Microdroplets as Microreactors for Fast Synthesis of Ketoximes and Amides

作者：Zhang, Wenwen; Yang, Shiwei; Lin, Qiuyu; Cheng, Heyong^*; Liu, Jinhua^*

来源：Journal of Organic Chemistry, 2019, 84(2): 851-859.

DOI：10.1021/acs.joc.8b02669

• BECKMANN REARRANGEMENT
• BOND FORMATION
• ACID
• EFFICIENT

The formation of amide bonds is one of the most valuable transformations in organic synthesis. Beckmann rearrangement is a well-known method for producing secondary amides from ketoximes. This study demonstrates the rapid synthesis of ketoximes and amides in microdroplets. Many factors are found to affect the yield, such as microdroplet generation devices, temperature, catalysts, and concentrations of reactants. In particular, the temperature has a great influence on the synthesis of amide, which is demonstrated by a sharp ascendance to the yield when the temperature was increased to 45 degrees C. The best amide yield (93.3%) can be obtained by using coaxial flowing devices, a sulfonyl chloride compound as a catalyst, and heating to SS degrees C in microdroplets. The yields can reach 78.7-91.3% for benzoylaniline and 87.2-93.4% for benzophenone oximes in several seconds in microdroplets compared to 10.1-66.1% and 82.5-93.3% in several hours in the bulk phase. Apart from the dramatically decreased reaction time and enhanced reaction yields, the microdroplet synthesis is also free of severe reaction environments (anhydrous and anaerobic conditions). In addition, the synthesis in microdroplets also saves reactants and solvents and reduces the waste amounts. All of these merits indicate that the microdroplet synthesis is a high-efficiency green methodology.

• 出版日期2019-1-18
• 单位杭州师范大学