CN110305083B - Process for preparing 5-chloromethyl furfural from fructose - Google Patents
Process for preparing 5-chloromethyl furfural from fructose Download PDFInfo
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- CN110305083B CN110305083B CN201910477157.6A CN201910477157A CN110305083B CN 110305083 B CN110305083 B CN 110305083B CN 201910477157 A CN201910477157 A CN 201910477157A CN 110305083 B CN110305083 B CN 110305083B
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- 229930091371 Fructose Natural products 0.000 title claims abstract description 28
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 title claims abstract description 28
- 239000005715 Fructose Substances 0.000 title claims abstract description 28
- KAZRCBVXUOCTIO-UHFFFAOYSA-N 5-(chloromethyl)furan-2-carbaldehyde Chemical compound ClCC1=CC=C(C=O)O1 KAZRCBVXUOCTIO-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000011541 reaction mixture Substances 0.000 claims abstract description 17
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 16
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 16
- 229960003178 choline chloride Drugs 0.000 claims abstract description 16
- 230000005496 eutectics Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims abstract description 3
- 238000005191 phase separation Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000005660 chlorination reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000374 eutectic mixture Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GANBJDIOIDQSGI-UHFFFAOYSA-N 2-(chloromethyl)furan Chemical compound ClCC1=CC=CO1 GANBJDIOIDQSGI-UHFFFAOYSA-N 0.000 description 1
- ZGXJTSGNIOSYLO-UHFFFAOYSA-N 88755TAZ87 Chemical compound NCC(=O)CCC(O)=O ZGXJTSGNIOSYLO-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229960002749 aminolevulinic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- VMXUWOKSQNHOCA-LCYFTJDESA-N ranitidine Chemical compound [O-][N+](=O)/C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-LCYFTJDESA-N 0.000 description 1
- 229960000620 ranitidine Drugs 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种以果糖制备5‑氯甲基糠醛的工艺。将果糖和氯化胆碱在一定温度下形成低共熔溶剂,以一定量的盐酸作为催化剂和氯代试剂，并在70～110℃下进行反应，反应结束后降至室温，并以去离子水溶解反应混合物，随后以有机溶剂萃取反应产物，经过有机相分离得到目标产物5‑氯甲基糠醛。本方法最高收率可达90％。该发明从生物质来源的果糖制备5‑氯甲基糠醛，具有工艺简单、条件较温和、产率高、催化剂价廉易得、无毒无害、对环境友好等特点，提供了一条制备生物质基高附加值产品的新途径。The invention discloses a process for preparing 5-chloromethylfurfural from fructose. The fructose and choline chloride are formed into a deep eutectic solvent at a certain temperature, a certain amount of hydrochloric acid is used as a catalyst and a chlorination reagent, and the reaction is carried out at 70-110 ° C. After the reaction is completed, it is lowered to room temperature and deionized. The reaction mixture is dissolved in water, then the reaction product is extracted with an organic solvent, and the target product 5-chloromethylfurfural is obtained through organic phase separation. The highest yield of this method can reach 90%. The invention prepares 5-chloromethylfurfural from biomass-derived fructose, and has the characteristics of simple process, mild conditions, high yield, cheap and easy-to-obtain catalysts, non-toxic and harmless, environment-friendly and the like, and provides a preparation method. A new approach to material-based high value-added products.
Description
Technical Field
The invention relates to a process for preparing 5-chloromethyl furfural from fructose.
Background
The English name of 5-chloromethyl furfural is 5-chloromethyl furan, which is called 5-CMF for short. The molecular weight of 5-chloromethyl furfural is 144, and the molecular formula is C6H5O2And (4) Cl. 5-chloromethyl furfural is a very potential platform compound and a chemical intermediate product, contains a chlorine atom and an aldehyde group in molecules, has good chemical reaction activity, has considerable application prospects in medicine synthesis, chemical synthesis and industrial production, and realizes the preparation of important medicines, such as 5-aminolevulinic acid, ranitidine and the like, by taking 5-CMF as a raw material by the prior art. Therefore, the preparation of 5-chloromethyl furfural by using biomass-based sugars with wide natural sources as raw materials has an important promotion effect on the research and development of novel platform compounds, and has a certain positive significance on the promotion of the recycling of renewable biomass. At present, researches on direct preparation of 5-CMF by using biomass as a raw material are few, and concentrated hydrochloric acid is used as a catalyst and a reaction solvent for 5-CMF reaction and dichloroethane is used as a reaction extractant in a catalytic system for preparing 5-CMF by dehydrating carbohydrate reported in the literature. The current preparation process of 5-CMF still existsThe method has many inevitable defects, such as environmental pollution and equipment corrosion easily caused by excessive concentrated hydrochloric acid serving as a reaction solvent, high toxicity of dichloroethane serving as a reaction extractant, easy harm to human health and environment, difficult product separation and difficulty in realizing large-scale production.
