Part I. Inhibition of the reactions of p-nitrocumyl chloride with nucleophiles by m- and p-dinitrobenzenes. Part II. The displacement of the nitro group of substituted nitrobenzenes. Part III. The synthesis of functionalized tetrasubstituted olefins: The use of calcium amalgam as a reducing agent
Abstract
Part I. The effect of 5 mol % of m- and p-dinitrobenzenes upon the rate of reaction of p-nitrocumyl chloride with sodium benzenesulfinate, sodium azide, sodium nitrite and sodium cyanide was studied. Except in two instances, definite rate retardation was observed. A radical anion-radical chain mechanism is proposed for these reactions. Part II. Nitrobenzenes substituted by six different electron withdrawing groups, namely, benzoyl, carbalkoxy, cyano, nitro, benzenesulfonyl and trifluoromethyl, have been studied and a variety of nucleophiles have been employed. With one exception, the nitro group is exclusively displaced under very mild condition. The yields of pure, isolated products range from 60% to 92%. Part III. A non-basic reducing agent, calcium amalgam, for the transformation of vicinal dinitro compounds bearing cyano, ester, keto and ether groups into functionalized tetra-substituted olefins, has been developed. Olefin formation takes place at room temperature and gives pure products in 65-87% yields.
Degree
Ph.D.
Advisors
Kornblum, Purdue University.
Subject Area
Chemistry
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