"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
Library of Congress Subject Headings
Print OCLC #
Electronic OCLC #
Link to Catalog Record
Electronic 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.
Share My Dissertation If you are the author of this work and would like to grant permission to make it openly accessible to all, please click the button above.