CN106008416A - Preparation method of 2,5-furan diformaldehyde - Google Patents
Preparation method of 2,5-furan diformaldehyde Download PDFInfo
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- CN106008416A CN106008416A CN201610528022.4A CN201610528022A CN106008416A CN 106008416 A CN106008416 A CN 106008416A CN 201610528022 A CN201610528022 A CN 201610528022A CN 106008416 A CN106008416 A CN 106008416A
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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 discloses a preparation method of 2,5-furan diformaldehyde. The method comprises the steps that 5-hydroxymethylfurfural is used as a raw material, Cu(NO3)2.3H2O is used as an oxidizing agent, and the 2,5-furan diformaldehyde is prepared in the water-acetonitrile/nonpolar solvent two-phase reaction system. No catalyst is adopted, the product is high in yield and easy to separate, reaction time is short, reaction conditions are mild, the production cost is low, and the preparation method is safe, free of hidden danger and environmentally friendly.
Description
Technical field
The present invention relates to field of organic compound preparation, particularly relate to a kind of DFF
Preparation method.
Background technology
Obtain oil product from biomass and chemicals contributes to alleviating the mankind for the fossil money day by day consumed
The heavy dependence in source.Under this background, 5 hydroxymethyl furfural (HMF) is as a kind of important biology
Matter based platform molecule receives extensive concern.It can be easily from fructose, glucose, even fiber
Element dehydration and prepare, simultaneously because the functional group that HMF self is abundant, may be used for synthesizing a series of
Important fuels and chemicals.2,5-furan can be obtained by catalytic selective oxidation from HMF
Dicarbaldehyde (DFF), the latter is a kind of important chemical intermediate, can be used for synthesizing fungicide, medicine
With functional high-polymer etc..
DFF has purposes widely as a kind of monomer in terms of macromolecule polymeric material,
And as raw material for medicine, antifungal, nematicide, macrocyclic ligand and other organic in
The synthesis of mesosome, such as battery separator, binding agent, electro-optical device, organic fluorescent powder and send out
Body of light etc., and it also can be used for synthesizing various functional material as a kind of monomer.
At present, the method for the production DFF of industrial unique feasible be use HMF be raw material, warp
Prepared by selective oxidation reaction.Owing to HMF is a kind of instability and the change of more difficult isolated
Compound so that its yield is the lowest, expensive, the most commercially circulates, thus
Make the route high cost using conventional oxidizing HMF to prepare DFF, the most not yet
Realize industrialized production.
At present, during 5 hydroxymethyl furfural oxidation generates DFF, conventional
Catalyst system includes mineral acid, slaine and load type metal catalyst etc..But these catalyst
System be not expensive be exactly that toxicity is big.Therefore, a kind of high efficiency, low cost low toxic and environment-friendly is developed
Oxidation system, has important practical significance.
The U.S. patent Nos document of Publication No. US 2008/0103318 A1 discloses a kind of 2,5-
The synthetic method of furan dicarbaldehyde, the γ-MnO2 of the method use activity is as catalyst, at dichloro
Back flow reaction 8h in methane, it is thus achieved that the DFF yield of 80%.But, this mistake
Journey employs the active γ-MnO2 more than 600wt% as catalyst, post processing difficulty；During reaction
Between the longest, catalyst activity is the lowest；The yield of product is relatively low.
The Chinese invention patent document of Publication No. CN 102731448 A discloses a kind of 2,5-furan
The preparation method of dicarbaldehyde, the method uses MnO2 to be catalyst, and DMF is molten
Agent, with oxygen as oxidant, at 110 DEG C, reacts 1.5h, it is thus achieved that the 2 of 98%, 5-furan
Dicarbaldehyde of muttering yield.But catalyst amount is relatively big, and post processing trouble.
The Chinese invention patent document of Publication No. CN 101987839 A discloses a kind of oxidation 5-hydroxyl
Methyl furfural prepares 2, the method for 5-diformyl furan, the method use vanadium oxysulfate as catalyst,
With pure acetonitrile as solvent, oxidant is oxygen, at 100 DEG C, reacts 8h, although have ratio
Higher yield, but catalytic component based on vanadium is relatively costly, toxic, environment there is is large effect.
