CN104098533A - Method for preparing 2,5-dimethyl acyl furan with glucose - Google Patents
Method for preparing 2,5-dimethyl acyl furan with glucose Download PDFInfo
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- CN104098533A CN104098533A CN201410364759.8A CN201410364759A CN104098533A CN 104098533 A CN104098533 A CN 104098533A CN 201410364759 A CN201410364759 A CN 201410364759A CN 104098533 A CN104098533 A CN 104098533A
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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
Abstract
The invention provides a method for preparing 2,5-dimethyl acyl furan with glucose. The method comprises the following steps: dissolving glucose and a metal catalyst into a solvent, stirring the solvent for mixing, and heating the mixture to the reaction temperature to obtain 5-hydroxymethyl furfural; directly adding an oxidation catalyst into the reacted solution, heating the solution to the reaction temperature, carrying out extraction with methylene chloride after the reaction is finished, carrying out separation, distillation and sublimation, and eventually obtaining solid 2,5-dimethyl acyl furan. The method has the advantages that (1) the method is a one-pot method, and separation and purification are not required after the first step, so that the steps are reduced; the catalysts in the first step and the second step are excellent in compatibility and cooperation effect, so that the productivity of DFF is higher; (2) the oxidant in the method is normal-pressure air, and the reaction conditions are simple and not rigorous; the additive LiBr is high in solubility and electrolysis capability, so that more Br anions can be provided as ligands of metal salts to better catalyze isomerization of glucose and dehydration of laevulose.
Description
Technical field
The invention belongs to industrial chemicals preparation field, relate in particular to a kind of environment-friendly preparation method thereof of multi-usage industrial chemicals.
Background technology
Along with the continuous exhaustion of petrochemical material, people improve day by day to the concern of renewable energy technologies.Saccharide compound is based on its recyclability, and cheap price, and the feature such as be easy to get, be regarded as a kind of green renewable raw materials that can substitute petrochemical material.About saccharide compound, to the conversion of liquid fuel and industrial chemicals, also become the hot issue of current research.
2,5-diformyl furans is a kind of multiduty industrial chemicals, can be used as presoma (the Katherine T.Hopkins of pharmacy, W.David Wilson, Brendan C.Bender, Donald R.McCurdy, James Edwin Hall, Richard R.Tidwell, Arvind Kumar, Miro Bajic, and David W.Boykin.Journal of Medicinal Chemistry, 1998,41,3872), sanitas (Del Poeta, M.; Schell, W.A.; Dykstra, C.C.; Jones, S.; Tidwell, R.R.; Czarny, A.; Bajic, M.; Bajic, M.; Kumar, A.; Boykin, D.; Perfect, J.R.Antimicrobial Agents and Chemotherapy, 1998,42,2495), the linking agent of polyvinyl alcohol (Dean W.Sheibley, Michelle A.Manzo, and Olga D.Gonzalez ?Sanabria.Journal of the Electrochemical Society, 1983,130,255), simultaneously at analytical chemistry (Dykstra, C.C.; Tidwell, R.R.; Boykin, D.W.; Wilson, W.D.U.S.Patent 5,667, and 975,1997), electron optics (Daub, J.; Rapp, K.M.; Seitz, P.; Wild, R.; Salbeck, J.U.S.Patent 5,091, and 538,1992), Metal plating aspect (Kuznetsov, V.V.; Grigor ' ev, V.P.; Fadeeva, O.V.; Nazarova, Z.N.IzV.Vyssh.Uchebn.ZaVed., Khim.Khim.Tekhnol.1978,21,1649) be all widely used.The furandicarboxylic acid that 2,5-diformyl furans generates after peroxidation also can be used as the surrogate of terephthalic acid for the production of reproducible class pet material.
Although there are various purposes, the application of 2,5-diformyl furans is still limited by its high preparation cost (～360/100mg).Instantly the most effectively prepare 2, the method for 5-diformyl furans is the selective oxidation by 5 hydroxymethyl furfural.Moreau etc. (C.Moreau, R.Durand, C.Pourcheron and D.Tichit, Stud.Surf.Sci.Catal., 1997,108,399) are with V
2o
5/ TiO
2for carrying out selective oxidation to 5 hydroxymethyl furfural in air, catalyzer obtains 2 of high yield (80%), 5-diformyl furans.(O.C.Navarro, A.Corma and S.Iborra, the Top.Catal. such as Navarro; 2009; 52,304) utilize efficient selective oxidation that the vanadium oxide compound be fixed on Polyvinylpyrolidone (PVP) realized 5 hydroxymethyl furfural for catalyzer in order to prepare 2,5-diformyl furans.(the G.A.Halliday such as Halliday, R.Y.Young and V.V.Grushin, Org.Lett., 2003,5,2003) with methyl-sulphoxide, be solvent, resin solid acid and vanadium oxide compound are catalyzer, successfully by fructose to the conversion of 5 hydroxymethyl furfural and the selective oxidation of 5 hydroxymethyl furfural in conjunction with together, simplified production stage, reduced preparation cost.
