Side-chain Nitrooxylation of Polyalkylbenzenes through Ionic Process

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The reaction of polyalkylated aromatic compounds with fuming nitric acid has been investigated with respect to the effects of substituents and added electrolytes on the ease and extent of the concurrent side-chain nitrooxylation and nuclear nitration. Relative reactivity of substituted pentamethylbenzenes C6(CH3)5X for side-chain substitution decreases from 1 to 2×10−2 to 4×10−4 to 3×10−6 with the change of substituent groups from methyl to hydrogen to bromine to nitro in accordance with the ionic character of the reaction. Added electrolytes have profound influence on the reaction rates, but the ratio of products from side chain nitrooxylation and nuclear nitration remains almost unchanged, indicating that both processes share a common intermediate. The relative amount of side-chain substitution depends closely on the positional relationship of alkyl groups in the nucleus, and preferential formation of p-alkylbenzyl nitrates is always observed. It is concluded from the results, that the side-chain nitrooxylation products are formed by way of the polar intermediate common with the ring nitration products. Some plausible reaction sequences are briefly discussed.
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