CN101768142A - Method for catalysis-synthesizing 2,5-dicarbaldehyde by carbohydrate - Google Patents
Method for catalysis-synthesizing 2,5-dicarbaldehyde by carbohydrate Download PDFInfo
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- CN101768142A CN101768142A CN201010028115A CN201010028115A CN101768142A CN 101768142 A CN101768142 A CN 101768142A CN 201010028115 A CN201010028115 A CN 201010028115A CN 201010028115 A CN201010028115 A CN 201010028115A CN 101768142 A CN101768142 A CN 101768142A
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Abstract
The invention relates to a method for catalysis-synthesizing 2,5-dicarbaldehyde by carbohydrate; carbohydrate is used as raw material, N,N-dimethylacetylamide is used as reaction medium, sodium bromide is used as additive, 5-hydroxymethylfurfural is dehydrated under acid catalysis, vandic salt is added as the catalyst, and air flows in under normal pressure to carry out oxidizing reaction, so as to synthesize 2,5-dicarbaldehyde; in the method, the reaction condition is mild, the raw materials and the catalyst are obtained easily, the method has high 2,5-dicarbaldehyde yield and the reaction process is easily operated.
Description
Technical field:
The present invention relates to by carbohydrate preparation 2, the two-step catalysis method of 5-furans dicarbaldehyde.
Background technology:
2,5-furans dicarbaldehyde (DFF) is a kind of multiduty organic synthesis intermediate.DFF itself can be used as starting material synthetic drugs, macrocyclic ligand, anti-mycotic agent and furans, and it also can be used as the polymeric monomer and forms various superpolymer, for example poly-tetramethyl ethylene ketone and polyethylene, and it can be used as the intermediate of synthetic pharmaceuticals in addition.
At present, adopting 5 hydroxymethyl furfural (HMF) is raw material, by the synthetic DFF of oxidizing reaction, is considered to industrial unique feasible method for preparing DFF.But need complicated separable programming because of obtaining HMF, make that the production cost of DFF is very high so HMF costs an arm and a leg, so the production of DFF does not have industrialization so far.Carbohydrate is regarded as most promising at present " renewable resources ".Directly as raw material, the two step conversion processes DFF that utilization need not be isolated HMF can avoid expensive HMF separating step, great advantage is not only arranged economically, and more meet the viewpoint of green Sustainable development with carbohydrate.
Moreau etc. adopt different organic solvents as reaction medium in patent WO9617836, at 75-200 ℃, have studied the reaction of heterogeneous metal oxide catalyst catalysis HMF oxidation under the air pressure of 10bar, and wherein best catalyzer is V
2O
5And V
2O
5/ TiO
2Make solvent with toluene,, adopt V under the air pressure of 10bar at 90 ℃
2O
5/ TiO
2Made catalyst reaction 4 hours, the transformation efficiency of HMF is 91%, and corresponding D FF selectivity is 93%., but need high catalyzer and substrate than (2/1wt/wt) and high air pressure but obtain such result.
Carlini etc. report that in Applied Catalysis A:General 289 (2005) 197 dimethyl sulfoxide (DMSO) (DMSO) is made solvent with air oxidant, adopt VOPO
42H
2O (VOP) catalysis HMF oxidation obtains DFF, in 150 ℃ down reaction obtain 84% transformation efficiency and 97% selectivity after 6 hours.Brought difficulty for the separation purification of target product owing to adopted high boiling DMSO to make solvent.Therefore, they adopt N, and the N dimethyl formamide is made solvent at 100 ℃, and the oxygen pressure of 0.1MPa is reaction down, has obtained high DFF selectivity (95%), but the but very low only 20%-56% of the transformation efficiency of HMF.
Chornet etc. report in Topics in Catalysis 52 (2009) 304 to be had metal load on the poly 4 vinyl pyridine of 33% divinyl benzene crosslinked, a series of Cu and V catalyzer have been prepared, the result shows that they all are to have actively and optionally to this reaction, and the more copper bearing polymkeric substance of polymkeric substance that contains vanadium has better catalytic activity.With the polymkeric substance that contains vanadium is catalyzer, at 130 ℃, under the pressure of 1MPa, air fed reaction in the phenylfluoroform solution contain HMF after 4 hours the HMF transformation efficiency be 77% and the selectivity of DFF up to 99%, but there is serious metal solution-off phenomenon in catalyzer under this system, reduce temperature of reaction and also can't effectively avoid this phenomenon, the repeated use effect of such catalyzer is bad.
