CN-121974876-A - Method for preparing 2, 5-furan dicarboxaldehyde by fructose one-pot one-step method

Abstract

The invention provides a method for preparing 2, 5-furan dicarboxaldehyde by a fructose one-pot one-step method, which comprises the steps of taking fructose as a raw material in an air atmosphere, adding a HCP-AQ-Mo-SO 3 H catalyst, heating in dimethyl sulfoxide under normal pressure for reaction, dehydrating and oxidizing to obtain the 2, 5-furan dicarboxaldehyde, wherein the HCP-AQ-Mo-SO 3 H catalyst can be reused after filtering, separating and washing. The catalyst can directly convert fructose into DFF through dehydration and oxidation reaction in an air environment, and the reaction atmosphere is not required to be switched, so that the operation convenience is greatly improved.

Inventors

• SHEN ZHENLU
• WANG XUEDONG
• Xia Jiehao
• WANG BI
• LI MEICHAO

Assignees

• 浙江工业大学

Dates

Publication Date

20260505

Application Date

20260122

Claims (10)

1. 1. A method for preparing 2, 5-furan dicarboxaldehyde by a fructose one-pot one-step method is characterized in that under the air atmosphere, fructose is used as a raw material, a HCP-AQ-Mo-SO 3 H catalyst is added, the mixture is heated and reacted in dimethyl sulfoxide under normal pressure to carry out dehydration and oxidation, SO that 2, 5-furan dicarboxaldehyde is prepared, and the HCP-AQ-Mo-SO 3 H catalyst can be reused after being filtered, separated and washed.
2. 2. The method of claim 1, wherein the HCP-AQ-Mo-SO 3 H catalyst is prepared by a process comprising the steps of: (1) Dispersing 2-hydroxy-N- (quinoline-8-yl) benzamide, p-dichlorobenzene and anhydrous ferric trichloride in a first organic solvent, heating to react in a nitrogen atmosphere, carrying out solid-liquid separation, washing the obtained solid, and drying to obtain a macromolecular ligand HCP-AQ; (2) Heating molybdenum acetylacetonate and macromolecular ligand HCP-AQ in a second organic solvent for reaction, carrying out solid-liquid separation, and washing the obtained solid to obtain HCP-AQ-Mo; (3) Stirring chlorosulfonic acid and HCP-AQ-Mo in a third organic solvent at normal temperature for reaction, pouring the reaction mixture into ice water, filtering and collecting solid, washing with water until the washing liquid is neutral, washing with methanol for three times, and drying and then marking as HCP-AQ-Mo-SO 3 H, namely the HCP-AQ-Mo-SO 3 H catalyst.
3. 3. The method of claim 2, wherein in the step (1), the molar ratio of the benzamide to the dibenzyl chloride to the anhydrous ferric trichloride is 1 (1-3): 2-5.
4. 4. The method according to claim 2, wherein in the step (1), the first organic solvent is selected from one of toluene, methanol, ethyl acetate, ethanol, methylene chloride and dichloroethane, the heating temperature is 50-120 ℃, and the reaction time is 10-30 hours.
5. 5. The method according to claim 2, wherein in the step (2), the mass ratio of the macromolecular ligand HCP-AQ to the molybdenum acetylacetonate is 1 (1-3).
6. 6. The method according to claim 2, wherein in the step (2), the second organic solvent is selected from one of toluene, methanol, ethyl acetate, ethanol and methylene dichloride, the heating temperature is 50-100 ℃, and the reaction time is 12-48 h.
7. 7. The method according to claim 2, wherein in the step (3), the mass ratio of the HCP-AQ-Mo to the chlorosulfonic acid is 1 (2-17), the third organic solvent is selected from one of toluene, methanol, ethyl acetate, ethanol and dichloromethane, and the reaction time is 10-70 h.
8. 8. The method according to claim 1, wherein the mass ratio of the HCP-AQ-Mo-SO 3 H catalyst to fructose is 1 (2-6).
9. 9. The method of claim 1, wherein the mass ratio of dimethyl sulfoxide to fructose is (10-25): 1.
10. 10. The method of claim 1, wherein the heating reaction temperature is 120-160 ℃ and the reaction time is 3-15 h.

