General Chemistry IV: CHEM-224

Lecture 5 Part I: Alkyl Halides

Module Lecturer: Davies Mweta PhD

April, 2023
 Halogenoalkanes: Definition
• Also called haloalkanes or alkyl halides
• contain aa halogen atom - fluorine, chlorine,
bromine or iodine - attached to an alkyl
group
• An organic compound containing at least one
carbon-halogen bond (C-X)
X (F, Cl, Br, I) replaces H
Can contain many C-X bonds

2
 Halogenoalkanes: Types
• Three types: primary, secondary and tertiary
• Primary:
The carbon which carries the halogen atom is only
attached to one other alkyl group

H
2 H
2
C
H3 B
r C
H3 C C
H C
3
C C C
l C
H I
H
2 H
2

C
H3

Exception: Still considered as primary

C
H
B
r
3 3
 Halogenoalkanes: Definition…
• Secondary:
The carbon which carries the halogen atom
is attached to two other alkyl group
H
2
C
H
3 C
H
3 C
H C
3
CH CH CH
3

C
l B
r

4
 Halogenoalkanes: Definition…
• Tertiary:
The carbon which carries the halogen atom
is attached to three other alkyl group
C
H
3 C
H
3H2
C
H
3 CH
3 C
H C
3
C C C
H
3

C
l B
r

5
 Alpha and beta carbons
• α and β
α−carbon : The carbon atom which carries the
halogen is called an alpha-carbon (α−carbon).
β−carbon : The carbon atom next to the
α−carbon is called a β−carbon.
β−hydrogen : The hydrogen atoms attached to
the β−carbon are called β−hydrogens.
 Uses of Halogenoalkanes
• Chlorofluorocarbons
CFC-11 (CCl3F) and CFC-12 (CCl2F2)
Refrigerants, propellants for aerosols, for
generating foamed plastics like expanded
polystyrene or polyurethane foam, and as
solvents for dry cleaning and for general
degreasing purposes
Later discovered to be responsible for ozone
depletion (global warming)
Abandoned and replaced by hydrofluorocarbons
7
 Uses of Halogenoalkanes…
• Fire-resistant solvents
Halon 1211 and halon 1301
• Pharmaceuticals and precursors
Used as solvents and precursors for synthesis of
other organic compounds
Chlorine containing antibiotic, chloramphenicol,
produced by soil microorganisms is very effective
for the treatment of typhoid fever

8
 Halogenoalkanes synthesis
• Alkyl halides can also be prepared by the
reaction of an alkane with chlorine or
bromine at high temperatures (greater than
300◦ C) or at room temperature in the
presence UV radiation
This reaction has limited synthetic utility as the
product is often a mixture of mono-, di-, tri-, etc.
halogenated alkanes.
This reaction consists of three steps: initiation,
propagation, and termination.
9
 Free Radical Substitution Reactions
Mechanism: Halogenation of Alkanes
 Halogenoalkanes synthesis: From
alcohols
• Hydrogen halides, with the exception of HF, react
with alkyl alcohols to give alkyl halides.
 Tertiary alkyl alcohols react readily with hydrogen halides
at room temperature.
 Secondary and primary alkyl alcohols are less reactive and
heating is often required.
 Heating may be detrimental to other functional groups in
the molecule and therefore other reagents that react at
moderate temperatures are used to make alkyl chlorides
and bromides from secondary and primary alkyl alcohols.
• These reagents include thionyl chloride (SOCl2) and
phosphorous tribromide (PBr3). 11
 Alcohols with HX
• Alcohols can be converted to the
corresponding halides by reaction with
concentrated HCl, HBr, or HI.
The order of reactivity of alcohols is 3° > 2° > 1°
methyl.
The order of reactivity of the hydrogen halides is
HI > HBr > HCl (HF is generally unreactive).
The reaction is acid catalysed
H H H H
H
I
H C C O
H H C C I +HO
2

12
H H H H
 Alcohols with HX..
H H

HI
C
H C CH CH3 C C
H 3 +H2O
3 3

OH I

CH C
H 3
3

HI
C
H C CH CH3 C C
H 3 +H2O
3 3

OH I

13
Alcohols with PX3 and SOCl2

14
 Halogenoalkanes from alkenes
• Alkyl halides can be made from the addition
of halogens to alkenes, and
hydrohalogenation of alkenes.

• Hydrohalogenation of alkenes
CH3CH=C(CH3)2 + HI  CH3CH2CI(CH3)2

H
C
3 C
H3
H
C
3 C
H3

H
I HC C I
CC
15
H C
H3
H C
H3
 Halogenoalkanes from alkenes
• Halogenation of alkenes
dihalide such as Cl2 or Br2 is added to a molecule
after breaking the carbon to carbon double bond.
The halides add to neighboring carbons from
opposite faces of the molecule.
The resulting product is a vicinal (neighboring)
dihalide
Br

Br2

16
Br
 Reactions Halogenoalkanes
• Alkyl halides undergo two major types of
reactions
Nucleophic substitution
Elimination

