Benzene and aromaticity

- in the early days of org chem, the word aromatic was used to describe such fragrant
substances as


Benzene from coal distillate
Benzaldehyde from cherries, peaches and almonds
Toluene from Tolu balsam

Today, aromatic refers to benzene and its structural relatives.
- chemists of the early 19
th
century were correct abt there being a difference b/w aromatic cpds
and others, but the assoctn of aromaticity w/ fragrance has long been lost.
- many cpds isolated from natural sources are aromatic in part










Steroidal hormone analgesic Synthetic drug tranquilizer

Benzene causes bone marrow depression and leukopenia (lowered WBC count) on prolonged
exposure
- should be handled cautiously when used as a laboratory solvent

Two sources of aromatic hydrocarbons: coal and petroleum
coal a complex mixture primarily made up of benzene-like rings
- thermal breakdown at 1000
o
C in the absence of air produces
volatile pdts called coal tar, whose fractional distn pdts include



















Petroleum cont few aromatic cpds and consists largely of alkanes
- during refining, aromatic molecules are formed when alkanes
are passed over a catalyst at abt 500
o
C at high P.
- for ex, heptane toluene

Naming aromatic cpds although the use of nonsystematic names is
discouraged, IUPAC rules allow for some of the more widely used names to be retained



















Monosubstituted benzenes are systematically named in the same manner as other hydrocarbons, with
benzene as the parent name.











dehydrogenation
cyclization

Arenes alkyl-substituted benzenes
- named in different ways depending on the size of the alkyl grp
- if the alkyl substituent is smaller than the ring ( 6 or fewer C), the arene is named as an alkyl-
substituted benzene
- if the alkyl substituent is larger than the ring (more than 6 C), the cpd is named as a phenyl-
substituted alkane
- phenyl, sometimes abbreviated as Ph or (phi), is used for
the C
6
H
5
unit when the benzene is considered as substituent
- phenyl comes from Greek pheno (I bear light) to commemorate that benzene was
discovered by Michael Faraday in 1825 from the oily residue in illuminating gas used in London street
lamps.









Disubstituted benzenes are named using one of the prefixes
ortho- (o)
meta- (m), or
para (p).









This system of nomenclature is also useful when discussing reactions.
For ex, Reaction of bromine with toluene occurs at the para position.













Benzenes with more than two substituents are named by numbering the position of each substituent so
that the lowest possible numbers are used.
- the substituents are listed alphabetically when writing the name









Note in the third example that toluene is used as the parent name rather than benzene.
Any of the monosubstituted aromatic cps previously retaining their nonsystematic names can serve as a
parent name, with the principal substituent (-CH
3
in toluene) assumed to be on C1.








Structure and stability of benzene









- Benzene is more stable than typical alkenes
- reacts slowly with Br2
- cyclic conjugation of the benzene ring is retained

A comparison of the heats of hydrogenation
- benzene is 150 kJ/mol or 36 kcal/mol more stable that might be expected for a cyclotriene.











Further evidence for the unusual nature of benzene
- all C-C bonds have the same length of 139 pm (value is intermediate b/w typical single bond of
154 pm, double bond of 134 pm

- electrostatic potential map shows that
e- density in all C-C bonds is identical.

Thus, benzene is
- planar molecular with the shape of a regular hexagon
- all C-C-C bond angles are 120
o

- all C atoms are sp
2
-hybridized
- each C atom has a p orbital perpendicular to the plane of the
6-membered ring

In benzene,
- each p orbital overlaps equally well with both neighboring p orbitals
- thus, all 6 pi e-s are completely delocalized around the ring
- structure is the hybrid of two equivalent forms









cyclohexene
cyclohexane

Alternative representations of benzene


circle representation must be used carefully since it does not indicate the no. of pi e-s in the ring.

Aromaticity and the Hckel 4n + 2 rule
Erich Hckel German physicist (1931)
- a molecule is aromatic only if
a. it has a planar, monocyclic system of conjugation
b. contains a total of 4n + 2 e-s
where n is an integer (n = 0, 1, 2, 3, )
thus, only molecules with 2, 6, 10, 14, 18, e-s can be aromatic

Some examples:

- Antiaromatic
- actually highly reactive and shows none of the properties assocd w/
aromaticity
- dimerizes by a self-Diels-Alder rxn
(one molecules behaves as a diene while the other as a dienophile)




Other examples of aromatic cpds following Hckel 4n + 2 rule

4n + 2 = 6 when n = 1
Thus, aromatic




- Not aromatic
- pi e-s are localized into four double bonds rather than delocalized
around the ring
- molecule is tub-shaped rather than planar


Aromatic ions
follows the Hckel 4n + 2 rule



The forms that are not ionic are not aromatic.































Only one which
is aromatic
Only one which
is aromatic

Aromatic heterocycles: pyridine and pyrrole
heterocycle a cyclic cpd that contains an atom or atoms other than carbon in its ring
--- Could be N, O, S, or P








Pyridine Pyrrole

Polycyclic aromatic cpds: Naphthalene
Hckel 4n + 2 rule is strictly applicable only to monocyclic cpds.
However, the concept of aromaticity can include polycyclic aromatic cpds;










One of cancer-causing substances isolated from tobacco smoke

All polycyclic aromatic HCs can be represented by resonance forms. Napthalene has three resonance
forms.



Naphthalene also shows many aromatic properties.
- heat of hydrogenation show aromatic stabilization E of 250 kJ/mol (60 kcal/mol)
- reacts slowly with electrophiles like Br2 to give substn rather than addn pdts


- full delocalization of the 10 pi e-s
throughout both rings



Practice problem
Thiophene, a sulfur-contg heterocycle, undergoes typical aromatic substitution reactions rather than
addition reactions. Explain why thiophene is aromatic.



Strategy
Aromatic cpds are planar, cyclic, conjugated, with 4n + 2 e-s.
See how these facts apply to thiophene.

Solution
Thiopene is the sulfur analog of pyrrole.
The sulfur atom is sp2-hybridized and has a lone pair of e-s in a p orbital perpendicular to the plane of
the ring.
Sulfur also has a second lone pair of e-s in the ring plane.