CN111825643A - Preparation method of 2, 5-dicyanofuran - Google Patents
Preparation method of 2, 5-dicyanofuran Download PDFInfo
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- CN111825643A CN111825643A CN201910298991.9A CN201910298991A CN111825643A CN 111825643 A CN111825643 A CN 111825643A CN 201910298991 A CN201910298991 A CN 201910298991A CN 111825643 A CN111825643 A CN 111825643A
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- Prior art keywords
- diformylfuran
- dicyanofuran
- catalyst
- ammonium
- nitrogen source
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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 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 claims abstract description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 13
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 8
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910003144 α-MnO2 Inorganic materials 0.000 claims description 4
- 229910006648 β-MnO2 Inorganic materials 0.000 claims description 4
- 229910006287 γ-MnO2 Inorganic materials 0.000 claims description 4
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- -1 3-methylacetoacetone Chemical compound 0.000 claims description 2
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 238000002390 rotary evaporation Methods 0.000 description 18
- 238000004817 gas chromatography Methods 0.000 description 12
- 238000000926 separation method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 9
- 238000004445 quantitative analysis Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000002955 isolation Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000004451 qualitative analysis Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940120638 avastin Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying 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
- C07D307/56—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a preparation method of 2, 5-dicyanofuran, which comprises the steps of reacting a mixture containing 2, 5-diformylfuran, a nitrogen source and a catalyst in the presence of an oxidant to obtain 2, 5-dicyanofuran; wherein the catalyst comprises a metal oxide modified with an organic compound. According to the method for preparing 2, 5-dicyanofuran by efficiently catalyzing ammoxidation of 2, 5-diformylfuran, high-quality 2, 5-dicyanofuran is prepared by highly selectively carrying out ammoxidation on 2, 5-diformylfuran under mild conditions. The method has high oxidation efficiency and high product yield; air or oxygen is used as an oxygen source, ammonium salt is used as a nitrogen source, the utilization rate of the nitrogen source is high, and the method is clean and environment-friendly; the product and the catalyst are easy to separate, the post-treatment is simple, and the method has good application prospect.
Description
Technical Field
The application relates to a preparation method of 2, 5-dicyanofuran, belonging to the technical field of chemical product preparation.
Background
The dinitrile is an important chemical intermediate and has very wide application. The derivative diamine shows unique and excellent performance in dye, medicine, curing agent, polymer, etc. At present, the dinitrile is mainly prepared by the gas phase ammoxidation of hydrocarbons, the reaction conditions are harsh, and the production process has high safety and environmental protection cost. In contrast, starting from biobased aldols, nitriles can be prepared by liquid phase ammoxidation under mild conditions. The development of a synthetic route of the bio-based dinitrile has important significance for improving the additional value of bio-based chemicals and relieving and partially replacing non-renewable fossil resources.
The biological and platform compound 2, 5-Diformylfuran (DFF) can be obtained by dehydration and oxidation of carbohydrate. The catalytic ammoxidation of aldehyde groups in DFF can be realized under mild conditions. However, DFF is susceptible to irreversible polycondensation with ammonia; on the other hand, two cyano groups in the 2, 5-dicyanofuran generated by the reaction have strong electron-withdrawing effect, and the cyano groups are easy to be further hydrolyzed to generate amide under the activation of acid-base active sites of the catalyst. There is still a great challenge to improve the selectivity of the ammoxidation of DFF to dinitriles.
Disclosure of Invention
According to one aspect of the application, a method for preparing 2, 5-dicyanofuran from 2, 5-diformylfuran is provided, the method is high in oxidation efficiency and high in product yield.
A method for preparing 2, 5-dicyanofuran is characterized in that a mixture containing 2, 5-diformylfuran, a nitrogen source and a catalyst is reacted in the presence of an oxidant to obtain 2, 5-dicyanofuran;
wherein the catalyst comprises a metal oxide modified with an organic compound.
The application provides a method for preparing 2, 5-dicyanofuran by catalytic ammoxidation of 2, 5-diformylfuran, which takes ammonium salt as a nitrogen source and air or oxygen as an oxidant, and under the action of an organic modified metal oxide catalyst, the 2, 5-diformylfuran is subjected to high-selectivity ammoxidation to form the 2, 5-dicyanofuran.
Alternatively, an organic compound and a metal oxide are put into a solvent, and then 2, 5-diformylfuran and a nitrogen source are added to react in the presence of an oxidizing agent to obtain 2, 5-dicyanofuran.
