John McMurry, Professor Emeritus

A fight between two bull moose with antlers locked.

Figure 11.1 Competition occurs throughout nature. In chemistry, competition often occurs between alternative reaction pathways, such as in the substitution and elimination reactions of alkyl halides. (credit: modification of work “Bull moose fight” by Grand Teton, National Parks Service/Flickr, Public Domain)

Chapter Contents

11.1 The Discovery of Nucleophilic Substitution Reactions

11.2 The S_N2 Reaction

11.3 Characteristics of the S_N2 Reaction

11.4 The S_N1 Reaction

11.5 Characteristics of the S_N1 Reaction

11.6 Biological Substitution Reactions

11.7 Elimination Reactions: Zaitsev’s Rule

11.8 The E2 Reaction and the Deuterium Isotope Effect

11.9 The E2 Reaction and Cyclohexane Conformation

11.10 The E1 and E1cB Reactions

11.11 Biological Elimination Reactions

11.12 A Summary of Reactivity: S_N1, S_N2, E1, E1cB, and E2

11 • Why This Chapter?

Nucleophilic substitution and base-induced elimination are two of the most widely occurring and versatile reactions in organic chemistry, both in the laboratory and in biological pathways. We’ll look at them closely in this chapter to see how they occur, what their characteristics are, and how they can be used. We’ll begin with substitution reactions.

We saw in the preceding chapter that the carbon–halogen bond in an alkyl halide is polar and that the carbon atom is electron-poor. Thus, alkyl halides are electrophiles, and much of their chemistry involves polar reactions with nucleophiles and bases. Alkyl halides do one of two things when they react with a nucleophile/base such as hydroxide ion: they either undergo substitution of the X group by the nucleophile, or they undergo elimination of HX to yield an alkene.

Substitution and elimination reactions, which take place between bromoalkane and a hydroxyl group. Substitution forms an alcohol and bromide ion. Elimination forms an alkene, water, and bromide ion.