AROMATIC HYDROCARBONS

the molecular structure incorporates one or more planar sets of six

carbon atoms that are connected by delocalised electrons numbering
the same as if they consisted of alternating single and double covalent
bonds.
The term 'aromatic‘ was derived from the fact that many of the
compounds have a sweet scent and was assigned before the physical
mechanism determining aromaticity was discovered.
The configuration of six carbon atoms in aromatic compounds is
known as a benzene ring, after the simplest possible such
hydrocarbon, benzene.
can be monocyclic or polycyclic.
Some non-benzene-based compounds called heteroarenes also
exist.
(abbreviated as AH) or arene
Aromatic Compounds, large group of organic chemical
compounds that usually contain closed rings of carbon
atoms. Some aromatic rings, however, may also contain
an oxygen or a nitrogen atom. The term was originally
restricted to the coal tar product benzene and its
derivatives, but it now includes about half of all organic
compounds, the remaining half being classified as
aliphatic compounds.
Important aromatic compounds include all hormones
and vitamins except vitamin C; virtually all
flavorings, perfumes, and organic dyes, synthetic
and natural; those alkaloids that are not alicyclic
(aliphatic bases such as putrescine are sometimes
incorrectly classified as alkaloids); some substances
of military importance, such as TNT and tear gas;
many drugs; and a wide variety of other substances.
 BENZENE
C6H6, is the simplest AH. It is sometimes abbreviated Ph–H.
was recognized as the first aromatic hydrocarbon, with the nature of its
bonding first being recognized by Friedrich August Kekulé von
Stradonitz in the 19th century.
Each carbon atom in the hexagonal cycle has four electrons to share.
One goes to the hydrogen atom, and one each to the two neighboring
carbons. This leaves one to share with one of its two neighboring
carbon atoms, which is why the benzene molecule is drawn with
alternating single and double bonds around the hexagon.
 BENZENE
Many chemists draw a circle around the inside of the ring to show
six electrons floating around in delocalized molecular orbitals the
size of the ring itself. This also accurately represents the
equivalent nature of the six bonds all of bond order ~1.5. This
equivalency is well explained by resonance forms. The electrons
float above and below the ring, and the electromagnetic fields they
generate keep the ring flat.
 GENERAL PROPERTIES OF
BENZENE
 Display aromaticity. Benzene is an aromatic hydrocarbon and
the second [n]-annulene ([6]-annulene), a cyclic hydrocarbon
with a continuous pi bond.
 The Carbon-Hydrogen ratio is very large.
 They undergo electrophilic substitution reactions and
nucleophilic aromatic substitutions. Resist addition reactions.
 Benzene is a colorless and inflammable liquid with a sweet
smell and a relatively high melting point.
 They burn with a sooty yellow flame because of the high
carbon-hydrogen ratio.
 Heats of hydrogenation and combustion are far lower than they
should be.
 From X-ray, all of the C—C bonds in benzene are the same
length and intermediate in length between single and double
bonds.
 It is carcinogenic
 Its use as an additive in gasoline is now limited, but it is an
important industrial solvent and precursor in the production of
drugs, plastics, synthetic rubber, and dyes.
 Benzene is a natural constituent of crude oil, but it is usually
synthesized from other compounds present in petroleum.
 Aromatic compounds were being extracted from coal tar as
early as the 1830s. As a result, many of these compounds were
given common names that are still in use today.
 BENZENE DERIVATIVES
Benzene derivatives have form one to six substituents attached
to the central benzene core. Benzene is the parent substance of
the aromatic compounds, a large and important group of organic
compounds.

methylbenzene hydroxybenzene methoxybenzene aminobenzene carboxybenzene

 NOMENCLATURE
Mono-Substituted Benzene Derivatives
If the substituent contains six carbons or fewer, then the
compound is named as a substituted benzene compound.
If the substituent contains seven or more carbons, then the
compound is named as a phenyl- or benzyl- substituted alkane:
Common Names
Aromatic compounds were being extracted from coal tar as early
as the 1830s. As a result, many of these compounds were given
common names that are still in use today. A few of these
compounds are shown below.
Di-Substituted Benzene Derivatives
There are three ways in which a pair of substituents can be
placed on an aromatic ring. In the ortho (o) isomer, the
substituents are in adjacent positions on the ring. In the meta (m)
isomer, they are separated by one carbon atom. In the para (p)
isomer, they are on opposite ends of the ring. Disubstituted
benzenes are named using ortho-, meta- and para- to describe
the substitution pattern (1,2 1,3 and 1,4 respectively) or simply by
numbering the substituents.

