α-乙酰基二硫缩烯酮α碳原子的酰化反应  

Acylation of α-Acetyl Ketendithioacetals with Acyl Chloride

作　　者：尹彦冰[1] 王岩[1] 赵玉龙[1] 谭晶[1] 刘群[1] 

机构地区：[1]东北师范大学化学学院

出　　处：《高等学校化学学报》2006年第12期2334-2336,共3页Chemical Journal of Chinese Universities

基　　金：教育部科学技术研究重大项目(批准号:10412)资助.

摘　　要：As a kind of versatile synthons, α-oxoketene dithioacetals have found their wide utilizations in organic synthesis. Owing to the interaction between two electron donating groups(RS) and an electron withdrawing group in the α position, the α-carbon atom of α-EWG ketene S,S-acetals shows a high nucleophilicity. In this paper, the reactions of α-acetyl cyclic ketendithioacetals with a series of acyl chlorides were performed and a new route to the C～C bond formation reaction at the α-carbon atom of α-oxoketene dithioacetals was described. By the above reactions, α-acetyl-α-acyl ketendithioacetals were prepared with good to high yields(55%～82%) via the acylation of α-acetyl cyclic ketendithioacetals at the α-carbon atom of α-acetyl ketendithioacetals mediated by titanium tetrachloride in dry dichloromethane at reflux temperature. The mechanism of the acylation between compound 1 and acyl chloride was proposed, which belongs to nucleophilic addition-elimination reaction.As a kind of versatile synthons, α-oxoketene dithioacetals have found their wide utilizations in organic synthesis. Owing to the interaction between two electron donating groups（RS） and an electron withdrawing group in the α position, the α-carbon atom ofα-EWG ketene S, S-acetals shows a high nucleophilicity. In this paper, the reactions of α-acetyl cyclic ketendithioacetals with a series of acyl chlorides were performed and a new route to the C--C bond formation reaction at the α-carbon atom of a-oxoketene dithioacetals was described. By the above reactions, α-acetyl-α-acyl ketendithioacetals were prepared with good to high yields （55%--82%） via the acylation of a-acetyl cyclic ketendithioacetals at the α-carbon atom of α-acetyl ketendithioacetals mediated by titanium tetrachloride in dry dichloromethane at reflux temperature. The mechanism of the acylation between compound 1 and acyl chloride was proposed, which belongs to nucleophilic additionelimination reaction.

关 键 词：α-乙酰基二硫缩烯酮 酰氯 酰化 α-乙酰基-α-酰基二硫缩烯酮 

分 类 号：O626[理学—有机化学]