The Connection Between S_N1 and E1

The E1 mechanism is nearly identical to the S_N1 mechanism, differing only in the course of reaction taken by the carbocation intermediate. As shown by the following equations, a carbocation bearing beta-hydrogens may function either as a Lewis acid (electrophile), as it does in the S_N1 reaction, or a Brønsted acid, as in the E1 reaction.

Thus, hydrolysis of tert-butyl chloride in a mixed solvent of water and acetonitrile gives a mixture of 2-methyl-2-propanol (60%) and 2-methylpropene (40%) at a rate independent of the water concentration. The alcohol is the product of an S_N1 reaction and the alkene is the product of the E1 reaction. The characteristics of these two reaction mechanisms are similar, as expected. They both show first order kinetics; neither is much influenced by a change in the nucleophile/base; and both are relatively non-stereospecific.

(CH₃)₃C–Cl + H₂O ——> [ (CH₃)₃C(+) ] + Cl^(–) + H₂O ——> (CH₃)₃C–OH + (CH₃)₂C=CH₂ + HCl + H₂O

To summarize, when carbocation intermediates are formed one can expect them to react further by one or more of the following modes:

1. The cation may bond to a nucleophile to give a substitution product.
2. The cation may transfer a beta-proton to a base, giving an alkene product.
3. The cation may rearrange to a more stable carbocation, and then react by mode #1 or #2.

Since the S_N1 and E1 reactions proceed via the same carbocation intermediate, the product ratios are difficult to control and both substitution and elimination usually take place.

Having discussed the many factors that influence nucleophilic substitution and elimination reactions of alkyl halides, we must now consider the practical problem of predicting the most likely outcome when a given alkyl halide is reacted with a given nucleophile. As we noted earlier, several variables must be considered, the most important being the structure of the alkyl group and the nature of the nucleophilic reactant. The nature of the halogen substituent on the alkyl halide is usually not very significant if it is Cl, Br or I. In cases where both S_N2 and E2 reactions compete, chlorides generally give more elimination than do iodides, since the greater electronegativity of chlorine increases the acidity of beta-hydrogens. Indeed, although alkyl fluorides are relatively unreactive, when reactions with basic nucleophiles are forced, elimination occurs (note the high electronegativity of fluorine).