Though direct oxidation HMF can highly selective be made DFF, does not have a kind of appropriate catalyst can obtain high DFF productive rate under the condition of gentleness, and the raw material costliness is that DFF fails the maximum obstruction of suitability for industrialized production so far.But owing to, set out by process study by carbohydrate so from the acquisition HMF of carbohydrate high yield, need not isolate HMF prepare DFF will have economically advantage and the prospect of industrial applications, at present seldom about the research report of this method.
Carlini etc. report the catalyzer that adopts VOP to make dehydration and oxidation step in Applied Catalysis A:General 289 (2005) 197, make raw material with fructose, obtained HMF in 2 hours 80 ℃ of following dehydration reactions, the aerating oxygen reaction obtained DFF in 1 hour again, the result shows that this reaction is that the productive rate of DFF in water medium or in the blending agent of water/methyl iso-butyl ketone (MIBK) is all very low, only 1%-3% (in fructose).
Grushin etc. in patent US20030130528A1 are that raw material adopts single jar of two step method directly to prepare DFF with fructose, have avoided the separation of intermediate HMF.The first step fructose obtains productive rate by the ion-exchange resin catalyzed dehydration of tart in DMSO be 75% HMF.Second step under the air pressure of 1bar, added the synthetic DFF of the catalyst based catalyzed oxidation HMF of solid oxyvanadium compound at 150 ℃ in the reaction solution of the first step, after the reaction long period (13-19h) to obtain the DFF yield be 35-45% (in fructose).Because disproportionation reaction can take place in DMSO under reaction conditions, generate (CH
3)
2S and (CH
3)
2SO
2, (CH wherein
3)
2S is a kind of gas of very difficult news, need handle deodorize by bleaching (NaClO) at gas outlet, and (CH
3)
2SO
2Be a kind of white powder, its generation has brought trouble for the separation and the purification of product.This method temperature of reaction height, yield is low, and by product is many, and is only applicable to the higher relatively fructose sources of price.
Summary of the invention:
It is more economical and practical to the purpose of this invention is to provide a kind of synthetic method, can be synthesized the method for DFF under relatively mild reaction conditions with high yield by the carbohydrate of cheapness, overcomes prior art cost height, the high and low defective of yield of energy consumption.
The invention main points: normal pressure is reaction down, with the carbohydrate is raw material, N, N-N,N-DIMETHYLACETAMIDE (DMA) is made reaction medium, Sodium Bromide is made additive, dehydration generates 5 hydroxymethyl furfural under acid catalysis, remove Sodium Bromide and solid catalyst after the cooling, with the vanadic salts is the catalyzer of oxidizing reaction, and bubbling air carries out the oxidizing reaction Synthetic 2 again, 5-furans dicarbaldehyde, wherein air velocity is 8-40mL/min, the consumption of vanadic salts is 0.032-0.160mmol, and temperature of reaction is 90-130 ℃, and the reaction times is 6-14 hour.Optimal reaction temperature is 110-120 ℃, and optimum reacting time is 8-10 hour, and the optimum air flow velocity is 24-32mL/min, and best vanadic salts consumption is 0.064-0.096mmol.
Carbohydrate of the present invention refers to glucose, fructose or sucrose, and vanadic salts refers to sodium metavanadate, ammonium meta-vanadate, vanadylic sulfate and acetic acid vanadyl, and best vanadic salts catalyzer is a sodium metavanadate.
The present invention compares with existing technology, as patent US20030130528A1, have following characteristics: 1. applicable raw materials of the present invention is wide, especially can obtain higher DFF productive rate as raw material with the glucose of cheapness, reduce manufacturing cost, had the industrial applications prospect; 2.DFF the productive rate height, in carbohydrate (glucose: 51%, fructose: 68%, sucrose: 50%); 3. catalyzer is cheap and easy to get, is easy to separate (centrifugation); 4. reaction conditions is gentle, normal pressure, and low temperature, the reaction times is shorter relatively; 5. reaction process is simple to operate, and byproduct of reaction is few, and is environmentally friendly.