The Eutectic solvent (Deep Eutectic Solvents), DES for short, refers to a two-component or three-component Eutectic mixture composed of hydrogen bond acceptors (such as quaternary ammonium salt) and hydrogen bond donors (such as amide, carboxylic acid and polyalcohol compounds) in a certain stoichiometric ratio, and the freezing point of the Eutectic mixture is significantly lower than the melting point of pure substances of each component. The physical and chemical properties of the eutectic solvent are very similar to those of the ionic liquid, so that the eutectic solvent is also classified as a novel ionic liquid or an ionic liquid analogue.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a process for preparing 5-chloromethyl furfural from fructose, and solves the problems in the background technology.
The technical scheme adopted by the invention for solving the technical problems is as follows: a process for preparing 5-chloromethyl furfural from fructose comprises the steps of mixing fructose and choline chloride, adding hydrochloric acid into the mixture of the fructose and the choline chloride, and stirring and reacting at 70-110 ℃ for 60-180 minutes to obtain a eutectic solvent system; dissolving the reaction mixture by deionized water, extracting the aqueous solution of the reaction mixture by an organic solvent, and carrying out organic phase separation to obtain a target product 5-chloromethyl furfural;
wherein the mass ratio of the fructose to the choline chloride to the hydrochloric acid is 1: 2-4: 0.5-2. Hydrochloric acid is used as an acid catalyst and a chlorinated raw material, and the mass fraction of the hydrochloric acid is 38%. Choline chloride, also known as 2-hydroxyethyl trimethylammonium chloride, can form a eutectic solvent with fructose well at a certain temperature, and the substance is green, environment-friendly and low in price.
In a preferred embodiment of the present invention, the organic solvent includes ethyl acetate, dichloromethane, and dichloroethane.
In a preferred embodiment of the present invention, the amount of the organic solvent is 20 to 40mL per gram of the fructose raw material.
In a preferred embodiment of the present invention, the mass ratio of the fructose, the choline chloride and the hydrochloric acid is 1:4: 1.
In a preferred embodiment of the present invention, the maximum yield of 5-chloromethylfurfural is 90.0%.
Compared with the background technology, the technical scheme has the following advantages:
1. compared with the traditional method for preparing 5-CMF by dehydrating saccharides by using excessive concentrated hydrochloric acid, the method disclosed by the invention uses low-dosage hydrochloric acid as a catalyst, and the dosage concentration of the hydrochloric acid is lower relative to that of the whole reaction system, namely in the eutectic reaction system, the dosage of the hydrochloric acid solution is 1/6 of the system, so that the 5-CMF can be efficiently prepared in a fructose/choline chloride DES system, and the method is more green and environment-friendly;
2. the invention greatly reduces the consumption of hydrochloric acid required in the production process of 5-CMF, reduces the corrosion risk of reaction equipment, and the highest yield of 5-CMF can reach 90%;
3. compared with the traditional hydrochloric acid/dichloroethane reaction system, the method adopts choline chloride and fructose to form a eutectic solvent as the reaction system, then dissolves in deionized water and uses an organic solvent to extract the 5-CMF product, can flexibly select the organic extractant, avoids directly using a highly toxic reaction solvent to be directly applied to reaction preparation, and provides a novel idea for the research of the 5-chloromethyl furfural and downstream products thereof in the future.
Drawings
FIG. 1 is a GC-MS spectrum of the 5-CMF product of example 1.
