Aromatic Hydrocarbons (Arenes)

benzene molecular formula C6H6, skeletal formula , structural/displayed formula

ALL bond angles 120o, symmetrical hexagonal ring, planar molecule

methylbenzene (toluene) C7H8, C6H5CH3

ethylbenzeneC8H10 and propylbenzene

phenylethene ('styrene'), C8H8, is named as a derivative of ethene,

the C6H5- aromatic ring grouping is called a phenyl group when quoted as a substituent  prefix.

So phenylethene is named as a derivative of ethene.

 
1,2-dimethylbenzene, C8H10, , 1,3-dimethylbenzene ,

1,4-dimethylbenzene

(once called xylenes, ortho, meta and para-xylene)

1-ethyl-2-methylbenzene, C9H12, and the two other positional

structural isomers

1-ethyl-3-methylbenzene, C9H12, and

1-ethyl-4-methylbenzene, C10H14,,

1,2-diethylbenzene, C10H14, , 1,3-dipropylbenzene

1-methyl-2-propylbenzene, C10H14, and the two other positional structural

isomers
1-methyl-3-propylbenzene, C10H14, and

1-methyl-4-propylbenzene, C10H14,

1-ethyl-4-propylbenzene, C11H16,

4-ethyl-1,2-dimethylbenzene, C10H14, (uses lower numbers than 1-...-3,4-...)

Halo-arenes - aryl 'halides'

or aryl halide, aromatic halogen compounds, the halogen is directly attached to the benzene
ring.

chlorobenzene, C6H5Cl, and

1,2 or 1,3 or 1,4-dichlorobenzene, C6H4Cl2, , ,

 
C7H7Cl, chloromethylbenzene, or (chloromethyl)benzene (benzyl chloride). It is
not a true aryl halogen compound, the halogen atom is in a non-aromatic side chain, so it is a primary
aliphatic halogenoalkane.

Three positional structural isomers of C7H7Cl

chloro-2-methylbenzene, chloro-3-methylbenzene and chloro-4-

methylbenzene,or 1-chloro-2-methylbenzene, 1-chloro-3-methylbenzene
and 1-chloro-4-methylbenzene (old names 0-chlorotoluene, m-
chlorotoluene and p-chlorotoluene). These are true aryl halides with the
halogen attached directly to the benzene ring and they are isomeric with
(chloromethyl)benzene above.

C7H6Cl2, 2,3-dichloromethylbenzene and

C8H9Cl, 1-chloro-2,4-dimethylbenzene

Phenols - aryl hydroxy compounds

If the OH group (hydroxy) is directly attached to a benzene ring, the molecule is classified as a
'phenol'.

If not, the molecule is classified as an aliphatic alcohol.

This difference is illustrated below with molecules containing a benzene ring (Phenols ROH, R=aryl
only)
 phenol.

Phenols form salts with strong bases e.g. the alkali sodium hydroxide gives ....

sodium phenoxide (old name sodium phenate?)

  C6H5OCl, 2-chlorophenol (o-chlorophenol)

C7H8O, 3-methylphenol (m-methylphenol, meta-cresol)

C6H7NO,  2-aminophenol, 4-aminophenol and 2-nitrophenol

C7H6O3, 3-hydroxybenzoic acid and 2-hydroxybenzoic acid

 
C7H6OCl2, 2,5-dichloro-4-methylphenol

C6H6O2, or 1,4-dihydroxybenzene (benzene-1,4-diol, 1,4-benzenediol, 'quinol')

which is oxidised to

C6H4O2, or 2,5-cyclohexadiene-1,4-dione (cycohexa-2,5-diene-1,4-dione, 'p-

quinone')

If the OH is not attached to a benzene ring you get an aliphatic alcohol which is isomeric with a
phenols or an ether.

C7H8O, phenylmethanol (old name 'benzyl alcohol') is a primary aliphatic alcohol

which is isomeric with methylphenols and the ether, methoxybenzene (anisole).

