A method for the electrocatalytic synthesis of aromatic nitriles using aromatic methyl compounds as raw materials

A compound, aromatic nitrile technology, applied in the field of electrocatalytic synthesis of aromatic nitrile, to achieve the effect of preventing substrate polymerization and electrode passivation, simple operation and high selectivity

Active Publication Date: 2021-10-15
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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  • A method for the electrocatalytic synthesis of aromatic nitriles using aromatic methyl compounds as raw materials
  • A method for the electrocatalytic synthesis of aromatic nitriles using aromatic methyl compounds as raw materials
  • A method for the electrocatalytic synthesis of aromatic nitriles using aromatic methyl compounds as raw materials

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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 (0.01M AgNO 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 aromatic nitrile compounds by using aromatic methyl compounds as raw materials. The method uses the aromatic methyl compounds represented by formula (II) as raw materials, and the The carbazole organic medium is used as an electrocatalyst, and hydroxylamine sulfate is used as a nitrogen source, and a three-electrode system is used to perform indirect electrocatalysis in an electrolyte to obtain an aromatic nitrile compound shown in formula (III). The present invention uses cheap and easy-to-obtain aromatic methyl compounds as substrates, and uses carbazole organic media as electrocatalysts to carry out indirect electrocatalytic synthesis of aromatic nitriles, which can effectively prevent the peroxidation reaction of the substrates on the electrodes and prevent the polymerization of the substrates. And electrode passivation, improve current efficiency; less intermediate products, high selectivity.

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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Patent Type & Authority Patents(China)
IPC IPC(8): C07D209/82C25B3/05C25B3/09C25B3/23C25B11/085
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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