17
 Nucleophilic Substitution
Reaction
• the electrophilic alkyl halide forms a new
bond with the nucleophile which substitutes
for (replaces) the halogen at the alpha-carbon.
Because carbon can only form four bonds, the
halogen must leave and is called the "Leaving
Group".
Alkyl halides are excellent electrophiles because
halogens share a polar bond with carbon, are
polarizable, and form relatively stable leaving
groups as halide anions
18
 Nucleophilic Substitution
Reactions
• A reaction where a nucleophile gets attached to the
positive charged atoms or molecules of the other
substance.
• Two mechanisms:
 SN1 (Substitution Nucleophilic Unimolecular) reaction and
 the SN2 (Substitution Nucleophilic bimolecular) reaction,
where S represents chemical substitution, N represents
nucleophilic, and the number stands for the kinetic order of a
reaction.
 SN2 Nucleophilic Substitution
Reactions
• SN2 stands for Substitution Nucleophilic bimolecular
• SN2 involves a substrate that has a leaving group (L),
which is replaced by a nucleophile (Nu⁻).
 the elimination of the leaving group and the addition of
the nucleophile occur simultaneously.
 SN2 takes place where the central carbon atom has easy
access to the nucleophile.
 SN2 Nucleophilic Substitution
Reactions…
• In SN2 reactions, the rate of the reaction is affected by
a few conditions.
 The numerical value 2 in SN2 states that there are two
concentrations of substances which affect the rate of
reaction, viz. nucleophile and substrate.
 The rate equation for the above reaction is written as Rate
= k [Sub][Nuc].
• An aprotic solvent such as acetone, DMSO, or DMF is
suited best for the SN2 reaction as they do not add
the H+ ions in the solution.
 SN2 Nucleophilic Substitution
Reactions

• In case if there are protons present, they react with the

H H H H

:OH- :Br-

Rate = k[C2H5Br][:OH-]
 SN1 Nucleophilic Substitution
Reactions
• SN1 stands for Substitution Nucleophilic
Unimolecular
Instead of two concentrations only one i.e., the
substrate affects the rate of reaction.
The rate equation for the above reaction is written
as Rate = k[Sub].
• The reaction rate is determined by its slowest
step.
Therefore, the leaving group leaves at a particular
rate which helps in determining the reaction speed.
 SN1 Nucleophilic Substitution
Reactions
• It is considered that the weaker the conjugate base,
the better is the leaving group.
• SN1 reactions can be determined by bulky groups that
are attached to the carbocations.
• The reaction of the tertiary carbocation is faster than
secondary carbocation which is faster than primary
carbocation.
• The nucleophile is not required in the rate-
determining step.
 SN1 Nucleophilic Substitution
Reactions Mechanism
• First, the carbocation is formed from the removal
of the leaving group.
• Then the carbocation is attacked by the
nucleophile.
• Finally, the deprotonation of the protonated
nucleophile takes place to give the required
product.
• The rate-determining step of this reaction depends
purely on the electrophilicity of the leaving group
and is not impacted at all by the nucleophile.
 Nucleophilic Substitution – SN1
Mechanism

CH3 CH3
CH3

+ H3C C CH3
H3C C CH3 H3C C CH3
+

- :OH- OH
Br

:Br-

Rate = k[C4H9Br]
 Elimination Reactions
• An elimination reaction is a reaction in which
atoms are removed as molecules or
compounds.
Elimination is generally catalysed by a metal, an
acid or base.
• Alkyl halides can also undergo elimination
reactions in the presence of strong bases.
The elimination of a beta-hydrogen (hydrogen on
a carbon vicinal to the alkyl halide carbon) and the
halide produces a carbon-carbon double bond to
form an alkene
 Elimination Reactions
• Example 2-bromopropane undergoes an
elimination reaction to give an alkene -
propene.
Br
NaOH
Ethanol
Heat
• In this reaction, a substrate an alkyl halide eliminates
one equivalent (unit) of acid to form an alkene.
• Two possible mechanisms for elimination reaction –
E1 and E2 mechanisms.
 Elimination reaction…
• Normally, elimination reactions are distinguished by
the kind of atoms or groups of atoms that leave the
molecule.
• There are two main methods involved in this type of
reaction;
 Dehydration: removal of water
 Dehydrohalogenation: removal of hydrogen and a halogen
• The elimination reaction consists of three
fundamental events:
Proton removal.
Formation of C-C pi bond.
Removal of the leaving group
 E1 reaction
• also known as unimolecular elimination.
• There are usually two steps involved – ionization and
deprotonation.
 During ionization, there is a formation of carbocation as an
intermediate.
 In deprotonation, a proton is lost by the carbocation.
• This happens in the presence of a base which further
leads to the formation of a pi-bond in the molecule.
• In E1, the reaction rate is also proportional to the
concentration of the substance to be transformed.
• It exhibits first-order kinetics.
E1 reaction Mechanism
E1 reaction Mechanism…
 E2 reaction
• Bimolecular elimination
• is a one-step mechanism.
• the carbon-hydrogen and carbon-halogen bonds
mostly break off to form a new double bond.
 However, in the E2 mechanism, a base is part of the rate-
determining step and it has a huge influence on the
mechanism.
 The reaction rate is mostly proportional to the
concentrations of both the eliminating agent and the
substrate.
 It exhibits second-order kinetics.
E2 reaction Mechanism
E1 reaction Mechanism…
 Comparing E1 and E2 reactions
• When considering whether an elimination
reaction is likely to occur via an E1 or E2
mechanism, we really need to consider three
factors:
1. The base: strong bases favor the E2 mechanism,
whereas, E1 mechanisms only require a weak base.
2. The solvent: good ionizing xolvents (polar protic)
favor the E1 mechanism by stabilizing the carbocation
intermediate.
3. The alkyl halide: primary alkyl halides have the only
structure useful in distinguishing between the E2 and
E1 pathways. Since primary carbocations do not
form, only the E2 mechanism is possible.
Comparing E1 and E2 reactions