CN104098533B - The method of 2,5-diformyl furans prepared by one glucose - Google Patents
The method of 2,5-diformyl furans prepared by one glucose Download PDFInfo
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- CN104098533B CN104098533B CN201410364759.8A CN201410364759A CN104098533B CN 104098533 B CN104098533 B CN 104098533B CN 201410364759 A CN201410364759 A CN 201410364759A CN 104098533 B CN104098533 B CN 104098533B
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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 the method that 2,5-diformyl furans prepared by one glucose: by glucose and metal catalyst dissolution in a solvent, be uniformly mixed and be heated to temperature of reaction, obtain 5 hydroxymethyl furfural; Add oxide catalyst directly in reaction soln, be heated to temperature of reaction, after reaction terminates, with dichloromethane extraction, be separated, distill, distil, finally obtain the solid of 2,5-diformyl furans.The advantage of the application comprises: (1) the application is one kettle way, does not need separating-purifying, simplify processing step after the first step completes; The catalyzer of the first step and second step reaction has well compatible 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 good, more bromine negative ion can be provided as the part of metal-salt with the better isomerization of catalysis glucose and the dehydration of fructose.
Description
Technical field
The invention belongs to industrial chemicals preparation field, particularly relate to a kind of environment-friendly preparation method thereof of multi-usage industrial chemicals.
Background technology
Along with the continuous exhaustion of petrochemical material, the concern of people to renewable energy technologies improves day by day.Saccharide compound is based on its recyclability, and cheap price, and the feature such as to be easy to get, be regarded as a kind of green renewable raw materials that can substitute petrochemical material.Also become the hot issue of current research to the conversion of liquid fuel and industrial chemicals about saccharide compound.
2,5-diformyl furans is a kind of multiduty industrial chemicals, can as the presoma (KatherineT.Hopkins of pharmacy, W.DavidWilson, BrendanC.Bender, DonaldR.McCurdy, JamesEdwinHall, RichardR.Tidwell, ArvindKumar, MiroBajic, andDavidW.Boykin.JournalofMedicinalChemistry, 1998,41,3872), sanitas (DelPoeta, 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.AntimicrobialAgentsandChemotherapy, 1998,42,2495), linking agent (DeanW.Sheibley, the MichelleA.Manzo of polyvinyl alcohol, andOlgaD.Gonzalez ?Sanabria.JournaloftheElectrochemicalSociety, 1983,130,255), simultaneously at analytical chemistry (Dykstra, C.C.; Tidwell, R.R.; Boykin, D.W.; Wilson, W.D.U.S.Patent5,667,975,1997), electron optics (Daub, J.; Rapp, K.M.; Seitz, P.; Wild, R.; Salbeck, J.U.S.Patent5,091,538,1992), 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 is various purposes, the application of 2,5-diformyl furans is still limited by its high preparation cost (~ 360/100mg).Instantly the method the most effectively preparing 2,5-diformyl furans is the selective oxidation by 5 hydroxymethyl furfural.Moreau etc. (C.Moreau, R.Durand, C.PourcheronandD.Tichit, Stud.Surf.Sci.Catal., 1997,108,399) are with V
2o
5/ TiO
2for catalyzer carries out to 5 hydroxymethyl furfural 2, the 5-diformyl furans that selective oxidation obtains high yield (80%) in atmosphere.(the O.C.Navarro such as Navarro; A.CormaandS.Iborra; Top.Catal.; 2009; 52; 304) efficient selective utilizing the vanadium oxide compound be fixed on Polyvinylpyrolidone (PVP) to achieve 5 hydroxymethyl furfural for catalyzer is oxidized in order to prepare 2,5-diformyl furans.(the G.A.Halliday such as Halliday, R.Y.YoungandV.V.Grushin, Org.Lett., 2003,5,2003) be solvent with methyl-sulphoxide, resin solid acid and vanadium oxide compound are catalyzer, successfully fructose is combined together to the conversion of 5 hydroxymethyl furfural and the selective oxidation of 5 hydroxymethyl furfural, simplify production stage, reduce preparation cost.
Although be that raw material is prepared 2,5-diformyl furans and greatly reduced production cost with fructose, fructose appoints so higher price ($540/1kg) limit its industrially scale operation.Therefore a kind of more cheap raw material is needed to reduce the preparation cost of 2,5-diformyl furans.
