CN105254598A - Method for synthesizing 3-tetrahydrofurfuryl alcohol - Google Patents
Method for synthesizing 3-tetrahydrofurfuryl alcohol Download PDFInfo
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- CN105254598A CN105254598A CN201510774897.8A CN201510774897A CN105254598A CN 105254598 A CN105254598 A CN 105254598A CN 201510774897 A CN201510774897 A CN 201510774897A CN 105254598 A CN105254598 A CN 105254598A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
Abstract
The invention relates to a method for synthesizing 3-tetrahydrofurfuryl alcohol. According to the technical scheme, 2-bromoethanol and diethyl malonate serve as starting materials, under the alkaline condition, 2-hydroxyethyl-diethyl malonate is generated through a reaction, hydrolysis is conducted on the 2-hydroxyethyl-diethyl malonate to generate 2-hydroxyethyl-malonate, catalyzing and high-pressure hydrotreatment are conducted on the 2-hydroxyethyl-malonate to generate 2-hydroxymethyl-1,4-butanediol, and dehydration cyclization is conducted on the 2-hydroxyethyl-1,4-butanediol to generate the 3-tetrahydrofurfuryl alcohol. According to the method for synthesizing the 3-tetrahydrofurfuryl alcohol, the yield can reach over 85 percent, the purity can reach above 95 percent, the reaction condition is mild, the cost is low, operation is easy, and the method has the advantage of being suitable for industrial production.
Description
Technical field
The present invention relates to a kind of novel synthesis of third generation nicotinic insecticide intermediate, be specifically related to a kind of method of synthesizing 3-tetrahydrofurfuryl carbinol, belong to veterinary drug technical field.
Background technology
3-tetrahydrofurfuryl carbinol is the important intermediate of synthesis third generation nicotinic insecticide MTI-446, MTI-446 is developed by Mitsui company, in 2002 in Japanese first registration registration listing, now obtain agriculture chemical registration in multiple country, MTI-446 has efficiently, the feature of wide spectrum, interior suction good penetrability, to hydrobiont, birds, mammalian safe.Be applicable to the insects such as vegetables, fruit tree, paddy rice and flowers control Hymenoptera, Diptera, Orthoptera, beetle order, lepidopteran and Hemiptera.
For the synthesis of 3-tetrahydrofurfuryl carbinol, the people such as bibliographical information Gilbert use prior synthesizing method as follows in European patent WO2005065689:
。
Use metal borohydride to make reductive agent in described synthetic route, increase considerably product cost.Therefore, a kind of method developing synthesis 3-tetrahydrofurfuryl carbinol is newly needed, to reduce costs, to alleviate agriculture burden.
Summary of the invention
Technical problem to be solved by this invention overcomes the defect of prior art, provides a kind of method of synthesis 3-tetrahydrofurfuryl carbinol newly, and it is low, simple to operate that the method for described synthesis 3-tetrahydrofurfuryl carbinol has cost, is suitable for the features such as suitability for industrialized production.
Technical problem of the present invention is solved by following technical scheme.
Synthesize a method for 3-tetrahydrofurfuryl carbinol, synthetic route is as follows:
。
The method of above-mentioned synthesis 3-tetrahydrofurfuryl carbinol, comprises the steps:
(1) with ethylene bromohyrin and diethyl malonate for raw material, in the basic conditions, 0 DEG C-100 DEG C reactions generate 2-hydroxyethyl-diethyl malonates;
(2) 2-hydroxyethyl-diethyl malonate is under highly basic or strong acid effect, and 10 DEG C-100 DEG C hydrolysis generate 2-hydroxyethyl-propanedioic acid;
(3) 2-hydroxyethyl-propanedioic acid generates 2-methylol-BDO through Hydrogenation;
(4) 2-methylol-BDO dehydration condensation under acid effect generates 3-tetrahydrofurfuryl carbinol.
