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A method for selective demethylation of n-methyl-n-(2-cyanoethyl) aniline under electrochemical conditions

An electrochemical and selective technology, applied in electrolytic components, electrolytic processes, electrolytic organic production, etc., can solve the problems of difficult to synthesize complex-type reagents, poor substrate applicability, and inconvenient operation, etc. Mild conditions, low pollution effect

Active Publication Date: 2021-09-21
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Although there are various ways of N-demethylation reaction, none of them can completely overcome the lack of substrate applicability, the use of expensive, toxic, difficult-to-synthesize complex reagents, harsh reaction conditions (anhydrous, oxygen-free, etc.) Lack of convenience

Method used

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  • A method for selective demethylation of n-methyl-n-(2-cyanoethyl) aniline under electrochemical conditions
  • A method for selective demethylation of n-methyl-n-(2-cyanoethyl) aniline under electrochemical conditions
  • A method for selective demethylation of n-methyl-n-(2-cyanoethyl) aniline under electrochemical conditions

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Experimental program
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Embodiment 1

[0028] In the round bottom flask, add 18.8mg (0.12mmol, the amount of catalyst is 20% of the amount of substance of reactant) TEMPO, 106.4mg (0.2mmol / mL) LiClO 4 , 96.2 mg (0.6 mmol) of N-methyl-N-(2-cyanoethyl) aniline; then 5 mL of acetonitrile and 0.4 mL of saturated aqueous sodium chloride were added. Insert two platinum electrodes, the electrode distance is 10mm, the DC power supply is 15mA, the reaction is stirred and monitored by TLC, and the reaction is complete in 3.5h. The crude product was extracted with ethyl acetate (15mL×3), the organic layers were combined, washed with saturated NaCl aqueous solution (40mL×1), anhydrous NaCl 2 SO 4 After drying and evaporating to dryness under reduced pressure, the product was isolated with a yield of 78%.

[0029]

Embodiment 2

[0031] Add 18.8mg (0.12mmol) TEMPO, 106.4mg (0.2mmol / mL) LiClO successively to the round bottom bottle 4 , 96.2mg (0.6mmol) N-methyl-N-(2-cyanoethyl) aniline; then add acetonitrile 5mL, saturated aqueous sodium chloride solution 0.4mL. Insert two platinum electrodes, the electrode distance is 10mm, the DC power supply is 10mA, the reaction is stirred, monitored by TLC, and the reaction is complete within 6 hours. The crude product was extracted with ethyl acetate (15mL×3), the organic layers were combined, washed with saturated NaCl aqueous solution (40mL×1), anhydrous NaCl 2 SO 4 After drying and evaporating to dryness under reduced pressure, the product was isolated with a yield of 49%.

Embodiment 3

[0033] In the round bottom flask, add 9.4mg (0.06mmol, the amount of catalyst is 10% of the amount of reactants) TEMPO, 106.4mg (0.2mmol / mL) LiClO 4 , 96.2mg (0.6mmol) N-methyl-N-(2-cyanoethyl) aniline; then add acetonitrile 5mL, saturated aqueous sodium chloride solution 0.4mL. Insert two platinum electrodes, the electrode distance is 10mm, the DC power supply is 15mA, the reaction is stirred and monitored by TLC, and the reaction is complete in 4.5h. The crude product was extracted with ethyl acetate (15mL×3), the organic layers were combined, washed with saturated NaCl aqueous solution (40mL×1), anhydrous NaCl 2 SO 4 After drying, evaporated to dryness under reduced pressure, the yield of the isolated product was 55%.

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Abstract

The invention discloses a method for selective demethylation of N-methyl-N-(2-cyanoethyl)aniline under electrochemical conditions. The method comprises the following steps: dissolving N-methyl-N-(2-cyanoethyl) aniline in a solvent, then adding a catalyst and an electrolyte; inserting an electrode into the reaction solution, conducting an electrification reaction under stirring at room temperature, and then extracting Separation and purification give N-(2-cyanoethyl)aniline. The present invention uses the effect of electric current to circulate in the reaction system with a catalytic amount of TEMPO to catalyze the selective demethylation of tertiary amines; it does not require expensive metal catalysts, equivalent oxidants, and stoichiometric acids or bases ; The reaction condition is very mild, the selectivity is good; the whole process is simple and easy, and the pollution is small, which is in line with the concept of green chemistry.

Description

technical field [0001] The invention belongs to the field of organic electrochemical synthesis, and relates to a method for synthesizing N-(2-cyanoethyl)aniline, in particular to a selective removal of N-methyl-N-(2-cyanoethyl)aniline under electrochemical conditions. Methyl method. Background technique [0002] Many small molecule analgesic and narcotic psychotropic drugs, such as cocaine, hyoscyamine, morphine, atropine, etc., all contain N-methyl tertiary amine structure. Pharmacological research has found that after N-demethylation, the pharmacological activities of these drug molecules have undergone tremendous changes, and some even have new drug activities. Therefore, it is particularly important to remove or replace N-methyl substituents in drug design. At the same time, secondary amines are easy to act as nucleophiles to react with partially positively charged carbon atoms such as halogenation and acylation, and are also easily oxidized to form nitrogen oxides. I...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C25B3/09C25B3/20
CPCC25B3/00
Inventor 黄精美杜克斯
Owner SOUTH CHINA UNIV OF TECH