PART I. THE REACTION OF BENZYLIC HALIDES WITH SODIUM 1-METHYL-2-NAPHTHOXIDE. PART II. RADICAL ANION SUBSTITUTION AT A TERTIARY CARBON: REACTIONS EMPLOYING SODIUM 1-METHYL-2-NAPHTHOXIDE AND SODIUM 2-NAPHTHOXIDE. PART III. HETEROGENEITY AS A FACTOR IN THE ALKYLATION OF AMBIDENT ANIONS: 1-METHYL-2-NAPHTHOXIDE ION. PART IV. MISCELLANEOUS REACTIONS OF SODIUM 1-METHYL-2-NAPHTHOXIDE AND SODIUM 2-NAPHTHOXIDE

DONALD HUDSON SNOW, Purdue University

Abstract

Part I. Sodium 1-methyl-2-naphthoxide reacts with benzyl chloride, bromide, and iodide, and m-nitrobenzyl chloride, bromide, and iodide to give the oxygen alkylate as the major product; the iodides give the most carbon alkylate (10-16%). In contrast, in the p-nitrobenzyl system the chloride gives the most carbon alkylate. Evidence is presented which supports the view that the carbon alkylation observed when p-nitrobenzyl chloride is employed derives from either a radical anion process or a carbene intermediate. Part II. Sodium 1-methyl-2-naphthoxide, and sodium 2-naphthoxide, react with p-nitrocumyl cloride, and with (alpha),p-dinitrocumene, to give the corresponding tertiary ethers. In contrast, m-nitrocumyl chloride, cumyl chloride, and (alpha)-nitrocumene do not alkylate the 1-methyl-2-naphthoxide ion. Evidence is presented which indicates that p-nitrocumyl chloride and (alpha),p-dinitrocumene react via radical anion and radical intermediates. Part III. In benzene, carbon tetrachloride, or cyclohexane the reaction of sodium 1-mety1-2-naphthoxide with benzylic chlorides is heterogeneity on ambident anion reactions is discussed. Part IV. The possibility that displacement of nitrite ion from p-dinitrobenzene by sodium 1-metyl-2-naphthoxide to give the ether may proceed via radical anion intermediates was explored; no evidence in support of this hypothesis was obtained. Sodium 2-naphthoxide does not react with p-nitrocumyl 1-methy1-2-naphthyl ether in DMF at room temperature. Thus, under these conditions, at least, the 1-methyl-2-naphthoxide ion is not displaced from the p-nitrocumyl group.

Degree

Ph.D.

Subject Area

Organic chemistry

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