Patent Application
20240294485
The present disclosure relates to the field of organic synthesis, and specifically relates to a method for preparing 2,5-bishydroxymethylfuran using 5-chloromethylfurfural.
2,5-Bishydroxymethylfuran (BHMF), a high value-added diol, has important applications in preparation and research of polyheterocyclic compounds in synthesis of fine chemicals, novel functionalized polyethers, polyurethanes, and drugs. Presently, a main raw material for synthesis of the BHMF is a biomass-based platform molecule, 5-hydroxymethylfurfural (HMF) (ACS Sustainable Chemistry & Engineering, 2021, 9(3): 1161-71; Applied Catalysis A: General, 2021, 609: 117892; Applied Catalysis B: Environmental, 2020, 277, 119273; ACS Sustainable Chemistry & Engineering, 2019, 7(12), 10670-8; Applied Catalysis a-General, 2019, 578, 122-33; Green Chemistry, 2019, 21(16), 4319-23; Applied Catalysis B: Environmental, 2019, 241, 270-83; Green Chemistry, 2018, 20(5), 1095-105). However, the existing raw materials for preparing the HMF are mainly high-cost materials, such as fructose, and there are difficulties of low yield and poor selectivity caused by directly preparing the HMF using cheap materials, such as cellulose and biomass, as the raw materials. In addition, the HMF is difficult to separate and purify due to instability and hydrophilicity thereof, and a process for preparing the BHMF using the HMF on a large scale is further limited.
5-Chloromethylfurfural (CMF) can be directly prepared using raw materials, such as fibers and biomass, with high yields under mild conditions. The CMF is more convenient to be separated and purified due to stability and hydrophobicity thereof, so CMF is considered as a novel biomass-based platform molecule to replace the HMF (ACS Sustainable Chemistry & Engineering, 2019, 7(6), 5588-601; Angew Chem, Int Ed, 2008, 47(41), 7924-6). However, relevant reports for directly converting the CMF into the BHMF using one step with a high selectivity are rarely disclosed.
Therefore, directly preparing the BHMF from the novel biomass-based platform molecule CMF instead of the HMF with high selectivity can not only greatly reduce production costs, but also provide a better prospect for industrialization.
An objective of the present disclosure is to provide a method for directly preparing 2,5-bishydroxymethylfuran using 5-chloromethylfurfural derived from biomass to overcome the deficiencies of the existing techniques, achieve reaction conditions that are mild, and achieve a yield that is high.
The following technical solution is used to solve the technical problem of the present disclosure:
The present disclosure discloses a method for preparing 2,5-bishydroxymethylfuran using 5-chloromethylfurfural, the method comprises adding the 5-chloromethylfurfural, a catalyst, a base neutralizer, sodium dithionite, and deionized water to a closed reactor, filling H2 into the closed reactor, and reacting by stirring at a speed of 400-800 revolutions per minute (rpm), a reaction formula is shown in
In a specific embodiment, a ratio of the 5-chloromethylfurfural and the deionized water is 1:50-250 g/mL, preferably 1:50-100 g/mL; a weight ratio of the 5-chloromethylfurfural and the catalyst is 1:0.5-1.5, preferably 1:1; a weight ratio of the 5-chloromethylfurfural and the sodium dithionite is 1:0.05-0.2, preferably 1:0.1; a molar ratio of the 5-chloromethylfurfural and the base neutralizer is 1:0.5-0.9, preferably 1:0.7; the filling H2 into the closed reactor comprises filling the H2 into the closed reactor until an initial pressure of H2 is 2-5 MPa, preferably 4 MPa; and the reacting by stirring at a speed of 400-800 rpm comprises reacting by stirring at the speed of 400-800 rpm at a temperature of 40-80° C. for 0.5-8 hours, preferably at the temperature of 60-70° C. for 2-5 hours.
In a specific embodiment, the base neutralizer is calcium carbonate, potassium bicarbonate, or sodium bicarbonate, preferably calcium carbonate.
In a specific embodiment, a weight ratio of the metal oxide, the RuCl3·3H2O, and the NaBH4 is 1:0.05-0.2:0.05-2.
The present disclosure has the following advantages.
