PART I. THE EFFECT OF SOLVENT, CATION AND LEAVING GROUP IN THE ALKYLATION OF A BETA-KETO ESTER. PART II. RADICAL ANIONS AS INTERMEDIATES IN THE SUBSTITUTION REACTIONS OF A BETA-KETO ESTER SALT
Abstract
In the alkylations of the salts of (beta)-hydroxycoumarilic acid ethyl ester (I), it is found that the amounts of carbon (II) and oxygen (III) alkylates produced depends on the hydrogen bonding ability. 93% C + 2% O water Na(I) + PhCH(,2)Br DMF 63% C + 28% O and the dielectric of the solvent. 84% C + 8% O MeOCH(,2)CH(,2)OMe Na(I) + PhCH(,2)Br DMF 63% C + 28% O and the size of the cation. DMF Li(I) + PhCH(,2)Br (--->) 71% C + 23% O DMF NMe(,4)(I) + PhCH(,2)Br (--->) 44% C + 48% O Similar results are obtained with methyl iodide. A leaving group effect is observed in the reactions of I with benzyl halides in DMF. Na(I) + PhCH(,2)Cl (--->) 42% C + 51% O Na(I) + PhCH(,2)Br (--->) 63% C + 28% O Na(I) + PhCH(,2)I (--->) 73% C + 20% O In 1,2-dimethoxyethane a marked difference in product distribution is found between the reaction of Na(I) with trimethyloxonium fluoroborate (100% O) and methyl iodide (90% C and 8% O). . . . (Author's abstract exceeds stipulated maximum length. Discontinued here with permission of school.) UMI
Degree
Ph.D.
Subject Area
Organic chemistry
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