Haloalkanes and alcohols Nucleophilic Substitution and

Elimination Reactions
Robert J. Ouellette, J. David Rawn, in Organic Chemistry (Second Edition), 2018
The SN2 Mechanism
The SN2 mechanism is a one-step process in which a nucleophile attacks the substrate, and a
leaving group, L, departs simultaneously. Because the reaction occurs in one step, it
is concerted. The substrate and the nucleophile are both present in the transition state for this
step. Because two molecules are present in the transition state, the reaction is bimolecular, as
indicated by the number 2 in the SN2 symbol. The rate of an SN2 reaction is first order in the
substrate and first order in the nucleophile. If the substrate concentration is doubled, the reaction
rate doubles. Similarly, if the concentration of the nucleophile is doubled, the rate again doubles.
This relationship between the rate and the concentration of the reactants exists because the
reactants must collide for reaction to occur. The probability that the nucleophile will collide with
the substrate increases if the concentration of either species is increased or if the concentrations
of both are increased.
Figure 9.3 shows the reaction coordinate diagram in the SN2 reaction of hydroxide ion
with chloromethane to give methanol and chloride ion. We see that the transition state contains
both hydroxide ion and the substrate. As the reaction proceeds through the transition state, a
bond forms between carbon and hydroxide ion, and the bond between carbon
and chlorine breaks. In the transition state, neither the nucleophile or the leaving group is fully
bonded to carbon. As we will establish shortly, the partial bonds to the nucleophile and leaving
group must be collinear. Figure 9.4 shows the energy landscape, which resembles a saddle. The
transition state is at the saddle point.

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The reaction of hydroxide ion with chloromethane occurs in a single step. The activation energy,  E , reflects
a

the stability of the transition state, which depends upon the structure of the substrate, the nucleophile, and the leaving

group.

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The point of maximum energy in the reaction coordinate diagram in  Figure 9.3 is the transition state. It is the

point of maximum energy on the pathway of minimum energy on the landscape from reactants to products. The

energy landscape resembles a saddle, and the transition state is at the saddle point.

The rate of reaction for haloalkanes by the SN2 mechanism is methyl > primary > secondary >>
tertiary. We attribute this order of reactivity to steric hindrance. Adding alkyl groups to the
carbon atom of the carbon–halogen bond shields the carbon atom from attack by nucleophiles in
the direction required for the transition state (Figure 9.5). Furthermore, the carbon atom bearing
the nucleophile and the leaving group is pentacoordinate in the transition state. As a
consequence, there is more crowding in the transition state. The energy barrier for the formation
of the transition state increases with the size of the groups bonded to the reactive center, so steric
effects are very important.
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Figure 9.5.  Effect of Steric Hindrance on an S 2 Reaction
N

The rate of an S N2 reaction decreases in the order methyl > primary > secondary >> tertiary as a

result of steric hindrance.

As hydrogen atoms are replaced one by one going from a methyl group to a tertiary halide, the
reaction becomes slower because the nucleophile cannot easily reach the electrophilic carbon of
the substrate. The electron density maps for these alkyl halides show this effect. The rate of an
SN2 reaction decreases in the order methyl > primary > secondary >> tertiary. In fact, for a
tertiary center, the SN2 mechanism is not observed. Instead, the mechanism changes from SN2 to
SN1, as we will shortly discover.
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Nucleophilic Substitution and Elimination Reactions
Robert J. Ouellette, J. David Rawn, in Principles of Organic Chemistry, 2015
The SN2 Mechanism
In the SN2 mechanism, a nucleophile attacks the substrate and the leaving group, L, departs
simultaneously. The reaction occurs in one step and is therefore concerted. The substrate and the
nucleophile are both present in the transition state for this step. Because two molecules are
present in the transition state, the reaction is bimolecular, as indicated by the number 2 in the
SN2 symbol. As a result, the reaction rate depends on the concentrations of both the nucleophile
and the substrate. If the substrate concentration is doubled, the reaction rate is doubled.
Similarly, if the concentration of the nucleophile is doubled, the rate again doubles. This
relationship between the rate and the concentration of the reactants exists because the reactants
must collide in the rate-determining step for the reaction to occur. The probability that the
nucleophile will collide with the substrate increases if the concentration of either or both species
is increased.
Let’s consider the SN2 reaction of the hydroxide ion with chloromethane to
give methanol and chloride ion. This reaction is shown with the energy diagram in Figure 7.1. In
this plot, the transition state, which occurs at the point of highest energy, contains the hydroxide
ion and the substrate. As the reaction proceeds through the transition state, a bond between
carbon and the hydroxide ion forms and the bond between carbon and chlorine breaks. The rates
of reaction for haloalkanes via the SN2 mechanism decrease in the order primary > secondary
>> tertiary. This trend is observed because alkyl groups block the approach of the nucleophile
and slow the rate of the reaction (Figure 7.2). This crowding of alkyl groups around the reactive
carbon atom is called steric hindrance.