CN108658904A - A method of preparing 5- ethoxymethyl furfurals using glucose - Google Patents
A method of preparing 5- ethoxymethyl furfurals using glucose Download PDFInfo
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- CN108658904A CN108658904A CN201810543431.0A CN201810543431A CN108658904A CN 108658904 A CN108658904 A CN 108658904A CN 201810543431 A CN201810543431 A CN 201810543431A CN 108658904 A CN108658904 A CN 108658904A
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- glucose
- ethoxymethyl
- furfurals
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 40
- 239000008103 glucose Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000004411 aluminium Substances 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 230000002195 synergetic effect Effects 0.000 claims abstract description 15
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 15
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 12
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000006184 cosolvent Substances 0.000 claims abstract description 5
- 239000007848 Bronsted acid Substances 0.000 claims description 7
- 239000002841 Lewis acid Substances 0.000 claims description 6
- 150000007517 lewis acids Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 3
- CCDRPZFMDMKZSZ-UHFFFAOYSA-N 5-(ethoxymethyl)furan-2-carbaldehyde Chemical compound CCOCC1=CC=C(C=O)O1 CCDRPZFMDMKZSZ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 abstract 2
- 239000012429 reaction media Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 229930091371 Fructose Natural products 0.000 description 4
- 239000005715 Fructose Substances 0.000 description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 4
- 206010043087 Tachyphylaxis Diseases 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- -1 glucose Aldehyde Chemical class 0.000 description 2
- 239000002035 hexane extract Substances 0.000 description 2
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000009229 glucose formation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0228—Sulfur-containing compounds with a metal-sulfur link, e.g. mercaptides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
Abstract
The invention discloses a kind of methods preparing 5 ethoxymethyl furfurals using glucose, this method is using glucose as reaction substrate, using the total solution system that absolute ethyl alcohol dimethyl sulfoxide (DMSO) forms as reaction medium, using the combination of trifluoromethanesulfonic acid aluminium and ion exchange resin Amberlyst 15 as synergistic catalyst, to form conversion reaction system, it is reacted at 140~160 DEG C of temperature and 5 ethoxymethyl furfurals is made, addition dimethyl sulfoxide (DMSO) can effectively inhibit the generation of side reaction as cosolvent, make glucose that can be converted to 5 ethoxymethyl furfural of target product with high selectivity, highest yield is up to 48.8%；The preparation method is simple and effective, catalyst is easily recycled and reuses, using derive from a wealth of sources, cheap glucose is as reaction raw materials, high financial profit has good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of methods preparing 5- ethoxymethyl furfurals, more particularly to are total to solution in ethyl alcohol-organic solvent
In system, using the combination of lewis acid and bronsted acid as synergistic catalyst, 5- ethoxymethyl chaffs are prepared using glucose
Aldehyde belongs to fine chemicals preparing technical field.
Background technology
With gradually decreasing for non-renewable fossil fuel reserves, environmental pollution and global warming increasingly aggravate, profit
Preparing chemicals and fuel with renewable biomass resources has own strategic significance.5- ethoxymethyl furfurals are considered a kind of
Important biomass-based platform chemicals can be used for producing a variety of high level chemical products and high-quality liquid fuel.In recent years, it
Preparation and application cause the more and more extensive concern of researcher.5- ethoxymethyl furfurals have good oxidation stability
With higher 16 octane number, its energy density reaches 8.7 kW h/L, the energy density (8.8 for the gasoline that is near the mark
kW• h/L）, it is far above bio-ethanol（6.1 kW• h /L）, these characteristics determine that it can be used as excellent potential replacement combustion
Material or fuel additive, are expected to play a significant role in the alternative energy source of rare-view set-up.Meanwhile it possesses as fuel
High oxidation stability can reduce the discharge of flue dust, oxysulfide and nitrogen oxides, and environmental benefit is good, be a kind of clean new
Type bio-fuel.In addition, 5- ethoxymethyls furfural also has good chemical reactivity, it can be used as chemical intermediate and synthesize it
Its industrial staple product, such as cyclopentenone.
