AROMATICITY

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AROMATICITY

Dr. Raju P. Kagne,


M.Sc. Ph.D., NET (JRF), SET, GATE
Willingdon College, Sangli
Definition

The term aromatic was originated from the word ‘aroma’ means
characteristic odour.

Ancient time benzene and compounds having benzene like


distinctive smell are called as aromatic compounds
Huckel rule of aromaticity
The characteristics of the aromatic compounds are as follows.
The molecule must be
• cyclic
• planar
• Fully conjugated with uninterrupted cloud of electrons
• It should posses (4n+2) electrons i.e. odd number of electron
pairs

Where ‘n’ is an integer


n= 0,1,2,3, 4………………
Pictorial representation of delocalization in benzene

The characteristics of the antiaromatic compounds are as follows.


The molecule must be cyclic, planar, conjugated with uninterrupted cloud of electrons
and posses (4n) electrons i.e. even number of electron pairs.
Where ‘n’ is an
integer
n= 0,1,2,3,
4…………

In non aromatic compounds are usually non-planar, conjugation of electron cloud is


not possible.

The stability order is:


Aromatic compound > non aromatic > antiaromatic
Three membered ring compounds

Cyclopropene
Cyclic, planar, 2 Pi electrons (n=0); delocalization due to SP3 methylene carbon
Nonaromatic

Cyclopropenyl cation
Cyclic, planar, 2 Pi electrons (n=0); delocalization is possible through the empty
'P'orbital
Aromatic

Resonance in cyclopropenyl cation Resonance Hybrid

Cyclopropenyl anion
4 electron (even number of pairs; 4n, n=1)
Antiaromatic; not stable
Four membered ring compounds

Cyclobutadiene

Cyclic, planar, continuous delocalization of Pi electrons, posses 4n Pi electrons


Antiaromatic

Cyclobutadienyl dication
Cyclic, planar, continuous delocalization of Pi electrons, posses (4n+2) Pi electrons
Aromatic

Being antiaromatic cyclobutadiene is unstable compared to cyclobutadienyl dication as it is aromatic


Five membered ring compounds

Cyclopentadiene
Cyclic, planar, posses 4n Pi electrons, delocalization of electrons interrupted
by SP3 hybridized carbon
Non aromatic

Cyclopentadienyl cation
Cyclic, planar, continuous delocalization of electrons, posses 4n Pi electrons
Antiaromatic

Cyclopentadienyl anion
Cyclic, planar, continuous delocalization of electrons, posses (4n+2) Pi
electrons
Aromatic
Seven membered ring compounds

Cycloheptatriene
Cyclic, planar, posses (4n+2) Pi electrons, no continuous
delocalization Pi electrons possible
Nonaromatic

Cycloheptatrienyl cation
Cyclic, planar, posses (4n+2) Pi electrons, continuous delocalization
Pi electrons possible
Aromatic

Cycloheptatrienyl anion
Cyclic, planar, posses (4n) Pi electrons, continuous delocalization Pi
electrons possible
Antiaromatic
Eight membered ring compounds

Cyclooctateraene is a 8 Pi electron system, completely planar molecule is antiaromatic.


The bond angle for a planar structure is 135 0 which can produce strain in a planar system
involving SP2 carbons. The molecule is boat shaped and nonaromatic.
Aromaticity in higher annulenes

In 10 annulenes steric interaction observed between hydrogens at C-1 and C-6


positions. The planar structure requires bond angle of 1440 which is too large
to accommodate in SP2 framework
[10]- annulene Nonaromatic

12 annulenes is cyclic , planar, continuous delocalisation of 4n pi electrons . It is


not stable above -500C
Antiaromatic

[12]- annulene

12 annulenes dianion is cyclic , planar, continuous delocalisation of (4n+2)


pi electrons . It is stable at 300C

Aromatic

[12]- annulene dianion


Aromaticity in higher annulenes

In 14 annulenes, planar structure is aromatic as it obeys Huckel rule inovlving the


delocalization of (4n+2) pi electrons. The bond lenths are in the range f rom 1.35-
1.47 A0

14 annulene

[16] annulene is nonplanar and shows signif icant bond alteration like polyene,
nonaroamtic in nature. Its dianion shows aromatic character

16 annulene

[18] annulene is planar, cavity is suf f iciently large and hence shows less
steric interactions of internal hydrogens. It shows continuous delocalization
of (4n+2) pi electrons and aromatic nature.

18 annulene
Homoaromaticity

In certain cases a stabilized conjugated system (4n+2) can be formed by


bypassing one saturated atom, that lead to homoaromaticity. Due to the poorer
orbital overlap the net stabilization is low compared with true aromatic
systems. The best example to demonstrate the homoaromaticity is the
formation of cyclooctatrienyl cation i.e. homotropylium ion from the reaction
of cyclooctateraene with concentrated sulphuric acid. The delocalization is
represented pictorially as below.

H H
H

H
Aromaticity in fused rings

Naphthalene Phenanthrene Crysene


10 pi electrons 14 pi electrons 18 pi electrons

The criterion used for the monocyclic hydrocarbon can also be applied
for the polycyclic hydrocarbons. The resonance energy per pi electron
decreases with increase in aromatic ring. Larger polynuclear
hydrocarbons have a tendency to undergo addition reaction. Example is
Diel’s Alder reaction
H Br
Br2

H Br

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