CN115925605A - Method and catalyst for continuously preparing pyrrole compounds - Google Patents
Method and catalyst for continuously preparing pyrrole compounds Download PDFInfo
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Abstract
The invention provides a method and a catalyst for green sustainable preparation of pyrrole compounds. The pyrrole compound is prepared by dehydrogenating and cross-condensing alcohol molecules and 2-amino alcohol molecules, wherein the alcohol molecules comprise ethanol, propanol, isopropanol, butanol and higher fatty alcohol, and the amino alcohol comprises 2-amino ethanol and substituted 2-amino alcohol. The catalyst is composed of composite oxide loaded metal nano particles, and the metal nano particles mainly comprise one or more of Ni, co and Cu; the composite oxide consists of two or three of nickel oxide, cobalt oxide, magnesium oxide, aluminum oxide, zinc oxide and zirconium oxide. The catalyst is used for preparing the pyrrole compound from an alcohol molecule and a 2-amino alcohol molecule for the first time under the condition of no additional alkali, and the yield can reach 99 percent to the maximum.
Description
Technical Field
The invention relates to the fields of chemistry and chemical engineering and catalysts, in particular to a method for preparing pyrrole compounds by efficiently catalyzing alcohol molecules and 2-amino alcohol molecules to undergo dehydrogenation and cross condensation and a catalyst thereof.
Background
Pyrrole is a very important five-membered nitrogen heterocyclic compound, and because of its biological activities of anti-tumor and sterilization, it is widely used in the medical field, such as synthetic key body for synthesizing drug molecules for treating gastric cancer and hypercholesterolemia, i.e. sumatinib and atorvastatin, and pyrrole is also an important constituent structural unit of chlorophyll in green plants and heme in human hemoglobin. Polypyrrole taking pyrrole as a monomer is used as a high-molecular conductive polymer and applied to battery and capacitor materials. Therefore, the research on the green sustainable preparation of the pyrrole compounds has important significance and value.
Industrially, the earliest industrial production method of pyrrole is to adopt 1,4-butynediol catalyzed by Pd, ru and the like to react with ammonia gas for preparation, the yield can reach more than 65%, and then MoO under the high-temperature condition is gradually developed x 、VO x And the like, the preparation of pyrrole by catalyzing furan with an acidic oxide, the preparation of pyrrole by catalyzing pyrrolidine dehydrogenation with a Pd or Rh-based catalyst, and the like. In the traditional industrial route for preparing the pyrrole compounds, the main existence that the raw materials mainly come from petrochemical industry, high temperature and high pressure are required, the reaction conditions are harsh, and the catalyst has high cost by taking the noble metal with high loading as an active center.
In the preparation of laboratory, the synthesis method of pyrrole is mainly divided into Knorr reaction of alpha-halogenated methyl ketone, beta-keto ester and ammonia condensation, pal-Knorr reaction of 1,4-diketone and primary amine or ammonia condensation, barton-Zard reaction of nitroolefin and alpha-isonitrile acetate reaction under alkaline condition to obtain pyrrole ring derivative, and Hantzsch reaction of carbonyl compound condensation of alpha-amino ketone and alpha position with electron-withdrawing group. In many of these pyrrole synthesis methods, the reaction conditions often require the participation of additional equivalents of strong acids/bases, the formation of halides which are environmentally hazardous, and the prior synthesis of specific reaction substrates. Therefore, the development of the green sustainable preparation method of the pyrrole compounds by using renewable, cheap and easily available reaction substrates without adding strong acid/strong base has great scientific significance and industrial value.