About the synthesis of 5- ethoxymethyl furfurals, most simply, 5 hydroxymethyl furfural is straight under acid catalysis with ethyl alcohol
5- ethoxymethyl furfurals can be generated by connecing etherificate, and can get up to 90% or more product yield（Fuel, 2014, 117:
68–73）.However, being limited to the limitations such as the high cost of 5 hydroxymethyl furfural, directly using abundant cheap glucide（If
Sugar, glucose, sucrose etc.）As one pot of selectivity synthesis 5- ethoxymethyls furfural of raw material obviously have more competitive advantage, also by
Scientific research personnel more concern and payes attention to.Existing numerous studies show that fructose is urged in ethanol system by specific acid at present
Change efficiently can directly be converted into 5- ethoxymethyl furfurals.In addition, synanthrin is as a kind of natural fructose polymer, same energy
Effectively direct Synthesis 5- ethoxymethyl furfurals.At present in the preparation process of 5- ethoxyl methyl furfurals, there are equipment
The a series of problems such as corrosion, catalyst preparation process is complicated, production cost is high, recycling is difficult, and side reaction is more.
Glucose is a kind of more rich, more cheap biomass material, is to produce biomass chemicals most research significance
One of with the raw material of development potentiality.Therefore, from the angle of economical and practical feasibility, directly glucose is utilized to prepare 5- ethoxies
Methyl furfural undoubtedly more with prospects and advantage are the important channels of scale exploitation 5- ethoxymethyl furfural products.With with
Fructose is compared as reaction raw materials, and direct transforming glucose is more difficult at 5- ethoxymethyl furfurals, and this is mainly due to head
First need glucose energy isomery at fructose, presently relevant effective research report is very few, and product yield only can reach 30% or so.
It can be seen that developing a kind of method that the direct transforming glucose of economical and efficient prepares 5- ethoxymethyl furfurals has important meaning
Justice provides Technical Reference to industrialize practical application for it.
Invention content
The purpose of the present invention is to provide a kind of direct method for preparing 5- ethoxymethyl furfurals using glucose, the present invention
The multi-functional concerted catalysis system that lewis acid combines bronsted acid is built under high relative humidity environment, can guarantee grape in this way
Sugared isomerization and subsequent reactions can be effectively performed, to for high selectivity 5- ethoxymethyl furfurals provide it is necessary before
Phase condition.Cosolvent system then is formed with absolute ethyl alcohol by adulterating specific aprotonic polar organic matter, formation can stablize guarantor
Protect product 5- ethoxymethyls furfural from degradation solvent adjustment and control system, make its selectivity synthesis even promote this directly react into
Row, to which structure can strengthen the Effective Regulation approaches and methods that glucose directly converts selectivity synthesis 5- ethoxymethyl furfurals.
The method of the present invention specifically comprises the following steps：
Using glucose as reaction substrate, in the cosolvent system of absolute ethyl alcohol-organic solvent, lewis acid and Bu Langsi is added
Special acid is used as synergistic catalyst, reacts while stirring, wherein stir speed (S.S.) be 700~900r/min, reaction temperature be 140~
160 DEG C, 4~10h of reaction time；After the completion of reaction, target product 5- ethoxymethyl furfurals, synergistic catalyst recycling used are obtained
Recycling.
The molar concentration of the reaction substrate glucose is 0.05~0.2mol/L.
The organic solvent is dimethyl sulfoxide (DMSO), and the volume ratio of absolute ethyl alcohol and dimethyl sulfoxide (DMSO) is 7:3~5:5.
The lewis acid is trifluoromethanesulfonic acid aluminium, and dosage is 0.025~0.07mol/L；It is bronsted acid for from
Sub-exchange resin Amberlyst 15, dosage are 2~14g/L.
The synergistic catalyst recycles and reuses method and is cooled to room temperature for reaction solution, is first separated by filtration to obtain Bu Langsi
Special acid and liquid substance, bronsted acid are reused after drying；Liquid substance is through being repeatedly distilled off low boiling point in system
Substance（Ethyl alcohol）, it is used in combination hexane to extract, collects hexane extract layer and distill to obtain 5- ethoxymethyl furfurals and slightly carry product；After extraction
Subnatant dimethyl sulfoxide (DMSO) and lewis acid mixed system are directly reused.
Beneficial effects of the present invention are：
With simple and high catalytic activity lewis acid catalyst trifluoromethanesulfonic acid aluminium and bronsted acid catalyst ion exchange
Resin A mberlyst 15 is used as synergistic catalyst, can stablize production at a relatively high temperature by the way that organic solvent dimethyl sulfoxide (DMSO) is added
Object 5- ethoxymethyl furfurals, effectively inhibit side reaction, effectively increase target product 5- ethoxymethyl furaldehyde yields, reaction
Spent acid is few afterwards, is easily processed, and environmental pollution is small, and catalyst easily recycles, and can significantly reduce being produced into for 5- ethoxymethyl furfurals
This, increases economic efficiency, has good prospects for commercial application.
