CN103436911A - Electrochemical catalytic synthesis method of aziridine compounds - Google Patents
Electrochemical catalytic synthesis method of aziridine compounds Download PDFInfo
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- CN103436911A CN103436911A CN2013103998570A CN201310399857A CN103436911A CN 103436911 A CN103436911 A CN 103436911A CN 2013103998570 A CN2013103998570 A CN 2013103998570A CN 201310399857 A CN201310399857 A CN 201310399857A CN 103436911 A CN103436911 A CN 103436911A
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000001541 aziridines Chemical class 0.000 title abstract 5
- 238000007036 catalytic synthesis reaction Methods 0.000 title abstract 3
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 55
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 26
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims abstract description 26
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims abstract description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 6
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- 235000015320 potassium carbonate Nutrition 0.000 claims description 24
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical group [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical class C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 11
- 238000010189 synthetic method Methods 0.000 claims description 6
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 4
- 150000008045 alkali metal halides Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- -1 iodate amine Chemical class 0.000 claims description 2
- KSILMCDYDAKOJD-UHFFFAOYSA-N 2-aminoisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(N)C(=O)C2=C1 KSILMCDYDAKOJD-UHFFFAOYSA-N 0.000 abstract description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052697 platinum Inorganic materials 0.000 abstract description 4
- 229910021397 glassy carbon Inorganic materials 0.000 abstract 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 2
- 239000010411 electrocatalyst Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 23
- DEUJSGDXBNTQMY-UHFFFAOYSA-N 1,2,2-trifluoroethanol Chemical compound OC(F)C(F)F DEUJSGDXBNTQMY-UHFFFAOYSA-N 0.000 description 22
- 238000004440 column chromatography Methods 0.000 description 22
- 229910052742 iron Inorganic materials 0.000 description 22
- 238000000926 separation method Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical group [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 19
- 239000007787 solid Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- FILKGCRCWDMBKA-UHFFFAOYSA-N 2,6-dichloropyridine Chemical compound ClC1=CC=CC(Cl)=N1 FILKGCRCWDMBKA-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- QPJORFLSOJAUNL-UHFFFAOYSA-N dibenzo[a,d][7]annulene Chemical compound C1=CC2=CC=CC=C2CC2=CC=CC=C21 QPJORFLSOJAUNL-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 2
- UFPDYXSNTNUEBO-UHFFFAOYSA-N 1-(2-bromophenyl)aziridine Chemical compound BrC1=CC=CC=C1N1CC1 UFPDYXSNTNUEBO-UHFFFAOYSA-N 0.000 description 1
- DQSSWRSJWZLDSA-UHFFFAOYSA-N 1-(4-bromophenyl)aziridine Chemical compound C1=CC(Br)=CC=C1N1CC1 DQSSWRSJWZLDSA-UHFFFAOYSA-N 0.000 description 1
- LDLKZJFSHAEEKE-UHFFFAOYSA-N 1-(4-chlorophenyl)aziridine Chemical compound C1=CC(Cl)=CC=C1N1CC1 LDLKZJFSHAEEKE-UHFFFAOYSA-N 0.000 description 1
- FOKDVFBDEKBAKV-UHFFFAOYSA-N 1-(4-fluorophenyl)aziridine Chemical compound C1=CC(F)=CC=C1N1CC1 FOKDVFBDEKBAKV-UHFFFAOYSA-N 0.000 description 1
- 0 Cc1ccccc1C(C1)N1NC(c1cccc*1C=O)=O Chemical compound Cc1ccccc1C(C1)N1NC(c1cccc*1C=O)=O 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical class CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an electrochemical catalytic synthesis method of aziridine compounds. The method comprises the following steps: by employing N-aminophthalimide and styrene or cycloolefin as raw materials in a single-room electrolytic tank, in electrolyte, employing halogenated tetra-alkylamine or alkali halide as an electrocatalyst, by employing lithium perchlorate or triethylamine/acetic acid as an supporting electrolyte, electrolyzing in the presence of alkali, wherein the reaction temperature is 0-40 DEG C, the current density is 4-12 mA/cm<2>, and thus obtaining the aziridine compounds after being electrified with the electric quantity of 2.5-3.5 F/mol. According to the electrochemical catalytic synthesis method of aziridine compounds, an indirect electrolysis method of electrochemical catalysis which is simple to operate is firstly employed to synthesize the aziridine compounds, the single-room electrolytic tank is used, constant-current electrolysis is employed, and glassy carbon electrodes are used as working electrodes, so that the conversion of the double-room electrolytic tank to the single-room electrolytic tank is achieved, and meanwhile, as the working electrodes are changed to be the glassy carbon electrodes in stead of previously used expensive platinum electrodes, the cost is greatly reduced, and the operation is much simpler, thus being more suitable for industrial production.
