RADICAL ANION SUBSTITUTION AT TERTIARY CARBON: PART I. REACTIONS EMPLOYING THE LITHIUM SALT OF 2-NITROPROPANE. PART II. REACTIONS EMPLOYING SODIUM THIOPHENOXIDE. PART III. REACTIONS EMPLOYING SODIO DIETHYL-N-BUTYL MALONATE: THE OXYGEN EFFECT
Abstract
The lithium salt of 2-nitropropane reacts with p-nitrocumyl chloride, and with (alpha),p-dinitrocumene, at 25(DEGREES) in DMF (or DMSO) to form the tertiary akylate I {A = -C(CH(,3))(,2)NO(,2)} in 60-70% yields. Evidence is presented in support of the view that these reactions proceed via a radical anion chain sequence. It is especially noteworthy that oxygen completely stops alkylation; and that both p-nitrocumyl chloride and (alpha),p-dinitrocumene are converted to p-nitrocumyl alcohol. In contrast, p-nitrocumyl chloride and (alpha),p-dinitrocumene are not affected by oxygen in the absence of the lithium salt of 2-nitropropane. m-Nitrocumyl chloride reacts with the 2-nitropropane salt to give ca. 20% yield of alkylate II {A = -C(CH(,3))(,2)NO(,2)} and 60% m-nitrocumyl alcohol. p-Nitrocumyl phenyl sulfide and (beta)-naphthyl-p-nitrocumyl ether also react with the lithium salt of 2-nitropropane but rather more vigorous conditions are required. Furthermore, in addition to alkylate I {A = -C(CH(,3))(,2)NO(,2)}, p-Nitrocumene is also formed. . . . (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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