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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。
In order to understand the efficiency of aroacylation and the formation of bisacyl derivatives, several typical morpholinoamines of aldehydes and ketones were investigated for o-nitrobenzoylation. Butyraldehyde and isobutyraldehyde morpholine enamine Acylation was normal and hydrolysis yielded 55% of 2- (o-nitrobenzoyl) butanal (2) and 46% of 2- (o-nitrobenzoyl) isobutyraldehyde (3) And morpholine enamine of 1, 3-dimethoxyacetone produced nicotinonitrobenzoates (4) and (5) of 37% and 14.8% of corresponding [beta] -diketones, respectively, upon acylation and hydrolysis ), The unexpected 1,5-3-acyl translocation of the acid hydrolysis of 4 and 5 led to the formation of 3,5-dimethyl-2,6-bis (o-nitrophenyl) pyran- 6) and 2-methoxy-2-methoxyacetyl-1,3-bis (o-nitrophenyl) -1,3-propanedione (7), cyclopentanone and cyclohexanonemorpholine Acylation of the amine yielded 9% and 34% of the bisacyl enamines (9a) and (9b), respectively, followed by acid hydrolysis to give 2- (o-nitrobenzoyl) cyclopentanone (11a) and -cyclohexanone 11b). In the direct hydrolysis of the total acylated product, the yield of 11a can reach 81%, while that of 11b is only 35%. Some discussion of bisacylation.