Doctoral Dissertations

Abstract

"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.

Advisor(s)

Hanna, Samir B.

Committee Member(s)

Stoffer, James O.
Robertson, B. Ken
Wulfman, David S., 1934-2013
Russell, Robert R.

Department(s)

Chemistry

Degree Name

Ph. D. in Chemistry

Publisher

University of Missouri--Rolla

Publication Date

1974

Pagination

ix, 149 pages

Note about bibliography

Includes bibliographical references (pages 144-148).

Rights

© 1974 Paul Henry Ruehle, All rights reserved.

Document Type

Dissertation - Open Access

File Type

text

Language

English

Subject Headings

Chemical kineticsChemical reactions

Thesis Number

T 3005

Print OCLC #

6011606

Electronic OCLC #

914174603

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