PhenylEthanone

Benzene C6H6 = Topic 18A.1 to 18A.3

Toluene C6H5CH3 = Topic 18A.2 & 3
PhenylEthanone C6H5COCH3 = Topic 18A.2 & 3
BenzeneSulfonic Acid C6H5SO3H = Topic 18A.3
Phenol C6H6O / C6H5OH = Topic 18A.4 SPECIFICATION
Phenyl C6H5 = iGCSE Unit 19.2 REFERENCE
Phenylamine C6H5NH2 = 19A.1 & 19A.3
18A 2 SOMEREACTIONS
OFBENZENE 18.4(i) 18.4(ii) 18.4(iii)
18.4(iv) 18.4(v)
Styrene
=Phenylethene (CH2CHC6H5) =iGCSE 19.2
Poly(phenylethene) = Polystyrene
(p226: substitution = ROOM TEMP (!) with a Halogen carrier catalyst,
[for Bromination [by substitution], this is Fe filings that react with the Bromine
BROM
INATION to form Fe(III)Br ])
LEARNING
OBJECTIVES The term 'bromination ' has more than one possible meaning. It
■ Know the following reactions of benzene, limited to : could refer to the addition reaction between benzene and bromine.
(i) oxygen in air (combustion to form a smoky flame) This reaction does occur in the presence of ultraviolet radiation ,
but it is of little importance. In this book , the term refers to a
(ii) bromine, in the presence of a catalyst ......as we usually want to keep the benzene ring structure
or substitution reaction. when putting-in Br and thus use substitution... (rather than break the ring
(iii) a mixture of concentrated nitric and sulfuric acids (LIQUID) structure /C=C bonding to ADD-in Br to the molecule by ADDition reaction).
Nitration / Sulfonation
(iv) fuming sulfuric acid Benzene and bromine are heated under reflux, in the presence of
***
(v) halogenoalkanes and acyl chlorides with aluminium a catalyst called a halogen carrier. Halogen carriers are usually NOT
chloride as catalyst (Friedel-Crafts reaction) . metal-halogen compounds such as aluminium chloride, aluminiumE:
bromide or iron(III) bromide. For bromination , it is enough to This
confli
add iron filings because they react with some of the bromine
cts
REACTIONS
ASA HYDROCARBON to form iron(III) bromide. The products are bromobenzene and with
In Section 18A.1, hydrogenation was mentioned. This reaction hydrogen bromide. The equation for the reaction is: p270
occurs in the same way with benzene as with alkenes. The same is
true for combustion.

HYDROGENATION @ + Br2 Fe-----+

@ room temp
with
filings ~
catalyst
~o Br+
HBr
(that
state
s
reacti
on
occu
This is done by mixing benzene with hydrogen and heating under SUBSTITUTION REACTION=> 2 reactants AND 2 products
( 1x Br is substituted for 1x H ) rs at
pressure with a nickel catalyst. The equation for the reaction can NITRATION thus 2 products! room
be shown using molecular or skeletal formulae: temp
Ni catalyst
This refers to the replacement of a hydrogen atom by a nitro
(ie
C6 H6 + 3H 2 ____,C6 H 12 group. The nitro group has the formula NO 2 and should not be REFL
with Heat & Pressure
or : confused with the gas nitrogen dioxide. The reaction is carried outUX
H H
H
by warming benzene with a mixture of concentrated nitric and NOT
H H H H H H sulfuric acids. The nitric acid can be considered as the source of need
ed!!)..
the NO 2 group and the sulfuric acid as a catalyst. The products are . and
H H H H H H
H
nitrobenzene and water. The equation for the reaction is: confli
H H
Nitration 22
cts
with

