Catalyst-free electrochemical deuteration method using deuterium oxide as deuterium source

Patent metadata

Field	Value
Publication number	US-2021404070-A1
Application number	US-202017281625-A
Country	US
Kind code	A1
Filing date	Sep 3, 2020
Priority date	Sep 5, 2019
Publication date	Dec 30, 2021
Grant date	—

Abstract

A catalyst-free electrochemical deuteration method using deuterium oxide as a deuterium source, adding an electrolyte, an organic compound containing an ethylenic bond or acetylenic bond, deuterium oxide, and an organic solvent into a reactor, applying a direct current voltage of 4-8 V between electrodes of a carbon felt in an atmosphere of an inert gas for an electrolytic reaction, to obtain a product, and purifying the product to obtain a deuterated product. In the method provided by the present disclosure, with the organic compound containing an ethylenic bond or acetylenic bond as a raw material, deuterium oxide as a deuterium source, cheap and readily available carbon electrode materials as cathodes and anodes, it is possible to obtain deuterated products by a direct current electrolysis in an organic solvent, without any transition metal catalysts.

First claim

1 ) A catalyst-free electrochemical deuteration method using deuterium oxide as a deuterium source, comprising,
adding an electrolyte, an organic compound containing an ethylenic bond or acetylenic bond, deuterium oxide, and an organic solvent into a reactor, applying a direct current voltage of 4-8 V between electrodes of a carbon felt in an atmosphere of an inert gas for an electrolytic reaction, to obtain a product, and purifying the product, to obtain a deuterated product; wherein the organic compound containing an ethylenic bond or acetylenic bond is selected from the group consisting of olefin, alkyne, unsaturated ester, unsaturated amide and unsaturated carboxylic acid.

2 ) The catalyst-free electrochemical deuteration method using deuterium oxide as a deuterium source as claimed in claim 1 , wherein the organic compound containing an ethylenic bond or acetylenic bond is selected from the group consisting of ethyl 3-phenylacrylate, butyl 3-phenylacrylate, 1-pentene-4-yl 3-phenylacrylate, cyclohexyl 3-phenylacrylate, tetrahydrofuran-3-yl 3-phenylacrylate, diethyl-phosphonomethyl 3-phenylacrylate, benzyl 3-phenylacrylate, phenyl 3-phenylacrylate, menthyl 3-phenylacrylate, 3-(3-phenylacrylyl) estrone, borneyl 3-phenylacrylate, pregnenolone 3-phenylacrylate, 3-(3-phenylacrylyl) estrone, and cholesteryl 3-phenylacrylate.

3 ) The catalyst-free electrochemical deuteration method using deuterium oxide as a deuterium source as claimed in claim 1 , wherein the electrolyte is selected from the group consisting of tetrabutylammonium tetrafluoroborate and LiClO 4 , and has a concentration of 0.02 mol/L.

4 ) The catalyst-free electrochemical deuteration method using deuterium oxide as a deuterium source as claimed in claim 1 , wherein a molar ratio of deuterium oxide to the organic compound containing an ethylenic bond or acetylenic bond is in a range of (5-20):1.

5 ) The catalyst-free electrochemical deuteration method using deuterium oxide as a deuterium source as claimed in claim 1 , wherein the organic solvent is selected from the group consisting of DMF and acetonitrile.

6 ) The catalyst-free electrochemical deuteration method using deuterium oxide as a deuterium source as claimed in claim 1 , wherein the inert gas is selected from the group consisting of nitrogen and argon.

7 ) The catalyst-free electrochemical deuteration method using deuterium oxide as a deuterium source as claimed in claim 1 , wherein purifying the product comprises steps:
extracting the product with ethyl acetate to obtain an organic phase, washing the organic phase with saturated salt water, then drying with anhydrous sodium sulfate, and filtering to obtain a filtrate; drying the filtrate with a rotary evaporator, to obtain a sample; subjecting the sample to a column chromatography by using a column chromatography technology, in which, 300-400 mesh silica gel is used as a stationary phase, and the sample is directly loaded on the silica gel, and eluted with a mixed solution of petroleum ether and ethyl acetate as an eluent, to obtain an eluate, which is detected by GC-MS; collecting and concentrating the eluate containing a deuterated product.

8 ) The catalyst-free electrochemical deuteration method using deuterium oxide as a deuterium source as claimed in claim 1 , wherein the electrolytic reaction is carried out for 2-10 h.

9 ) The catalyst-free electrochemical deuteration method using deuterium oxide as a deuterium source as claimed in claim 6 , wherein purifying the product comprises steps:
extracting the product with ethyl acetate to obtain an organic phase, washing the organic phase with saturated salt water, then drying with anhydrous sodium sulfate, and filtering to obtain a filtrate; drying the filtrate with a rotary evaporator, to obtain a sample; subjecting the sample to a column chromatography by using a column chromatography technology, in which, 300-400 mesh silica gel is used as a stationary phase, and the sample is directly loaded on the silica gel, and eluted with a mixed solution of petroleum ether and ethyl acetate as an eluent, to obtain an eluate, which is detected by GC-MS; collecting and concentrating the eluate containing a deuterated product.

Assignees

• Nanjing University Of Technology
• Nanxin Pharmaceuticals Tech Research Institute Co Ltd

Inventors

• Cheng Xu
• Liu Xu

Classifications

• G01N2030/884

  organic compounds · CPC title

• G01N30/88

  Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 · CPC title

• C25B3/11

  Halogen containing compounds · CPC title

• C25B3/09

  Nitrogen containing compounds · CPC title

• C25B15/085

  Removing impurities · CPC title