CN113105381A - Preparation method of biomass-based 2, 5-dimethyl-N-substituted pyrrole derivative - Google Patents

Preparation method of biomass-based 2, 5-dimethyl-N-substituted pyrrole derivative Download PDF

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CN113105381A
CN113105381A CN202110379559.XA CN202110379559A CN113105381A CN 113105381 A CN113105381 A CN 113105381A CN 202110379559 A CN202110379559 A CN 202110379559A CN 113105381 A CN113105381 A CN 113105381A
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李虎
杨英
王克平
郭珍燕
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Guizhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
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Abstract

The invention discloses a preparation method of a 2, 5-dimethyl-N-substituted pyrrole derivative, which comprises the following steps: adding 2, 5-dimethylfuran, an amine compound, a catalyst, distilled water and 2mL of a solvent into a reaction kettle, and putting the reaction kettle into an oil bath pot for heating. The 2, 5-dimethyl-N-substituted pyrrole derivative can be obtained after the reaction time is 1-3h at the temperature of 110-170 ℃, the consumption of distilled water is 0-250 mu L and the consumption of a catalyst is 5-10 wt%. The method overcomes the defects of high cost and difficult separation and recovery of the existing catalyst or catalyst system.

Description

Preparation method of biomass-based 2, 5-dimethyl-N-substituted pyrrole derivative
Technical Field
The invention relates to a method for preparing a 2, 5-dimethyl-N-substituted pyrrole derivative by using renewable magnetic carbon-based sulfonic acid as a catalyst and biomass-based 2, 5-dimethylfuran as a raw material through ring opening to generate 2, 5-hexanedione and amine condensation dehydration reaction in sequence.
Background
Due to the increasing problems of resource shortage, environmental badness and the like, industrial production raw materials are gradually shifted from the traditional petrochemical resources to renewable biomass. Nitrogen-containing compounds are important organic compounds and play a significant role in medicine, pesticides, materials and dyes. At present, the synthesis method of the biomass-based nitrogen-containing compound mainly comprises the following 4 methods: (A) directly catalyzing and degrading natural nitrogenous biomass such as protein and chitin; (B) aldehyde/ketone reductive amination; (C) alcohol amination by hydrogen; (D) alkene/alkyne hydroamination reaction. These methods are effective in promoting the formation of C-N bonds, especially supported noble metals and homogeneous organometallic catalysts, which promote the production of higher yields of amides. In contrast, the non-noble metal has a large reserve and is cheap, and has application potential in the aspect of heterogeneous catalytic synthesis of biomass-based nitrogen-containing compounds, but the stability of the corresponding catalyst is poor, and side reactions such as over-alkylation and the like are difficult to avoid. Therefore, the design and preparation of the non-noble metal functional material which is easy to separate and recycle and is green have important research value for catalyzing the biomass raw material to be converted into the nitrogen-containing compound with high efficiency and high selectivity.
The pyrrole derivatives are important five-membered nitrogen heterocyclic compounds, and besides having excellent biological activity, the pyrrole derivatives are also widely applied to the fields of macromolecules, catalysts, dyes, foods and the like. Based on petrochemical products, the pyrrole derivative can be prepared by the reactions of Knorr, pal-Knorr, Barton-Zard, multi-component condensation, cycloaddition and the like. In recent years, domestic and foreign subject groups such as professor yao of science and technology university of china, professor jinguang of shanghai transportation university, George w.huber professor of madison university of wisconsin, professor Ning Yan of singapore national university, professor SanghoKoo of korea university of science and technology university of wisconsin, and the like, have reported that the pyrrole derivatives are synthesized by directly catalyzing biomass raw materials such as chitin, shrimp shells, bagasse and the like, but the obtained yield (20%) is not ideal and the reaction conditions are harsh (300 + 600 ℃). In addition, the biomass platform small molecules (furan, 2, 5-hexanedione and the like) are selected as raw materials in subject groups such as professor Cao Yong of compound denier university, professor Zhang Zeuze of Zhongnan university, professor Johannes G.de Vries of Germany Labrunitz catalysis research institute, and the like, so that high catalytic amination activity can be obtained under mild reaction conditions. Doulei et al, the research institute of science and technology of the university of Compound Dan, selects zeolite solid acid as a catalyst to catalyze the reaction of 2, 5-dimethylfuran and amine compounds. Although the yield of the obtained pyrrole is high, the used catalyst has the defects of high energy consumption, complicated operation process and the like.