The Chinese invention patent document of Publication No. CN 103755668 A discloses a kind of support type
V2O5Catalyst prepares 2, and the method for 5-diformyl furan employs support type in the method
VO catalyst, is solvent with DMF, and use oxygen is oxidant, at 110 DEG C
Lower reaction 5h.Feed stock conversion is 60.4%, and DFF selectivity is 70.3%.This
Method is the most relatively costly, toxic, and DFF yield is relatively low.
The Chinese invention patent document of Publication No. CN 104478834 A discloses a kind of catalyst system and catalyzing
The preparation method of the DFF that can be recycled, the method uses piperidines nitrogen oxides for urging
Agent, ferric nitrate is catalyst activator, is solvent with dichloroethanes, and oxygen is oxidant.In room
Stirring 12h under temperature, the DFF yield obtained is 92%.But this catalyst makes fiber crops
Tired, catalyst system and catalyzing is complicated, is unfavorable for industrialization.
Summary of the invention
Present invention aims to above-mentioned technical Analysis and existing problems, it is provided that a kind of high efficiency selected
Property the oxidation 5 hydroxymethyl furfural method of preparing DFF, this preparation method is urged without using
Agent, product yield are high and be easily isolated, response time section, reaction condition are gentle, production cost is low,
Safety is without hidden danger and environmentally friendly.
The present invention adopts the following technical scheme that
A kind of preparation method of DFF, including: with 5 hydroxymethyl furfural as raw material, nitre
Acid copper is oxidant, prepares DFF in water-acetonitrile/non-polar solven two-phase reaction system.
Described copper nitrate be anhydrous nitric acid copper, 2.5 water copper nitrates, nitrate trihydrate copper, Copper nitrate hexahydrate and
At least one in nine water copper nitrates.
5 hydroxymethyl furfural (HMF) as shown in structural formula I, DFF (DFF) as
Shown in structure formula II:
The dosage of described oxidant is the 60～240% of 5 hydroxymethyl furfural quality.Oxidation is substantially adopted
Use Cu+(CH3CN)nAnd NO3 -For oxidant, in formula, n is the integer of 1～20, only needs in course of reaction
Consumption NO3 -, and Cu+Can recycle.
Oxidation reaction mechanism:
1) copper ion (Cu is obtained after copper nitrate is soluble in the aqueous phase2+) and nitrate anion (NO3 -), at copper ion (Cu2+)
Activation under 5 hydroxymethyl furfural is oxidized to DFF, copper ion (Cu simultaneously2+)
It is reduced to cuprous ion (Cu+)；
2) cuprous ion (Cu+) in aqueous phase with acetonitrile (CH3CN) formation Cu (CH is combined3CN)n +,
Cu(CH3CN)n +At nitrate anion (NO3 -) effect under be oxidized to copper ion (Cu2+), and discharge
Acetonitrile (CH3CN), nitrate anion (NO3 -) it is reduced to oxynitride (NO1～2)。
As preferably, after reacted water-acetonitrile supplements dust technology mutually, as next batch reaction
Water-acetonitrile phase.The mass fraction of described dust technology is 40～60%, and the magnitude of recruitment of described dust technology is for being somebody's turn to do
The 40～80% of batch reaction raw materials 5 hydroxymethyl furfural quality.
In reaction system, the concentration of 5 hydroxymethyl furfural is 10～25g/L.
In described two-phase reaction system, the volume ratio of acetonitrile, water and non-polar solven is 25～150:
300～700:300～700.
The technical program uses water-acetonitrile/non-polar solven two-phase reaction system, and oxidant copper nitrate is molten
Xie Yushui-acetonitrile mutually in, the oxidation reaction of 5 hydroxymethyl furfural occurs in water-acetonitrile phase, and reacts product
Thing DFF is more than its dissolubility in water-acetonitrile phase at the dissolubility of non-polar solven phase,
Make product be extracted to non-polar solven phase, thus reach to promote oxidation reaction, shorten the response time
Purpose.
Described non-polar solven be dimethylbenzene, isopropylbenzene, biphenyl, dichloromethane, methyl iso-butyl ketone (MIBK),
At least one of n-butyl alcohol and toluene.As preferably, described non-polar solven is toluene.
The temperature of described reaction is 50～180 DEG C.As preferably, the temperature of described reaction is 80～120 DEG C.
The time of described reaction is 0.5～15h.As preferably, the time of described reaction is 0.5～3h.