The method of above-mentioned synthesis 3-tetrahydrofurfuryl carbinol, in step (1), the mol ratio of described ethylene bromohyrin and diethyl malonate is 1.0 ~ 2.0:1; Described alkali is selected from potassium hydroxide, salt of wormwood, sodium bicarbonate, sodium methylate, sodium ethylate, sodium tert-butoxide, sodium isopropylate, potassium tert.-butoxide, sodium hydride, and the mol ratio of itself and diethyl malonate is 1.0 ~ 1.5:1.
The method of above-mentioned synthesis 3-tetrahydrofurfuryl carbinol, in step (2), described alkali is mass concentration 20% sodium hydroxide solution, and the mass ratio of itself and 2-hydroxyethyl-diethyl malonate is 3.0 ~ 5.0:1; Described acid is the hydrochloric acid of mass concentration 20%, and the mass ratio of itself and 2-hydroxyethyl-diethyl malonate is 3.5 ~ 5.0:1
The method of above-mentioned synthesis 3-tetrahydrofurfuryl carbinol, in step (3), the condition of described Hydrogenation is: pressure 2.0 ~ 20.0MPa, and hydrogenation catalyst is Ru/C, Pb/C, Rh/C, Ru-Sn/ZnCl
2, Ru-Sn/C, Cu/SiO
2deng, hydrogenation temperature is 110 DEG C ~ 300 DEG C.
The method of above-mentioned synthesis 3-tetrahydrofurfuryl carbinol, in step (4), under described acid or catalyst action, the condition of dehydration condensation is: acid is selected from methylsulphonic acid, the vitriol oil, polyphosphoric acid, tosic acid or Catalysts Cu/ZnO/ZrO
2, the mass ratio of itself and 2-methylol-BDO is 0.05 ~ 0.2:1.; Cyclization temperature is 80 DEG C ~ 200 DEG C; Cyclization solvent is selected from toluene or dimethylbenzene.
The method of above-mentioned synthesis 3-tetrahydrofurfuryl carbinol, in step (1), described alkali is sodium ethylate, sodium methylate, sodium tert-butoxide, sodium isopropylate, potassium tert.-butoxide etc., preferred alcohol sodium
The method of above-mentioned synthesis 3-tetrahydrofurfuryl carbinol, in step (3), the condition of described Hydrogenation is pressure 7.0-15.0MP, and hydrogenation catalyst is Ru/C, and hydrogenation temperature is 150 DEG C ~ 200 DEG C.
The method of above-mentioned synthesis 3-tetrahydrofurfuryl carbinol, in step (4), the condition of the lower dehydration condensation of described acid effect is: acid is methylsulphonic acid; Cyclization temperature is 50 DEG C ~ 150 DEG C; Cyclization solvent is toluene.
The method of synthesis 3-tetrahydrofurfuryl carbinol of the present invention, four step total recoverys can reach more than 73%, 3-tetrahydrofurfuryl carbinol purity can reach more than 95%, and reaction conditions is gentle, cost is low, simple to operate, is suitable for suitability for industrialized production.With greatly produce now diethyl malonate and ethyl bromoacetate and react and generate ethane-1,1,2-tricarboxylic acid ethyl ester, ethane-1,1,2-tricarboxylic acid ethyl ester is reduced into 2-methylol-BDO through metal borohydride, 2-methylol-1,4-butyleneglycol dehydration condensation under acidity or catalyzer existence condition generates 3-tetrahydrofurfuryl carbinol route and compares, and eliminates reduction ethane-1,1, the metal borohydride of 2-tricarboxylic acid ethyl ester, greatly reduces production cost.
Embodiment
Below by specific embodiment, the present invention is described in further detail, but these embodiments are only used for explaining the present invention, do not really want to limit the protection domain of embodiments of the present invention or patent.
