Nikishin Gennady I, Kapustina Nadezhda I, Sokova Liubov L, Bityukov Oleg V, Terent'ev Alexander O
N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences 47 Leninsky prosp. Moscow 119991 Russian Federation
RSC Adv. 2018 Aug 10;8(50):28632-28636. doi: 10.1039/c8ra04885a. eCollection 2018 Aug 7.
In this work we found that a HO-HBr(aq) system allows synthesis of α-monobromo ketones and α,α'-dibromo ketones from aliphatic and secondary benzylic alcohols with yields up to 91%. It is possible to selectively direct the process toward the formation of mono- or dibromo ketones by varying the amount of hydrogen peroxide and hydrobromic acid. The convenience of application, simple equipment, multifaceted reactivity, and compliance with green chemistry principles make the application of the HO-HBr(aq) system very attractive in laboratories and industry. The proposed oxidation-bromination process is selective in spite of known properties of ketones to be oxidized by the Baeyer-Villiger reaction or peroxidated with the formation of compounds with the O-O moiety in the presence of hydrogen peroxide and Bronsted acids.
在本研究中，我们发现HO-HBr（水溶液）体系能够从脂肪族和仲苄醇合成α-单溴代酮和α,α'-二溴代酮，产率高达91%。通过改变过氧化氢和氢溴酸的用量，可以选择性地引导反应生成单溴代酮或二溴代酮。该体系应用方便、设备简单、反应具有多面性且符合绿色化学原则，使得HO-HBr（水溶液）体系在实验室和工业中极具吸引力。尽管已知酮类在过氧化氢和布朗斯特酸存在下会被拜耳-维利格反应氧化或过氧化形成含O-O部分的化合物，但所提出的氧化溴化过程具有选择性。
