CHE232

Aromatic Compounds

Aromaticity

Benzene, C6H6 is the parent hydrocarbon of the especially stable compounds known as aromatic compounds.
Kekule's structures of benzene H H H H H H H H H H H H

*6 C atoms located at the corners of a regular hexagon, each C bonded to one H atom. The double and single bonds alternate around the ring, this exchange is so rapid that benzene cannot undergo same reactions as alkenes and alkynes, eg permangnate test, bromine test etc.

Aromaticity cont
Kekules structure not entirely correct, there are no single or double bonds in benzene.
H H H H H H H H H H H H

Benzene is planar, each C atom is at the corner of a regular hexagon. All the CC bond lengths are identical, 1.39 . Orbital theory: Each C atom is sp2 hybridized, two sp2 orbitals overlap with similar orbitals of adjacent C atoms to form bonds of the hexagonal ring. The 3rd sp2 orbital overlap with 1s orbital of H atom. The remaining p orbital (containing one electron) is perpendicular to the plane of the three sp2 orbitals. The six p orbitals can overlap laterally to form orbitals that create a cloud of electrons above and below the plane of the ring.

Aromaticity cont..
Two criteria for aromaticity are: 1.

2.

The compound must have an uninterrupted cyclic cloud of electrons above and below the plane of the molecule; i.e. the molecule must be cyclic, have a p orbital that can overlap with other p orbitals on either side of it, therefore, the molecule must be planar. The cloud must contain an odd number of of pairs of electrons.

Which of the following compounds are aromatic ?

a.

b.

c.

d. H2C C C C C CH2 H H H H

Aromaticity cont..
Two criteria for aromaticity are: 1.

2.

The compound must have an uninterrupted cyclic cloud of electrons above and below the plane of the molecule; I.e the molecule must be cyclic, have a p orbital that can overlap with other p orbitals on ether side of it, therefore, the molecule must be planar. The cloud must contain an odd number of pairs of electrons.

Which of the following compounds as aromatic ?

N pyridine

N H pyrrole

O furan

S thiopene

6 Nomenclature of Aromatic Compounds

Common names for benzene derivatives accepted by IUPAC
CH3 OH OCH3

benzene NH2

toluene O C H

phenol O C CH3

anisole CO2H

aniline

benzaldehyde

acetophenone

benzoic acid

H3C H CH3 C

H2C

CH

cumene

styrene

7 Nomenclature of Aromatic Compounds

Monosubstituted benzenes are named as derivatives of benzene

Br

Cl

NO2

bromobenzene

chlorobenzene

nitrobenzene

CH2CH3

CH2CH2CH3

ethylbenzene

propylbenzene

8 Nomenclature cont
When two susbtituents are present, three isomeric structures are possible; ortho-, meta-, and para- usually abbreviated as o-, m- and p-

X O m p
Cl
Cl Cl Cl meta-dichlorobenzene or 1,3-dichlorobenzene Cl

O m

ortho-dichlorobenzene or 1,2-dichlorobenzene

Cl para-dichlorobenzene or 1,4-dichlorobenzene

9 Nomenclature cont
NO2
Cl CH CH2

CH3 meta-nitrotoluene or 1-methyl-3-nitrobenzene

para-chlorostyrene or 1-chloro-4-vinylbenzene

NH2 CH3CH2

OH

ortho-ethylaniline or 2-ethylaniline

Cl m-chlorophenol or 3-chlorophenol

10 Nomenclature cont
CH2
or C6H5 phenyl or Ph

or C6H5CH2- or bnz benzyl

CH3CHCH2CH2CH3

Ph

Ph

2-phenylpentane

phenylcyclopropane or cyclopropylbenzene

Ph 1,3,5-triphenylbenzene

CH2Br

NO2

OH CH2 CH2OH

benzylbromide

m-nitrobenzyl alcohol

o-benzylphenol or 2-benzylphenol

11 Reactions of Benzene
The most common reactions of aromatic compounds are electrophilic aromatic substitutions, i.e. the electrophile susbtitute one of the H atoms in the ring.

H H H H H H Y + an electrophile H H

H Y H H + H

12 Reactions of Benzene
General mechanism:

B H + Y slow Y H Y H Y fast + HB Y

Halogenation of Benzene
Bromination
+ Br Br2 FeBr3

13

Mechanism:
Br Br + FeBr3 Br Br FeBr3 better electrophile B H Br
+ HB

Br

+ Br

Br FeBr3 + FeBr4

Chlorination: Same mechanism as above.

