Topic 6

Alkyl Halides

© 2016 Pearson Education, Inc.

 The Compounds in Alkyl Halides
are Electrophiles

Alkyl halides have an electron withdrawing atom or group that

is attached to an sp3 carbon.

© 2016 Pearson Education, Inc.

 Because Alkyl Halides are
Electrophiles, they react with Nucleophiles

Substitution reaction—the electronegative group is replaced

by another group.

Elimination reaction—the electronegative group is eliminated

along with a hydrogen.

© 2016 Pearson Education, Inc.

 Alkyl Halides

This chapter discusses the substitution reactions of alkyl

halides.

Alkyl halides have good leaving groups.

© 2016 Pearson Education, Inc.

 The SN2 Reaction

The substitution reaction is more precisely called a

nucleophilic substitution reaction because the atom replacing
the halogen is a nucleophile.

© 2016 Pearson Education, Inc.

 What is the Mechanism
of the Reaction?

The kinetics of a reaction—the factors that affect the rate of

the reaction—can help determine the mechanism.

an SN2 reaction
© 2016 Pearson Education, Inc.
 Relative Rates of an SN2 Reaction

© 2016 Pearson Education, Inc.

 Inverted Configuration

If the halogen is bonded to an asymmetric center, the product

will have the inverted configuration.

© 2016 Pearson Education, Inc.

 Summary of the Experimental Evidence
for the Mechanism of an SN2 Reaction

1. The rate of the reaction is dependent on the concentration

of both the alkyl halide and the nucleophile.

1. The relative rate of the reaction is:

primary alkyl halide > secondary alkyl halide > tertiary alkyl halide.

3. The configuration of the product is inverted compared to

the configuration of the reacting chiral alkyl halide.

© 2016 Pearson Education, Inc.

 Mechanism for the SN2 Reaction
of an Alkyl Halide

© 2016 Pearson Education, Inc.

 Why Bimolecular?

© 2016 Pearson Education, Inc.

 Why do Methyl Halides react the fastest
and Tertiary the Slowest?

steric hindrance
© 2016 Pearson Education, Inc.
 Why do Methyl Halides react the fastest
and Tertiary the slowest?

The relative lack of steric hindrance causes methyl halides

and primary alkyl halides to be the most reactive alkyl halides
in SN2 reactions.

Tertiary alkyl halides cannot undergo SN2 reactions.

© 2016 Pearson Education, Inc.

 Why Steric Hindrance
decreases the rate

© 2016 Pearson Education, Inc.

 Both are Primary Alkyl Halides
but they react at different rates

© 2016 Pearson Education, Inc.

 Why the configuration of the
Product is inverted

© 2016 Pearson Education, Inc.

 The rate of an SN2 Reaction
is affected by the Leaving Group

© 2016 Pearson Education, Inc.

 The Weakest Base is the
best Leaving Group

© 2016 Pearson Education, Inc.

 Base Strength and
Nucleophile Strength

If atoms are in the same row, the strongest base is the best
nucleophile.

© 2016 Pearson Education, Inc.

 Base Strength and
Nucleophile Strength

A negatively charged atom is a stronger base and a better

nucleophile than the same atom that is neutral.

© 2016 Pearson Education, Inc.

 Steric Hindrance Decreases
Nucleophilicity

Even though the tert-butoxide ion

is a stronger base, it is a poorer
nucleophile because nucleophilic
attack is more sterically hindered
than proton removal.

© 2016 Pearson Education, Inc.

 SN2 Reactions can be used to make
a variety of Compounds

The reactions are

irreversible because a
strong base displaces
a weak base.

© 2016 Pearson Education, Inc.

 The SN1 Reaction

A tertiary alkyl halide and a poor nucleophile

The reaction is surprisingly fast, so it must be taking place

by a different mechanism.

Most SN1 reactions are solvolysis reactions: the solvent is

the nucleophile.
© 2016 Pearson Education, Inc.
 The rate of an SN1 Reaction depends only
on the Alkyl Halide Concentration

© 2016 Pearson Education, Inc.

 Summary of the Experimental Evidence
for the Mechanism of an SN1 Reaction

1. The rate of the reaction depends only on the

concentration of the alkyl halide.

1. Tertiary alkyl halides react the fastest.

1. If the halogen is attached to an asymmetric center the

product will be a pair of enantiomers.

© 2016 Pearson Education, Inc.

 The Mechanism

The leaving group departs before the nucleophile approaches.

© 2016 Pearson Education, Inc.