Description
Technical field
The present invention relates to a kind of electrochemical catalysis synthetic method of ethylenimine compounds.
Background technology
The ethylenimine compounds is widely used in pharmaceutical chemistry and synthetic chemistry, so the synthetic of this compounds is the focus that people pay close attention to always.
Electrochemical oxidation process is a kind of wherein method of synthesis of azacyclic propane compounds.The people such as Yudin (Ref.Yudin.et al.J.Am.Chem.Soc., 2002,124,530-531; Yudin.et al.J.Org.Chem., 2005,70,932-937.) reported a kind of aziridination of practical alkene.The method is in the electrolyzer of two chambers, take platinized platinum as anode, and the acetonitrile solution of triethylamine/acetic acid is supporting electrolyte, under the condition of controlling current potential (being 1.8V with respect to silver-colored line), olefin(e) compound reacts with N-amido phthalic imidine, generates the ethylenimine compounds.The subject matter that the method exists is as follows:
(1) the method must be carried out in the electrolyzer of two chambers.Two chambers electrolyser construction complexity, equipment cost is high; Two chambers electrolyzer internal resistance is large, required decomposition voltage is larger during electrolysis, and energy consumption is high; Barrier film (dividing plate) life-span that two chambers electrolyzer is used is limited, needs periodic replacement;
(2) because the method adopts the potentiostatic deposition method, use three-electrode system, accurately control the current potential Direct Electrolysis between working electrode and reference electrode by electrochemical workstation, therefore cause the electrolyzer complexity, influence factor is many, and need expensive electrochemical workstation (potentiometer), be not suitable for suitability for industrialized production;
(3) the method must be used expensive platinum electrode as working electrode, so cost is high.
At present, the electrochemical catalysis synthetic method of ethylenimine compounds under single compartment electrolytic cell and constant current conditions there is not yet the domestic and foreign literature report.
Summary of the invention
The electrochemical catalysis synthetic method that the purpose of this invention is to provide a kind of simple to operate and ethylenimine compounds that cost is low.
The electrochemical catalysis synthetic method of ethylenimine compounds provided by the present invention, its step is to take N-amido phthalic imidine and the formula (IV) that formula (III) means to mean that the cycloolefin that vinylbenzene or formula (V) mean is raw material in single compartment electrolytic cell, in electrolytic solution, halogenation tetraalkyl amine or the alkali metal halide of catalytic amount of take is eelctro-catalyst, take lithium perchlorate or triethylamine/acetic acid as supporting electrolyte, electrolysis under the existence of alkali, 0～40 ℃ of temperature of reaction, current density 4～12mA/cm
2, after the electric weight by 2.5～3.5F/mol, obtain the ethylenimine compounds that formula (I) or formula (II) mean,
Wherein, R
1expression-H ,-CH
3,-F ,-Cl or-Br, R
1be positioned at ortho position or contraposition; R
2expression-H or-CH
3; R
3expression-H or-CH
3; N is 1 or 2.
Above-mentioned electrolytic solution is trifluoroethanol or acetonitrile, preferably trifluoroethanol.
