Fluorine-containing furyl compound as well as preparation method and application thereof

Abstract

The invention provides a fluorine-containing furyl compound as well as a preparation method and application thereof. The fluorine-containing furyl compound has a structure as shown in a formula I or a formula II. According to the fluorine-containing furyl compound, bio-based 5-hydroxymethylfurfural and derivatives thereof are taken as sources, a new path of biomass resource proliferation is expanded, and the fluorine-containing furyl compound can be further converted into important organic synthesis intermediates. According to the technical scheme, the fluorine-containing furyl compound is used as a polyester precursor or a polyurethane precursor.

Description

Technical Field

[0001] The present invention belongs to the technical field of compounds, and in particular relates to a fluorine-containing furanyl compound, a preparation method thereof and an application thereof. Background Art

[0002] Biomass, as a renewable and sustainable organic carbon resource, is considered to be the most promising alternative to petroleum derivatives. Fluorine is widely used in the production of pharmaceuticals, polymer materials, agricultural chemicals and organic synthesis. The introduction of fluorine atoms or fluorine-containing groups into drug molecules can change the permeability and metabolic stability of drug molecules, regulate their pKa and lipid solubility, and affect the absorption, distribution and interaction of drug molecules with biological targets. Fluorine-substituted furan structures are also of great significance in the development of new drugs. Summary of the invention

[0003] In view of this, the object of the present invention is to provide a fluorinated furanyl compound, a preparation method thereof and an application thereof. The fluorinated furanyl compound is derived from bio-based 5-hydroxymethylfurfural and its derivatives, which expands a new path for the value-added of biomass resources and can be further converted into important organic synthesis intermediates.

[0004] The present invention provides a fluorine-containing furanyl compound having a structure of Formula I or Formula II:

[0005]

[0006] R is selected from an alkyl group, a hydroxymethyl group, an aldehyde group, a chloromethyl group, a carboxyl group, an ester group or a fluoroalkyl group; 1≤n≤7, 1≤m≤15;

[0007] or

[0008] The R′ is selected from hydroxymethyl, aldehyde or fluoroalkyl; the X is a heteroatom; 1≤p≤7, 1≤q≤15.

[0009] Preferably, 1≤n≤4, 1≤m≤10;

[0010] 1≤p≤4, 1≤q≤10.

[0011] Preferably, the heteroatom is oxygen, sulfur or nitrogen.

[0012] The present invention provides a method for preparing the fluorine-containing furanyl compound described in the above technical solution, comprising the following steps:

[0013] 5-Hydroxymethylfurfural and its derivatives are used as raw materials, mixed with fluorine-containing building block reagents, catalysts, and solvents to obtain fluorine-containing furanyl compounds having a structure of formula I or formula II;

[0014]

[0015] R is selected from an alkyl group, a hydroxymethyl group, an aldehyde group, a chloromethyl group, a carboxyl group, an ester group or a fluoroalkyl group; 1≤n≤7, 1≤m≤15;

[0016] or

[0017] The R′ is selected from hydroxymethyl, aldehyde or fluoroalkyl; the X is a heteroatom; 1≤p≤7, 1≤q≤15.

[0018] Preferably, the 5-hydroxymethylfurfural and its derivatives are selected from any one of the following:

[0019]

[0020] The R1 is methyl or ethyl; The R2 is Ar or an alkyl group;

[0021] Preferably, the fluorine-containing building block reagent is selected from any one or more of the following:

[0022]

[0023] Preferably, the catalyst is selected from one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, cesium carbonate, lithium carbonate, ammonium carbonate, sodium acetate, cesium fluoride, potassium phosphate and dipotassium hydrogen phosphate;

[0024] The solvent is selected from one or more of N,N-dimethylformamide, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, γ-valerolactone, N-methylpyrrolidone and 1,5-dimethyl-2-pyrrolidone.

[0025] Preferably, the molar ratio of the fluorine-containing building block reagent to 5-hydroxymethylfurfural and its derivatives is (3:1) to (1:1).

