Studies on the Mechanism of Deacylation and Condensation Reactions of α,α-Diacetyl Ketene Dibenzylthioacetal

Abstract

Abstract: The behavior of α,α-diacetyl ketene dibenzylthioacetal 1a under basic conditions was studied. Catalyzed by steric hindered base ast-BuONa(int-BuOH), α-acetyl ketene dibenzylthioacetal 2a could be obtained in 98% yield within 3 min via deacylation of 1a. Assisted byt-BuONa(int-BuOH), α-cinnamoyl ketene dibenzylthioacetals were produced in high yields by reacting both 1a and 2a with arylaldehydes; whereas, under the same conditions, the corresponding α,α-dicinnamoyl ketene dibenzylthioacetals 4 were formed when furan-2-carbaldehyde and thiophene-2-carbaldehyde were used asthe electrophiles. These evidences support the proposed mechanism that, catalyzed byt-BuONa (int-BuOH), the reaction of 1a with arylaldehydes may normally proceed via a sequential deacylation-condensation process and the formation of double condensation products 4 may be due to the higher activity of furan-2-carbaldehyde and thiophene-2-carbaldehyde under the selected reaction conditions.

Key words: α,α-Diacetyl ketene dibenzylthioacetal, Deacylation, Condensation

CLC Number:

O626

TrendMD:

AI Lin, XIAO You-Ping, LIU Qun, ZHANG Qian, WANG Mang . Studies on the Mechanism of Deacylation and Condensation Reactions of α,α-Diacetyl Ketene Dibenzylthioacetal[J]. Chem. J. Chinese Universities, 2004, 25(5): 877.

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Studies on the Mechanism of Deacylation and Condensation Reactions of α,α-Diacetyl Ketene Dibenzylthioacetal

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