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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
unreactive:
no reaction
KMnO4
Br2

C6H6

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
compounds
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
Pt
no reaction

Some proposed structures for benzene that were wrong.


Note the formula for all of the compounds is C6H6.

Dewar Benzene

Ladenburg

made in 1962

(Prismane)
made in 1973

Benzvalene

The mystery of the structure of benzene was


solved by August Kekul in 1872.

Fulvene

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
aromaticity.

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
bonds.

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
cyclohexene.
The difference is known as the resonance energy of
benzene.

One way to estimate the resonance energy of benzene is


to compare the heats of hydrogenation of benzene and
cyclohexene.

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).

Aromaticity
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).

benzene

hexatriene

cycloheptatriene

naphthalene

cyclooctatetraene

aromatic

non-aromatic

non-aromatic

aromatic

non-aromatic

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)

Atorvastatin
(Lipitor) (anticholestrol drug)

Furan
Please commit these names and structures to memory

Dabigatran (anticoagulant)

CoQ10 - enzyme in cell organelles


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

Nomenclature
When benzene is considered to be the parent ring,
functional groups are indicated with prefixes.
NO2

OC2H5

C4H9

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
(1,4-)

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.

CH2

Br

Br

benzyl bromide is
reactive to both
SN1 or SN2

bromobenzene
does not react via
SN1 or SN2

Nu-

Br

CH2

CH2

Br

X
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


mechanism.
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
hydrogen.

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
chlorobenzene.

Nitration
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.

Sulfonation
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,
HSO3+.

Sulfonic acids are very acidic (like sulfuric acid).


The conjugate bases (sulfonates) are used in
detergents.

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
bond.

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


alkylations.
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
while).

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
carbocations.
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.
Orientation
Certain substituents direct a new substitution
preferentially toward the ortho-para positions, others
direct preferentially toward the meta positions.

Rate

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


products.

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
reaction.

-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
attack.

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).
CH3

CH3

CH3

CH3

CH3

CH3
O

O
E

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
positions.

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
products.

-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


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

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.
O

O
N

O
N

O
N

O
N

O
N

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.

Generalizations
1. Groups which are ortho-para directing.
a.
b.
c.

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


crucial.

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
ring.

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Phenols
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.

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