Although the fructose of take is prepared 2,5-diformyl furans as raw material and greatly reduced production cost, fructose is appointed so higher price ($540/1kg) limited it in industrial scale operation.Therefore need a kind of more cheap raw material to reduce the preparation cost of 2,5-diformyl furans.
In patent (CN 103739573 A), the people such as Sun Yong be take glucose as reaction substrate by using, and DMF is solvent, and NaBr is promotor, under AlCl36H2O catalyst action, generates 5 hydroxymethyl furfural; Then carry out oxidizing reaction, obtain 2,5-diformyl furans.A kind of method for transformation through Lewis acid-catalyzed dehydration and molecular oxygen auxiliary catalysis oxidation two-step approach reaction in－situ generation DFF is provided; For two-step reaction, adopt differential responses device, glucose catalytic dehydration step is wherein under AlCl36H2O and NaBr effect, in Hastelloy reaction kettle for reaction, generates HMF; Oxidation step needs separation in advance to remove catalyzer and the additive in dehydrating step, carries out the regulation and control of oxygen-supply quantity by different oxygen pneumatic are set, and finally obtains the Biomass-based chemicals DFF of high added value.
Summary of the invention
The technical problem to be solved in the present invention is: overcome in prior art and prepare 2 by glucose; the method of 5-diformyl furans needs separated catalyzer and the additive of removing in dehydrating step not enough; provide a kind of and prepare 2 by glucose; the method of 5-diformyl furans; present method is one kettle way, after formation intermediate product, does not need to remove catalyzer and additive.
For solving the problems of the technologies described above the technical solution used in the present invention, be: a kind of method of preparing 2,5-diformyl furans with glucose, comprises the steps:
(1) glucose and metal catalyst are dissolved in solvent, are uniformly mixed and are heated to temperature of reaction, obtain intermediate product, 5 hydroxymethyl furfural; (2) without separating-purifying, directly in reaction soln, add oxide catalyst, be heated to temperature of reaction, after reaction finishes, with dichloromethane extraction, separated, distillation, distillation, finally obtain the solid of 2,5-diformyl furans; Wherein said glucose molecule formula is C
6h
12o
6.
Further, described metal catalyst is MCl
x, wherein M is any one in Al, Cr, Ge, La or Sn, x is 2-4; Described oxide catalyst is V
2o
5, VOPO
4or VO (PO
3)
2wherein a kind of.
As preferably, described metal catalyst is AlCl
3; Described oxide catalyst is V
2o
5.
As preferably, described reaction solvent is methyl-sulphoxide or has added the lithiumbromide of 10wt% as the methyl-sulphoxide of additive.
Particularly, the mol ratio of described glucose and metal catalyst is 10:1～5; Described glucose and oxide catalyst mol ratio are 10:0.5～2.
As preferably, the mol ratio of described glucose and metal catalyst is 10:3～5; Described glucose and oxide catalyst mol ratio are 10:1.
Further, described temperature of reaction is 100～160 ℃.
As preferably, in step (1), temperature of reaction is 120 ℃; In step (2), temperature of reaction is 150 ℃.
Compared with prior art, the application's advantage comprises the following aspects:
(1) the application is one kettle way, after the first step completes, does not need separating-purifying, has simplified processing step; The catalyzer of the first step and second step reaction has good compatibility and synergy, and DFF productive rate is higher;
(2) in the application, oxygenant is the air under normal pressure, and reaction conditions is simply not harsh;
(3) additive therefor LiBr solvability and electrolyte are good, can provide more bromine negative ion as the part of metal-salt with the isomerization of better catalysis glucose and the dehydration of fructose.
Embodiment
Below by embodiment, further illustrate technical scheme of the present invention.
The interval value that the present invention provides not be the accurate end value of mathematical concept, and test and Selection has association when interval, suitably departs from end value and not cannot.
Below in conjunction with several specific embodiments; the present invention is further understood in exemplary illustration and help; but embodiment detail is only for the present invention is described; do not represent that the present invention conceives lower whole technical scheme; therefore should not be construed as the total technical scheme of the present invention is limited, some do not depart from the unsubstantiality of inventive concept and change In the view of technician; for example, to there is simple the change or replacement of technical characterictic of same or similar technique effect, all belong to protection domain of the present invention.
