ARENES AND PHENOLS

TR. REHAB ISMAIL

 a) Use the general, structural, displayed and skeletal formulae of benzene and
simple aromatic molecules with one benzene ring and one or more simple
substituents, for example 3-nitrobenzoic acid or 2,4,6-tribromophenol
b) Draw and use systematic nomenclature of simple aromatic molecules
with one

LEARNING OBJECTIVES
benzene ring and one or more simple substituents for example 3-nitrobenzoic
acid or 2,4,6-tribromophenol
c) Understand and use the following terminology associated with types of
organic
reactions:
i. electrophilic substitution
ii. addition-elimination
d) Describe the chemistry of arenes as exemplified by the following reactions
of
benzene and methylbenzene:
i. substitution reactions with Cl2 and with Br2 in the presence of a catalyst,
AlCl3 or AlBr3, to form halogenoarenes (aryl halides)
ii. Friedel–Crafts alkylation by CH3Cl and AlCl3 and heat
iii. complete oxidation of the side-chain using hot alkaline KMnO4 and then
dilute acid to give a benzoic acid
iv. hydrogenation of the benzene ring using H2 and Pt/Ni catalyst and heat to
form a cyclohexane ring
e) Explain the difference in reactivity between a halogenoalkane and a
halogenoarene as exemplified by chloroethane and chlorobenzene
There are two major classes of organic chemicals
aliphatic : straight or branched chain organic substances
aromatic or arene: includes one or more ring of six carbon atoms with delocalised bonding

The six electrons in the pi bonds are delocalised and spread out over
the whole ring. Delocalised means not attached to a particular atom

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Arenes are aromatic compounds that contain a benzene ring
Chemical properties
 Due to the delocalised electron ring (π system of electrons), these compounds
are electron-rich and therefore can undergo electrophilic attack under the right conditions

 However, because the delocalised electron ring system makes benzene so

stable, it is resistant to addition reactions

 This is very different to alkenes, which are very reactive and readily undergo addition reactions

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 Property Benzene Alkene (cyclohexene)

Shape Symmetrical hexagonal. All C-C Unsymmetrical hexagon

bond lengths are equal,
creating a planer regular
hexagonal shape
Stability Stable ring of 6 electrons. Stable π bond of 2 electrons
The delocalization of the π
electrons in benzene make
benzene more stable
Reactivity Less reactive reactive
Type of reaction Electrophilic substitution Electrophilic addition reaction.
reaction.
Benzene undergoes
electrophilic substitution
reaction
Shaking with oxidizing agent or No reaction decolonization
Br2
Reaction with H2 in presence of Very slow rection at 100 C and Rapid reaction at 20 C and 1
Ni catalyst 100 atm atm

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Physical properties
 Benzene has van der Waals dispersion forces of attraction between the molecules and has
a boiling point of 80 C
 The presence of the non-polar hydrocarbon part in the arene functional group means that
these compounds are often insoluble in water
 Benzene would have to break many hydrogen bonds between the water molecules to be
soluble in water, which does not happen as it is not energetically favorable

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Halogenoarenes
 These are aromatic compounds that contain a halogen bonded to a benzene ring
 They are also known as aryl halides
Chemical properties
 These compounds are also prone to electrophilic attack because of the π system of
delocalised electrons
 The halogens can also take part in substitution reactions
Physical properties
 Chlorobenzene, bromobenzene and iodobenzene are all liquid at room
temperature with an oily texture

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 As you might expect, the boiling points increase as the size of the halogen attached increases, because the
number of electrons within the molecule increases
 Like other arenes, halogenoarenes are insoluble in water because of the non-polar hydrocarbon part of the
ring
 These molecules are large relative to the size of water molecules, and as with the arenes it is not energetically
favourable for the halogenoarene molecules to break the hydrogen bonds between the water molecules, so it
does not happen

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Naming aromatic molecules

1. If two or more substituents are present on the benzene ring, their positions must be indicated by the use of numbers. This
should be done to give the lowest possible numbers to the substituents. When two or more different substituents are
present, they are listed in alphabetical order and di, tri prefixes should be used

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In other molecules the benzene ring can be regarded as a substituent side group on another molecule, like alkyl groups are.
The C6H5-group is known as the phenyl group

If there are two different substituents one of them will be defined as the root group
according to their order of precedence
COOH < -OH < -NH2 < _CH3< -X < _NO2

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Name the following compounds:

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•What is the name of the following compound

•3-hydroxy benzoic acid

•2-hydroxy benzoic acid
•3- hydroxyl benzaldehyde
•2-hydroxy benzaldehyde

Which of the following compounds is phenyl ethanone

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Terminology Used in Reaction

 Electrophiles are species that are electron deficient and can act as an electron pair acceptor
Electrophiles are ʻelectron lovingʼ species

