CN114716371A - N-containing active center metal organic catalyst for synthesizing cyclic carbonate and preparation method and application thereof - Google Patents
N-containing active center metal organic catalyst for synthesizing cyclic carbonate and preparation method and application thereof Download PDFInfo
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- CN114716371A CN114716371A CN202210233303.2A CN202210233303A CN114716371A CN 114716371 A CN114716371 A CN 114716371A CN 202210233303 A CN202210233303 A CN 202210233303A CN 114716371 A CN114716371 A CN 114716371A
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Abstract
The invention relates to a metal organic catalyst, in particular to an N-containing active center metal organic catalyst for synthesizing cyclic carbonate, a preparation method and application thereof, wherein the N-containing active center metal organic catalyst comprises an N active center and a metal active center, and the structural formula is as follows:
or
Wherein M isA metal. Compared with the prior art, the catalyst has the advantages of few synthesis steps, wide raw material source, safe and simple operation method, high catalytic efficiency, environmental friendliness, no need of adding a cocatalyst, stability and easy storage. When the compound is used for synthesizing cyclic carbonate through cycloaddition reaction of carbon dioxide and epoxide, the compound has high activity and high selectivity under mild conditions, and has good industrial application value.
Description
Technical Field
The invention relates to a metal organic catalyst, in particular to a metal organic catalyst containing N active center for synthesizing cyclic carbonate, a preparation method and application thereof.
Background
Carbon dioxide (CO)2) Is one of the major greenhouse gases that pose global environmental problems, and its chemical conversion to useful chemicals is receiving extensive attention from the chemical industry. CO 22The C1 resource is an ideal resource widely existing in nature and industrial waste gas, and the effective utilization of carbon dioxide can not only promote economic development but also is beneficial to environmental protection. Wherein CO is2The atom utilization rate of the cyclic carbonate generated by the reaction of the cyclic carbonate and epoxide is up to 100 percent, and the existence of the cyclic carbonate can directly promote the development of various industries. The reaction has high selectivity and few byproducts, and meets the requirements of green chemistry and atom economy. The cyclic carbonate product obtained by the reaction is a synthesis intermediate with wide application and a high-boiling-point and high-polarity organic solvent with excellent performance, and can be applied to various fields of organic synthesis, gas separation, battery dielectric substances, metal extraction and the like. Therefore, the cycloaddition reaction of the carbon dioxide and the epoxide has important application value and wide market prospect in consideration of resources and environment factors.
To date, a variety of catalytic systems have been investigated and reported, and these catalysts can be broadly divided into two categories: metal complex catalysts and metal-free organic catalysts. Although organic catalysts have been developed in recent years, their catalytic activity is lower than that of metal complex catalysts. In contrast, metal complex catalysts have a wide variety of central metals from which to choose, including main group metals to transition metals, such as magnesium, aluminum, iron, chromium, cobalt, rare earths, and the like, can be used in the synthesis of the complexes. Since 1975 when it was discovered that transition metal complexes could activate carbon dioxide, chemists have conducted a great deal of research in this area. Organic ligand skeletons used for coordinating with central metal ions in the metal complex, such as beta-diimine ligands, bisphenol ligands, phthalocyanines, porphyrins, pyridine, tetradentate Schiff base and other ligands, can regulate and control the electron cloud density of the central metal of the complex by changing the structure of the organic ligand skeletons, further change the acid-base property, steric hindrance and other parameters of the central metal ions, further regulate and control the catalytic reaction activity, product selectivity and other advantages, and are widely concerned by chemists.
Compared with other metals, the aluminum and iron elements have the characteristics of abundant reserves in the earth crust, no toxicity, strong Lewis acidity and the like, and are subjected to ring opening and CO generation in Propylene Oxide (PO)2The method has the advantages that the iron complex in the prior literature mainly adopts phenoxy ligand, and nucleophilic reagent (mainly quaternary ammonium salt negative ions) is integrated into a ligand framework to form the bifunctional single-component metal complex, so that the iron complex has high catalytic activity substrate epoxide conversion rate in cycloaddition reaction and mild reaction conditions, but has the disadvantages of low product selectivity, easy generation of polycarbonate with large molecular weight, long synthetic route of the ligand, relatively low recovery and reuse times of the complex, and is not suitable for large-scale production.
Disclosure of Invention
The invention aims to solve at least one of the problems, and provides an N-containing active center metal organic catalyst for synthesizing cyclic carbonate, a preparation method and application thereof, wherein the catalyst has high activity, simple and easily obtained synthetic raw materials, low price and high yield; and its catalyzed CO2The catalyst has the advantages of mild reaction conditions with epoxide, good selectivity and wide substrate universality, and can also obtain good catalytic effect on part of disubstituted alkylene oxide.
The purpose of the invention is realized by the following technical scheme:
the invention discloses a N-containing active center metal organic catalyst for synthesizing cyclic carbonate, which comprises an N active center and a metal active center, and has the structural formula as follows:
wherein M is a metal. The structural formulas are respectively named as M-PYPA-2, M-PYPA-3 and M-PYPA-4 for distinguishing and representing.
Preferably, said M comprises Fe2+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+、Ag+、Cr3+Or Mn2+And (4) plasma metal ions.
Preferably, M is Fe ion. Lewis acidity of metals on CO in reaction2The activation has a promoting effect, and the valence change of the Fe ions in the catalytic process is possibly more favorable for the catalytic activity and selectivity, so that the catalytic performance of adopting the Fe ions as metal ligands is better than that of other metal complexes. Meanwhile, the content of iron in the earth crust is second to that of aluminum and is positioned at the second place of the metal element, so that the iron has better source advantage, and is preferably used as a metal active center.
In a second aspect, the present invention discloses a method for preparing an N-containing active center metal organic catalyst for the synthesis of cyclic carbonates as defined above, comprising the steps of:
s1: reacting pyridine-2-formic acid hydrochloride with an acylating reagent in a solvent to obtain pyridine-2-acyl chloride;
s2: dissolving the pyridine-2-acyl chloride obtained in the step S1 in a solvent; dissolving aminopyridine in a solvent containing an acid-binding agent, and reacting after mixing to obtain an intermediate ligand;
s3: and (4) reacting the intermediate ligand obtained in the step (S2) with metal salt in absolute ethyl alcohol to obtain the N-containing active center metal organic catalyst.