Embodiment 1
Take 1mmol glucose and 0.1mmol AlCl
3be put in round-bottomed flask, then add wherein 5mL methyl-sulphoxide, at room temperature stir 10 minutes post-heating to 100 ℃, at this temperature, react 3h, be then cooled to room temperature.Add wherein again 0.0.05mmol V
2o
5, the post-heating to 160 ℃ that stirs reacts 5h at this temperature.After reaction finishes, add 20mL water and 30mL methylene dichloride, separation, underpressure distillation is except desolventizing, and purified product distils.The first step after having reacted is purified portioned product, and HMF yield is 75.6% after measured, and final DFF yield (based on glucose) is 40.9%.
Embodiment 2
Take 1mmol glucose and 0.3mmol CrCl
3be put in round-bottomed flask, then add wherein 5mL methyl-sulphoxide, add 0.5g lithiumbromide simultaneously, at room temperature stir 10 minutes post-heating to 120 ℃, at this temperature, react 3h, be then cooled to room temperature.Add wherein again 0.1mmol V
2o
5, the post-heating to 150 ℃ that stirs reacts 5h at this temperature.After reaction finishes, add 20mL water and 30mL methylene dichloride, separation, underpressure distillation is except desolventizing, and purified product distils.The first step after having reacted is purified portioned product, and HMF yield is 80.7% after measured, and final DFF yield (based on glucose) is 45.6%.
Embodiment 3
Take 1mmol glucose and 0.5mmol GeCl
4be put in round-bottomed flask, then add wherein 5mL methyl-sulphoxide, add 0.5g lithiumbromide simultaneously, at room temperature stir 10 minutes post-heating to 120 ℃, at this temperature, react 3h, be then cooled to room temperature.Add wherein again 0.1mmol V
2o
5, the post-heating to 150 ℃ that stirs reacts 5h at this temperature.After reaction finishes, add 20mL water and 30mL methylene dichloride, separation, underpressure distillation is except desolventizing, and purified product distils.The first step after having reacted is purified portioned product, and HMF yield is 78.6% after measured, and final DFF yield (based on glucose) is 42.5%.
Embodiment 4
Take 1mmol glucose and 0.4mmol LaCl
3be put in round-bottomed flask, then add wherein 5mL methyl-sulphoxide, add 0.5g lithiumbromide simultaneously, at room temperature stir 10 minutes post-heating to 120 ℃, at this temperature, react 3h, be then cooled to room temperature.Add wherein again 0.1mmol V
2o
5, the post-heating to 150 ℃ that stirs reacts 5h at this temperature.After reaction finishes, add 20mL water and 30mL methylene dichloride, separation, underpressure distillation is except desolventizing, and purified product distils.The first step after having reacted is purified portioned product, and HMF yield is 75.3% after measured, and final DFF yield (based on glucose) is 45.3%.
Embodiment 5
Take 1mmol glucose and 0.2mmol SnCl
4be put in round-bottomed flask, then add wherein 5mL methyl-sulphoxide, at room temperature stir 10 minutes post-heating to 140 ℃, at this temperature, react 3h, be then cooled to room temperature.Add wherein again 0.2mmol V
2o
5, the post-heating to 100 ℃ that stirs reacts 5h at this temperature.After reaction finishes, add 20mL water and 30mL methylene dichloride, separation, underpressure distillation is except desolventizing, and purified product distils.The first step after having reacted is purified portioned product, and HMF yield is 78.8% after measured, and final DFF yield (based on glucose) is 41.2%.
Embodiment 6
Take 1mmol glucose and 0.3mmol AlCl
3be put in round-bottomed flask, then add wherein 5mL methyl-sulphoxide, at room temperature stir 10 minutes post-heating to 120 ℃, at this temperature, react 3h, be then cooled to room temperature.Add wherein again 0.1mmolVOPO
4, the post-heating to 150 ℃ that stirs reacts 5h at this temperature.After reaction finishes, add 20mL water and 30mL methylene dichloride, separation, underpressure distillation is except desolventizing, and purified product distils.The first step after having reacted is purified portioned product, and HMF yield is 84.9% after measured, and final DFF yield (based on glucose) is 46.7%.
Embodiment 7
Take 1mmol glucose and 0.4mmol CrCl
3be put in round-bottomed flask, then add wherein 5mL methyl-sulphoxide, at room temperature stir 10 minutes post-heating to 120 ℃, at this temperature, react 3h, be then cooled to room temperature.Add wherein again 0.1mmol VOPO
4, the post-heating to 150 ℃ that stirs reacts 5h at this temperature.After reaction finishes, add 20mL water and 30mL methylene dichloride, separation, underpressure distillation is except desolventizing, and purified product distils.The first step after having reacted is purified portioned product, and HMF yield is 78.6% after measured, and final DFF yield (based on glucose) is 42.2%.