There is advantages that
(1) oxidant used is copper nitrate, cheap and easy to get；
(2) have employed liquid-liquid two-phase extraction reaction system in the reaction, exist by non-polar solven
Selective extraction effect to product DFF in course of reaction so that reaction rate is accelerated,
Response time is greatly shortened；
(3) without using catalyst, reaction condition is gentle, and reaction temperature is relatively low, and reaction is at 0.5h
I.e. can complete, conversion ratio and the target product DFF of raw material 5 hydroxymethyl furfural can be made
Yield all more than 99%, and product is easily separated, and by-product is few, and reaction cost is low, has the biggest
Industrial application value.
Accompanying drawing explanation
Fig. 1 is the reaction mechanism figure that the present invention prepares 2,5-furan dicarbaldehyde.
Detailed description of the invention
The present invention prepares the reaction mechanism figure of DFF as it is shown in figure 1, in figure, n is 1～20
Integer.
The detection of target product DFF, DFF yield and HMF conversion ratio in following example are pressed
Method of stating measures:
(1) detection of target product DFF
Gas chromatograph (Agilent 7890) is carried out, with N2For carrier gas, hydrogen flame ion detects
Device detects, nonpolar capillary column (HP-5,30m × 0.32mm × 0.25 μm), sample size 0.4 μ L,
Inlet temperature 250 DEG C, detector temperature 260 DEG C, split ratio 1:10, column temperature uses programmed temperature method
(initial temperature 100 DEG C, with 5 DEG C of min-1Speed rise to 250 DEG C, and this temperature retain 10
Min), with dodecane as internal standard substance, use inner mark method ration.
(2) calculating of DFF yield
(3) calculating of HMF conversion ratio
Embodiment 1
Set to 0 .2g raw material 5 hydroxymethyl furfural, 0.36g oxidant Cu (NO3)2·3H2O is in 2.5mL
In the mixed solution of acetonitrile and 5mL water, be stirring evenly and then adding into 5mL toluene, temperature be 80 DEG C,
Reacting 8h under the conditions of speed of agitator 1200rpm, reaction terminates rear split-phase, and non-polar solven reduces pressure mutually
DFF crude product is obtained, with obtaining DFF essence after dichloromethane recrystallization after concentration
Product.
After testing, DFF yield is 99.6%, and 5 hydroxymethyl furfural conversion ratio is 99.6%.
Embodiment 2
Set to 0 .2g raw material 5 hydroxymethyl furfural, 0.36g oxidant Cu (NO3)2·3H2O is in 2.5mL
In the mixed solution of acetonitrile and 5mL water, it is stirring evenly and then adding into 5mL toluene, is 120 in temperature
DEG C, react 1h under the conditions of speed of agitator 1200rpm, reaction terminates rear split-phase, non-polar solven phase
DFF crude product is obtained after concentrating under reduced pressure, with obtaining 2 after dichloromethane recrystallization, 5-furan diformazan
Aldehyde fine work.
After testing, DFF yield is 85.3%, and 5 hydroxymethyl furfural conversion ratio is 95.9%.
Embodiment 3
Set to 0 .2g raw material 5 hydroxymethyl furfural, 0.36g oxidant Cu (NO3)2·3H2The dilute nitre of O, 0.1g
Acid (mass fraction of dust technology is 60%) in the mixed solution of 2.5mL acetonitrile and 5mL water,
Be stirring evenly and then adding into 5mL toluene, temperature be 80 DEG C, under the conditions of speed of agitator 1200rpm
Reaction 0.5h, reaction terminates rear split-phase, obtains DFF after non-polar solven phase concentrating under reduced pressure
Crude product, with obtaining DFF fine work after dichloromethane recrystallization.
After testing, DFF yield is 90.2%, and 5 hydroxymethyl furfural conversion ratio is 91.0%.
Embodiment 4
Water-acetonitrile reacted in embodiment 1 is added 0.1g dust technology mutually, and (quality of dust technology is divided
Number is 60%), add 0.2g raw material 5 hydroxymethyl furfural, be stirring evenly and then adding into 5mL toluene,
Being 80 DEG C in temperature, react 0.5h under the conditions of speed of agitator 1200rpm, reaction terminates rear split-phase,
Obtain DFF crude product after non-polar solven phase concentrating under reduced pressure, obtain with after dichloromethane recrystallization
2,5-furan dicarbaldehyde fine work.