Preferably, in step S1:
the solvent comprises dichloromethane;
the acylating agent includes but is not limited to oxalyl chloride, thionyl chloride, phosphorus oxychloride or phosphorus oxybromide;
the dosage molar ratio of the pyridine-2-formic acid hydrochloride to the acylating reagent is 1: 1-2;
the reaction temperature is 60-75 ℃ and the reaction time is 2-6 h.
The reaction is carried out in a reflux mode, and pyridine-2-acyl chloride is obtained by vacuum spin drying after the reaction is finished. The reaction under reflux can effectively prevent the solvent from volatilizing.
The structural formula of the pyridine-2-acyl chloride obtained in the step S1 is as follows:
preferably, in step S2:
the solvent comprises dichloromethane;
the aminopyridine comprises 2-aminopyridine, 3-aminopyridine or 4-aminopyridine;
the acid-binding agent comprises triethylamine and other acid-binding agents, and the volume content of the acid-binding agent is 20-16% of that of the solvent; the addition of the acid-binding agent can accelerate the occurrence of acylation reaction and simultaneously prevent the generation of alkyl chloride.
The molar ratio of the pyridine-2-acyl chloride to the aminopyridine is 1: 1;
the reaction is carried out at room temperature for 2-6 h.
The structural formula of the intermediate ligand obtained in step S2 is:
the three structures are respectively obtained by the reaction of pyridine-2-acyl chloride and 2-aminopyridine, pyridine-2-acyl chloride and 3-aminopyridine, and pyridine-2-acyl chloride and 4-aminopyridine. The above structural formulas are respectively named as PYPA-2, PYPA-3 and PYPA-4 for distinguishing.
The mixing in step S2 is specifically to drop the solvent a dissolved with pyridine-2-acyl chloride into the solvent B dissolved with aminopyridine at low temperature, then react for a certain time at room temperature, and obtain an intermediate ligand after washing, drying, concentrating and purifying.
Preferably, the low temperature is in the range of-5 to 5 ℃.
Preferably, in step S3:
the metal ion of the metal salt includes but is not limited to Fe3+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Ag+、Mn2+Or Cr3+Anions include but are not limited to Cl-, NO3-or SO4 2-；
The molar ratio of the intermediate ligand to the metal salt is 2: 1;
the reaction temperature is 60-100 ℃ and the reaction time is 2-6 h.
The third aspect of the invention discloses the application of the N-containing active center metal organic catalyst for synthesizing the cyclic carbonate, which is used for catalyzing CO2And a reaction of synthesizing a cyclic carbonate with an epoxy compound in a solvent.
Preferably, the epoxy compound includes, but is not limited to, ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, octylene oxide, epichlorohydrin, 2- (1-methylethylene) ethylene oxide, styrene oxide, 2- (phenoxymethyl) ethylene oxide, 2-methylpropylene oxide, 1-allyloxy-2, 3-propylene oxide, butoxymethylethylene oxide, cyclohexene oxide, or 1, 2-epoxy-5-hexene.
Preferably, the molar ratio of the catalyst to the epoxy compound is 1: 10-200 parts of;
initial CO of said reaction2The pressure is 0-4MPa, the temperature is 60-140 ℃, and the time is 1-12 h;
such solvents include, but are not limited to, DMF, toluene, N-dimethylacetamide, N-methylpyrrolidone, ethylene glycol dimethyl ether, or DMSO.
CO2The reaction formula for synthesizing the cyclic carbonate with the epoxy compound is as follows:
compared with the prior art, the invention has the following beneficial effects:
1. the complex catalyst contains pyridyl active groups, the pyridyl active groups are connected with the metal active center, and N atoms on the pyridyl active groups have space distribution of lone pair electron adjustable metal active centers, so that the active sites are more uniformly distributed, and the complex catalyst has higher catalytic activity under the synergistic action of the N active centers and the metal active centers, thereby effectively ensuring the stability of reaction and improving the production efficiency. Meanwhile, the pressure requirement on carbon dioxide in the reaction process is low, so that the production cost can be effectively reduced, the production safety is improved, and the method has a good industrial application prospect.
2. The catalyst provided by the invention has the advantages of easily available raw materials, few synthesis steps, high yield, safe and simple operation method, environmental friendliness, and stability and easiness in storage. The catalyst can make CO under mild condition2The cyclic carbonate is synthesized by cycloaddition reaction with epoxy compound, and the reaction has high activity, high conversion rate and high selectivity, and has good industrial application value.
3. The catalyst can achieve high conversion rate and high selectivity without adding any cocatalyst in the cycloaddition reaction process, and the conversion rate and the selectivity of the cycloaddition reaction are both higher than 95% under the optimal reaction conditions, so that the catalyst has a good catalytic effect.
4. CO using the catalyst2The substrate universality of the cycloaddition reaction with epoxy compounds is wide. Even a partially disubstituted alkylene oxide can obtain good catalytic effect.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum analysis spectrum of an intermediate ligand PYPA-4;
FIG. 2 is the NMR spectrum of Fe-PYPA-4 prepared in example 3 and example 4;
FIG. 3 is a NMR chart of propylene carbonate as a catalytic product of cycloaddition reaction in example 5 and example 13;
FIG. 4 shows the different COs in example 102Schematic representation of the effect of Fe-PYPA-4 under pressure on catalytic activity;
FIG. 5 is a graph showing the effect of Fe-PYPA-4 on catalytic activity at different reaction temperatures in example 11;
FIG. 6 is a graph showing the effect of Fe-PYPA-4 on catalytic activity at various reaction times in example 12;
FIG. 7 is a graphical representation of the effect of varying molar ratios of substrate to catalyst Fe-PYPA-4 on catalytic activity in example 13.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The starting materials and methods used in the following examples are not specifically described, and commercially available products and conventional methods which can be conventionally obtained by those skilled in the art can be used.
