CN108299347B - Method for preparing furan by converting furfural and 5-hydroxymethylfurfural in one pot - Google Patents
Method for preparing furan by converting furfural and 5-hydroxymethylfurfural in one pot Download PDFInfo
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- CN108299347B CN108299347B CN201810173140.7A CN201810173140A CN108299347B CN 108299347 B CN108299347 B CN 108299347B CN 201810173140 A CN201810173140 A CN 201810173140A CN 108299347 B CN108299347 B CN 108299347B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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Abstract
A method for preparing furan by converting furfural and 5-hydroxymethylfurfural in one pot is characterized by comprising the following steps: sequentially adding furfural, 5-hydroxymethylfurfural, a catalyst and a solvent into a reactor with a condensing device, stirring at a reaction temperature of 80-250 ℃ in an inert atmosphere, reacting for 0.5-30 h, and cooling in an ice water bath. According to the invention, two substrates of furfural and 5-hydroxymethylfurfural are converted in one pot to prepare furan, so that the operation flow is simplified, the material loss caused by intermediate steps is avoided, and the maximum utilization of resources is realized; under proper process conditions, the reaction time is greatly shortened, the production cost is reduced, and the production efficiency is improved; the method is carried out under the mild condition of normal pressure, has low requirements on production equipment and accords with the principle of safe production; the method is suitable for preparing furan by one-pot conversion of a furfural and 5-hydroxymethylfurfural mixture generated by acid catalysis of lignocelluloses pretreated lignocellulose, and is favorable for producing tetrahydrofuran from biomass resources.
Description
Technical Field
The invention belongs to the field of compound synthesis methods.
Background
The conversion of biomass into valuable chemicals is of great significance for sustainable survival and development. Lignocellulose is the most abundant biomass resource on earth and mainly consists of three parts, namely cellulose (accounting for 30-50% of dry matter weight), hemicellulose (accounting for 20-40% of dry matter weight) and lignin (accounting for 15-25% of dry matter weight). Furfural and 5-hydroxymethylfurfural are very attractive biomass-based platform compounds derived from hydrolysates of hemicellulose and cellulose, respectively.
Furan is the simplest oxygen-containing five-membered heterocyclic compound, wherein the furan ring has aromatic ring property, electrophilic substitution reactions such as halogenation, nitration and sulfonation can occur, and the furan can be directly used as a solvent and can also be used for organic synthesis, such as pyrrole, thiophene, tetrahydrofuran and the like. Tetrahydrofuran is an important organic synthetic raw material and is a solvent with excellent performance, is particularly suitable for dissolving polyvinyl chloride, polyvinylidene chloride and butylaniline, and is widely used as a solvent for surface coatings, anticorrosive coatings, printing inks and film coatings and also used as a reaction solvent. The decarbonylation of furfural, which is obtained by the dehydrocyclization of five-carbon sugars, to prepare furan followed by further catalytic hydrogenation is considered as a promising effective alternative to the industrial production of tetrahydrofuran from fossil fuels, and researchers have conducted a great deal of research work (Jung, k.j., Gaset, a.,1988.Biomass 16, 63-76; Zhang w., Zhu y., Niu s., et al.,2011. j.mol.cat.a 335, 71-81; Ishida t., Kume k., Kinjo k., et al.,2016.ChemSusChem 9, 1-8; dik., Shi x., Alotaibi r., et al.,2017.j.org.chem.82, 4924-4929). However, research on preparation of furan from 5-hydroxymethylfurfural synthesized from hexose is only reported, and the development of a simple method for preparing furan by converting furfural and 5-hydroxymethylfurfural simultaneously is the most important link for converting lignocellulose into furan to the maximum extent.
Disclosure of Invention
In order to break the limitation that the industry mainly uses increasingly deficient fossil fuels to produce tetrahydrofuran at the present stage and search a new path for preparing tetrahydrofuran by taking lignocellulose with rich resources as a raw material, the invention provides a method for preparing furan by simultaneously converting furfural and 5-hydroxymethylfurfural by adopting a simple pot method under mild normal pressure conditions:
the method has the advantages of simplicity, high efficiency, low industrialization cost and easy industrialization. So far, the research of simultaneously catalyzing and converting furfural and 5-hydroxymethyl furfural in one pot to obtain furan as a main product is not reported in domestic and foreign documents, and the research has important significance.
