CN104193703B - FeCl is used in containing dark common melt and dissolved dose of HACC 3the method of 5-2 '-hydroxyethyl oxygen methyl furfural is prepared in catalysis - Google Patents
FeCl is used in containing dark common melt and dissolved dose of HACC 3the method of 5-2 '-hydroxyethyl oxygen methyl furfural is prepared in catalysis Download PDFInfo
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- CN104193703B CN104193703B CN201410337076.3A CN201410337076A CN104193703B CN 104193703 B CN104193703 B CN 104193703B CN 201410337076 A CN201410337076 A CN 201410337076A CN 104193703 B CN104193703 B CN 104193703B
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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
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Abstract
The present invention relates to and a kind ofly using FeCl in melt and dissolved dose altogether containing the dark of HACC
3the method of 5-2 '-hydroxyethyl oxygen methyl furfural is prepared in catalysis, belongs to green organic synthesis field, and described dark common melt and dissolved dose is made up of HACC and ethylene glycol, and 5-2 '-hydroxyethyl oxygen methyl furfural is by FeCl
3dark altogether in melt and dissolved dose catalysis D-Fructose obtain, in the present invention, HACC is nontoxic, and have good biocompatibility and the performance such as biodegradable and low price, the dark melt and dissolved dose of synthesis technique altogether formed with ethylene glycol is simple, stable chemical nature; The 5-2 ' transformed by D-Fructose-hydroxyethyl oxygen methyl furfural, its productive rate reaches as high as 70.8%; Present method is not only simple, environmental protection, and with low cost.
Description
Technical field
The invention belongs to green organic synthesis field, be specifically related to a kind ofly using FeCl in melt and dissolved dose altogether containing the dark of HACC
3the method of 5-2 '-hydroxyethyl oxygen methyl furfural is prepared in catalysis.
Background technology
In recent years due to the minimizing of fossil fuel reserves, the requirement of social sustainable development can not be met
[1], the biomass resource large, renewable by resource quantity, cost is low has caused the great attention of people as the substitute of the existing energy
[2].Therefore, the biomass resource that exploitation is enriched just becomes the mankind and tackles one of effective way of fossil resource exhaustion and the deterioration of the ecological environment, is the development trend that chemical industrial product has become chemical industry by Wood Adhesives from Biomass.Derivative the 5-2 '-hydroxyethyl oxygen methyl furfural of 5 hydroxymethyl furfural (5-HMF) is that important industrial chemicals can be used as excellent fuel dope, adopt fructose, glucose and biomass etc. are converted into the research of 5-HMF by extensive concern, particularly prepare 5-HMF to have selectivity high using ionic liquid as reaction solvent, reaction conditions is gentle, the advantages such as the fast and side reaction of speed of reaction is less, but due to the complicated process of preparation of ionic liquid own, and a large amount of organic solvent used not only causes environmental pollution, and involve great expense, reclaim difficulty, be unfavorable for industrial application, therefore, develop nontoxic, inexpensive green solvent is a very important problem for biochemical
[3].
The dark melt and dissolved dose of a kind of novel dissolvent being developed recently and getting up altogether, character and ionic liquid similar.Dark altogether melt and dissolved dose not only there is the advantage similar to ionic liquid, as good chemical stability, designability with can be recycled, also there is synthesis technique simple, the advantages such as environmental protection.Therefore, " the green solvent that melt and dissolved dose is considered to the alternative volatile organic solvent of equal importance with ionic liquid is deeply total to
[4-6].
At present, about the dark melt and dissolved dose of research preparing 5-2 '-hydroxyethyl oxygen methyl furfural as reaction solvent altogether yet there are no report.
[1]HuS,ZhangZ,ZhauY,etal.Conversionoffructoseto5-hydroxymethylfurfuralusingionicliquidspreparedfromrenewablematerials.GreenChem.,2008,10:1280-1283.
[2]ShiCY,ZhaoYL,XinJY,etal.Effectsofcationsandanionsofionicliquidsontheproductionof5-hydroxymethylfurfuralfromfructose.Chem.Commun.,2012,48,4103-4105.
[3]RuβC,KonigB,Lowmeltingmixturesinorganicsynthesis–analternativetoionicliquids？GreenChem.,2012,14,2969-2982.
[4]ZhangQH,VigierKO,RoyerS,etal.Deepeutecticsolvents:syntheses,propertiesandapplications.Chem.Soc.Rev.,2012,41:7108-7146.
