SN1 reaction

The unimolecular nucleophilic substitution (S_N1) reaction is a substitution reaction in organic chemistry. The Hughes-Ingold symbol of the mechanism expresses two properties—"S_N" stands for "nucleophilic substitution", and the "1" says that the rate-determining step is unimolecular.^[1][2] Thus, the rate equation is often shown as having first-order dependence on the substrate and zero-order dependence on the nucleophile. This relationship holds for situations where the amount of nucleophile is much greater than that of the intermediate. Instead, the rate equation may be more accurately described using steady-state kinetics. The reaction involves a carbocation intermediate and is commonly seen in reactions of secondary or tertiary alkyl halides under strongly basic conditions or, under strongly acidic conditions, with secondary or tertiary alcohols. With primary and secondary alkyl halides, the alternative S_N2 reaction occurs. In inorganic chemistry, the S_N1 reaction is often known as the dissociative substitution. This dissociation pathway is well-described by the cis effect. A reaction mechanism was first introduced by Christopher Ingold et al. in 1940.^[3] This reaction does not depend much on the strength of the nucleophile, unlike the S_N2 mechanism. This type of mechanism involves two steps. The first step is the ionization of alkyl halide in the presence of aqueous acetone or ethyl alcohol. This step provides a carbocation as an intermediate.

In the first step of S_N1 mechanism, a carbocation is formed which is planar and hence attack of nucleophile (second step) may occur from either side to give a racemic product, but actually complete racemization does not take place. This is because the nucleophilic species attacks the carbocation even before the departing halides ion has moved sufficiently away from the carbocation. The negatively charged halide ion shields the carbocation from being attacked on the front side, and backside attack, which leads to inversion of configuration, is preferred. Thus the actual product no doubt consists of a mixture of enantiomers but the enantiomers with inverted configuration would predominate and complete racemization does not occurs.