Embodiment 1, synthesis 3-tetrahydrofurfuryl carbinol
(1) in 500ml tetra-mouthfuls of reaction flasks, diethyl malonate 54g(0.3375mol is added) and the t-butanol solution 227g of 20% potassium tert.-butoxide of 45.4g potassium tert.-butoxide preparation, stirring at room temperature 30 minutes, temperature control 25 DEG C ~ 28 DEG C starts to drip ethylene bromohyrin 46.5g(0.3720mol), drip to finish and be warming up to 50 DEG C, insulation reaction 1.5 hours, less than 75 DEG C Rotary Evaporators steam solvent, suction filtration obtains colourless oil liquid 2-hydroxyethyl-diethyl malonate 64.6g(0.3167mol), purity 97%(GC), yield 91%;
(2) in 500ml tetra-mouthfuls of reaction flasks, 2-hydroxyethyl-diethyl malonate 64.6g (0.3167mol) is added, add 20% sodium hydroxide solution 76g, be warming up to 45 DEG C, stirring reaction 2 hours, be cooled to 25 DEG C, add 20% hydrochloric acid and be about 69.3g, adjust PH=6-7, less than 80 DEG C evaporated under reduced pressure, filter, obtain colourless oil liquid 2-hydroxyethyl-propanedioic acid 45.9g(0.3040mol), purity: 95%(GC), yield: 96%;
(3) in autoclave, 2-hydroxyethyl-propanedioic acid 45.9g(0.3040mol is dropped into), water 50g, Ru/C2.3g, nitrogen replacement reactor 3-5 time, makes hydrogen pressure reach 7.0MPa gauge pressure, 220 DEG C are reacted 4 hours, cooling, filtration catalizer obtains colourless or pale yellow oil 2-methylol-BDO 35.0g(0.2797mol), purity: 96%(GC), yield 92%;
(4) in the 500ml reaction flask that reflux exchanger is housed, 2-methylol-1 is added, 4-butyleneglycol 35.0g(0.2797mol), toluene 150g, vitriol oil 2.3g, heating reflux reaction 5 hours, terminates, decompression steams solvent, obtain pale yellow oil 3-tetrahydrofurfuryl carbinol 25.5g(0.1918mol), purity 95%(GC), yield 85%.
1H-NMR(400MHz,CDCl
3)&(ppm)1.647(m,1H),1.989(m,1H),2.187(m,1H,D
2O),OH),2.42(m,1H),3.468-3.62(m,4H),3.661-3.867(m,2H)
Embodiment 2
(1) in 500ml tetra-mouthfuls of reaction flasks, diethyl malonate 54g(0.3375mol is added) and by the methanol solution 194.4g of 20% sodium tert-butoxide of 38.9g sodium tert-butoxide preparation, stirring at room temperature 40 minutes, start to drip ethylene bromohyrin 46.5g, drip to finish and be warming up to 50 DEG C, react 2 hours, less than 75 DEG C Rotary Evaporators steam solvent, and suction filtration obtains 2-hydroxyethyl-diethyl malonate 63.2g(0.3304mol), purity 97%(GC), yield 89%;
(2) in 500ml tetra-mouthfuls of reaction flasks, 2-hydroxyethyl-diethyl malonate 63.2g(0.3304mol is added), add 20% hydrochloric acid 72.4g, be warming up to 45 DEG C, stirring reaction 3 hours, be cooled to 25 DEG C, add 20% sodium hydroxide solution and be about 79g, adjust PH=6-7, less than 80 DEG C evaporated under reduced pressure, filter, obtain 2-hydroxyethyl-propanedioic acid 47.1g(0.3106mol), purity: 95%(GC), yield: 94%;
(3) in autoclave, 2-hydroxyethyl-propanedioic acid 47.1g(0.3106mol is dropped into), water 45g, Pb/C2.0g, nitrogen replacement reactor 3-5 time, makes hydrogen pressure reach 9.0MPa gauge pressure, 240 DEG C are reacted 4 hours, cooling, filtration catalizer obtains 2-methylol-BDO 33.0g(0.2640mol), purity: 96%(GC), yield 85%;
(4) in the 500ml reaction flask that reflux exchanger is housed, 2-methylol-1 is added, 4-butyleneglycol 33.0g(0.2640mol), toluene 120g, polyphosphoric acid 2.0g, heating reflux reaction 5 hours, terminates, decompression steams solvent, obtain 3-tetrahydrofurfuryl carbinol 24.9(0.2323mol) g, purity 95%(GC), yield 88%.
