CN104402846A - Method for preparing 2,5-diformyfuran (DFF) through carbohydrate synthesis - Google Patents
Method for preparing 2,5-diformyfuran (DFF) through carbohydrate synthesis Download PDFInfo
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- CN104402846A CN104402846A CN201410682611.9A CN201410682611A CN104402846A CN 104402846 A CN104402846 A CN 104402846A CN 201410682611 A CN201410682611 A CN 201410682611A CN 104402846 A CN104402846 A CN 104402846A
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- C—CHEMISTRY; METALLURGY
- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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Abstract
The invention discloses a method for preparing 2,5-diformyfuran (DFF) through carbohydrate synthesis. Carbohydrate serves as a raw material, acid ionic liquid serves as a solvent, molybdenum-vanadium-phosphorus heteropoly acid of a Keggin structure serves as a catalyst, air serves as an oxidizing agent, and all the components have a reaction at atmospheric pressure to prepare DFF. The reaction condition of the method is mild, only a few operation steps are needed, the energy consumption is low, the catalyst is safe, free of poison, easy to prepare and high in activity and the method has good industrial application prospects.
Description
Technical field
The present invention relates to a kind of method of being synthesized DFF by carbohydrate.
Background technology
DFF (DFF) is a kind of important furan derivative, is the organic synthesis intermediate served many purposes.It can be used as to produce the monomer of polymkeric substance, also can be used for synthetic drugs, pharmaceutical intermediate, anti-mycotic agent, macrocyclic ligand etc. as raw material.At present, the method for the production DFF of industrial unique feasible adopts 5 hydroxymethyl furfural (HMF) to be raw material, obtains via selective oxidation reaction.Because HMF is a kind of instability and the compound that obtains of more difficult separation, make its output very low, expensive, only commercially circulate in grams, thus make to adopt conventional oxidizing HMF to prepare the route high cost of DFF, at present still unrealized suitability for industrialized production.
Biomass are a kind of renewable resourcess, can in order to substitute day by day exhausted fossil resource.Carbohydrate is the main component of biomass.Direct is raw material with carbohydrate, by the synthesis HMF intermediate that first dewaters, need not isolate the situation of HMF, make HMF situ selective oxidative synthesis DFF, just can realize directly preparing chemical products with high added-value by biomass resource.This is for economizing on resources, reducing energy consumption and develop further reproducible biomass resource and have great importance.
Synthesize DFF in prior art, process is comparatively complicated, troublesome poeration, and energy consumption is higher.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of being synthesized DFF by carbohydrate of easy, less energy-consumption, and to overcome, step length in prior art, complicated operation, energy consumption are high, high in cost of production shortcoming.
Technical problem to be solved by this invention is achieved by the following technical programs:
One catalyzes and synthesizes 2 by carbohydrate, the method of 5-furans dicarbaldehyde, it is characterized in that with glucose, fructose or sucrose for raw material, acidic ion liquid is solvent, and the molybdenum vanadium phospha polyacid of structure with Keggin is catalyzer, and air is oxygenant, reaction obtained 2 at ambient pressure, 5-furans dicarbaldehyde, wherein carbohydrate concentration is 30.0-45.0g/L, and the molecular formula of molybdenum vanadium phospha polyacid is H
4pMo
11vO
4012H
2o, H
5pMo
10v
2o
4014H
2o or H
6pMo
9v
3o
4012H
2o, catalyst levels is 1.0-10.0g/L, and temperature of reaction is 80-120 DEG C, and the reaction times is 0.5-2 hour.
Described acidic ion liquid is 1-(3-sulfonic acid)-propyl group-3-ethyl imidazol(e) hydrochloride-[HO
3s-(CH
2)
3-min] Cl, 1-(3-sulfonic acid)-propyl group-3-ethyl imidazol(e) phosphoric acid salt-[HO
3s-(CH
2)
3-min] H
2pO
4, 1-(3-sulfonic acid)-propyl group-3-ethyl imidazol(e) vitriol-[HO
3s-(CH
2)
3-min] HSO
4, 1-(3-sulfonic acid)-propyl group-3-ethyl imidazol(e) benzene sulfonate-[HO
3s-(CH
2)
3-min] TsA, 1-butyl-3-methylimidazolium chloride-[C
4min] Cl.