Description of the drawings
Fig. 1 is the recycling process schematic of synergistic catalyst.
Specific implementation mode
With reference to embodiment, invention is further described in detail, but the scope of the present invention is not limited in described
Hold.
Embodiment 1：This utilizes the method that glucose prepares 5- ethoxymethyl furfurals, specifically comprises the following steps：
Using glucose as substrate, trifluoromethanesulfonic acid aluminium and ion exchange resin Amberlyst 15 are used as synergistic catalyst, add
Enter in the stainless steel autoclave equipped with 5mL absolute ethyl alcohols and 5mL dimethyl sulfoxide (DMSO)s, passes through magnetic at 150 DEG C of oil bath temperature
Power is stirred with the tachyphylaxis 8.2h of 800r/min, is waited for after reaction, immerses in cold water reaction kettle cool down immediately, reaction kettle
After temperature is down to room temperature, reaction mixture filters and collects filtrate, high performance liquid chromatograph（HPLC）Target is calculated in analysis
Product 5- ethoxymethyl furaldehyde yields are 48.8%, and wherein the additive amount of glucose is 0.2mol/L, trifluoromethanesulfonic acid aluminium dosage
Dosage for 0.052mol/L, ion exchange resin Amberlyst 15 is 5.56g/L.
The method that synergistic catalyst system recycles and reuses is：Reaction mixture filters and collects filtrate, filter residue be from
Sub-exchange resin Amberlyst 15, is reused after drying；Filtrate is through being repeatedly distilled off low-boiling point material second in system
Then alcohol is extracted with hexane, obtaining 5- ethoxymethyl furfurals after collection hexane extract layer distillation slightly carries product；Lower layer after extraction
Liquid dimethyl sulfoxide (DMSO) and trifluoromethanesulfonic acid aluminium mixed system are directly reused, and specific steps are as shown in Figure 1.Caltalyst ties up to
Reuse experiment specific steps in the reaction of glucose Synthesis 5- ethoxymethyl furfurals and the same embodiment of reaction condition
1, the results are shown in Table 1 for reuse；
Table 1：The reuse effect of synergistic catalyst
From table 1 it follows that the catalyst system and catalyzing is after recycling three times, the conversion ratio and 5- ethoxymethyl chaffs of glucose
The yield of aldehyde is held essentially constant, and illustrates that the catalyst system and catalyzing can be recycled, and its catalytic activity is not substantially reduced.
Embodiment 2：This utilizes the method that glucose prepares 5- ethoxymethyl furfurals, specifically comprises the following steps：
Using glucose as substrate, trifluoromethanesulfonic acid aluminium and ion exchange resin Amberlyst 15 are used as synergistic catalyst, add
Enter in the stainless steel autoclave equipped with 7mL absolute ethyl alcohols and 3mL dimethyl sulfoxide (DMSO)s, passes through magnetic at 160 DEG C of oil bath temperature
Power is stirred with the tachyphylaxis 5h of 700r/min, is waited for after reaction, immerses in cold water reaction kettle cool down immediately, react kettle temperature
After degree is down to room temperature, reaction mixture filters and collects filtrate, high performance liquid chromatograph（HPLC）Target production is calculated in analysis
Object 5- ethoxymethyl furaldehyde yields are 41.1%, and the wherein additive amount of glucose is 0.1mol/L, and trifluoromethanesulfonic acid aluminium dosage is
The dosage of 0.03mol/L, ion exchange resin Amberlyst 15 are 10g/L.
Embodiment 3：This utilizes the method that glucose prepares 5- ethoxymethyl furfurals, specifically comprises the following steps：
Using glucose as substrate, trifluoromethanesulfonic acid aluminium and ion exchange resin Amberlyst 15 are used as synergistic catalyst, add
Enter in the stainless steel autoclave equipped with 6mL absolute ethyl alcohols and 4mL dimethyl sulfoxide (DMSO)s, passes through magnetic at 140 DEG C of oil bath temperature
Power is stirred with the tachyphylaxis 10h of 900r/min, is waited for after reaction, immerses in cold water reaction kettle cool down immediately, reaction kettle
After temperature is down to room temperature, reaction mixture filters and collects filtrate, high performance liquid chromatograph（HPLC）Target is calculated in analysis
Product 5- ethoxymethyl furaldehyde yields are 38.5%, and wherein the additive amount of glucose is 0.05 mol/L, and trifluoromethanesulfonic acid aluminium is used
Amount is 0.07mol/L, and the dosage of ion exchange resin Amberlyst 15 is 13g/L.