Embodiment 3
(1) in 500ml tetra-mouthfuls of reaction flasks, add diethyl malonate 54g(0.3375mol) and 21.9g sodium methylate preparation 30% methanol solution of sodium methylate 72.9g, stirring at room temperature 30 minutes, start to drip ethylene bromohyrin 46.2g, drip to finish and be warming up to 50 DEG C, insulation reaction 1 hour, less than 75 DEG C Rotary Evaporators steam solvent, and suction filtration obtains 2-hydroxyethyl-diethyl malonate 60.3g(0.2869mol), purity 97%(GC), yield 85%;
(2) in 500ml tetra-mouthfuls of reaction flasks, 2-hydroxyethyl-diethyl malonate 60.3g(0.2869mol is added), add 20% sodium hydroxide solution 69g, be warming up to 45 DEG C, stirring reaction 3 hours, be cooled to 25 DEG C, add 20% hydrochloric acid and be about 63g, adjust PH=6-7, less than 80 DEG C evaporated under reduced pressure, filter, obtain 2-hydroxyethyl-propanedioic acid 42.5g(0.2726mol), purity: 95%(GC), yield: 95%.
(3) in autoclave, 2-hydroxyethyl-propanedioic acid 42.5g(0.2726mol is dropped into), water 50g, Ru-Sn/ZnCl
24.2g, nitrogen replacement reactor 3-5 time, makes hydrogen pressure reach 9.0MPa gauge pressure, and 260 DEG C are reacted 4 hours, and filtration catalizer obtains 2-methylol-BDO 29.0g(0.2317mol), purity: 96%(GC), yield 85%.
(4) in the 500ml reaction flask that reflux exchanger is housed, 2-methylol-1 is added, 4-butyleneglycol 29.0g(0.2317mol), toluene 120g, tosic acid 1.8g, heating reflux reaction 5 hours, terminates, decompression steams solvent, obtain 3-tetrahydrofurfuryl carbinol 21.4g(0.1993mol), purity 95%(GC), yield 86%.
Embodiment 4
(1) in 500ml tetra-mouthfuls of reaction flasks, diethyl malonate 54g(0.3375mol is added) and the ethanolic soln 137.7g4 of 20% sodium ethylate of 27.6g sodium ethylate preparation, stirring at room temperature 30 minutes, temperature control 25 DEG C ~ 28 DEG C starts to drip ethylene bromohyrin 46.5g(0.3720mol), drip to finish and be warming up to 50 DEG C, insulation reaction 1.5 hours, less than 75 DEG C Rotary Evaporators steam solvent, suction filtration obtains colourless oil liquid 2-hydroxyethyl-diethyl malonate 66.0g(0.3139mol), purity 97%(GC), yield 93%;
(2) in 500ml tetra-mouthfuls of reaction flasks, 2-hydroxyethyl-diethyl malonate 66.0g(0.3139mol is added), add 20% hydrochloric acid 68.7g, be warming up to 45 DEG C, stirring reaction 2 hours, be cooled to 25 DEG C, add 20% sodium hydroxide solution and be about 75.3g, adjust PH=6-7, less than 80 DEG C evaporated under reduced pressure, filter, obtain colourless oil liquid 2-hydroxyethyl-propanedioic acid 47.4g(0.3041mol), purity: 95%(GC), yield: 97%;
(3) in autoclave, 2-hydroxyethyl-propanedioic acid 47.4g(0.3041mol is dropped into), water 50g, Ru-Sn/C2.3g, nitrogen replacement reactor 3-5 time, makes hydrogen pressure reach 11.0MPa gauge pressure, and 230 DEG C are reacted 4 hours, filtration catalizer obtains colourless or pale yellow oil 2-methylol-1,4-butyleneglycol 36.9g(0.2950mol), purity: 96%(GC), yield 95%;
(4) in the 500ml reaction flask that reflux exchanger is housed, 2-methylol-BDO 36.9g(0.2950mol is added), toluene 150g, Cu/ZnO/ZrO
2 .3g, heating reflux reaction 5 hours, terminates, and decompression steams solvent, obtains pale yellow oil 3-tetrahydrofurfuryl carbinol 26.3g(0.2449mol), purity 95%(GC), yield 83%.
