CN117567409A - Preparation method of 2, 5-furandinitrile - Google Patents
Preparation method of 2, 5-furandinitrile Download PDFInfo
- Publication number
- CN117567409A CN117567409A CN202311546131.5A CN202311546131A CN117567409A CN 117567409 A CN117567409 A CN 117567409A CN 202311546131 A CN202311546131 A CN 202311546131A CN 117567409 A CN117567409 A CN 117567409A
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- CN
- China
- Prior art keywords
- furandinitrile
- reaction
- thionyl chloride
- drying
- solid
- Prior art date
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- KCSYJHQYWTYFCM-UHFFFAOYSA-N furan-2,5-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)O1 KCSYJHQYWTYFCM-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 47
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000005191 phase separation Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- -1 amide compound Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- YXDXXGXWFJCXEB-UHFFFAOYSA-N 2-furonitrile Chemical compound N#CC1=CC=CO1 YXDXXGXWFJCXEB-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- TVFIYRKPCACCNL-UHFFFAOYSA-N furan-2-carboxamide Chemical compound NC(=O)C1=CC=CO1 TVFIYRKPCACCNL-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 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
- C07D307/56—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a preparation method of 2, 5-furandinitrile, which comprises the following steps: s1, placing 2, 5-furandimethyloxime and a reaction solvent in a reactor to obtain a mixed solution; s2, adding thionyl chloride into the mixed solution obtained in the step S1, and carrying out reflux stirring reaction; s3, spin-drying the solution obtained by the reaction of S2, and removing the solvent and the residual thionyl chloride; s4, placing the solid obtained in the step S3 in a container and adding water and dichloromethane; s5, carrying out two-phase separation on the solution obtained in the step S4; s6, spin-drying the dichloromethane phase obtained by separating the S5 to obtain a solid; s7, drying the solid obtained in the step S6 to obtain the 2, 5-furandinitrile. The invention solves the problems of low efficiency, high production cost, high reaction danger and incapability of industrialized production in the production of 2, 5-furandinitrile in the prior art.
Description
Technical Field
The invention relates to the field of bio-based chemicals, in particular to a preparation method of 2, 5-furandinitrile.
Background
2, 5-furandinitrile is an important biomass-derived platform compound, mainly used for the preparation of biobased adiponitrile, which is a key precursor for the synthesis of nylon 66 and 1,6 Hexamethylene Diisocyanate (HDI).
Chinese patent application publication No. CN116867772a (202280016097.8) discloses a method of supporting molybdenum (Mo) on SiO 2 Mo/SiO obtained on a structured carrier 2 Catalytic reactionA process for producing 2-furancarbonitrile by dehydrating 2-furancarboxamide in the presence of an agent. In this embodiment, the dehydration is preferably performed in the presence of a drying agent such as a molecular sieve. In this embodiment, the production (regeneration) from the amide compound to the nitrile compound can be efficiently performed. That is, in the dehydration reaction of the amide compound used for the regeneration, the formation of by-products can be suppressed, and the target compound can be selectively obtained in high yield. However, this solution is not suitable for preparing 2, 5-furandinitrile from 2, 5-furandimethyloxime.
Therefore, the invention needs to seek a method for industrially producing 2, 5-furandinitrile with lower cost, concise purification mode, mild reaction and higher yield.
Disclosure of Invention
The invention aims to provide a preparation method of 2, 5-furandinitrile, which aims to solve the problems of low efficiency, high production cost, high reaction risk and incapability of industrial production in the production of 2, 5-furandinitrile in the prior art.
In order to solve the problems, the invention provides a preparation method of 2, 5-furandinitrile, which comprises the following steps:
s1, placing 2, 5-furandimethyloxime and a reaction solvent in a container, and cooling;
s2, adding thionyl chloride into the solution obtained in the step S1 in batches, and carrying out reflux stirring reaction at a high temperature of 55 ℃;
s3, spin-drying the solution S2 obtained by the reaction, and removing the solvent and the rest thionyl chloride;
s4, placing the solid obtained in the step S3 in a container and adding water and dichloromethane;
s5, carrying out two-phase separation on the solution obtained in the step S4;
s6, spin-drying the dichloromethane phase obtained by separating the S5 to obtain a solid;
s7, drying the solid obtained in the step S6 to obtain the 2, 5-furandinitrile.
In step S1, the reaction solvent is dichloromethane or tetrahydrofuran.
The molar ratio of the 2, 5-furandimethyloxime to the thionyl chloride is 1:1.5 to 2.5, more preferably 1:1.9 to 2.1.
In step S2, thionyl chloride is added to the mixed solution obtained in step S1 in batches.
In the step S2, the reaction is carried out at 50-60 ℃ under reflux and stirring for 10-20 hours, and more preferably, the reaction is carried out at 55 ℃ under reflux and stirring for 15 hours.
The invention provides a method for synthesizing 2, 5-furandinitrile from 2, 5-furandimethyloxime. The preparation method has the advantages of high production efficiency, low cost, convenient operation and the like, and the production and purification of the target product are relatively simple, thus having great significance for industrial production.