[0026] Preferably, the reaction temperature is 0-50°C.

[0027] The fluorine-containing furanyl compound described in the above technical solution is used as a polyester precursor or a polyurethane precursor.

[0028] The present invention provides a fluorine-containing furanyl compound having a structure of formula I or formula II. The fluorine-containing furanyl compound is derived from bio-based 5-hydroxymethylfurfural and its derivatives, expands a new path for the value-added of biomass resources, and can be further converted into an important organic synthesis intermediate. The fluorine-containing furanyl compound described in the above technical solution is used as a polyester precursor or a polyurethane precursor. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 1 of the present invention;

[0030] Figure 2 This is the carbon NMR spectrum of the product prepared in Example 1 of the present invention;

[0031] Figure 3 This is the nuclear magnetic resonance fluorine spectrum of the product prepared in Example 1 of the present invention;

[0032] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 2 of the present invention;

[0033] Figure 5 This is the carbon NMR spectrum of the product prepared in Example 2 of the present invention;

[0034] Figure 6 This is the nuclear magnetic resonance fluorine spectrum of the product prepared in Example 2 of the present invention;

[0035] Figure 7 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 3 of the present invention;

[0036] Figure 8 This is the carbon NMR spectrum of the product prepared in Example 3 of the present invention;

[0037] Fig. 9 This is the nuclear magnetic resonance fluorine spectrum of the product prepared in Example 3 of the present invention;

[0038] Fig.10 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 4 of the present invention;

[0039] Fig.11 This is the carbon NMR spectrum of the product prepared in Example 4 of the present invention;

[0040] Fig.12 This is the nuclear magnetic resonance fluorine spectrum of the product prepared in Example 4 of the present invention;

[0041] Fig.13 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 5 of the present invention;

[0042] Fig.14 This is the carbon NMR spectrum of the product prepared in Example 5 of the present invention;

[0043] Fig.15 This is the nuclear magnetic resonance fluorine spectrum of the product prepared in Example 5 of the present invention;

[0044] Fig.16 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 6 of the present invention;

[0045] Fig.17 This is the carbon NMR spectrum of the product prepared in Example 6 of the present invention;

[0046] Fig.18 This is the nuclear magnetic resonance fluorine spectrum of the product prepared in Example 6 of the present invention; DETAILED DESCRIPTION

[0047] The present invention provides a fluorine-containing furanyl compound having a structure of Formula I or Formula II:

[0048]

[0049] R is selected from an alkyl group, a hydroxymethyl group, an aldehyde group, a chloromethyl group, a carboxyl group, an ester group or a fluoroalkyl group; 1≤n≤7, 1≤m≤15;

[0050] or

[0051] The R′ is selected from hydroxymethyl, aldehyde or fluoroalkyl; the X is a heteroatom; 1≤p≤7, 1≤q≤15.

[0052] The fluorine-containing furanyl compound provided by the present invention can be further converted into other important organic synthesis intermediates, such as precursors of polyester and polyurethane.

[0053] In the present invention, 1≤n≤4, 1≤m≤10; 1≤p≤4, 1≤q≤10.

[0054] In the present invention, X is a heteroatom, and the heteroatom is preferably oxygen, sulfur or nitrogen.

[0055] In the present invention, the fluorine-containing furanyl compound is any one of the following structures:

[0056]

[0057] The present invention provides a method for preparing the fluorine-containing furanyl compound described in the above technical solution, comprising the following steps:

[0058] 5-Hydroxymethylfurfural and its derivatives are used as raw materials, mixed with fluorine-containing building block reagents, catalysts, and solvents to obtain fluorine-containing furanyl compounds having a structure of formula I or formula II;

[0059]

[0060] R is selected from an alkyl group, a hydroxymethyl group, an aldehyde group, a chloromethyl group, a carboxyl group, an ester group or a fluoroalkyl group; 1≤n≤7, 1≤m≤15;

[0061] or

[0062] The R′ is selected from hydroxymethyl, aldehyde or fluoroalkyl; the X is a heteroatom; 1≤p≤7, 1≤q≤15.