The purpose of the invention is realized by the following technical scheme.
The invention relates to a method for preparing furan by converting furfural and 5-hydroxymethylfurfural in one pot, which comprises the following steps: sequentially adding furfural, 5-hydroxymethylfurfural, a catalyst and a solvent into a reactor with a condensing device, stirring at a reaction temperature of 80-250 ℃ in an inert atmosphere, reacting for 0.5-30 h, and cooling in an ice water bath.
The catalyst may be a common noble metal homogeneous catalyst, such as bis (cyclooctene) iridium chloride dimer ([ Ir (coe))2Cl]2) 1, 5-cyclooctadiene iridium chloride dimer ([ Ir (cod) Cl)]2) Ruthenium (Ru (cod) Cl) chloride (1, 5-cyclooctadiene)2) Or dodecacarbonyltriruthenium (Ru)3(CO)12) Etc. are one kind orAnd a plurality of heterogeneous catalysts, such as one or more supported catalysts of Ru, Rh, Pd, Pt, Ir, Fe, Ni, etc.
The dosage of the catalyst (measured by active components) is 0.01-10 mol% of reaction substrates of furfural and 5-hydroxymethyl furfural.
In the reaction, the ratio of the amounts of the reaction substrates furfural and 5-hydroxymethylfurfural is any ratio.
Further, the present invention may also include simultaneously adding a ligand including, but not limited to, (S) -1,1' -binaphthyl-2, 2' -diphenylphosphine (S-BINAP), R- (+) -1,1' -binaphthyl-2, 2' -diphenylphosphine (rac-BINAP), 2' -bis (diphenylphosphino) Biphenyl (BIPHEP), or tris (o-methylphenyl) phosphorus (P (o-tolyl)3) And the like.
The dosage of the ligand (measured by active components) is 0.1-25 mol% of reaction substrates of furfural and 5-hydroxymethyl furfural.
Such solvents include, but are not limited to, toluene, p-xylene, m-trimethylbenzene, p-cymene, or diethylene glycol diethyl ether, and the like.
The dosage of the solvent is 20-100 times of the mass of the reaction substrate.
The invention can replace a condensing device with a rectifying device in the actual production process, distill out the target product furan, and collect non-condensable synthesis gas (hydrogen and carbon monoxide) for other use.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, two substrates of furfural and 5-hydroxymethylfurfural are converted in one pot to prepare furan, so that the operation process is simplified, the material loss caused by intermediate steps is avoided, and the maximum utilization of resources is realized.
(2) The invention converts furfural and 5-hydroxymethyl furfural into furan in one pot, greatly shortens the reaction time, reduces the production cost and improves the production efficiency under proper process conditions.
(3) The invention can prepare furan by converting furfural and 5-hydroxymethyl furfural in one pot under normal pressure and mild conditions, has low requirement on production equipment and conforms to the principle of safe production.
(4) The method is suitable for preparing furan by one-pot conversion of a furfural and 5-hydroxymethyl furfural mixture generated by acid catalysis of lignocelluloses pretreated lignocellulose, and is favorable for producing tetrahydrofuran from biomass resources.
Detailed Description
The present invention will be described in further detail with reference to examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available by purchase.
Example 1.
20.2mg of [ Ir (cod) Cl were added successively to a round-bottomed flask equipped with a low-temperature (5 ℃ C.) reflux condenser]237.4mg of s-BINAP, 0.1261g of 5-hydroxymethylfurfural and 5ml of m-trimethylbenzene, the air in the reactor was replaced with nitrogen, and the round-bottomed flask was placed in an electric heating mantle at 164 ℃ under normal pressure, and reacted for 20 hours with stirring under reflux. After the reaction, gas chromatography analysis is carried out, and the calculation by an area normalization method shows that the 5-hydroxymethylfurfural is completely converted, and the percentage content of the target product furan is 52.74% (as shown in table 1).
