Chapter 7, Haloalkanes,

Properties and Substitution Reactions

of Haloalkanes
 Table of Contents
1. Alkyl Halides (Haloalkane)
2. Nucleophilic Substitution Reactions (SNX, X=1 or 2)
3. Nucleophiles (Acid-Base Chemistry, pka)
4. Leaving Groups (Acid-Base Chemistry, pka)
5. Kinetics of a Nucleophilic Substitution Reaction: An
SN2 Reaction
6. A Mechanism for the SN2 Reaction
7. The Stereochemistry of SN2 Reactions
8. A Mechanism for the SN1 Reaction
9. Carbocations,  SN1, E1
10. Stereochemistry of SN1 Reactions
11. Factors Affecting the Rates of SN1 and SN2
Reactions
12. --Eliminations, E1 and E2
13. E2 and E1 mechanisms and product predictions
In this chapter we will consider:
 What groups can be replaced (i.e.,
substituted) or eliminated

 The various mechanisms by which such

processes occur

 The conditions that can promote such

reactions
Alkyl Halides (Haloalkane)
 An alkyl halide has a halogen atom
bonded to an sp3-hybridized
(tetrahedral) carbon atom

 The carbon–chlorine and carbon–

bromine bonds are polarized because
the halogen is more electronegative
than carbon
 The carbon-iodine bond do not have a per-
manent dipole, the bond is easily polarizable
 Iodine is a good leaving group due to its
polarizability, i.e. its ability to stabilize a charge
due to its large atomic size
 Generally, a carbon-halogen bond is polar with
a partial positive () charge on the carbon
and partial negative () charge on the
halogen  
 
C X X = Cl, Br, I
Different Types of Organic Halides
 Alkyl halides (haloalkanes)

sp3-hybridized

Attached to Attached to Attached to

1 carbon atom 2 carbon atoms 3 carbon atoms
C C C

C Cl C Br C I
a 1o chloride a 2o bromide a 3o iodide
 Vinyl halides (Alkenyl halides)
sp2

X
 Aryl halides
sp2
X

benzene or aromatic ring

 Acetylenic halides (Alkynyl halides)

sp

X
 3
 Alkyl halides are prone to
sp
undergo Nucleophilic

 C X Substitutions (SN) and
Elimination Reactions (E)
Alkyl halides

sp2
sp2 sp
X X X

 Alkenyl halides, aryl (phenyl) halides, and

alkynyl halides have different reactivity than
alkyl halides, and do not generally undergo
SN or E reactions
Nomenclature - IUPAC
● Locate the parent alkane.
● Number the parent chain to give the substituent en-
countered first the lower number.
● Show halogen substituents by the prefixes fluoro-,
chloro-, bromo-, and iodo- and list them in alpha-
betical order with other substituents.
● Locate each halogen on the parent chain.
Nomenclature
 Several polyhaloalkanes are common
solvents and are generally referred to
by their common or trivial names.
Freons & Their Alternatives
 The Freons are chlorofluorocarbons (CFCs)
● Among the most widely used were:
● Much lower ozone-depleting alternatives are the hydro-
fluorocarbons (HFCs) and the hydrochlorofluorocarbons
(HCFCs), including:
Substitution & Elimination
 In this chapter we, concentrate on two types
of reactions:
● nucleophilic substitution
● -elimination
Nucleophilic Substitution
 In the following general reaction, sub-
stitution takes place on an sp3 hybridized
(tetrahedral) carbon.
Nucleophilic Substitution
Mechanisms, SN2 and SN1
 There are two mechanisms for nucleophilic
substitutions.
● A fundamental difference between them is
the timing of the bond-breaking and bond-
forming steps.

 At one extreme, designated SN2, the two

processes take place simultaneously;
S = substitution
N = nucleophilic
2 = bimolecular (two species are involved in the
rate-determining step)
rate = k[haloalkane][nucleophile]
SN2
● Both reactants are involved in the transition state
of the rate-determining step.

● The nucleophile attacks the reactive center from

the side opposite the leaving group. The key step
is reaction of a nucleophile and an
electrophile to form a new covalent bond.
SN2
Figure 7.1 An energy diagram for an SN2 reaction.
 There is one transition state and no reactive
intermediate.
SN1
 In the other limiting mechanism, bond breaking
between carbon and the leaving group is
entirely completed before bond forming with the
nucleophile begins.

 This mechanism is designated SN1 where

S = substitution
N = nucleophilic
1 = unimolecular (only one species, RX is in-
volved in the rate-determining step)
rate = k[haloalkane]
SN1
 SN1 is illustrated by the solvolysis of tert-butyl
bromide. Methanol is the solvent.
● Step 1: Break a bond to form a stable ion or
molecule. Ionization of the C-X bond gives a 3°
carbocation intermediate and bromide ion.
SN1
● Step 2: Reaction of a nucleophile and an
electrophile to form a new covalent bond.

