Aromaticity

Hckel

Benzene

H
All C-C 1.39

Naphtalene

1.37
1.41

6Memberedringheteroaromatics
Pyridine
N

2.2D

1.40

1.39

1.34

Pyridineasabaseandthepyridiniumcation

pKa:5.2

N
H

H
N

H
H

Thepyryliumcation
N
H

Antocyanines (red / blue pigments) d

erivatives of the flavylium ion
O

R'

R
O

NH3

See chapter 8

Flavonoids (yellow pigments)

derivatives of flavon

N
O
O

Tautomerism
Pyridones/Hydroxypyridines
2-Pyridone

3-Hydroxtpyridine
OH

HO
HO

N
H

4-Pyridone
O
DMF

N
H

2 Me sign in NMR - Partial N=C bond

O
O

N
H

N
H

2and4pyrones

?
HX

XH

N
H

X=O: one / hydroxy

X=NR: imino / amino
X=S: thione (6-membered rings) /
thiol (5 membered)

N
H

O
H 2N

HN

N
H

HN

N
H

HN
O

N
H

Uracil

HO

N
H

NH2

N
H

N
H

Cytosine

5Memberedringheteroaromatics
S

Cyclopentadienyl anion

Thiophene

X
X: S, Se

e- in d-orb.

Pyrrole

Thiophene

1.43
1.37

Furan

1.42

1.44

1.37
N
H

1.38

1.71

1.35
S

1.37

NMRSpectroscopy

Benzene: 7.3ppm, 128ppm

7.5 ppm
136 ppm H

H J 7.5
H
J 5
N H

7.1 ppm
H 124 ppm

H 8.5 ppm
150 ppm

N
H
J 3.4
H
H
N
H

H 6.6 ppm
117 ppm

H 7.2 ppm
126 ppm

S
J 3.4
H
H

J 2.6
H

7.1 ppm
H 127 ppm

6.2 ppm
108 ppm

J 4.7
H

Inductive
effect

J 3.5
H
H
O

6.3 ppm
110 ppm

H
O

H 7.4 ppm
144 ppm

X
X: S, Se

e- in d-orb.
J 1.8
H

MeNO 2
0 ppm

N
N

-63 ppm

-82 ppm

N
H
-171 ppm

N
H
-231 ppm

-301ppm
-302ppm
-146ppm
-147ppm

NH2

N
N
-151ppm
-156ppm

N
N
R

-155ppm
-142ppm

-211ppm
-216ppm

R=H
R=Et

NH3
-380

Bakkestuen,etal.
Org.Biol.Chem,2005,3,1025