[0063] The raw materials used in the method provided by the present invention are renewable biomass resources, the method is simple to operate, the conditions are mild, the products are easy to separate, the product yield is high, the products have high added value, and after further transformation, they can be used for the synthesis of various fluorine-containing group molecules and the introduction of fluorine-containing groups at specific sites.

[0064] The 5-hydroxymethylfurfural and its derivatives described in the present invention are renewable biomass resources, wherein fluorine-containing building blocks are introduced to synthesize trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl and polyfluoroalkyl substituted furan compounds, providing a new path for expanding the value-added of biomass resources; the 5-hydroxymethylfurfural and its derivatives described in the present invention are selected from any one of the following:

[0065]

[0066] The R1 is methyl or ethyl; The R2 is Ar or an alkyl group;

[0067] The fluorine-containing building block reagent described in the present invention is used as a source of fluorine-containing groups to introduce fluorine-containing building blocks into 5-hydroxymethylfurfural and its derivatives to synthesize trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl and polyfluoroalkyl substituted furan compounds, thereby promoting the high-value conversion and utilization of biomass resources. The fluorine-containing building block reagent described in the present invention is selected from any one or more of the following:

[0068] (TMSCF3);

[0069] The molar ratio of the fluorine-containing building block reagent described in the present invention and the 5-hydroxymethylfurfural and its derivative compounds described in the above technical solution is (3:1) to (1:1). In certain specific embodiments of the present invention, for the trifluoromethylation reaction of 5-hydroxymethylfurfural, the molar ratio of TMSCF3 to 5-hydroxymethylfurfural and its derivative compounds is 3:1; for the monotrifluoromethylation reaction of 2,5-furandicarboxaldehyde, the molar ratio of TMSCF3 to 5-hydroxymethylfurfural and its derivative compounds is 1:1; for the ditrifluoromethylation reaction of 2,5-furandicarboxaldehyde, the molar ratio of TMSCF3 to 5-hydroxymethylfurfural and its derivative compounds is 3:1; for other fluorine-containing building block reagents, their molar ratios to the raw materials are the same as TMSCF3 in the corresponding reactions.

[0070] The catalyst in the present invention is selected from one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, cesium carbonate, lithium carbonate, ammonium carbonate, sodium acetate, cesium fluoride, potassium phosphate and dipotassium hydrogen phosphate; preferably potassium carbonate. The amount of the catalyst is 1 mol% to 5 mol% of the 5-hydroxymethylfurfural and its derivative compounds described in the above technical solution, specifically 1 mol%, 2 mol%, 3 mol%, 4 mol%, or 5 mol%.

[0071] The solvent in the present invention is selected from one or more of N,N-dimethylformamide, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, γ-valerolactone, N-methylpyrrolidone and 1,5-dimethyl-2-pyrrolidone, preferably N,N-dimethylformamide and / or ethyl acetate. The amount of solvent used is that the concentration of 5-hydroxymethylfurfural and its derivative compounds described in the above technical scheme is 1 / 12 to 2 mol / L, specifically 1 / 12 mol / L, 1 / 6 mol / L, 1 / 3 mol / L, 1 / 2 mol / L, 1 mol / L, 1.5 mol / L, or 2 mol / L.

[0072] In some specific embodiments of the present invention, the fluorine-containing building block reagent is TMSCF3, and the solvent is N,N-dimethylformamide or ethyl acetate;

[0073] In certain specific embodiments of the present invention, the fluorine-containing building block reagent is TMSCF2H or TMSC2F5, and the solvent is N,N-dimethylformamide;

[0074] In some specific embodiments of the present invention, the fluorine-containing building block reagent is TMSCF3, and the catalyst is potassium carbonate;

[0075] In some specific embodiments of the present invention, the fluorine-containing building block reagent is TMSCF2H, and the catalyst is cesium fluoride;

[0076] In certain specific embodiments of the present invention, the fluorine-containing building block reagent is TMSC2F5, and the catalyst is sodium acetate.

