Alkyl halides (Ch 21.

2)

Alkyl halides can be thought of as derivatives of the relevant parent alkane.

As with alkanes, you can think of families of homologous series with gradually
changing properties as you progress through the series.

Formula Name Boiling Point

oC

CH3Cl chloromethane -21.8

CH3CH2Cl chloroethane 12.3
CH3CH2CH2Cl 1-chloropropane 46
CH3CH2CH2CH2Cl 1-chlorobutane 78
CH3CH2CH2CH2CH2Cl 1-chloropentane 108

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Naming Alkyl halides (Ch 21.3)
Alkyl halides are named in the same corresponding way as alkanes
Naming steps
1. Number the longest carbon chain (beginning at the end nearest the first
substituent
2. Find name of longest chain, name it as the parent
3. Find name of any side-chain
4. Tell us where the branch is (or branches are), ensure that you number
with the lowest number possible
5. List all substituents in alphabetical order.

C H3 Br Br C H3

CH3CHCH2CHCHCH2CH3 CH3CHCH2CHCHCH2CH3
1 2 3 4 5 6 7 1 2 3 4 5 6 7
C H3 C H3

5-bromo-2,4-dimethylheptane 2-bromo-4,5-dimethylheptane

Not 3-bromo-4,6-dimethylheptane Not 7-bromo-3,4-dimethylheptane 2

Synthesis of alkyl halides (Ch 21.4)

As previously seen, alkyl halides can be made from addition reactions with alkenes

Alkanes undergo relatively few reactions compared to derivatised alkanes. One

reaction that alkanes do undergo is free radical initiated substitution.

The light (h) causes the halogen molecule to split apart to form free radicals that
are then able to react with the alkane and form an alkyl halide. 3
Typically, alkyl halides can be prepared from substitution of an alcohol

The reaction usually works best with tertiary alcohols. Typical reagents used
are SOCl2, PCl5 and PBr3

4
These reactions normally take place in high yield.

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Nucleophilic substitution reactions of alkyl halides (Ch21.5)

The greater electronegativity of halogen

atoms compared to carbon means that the C-
X bond is permanently polarised.

The electron deficient carbon (+) is therefore susceptible to attack from

electron rich species (nucleophiles). The carbon atom itself can be classed
as an electrophile, it can be attacked to undergo substitution to displace the
suitable leaving group.

This will be a recurrent theme in many organic chemistry reactions, a

nucleophile will combine with an electrophile to produce a chemical reaction.

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Substitution Reactions

Substitution reactions usually involve saturated compounds, i.e. those that contain only
single bonds

H HO- H
H C Br H C OH + Br-
H H

bromomethane methanol

In most such cases, such as the one shown, the mechanism involves nucleophilic
substitution
+ -
The C-Br bond in bromomethane is polarised

The carbon atom is therefore an attractive target for nucleophiles such as OH-

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Nucleophilic Substitution

+ -
OH-
A C-O bond is formed and a bromide anion released
A nucleophilic substitution reaction mechanism can be categorised as either
SN1 or SN2 depending upon how many species are involved in the slowest
rate determining step of the reaction
SN1 means substitution, nucleophilic, unimolecular, .i.e., a reaction involving
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only a single species (splitting apart) in the slowest step of the reaction. Any
subsequent steps are relatively fast steps. This is effectively a two step
reaction.
SN2 means substitution, nucleophilic, bimolecular. This means that there are
two discrete species involved colliding together in the slowest step. This is
effectivley a one step reaction. 8
SN2 reaction and stereochemical implications

This mechanism necessarily requires the attacking

nucleophile to approach the molecule from a
position opposite the leaving group.

The new bond begins to form between the

attacking nucleophile and the carbon atom at the
same time as the bond with the leaving group
begins to break.

This species is not a discrete intermediate

formed for any length of time. It is an extremely
transient species, a transition state!

The new bond is fully formed and the old bond if

completely broken to give the new product. If
the central carbon atom were chiral we would
have full inversion, as opposed to retention, of
configuration. 9
Steric effects in the SN2 mechanism
The ease with which a compound reacts by this mechanism depends upon
spacial accessibility, or ease of access of the approaching nucleophile.

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The leaving group in the SN2 mechanism
The best leaving groups are those that give the most stable anions.

The first four are rarely leaving groups, Cl-, Br- and I- are good leaving groups.

The SN1 mechanism for substitution reactions

How do we explain the fact that in this reaction the original stereochemical
configuration of the starting material is racemized to give a 50:50 mix of mirror
image enantiomers? 11
Stereochemistry of the SN1 reaction
A single species, the alkyl halide, is involved in the rate determining step and it
will dissociate (split apart) to form an intermediate carbocation.

Carbocations are sp2 hybridised and necessarily flat (trigonal; planar) in nature.
Once formed in the slow step, the nucleophile can attack in the fast step but can
approach from either side with equal likelihood to give 50% inversion of
configuration and 50% retention of configuation in the product mixture.

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Relative reactivity of substrates in the SN1 mechanism

The mechanism explains why tertiary compounds react much more rapidly than
primary via this mechanism. SN1 reactions tend to occur only when a stable
carbocation can be formed.

The more stable the cation, the faster the rate of the SN1 reaction. This explains
the reactivity order of alcohols reacting with HBr (R3COH >> R2CHOH >
RCH2OH > CH3OH, i.e., 3o carbocations are more stable than 2o carbocations
that are, in turn, more stable than 1o carbocations.

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Leaving groups in the SN1 mechanism

Similar to SN2 reactions, the best leaving groups in SN1 reactions are those
that give the most stable anion.

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