Condensations at the Methyl Group Rather than the Methylene Group of Benzoyl-and Acetylacetone Through Intermediate Dipotassio Salts1
Condensations at the Methyl Group Rather than the Methylene Group of Benzoyl-and Acetylacetone Through Intermediate Dipotassio Salts1
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DOI：
10.1021/ja01556a049
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发表时间：
1958-12
影响因子：
15
通讯作者：
C. Hauser;T. Harris
中科院分区：
文献类型：
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作者：
C. Hauser;T. Harris
与苯甲酰基丙酮和乙酰丙酮的亚甲基上的常见反应不同，这些β-二酮的甲基上实现了几种类型的碳碳缩合反应，包括烷基化、酰化和碳酸化。这些反应通过中间体二钾盐进行，该中间体二钾盐是通过两当量的氨基钾在液氨中制备的。β-二酮如苯甲酰基丙酮和乙酰丙酮可与某些试剂在亚甲基上缩合，生成钠盐1a和1b，后者可用钠或乙醇钠制备。例如，这些盐可以用苄基氯烷基化以分别形成3-苄基衍生物IIa 3和IIb 4。
In contrast to the common reactions at the methylene group of benzoyl-and acetylacetone, several types of carboncarbon condensations including alkylation, acylation and carbonation were realized at the methyl group of these/3-diketones. These reactions were effected through intermediate dipotassiosalts, which were prepared by means of two equivalents of potassium amide in liquid ammonia. Mechanisms and synthetic applications are indicated.It is well known that/3-diketones such as benzoyl-and acetylacetone can condense at the methylene group with certain reagents through the intermedi-ate formation of the monosodio salts la and lb, which can be prepared by means of sodium or sodium ethoxide. For example, these salts can be alkylated with benzyl chloride to form the 3-benzyl derivatives Ila3 and lib, 4 respectively.