Example 1
Weighing 3.16g (20mmol) of pyridine-2-formate, adding the pyridine-2-formate into a 100mL round-bottom flask containing 50mL of dichloromethane, dropwise adding 3 drops of DMF (dimethyl formamide) into 15mL of thionyl chloride, refluxing at 65 ℃ for 3 hours, performing rotary drying under vacuum condition after the reaction is finished to obtain an intermediate pyridine-2-acyl chloride crude product, and adding 50mL of DCM (diethyl formamide) into the pyridine-2-acyl chloride crude product to dissolve the pyridine-2-acyl chloride crude product to obtain a DCM solution of pyridine-2-acyl chloride solution for later use; 1.88g of 2-aminopyridine is added into a 100mL round-bottom flask, 50mL of DCM and 10mL of TEA are used as solvents, a DCM solution of pyridine-2-acyl chloride is slowly added dropwise at the temperature of 0 ℃, and the mixture is stirred for 2 hours at normal temperature. After the crude ligand preparation was complete, extraction was performed, water (50mL) was added thereto, the aqueous phases were separated and washed with DCM (30mL), and the combined organic phases were washed with saturated brine (40mL) and Na2SO4After drying, filtration and concentration, the product PYPA-2 was isolated by silica gel column chromatography (petroleum ether: ethyl acetate: 1:2-1:1) as a white solid (3.70g, yield: 92.5%).
2.00g (10mmol) of PYPA-2 and 1.3g (5mmol) of ferric sulfate hexahydrate are respectively placed into a 100mL round-bottom flask, 30mL of absolute ethyl alcohol serving as a solvent is added, the mixture is condensed and refluxed at 60 ℃ for 3 hours, and then is dried in vacuum to obtain a brown oily catalyst Fe-PYPA-2, and the brown oily catalyst Fe-PYPA-2 is dried in a vacuum oven and is stored at 10 ℃ (2.11g and 92.9%). Wherein the structural formula of Fe-PYPA-2 is as follows:
is equipped with stirringStirring in a 50mL stainless steel autoclave, adding 10mmol of ethylene oxide, 21.0 mol% of catalyst Fe-PYPA-21.0 mol% and 10mL of solvent DMF, and reacting with CO2After replacing air for three times, recharging CO2Pressurizing the reactor to 2MPa, putting the reaction kettle into a heating jacket, heating to 120 ℃, stirring at the speed of 350r/min for reaction for 8 hours, cooling the reactor to the ambient temperature after the reaction is finished, and reacting unreacted CO2Is slowly released. The product was collected and identified by gas phase analysis and determined to have a conversion of 73% and a selectivity of 89%.
Example 2
Weighing 3.16g (20mmol) of pyridine-2-formate, adding the pyridine-2-formate into a 100mL round-bottom flask containing 50mL of dichloromethane, dropwise adding 3 drops of DMF (dimethyl formamide) into 15mL of thionyl chloride, refluxing at 65 ℃ for 3 hours, performing rotary drying under vacuum condition after the reaction is finished to obtain an intermediate pyridine-2-acyl chloride crude product, and adding 50mL of DCM (diethyl formamide) into the pyridine-2-acyl chloride crude product to dissolve the pyridine-2-acyl chloride crude product to obtain a DCM solution of pyridine-2-acyl chloride solution for later use; 1.88g of 3-aminopyridine is added into a 100mL round-bottom flask, 50mL of DCM and 10mL of TEA are used as solvents, a DCM solution of pyridine-2-acyl chloride is slowly added dropwise at the temperature of 0 ℃, and the mixture is stirred for 2 hours at normal temperature. After the crude ligand preparation was complete, extraction was performed, water (50mL) was added thereto, the aqueous phases were separated and washed with DCM (30mL), and the combined organic phases were washed with saturated brine (40mL) and Na2SO4After drying, filtration, concentration and isolation by silica gel column chromatography (petroleum ether: ethyl acetate ═ 1:2-1:1) gave PYPA-3(3.66g, yield 91.5%) as a white solid.
2.0g (10mmol) of PYPA-3 and 1.3g (5mmol) of ferric sulfate hexahydrate are respectively put into a 100mL round-bottom flask, 30mL of absolute ethyl alcohol serving as a solvent is added, the mixture is condensed and refluxed for 3h at 60 ℃, and then is dried in vacuum to obtain a brown oily catalyst Fe-PYPA-3, and the catalyst is dried in a vacuum oven and stored at 10 ℃ (2.15g, 94.9%). Wherein the structural formula of Fe-PYPA-3 is as follows:
a50 mL stainless steel autoclave equipped with stirring was charged with 10mmol of ethylene oxide, 31.0 mol% of Fe-PYPA-catalyst and 10mL of DMF solvent, and then treated with CO2After the air is exhausted by the replacement for three times,refilling with CO2Pressurizing the reactor to 2MPa, putting the reaction kettle into a heating jacket, heating to 120 ℃, stirring at the speed of 350r/min for reaction for 8 hours, cooling the reactor to the ambient temperature after the reaction is finished, and reacting unreacted CO2Is slowly released. The product was collected and identified by gas phase analysis and determined to have a conversion of 69% and a selectivity of 92%.
Example 3
Weighing 3.16g (20mmol) of pyridine-2-formate, adding the pyridine-2-formate into a 100mL round-bottom flask containing 50mL of dichloromethane, dropwise adding 3 drops of DMF (dimethyl formamide) into 15mL of thionyl chloride, refluxing at 65 ℃ for 3 hours, performing rotary drying under vacuum condition after the reaction is finished to obtain an intermediate pyridine-2-acyl chloride crude product, and adding 50mL of DCM (diethyl formamide) into the pyridine-2-acyl chloride crude product to dissolve the pyridine-2-acyl chloride crude product to obtain a DCM solution of pyridine-2-acyl chloride solution for later use; 1.88g of 4-aminopyridine is added into a 100mL round-bottom flask, 50mL of DCM and 10mL of TEA are used as solvents, a DCM solution of pyridine-2-acyl chloride is slowly added dropwise at the temperature of 0 ℃, and the mixture is stirred for 2 hours at normal temperature. After the crude ligand preparation was complete, extraction was performed, water (50mL) was added thereto, the aqueous phases were separated and washed with DCM (30mL), and the combined organic phases were washed with saturated brine (40mL) and Na2SO4Drying, filtering, concentrating and isolating by silica gel column chromatography (petroleum ether: ethyl acetate: 1:2-1:1) to give PYPA-4(3.1g, yield 90.6%) as a white solid product1The H-NMR is shown in FIG. 1.
