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Method for realizing N-N coupling of secondary arylamine by utilizing electrochemical reaction

A technology of chemical reaction and secondary aromatic amine, which is applied in the field of N-N coupling of secondary aromatic amine by electrochemical reaction, which can solve the problems of expensive catalyst, small substrate application range, unfriendly environment, etc., and achieve shortened reaction time and less restrictions , economical effect

Active Publication Date: 2020-12-25
CHINA PHARM UNIV
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  • Abstract
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AI Technical Summary

Problems solved by technology

[0004] In view of the deficiencies in the prior art, especially in the existing multi-substituted hydrazine compound synthesis methods, there are disadvantages such as the need for external chemical oxidants, alkali additives or transition metal catalysis, the scope of substrate application is small, the catalyst is expensive, and the environment is not friendly.

Method used

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  • Method for realizing N-N coupling of secondary arylamine by utilizing electrochemical reaction
  • Method for realizing N-N coupling of secondary arylamine by utilizing electrochemical reaction
  • Method for realizing N-N coupling of secondary arylamine by utilizing electrochemical reaction

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Experimental program
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Effect test

Embodiment 1

[0045]

[0046] in such asFigure 8 Add 0.3mmol of N-methylaniline, 0.6mmol of sodium nitrite as electrolyte, 4.8mL of acetonitrile, 1.0mL of water and 1.2mL of ethanol in sequence to the 30mL electrolytic cell shown, and then put in a magnetic Stirrer, respectively add graphite carbon rod (Φ6mm), platinum sheet (1.0cm×1.0cm) as anode and cathode, turn on the power, adjust the current to 8.0mA, react at 450rpm, 50°C for 5 hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was poured into 10 mL of water, extracted three times with ethyl acetate (10 mL), the organic phases were combined, and anhydrous Na 2 SO 4 Drying, concentration, separation by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane=1 / 8), the target product was obtained, and the yield was 80% of N-N coupled tetrasubstituted hydrazine compounds. figure 1 and figure 2 shown. 1 HNMR (400MHz, CDCl 3 )δ7.20–7.16(m,4H),6.80–6.71(m,6H),2.92(...

Embodiment 2

[0048]

[0049] in such as Figure 8 Add 0.3mmol of N-methylbenzylamine, 0.6mmol of sodium nitrite as the electrolyte, 4.8mL of acetonitrile, 1.0mL of water and 1.2mL of ethanol in sequence to the 30mL electrolytic cell shown, and then add an appropriate size A magnetic stirrer was added with a graphite carbon rod (Φ6mm) and a platinum sheet (1.0cm×1.0cm) as the anode and cathode respectively. The power was turned on, the current was adjusted to 8.0mA, and the reaction was carried out at 450rpm and 50°C for 5 hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was poured into 10 mL of water, extracted three times with ethyl acetate (10 mL), the organic phases were combined, and anhydrous Na 2 SO 4 Drying, concentration, silica gel chromatography column separation (developing solvent: ethyl acetate / n-hexane = 1 / 8) to obtain the target product, the yield of N-N coupled tetrasubstituted hydrazine compounds was 77%. image 3 and ...

Embodiment 3

[0051]

[0052] in such as Figure 8 Add 0.3mmol of diphenylamine, 0.6mmol of sodium nitrite as electrolyte, 4.8mL of acetonitrile, 1.0mL of water and 1.2mL of ethanol in sequence to the 30mL electrolytic cell shown, and then put in a magnetic stirrer of appropriate size, Add graphite carbon rods (Φ6mm) and platinum sheets (1.0cm×1.0cm) as anode and cathode respectively, turn on the power, adjust the current to 8.0mA, and react at 450rpm and 50°C for 5 hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was poured into 10 mL of water, extracted three times with ethyl acetate (10 mL), the organic phases were combined, and anhydrous Na 2 SO 4 Drying, concentration, silica gel chromatography column separation (developing solvent: ethyl acetate / n-hexane = 1 / 8), to obtain the target product, the yield of 69% N-N coupled tetrasubstituted hydrazine compounds, NMR as shown in Figure 5 and Figure 6 shown. 1 HNMR (400MHz, CDCl 3 )δ7...

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Abstract

The invention relates to the technical field of organic synthesis, and discloses a method for realizing the N-N coupling of secondary arylamine by utilizing electrochemical reaction, i.e., in a deviceprovided with an anode and a cathode, an Nmethylaniline analogue shown as a formula I is used as a raw material, and an electrolyte and a solvent are added to carry out an electrolytic reaction, so that a tetra-substituted hydrazine compound shown as a formula II is obtained. Compared with the prior art, the method has the advantages that simple, cheap and easily available starting raw materialsare adopted, a substrate is sequentially subjected to anodic oxidation and cathodic reduction under mild electrochemical conditions, and the polysubstituted hydrazine compound is efficiently synthesized through single-component self-coupling of the Nmethylaniline compound; metal catalysis, strong alkali additives, strong oxidant oxidation and the like are avoided, and important intermediate compounds are prepared in a greener manner.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a method for realizing N-N coupling of secondary aromatic amines through electrochemical reaction. Background technique [0002] N, N-multi-substituted hydrazine compounds are widely used as a very important chemical raw material and intermediate in organic synthesis and medicinal chemistry. In aerospace, it can be used as a rocket propellant, and in medicine, it can be used to synthesize new antibacterial drugs, antidiabetic drugs, anticancer drugs, anti HIV virus drugs, antihypertensive drugs, etc. In addition, it also has broad application prospects in chemical catalysts, synthetic pesticides, synthetic charge transport materials, dye industry, polymers and other fine chemical industries. In general, the direct oxidative coupling of two amine molecules is one of the most direct and atomic-step economical methods to form N–N bonds. So far, many methods have been dev...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C25B3/10C07C243/22C07C243/18
CPCC07C243/18C07C243/22
Inventor 杨照韩慧敏方正秦红王志祥
Owner CHINA PHARM UNIV
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