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A method for the synthesis of α,α-dibromoketones by electrochemical oxidation of dihalogenated alkynes without diaphragm

A compound and electrochemical technology, which is applied in the field of diaphragmless electrochemical oxidation of dihalogenated alkynes to synthesize α,α-dibromoketones, which can solve the problems of inactive halide ions, low efficiency of halogen atoms, complex reactions, etc. , to achieve the effect of eliminating metal residues, high economic applicability, and simple operation

Inactive Publication Date: 2021-03-26
NANJING FORESTRY UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0002] For the method of synthesizing ɑ, ɑ-dihalogenated ketones, at present, the main synthesis method is: through ketones, adding additional strong oxidant hydrogen peroxide or oxygen under strong conditions, and commonly used electrophilic halogen sources NBS, NCS, etc., these reactions are characterized by complex and cumbersome reactions, and the atomic efficiency of halogens is not high
[0003] Dihaloacetophenones are produced by haloperoxidases and halogenases as well as inorganic halogen salts. Normally, halide ions are generally inactive unless there are strong oxidizing agents that make sensitive groups incompatible. The emergence of tolerance and the recent use of complex systems for photocatalysis and the need for metal salts, although effective, these methods usually require the use of expensive metals and their strong oxidation systems, which have great disadvantages

Method used

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  • A method for the synthesis of α,α-dibromoketones by electrochemical oxidation of dihalogenated alkynes without diaphragm
  • A method for the synthesis of α,α-dibromoketones by electrochemical oxidation of dihalogenated alkynes without diaphragm
  • A method for the synthesis of α,α-dibromoketones by electrochemical oxidation of dihalogenated alkynes without diaphragm

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Experimental program
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Effect test

Embodiment 1

[0033] (1) In an oven-dried three-necked flask (25 mL) equipped with a stirring bar, phenylacetylene (0.3 mmol), LiClO4 (1.0 equivalent), nBu4NI (0.8 equivalent), H2O (2.0 equivalent), dibromomethane (33 equiv) and CH3CN (9.8 mL) were mixed and added to give a reaction mixture.

[0034] (2) Platinum electrodes (1.0 cm×1.0 cm×0.2 mm) were installed in the flask as anode and cathode. The reaction mixture was stirred and electrolyzed at room temperature at a constant current of 10 mA for 6 h. After completion, the reaction system in the test tube was transferred to a 25mL eggplant-shaped bottle without any post-processing operation. Using a Heidolph rotary evaporator, the rotation speed was 80-100rpm, the temperature was 38°C, the vacuum degree was 0.1Mpa, and the reaction system was treated for 3 minutes. The residue was subjected to column chromatography using 200-mesh column chromatography silica gel, and the developer was petroleum ether: ethyl acetate = 20:1, and 61.7 mg of...

Embodiment 2

[0039] (1) In an oven-dried three-necked flask (25 mL) equipped with a stirring bar, p-tolylphenylene vinylene (0.3 mmol), LiClO4 (1.0 equivalent), nBu4NI (0.8 equivalent), H2O (2.0 equivalent) , dibromomethane (33 equiv) and CH3CN (9.8 mL) were combined and added to give a reaction mixture.

[0040] (2) 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 stirred and electrolyzed at room temperature at a constant current of 10 mA for 6 h. After completion, the reaction system in the test tube was transferred to a 25mL eggplant-shaped bottle without any post-processing operation. Using a Heidolph rotary evaporator, the rotation speed was 80-100rpm, the temperature was 38°C, the vacuum degree was 0.1Mpa, and the reaction system was treated for 3min. The residue was subjected to column chromatography using 200-mesh column chromatography silica gel, and the developer was petroleum ether: ethyl acetate = 20:1, a...

Embodiment 3

[0045] (1) In an oven-dried three-neck flask (25 mL) equipped with a stirring bar, mix p-tert-butylphenylacetylene (0.3 mmol), LiClO4 (1.0 equivalent), nBu4NI (0.8 equivalent), H2O (2.0 eq), dibromomethane (33 eq), and CH3CN (9.8 mL) were mixed and added to give a reaction mixture.

[0046] (2) 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 stirred and electrolyzed at room temperature at a constant current of 10 mA for 6 h. After completion, the reaction system in the test tube was transferred to a 25mL eggplant-shaped bottle without any post-processing operation. Using a Heidolph rotary evaporator, the rotation speed was 80-100rpm, the temperature was 38°C, the vacuum degree was 0.1Mpa, and the reaction system was treated for 3min. The residue was subjected to column chromatography using 200-mesh column chromatography silica gel, and the developing solvent was petroleum ether: ethyl acetate = 20:1, an...

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Abstract

The invention discloses a method for synthesizing α,α-dibromoketones by electrochemically oxidizing dihalogenated alkynes without a diaphragm. 4 、nBu 4 NI, H 2 O, halogen solvents and CH 3 CN mixed, stirred and electrolyzed at room temperature with a constant current of 10mA for 6h, after the reaction was completed, the solvent was removed by rotary evaporation to obtain the initial product of the reaction; using petroleum ether and ethyl acetate as eluents, the initial product of the reaction was chromatographed through a 200-mesh column Perform column chromatography on silica gel and separate to obtain the α,α-dibromoketone compounds. The invention is simple in operation, high in yield, and has a purity of more than 98%. The whole reaction does not require metal catalysis. In an organic solvent system, it is especially suitable for the synthesis of some drugs, fundamentally eliminating problems such as metal residues, and has high economical efficiency. applicability.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a method for synthesizing α,α-dibromoketones by electrochemically oxidizing dihalogenated alkynes without a diaphragm. Background technique [0002] For the method of synthesizing ɑ, ɑ-dihalogenated ketones, at present, the main synthesis method is: through ketones, adding additional strong oxidant hydrogen peroxide or oxygen under strong conditions, and commonly used electrophilic halogen sources NBS, NCS, etc., these reactions are characterized by complex and cumbersome reactions, and the atomic efficiency of halogens is not high. [0003] Dihaloacetophenones are produced by haloperoxidases and halogenases as well as inorganic halogen salts. Normally, halide ions are generally inactive unless there are strong oxidizing agents that make sensitive groups incompatible. The emergence of the situation of tolerance and the recent use of complex systems and the...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C25B3/23C25B3/07C25B3/11
CPCC25B3/23
Inventor 孟祥太徐鹤华王亚铭朱圣臻陈登峰刘玖洋黄申林
Owner NANJING FORESTRY UNIV
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