Aromatic Chemistry

R W Grime Ripon Grammar School

STRUCTURE OF BENZENE
Benzene = C6H6

Its structure was a mystery for many years - until Kekules dream.

STRUCTURE OF BENZENE
Problems with Kekules structure:

1) C-C bonds are all the same length (between C-C and C=C length).
2) Benzene does not undergo addition reactions readily (e.g. with bromine water).

3) Do not get isomers like this:

Br across C=C Br Br Br across C-C

4) H hydrogenation about 152 kJ mol-1 less than expected.

STRUCTURE OF BENZENE

C
H

C
C H

6 electrons in a delocalised bond

above and below the plane of the atoms

C
C H C

STRUCTURE OF BENZENE

H C H C C H C

C C H

STRUCTURE OF BENZENE

STRUCTURE OF BENZENE

HYDROGENATION OF BENZENE
-152 kJmol-1 delocalisation energy + 3H2

Enthalpy (kJ mol-1)

+ -3602H2 theoretical
+ H2 -120 value -240 H2 + -120

+ 3H2

-208 real value

NAMING AROMATIC COMPOUNDS

CH3 Cl NO2 COOH

methylbenzene (toluene)

chlorobenzene

nitrobenzene

benzenecarboxylic acid (benzoic acid)

NAMING AROMATIC COMPOUNDS

CH3
1,3-dimethylbenzene (m-xylene)

CH3

CH3
Cl

4-methyl-1-chlorobenzene

COOH OH

COOH

O2N
2-hydroxybenzenecarboxylic acid

NO2
3,5-dinitrobenzenecarboxylic acid

NAMING AROMATIC COMPOUNDS

NH2
phenylamine (aniline)

CH3

CH2

CH2

CH3

2-phenylbutane

O
CH CH2

CH3 C

phenylethene

phenylethanone

NAMING AROMATIC COMPOUNDS

O C O CH3

O C

O CH3

phenylethanoate

methyl benzenecarboxylate (methyl benzoate)

O NH C CH3

N-phenylethanamide

NAMING AROMATIC COMPOUNDS

OH
OH OH
phenol

benzene-1,2-diol

OH Cl Cl
2,4,6-trichlorophenol (TCP)

OH NO2
2-nitrophenol

Cl

NITRATION
NO2 + HNO 3
nitrobenzene

H 2O

Conditions

conc HNO3 conc H2SO4 catalyst 50C

NITRATION ELECTROPHILIC SUBSTITUTION

Formation of electrophile

HNO3 + 2 H2SO4

NO2

+ 2 HSO4- + H3O+

nitronium ion

Reaction of electrophile with aromatic compound

NO2 +

NO2 H

-H

NO2

NITRATION
CH3 NO2

CH3

Equation (name product)

Conditions Mechanism

NITRATION
CH3 + HNO CH3 NO2
3

+
2-methylnitrobenzene

H 2O

Conditions

conc HNO3 conc H2SO4 catalyst 50C

NITRATION
Uses of nitro compounds: 1) as explosives 2) to make aromatic amines (used to make dyes)
CH3 O2N NO2

NO2

1,3,5-trinitrotoluene TNT

FRIEDEL-CRAFTS ACYLATION
R C O + R C Cl + HCl O

R C O + R C O O C R

O O + R C OH

aromatic ketone

Conditions

AlCl3 catalyst

FRIEDEL-CRAFTS ACYLATION
WARNING! - do not mix
Friedel-Crafts acylation & other acylations

(needs AlCl3)
H

H H H N O R R

Swap H on benzene ring for acyl group

Swap H on O/N for acyl group

FRIEDEL-CRAFTS ACYLATION
WARNING! - Classic question to test this
NH2 CH3COCl NHCOCH3

H replaced is on N not benzene ring. This is NOT Friedel-Crafts acylation!

FRIEDEL-CRAFTS ACYLATION ELECTROPHILIC SUBSTITUTION

Formation of electrophile

O
AlCl4 + R
+ acylium ion

AlCl3

+ RCOCl

OR

AlCl3 + R-C-O-C-R

R-C-O-AlCl3

+ acylium ion

FRIEDEL-CRAFTS ACYLATION ELECTROPHILIC SUBSTITUTION

Reaction of electrophile with aromatic compound

O
C
+

O R +

C
H

O -H
+

Regeneration of catalyst

AlCl4

H+

AlCl3 + HCl O
or

O R-C-O-AlCl3 + H+

R-C-OH + AlCl3

FRIEDEL-CRAFTS ACYLATION
CH3 CH3

C O
Equation
Conditions Mechanism

CH2CH3

FRIEDEL-CRAFTS ACYLATION
CH3 O + CH3CH2 C Cl C O CH2CH3 + HCl CH3

Conditions

AlCl3 catalyst