Detailed Description
Example 1
Putting 1g of fructose, 4g of choline chloride and 1g of hydrochloric acid (the mass fraction is 38%) in a round-bottom flask, uniformly mixing, heating to 80 ℃ in an oil bath kettle, reacting for 120min, after the reaction is finished, cooling the reaction mixture to room temperature, dissolving the reaction mixture in 20mL of deionized water, extracting the reaction product with 40mL of ethyl acetate, and measuring the yield of 5-CMF to be 90.0%. (as shown in FIG. 1)
Example 2
1g of fructose, 2g of choline chloride and 0.5g of hydrochloric acid (the mass fraction is 38%) are placed in a round-bottom flask and uniformly mixed, the mixture is heated to 110 ℃ in an oil bath kettle and reacted for 60min, after the reaction is finished, the reaction mixture is cooled to room temperature, the reaction mixture is dissolved in 20mL of deionized water, the reaction product is extracted by 30mL of dichloroethane, and the yield of 5-CMF is 35.3%.
Example 3
Putting 1g of fructose, 4g of choline chloride and 2g of hydrochloric acid (the mass fraction is 38%) in a round-bottom flask, uniformly mixing, heating to 80 ℃ in an oil bath kettle, reacting for 180min, after the reaction is finished, cooling the reaction mixture to room temperature, dissolving the reaction mixture in 20mL of deionized water, extracting the reaction product with 30mL of dichloromethane, and measuring the yield of 5-CMF to be 46.4%.
Example 4
1g of fructose, 3g of choline chloride and 1.5g of hydrochloric acid (the mass fraction is 38%) are placed in a round-bottom flask and uniformly mixed, the mixture is heated to 100 ℃ in an oil bath kettle and reacts for 120min, after the reaction is finished, the reaction mixture is cooled to room temperature, the reaction mixture is dissolved in 10mL of deionized water, the reaction product is extracted by 20mL of ethyl acetate, and the yield of 5-CMF is 70.5%.
Example 5
1g of fructose, 2g of choline chloride and 0.8g of hydrochloric acid (the mass fraction is 38%) are placed in a round-bottom flask and uniformly mixed, the mixture is heated to 70 ℃ in an oil bath kettle and reacts for 80min, after the reaction is finished, the reaction mixture is cooled to room temperature, the reaction mixture is dissolved in 20mL of deionized water, 40mL of dichloroethane is used for extracting a reaction product, and the yield of 5-CMF is 32.6%.
Example 6
Putting 1g of fructose, 4g of choline chloride and 1g of hydrochloric acid (the mass fraction is 38%) in a round-bottom flask, uniformly mixing, heating to 100 ℃ in an oil bath kettle, reacting for 160min, after the reaction is finished, cooling the reaction mixture to room temperature, dissolving the reaction mixture in 20mL of deionized water, extracting the reaction product by using 40mL of dichloroethane, and measuring the yield of 5-CMF to be 88.1%.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (3)
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626725A (en) * | 2013-11-14 | 2014-03-12 | 华南理工大学 | Method for preparing 5-chloromethyl furfural |
| CN104844543A (en) * | 2015-05-27 | 2015-08-19 | 厦门大学 | Method for preparing 5-hydroxymethylfurfural from fructose |
| CN107674049A (en) * | 2016-08-02 | 2018-02-09 | 远东新世纪股份有限公司 | Process for the preparation of 5- (chloromethyl) furfural |
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- 2019-06-03 CN CN201910477157.6A patent/CN110305083B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626725A (en) * | 2013-11-14 | 2014-03-12 | 华南理工大学 | Method for preparing 5-chloromethyl furfural |
| CN104844543A (en) * | 2015-05-27 | 2015-08-19 | 厦门大学 | Method for preparing 5-hydroxymethylfurfural from fructose |
| CN107674049A (en) * | 2016-08-02 | 2018-02-09 | 远东新世纪股份有限公司 | Process for the preparation of 5- (chloromethyl) furfural |
Non-Patent Citations (1)
| Title |
|---|
| Green catalytic conversion of bio-based sugars to 5-chloromethyl furfural in deep eutectic solvent catalyzed by metal chlorides;Miao Zuo et al.;《RSC Advances》;20160307;第6卷;第27004–27007页 * |
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