Method for producing 2,5-furandicarboxylic acid

Abstract

The present invention aims to provide a method for producing 2,5-furandicarboxylic acid (FDCA) in high purity and high yield from 5-hydroxymethylfurfural (HMF) via a chemoselective oxidation reaction based on an environmentally friendly protocol using an alkali metal (or alkaline earth metal) compound and oxygen (or air) without using a transition metal catalyst. [Solution] A method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural by a chemoselective oxidation reaction, characterized in that the chemoselective oxidation reaction is carried out using oxygen or air as an oxidizing agent in the presence of an alkali metal or alkaline earth metal compound as a promoter.

Description

[Technical Field]

[0001] The present invention relates to a method for producing 2,5-furandicarboxylic acid, and more particularly, to a more efficient and economical method for producing 2,5-furandicarboxylic acid having various functions in high purity and high yield without using a transition metal catalyst. [Background technology]

[0002] 2,5-Furandicarboxylic acid (FDCA) is a very useful material with various functions and is widely used in the packaging industry (polyamides, polyesters, polyurethanes, etc.), automobiles, pharmaceuticals, fine chemicals, etc. In addition, polyethylene furanoate (PEF), a bioplastic developed as a substitute for polyethylene terephthalate (PET), can be obtained from FDCA, making it highly worthy of research.

[0003] A method for obtaining 2,5-furandicarboxylic acid (FDCA) by oxidizing 5-hydroxymethylfurfural (HMF) is known. However, this conventional method requires the reaction to be carried out under extremely harsh and delicate conditions using an excess equivalent of nitric acid as an oxidant, making it impossible to avoid the production of undesirable by-products. Subsequently, techniques for the chemoselective synthesis of 2,5-furandicarboxylic acid (FDCA) have been developed using various transition metals, such as gold, platinum, palladium, and titanium, and oxygen as an oxidant (e.g., Patent Documents 1 and 2). However, these methods require expensive transition metal catalysts and the reaction must be carried out at high temperatures or under high pressures, making them difficult to commercialize.

[0004] Therefore, there is a need for the development of a process for producing 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF) in high purity and high yield using oxygen (or air) as an oxidizing agent without using a transition metal catalyst. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Korean Patent Publication No. 10-2018-0090840 [Patent Document 2] Korean Patent Publication No. 10-2018-0107143 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to solve the problems of the prior art described above, and aims to provide a method for producing 2,5-furandicarboxylic acid (FDCA) in high purity and high yield from 5-hydroxymethylfurfural (HMF) through a chemoselective oxidation reaction based on an environmentally friendly protocol using an alkali metal (or alkaline earth metal) compound and oxygen (or air) without using a transition metal catalyst. [Means for solving the problem]

[0007] In order to solve the above-mentioned problems, the present invention provides a method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural by a chemoselective oxidation reaction, in which the chemoselective oxidation reaction is carried out using oxygen or air as an oxidant in the presence of an alkali metal or alkaline earth metal compound as a promoter. [Effects of the Invention]

[0008] According to the present invention, high-purity 2,5-furandicarboxylic acid (FDCA), which is widely and conveniently used in various fields such as the packaging industry, automobiles, pharmaceuticals, and fine chemistry, can be produced from 5-hydroxymethylfurfural (HMF) in a more economical, efficient, and environmentally friendly manner. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will now be described in more detail. The present invention relates to a method for producing 2,5-furandicarboxylic acid (FDCA) via a chemoselective oxidation reaction in which an alcohol functional group and an aldehyde functional group in a molecule of 5-hydroxymethylfurfural (HMF) are oxidized, as shown in Reaction Scheme 1 below.

[0010] (Reaction Scheme 1)

[0011] [ka]

[0012] In the method for producing 2,5-furandicarboxylic acid of the present invention, the chemoselective oxidation reaction is carried out in the presence of an alkali metal or alkaline earth metal compound as a promoter.

[0013] In one embodiment, the alkali metal may be lithium, sodium, potassium, rubidium, cesium, or a combination thereof, and the alkaline earth metal may be barium, magnesium, or a combination thereof.

[0014] In one embodiment, the alkali metal or alkaline earth metal compound used as a promoter may be represented by Formula 1:

[0015] MOR formula 1 (wherein M is an alkali metal or alkaline earth metal; and R is an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group).

[0016] More specifically, in the formula 1, R is (C1 to C 10 ) alkyl group, (C6-C 10 ) aryl group, (C1-C 10 ) Alkyl (C6-C 10 ) aryl group or (C6-C 10 ) Aryl (C1-C 10) alkyl group, more specifically, R may be a (C1-C6) alkyl group, a (C6) aryl group, a (C1-C6) alkyl(C6) aryl group, or a (C6) aryl(C1-C6) alkyl group.