In patent (CN103739573A), the people such as Sun Yong are reaction substrate by using with glucose, and DMF is solvent, and NaBr is promotor, under AlCl36H2O catalyst action, generate 5 hydroxymethyl furfural; Then carry out oxidizing reaction, obtain 2,5-diformyl furans.A kind of method for transformation generating DFF through Lewis acid-catalyzed dehydration and molecular oxygen auxiliary catalysis oxidation two-step approach reaction in－situ is provided; For two-step reaction, adopt differential responses device, glucose catalytic dehydration step is wherein under AlCl36H2O and NaBr effect, generates HMF in Hastelloy reaction kettle for reaction; Oxidation step need be separated catalyzer in removing dehydrating step and additive in advance, carries out the regulation and control of oxygen-supply quantity, the final Biomass-based chemicals DFF obtaining high added value by arranging different oxygen pneumatic.
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 to be separated the catalyzer in removing dehydrating step and additive deficiency; there is provided a kind of and prepare 2 by glucose; the method of 5-diformyl furans; present method is one kettle way, does not need removing catalyzer and additive after forming intermediate product.
For solving the problems of the technologies described above the technical solution used in the present invention be: the method for 2,5-diformyl furans prepared by one glucose, comprises the steps:
(1) by glucose and metal catalyst dissolution in a solvent, be uniformly mixed and be heated to temperature of reaction, obtain intermediate product, 5 hydroxymethyl furfural; (2) add oxide catalyst without separating-purifying directly in reaction soln, be heated to temperature of reaction, after reaction terminates, with dichloromethane extraction, be separated, distill, distil, 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, and x is 2-4; Described oxide catalyst is V
2o
5, VOPO
4or VO (PO
3)
2one wherein.
As preferably, described metal catalyst is AlCl
3; Described oxide catalyst is V
2o
5.
As preferably, described reaction solvent is methyl-sulphoxide or the methyl-sulphoxide of lithiumbromide as additive that with the addition of 10wt%.
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 DEG C.
As preferably, in step (1), temperature of reaction is 120 DEG C; In step (2), temperature of reaction is 150 DEG C.
Compared with prior art, the advantage of the application comprises the following aspects:
(1) the application is one kettle way, does not need separating-purifying, simplify processing step after the first step completes; The catalyzer of the first step and second step reaction has well compatible 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 good, more bromine negative ion can be provided as the part of metal-salt with the better isomerization of catalysis glucose and the dehydration of fructose.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
The interval value that the present invention provides, the not 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; exemplary illustration and help understand the present invention further; but embodiment detail is only in order to the present invention is described; do not represent the present invention and conceive lower whole technical scheme; therefore should not be construed as the technical scheme total to the present invention to limit, some are In the view of technician, and the unsubstantiality not departing from inventive concept is changed; such as simply change with the technical characteristic with same or similar technique effect or replace, all belonging to scope.
Embodiment 1
Take 1mmol glucose and 0.1mmolAlCl
3be put in round-bottomed flask, then add 5mL methyl-sulphoxide wherein, at room temperature stir 10 minutes post-heating to 100 DEG C, react 3h at such a temperature, be then cooled to room temperature.Add 0.0.05mmolV wherein again
2o
5, stir post-heating to 160 DEG C, reacts 5h at this temperature.After reaction terminates, add 20mL water and 30mL methylene dichloride, be separated, underpressure distillation removes desolventizing, sublimation purification product.Portioned product is purified after having reacted by the first step, and HMF yield is 75.6% after measured, and final DFF yield (based on glucose) is 40.9%.
Embodiment 2
Take 1mmol glucose and 0.3mmolCrCl
3be put in round-bottomed flask, then add 5mL methyl-sulphoxide wherein, add 0.5g lithiumbromide simultaneously, at room temperature stir 10 minutes post-heating to 120 DEG C, react 3h at such a temperature, be then cooled to room temperature.Add 0.1mmolV wherein again
2o
5, stir post-heating to 150 DEG C, reacts 5h at this temperature.After reaction terminates, add 20mL water and 30mL methylene dichloride, be separated, underpressure distillation removes desolventizing, sublimation purification product.Portioned product is purified after having reacted by the first step, and HMF yield is 80.7% after measured, and final DFF yield (based on glucose) is 45.6%.