Disclosure of Invention
The invention aims to: the method uses renewable biomass-based 2, 5-dimethylfuran and amine compounds as raw materials, and synthesizes the 2, 5-dimethyl-N-substituted pyrrole derivative by heating in an oil bath kettle so as to overcome the defects of higher cost of the existing catalyst or catalyst system, unsustainable reaction process and the like.
In order to achieve the purpose, the invention adopts the technical scheme that: dissolving 2, 5-dimethylfuran and amine compounds in an organic solvent, and reacting at a certain temperature and time to prepare the 2, 5-dimethyl-N-substituted pyrrole derivative. The principle of synthesizing the 2, 5-dimethyl-N-substituted pyrrole derivative is shown in the following figure: the 2, 5-dimethylfuran is subjected to ring opening under the action of heating and a magnetic acid catalyst to generate an intermediate of 2, 5-hexanedione, and then the intermediate and amine substances are subjected to amination, ring closing and dehydration to obtain a final product.
Figure BDA0003012433460000021
Wherein R is substituted phenyl, thiophene or furan; the substituent on the substituted phenyl is bromine, fluorine, nitro, hydroxyl or methoxy.
The preparation of the 2, 5-dimethyl-N-substituted pyrrole derivative is carried out in an oil bath kettle which is equipped with magnetic stirring, the oil bath kettle is opened, the specified reaction temperature is set, the reaction system is rapidly heated to the specified temperature through heat transfer, and the reaction temperature is kept constant by the temperature control of a thermocouple. The preparation process of the 2, 5-dimethyl-N-substituted pyrrole derivative comprises the following steps: putting 2, 5-dimethylfuran, an amine compound, a catalyst, distilled water and 2mL of solvent into a reaction kettle; and putting the assembled reaction kettle into an oil bath pan for heating. The reaction temperature is 110-170 ℃, the reaction time is 1-3h, and the consumption of distilled water is 0-250 mu L. After the reaction, the catalyst was separated from the reaction mixture system by a magnet.
The mass ratio of the 2, 5-dimethylfuran to the amine compound is 1: 1.
The amine compound is p-methoxyaniline, 3-fluoroaniline, 3-methoxyaniline, m-toluidine, o-toluidine, n-butylamine, 3-nitroaniline, 4-nitroaniline, p-trifluoromethylaniline, p-hydroxyphenylamine, n-hexylamine, furfurylamine, 2-thiophenemethylamine or benzylamine.
The organic solvent is absolute methanol, absolute ethanol, propanol, isopropanol, n-butanol, toluene, cyclohexane, dichloroethane or tetrahydrofuran.
Catalyst Fe of the invention3O4@SiO2@CS-SO3The amount of H is 5-20 wt%.
Compared with the prior art, the invention has the advantages that:
(1) the invention takes biomass-based 2, 5-dimethylfuran as a raw material, so that the whole reaction is more environment-friendly and sustainable.
(2) Compared with other similar catalytic systems, the magnetic catalyst used in the invention is cheaper and easy to recover, namely, the catalyst is separated from the reaction mixed system by using a magnet.
Drawings
FIG. 1 shows catalyst Fe3O4@SiO2@CS-SO3NH of H3-a TPD map;
FIG. 2 shows catalyst Fe3O4@SiO2@CS-SO3XRD pattern of H;
FIG. 3 shows catalyst Fe3O4@SiO2@CS-SO3A TGA profile of H;
FIG. 4 shows catalyst Fe3O4@SiO2@CS-SO3FT-IR plot of H;
FIG. 5 shows catalyst Fe3O4@SiO2@CS-SOH3XPS spectrum (A is scanning catalyst Fe)3O4@SiO2@CS-SOH3B is Fe 2p, C is O1 s);
FIG. 6 is a mass spectrum of 2, 5-dimethyl-1-phenylpyrrole.
Detailed Description
The technical solutions of the present invention will be described in further detail with reference to examples, but they are not intended to limit the present invention.
