A preparation method for electrochemical oxidation of chlorinated alkyne compounds in a diaphragmless electrolyzer

A technology for chemical oxidation and chlorination of alkynes, which is applied in the direction of electrolytic components, electrolytic process, electrolytic organic production, etc., can solve the problems of expensive, low atomic efficiency, excessive strong oxidant, etc., and achieve the elimination of metal residues, high economic applicability, Broad substrate range effect

Inactive Publication Date: 2021-07-02
NANJING FORESTRY UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Through ketone compounds, add additional strong oxidizing agent hydrogen peroxide or oxygen under strong conditions, and commonly used electrophilic halogen sources N-bromosuccinimide, N-chlorosuccinimide, etc. , these reactions are characterized by the complexity and tediousness of the reaction, the atomic inefficiency of the halogen, and more recently, the halide ion has replaced the electrophilic halogen source
Although efficient, these synthetic schemes are often limited, including the use of excess strong oxidizing agents, expensive / toxic halogenation reagents, high reaction temperatures, and low atomic efficiency

Method used

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  • A preparation method for electrochemical oxidation of chlorinated alkyne compounds in a diaphragmless electrolyzer
  • A preparation method for electrochemical oxidation of chlorinated alkyne compounds in a diaphragmless electrolyzer
  • A preparation method for electrochemical oxidation of chlorinated alkyne compounds in a diaphragmless electrolyzer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033]

[0034] In an oven-dried three-necked flask (25 mL) equipped with a stir bar, combine phenylacetylene (0.3 mmol), LiClO 4 (1.0 equivalent), nBu 4 NI (0.8 equiv.), H 2 O (2.0 equiv), chloroform (33 equiv) and CH 3 CN (9.8 mL) was mixed and added. The flask was equipped with platinum electrodes (1.0 cm x 1.0 cm x 0.2 mm) as anode and cathode. The reaction mixture was electrolyzed at room temperature with constant current stirring at 10 mA for 6 h. After completion, without post-processing operation, transfer the reaction system in the test tube to a 25mL eggplant-shaped bottle, use a Heidolph rotary evaporator, the rotation speed is 80-100rpm, the temperature is 38°C, and the vacuum degree is 0.1Mpa. The residue was then subjected to column chromatography using 200-mesh column chromatography silica gel, the developing solvent was petroleum ether:ethyl acetate=20:1, and the target compound (48.8 mg, the yield was 86%, and the purity was 98 by HPLC analysis) was iso...

Embodiment 2

[0037]

[0038] In an oven-dried three-necked flask (25 mL) equipped with a stir bar, p-methoxyphenylacetylene (0.3 mmol), LiClO 4 (1.0 equivalent), nBu 4 NI (0.8 equiv.), H 2 O (2.0 equiv), chloroform (33 equiv) and CH 3 CN (9.8 mL) was mixed and added. The flask was equipped with platinum electrodes (1.0 cm x 1.0 cm x 0.2 mm) as anode and cathode. The reaction mixture was electrolyzed at room temperature with constant current stirring at 10 mA for 6 h. After completion, without post-processing operation, transfer the reaction system in the test tube to a 25mL eggplant-shaped bottle, use a Heidolph rotary evaporator, the rotation speed is 80-100rpm, the temperature is 38°C, and the vacuum degree is 0.1Mpa. The residue was then subjected to column chromatography using 200-mesh column chromatography silica gel, and the developing solvent was petroleum ether:ethyl acetate=20:1, and the target compound (51.9 mg, yield 79%, purity 98% by HPLC analysis) was isolated. %, it ...

Embodiment 3

[0041]

[0042] In an oven-dried three-necked flask (25 mL) equipped with a stir bar, p-tert-butylphenylacetylene (0.3 mmol), LiClO 4 (1.0 equivalent), nBu 4 NI (0.8 equiv.), H 2 O (2.0 equiv), chloroform (33 equiv) and CH 3 CN (9.8 mL) was mixed and added. The flask was equipped with platinum electrodes (1.0 cm x 1.0 cm x 0.2 mm) as anode and cathode. The reaction mixture was electrolyzed at room temperature with constant current stirring at 10 mA for 6 h. After completion, without post-processing operation, transfer the reaction system in the test tube to a 25mL eggplant-shaped bottle, use a Heidolph rotary evaporator, the rotation speed is 80-100rpm, the temperature is 38°C, and the vacuum degree is 0.1Mpa. The residue was then subjected to column chromatography using 200-mesh column chromatography silica gel, the developing solvent was petroleum ether:ethyl acetate=20:1, and the target compound (55.1 mg, the yield was 75%, and the purity was 98 by HPLC analysis) was i...

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Abstract

The invention discloses a preparation method for electrochemically oxidizing chlorinated alkyne compounds in an electrolytic cell without a diaphragm, wherein the preparation method for electrochemically oxidizing chlorinated alkyne compounds in an electrolytic cell without a diaphragm comprises: adding alkyne Compounds, LiClO 4 、nBu 4 NI, H 2 O, halogen solvent, mixed; Stirring electrolysis by passing through electric current; Carry out chromatographic separation after rotary steaming; Wherein, described alkyne compound, it and described LiClO 4 , the nBu 4 NI and the H 2 The molar ratio of O is 1:0.5-1.5:0.5-1.5:0-3. The whole reaction does not need metal catalysis, and is especially suitable for the synthesis of some drugs in an organic solvent system, which fundamentally eliminates problems such as metal residues, has high economic applicability, high yield, and a purity of more than 98%.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a preparation method for electrochemically oxidizing and chlorinating alkyne compounds in a non-diaphragm electrolytic cell. Background technique [0002] For the synthesis of ɑ,ɑ-dihalogenated ketones, currently, the main synthesis methods are as follows: in nature, dihalogenated acetophenones are produced by haloperoxidase and halogenase and inorganic halogen salts. Through ketone compounds, adding additional strong oxidant hydrogen peroxide or oxygen under strong conditions, and commonly used electrophilic halogen sources N-bromosuccinimide, N-chlorosuccinimide, etc. , these reactions are characterized by complex and cumbersome reactions, low atomic efficiency of halogens, and recently, halide ions have replaced electrophilic halogen sources. While effective, these synthetic schemes are often limited, including the use of excess strong oxidants, expensi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C25B3/27C25B3/11C25B9/17C25B15/00C25B3/23
CPCC25B15/00C25B3/27C25B3/23C25B9/17
Inventor 孟祥太徐鹤华张颖茵朱圣臻陈登峰刘玖洋黄申林
Owner NANJING FORESTRY UNIV
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