Aromaticity & Aromatic

Reactions

Lecture 1 Lance Twyman

 Key sources of information
• Books
– ‘Aromaticity’ 1971 (McGraw Hill), Peter J. Garratt.
– 'Aromatic Chemistry' 1992 (Oxford Chemistry Primer), Malcolm Sainsbury.
– 'A Guidebook to Mechanism in Organic Chemistry' 1986 (Longmann), Peter
Sykes.
– 'Frontier Orbitals and Organic Chemical Reactions' 1976 (Wiley-Interscience),
Ian Fleming.

• Reviews
– J.A. Berson, ‘Erich Hückel, pioneer of organic quantum chemistry: reflections
on theory and experiment’ Angew. Chem. Int. Ed. Engl. 1996, 35, 2750.
– A.M. Rouhi, ‘Scientists localise benzenes electrons, trap elusive
cyclohexatriene motif’ Chem. Eng. News 1996, April, 27.
– A.J. Rocke, ‘Waking up to the facts?’ Chem. Br. 1993, May, 401.
 Format and scope of lectures

• Introduction
• Chemistry of simple alkenes and conjugated alkenes
• Aromaticity: what is it?
• Orbital discription of benzene and Hückel’s rule
• Simple Electrophilic aromatic substitution (SEAr)
• Electrophilic aromatic substitution on substituted
benzene.
• Nucleophilic aromatic substitution (SNAr etc.)
 Aromatic Compounds

O
H

Bitter almonds, are a good source of benzaldehyde

 Discovery of Benzene

• Discovered in 1825 by Michael Faraday.

• Isolated from the oily residue left in London’s gas lamps.
• Some aromatic compounds are referred to as phenyl;
comes from the Greek “pheno” I bear light.
 Sources of Aromatics: Coal Tar
• Numerous low molecular weight aromatic & fused aromatic hydrocarbons are
obtained by fractional distillation of coal tar:

Me Me

Me
benzene toluene xylene indene naphthalene

anthracene phenanthrene fluorene

Some Aromatic Secondary Metabolites
O
Me
HO
NHMe Me
Me H
Me O R

H H
OH HO HO
OH Me

adrenalin vitamin E estrone

(-tocopherol)

MeO

HO
N H
O O
H
O MeO

N
Me
N H
MeO O
OMe

morphine quinine rotenone OMe

 Some Aromatic Pharmaceuticals
O NEt2
O
Me
N

NMe NMe.HCl
Cl N
H

methamphetamine
hydrochloride
N ('speed')
H
diazepam (vallium) LSD

O O CO2Me

H2N NEt2
O
OH

O
OH O OH
Proparacaine
Alkavinone
Aromatic Molecules Containing
More than 6 Carbons
 Aromatics and Myoglobin

O
HO

HO N

N Fe N

N
 Aromatics and Haemoglobin

O
HO

HO N

N Fe N

N
 Shikimate Biosynthesis
• The aromatic amino acids (phenylalanine, tyrosine, tryptophan), phenolic lignans &
flavenoids are derived biosynthetically via the Shikimate pathway:

CO2H
HO CO2H
PO
O
O CO2H
+ HO HO OH
O OH
EnzS O
OH OH OH
phosphoenol pyruvate erythrose-4-phosphate dehydroquinic acid shikimic acid

PO CO2H

CO2 CO2H
HO2C CO2H
Claisen
NH3 rearrangement
O

O CO2H
OH OH
OH tyrosine prephenic acid chorismic acid
 Poylketide Biosynthesis
• Many other aromatic natural products are derived biosynthetically via polyketide
dehydrative aromatisation:

O O Me

EnzS Me O O O
SEnz
OH O
O O mellein
 Dötz Benzannulation

OH
R'  R'
Cr(CO)5 +
R
OMe R
OMe

hydroquinones
 Vollhardt [2+2+2] cycloaddition

R R
R'' 
Cp-Co(CO)2 R'' R
R

R' [2+2+2]
R'' R'
R''
R' R'
Introduction to the Chemistry of Alkenes

lycopene

carotene
 MO description of bonding
Atomic orbitals are waves (i.e. the s p d….orbitals).

Their shapes are determined the by solution of quantum mechanical wave equations.
 MO description of bonding
Waves combine favorably when their phases are the same; reinforcement

Waves combine unfavorably when their phases are opposite; destructive

The same principle applies to atomic orbitals; best

overlap between orbitals of the same phase (i.e. bonding)
Bonding in Alkenes
 NMR of Alkenes
Circulating electrons

Induced mag field

At the edge of the double bond (where the

hydrogens are) the local field reinforces the
applied field, therefore LESS energy is
required to bring about resonance. These
hydrogens are strongly DESHIELDED.

Applied mag field

NMR of Alkenes
NMR of Alkenes
 Conjugated Alkenes
Non-cyclic polyenes

rotation

cis hexatriene

trans hexatriene
 Conjugated Alkenes
The structure for the cis and the trans isomers have been
determined via electron diffraction.

137 pm

• Both the cis and the trans are planar.

• There are double and single bonds,

the central double bond is longer than
the double bonds at the end.
134pm
147 pm
• In addition, the single bonds are
slightly shorter than a standard single
bond. Standard values:
single = 154pm
double = 134pm
 Conjugated Alkenes

H
H

rotation requires 3 KJ mol-1

rotation requires 30 KJ mol-1

 Conjugated Alkenes
The electrons are not associated with a particular atom, but are delocalised across the
whole  system. This is only possible when we have alternating single/double bounds.

double bonds formed by

overlap of p orbitals

This delocalisation accounts for the planar

However, the central p
orbitals can also interact. structure observed in conjugated polyenes.
 MO Description of Butadiene

4 AO (1 per carbon), we
must therefore have 4 MO