Example 1
One-pot method for catalytic synthesis of 2, 5-dimethyl-1-phenylpyrrole by using magnetic catalyst
1mmol of 2, 5-dimethylfuran, 1mmol of aniline, 14.4mg of catalyst, 200. mu.L of distilled water and 2mL of anhydrous methanol were put into a high-pressure reactor and reacted at 170 ℃ for 3 hours. The conversion of 2, 5-dimethylfuran was determined by GC to be 96.1% and the yield of 2, 5-dimethyl-1-phenylpyrrole was determined to be 79.9%.
Example 2
One-pot method for catalytic synthesis of 2, 5-dimethyl-1-phenylpyrrole by using magnetic catalyst
1mmol2, 5-dimethylfuran, 1mmol aniline, 14.4mg catalyst, 200. mu.L distilled water and 2mL absolute methanol were added to an autoclave and reacted at 150 ℃ for 3 hours. The conversion of 2, 5-dimethylfuran was determined by GC to be 96.1% and the yield of 2, 5-dimethyl-1-phenylpyrrole was determined to be 79.7%
Example 3
One-pot method for catalytic synthesis of 2, 5-dimethyl-1-phenylpyrrole by using magnetic catalyst
1mmol of 2, 5-dimethylfuran, 1mmol of aniline, 14.4mg of catalyst, 200. mu.L of distilled water and 2mL of anhydrous methanol were put into a high-pressure reactor and reacted at 110 ℃ for 3 hours. The conversion of 2, 5-dimethylfuran was 77.6% and the yield of 2, 5-dimethyl-1-phenylpyrrole was 29.2% by GC.
Example 4
One-pot method for catalytic synthesis of 2, 5-dimethyl-1-phenylpyrrole by using magnetic catalyst
1mmol2, 5-dimethylfuran, 1mmol aniline, 14.4mg catalyst, 200. mu.L distilled water and 2mL anhydrous methanol were added to an autoclave and reacted at 170 ℃ for 2.5 h. The conversion of 2, 5-dimethylfuran was determined by GC to be 95.8% and the yield of 2, 5-dimethyl-1-phenylpyrrole to be 83.8%.
Example 5
One-pot method for catalytic synthesis of 2, 5-dimethyl-1-phenylpyrrole by using magnetic catalyst
1mmol of 2, 5-dimethylfuran, 1mmol of aniline, 14.4mg of catalyst, 200. mu.L of distilled water and 2mL of anhydrous methanol were put into a high-pressure reactor and reacted at 110 ℃ for 1 hour. The conversion of 2, 5-dimethylfuran was determined by GC to be 51.2% and the yield of 2, 5-dimethyl-1-phenylpyrrole was 8.8%.
Example 6
One-pot method for catalytic synthesis of 2, 5-dimethyl-1-phenylpyrrole by using magnetic catalyst
1mmol of 2, 5-dimethylfuran, 1mmol of aniline, 14.4mg of catalyst, 200. mu.L of distilled water and 2mL of an organic solvent (methanol, DMF, dichloromethane, absolute ethanol, tetrahydrofuran, cyclohexane, n-propanol or n-butanol) were put into a high-pressure reactor and reacted at 170 ℃ for 2.5 hours. The yields of 2, 5-dimethyl-1-phenylpyrrole determined by GC are shown in table 1.
TABLE 1 yield of 2, 5-dimethyl-1-phenylpyrrole in different solvents
Figure BDA0003012433460000041
Figure BDA0003012433460000051
Example 7
One-pot method for catalytic synthesis of 2, 5-dimethyl-1-phenylpyrrole by using magnetic catalyst
1mmol of 2, 5-dimethylfuran, 1mmol of aniline, 14.4mg of catalyst, distilled water (50-300. mu.L) and 2mL of methanol as solvents were added together to a high-pressure reaction vessel and reacted at 170 ℃ for 2.5 hours. The yields of 2, 5-dimethyl-1-phenylpyrrole determined by GC are shown in table 2.