[0077] In the present invention, the reaction temperature is 0-50°C, specifically 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C; the present invention has experimentally found that a higher product yield can be obtained at room temperature of 20-30°C. In a specific embodiment, the reaction temperature is 26°C, 0°C, 40°C, 50°C. The reaction time is 0.1 to 15 hours; specifically 0.1h, 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h, 6.0h, 6.5h, 7.0h, 7.5h, 8h, 8.5h, 9.0h, 9.5h, 10.0h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13.0h, 13.5h, 14.0h, 14.5h, 15h; in a specific embodiment, the reaction time is 0.5h, 1h, 12h. Using DMF as a solvent, a higher yield can be obtained in 1 hour; using ethyl acetate (EA) as a solvent, a higher yield can be obtained by reacting for at least 12 hours.

[0078] The present invention provides the fluorine-containing furanyl compound described in the above technical solution as a polyester precursor or a polyurethane precursor.

[0079] The fluorine-containing furan-based product contains a diol structure, which can be used as a precursor of polyester and polyurethane.

[0080] The present invention introduces H2 into the fluorine-containing furanyl compound in the presence of a Rh / C catalyst and a H3PO4 aqueous solution to react and obtain a fluorine-substituted dicarbonyl compound.

[0081] The temperature of the above reaction is 95-105°C, the time is 2.5-3.5h; the pressure of H2 is 0.35-0.5MPa.

[0082] In a specific embodiment, Reaction with H2 gives

[0083] In order to further illustrate the present invention, a fluorine-containing furanyl compound provided by the present invention, its preparation method and application are described in detail below in combination with examples, but they should not be construed as limiting the scope of protection of the present invention.

[0084] Example 1

[0085] N,N-dimethylformamide as solvent: 126mg 5-hydroxymethylfurfural was added to a 10mL Schlenk reaction tube, 3mL N,N-dimethylformamide was added and stirred at room temperature (20-30°C) until dissolved, a balloon was inserted above the Schlenk reaction tube to slowly release the pressure change, and then 443μLTMSCF3 was added dropwise for 5 minutes, followed by reaction at room temperature for 1 hour; after the reaction was completed, 15mL ethyl acetate was added, the organic phase was washed with 3*20mL water, the organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation to obtain a crude product; the crude product was dissolved in 3mL tetrahydrofuran, and a dilute hydrochloric acid aqueous solution (0.17mol / L, 3mL) was slowly added dropwise and reacted at room temperature for 30 minutes; after the reaction was completed, 15mL ethyl acetate was added, the organic phase was washed with 3*20mL water, the organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation to obtain the product, with an isolated yield of 99%.

[0086] Ethyl acetate as solvent: 126 mg of 5-hydroxymethylfurfural was added to a 10 mL Schlenk reaction tube, 3 mL of ethyl acetate was added and stirred at room temperature (20-30°C) until dissolved, a balloon was inserted above the Schlenk reaction tube to slow down the pressure change, and then 443 μL of TMSCF3 was added dropwise for 5 minutes, followed by reaction at room temperature for 12 hours; after the reaction, the solvent was removed by rotary evaporation to obtain a crude product; the crude product was dissolved in 3 mL of tetrahydrofuran, and a dilute hydrochloric acid solution (0.17 mol / L, 3 mL) was slowly added dropwise and reacted at room temperature for 30 minutes; after the reaction, 15 mL of ethyl acetate was added, the organic phase was washed with 3*20 mL of water, the organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation to obtain the product, with an isolated yield of 99%.

