CHEN 2231

Organic Chemistry

Sulaiman Al-Isaee
Department of Engineering
College of Applied
Sciences-Suhar
Chapter 6: Organic Halogen Compounds; Substitution and
Elimination Reactions
Nucleophilic Substitution

Examples of nucleophilic substitution reactions

Nucleophile

Substrate

Leaving group
1. If the nucleophile and substrate are neutral (eq. 6.2), the
product will be positively charged.

2. If the nucleophile is a negative ion and the substrate is

neutral (eq. 6.3), the product will be neutral.
Reaction of sodium ethoxide with bromoethane
Nucleophilic Substitution
Limitations
The substitution reactions have some limitations with
respect to the structure of the R group in the alkyl
halide.
Aryl halides and vinyl halides, in which the halogen is
bonded to sp2-hybridized carbon, do not undergo this
type of nucleophilic substitution reaction.
Nucleophilic Substitution
Mechanisems

There are two main nucleophilic substitution

mechanisms. These are described by the symbols SN2
and SN1, respectively.
The SN2 Mechanism
 The SN2 Mechanism

- The nucleophile attacks from the backside of the C-L

bond.
-At the transition state, the nucleophile and the leaving
group are both partly bonded to the carbon at which
substitution occurs.
-As the leaving group departs with its electron pair, the
nucleophile supplies another electron pair to the
carbon atom
 The SN2 Mechanism
How can we recognize when a particular nucleophile and
substrate react by the SN2 mechanism?
1. The rate of the reaction depends on both the nucleophile
and the substrate concentrations.
 The SN2 Mechanism

How can we recognize when a particular nucleophile and

substrate react by the SN2 mechanism?

Every SN2 displacement occurs with inversion of

configuration.
For example, if we treat (R)-2-bromobutane with sodium
hydroxide, we obtain (S)-2-butanol.
 The SN2 Mechanism
The reaction is fastest when the alkyl
group of the substrate is methyl or
primary and slowest when it is tertiary.
Secondary alkyl halides react at an
intermediate rate. The reason for this
reactivity order is fairly obvious if we
think about the SN2 mechanism. The rear
side of the carbon, where displacement
occurs, is more crowded if more alkyl
groups are attached to it, thus slowing
down the reaction rate
The SN2 Mechanism
The SN1 mechanism is a two-step process. In the first
step, which is slow, the bond between the carbon and
the leaving group breaks as the substrate dissociates
(ionizes).
In the second step, which is fast, the carbocation
combines with the nucleophile to give the product.

When the nucleophile is a neutral molecule, such as

water or an alcohol, loss of a proton from the
nucleophilic oxygen, in a third step, gives the final
product
How can we recognize when a particular nucleophile
and substrate react by the SN1 mechanism? Here are
the signs:
1. The rate of the reaction does not depend on the
concentration of the nucleophile. The first step is rate-
determining, and the nucleophile is not involved in this
step.
2. If the carbon bearing the leaving group is
stereogenic, the reaction occurs mainly with loss of
optical activity (that is, with racemization).
3. The reaction is fastest when the alkyl group of the
substrate is tertiary and slowest when it is primary. The
reason is that SN1 reactions proceed via carbocations, so
the reactivity order corresponds to that of carbocation
stability (3° . 2° . 1°).

To summarize, the SN1 mechanism is a two-step process

and is favored when the alkyl halide is tertiary. Primary
halides normally do not react by this mechanism. The
SN1 process occurs with racemization, and its rate is
independent of the nucleophile’s concentration
Which of the following bromides will react faster with methanol (via S N1
reaction)? and what are the reaction products in each case.
Primary halides almost always react by the SN2 mechanism,
whereas tertiary halides react by the SN1 mechanism. Only with
secondary halides are we likely to encounter both possibilities.

The rate of SN1 processes is enhanced by polar solvents.

Dehydrohalogenation, and Elimination Reaction; The E2
and E1 Mechanisms

Elimination reactions provide a useful way to prepare

compounds with double or triple bonds.
As with substitution reactions, there are two main
mechanisms for elimination reactions, designated E2
and E1.
E2 mechanism

The E2 mechanism is a one-step process.

The nucleophile, acting as a base, removes the proton

(hydrogen) on a carbon atom adjacent to the one that
bears the leaving group.

At the same time, the leaving group departs and a

double bond is formed.

The bond breaking and bond making that occurs during

an E2 reaction is shown by the curved arrows:
E2 mechanism
E1 mechanism
The E1 mechanism is a two step process and has the
same first step as the SN1 mechanism,
the slow and rate-determining ionization of the
substrate to give a carbocation.

Two reactions are then possible for the carbocation. It

may combine with a nucleophile (the SN1 process), or it
may lose a proton from a carbon atom adjacent to the
positive carbon, as shown by the curved arrow, to give
an alkene (the E1 process).
If we use a strong nucleophile (which can act as a base) instead
of a weak one, and if we use a less polar solvent, we favor
elimination by the E2 mechanism.
Thus, with OH− or CN− as nucleophiles, only elimination occurs
and the exclusive product is the alkene.
Only the SN2 and E2 mechanisms are possible, because ionization
to a primary carbocation, the first step required for the SN1 or E1
mechanisms, does not occur
All four mechanisms, SN2 and E2 as well as SN1 and E1, are
possible. The product composition is sensitive to the
nucleophile (its strength as a nucleophile and as a base) and to
the reaction conditions (solvent, temperature). In general,
substitution is favored with stronger nucleophiles that are not
strong bases (SN2) or by weaker nucleophiles in polar solvents
(SN1).
Elimination is favored by strong bases (E2).