Fundamental Chemistry

Aromatic Compounds
At the end of this chapter, you should be able to:
• Name benzene derivatives
• Use Huckel's rule to determine aromaticity
• Describe electrophilic substitution mechanism for aromatic
compounds
Nomenclature of Benzene
Derivatives
❖ Naming monosubstituted benzenes
● In many simple compounds, benzene is
the parent name and the substituent is
simply indicated by a prefix
● For other simple and common
compounds, the substituent and the
benzene ring taken together may form a
commonly accepted parent name
❖ Naming disubstituted benzenes
● When two substituents are present, their
relative positions are indicated by the
prefixes ortho-, meta-, and para-
(abbreviated o-, m-, and p-) or by the
use of numbers
● Other examples
● Benzyl is an alternative name for the
phenylmethyl group. It is sometimes
abbreviated Bn
Thermodynamic Stability of Benzene

p-electrons above
and below ring

● Planar structure
● All carbons sp2 hybridized
 Hückel’s aromatic rules
✓ Be cyclic
✓ have one p orbital on each atom in the ring
✓ be planar or nearly planar
✓ have (4n + 2)π electrons (n = 0, 1, 2, etc.), hence
2, 6, 10, 14 etc

Planar rings containing (4n+2) π e (2, 6,10, 14,..) are aromatic

❖ All these (4n + 2)p, planar
annulenes are aromatic

[10]naphthalene
❖ (4n)p non-planar annulenes are
antiaromatic
Chemistry Connection
Harmful Arenes
Chimney sweepers during 17th – 18th had abnormally high rates of
testicular cancer – due to _______________
polycyclic hydrocarbons in chimney soot

-binds to DNA
Heterocyclic Compounds

❖ Cyclic compounds that include an

element other than carbon are called
heterocyclic compounds
Are these compounds aromatic?

furan thiophene
pyridine pyrrol

pyridine pyrrol
Aromatic heterocycles
Is the molecule below aromatic, anti-
aromatic or non-aromatic?

H
N
N N
❖ Examples of useful heterocyclic
aromatic compounds
Quinine- treatment of
Campthothecin analogue -
malaria
treatment of stomach ulcers

Plasmodium falciparum
Camptotheca acuminata
❖ Benzene undergoes substitution but not
addition
Reactions of Benzene
Electrophilic Aromatic
Substitution Reactions
❖ Overall reaction
A General Mechanism for Electrophilic
Aromatic Substitution
● Step 1
❖ Mechanism
● Step 2
1. Halogenation of Benzene
❖ Examples
2. Nitration of Benzene


❖ Electrophile in this case is NO2
(nitronium ion)
3. Sulfonation of Benzene
4. Friedel–Crafts Alkylation


❖ Electrophile in this case is R
o o
● R = 2 or 3
4. Friedel–Crafts Acylation

❖ Acyl group:


❖ Electrophile in this case is R–C≡O
(acylium ion)
❖ Acid chlorides (or acyl chlorides)

● Can be prepared by
Substituents Can Affect Both the
Reactivity of the Ring and the
Orientation of the Incoming Group

❖ Two questions we would like to address

here
● Reactivity
● Regiochemistry
 ● Reactivity

faster or
slower than

Y = EDG (electron-donating group) or

EWG (electron-withdrawing group)
Z donates Y withdraws
electrons electrons

The ring is more The ring is electron

electron rich and poor and reacts
reacts faster with more slowly with
an electrophile an electrophile
● Reactivity
Since electrophilic aromatic
substitution is electrophilic in nature,
and the r.d.s. is the attack of an

electrophile (E ) with the benzene p-
electrons, an increase in e density
in the benzene ring will increase the
reactivity of the aromatic ring
towards attack of an electrophile, and
result in a faster reaction
● Reactivity

On the other hand, decrease in e

density in the benzene ring will
decrease the reactivity of the
aromatic ring towards the attack of
an electrophile, and result in a slower
reaction
● Reactivity

EDG (electron-donating group)

on benzene ring
❑ Increases electron density in
the benzene ring
❑ More reactive towards
electrophilic aromatic
substitution
● Reactivity

EWG (electron-withdrawing
group) on benzene ring
❑ Decreases electron density in
the benzene ring
❑ Less reactive towards
electrophilic aromatic
substitution
● Reactivity towards electrophilic
aromatic substitution
● Regiochemistry

Statistical mixture of o-, m-, p-

products or any preference?
❖ Regiochemistry: directing effect

● General aspects
Either o-, p- directing or m-
directing
Rate-determining-step is p-
electrons on the benzene ring

attacking an electrophile (E )
❖ If you look at these
resonance structures
closely, you will notice
that for ortho- or para-
substitution, each has
one resonance form with
the positive charge
attached to the carbon
that directly attached to
the substituent Y (o-I
and p-II)
❖ When Y = EWG, these resonance forms
(o-I and p-II) are highly unstable and
unfavorable to form, thus not favoring
the formation of o- and p-
regioisomers, and m- product will form
preferentially
❖ On the other hand, if Y = EDG, these
resonance forms (o-I and p-II) are
extra-stable (due to positive mesomeric
effect or positive inductive effect of Y)
and favorable to form, thus favoring
the formation of o- and p- regioisomers
❖ Classification of different substituents
Y (EDG)
–NH2, –NR2 Strongly o-, p-
-
–OH, –O activating directing

–NHCOR Moderately o-, p-

–OR activating directing

–R (alkyl) Weakly o-, p-

–Ph activating directing
–H NA NA
❖ Classification of different substituents
Y (EWG)

–Halide Weakly o-, p-

(F, Cl, Br, I) deactivating directing
–COOR, –COR,
Moderately m-
–CHO, –COOH,
deactivating directing
–SO3H, –CN
–CF3 , –CCl3 , Strongly m-
–NO2 , – NR3 deactivating directing
 EDG EWG
Weakly
Strongly –NH2, –NR2 –Halide
- deactivating
activating –OH, –O (F, Cl, Br, I)
–COOR, –COR,
–NHCOR
–CHO, –COOH,
–OR
–SO3H, –CN
–R (alkyl) –CF3 , –CCl3 ,
–Ph –NO2 , – NR3
Weakly Strongly
activating deactivating
Synthetic Applications
❖ CH3 group: ortho-, para-directing
❖ NO2 group: meta-directing
❖ If the order is reversed the wrong
regioisomer is given