Embodiment 5
(1) in 500ml tetra-mouthfuls of reaction flasks, diethyl malonate 54g(0.3375mol is added) and the aqueous isopropanol 152.2g of 20% sodium isopropylate of 27.6g sodium isopropylate preparation, stirring at room temperature 30 minutes, temperature control 25 DEG C ~ 28 DEG C starts to drip ethylene bromohyrin 46.5g(0.3720mol), drip to finish and be warming up to 50 DEG C, insulation reaction 1.5 hours, less than 75 DEG C Rotary Evaporators steam solvent, suction filtration obtains colourless oil liquid 2-hydroxyethyl-diethyl malonate 66.7g(0.3172mol), purity 97%(GC), yield 94%;
(2) in 500ml tetra-mouthfuls of reaction flasks, 2-hydroxyethyl-diethyl malonate 66.7g(0.3172mol is added), add 20% sodium hydroxide solution 76.1g, be warming up to 45 DEG C, stirring reaction 2 hours, be cooled to 25 DEG C, add 20% hydrochloric acid and be about 69.5g, adjust PH=6-7, less than 80 DEG C evaporated under reduced pressure, filter, obtain colourless oil liquid 2-hydroxyethyl-propanedioic acid 47.4g(0.3045mol), purity: 95%(GC), yield: 96%; .
(3) in autoclave, 2-hydroxyethyl-propanedioic acid 47.4g(0.3045mol is dropped into), water 50g, Cu/SiO
22.3g, nitrogen replacement reactor 3-5 time, makes hydrogen pressure reach 12.0MPa gauge pressure, and 240 DEG C are reacted 4 hours, and filtration catalizer obtains colourless or pale yellow oil 2-methylol-BDO 36.2g(0.2797mol), purity: 96%(GC), yield 95%;
(4) in the 500ml reaction flask that reflux exchanger is housed, 2-methylol-1 is added, 4-butyleneglycol 36.2g(0.2797mol), toluene 150g, methylsulphonic acid 1.6g, heating reflux reaction 5 hours, terminates, decompression steams solvent, obtain pale yellow oil 3-tetrahydrofurfuryl carbinol 25.2g(0.1918mol), purity 95%(GC), yield 86%.
Below be only the preferred embodiments of the present invention, to those skilled in the art, under the premise without departing from the principles of the invention, the improvement that can make, modification, equivalent replacement etc., all should be included within protection scope of the present invention.
Claims (8)
1. synthesize a method for 3-tetrahydrofurfuryl carbinol, it is characterized in that, comprise the steps:
(1) with ethylene bromohyrin and diethyl malonate for raw material, in the basic conditions, 0 DEG C-100 DEG C reactions generate 2-hydroxyethyl-diethyl malonates;
(2) 10 DEG C-100 DEG C hydrolysis under highly basic or strong acid effect of 2-hydroxyethyl-diethyl malonate generate 2-hydroxyethyl-propanedioic acid;
(3) 2-hydroxyethyl-propanedioic acid generates 2-methylol-BDO through Hydrogenation;
(4) 2-methylol-BDO dehydration condensation under acid or catalyst action generates 3-tetrahydrofurfuryl carbinol.
2. the method for synthesis 3-tetrahydrofurfuryl carbinol according to claim 1, it is characterized in that, in step (1), the mol ratio of described ethylene bromohyrin and diethyl malonate is 1.0 ~ 2.0:1; Described alkali is selected from sodium methylate, sodium ethylate, sodium tert-butoxide, sodium hydride, potassium hydride KH, potassium tert.-butoxide, sodium isopropylate, potassium hydroxide, salt of wormwood, sodium bicarbonate, and the mol ratio of itself and diethyl malonate is 1.0 ~ 1.5:1.
3. the method for synthesis 3-tetrahydrofurfuryl carbinol according to claim 1 and 2, it is characterized in that, in step (2), described alkali is sodium hydroxide in 20% sodium hydroxide solution, is 3.0 ~ 5.0:1. with the mass ratio of 2-hydroxyethyl-diethyl malonate; Described acid is hydrochloric acid in 20% hydrochloric acid, is 3.5 ~ 5.0:1 with the mass ratio of 2-hydroxyethyl-diethyl malonate.