[§r
Note the plain hexagon (without a circle) used for the skeletal H2S0 4 N0+
that
formula for cyclohexane. + HNO 3 - stated
warming
(for
COMBUSTION Nitro-benzene + water Chlori
As with all hydrocarbons, benzene bums in air; although with a The reaction is carried out between 50 and 60 ·c.
At lower natio
n and
smoky flame. This is typical of many compounds with a high temperatures the reaction is too slow. At higher temperatures it isBromi
carbon-to-hydrogen ratio. The equation for complete combustion is: possible to form dinitrobenzene, and even trinitrobenzene . natio
n of
*** 5mins: Ask students to research TriNitroToluene!
C H + 7210 6CO + 3Hz0
2 ____,
When 6 6 2 FRIEDEL-CRAFTS REACTIONS => Draw structure and name its use... Benz
C:H = 1:1 (as ring structure with a "pi bond system" / multiple C=C double bonds) =>> typically smoky ene)
Reactions with this name were developed by Charles Friedel at:
REACTIONS
ASANARENE
(AROMATIC HYDROCARBON
...with C=C double bond / 'pi (π) bond system' (a French chemist) and James Crafts (an American chemist). https:/
The most important reactions of benzene are substitution There are several types of reaction bearing their names, but we /
www.
reactions , in which the products are also aromatic. We will will consider only two of them: alkylation and acylation. They chemg
consider the mechanisms of these reactions in the next section both have these features in common: uide.c
(Section 18A.3). • using a reagent represented by XY,one of the hydrogen atoms o.uk/
organi
in benzene is substituted by Y, and the other product is HX cprops
• a catalyst is needed - often aluminium chloride , although other/
Bromination refers to putting bromine into a molecule . This could be arenes
by an addition reaction , but in this section it refers only to a
halogen carriers such as iron(III) chloride and iron(III) bromide/
substitution reaction. also work haloge
• anhydrous conditions are needed because water would react nation
.html
with the catalyst and sometimes also with the organic product.
 TOPIC18 18A.2SOMEREACTIONS
OFBENZENE 227
FRIEDEL-CRAFTS ALKYLATION REACTIONS
Alkylation means the substitution of one of the hydrogen atoms of benzene by an alkyl group. The
reagent is a halogenoalkane , and the product s are an alkylben zene (methylbenzene) and hydrogen
chloride. The equation for the reaction with chloromethane is:

@ @rCH
~ HCl

Remember: Acyl chlorides (15C.2, p 125: produced by reacting

FRIEDEL-CRAFTS ACYLATION REACTIONS Carboxylic Acids with PCl5 (Phosphorous pentachloride) pronounced: Ay-cyle

Acylation mean s the substitution of one of the hydrogen atom s in ben zene by an acyl group. Th e
reagent is an acyl chloride , and the product s are a ketone (phenylethanone) and hydrogen chloride.
Th e equation for the reaction with ethano yl chlorid e is:

@rCOCH
,+
@ HCl

Note, of course, the Ketone functional group -CO, is always between

phenylethanone two C atoms... and thus METHANone and ETHANone don't exist on
their own!! Ethanone only exists here ('in' phenylethanone since it is a
component part and 'borrows' a C atom from phenyl, that allows it to
SULFONATION have the -CO between two C atoms.
Sulfonation refers to the replacement of a hydrogen atom by a -SO 3 H group . The reaction is carried
out by warming benzene with fuming sulfuric acid at 40 °C for 20 to 30 minutes. SO is the 3
Sulfonation

@ + H,so,
fuming sulfuric acid
40 °c
ATTACKING
elecrophile!

benzenesulfonic acid
The product is benzenesu lfonic acid.
Benzene-sulfonic acid + water
Fuming sulfuric acid is made by dissolving sulfur(VI) oxide (sulfur trioxide , SO 3 ) in concentrated
sulfuric acid .

The equation for sulfonation may also be written as

fuming sulfuric acid

40 °c

Which equation you use depends on the question you are being asked. If the question is about the reaction
with sulfuric acid, then you must use the equation with H2 SO4 . If the question has SO3 as the electrophile,
then you could use this equation .

NAMING
AROMATIC
COMPOUNDS
The rules for naming aromatic compounds are similar to tho se used for aliphatic compounds.
Prefixes , locant s, hyphen s and commas , and multiplying prefixes are used in the same way In some fig A Shoe polish is one of
name s, you will see 'phen ' or 'phenyl' used to represent the benzene ring when it is attached to the many commercial products
containing aromatic compounds.
another functional group. For example , the organic product of the last reaction is phen ylethanone:
'ethan ' refers to the two carbon atoms in CH 3CO, 'one ' indicate s that the compound is a ketone and
'phen yl' refers to the C6 H 5 group. You might expect 'benzyl' to be used rath er than 'phenyl', but it is SUBJECT
VOCABULARY
not. The explanation for this is beyond the aim s of this book. halogen carrier a compound
such as AIX3 or FeX3 , where X is
CHECKPOINT a halogen, that can catalyse the
halogenation of arenes. They
1. Write an equation for the reaction between benzene and 2-bromopropane . produce a stronger electrophile,
2. What is the name of the organic product formed in the reaction between benzene and butanoyl chloride? such as Br•