Embodiment 8
Take 1mmol glucose and 0.1mmolGeCl
4be put in round-bottomed flask, then add wherein 5mL methyl-sulphoxide, at room temperature stir 10 minutes post-heating to 160 ℃, at this temperature, react 3h, be then cooled to room temperature.Add wherein again 0.1mmol VOPO
4, the post-heating to 160 ℃ that stirs reacts 5h at this temperature.After reaction finishes, add 20mL water and 30mL methylene dichloride, separation, underpressure distillation is except desolventizing, and purified product distils.The first step after having reacted is purified portioned product, and HMF yield is 75.3% after measured, and final DFF yield (based on glucose) is 41.4%.
Embodiment 9
Take 1mmol glucose and 0.1mmol LaCl
3be put in round-bottomed flask, then add wherein 5mL methyl-sulphoxide, at room temperature stir 10 minutes post-heating to 120 ℃, at this temperature, react 3h, be then cooled to room temperature.Add wherein again 0.1mmol VOPO
4, the post-heating to 150 ℃ that stirs reacts 5h at this temperature.After reaction finishes, add 20mL water and 30mL methylene dichloride, separation, underpressure distillation is except desolventizing, and purified product distils.The first step after having reacted is purified portioned product, and HMF yield is 70.1% after measured, and final DFF yield (based on glucose) is 40.8%.
Embodiment 10
Take 1mmol glucose and 0.1mmol SnCl
4be put in round-bottomed flask, then add wherein 5mL methyl-sulphoxide, at room temperature stir 10 minutes post-heating to 120 ℃, at this temperature, react 3h, be then cooled to room temperature.Add wherein again 0.1mmol VOPO
4, the post-heating to 150 ℃ that stirs reacts 5h at this temperature.After reaction finishes, add 20mL water and 30mL methylene dichloride, separation, underpressure distillation is except desolventizing, and purified product distils.The first step after having reacted is purified portioned product, and HMF yield is 72.3% after measured, and final DFF yield (based on glucose) is 41.5%.
Embodiment 11
Take 1mmol glucose and 0.1mmol AlCl
3be put in round-bottomed flask, then add wherein 5mL methyl-sulphoxide, add 0.5g lithiumbromide simultaneously.At room temperature stir 10 minutes post-heating to 120 ℃, at this temperature, react 3h, be then cooled to room temperature.Add wherein again 0.1mmol V
2o
5, the post-heating to 150 ℃ that stirs reacts 5h at this temperature.After reaction finishes, add 20mL water and 30mL methylene dichloride, separation, underpressure distillation is except desolventizing, and purified product distils.The first step after having reacted is purified portioned product, and HMF yield is 76.1% after measured, and final DFF yield (based on glucose) is 43.8%.
Comparative example 1
By 5mL methyl-sulphoxide in embodiment 2 and 0.5g lithiumbromide, replace with 5mLN, dinethylformamide and 0.5gNaBr are constant for his condition.The first step after having reacted is purified portioned product, and HMF yield is 60.5% after measured, and final DFF yield (based on glucose) is 32.4%.
Comparative example 2
After embodiment 2 the first steps have been reacted, solid in centrifugation removal system (catalyzer and additive lithiumbromide), other conditions are constant, and HMF yield is 78.6% after measured, and final DFF yield (based on glucose) is 40.6%.
Comparative example 3
By 0.1mmolV in embodiment 2
2o
5replace with 0.1mmol KVO
3, other conditions are constant.The first step after having reacted is purified portioned product, and HMF yield is 78.6% after measured, and final DFF yield (based on glucose) is 25.7%.When evidence replaces with other metavanadates by the vanadium compound oxide catalyst in the application (the first step is identical with the application), final DFF yield (based on glucose) is no more than 28%.
From above-described embodiment 2 and the Data Comparison of comparative example 1～3, can find out, in the application, adopt the synergistic action effect of methyl-sulphoxide and lithiumbromide much larger than the synergy of DMF and NaBr; Wherein the first step gold trichloride metal catalyst has a certain impact to metavanadate catalytic oxidation tool, and DFF yield is greatly reduced; In addition, if the first step reaction finishes after in the application's method, the first step catalyzer and additive (lithiumbromide) are removed, the yield of final DFF decreases on the contrary with respect to the application's one kettle way, the catalyzer that in visible the application, the first step adopts and additive have certain promoter action to the reaction of second step, and this may be that in the application, the first step adopts in gold trichloride metal catalyst and the application the vanadium compound catalyzer that adopts in second step to have certain synergy.
