对羟基苯乙酮及其类似物的烷羰C—C键的断裂  

A Novel Scission of Alkyl- Carbonyl C-C Bond by Alkyl p - Hydroxyphenyl Ketones

作　　者：高鹏[1] 利群[1] 王世玉[1] 唐恢同[1] 张滂[1] 

机构地区：[1]北京大学化学与分子工程学院,

出　　处：《化学学报》2001年第10期1697-1701,共5页Acta Chimica Sinica

基　　金：国家自然科学基金，高等学校博士学科点专项科研项目

摘　　要：甲基、乙基、正丙基和苄基对羟苯基酮和6-羟基四氢萘-1-酮经证实在合成乙二醇缩酮的条件下发生烷碳C-C键的断裂,而对羟基二苯酮、对羟基苯异丁酮和5-羟基二氢茚-1-酮却不发生这一断键反应.经推论这一断链反应首先是发生羟醛缩合,继以在酚羟基参与下引发烷羰C-C键断裂的;还应指出,也是由于对位羟基的参与,这些烷基对羟苯基酮不形成它们的乙二醇缩酮.Methyl, ethyl, n-propyl, and benzyl p-hydroxyphenyl ketones and 6-hydroxy-1-tetralone are shown under the condition of ethylene ketal formation to undergo alkyl-carbonyl C-C bond scission, but not with p-hydroxy-benzophenone, p-hydroxyisobutyrophenone, and 5-hydroxy-1-indanone. It is suggested that the scission is preceded by an aldol condensation, followed by a phenolic hydroxyl participation with scission of the C-C in the beta -hydroxy-ketone formed. It should be noted that the participation by phenolic hydroxyl is also the cause of nonformation of ethylene ketals by those ketones mentioned.

关 键 词：羟醛缩合 烷羰C-C 断裂 对羟基苯乙酮 碳-碳链 合成 

分 类 号：O625.42[理学—有机化学]