Embodiment:
Embodiment 1:
In a single necked round bottom flask, add 0.08g glucose (0.45mmol) successively, 1mLDMA, 0.007g CrCl
36H
2O and 0.08gNaBr.Connect prolong and be placed in the oil bath pan, oil bath pan is warming up to 100 ℃, constant temperature stirs, and back flow reaction is stopped reaction after 6 hours.Reaction system is naturally cooled to room temperature, and centrifugation goes out CrCl
36H
2O and NaBr, the productive rate of GC analysis revealed HMF is 74%.In this reaction solution, add 0.096mmolNaVO
32H
2O, with the flow velocity of 24mL/min with air in the mode of bubbling by this mixed solution, oil bath pan is warming up to 110 ℃, constant temperature stirs, back flow reaction is stopped reaction after 10 hours.Reaction system is naturally cooled to room temperature, and centrifugation goes out NaVO
32H
2O, the GC analysis revealed is 70% with the selectivity that HMF calculates DFF, and productive rate is 69%, and obtaining the DFF productive rate with glucose calculating is 51%.
Embodiment 2-5:
Prepare four reaction solutions that contain HMF according to the method for embodiment 1, and add NaVO respectively
32H
2O0.032mmol, 0.064mmol, 0.128mmol, 0.160mmol, and with the flow velocity of 24mL/min with air in the mode of bubbling by four mixed solutions, oil bath pan is warming up to 110 ℃, constant temperature stirs, back flow reaction is stopped reaction after 10 hours.Reaction system is naturally cooled to room temperature, and centrifugation goes out NaVO
32H
2O.Reaction solution detects with GC, and the result that reaction obtains under the catalyzer of different amounts is set forth in the table 1.
Table 1
| The implementation column sequence number | ??NaVO 3·2H 2O??(mmol) | DFF selectivity (%) is in HMF | DFF productive rate (%) is in HMF | DFF productive rate (%) is with glucose meter |
| ??2 | ??0.032 | ?61 | ?60 | ?44 |
| ??3 | ??0.064 | ?65 | ?64 | ?47 |
| ??4 | ??0.128 | ?68 | ?67 | ?49 |
| ??5 | ??0.160 | ?66 | ?65 | ?48 |
Embodiment 6-9:
Prepare four reaction solutions that contain HMF according to the method for embodiment 1, add 0.096mmol NaVO
32H
2O, and respectively with the flow velocity of 8mL/min, 16mL/min, 32mL/min, 40mL/min with air in the mode of bubbling by four mixed solutions, oil bath pan is warming up to 110 ℃, constant temperature stirs, back flow reaction is stopped reaction after 10 hours.Reaction system is naturally cooled to room temperature, and centrifugation goes out NaVO
32H
2O.Reaction solution detects with GC, and the result that reaction obtains under the different air velocitys is set forth in the table 2.
Table 2
| The implementation column sequence number | Air velocity (mL/min) | DFF selectivity (%) is in HMF | DFF productive rate (%) is in HMF | DFF productive rate (%) is with glucose meter |
| ??6 | ??8 | ?50 | ?49 | ?36 |
| ??7 | ??16 | ?65 | ?64 | ?47 |
| ??8 | ??32 | ?68 | ?67 | ?49 |
| ??9 | ??40 | ?69 | ?68 | ?50 |
Embodiment 10-13:
Prepare four reaction solutions that contain HMF according to the method for embodiment 1, add 0.096mmol NaVO
32H
2O, with the flow velocity of 24mL/min with air in the mode of bubbling by four mixed solutions, the temperature of oil bath pan is risen to 90 ℃, 100 ℃, 120 ℃, 130 ℃ respectively, constant temperature stirs, back flow reaction is stopped reaction after 10 hours.Reaction system is naturally cooled to room temperature, and centrifugation goes out NaVO
32H
2O.Reaction solution detects with GC, and the result that reaction obtains under the differential responses temperature is set forth in the table 3.