Cl + Cl2 FeCl3

Halogenation of Benzene

14

I + I2 FeI3 too slow to be practical

F + F2 FeF3 too vigorous difficult to control

Iodination and fluorination of benzene can be achieved by using diazonium salt synthesis. REFER TO SLIDE 38

Nitration of Benzene
NO2 + HNO3 H2SO4 + H2O

15

Mechanism:

HO

NO2

OSO3H

HO H

NO2

NO2

H2O

nitronium ion

B H NO2 + NO2 + HB NO2

Sulfonation of Benzene
SO3H + H2SO4 + H2O

16

Mechanism:

HO

SO3H

OSO3H

HO H

SO3H

SO3H + sulfonium ion

H2O

B H SO3H + SO3H + HB SO3H

Friedel-Crafts Acylation of Benzene

O O + R Cl AlCl3 R + HCl

17

Mechanism:
O R Cl + AlCl3 R C O acylium ion + AlCl4

an acyl chloride

B H R + R C O O + HB
O O + H3C Cl AlCl3 CH3 + HCl

O R

Example

Friedel-Crafts Alkylation of Benzene

R + RCl AlCl3 + HCl

18

Mechanism:
R + Cl AlCl3 R + AlCl4 a carbocation

an alkyl halide

B H R + R + HB R

Example
+ CH3CH2Cl AlCl3 CH2CH3 + HCl

Alkylation of Benzene by an alkene

CH3 + CH3CH CHCH3 HF CH2CH3

19

Mechanism:
CH3CH CHCH3 H F CH3CH CH2CH3

CH3 CH2CH3 CH3CH CH2CH3 H F

CH3 CH2CH3

Chemical changes on some benzene substituents

Clemenson reduction O CH3 + Zn-Hg/ HCl CH2CH3 H2,Pd/C NH2-NH2 OHWolfkishner
H2 NO2 Pd/C NH2

20

OR
1. SnCl2/ HCl 2. NaOH/H2O

SO3H

O-Na+

OH

NaOH

200 oC

H+

Chemical changes on some benzene substituents

CH3 H2CrO4 heat CH3 CH2CH3 H2CrO4 heat CH2CH2CH3 CH3 CH3 H2CrO4 heat COOH COOH

21

COOH

The alkyl side chain will be oxidised to the carboxylic Group (COOH) regardless of the alkyl chain length.

Chemical changes on some benzene substituents

22

CH3 CH CH3 3 H2CrO4 heat No reaction

If there are no benzylic Hs then the oxidation reaction does not take place. This is because the first step of the oxidation reaction involves the removal of benzylic H.

Substituents effects on reactivity

23

Substituents not only affect the position of substitution, they also affect the rate of substitution. 1. When a monosusbstituted benzene undergoes eletrophilic aromatic substitution reaction there are three possible isomeric products; I. e. o, m- and p-. The three products are formed depending on the nature of the substituents already present on the benzene ring.

2. Some susbtituents make the aromatic ring more reactive than benzene, while some make the ring less reactive than benzene.

Substituents effects on reactivity

24

All activating substituents are able to donate electrons to the benzene ring, thereby stabilizing the carbocation intermediate. Aromatic rings with electron donating groups are more reactive toward electrophiles than benzene. All deactivating groups withdraw electrons from the aromatic ring, thereby destabilizing the carbocation intermediate, therefore, aromatic rings with electron withdrawing groups are less reactive toward electrophilic aromatic substitution reactions than benzene. Substituents withdraw or donate electrons in two ways: 1. By inductive effect 2. By resonance effect

Substituents effects on reactivity

Inductive Effects:

25

-are due to the intrinsic electronegativity of atoms and to bond polarity in functional groups. Atoms/groups withdraw/donate electrons through the bonds, e.g. halogens: F, Cl, Br, I, whereas carbonyl, cyano and nitro groups inductively withdraw electrons because of polarity of the bonds. Alkyl groups donate electrons through inductive effect. Resonance effects: -Operate by withdrawing or donating electrons through bonds, by overlap of a p orbital on the substituent with a p orbital on the aromatic ring. E.g carbonyl, cyano and nitro groups withdraw electrons by resonance effects.