After testing, DFF yield is 95.3%, and 5 hydroxymethyl furfural conversion ratio is 96.5%.
Embodiment 5
Set to 0 .2g raw material 5 hydroxymethyl furfural, 0.36g oxidant Cu (NO3)2·3H2O is in 2.5mL
In the mixed solution of acetonitrile and 5mL water, it is stirring evenly and then adding into 10mL toluene, is 80 in temperature
DEG C, react 0.5h under the conditions of speed of agitator 1200rpm, reaction terminates rear split-phase, non-polar solven
DFF crude product is obtained after phase concentrating under reduced pressure, with obtaining 2 after dichloromethane recrystallization, 5-furan two
Formaldehyde fine work.
After testing, DFF yield is 81.7%, and 5 hydroxymethyl furfural conversion ratio is 82.6%.
Embodiment 6
Set to 0 .2g raw material 5 hydroxymethyl furfural, 0.36g oxidant Cu (NO3)2·3H2O is in 2.5mL
In the mixed solution of acetonitrile and 5mL water, it is stirring evenly and then adding into 5mL dichloromethane, in temperature
Being 120 DEG C, react 0.5h under the conditions of speed of agitator 1200rpm, reaction terminates rear split-phase, non-pole
Property solvent phase concentrating under reduced pressure after DFF crude product, with after dichloromethane recrystallization 2,5-
Furan dicarbaldehyde fine work.
After testing, DFF yield is 70.6%, and 5 hydroxymethyl furfural conversion ratio is 71.2%.
Embodiment 7
Set to 0 .2g raw material 5 hydroxymethyl furfural, 0.36g oxidant Cu (NO3)2·3H2O is in 2.5mL
In the mixed solution of acetonitrile and 5mL water, it is stirring evenly and then adding into 5mL n-butyl alcohol, in temperature is
120 DEG C, react 0.5h under the conditions of speed of agitator 1200rpm, reaction terminates rear split-phase, nonpolar
DFF crude product is obtained after solvent phase concentrating under reduced pressure, with obtaining 2 after dichloromethane recrystallization, 5-furan
Dicarbaldehyde of muttering fine work.
After testing, DFF yield is 96.5%, and 5 hydroxymethyl furfural conversion ratio is 98.9%.
Embodiment 8
Set to 0 .8g raw material 5 hydroxymethyl furfural, 1.44g oxidant Cu (NO3)2·3H2O is in 10mL second
In the mixed solution of nitrile and 20mL water, it is stirring evenly and then adding into 20mL toluene, is 120 in temperature
DEG C, react 1h under the conditions of speed of agitator 1200rpm, reaction terminates rear split-phase, non-polar solven phase
DFF crude product is obtained after concentrating under reduced pressure, with obtaining 2 after dichloromethane recrystallization, 5-furan diformazan
Aldehyde fine work.
After testing, DFF yield is 96.5%, and 5 hydroxymethyl furfural conversion ratio is 97.3%.
Embodiment 9
Put 8g raw material 5 hydroxymethyl furfural, 14.4g oxidant Cu (NO3)2·3H2O is in 100mL second
In the mixed solution of nitrile and 200mL water, it is stirring evenly and then adding into 200mL toluene, in temperature is
120 DEG C, react 2h under the conditions of speed of agitator 1200rpm, reaction terminates rear split-phase, nonpolar molten
DFF crude product is obtained after agent phase concentrating under reduced pressure, with obtaining 2 after dichloromethane recrystallization, 5-furan
Dicarbaldehyde fine work.
After testing, DFF yield is 90.1%, and 5 hydroxymethyl furfural conversion ratio is 91.0%.
Embodiment 10
Put 2g raw material 5 hydroxymethyl furfural, 3.6g oxidant Cu (NO3)2·3H2O is in 25mL acetonitrile
With in the mixed solution of 50mL water, be stirring evenly and then adding into 50mL toluene, temperature be 120 DEG C,
Reacting 1h under mechanical agitation, reaction terminates rear split-phase, after non-polar solven phase concentrating under reduced pressure
DFF crude product, with obtaining DFF fine work after dichloromethane recrystallization.
After testing, DFF yield is 99.1%, and 5 hydroxymethyl furfural conversion ratio is 99.5%.