Above-mentioned halogenation tetraalkyl amine is tetrabutylammonium iodide, tetraethyl ammonium iodide or Tetrabutyl amonium bromide, preferably tetrabutyl iodate amine.
Above-mentioned alkali metal halide is sodium iodide or Sodium Bromide, preferably sodium iodide.
The consumption of above-mentioned catalyzer is 0.1 equivalent preferably.
The preferred lithium perchlorate of above-mentioned supporting electrolyte.
Above-mentioned alkali is salt of wormwood or 2,6-dichloropyridine, preferably salt of wormwood.
The anode that above-mentioned electrolysis is used is glass-carbon electrode.
The preferred room temperature of above-mentioned temperature of reaction.
The preferred 4mA/cm of above-mentioned current density
2.
The preferred 3F/mol of the above-mentioned electric weight passed through.
The inventive method compared with prior art, has following beneficial effect:
(1) adopt the indirect electrolytic method of electrochemical catalysis simple to operate to synthesize the ethylenimine compounds, the electrochemical method for synthesizing that before not only greatly having improved, the people such as Yudin uses, also realized the conversion to single compartment electrolytic cell by two chambers electrolyzer.The single compartment electrolytic cell internal resistance is less, and during electrolysis, decomposition voltage is little, thereby greatly reduces energy consumption, and simultaneously, the single compartment electrolytic cell device is simple, with common beaker, gets final product.
(2) adopt the constant-current electrolysis method, the method required equipment cost is low, operates also more simply than potentiostatic deposition, and simultaneously, constant-current electrolysis is more suitable for suitability for industrialized production.
(3) working electrode is also changed into glass-carbon electrode by the platinum electrode of the costliness of using before, makes cost greatly reduce.
(4) the inventive method is used industrial common reagent and conventional working condition, and the reaction conditions gentleness is simple to operate, and electrode materials is cheap and easy to get simultaneously.Electronics using in reaction process as oxygenant, is also a kind of clean production process.
Embodiment
Embodiment 1: cinnamic electrochemical catalysis nitrogen heterocyclic third is changed
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.2mmol) are joined to the 15mL2 that is dissolved with 0.1M triethylamine/acetic acid, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 50%.
yellow?solid;149.4-150.3℃；
1H?NMR(400MHz，CDCl3)：δ＝7.83-7.80(m,2H),7.73-7.71(m,2H),7.37(d,J=8Hz,2H),7.22(d,J=8Hz,2H),3.59(dd,J=8.0,6.0Hz,1H),2.89(dd,J=8,2.4Hz,1H),2.81(dd,J=6,2.4Hz,1H).
Embodiment 2: cinnamic electrochemical catalysis nitrogen heterocyclic third is changed
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.2mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 67%.
Embodiment 3: cinnamic electrochemical catalysis nitrogen heterocyclic third is changed
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and tetraethyl ammonium iodide (0.2mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 51%.
Embodiment 4: cinnamic electrochemical catalysis nitrogen heterocyclic third is changed
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and sodium iodide (0.2mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 48%.
Embodiment 5: cinnamic electrochemical catalysis nitrogen heterocyclic third is changed
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and Tetrabutyl amonium bromide (0.2mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 36%.
Embodiment 6: cinnamic electrochemical catalysis nitrogen heterocyclic third is changed
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and Sodium Bromide (0.2mmol) are joined to the 15mL2 that is dissolved with 0.05 lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 27%.
Embodiment 7: cinnamic electrochemical catalysis aziridination
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 65%.
Embodiment 8: cinnamic electrochemical catalysis aziridination
In the single compartment electrolytic cell of 50mL, by N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), 2,6-dichloropyridine (1mmol) and tetrabutylammonium iodide (0.1mmol) join the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 21%.
Embodiment 9: cinnamic electrochemical catalysis aziridination
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 8mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 49%.
