PHYSICAL AND CHEMICAL PRINCIPLES 14

ORGANIC AND BIOCHEMISTRY

BENZENE AND AROMATIC COMPOUNDS

A. STRUCTURE OF BENZENE

 Benzene contains a six-membered ring and three additional

degrees of unsaturation. Benzene is planar and all carbon-carbon
bonds are equal.
 The six adjacent 𝑝 orbitals overlap, thus the electrons over the six
carbon atoms are delocalized. Image source: http://wps.prenhall.com/wps/media/
objects/724/741576/chapter_07.html
B. NOMENCLATURE

 The table below contains some aromatic compounds and their common names. For disubstituted
benzenes, the prefixes ortho-, meta- and para- are used.

Table 3.10. Aromatic compounds and their common names.

toluene styrene naphthalene phenol

benzaldehyde acetophenone benzoic acid aniline

C. CRITERIA FOR AROMATICITY

There are four structural features that a molecule must exhibit to be aromatic:

 Cyclic - each 𝑝 orbital must overlap with 𝑝 orbitals on two adjacent atoms.
 Planar - all adjacent 𝑝 orbitals must be aligned so that the π electron density can be delocalized.
 Completely conjugated - aromatic compounds must have a 𝑝 orbital on every atom.
 Contain 𝟒𝒏 + 𝟐 𝝅 electrons - aromatic compounds must follow Hϋckel’s rule.

pyrrole furan
6 𝜋 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 6 𝜋 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠

Image source: http://wps.prenhall.com/wps/media/objects/724/741576/chapter_15.html

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 PHYSICAL AND CHEMICAL PRINCIPLES 15
ORGANIC AND BIOCHEMISTRY

D. ELECTROPHILIC AROMATIC SUBSTITUTION

 Since the benzene ring has six π electrons satisfying Hückel’s rule, it is especially stable. Reactions that
keep the aromatic ring intact are therefore favored. The loosely held π electrons make the benzene ring
electron rich, and so it reacts with electrophiles. This reaction of benzene is called electrophilic
aromatic substitution (EAS) where a hydrogen atom is replaced by an electrophile (Smith, 2011).

 Moreover, substituents on the benzene ring affect both the reactivity of the ring toward further
substitution and the orientation of that substitution. Groups can be classified as ortho- and para-directing
activators, ortho- and para-directing deactivators, or meta-directing deactivators (McMurry, 2012).

Table 3.11. Electrophilic Aromatic Substitution reactions of benzene and its derivatives.

EAS Reaction General Reaction Features of the Reaction

 X = Cl or Br
 FeX3 is a Lewis acid catalyst making
1. Halogenation
X2 more electrophilic by polarizing the
X−X bond

 electrophile = +NO2, nitronium ion

 nitration is important in the laboratory
2. Nitration
because nitrobenzenes can be
reduced to arylamines

 electrophile = +SO3H
 reversible reaction: sulfonation is
3. Sulfonation favored in strong acid while
desulfonation is favored in hot, dilute
aqueous acid

 AlCl3 is a Lewis acid catalyst making

RX more electrophilic by polarizing
4. Friedel-Crafts the R−X bond
Alkylation  carbocation rearrangements can
occur yielding a mixture of products
 polyalkylation often occurs

Classification of substituent effects in electrophilic aromatic substitution (McMurry, 2012)

No part of this review guide may be reproduced without the written permission of
QUANTUM REVIEW CENTER, Los Baños, Laguna.