Chem Factsheet

September 2002 Number 40

Reaction Mechanisms
To succeed in this topic you need to:
Exam Hint: - Reaction mechanisms are commonly examined. As
• Have a good knowledge of the AS and A2 level organic chemistry
well as learning the standard examples given here, you need to practise
reactions covered so far; applying the mechanisms to other similar reactions.
• Be confident in using organic terminology, nomenclature and structural
formulae.
After working through this Factsheet you will: 2. Homolytic Free Radical Addition.
• Be able to represent movement of electron using the “curly arrow” Example: Polymerisation of ethene.
convention;
• Have been shown the key reaction mechanisms. The initiator is a free radical, R.(which could be a peroxide radical from
the oxygen catalyst).
All chemical reactions involve the movement of electrons, and reaction H H
Stage 1 - Initiation.
mechanisms allow us to display these movements and understand more H
about how a reaction occurs. R.
H
C C R C C.
H H
In this Factsheet you will meet organic reactions which you have come H H
across before. You should already be able to recall the overall reaction The new radical formed can then react with further ethene molecules to
equations and conditions required. The reaction mechanisms, which also lengthen the polymer chain.
require learning, often split these reactions up into several steps, each step Stage 2 - Propagation.
involving the movement of electrons. This should give an insight into how H H H H H H
H
C C C C.
a reaction occurs. . H
R C C C C R
H H
You need to be able to represent the movement of electrons using the H H H H H H
“curly arrow” convention: Termination can occur when two radical chains meet, or when a radical
chain attacks an established chain.
represents the movement of an electron pair Stage 3 - Termination.
H H H H H H H H
represents the movement of a single electron. n C C . .C C n n C C C C n

H H H H H H H H
When using curly arrows it is vital that you position each end of the arrows
carefully, so that you clearly show the examiner that you know where the The end product, polyethene, consists of long chain molecules (of varying
electrons are moving from and to. length) which are branched.

1. Homolytic Free Radical Substitution Stage 3 - Termination

These reactions involve free radicals, very reactive species which have
a single, unpaired electron. Cl . .Cl Cl Cl

Example: Alkanes with chlorine. Cl . .CH3 Cl CH 3

The reaction between methane and chlorine occurs in 3 stages. Free radicals are used up and not regenerated, causing the reaction to
eventually stop.
Stage 1 - Initiation
The overall reaction equation is as follows:
Cl . + Cl .
uv light
Cl Cl
uv light
The Cl-Cl bond is broken homolytically to form two chlorine free radicals. CH4 + Cl2 CH3Cl + HCl
Energy is required to break the bond, hence the reaction only begins in the
presence of UV light. But be aware that “by-products” are also formed in such reactions, e.g.
the formation of ethane (when chloromethane is the target molecule).
Stage 2 - Propagation
H H CH3 + CH3 C 2H 6
H C H Cl H C. + HCl
Most free radical reactions are extremely unstable and explosive. This
H H
reaction between methane and chlorine is controlled using subdued UV
H3C . Cl Cl H3C Cl + Cl . light.

Any such reaction caused by a free radical, where “replacement” free

radicals are produced by the reaction, hence the reaction process continues
unaided.

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Reaction mechanisms Chem Factsheet

3. Heterolytic Electrophylic Addition Note the formation of a carbocation (C + ) intermediate. The most stable
Example: Alkenes with halogens or hydrogen halides. position for the carbocation will be the carbon with the least hydrogen
atoms around it.
Consider the addition of bromine to propene.
H H H H H
H
H3C C C H hence CH 3 C C H was formed, not CH 3 C C H
+ +
δ +

Br Br Br
δ− Br There is a similar reaction mechanism for the addition of hydrogen halides
to alkenes.
The electrons in the double bond repel the electrons in the approaching
Br2 molecule, causing a dipole. H H H H H
H
The δ+ end of the halogen molecule is electrophilic, and can attack the CH 3 C C → CH 3 C C H → CH 3 C C H
H +
electron rich π-bond. δ+ H H Br H
−
Meanwhile, the δ end of the halogen molecule will accept both of the
− :Br
bond pair of electrons, forming a negative anion. δ − Br

H H H H H
H Markownikov’s Rule
CH 3 C C H → CH3 C C H → CH 3 C C H
+ When a hydrogen halide is added to a C=C double bond, the hydrogen
Br − Br Br Br atom is added to the carbon atom that already carries more hydrogens.
:Br
Br

4. Heterolytic Electrophilic Substitution (b) Bromination of benzene

Examples: Reactions of benzene (see Chem Factsheet 39). Bromine reacts with benzene in the presence of an iron wire catalyst in
(a) Nitration of benzene dry conditions at room temperature.
Benzene reacts with a mixture of conc. nitric acid and conc. sulphuric Br
acid at 50oC to form nitrobenzene.
Fe cat. + HBr
conc. H 2SO4 Br2 +
+ HNO3 0 NO 2 + H2 O
50 C