[0087]

[0088] The operation process is similar to that of Example 1, with different time, TMSCF3 equivalent, solvent and catalyst, 5-HMF is 1 mmol, its synthesis formula is shown in the above reaction formula 1, and the reaction effect is shown in Table 1 (yield is expressed as 19 F NMR and 1 H NMR calibration, internal standard is trifluorotoluene, instrument is Bruker AVANCE NEO 400MHz NMR spectrometer):

[0089] Table 1[a] 19 F NMR calibration nuclear magnetic yield. [b] 1 H NMR calibration nuclear magnetic yield. [c]rt=26℃

[0090]

[0091] From the data in Table 1, it can be seen that the reaction effect becomes better with the increase of TMSCF3 addition, and the most ideal reaction effect is achieved by adding 3 equivalents. In terms of catalysts, phosphate, hydrogen phosphate and fluoride ions cannot combine well with silicon bases and cannot achieve the same catalytic effect. Among carbonates, potassium carbonate is the best, sodium ions are slightly worse, and the yield of cesium ions is significantly reduced. N, N-dimethylformamide and ethyl acetate are the best solvents. Ethyl acetate is simpler to operate than N, N-dimethylformamide in post-treatment, but the reaction time is longer. Ethyl acetate takes 12 hours to react completely, while N, N-dimethylformamide only takes 1 hour. Temperature conditions show that the reaction can achieve a higher yield at room temperature, and the yield at elevated temperature decreases. The reaction time shows that using DMF as a solvent, a 99% yield can be obtained in 1 hour; using ethyl acetate (EA) as a solvent, a 99% yield can be obtained after 12 hours of reaction.

[0092] Example 2

[0093] The operation process is similar to that of Example 1.

[0094] TMSCF2H: The catalyst was changed to cesium fluoride (3 equivalents), and the isolated yield was 88%.

[0095] Its synthetic formula is as follows:

[0096]

[0097] The catalyst used is cesium fluoride, and the potassium carbonate in Example 1 cannot catalyze the reaction of TMSCF2H to achieve the same yield as cesium fluoride.

[0098] Example 3

[0099] The operation process is similar to that of Example 1.

[0100] TMSC2F5: The catalyst was changed to sodium acetate (0.3 eq.), and the isolated yield was 99%.

[0101] Its synthetic formula is as follows:

[0102]

[0103] Sodium acetate is the best catalyst. Potassium carbonate in Example 1 cannot catalyze the reaction of TMSC2F5 to achieve the same yield as sodium acetate.

[0104] Example 4

[0105] N,N-dimethylformamide as solvent: 124 mg of 2,5-furandicarboxaldehyde was added to a 10 mL Schlenk reaction tube, 3 mL of N,N-dimethylformamide was added and stirred at room temperature (20-30°C) until dissolved, a balloon was inserted above the Schlenk reaction tube to slow down the pressure change, and then 148 μL of TMSCF3, the dropwise addition time is 5 minutes, followed by reaction at room temperature for 1 hour; after the reaction is completed, 15 mL of ethyl acetate is added, the organic phase is washed with 3*20 mL of water, the organic phase is dried over anhydrous sodium sulfate, and the silyl intermediate product is obtained by purification through a silica gel column (the eluent polarity is petroleum ether: ethyl acetate = 6:1), with a separation yield of 41%, and the raw material 2,5-furandicarboxaldehyde is recovered at the same time; the intermediate product is dissolved in 3 mL of tetrahydrofuran, and a dilute hydrochloric acid aqueous solution (0.17 mol / L, 3 mL) is slowly added dropwise and reacted at room temperature for 30 minutes; after the reaction is completed, 15 mL of ethyl acetate is added, the organic phase is washed with 3*20 mL of water, the organic phase is dried over anhydrous sodium sulfate, and the product is purified through a silica gel column (the eluent polarity is petroleum ether: ethyl acetate = 3:1), with a separation yield of 99%.