Ortho (o) Meta (m) Para (p)

1,2- 1,3- 1,4-
 1-ethyl, 2-iodobenzene 1-bromo, 3-nitrobenzene 1-chloro, 4-iodobenzene
o-ethyliodobenzene m-bromonitrobenzene p-chloroiodobenzene
Many di-substituted benzenes also have common names.

hydroquinone resorcinol o-toluidine o-xylene p-cresol

Many of these common names are acceptable "parents" with
regard to nomenclature. When one of these is used as the
parent chain, the substituent is position #1, by definition.

o-bromotoluene m-chlorophenol p-nitroaniline

Poly-Substituted Benzene Derivatives
Benzene derivatives with more than two substituents are
named by numbering the position of each substituent. List the
substituents alphabetically, with the numbers having the lowest
possible sum. Substituents are numbered to give the lowest
possible number sequence at the first point of difference, assigning
priorities alphabetically if there is a "tie".
 5-bromo-2-nitrotoluene 4-bromo-2-chloro-phenol 2-ethyl-4-iodoaniline

4-bromo-1,2-dimethylbenzene

2-chloro-1-ethyl-4-nitrobenzene 5-chloro-3-fluoro-2-nitro-benzoic acid

Many benzene derivatives are also components of drugs.

Amphetamine methamphetamine acetylsalicylic acid

“speed” “aspirin”

picric acid paracetamol salicylic acid phenacetin

 Substitution Reactions of Benzene
Reaction Type Equation

Halogenation: C6H6 +   Cl2 & heat  C6H5Cl   +   HCl

    FeCl3 catalyst Chlorobenzene
Nitration: C6H6 +   HNO3 & heat  C6H5NO2   +   H2O
    H2SO4 catalyst Nitrobenzene

Sulfonation: C6H6 +   H2SO4 + SO3  C6H5SO3H   +   H2O

    & heat Benzenesulfonic acid
Alkylation: C6H6 +   R-Cl & heat  C6H5-R   +   HCl
Friedel-Crafts     AlCl3 catalyst An Arene
Acylation: C6H6 +   RCOCl & heat  C6H5COR   +   HCl
Friedel-Crafts     AlCl3 catalyst An Aryl Ketone
 POLYCYCLIC AROMATIC HYDROCARBONS
 Polycyclic aromatic hydrocarbons (PAHs) are chemical
compounds that consist of fused aromatic rings and do not
contain heteroatoms or carry substituents.
 PAHs occur in oil, coal, and tar deposits, and are produced as
byproducts of fuel burning (whether fossil fuel or biomass).
 As a pollutant, they are of concern because some compounds
have been identified as carcinogenic, mutagenic, and
teratogenic.
 PAHs are also found in cooked foods, such as grilled meats.
 Polycyclic aromatic hydrocarbons are lipophilic, meaning they
mix more easily with oil than water.
 PAHs are one of the most widespread organic pollutants.
 In addition to their presence in fossil fuels they are also formed
by incomplete combustion of carbon-containing fuels such as
wood, coal, diesel, fat, tobacco, or incense.
 PAH compounds

Naphthalene Pentacene

Benzo[a]pyrene
Coronene
Anthracene
Chrysene
Pyrene

Phenanthrene

Ovalene
Naphthacene Triphenylene Corannulene
Naphthalene (C10H8 constituent of mothballs), consisting of two
coplanar six-membered rings sharing an edge, is another aromatic
hydrocarbon.
PAHs known for their carcinogenic, mutagenic and teratogenic
properties are benz[a]anthracene and chrysene ,
benzo[b]fluoranthene, benzo[j]fluoranthene, benzo[k]fluoranthene,
benzo[a]pyrene, benzo[ghi]perylene, coronene,
dibenz[a,h]anthracene (C20H14), indeno[1,2,3-cd]pyrene (C22H12) and
ovalene
Benzo[a]pyrene is notable for being the first chemical carcinogen to
be discovered and is one of many carcinogens is found in coal tar,
in automobile exhaust fumes (especially from diesel engines),
tobacco smoke, wood smoke, and in charbroiled food. Recent
studies have revealed that levels of benzo[a]pyrene in burnt toast
are significantly higher than once thought, although it is unproven
whether burnt toast is itself carcinogenic.
 HETEROCYCLIC COMPOUNDS
Heterocyclic compounds are organic compounds containing at
least one atom of carbon, and at least one element other than
carbon, such as sulfur, oxygen or nitrogen within a ring structure.
The hetero- part of the name means that more than one kind of
element is included within the ring and -cyclic, of course, indicates
that there is at least one ring present in the compound.
These structures may comprise either simple aromatic rings or
non-aromatic rings. Some examples are pyridine (C 5H5N) and
pyrimidine (C4H4N2).

pyridine pyrimidine uracyl

HETEROCYCLIC POLYCYCLIC COMPOUNDS

thymine adenine guanine

caffeine
cytosine