Nitrobenzene The electrophile Br+ must be generated to attack the benzene ring.
The reaction of benzene with nitric acid alone is slow and pure sulphuric 2Fe + 3Br2 → 2FeBr3
acid at 500C has little or no effect on benzene.
+ −
Therefore, sulphuric acid must react with nitric acid forming a species Br Br FeBr3 Br FeBr4
which will attack the benzene ring. Then:
Br Br
Evidence suggests that this is the NO2+ species - an electrophile formed + +
Br H + H
by the removal of OH − from HNO3. +
HNO3 + 2H2SO4 → NO2+ + 2HSO4- + H3O + Bromobenzene
Note that the nitric acid is acting as a base (proton acceptor) in the Bromobenzene is formed and the H + is the removed by FeBr4 − to regenerate
presence of a stronger acid. the FeBr3.
The NO2+ ion is a strong electrophile, so attacks the delocalised π- + −
H + FeBr4 HBr + FeBr3
electron system in the benzene ring.
First a “loose” association is formed. (c) Alkylation of benzene with chloroalkanes or acyl chlorides
+ +
Benzene reacts with chloroalkanes in the presence of anhydrous aluminium
+ NO2 → NO 2 chloride to give an alkylbenzene.
C2H5
AlCl 3
NO2+ then attacks a C atom, forming a bond and distrupting the + C2H5Cl + HCl
delocalised π-system. NO 2
+
The mechanism is as follows:
+ H
NO 2 → H H +
CH 2CH3 −
C Cl AlCl3 + AlCl4
Note that a considerable amount of energy is required to disrupt the H
CH 3
very stable π-system, therefore this step has a very high activation
energy.
CH2CH 3 + HCl + AlCl3
The intermediate cation will then break down to either reform benzene,
or form nitrobenzene. ethylbenzene
The delocalised system reforms, hence energy is released. A similar reaction mechanism occurs when benzene reacts with acid
+ chlorides and AlCl3 to give ketones.
NO 2 + NO2
+
O O
H or AlCl 3
NO 2 + CH 3 C + HCl
+ C
+ H Cl Cl
Nitrobenzene

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Reaction mechanisms Chem Factsheet

5. Heterolytic Nucleophilic Substitution (2) SN2 mechanism

Example: Halogenoalkanes with hydroxide ions and cyanide ions. The mechanism involves the substitution of a nucleophile which is
This mechanism is associated with polar covalent bonds (e.g. carbon-halogen). second order (two molecules in rate determining step).
δ+ δ− The nucleophile attacks the Cδ+ and starts to form a covalent bond
C Br with it. At the same time the C δ+-Hal δ− bond starts to break
heterolytically.
The positive charge on the carbon allows attack by nucleophiles such
as :OH− or :CN− which have lone pairs to donate. This is one continuous process with the carbon-nucleophile bond
getting stronger and the carbon-halogen getting weaker.
There are two mechanisms for nucleophilic substitution, (1) SN1 and (2) SN2.
The “transition state” (corresponding to the activation energy peak)
is when both are of equal strength.
(1) SN1 mechanism CH 3 - CH 3
CH
This mechanism involves the substitution of a nucleophile which is - 3
-
HO : C Br HO C Br HO C : Br
first order (one molecule in rate determining step).
H H H H H
This mechanism occurs in two stages: H
transition state
Stage 1: (The rate determining step)
CH3 CH 3 The formation of the transition state represents the rate determining
- step. This step is first order with respect to the halogenoalkane and
CH 3 C CH3 C
+ + Br the nucleophile.
Br
CH3 CH 3 Rate = k[CH3CH2Br][OH − ]
Stage 2:
CH 3 CH 3 SN1 or SN2?
- To find out which mechanism is followed for such nucleophilic substitution
CH 3 C + + :OH CH 3 C OH reactions, the reaction rate must be followed by experiment and the rate
CH 3 CH3 order with respect to the nucleophile discovered.
The first stage is rate determining as the second stage occurs much faster. In general the mechanism depends on the stability of the carbocation.
Therefore the rate equation is: Alkyl groups are more “electron donating” than hydrogen atoms, so the
Rate = k[(CH3)3CBr] carbocation of a tertiary group is more stable than that of a primary
group. H R1 R1
The reaction is zero order with respect to the nucleophile (OH − ) as it
does not take part in the rate determining step. R C + R2 C + R2 C +
This mechanism involves the formation of an intermediate - the carbocation. H H R3
Primary Secondary Tertiary

favour SN2 favour SN1

Answers
6. Heterolytic Nucleophilic Addition
1. Homolytic fission is when a bond breaks with one electron going to
Example: Carbonyl compounds and hydrogen cyanide.
each of the bonded atoms forming two free radical species. Heterolytic
A nucleophile will attack the δ+ carbon in the C=O group. fission is when a bond breaks with both of the bond pair electrons
going to one of the bonded atoms, forming a cation and anion.
R - O: H+ R OH
R δ+ δ− R + - 2. (a) HNO3 + 2H2SO4 → NO2+ + 2HSO4− + H3O+
C O C O C C
R R - +
NO 2 NO 2
:CN R CN R CN + +
+ NO2 → NO 2 → + H → + H

(b) H H H H H
Questions. H
1. What is this difference between homolytic and heterolytic fission of C 2H 5 C C → C 2H 5 C C H → C2H 5 C C H
H +
bonds? H H Br H
−
2. Show the reaction mechanisms for the following reactions: :Br
(a) C6H6 + HNO3 → C6H5NO2 + H2O Br
(c)
C 2H 5 δ+ δ− C2H5 + - C2H 5 O: H+
(b) C2H5CHCH2 + HBr → C2H5CHBrCH3 C O → C O → C
CH 3 CH 3 - CH3 CN
(c) C2H5COCH3 + HCN → C2H5C(OH)CH3CN :CN

C2H5 OH
C
Acknowledgements:
This Factsheet was researched and written by Kieron Heath CH 3 CN
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham, B18 6NF
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