[5]FranciscoM,BruinhorstA,KroomMC.Low-transition-temperaturemixtures(LTTMs):anewgenerationofdesignersolvents.Angew.Chem.Int.Ed.2013,52:2-14.
[6]VigierKO,BenguerbaA,BarraultJ,etal.Conversionoffructoseandinulinto5-hydroxymethylfurfuralinsustainablebetainehydrochloride-basedmedia.GreenChem.,2012,14:285-289.
Summary of the invention
Ionic liquid can cause environmental pollution in building-up process, reclaim the problems such as difficulty, be unfavorable for industrial application, when using ionic liquid to prepare the derivative of 5-HMF, its complicated process of preparation, cost are high, and the present invention solves the problem to provide a kind ofly using FeCl in melt and dissolved dose altogether containing the dark of HACC
3the method of 5-2 '-hydroxyethyl oxygen methyl furfural is prepared in catalysis, uses the 2-HACC (HACC) of environmental protection and dark melt and dissolved dose altogether of ethylene glycol composition, at FeCl
3prepare 5-2 '-hydroxyethyl oxygen methyl furfural by D-Fructose under katalysis, not only technique is simple, and stable chemical nature also effectively reduces costs.
Technical solution of the present invention is as follows: a kind ofly using FeCl in melt and dissolved dose altogether containing the dark of HACC
3the method of 5-2 '-hydroxyethyl oxygen methyl furfural is prepared in catalysis, and described dark common melt and dissolved dose is made up of HACC and ethylene glycol, and described 5-2 '-hydroxyethyl oxygen methyl furfural is by FeCl
3in being deeply total to melt and dissolved dose, catalysis D-Fructose obtains.
The method comprises the following steps:
(1) form dark melt and dissolved dose altogether by HACC and ethylene glycol, wherein the concentration of HACC in ethylene glycol is 0.07g/ml ~ 0.464g/ml, then is joined by D-Fructose and deeply obtain solution I in melt and dissolved dose altogether;
(2) in above-mentioned solution I, FeCl is added
3obtain reaction solution, FeCl
3be 0.08 ~ 0.2 with the mol ratio of D-Fructose;
(3) by gained reaction solution heated and stirred at temperature is 110 ~ 130 DEG C in step (2), heat-up time, 2 ~ 6h, obtained solution II;
(4), after reaction terminates, in above-mentioned solution II, add distilled water, then be extracted with ethyl acetate the aqueous solution, obtain ethyl acetate layer;
(5) concentrating extracting the ethyl acetate layer obtained, obtaining product.
Further, describedly FeCl is being used in melt and dissolved dose altogether containing the dark of HACC
3the method of 5-2 '-hydroxyethyl oxygen methyl furfural is prepared in catalysis, comprise the following steps: form dark melt and dissolved dose altogether by HACC and 5.6ml ethylene glycol, the concentration of HACC in ethylene glycol is 0.114g/ml, by 0.01molD-fructose, join in being deeply total to melt and dissolved dose and obtain solution I, in above-mentioned solution I, add 1.7 × 10
-3molFeCl
3obtain reaction solution, by reaction solution heated and stirred at 130 DEG C, heat-up time, 3h, obtained solution II, after reaction terminates, adds distilled water, then be extracted with ethyl acetate the aqueous solution in above-mentioned solution II, concentrating, obtaining product by extracting the ethyl acetate layer obtained.When calculating productive rate, take 0.0225g enriched material and use 50ml acetonitrile constant volume, and using high-efficient liquid phase chromatogram technique analysis.
When the present invention efficiently solves in prior art and uses ionic liquid to prepare the derivative of 5-HMF, processing method is complicated, high in cost of production problem; Adopt nontoxic, inexpensive, HACC and the ethylene glycol with good biocompatibility and the performance such as biodegradable form dark melt and dissolved dose altogether, and synthesis technique is simple, stable chemical nature, the 5-HMF derivative 5-2 ' transformed by D-Fructose-hydroxyethyl oxygen methyl furfural, its productive rate reaches as high as 70.8%; Present method not only environmental protection, with low cost and simple.
Accompanying drawing explanation
Fig. 1 is the high efficiency liquid phase chromatographic analysis method spectrogram of embodiment 8.
Embodiment
For understanding the present invention further, with the following Examples embodiment of the present invention is described.
