Issue 12, 1996

The kinetics and mechanism of the reaction of p-nitrocumyl bromide with nitrite ions in dimethyl sulfoxide. Evidence for a non-chain reaction giving a high nitro/nitrite ratio in the product

Abstract

The reaction of p-nitrocumyl bromide (RBr) with sodium nitrite in [2H6]dimethyl sulfoxide gives none of the conventional evidence for an SRN1 chain reaction but the initial values of the [RNO2]/[RONO] ratio (2.5–5) are far higher than would be expected for the attack of a nitrite ion on the carbocation R+ and increase with the concentration of nitrite ions. The high values of [RNO2]/[RONO] are considered to derive from a mechanism in which a nitrite ion attacks a π-complex derived from the carbocation R+ and a second nitrite ion. This interpretation is supported by a kinetic term that is second order with respect to nitrite ions. An attempt to provide evidence for alternative radical pair intermediates from 15N CIDNP effects was unsuccessful.

Article information

Article type
Paper

J. Chem. Soc., Perkin Trans. 2, 1996, 2577-2581

The kinetics and mechanism of the reaction of p-nitrocumyl bromide with nitrite ions in dimethyl sulfoxide. Evidence for a non-chain reaction giving a high nitro/nitrite ratio in the product

S. W. Paine and J. H. Ridd, J. Chem. Soc., Perkin Trans. 2, 1996, 2577 DOI: 10.1039/P29960002577

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