Aromatic
Aromatic
Aromatic
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.
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.
N pyridine
N H pyrrole
O furan
S thiopene
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
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
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
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
Halogenation of Benzene
14
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
Sulfonation of Benzene
SO3H + H2SO4 + H2O
16
Mechanism:
HO
SO3H
OSO3H
HO H
SO3H
H2O
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
18
Mechanism:
R + Cl AlCl3 R + AlCl4 a carbocation
an alkyl halide
B H R + R + HB R
Example
+ CH3CH2Cl AlCl3 CH2CH3 + HCl
19
Mechanism:
CH3CH CHCH3 H F CH3CH CH2CH3
CH3 CH2CH3
20
OR
1. SnCl2/ HCl 2. NaOH/H2O
SO3H
O-Na+
OH
NaOH
200 oC
H+
21
COOH
The alkyl side chain will be oxidised to the carboxylic Group (COOH) regardless of the alkyl chain length.
22
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.
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.
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
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.
26
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 NO2
CH3
CH3
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.
29
OH and NH2 groups stabilize the carbocation intermediate through resonance electron donating effect which is more pronounced at o- and p- positions.
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.
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.
32
CH2CH2CH3
Br
a.
b.
c.
d.
HNO3 H2SO4 rt
COOH
e.
HNO3 H2SO4 rt
f.
HNO3 H2SO4 rt
33
NO2
a.
Cl NO2
b.
Cl CH2CH3
c.
SO3H
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
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.
36
NH2
N Cl
+ diazonium salt
2 H2O
Arenediazonium salts are useful in synthesis because the diazonio group (N2+ ) can be replaced by nucleophiles.
37
38
N N
OH
OH
N N
OH
Methyl orange