The general preparation method of described acidic ion liquid is as follows: in the 100mL there-necked flask that stirring, thermometer, prolong are housed, add 1,3-propane sultone, then appropriate deionized water dissolving is added, to be dissolved completely after, slow dropping is sour accordingly, and the temperature remains within the normal range reacts 30min, is then slowly warming up to 90 DEG C, last decompression dehydration, to obtain final product.
The preferred 35g/L of described carbohydrate concentration.
The preferred H of molecular formula of described molybdenum vanadium phospha polyacid
4pMo
11vO
4012H
2o.
The preferred 2.5-5.0g/L of described catalyst levels.
The preferred 110-120C of described temperature of reaction.
Preferably 1 hour described reaction times.
The present invention has following beneficial effect: synthesis technique step is one pot of one step only, operational safety, without equipment corrosion, has good industrial applications prospect.2. molybdenum vanadium phospha polyacid has acidity and oxidisability concurrently, and high to goal response activity, by product is few; 3. molybdenum vanadium phospha polyacid is heterogeneous catalyst, is easy to preparation, stable in properties, nontoxic, is easy to be separated; 4. reaction adopts acidic ion liquid as solvent, and product yield is high, and selectivity is good, and aftertreatment is simple, carries out under mild conditions, normal pressure, less energy-consumption.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, is not limitation of the invention.
Embodiment 1
Rotor, 45.0mg fructose, 1mL 1-(3-sulfonic acid)-propyl group-3-ethyl imidazol(e) hydrochloride-[HO is added successively in a single necked round bottom flask
3s-(CH
2)
3-min] Cl and 20.0mg PMo
11v
1catalyzer, connects prolong.Oil bath pan temperature is risen to 120 DEG C, is put into by flask after homo(io)thermism, in air atmosphere, stirring and refluxing reacts 1 hour.After reaction stops, reaction system is naturally cooled to room temperature, and centrifugation goes out catalyst fines, and solution carries out GC and HPLC and analyzes, and DFF yield is 45%.
Embodiment 2
Rotor, 45.0mg fructose, 1mL1-(3-sulfonic acid)-propyl group-3-ethyl imidazol(e) benzene sulfonate-[HO is added successively in a single necked round bottom flask
3s-(CH
2)
3-min] TsA and 20.0mg PMo
11v
1catalyzer, connects prolong.Oil bath pan temperature is risen to 110 DEG C, is put into by flask after homo(io)thermism, in air atmosphere, stirring and refluxing reacts 1 hour.After reaction stops, reaction system is naturally cooled to room temperature, and centrifugation goes out catalyst fines, and solution carries out GC and HPLC and analyzes, and DFF yield is 42%.
The above embodiment only have expressed embodiments of the present invention; it describes comparatively concrete and detailed; but therefore can not be interpreted as the restriction to the scope of the claims of the present invention; in every case the technical scheme adopting the form of equivalent replacement or equivalent transformation to obtain, all should drop within protection scope of the present invention.
Claims (7)
1. one kind is synthesized 2 by carbohydrate, the method of 5-furans dicarbaldehyde, it is characterized in that, with glucose, fructose or sucrose for raw material, acidic ion liquid is solvent, the molybdenum vanadium phospha polyacid of structure with Keggin is catalyzer, air is oxygenant, at ambient pressure the obtained DFF of reaction, wherein carbohydrate concentration is 30.0-45.0g/L, and the molecular formula of molybdenum vanadium phospha polyacid is H
4pMo
11vO
4012H
2o, H
5pMo
10v
2o
4014H
2o or H
6pMo
9v
3o
4012H
2o, catalyst levels is 1.0-10.0g/L, and temperature of reaction is 80-120 DEG C, and the reaction times is 0.5-2 hour.
2. method of being synthesized DFF by carbohydrate according to claim 1, it is characterized in that, described acidic ion liquid is 1-(3-sulfonic acid)-propyl group-3-ethyl imidazol(e) hydrochloride-[HO
3s-(CH
2)
3-min] Cl, 1-(3-sulfonic acid)-propyl group-3-ethyl imidazol(e) phosphoric acid salt-[HO
3s-(CH
2)
3-min] H
2pO
4, 1-(3-sulfonic acid)-propyl group-3-ethyl imidazol(e) vitriol-[HO
3s-(CH
2)
3-min] HSO
4, 1-(3-sulfonic acid)-propyl group-3-ethyl imidazol(e) benzene sulfonate-[HO
3s-(CH
2)
3-min] TsA, 1-butyl-3-methylimidazolium chloride-[C
4min] Cl.