Embodiment 10: cinnamic electrochemical catalysis aziridination
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 12mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, slough solvent, dissolve with methylene dichloride, and wash with water three times, through column chromatography for separation, obtain N-(aminophthalimide)-2-phenyl ethylenimine yield: 28%.
Embodiment 11: cinnamic electrochemical catalysis aziridination
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 2.5F/mol, stop electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 61%.
Embodiment 12: cinnamic electrochemical catalysis aziridination
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3.5F/mol, stop electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 63%.
Embodiment 13: cinnamic electrochemical catalysis aziridination
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stir under 40 ℃ of conditions, when the energising amount reaches 3F/mol, stop electrolysis, slough solvent, dissolve with methylene dichloride, and wash with water three times, through column chromatography for separation, obtain N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 41%.
Embodiment 14: cinnamic electrochemical catalysis aziridination
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), vinylbenzene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stir under 0 ℃ of condition, when the energising amount reaches 3F/mol, stops electrolysis, sloughs solvent, dissolves with methylene dichloride, and wash with water three times, through column chromatography for separation, obtains N-(aminophthalimide)-2-phenyl ethylenimine.Yield: 28%.
Embodiment 15: the electrochemical catalysis aziridination of p-methylstyrene
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), p-methylstyrene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, slough solvent, dissolve with methylene dichloride, and wash with water three times, through column chromatography for separation, obtain the p-methyl of N-(aminophthalimide)-2--phenyl ethylenimine.Yield: 71%.
white?solid;mp120.2-121.6℃；
1H?NMR(400MHz,CDCl
3：δ=7.83-7.80(m,2H),7.73-7.70(m,2H),7.37(d,J=8Hz,2H),7.22(d,J=24.4Hz,2H),3.58(dd,J=8.0,2.4Hz,1H),2.89(dd,J=8.0,2.4Hz,1H),2.81(dd,J=6,2.4Hz,1H),2.38(s,3H).
Embodiment 16: the electrochemical catalysis aziridination of pfluorostyrene
In the single compartment electrolytic cell of 50mL, by N-aminophthalimide (1.3mmol), pfluorostyrene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) join the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate is negative electrode, electrolysis under the 4mA/cm2 constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, slough solvent, with methylene dichloride, dissolve, and wash with water three times, through column chromatography for separation, obtain the p-fluoro-phenyl ethylenimine of N-(aminophthalimide)-2-.Yield: 63%.
yellow?solid;mp140.5-141.3℃;
1H?NMR(400MHz,CDCl
3：δ=7.83-7.81(m,2H),7.74-7.72(m,2H),7.49-7.28(m,2H),7.11-7.07(m,2H),3.61(dd,J=8.0,6.0Hz,1H),2.91(dd,J=8.0,2.4Hz,1H),2.79(dd,J=6,2.4Hz,1H).
Embodiment 17: to the electrochemistry aziridination of chloro-styrene
In the single compartment electrolytic cell of 50mL, by N-aminophthalimide (1.3mmol), chloro-styrene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, slough solvent, dissolve with methylene dichloride, and wash with water three times, through column chromatography for separation, obtain the p-chloro-phenyl ethylenimine of N-(aminophthalimide)-2-.Yield: 65%.
white?solid;mp153.8-154.9℃;
1H?NMR(400MHz,CDCl
3):δ=7.88-7.79(m,2H),7.75-7.72(m,2H),7.43-7.38(m,2H),7.37-7.28(m,2H),3.59(dd,J=7.6,5.6Hz,1H),2.93(dd,J=8.0,2.4Hz,1H),2.79(dd,J=5.6,2.4Hz,1H).