C8H10O, 1-phenylethanol, which is  isomeric with the ether

C8H10O, ethoxybenzene (phenetole) and the ethylphenols or
dimethylphenols.

Aromatic aldehydes and ketones

True aromatic aldehydes, R-CHO, have the aldehyde group -CHO directly attached to the ring e.g.

C7H6O, or benzaldehyde, and

 C7H6O2, 2-hydroxybenzaldehyde

Ketones, R2C=O, are often 'mixed' aliphatic-aromatic in the sense that one R group is alkyl and the
other is aryl e.g.

1-phenylethanone (acetophenone, methyl phenyl ketone), C8H8O,   , and C8H8O2,

Diphenylmethanone (diphenyl ketone), C13H10O, , is a completely aromatic

ketone.

Aromatic acids and their derivatives

Note: quite a few of the 'old' names are still used and accepted

C7H6O2, , , , , benenecarboxylic acid, benzoic

acid

C7H5OCl, , , , , benzenecarbonyl chloride, benzoyl

chloride

C7H7ON, ,  , , , benzenecarboxamide,
benzamide

C8H8O2, , , , , methyl
benzenecarboxylate, methyl benzoate

 
C8H8O3, methyl 2-hydroxybenzoate

C9H10O2, , , , ethyl
benzenecarboxylate, ethyl benzoate

 C10H12O2, , , , propyl
benzenecarboxylate, propyl benzoate

  C7H5O3, 2 3 or 4-hydroxybenzenecarboxylic acid, 2 3 or 4-

hydroxybenzoic acid

C7H5ClO2, 2-chlorobenzoic acid

 
C8H6O4, benzene-1,2-dicarboxylic acid (or 1,3 or 1,4)

Primary AROMATIC amines

(primary, 2 H's and only one R group attached to the N of the amine group, R-NH 2 where R = alkyl or
aryl)

The amino (prefix) or amine (suffix) group is directly attached to the aromatic benzene ring

e.g. C6H7N, the simplest is C6H5NH2, phenylamine

C6H6NCl, 2- or 3- or 4-chlorophenylamine

C6H8N2, 1,3-diaminobenzene,  ,  3-aminobenzoic acid, 

C7H9N, 2-methylphenylamine, methyl-2-phenylamine, 1-amino-2-methylbenzene  or

2-aminomethylbenzene
This is isomeric with benzylamine which is a primary aliphatic amine because the
amine group is not directly attached to the ring.

Secondary AROMATIC amines

(secondary, one H and two R groups attached to the N of the amine group, R 2NH where R = alkyl or
aryl)

C7H9N, N-methylphenylamine , and C8H11N, N-ethylphenylamine

and C10H11N, diphenylamine

TERTIARY AMINES

(tertiary, no H and three R groups attached to the N of the amine group, R 3N where R = alkyl or aryl)

N,N-dimethylphenylamine, C8H11N,  , N,N-diethylphenylamineC10H15N,

 
and C18H15N, triphenylamine

PRIMARY ACID AMIDES

(primary, no alkyl/aryl R group and 2H's on the N of amide group)

The simplest primary aromatic acid amide is

benzamide or benzenecarboxamide, C7H7NO, , ,

SECONDARY ACID AMIDES

(secondary, 1 alkyl/aryl R group and 1H on the N of amide group)

N-phenylethanamide, C8H9NO, (this is really a phenyl derivative of an

aliphatic amide)

N-methylbenzamide, C8H9NO,  , and

N-phenylbenzamide, C13H11NO,     (both true secondary aromatic

amide)
POLYAMIDES

Are secondary amides formed in a condensation reaction between a carboxylic acid and an
amine.

Water is eliminated between the two 'monomers' to give the secondary, polyamide (polymer) 
linkage ...

-COOH + H2N- ==> -CO-NH- + H2O

KEVLAR is an aromatic polyamide formed from benzene-1,4-dicarboxylic acid and 1,4-

diaminobenzene

TERTIARY ACID AMIDES

Tertiary amides would have no H and 2 aryl/alkyl groups on N of amide group.