Substituents effects on reactivity

O N O O N O O N O O N

26

NB: Effect felt most strongly at o- and p- positions

Conversely, hydroxyl, methoxyl and amino substituents activate the aromatic ring by resonance effects. The electrons flow from the substituent to the aromatic ring, thereby stabilizing the carbocation intermediate.
R O R O R O R O

NB: Effect felt most strongly at o- and p- positions

Orientation: Ortho-Para directors

27

In addition to affecting the reactivity of the aromatic ring, substituents can influence the position of further electrophilic aromatic susbstitution. Some groups show strong ortho-para directing effect, for example alkyl, hydroxyl, methoxyl and amino susbstituents, whereas others show strong meta-directing effect; e. g.cyano, nitro, carbonyl etc.
O-p directors activate the aromatic ring at all positions, its just that o- and p- positions are acivated more than the m- position. Example: nitration of toluene gives three isomeric products in the ratios shown, WHY?

CH3 HNO3 H2SO4 rt

CH3 NO2

CH3

CH3

NO2 63% 3% NO2 34%

Orientation: Ortho-Para directors

28

For ortho and para positions, the positive charge is placed directly on the C atom carrying the methyl group, i.e. 3 carbocation, the most stabilized carbocation intermediate, hence, o- and p- intermediates are lower in energy than the m- intermediate. No such structure is possible for the mcarbocation intermediate.

Orientation: Ortho-Para directing activators

29

OH and NH2 groups stabilize the carbocation intermediate through resonance electron donating effect which is more pronounced at o- and p- positions.

Orientation: Ortho-Para directing deactivators

30

Halogens deactivate the aromatic ring due their strong electron withdrawing inductive effect. The o- and p- positions are deactivated less than the m- position. How do they o- and p- direct? Halogens also have electron donating resonance effect, because they have filled p-orbitals (lone pairs) which can overlap with the p orbital of the aromatic ring thereby stabilizing the carbocation intermediate. The effect is most felt at the o- and p-positions.

Orientation: Meta directing deactivators

31

All positions in the aromatic ring will be deactivated, but the effect is most felt at the o- and p- positions.

For o- and p- positions, the positive charge is placed directly on the C atom carrying the deactiavting group, hence o- and p- products formation is disfavoured.

Synthesis of disubstituted benzene derivatives

What are the products of the following reactions?

32

CH2CH2CH3

Br

a.

HNO3 H2SO4 rt O H HNO3 H2SO4 rt

b.

HNO3 H2SO4 rt SO3H

c.

d.

HNO3 H2SO4 rt

COOH

e.

HNO3 H2SO4 rt

f.

HNO3 H2SO4 rt

Synthesis of disubstituted benzene derivatives

How would you synthesize the following compounds starting with benzene?

33

NO2

a.
Cl NO2

b.
Cl CH2CH3

c.

SO3H

Synthesis of disubstituted benzene derivatives

34

The nitroso group, -N=O, is one of the very few nonhalogens that is o- and p-directing deactivating group. Draw resonance structures of intermediates in o, m and p electrophilic attack on nitrosobenezene and explain why o and p attack intermediates are favoured over the the intermediate from meta attack.
O

N HNO3 H2SO4 rt

Synthesis of disubstituted benzene derivatives

35

Using benzene or toluene as the only aromatic organic starting material, devise the synthesis for each of the following:

NO2 a. b.

CH2CH3

Br CH3

NO2 CO2H

c. SO3H

d.

Diazotization reaction and its Uses

Primary aromatic amines react with nitrous acid (HONO) to give a stable arenediazonium salts.

36

NH2

nitrous acid HONO NaNO2/ HCl 0-5

oC

N Cl

+ diazonium salt

2 H2O

Arenediazonium salts are useful in synthesis because the diazonio group (N2+ ) can be replaced by nucleophiles.

Diazotization reaction and its Uses

37

Diazotization reaction and its Uses

Aryldiazonium ions react with strongly activated aromatic rings to give azo compounds. All azo compounds are coloured.

38

N N

OH

OH

N N

OH

p-hydroxyazobenzene yellow leaflets

Problem: How would you synthesize methyl orange from p-aminobenzenesulfonic

acid and N,N-dimethylaniline?

H3C N H3C N N SO3-Na+

Methyl orange