 Substitution reactions are reactions that involve the replacement of one atom or
group of atoms by another
Electrophilic substitution reactions are therefore reactions in which an atom or
group of atoms are replaced by an electrophile after initial attack by the electron- deficient species

Addition- elimination
Other common organic reactions include addition and elimination reactions
In an addition reaction, two or more molecules combine to give a single product only

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Reactions of Benzene
Addition reactions of benzene:

 Reaction of alkyl benzene – hydrogenation

Reagent: Hydrogen gas, H2

Condition: Heat in the presence of nickel, Ni catalyst at 300°C
Product: Cyclohexane
In hydrogenation, hydrogen atoms are added to the benzene ring. The delocalized electron system is permanently broken

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Reactions of Benzene
 Halogenation of Benzene
Change in functional group:
benzene Bromobenzene
Reagents: Br2
Bromine Conditions: Iron(III) bromide catalystFeBr3
Mechanism: Electrophilic Substitution

This reaction can be done with chlorine.

The catalyst can be AlCl3or FeCl3
It is possible to create the iron(III)bromide in situ by reacting iron with bromine

Equation for Formation of electrophiles:

AlCl3+ Cl2 AlCl4–+ Cl+

FeBr3+Br2 FeBr4–+Br+

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 The Br2 molecule forms a dative (co-ordinate) bond with Iron (III) bromide by donating a lone pair of electrons from one
bromine atom into an empty 3d orbital in the iron. This draws electrons from the other bromine atom in the Br2 molecule
making it partially positive, creating the electrophile (Br+):

Mechanism done at r.t.p & FeCl3, AlCl3 and FeBr3 (halogen

carriers) catalyst

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 Again, due to the electron-donating alkyl groups in
alkylarenes, nitration of
methylbenzene will occur on the 2 and 4 position

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 Friedel Crafts Alkylation

Change in functional group:

benzene alkylbenzene
Reagents: Chloro alkane in the presence of anhydrous aluminum
chloride catalyst
Conditions: heat under reflux
Mechanism: Electrophilic substitution

Any chloroalkane can be used RCl where R is any alkyl group

Eg –CH3,-C2H5.The electrophile is the R

formation of electrophile

AlCl3+ CH3CH2Cl CH3CH2+AlCl4-

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 Reaction of alkyl benzene

 Reagent: Chlorine/bromine gas, Cl2/Br2

 Condition:
- Into the ring - Aluminum chloride, AlCl3or iron(III) chloride, FeCl3as catalyst, absence of UV light
-Into the alkyl group - Absence of catalyst but presence of UV light
 Product: Halo-alkyl benzene

o In the presence of halogen carriers and the absence of UV light at room temperature, the halogen is substituted into the
ring via electrophilic substitution.

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 In the presence of UV light and the absence of halogen carriers, the halogen is
substituted into the alkyl group via free-radical substitution. Take methylbenzene as an
example, (chloromethyl) benzene is produced.

o Further substitutions are possible, producing (dichloromethyl) benzene and (trichloromethyl) benzene

Alkyl halids reacts with strong alkaline solution (KOH, NaOH)

The name of the reaction is nucleophilic substitution reaction

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  Complete oxidation

 Normally, alkanes are not oxidized by oxidizing agents such as potassium manganate (VII) (KMnO4)
 However, the presence of the benzene ring in alkyl arenes affect the properties of the alkyl side-chain
 The alkyl side-chains in alkyl arenes are oxidized to carboxylic acids when refluxed with alkaline potassium
manganate(VII) and then acidified with dilute sulfuric acid (H2SO4)

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 Reactivity of Benzene & Chlorobenzene
Chlorobenzene is less reactive than benzene because:
 Chlorine is a ring deactivating group
 Chlorine is more electronegative than carbon, and draws electrons in the ring towards itself.
 Hence electron density around ring decreases, less attractive for electrophiles and so reaction is slower
Ring Activating Ring Deactivating
Ring Activating/Deactivating Groups Alkyls, NH , OH Cl, NO , COOH
2 2

Donates e- to the ring Withdraws e-

from ring

+ve inductive effect -ve inductive effect

electro-sub faster electro-sub slower
Increase e- density at Sub. occurs at pos. 3 &
position 2 and 4 5

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Difference in Reactivity of Halogenoalkanes & Halogenoarenes

•Halogenoarenes are very unreactive compared to halogenoalkanes

•The difference in reactivity between the two compounds is because of the carbon-halogen bond strengths

Halogenoalkanes
•The halogenoalkane chloroethane can take part in nucleophilic substitution reactions
•A nucleophile, such as a hydroxide (OH-) ion, will attack the slightly positive carbon atom
•A covalent bond is formed between that carbon atom and the nucleophile which causes the carbon-halogen bond to break
•Overall, the halogen is replaced by the nucleophile

