BS(IV)

HETEROCYCLIC AROMATIC
COMPOUNDS:
PYRROLE
Pyrrole:
INTRODUCTION:
PYRROLE is a heterocyclic
aromatic organic compound, a
five-membered ring with the
formula ( C4H4NH ). It is a
colourless volatile liquid that
darkens readily upon exposure to
air. Substituted derivatives are
also called pyrroles.
Resonance structure :
The lone pair on nitrogen is in the p
orbital so it is involved in the 6 pi-
electron aromatic system. Hence
pyrrole is not very nucleophilic and is
only weakly basic at nitrogen. Looking
at the HOMO of pyrrole the lobes are
much bigger at the 2- and 5- positions,
this indicates that the reactions are
most likely to take place at these
positions
The resonance contributors of pyrrole
provide insight to the reactivity of the
compound. Likefuranandthiophene,
pyrrole is more reactive than benzene
towards
electrophilic aromatic substitution
because it is able to stabilize the
positive charge of the intermediate
carbocation.
 SYNTHESIS OF
PYRROLE:
Pyrrole could be obtained
through the following reaction: It
could be achieved by treating
Furan with Ammonia with the
exsitence of solid acid catalysts.
2.Synthesis :
PYRROLE can e obtained by
heating acetylene and ammonia
over red hot tube.
Acidic property of pyrrole:
Due to participation of Ns lone
pair in resonance/aromaticity
pyrrole has exceptional strong
acidic property.
(that is,it can loss the hydrogen
attached with NITROGEN when
reacting with any base)
Acidic property of pyrrole:
PYRROLE can react with
Strong base,
Grignard reagent,
potassium metal etc to give salt
like compounds.
Sensitivity towards strong
acids:
Pyrrole is sensitive towards strong
acids.
This is due to protonation occur at one
of the carbon and the resulting
protonated molecule will add to
another unprotonated pyrrole
molecule this continues until a pyrrole
trimer is formed.
The reaction is considered as
electrophilic addition of pyrrole.
ELECTROPHILIC SUBSITUTION IN
PYRROLE:
Pyrrole is reactive towards electrophilic
substitution reaction.
It is more reactive than benzene because of
the resonances that pushes away the
electron density from nitrogen towards
carbons ,thus making the ring electron rich.
The substitution is easier and mild reagents
can be used.
ELECTROPHILIC SUBSTITUTION
OCCURS AT CARBONS(THE RING)
NOT NITROGEN.
(obviously)
Preferable position is C-2, the
carbon next to the heteroatom.
If there is an already substitution
on C-2 then C-3.
The first substitution is on C-2
because it has more stable
intermediates(it stabilizes three
resonances structure)
The intermediate resulted from
C-3 attack is stabilizes by two
resonance structure.
FRIDEL CRAFT ACYLATION

HALOGENATION

MULTI HALOGENATION

DIAZONIUM ION
FORMATION

NITRATION

SULPHONATION
PYRIDINE:
Introduction:
Pyridine is a basic heterocyclic organic
compound with the chemical formula
C5H5N. It is structurally related to
benzene, with one methine group (=CH-)
replaced by a nitrogen atom. Pyridine
have 5 carbon atoms and one nitrogen
atom. All are sp hybridized. The p-orbital
of nitrogen and all carbon atoms lie in the
same plane. Overlapping of p-orbitals
result in delocalization of six -electrons in
the cyclic ring, following Hckel rule,
imparts aromatic character to pyridine
History
Impure pyridine was undoubtedly prepared by
early alchemists by heating animal bones and
other organic matter, but the earliest documented
reference is attributed to the Scottish scientist
Thomas Anderson. In 1849, Anderson examined
the contents of the oil obtained through high-
temperature heating of animal bones. Among
other substances, he separated from the oil a
colorless liquid with unpleasant odor, from which
he isolated pure pyridine two years later. He
described it as highly soluble in water, readily
soluble in concentrated acids and salts upon
heating, and only slightly soluble in oils.
Occurrance
Pyridine is not abundant in nature. In
daily life, trace amounts of pyridine
are components of thevolatile organic
compoundsthat are produced in
roasting andcanningprocesses,
roasted coffee,potato chips,
sunflower honey etc
SYNTHESIS
Hantzsch pyridine synthesis
It is a multi-component organic reaction
between an aldehyde such as
formaldehyde, 2 equivalents of a -keto
ester such as ethyl acetoacetate and a
nitrogen donor such as ammonium acetate
or ammonia. The initial reaction product is
a dihydropyridine which can be oxidized in
a subsequent step to a pyridine. The
driving force for this second reaction step
is aromatization.
Chemical properties
Pyridine is miscible with water
and virtually all organic solvents
It is weakly basic
pyridine behaves both as a
tertiaryamine
Resonance structure:

Electron density is on nitrogen as

its lone pair is not taking part in
resonance
Positive charge occur on ortho
and para carbons.
Basic property:
The nitrogen center of pyridine
features a basic lone pair of electrons.
Because this lone pair is not part of
the aromatic ring, pyridine is a base,
having chemical properties similar to
those of tertiary amines.
Pyridine can act asLewis base,
donating its pair of electron to a Lewis
acid as in thesulfur trioxide pyridine
complex.
Pyridine as nucleophile:
Pyridine is a nucleophile as
NITROGEN because its lone pair
is not delocalized,
The ring as nucleophile :

Electronegative atom like

nitrogen lowers the energy of the
ring, this means a less reactive
nucleophile
The
. ring as ELECTROPHILE:
But LUMO means a more reactive ELECTROPHILE
Benzene VS pyridine:
Itis less reactive than benzene in
electrophile substitution.

But nucleophile substitution

which is hard for benzene comes
easy for pyridine.
Electrophile substitution:
Many electrophilic substitutions
on pyridine either do not proceed
or proceed only partially they
lead only to the addition at the
nitrogen atom.
Nucleophile substitution
reactions:
 FURAN

THIOPHENE
SYNTHESIS :
RESONANCE STRUTURES:
REACTIVITY:
PYRROLE > FURAN >
THIOPHENE >> BENZENE
ACCORDING TO THE MOST
ELECTRONE.ATIVE ATOM
ATTACHED.
NITRATION:
SULPHONATION:
 PYRROLE,FURAN,
THIOPHENE undergo
ELECTROPHILIC SUBSTITUTION
Easily.

PYRIDINE UNDER
NUCLEOPHILIC SUBSTITUTION