Aromaticity

hydrocarbons
aliphatic aromatic

alkanes alkenes

alkynes

Aliphatic compounds: open-chain compounds and ring compounds that are chemically similar to openchain compounds. Alkanes, alkenes, alkynes, dienes, alicyclics, etc.

Aromatic compounds: unsaturated ring compounds that are far more stable than they should be and resist the addition reactions typical of unsaturated aliphatic compounds. Benzene and related compounds.

The structure of benzene

This new hydrocarbon isolated by Michael Faraday in 1825

The molecular formula is C6H6 suggesting that the molecule contained a large number of double bonds. All the chemistry they knew suggested that any substance with a double or triple bond would be very reactive and react readily with HBr in the dark.

Benzene did not, it was surprisingly unreactive

Benzene. This aromatic hydrocarbon was first discovered in 1825 but its structure was not generally agreed upon until 1946 In 1865 after a dream about a snake biting its own tale, Kekul suggested the following structure for benzene

Facts about benzene:

a) Formula = C6H6 b) Isomer number: one monosubstituted isomer C6H5Y three disubstituted isomers C6H4Y2

c) Benzene resists addition reaction, undergoes substitution reactions.

d) From X-ray, all of the CC bonds in benzene are the same length and intermediate in length between single and double bonds.

Benzene is a flat molecule, with all atoms in the same plane, (bond angle 120)
When the benzene ring is attached to an aliphatic skeleton, it is called the phenyl group. The formula of a phenyl group id C6H5. Any compound where the ratio of C:H is about 1:1 is likely to contain a benzene ring.

ISOMER

Reactions of benzene: 1. Nitration C6H6 + HNO3 C6H5NO2 + H2O 2. Sulfonation C6H6 + H2SO4 C6H5SO3H + H2O

3. Halogenation
C6H6 + X2 C6H5X + HX 4. Freidel-Crafts alkylation C6H6 + RX C6H5R + HX substitutions

Hckels Rule
If the compound has a continuous ring of overlapping p orbitals and has 4N + 2 electrons, it is aromatic. If the compound has a continuous ring of overlapping p orbitals and has 4N electrons, it is antiaromatic.
=>

4n + 2 = 4 n = 0.5 not aromatic antiaromatic

4n + 2 = 8 n = 1.5 nonplanar nonaromatic

4n + 2 = 10 n=2

Naming benzene molecules

1.2-dimethyl benzene

1,3-dimethyl benzene

1,4-dimethyl benzene

Fused ring systems

naftalen

antracen

fenantren

tetracen

trifenilen

piren

krisen

H H H H

H H H H

Naftalen

H H H H

H H H

Antracen

H H H

H H

Fenantren

H H H
H H H H

H H

Koronen

H H H H H

Naftalen: nomenklature monosubstitusi: 12NO2

2-nitronaphthalene 2-nitronaftalen -nitronaphthalene

-nitronaftalen

OH

NH2

SO3H

-naphthol
also

-naphthylamine -naphthalenesulfonic acid

1-bromnaftalen

1-nitronaftalen -nitronaftalen

Common Names of Benzene Derivatives

OH CH3 NH2 OCH3

phenol
H C CH2

toluene
O C CH3

aniline
O C H

anisole
O C OH

styrene

acetophenone

benzaldehyde

benzoic acid

=>


Mercedes Benzene

Disubstituted Benzenes
The prefixes ortho-, meta-, and para- are commonly used for the 1,2-, 1,3-, and 1,4positions, respectively.
Br Br o-dibromobenzene or 1,2-dibromobenzene

NO2 HO p-nitrophenol or 4-nitrophenol

=>

NO2 Br Br Cl

CH3

Br o-dibromobenzene 1,2-dibromobenzene m-chloronitrobenzene 3-chloro-1-nitrobenzene p-bromotoluene 4-bromotoluene

If more than two groups on the ring, use numbers!

Br Br Br Br

NH2 Br

Br 1,2,4-tribromobenzene 2,4,6-tribromoaniline

3 or More Substituents
Use the smallest possible numbers, but the carbon with a functional group is #1.
OH
O 2N NO 2

O2N

NO2

NO 2 1,3,5-trinitrobenzene

NO2 2,4,6-trinitrophenol

=>

Common Names for Disubstituted Benzenes

CH3 CH3 O OH C CH3 CH3 m-xylene H3C CH3 mesitylene OH

o-toluic acid

H3C

p-cresol

=>

2-hydroxybenzoic acid

benzene-1,4-dicarboxylic acid phenylamine chlorobenzene nitrobenzene Methyl 3-nitrobenzoate Chloro Methyl benzene 2,4,6-trichlorophenol phenyl ethanoate phenylethanone phenol Benzoic acid

phenylethene

Phenyl and Benzyl

Phenyl indicates the benzene ring attachment. The benzyl group has an additional carbon.
Br
CH2Br

phenyl bromide

benzyl bromide

See you..