N,N-dimethylbenzamide, C9H11NO,  

DIAZONIUM SALTS and AZO DYES:

Diazonium salts are formed when primary aromatic amines reaction with nitrous acid

e.g. C6H5NH2(aq) + HNO2(aq) + H+(aq) ==> C6H5N2+(aq) + 2H2O(l)

The diazonium cation has a nitrogen-nitrogen triple bond system directly attached to the
benzene ring e.g.

(1) from phenylamine

(2) from 4-methylphenylamine

(3) from 2-aminobenzoic acid.

In alkaline solution these diazonium salts couple with phenols and aromatic amines to form
azo dyes.

These dyes have benzene rings linked with an azo -N=N- bond system e.g.

reacting (1) with phenol gives

reacting (1) with phenylamine gives

reacting (2) with phenol gives  

reacting (2) with phenylamine gives

NITRO-AROMATICS

These have the nitro -NO2 group directly attached to the ring. On reduction they form primary
aromatic amines.

nitrobenzene, C6H5NO2, and , C6H4N2O4,   1,3-dinitrobenzene,

 
3 isomers of C6H4NO2Cl, 1-chloro-2-nitrobenzene , 1-chloro-3-nitrobenzene ,

1-chloro-4-nitrobenzene  

C7H7NO2,  methyl-2-nitrobenzene, or 1-methyl-2-nitrobenzene (o-nitrotoluene, ortho

nitrotoluene)

and the two other positional structural isomers

methyl-3-nitrobenzene, or 1-methyl-3-nitrobenzene (m-nitrotoluene, meta

nitrotoluene)

and

methyl-4-nitrobenzene, or 1-methyl-4-nitrobenzene (p-nitrotoluene, para nitrotoluene)

and a substituted aromatic carboxylic acid, C7H5NO3, 3-nitrobenzoic acid,

Sulphonic Acids (sulfonic acids)

These molecules have a strongly mono-basic acidic group -SO 2OH directly attached to the
benzene ring e.g.

benzenesulphonic acid, C6H6SO3, C6H5SO3H, C6H5SO2OH, (or

benzenesulphonic acid)

2-, 3- or 4-methylbenzenesulfonic acid, C7H8SO3, CH3C6H5SO2OH, , ,

(or 2-, 3- or 4-methylbenzenesulphonic acid)

10.8.2 The electrophilic substitution of an arene - nitration mechanism

 What is the mechanism for nitrating benzene? or methyl benzene?

 for benzene : C6H6 + HNO3 ==> C6H5NO2 + H2O    [see mechanism 19 below]
 for methyl benzene: C6H5CH3 + HNO3 ==> O2NC6H4CH3 + H2O
 The nitrating mixture consists of concentrated nitric acid (source of the nitro group -NO2)
and concentrated sulphuric acid which acts as a catalyst and as a strong acid.

mechanism 19 - electrophilic substitution in the nitration of the benzene ring

 [mechanism 19 above] Benzene is converted into nitrobenzene, when R = H.

 When R = CH3, methylbenzene will form a mixture of the three possible substitution products
methyl-2/3/4-nitrobenzene,
o and methyl-3-nitrobenzene is the minority product, the mechanism above would show
the formation of one of the major products methyl-2-nitrobenzene.
 Step (1) The sulphuric acid protonates the nitric acid (strong acid, but weaker than
H2SO4)
 Step (2) The protonated nitric acid loses a water molecule via a sulphuric acid molecule, to
generate the electrophile, the nitronium ion, NO2+. This is a much more powerful
electrophile, i.e. electron pair acceptor, than the original nitric acid, and is needed to attack
the very stable aromatic ring of benzene.
o Steps (1) and (2) can be written as: 2H2SO4 + HNO3 ==> NO2+ + H3O+ + 2HSO4- 
 Step (3) An electron pair from the delocalised pi electrons of the benzene ring forms a C-N
bond with the electron pair accepting nitronium ion forming a highly unstable carbocation. It is
very unstable because the stable electron arrangement of the benzene ring is partially broken
to give a 'saturated' C (top right of ring).
 Step (4) The hydrogensulphate ion (HSO4-, formed in step (1), abstracts a proton from the
highly unstable intermediate carbocation to give the nitro-aromatic product and reform the
sulphuric acid catalyst as well as the stable benzene ring.
o Note that the hydrogensulphate ion, HSO4- has been shown in the style of -:O-SO2-
OH, to emphasize the importance a lone pair on the oxygen abstracting the proton
from the aromatic carbocation.