Embodiment 3
Take 1mmol glucose and 0.5mmolGeCl
4be put in round-bottomed flask, then add 5mL methyl-sulphoxide wherein, add 0.5g lithiumbromide simultaneously, at room temperature stir 10 minutes post-heating to 120 DEG C, react 3h at such a temperature, be then cooled to room temperature.Add 0.1mmolV wherein again
2o
5, stir post-heating to 150 DEG C, reacts 5h at this temperature.After reaction terminates, add 20mL water and 30mL methylene dichloride, be separated, underpressure distillation removes desolventizing, sublimation purification product.Portioned product is purified after having reacted by the first step, and HMF yield is 78.6% after measured, and final DFF yield (based on glucose) is 42.5%.
Embodiment 4
Take 1mmol glucose and 0.4mmolLaCl
3be put in round-bottomed flask, then add 5mL methyl-sulphoxide wherein, add 0.5g lithiumbromide simultaneously, at room temperature stir 10 minutes post-heating to 120 DEG C, react 3h at such a temperature, be then cooled to room temperature.Add 0.1mmolV wherein again
2o
5, stir post-heating to 150 DEG C, reacts 5h at this temperature.After reaction terminates, add 20mL water and 30mL methylene dichloride, be separated, underpressure distillation removes desolventizing, sublimation purification product.Portioned product is purified after having reacted by the first step, and HMF yield is 75.3% after measured, and final DFF yield (based on glucose) is 45.3%.
Embodiment 5
Take 1mmol glucose and 0.2mmolSnCl
4be put in round-bottomed flask, then add 5mL methyl-sulphoxide wherein, at room temperature stir 10 minutes post-heating to 140 DEG C, react 3h at such a temperature, be then cooled to room temperature.Add 0.2mmolV wherein again
2o
5, stir post-heating to 100 DEG C, reacts 5h at this temperature.After reaction terminates, add 20mL water and 30mL methylene dichloride, be separated, underpressure distillation removes desolventizing, sublimation purification product.Portioned product is purified after having reacted by the first step, and HMF yield is 78.8% after measured, and final DFF yield (based on glucose) is 41.2%.
Embodiment 6
Take 1mmol glucose and 0.3mmolAlCl
3be put in round-bottomed flask, then add 5mL methyl-sulphoxide wherein, at room temperature stir 10 minutes post-heating to 120 DEG C, react 3h at such a temperature, be then cooled to room temperature.Add 0.1mmolVOPO wherein again
4, stir post-heating to 150 DEG C, reacts 5h at this temperature.After reaction terminates, add 20mL water and 30mL methylene dichloride, be separated, underpressure distillation removes desolventizing, sublimation purification product.Portioned product is purified after having reacted by the first step, and HMF yield is 84.9% after measured, and final DFF yield (based on glucose) is 46.7%.
Embodiment 7
Take 1mmol glucose and 0.4mmolCrCl
3be put in round-bottomed flask, then add 5mL methyl-sulphoxide wherein, at room temperature stir 10 minutes post-heating to 120 DEG C, react 3h at such a temperature, be then cooled to room temperature.Add 0.1mmolVOPO wherein again
4, stir post-heating to 150 DEG C, reacts 5h at this temperature.After reaction terminates, add 20mL water and 30mL methylene dichloride, be separated, underpressure distillation removes desolventizing, sublimation purification product.Portioned product is purified after having reacted by the first step, 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 5mL methyl-sulphoxide wherein, at room temperature stir 10 minutes post-heating to 160 DEG C, react 3h at such a temperature, be then cooled to room temperature.Add 0.1mmolVOPO wherein again
4, stir post-heating to 160 DEG C, reacts 5h at this temperature.After reaction terminates, add 20mL water and 30mL methylene dichloride, be separated, underpressure distillation removes desolventizing, sublimation purification product.Portioned product is purified after having reacted by the first step, and HMF yield is 75.3% after measured, and final DFF yield (based on glucose) is 41.4%.
Embodiment 9
Take 1mmol glucose and 0.1mmolLaCl
3be put in round-bottomed flask, then add 5mL methyl-sulphoxide wherein, at room temperature stir 10 minutes post-heating to 120 DEG C, react 3h at such a temperature, be then cooled to room temperature.Add 0.1mmolVOPO wherein again
4, stir post-heating to 150 DEG C, reacts 5h at this temperature.After reaction terminates, add 20mL water and 30mL methylene dichloride, be separated, underpressure distillation removes desolventizing, sublimation purification product.Portioned product is purified after having reacted by the first step, and HMF yield is 70.1% after measured, and final DFF yield (based on glucose) is 40.8%.
