PART I. SUBSTITUTION REACTIONS PROCEEDING VIA RADICAL ANION AND FREE RADICAL INTERMEDIATES: STEREOCHEMISTRY. PART II. SUBSTITUTION REACTIONS PROCEEDING VIA RADICAL ANION AND FREE RADICAL INTERMEDIATES: THE EFFECT OF LIGHT. PART III. (A) THE DARK REACTION OF PARA-NITROCUMYL CHLORIDE AND SODIUM AZIDE: A PRELIMINARY STUDY. (B) SUBSTITUTION AT TERTIARY CARBON: A PRELIMINARY STUDY OF AZIDE AS THE LEAVING GROUP. PART IV. A MILD, NONACIDIC METHOD FOR CONVERT
Abstract
Part I. Substitution reactions of optically active 2-{p-nitrophenyl}-2-nitrobutane are described. Treatment with sodium azide, sodium thiophenoxide, sodium benzene sulfinate, and the lithium salt of 2-nitropropane leads to the corresponding tertiary alkylates in high yields; all of these products are racemic. Furthermore, sodium nitrite racemizes the optically active dinitro compond. These results fully accord with a radical anion-free radical chain mechanism. Part II. Quantum yields have been determined for several substitution reactions which are believed to proceed via radical anion-free radical chain sequences. The reaction of p-nitrocumyl chloride with sodium azide has a quantum yield, (phi), of 6,000; with quinuclidine (phi) is only 3.5. The quantum yield for the reaction of (alpha),p-dinitrocumene with sodium azide is 570. That for the reaction of ethyl (alpha)-nitroisobutyrate with the lithium salt of 2-nitropropane is 220. The average chain length for each of these reactions is greater than or equal to the corresponding quantum yield. Electronic absorption spectra indicate that charge-transfer complexes are formed. Evidence which suggests that photochemical initiation proceeds through these complexes derives from the wavelength dependence of the quantum yields. Part IIIa. The effects of di-t-butyl nitroxide and m-dinitrobenzene on the dark reaction of p-nitrocumyl chloride with sodium azide are described. Part IIIb. The anion of 2-nitropropane displaces the azido group of p-nitrocumyl azide; an 83% yield of pure carbon alkylate is isolated. Part IV. Secondary nitro compounds are converted to ketones by the joint action of a nitrite ester and sodium nitrite under exceptionally mild conditions. The yields of pure, isolated products range from 67% to 88%.
Degree
Ph.D.
Subject Area
Organic chemistry
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