2.0g (10mmol) of PYPA-4 and 1.3g (5mmol) of ferric sulfate hexahydrate are respectively placed into a 100mL round-bottom flask, 30mL of absolute ethyl alcohol serving as a solvent is added, the mixture is condensed and refluxed at 60 ℃ for 3 hours, and then vacuum spin-dried to obtain a brown oily catalyst Fe-PYPA-4, and the brown oily catalyst Fe-PYPA-4 is dried in a vacuum oven and then is dried and stored at 10 ℃ (2.13g, 93.9%). Wherein the structural formula of the Fe-PYPA-4 is as follows:
it is composed of1The H-NMR is shown in FIG. 2.
A50 mL stainless steel autoclave equipped with stirring was charged with 10mmol of ethylene oxide, 41.0 mol% of Fe-PYPA as a catalyst and 10mL of DMF as a solvent, and the mixture was stirred with CO2After replacing air for three times, recharging CO2Pressurizing the reactor to 2MPa, putting the reaction kettle into the reactor, and heatingHeating the reactor to 120 deg.C in a jacket while stirring at a rate of about 350r/min for 8h, after the reaction is complete, the reactor is cooled to ambient temperature and the unreacted CO2Is slowly released. The product was collected and identified by gas phase analysis and determined to have a conversion of 95.6% and a selectivity of 98.6%.
As can be seen from comparative examples 1-3, the catalyst synthesized by selecting the ligand PYPA-4 (comprising pyridine-2-acyl chloride and 4-aminopyridine) has better performance, and then the PYPA-4 is continuously used as the ligand for research.
Example 4
Weighing 1.58g (10mmol) of pyridine-2-formic acid hydrochloride, adding the pyridine-2-formic acid hydrochloride into a 50mL round-bottom flask containing 20mL of dichloromethane, adding 7.5mL of thionyl chloride, dropwise adding 2 drops of DMF, refluxing at 75 ℃ for 2 hours, performing rotary drying under vacuum conditions after the reaction is finished to obtain an intermediate pyridine-2-acyl chloride crude product, and adding 20mL of DCM into the pyridine-2-acyl chloride crude product to dissolve the pyridine-2-acyl chloride crude product to obtain a DCM solution of pyridine-2-acyl chloride solution for later use; 0.94g of 4-aminopyridine was added to a 100mL round-bottom flask, 25mL of DCM and 5mL of TEA were used as solvents, and a solution of pyridine-2-carbonyl chloride in DCM was slowly added dropwise at 5 ℃ and stirred at 25 ℃ for 4 h. After the crude ligand preparation was complete, extraction was performed, water (30mL) was added thereto, the aqueous phases were separated and washed with DCM (20mL), and the combined organic phases were washed with saturated brine (30mL) and MgSO4After drying, filtration, concentration and isolation by silica gel column chromatography (petroleum ether: ethyl acetate 1:2-1:1) gave the product as a white solid (1.81g, 90.5%) which1The H-NMR is shown in FIG. 1.
1.0g (5mmol) of PYPA-4 and 0.65g (2.5mmol) of ferric sulfate hexahydrate are respectively put into a 100mL round-bottom flask, 30mL of absolute ethyl alcohol serving as a solvent is added, the mixture is condensed and refluxed for 2 hours at the temperature of 80 ℃, and then vacuum-dried to obtain a brown oily catalyst Fe-PYPA-4, and the brown oily catalyst Fe-PYPA-4 is dried in a vacuum oven and then is dried and stored at the temperature of 10 ℃ (0.91g, 91.1%). Wherein the structural formula of Fe-PYPA-4 is as follows:
it is composed of1H-NMR is shown in FIG. 2.
In a 50mL stainless steel autoclave equipped with stirring, 10mmol of ethylene oxide, the catalyst Fe-PYPA-41.0 mol% and the solvent DMF 10mL were added with CO2After replacing air for three times, recharging CO2Pressurizing the reactor to 2MPa, putting the reaction kettle into a heating jacket, heating to 120 ℃, stirring at the speed of 350r/min for reaction for 8 hours, cooling the reactor to the ambient temperature after the reaction is finished, and reacting unreacted CO2Is slowly released. The product was collected and identified by gas phase analysis and determined to have a conversion of 95.8% and a selectivity of 98.6%.
Example 5
Weighing 6.32g (40mmol) of pyridine-2-formate, adding the pyridine-2-formate into a 250mL round-bottom flask containing 100mL dichloromethane, adding 30mL thionyl chloride and 4 drops of DMF dropwise, refluxing for 6h at 60 ℃, after the reaction is finished, performing spin drying under vacuum condition to obtain an intermediate pyridine-2-acyl chloride crude product, and adding 100mL DCM into the pyridine-2-acyl chloride crude product to dissolve the pyridine-2-acyl chloride to obtain a DCM solution of pyridine-2-acyl chloride for later use; 3.76g of 4-aminopyridine were added to a 250mL round-bottom flask, with 125mL of DCM and 20mL of TEA as solvents, and a solution of pyridine-2-carbonyl chloride in DCM was added slowly dropwise at-5 deg.C and stirred for 6h at 20 deg.C. Extraction was performed after the crude ligand preparation was complete, water (100mL) was added to it, the aqueous phases were separated and washed with DCM (80mL), the combined organic phases were washed with saturated brine (90mL) and MgSO4After drying, filtration, concentration and isolation by silica gel column chromatography (petroleum ether: ethyl acetate 1:2-1:1) gave the product as a white solid (7.56g, 94.5%), which was1The H-NMR is shown in FIG. 1.