B2 C2.5 N3 O3.5 F4
Cl 3
EN chart Br 2.8
I 2.5
At 2.2
 Benzene C6H6 = Topic 18A.1 to 18A.3 Nucleophile, in chemistry, an atom or molecule that in chemical reaction that:
- donates an electron pair to an electrophile
Toluene C6H5CH3 = Topic 18A.3 - seeks a positive centre, such as the nucleus of an atom
PhenylEthanone C6H5COCH3 = Topic 18A.3
Electrophiles generally,
Phenol C6H6O / C6H5OH = Topic 18A.4 - positively charged species that are attracted to an electron rich center / electron
Phenyl C6H5 = iGCSE Unit 19.2 pair available for bonding
(electrophilic substances are Lewis acids [compounds that accept electron pairs])
Phenylamine C6H5NH2 = 19A.1 & 19A.3
SPECIFICATION
REFERENCE
18A 3 ELECTROPHILIC
SUBSTITUTION 18.5

Styrene
MECHANISMS
=Phenylethene (CH2CHC6H5) =iGCSE 19.2
Poly(phenylethene) = Polystyrene

Note that the H

H atom shown in the product of this step is already
LEARNING
OBJECTIVES present in benzene , although it is not shown. It is shown here
because it will be lost in Step 3.
■ Understand the mechanism of the electrophilic
1. 2. Step 3: formation of the aromatic product
substitution reaction s of benzene in halogenation , nit ration

@f: ~ @JB'
Product
and Friedel- Crafts reactions, including the generatio n of #1

the electrophile . (Alkylation & Acylation)

C
3. 4. H + H
Br
ELECTROPHILIC
SUBSTITUTION Step 4: regeneration of the catalyst
Product
Although you have not seen this mechanism before , you have A1Br4 + H
H+ --+ A1Br3 + H
HBr#2
After catalyst is regenerated, the 2nd product, HBr, is produced
studied substitution reactions in Topics 4 and 10 (Book 1: IAS),
and electrophilic addition reactions in Topic 5 (Book 1: IAS).
5A.4. p137-9 (Recall the polar H-Br 'attacking the C=C in ethene, & being 'added-in' to make Bromoethane?) 2.NITRATIONNitration
Before we consider the mechanisms of the individual reactions, it Step 1: formation of the electrophile
is worth considering what they all have in common: Nitric acid and sulfuric acid react to form NO/ (the nitryl ion or
• The benzene ring is electron-rich. Although it is electrically nitronium ion): Product
system" Reactant
neutral, the delocalised electrons in the " pi (7r)bond above #1 HN0
3 + H 2S0 4 --+ N0 2 + HS0 4 +#1 H 20
and below the atoms mean that the molecule attracts
electrophiles - species attracted to negative charge. Step 2: electrophilic attack
electrophile
generally, positively charged species Reactant
#2
~
~~0H C
• Using y+ to represent the electrophile, as y+ approaches the /N0 2
~N0 2

H
system"
delocalised " 71"-bond,it attracts two of the six electrons, which
form a covalent bond with it. This gives an intermediate
species with a positive charge (shown by convention in the Intermediate

centre of the hexagon) , in which one C

both Y and H
carbon atom is joined to
H. There are now only four de localised electrons,
and these are represented by two-thirds of a circle.
• This intermediate species lacks the stability of an aromatic
Step 3: formation of the aromatic product

C H
N0
H
2

_
@JN0
0
Product
#2
2

+ H
H+

compound (because the circle is broken) , so in the next step the r

H leaves as H+ and the two electrons in the C-H bond join Nitro-benzene + water
system" Step 4: regeneration of the catalyst SUBSTITUTION REACTION
the remaining four to restore the delocalised " 7r-bond (with its
H+ --+ H
HS0 4 + H H 2S0 4 Here 2 reactants ==> So 2 products
relatively high stability).
When drawing these mechanisms, or skeletal formulae, a EXAM
HINT
substituent on the benzene ring can be shown in any of the six The formation of the electrophile in this reaction involves nitric acid
positions. It is usually shown at the top of the hexagon or the next acting as a base. This is because it accepts a proton from the sulfuric
position clockwise. acid (see Topic 14).

To help you see the similarities and differences in these ·. 3. ALKYLATION

mechanisms, they are all set out in the same way
Step 1: formation of the electrophile
1. BROMINATION =Halogenation Chloromethane reacts with the catalyst to form CHj:
Reactant
Step 1: formation of the electrophile #1 CH Cl --+ CH + A1Cl
AIC13 + 3 3 4
Bromine reacts with the catalyst to form Br+: Step 2: electrophilic attack
Reactant
electrophile
A1Br3 +#1Br2 --+ Br+ + A!Br4 Reactant
#2
~ )CH
~~0H ~CH C
3 3
Step 2: electrophilic attack H
Reactant
#2 electrophile
~Br C
H Intermediate
~H
Intermediate

Br Br

**SUBSTITUTION REACTION, Here 2 reactants => So 2 products will be produced (1x Br is substituted for 1x H ).....