Optionally, the organic compound comprises at least one of acetylacetone, 3-methylacetoacetone, 1,1, 1-trifluoroacetylacetone, hexafluoroacetylacetone, N-dimethylcyclohexylamine, N-methylpiperidine, N-methyltetrahydropyrrole, proline.
Optionally, the metal oxide comprises at least one of an oxide of manganese, an oxide of cobalt, and an oxide of nickel.
In particular, the oxide of cobalt is Co3O4And CoO.
The oxide of nickel is NiO.
Preferably, the manganese oxide comprises amorphous manganese dioxide, alpha-MnO2、β-MnO2、γ-MnO2、-MnO2At least one of (1).
Optionally, the metal oxide is amorphous manganese dioxide, alpha-MnO2、β-MnO2、γ-MnO2、-MnO2、NiO、Co3O4And CoO.
Optionally, the number of moles of the organic compound is 0.5 to 5% of the number of moles of 2, 5-diformylfuran.
The upper limit of the percentage of moles of organic compound to moles of 2, 5-diformylfuran is selected from 1%, 2%, 3%, 4% or 5%; the lower limit of the percentage of moles of organic compound to moles of 2, 5-diformylfuran is selected from 0.5%, 1%, 2%, 3% or 4%.
Optionally, the amount of the catalyst is 5-20 mol% of 2, 5-diformylfuran;
wherein the moles of the catalyst are based on the moles of the metal oxide.
The upper limit of the percentage of moles of catalyst to moles of 2, 5-diformylfuran is selected from 10%, 15% or 20%; the lower limit of the percentage of moles of catalyst to moles of 2, 5-diformylfuran is selected from 5%, 10% or 15%.
Optionally, the molar ratio of the nitrogen source to the 2, 5-diformylfuran is 1-9: 1;
wherein the number of moles of the nitrogen source is based on the number of moles of the nitrogen source itself.
Optionally, the nitrogen source is selected from at least one of ammonium salts.
Preferably, the ammonium salt is selected from at least one of ammonium formate, ammonium acetate, ammonium oxalate, ammonium carbonate, ammonium bicarbonate, ammonium phosphate.
Optionally, the molar ratio of the ammonium salt to the 2, 5-diformylfuran is 1-9: 1.
optionally, the oxidant comprises an oxygen-containing atmosphere.
Optionally, the oxygen partial pressure of the oxygen-containing atmosphere is 0.1 to 5 MPa.
Preferably, the oxygen-containing atmosphere is selected from oxygen or air.
The upper pressure limit of the oxygen-containing atmosphere is selected from 0.5MPa, 1MPa, 2MPa, 3MPa or 5 MPa; the lower limit of the pressure of the oxygen-containing atmosphere is selected from 0.1MPa, 0.5MPa, 1MPa, 2MPa or 3 MPa.
Optionally, the reaction conditions are: the reaction temperature is 30-120 ℃; the reaction time is 0.5-48 h.
In the present application, the upper limit of the reaction temperature is selected from 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 120 ℃; the lower limit of the reaction temperature is selected from 30 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃.
The upper limit of the reaction time is selected from 5h, 6h, 8h, 12h and 48 h; the lower limit of the reaction time is selected from 0.5h, 5h, 6h, 8h and 12 h.
Optionally, the mixture further comprises a solvent;
the solvent comprises any one of acetonitrile, dioxane, tertiary butanol, tertiary amyl alcohol, toluene and p-xylene.
Alternatively, the method of preparing the catalyst comprises: by using the technology reported by the inventor (Nature Commun, 2018,9:933), the organic compound is modified on the metal oxide by putting the metal oxide and the organic compound into a reaction vessel, adding a solvent, and stirring for 70-75 hours at 25-35 ℃ to obtain the catalyst.
After preparing the catalyst, adding the 2, 5-diformylfuran and a nitrogen source, charging air or oxygen, and reacting to obtain the 2, 5-dicyanofuran.
A preferred method of preparation is described below:
the preparation method comprises the following steps of putting metal oxide and organic modified molecules (namely organic compounds) into a 20mL reaction kettle with a lining, adding a solvent, stirring for 72 hours at 30 ℃, adding 2, 5-diformylfuran and ammonium salt after finishing modification, introducing air or oxygen, reacting for 0.5-48 hours after temperature programming is increased to 30-120 ℃, and oxidizing the 2, 5-diformylfuran into 2, 5-dicyanofuran by ammonia.