Embodiment 4：This utilizes the method that glucose prepares 5- ethoxymethyl furfurals, specifically comprises the following steps：
Using glucose as substrate, trifluoromethanesulfonic acid aluminium and ion exchange resin Amberlyst 15 are used as synergistic catalyst, add
Enter in the stainless steel autoclave equipped with 5mL absolute ethyl alcohols and 5mL dimethyl sulfoxide (DMSO)s, passes through magnetic at 140 DEG C of oil bath temperature
Power is stirred with the tachyphylaxis 9h of 800r/min, is waited for after reaction, immerses in cold water reaction kettle cool down immediately, react kettle temperature
After degree is down to room temperature, reaction mixture filters and collects filtrate, high performance liquid chromatograph（HPLC）Target production is calculated in analysis
Object 5- ethoxymethyl furaldehyde yields are 41.5%, and the wherein additive amount of glucose is 0.15mol/L, and trifluoromethanesulfonic acid aluminium dosage is
The dosage of 0.045mol/L, ion exchange resin Amberlyst 15 are 5g/L.
Embodiment 5:Contrast experiment
The method for directly utilizing glucose to prepare 5- ethoxymethyl furfurals described in the present embodiment, specific steps are different with embodiment 1
It is that only spent ion exchange resin Amberlyst 15 is used as catalyst, passes through high performance liquid chromatograph（HPLC）Analysis calculates
It is 0.92% to target product 5- ethoxymethyl furaldehyde yields.
Embodiment 6：Contrast experiment
The method for directly utilizing glucose to prepare 5- ethoxymethyl furfurals described in the present embodiment, specific steps are different with embodiment 1
It is only to use trifluoromethanesulfonic acid aluminium as catalyst, passes through high performance liquid chromatograph（HPLC）Target product is calculated in analysis
5- ethoxymethyl furaldehyde yields are 20.63%.
Embodiment 7：Contrast experiment
The method for directly utilizing glucose to prepare 5- ethoxymethyl furfurals described in the present embodiment, specific steps are different with embodiment 1
It is, using 10mL absolute ethyl alcohols as single dicyandiamide solution, to pass through high performance liquid chromatograph（HPLC）Target product is calculated in analysis
5- ethoxymethyl furaldehyde yields are 0.92%.
Above-described embodiment is the result shows that in absolute ethyl alcohol-dimethyl sulfoxide (DMSO) mixed system, trifluoromethanesulfonic acid aluminium and ion
Exchanger resin Amberlyst 15 be used as synergistic catalyst, to glucose one kettle way convert prepare 5- ethoxymethyl furfurals have compared with
Good catalytic effect, in addition, by that can be obtained with the comparison of contrast experiment 7, addition dimethyl sulfoxide (DMSO) can be opposite as cosolvent
High temperatures product 5- ethoxymethyl furfurals, effectively increase target product 5- ethoxymethyl furaldehyde yields.
Claims (4)
1. a kind of method preparing 5- ethoxymethyl furfurals using glucose, it is characterised in that：Using glucose as reaction substrate,
In the cosolvent system of absolute ethyl alcohol-organic solvent, lewis acid is added and bronsted acid is used as synergistic catalyst, side stirring
Side is reacted, and wherein stir speed (S.S.) is 700~900r/min, reaction temperature is 140~160 DEG C, 4~10h of reaction time；It has reacted
Cheng Hou obtains target product 5- ethoxymethyl furfurals.
2. the method according to claim 1 for preparing 5- ethoxymethyl furfurals using glucose, it is characterised in that：React bottom
The additive amount of object glucose is 0.05~0.2mol/L.
3. the method according to claim 1 for preparing 5- ethoxymethyl furfurals using glucose, it is characterised in that：It is organic molten
Agent is dimethyl sulfoxide (DMSO), and the volume ratio of absolute ethyl alcohol and dimethyl sulfoxide (DMSO) is 7:3~5:5.
4. the method according to claim 1 for preparing 5- ethoxymethyl furfurals using glucose, it is characterised in that：Louis
Acid is trifluoromethanesulfonic acid aluminium, and dosage is 0.025~0.07mol/L；Bronsted acid is ion exchange resin Amberlyst
15, dosage is 2~14g/L.
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