Description

Method for preparing 2, 5-furan dicarboxaldehyde by fructose one-pot one-step method Technical Field The invention relates to the technical field of preparation of bio-based polymer monomers, in particular to a method for preparing 2, 5-furan dicarboxaldehyde by a fructose one-pot one-step method. Background In recent years, renewable biomass energy is the most ideal alternative energy source in the case of the progressive exhaustion of traditional fossil energy sources. The conversion and utilization of biomass energy marks an important step for the transition of sustainable energy sources. Notably, biomass resources have many advantages over fossil resources, such as renewable, widely available, and green carbon production. Partial replacement of fossil resources with biomass helps alleviate some of the energy and environmental problems associated with excessive consumption of these non-renewable resources. Lignin is an important component in biomass, and is attractive because of its characteristics of large quantity, low cost, easy availability, little pollution, etc. It can obtain fructose as one of six carbon sugars through simple cleavage and separation. The fructose can be converted into chemical 5-Hydroxymethylfurfural (HMF), and the HMF can be further converted into a series of high-added-value chemicals such as 2, 5-furandicarboxaldehyde (DFF), 2, 5-furandicarboxylic acid (FDCA), 2, 5-furandimethanol (BHMF), 2, 5-furandicarboxylic acid dimethyl ester (DMFD) and the like. The DFF can be used for preparing medical intermediates, antibacterial agents, binders, fluorescent agents and the like, has application value in research of macrocyclic ligands and organic conductors, and can be used for synthesizing various novel high polymer materials such as biomass-based novel resins, fluorescent materials, polyalcohols, polyethylene and the like. At present, two schemes for converting fructose into DFF exist, namely, the fructose is dehydrated to generate an HMF intermediate, and the HMF is selectively catalyzed and oxidized to prepare the DFF. The scheme is completed through two independent reactions, and the production cost is higher due to complex operation. Another proposal is to directly dehydrate and oxidize fructose by a one-pot method to obtain DFF. This solution requires that the reaction system is capable of both dehydration and oxidation. Therefore, a bifunctional catalyst which has dehydration function and catalytic oxidation capability and can directly convert fructose into DFF is developed, the operation convenience is improved, the economic cost is reduced, the reaction process is simplified, and the catalyst is a key suitable for industrial production. Disclosure of Invention In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a method for preparing 2, 5-furan dicarboxaldehyde by a one-pot one-step method, which is used for solving the problems that in the existing process for preparing DFF by one-pot method, N 2 is required to be protected in the dehydration reaction process, catalytic oxidation is performed in the O 2 environment after dehydration is completed, the operation is complicated, and the cost is high. In order to achieve the above and other related objects, the invention provides a method for preparing 2, 5-furan dicarboxaldehyde by a fructose one-pot one-step method, which comprises the steps of taking fructose as a raw material, adding a HCP-AQ-Mo-SO 3 H catalyst into dimethyl sulfoxide, heating under normal pressure for reaction to dehydrate and oxidize to obtain 2, 5-furan dicarboxaldehyde, and filtering, separating and washing the HCP-AQ-Mo-SO 3 H catalyst for reuse. Preferably, the HCP-AQ-Mo-SO 3 H catalyst is prepared by a method comprising the following steps: (1) Dispersing 2-hydroxy-N- (quinoline-8-yl) benzamide, p-dichlorobenzene and anhydrous ferric trichloride in a first organic solvent, heating to react in a nitrogen atmosphere, carrying out solid-liquid separation, washing the obtained solid, and drying to obtain the macromolecular ligand HCP-AQ. (2) Heating molybdenum acetylacetonate and macromolecular ligand HCP-AQ in a second organic solvent for reaction, carrying out solid-liquid separation, and washing the obtained solid to obtain HCP-AQ-Mo; (3) Stirring chlorosulfonic acid and HCP-AQ-Mo in a third organic solvent at normal temperature for reaction, pouring the reaction mixture into ice water, filtering and collecting solid, washing with water until the washing liquid is neutral, washing with methanol for three times, and drying and then marking as HCP-AQ-Mo-SO 3 H, namely the HCP-AQ-Mo-SO 3 H catalyst. The synthetic route for the HCP-AQ-Mo-SO 3 H catalyst is shown below: 。 The HCP-AQ-Mo-SO 3 H catalyst is prepared by adopting a method comprising the following steps: (1) 2-hydroxy-N- (quinoline-8-yl) benzamide, p-dichlorobenzene, anhydrous ferric trichloride and an organic solvent are added into a reaction bottle to