Optionally, after the reaction, separation and purification are carried out to obtain the 2, 5-dicyanofuran.
Specifically, purifying 2, 5-dicyanofuran, cooling the reaction mixture to room temperature, centrifuging to remove the catalyst, performing rotary evaporation to remove the solvent, adding water, then adding ethyl acetate for extraction, performing rotary evaporation to remove the solvent, performing vacuum drying, and weighing to calculate the separation yield.
The beneficial effects that this application can produce include:
the application provides a method for preparing 2, 5-dicyanofuran by efficiently catalyzing ammoxidation of 2, 5-diformylfuran, and the high-quality 2, 5-dicyanofuran is prepared by performing high-selectivity ammoxidation on the 2, 5-diformylfuran under mild conditions. The method has high oxidation efficiency and high product yield; air or oxygen is used as an oxygen source, ammonium salt is used as a nitrogen source, the utilization rate of the nitrogen source is high, and the method is clean and environment-friendly; the product and the catalyst are easy to separate, the post-treatment is simple, and the method has good application prospect.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The conversion of 2, 5-diformylfuran ═ 100% (moles of 2, 5-diformylfuran converted/moles of 2, 5-diformylfuran in the starting material); wherein "the number of moles of 2, 5-diformylfuran converted" is "the number of moles of 2, 5-diformylfuran in the starting material-the number of moles of 2, 5-diformylfuran in the product".
Selectivity of 2, 5-dicyanofuran (moles of 2, 5-dicyanofuran produced/moles of 2, 5-diformylfuran converted) x 100%
The product is qualitatively analyzed by gas chromatography-mass spectrometry and compared with the retention time of a standard sample; quantitative analysis was carried out by gas chromatography using an internal standard method. Wherein, the standard sample refers to: 2, 5-dicyanofuran (purity: > 98%; source: avastin).
The gas chromatograph is model Agilent 7890A.
The gas chromatograph-mass spectrometer is in the model of Agilent 6890N GC/5973 MS.
Example 1
Putting 0.05mmol of amorphous manganese dioxide and 0.005mmol of acetylacetone into a 20mL reaction kettle with a lining, adding 10mL of acetonitrile, stirring at 30 ℃ for 72h, then adding 1mmol of 2, 5-diformylfuran and 2.4mmol of ammonium acetate, charging 0.1MPa of air, and carrying out temperature programming to 30 ℃ for reaction for 48h to obtain 2, 5-dicyanofuran.
Then cooling the mixed solution to room temperature, centrifuging to remove the catalyst, removing the solvent by rotary evaporation, adding water, then adding ethyl acetate for extraction, removing the solvent by rotary evaporation, drying in vacuum at 40 ℃, weighing and calculating the separation yield.
The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion of 2, 5-diformylfuran was 80% and the selectivity of 2, 5-dicyanofuran was 92%. The isolation yield of 2, 5-dicyanofuran was 70% and the gas chromatography purity was 99.1%.
Example 2
Adding 0.1mmol of alpha-MnO2And 0.01mmol of 3-methylacetoacetone are put into a 20mL reaction kettle with a lining, 10mL dioxane is added, stirring is carried out for 72h at the temperature of 30 ℃, then 1mmol of 2, 5-diformylfuran and 4.5mmol of ammonium acetate are added, 0.5MPa air is filled, the temperature is programmed to 60 ℃, and the reaction is carried out for 12h, so as to obtain the 2, 5-dicyanofuran.
Then cooling the mixed solution to room temperature, centrifuging to remove the catalyst, removing the solvent by rotary evaporation, adding water, then adding ethyl acetate for extraction, removing the solvent by rotary evaporation, drying in vacuum at 40 ℃, weighing and calculating the separation yield.
The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion of 2, 5-diformylfuran was 91% and the selectivity of 2, 5-dicyanofuran was 96%. The isolation yield of 2, 5-dicyanofuran was 80% and the gas chromatography purity was 99.0%.
Example 3
Adding 0.2mmol of beta-MnO2And 0.03mmol of 1,1, 1-trifluoroacetylacetone are put into a 20mL reaction kettle with a lining, 10mL of tert-butyl alcohol is added, stirring is carried out for 72 hours at the temperature of 30 ℃, then 1mmol of 2, 5-diformylfuran and 2.2mmol of ammonium formate are added, 1MPa of oxygen is filled, the temperature is programmed to 90 ℃, and reaction is carried out for 6 hours, so that the 2, 5-dicyanofuran is obtained.