4. the method for synthesis 3-tetrahydrofurfuryl carbinol according to claim 3, it is characterized in that, in step (3), the condition of described Hydrogenation is: pressure 2.0 ~ 20.0MP, and hydrogenation catalyst is Ru/C, Pb/C, Rh/C or Ru-Sn/ZnCl
2, Ru-Sn/C, Cu/SiO
2, hydrogenation temperature is 210 DEG C ~ 300 DEG C.
5. the method for synthesis 3-tetrahydrofurfuryl carbinol according to claim 4, is characterized in that, in step (4), the condition of the lower dehydration condensation of described acid effect is: acid is selected from methylsulphonic acid, the vitriol oil, polyphosphoric acid, tosic acid, Cu/ZnO/ZrO
2, the mol ratio of itself and 2-methylol-BDO is 0.05 ~ 0.2:1; Cyclization temperature is 50 DEG C ~ 200 DEG C; Cyclization solvent is selected from toluene, dimethylbenzene.
6. the method for synthesis 3-tetrahydrofurfuryl carbinol according to claim 5, is characterized in that, in step (1), described alkali be sodium ethylate, sodium methylate, sodium tert-butoxide, sodium isopropylate, potassium tert.-butoxide etc., preferred alcohol sodium.
7. the method for synthesis 3-tetrahydrofurfuryl carbinol according to claim 6, it is characterized in that, in step (3), the condition of described Hydrogenation is pressure 7.0-15.0MP, and hydrogenation catalyst is Rh/C, and hydrogenation temperature is 150 DEG C ~ 200 DEG C.
8. the method for synthesis 3-tetrahydrofurfuryl carbinol according to claim 7, is characterized in that, in step (4), the condition of the lower dehydration condensation of described acid effect is: acid is polyphosphoric acid; Cyclization temperature is 50 DEG C ~ 150 DEG C; Cyclization solvent is toluene.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107793383A (en) * | 2017-12-06 | 2018-03-13 | 成都化润药业有限公司 | A kind of preparation method of 3 hydroxymethyl tetrahydrofuran |
CN108620103A (en) * | 2018-04-23 | 2018-10-09 | 南京工业大学 | A kind of catalyst preparing (S) -3- hydroxyl tetrahydrofurans and its preparation and application method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104193701A (en) * | 2014-08-25 | 2014-12-10 | 西安近代化学研究所 | Synthetic method for 3-hydroxymethyl tetrahydrofuran |
-
2015
- 2015-11-13 CN CN201510774897.8A patent/CN105254598A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104193701A (en) * | 2014-08-25 | 2014-12-10 | 西安近代化学研究所 | Synthetic method for 3-hydroxymethyl tetrahydrofuran |
Non-Patent Citations (5)
Title |
---|
上海科学技术情报研究所: "加氢反应", 《国外催化剂发展概况 2 催化剂的应用》 * |
侯芙生: "加氢裂化催化剂", 《中国炼油技术 第3版》 * |
张峻炜等: "脂肪酸酯催化加氢制脂肪醇研究进展", 《广州化工》 * |
王科等: "草酸酯加氢制乙二醇Cu/SiO2 催化剂的制备及性能研究", 《天然气化工》 * |
黄维捷等: "草酸二甲酯加氢制乙二醇Cu/SiO2催化剂的制备与改性", 《工业催化》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107793383A (en) * | 2017-12-06 | 2018-03-13 | 成都化润药业有限公司 | A kind of preparation method of 3 hydroxymethyl tetrahydrofuran |
CN108620103A (en) * | 2018-04-23 | 2018-10-09 | 南京工业大学 | A kind of catalyst preparing (S) -3- hydroxyl tetrahydrofurans and its preparation and application method |
CN108620103B (en) * | 2018-04-23 | 2021-07-06 | 南京工业大学 | Catalyst for preparing (S) -3-hydroxytetrahydrofuran and preparation and use methods thereof |
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