In 2013, kempe et al first reported that an Ir-PNP complex catalyzed the reaction of aromatic and aliphatic secondary alcohols with substituted 2-aminoethanol to produce 1,4-disubstituted pyrroles with a yield of 42-97% under the condition of 1.1equiv.KOt Bu added. Subsequently, the Saito topic group reported as CpRuCl (PPh) 3 ) 2 As a catalyst, pyrrole compounds were synthesized in yields of 59-89% by catalyzing aromatic and aliphatic secondary alcohols with substituted 2-aminoalcohols at 10mol% KOt Bu. Later on, the reaction was gradually developed with RuHCl (CO) (PPh) 3 ) 3 And [ (OC) 5 H 3 N-CO-C 5 H 3 N-C 5 H 4 N)Ru(PPh 3 ) 2 (CO)]Cl - The catalyst, however, is still limited to the reaction of aromatic and aliphatic secondary alcohols with substituted 2-aminoalcohols, and the addition of the strong organic base KOtBu is likewise necessary, otherwise pyrrole compounds are not available. In 2016, milstein et al reported Co-PNN forcipate chelates, catalyzed by aliphatic secondary diols reacting with aromatic and aliphatic long-chain primary amines to synthesize N-substituted 1,4-disubstituted pyrroles with yields of 22-93% under the condition of 5mol% KOtBu, noting that 1,4-butanediol can also react, but one primary diol does not report the reaction of other primary diols, and then the Banerjee team in 2019 reported the reaction of NiBr 2 Forming a complex with phenonthroline ligand, catalyzing aromatic secondary alcohol to react with substituted 2-aminoethanol in the presence of 1.0equiv.KOtBu to generate 1,4-disubstituted pyrrole compounds, wherein the yield is 31-60%. In 2014, kempe et al reported that the first multi-phase catalytic synthesis of pyrroles using equivalent amounts of KOtBu and 1.27wt% Ir/SiCN catalyzed synthesis of pyrroles from aromatic and aliphatic secondary alcohols and substituted 2-aminoalcohols yielded up to 90%. In 2016, shimizu catalyzed synthesis of pyridine with amino alcohols using equivalent weights of KOtBu and 5wt% of Pt/CPyrrole, 92% yield can be obtained, but the substrate is limited to the reaction of a secondary alcohol with a substituted 2-aminoalcohol.
However, in the synthesis of pyrrole compounds reported in the prior literature, the substrates are limited to the reaction of aromatic and aliphatic secondary alcohols with substituted 2-amino alcohols, but the synthesis of aromatic and aliphatic primary alcohols derived from green and renewable biomass resources, such as ethanol, propanol, butanol, furan alcohol and aromatic alcohol, is difficult to realize. In addition, the existing system needs additional equivalent organic strong base KOtBu, the reaction condition is harsh, the requirement on production equipment is high, and the separation and purification of the product are complex and difficult. The development of biomass-derived primary alcohol for preparing pyrrole compounds is a green sustainable process, and has great research value and industrial value.
Disclosure of Invention
The invention provides a method for green sustainable preparation of pyrrole compounds, and the route is shown as formula I. The pyrrole compound is prepared by utilizing biomass derived alcohol and 2-amino alcohol molecules through dehydrogenation and cross condensation with high selectivity, and the yield of the pyrrole compound can reach 99 percent to the maximum. The alcohol molecules comprise ethanol, propanol, isopropanol, butanol and higher fatty alcohol, and the amino alcohol comprises 2-aminoethanol and substituted 2-amino alcohol.
The technical scheme of the invention is as follows:
the catalytic reaction is carried out at a certain temperature, pressure and atmosphere, a certain amount of alcohol molecules, 2-amino alcohol molecules and a certain amount of catalyst are added into a certain type of reactor to react for a period of time, after the reaction is finished, the reaction is cooled, a certain amount of products are taken, and the yield of the pyrrole compounds is determined through gas chromatography and nuclear magnetic resonance spectrum analysis.
Further, the R1 and R2 groups in the alcohol molecule can be respectively composed of one or more of H, methyl, ethyl, propyl, phenyl, furyl and the like.
Further, the groups of the 2-aminoalcohol molecules R3 and R4 can be respectively one or more of H, methyl, ethyl, propyl, phenyl, furyl and the like.
Further, the selected reactor is one of a glass tube reactor, a stainless steel reactor with a polytetrafluoroethylene lining and a fixed bed reactor.
Further, the molar ratio of the alcohol molecules to the 2-aminoalcohol molecules (2-100): 1.
Further, the reaction temperature is selected to be 50-250 ℃.
Further, the reaction pressure is selected to be 0.1-2.0MPa.
Further, the reaction atmosphere selected is one of air, nitrogen, argon, and the like.
Further, the reaction time is 0.5-30h.
Furthermore, the adding amount of the catalyst is 1-90% of the mole number of the 2-amino alcohol molecules.