TABLE 2 yield of 2, 5-dimethyl-1-phenylpyrrole at different water contents
Serial number Water content (μ L) Yield (%)
1 50 66.0
2 100 82.9
3 150 82.1
4 200 88.9
5 250 82.3
6 300 68.6
Example 8
Catalytic synthesis of 2, 5-dimethyl-1- (3-methylphenyl) -pyrrole by oil bath pan
1mmol2, 5-dimethylfuran, 1mmol 3-methylaniline, 14.4mg catalyst, 200. mu.L distilled water and 2mL of anhydrous methanol were added to a high pressure reaction vessel and reacted at 170 ℃ for 2.5 hours. Determination of 2, 5-dimethyl-1- (3-methyl) by GCPhenyl) -pyrrole yield was 82.5%. Mass spectrum data of 2, 5-dimethyl-1- (3-methylphenyl) -pyrrole is M/z 185.7 (M)+)、170.2、154.4、129.2、91.5、65.3、51.7。
Example 9
Catalytic synthesis of 2, 5-dimethyl-1- (2-methylphenyl) -pyrrole by oil bath pan
1mmol2, 5-dimethylfuran, 1mmol 2-methylaniline, 14.4mg catalyst, 200uL distilled water and 2mL of anhydrous methanol were added to a high pressure reaction vessel and reacted at 170 ℃ for 2.5 h. The yield of 2, 5-dimethyl-1- (2-methylphenyl) -pyrrole was 78.3% by GC. Mass spectral data of 2, 5-dimethyl-1- (2-methylphenyl) -pyrrole is M/z 185.7 (M)+)、170.2、154.4、91.5、51.7。
Example 10
Oil bath pan catalyzed synthesis of 2, 5-dimethyl-1- (4-methoxyphenyl) -pyrrole
Adding 1mmol2, 5-dimethylfuran, 1mmol p-anisidine, 14.4mg catalyst, 2mL absolute methanol and 200uL distilled water into a high-pressure reaction kettle, and reacting at 170 ℃ for 2.5h to obtain the product. The yield of 2, 5-dimethyl-1- (3-fluorophenyl) -pyrrole was 46.65% by GC. Mass spectrum data of 2, 5-dimethyl-1- (4-methoxyphenyl) -pyrrole is M/z 201.8 (M)+)、186.7、160.2、144.8、117.6、77.2、62.8、39.1。
Example 11
Oil bath pan catalyzed synthesis of 2, 5-dimethyl-1-butyl-pyrrole
1mmol of 2, 5-dimethylfuran, 1mmol of n-butylamine, 14.4mg of a catalyst, 200uL of distilled water and 2mL of anhydrous methanol were put into a high-pressure reaction vessel and reacted at 170 ℃ for 2.5 hours. The yield of 2, 5-dimethyl-1-butyl-pyrrole was determined by GC to be 2.3%. Mass spectral data of 2, 5-dimethyl-1-butyl-pyrrole is M/z151.6 (M)+)、136.2、108.2、94.2。

Claims (7)

1. A preparation method of biomass-based 2, 5-dimethyl-N-substituted pyrrole derivatives is characterized by comprising the following steps: the method takes renewable biomass-based furan compounds as raw materials and magnetic carbon-based sulfonic acid as a catalyst, and prepares the 2, 5-dimethyl-N-substituted pyrrole derivative through a multi-step reaction path of ring opening, (reduction) amination, ring closing and dehydration.
2. The method for preparing biomass-based 2, 5-dimethyl-N-substituted pyrrole derivative according to claim 1, wherein the method comprises the following steps: the preparation method comprises the following steps:
s1, preheating the oil bath pan, and adjusting to the specified temperature and rotation speed;
s2, weighing amine substances and 2, 5-dimethylfuran into a reaction kettle, adding a solvent and a magnetic carbon-based sulfonic acid catalyst, keeping the temperature to a specified temperature, and putting the reaction kettle into an oil bath kettle for reaction to obtain the 2, 5-dimethyl-N-substituted pyrrole derivative.
