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Benzene and its Derivatives

History of Benzene
Michael Faraday isolated a compound from coal gas
(1825) with the molecular formula C6H6
Although very unsaturated, the compound was quite
no reaction


Charles Mansfield isolated benzene from coal tar

in 1845.
Other compounds derived from coal tar also
showed reduced reactivity towards addition and
because of their smell were termed aromatic
Benzene in the middle of the 19th century was very
much a molecule of mystery.
1. What structure with six carbons could have 4
degrees of unsaturation?
2. Why does a molecule with so much
unsaturation not react like an alkene?

no reaction

H2 , 1 atm
no reaction

Some proposed structures for benzene that were wrong.

Note the formula for all of the compounds is C6H6.

Dewar Benzene


made in 1962

made in 1973


The mystery of the structure of benzene was

solved by August Kekul in 1872.


made in 1971

This structure, however, did not account for the unusual

chemical reactivity (or nonreactivity) of benzene.
That would come later with Erich Huckels ideas of

Structure of Benzene
The concepts of hybridization of atomic orbitals
and the theory of resonance, developed in the
1930s, provided the first adequate description of
benzenes structure.

The carbon framework; the six parallel 2p orbitals, each

with one electron, are shown uncombined.
Overlap of the six 2p orbitals forms a continuous pi
cloud, shown as one torus above the plane of the ring,
the other below it.

The carbon skeleton is a regular hexagon, with all CC-C and H-C-C bond angles 120.

We often represent benzene as a hybrid of two

equivalent Kekul structures.
Each Kekul structure makes an equal contribution to
the hybrid.
The C-C bonds are neither double nor single but
something in between (like a 1 bond).

Resonance energy: The difference in energy

between a resonance hybrid and its most stable
hypothetical contributing structure in which electrons
are localized on particular atoms and in particular

Polycyclic aromatic hydrocarbons (PAH)

Contain two or more fused aromatic rings.
Polycyclic aromatic hydrocarbons have
multiple resonance structures as well.
Many PAHs are carcinogenic.

Note the heat of hydrogenation for benzene is much

less than 3 times the heat of hydrogenation for
The difference is known as the resonance energy of

One way to estimate the resonance energy of benzene is

to compare the heats of hydrogenation of benzene and

Heats of hydrogenation for both cyclohexene and

benzene are negative (heat is liberated).

Resonance energies [kJ/mol and kcal/mol] for

benzene and several other polycyclic
aromatic hydrocarbons (PAH).

The criteria for aromaticity were recognized in the
early 1930s by Erich Hckel.
To be aromatic, a ring must:
1. have one occupied 2p orbital on each atom of the ring.
2. be planar or nearly planar, so that overlap of all 2p
orbitals of the ring is continuous or nearly continuous.
3. have 2, 6, 10, 14, 18, and so forth pi electrons in the
cyclic arrangement of 2p orbitals.

Benzene meets these criteria

Know the name and structure for

naphthalene, anthracene, phenanthrene.

It is cyclic, planar, has one 2p orbital on each atom of the

ring, and has 6 pi electrons (the aromatic sextet) in the
cyclic arrangement of its 2p orbitals.

Aromatic compounds are exceedingly stable because

the pi electrons are spread out.
The second mystery of benzene is solved!
The other polycyclic aromatic hydrocarbons are
aromatic as well.

Hexatriene is not aromatic because it is not cyclic.

Cycloheptatriene is not aromatic because its double
bonds are not alternating.
One of the carbons in the ring is an sp3 carbon rather than
an sp2 carbon.

Naphthalene is aromatic since every carbon is an sp2

carbon and it has 10 pi electrons (not 8 or 12).
Cyclooctatetraene has alternating double bonds, but
only 8 pi electrons (rather than 6 or 10).











Many different compounds are aromatic, including

heterocyclic compounds.
An example is pyridine C5H5N.
The nitrogen atom of pyridine is sp2 hybridized.
The unshared pair of electrons lies in an sp2 hybrid
orbital and is not a part of the six pi electrons of the
aromatic sextet.
Pyridine has a resonance energy of 32 kcal (134 kJ/mol),
slightly less than that of benzene.

Other heterocyclic aromatic compounds

Heterocyclic Aromatics
Heterocyclic compound: A compound that
contains one or more atoms other than carbon
(heteroatoms) in its ring (nitrogen, oxygen,
sulfur, etc).
Heterocyclic aromatic compound: A
heterocyclic compound whose ring is aromatic.
Pyridine and pyrimidine are heterocyclic analogs of
benzene; each is aromatic.

Other examples of aromatic heterocyclic

compounds are furan and pyrrole.
Note the difference in the lone pair of each
In furan, the lone pair is not part of the system.
In pyrrole, the lone pair is part of the system.

Consumer compounds that are aromatic

2,4-D (Weed-B-Gon)

(Lipitor) (anticholestrol drug)

Please commit these names and structures to memory

Dabigatran (anticoagulant)

CoQ10 - enzyme in cell organelles

(especially mitochondria) that assists
in ATP (energy) production

When benzene is considered to be the parent ring,
functional groups are indicated with prefixes.



