CN105669610A - Method for preparing 5-hydroxymethylfurfural (5-HMF) by converting galactose - Google Patents

Method for preparing 5-hydroxymethylfurfural (5-HMF) by converting galactose Download PDF

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Publication number
CN105669610A
CN105669610A CN201610129261.2A CN201610129261A CN105669610A CN 105669610 A CN105669610 A CN 105669610A CN 201610129261 A CN201610129261 A CN 201610129261A CN 105669610 A CN105669610 A CN 105669610A
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hmf
reaction
dmso
lactosi
semi
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贾松岩
何阳东
王国胜
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Shenyang University of Chemical Technology
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Shenyang University of Chemical Technology
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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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  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract

The invention relates to a method for preparing 5-hydroxymethylfurfural (5-HMF) by converting galactose, relating to a method for preparing biomass 5-HMF and belonging to the field of preparation of high-added-value chemicals and alternative energy sources from renewable biomass resources. According to the method, galactose is converted into 5-HMF in a water-organic solvent two-element mixture system by using a metal salt as a catalyst. By using the galactose as the raw material, the galactose can be directly and quickly converted into the 5-HMF under mild conditions. The method is simple in process and easy to operate, has the advantages of mild conditions and efficient reaction performance, provides a favorable reference for galactose conversion, and provides useful information for the development of new energy technology by using saccharide biomass as the raw material in future. The catalytic reaction system in the method is a favorable system capable of selectively converting hexose raw materials.

