烯丙基醇类化合物氧化反应研究
发布时间：2019-06-05 05:39
【摘要】：α,β-不饱和酮不仅自身具有一定的药理作用,而且是一种广泛应用于医药农药制造及香料生产等工业过程的合成中间体。在合成许多药物分子时,为实现羰基的1,3-迁移,首先需要通过金属试剂将α,β-不饱和酮转换为相应的烯醇化合物,然后通过氧化重排实现上述过程,目前常使用的氧化剂是有毒的金属铬试剂,本文以温和的邻苯二甲酰过氧化物为氧化剂,实现了对2-氧代烯丙醇类化合物氧化重排生成羰基迁移的α,β-不饱和酮反应。经过对反应条件的筛选,将1当量的2 -氧代烯丙醇类底物与1.5当量的邻苯二甲酰过氧化物,在80 ℃、N2气氛、1,2-二氯乙烷(0.2 M)溶剂中反应可以得到最佳收率。后尝试扩展反应底物22个,发现该反应反应条件较温和,易操作,后处理简单,且具有一定的官能团容忍度,产率介于低到中等(10%-55%)。将是实验中副产物通过GC-MS、核磁共振进行了相应的表征分析,预测了可能存在的反应机理为:底物的碳碳双键的富电子进攻酰基过氧化物的过氧键,在羟基的β位生成碳正离子,后发生分子内的1,2-H迁移,邻苯二甲酸酐离去生成目标产物。而副产物则可能由于逆羟醛缩合反应引起。在对上述反应的研究过程中,发现将过硫酸钾作用于2-氧代烯丙醇类底物可以得到环内双键迁移的二烯化合物,经过对反应条件的筛选,将1当量的2-氧代烯丙醇类底物与2当量的过硫酸钾,在80 ℃、N2气氛、甲苯(0.1 M)溶剂中反应作为最优反应条件,同时将16个底物用于该反应的尝试,发现反应对含吸电子及给电子基团的底物均表现良好的容忍性,且产率达到中等(10%-71%)的水平,但当底物空间位阻过大时,则反应无法发生。
[Abstract]:伪, 尾-unsaturated ketones not only have certain pharmacological effects, but also are widely used in pharmaceutical pesticide manufacturing and flavor production. In the synthesis of many drug molecules, in order to realize the 1, 3-migration of carbonyl groups, 伪, 尾-unsaturated ketones need to be converted into corresponding enol compounds by metal reagents, and then the above process is realized by oxidation rearrangement. At present, the oxidant commonly used is a toxic metal chromium reagent. In this paper, the oxidation rearrangement of 2-oxo-allyl alcohol compounds to form carbonyl transfer 伪, 尾-unsaturated ketone reaction was realized by using mild phthalyl peroxide as oxidant. After screening the reaction conditions, the optimum yield of 2-dichloroethane (0.2 M) was obtained by the reaction of 1 equivalent 2-oxoallyl alcohol substrate with 1.5 equivalent phthalyl peroxide in 80 鈩，
本文编号：2493295
[Abstract]:伪, 尾-unsaturated ketones not only have certain pharmacological effects, but also are widely used in pharmaceutical pesticide manufacturing and flavor production. In the synthesis of many drug molecules, in order to realize the 1, 3-migration of carbonyl groups, 伪, 尾-unsaturated ketones need to be converted into corresponding enol compounds by metal reagents, and then the above process is realized by oxidation rearrangement. At present, the oxidant commonly used is a toxic metal chromium reagent. In this paper, the oxidation rearrangement of 2-oxo-allyl alcohol compounds to form carbonyl transfer 伪, 尾-unsaturated ketone reaction was realized by using mild phthalyl peroxide as oxidant. After screening the reaction conditions, the optimum yield of 2-dichloroethane (0.2 M) was obtained by the reaction of 1 equivalent 2-oxoallyl alcohol substrate with 1.5 equivalent phthalyl peroxide in 80 鈩，
本文编号：2493295
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2493295.html
教材专著