3., according to the arbitrary described method of being synthesized DFF by carbohydrate of claim 1 or 2, it is characterized in that, carbohydrate concentration is 35g/L.
4., according to the arbitrary described method of being synthesized DFF by carbohydrate of claim 1 or 2, it is characterized in that, the molecular formula of molybdenum vanadium phospha polyacid is H
4pMo
11vO
4012H
2o.
5., according to the arbitrary described method of being synthesized DFF by carbohydrate of claim 1 or 2, it is characterized in that catalyst levels is 2.5-5.0g/L.
6., according to the arbitrary described method of being synthesized DFF by carbohydrate of claim 1 or 2, its feature is 110-120C in temperature of reaction.
7., according to the arbitrary described method of being synthesized DFF by carbohydrate of claim 1 or 2, it is characterized in that the reaction times is 1 hour.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106732803A (en) * | 2016-10-17 | 2017-05-31 | 南京工业大学 | Composite catalyst, preparation method and application thereof |
CN109867641A (en) * | 2019-02-27 | 2019-06-11 | 天津大学 | Utilize the method for Ce-Mo composite oxide catalytic fructose preparation 2,5-furandaldehyde |
Citations (3)
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CN102850302A (en) * | 2012-10-08 | 2013-01-02 | 天津工业大学 | Method for preparing 5-hydroxymethyl furfural |
CN103113327A (en) * | 2013-01-24 | 2013-05-22 | 四川大学 | Method for synthesizing furan-2,5-dicarbaldehyde through one-step catalysis of carbohydrate |
WO2014121513A1 (en) * | 2013-02-08 | 2014-08-14 | Rhodia Operations | Oxydation of alcohol compounds via mesostructured vpo catalysts |
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2014
- 2014-11-24 CN CN201410682611.9A patent/CN104402846A/en active Pending
Patent Citations (3)
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CN102850302A (en) * | 2012-10-08 | 2013-01-02 | 天津工业大学 | Method for preparing 5-hydroxymethyl furfural |
CN103113327A (en) * | 2013-01-24 | 2013-05-22 | 四川大学 | Method for synthesizing furan-2,5-dicarbaldehyde through one-step catalysis of carbohydrate |
WO2014121513A1 (en) * | 2013-02-08 | 2014-08-14 | Rhodia Operations | Oxydation of alcohol compounds via mesostructured vpo catalysts |
Non-Patent Citations (7)
Title |
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ATSUSHI TAKAGAKI ET AL.: "One-Pot Synthesis of 2,5-Diformylfuran from Carbohydrate Derivatives by Sulfonated Resin and Hydrotalcite-Supported Ruthenium Catalysts", 《ACS CATAL.》 * |
GARY A. HALLIDAY ET AL.: "One-Pot, Two-Step, Practical Catalytic Synthesis of 2,5-Diformylfuran from Fructose", 《ORGANIC LETTERS》 * |
KUMAR KARITKEY YADAV ET AL.: "Elucidating the role of cobalt phthalocyanine in the dehydration of carbohydrates in ionic liquids", 《JOURNAL OF MOLECULAR CATALYSIS A:CHEMICAL》 * |
QUAN CAO ET AL.: "Conversion of hexose into 5-hydroxymethylfurfural in imidazolium ionic liquids with and without a catalyst", 《CARBOHYDRATE RESEARCH》 * |
XI XIANG ET AL.: "One-Pot Production of 2,5-diformylfuran From Glucose", 《CATAL LETT》 * |
ZHEN-ZHEN YANG ET AL.: "A one-pot approach for conversion of fructose to 2,5-diformylfuran by combination of Fe3O4-SBA-SO3H and K-OMS-2", 《GREEN CHEMISTRY》 * |
欧阳四余: "生物质转化制 5-羟甲基糠醛的酸催化研究新进展", 《化工进展》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106732803A (en) * | 2016-10-17 | 2017-05-31 | 南京工业大学 | Composite catalyst, preparation method and application thereof |
CN109867641A (en) * | 2019-02-27 | 2019-06-11 | 天津大学 | Utilize the method for Ce-Mo composite oxide catalytic fructose preparation 2,5-furandaldehyde |
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Application publication date: 20150311 |