Then cooling the mixed solution to room temperature, centrifuging to remove the catalyst, removing the solvent by rotary evaporation, adding water, then adding ethyl acetate for extraction, removing the solvent by rotary evaporation, drying in vacuum at 40 ℃, weighing and calculating the separation yield.
The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion of 2, 5-diformylfuran was 81% and the selectivity of 2, 5-dicyanofuran was 94%. The isolation yield of 2, 5-dicyanofuran was 65% and the gas chromatographic purity was 99.2%.
Example 4
Adding 0.15mmol of gamma-MnO2And 0.05mmol of hexafluoroacetylacetone are put into a 20mL reaction kettle with an inner liner, 10mL of tertiary amyl alcohol is added, stirring is carried out for 72 hours at the temperature of 30 ℃, then 1mmol of 2, 5-diformylfuran and 3.9mmol of ammonium acetate are added, 2MPa of air is filled, the temperature is programmed to 120 ℃, and 2, 5-dicyanofuran is obtained after reaction is carried out for 0.5 hour.
Then cooling the mixed solution to room temperature, centrifuging to remove the catalyst, removing the solvent by rotary evaporation, adding water, then adding ethyl acetate for extraction, removing the solvent by rotary evaporation, drying in vacuum at 40 ℃, weighing and calculating the separation yield.
The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion of 2, 5-diformylfuran was 90% and the selectivity of 2, 5-dicyanofuran was 95%. The isolation yield of 2, 5-dicyanofuran was 75% and the gas chromatographic purity was 99.4%.
Example 5
Adding 0.1mmol-MnO2And 0.02mmol of N, N-dimethylcyclohexylamine are put into a 20mL reaction kettle with a liner, 10mL of p-xylene is added, the mixture is stirred for 72 hours at the temperature of 30 ℃, then 1mmol of 2, 5-diformylfuran and 1.1mmol of ammonium oxalate are added, 2MPa of air is filled, the temperature is programmed to 80 ℃, and the reaction is carried out for 5 hours, so that the 2, 5-dicyanofuran is obtained.
Then cooling the mixed solution to room temperature, centrifuging to remove the catalyst, removing the solvent by rotary evaporation, adding water, then adding ethyl acetate for extraction, removing the solvent by rotary evaporation, drying in vacuum at 40 ℃, weighing and calculating the separation yield.
The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion of 2, 5-diformylfuran was 83% and the selectivity of 2, 5-dicyanofuran was 96%. The isolation yield of 2, 5-dicyanofuran was 69%, and the gas chromatography purity was 99.7%.
Example 6
0.1mmol of Co3O4Adding 0.01mmol of N-methylpiperidine and 0.01mmol of N-methylpiperidine into a 20mL reaction kettle with an inner liner, adding 10mL of toluene, stirring for 72h at the temperature of 30 ℃, then adding 1mmol of 2, 5-diformylfuran and 1.5mmol of ammonium carbonate, introducing 3MPa of air, and carrying out temperature programming to 70 ℃ for reaction for 8h to obtain 2, 5-dicyanofuran.
Then cooling the mixed solution to room temperature, centrifuging to remove the catalyst, removing the solvent by rotary evaporation, adding water, then adding ethyl acetate for extraction, removing the solvent by rotary evaporation, drying in vacuum at 40 ℃, weighing and calculating the separation yield.
The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion of 2, 5-diformylfuran was 88% and the selectivity of 2, 5-dicyanofuran was 98%. The isolation yield of 2, 5-dicyanofuran was 73% and the gas chromatographic purity was 99.6%.
Example 7
Adding 0.05mmol of NiO and 0.005mmol of N-methyl tetrahydropyrrole into a 20mL reaction kettle with a lining, adding 10mL of toluene, stirring at 30 ℃ for 72h, then adding 1mmol of 2, 5-diformylfuran and 6mmol of ammonium bicarbonate, charging 5MPa of air, and carrying out temperature programming to 70 ℃ for reaction for 8h to obtain 2, 5-dicyanofuran.
Then cooling the mixed solution to room temperature, centrifuging to remove the catalyst, removing the solvent by rotary evaporation, adding water, then adding ethyl acetate for extraction, removing the solvent by rotary evaporation, drying in vacuum at 40 ℃, weighing and calculating the separation yield.
The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion of 2, 5-diformylfuran was 65% and the selectivity of 2, 5-dicyanofuran was 97%. The isolation yield of 2, 5-dicyanofuran was 43% and the gas chromatographic purity was 99.1%.
