OVERVIEW OF ALKYL
HALIDES
CAPE Chemistry Unit 2
Mr. Banton
OBJECTIVES
1) Name 2) Describe via 3) Describe the 4) Distinguish
monosubstituted alkyl mechanisms Sn1 and conditions required between stepwise and
halides using IUPAC Sn2 reactions for for Sn1 and Sn2 concerted reactions
rules alkyl halides reactions
INTRODUCTION TO ALKYL HALIDES
• Alkyl halides are alkane derivatives in which hydrogen
atoms of an alkane have been replaced with halogen
atoms
• Alkyl halides are typically used as solvents or as the
starting materials for chemical synthesis
• Monosubstituted alkyl halides can be classified as
primary, secondary or tertiary based on the number of
alkyl groups attached to the carbon bearing the
halogen atom
CLASSIFICATIONS OF ALKYL HALIDES
Methyl Alkyl Primary Alkyl Secondary Alkyl Tertiary Alkyl
Halide Halide Halide Halide
Carbon bearing Carbon bearing Carbon bearing Carbon bearing
the halogen is the halogen is the halogen is the halogen is
attached to no attached to attached to attached to
alkyl group one alkyl group two alkyl three alkyl
groups groups
TYPICAL ALKYL HALIDES
Alkyl halides are named using most of the IUPAC rules specified for alkanes.
However, the location, number and type of each halogen atom present must be
specified. Where applicable, alphabetical priority in naming substituents must
also be observed.
POLARITY OF ALKYL HALIDES
• The carbon-halogen bond in alkyl halides is weakly
polar.
• The polarity of the carbon-halogen bond leads to alkyl
halides exhibiting higher melting/boiling points than
those of their alkane counterparts
• Strong nucleophiles can attack alkyl halides leading to
the substitution of the halogen atom with the
nucleophilic species. Such reactions are called
nucleophilic substitution reactions
NUCLEOPHILIC SUBSTITUTION OF
ALKYL HALIDES
• Alkyl halides react with hydroxide ions (which are strong
nucleophiles) to form alcohols.
• The outcome and mechanism of such reactions depend upon
the following factors:
❑ Type of alkyl halide (whether primary, secondary or
tertiary)
❑ Type of solvent used
❑ The rate law followed by the reaction
❑ The nature of the leaving group
NUCLEOPHILIC SUBSTITUTION OF
ALKYL HALIDES
• The generic reaction of alkyl halides with hydroxide ions is
shown below:
Hydroxide Alkyl Halide
Alcohol
ion Halide (leaving group)
NUCLEOPHILIC SUBSTITUTION MECHANISMS
• Nucleophilic substitution in alkyl
halides occur by the following
reaction pathways:
❑ SN1 (Substitution Nucleophilic
Unimolecular)
❖ Rate = k[A]
❑ SN2 (Substitution Nucleophilic
Bimolecular)
❖ Rate = k[A][B]
NUCLEOPHILIC SUBSTITUTION MECHANISMS
SN1 Reactions SN2 Reactions
Occur predominantly with tertiary alkyl Occurs predominantly with primary alkyl
halides halides
Occurs in stepwise fashion Occurs in concerted fashion
The rate of the reaction depends on the alkyl The rate of reaction depends on both the alkyl
halide concentration solely halide and the hydroxide concentrations
Racemic mixtures ( a mixture of enantiomers) An inversion in stereochemistry occurs
are formed if the alkyl halide which reacts is
chiral
Polar, protic solvents are used Polar, aprotic solvents are used
THE SN1 MECHANISM
Key Steps
1. Heterolytic cleavage of the
carbon-halogen bond to form
a carbocation and a halide ion
2. Attack of nucleophile (for our
purposes, a hydroxide ion)
above or below the trigonal
planar carbocation
3. Formation of a mixture of
enantiomers (a racemic
mixture). The ration of
enantiomers present is 1: 1
KEY POINTS RE SN1
• Tertiary alkyl halides form tertiary
carbocations when the carbon-halogen
bond breaks heterolytically. Tertiary
carbocations are more stable than primary
or secondary carbocations.
• Polar, protic solvents help to stabilize the
tertiary carbocation through solvation
• The cleavage of the carbon-halogen bond
is the rate-determining step
THE SN2 MECHANISM
Key Steps
1. Heterolytic cleavage of the
carbon-halogen bond occurs at
the same time as the formation
of a bond between the
nucleophile and the central
carbon
2. A transition state is formed
3. The product formed has a
different stereochemistry from
the alkyl halide from which it
is produced. (inversion of
stereochemistry)
NB. For our purposes, since primary alkyl halides react preferentially via this
mechanism, R2 and R3 are to be replaced with H atoms
KEY POINTS RE SN2
• Primary alky halides are less sterically hindered
than secondary or tertiary alkyl halides; hence,
they undergo substitution readily via an Sn2
mechanism
• Polar, aprotic solvents do not solvate the
hydroxide ions. If a protic solvent was used, the
hydroxide ions would have been hindered from
reaching the alkyl halide
• The rate of the reaction depends on both the
concentration of the alkyl halide and the
concentration of the nucleophile
KEY POINTS RE LEAVING GROUPS
• The ranking of halide leaving groups are as follows:
I- > Br- > Cl- >>F-
• The carbon –iodine bond will break most readily, leading to a fast rate of
reaction. The carbon-fluorine bond will break least readily, leading to a slow
rate of reaction