4.0g (20mmol) of PYPA-4 and 2.5g (10mmol) of cobalt acetate tetrahydrate are put into a 100mL round-bottom flask, 30mL of solvent absolute ethyl alcohol is added, the mixture is condensed and refluxed for 6h at 80 ℃, and then is dried in vacuum to obtain a purple solid catalyst Co-PYPA-4, and the purple solid catalyst Co-PYPA-4 is dried in a vacuum oven and stored at 10 ℃ (4.07g, 89.5%). Wherein the structural formula of the Co-PYPA-4 is as follows:
a50 mL stainless steel autoclave equipped with stirring was charged with 10mmol of propylene oxide, 3.0 mol% of catalyst Co-PYPA-4 and 10mL of solvent DMSO, using CO2After replacing air for three times, recharging CO2Pressurizing the reactor to 2MPa, putting the reaction kettle into a heating jacket, heating to 60 ℃ at the same time of about 250 DEG CStirring at r/min for 4h, cooling to ambient temperature, and reacting with unreacted CO2Is slowly released. The product (which is collected)1H-NMR is shown in fig. 3) and identified by gas phase analysis, the conversion was determined to be 58% and the selectivity was 66%.
Example 6
Weighing 1.58g (10mmol) of pyridine-2-formic acid hydrochloride, adding the pyridine-2-formic acid hydrochloride into a 50mL round-bottom flask containing 20mL of dichloromethane, adding 7.5mL of thionyl chloride, dropwise adding 2 drops of DMF, refluxing at 75 ℃ for 2 hours, performing rotary drying under vacuum conditions after the reaction is finished to obtain an intermediate pyridine-2-acyl chloride crude product, and adding 20mL of DCM into the pyridine-2-acyl chloride crude product to dissolve the pyridine-2-acyl chloride crude product to obtain a DCM solution of pyridine-2-acyl chloride solution for later use; 0.94g of 4-aminopyridine was added to a 100mL round-bottom flask, 25mL of DCM and 5mL of TEA were used as solvents, and a solution of pyridine-2-carbonyl chloride in DCM was slowly added dropwise at 5 ℃ and stirred at 25 ℃ for 4 h. After the crude ligand preparation was complete, extraction was performed, water (30mL) was added thereto, the aqueous phases were separated and washed with DCM (20mL), and the combined organic phases were washed with saturated brine (30mL) and MgSO4Drying, filtration, concentration and isolation by silica gel column chromatography (petroleum ether: ethyl acetate 1:2-1:1) gave the product as a white solid (1.81g, 90.5%), which1The H-NMR is shown in FIG. 1.
4.0g (20mmol) of PYPA-4 and 2.49g (10mmol) of nickel acetate tetrahydrate are put into a 100mL round-bottom flask, 30mL of absolute ethyl alcohol serving as a solvent is added, the mixture is condensed and refluxed for 3 hours at 70 ℃, and then is dried in vacuum to obtain a black green solid catalyst Ni-PYPA-4, and the dried catalyst is dried in a vacuum oven and stored at 10 ℃ (4.02g, 88.6%). Wherein the structural formula of the Ni-PYPA-4 is as follows:
a50 mL stainless steel autoclave equipped with stirring was charged with 10mmol of ethylene oxide, 41.0 mol% of Ni-PYPA-catalyst and 10mL of DMF solvent, and the mixture was stirred with CO2After replacing air for three times, recharging CO2Pressurizing the reactor to 2MPa, putting the reaction kettle into a heating jacket, heating to 120 ℃, stirring at the speed of 350r/min for reaction for 8 hours, cooling the reactor to the ambient temperature after the reaction is finished, and reacting unreacted CO2Is slowly released. The product was collected and identified by gas phase analysis and determined to have a conversion of 65.4% and a selectivity of 88.6%.
Example 7
Weighing 3.16g (20mmol) of pyridine-2-formate, adding the pyridine-2-formate into a 100mL round-bottom flask containing 50mL of dichloromethane, dropwise adding 3 drops of DMF (dimethyl formamide) into 15mL of thionyl chloride, refluxing at 65 ℃ for 3 hours, performing rotary drying under vacuum condition after the reaction is finished to obtain an intermediate pyridine-2-acyl chloride crude product, and adding 50mL of DCM (diethyl formamide) into the pyridine-2-acyl chloride crude product to dissolve the pyridine-2-acyl chloride crude product to obtain a DCM solution of pyridine-2-acyl chloride solution for later use; 1.88g of 4-aminopyridine is added into a 100mL round-bottom flask, 50mL of DCM and 10mL of TEA are used as solvents, a DCM solution of pyridine-2-acyl chloride is slowly added dropwise at the temperature of 0 ℃, and the mixture is stirred for 2 hours at normal temperature. After the crude ligand preparation was complete, extraction was performed, water (50mL) was added thereto, the aqueous phases were separated and washed with DCM (30mL), and the combined organic phases were washed with saturated brine (40mL) and Na2SO4After drying, filtration, concentration and isolation by silica gel column chromatography (petroleum ether: ethyl acetate 1:2-1:1) gave the product as a white solid (3.4g, 92.5%), which was1The H-NMR is shown in FIG. 1.
4.0g (20mmol) of PYPA-4 and 2.88g (10mmol) of zinc sulfate heptahydrate are put into a 100mL round-bottomed flask, 30mL of absolute ethyl alcohol serving as a solvent is added, the mixture is condensed and refluxed for 3 hours at 60 ℃, and then is dried in vacuum to obtain a white solid catalyst Zn-PYPA-4, and the white solid catalyst Zn-PYPA-4 is dried in a vacuum oven and stored at 10 ℃ (4.3g and 92.5%). Wherein the structural formula of Zn-PYPA-4 is as follows:
a50 mL stainless steel autoclave equipped with stirring was charged with 10mmol of ethylene oxide, 41.0 mol% of Zn-PYPA-catalyst and 10mL of DMF solvent, and then treated with CO2After replacing air for three times, recharging CO2Pressurizing the reactor to 2MPa, putting the reaction kettle into a heating jacket, heating to 120 ℃, stirring at the speed of 350r/min for reaction for 8 hours, cooling the reactor to the ambient temperature after the reaction is finished, and reacting unreacted CO2Is slowly released. The product was collected and identified by gas phase analysis and determined to have a conversion of 34.6% and a selectivity of 58.2%.
