POC-II UNIT 1

1. 1
UNIT I: Benzene and its
derivatives
1. Substituent's
2. Effect of substituent's on reactivity and
orientation of mono substituted benzene
compounds towards electrophilic
substitution reaction

2. 2

3. 3

4. 4

5. Substitution Reactions of Benzene Derivatives
Two related features must be considered:
I. The first is the relative reactivity of the compound compared with benzene itself.
Experiments have shown that substituent's on a benzene ring can influence reactivity
in a profound manner.
For example, a hydroxy or methoxy substituent increases the rate of electrophilic
substitution about ten thousand fold, as illustrated by the case of anisole in the virtual
demonstration. In contrast, a nitro substituent decreases the ring's reactivity by roughly
a million. This activation or deactivation of the benzene ring toward electrophilic
substitution may be correlated with the electron donating or electron withdrawing
influence of the substituent's, as measured by molecular dipole moments.
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6. 6

7. The second effect is the result of conjugation of a substituent function with the aromatic ring This
conjugative interaction facilitates electron pair donation or withdrawal, to or from the benzene ring, in
a manner different from the inductive shift.
If the atom bonded to the ring has one or more non-bonding valence shell electron pairs, as do
nitrogen, oxygen and the halogens, electrons may flow into the aromatic ring by p-π conjugation
(resonance), as in the middle diagram.
Finally, polar double and triple bonds conjugated with the benzene ring may withdraw electrons, as in
the right-hand diagram.
The first is the inductive effect of the substituent.
Most elements other than metals and carbon have a
significantly greater electronegativity than hydrogen.
Consequently, substituents in which nitrogen, oxygen
and halogen atoms form sigma-bonds to the aromatic
ring exert an inductive electron withdrawal, which
deactivates (left-hand diagram below).
The influence a substituent exerts on the reactivity of a benzene
ring may be explained by the interaction of two effects:
“Sigma” (σ) donors and
acceptors (otherwise
known as “inductive
effects”)
Pi ( π) Donors and
Acceptors
(otherwise known
as “Resonance”)
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12. II. The second factor that becomes important in reactions of substituted benzenes concerns
the site at which electrophilic substitution occurs.
Since a mono-substituted benzene ring has two equivalent ortho-sites, two equivalent meta-
sites and a unique para-site, three possible constitutional isomers may be formed in such a
substitution.
If reaction occurs equally well at all available sites, the expected statistical mixture of
isomeric products would be 40% ortho, 40% meta and 20% para.
Again we find that the nature of the substituent influences this product ratio in a dramatic
fashion. Bromination of methoxybenzene (anisole) is very fast and gives mainly the para-
bromo isomer, accompanied by 10% of the ortho-isomer and only a trace of the meta-
isomer.
Bromination of nitrobenzene requires strong heating and produces the meta-bromo isomer as
the chief product.
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14. 14
HAAAT
NCCC=S
N

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21. 21
Attack of the electrophile at C-3 results in a carbocation which can be
delocalized via resonance to C2, C4, and C6. However, there’s no way to “move”
the carbocation to C1, which means that there’s no reasonable resonance form
where all atoms have full octets.
This makes the meta- carbocation intermediate much less stable than the ortho-
carbocation intermediate.

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24. 24
Why are halogens ortho- para-
directors?