3. The method for preparing biomass-based 2, 5-dimethyl-N-substituted pyrrole derivative according to claim 1 or 2, wherein: the preparation method of the magnetic carbon-based sulfonic acid catalyst comprises the following steps:
s1, adding FeCl into the reaction vessel3·6H2O、FeSO4·7H2Rapidly stirring O and deionized water at 25 deg.C until completely dissolved, adjusting pH of the mixed solution to 10, transferring the reaction container into oil bath for reaction, separating with magnet after reaction, and drying the obtained solid to obtain Fe3O4；
S2, adding Fe into the reactor3O4Solids, ethanol, distilled water and NH4OH, stirring uniformly, adding tetraethyl orthosilicate, stirring magnetically at room temperature, separating solid and liquid in a round-bottom flask by using a magnet, washing the obtained solid with distilled water for 2-3 times, then washing with fifty-ethanol for 2-3 times, and finally drying to obtain powdery Fe3O4@SiO2；
S3, dissolving chitosan in acetic acid water solution, and adding Fe3O4@SiO2Stirring, adding p-toluenesulfonic acid, stirring, slowly adding glutaraldehyde, stirring to obtain gel-like solid, drying, grinding into small granules, washing with anhydrous ethanol for 3-4 times, addingMagnetic separation and drying are carried out to obtain the catalyst Fe3O4@SiO2@CS-SO3H。
4. The method for preparing biomass-based 2, 5-dimethyl-N-substituted pyrrole derivative according to claim 1 or 2, wherein: the mass ratio of biomass-based 2, 5-dimethylfuran to amine compounds is 1:1, the reaction temperature is 110-170 ℃, the reaction time is 1-3h, the water content is 50-250 mu L, and the dosage of the magnetic carbon-based sulfonic acid catalyst is 5-20 wt%.
5. The method for preparing biomass-based 2, 5-dimethyl-N-substituted pyrrole derivative according to claim 1, wherein the method comprises the following steps: the biomass furan compound is 2, 5-dimethylfuran, and the amine compound is p-anisidine, 3-fluoroaniline, 3-anisidine, m-toluidine, o-toluidine, n-butylamine, 3-nitroaniline, 4-nitroaniline, p-trifluoromethylaniline, p-hydroxyphenylamine, n-hexylamine, furfurylamine, 2-thiophenemethylamine or benzylamine.
6. The method for preparing biomass-based 2, 5-dimethyl-N-substituted pyrrole derivative according to claim 1, wherein the method comprises the following steps: the 2, 5-dimethyl-N-substituted pyrrole derivative is 2, 5-dimethyl-1- (4-methoxyphenyl) -pyrrole, 2, 5-dimethyl-1- (3-fluorophenyl) -pyrrole, 2, 5-dimethyl-1- (3-methoxyphenyl) -pyrrole, 2, 5-dimethyl-1- (3-methylphenyl) -pyrrole, 2, 5-dimethyl-1- (2-methylphenyl) -pyrrole, 2, 5-dimethyl-1-butyl-pyrrole, 2, 5-dimethyl-1- (3-nitrophenyl) -pyrrole, 2, 5-dimethyl-1- (4-nitrophenyl) -pyrrole, or a salt thereof, 2, 5-dimethyl-1- (4-trifluorophenyl) -pyrrole, 2, 5-dimethyl-1- (4-hydroxyphenyl) -pyrrole, 1-hexyl-2, 5-dimethyl-1-pyrrole, 2, 5-dimethyl-1- (2-methylenefuran) -pyrrole, 2, 5-dimethyl- (2-methylenethiophene) -pyrrole or 1-benzyl-2, 5-dimethyl-1-pyrrole.
7. The method for preparing biomass-based 2, 5-dimethyl-N-substituted pyrrole derivative according to claim 1, wherein the method comprises the following steps: the solvent is absolute methanol, absolute ethanol, propanol, isopropanol, n-butanol, toluene, cyclohexane, dichloromethane or tetrahydrofuran.
CN202110379559.XA 2021-04-08 2021-04-08 Preparation method of biomass-based 2, 5-dimethyl-N-substituted pyrrole derivative Pending CN113105381A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006032959A2 (en) * 2004-08-06 2006-03-30 Glenmark Pharmaceuticals Limited Processes for the preparation of pyrrole derivatives
CN110372563A (en) * 2019-07-23 2019-10-25 大连理工大学 A kind of mild substituted azole sulfonamide deprotection method
CN111574424A (en) * 2020-06-04 2020-08-25 南京林业大学 Method for preparing N-aryl pyrrole compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006032959A2 (en) * 2004-08-06 2006-03-30 Glenmark Pharmaceuticals Limited Processes for the preparation of pyrrole derivatives
CN110372563A (en) * 2019-07-23 2019-10-25 大连理工大学 A kind of mild substituted azole sulfonamide deprotection method
CN111574424A (en) * 2020-06-04 2020-08-25 南京林业大学 Method for preparing N-aryl pyrrole compound

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