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OC04 Arenes Tutorial Answers
OC04 Arenes Tutorial Answers
4 Arenes
SUMMARY
Complete the following table
Cl
CH2CH3
NO2
substitution
1 For the following compounds given by their IUPAC name, draw their condensed
structural formula.
Cl
CH3
2 Draw the skeletal formula for all arenes with the molecular formula C9H12 (Hint: 8
isomers).
CH3 CH3
CH3
CH3
CH3
CH3
H3C CH3
CH3
D D
NO2
deuteriobenzene 3-nitrodeuteriobenzene
A 16 % B 20 % C 33 % D 45 %
NO2 D D D
NO2
NO2
NO2
CH3
NO2
and NO2
(b) Briefly outline the mechanism of this reaction for one of the isomers.
Electrophilic substitution
HNO3 + 2H2SO4 ⇌ NO2+ + H3O+ + 2HSO4‾‾
H NO2
+ NO2+
slow
+
CH3 CH3
H NO2 NO2
.. -
HSO4 + + fast
+ H2SO 4
CH3 CH3
(c) What is the reason for adding concentrated sulfuric acid to concentrated nitric
acid in the preparation of nitrobenzene?
To act as a Brønsted-Lowry acid (so as to protonate HNO3) resulting in the
production of NO2+ which is a stronger electrophile than HNO3.
7 During the nitration of benzene, a nitro group substitutes at a carbon atom. Which
one of the following gives the arrangement of the bonds at this carbon atom
during the reaction?
at the start of the in the intermediate at the end of the
reaction complex reaction
A Planar Planar Planar
B Planar Tetrahedral Planar
C Planar Planar Tetrahedral
D Tetrahedral Tetrahedral Tetrahedral
+
hybridisation sp2 sp3 sp2
No. of lone 3 bond pairs 4 bond pairs 3 bond pairs
pairs and 0 lone pair 0 lone pair 0 lone pair
bond pairs
A CH3 B CH2Cl
Cl
C CH3 D COOH
Br
I CO2H
II
CH3 CH2Cl
III
CH3
Cl
A
Reaction I II III
KMnO4(aq), Cl2(g), uv light Cl2(g), anhydrous
Reagents and
H2SO4(aq), heat AlCl3
conditions
under reflux
Side chain Free radical Electrophilic
Type of reaction oxidation substitution substitution
(b) There are two other positional isomers of A. Draw their structural formulae and
suggest which one is more likely to be formed along with A in reaction III.
CH3 CH3
Cl
Cl
minor product major product
Electrophilic substitution
slow
+ Cl+ + H
Cl
CH3 CH3
.. fast
+ H + AlCl 4
-
+ HCl + AlCl 3
Cl Cl
CH3 CH3
(d) The reaction in (c) can only take place under anhydrous conditions. Suggest a
reason to explain why it is so.
Br
Br
Br
Br
or
Br
Br
Br
(ii) cold, alkaline KMnO4 (iv) alkaline KMnO4, heat under reflux
_
COO
OH
OH
NO2 NO2
(ii)
CH3 COOH COOH
Step 1 Step 2
NO2
12 For each of the following pair of compounds, describe one simple chemical test
that would enable you to distinguish between them. State clearly the observations
each compound will produce.
Note: Distinguishing tests are carried out in the laboratory by placing small
quantities of the unknown samples in test tubes. For reactions that require
heating, the reflux setup is not required, i.e. do not heat under reflux. Where
possible, free radical substitution of alkyl groups and electrophilic substitution of
benzene are not used in distinguishing tests.
(a)
Reagents and Conditions:
A. Aqueous Br2
B. Br2 in CCl4
C. KMnO4(aq), H2SO4(aq), heat (Do not heat under reflux)
(b)
Reagents and Conditions:
KMnO4(aq), H2SO4(aq), heat (Do not heat under reflux)
CH3
(c)
Reagents and Conditions:
KMnO4(aq), H2SO4(aq), heat (Do not heat under reflux)
CH3 CH2CH3
13(a) State the reagents and conditions to prepare methylbenzene from benzene.