The present disclosure will be further described below in combination with the accompanying embodiment. Unless otherwise specified, the reagents and instruments used in the following embodiments are commercially available products. The specific embodiments are as follows:
Step 1) 0.103 g of RuCl3·3H2O is dissolved in 30 mL of deionized water to obtain a solution, and 1 g of CuO is then added to the aqueous solution and stirred for 2 hours. NaBH4 solution (in which 0.3 g of NaBH4 is dissolved in 20 mL of deionized water) is then added dropwise and stirred for 1 hour. A catalyst of Ru/CuO is obtained by centrifugation, washing using 30 mL of deionized water for 3 times, and freeze drying. A loading amount of Ru is 5 wt % Ru relative to a carrier of CuO. Step 2) 0.1 g of 5-chloromethylfurfural, 0.1 g of the catalyst Ru/CuO, 0.05 g of calcium carbonate as a base neutralizer, 0.01 g of sodium dithionite, and 10 mL of deionized water are added to a stainless steel closed reactor, H2 is filled into the stainless steel closed reactor until an initial H2 pressure is 4 MPa, heated to 70° C. while stirring at a speed of 500 revolutions per minute (rpm), and reacted for 2 hours to obtain a reaction solution involving 2,5-bishydroxymethylfuran. After the reaction is complete, solid-liquid separation of the reaction solution involving 2,5-bishydroxymethylfuran is performed by a centrifuge machine at a speed of 8000 rpm for 5 minutes, and quantitative analysis is performed by high performance liquid chromatography (HPLC, Agilent 1260). Qualitative analysis is performed using gas chromatography-mass spectrometry (GC-MS, Thermo Scientific). The results are as follows: a molar yield of 2,5-bishydroxymethylfuran is 76%.
Step 1) The catalyst is prepared according to the method of Embodiment 1 for use. This embodiment differs from Embodiment 1 in that the carrier of the catalyst is Co3O4, so that a catalyst of Ru/Co3O4 is obtained. A loading amount of Ru is 5 wt % Ru relative to the carrier of Co3O4.
Step 2) The step 2 of Embodiment 2 is performed according to the step 2 of the method of Embodiment 1 using the catalyst of Ru/Co3O4. The results are as follows: a molar yield of 2,5-bishydroxymethylfuran is 34%.
Step 1) Four catalysts are prepared according to the method of Embodiment 1 for use. Embodiments 3-6 differ from Embodiment 1 in that 0.0205 g (1 wt %), 0.0616 g (3 wt %), 0.144 g (7 wt %), or 0.185 g (9 wt %) of RuCl3-3H2O are added, respectively. The loading amount of Ru is 1 wt % Ru, 3 wt % Ru, 7 wt % Ru, or 9 wt % Ru relative to the carrier of CuO, respectively.
Step 2) The step 2 of each of Embodiments 3-6 is performed according to the step 2 of the method of Embodiment 1 using the four catalysts. The results are as follows: molar yields of 2,5-bishydroxymethylfuran are 13%, 39%, 74%, and 55%, respectively.
Embodiments 7-8 differ from Embodiment 1 in that the base neutralizer is NaHCO3 and KHCO3, respectively. The results are as follows: molar yields of 2,5-Bishydroxymethylfuran are 56% and 47%, respectively.
Embodiments 9-13 differ from Embodiment 1 in that the reaction for obtaining 2,5-bishydroxymethylfuran using 5-chloromethylfurfural is performed for 1 hour, 3 hours, 4 hours, 5 hours, and 6 hours, respectively. The results are as follows: molar yields of 2,5-Bishydroxymethylfuran are 51%, 78%, 81%, 76%, and 75%, respectively.
Embodiments 14-16 differ from Embodiment 1 in that the reaction for obtaining 2,5-bishydroxymethylfuran using 5-chloromethylfurfural is performed for 4 hours at 40° C., 50° C., and 60° C., respectively. The results are as follows: molar yields of 2,5-bishydroxymethylfuran are 28%, 73%, and 91%, respectively.
Embodiments 17-19 differ from Embodiment 1 in that the reaction for obtaining 2,5-bishydroxymethylfuran using 5-chloromethylfurfural is performed at 60° C. with the initial H2 pressure of 2 MPa, 3 MPa, and 5 MPa for 4 hours. The results are as follows: molar yields of 2,5-bishydroxymethylfuran are 39%, 58%, and 84%, respectively.
The above-mentioned results are summarized in the following table:
Based on the results of the above-mentioned embodiments, it is shown that the catalyst (Ru/CuO, especially when the loading amount of Ru is 5 wt % relative to carrier CuO) and the base neutralizer (especially CaCO3) provided by the present disclosure can be effectively used in a preparation of 2,5-bishydroxymethylfuran (a high value-added fine chemical product) by hydrogenation of 5-chloromethylfurfural. The molar yield of 2,5-bishydroxymethylfuran is 91% under an optimal reaction condition, i.e., a temperature of the reaction is 60° C., a time of the reaction is 4 hours, and the initial pressure of H2 is 4 MPa.
The embodiments are merely used for an objective of providing exemplary illustrations, and the protective scope of the present disclosure is not limited thereto in any way. Thus, it is intended that the protective scope of the present disclosure cover improvements and modifications provided they are improved or modified based on the aforementioned illustrations by person skilled in the art.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202111298723.0 | Nov 2021 | CN | national |
This application is a continuation of International patent application PCT/CN2022/099830, filed on Jun. 20, 2022, which claims priority to Chinese patent application 202111298723.0, filed on Nov. 4, 2021. International patent application PCT/CN2022/099830 and Chinese patent application 202111298723.0 are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2022/099830 | Jun 2022 | WO |
| Child | 18655540 | US |
