Chapter 18.

Aromatic Compounds
________________ compounds or ___________ include benzene and benzene derivatives.

Many aromatic compounds were originally isolated from _____________ oils.

However, many aromatic compounds are odorless.
18.2 Nomenclature of Benzene Derivatives
_____________ is generally the parent name for monosubstituted derivatives.

Many benzene derivatives have common names.

For some compounds, the ______________ name becomes the ___________ name.
Memorize these common/parent names:

If the substituent is larger than the ring, the ______________ becomes the
_____________chain.

Aromatic rings are often represented with a Ph (for phenyl) or with a (phi) symbol.

The common name for dimethyl benzene derivatives is _____________.

Memorize:

Identify the parent chain (the longest consecutive chain of carbons).

Identify and name the substituents.
Number the parent chain and assign a locant (and prefix if necessary) to each substituent.
Give the first substituent the lowest number possible.
List the numbered substituents before the parent name in alphabetical order.
Ignore prefixes (except iso) when ordering alphabetically.

____________________________________
____________________________________
______or ________________________

________________________________________
_________________________________
or _____________________________________
_______________________________

or

If there are more than two substituents you cannot use ortho, meta or para. Instead use
locant numbers.
CH3

OH

O 2N

NO2

Cl

Br

____________________
18.3 Structure of Benzene

NO2

(TNT)

___________________________________

In 1866, August Kekul proposed that benzene is a ring comprised of alternating double and
single bonds. He suggested that the exchange of double and single bonds was an equilibrium
process. We now know that the aromatic structures are _______________ contributors rather
than in equilibrium.

Sometimes the ring is represented with a circle in it

18.4 Stability of Benzene
The _____________ that results from a ring being aromatic is striking.
Recall that in general, alkenes readily undergo addition reactions.
Aromatic rings are stable enough that they do ____ undergo ____________ reactions.
Heats of hydrogenation can be used to quantify aromatic stability.

Does every fully conjugated cyclic compound have aromatic stability? ____
Some fully conjugated cyclic compounds are reactive rather than being stable like benzene.
cyclooctatetraene (antiaromatic)
cyclobutadiene (antiaromatic)
AROMATIC compounds fulfill two criteria:
A _________ ______________ ring with overlapping p-orbitals
Meets HCKELS RULE: an ____ number of electron pairs or 4n+2 total __ ___________
where n = 0, 1, 2, 3, 4, etc.
ANTIAROMATIC compounds fulfill two criteria
A fully conjugated ring with overlapping p-orbitals
An _______ number of electron pairs or 4n total electrons where n = 0, 1, 2, 3, 4, etc.

Annulenes are rings that are fully conjugated.

[10]Annulene is neither aromatic nor antiaromatic, because sterics do not allow it to adopt a
flat structure.

Exception: Pyrene is aromatic even though it has 16 pi electrons. The C=C double bond in
the center is not part of the aromatic system. The 14 pi electrons around the outside of the
molecule give 4n+2=14 when n=3, so it is aromatic.
The pKa value for cyclopentadiene is much lower than typical C-H bonds. (More acidic)
Giving up a proton is easier when the resulting anion has aromatic stability.

vs

18.5 Aromatic Compounds Other Than Benzene

_______________ (atoms other than C or H) can also be part of an aromatic ring.

p orbital

If the heteroatoms lone pair is necessary, it will be included in the HCKEL number of pi
electrons.
If the lone pair is necessary to make it aromatic, the electrons will not be as basic.

pKa = 5.2

pKa = 0.4
The difference in electron density can also be observed by viewing the electrostatic potential
maps.

Will the compounds below be aromatic, antiaromatic, or non aromatic?

1.

2.

3.

4.

________________ the lone pair is perpendicular to the plane of the pi electrons,

so it cannot be involved in any aromaticity. That leaves 8 pi electrons, which is
antiaromatic.
The ring cant be conjugated unless the oxygen is sp2 and has a lone pair involved in the
resonance, but the participation of that lone pair would give 8 pi electrons, which would be
unstable and antiaromatic. To avoid that instability, the oxygen will remain sp3, breaking up
the conjugation and making it _________________.
Including the lone pair, 10 pi electrons are ______________. Also fully conjugated.
8 pi electrons but the ring is not fully conjugated, so ________________.

The lone pair electrons on the top N in the following compound are in a p orbital and part of
the aromatic pi system
N

Histamine

NH2

The lone pair electrons on the lower N are in a sp2 orbital and not involved in the aromatic pi
system (available to act as a base)
3 electron pairs (______ #) or _______________ pi electrons so aromatic
Many polycyclic compounds are also aromatic.

18.6 Reactions at the Benzylic Position

A carbon that is attached to a benzene ring is _______________.

Recall that aromatic rings and alkyl groups are not easily oxidized.

In general, benzylic positions can readily be fully _______________

The benzylic position needs to have at least ___ ____________ attached to undergo
oxidation.

__________________ can also be used as an oxidizing reagent.

BENZYLIC positions have similar reactivity to ____________positions, because both

involve pi systems that can use _____________to stabilize charges or radical intermediates.
Resonance structures of the benzylic carbocation:

Benzylic positions readily undergo free radical ________________ using NBS

NBS = N-bromosuccinamide (see Chapter 11.6) used for allylic bromination rather than Br2
and light.

Once the benzylic position is substituted with a bromine atom, a range of functional group
transformations are possible.

Give necessary reagents for the reactions below.

Br

Br

HO2C

CO2H
CO2H

CO2H

18.7 Reduction of the Aromatic Moiety

Vinyl side groups can be selectively reduced.

Reductions of the benzene ring are not common and will not be covered in this course.
18.8 Spectroscopy of Aromatic Compounds
IR spectra for ethylbenzene:

NMR Spectroscopy of Aromatic Compounds

The integration and splitting of protons in the aromatic region of the 1H NMR (7 ppm) in
often very useful.

Graphite, Buckyballs, and Nanotubes

______________ consists of layers of sheets of fused aromatic rings. ______________ are
C60 spheres made of interlocking aromatic rings. Fullerenes can also be made into tubes
(___________________).
Many applications: Conductive Plastics, Energy Storage, Conductive Adhesives, Molecular
Electronics, Thermal Materials, Fibres and Fabrics, Catalyst Supports, Biomedical
Applications

Extra examples: 28, 29, 34, 36, 41, 43, 47, 59, 60
O

and
Homework: Chapter 18: 1, 2, 3, 5, 8, 11, 13, 15(a-e), 19, 20 and 26