Preparation method for 5-hydroxymethylfurfural

A technology of hydroxymethyl furfural and dimethyl sulfoxide, applied in the field of preparation of 5-hydroxymethyl furfural, can solve the problems of unsuitability for mass production, high catalyst toxicity, adhesion of by-products, etc., and avoid highly toxic chemical raw materials The use of the substrate, the wide range of substrates, and the effect of mild reaction conditions

Inactive Publication Date: 2014-05-14
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] At present, the preparation of HMF is generated by the dehydration of sugars, but there are still some other defects in the current method: the yield of the reaction is low, and the synthesis requires Expensive ionic liquids and highly toxic heavy metal salts are used as catalysts, and there are quite high requirements on the reaction device
However, this preparation method has higher requirements on the reaction device, and the yield is low
In 2009 [Chemical Communications 2009,41, 6276-6278], K. Ebitani group prepared under a mild condition under the combined action of solid acid and alkali HMF is used, but the final yield obtained by this method is low, and the by-products in the reaction process will adhere to the surface of the catalyst, and the recovery is more troublesome
In 2011 [Chemical Communications 2011,47 (15), 4469-4471], Y. Du group developed a water-sec-butanol two-phase system using A solid acid catalyst catalyzes the method of preparing HMF by dehydration of glycosides, but the catalyst used in this method is relatively complicated, which is only suitable for laboratory research and is not suitable for industrial mass production
In 2013 [Journal of the American Chemical Society2013, 135 (10), 3997-4006], the method used by S. I. Sandler and D. G. Vlachos is in Lewis acid (CrCl3) Under the joint action of Bronsted acid (HCl), HMF is prepared by isomerizing glucose into fructose and then dehydrating, but this method generates a large amount of by-product levulinic acid, and at the same time, the final HMF yield is not high (59 %)
[0006] In summary, the method for preparing 5-hydroxymethylfurfural (HMF) in the prior art has the disadvantages of large consumption of raw materials, low yield and high toxicity of the catalyst And the recovery is difficult, and the requirements for the reaction device are high

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] 1 g (2.92 mmol) sucrose and 406 mg (0.56 mmol) FeCl 3 ·6H 2 O / C (1:3) was dissolved in 10 mL of acetonitrile, and stirred and heated at 60°C, reacted for 6 hours, and the reaction was terminated after the complete conversion of sucrose was monitored by TLC (chloroform / methanol / water=3:3:1). Then the catalyst in the reaction system was filtered out, washed with ethyl acetate (EtOAc), recovered and recycled. The combined filtrate and washing liquid were washed with saturated brine, the organic phase was separated, and the aqueous phase was extracted several times with ethyl acetate. After the organic phase was combined, the organic phase was washed again with saturated brine and the organic phase was separated. After drying with sodium sulfate, rotary evaporation under reduced pressure and separation and purification by column chromatography gave 478 mg of 5-hydroxymethylfurfural with a yield of 65%.

Embodiment 2

[0018] 1 g (5.6 mmol) of glucose and 406 mg (0.56 mmol) of FeCl 3 ·6H 2 O / C (1:5) was dissolved in 10 mL polyethylene glycol 400, stirred and heated at 100°C, and reacted for 6 hours. The reaction was completed after the complete conversion of glucose was monitored by TLC, and then the catalyst in the reaction system was filtered out. Wash with ethyl acetate (EtOAc), recover and recycle. The combined filtrate and washing liquid were washed with saturated brine, the organic phase was separated, and the aqueous phase was extracted several times with ethyl acetate. After the organic phase was combined, the organic phase was washed again with saturated brine and the organic phase was separated. After drying over magnesium sulfate, concentrate under reduced pressure and separate and purify by column chromatography to obtain 353 mg of 5-hydroxymethylfurfural with a yield of 50%.

Embodiment 3

[0020] Mix 1 g (5.6 mmol) fructose and 406 mg (0.56 mmol) FeCl 3 ·6H 2 O / C (1:1) was dissolved in 10 mL dimethyl sulfoxide (DMSO), heated at 80°C for 3 hours, and the reaction was completed after the conversion of fructose was monitored by TLC, then the catalyst in the reaction system was filtered out, and used Ethyl acetate (EtOAc) washing, recovery and recycling. The combined filtrate and washing liquid were washed with saturated brine, the organic phase was separated, and the aqueous phase was extracted several times with ethyl acetate. After the organic phase was combined, the organic phase was washed again with saturated brine and the organic phase was separated. After drying over sodium sulfate, vacuum rotary evaporation and column chromatography separation and purification gave 593 mg of 5-hydroxymethylfurfural, with a yield of 84%.

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Abstract

The invention discloses a preparation method for 5-hydroxymethylfurfural. The preparation method is characterized by comprising the steps of mixing fructose, glucose or saccharose and dimethylsulfoxide, n-butyl alcohol, sec-butyl alcohol, cyclohexanol, 1,4-dioxane, polyethylene glycol 400 or acetonitrile according to the mass volume ratio of 1g: (5-10ml) and stirring; performing heating reaction in the presence of a solid acidic catalyst FeCl3.6H2O / C, and concentrating and purifying reaction liquid to obtain a product 5-hydroxymethylfurfural. Compared with the prior art, the preparation method disclosed by the invention has the characteristics of simple technology, convenient operation, low production cost, high yield and mild reaction conditions; the use of high-toxicity chemical raw materials is avoided, and the environment cannot be polluted; furthermore, the catalyst is low in price, readily available and high in efficiency and can be recycled for multiple times; environment protection aims of environment friendliness, low carbon, low price, ready availability and circulating sustainable development are fulfilled; and the preparation method is particularly suitable for industrial large-scale production.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a preparation method of 5-hydroxymethylfurfural. Background technique [0002] 5-Hydroxymethylfurfural (HMF) is a very representative biomass material monomer and an intermediate in organic synthesis. HMF molecules contain active groups - aldehyde groups and hydroxymethyl groups, which are chemically active and can be used as intermediates for many organic reactions, raw materials for the synthesis of macrocyclic compounds, monomers for the synthesis of polymer materials, solvents, biofuels, etc. [0003] At present, the preparation of HMF is produced by dehydration of sugars, but there are still some other defects in the current method: such as the low yield of the reaction, and the synthesis requires the use of expensive ionic liquids and toxic heavy metal salts as catalysts , and has quite high requirements on the reaction device. [0004] In 2003, the group of H. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D307/46
CPCC07D307/46
Inventor 张剑波骆小胜吴宇惠周梦琪喻超马慧隆双河张婉陈和善
Owner EAST CHINA NORMAL UNIV
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