 GENERAL COMMENT to compare aromatic electrophilic substitution with the

electrophilic addition with alkenes:
o Like alkenes, arenes are susceptible to electrophilic attack because of the high
electron density of the pi electrons involved in the carbon-carbon bonding and
both show little reactivity towards nucleophilic reagents.
o However two points should be considered because of the particular stability of the
aromatic (benzene) ring.
1. This makes aromatic compounds less reactive than alkenes, which readily
undergo addition rather than substitution.
2. Aromatics do not usually undergo addition because this will remove the
stability conferred on the molecule by the benzene ring. By under going
substitution rather than addition, the stable aromatic ring is preserved.
 FURTHER COMMENTS
o The overall nitration reaction is the substitution of -H by -NO2 

10.8.3 The electrophilic substitution of an arene - chlorination mechanism

(example of aromatic halogenation)

 What is the mechanism for chlorinating benzene? or methyl benzene?

 C6H6 + Cl2 ==> C6H5Cl + HCl    [see mechanism 21 below]
 Chlorine is bubbled into a mixture of the arene and anhydrous aluminium chloride catalyst.
Other catalysts like anhydrous iron(III) chloride can be used, and they are collectively known
as halogen carriers.
 mechanism 21 - electrophilic substitution by halogen in a benzene ring

 [mechanism 21 above] When R = H, benzene forms chlorobenzene.

o Step (1) The non-polar and uncharged chlorine molecule is not a strong enough an
electrophile to disrupt the pi electron system of the benzene ring. The aluminium
chloride reacts with a chlorine molecule to form a positive chlorine ion Cl+ which is a
much stronger electron pair accepting electrophile and a tetrachloroaluminate(III)
ion (either this or an AlCl3-Cl2 complex - details not needed for A level).
o Step (2) An electron pair from the delocalised pi electrons of the benzene ring forms
a C-Cl bond with the electron pair accepting positive chlorine ion forming a highly
unstable carbocation. It is very unstable because the stable electron arrangement of
the benzene ring is partially broken to give a 'saturated' C (top right of ring).
o Step (3) The tetrachloroaluminate(III) ion, formed in step (1), abstracts a proton from
the highly unstable intermediate carbocation to give the chloro-aromatic product,
hydrogen chloride gas and reform the aluminium chloride catalyst.
 Also consider C6H5CH3 + Cl2 ==> ClC6H4CH3 + HCl
 when R = CH3, methylbenzene forms a mixture of chloro-2/3/4-
methylbenzene.
o chloro-3-methylbenzene is the minority product and the mechanism above would
show the formation of chloro-2-methylbenzene.
 FURTHER COMMENTS
o The overall halogenation reaction is the substitution of -H by -Cl 
o Bromination can be carried in the same way by mixing bromine, the aromatic
hydrocarbon (arene) with a halogen carrier catalyst such as anhydrous AlBr 3 or
FeBr3.
o Why do aromatic compounds tend to react by electrophilic substitution BUT
alkenes tend to react by electrophilic addition?
 They both interact with electrophiles because they both have 'electron rich'
electron pair donating bonding systems i.e. the >C=C< double bond in
alkenes and the delocalised ∏ electrons of the benzene ring, but the benzene
ring has a particularly high stability which is preserved on substitution. For the
same reason alkenes are generally more reactive than arenes.
o If methyl benzene is reacted with chlorine in the presence of uv light, substitution
takes place in the alkyl side chain. In other words it behaves like an alkane and
undergoes a free radical substitution reaction. The initial product is
chloromethylbenzene, C6H5CH2Cl, and further substitution products can be formed
C6H5CHCl2 and C6H5CCl3. This illustrates the significance of changing reaction
conditions which function via a different mechanism to give a different product.
 initiation:
 Cl-Cl ==> Cl. + Cl. 
 chain propagations:
 Cl. + C6H5CH3 ==> HCl + C6H5CH2.
 then C6H5CH2. + Cl-Cl ==> C6H5CH2Cl + Cl. 
 chain terminations:
 2C6H5CH2. ==> C6H5CH2CH2C6H5 or 2Cl. ==> Cl2 or C6H5CH2. + Cl.
==> C6H5CH2Cl
  

