几个烯胺的邻硝基苯甲酰化和在酸水解中发生的重排  

o-Nitrobenzoylation of Some Enamines and Rearrangements Involved in Acid Hydrolysis

作　　者：铁宏[1] 马振坤[1] 李良助 张滂[1] 

机构地区：[1]北京大学化学

出　　处：《化学学报》1990年第7期720-725,共6页Acta Chimica Sinica

基　　金：国家自然科学基金;教育委员会自然科学基金资助的课题

摘　　要：为了了解芳酰基化的效率和双酰基衍生物的形成,对几个典型醛和酮的吗啉烯胺进行了邻硝基苯甲酰化的探索,丁醛和异丁醛吗啉烯胺的酰化正常,水解分别生成55％的2-(邻硝基苯里酰基)丁醛(2)和46％的2-(邻硝基苯甲酰基)异丁醛(3),3-戊酮和1,3-二甲氧基丙酮的吗啉烯胺在酰化和水解时分别生成37％和14.8％相应的β-二酮的烯醇邻硝基苯甲酸酯(4)和(5),4和5的酸水解发生意外的1,5-3-酰基转位,分别生成3,5-二甲基-2,6-双(邻硝基苯基)吡喃-4-酮(6)和2-甲氧基-2-甲氧乙酰基-1,3-双(邻硝基苯基)-1,3-丙二酮(7),环戊酮和环己酮吗啉烯胺的酰化分别产生9％和34％的双酰基烯胺(9a)和(9b),逐次酸水解得到2-(邻硝基苯甲酰基)环戊酮(11a)和-环己酮(11b),在总酰化产物的直接水解中,11a的产率可以达到81％,而11b只有35％。对双酰化进行了一些讨论。o-Nitrobenzoylation of some typical aldehyde and ketone enamines were studied with regard to yields and formation of diacyl derivatives. The acylations of butyraldehyde and isobutyraldehyde morpholine onamines were normal and yielded 55％ 2-(o-nitrobenzoyl) butyraldehydo (2) and 46％ 2-(o-nitrobenzoyl)-isobutyraldehyde (3) on acid hydrolysis. 3-Pontanono and 1, 3-dimethoxyacetone morpholino enamines on acylation followed by acid hydrolysis gave rise to β-diketone enol o-nitrobonzoates (4) and (5) in 37％ and 14.8％ yields respectively. Quite unexpectedly, 4 and 5 on acid hydrolysis underwent 1, 5-and 1, 3-shifts respectively with formation of 3, 5-dimethyl-2, 6-bis (o-nitrophenyl)-4-pyrono (6) and 2-methoxy-2-methoxyacetyl-1, 3-bis (o-nitrophenyl)propan-1, 3-dione (7). Cyclopentanone and cyclohexanono morpholine enamines in contrast to each other on acylation yielded 9％ and 45％ diacyl enamines (9a) and (9b) respectively which on acid hydrolysis gave 2-(o-nitrobenzoyl) cyclopentanone (11a) and-cyclohexanone (11b) in high yields and no acyl shift was detected. Diacylation seemed, therefore, to depend upon stric hindrance as well as conformation.

关 键 词：吗啉烯胺 苯甲酰化 邻硝基 

分 类 号：O626.4[理学—有机化学]