Embodiment 11
Put 8g raw material 5 hydroxymethyl furfural, 14.4g oxidant Cu (NO3)2·3H2O is in 100mL second
In the mixed solution of nitrile and 200mL water, it is stirring evenly and then adding into 200mL toluene, in temperature is
120 DEG C, react 2h under mechanical agitation, reaction terminates rear split-phase, and non-polar solven reduces pressure dense mutually
DFF crude product is obtained, with obtaining DFF fine work after dichloromethane recrystallization after contracting.
After testing, DFF yield is 97.3%, and 5 hydroxymethyl furfural conversion ratio is 97.9%.
Comparative example 1
Set to 0 .2g raw material 5 hydroxymethyl furfural, 0.36g oxidant Cu (NO3)2·3H2O is in 2.5mL
In the mixed solution of acetonitrile and 5mL water, it is 80 DEG C, speed of agitator 1200rpm condition in temperature
Lower reaction 18h, reaction terminates rear split-phase, obtains 2,5-furan two after non-polar solven phase concentrating under reduced pressure
Formaldehyde crude product, with obtaining DFF fine work after dichloromethane recrystallization.
After testing, DFF yield is 89.9%, and 5 hydroxymethyl furfural conversion ratio is 90.2%.
Comparative example 2
Set to 0 .2g raw material 5 hydroxymethyl furfural, 0.36g oxidant Cu (NO3)2·3H2O is in 5mL first
In the mixed solution of benzene and 5mL water, temperature be 80 DEG C, under the conditions of speed of agitator 1200rpm
Reaction 8h, reaction terminates rear split-phase, obtains DFF after non-polar solven phase concentrating under reduced pressure
Crude product, with obtaining DFF fine work after dichloromethane recrystallization.
After testing, DFF yield is 16.2%, and 5 hydroxymethyl furfural conversion ratio is 98.7%.
By comparative example 1, use liquid-liquid two-phase reaction system, reaction rate can be made to accelerate,
Shorten the response time.By comparative example 2, acetonitrile plays an important role in the reaction, uses water
When/toluene two-phase reaction system reacts, DFF yield substantially reduces.Use water-
Acetonitrile/non-polar solven two-phase reaction system, it is not necessary to use catalyst, reaction condition is gentle, oxidant
Inexpensively, the conversion ratio of 5 hydroxymethyl furfural and the yield of DFF all can more than 99%,
It is easily isolated and purifies.There is higher industrial value.
Claims (8)
1. the preparation method of a DFF, it is characterised in that including: with 5-methylol
Furfural is raw material, and copper nitrate is oxidant, makes in water-acetonitrile/non-polar solven two-phase reaction system
Obtain 2,5-furan dicarbaldehyde.
The preparation method of DFF the most according to claim 1, it is characterised in that
The dosage of described oxidant is the 60～240% of 5 hydroxymethyl furfural quality.
The preparation method of DFF the most according to claim 1, it is characterised in that
In reaction system, the concentration of 5 hydroxymethyl furfural is 10～25g/L.
The preparation method of DFF the most according to claim 1, it is characterised in that
In described two-phase reaction system, the volume ratio of acetonitrile, water and non-polar solven is: 25～150:
300～700:300～700.
The preparation method of DFF the most according to claim 1, it is characterised in that
Described non-polar solven is dimethylbenzene, isopropylbenzene, biphenyl, dichloromethane, methyl iso-butyl ketone (MIBK), just
At least one of butanol and toluene.
The preparation method of DFF the most according to claim 5, it is characterised in that
Described non-polar solven is toluene.
The preparation method of DFF the most according to claim 1, it is characterised in that
The temperature of described reaction is 50～180 DEG C.
The preparation method of DFF the most according to claim 1, it is characterised in that
The time of described reaction is 0.5～15h.
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| CN110452195A (en) * | 2019-09-03 | 2019-11-15 | 河北工业大学 | A kind of method that 5 hydroxymethyl furfural dehydrogenation prepares 2,5- furans dicarbaldehyde |
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Cited By (3)
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| 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 |
| CN110452195A (en) * | 2019-09-03 | 2019-11-15 | 河北工业大学 | A kind of method that 5 hydroxymethyl furfural dehydrogenation prepares 2,5- furans dicarbaldehyde |
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