Further, the catalyst is composed of composite oxide supported metal nanoparticles, the metal nanoparticles are composed of one or more of Ni, co and Cu, the composite oxide is composed of one or more of nickel oxide, cobalt oxide, copper oxide, magnesium oxide, aluminum oxide, iron oxide, zinc oxide and zirconium oxide, wherein,
the loading amount of the metal nanoparticles is 5 to 30% based on the mass of the composite oxide.
Further, the preparation method of the catalyst comprises the following steps:
step 1) preparation of composite Metal oxide
Precipitating and calcining more than two of divalent metal, trivalent metal and tetravalent metal to form composite metal oxide;
step 2) reduction of composite metal oxide
And reducing the composite metal oxide to obtain the composite oxide-loaded metal nanoparticles, namely the catalyst.
Further, in the step 1), the divalent metal is one or more of Ni, co, cu, mg and Zn.
Further, in the step 1), the trivalent metal is one or two of Al and Fe.
Further, in the step 1), the tetravalent metal is one or two of Zr and Ga.
Further, in the step 1), the mole ratio of the divalent metal oxide to the trivalent metal oxide or the tetravalent metal oxide is (2-4): 1, wherein when the divalent metal oxide, the trivalent metal oxide and the tetravalent metal oxide are compounded, the molar ratio of the trivalent metal oxide to the tetravalent metal oxide is (5-20): 1.
Further, in step 1), the precursor of the divalent, trivalent metal and tetravalent metal is one or more of nitrate, sulfate, chloride and organic salt containing the divalent or trivalent metal.
Further, in step 1), the pH value of the divalent, trivalent and tetravalent metal precipitates is 8.0-11.
Further, in the step 1), the precipitation time of the metal salt is 0.5-5h.
Further, in step 1), the condition that the metal salt forms a precipitate is that the pH of the precipitate is controlled by adding an inorganic base or an organic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, urea, hexamethylenetetramine, or the like.
Further, in the step 1), the drying temperature of the formed metal precipitate is 60-120 ℃, and the drying time is 2-24h.
Further, in the step 1), the calcination temperature of the metal precipitate is 300-800 ℃, the metal precipitate is kept for 0.01-5h, and then the metal precipitate is cooled to the room temperature.
Further, in step 1), the atmosphere for calcining the metal precipitate is one of air, nitrogen and argon.
Further, in the step 2), the metal nanoparticles are composed of one or more of Ni, co and Cu.
Further, in the step 2), a certain amount of the composite metal oxide is weighed and placed in a tube furnace, and the temperature is raised to 300-800 ℃ in a hydrogen atmosphere and is kept for 0.01-5h, so that the metal nano-particles loaded with the composite oxide are obtained.
Further, in the step 2), the solid powder of the composite metal oxide is flatly laid at the bottom of a porcelain boat, then the porcelain boat is placed in a central constant-temperature area of a quartz tube of a tube furnace, the temperature of the tube furnace is gradually increased at a temperature increasing rate of 1-20 ℃/min, when the temperature of the central constant-temperature area of the quartz tube reaches 300-800 ℃, the temperature is kept for 0.01-5h, and then the temperature is cooled to room temperature, so that the metal nano-particles loaded by the composite metal oxide are obtained.
The invention has the beneficial effects that:
1. the catalyst can realize the high-efficiency synthesis of pyrrole compounds by dehydrogenating and cross-condensing alcohol molecules and 2-amino alcohol molecules for the first time without adding alkali, and develops the reaction of substrate alcohol from only aromatic primary alcohol or secondary alcohol to aliphatic primary alcohol for the first time, thereby providing a more green and sustainable method for preparing pyrrole compounds.
2. In the catalyst, because the metal nanoparticles are loaded on the acid-base bifunctional composite oxide carrier to form a synergistic catalysis effect, in the reaction of catalyzing alcohol molecules and 2-amino alcohol molecules to prepare pyrrole, metal cations on the acid-base bifunctional composite oxide carrier are used as Lewis bases to promote the activation of O-H bonds in alcohol/2-amino alcohol to generate corresponding alkoxy species, then the alkoxy species are adsorbed in the metal nanoparticles and then activated by C alpha-H to generate C = O bonds, and the generated carbonyl compound and amine are subjected to cross condensation on the acid-base bifunctional composite oxide carrier, wherein acid centers on the composite oxide can activate the C = O bonds and alkali centers activate the N-H bonds, so that the condensation and dehydration of the C = O bonds and the alkali centers are promoted to generate imine compounds, and then intramolecular dehydration and cyclization are continuously performed on the composite oxide to generate pyrrole compounds.