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Halogenoarenes
•Halogenoarenes, such as chlorobenzene, do not readily undergo nucleophilic substitution reactions
• Only under extremely harsh conditions, such as temperatures of 200 oC and a pressure of 200 atmospheres, will the
chlorine in chlorobenzene get replaced by a nucleophile such as a hydroxide (OH -) ion
•This is because the carbon-chlorine bond is very strong and cannot be easily broken
• One of the lone pairs of electrons on the chlorine will interact with the π system of the ring
• This causes the carbon-chlorine bond to have a partial double-bond character, which strengthens the bond

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•The unreactivity of halogenoarenes can therefore be explained by the delocalisation of a
lone pair on the halogen over the benzene
•This causes additional stabilisation of the system and strengthens the carbon-halogen bond,
which affects the reactions that halogenoarenes will undergo
•It gets harder to break the carbon-halogen bond in halogenoarenes, which decreases
reactivity

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PHENOLS

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 a) Recall the reactions (reagents and conditions) by
which phenol can be produced:
i. reaction of phenylamine with HNO2 or NaNO2 and
dilute acid below 10°C to produce the diazonium salt;
further warming of the diazonium salt with H2O to give
LEARNING phenol
b) Recall the chemistry of phenol, as exemplified by the
OUTCOMES following reactions:
i. with Na(s) to produce sodium phenoxide and H2(g)
ii. bromination of the aromatic ring with Br2(aq) to form
2,4,6-
tribromophenol
c) Explain the acidity of phenol
d) Describe and explain the relative acidities of water,
phenol and ethanol

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Introduction to Phenols

What are phenols?

Phenols are benzene compounds which have an -OH group attached directly to it.
In a phenol molecule, one of the lone pairs on the oxygen overlaps with the
delocalized electron system to give a structure like this:

This increases the electron density of the delocalized electron system. It makes phenols much more reactive than
benzene itself. Also, it increases the acidity of phenol as well.

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 Production of phenol
Phenols can be prepared from phenylamines under the following reaction
conditions:
 NaNO3 with dilute acid (to form HNO2)
 Ice to keep the temperature below 10 C (step 1)
 Heat (step 3)

This reaction involves three steps:

Step 1 - The HNO2 is so unstable that it needs to be prepared in a test-tube by reacting sodium nitrate (NaNO3 ) and dilute
hydrochloric acid (HCl) while keeping the temperature below 10 C using ice

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Step 2 - Phenyl amine is then reacted with the HNO2 to form an unstable diazonium salt

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Step 3 - The diazonium salt is so unstable that it will thermally decompose when heated to form a phenol

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Reactions of Phenol
Reactions of the -OH group in phenols
 The -OH group in phenols has a slightly acidic character
 It can therefore act as an acid and take part in acid-base reactions

 Reaction with reactive metals

 Molten phenols react vigorously with reactive metals such as sodium (Na)
 This is also an acid-base reaction
 Now, a soluble salt is formed, and hydrogen gas is given off

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Bromination
 Phenols also undergo electrophilic substitution reactions when reacted with bromine water at room
temperature
 Phenol decolourises the orange bromine solution to form a white precipitate of 2,4,6-tribromophenol
 This is also known as the bromination of phenol

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Acidity of Phenols

Although phenol compounds contain an alcohol (-OH) group, they are weakly acidic
 This is due to the delocalisation of one of the lone pairs from the oxygen atom into the aromatic ring
 This increases the electron density of the ring and increases the acidic behaviour Delocalisation of charge density
 The conjugate base of phenol is the phenoxide ion
 In the phenoxide ion, the negative charge on the oxygen is spread out over the entire ion
 This is possible as one of the lone pairs on the oxygen atom overlaps with the delocalised π system of the ring
 Because of this delocalisation, there is less charge density on the oxygen atom
 The H ions are therefore not strongly attracted to the phenoxide ion and are less likely to reform the phenol molecule
 This means that phenol is more likely to lose a proton (and act as an acid) rather than to gain a proton (and act as a base
)

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Stability of the conjugate base
 Phenol ionises to form a more stable negative phenoxide ion with its negative charge spread out
 This means that phenol is more likely to undergo ionisation
 The equilibrium position, therefore, lies further to the right and a higher proportion of phenol molecules donate
a proton compared to for example water and ethanol
 The phenol compound is, therefore, more likely to act as an acid rather than a base

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Relative Acidities of Water, Phenol & Ethanol

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Delocalisation of charge density
o In the phenoxide ion (which is the conjugate base of phenol) the charge density on the oxygen atom is spread out over the
entire ion

o As a result, the electrons on the oxygen atom are less available for bond formation with a proton (H ion)

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o The conjugate base of ethanol is the ethoxide ion
o The ethyl group in the ion is an electron-donating group that donates electron density to the oxygen atom
o As a result, the electron density on the oxygen atom is more readily available for bond formation with an H ion

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thank you
TR. REHAB ISMAIL
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