Example 8
Weighing 3.16g (20mmol) of pyridine-2-formate, adding the pyridine-2-formate into a 100mL round-bottom flask containing 50mL dichloromethane, adding 15mL thionyl chloride and 3 drops of DMF dropwise, refluxing for 3h at 65 ℃, after the reaction is finished, performing spin drying under vacuum condition to obtain an intermediate pyridine-2-acyl chloride crude product, and adding 50mL DCM into the pyridine-2-acyl chloride crude product to dissolve the pyridine-2-acyl chloride to obtain a DCM solution of pyridine-2-acyl chloride for later use; 1.88g of 4-aminopyridine is added into a 100mL round-bottom flask, 50mL of DCM and 10mL of TEA are used as solvents, and a DCM solution of pyridine-2-acyl chloride is slowly added dropwise at 0 ℃, and the mixture is stirred for 2h at normal temperature. After the crude ligand preparation was complete, extraction was performed, water (50mL) was added thereto, the aqueous phases were separated and washed with DCM (30mL), and the combined organic phases were washed with saturated brine (40mL) and Na2SO4After drying, filtration, concentration and isolation by silica gel column chromatography (petroleum ether: ethyl acetate 1:2-1:1) gave the product as a white solid (3.4g, 92.5%), which was1The H-NMR is shown in FIG. 1.
2.0g (10mmol) of PYPA-4 and 1.25g (5mmol) of copper sulfate pentahydrate are put into a 100mL round-bottom flask, 30mL of solvent absolute ethyl alcohol is added, after condensation and reflux are carried out for 3h at 60 ℃, vacuum spin-drying is carried out to obtain a blue-black solid catalyst Cu-PYPA-4, and after drying in a vacuum oven, dry preservation is carried out at 10 ℃ (2.16g, 93.2%). Wherein the structural formula of Cu-PYPA-4 is as follows:
a50 mL stainless steel autoclave equipped with stirring was charged with 10mmol of ethylene oxide, the catalyst Cu-PYPA-41.0 mol% and the solvent DMF 10mL, using CO2After replacing air for three times, recharging CO2Pressurizing the reactor to 2MPa, putting the reaction kettle into a heating jacket, heating to 120 ℃, stirring at the speed of 350r/min for reaction for 8 hours, cooling the reactor to the ambient temperature after the reaction is finished, and reacting unreacted CO2Is slowly released. The product was collected and identified by gas phase analysis and determined to have a conversion of 29.5% and a selectivity of 33.2%.
Example 9
3.16g (20mmol) of pyridine-2-carboxylate was weighed out and added to a solution containing 50mL of bis (phenol-bis) acetateIn a 100mL round-bottom flask of chloromethane, 15mL thionyl chloride is added with 3 drops of DMF dropwise, reflux is carried out for 3 hours at 65 ℃, after the reaction is finished, the reaction product is dried in vacuum to obtain an intermediate pyridine-2-acyl chloride crude product, and 50mL of DCM is added into the pyridine-2-acyl chloride crude product to be dissolved to obtain a DCM solution of pyridine-2-acyl chloride for standby; 1.88g of 4-aminopyridine is added into a 100mL round-bottom flask, 50mL of DCM and 10mL of TEA are used as solvents, a DCM solution of pyridine-2-acyl chloride is slowly added dropwise at the temperature of 0 ℃, and the mixture is stirred for 2 hours at normal temperature. After the crude ligand preparation was complete, extraction was performed, water (50mL) was added thereto, the aqueous phases were separated and washed with DCM (30mL), and the combined organic phases were washed with saturated brine (40mL) and Na2SO4After drying, filtration, concentration and isolation by silica gel column chromatography (petroleum ether: ethyl acetate 1:2-1:1) gave the product as a white solid (3.4g, 92.5%), which was1H-NMR is shown in FIG. 1.
2.0g (10mmol) of PYPA-4 and 2.00g (5mmol) of chromium nitrate nonahydrate are put into a 100mL round-bottom flask, 30mL of anhydrous ethanol serving as a solvent is added, the mixture is condensed and refluxed for 3h at 60 ℃, and then is dried in vacuum to obtain a black solid catalyst Cr-PYPA-4, and the black solid catalyst Cr-PYPA-4 is dried in a vacuum oven and is stored at 10 ℃ (2.11g, 93.6%). Wherein the structural formula of Cr-PYPA-4 is as follows:
a50 mL stainless steel autoclave equipped with stirring was charged with 10mmol of ethylene oxide, the catalyst Zn-PYPA-41.0 mol% and the solvent DMF 10mL, the reactor was heated to 120 ℃ in a heating mantle while stirring at about 350r/min for 8h, after the reaction was complete, the reactor was cooled to ambient temperature and the unreacted CO was allowed to cool2Is slowly released. The product was collected and identified by gas phase analysis and determined to have a conversion of 84.6% and a selectivity of 79.2%.
In combination with examples 4-9, Fe-PYPA-4 has the highest catalytic activity, and according to the catalytic reaction mechanism, it is possible that the Fe element has stronger Lewis acidity relative to other metal elements, so that the Fe element can better activate CO2Thus, the conversion rate of the substrate and the selectivity of the product are better.