 The Slow Step is
Formation of the Carbocation

Tertiary alkyl halides

react the fastest;
they form the most
stable carbocations.

Secondary and
primary alkyl halides
do not undergo SN1
reactions.

© 2016 Pearson Education, Inc.

 The Product is a Pair of Enantiomers

© 2016 Pearson Education, Inc.

 The Product is a Pair of Enantiomers

If the halogen is bonded to an asymmetric center, the product

will be a pair of enantiomers.

© 2016 Pearson Education, Inc.

 The Leaving Group in
an SN1 Reaction

© 2016 Pearson Education, Inc.

 The Nucleophile in
an SN1 Reaction

Most SN1 reactions are solvolysis reactions; the nucleophile

is the solvent.

© 2016 Pearson Education, Inc.

 Comparing SN2 and SN1 Reaction

© 2016 Pearson Education, Inc.

 Alkyl Halides undergo
Substitution and Elimination Reactions

In an elimination reaction
a halogen is removed from one carbon and
a hydrogen is removed from an adjacent carbon.

a double bond is formed between the two carbons

from which the atoms were removed.
© 2016 Pearson Education, Inc.
 An E2 Reaction

© 2016 Pearson Education, Inc.

 Mechanism for an E2 Reaction

© 2016 Pearson Education, Inc.

 The Halogen comes off the Alpha Carbon;
the Hydrogen comes off the Beta Carbon

dehydrohalogenation

© 2016 Pearson Education, Inc.

 An E1 Reaction

© 2016 Pearson Education, Inc.

 The Mechanism for an E1 Reaction

© 2016 Pearson Education, Inc.

 An E2 Reaction is Regioselective

The major product is the most stable alkene.

The most stable alkene is (generally) obtained by removing

a hydrogen from the beta carbon that is bonded to the
fewest hydrogens.

© 2016 Pearson Education, Inc.

 Alkene-Like Transition State

© 2016 Pearson Education, Inc.

 The more stable Alkene
has the more stable Transition State

© 2016 Pearson Education, Inc.

 More Regioselective E2 Reactions

© 2016 Pearson Education, Inc.

 An E1 Reaction is Regioselective

The major product is the more stable alkene.

The most stable alkene is obtained by removing a hydrogen

from the beta carbon that is bonded to the fewest
hydrogens.

© 2016 Pearson Education, Inc.

 The more stable Alkene is
the major product

© 2016 Pearson Education, Inc.

 Both E2 and E1 Reactions
are Regioselective

© 2016 Pearson Education, Inc.

 E2 and E1 Reactions
are Stereoselective

© 2016 Pearson Education, Inc.

 E2 and E1 Reactions
are Stereoselective

© 2016 Pearson Education, Inc.

 E2 and E1 Reactions
are Stereoselective

© 2016 Pearson Education, Inc.

 Relative Reactivities of Alkyl Halides
in an E2 Reaction

© 2016 Pearson Education, Inc.

 Does a Tertiary Alkyl Halide undergo
SN2/E2 or SN1/E1 Reactions?

© 2016 Pearson Education, Inc.

 Competition between
Substitution and Elimination

© 2016 Pearson Education, Inc.

 Under SN2/E2 conditions, a Primary Alkyl Halide
forms primarily a Substitution Product

© 2016 Pearson Education, Inc.

Under SN2/E2 conditions, a Secondary Alkyl Halide
forms Substitution and Elimination Products

Substitution is favored by a weak base.

Elimination is favored by a strong base.

© 2016 Pearson Education, Inc.

 Under SN2/E2 conditions, a Tertiary Alkyl Halide
forms only an Elimination Product

© 2016 Pearson Education, Inc.

 Under SN1/E1 conditions, a Tertiary Alkyl Halide
forms Substitution and Elimination Products

© 2016 Pearson Education, Inc.

 Tertiary (SN1/E1): Substitution is Favored
Tertiary (SN2/E2): Only Elimination

© 2016 Pearson Education, Inc.

 Summary of the products obtained from
Substitution and Elimination Reactions

© 2016 Pearson Education, Inc.

 William Ether Synthesis:
an SN2 Reaction

© 2016 Pearson Education, Inc.

 Forming an Alkoxide Ion

© 2016 Pearson Education, Inc.

 Synthesizing Butyl Propyl Ether

© 2016 Pearson Education, Inc.

 Synthesizing tert-Butyl Ethyl Ether

The less hindered group should be provided by the alkyl

halide.

© 2016 Pearson Education, Inc.

 END OF TOPIC 6

© 2016 Pearson Education, Inc.