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040 Reactions Mechanisms

040 Reactions Mechanisms

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2. Homolytic Free Radical Addition.
Example: Polymerisation of ethene.The initiator is a free radical, R
 
(which could be a peroxide radical fromthe oxygen catalyst).Stage 1 - Initiation.The new radical formed can then react with further ethene molecules tolengthen the polymer chain.Stage 2 - Propagation.Termination can occur when two radical chains meet, or when a radicalchain attacks an established chain.Stage 3 - Termination.The end product, polyethene, consists of long chain molecules (of varyinglength) which are branched.Any such reaction caused by a free radical, where “replacement” freeradicals are produced by the reaction, hence the reaction process continuesunaided.
Reaction Mechanisms
C
 hem
 F
 actsheet
September 2002Number 40
1
Exam Hint: - 
Reaction mechanisms are commonly examined. As well as learning the standard examples given here, you need to practise applying the mechanisms to other similar reactions.
1. Homolytic Free Radical Substitution
These reactions involve
free radicals
, very reactive species which havea single, unpaired electron.Example: Alkanes with chlorine.The reaction between methane and chlorine occurs in 3 stages.Stage 1 - InitiationThe Cl-Cl bond is broken homolytically to form two chlorine free radicals.Energy is required to break the bond, hence the reaction only begins in thepresence of UV light.Stage 2 - PropagationClCl
uv light
Cl
 .
Cl
 .
+
HCl
+
Cl
 .
HHHHCHHHC
 .
H
3
CClClH
3
CCl
+
Cl
 .
Cl
 . .
ClClClCl
 .
CH
3
 .
ClCH
3
uv light
Free radicals are used up and not regenerated, causing the reaction toeventually stop.The overall reaction equation is as follows:CH
4
+ Cl
2
CH
3
Cl + HClBut be aware that “by-products” are also formed in such reactions, e.g.the formation of ethane (when chloromethane is the target molecule).CH
3
+ CH
3
C
2
H
6
Most free radical reactions are extremely unstable and explosive. Thisreaction between methane and chlorine is controlled using subdued UVlight.
To succeed in this topic you need to:
Have a good knowledge of the AS and A2 level organic chemistryreactions covered so far;
Be confident in using organic terminology, nomenclature and structuralformulae.
After working through this Factsheet you will:
Be able to represent movement of electron using the “curly arrow”convention;
Have been shown the key reaction mechanisms.All chemical reactions involve the movement of electrons, and reactionmechanisms allow us to display these movements and understand moreabout how a reaction occurs.In this Factsheet you will meet organic reactions which you have comeacross before. You should already be able to recall the overall reactionequations and conditions required. The reaction mechanisms, which alsorequire learning, often split these reactions up into several steps, each stepinvolving the movement of electrons. This should give an insight into howa reaction occurs.You need to be able to represent the movement of electrons using the“curly arrow” convention:represents the movement of an electron
pair
represents the movement of a
single
electron.When using curly arrows it is vital that you position each end of the arrowscarefully, so that you clearly show the examiner that you know where theelectrons are moving
from
and
to
.Stage 3 - TerminationCCHHHHR
 . .
RCCHHHH
 .
RCCHHHHCCHHHHRCCHHHH
 .
CCHHHH
 .
CCHHHH
 .
CCHHHH
nn
CCHHHHCCHHHH
nn
 .
 
Chem Factsheet
2
Reaction mechanisms
4. Heterolytic Electrophilic Substitution
Examples: Reactions of benzene (see Chem Factsheet 39).
(a) Nitration of benzene
Benzene reacts with a mixture of conc. nitric acid and conc. sulphuricacid at 50
o
C to form nitrobenzene.
3. Heterolytic Electrophylic Addition
Example: Alkenes with halogens or hydrogen halides.Consider the addition of bromine to propene.The electrons in the double bond repel the electrons in the approachingBr
2
molecule, causing a dipole.The
δ
+
end of the halogen molecule is electrophilic, and can attack theelectron rich
π
-bond.Meanwhile, the
δ
end of the halogen molecule will accept both of thebond pair of electrons, forming a negative anion.H
3
CCHCHH
δ
+
δ
BrNote the formation of a carbocation (C
+
) intermediate. The most stableposition for the carbocation will be the carbon with the least hydrogenatoms around it.The reaction of benzene with nitric acid alone is slow and pure sulphuricacid at 50
0
C has little or no effect on benzene.Therefore, sulphuric acid must react with nitric acid forming a specieswhich
will
attack the benzene ring.Evidence suggests that this is the NO
2+
species - an electrophile formedby the removal of OH
from HNO
3
.HNO
3
+ 2H
2
SO
4
NO
2+
+ 2HSO
4-
+ H
3
O
+
Note that the nitric acid is acting as a base (proton acceptor) in thepresence of a stronger acid.The NO
2+
ion is a strong electrophile, so attacks the delocalised
π
-electron system in the benzene ring.First a “loose” association is formed.CH
3
CHCHH
CH
3
CHCHHBr
CH
3
CHCHHBrBrBrBrBr
+
Br
:
CH
3
CHCHHBr
+
hencewas formed,
not
CH
3
CHCHHBr
+
There is a similar reaction mechanism for the addition of hydrogen halidesto alkenes.CH
3
CCHHCH
3
CHCHHH
+
 
HHBr
δ
+
δ
Br
:
CH
3
CHCHHHBrMarkownikov’s RuleWhen a hydrogen halide is added to a C=C double bond, the hydrogenatom is added to the carbon atom that already carries more hydrogens.+ HNO
3
conc. H
2
SO
4
50
0
C
NO
2
+ H
2
ONitrobenzene+ NO
2
 
+
NO
2
 
+
NO
2+
then attacks a C atom, forming a bond and distrupting thedelocalised
π
-system.NO
2
 
+
HNO
2
 
+
Note that a considerable amount of energy is required to disrupt thevery stable
π
-system, therefore this step has a very high activationenergy.The intermediate cation will then break down to either reform benzene,or form nitrobenzene.The delocalised system reforms, hence energy is released.HNO
2
 
+
orNO
2
+ H
 
+
Nitrobenzene+ NO
2
 
+
(b) Bromination of benzene
Bromine reacts with benzene in the presence of an iron wire catalyst indry conditions at room temperature.Br
2
+
Fe cat.
Br+ HBrThe electrophile Br
+
must be generated to attack the benzene ring.
 
2Fe + 3Br
2
2FeBr
3
BrBrFeBr
3
Br
 
+
FeBr
4
 
Then:Br
 
+
BrH
 
+
Br+ H
 
+
BromobenzeneBromobenzene is formed and the H
+
is the removed by FeBr
4
to regeneratethe FeBr
3
.
(c) Alkylation of benzene with chloroalkanes or acyl chlorides
Benzene reacts with chloroalkanes in the presence of anhydrous aluminiumchloride to give an alkylbenzene.H
 
+
+ FeBr
4
 
HBr + FeBr
3
+ C
2
H
5
Cl
AlCl
3
C
2
H
5
+ HClCCH
3
ClHHAlCl
3
HCH
2
CH
3
+ AlCl
4
 
+
 
CH
2
CH
3
+ HCl + AlCl
3
ethylbenzeneA similar reaction mechanism occurs when benzene reacts with acidchlorides and AlCl
3
to give ketones.The mechanism is as follows:+CH
3
COCl
AlCl
3
COCl+ HCl

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