Example 10
In 6 stainless steel autoclaves with stirring, 10mmol of butylene oxide, 10.0 mol% of the catalyst Fe-PYPA-4 from example 4 and 10mL of DMF solvent were placed respectively, and CO was introduced into each autoclave2Purging three times and using CO2Pressurizing each reaction kettle to 0MPa, 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa and 2.5MPa respectively, putting 6 reaction kettles into a heating jacket, heating to 120 ℃, stirring at the speed of 350r/min for reaction for 8h, cooling the reactor to the ambient temperature after the reaction is finished, and reacting unreacted CO2Is slowly released. The products were collected and identified by gas phase analysis and determined to have 55%, 63%, 70%, 87%, 95% respectively and 70%, 83%, 87%, 93%, 99% respectively for conversion as shown in figure 4. It can be seen that at pressures below 2.0MPa, selectivity and conversion increase with increasing pressure; the conversion rate and the selectivity of the reaction are basically not influenced after the reaction pressure is higher than 2.0 MPa.
Example 11
In 4 stainless steel autoclaves equipped with a stirrer and having a volume of 50mL, 10mmol of epichlorohydrin, 45.0 mol% of the catalyst Fe-PYPA-45.0 prepared in example 4 and 10mL of the solvent N, N-dimethylformamide were placed, and CO was introduced into each autoclave2Purging three times and using CO2Pressurizing the reaction kettles to 2.0MPa, respectively, placing the reaction kettles into heating jackets, heating to 140 deg.C, 120 deg.C, 100 deg.C, 80 deg.C, respectively, stirring at a speed of 350r/min, reacting for 8 hr, cooling the reactor to ambient temperature, and reacting with unreacted CO2Is slowly released. The products were collected and identified by gas phase analysis and determined to have conversions of 52%, 93%, 95%, and selectivities of 91%, 98%, 99%, respectively, as shown in figure 5. It can be seen that at temperatures below 100 ℃ the selectivity and conversion increase substantially with increasing pressure; the conversion rate and the selectivity of the reaction are slightly changed after the temperature is higher than 100 ℃; after continuing to increase the temperature to 120 ℃, the conversion and selectivity were substantially unaffected.
Example 12
In 5 stainless steel autoclaves of 50mL equipped with stirring, 10mmol of epichlorohydrin and the catalyst obtained in example 4 were addedFe-PYPA-45.0 mol% and solvent N, N-dimethylformamide 10mL, and CO is introduced into each autoclave2Purging three times and using CO2Pressurizing the reaction kettles to 2.0MPa, putting the reaction kettles into a heating jacket, heating the reaction kettles to 120 ℃, stirring the reaction kettles at the speed of 350r/min, and reacting the reaction kettles for 12h, 10h, 8h, 6h and 4h, cooling the reactor to the ambient temperature after the reaction is finished, and cooling the unreacted CO2Is slowly released. The products were collected and identified by gas phase analysis, and the conversion rates were determined to be 55%, 90%, 95%, 96%, respectively, and the selectivities to be 70%, 94%, 99%, respectively, as shown in fig. 6. It can be seen that when the reaction time is less than 6h, the selectivity and the conversion rate are greatly increased along with the increase of the pressure; the conversion rate and selectivity of the reaction are changed little after the reaction lasts for more than 6 hours; after the reaction is continued for 10 hours, the conversion rate and the selectivity are basically not influenced.
Example 13
In 5 stainless steel autoclaves of 50mL equipped with stirring, the molar ratio of the substrate propylene oxide to the catalyst Fe-PYPA-4 obtained in example 4 was adjusted to 200:1, 100:1, 50:1, 25:1 and 10:1, respectively, and 10mL of N, N-dimethylformamide as a solvent was added, and CO was introduced into each autoclave2Purging three times and using CO2Pressurizing the reaction kettles to 2.0MPa, respectively, placing the reaction kettles into heating jackets, heating to 120 ℃, stirring at the speed of 350r/min, and reacting for 8h, cooling the reactor to ambient temperature, and reacting unreacted CO2Is slowly released. The product (which is collected)1H-NMR shown in fig. 3) and identified by gas phase analysis, the conversions were determined to be 73.2%, 95.8%, 98.4%, 98.6%, 93.9%, and the selectivities to be 88.2%, 98.6%, 97.2%, 96.4%, 94.6%, respectively, as shown in fig. 7. It can be seen that when the molar ratio of reactants to catalyst is lower than 100:1, selectivity and conversion increase substantially with increasing pressure; and higher than 100: the conversion rate of the reaction after 1 is changed slightly, and the selectivity is slightly reduced; the change to 25 is continued: after 1, both the conversion and the selectivity showed a downward trend. There is thus a preferred range of molar ratios of reactants to catalyst.
Example 14
A50 mL stainless steel autoclave equipped with stirring was charged with 10mmol cyclohexene oxide, the catalyst Fe-PYPA-41.0 mol% obtained in example 4 and 10mL DMF as a solvent, and the mixture was stirred with CO2After replacing air for three times, recharging CO2Pressurizing the reactor to 2MPa, putting the reactor into a heating jacket, heating the reactor to 120 ℃, simultaneously stirring the reactor at a speed of 350r/min for reacting for 8 hours, cooling the reactor to the ambient temperature after the reaction is finished, and reacting unreacted CO2Is slowly released. The product was collected and identified by gas phase analysis and determined to have a conversion of 91.3% and a selectivity of 94.2%.
