Electrochemical catalyzed synthesis method for acyl substituted electron-deficient nitrogen-containing heterocyclic compound

The technology of a nitrogen heterocyclic compound and its synthesis method, which is applied in the field of electrochemical catalytic synthesis, can solve the problems of poor chemical selectivity, incomplete reaction of raw materials, long reaction time, etc., and achieve reduced energy consumption, low equipment cost, and simple operation Effect

Active Publication Date: 2017-12-12
BEIJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] (1) Using expensive silver nitrate as a catalyst, stoichiometric (NH 4 ) 2 S 2 o 8 It is an oxidizing agent, and the post-treatment is complicated;
[0005] (2) Since the acyl product is more active than the raw material, it is easier to further react with free radicals to generate a double-substituted product, so the chemoselectivity is not good;
[0006] (3) The reaction time is long and the reaction of raw materials is not complete
[0007] At present, the synthesis of heterocyclic acyl compounds by electrochemical catalysis has not been reported in the literature at home and abroad.

Method used

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  • Electrochemical catalyzed synthesis method for acyl substituted electron-deficient nitrogen-containing heterocyclic compound
  • Electrochemical catalyzed synthesis method for acyl substituted electron-deficient nitrogen-containing heterocyclic compound
  • Electrochemical catalyzed synthesis method for acyl substituted electron-deficient nitrogen-containing heterocyclic compound

Examples

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Effect test

Embodiment 1

[0032] Example 1: Synthesis under electrochemical conditions to realize the Minisci acylation reaction of α-keto acid and nitrogen-containing heterocyclic aromatic compound

[0033] In a 50 mL single-chamber electrolytic cell, quinoxaline (1.0 mmol), pyruvic acid (3.0 mmol), HFIP (2.0 mmol) and ammonium iodide (0.15 mmol) were added to 15 mL of 0.1 M lithium perchlorate In the acetonitrile solution, with the graphite sheet electrode as the anode and the graphite sheet as the cathode, at 3mA / cm 2 Electrolyze at a constant current, stir at 70°C, stop electrolysis when the current flow reaches 2.7 F / mol, remove the solvent, dissolve with dichloromethane, wash with water three times, and separate by column chromatography to obtain acetylquinoxaline. Yield: 56%.

[0034]

[0035] yellow solid; 1 H NM R (400MHz, CDCl 3 )δ2.84(s,3H),7.82-7.90(m,2H),8.14-8.19(m,2H),9.47(s,1H);

Embodiment 2

[0036] Example 2: Synthesis under electrochemical conditions to realize the Minisci acylation reaction of α-keto acid and nitrogen-containing heterocyclic aromatic compound

[0037] In a 50mL single-chamber electrolytic cell, quinoxaline (1.0mmol), pyruvic acid (3.0mmol), and ammonium bromide (0.15mmol) were added to 15mL of acetonitrile solution dissolved in 0.1M lithium perchlorate, and graphite The sheet electrode is the anode, the graphite sheet is the cathode, at 3mA / cm 2 Electrolyze at a constant current, stir at 25°C, stop electrolysis when the current flow reaches 2.7F / mol, remove the solvent, dissolve with dichloromethane, wash with water three times, and separate by column chromatography to obtain acetylquinoxaline. Yield: 5%.

Embodiment 3

[0038] Example 3: Synthesis under electrochemical conditions to realize the Minisci acylation reaction of α-keto acid and nitrogen-containing heterocyclic aromatic compound

[0039] In a 50mL single-chamber electrolytic cell, quinoxaline (1.0mmol), pyruvic acid (3.0mmol), and ammonium bromide (0.15mmol) were added to 15mL of acetonitrile solution dissolved in 0.1M lithium perchlorate, and graphite The sheet electrode is the anode, the graphite sheet is the cathode, at 3mA / cm 2 Electrolyze at a constant current, stir at 40°C, stop electrolysis when the current flow reaches 2.7 F / mol, remove the solvent, dissolve with dichloromethane, wash with water three times, and separate by column chromatography to obtain acetylquinoxaline. Yield: 17%.

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Abstract

The invention relates to an electrochemical catalyzed synthesis method for an acyl substituted electron-deficient nitrogen-containing heterocyclic compound, and belongs to the technical field of acyls nitrogen-containing aromatic heterocyclic compounds. The method comprises the following steps: taking alpha-ketonic acid and an electron-deficient nitrogen-containing heterocyclic compound as raw materials in an electrolytic cell; taking halide ions as an electrocatalyst in electrolyte; carrying out electrolysis in the presence of additives, wherein the reaction temperature is 25-70 DEG C, and the current density is 1-5 mA / cm<2>; and consuming 2.0-3.5 F / mol of quantity of electric charge to obtain an acyls nitrogen-containing aromatic heterocyclic compound. According to the method, the acyls nitrogen-containing aromatic heterocyclic compound is synthesized by an electrochemical catalyzed indirect electrolyzing method which is simple to operate for the first time, use of expensive metal compounds such as silver nitrate and peroxide such as stoichiometric (NH4)2S2O8 is avoided, therefore, the atom economy can be realized, the cost is greatly reduced, operation is simplified, and the acyls nitrogen-containing aromatic heterocyclic compound is suitable for being produced industrially.

Description

technical field [0001] The invention relates to an electrochemical catalytic synthesis method of an acyl-substituted electron-deficient nitrogen-containing heterocyclic compound, and belongs to the technical field of acyl nitrogen-containing aromatic heterocyclic compounds. Background technique [0002] Heterocyclic acyl compounds are widely used in medicinal chemistry and synthetic chemistry, so the synthesis of these compounds has always been the focus of attention. [0003] Minisci acylation reaction is one of the methods for the synthesis of heterocyclic acyl compounds. Reported by Sato et al. (L. Desaubry and J.J. Bourguignon, Tetrahedron Lett, 1995, 43, 7875–7876; N. Sato and T. Matsuura, J. Chem. Soc., Perkin Trans. 1, 1996, 1, 2345–2350) A chemical method for the synthesis of heterocyclic acyl compounds was developed. This method uses silver nitrate as catalyst, (NH 4 ) 2 S 2 o 8 As the oxidizing agent, water and acetonitrile are used as the solvent, and a seri...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C25B3/00
CPCC25B3/00
Inventor 曾程初王晴晴胡利明
Owner BEIJING UNIV OF TECH
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