3. By using the catalyst of the invention, the yield of the pyrrole compound is 30-99%.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 Ni-loaded catalyst for high-selectivity synthesis of pyrrole from ethanol and 2-aminoethanol
The preparation of the catalyst comprises the steps of weighing 0.02mol, 0.009mol and 0.001mol of each of nickel nitrate, aluminum nitrate and zirconium nitrate, respectively, and fully and completely dissolving the nickel nitrate, the aluminum nitrate and the zirconium nitrate in 150mL of deionized water, then weighing 0.06mol of sodium hydroxide and fully and completely dissolving the sodium hydroxide in 150mL of deionized water, and meanwhile weighing 0.005mol of sodium carbonate and dissolving the sodium carbonate in a four-neck flask filled with 150mL of deionized water. And (3) simultaneously dripping a metal salt solution and a sodium hydroxide solution into the four-neck flask, and after the dripping of the metal salt solution is finished, transferring the four-neck flask into a constant-temperature water bath kettle at 60 ℃ to continue stirring and crystallizing for 24 hours. And (3) carrying out vacuum filtration, washing with deionized water to neutrality, washing with absolute ethyl alcohol once, carrying out vacuum filtration, and drying in an oven. And reducing the prepared precursor in hydrogen to prepare the supported Ni catalyst.
And (3) carrying out catalytic reaction, namely accurately measuring 3.0mL of ethanol, 0.5mmol of 2-aminoethanol and 30mg of catalyst in a 20mL glass reaction tube, then placing the glass tube reactor in an oil bath kettle at 120 ℃, and continuing to react for 24 hours. After the reaction, the reactor was rapidly cooled to room temperature. The liquid product was analyzed by gas chromatography. The conversion rate of the 2-aminoethanol is more than 99 percent, and the yield of the pyrrole is 93.3 percent.
Example 2 high-selectivity synthesis of 3-methylpyrrole from propanol and 2-aminoethanol by using Ni-loaded catalyst
Preparing a catalyst: respectively weighing 0.02mol, 0.009mol and 0.001mol of each of nickel nitrate, aluminum nitrate and zirconium nitrate, fully and completely dissolving in 150mL of deionized water, then weighing 0.06mol of sodium hydroxide, fully and completely dissolving in 150mL of deionized water, and meanwhile weighing 0.005mol of sodium carbonate to dissolve in a four-neck flask filled with 150mL of deionized water. And simultaneously dripping the metal salt solution and the sodium hydroxide solution into the four-neck flask, and after the dripping of the metal salt solution is finished, transferring the four-neck flask into a constant-temperature water bath kettle at the temperature of 60 ℃ to continue stirring and crystallizing for 24 hours. And (3) carrying out vacuum filtration, washing with deionized water to neutrality, washing with absolute ethyl alcohol once, carrying out vacuum filtration, and drying in an oven. And reducing the prepared precursor in hydrogen to prepare the supported Ni catalyst.
And (3) catalytic reaction: 3.0mL of propanol, 0.5mmol of 2-aminoethanol and 30mg of catalyst are accurately weighed in a 20mL glass reaction tube, and then the glass tube reactor is placed in an oil bath kettle at 120 ℃ to continue the reaction for 24h. After the reaction, the reactor was rapidly cooled to room temperature. The liquid product was analyzed by gas chromatography. The conversion rate of the 2-aminoethanol is more than 99 percent, and the yield of the 3-methylpyrrole is 89.2 percent.
