Electrochemical catalytic synthesis method of aziridine compounds

The technology of aziridine and synthesis method is applied in the field of electrochemical catalytic synthesis of aziridine compounds, which can solve the problems of complex electrolysis device, high decomposition voltage and high cost, and achieve cheap and easy-to-obtain electrode materials and high reaction efficiency. The effect of mild conditions and low equipment cost

Active Publication Date: 2013-12-11
BEIJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The structure of the double-chamber electrolytic cell is complicated, and the cost of equipment is high; the internal resistance of the double-chamber electrolytic cell is large, the decomposition voltage required for electrolysis is large, and the energy consumption is high; the diaphragm (partition) used in the double-chamber electrolytic cell has a limited life and needs to be replaced regularly;
[0005] (2) Since this method adopts a constant potential electrolysis method, uses a three-electrode system, and precisely controls the potential between the working electrode and the refer

Method used

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  • Electrochemical catalytic synthesis method of aziridine compounds
  • Electrochemical catalytic synthesis method of aziridine compounds
  • Electrochemical catalytic synthesis method of aziridine compounds

Examples

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Effect test

Embodiment 1

[0028] Example 1: Electrochemically catalyzed aziridine of styrene

[0029] In a 50mL single-chamber electrolytic cell, add N-aminophthalimide (1.3mmol), styrene (1mmol), potassium carbonate (1mmol) and tetrabutylammonium iodide (0.2mmol) to the solution In 15mL 2,2,2-trifluoroethanol solution with 0.1M triethylamine / acetic acid, with glassy carbon electrode as anode and iron plate as cathode, the temperature is 4mA / cm 2 Electrolysis under constant current, stirring at room temperature, when the energization reaches 3F / mol, stop the electrolysis, remove the solvent, dissolve with dichloromethane, wash three times with water, and separate by column chromatography to obtain N-(aminophthaloyl Imine)-2-phenylaziridine. Yield: 50%.

[0030]

[0031] yellow solid;149.4-150.3℃; 1 H 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

[0032] Example 2: Electrochemically catalyzed aziridine of styrene

[0033] In a 50mL single-chamber electrolytic cell, add N-aminophthalimide (1.3mmol), styrene (1mmol), potassium carbonate (1mmol) and tetrabutylammonium iodide (0.2mmol) to the solution In 15mL 2,2,2-trifluoroethanol solution containing 0.05M lithium perchlorate, the glassy carbon electrode is used as the anode and the iron sheet is used as the cathode. The temperature is 4mA / cm 2 Electrolysis under constant current, stirring at room temperature, when the energization reaches 3F / mol, stop the electrolysis, remove the solvent, dissolve with dichloromethane, wash three times with water, and separate by column chromatography to obtain N-(aminophthaloyl Imine)-2-phenylaziridine. Yield: 67%.

Embodiment 3

[0034] Example 3: Electrochemically catalyzed aziridine of styrene

[0035] In a 50mL single-chamber electrolytic cell, add N-aminophthalimide (1.3mmol), styrene (1mmol), potassium carbonate (1mmol) and tetraethylammonium iodide (0.2mmol) to the solution In 15mL 2,2,2-trifluoroethanol solution containing 0.05M lithium perchlorate, the glassy carbon electrode is used as the anode and the iron sheet is used as the cathode. The temperature is 4mA / cm 2 Electrolysis under constant current, stirring at room temperature, when the energization reaches 3F / mol, stop the electrolysis, remove the solvent, dissolve with dichloromethane, wash three times with water, and separate by column chromatography to obtain N-(aminophthaloyl Imine)-2-phenylaziridine. Yield: 51%.

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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 [0001] The invention relates to an electrochemical catalytic synthesis method of aziridine compounds. Background technique [0002] The aziridine compounds are widely used in medicinal chemistry and synthetic chemistry, so the synthesis of these compounds has always been the focus of attention. [0003] Electrochemical oxidation is one of the methods to synthesize aziridine compounds. Yudin et al. (Ref.Yudin.et al.J.Am.Chem.Soc.,2002,124,530-531; Yudin.et al.J.Org.Chem.,2005,70,932-937.) reported a practical The aziridine reaction of type olefins. The method is to use platinum sheet as anode and acetonitrile solution of triethylamine / acetic acid as supporting electrolyte in a two-chamber electrolytic cell. Under the condition of controlled potential (1.8V relative to silver wire), olefin compounds and N- The amino phthalimide reacts to generate aziridine compounds. The main problems of this method are as follows: [0004] (1) This method must be carried out in a ...

Claims

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Application Information

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IPC IPC(8): C25B3/02C25B3/23
Inventor 曾程初陈杰陆楠宁胡利明
Owner BEIJING UNIV OF TECH
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