Method for electrocatalytically synthesizing aromatic nitrile by taking aromatic methyl compound as raw material

A technology of compound and aromatic nitrile, which is applied in the direction of electrodes, electrolysis process, electrolysis components, etc., to prevent substrate polymerization and electrode passivation, prevent peroxidation reaction, and obtain cheap and easy raw materials

Active Publication Date: 2021-01-08
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But these methyl cyanides inevitably require the use of excess oxidants, toxic reagents and transition metal catalysts

Method used

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  • Method for electrocatalytically synthesizing aromatic nitrile by taking aromatic methyl compound as raw material
  • Method for electrocatalytically synthesizing aromatic nitrile by taking aromatic methyl compound as raw material
  • Method for electrocatalytically synthesizing aromatic nitrile by taking aromatic methyl compound as raw material

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Embodiment 1: the preparation of p-methoxybenzonitrile (formula (2-1)):

[0040] Add 0.0244g p-methoxytoluene, 0.0048g electrocatalyst 3c, 0.0492g hydroxylamine sulfate, 0.3419g tetrabutylammonium perchlorate, 8mL solvent (CH 3 CN:CH 2 Cl 2 =4:1), 2mL distilled water, 50℃, Pt as anode, Pt as cathode, Ag / AgNO 3 (0.01MAgNO 3 Acetonitrile solution) electrode was used as a reference electrode, and electrolyzed at a constant potential of 1.5V for 12h to obtain the product p-methoxybenzonitrile. The yield of electrolysis products was analyzed by gas chromatography GC, and the analysis method was the area normalization method. The product yield is 93% as shown in Table 1. The reaction solution was extracted with anhydrous ether (5mL×3), dried over anhydrous sodium sulfate, purified by column chromatography (petroleum ether / ethyl acetate=15:1), and then subjected to structural characterization.

[0041] The product is characterized by: 1 HNMR (500MHz, CDCl 3 )δ: 3.86(s,...

Embodiment 2-5

[0042]Embodiment 2-5: The reaction steps are the same as the reaction process of Example 1, the difference is that the electrocatalyst is replaced by equimolar 0.0033g 1c, 0.0040g 2c, 0.0045g 4c and no electrocatalyst is added, and the above constant potential is carried out Electrolysis experiments, the results are listed in Table 1.

[0043] Table 1 Electrolysis of p-methoxytoluene under the action of different electrocatalysts to generate p-methoxybenzonitrile

[0044]

[0045] It can be seen from Table 1 that the yield of aromatic nitriles is 75-93% when electrocatalyst is added, and the yield of aromatic nitriles without electrocatalysis is 50%. It can be seen that electrocatalysts 1c-4c can be used as high-efficiency electrocatalysts for aromatic nitriles. The field of electrocatalytic synthesis of aromatic nitriles from methyl compounds. Due to the low oxidation potential of electrocatalysts 1c and 2c, the catalytic effect in this system is lower than that of 3c, wh...

Embodiment 6

[0046] Embodiment 6: the preparation of p-methoxybenzonitrile (formula (2-1)):

[0047] The difference between the reaction steps and Example 1 is that the electrolyte is 0.1064g lithium perchlorate, and the yield of p-methoxybenzonitrile finally obtained is 68%.

[0048] From the above reaction results, the supporting electrolyte is preferably tetrabutylammonium perchlorate (Example 1).

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Abstract

The invention discloses a method for electrocatalytically synthesizing an aromatic nitrile compound by taking an aromatic methyl compound as a raw material. The method comprises the following step: with the aromatic methyl compound shown in a formula (II) as the raw material, a carbazole organic medium shown in a formula (I) as an electrocatalyst, hydroxylamine sulfate as a nitrogen source, carrying out indirect electrocatalysis in an electrolyte by adopting a three-electrode system to obtain the aromatic nitrile compound shown in the formula (III). According to the invention, the cheap and easily available aromatic methyl compound is used as a substrate, and the carbazole organic medium is used as the electrocatalyst for indirect electrocatalytic synthesis of aromatic nitrile, so a peroxidation reaction of the substrate on electrodes can be effectively prevented, substrate polymerization and electrode passivation are prevented, current efficiency is improved, few intermediate productsare generated, and the selectivity of aromatic nitrile is high.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and relates to a method for electrocatalytically synthesizing aromatic nitriles by using aromatic methyl compounds as raw materials. Background technique [0002] As an important intermediate in organic synthesis, aromatic nitrile compounds have been widely used in the synthesis of natural products, functional materials, medicines, pesticides and dyes. The synthesis methods of aromatic nitriles include Sandmeyer reaction, Rosenmund-von Braun reaction, transition metal catalyzed halogenated aromatic hydrocarbon reaction and amide (aldoxime) dehydration reaction, etc. The Sandmeyer reaction and the Rosenmund-von Braun reaction require the use of a stoichiometric metal cyanide source (CuCN), and the reaction is relatively violent. The transition metal-catalyzed cyanation reaction route of halogenated aromatic hydrocarbons requires the use of toxic cyanide sources (such as NaCN, KCN, TMSCN, etc.) in...

Claims

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Application Information

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IPC IPC(8): C25B3/05C25B3/09C25B3/23C25B11/085
Inventor 朱英红王乙龙葛展榜焦玉峰陈赵扬
Owner ZHEJIANG UNIV OF TECH
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