● Step 3: Take a proton away. Proton transfer

to methanol completes the reaction.
SN1
Figure 7.2 An energy diagram for an SN1 reaction.
There are two transition states and one intermediate.
The first step is rate-determining.
SN1  For an SN1 reaction at a
stereocenter, the product is a
racemic mixture.
Evidence for SN Reactions
 Let us examine some of the experimental
evidence on which these two mechanisms are
based and, as we do, consider the following
questions.
● What affect does the structure of the nucleophile
have on the rate of reaction?

● What effect does the structure of the haloalkane

have on the rate of reaction?

● What effect does the structure of the leaving group

have on the rate of reaction?

● What is the role of the solvent?

Nucleophilicity
 Nucleophilicity: a kinetic property mea-
sured by the rate at which a Nu: attacks a
reference compound under a standard set of
experimental conditions.
● For example, the rate at which a set of
nucleophiles displaces bromide ion from
bromoethane in ethanol at 25 °C.

 Table 7.2 shows common nucleophiles and

their relative nucleophilicities (next).
Relative Nucleophilicity
Structure of the Haloalkane
 SN1 reactions
● Governed by electronic factors,
namely the relative stabilities of
carbocation intermediates.
● Relative rates: 3° > 2° > 1° > methyl

 SN2 reactions
● Governed by steric factors, namely
the relative ease of approach of the
nucleophile to the site of reaction.
● Relative rates: methyl > 1° > 2° > 3°
Structure of the Haloalkane
 Steric factors
● Compare access to the reaction
center in bromoethane and 2-bromo-
2-methylpropane (tert-butyl chloride).
Structure of the Haloalkane
 Figure 7.3 Effect of electronic and steric
factors on competition between SN1 and
SN2 reactions of haloalkanes.
The Leaving Group
● The best leaving groups in this series are
the halogens I–, Br–, and Cl–.
● OH–, RO–, and NH2– are such poor leaving
groups that they are rarely if ever
displaced in nucleophilic substitution
reactions.
The Leaving Group
 Hydroxide ion, OH–, is a poor leaving.
However, the –OH group of an alcohol can
act as a leaving group, H2O, if the –OH group
is first protonated by an acid to form —OH2+,
a better leaving group.
The Solvent
 Protic solvent: a solvent that contains an
–OH group and is a hydrogen bond donor.
The Solvent
 Aprotic solvent: A solvent that does not
contain an –OH group and is not a hydrogen
bond donor.
● Aprotic solvents favor SN2 reactions. Although the
solvents at the top of the table are polar, formation of
carbocations in them is more difficult than in protic
solvents.
Summary of SN1 and SN2 Reactions
of Haloalkanes
Nucleophilic Substitution
Example: Predict the product of each
reaction, the reaction mechanism, and the
stereochemistry of the product.
-Elimination
 -Elimination: Removal of atoms or
groups of atoms from adjacent carbons to
form a carbon-carbon double bond.
● We study a type of -elimination
called dehydrohalogenation (the
elimination of HX).
-Elimination
 Zaitsev’s rule: The major product of a -elimination
is the more stable (the more highly substituted)
alkene. When cis-trans isomerism is possible, the
trans isomer is favored.
-Elimination
 There are two limiting mechanisms for
-elimination reactions.

 E1 mechanism: at one extreme, breaking of

the C-X bond is complete before reaction with
base breaks the C-H bond.
● Only R-X is involved in the rate-
determining step.

 E2 mechanism: at the other extreme,

breaking of the C-X and C-H bonds is
concerted.
● Both R-X and base are involved in the
rate-determining step.
E1 Mechanism
● Step 1: Break a bond to give a stable molecule or
ion. Rate-determining ionization of C-X gives a
carbocation intermediate and halide ion.

● Step 2: Take a proton away. Proton transfer from the

carbocation to a base (in this case, the solvent) gives the
alkene.
E2 Mechanism
 A one-step mechanism; all bond-breaking
and bond-forming steps are concerted.
Simultaneously (1) take a proton away
and (2) break a bond to form a stable ion
or molecule.
Elimination Reactions
(-Elimination)
Substitution versus Elimination
 Because many nucleophiles are also
strong bases (OH– and RO–), SN and E
reactions often compete.

● The ratio of SN/E products depends

on the relative rates of the two
reactions.
SN1 versus E1
 Reactions of 2° and 3° haloalkanes in polar protic
solvents give mixtures of substitution and elimination
products. Product ratios are difficult to predict.
SN2 versus E2
 It is considerably easier to predict the
ratio of SN2 to E2 products.
Summary of SN versus E
for Haloalkanes
● For Methyl and Primary Haloalkanes
Summary of SN versus E
for Haloalkanes
● For Secondary and Tertiary Halo-
alkanes
Summary of SN versus E
for Haloalkanes
● Examples: Predict the major product
and the mechanism for each reaction.