CN117050039A - Preparation method of bis- (5-hydroxymethyl furfuryl) ether - Google Patents
Preparation method of bis- (5-hydroxymethyl furfuryl) ether Download PDFInfo
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- CN117050039A CN117050039A CN202311024846.4A CN202311024846A CN117050039A CN 117050039 A CN117050039 A CN 117050039A CN 202311024846 A CN202311024846 A CN 202311024846A CN 117050039 A CN117050039 A CN 117050039A
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- Prior art keywords
- bis
- ether
- reaction
- furfuryl
- hydroxymethyl
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 7
- TZTWOBUHCLWLNK-UHFFFAOYSA-N 5-[(5-formylfuran-2-yl)methoxymethyl]furan-2-carbaldehyde Chemical compound O1C(C=O)=CC=C1COCC1=CC=C(C=O)O1 TZTWOBUHCLWLNK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- -1 sodium triacetoxyborohydride Chemical compound 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 4
- 238000010791 quenching Methods 0.000 claims abstract description 4
- 239000012321 sodium triacetoxyborohydride Substances 0.000 claims abstract description 4
- 229910000085 borane Inorganic materials 0.000 claims abstract description 3
- UWTDFICHZKXYAC-UHFFFAOYSA-N boron;oxolane Chemical compound [B].C1CCOC1 UWTDFICHZKXYAC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000171 quenching effect Effects 0.000 claims abstract description 3
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- PYLNCKLYWMVDNC-UHFFFAOYSA-N [5-[[5-(hydroxymethyl)furan-2-yl]methoxymethyl]furan-2-yl]methanol Chemical compound O1C(CO)=CC=C1COCC1=CC=C(CO)O1 PYLNCKLYWMVDNC-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000012824 chemical production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012065 filter cake Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses a preparation method of bis- (5-hydroxymethyl furfuryl) ether, which comprises the following steps: s1, replacing a reaction container with a protective gas, starting stirring, adding bis- (5-formylfurfuryl) ether, and adding a solvent; s2, controlling the temperature to be between 20 ℃ below zero and 20 ℃, and adding a solution containing one or any combination of sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride, lithium aluminum hydride or borane and tetrahydrofuran borane in batches; s3, controlling the temperature to be 0-100 ℃, and stirring and reacting for 0.1-24 hours; s4, adding water into the water quenching reaction system after the reaction is finished; s5, separating solid and liquid phases, and transferring the obtained solid to an oven for drying to obtain the bis- (5-hydroxymethyl furfuryl) ether. The invention adopts bis- (5-formylfurfuryl) ether as a raw material, and the product is obtained through reduction by a common reducing agent. Less byproducts and simple operation, and the method is suitable for large-scale chemical production.
Description
Technical Field
The invention relates to the field of preparation of bis- (5-hydroxymethyl furfuryl) ether, in particular to a preparation method of bis- (5-hydroxymethyl furfuryl) ether.
Background
Currently, bis- (5-hydroxymethylfurfuryl) ether is generally prepared by reduction of bis- (5-formylfurfuryl) ether. According to literature reports, bis- (5-formylfurfuryl) ether may be reduced to bis- (5-hydroxymethylfurfuryl) ether under hydrogen at a pressure in the presence of a palladium on carbon catalyst. However, noble metal catalysts, especially noble metal catalysts having a palladium content of up to 30%, lead to high production costs and are therefore not ideal commercial routes. In addition, compared with the hydrogenation reduction carried out in a pressure vessel, the chemical oxidation, especially the chemical oxidation carried out in a solvent such as methanol, has the advantages of mild reaction and simple operation, and is more suitable for the industrial production of special and special chemicals. However, bis- (5-hydroxymethylfurfuryl) ether is hardly soluble in water compared to other bio-based chemicals such as 5-hydroxymethylfuran-2-carbaldehyde which are easily dissolved in solvents such as methanol, making the chemical reduction process in solvents such as methanol difficult.
In view of this, it is an urgent need to solve the above-mentioned deficiencies of the prior art how to achieve the synthesis of bis- (5-hydroxymethyl furfuryl) ether by a mild, efficient and low cost method.
Disclosure of Invention
The invention aims to provide a preparation method of bis- (5-hydroxymethyl furfuryl) ether, which optimizes a treatment process, and can realize the large-scale production from kilogram level to ton level so as to solve the problem of blank production of bis- (5-formoxyl) hydroxy) ether in the existing market.
In order to solve the problems, the invention provides a preparation method of bis- (5-hydroxymethyl furfuryl) ether, which comprises the following steps:
s1, replacing nitrogen in a reaction container for three times, starting stirring, adding bis- (5-formylfurfuryl) ether, adding one solvent of methanol or tetrahydrofuran or 2-methyltetrahydrofuran or toluene into the container, and adding the solvent into the container;
s2, controlling the temperature to be between 20 ℃ below zero and 20 ℃, and adding sodium borohydride or sodium cyanoborohydride or sodium triacetoxyborohydride or lithium aluminum hydride or borane or tetrahydrofuran borane solution or any combination of the reducing agents in batches;
s3, controlling the temperature between 0 ℃ and 100 ℃ and stirring and reacting for 0-24 hours;
s4, adding water into the water quenching reaction system after the reaction is finished;
s5, separating solid and liquid phases, transferring the obtained solid to an oven for drying, and obtaining the bis- (5-hydroxymethyl furfuryl) ether with the purity of more than 99%.
The present invention prepares bis- (5-hydroxymethyl furfuryl) ether by bis- (5-formylfurfuryl) ether as follows:
the invention obtains the high-purity product by adding water to quench the reducer and separating out the product and then carrying out solid-liquid separation.