Example 3 high-selectivity synthesis of 3-ethylpyrrole from butanol and 2-aminoethanol under catalysis of Ni-loaded catalyst
Preparing a catalyst: respectively weighing 0.02mol, 0.009mol and 0.001mol of each of nickel nitrate, aluminum nitrate and zirconium nitrate, fully and completely dissolving in 150mL of deionized water, then weighing 0.06mol of sodium hydroxide, fully and completely dissolving in 150mL of deionized water, and meanwhile weighing 0.005mol of sodium carbonate to dissolve in a four-neck flask filled with 150mL of deionized water. And simultaneously dripping the metal salt solution and the sodium hydroxide solution into the four-neck flask, and after the dripping of the metal salt solution is finished, transferring the four-neck flask into a constant-temperature water bath kettle at the temperature of 60 ℃ to continue stirring and crystallizing for 24 hours. And (3) carrying out vacuum filtration, washing with deionized water to neutrality, washing with absolute ethyl alcohol once, carrying out vacuum filtration, and drying in an oven. And reducing the prepared precursor in hydrogen to prepare the supported Ni catalyst.
And (3) catalytic reaction: accurately measuring 3.0mL of butanol, 0.5mmol of 2-aminoethanol and 30mg of catalyst in a 20mL glass reaction tube, then placing the glass tube reactor in an oil bath kettle at 120 ℃, and continuing to react for 24 hours. After the reaction, the reactor was rapidly cooled to room temperature. The liquid product was analyzed by gas chromatography. The conversion rate of the 2-aminoethanol is more than 99 percent, and the yield of the 3-ethylpyrrole is 98.9 percent.
Example 4 high-selectivity synthesis of 2-methylpyrrole from isopropanol and 2-aminoethanol by using Ni-loaded catalyst
Preparing a catalyst: respectively weighing 0.02mol, 0.009mol and 0.001mol of each of nickel nitrate, aluminum nitrate and zirconium nitrate, fully and completely dissolving in 150mL of deionized water, then weighing 0.06mol of sodium hydroxide, fully and completely dissolving in 150mL of deionized water, and meanwhile weighing 0.005mol of sodium carbonate to dissolve in a four-neck flask filled with 150mL of deionized water. And simultaneously dripping the metal salt solution and the sodium hydroxide solution into the four-neck flask, and after the dripping of the metal salt solution is finished, transferring the four-neck flask into a constant-temperature water bath kettle at the temperature of 60 ℃ to continue stirring and crystallizing for 24 hours. And (4) carrying out vacuum filtration, washing with deionized water to be neutral, washing with absolute ethyl alcohol once, carrying out vacuum filtration, and drying in an oven. And reducing the prepared precursor in hydrogen to prepare the supported Ni catalyst.
And (3) catalytic reaction: accurately measuring 3.0mL of isopropanol, 0.5mmol of 2-aminoethanol and 30mg of catalyst in a 20mL glass reaction tube, then placing the glass tube reactor in an oil bath kettle at 120 ℃, and continuing to react for 24 hours. After the reaction, the reactor was rapidly cooled to room temperature. The liquid product was analyzed by gas chromatography. The yield of 2-methylpyrrole was 99%.
Example 5 Co-loaded catalyst for high-selectivity synthesis of pyrrole from ethanol and 2-aminoethanol
Preparing a catalyst: respectively weighing 0.02mol and 0.01mol of each of cobalt nitrate and aluminum nitrate, fully and completely dissolving the cobalt nitrate and the aluminum nitrate in 150mL of deionized water, then weighing 0.06mol of sodium hydroxide, fully and completely dissolving the sodium hydroxide in 150mL of deionized water, and meanwhile weighing 0.005mol of sodium carbonate to dissolve in a four-neck flask filled with 150mL of deionized water. And simultaneously dripping the metal salt solution and the sodium hydroxide solution into the four-neck flask, and after the dripping of the metal salt solution is finished, transferring the four-neck flask into a constant-temperature water bath kettle at the temperature of 60 ℃ to continue stirring and crystallizing for 24 hours. And (3) carrying out vacuum filtration, washing with deionized water to neutrality, washing with absolute ethyl alcohol once, carrying out vacuum filtration, and drying in an oven. And reducing the prepared precursor in hydrogen to prepare the supported Co catalyst.
And (3) catalytic reaction: accurately measuring 3.0mL of ethanol, 0.5mmol of 2-aminoethanol and 30mg of catalyst in a 20mL glass reaction tube, then placing the glass tube reactor in an oil bath kettle at 120 ℃, and continuing to react for 24 hours. After the reaction, the reactor was rapidly cooled to room temperature. The liquid product was analyzed by gas chromatography. The conversion rate of the 2-aminoethanol is more than 99 percent, and the yield of the pyrrole is 44.2 percent.
