
%0 Journal Article
%A Norris, RK 
%A Randles, D 
%T The Effect of Steric Hindrance on Radical and Ionic Substitution Reactions of Nucleophiles with Some &#945;-Alkyl-<I>p</I>-Nitrobenzyl Chlorides
%J Australian Journal of Chemistry
%D 1979/07/01
%V 32
%N 7
%P 1487-1509
%K 
%R https://doi.org/10.1071/CH9791487
%U https://www.publish.csiro.au/paper/CH9791487 
%X The reactions of the &#945;-alkyl p-nitrobenzyl chlorides, p-NO2C6H4CH(CI)R(R = Me, Pr1, But), with nucleophiles, e.g, nitrite, nitroethanide, benzenethiolate and p-toluenesulfinate ions and the anion derived from diethyl 2-methylmalonate, in dimethyl sulfoxide have been studied. When R = But, SRNl reactions take place and give, in the reaction with p-toluenesulfinate and the anion from diethyl 2-methylmalonate, extremely sterically crowded molecules, which, as a result of bond formation between the more hindered atom in the ambident nucleophile and the benzylic carbon, display dynamic 1H N.M.R. effects. The derivatives where R = Me or Pri undergo radical and/or ionic processes depending on the nucleophile being used. Pathways accounting for some of the unusual compounds produced, e.g. 5-methyl-3,5-bis(p-nitropheny1)-2-isoxazoline N-oxide and (E)- and (Z)-p-nitroiso-butyrophenone O-(p-nitrobenzoyl) oximes from reaction of nitrite ion with the &#945;-methyl and &#945;- isopropyl compounds respectively, are proposed. 