Embodiment 1
D-Fructose (1.80g, 0.01mol) is added, FeCl in 5.6ml ethylene glycol
3(0.16g, 1 × 10
-3mol), HACC1.71g, makes reaction solution heated and stirred at 130 DEG C, heat-up time 3h.After reaction terminates, add 20ml distilled water, three extraction water solution are divided again by ethyl acetate, each consumption 50ml, concentrate extracting the ethyl acetate layer obtained, take 0.0225g enriched material and with 50ml acetonitrile constant volume, calculate the productive rate of 5-2 '-hydroxyethyl oxygen methyl furfural with high-efficient liquid phase technique analysis, its productive rate is 13.1%.
Embodiment 2
D-Fructose (1.80g, 0.01mol) is added, FeCl in 5.6ml ethylene glycol
3(0.27g, 1.7 × 10
-3mol), HACC1.71g, makes reaction solution heated and stirred at 130 DEG C, heat-up time 3h.After reaction terminates, add 20ml distilled water, three extraction water solution are divided again by ethyl acetate, each consumption 50ml, concentrate extracting the ethyl acetate layer obtained, take 0.0225g enriched material and with 50ml acetonitrile constant volume, calculate the productive rate of 5-2 '-hydroxyethyl oxygen methyl furfural with high-efficient liquid phase technique analysis, its productive rate is 16.1%.
Embodiment 3
D-Fructose (1.80g, 0.01mol) is added, FeCl in 5.6ml ethylene glycol
3(0.27g, 1.7 × 10
-3mol), HACC1.71g, makes reaction solution heated and stirred at 130 DEG C, heat-up time 4h.After reaction terminates, add 20ml distilled water, three extraction water solution are divided again by ethyl acetate, each consumption 50ml, concentrate extracting the ethyl acetate layer obtained, take 0.0225g enriched material and with 50ml acetonitrile constant volume, calculate the productive rate of 5-2 '-hydroxyethyl oxygen methyl furfural with high-efficient liquid phase technique analysis, its productive rate is 16.5%.
Embodiment 4
D-Fructose (1.80g, 0.01mol) is added, FeCl in 5.6ml ethylene glycol
3(0.27g, 1.7 × 10
-3mol), HACC1.71g, makes reaction solution heated and stirred at 110 DEG C, heat-up time 3h.After reaction terminates, add 20ml distilled water, three extraction water solution are divided again by ethyl acetate, each consumption 50ml, concentrate extracting the ethyl acetate layer obtained, take 0.0225g enriched material and with 50ml acetonitrile constant volume, calculate the productive rate of 5-2 '-hydroxyethyl oxygen methyl furfural with high-efficient liquid phase technique analysis, its productive rate is 4.5%.
Embodiment 5
D-Fructose (1.80g, 0.01mol) is added, FeCl in 5.6ml ethylene glycol
3(0.27g, 1.7 × 10
-3mol), HACC1.71g, makes reaction solution heated and stirred at 120 DEG C, heat-up time 3h.After reaction terminates, add 20ml distilled water, three extraction water solution are divided again by ethyl acetate, each consumption 50ml, concentrate extracting the ethyl acetate layer obtained, take 0.0225g enriched material and with 50ml acetonitrile constant volume, calculate the productive rate of 5-2 '-hydroxyethyl oxygen methyl furfural with high-efficient liquid phase technique analysis, its productive rate is 12%.
Embodiment 6
D-Fructose (1.80g, 0.01mol) is added, FeCl in 5.6ml ethylene glycol
3(0.27g, 1.7 × 10
-3mol), HACC0.40g, makes reaction solution heated and stirred at 130 DEG C, heat-up time 3h.After reaction terminates, add 20ml distilled water, three extraction water solution are divided again by ethyl acetate, each consumption 50ml, concentrate extracting the ethyl acetate layer obtained, take 0.0225g enriched material and with 50ml acetonitrile constant volume, calculate the productive rate of 5-2 '-hydroxyethyl oxygen methyl furfural with high-efficient liquid phase technique analysis, its productive rate is 70.6%.
Embodiment 7
D-Fructose (1.80g, 0.01mol) is added, FeCl in 5.6ml ethylene glycol
3(0.27g, 1.7 × 10
-3mol), HACC2.60g, makes reaction solution heated and stirred at 130 DEG C, heat-up time 3h.After reaction terminates, add 20ml distilled water, three extraction water solution are divided again by ethyl acetate, each consumption 50ml, concentrate extracting the ethyl acetate layer obtained, take 0.0225g enriched material and with 50ml acetonitrile constant volume, calculate the productive rate of 5-2 '-hydroxyethyl oxygen methyl furfural with high-efficient liquid phase technique analysis, its productive rate is 4.9%.