Example 6 Cu-loaded catalyst for catalyzing ethanol and 2-aminoethanol to synthesize pyrrole at high selectivity
Preparing a catalyst: copper nitrate, zinc nitrate and aluminum nitrate, 0.005mol, 0.02mol and 0.01mol, respectively, were weighed and fully dissolved in 150mL of deionized water, then sodium hydroxide, 0.06mol, was weighed and fully dissolved in 150mL of deionized water, and at the same time, 0.005mol of sodium carbonate was weighed and dissolved in a four-necked flask with 150mL of deionized water. And simultaneously dripping the metal salt solution and the sodium hydroxide solution into the four-neck flask, and after the dripping of the metal salt solution is finished, transferring the four-neck flask into a constant-temperature water bath kettle at the temperature of 60 ℃ to continue stirring and crystallizing for 24 hours. And (3) carrying out vacuum filtration, washing with deionized water to neutrality, washing with absolute ethyl alcohol once, carrying out vacuum filtration, and drying in an oven. And reducing the prepared precursor in hydrogen to prepare the supported Cu catalyst.
And (3) catalytic reaction: accurately measuring 3.0mL of ethanol, 0.5mmol of 2-aminoethanol and 30mg of catalyst in a 20mL glass reaction tube, then placing the glass tube reactor in an oil bath kettle at 120 ℃, and continuing to react for 24 hours. After the reaction, the reactor was rapidly cooled to room temperature. The liquid product was analyzed by gas chromatography. The conversion rate of the 2-aminoethanol is more than 99 percent, and the yield of the pyrrole is 30 percent.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, but any modifications or equivalent variations made according to the technical spirit of the present invention are within the scope of the present invention as claimed.
Claims (13)
1. The method for continuously preparing the pyrrole compound is characterized in that raw materials consist of abundant and easily-obtained alcohol molecules and 2-amino alcohol molecules.
2. The method for preparing pyrrole compounds according to claim 1, wherein the R1 and R2 groups in the alcohol molecule are independently one or more of H, methyl, ethyl, propyl, phenyl, furyl, etc.
3. The method for preparing pyrrole compounds according to claim 1, wherein the groups R1 and R2 of the 2-aminoalcohol molecules are independently one or more selected from H, methyl, ethyl, propyl, phenyl, furyl, etc.
4. The method for preparing pyrrole compounds according to claim 1, wherein the alcohol molecule is both a reactant and a reaction solvent, the molar ratio of the alcohol molecule to the 2-aminoalcohol molecule is (2-100): 1, the catalyst is added in an amount of 1-90% of the molar amount of the 2-aminoalcohol molecule added, the reaction temperature is 50-250 ℃, and the reaction time is 0.5-30h.
5. The process for preparing azoles according to claim 1, wherein the reaction temperature is 50-250 ℃.
6. The process for preparing azoles according to claim 1, wherein the reaction time is 0.5 to 30 hours.
7. The method for preparing the pyrrole compounds according to claim 1, wherein the reactor is one of a glass tube reactor, a stainless steel reactor with a polytetrafluoroethylene lining and a fixed bed reactor.
8. The process for preparing azoles of claim 1, wherein the reaction atmosphere is one of air, nitrogen, argon, etc., and the pressure is 0.1 to 2.0MPa.
9. The method for preparing pyrrole compound according to claim 4, wherein the catalyst is composed of composite oxide supported metal nanoparticles.
10. The method for preparing pyrrole compound according to claim 9, wherein the composite oxide comprises two or three of nickel oxide, cobalt oxide, magnesium oxide, aluminum oxide, zinc oxide, and zirconium oxide.
11. The method of claim 10, wherein the metal nanoparticles are substantially composed of one or more of Ni, co, and Cu.
12. The method for preparing azole compounds according to claim 11, wherein said complex oxide is composed of a divalent metal oxide and a trivalent or tetravalent metal oxide.
13. The method for preparing pyrrole compounds according to claim 12, wherein the molar ratio of the divalent metal oxide to the trivalent or tetravalent metal oxide is (2-4): 1; wherein when the divalent metal oxide, the trivalent metal oxide and the tetravalent metal oxide are compounded, the molar ratio of the trivalent metal oxide to the tetravalent metal oxide is (5-20): 1.
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