NEW AND FACILE SUBSTITUTION REACTIONS AT TERTIARY CARBON

ROGER THOMAS SWIGER, Purdue University

Abstract

Part I. Sodium benzene sulfinate reacts with p-nitrocumyl chloride, (alpha),p-dinitrocumene, and m-nitrocumyl chloride to give the corresponding tertiary sulfones. The yield of sulfone is high (ca. 95% yield) when p-nitrocumyl chloride or (alpha),p-dinitrocumene are employed, but relatively low (ca. 45% yield) when m-nitrocumyl chloride is used. Evidence is presented which supports the view that p-nitrocumyl chloride and (alpha),p-dinitrocumene react via a radical chain pathway. Part II. The effect of 1 and 5 mole % oxygen upon the rate of reaction of p-nitrocumyl chloride and (alpha),p-dinitrocumene with various nucleophiles was studied. Definite rate retardation was observed and this rate retardation is strong evidence that the reactions of p-nitrocumyl chloride and (alpha),p-dinitrocumene proceed by a radical chain mechanism. Part III. Eight entrainment examples involving reactions of p-nitrocumyl chloride and (alpha),p-dinitrocumene with various nucleophiles are reported. These entrainment results support the view that p-nitrocumyl chloride and (alpha),p-dinitrocumene react via a radical chain sequence. Part IV. The following preliminary results are contained in this section: (1) the entrainment of m-nitrocumyl chloride, (2) reactions involving the p-cyanocumyl system, (3) the stability of the lithium salt of 2-niropropane, (4) the entrainment of (alpha),p-dinitrocumene with sodium methoxide and tetraethylammonium fluoride, and (5) a study of an intermediate (thought to be the nitronic ester) produced in the reaction of m-nitrocumyl chloride with the lithium salt of 2-nitropropane.

Degree

Ph.D.

Subject Area

Organic chemistry

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