Embodiment 10
Take 1mmol glucose and 0.1mmolSnCl
4be put in round-bottomed flask, then add 5mL methyl-sulphoxide wherein, at room temperature stir 10 minutes post-heating to 120 DEG C, react 3h at such a temperature, be then cooled to room temperature.Add 0.1mmolVOPO wherein again
4, stir post-heating to 150 DEG C, reacts 5h at this temperature.After reaction terminates, add 20mL water and 30mL methylene dichloride, be separated, underpressure distillation removes desolventizing, sublimation purification product.Portioned product is purified after having reacted by the first step, and HMF yield is 72.3% after measured, and final DFF yield (based on glucose) is 41.5%.
Embodiment 11
Take 1mmol glucose and 0.1mmolAlCl
3be put in round-bottomed flask, then add 5mL methyl-sulphoxide wherein, add 0.5g lithiumbromide simultaneously.At room temperature stir 10 minutes post-heating to 120 DEG C, react 3h at such a temperature, be then cooled to room temperature.Add 0.1mmolV wherein again
2o
5, stir post-heating to 150 DEG C, reacts 5h at this temperature.After reaction terminates, add 20mL water and 30mL methylene dichloride, be separated, underpressure distillation removes desolventizing, sublimation purification product.Portioned product is purified after having reacted by the first step, 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, constant for his condition.Portioned product is purified after having reacted by the first step, 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 step has been reacted, solid (catalyzer and additive lithiumbromide) in centrifugation removal system, 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 0.1mmolKVO
3, other conditions are constant.Portioned product is purified after having reacted by the first step, and HMF yield is 78.6% after measured, and final DFF yield (based on glucose) is 25.7%.When test proves the vanadium compound oxide catalyst in the application to be replaced with other metavanadates (the first step is identical with the application), final DFF yield (based on glucose) is no more than 28%.
As can be seen from Data Comparison with comparative example 1 ~ 3 of above-described embodiment 2, 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 terminates after the first step catalyzer in the application's method and additive (lithiumbromide) removing, the yield of final DFF decreases on the contrary relative to the one kettle way of the application, the catalyzer that in visible the application, the first step adopts and the reaction of additive to second step have certain promoter action, this may be in the application the first step to adopt in gold trichloride metal catalyst and the application in second step adopt vanadium compound catalyzer to have certain synergy.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (4)
1. prepare the method for 2,5-diformyl furans with glucose for one kind, it is characterized in that, comprise the steps:
(1) by glucose and metal catalyst dissolution in a solvent, be uniformly mixed and be heated to temperature of reaction, obtain intermediate product, 5 hydroxymethyl furfural,
Described metal catalyst is MCl
x, wherein M is any one in Al, Cr, Ge, La or Sn, and x is 2-4,
Described reaction solvent is methyl-sulphoxide or the methyl-sulphoxide of lithiumbromide as additive that with the addition of 10wt%,
The mol ratio of described glucose and metal catalyst is 10:1 ~ 5;
(2) add oxide catalyst without separating-purifying directly in reaction soln, be heated to temperature of reaction, after reaction terminates, with dichloromethane extraction, be separated, distill, distil, finally obtain the solid of 2,5-diformyl furans; Wherein said glucose molecule formula is C
6h
12o
6,
Described oxide catalyst is V
2o
5, VOPO
4or VO (PO
3)
2one wherein, described glucose and oxide catalyst mol ratio are 10:0.5 ~ 2;
Described temperature of reaction is 100 ~ 160 DEG C.
2. the method for 2,5-diformyl furans prepared by glucose according to claim 1, it is characterized in that: described metal catalyst is AlCl
3; Described oxide catalyst is V
2o
5.
3. the method for 2,5-diformyl furans prepared by glucose according to claim 1, 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.
4. the method for 2,5-diformyl furans prepared by glucose according to claim 1, it is characterized in that: in step (1), temperature of reaction is 120 DEG C; In step (2), temperature of reaction is 150 DEG C.
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| CN1555368A (en) * | 2001-09-17 | 2004-12-15 | ��Ļ���Ű˾ | Process for preparing 2,5-diformylfuran from carbohydrates |
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-
2014
- 2014-07-28 CN CN201410364759.8A patent/CN104098533B/en not_active Expired - Fee Related
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| 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 |
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