PART I. THE REACTION OF 1-CARBON-14-ALLYL CHLORIDE WITH SILVER METHANESULFONATE. PART II. RADICAL ANION SUBSTITUTION AT TERTIARY CARBON: REACTIONS EMPLOYING SODIO-DIETHYL MALONATE. PART III. THE REACTIONS OF SODIO-DIETHYL MALONATE WITH META- AND PARA-NITROBENZYL HALIDES
Abstract
The reaction of silver methanesulfonate (mesylate) with 1-C('14)-allyl chloride in acetonitrile produces unrearranged 1-C('14)-allyl mesylate. This result is consonant with the view that the reactions of silver salts with alkyl halides are concerted S(,N)1-S(,N)-S(,N)2 processes. A by-product of this investigation is the observation that allyl mesylate can be heated to 80(DEGREES)C. without rearrangement. Sodio-diethyl malonate reacts with p-nitrocumyl chloride, and with (alpha),p-dinitrocumene, to give the tertiary alkylate (I) in high yield. Evidence is presented in support of the view that these reactions proceed via a radical anion chain mechanism. The fact that oxygen completely stops these alkylations provides strong support for this mechanism. When oxygen is present the starting p-nitrocumyl system is converted into p-nitrocumyl alcohol, a result which would be anticipated if p-nitrocumyl radicals were scavenged by oxygen. . . . (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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