As a branch, the benzene ring is known as a

phenyl branch.
The term benzyl is reserved for a benzene ring
with an additional carbon as a branch point.
The carbon at the branch point is called a benzylic
carbon and the hydrogens are benzylic hydrogens.

nitrobenzene ethoxybenzene fluorobenzene butylbenzene

Monosubstituted alkylbenzenes are named as

derivatives of benzene.
Many common names are retained.

Disubstituted benzenes
Locate substituents by lowest numbers or
Use the locators ortho (1,2-), meta (1,3-), and para

Where one group imparts a special name, name

the compound as a derivative of that molecule.

Know these derivatives as well as xylene.

Xylene = benzene + 2 methyl branches

The Benzylic Position

Polysubstituted benzenes
With three or more substituents, number the atoms of
the ring.
If one group imparts a special name, it becomes the
parent name and the group branches from carbon 1.
If no group imparts a special name, number to give
the smallest set of numbers, and list alphabetically.




benzyl bromide is
reactive to both
SN1 or SN2

does not react via
SN1 or SN2






unstable carbocation
no SN1

Nustable, delocalized carbocation

backside attack not possible
no SN2

backside attack possible

no SN2 and stablized by the
arene ring

Benzylic Oxidation
Benzene is unaffected by strong oxidizing
agents such as H2CrO4 and KMnO4.
The benzylic hydrogens are quite acidic.
An alkyl group with at least one hydrogen on the
benzylic carbon is oxidized to a carboxyl group (and
thus a benzoic acid).
Halogen and nitro substituents are unaffected by
these reagents.

Reactions of Benzene
The most characteristic reaction of aromatic
compounds is substitution at a ring carbon.

Electrophilic Aromatic Substitution

Electrophilic Aromatic Substitution (EAS): A
reaction in which an electrophile, E+, substitutes
for an H on an aromatic ring.

If there is more than one one-carbon branch,

each is oxidized to a -COOH group.

Terephthalic acid is one of the two monomers

required for the synthesis of poly(ethylene
terephthalate) (recycling code 1), a polymer that
can be fabricated into Dacron polyester fibers,
Mylar films as well as soda bottles.

Other functional groups that can be added to the

benzene ring is the sulfonyl group, and alkyl
group and an acyl group.

All EAS reactions occur by a three-step

Step 1: Generation of the electrophile.

Step 2: Reaction of an electrophile and a

nucleophile (pi bond) to form a new covalent bond.
In this section, well consider

several common types of electrophiles.

how each electrophile is generated.
the mechanism by which each electrophile replaces

Step 3: Base takes a proton away to

regenerate the aromatic ring.

Chlorination and Bromination

Step 1: Formation of the electrophile (a
chloronium ion).
Fe3+ (a Lewis acid) reacts with chlorine (a Lewis
base) to induce the formation of Cl+, the
chloronium ion.

Step 2: Reaction of the electrophile (the

chloronium ion and a nucleophile to form a
new covalent bond.

Step 3: Proton transfer to FeCl4 forms HCl,

regenerates the Lewis acid catalyst, and gives

The electrophile, NO2+, is generated in two steps.
Step 1: Add a proton (from a strong acid like sulfuric
acid) to nitric acid to make water as a leaving group.

Step 2: Water breaks off forming the nitronium ion, NO2+.

Finish reaction by having NO2+ use pi electrons to

create new bond and have proton transfer back
into solution.

The electrophile, HSO3+, is generated in two steps.
Step 1: Add a proton (one molecule of sulfuric acid
protonates another sulfuric acid) to make water as a
leaving group.

HSO3+ attacks pi electrons in aromatic ring to

create new bond.
Proton on ring is transferred back into solution.

benzenesulfonic acid
Step 2: Water breaks off forming the sulfonium ion,

Sulfonic acids are very acidic (like sulfuric acid).

The conjugate bases (sulfonates) are used in

Friedel-Crafts Alkylation
Friedel-Crafts alkylation forms a new C-C bond
between an aromatic ring and an alkyl group.

Step 2: Reaction of an electrophile (carbocation) and

a nucleophile (pi electrons) to form a new covalent

Step 1: Formation of an electrophile.

A Lewis acid (AlCl3) reacts with alkyl chloride to
form carbocation.

There are two major limitations on Friedel-Crafts

It is practical only with stable carbocations, such as 2
and 3 carbocations.
It fails on benzene rings bearing one or more of these
strongly electron-withdrawing groups (more in a little

Step 3: Take a proton away. Metal complex acts a

Lewis base to react with hydrogen ion (a Lewis acid)
to regenerate the aromatic ring.

Other methods to alkylate an aromatic ring

depend on alternative methods to create
Treating an alkene with a protic acid, most commonly
H2SO4 or H3PO4.

Friedel-Crafts Acylations
Treating an aromatic ring with an acid chloride in
the presence of AlCl3.
Acid (acyl) chloride: a derivative of a carboxylic acid
in which the -OH is replaced by a chlorine.