[0017] According to the present invention, 2,5-furandicarboxylic acid (FDCA) can be produced in high purity and high yield from 5-hydroxymethylfurfural (HMF) without using an expensive transition metal catalyst. Therefore, in a preferred embodiment of the method for producing 2,5-furandicarboxylic acid of the present invention, a transition metal catalyst is not used.

[0018] In the method for producing 2,5-furandicarboxylic acid of the present invention, the chemoselective oxidation reaction can be carried out in various solvents.

[0019] The solvent is water, an organic solvent, or a combination thereof, and the organic solvent may be a non-polar organic solvent, a polar protic organic solvent, a polar aprotic organic solvent, or a combination thereof.

[0020] In one embodiment, the solvent may be water, n-propanol, isopropanol, n-butanol, tert-butanol, tert-amyl alcohol, tetrahydrofuran, 1,4-dioxane, dichloromethane, 1,2-dichloroethane, chlorobenzene, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, benzene, toluene, or a mixture of two or more thereof.

[0021] In one embodiment, the promoter of an alkali metal or alkaline earth metal compound (e.g., alkoxide) can be used in an amount of 1 to 10 equivalents relative to 5-hydroxymethylfurfural (HMF), and it is preferred to use an amount of 3 to 4 equivalents relative to 5-hydroxymethylfurfural (HMF) to obtain a more efficient yield.

[0022] In one embodiment, the chemoselective oxidation reaction can be carried out at a temperature of 20°C to 100°C, more specifically, at a temperature of 20°C to 60°C, and even more specifically, preferably at a temperature of 40°C to 60°C.

[0023] In one embodiment, the chemoselective oxidation reaction can be carried out under conditions of 1 to 10 atmospheres, more specifically, 3 to 5 atmospheres, and even more specifically, 1 to 2 atmospheres.

[0024] In the method for producing 2,5-furandicarboxylic acid of the present invention, the alkali metal or alkaline earth metal compound used as a promoter and oxygen or air used as an oxidant are themselves highly reactive, so that 2,5-furandicarboxylic acid can be produced in excellent yield even when the chemoselective oxidation reaction is carried out under relatively low temperature conditions (e.g., about 40°C) and relatively low pressure conditions (e.g., 2 atmospheres). Therefore, the method for producing 2,5-furandicarboxylic acid of the present invention is very useful for industrialization for mass production.

[0025] The present invention will be described in more detail through the following examples and comparative examples, but the scope of the present invention is not limited thereby in any way. [Example]

[0026] In the following Examples 1 to 4, the solvent used was tert-butanol, and the promoters used were sodium tert-butoxide, sodium tert-amylate, sodium ethoxide, and sodium methoxide, respectively. The reaction was carried out at a reaction temperature of about 30°C under oxygen conditions at normal pressure for about 1 day.

[0027] In the following Examples 5 to 8, the solvent used was tert-butanol, and the promoters used were lithium tert-butoxide, potassium tert-butoxide, magnesium tert-butoxide, and barium tert-butoxide, respectively. The reaction was carried out at a reaction temperature of about 30°C under oxygen conditions at normal pressure for about 1 day.

[0028] In the following Examples 9 to 23, the solvents used were tetrahydrofuran, 1,4-dioxane, dichloromethane, 1,2-dichloroethane, chlorobenzene, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, benzene, toluene, n-butanol, tert-amyl alcohol, N,N-dimethylacetamide, isopropanol, and n-propanol, respectively, the promoter used was sodium tert-butoxide, and the reaction was carried out at a reaction temperature of about 25°C under oxygen conditions at normal pressure for about 1 day.

[0029] In the following Examples 24 to 27, the solvents used were n-butanol and tert-butanol, the promoter used was sodium tert-butoxide, and the reactions were carried out at reaction temperatures of 45°C and 55°C, respectively, under oxygen conditions at atmospheric pressure for about 1 day.

[0030] Example 1 At 30°C, 3 mL of tert-butanol was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 98% yield.

[0031] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0032] Example 2 At 30 °C, 3 mL of tert-butanol was added to sodium tert-amylate (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 89% yield.

[0033] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0034] Example 3 At 30 °C, 3 mL of tert-butanol was added to sodium ethoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 75% yield.

[0035] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0036] Example 4 At 30 °C, 3 mL of tert-butanol was added to sodium methoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 56% yield.

[0037] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0038] Example 5 At 30 °C, 3 mL of tert-butanol was added to lithium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 88% yield.