Compared with the prior art, the invention has the following advantages:
the invention adopts bis- (5-formylfurfuryl) ether as a raw material, and the product is obtained through reduction by a common reducing agent. Less byproducts and simple operation, and the method is suitable for large-scale chemical production.
The whole process of the invention has short reaction time and high efficiency. The method has the advantages of mild reaction, low cost and simple operation, and is suitable for large-scale industrial production.
Drawings
Fig. 1 is a mass spectrum ([ m+na ] = 261) of bis- (5-hydroxymethylfurfuryl) ether prepared in example 1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of bis- (5-hydroxymethylfurfuryl) ether prepared in example 1.
Detailed Description
Example 1
1L reaction flask, nitrogen gas is replaced for three times, stirring is started, 100.0g of bis- (5-formylfurfuryl) ether is added, 237.0g of methanol is added, the temperature is controlled to be 0-5 ℃, 8.08g of sodium borohydride is added in batches, the reaction is stirred for 0.5h, 100.0g of water is added, the temperature is kept at 5+/-10 ℃ for stirring for 1h, suction filtration is carried out, a filter cake is leached with 150.0g of water for three times, the filter cake is transferred to an oven, and the filter cake is dried at 45 ℃ to obtain the product bis- (5-hydroxymethyl furfuryl) ether.
As shown in FIG. 1, the relative molecular masses of the synthetic compounds were shown to be identical to that of bis- (5-hydroxymethylfurfuryl) ether.
As shown in FIG. 2, the chemical shift of the hydrogen of the synthesized compound is shown to coincide with the chemical shift of the bis- (5-hydroxymethyl furfuryl) ether.
Example 2
1L reaction flask, nitrogen gas replace three times, start stirring, add bis- (5-formylfurfuryl) ether 100.0g, add acetic acid 314.8g, control temperature 0-5 deg.C, add cyano sodium borohydride 53.6g in batches, after adding, stir and react for 0.5h, concentrate the system until there is no obvious fraction, concentrate the obtained solid and add 300.0g water, stir for 1h, suction filter, filter cake three times with 150.0g water, filter cake transfer to oven, oven dry at 45 deg.C, get the product bis- (5-hydroxymethyl furfuryl) ether.
Example 3
1L reaction flask, nitrogen gas replace three times, start stirring, add bis- (5-formylfurfuryl) ether 100.0g, add dichloromethane 397.5g, control temperature 0-5 deg.C, add sodium triacetoxyborohydride 180.96g in batches, after addition, stir and react for 0.5h, concentrate the system until no obvious fraction, concentrate the obtained solid and add 300.0g water, stir for 1h, suction filter, filter cake three times with 150.0g water, filter cake transfer to oven, oven dry at 45 deg.C, get the product bis- (5-hydroxymethyl furfuryl) ether.
Example 4
1L reaction bottle, nitrogen gas is replaced for three times, stirring is started, 100.0g of bis- (5-formylfurfuryl) ether is added, 267.0g of tetrahydrofuran is added, the temperature is controlled to be 0-5 ℃, 8.1g of lithium aluminum hydride is slowly added in batches, after the addition, stirring is carried out for 0.5h, 100.0g of water is added, the temperature is kept at 5+/-10 ℃ for stirring for 1h, suction filtration is carried out, the filter cake is leached with 150.0g of water for three times, the filter cake is transferred to an oven, and the filter cake is dried at 45 ℃ to obtain the product bis- (5-hydroxymethyl furfuryl) ether.
Claims (6)
1. A method for preparing bis- (5-hydroxymethyl furfuryl) ether, which is characterized by comprising the following steps:
s1, replacing a reaction container with a protective gas, starting stirring, adding bis- (5-formylfurfuryl) ether, and adding a solvent;
s2, controlling the temperature to be between 20 ℃ below zero and 20 ℃, and adding a solution containing one or any combination of sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride, lithium aluminum hydride or borane and tetrahydrofuran borane in batches;
s3, controlling the temperature to be 0-100 ℃, and stirring and reacting for 0.1-24 hours;
s4, adding water into the water quenching reaction system after the reaction is finished;
s5, separating solid and liquid phases, and transferring the obtained solid to an oven for drying to obtain the bis- (5-hydroxymethyl furfuryl) ether.
2. The method for producing bis- (5-hydroxymethylfurfuryl) ether according to claim 1, wherein in step S1, the reaction vessel is replaced with nitrogen three times.
3. The method for preparing bis- (5-hydroxymethyl furfuryl) ether according to claim 1, wherein in step S1, the solvent is methanol, tetrahydrofuran, 2-methyltetrahydrofuran or toluene.
4. The method for producing bis- (5-hydroxymethylfurfuryl) ether according to claim 1, wherein in step S3, the reaction is carried out at a temperature of 0℃to 10℃with stirring for 0.1 to 2 hours.
5. The method for preparing bis- (5-hydroxymethyl furfuryl) ether according to claim 1, wherein in step S3, after separating the solid phase from the liquid phase, the solid phase is rinsed with water and then transferred to an oven for drying.
6. The method for preparing bis- (5-hydroxymethyl furfuryl) ether according to claim 1, wherein in step S3, the condition of drying is: drying at 40-50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311024846.4A CN117050039A (en) | 2023-08-15 | 2023-08-15 | Preparation method of bis- (5-hydroxymethyl furfuryl) ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311024846.4A CN117050039A (en) | 2023-08-15 | 2023-08-15 | Preparation method of bis- (5-hydroxymethyl furfuryl) ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117050039A true CN117050039A (en) | 2023-11-14 |
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ID=88668707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311024846.4A Pending CN117050039A (en) | 2023-08-15 | 2023-08-15 | Preparation method of bis- (5-hydroxymethyl furfuryl) ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117050039A (en) |
-
2023
- 2023-08-15 CN CN202311024846.4A patent/CN117050039A/en active Pending
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