10.8.4 The electrophilic substitution of an arene - alkylation mechanism (Friedel-

Crafts reaction)

 What is the mechanism for alkylating benzene? or methyl benzene?

 C6H6 + R3C-Cl ==> C6H5-CR3 + HCl (R = H, alkyl, aryl)   [see mechanism 23 below]
 The arene is refluxed with a chloroalkane and anhydrous aluminium chloride catalyst.

mechanism 23 - electrophilic substitution by an alkyl group in the benzene ring

 [mechanism 23 above] If R' = H, benzene would form methylbenzene if chloromethane was

used.
o Step (1) The weakly polar and uncharged halogenoalkane molecule is not a strong
enough an electrophile to disrupt the pi electron system of the benzene ring. The
aluminium chloride reacts with the halogenoalkane molecule to form a carbocation
which is a much stronger electron pair accepting electrophile than the original acid
chloride (either this or an AlCl3-R3Cl complex - details not needed for A level).
o Step (2) An electron pair from the delocalised ∏ electrons of the benzene ring forms
a C-C bond with the electron pair accepting carbocation forming a second highly
unstable carbocation. It is very unstable because the stable electron arrangement of
the benzene ring is partially broken to give a 'saturated' C (top right of ring).
o Step (3) is a proton transfer, as the tetrachloroaluminate(III) ion [formed in step (1)],
abstracts a proton from the highly unstable intermediate carbocation to give the alkyl-
aromatic product, hydrogen chloride gas and reform the aluminium chloride catalyst.
 If R' = CH3 methylbenzene: C6H5CH3 + R3C-Cl ==> R3C-C6H4CH3 + HCl
 A mixture of polysubstituted alkyl aromatic compounds are formed.
o e.g. using chloromethane, 1,2- or 1,3- or 1,4-dimethylbenzene will be formed,
 so if R=H, the mechanism above would show the formation of 1,2-
dimethylbenzene.

 FURTHER COMMENTS
o The overall alkylation reaction is the substitution of -H by -CR3 
o Bromoalkanes can also be used for alkylation, but more expensive. Similar catalysts
can be used e.g. anhydrous AlBr3 or FeBr3.
  

10.8.5 The electrophilic substitution of an arene - acylation mechanism (Friedel-

Crafts reaction)

 What is the mechanism for acylating benzene? or methyl benzene?

 for R = H, benzene: C6H6 + R'COCl ==> C6H5COR' + HCl   [see mechanism 25 below]
 Benzene is refluxed with an acid chloride and anhydrous aluminium chloride catalyst and
a ketone is formed.

