridine Formylation Reaction Catalyzed with a POMP 1b of 1/10,000 Molar Equivalent

[0118] ##STR00025##

[0119] Under an air atmosphere, the 2-methylaminopyridine (10 mmol, 1.08 g), a solid catalyst POMP 1b (100 ppm, 24 mg) and methanol (2 mL) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. The resulting mixture was filtered by a short silica gel column (about 2 cm), and washed with ethyl acetate (5 mL×3); the resulting filtrate was dried with anhydrous sodium sulfate; and the solvent was removed by rotary evaporation to obtain a yellow liquid (1.13 g) of N-(pyridin-2-ylmethyl)formamide, with a yield of up to 83%.

[0120] .sup.1H NMR (400 MHz, DMSO) δ 8.60 (br, 1H), 8.50 (d, J=4.8 Hz, 0.86H), 8.17 (s, 1H), 7.76 (d, J=4.8 Hz, 1H), 7.30 (m, 2H), 4.41 (s, 1H) ppm; .sup.13C NMR (100 MHz, CDCl.sub.3) δ 165.5 (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.

Embodiment 20: Amlodipine Base Formylation Reaction Catalyzed with POMP 1b of 1/10,000 Molar Equivalent

[0121] ##STR00026##

[0122] Under an air atmosphere, the amlodipine base (1 mmol, 0.41 g), a solid catalyst POMP 1b (100 ppm, 2.4 mg) and methanol (2 mL) were added into a stainless steel autoclave with a magnetic stir bar. The autoclave was tightened, purged three times with carbon dioxide, charged with 30 atm carbon dioxide, and then charged with 30 atm hydrogen until a total pressure reaches 60 atm. Afterwards, the reaction system was stirred in an oil bath pan of 120° C. for 24 hours. Upon completion of the reaction, the autoclave was cooled down to the room temperature, and the pressure was released slowly. The resulting mixture was separated by a silica gel column (about 5 cm) to obtain a white solid (0.35 g) of formamide products, with a yield of up to 81%.

[0123] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.27 (s, 1H), 7.37 (d, J=7.7 Hz, 1H), 7.22 (d, J=7.9 Hz, 1H), 7.14 (dd, J=16.3, 8.9 Hz, 2H), 7.04 (t, J=7.6 Hz, 1H), 5.88 (s, 1H), 5.40 (s, 1H), 4.72 (dd, J=36.6, 15.7 Hz, 2H), 4.04 (ddt, J=10.2, 6.8, 3.6 Hz, 2H), 3.73-3.50 (m, 8H), 2.37 (s, 3H), 1.18 (t, J=7.1 Hz, 3H).

[0124] .sup.13C NMR (100 MHz, CDCl.sub.3) δ 168.11, 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.

[0125] Those of ordinary skill in the art can understand that the above-mentioned implementation modes are the embodiments for realizing the present invention, whereas in practical applications, various modifications can be made in forms and details without deviating from the spirit and scope of the present invention.