[0039] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0040] Example 6 At 30 °C, 3 mL of tert-butanol was added to potassium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 92% yield.

[0041] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0042] Example 7 At 30 °C, 3 mL of tert-butanol was added to magnesium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 75% yield.

[0043] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0044] Example 8 At 30 °C, 3 mL of tert-butanol was added to barium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 73% yield.

[0045] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0046] Example 9 At 25 °C, 3 mL of tetrahydrofuran was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 81% yield.

[0047] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0048] Example 10 At 25 °C, 3 mL of 1,4-dioxane was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 77% yield.

[0049] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0050] Example 11 At 25 °C, 3 mL of dichloromethane was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 82% yield.

[0051] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0052] Example 12 At 25 °C, 3 mL of 1,2-dichloroethane was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 80% yield.

[0053] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0054] Example 13 At 25 °C, 3 mL of chlorobenzene was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 78% yield.

[0055] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0056] Example 14 At 25 °C, 3 mL of acetonitrile was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 75% yield.

[0057] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0058] Example 15 At 25 °C, 3 mL of dimethyl sulfoxide was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 83% yield.

[0059] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0060] Example 16 At 25 °C, 3 mL of N,N-dimethylformamide was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 86% yield.

[0061] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0062] Example 17 At 25 °C, 3 mL of benzene was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 59% yield.

[0063] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0064] Example 18 At 25 °C, 3 mL of toluene was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 71% yield.

[0065] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0066] Example 19 At 25 °C, 3 mL of n-butanol was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 85% yield.

[0067] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0068] Example 20 At 25 °C, 3 mL of tert-amyl alcohol was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 80% yield.

[0069] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0070] Example 21 At 25 °C, 3 mL of N,N-dimethylacetamide was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 77% yield.

[0071] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0072] Example 22 At 25 °C, 3 mL of isopropanol was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 65% yield.

[0073] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0074] Example 23 At 25 °C, 3 mL of n-propanol was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 68% yield.

[0075] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0076] Example 24 At 45 °C, 3 mL of n-butanol was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 87% yield.

[0077] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0078] Example 25 At 45 °C, 3 mL of tert-butanol was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 82% yield.

[0079] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0080] Example 26 At 55 °C, 3 mL of n-butanol was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 78% yield.

[0081] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0082] Example 27 At 55 °C, 3 mL of tert-butanol was added to sodium tert-butoxide (3 equivalents) and stirred for 5 minutes. 5-Hydroxymethylfurfural (HMF, 0.5 mmol) was added, and the atmosphere was replaced with oxygen, followed by stirring at room temperature for 1 day. A trace of distilled water was added to the resulting mixture to quench the reaction. The acidity (pH) of the mixture was reduced to 1 with 1N HCl solution, and then the mixture was concentrated. The residue was purified using seed crystals to obtain 2,5-furandicarboxylic acid (FDCA) in 73% yield.

[0083] 1 H NMR(500MHz,DMSO-d6):δ13.62(br,2H),7.29(s,2H) 13 C NMR(125MHz,DMSO-d6):δ158.91,147.04,118.40

[0084] The reaction conditions and results of Examples 1 to 27 are summarized in Tables 1 to 3 below.

[0085] [Table 1]

[0086] [Table 2]

[0087] [Table 3]

[0088] As can be seen from the above, according to the present invention, high-purity 2,5-furandicarboxylic acid (FDCA) can be produced more efficiently and economically through a chemoselective oxidation reaction based on an environmentally friendly protocol using an alkali metal (or alkaline earth metal) compound as a promoter and oxygen (or air) as an oxidant.

Claims

1. A method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural by a chemical selective oxidation reaction, comprising: (1) mixing an accelerator, which is an alkali metal compound, with a solvent containing tert-butanol at a temperature of 25°C to 30°C; and (2) adding 5-hydroxymethylfurfural to the mixture obtained in the step (1) and carrying out a chemoselective oxidation reaction using oxygen or air as an oxidizing agent; Including, The alkali metal compound is represented by the following formula (1): MOR (1) (wherein M is lithium, sodium, potassium, or a combination thereof, and R is a (C 4 -C 6 ) alkyl group).

2. The method for producing 2,5-furandicarboxylic acid according to claim 1, wherein no transition metal catalyst is used.

3. The method for producing 2,5-furandicarboxylic acid according to claim 1, wherein the chemoselective oxidation reaction is carried out at a temperature of 20°C to 100°C.

4. The method for producing 2,5-furandicarboxylic acid according to claim 1, wherein the chemoselective oxidation reaction is carried out at 1 to 10 atmospheres.

Images