The following formula is a route to furan by the one-pot conversion of 5-hydroxymethylfurfural as in example 1.
Example 2.
20.2mg of [ Ir (cod) Cl were added successively to a round-bottomed flask equipped with a low-temperature (5 ℃ C.) reflux condenser]237.4mg of s-BINAP, 83ul of furfural and 5ml of m-trimethylbenzene, the air in the reactor was replaced by nitrogen, and the round-bottom flask was placed in an electric heating mantle at 164 ℃ under normal pressure, and the reaction was stirred under reflux for 20 hours. Performing gas chromatography analysis after reaction, and calculating by area normalization to obtain branThe aldehyde was completely converted and the target furan content was 95.84% (table 1).
Example 3.
20.2mg of [ Ir (cod) Cl were added successively to a round-bottomed flask equipped with a low-temperature (5 ℃ C.) reflux condenser]237.4mg s-BINAP, 0.063g 5-hydroxymethyl furfural, 41ul furfural and 5ml m-trimethylbenzene, and replacing the air in the reactor with nitrogen, placing the round bottom flask in an electric heating jacket at 164 ℃ under normal pressure, and carrying out reflux stirring reaction for 20 hours. After the reaction, gas chromatography analysis is carried out, and the area normalization method is used for calculating that the furfural and the 5-hydroxymethyl furfural are completely converted, and the percentage content of the target product furan is 68.19% (shown in table 1).
TABLE 1 percent product content for one-pot conversion of furfural, 5-hydroxymethylfurfural
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A method for preparing furan by converting furfural and 5-hydroxymethylfurfural in one pot is characterized by comprising the following steps: sequentially adding furfural, 5-hydroxymethylfurfural, a catalyst and a solvent into a reactor with a condensing device, stirring at a reaction temperature of 80-250 ℃ in an inert atmosphere, reacting for 0.5-30 h, and cooling in an ice water bath;
the catalyst is 1, 5-cyclooctadiene iridium chloride dimer;
the solvent is toluene, p-xylene, m-trimethylbenzene, p-cymene or diethylene glycol diethyl ether;
the ligand (S) -1,1 '-binaphthyl-2, 2' -diphenylphosphine is added into the reactor at the same time.
2. The method for preparing furan by converting furfural or 5-hydroxymethylfurfural in one pot according to claim 1, wherein the amount of the catalyst is 0.01-10 mol% of the reaction substrates furfural or 5-hydroxymethylfurfural based on the active components.
3. The method for preparing furan by converting furfural or 5-hydroxymethylfurfural in one pot according to claim 1, wherein the amount of the ligand is 0.1-25 mol% of the reaction substrates furfural or 5-hydroxymethylfurfural based on the active components.
4. The method for preparing furan by converting furfural or 5-hydroxymethylfurfural in one pot according to claim 1, wherein the amount of the solvent is 20-100 times of the mass of a reaction substrate.
5. The method for preparing furan by converting furfural and 5-hydroxymethylfurfural in one pot according to claim 1, wherein a rectifying device is used for replacing a condensing device.
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| JP2015140311A (en) * | 2014-01-28 | 2015-08-03 | 国立大学法人九州大学 | Method for producing furan compound |
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| JP2015140311A (en) * | 2014-01-28 | 2015-08-03 | 国立大学法人九州大学 | Method for producing furan compound |
Non-Patent Citations (2)
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| Selective Metal-Catalyzed Transfer of H2 and CO from Polyols to Alkenes;J. Johan Verendel et al.;《ChemSusChem》;20130109;第6卷;第426-429页 * |
| The role of water on the selective decarbonylation of 5-hydroxymethylfurfural over Pd/Al2O3 catalyst: Experimental and DFT studies;Qingwei Meng et al.;《Applied Catalysis B: Environmental》;20170426;第212卷;第15-22页 * |
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