[0106] Ethyl acetate as solvent: 124 mg of 2,5-furandicarboxaldehyde was added to a 10 mL Schlenk reaction tube, 3 mL of ethyl acetate was added and stirred at room temperature (20-30°C) until dissolved, a balloon was inserted above the Schlenk reaction tube to slow down the pressure change, and then 148 μL of TMSCF3 was added dropwise for 5 minutes, followed by reaction at room temperature for 12 hours; after the reaction, the silyl intermediate product (eluent polarity is petroleum ether: ethyl acetate = 6:1) was purified by silica gel chromatography, with an isolation yield of 41%, and the raw material 2,5-furandicarboxaldehyde was recovered at the same time; the crude product was dissolved in 3 mL of tetrahydrofuran, and a dilute hydrochloric acid solution (0.17 mol / L, 3 mL) was slowly added dropwise and reacted at room temperature for 30 minutes; after the reaction, 15 mL of ethyl acetate was added, the organic phase was washed with 3*20 mL of water, the organic phase was dried over anhydrous sodium sulfate, and the product was purified by silica gel chromatography (eluent polarity is petroleum ether: ethyl acetate = 3:1), with an isolation yield of 99%.

[0107] Its synthetic formula is as follows:

[0108]

[0109] Example 5

[0110] 124 mg of 2,5-furandicarboxaldehyde was added to a 10 mL Schlenk reaction tube, 3 mL of ethyl acetate was added and stirred at room temperature (20-30°C) until dissolved, a balloon was inserted above the Schlenk reaction tube to slow down the pressure change, and then 350 μL of TMSCF3 was added dropwise for 10 minutes, followed by reaction at room temperature for 12 hours; after the reaction, the silyl intermediate product was purified by silica gel chromatography (eluent polarity was petroleum ether: ethyl acetate = 6:1), with an isolated yield of 85%; the crude product was dissolved in 3 mL of tetrahydrofuran, and a dilute hydrochloric acid solution (0.17 mol / L, 3 mL) was slowly added dropwise and reacted at room temperature for 30 minutes; after the reaction, 20 mL of ethyl acetate was added, the organic phase was washed with 3*20 mL of water, the organic phase was dried over anhydrous sodium sulfate, and the product was purified by silica gel chromatography (eluent polarity was petroleum ether: ethyl acetate = 2:1), with an isolated yield of 99%.

[0111] Its synthetic formula is as follows:

[0112]

[0113] Example 6

[0114] The fluorinated furan-based products in Example 1, Example 2, Example 3, and Example 5 contain dihydroxy structures, which can be used as precursors of polyesters and polyurethanes. At the same time, the furan structure can also be further catalytically converted to prepare important organic intermediates.

[0115] The product in Example 1 was used to selectively prepare a fluorine-substituted dicarbonyl compound using a Rh / C catalyst and controllable catalytic hydrogenation. The structure of the product is shown in the following figure.

[0116] The specific operation is as follows: 196 mg of the product in Example 1, Rh / C (5 mg), and H3PO4 (4 mL, 0.5 M aqueous solution) are added to a 25 mL high-pressure reactor, followed by the introduction of hydrogen (0.4 MPa), and then reacted at 100°C for 3 hours; after the reaction is completed, the reactor is cooled, the reactor is opened, 15 mL of ethyl acetate is added to the reactor, the organic phase is washed with 3*20 mL of water, the organic phase is dried over anhydrous sodium sulfate, and purified by silica gel chromatography (the polarity of the eluent is petroleum ether: ethyl acetate), with a separation yield of 65%, and 18% of the raw materials are recovered at the same time.