mechanism 25 - electrophilic substitution by an acyl group in the benzene ring

 [mechanism 25 above] If ethanoyl chloride, CH3COCl, was used (R=CH3-), benzene forms
phenylethanone, C6H5-CO-CH3.
o Step (1) Although the acid chloride molecule is polar, it is still not a strong enough
electrophile to disrupt the pi electron system of the benzene ring. The aluminium
chloride reacts with an acid chloride molecule to form a carbocation (acylonium ion,
RCO+) which is a much stronger electron pair accepting electrophile than the
original acid chloride (either this or an AlCl3-RCOCl complex - details not needed for
A level).
o Step (2) An electron pair from the delocalised pi electrons of the benzene ring forms
a C-C bond with the electron pair accepting carbocation forming a second highly
unstable carbocation. It is very unstable because the stable electron arrangement of
the benzene ring is partially broken to give a 'saturated' C (top right of ring.
o Step (3) is a proton transfer, as the tetrachloroaluminate(III) ion [formed in step (1)],
abstracts a proton from the second highly unstable intermediate carbocation to give
the ketone product, hydrogen chloride gas and reforming the aluminium chloride
catalyst.
 for R = CH3, benzene: C6H5CH3 + R'COCl ==> R'COC6H4CH3 + HCl
o and again there is the potential to form three position isomers by substituting in the 2,
3 or 4 position on the ring.
 FURTHER COMMENTS
o The overall acylation reaction is the substitution of -H by RCO
  

10.8.6 The electrophilic substitution of an arene - sulphonation mechanism

 What is the mechanism for sulphonating/sulfonating benzene? or methyl benzene?

 for R = H, benzene: C6H6 + SO3 ==> C6H5SO2OH  [see mechanism 44 below]
 or C6H6 + H2SO4 ==> C6H5SO2OH + H2O
 Benzene is heated with concentrated sulphuric acid or even better, 'fuming' sulphuric acid,
which has a higher sulphur trioxide content and more efficient at introducing the sulphonic
acid group into the benzene ring.

mechanism 25 - electrophilic substitution by an acyl group in the benzene ring

 [mechanism 44 above]  
o Step (1) Sulphur trioxide is formed (or already present). It is a powerful
electrophile, i.e. electron pair acceptor because of the effect of the three very
electronegative oxygen atoms bonded to the central sulphur atom.
o Step (2) An electron pair from the delocalised pi electrons of the benzene ring forms
a C-S bond with the electron pair accepting sulphur trioxide forming a second highly
unstable carbocation. It is very unstable because the stable electron arrangement of
the benzene ring is partially broken to give a 'saturated' C (top right of ring).
o Step (3) A hydrogensulphate ion removes a proton and the complete benzene ring is
reformed giving the anion of the aromatic sulphonic acid.
o Step (4) is a proton transfer to give the sulphonic acid.
 for R = CH3, benzene: C6H5CH3 + H2SO4 ==> CH3C6H4SO2OH + H2O
o and again there is the potential to form three position isomers by substituting in the 2,
3 or 4 position on the ring, the mechanism diagram shows the formation of methyl-2-
benzenesulphonic acid.
 FURTHER COMMENTS
o The overall sulfonation reaction is the substitution of -H by -SO2OH

 
  

10.8.7 The orientation of products in aromatic electrophilic substitution

reactions

 Certain groups, already present, can increase the electron density of the benzene ring
and make the aromatic compound more reactive towards electrophiles such as those
described above. However the effect seems to enhance the reactivity at the 2 and 4
substitution positions more than the 3 substitution position.
o Groups that increase reactivity are e.g. -CH3, -Cl, -OH, -NH2, -NHCOCH3, and
favour substitution at the 2 and 4 positions (typically 90-100% combined).
o They all, by some means, have a small, but significant, electron donating (+I
inductive effect) on the ring of pi electrons.
o For example, methyl benzene is significantly more reactive than benzene and
when nitrated, over 90% of the products are either methyl-2-nitrobenzene or methyl-
4-nitrobenzene.
 Certain groups, already present, can decrease the electron density of the benzene ring
and make the aromatic compound less reactive towards electrophiles such as described
above. However the effect seems to decrease the reactivity at the 2 and 4 substitution
positions more than the 3 substitution position.
o Groups that decrease reactivity, by some means, are e.g. -NO2, COOH, -CHO,
-SO2OH, and favour substitution at the 3 position (typically 70-90%) and their effect
does fit in with them all being strongly electronegative groupings giving a -I inductive
effect.
o For example, nitrobenzene is much less reactive than benzene and on nitration,
93% of the product is 1,3-dinitrobenzene.