Treating an alcohol with H2SO4 or H3PO4.

Product is a ketone. (with aromatic ring on one

side of the carbonyl group)

Di- and Polysubstituted Benzenes

Step 1: Formation of the electrophile.

Existing groups on a benzene ring influence

further substitution in both orientation and rate.
Certain substituents direct a new substitution
preferentially toward the ortho-para positions, others
direct preferentially toward the meta positions.


Step 2: Reaction of an electrophile (acylium

ion) and a nucleophile (pi electrons) to form a
new covalent bond.

Certain substituents are activating (rxn goes faster)

toward further substitution, others are deactivating
(rxn goes slower) toward further substitution.

Step 3: Take a proton away. Proton transfer to

AlCl4 forms HCl, regenerates the Lewis acid
catalyst, and gives a ketone.

For ortho-para directors, ortho-para attack

forms a more stable cation than meta attack.

Theory of Directing Effects

The rate of electrophilic aromatic substitution

Also, ortho-para products are formed faster than meta


The rate of EAS is determined by the slowest step in

the reaction.
For almost every EAS, the rate-determining step is
attack of E+ on the aromatic ring to give a resonancestabilized cation intermediate.
The more stable this cation intermediate, the faster
the rate-determining step and the faster the overall

-OCH3 is ortho-para directing.

Note the resonance structures for ortho attack of

the methoxy group (which are almost the same
for para attack) are more stable than those from
meta attack.

The resonance structures for meta attack of the

methoxy group are less stable than those for
ortho/para attack.
These meta attack resonance structures are not
unstable, just less stable than those for ortho/para

The ortho (and para) resonance structures include a

quasi-tertiary carbocation that is converted an
oxonium ion that is formed from having a lone pair of
electrons on an atom that is adjacent to a ring. Thus
the positive charge is more delocalized and the cation
is more stable (than the corresponding meta cation).







Activating Directors

The resonance structures for para attack for

the methoxy group OCH3 by NO2.

Any resonance effect for electron-donating

groups such as NH2, OH, and OR, which
delocalizes the positive charge on the cation
intermediate, lowers the activation energy for
its formation and activates the ring toward
further EAS.
These groups on the benzene ring make
electrophilic aromatic substitution faster.
They direct substitution to the ortho and para

Possible transition states for ortho, meta or para

attack on an activated arene.

For meta directors, meta attack forms a more

stable cation than ortho-para attack.
Also, meta products are formed faster than ortho-para

-NO2 is meta directing.

Note the resonance structures for meta attack of

the nitro group versus the resonance structures
for ortho/para.

This repulsion makes the resonance structure less

Since the meta resonance structures dont have a
similar structure, by default, such an attack is

The ortho (and para) resonance structures include a

structure where the positive carbocation charge is
adjacent to the positive formal charge of the nitrogen
atom in the nitro group.






Deactivating Directors
Any resonance or inductive effect for electronwithdrawing groups such as NO2, C=O,
-SO3H, NR3+, CCl3, and CF3, which
decreases electron density on the ring,
deactivates the ring toward further EAS.
These groups on the benzene ring make
electrophilic aromatic substitution slower.
They direct substitution to the meta position.

Halogens: the resonance and inductive effects

operate in opposite directions.
The inductive effect: halogens have an electronwithdrawing inductive effect; therefore, aryl halides
react more slowly in EAS than benzene.
The resonance effect: a halogen ortho or para to the
site of electrophilic attack stabilizes the cation
intermediate by delocalizing the positive charge;
halogen, therefore, is ortho-para directing.

Possible transition states for ortho, meta or para

attack on an deactivated arene.

Note that activating (and ortho/para) directors

have lone pairs that can participate in
resonance structures.

1. Groups which are ortho-para directing.

In a multi-step synthesis, the order of steps is


Alkyl groups
Phenyl groups
Substituents in which the atom bonded to the ring has
an unshared pair of electrons

2. All ortho-para directing groups are activating

toward further substitution; the exceptions to
this generalization are the halogens, which are
weakly deactivating.

Disubstituted and trisubstituted rings are likely with

excess reagent.

3. All other substituents are meta directing.

4. All meta directing groups carry either a partial or
full positive charge on the atom bonded to the


The functional group of a phenol is an -OH
group bonded to a benzene ring.

The greater acidity of phenols compared with

alcohols is the result of the greater stability of the
phenoxide ion relative to an alkoxide ion.

Chemical Properties of Phenols

Phenols are significantly more acidic than alcohols.

Electron-withdrawing groups, particularly

halogens and nitro groups, increase the acidity
of phenols by a combination of resonance and
inductive effects.

Because phenols are stronger weak acids than

most, they are often water-soluble.

As weak acids, phenols react with strong bases

to form water-soluble salts.

They do not react with weak bases, such as

sodium bicarbonate.

Phenols and related compounds act as antioxidants.

Vitamin E is a natural antioxidant.

BHT and BHA are synthetic antioxidants.