[0117] Its synthetic formula is as follows:

[0118]

[0119] Example 7

[0120] 234 mg of bis-(5-formylfurfuryl) ether was added to a 10 mL Schlenk reaction tube, 3 mL of ethyl acetate was added and stirred at room temperature (20-30° C.) until dissolved, a balloon was inserted above the Schlenk reaction tube to slow the pressure change, and then 350 μL of TMSCF3 was added dropwise for 10 minutes, followed by reaction at room temperature for 12 hours; after the reaction, the silyl intermediate product was purified by silica gel chromatography (eluent polarity was petroleum ether: ethyl acetate = 6:1), with an isolated yield of 83%; the crude product was dissolved in 3 mL of tetrahydrofuran, and a dilute hydrochloric acid solution (0.17 mol / L, 3 mL) was slowly added dropwise and reacted at room temperature for 30 minutes; after the reaction, 20 mL of ethyl acetate was added, the organic phase was washed with 3*20 mL of water, the organic phase was dried over anhydrous sodium sulfate, and the product was purified by silica gel chromatography (eluent polarity was petroleum ether: ethyl acetate = 2:1), with an isolated yield of 99%.

[0121] Its synthetic formula is as follows:

[0122]

[0123] It can be seen from the above embodiments that the present invention provides a fluorine-containing furanyl compound having a structure of formula I or formula II. The fluorine-containing furanyl compound is derived from bio-based 5-hydroxymethylfurfural and its derivatives, which expands a new path for the value-added of biomass resources and can be further converted into an important organic synthesis intermediate. The fluorine-containing furanyl compound described in the above technical scheme is used as a polyester precursor or a polyurethane precursor. The experimental results show that the yield of the fluorine-containing furanyl compound is 83-99%; the yield of the fluorine-substituted dicarbonyl compound is 65%.

[0124] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A fluorine-containing furanyl compound having a structure of Formula I or Formula II: R is selected from an alkyl group, a hydroxymethyl group, an aldehyde group, a chloromethyl group, a carboxyl group, an ester group or a fluoroalkyl group; 1≤n≤7, 1≤m≤15; or The R′ is selected from hydroxymethyl, aldehyde or fluoroalkyl; the X is a heteroatom; 1≤p≤7, 1≤q≤15.

2. The fluorine-containing furanyl compound according to claim 1, characterized in that 1≤n≤4, 1≤m≤10; 1≤p≤4, 1≤q≤10.

3. The fluorine-containing furanyl compound according to claim 1, characterized in that The heteroatom is oxygen, sulfur or nitrogen.

4. A method for preparing the fluorine-containing furanyl compound according to any one of claims 1 to 3, comprising the following steps: 5-Hydroxymethylfurfural and its derivatives are used as raw materials, mixed with fluorine-containing building block reagents, catalysts, and solvents to obtain fluorine-containing furanyl compounds having a structure of formula I or formula II; R is selected from an alkyl group, a hydroxymethyl group, an aldehyde group, a chloromethyl group, a carboxyl group, an ester group or a fluoroalkyl group; 1≤n≤7, 1≤m≤15; or The R′ is selected from hydroxymethyl, aldehyde or fluoroalkyl; the X is a heteroatom; 1≤p≤7, 1≤q≤15.

5. The preparation method according to claim 4, characterized in that: The 5-hydroxymethylfurfural and its derivatives are selected from any one of the following: The R1 is methyl or ethyl; The R2 is Ar or an alkyl group; 6. The preparation method according to claim 4, characterized in that: The fluorine-containing building block reagent is selected from any one or more of the following:

7. The preparation method according to claim 4, characterized in that: The catalyst is selected from one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, cesium carbonate, lithium carbonate, ammonium carbonate, sodium acetate, cesium fluoride, potassium phosphate and dipotassium hydrogen phosphate; The solvent is selected from one or more of N,N-dimethylformamide, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, γ-valerolactone, N-methylpyrrolidone and 1,5-dimethyl-2-pyrrolidone.

8. The preparation method according to claim 7, characterized in that: The molar ratio of the fluorine-containing building block reagent to 5-hydroxymethylfurfural and its derivatives is (3:1) to (1:1).

9. The preparation method according to claim 7, characterized in that: The reaction temperature is 0-50°C.

10. The fluorine-containing furanyl compound according to any one of claims 1 to 3 as a polyester precursor or a polyurethane precursor.

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