"The base-induced reactions of several p-nitrobenzyl compounds were studied. The products varied with changes in the leaving groups. With relatively poor leaving groups (Cl, S⁺(Me)₂), p,p'- dinitrostilbene was produced in good yield. The products of the reaction of p-nitrobenzyl chloride and hydroxide ion in 50% aqueous dioxane were 52.0% p,p'-dinitrostilbene, 43.9% cis- and trans-p,p'-dinitrostilbene oxides, 3.2% p-nitrobenzyl alcohol, and traces of other compounds. With dissolved oxygen, no stilbene was produced; the main product was 88% cis- and trans-p,p'-dinitrostilbene oxides. The addition of small amounts of di-t-butyl nitroxide caused a decrease in both the rate of the reaction and the amount of the stilbene produced. Larger amounts (40 mol %) completely inhibited the formation of the stilbene. Oxygen and di-t-butyl nitroxide had similar but smaller effects on the reaction of both p-nitrobenzyl-dimethylsulfonium bromide and tosylate. Compounds with good leaving groups (Br, I, Ots) gave only small amounts of the stilbene; instead, the major product was the corresponding alcohol. For p-nitrobenzyl bromide, the major product was not p,p'-dinitrobibenzyl ether, as previously reported; 4.8% of the ether, and 66.7% p-nitrobenzyl alcohol were found.
Deuterium and chlorine kinetic isotope effects were determined for the reaction of p-nitrobenzyl chloride. In addition to the previously suggested alkylation-dehydrohalogenation and α-elimination mechanisms, a radical anion mechanism is proposed"--Abstract, page ii.
Hanna, Samir B.
Stoffer, James O.
Robertson, B. Ken
Wulfman, David S., 1934-2013
Russell, Robert R.
Ph. D. in Chemistry
University of Missouri--Rolla
ix, 149 pages
© 1974 Paul Henry Ruehle, All rights reserved.
Dissertation - Restricted Access
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Link to Catalog RecordElectronic access to the full-text of this document is restricted to Missouri S&T users. Otherwise, request this publication directly from Missouri S&T Library or contact your local library. http://laurel.lso.missouri.edu/record=b1067297~S5
Ruehle, Paul Henry, "Base-induced reactions of p-Nitrobenzyl compounds" (1974). Doctoral Dissertations. 311.