Table 3
| The implementation column sequence number | Temperature of reaction (℃) | DFF selectivity (%) is in HMF | DFF productive rate (%) is in HMF | DFF productive rate (%) is with glucose meter |
| ??10 | ??90 | ?34 | ?29 | ?21 |
| ??11 | ??100 | ?58 | ?42 | ?31 |
| ??12 | ??120 | ?68 | ?67 | ?49 |
| ??13 | ??130 | ?58 | ?58 | ?43 |
Embodiment 14-17:
Prepare four reaction solutions that contain HMF according to the method for embodiment 1, add 0.096mmol NaVO
32H
2O, with the flow velocity of 24mL/min with air in the mode of bubbling by four mixed solutions, oil bath pan is warming up to 110 ℃, constant temperature stirs, respectively stopped reaction behind back flow reaction 6h, 8h, 12h, the 14h.Reaction system is naturally cooled to room temperature, and centrifugation goes out NaVO
32H
2O.Reaction solution detects with GC, and the result that reaction obtains under the differential responses time is set forth in the table 4.
Table 4
| The implementation column sequence number | Reaction times (h) | DFF selectivity (%) is in HMF | DFF productive rate (%) is in HMF | DFF productive rate (%) is with glucose meter |
| ??14 | ?6 | ?67 | ?50 | ?37 |
| ??15 | ?8 | ?69 | ?68 | ?50 |
| ??16 | ?12 | ?69 | ?69 | ?51 |
| ??17 | ?14 | ?67 | ?67 | ?49 |
Embodiment 18-20:
Prepare three reaction solutions that contain HMF according to the method for embodiment 1, add 0.096mmol NH respectively
4VO
3, VOSO
4XH
2O and VO (AcO)
2, with the flow velocity of 24mL/min air is passed through three mixed solutions in the mode of bubbling, oil bath pan is warming up to 110 ℃, constant temperature stirs stopped reaction behind the back flow reaction 10h.Reaction system is naturally cooled to room temperature, and centrifugation goes out vanadic salts.Reaction solution detects with GC, and the result that different vanadic salts catalysis obtain is set forth in the table 5.
Table 5
| The implementation column sequence number | Catalyzer | DFF selectivity (%) is in HMF | DFF productive rate (%) is in HMF | DFF productive rate (%) is with glucose meter |
| ??18 | ??NH 4VO 3 | ?44 | ?44 | ?32 |
| ??19 | ??VOSO 4·xH 2O | ?66 | ?66 | ?48 |
| ??20 | ??VO(AcO) 2 | ?61 | ?58 | ?44 |
Embodiment 21:
In a single necked round bottom flask, add 0.08g fructose (0.45mmol) successively, 1mLDMA, 0.003gH
2SO
4And 0.08gNaBr.Connect prolong and be placed in the oil bath pan, oil bath pan is warming up to 100 ℃, constant temperature stirs, and back flow reaction is stopped reaction after 2 hours.Reaction system is naturally cooled to room temperature, and centrifugation goes out NaBr, and the productive rate of GC analysis revealed HMF is 90%.In this reaction solution, add 0.096mmolNaVO
32H
2O, with the flow velocity of 24mL/min with air in the mode of bubbling by this mixed solution, oil bath pan is warming up to 110 ℃, constant temperature stirs, back flow reaction is stopped reaction after 10 hours.Reaction system is naturally cooled to room temperature, and centrifugation goes out NaVO
32H
2O, the GC analysis revealed is 76% with the selectivity that HMF calculates DFF, and productive rate is 75%, and calculating the DFF productive rate with fructose is 68%.
Embodiment 22:
In a single necked round bottom flask, add 0.075g sucrose (0.22mmol) successively, 1mL DMA, 0.007g CrCl
36H
2O and 0.075gNaBr.Connect prolong and be placed in the oil bath pan, oil bath pan is warming up to 100 ℃, constant temperature stirs, and back flow reaction is stopped reaction after 6 hours.Reaction system is naturally cooled to room temperature, and centrifugation goes out CrCl
36H
2O and NaBr, the productive rate of GC analysis revealed HMF is 70%.In this reaction solution, add 0.096mmolNaVO
32H
2O, with the flow velocity of 24mL/min with air in the mode of bubbling by this mixed solution, oil bath pan is warming up to 110 ℃, constant temperature stirs, back flow reaction is stopped reaction after 10 hours.Reaction system is naturally cooled to room temperature, and centrifugation goes out NaVO
32H
2O, the GC analysis revealed is 72% with the selectivity that HMF calculates DFF, and productive rate is 71%, and calculating the DFF productive rate with sucrose is 50%.