Description

A kind of semi-lactosi transforms the method preparing 5 hydroxymethyl furfural
Technical field
The present invention relates to a kind of method preparing biomass 5 hydroxymethyl furfural, particularly relate to a kind of semi-lactosi and transform the method preparing 5 hydroxymethyl furfural.
Background technology
Catalyze and synthesize 5 hydroxymethyl furfural (5-HMF) and attract extensive concern in recent years. 5-HMF is obtained by the dehydration of renewable hexose class matter selective, meets continuable development principle. 5-HMF is a kind of furan compound, has aromatic structure feature, and 2 of its molecular structure and 5 contain hydroxyl and aldehyde radical Liang Zhong functional group, and character is flexible and changeable. Take 5-HMF as platform chemicals, by reaction process process such as selective oxidation, hydrogenation, etherificate, amination, condensations, its associated products can be made to have important application (Chem.Rev.2011 in fields such as fuel and oil dope, macromolecular material, spices, medicine synthesis, 111,397-417). Therefore, an important development direction of to take 5-HMF as the complete processing of platform chemicals be following chemical field.
Carbohydrate raw material mainly fructose and these two kinds of hexoses of glucose of synthesis 5-HMF at present. The people such as Dumesic take hydrochloric acid as catalyzer, are water (H in main component2O) and in the diphasic system of mibk (MIBK) transforming fructose 5-HMF, its product rate can reach more than 75% (Science2006,312,1933-1937). The people such as Zhang adopt various metals salt to be catalyzer, transform fructose 5-HMF in 1-ethyl-3-Methylimidazole villaumite ionic liquid, and its product rate can reach 60 ~ 80%. Adopt CrCl2During for catalyzer, glucose can effectively transform in 1-ethyl-3-Methylimidazole villaumite ionic liquid, and 5-HMF product rate can reach about 70%(Science2007,316,1597-1600). Above-mentioned research is that catalyzing and synthesizing of 5-HMF provides important reference. Semi-lactosi is the epimer of glucose C-4 position, but its catalyzed conversion performance and glucose have bigger gap. How effectively to transform semi-lactosi 5-HMF and it is not subject to extensive concern all the time. Reporting according to few quantifier elimination, the people such as Raines adopt CrCl2For catalyzer, transforming semi-lactosi and prepare 5-HMF in dimethyl sulfoxide (DMSO) (DMSO), product rate is 22%(EnergyEnviron.Sci.2010,3,765-771).The people such as Shi, in 1-allyl group-3-Methylimidazole villaumite ionic liquid, add a kind of sulfuric acid functionalized ion liquid and CoCl2As catalyzer, it is 19.7%(Catal.Lett.2014,144,252-260 that semi-lactosi is converted into the product rate of 5-HMF). The people such as Su are in 1-ethyl-3-Methylimidazole villaumite ionic liquid, and adding tyrosine is catalyzer, and the product rate that semi-lactosi is converted into 5-HMF is about 13%(J.Mol.Catal.A, 2013,379,350-354). Above-mentioned catalytic effect can not allow people satisfied, so far, rarely has about the research report how effectively transforming semi-lactosi 5-HMF mono-class chemical intermediate. Therefore, we propose at H2In O DMSO binary mixed solvent system, adopting metal-salt as catalyzer, 5-HMF prepared by catalyzed conversion semi-lactosi.
Summary of the invention
It is an object of the invention to provide a kind of semi-lactosi and transform the method preparing 5 hydroxymethyl furfural, the present invention adopts comparatively cheap metal-salt as catalyzer, and catalysis semi-lactosi is at H2O DMSO binary mixture solvent system transforms, obtains the 5-HMF of higher yields.
It is an object of the invention to be achieved through the following technical solutions:
Semi-lactosi transforms the method preparing 5 hydroxymethyl furfural, and described method comprises following process:
With organic solvent dimethyl sulfoxide (DMSO) (DMSO) or water (H2O) DMSO binary mixture is solvent, adds semi-lactosi as reaction raw materials, with metal-salt NiCl2, FeCl3, CuCl2, MnCl2, CoCl2, ZnCl2, CrCl3, SnCl4, AlCl3, LaCl3, AlBr3, AlI3, Al (NO3)3, Al2(SO4)3For catalyzer, the usage quantity of catalyzer is 2.5 ~ 25mol% of raw material semi-lactosi, temperature of reaction is 110 ~ 140 DEG C, reaction times is 5 ~ 90min, reactor is placed in ice-water bath cancellation reaction by reaction after terminating, and adds appropriate deionized water in reactor and dilute, and obtains the dilute solution of mixed solution after feedstock conversion, utilize high performance liquid chromatography or ultraviolet-visible pectrophotometer to measure the content of 5-HMF in mixed solution after above-mentioned reaction, and calculate the product rate of 5-HMF.
Described a kind of semi-lactosi transforms the method preparing 5 hydroxymethyl furfural, and described reaction solvent is H2The binary mixture of O and DMSO composition, H2The volume ratio of O and DMSO is the molar fraction χ of 1/19(waterw=0.17) the molar fraction χ of ~ 1/9(waterw=0.3).
Described a kind of semi-lactosi transforms the method preparing 5 hydroxymethyl furfural, and described catalyzer is AlCl3Or AlBr3Or Al (NO3)3。
Advantage and the effect of the present invention be:
1. the catalyst A lCl adopted3Or AlBr3Or Al (NO3)3, cheapness easily obtains, and catalytic activity is higher, and the selectivity that catalysis semi-lactosi is converted into 5-HMF is better, and product rate is higher.
2. containing appropriate water in solvent, it is possible to improve AlCl3Or AlBr3Or Al (NO3)3Solubleness in DMSO, and reduction semi-lactosi generation is intermolecular, the possibility of intramolecular dehydration side reaction, it is to increase the selectivity of product 5-HMF.
3. system adds appropriate water can the usage quantity of corresponding some DMSO of reduction, reduce the cost using DMSO and alleviate the pollution hazard that DMSO may cause.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
The present invention is with organic solvent DMSO or H2O DMSO binary mixture is solvent, adds semi-lactosi as reaction raw materials, with metal-salt NiCl2, FeCl3, CuCl2, MnCl2, CoCl2, ZnCl2, CrCl3, SnCl4, AlCl3, LaCl3, AlBr3, AlI3, Al (NO3)3, Al2(SO4)3For catalyzer, catalyst levels is 2.5 ~ 25mol% of raw material semi-lactosi, temperature of reaction is 110 ~ 140 DEG C, reaction times is 5 ~ 90min, reactor is placed in ice-water bath cancellation reaction by reaction after terminating, and adds appropriate deionized water in reactor and dilute, and obtains the dilute solution of mixed solution after feedstock conversion, utilize high performance liquid chromatography or ultraviolet-visible pectrophotometer to measure the content of 5-HMF in mixed solution after above-mentioned reaction, and calculate the product rate of 5-HMF.Catalyst A lCl3Or AlBr3Or Al (NO3)3Catalytic effect best, solvent forms with H2O and DMSO volume ratio is the molar fraction χ of 1/19(waterw=0.17) the molar fraction χ of ~ 1/9(waterw=0.3) mixture is best. Reaction under the natural pressure that under relevant temperature, solvent produces in sealed reactor. Solvent adds water, AlCl can be improved3, AlBr3, Al (NO3)3Solvability in DMSO, and reduce semi-lactosi and the possibility intermolecular, intramolecular dehydration generates other by products occurs, it is to increase the selectivity of 5-HMF and product rate. With H2O and DMSO volume ratio is the molar fraction χ of 1/19(waterw=0.17) the molar fraction χ of ~ 1/9(waterw=0.3) mixture is solvent, AlCl3Or AlBr3Or Al (NO3)3For catalyzer, the catalytic conversion efficiency that semi-lactosi is converted into 5-HMF is best.
Embodiment 1 ~ 10
Taking DMSO as solvent system, cumulative volume is 1mL, adds 50mg(0.2775mmol) semi-lactosi, respectively with NiCl2, FeCl3, CuCl2, MnCl2, CoCl2, ZnCl2, CrCl3, SnCl4, AlCl3, LaCl3For catalyzer, catalyst levels is the 10mol% of raw material semi-lactosi. 30min is reacted at 130 DEG C, then reactor is placed in ice-water bath cancellation reaction, in reactor, add appropriate deionized water again dilute, finally utilize high performance liquid chromatography or ultraviolet-visible pectrophotometer to measure the content of 5-HMF in mixed solution after above-mentioned reaction, and calculate the product rate of 5-HMF.
Table 1 different metal salt catalyst double Lactose conversion in DMSO is the impact of 5-HMF
。
Embodiment 11 ~ 19
With reference to the step of embodiment 1, consist of H the difference is that: reaction solvent2The binary mixture of O and DMSO, cumulative volume is 1mL, H2The volume of O and DMSO is the molar fraction χ of 1/19(waterw=0.17) the molar fraction χ of ~ 1/4(waterw=0.5), catalyzer is CrCl3, SnCl4, AlCl3, repeat above-mentioned experiment, the content of 5-HMF in mixed solution after detection reaction, and calculate the product rate of 5-HMF.
Table 2CrCl3, SnCl4, AlCl3At H2In O DMSO binary mixture solvent, double Lactose conversion is the impact of 5-HMF
。
Embodiment 20 ~ 23
With reference to the step of embodiment 1, consist of H the difference is that: reaction solvent2The binary mixture of O and DMSO, cumulative volume is 1mL, H2The volume of O and DMSO is the molar fraction χ of 1/9(waterw=0.3), catalyzer is AlBr3, AlI3, Al (NO3)3, Al2(SO4)3, repeat above-mentioned experiment, the content of 5-HMF in mixed solution after detection reaction, and calculate the product rate of 5-HMF.
Table 3 different aluminum salt is at H2In O DMSO binary mixture solvent, double Lactose conversion is the impact of 5-HMF
。
Embodiment 24 ~ 26
With reference to the step of embodiment 1, consist of H the difference is that: reaction solvent2The binary mixture of O and DMSO, cumulative volume is 1mL, H2The volume of O and DMSO is the molar fraction χ of 1/9(waterw=0.3), catalyzer is AlCl3, temperature of reaction is respectively 110 DEG C, 120 DEG C, 140 DEG C, repeats above-mentioned experiment, the content of 5-HMF in mixed solution after detection reaction, and calculates the product rate of 5-HMF.
AlCl under table 4 differing temps3At H2In O DMSO binary mixture solvent, double Lactose conversion is the impact of 5-HMF
。