Embodiment 18: to the electrochemistry aziridination of bromstyrol
In the single compartment electrolytic cell of 50mL, by N-aminophthalimide (1.3mmol), bromstyrol (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, slough solvent, dissolve with methylene dichloride, and wash with water three times, through column chromatography for separation, obtain the p-bromo-phenyl ethylenimine of N-(aminophthalimide)-2-.Yield: 68%.
white?solid;mp142.6-144.0℃;
1H?NMR(400MHz,CDCl
3:δ=7.83-7.80(m,2H),7.79-7.71(m,2H),7.53-7.51(m,2H),7.37-7.28(m,2H),3.57(dd,J=8.0,6.0Hz,1H),2.92(dd,J=8.0,2.4Hz,1H),2.76(dd,J=6,2.4Hz,1H).
The electrochemistry aziridination of embodiment 19:2-bromstyrol
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), 2-bromstyrol (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, slough solvent, dissolve with methylene dichloride, and wash with water three times, through column chromatography for separation, obtain the o-bromo-phenyl ethylenimine of N-(aminophthalimide)-2-.Yield: 57%.
white?solid;mp141.7-142.5℃;
1H?NMR(400MHz,CDCl
3：δ=7.84-7.82(m,2H),7.74-7.72(m,2H),7.62-7.57(m,2H),7.37-7.28(m,1H),7.20(s,1H),3.82(dd,J=8.0,6.0Hz,1H),3.07(dd,J=8.0,2.0Hz,1H),2.57(dd,J=6,2.0Hz,1H).
Embodiment 20: the cinnamic electrochemical catalysis aziridination of trans-Beta-methyl
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), trans-Beta-methyl vinylbenzene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, slough solvent, dissolve with methylene dichloride, and wash with water three times, through column chromatography for separation, obtain trans-N-(aminophthalimide)-2-methyl-3-phenyl ethylenimine.Yield: 62%.
yellow?solid;mp73.2-73.8℃;
1H?NMR(400MHz,CDCl
3):δ=7.81-7.76(m,2H),7.72-7.76(m,2H),7.50(d,J=7.5Hz,2H),7.38(d,J=8.0Hz,2H),7.33-7.28(m,2H),3.75(d,J=8.0Hz,1H),2.99(dq,J=8.0,6.0Hz,1H),1.26(d,J=6.0Hz,3H).
The electrochemistry aziridination of embodiment 21:1-tetrahydrotoluene
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), 1-tetrahydrotoluene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, slough solvent, dissolve with methylene dichloride, and wash with water three times, through column chromatography for separation, obtain N-(aminophthalimide)-1-methyl-7-azabicyclo [4.1.0] heptane.Yield: 27%.
yellow?oil;
1H?NMR(400MHz,CDCl3):δ=7.78-7.67(m,2H),7.28-7.67(m,2H),2.93(d,J=1.2Hz,1H),7.36(s,1H),7.20(s,1H),3.82(d,J=2.8Hz,2H),2.25-2.05(m,1H),1.75-1.50(m,1H),1.48-1.44(m,1H),1.36-1.24(m,7H).
Embodiment 22: the electrochemical catalysis aziridination of suberene
In the single compartment electrolytic cell of 50mL, N-aminophthalimide (1.3mmol), suberene (1mmol), salt of wormwood (1mmol) and tetrabutylammonium iodide (0.1mmol) are joined to the 15mL2 that is dissolved with the 0.05M lithium perchlorate, 2, in 2-trifluoroethanol solution, take glass-carbon electrode as anode, iron plate be negative electrode, at 4mA/cm
2electrolysis under constant current, stirring at room, when the energising amount reaches 3F/mol, stop electrolysis, slough solvent, dissolve with methylene dichloride, and wash with water three times, through column chromatography for separation, obtain N-(aminophthalimide)-1-methyl-8-azabicyclo [5.1.0] octane.Yield: 25%.
yellow?oil;
1H?NMR(400MHz,CDCl
3：δ=7.77-7.75(m,2H),7.69-7.66(m,2H),2.70-2.69(m,2H),2.19-2.05(m,2H),1.67-1.50(m,2H),1.45-1.27(m,6H).