Claims (7)
1. one kind by carbohydrate catalysis Synthetic 2, the method of 5-furans dicarbaldehyde, with the carbohydrate is raw material, N, the N-N,N-DIMETHYLACETAMIDE is made reaction medium, Sodium Bromide is made additive, dehydration generates 5 hydroxymethyl furfural under acid catalysis, it is characterized in that being the catalyzer of oxidizing reaction with the vanadic salts under normal pressure again, bubbling air carries out oxidizing reaction and generates 2,5-furans dicarbaldehyde, wherein air velocity is 8-40mL/min, the vanadic salts consumption is 0.032-0.160mmol, temperature of reaction is 90-130 ℃, and the reaction times is 6-14h.
2. method according to claim 1 is characterized in that used carbohydrate is a glucose.
3. method according to claim 1 is characterized in that used vanadic salts is a sodium metavanadate.
4. method according to claim 1 is characterized in that air velocity is 24-32mL/min.
5. method according to claim 1 is characterized in that the vanadic salts consumption is 0.064-0.096mmol.
6. method according to claim 1 is characterized in that temperature of reaction is 110-120 ℃.
7. method according to claim 1 is characterized in that the reaction times is 8-10h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477020A (en) * | 2010-11-29 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethyl furfural by catalysis of carbohydrate |
| CN102731448A (en) * | 2012-06-27 | 2012-10-17 | 北京大学 | Preparation method for furan-2,5-dicarbaldehyde |
| 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 |
| CN103635583A (en) * | 2011-06-15 | 2014-03-12 | 赢创德固赛有限公司 | Enzymatic amination |
| 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 |
| WO2014121513A1 (en) * | 2013-02-08 | 2014-08-14 | Rhodia Operations | Oxydation of alcohol compounds via mesostructured vpo catalysts |
| CN104327019A (en) * | 2014-11-24 | 2015-02-04 | 苏州乔纳森新材料科技有限公司 | Method for catalytically synthesizing 2,5-furyldiformaldehyde from carbohydrates |
| CN107011296A (en) * | 2017-04-27 | 2017-08-04 | 广西科学院 | The method for 2,5 furans dicarbaldehydes of preparation of being degraded using saccharide compound |
| 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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| CN103739573A (en) * | 2014-02-11 | 2014-04-23 | 厦门大学 | Method of performing catalytic conversion to biomass glucose to prepare 2,5-diformylfuran |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6706900B2 (en) * | 2001-09-17 | 2004-03-16 | E. I. Du Pont De Nemours And Company | Process for preparing 2,5-diformylfuran from carbohydrates |
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|---|---|---|---|---|
| WO2012071708A1 (en) * | 2010-11-29 | 2012-06-07 | 中国科学院大连化学物理研究所 | Preparation method of catalyzing carbohydrate into 5-hydroxymethylfurfural |
| CN102477020A (en) * | 2010-11-29 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethyl furfural by catalysis of carbohydrate |
| CN103635583A (en) * | 2011-06-15 | 2014-03-12 | 赢创德固赛有限公司 | Enzymatic amination |
| CN102731448B (en) * | 2012-06-27 | 2014-08-13 | 北京大学 | Preparation method for furan-2,5-dicarbaldehyde |
| CN102731448A (en) * | 2012-06-27 | 2012-10-17 | 北京大学 | Preparation method for furan-2,5-dicarbaldehyde |
| 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 |
| CN103113327B (en) * | 2013-01-24 | 2015-06-03 | 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 |
| 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 |
| CN104327019A (en) * | 2014-11-24 | 2015-02-04 | 苏州乔纳森新材料科技有限公司 | Method for catalytically synthesizing 2,5-furyldiformaldehyde from carbohydrates |
| CN107011296A (en) * | 2017-04-27 | 2017-08-04 | 广西科学院 | The method for 2,5 furans dicarbaldehydes of preparation of being degraded using saccharide compound |
| CN107011296B (en) * | 2017-04-27 | 2019-04-19 | 广西科学院 | The method for preparing 2,5- furans dicarbaldehyde using saccharide compound degradation |
| 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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