Compared with the prior art, the invention has the following advantages:
the invention adopts 2, 5-furan dimethyl oxime as raw material, adopts thionyl chloride, firstly chloridizes and then eliminates to remove hydroxyl, has fewer byproducts, is easy to remove, and the purification method is suitable for large-scale chemical production.
The whole process of the invention has short reaction time and high efficiency. The reaction temperature is low, the cost is low, the purification mode is simple and easy to operate, and the method is suitable for large-scale industrial production.
Drawings
FIG. 1 is a scheme showing the reaction for synthesizing a compound of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the compound of example 1 of the present invention.
Detailed Description
EXAMPLE 1 Synthesis of 2, 5-Furanodicarbonitrile
Thionyl chloride (154 g,1.29 mol) was slowly added dropwise to a mixture of 2, 5-furandimethyloxime (100 g,0.649 mol) and methylene chloride (300 ml) at room temperature at 25℃and the mixture was stirred at 55℃under reflux for 15.0 hours. The reaction solution was dried by spin-drying to remove dichloromethane and remaining thionyl chloride. The obtained solid is placed in a container, water and methylene dichloride are added, filtration and filtrate separation are carried out, the methylene dichloride obtained by separation is dried by spinning, 51g of solid (yield 66.56% and purity 98.3%) is obtained, and the solid is dried, and the nuclear magnetic resonance spectrum is shown as figure 2, so that the obtained product 2, 5-furandinitrile is indicated.
EXAMPLE 2 Synthesis of 2, 5-Furanodicarbonitrile
Thionyl chloride (154 g,1.29 mol) was slowly added dropwise to a mixture of 2, 5-furandimethyloxime (100 g,0.649 mol) and tetrahydrofuran (300 ml) at room temperature at 25℃and the mixture was stirred at 50℃under reflux for 20.0 hours. The reaction solution was dried by spin-drying, and the solvent and the remaining thionyl chloride were removed. Placing the obtained solid in a container, adding water and dichloromethane, filtering, separating filtrate, spin-drying the separated dichloromethane phase to obtain 40g (yield 52.18%, purity 97.4%) of solid, and drying the solid to obtain the product 2, 5-furandinitrile.
EXAMPLE 3 Synthesis of 2, 5-furandinitrile
Thionyl chloride (154 g,1.29 mol) was slowly added dropwise to a mixture of 2, 5-furandimethyloxime (100 g,0.649 mol) and methylene chloride (300 ml) at room temperature at 25℃and the mixture was stirred at 60℃under reflux for 10.0 hours. The reaction solution was dried by spin-drying, and the solvent and the remaining thionyl chloride were removed. The obtained solid is placed in a container, water and methylene dichloride are added, filtration and liquid separation are carried out on the filtrate, the methylene dichloride obtained by separation is dried by spinning, 36g of solid (yield 46.96 percent and purity 98.6 percent) is obtained, and the solid is dried, thus obtaining the product 2, 5-furandinitrile.
Claims (6)
1. The preparation method of the 2, 5-furandinitrile is characterized by comprising the following steps:
s1, placing 2, 5-furandimethyloxime and a reaction solvent in a reactor to obtain a mixed solution;
s2, dropwise adding thionyl chloride into the mixed solution obtained in the step S1, and carrying out reflux stirring reaction;
s3, spin-drying the solution obtained by the reaction of S2, and removing the solvent and the residual thionyl chloride;
s4, placing the solid obtained in the step S3 in a container and adding water and dichloromethane;
s5, carrying out two-phase separation on the solution obtained in the step S4;
s6, spin-drying the dichloromethane phase obtained by separating the S5 to obtain a solid;
s7, drying the solid obtained in the step S6 to obtain the 2, 5-furandinitrile.
2. The process for preparing 2, 5-furandinitrile according to claim 1, wherein in step S1, the reaction solvent is dichloromethane or tetrahydrofuran.
3. The method for preparing 2, 5-furandinitrile according to claim 1, wherein the molar ratio of 2, 5-furandimethyloxime to thionyl chloride is 1:1.5 to 2.5.
4. The process for producing 2, 5-furandinitrile according to claim 3, wherein the molar ratio of 2, 5-furandimethyloxime to thionyl chloride is 1:1.9 to 2.1.
5. The process for producing 2, 5-furandinitrile according to claim 1, wherein in step S2, thionyl chloride is added to the mixed solution obtained in step S1 in portions.
6. The process for producing 2, 5-furandinitrile according to claim 1, wherein in step S2, the reaction is carried out at 50 to 60℃under reflux with stirring for 10 to 20 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311546131.5A CN117567409A (en) | 2023-11-20 | 2023-11-20 | Preparation method of 2, 5-furandinitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311546131.5A CN117567409A (en) | 2023-11-20 | 2023-11-20 | Preparation method of 2, 5-furandinitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117567409A true CN117567409A (en) | 2024-02-20 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311546131.5A Pending CN117567409A (en) | 2023-11-20 | 2023-11-20 | Preparation method of 2, 5-furandinitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117567409A (en) |
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2023
- 2023-11-20 CN CN202311546131.5A patent/CN117567409A/en active Pending
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