RADICAL ANIONS AS INTERMEDIATES IN SUBSTITUTION REACTIONS (PARA-NITROCUMYL CHLORIDE)

JOSEPH WILLIAM MANTHEY, Purdue University

Abstract

Part I. Sodium azide reacts with p-nitrocumyl choloride, m-nitrocumyl chloride, cumyl chloride, and (alpha),p-dinitrocumene to give the corresponding tertiary azides in good to excellent yields. Evidence is presented which indicates that p-nitrocumyl chloride and (alpha),p-dinitrocumene react via radical anion and radical intermediates. m-Nitrocumyl chloride and cumyl chloride, on the other hand, appear to react by a different mechanism(s); several possibilities are discussed. Part II. Various non-carbanionic nucleophiles were allowed to react with p-nitrocumyl chloride and/or (alpha),p-dinitrocumene. However, only sodium methoxide was able to effect a significant amount of tertiary substitution. Attempts were made to scavenge p-nitrocumyl radicals, the alleged intermediate, in the reactions of sodium thiophenoxide with p-nitrocumyl chloride, m-nirocumyl chloride, and (alpha),p-dinitrocumene. Oxygen was effective at trapping the intermediate radicals, but thiophenol was not. (alpha),m-Dinitrocumene was synthesized and was allowed to react with various nucleophiles. Part III. It was suggested that some or all nucleophilic aromatic displacement reactions might be proceeding via radical anion intermediates. However, no evidence could be found which supported this hypothesis. Part IV. 2,3-Dimethy1-2-nitro-3-(p-nitrophenyl)butane (I) was converted to two new compounds whose properties corresponded to those expected. This and other evidence firmly establish the structure of I.

Degree

Ph.D.

Subject Area

Organic chemistry

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