Embodiment 8
D-Fructose (1.80g, 0.01mol) is added, FeCl in 5.6ml ethylene glycol
3(0.27g, 1.7 × 10
-3mol), HACC0.64g, makes reaction solution heated and stirred at 130 DEG C, heat-up time 3h.After reaction terminates, add 20ml distilled water, three extraction water solution are divided again by ethyl acetate, each consumption 50ml, concentrate extracting the ethyl acetate layer obtained, take 0.0225g enriched material and use 50ml acetonitrile constant volume, the productive rate of 5-2 '-hydroxyethyl oxygen methyl furfural is calculated with high-efficient liquid phase technique analysis, HPLC condition: reverse-phase chromatographic column C18 (2.1 × 150mm), moving phase is the aqueous acetic acid volume ratio of methyl alcohol: 1wt% is 5:95, flow velocity is 0.2ml/min, and sample feeding amount is 20 μ l; The retention time of target product is 5.77min, and calculating its productive rate is 70.8%.
Claims (2)
1. in containing dark common melt and dissolved dose of HACC, use FeCl for one kind
3the method of 5-2 '-hydroxyethyl oxygen methyl furfural is prepared in catalysis, it is characterized in that, comprises the following steps:
(1) form dark melt and dissolved dose altogether by HACC and ethylene glycol, wherein the concentration of HACC in ethylene glycol is 0.07g/ml ~ 0.464g/ml, then is joined by D-Fructose and deeply obtain solution I in melt and dissolved dose altogether;
(2) in above-mentioned solution I, FeCl is added
3obtain reaction solution, FeCl
3be 0.08 ~ 0.2 with the mol ratio of D-Fructose;
(3) by gained reaction solution heated and stirred at temperature is 110 ~ 130 DEG C in step (2), heat-up time, 2 ~ 6h, obtained solution II;
(4), after reaction terminates, in above-mentioned solution II, add distilled water, then be extracted with ethyl acetate the aqueous solution, obtain ethyl acetate layer;
(5) concentrating extracting the ethyl acetate layer obtained, obtaining product.
2. according to claim 1ly using FeCl in melt and dissolved dose altogether containing the dark of HACC
3the method of 5-2 '-hydroxyethyl oxygen methyl furfural is prepared in catalysis, it is characterized in that, comprise the following steps: form dark melt and dissolved dose altogether by HACC and 5.6ml ethylene glycol, the concentration of HACC in ethylene glycol is 0.114g/ml, by 0.01molD-fructose, join in being deeply total to melt and dissolved dose and obtain solution I, in above-mentioned solution I, add 1.7 × 10
-3molFeCl
3obtain reaction solution, by reaction solution heated and stirred at 130 DEG C, heat-up time, 3h, obtained solution II, after reaction terminates, adds distilled water, then be extracted with ethyl acetate the aqueous solution in above-mentioned solution II, concentrating, obtaining product by extracting the ethyl acetate layer obtained.
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| CN201410337076.3A CN104193703B (en) | 2014-07-15 | 2014-07-15 | FeCl is used in containing dark common melt and dissolved dose of HACC 3the method of 5-2 '-hydroxyethyl oxygen methyl furfural is prepared in catalysis |
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| CN201410337076.3A CN104193703B (en) | 2014-07-15 | 2014-07-15 | FeCl is used in containing dark common melt and dissolved dose of HACC 3the method of 5-2 '-hydroxyethyl oxygen methyl furfural is prepared in catalysis |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2033958A1 (en) * | 2007-09-07 | 2009-03-11 | Furanix Technologies B.V | Hydroxymethylfurfural ethers from sugars and di- and triols |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2033958A1 (en) * | 2007-09-07 | 2009-03-11 | Furanix Technologies B.V | Hydroxymethylfurfural ethers from sugars and di- and triols |
Non-Patent Citations (1)
| Title |
|---|
| 《Conversion of xylose and xylan into furfural in biorenewable choline chloride–oxalic acid deep eutectic solvent with the addition of metal chloride》;Lu-Xin Zhang et.al;《 Chinese Chemical Letters》;20140327;第25卷;1132-1136 * |
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