Applicant's statement, the present invention illustrates detailed method of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed method, does not mean that the present invention must rely on above-mentioned detailed method and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (8)
1. a method of preparing 2,5-diformyl furans with glucose, is characterized in that: comprise the steps:
(1) glucose and metal catalyst are dissolved in solvent, are uniformly mixed and are heated to temperature of reaction, obtain intermediate product, 5 hydroxymethyl furfural;
(2) without separating-purifying, directly in reaction soln, add oxide catalyst, be heated to temperature of reaction, after reaction finishes, with dichloromethane extraction, separated, distillation, distillation, finally obtain the solid of 2,5-diformyl furans; Wherein said glucose molecule formula is C
6h
12o
6.
2. the method for preparing 2,5-diformyl furans with glucose according to claim 1, is characterized in that: described metal catalyst is MCl
x, wherein M is any one in Al, Cr, Ge, La or Sn, x is 2-4; Described oxide catalyst is V
2o
5, VOPO
4or VO (PO
3)
2wherein a kind of.
3. the method for preparing 2,5-diformyl furans with glucose according to claim 1, is characterized in that: described metal catalyst is AlCl
3; Described oxide catalyst is V
2o
5.
4. the method for preparing 2,5-diformyl furans with glucose according to claim 1, is characterized in that: described reaction solvent is methyl-sulphoxide or has added the lithiumbromide of 10wt% as the methyl-sulphoxide of additive.
5. according to preparing the method for 2,5-diformyl furans with glucose described in claim 1～4 any one, it is characterized in that: the mol ratio of described glucose and metal catalyst is 10:1～5; Described glucose and oxide catalyst mol ratio are 10:0.5～2.
6. according to preparing the method for 2,5-diformyl furans with glucose described in claim 1～4 any one, it is characterized in that: the mol ratio of described glucose and metal catalyst is 10:3～5; Described glucose and oxide catalyst mol ratio are 10:1.
7. the method for preparing 2,5-diformyl furans with glucose according to claim 1, is characterized in that: described temperature of reaction is 100～160 ℃.
8. the method for preparing 2,5-diformyl furans with glucose according to claim 1, is characterized in that: in step (1), temperature of reaction is 120 ℃; In step (2), temperature of reaction is 150 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1555368A (en) * | 2001-09-17 | 2004-12-15 | ��Ļ���Ű˾ | Process for preparing 2,5-diformylfuran from carbohydrates |
| CN103755668A (en) * | 2014-02-11 | 2014-04-30 | 厦门大学 | Method for preparing 2, 5-diformylfuran by catalysis of load-type V2O5catalyst |
| CN103819431A (en) * | 2014-02-11 | 2014-05-28 | 厦门大学 | Method for preparing 2, 5-diformylfuran by using molecular oxygen-assisted CuCl+KVO3co-catalysis method |
-
2014
- 2014-07-28 CN CN201410364759.8A patent/CN104098533B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1555368A (en) * | 2001-09-17 | 2004-12-15 | ��Ļ���Ű˾ | Process for preparing 2,5-diformylfuran from carbohydrates |
| CN103755668A (en) * | 2014-02-11 | 2014-04-30 | 厦门大学 | Method for preparing 2, 5-diformylfuran by catalysis of load-type V2O5catalyst |
| CN103819431A (en) * | 2014-02-11 | 2014-05-28 | 厦门大学 | Method for preparing 2, 5-diformylfuran by using molecular oxygen-assisted CuCl+KVO3co-catalysis method |
Non-Patent Citations (4)
| Title |
|---|
| CARLO CARLINI等: "Selective oxidation of 5-hydroxymethyl-2-furaldehyde to furan-2,5-dicarboxaldehyde by catalytic systems based on vanadyl phosphate", 《APPLIED CATALYSIS A》 * |
| ZHEN-ZHEN YANG等: "A one-pot approach for conversion of fructose to 2,5-diformylfuran by combination of Fe3O4-SBA-SO3H and K-OMS-2†", 《GREEN CHEMISTRY》 * |
| ZHEN-ZHEN YANG等: "A one-pot approach for conversion of fructose to 2,5-diformylfuran by combination of Fe3O4-SBA-SO3H and K-OMS-2†", 《GREEN CHEMISTRY》, vol. 14, 31 December 2012 (2012-12-31) * |
| 王超: "金属氯化物催化葡萄糖和蔗糖高效转化为5-羟甲基糠醛的研究", 《天津大学硕士论文》 * |
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