Rationalization of the effects of hydrogen bond donor solvent and nucleofugicity of fluoride ion on nucleophilic aromatic substitution reactions in non-polar aprotic solvent: reaction of 2,4-dinitrofluorobenzene with cyclohexylamine in toluene and toluene

The kinetics of the reaction of 2,4-dinitrofluorobenzene with cyclohexylamine were studied at different concentrations in toluene and toluene-alkanol mixtures. The reaction was not base-catalysed in toluene. Addition of small amounts of hydrogen-bond donor solvent, alkanol (ranging from methanol to hexanol) to the toluene medium of the reactions produced a different effect in comparison to uncatalysed reactions — slight increase in rate of reaction. The results are rationalized in terms of the effect of amine-solvent interaction on the nucleophilicity of the amine in addition to some other factors operating through cyclic transition states leading to products. It is also attributed to the peculiar nature of fluoride ion as a leaving group.