Claims (10)
1. the electrochemical catalysis synthetic method of an ethylenimine compounds, its step is to take N-amido phthalic imidine and the formula (IV) that formula (III) means to mean that the cycloolefin that vinylbenzene or formula (V) mean is raw material in single compartment electrolytic cell, in electrolytic solution, halogenation tetraalkyl amine or the alkali metal halide of catalytic amount of take is eelctro-catalyst, take lithium perchlorate or triethylamine/acetic acid as supporting electrolyte, electrolysis under the existence of alkali, 0～40 ℃ of temperature of reaction, current density 4～12mA/cm
2, after the electric weight by 2.5～3.5F/mol, obtain the ethylenimine compounds that formula (I) or formula (II) mean,
Wherein, R
1expression-H ,-CH
3,-F ,-Cl or-Br, R
1be positioned at ortho position or contraposition; R
2expression-H or-CH
3; R
3expression-H or-CH
3; N is 1 or 2.
2. according to the method for claim 1, it is characterized in that described electrolytic solution is trifluoroethanol.
3. according to the method for claim 1, it is characterized in that described halogenation tetraalkyl amine is tetrabutyl iodate amine.
4. according to the method for claim 1, it is characterized in that described alkali metal halide is sodium iodide.
5. according to the method for claim 1, it is characterized in that described supporting electrolyte is lithium perchlorate.
6. according to the method for claim 1, it is characterized in that described alkali is salt of wormwood.
7. according to the method for claim 1, it is characterized in that the anode that electrolysis is used is glass-carbon electrode.
8. according to the method for claim 1, it is characterized in that described temperature is room temperature.
9. according to the method for claim 1, it is characterized in that described current density is 4mA/cm
2.
10. according to the method for claim 1, it is characterized in that the described electric weight passed through is 3F/mol.
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| CN106567104A (en) * | 2016-10-31 | 2017-04-19 | 华南理工大学 | Electrochemical synthesis method of 1,1'-diindolylmethane derivatives |
| CN107460497A (en) * | 2017-07-07 | 2017-12-12 | 北京工业大学 | The electrochemical catalysis synthetic method of the electron deficient nitrogen-containing heterocycle compound of acyl group substitution |
| CN114941145A (en) * | 2022-01-14 | 2022-08-26 | 天津理工大学 | Synthetic method of aziridine derivative |
Citations (1)
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|---|---|---|---|---|
| CN101838816A (en) * | 2010-04-09 | 2010-09-22 | 北京工业大学 | Method for electrochemically preparing 5,5'-dihydroxyl-4,4'-dipyrazole compound |
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Non-Patent Citations (2)
| Title |
|---|
| TUNG SIU: "Development of electrochemical processes for nitrene generation and transfer", 《J.ORG.CHEM》, 7 January 2005 (2005-01-07), pages 932 - 937 * |
| TUNG SIU: "Practical olefin Aziridination with a board substrate scope", 《JACS》, 5 January 2002 (2002-01-05), pages 530 - 531 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106567104A (en) * | 2016-10-31 | 2017-04-19 | 华南理工大学 | Electrochemical synthesis method of 1,1'-diindolylmethane derivatives |
| CN106567104B (en) * | 2016-10-31 | 2018-12-11 | 华南理工大学 | The electrochemical method for synthesizing of 1,1 '-di-indole methyl hydride analog derivatives |
| CN107460497A (en) * | 2017-07-07 | 2017-12-12 | 北京工业大学 | The electrochemical catalysis synthetic method of the electron deficient nitrogen-containing heterocycle compound of acyl group substitution |
| CN107460497B (en) * | 2017-07-07 | 2019-02-26 | 北京工业大学 | The electrochemical catalysis synthetic method for the electron deficient nitrogen-containing heterocycle compound that acyl group replaces |
| CN114941145A (en) * | 2022-01-14 | 2022-08-26 | 天津理工大学 | Synthetic method of aziridine derivative |
| CN114941145B (en) * | 2022-01-14 | 2023-08-18 | 天津理工大学 | Synthesis method of aziridine derivatives |
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