Comparative example
Taking 5 100mL round-bottom flasks, respectively adding 2.0g (10mmol) of N-phenylpyridine formamide (hereinafter referred to as NPPA), respectively adding 1.3g (5mmol) of ferric sulfate hexahydrate, 1.25g (5mmol) of copper sulfate pentahydrate, 1.44g (5mmol) of zinc sulfate heptahydrate, 2.00g (5mmol) of chromium nitrate nonahydrate and 1.25g (5mmol) of cobalt acetate tetrahydrate into the 5 round-bottom flasks, respectively adding 30mL of solvent anhydrous ethanol, condensing, refluxing for 3h at 60 ℃, vacuum spin-drying to obtain comparative catalysts Fe-NPPA, Cu-NPPA, Zn-NPPA, Cr-NPPA and Co-NPPA without N active centers, respectively, drying in a vacuum oven, and then drying at 10 ℃ for storage. The general structural formula is as follows:
wherein M is Fe3+，Cu2+，Zn2+，Cr3+And Co2 +。
In 5 stainless steel autoclaves of 50mL equipped with stirring, 10mmol of ethylene oxide were added, the catalysts Fe-NPPA, Cu-NPPA, Zn-NPPA, Cr-NPPA, Co-NPPA 1.0 mol% and the solvent DMF 10mL were added, respectively, with CO2After the air is exhausted for three times, CO is respectively filled in2Pressurizing the reactor to the required pressure of 2MPa, putting the reactor into a heating jacket, heating the reactor to 120 ℃, simultaneously stirring the reactor at the speed of 350r/min for reacting for 8 hours, cooling the reactor to the ambient temperature after the reaction is finished, and reacting unreacted CO2Is slowly released. The product was collected and identified by gas phase analysis, and the conversion rates were determined to be 79.6%, 12.3%, 27.3%, 73.2% and 50.7%, respectively,the selectivities were 88.3%, 27.5%, 60.1%, 65.7% and 60.5%, respectively.
Comparing example 4, example 5 and examples 7-9 with the comparative example, it can be seen that the above examples show that organometallic complexes having both N active sites and catalytic sites are useful for the catalytic conversion of CO2And the cyclic carbonate prepared by the epoxy compound has excellent catalytic activity (improved selectivity and conversion rate) which is obviously higher than that of a metal organic complex without an N active center, which shows that the improvement of the catalytic activity is benefited by the synergistic catalytic action of the N active center and the metal catalytic center.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. An N-containing active center metal organic catalyst for synthesizing cyclic carbonate, which is characterized in that the catalyst comprises an N active center and a metal active center, and the structural formula is as follows:
wherein M is a metal.
2. The N-containing active site metal organic catalyst for the synthesis of cyclic carbonates of claim 1, wherein M comprises Fe2+、Fe3+、Co2+、Ni2+、Cu2+、Zn2+、Ag+、Cr3+Or Mn2+。
3. The N-containing active center metal organic catalyst for synthesizing cyclic carbonate according to claim 2, wherein M is Fe ion.
4. A process for preparing an N-containing active site metal organic catalyst for the synthesis of cyclic carbonates according to any of claims 1 to 3, characterized in that it comprises the following steps:
s1: reacting pyridine-2-formic acid hydrochloride with an acylating reagent in a solvent to obtain pyridine-2-acyl chloride;
s2: dissolving the pyridine-2-acyl chloride obtained in the step S1 in a solvent; dissolving aminopyridine in a solvent containing an acid-binding agent, and reacting after mixing to obtain an intermediate ligand;
s3: and (4) reacting the intermediate ligand obtained in the step (S2) with metal salt in absolute ethyl alcohol to obtain the N-containing active center metal organic catalyst.
5. The method of claim 4, wherein in step S1:
the solvent comprises dichloromethane;
the acylating agent comprises oxalyl chloride, thionyl chloride, phosphorus oxychloride or phosphorus oxybromide;
the dosage molar ratio of the pyridine-2-formic acid hydrochloride to the acylating reagent is 1: 1-2;
the reaction temperature is 60-75 ℃ and the reaction time is 2-6 h.
6. The method of claim 4, wherein in step S2:
the solvent comprises dichloromethane;
the aminopyridine comprises 2-aminopyridine, 3-aminopyridine or 4-aminopyridine;
the acid-binding agent comprises triethylamine, and the volume content of the acid-binding agent is 20-16% of that of the solvent;
the molar ratio of the pyridine-2-acyl chloride to the aminopyridine is 1: 1;
the reaction is carried out at room temperature for 2-6 h.
7. The method of claim 4, wherein in step S3:
the metal ion of the metal salt comprises Fe3+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Ag+、Mn2+Or Cr3+The anion includes Cl-、NO3 -Or SO4 2-；
The molar ratio of the intermediate ligand to the metal salt is 2: 1;
the reaction temperature is 60-100 ℃ and the reaction time is 2-6 h.
8. Use of the N-containing active site metal organic catalyst according to any of claims 1 to 3 for the synthesis of cyclic carbonates, characterized in that the catalyst is used to catalyze CO2And a reaction of synthesizing a cyclic carbonate with an epoxy compound in a solvent.
9. Use of an N-containing active site metal organic catalyst for the synthesis of cyclic carbonates according to claim 8 wherein the epoxide compound comprises ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, octylene oxide, epichlorohydrin, 2- (1-methylethylene) ethylene oxide, styrene oxide, 2- (phenoxymethyl) ethylene oxide, 2-methylpropylene oxide, 1-allyloxy-2, 3-propylene oxide, butoxymethylethylene oxide, cyclohexene oxide or 1, 2-epoxy-5-hexene.
10. The use of an N-containing active site metal organic catalyst for the synthesis of cyclic carbonates according to claim 8 wherein the molar ratio of catalyst to epoxide is 1: 10-200 parts of;
initial CO of said reaction2The pressure is 0-4MPa, the temperature is 60-140 ℃, and the time is 1-12 h;
the solvent comprises DMF, toluene, N-dimethylacetamide, N-methylpyrrolidone, ethylene glycol dimethyl ether or DMSO.
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| CN115710244A (en) * | 2022-11-04 | 2023-02-24 | 万华化学集团股份有限公司 | Preparation method of coumarin |
| CN115710244B (en) * | 2022-11-04 | 2024-04-09 | 万华化学集团股份有限公司 | Preparation method of coumarin |
| CN116041284A (en) * | 2022-12-13 | 2023-05-02 | 中国科学院大连化学物理研究所 | Application of metal nitrogen turnover porphyrin-cobalt carbonyl multifunctional catalyst in preparation of beta-lactone by catalyzing epoxide |
| CN116041284B (en) * | 2022-12-13 | 2024-03-15 | 中国科学院大连化学物理研究所 | Application of metal nitrogen turnover porphyrin-cobalt carbonyl multifunctional catalyst in preparation of beta-lactone by catalyzing epoxide |
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