Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (6): 582-587.DOI: 10.6023/A23030075 Previous Articles     Next Articles


电化学条件下α,α,α-三卤(氯, 溴)甲基酮类化合物的选择性脱卤反应研究

坎比努尔•努尔买买提a, 王超a, 罗时玮a,b,*(), 阿布都热西提•阿布力克木a,*()   

  1. a 新疆师范大学化学系 乌鲁木齐 830054
    b 中国科学技术大学化学系 合肥 230026
  • 投稿日期:2023-03-10 发布日期:2023-05-15
  • 基金资助:
    新疆维吾尔自治区自然科学基金(2022D01A207); 国家自然科学基金(地区基金)项目(22161046)

Research on Selective Dehalogenation of α,α,α-Trihalogen (Chloro, Bromo) methyl Ketones Under Electrochemical Conditions

Kanbinuer Nuermaimaitia, Chao Wanga, Shiwei Luoa,b(), Abudu Rexit Abulikemua()   

  1. a Department of Chemistry, Xinjiang Normal University, Urumqi 830054, China
    b Department of Chemistry, University of Science and Technology of China, Hefei 230026, China
  • Received:2023-03-10 Published:2023-05-15
  • Contact: *E-mail:;
  • Supported by:
    Natural Science Foundation of Xinjiang Uygur Autonomous Region of China(2022D01A207); National Natural Science Foundation of China(22161046)

The regulation of reaction to efficient and highly selective transformation into distinct valuable molecules separately from the same materials is a remarkable fundamental process in organic synthesis. Selective halogenation and dehalogenation could greatly benefit as organohalogen compounds are versatile building blocks, key intermediates and pharmaceutically essential molecules. α,α-Dihalomethyl ketones have many unique biological and organic synthetic properties. They are valuable structural frameworks in natural products, pharmaceuticals, agrochemicals and organic synthesis. α,α-Dihalomethyl ketones are one of the most important intermediates in organic synthesis. Electrochemistry has become a powerful tool in organic synthesis to avoid the use of expensive and toxic oxidants or reductants to reduce the production of harmful and toxic by-products. Therefore, in this paper, the selective dehalogenation of α,α,α-trihalogen (chloro, bromo) methyl ketones under electrochemical conditions was studied, and 17 kinds of α,α-dibromomethyl ketones and 17 kinds of α,α-dichloromethyl ketones were prepared with the highest yield of 92%. The reaction has the advantages of mild conditions, simple operation and high tolerance of functional groups. The typical procedure is as follows: the electrolysis was carried out in an undivided electrolytic cell, with a platinum anode (10 mm×10 mm×0.2 mm), and a platinum cathode (10 mm×10 mm×0.2 mm). α,α,α-Trihalomethyl ketones (0.5 mmol, 1.0 equiv.) and electrolyte (n-Bu4NHSO4 or tetrabutylammonium fluoride, 0.25 mmol, 0.5 equiv.) were dissolved in 5 mL solvent (ClCH₂CH₂Cl or CH3CN). The reaction mixture was electrolyzed under a constant current of 10 mA and at room temperature until the complete consumption of starting material as monitored by TLC or NMR. After the reaction, EtOAc (10 mL×3) was added, and then washed with water (10 mL×3) and then with brine (10 mL). The organic fraction was dried and concentrated with anhydrous MgSO4. The residue was purified by silica gel chromatography to give the dehalogenated product.

Key words: α,α-dibromomethyl ketones, α,α-dichloromethyl ketones, selective dehalogenation, organic electrosynthesis