Example 8
Adding 0.05mmol CoO and 0.005mmol proline into a 20mL reaction kettle with a lining, adding 10mL toluene, stirring at 30 ℃ for 72h, then adding 1mmol 2, 5-diformylfuran and 8mmol ammonium phosphate, charging 5MPa air, and carrying out temperature programming to 70 ℃ for reaction for 8h to obtain 2, 5-dicyanofuran.
Then cooling the mixed solution to room temperature, centrifuging to remove the catalyst, removing the solvent by rotary evaporation, adding water, then adding ethyl acetate for extraction, removing the solvent by rotary evaporation, drying in vacuum at 40 ℃, weighing and calculating the separation yield.
The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, and the quantitative analysis is realized by gas chromatography. The conversion of 2, 5-diformylfuran was 65% and the selectivity of 2, 5-dicyanofuran was 97%. The isolation yield of 2, 5-dicyanofuran was 43% and the gas chromatographic purity was 99.1%.
The application provides a method for preparing 2, 5-dicyanofuran by selective ammoxidation of 2, 5-diformylfuran, the catalyst system is simple and efficient, the byproducts are few, the catalyst and the product are easy to separate, and the method has a good application prospect.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for preparing 2, 5-dicyanofuran is characterized in that a mixture containing 2, 5-diformylfuran, a nitrogen source and a catalyst is reacted in the presence of an oxidant to obtain 2, 5-dicyanofuran;
wherein the catalyst comprises a metal oxide modified with an organic compound.
2. The method of claim 1, wherein the oxidant comprises an oxygen-containing atmosphere;
the oxygen partial pressure of the oxygen-containing atmosphere is 0.1-5 MPa;
preferably, the oxygen-containing atmosphere is selected from oxygen or air.
3. The method according to claim 1, wherein the molar ratio of the nitrogen source to the 2, 5-diformylfuran is 1 to 9: 1;
wherein the number of moles of the nitrogen source is based on the number of moles of the nitrogen source itself.
4. The method according to claim 1, wherein the nitrogen source is at least one selected from ammonium salts;
preferably, the ammonium salt is selected from at least one of ammonium formate, ammonium acetate, ammonium oxalate, ammonium carbonate, ammonium bicarbonate, ammonium phosphate.
5. The preparation method according to claim 1, wherein the reaction temperature is 30-120 ℃;
the reaction time is 0.5-48 h.
6. The preparation method according to claim 1, wherein the amount of the catalyst is 5 to 20 mol% of 2, 5-diformylfuran;
wherein the moles of the catalyst are based on the moles of the metal oxide.
7. The method according to claim 1, wherein the organic compound comprises at least one of acetylacetone, 3-methylacetoacetone, 1,1, 1-trifluoroacetylacetone, hexafluoroacetylacetone, N-dimethylcyclohexylamine, N-methylpiperidine, N-methyltetrahydropyrrole, and proline.
8. The production method according to claim 1, wherein the metal oxide includes at least one of an oxide of manganese, an oxide of cobalt, and an oxide of nickel;
preferably, the manganese oxide comprises amorphous manganese dioxide, alpha-MnO2、β-MnO2、γ-MnO2、-MnO2At least one of (1).
9. The method according to claim 1, wherein the organic compound is present in a molar amount of 0.5 to 5% based on the molar amount of 2, 5-diformylfuran.
10. The method of claim 1, wherein the mixture further comprises a solvent;
the solvent comprises any one of acetonitrile, dioxane, tertiary butanol, tertiary amyl alcohol, toluene and p-xylene.
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| CN104860824A (en) * | 2014-02-24 | 2015-08-26 | 中国科学院大连化学物理研究所 | Method for preparing pyruvate through catalyzing oxygen to oxidize lactate |
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| CN104860824A (en) * | 2014-02-24 | 2015-08-26 | 中国科学院大连化学物理研究所 | Method for preparing pyruvate through catalyzing oxygen to oxidize lactate |
| CN107814782A (en) * | 2016-09-14 | 2018-03-20 | 中国科学院大连化学物理研究所 | A kind of method that catalytic ammoxidation prepares the furans nitrile of 5 methylol 2 |
| CN107814780A (en) * | 2016-09-14 | 2018-03-20 | 中国科学院大连化学物理研究所 | A kind of method that diformyl furans of catalytic ammoxidation 2,5 prepares 2,5 furans dintrile |
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