Electrophilic substitution
14 Iodine monochloride, ICl, can be prepared by passing chlorine gas over iodine
crystals and it is collected as a dark brown liquid. Draw the structure of the likely
organic product of the reaction of ICl with methylbenzene, in the presence of
anhydrous AlCl3.
CH3 CH3
or
However, there could be Cl+ electrophile generated due to halogen exchange, leading to side
products.
(a) The structure of ethene, C2H4, may be described in terms of the hybridisation of
orbitals.
sp2
(ii) Sketch the shapes of the hybrid orbitals around one carbon atom in the
ethene molecule.
Each carbon atom forms three bonds as shown in figure 14. 1 below.
H H
C C
H H
Fig. 15.1
(i) On figure 15.1, sketch the bond that is also present in ethene.
(ii) Give one physical and one chemical property that supports this structure.
physical
chemical
(d) When ethene is reacted with HCl(g), C2H5Cl is the only product.
Benzene has no reaction with HCl(g).
Electrophilic addition
(iii) Suggest why ethene reacts readily with HCl(g) but benzene does not.
(iv) Explain why benzene prefers to undergo substitution rather than addition
reactions.
Benzene does not undergo addition reactions as these would break the
ring of delocalised electrons and result in the loss of aromatic stability.
Instead, benzene tends to undergo substitution reactions so that its
electron ring remains intact.
16 An organic compound, C8H7Cl, burns with a smoky flame and is a mixture of two
isomers, A and B. The two isomers react with Br2 in a 1:1 mole ratio to form the
same compound, C. Both A and B are oxidised by hot acidified KMnO4 to produce
the same compound D. D reacts with a mixture of concentrated nitric and sulfuric
acids to give E.
The two isomers react with Electrophilic addition Presence of one alkene
Br2 in a 1:1 mole ratio to
in A and B
form the same compound,
C.
Presence of alkene in A
Oxidative cleavage and B
Both A and B are oxidised
(or side chain oxidation) (or the carbon atom
by hot acidified KMnO4 to
bonded to benzene has
produce the same
at least one hydrogen
compound D.
atom)
Substituent on benzene
Electrophilic substitution ring in D is 3-directing
and results in only 1
D reacts with a mixture of nitrated product.
concentrated nitric and
sulfuric acids to give E. FYI: 2, 4-directing
substituents would give
rise to two nitrated
products.
Structures of A, B, C, D and E:
H
H H H Cl
Cl H
Br
Br
H Cl
A BH3 CH4
COOH COOH
NO2
DH E
A A
NO2
NO2
+ H
2-position
isomer 2-position
A A A
3-position
+
NO2
NO2
H isomer 3-position
4-position
A A
+
H NO2
NO2
isomer 4-position
Fig. 16.1
Use this information to predict which substituted isomers in Fig. 16.1 will be
formed the least and the most when A is a (CH3)3C— group. Explain your
reasoning.
Reason Due to the close proximity, the incoming –NO2 group/electrophile will
experience steric hinderance from the bulky (CH3)3C– group as it approaches the
2-position. This destabilises the carbocation intermediate for isomer 2-position.
Hence, isomer 4-position will be formed the most.
Consider the two properties of the existing substituent attached to the ring.
Based on the structures of the three intermediates, what factor affects the
number of electron donating alkyl groups which determines the type of carbocation (primary,
secondary or tertiary)
proximity to bulky substituent (e.g. highly branched alkyl group and large phenyl ring)
Comments
Some strong and clear answers were seen. Most candidates were able to predict which
isomer will be formed the most and the least and to give some relevant reasoning.
However, a clear explanation in terms of the stability of the carbocations was normally
absent.
Do not accept
electron withdrawing NO2 group is closest to positive charge in the intermediate for
isomer 2-position as the positive charge can be delocalised to be further away (as
shown in following resonance diagrams.)
P P P
Acceptable
In the 4-posiiton intermediate, p orbital of carbocation is between π orbital of two
C=C hence they can overlap, resulting in the positive charge of carbocation being
dispersed over the 2 C=C, stabilising it to a greater extent than the 2-positon
intermediate. This is also applicable to intermediates of other isomers due to
resonance structures (see above 2nd resonance diagram for 3-posiiton):