Claims (3)

1. a semi-lactosi transforms the method preparing 5 hydroxymethyl furfural, it is characterised in that, described method comprises following process:
With organic solvent dimethyl sulfoxide (DMSO) (DMSO) or water (H2O) DMSO binary mixture is solvent, adds semi-lactosi as reaction raw materials, with metal-salt NiCl2, FeCl3, CuCl2, MnCl2, CoCl2, ZnCl2, CrCl3, SnCl4, AlCl3, LaCl3, AlBr3, AlI3, Al (NO3)3, Al2(SO4)3For catalyzer, the usage quantity of catalyzer is 2.5 ~ 25mol% of raw material semi-lactosi, temperature of reaction is 110 ~ 140 DEG C, reaction times is 5 ~ 90min, reactor is placed in ice-water bath cancellation reaction by reaction after terminating, and adds appropriate deionized water in reactor and dilute, and obtains the dilute solution of mixed solution after feedstock conversion, utilize high performance liquid chromatography or ultraviolet-visible pectrophotometer to measure the content of 5-HMF in mixed solution after above-mentioned reaction, and calculate the product rate of 5-HMF.
2. a kind of semi-lactosi according to claim 1 transforms the method preparing 5 hydroxymethyl furfural, it is characterised in that, described reaction solvent is H2The binary mixture of O and DMSO composition, H2The volume ratio of O and DMSO is the molar fraction χ of 1/19(waterw=0.17) the molar fraction χ of ~ 1/9(waterw=0.3).
3. a kind of semi-lactosi according to claim 1 transforms the method preparing 5 hydroxymethyl furfural, it is characterised in that, described catalyzer is AlCl3Or AlBr3Or Al (NO3)3。
CN201610129261.2A 2016-03-08 2016-03-08 Method for preparing 5-hydroxymethylfurfural (5-HMF) by converting galactose Pending CN105669610A (en)

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