Ch-03-Hetrocyclic Compounds

Heterocyclic compounds
1. Give one method for the preparation of furan with the required equation.(2m)
Furfural is treated with acidified potassium dichromate solution to get oxidized to furoic acid,
which on decarboxylation using soda lime, furan is obtained.
Oxidation Decarboxylation
- CO2
+ [O]
Furfural Furoic acid Furan
2. How is pyridine prepared from nicotinic acid? Give the chemical equation.(2m)
Nicotinic acid on heating with soda lime, decarboxylation takes place to give pyridine
Decarboxylation - CO2
3. Explain Chichibabin reaction of pyridine with equation.(2m)

Pyridine reacts with sodamide, undergoes nucleophilic substitution reaction forming 2-amino
pyridine, the reaction is called Chichibabin reaction.
4. Give the method of preparation of Thiophene.(2m)

Acetylene and hydrogen sulphide is passed through a tube containing alumina (Al2O3) at 3000C,
thiophene is obtained
5. How is pyrrole prepared from ammonium mucate?

Ammonium mucate is heated with glycerol, forming mucic acid which undergoes dehydration,
decarboxylation and ring closure by reaction with ammonia, forming pyrrole
6. Explain the Friedel craft’s reaction of thiophene.(2m)

Thiophene is heated with acetic anhydride in presence of ortho phosphoric acid to give 2-acetyl
thiophene
7. Write the structure of Indole.(2m)
Structure of Indole
8. Give one reaction to show that furan undergoes electrophilic substitution reaction.(2m)
Furan undergoes electrophilic substitution reactions under milder conditions due to its greater
reactivity. The substituent enters in 2 or 5 position.It is highly sensitive to strong acids even at
low temperature resulting in polymerization reaction.
9. How is thiophene prepared from acetylene? Give the chemical equation.(2m)

Acetylene and hydrogen sulphide is passed through a tube containing alumina (Al2O3) at 3000C,
thiophene is obtained.
10. How is Indole converted in to 3-nitro indole? or

What happens when indole is nitrated? Give equation.(2m)
When Indole is nitrated by heating with nitro ethane and sodium ethnocide mixture, nitro Indole
is obtained:
11. Give an example for the nucleophilic substitution reaction of pyridine. (2m)
Pyridine reacts with sodamide, undergoes nucleophilic substitution reaction forming 2-amino
pyridine, the reaction is called Chichibabin reaction.
13. Explain the aromaticity of pyrrole (3m)

 In pyrrole, the nitrogen atom and the four C atoms are sp2 hybridized. The sp2 hybrid
orbitals overlap with each other and with s orbital of five hydrogen atoms forming C-C,
C-N, C-H and N-H bonds. The pentagon obtained is planar.
 Each C atom and nitrogen atom possesses an unhybridized p orbital and these are
perpendicular to the plane containing the sigma bonds.
 The p orbitals on carbons contain one electron and p orbtials on the nitrogen atom
contains a lone pair of electrons. The lateral overlaps of these p orbitals above and
below the plane produces pi molecular orbital containing six electrons.
 Thus it satisfied the Huckel’s rule of aromaticity with (4n+2)π electrons where n=1,
delocalized over a cyclic planar system
 Pyrrole is stabilized due to the following resonance hybrid of the following structures
14. Explain the aromaticity of Furan (3m) Or Explain the aromaticity of Furan on the basis of
resonance theory(4m)
* In furan, the oxygen atom and the four C atoms are sp 2 hybridized. The sp2 hybrid orbitals
overlap with each other and with s orbital of five hydrogen atoms forming C-C, C-H bonds. The
pentagon obtained is planar.
* Each C atom and nitrogen atom possesses an unhybridized p orbital and these are
perpendicular to the plane containing the sigma bonds.
* The p orbitals on carbons contain one electron and p orbtials on the oxygen atom contains a
lone pair of electrons. The lateral overlaps of these p orbitals above and below the plane
produces pi molecular orbital containing six electrons.
* Thus it satisfied the Huckel’s rule of aromaticity with (4n+2)π electrons where n=1,
delocalized over a cyclic planar system.
* Furan is stabilized due to the following resonance hybrid of the following structures
15. Explain the aromaticity of Thiophene (3m)
* In Thiophene, the sulphur atom and the four C atoms are sp2 hybridized. The sp2 hybrid
orbitals overlap with each other and with s orbital of five hydrogen atoms forming C-C, C-H
bonds. The pentagon obtained is planar.
* Each C atom and sulphur atom possesses an unhybridized p orbital and these are perpendicular
to the plane containing the sigma bonds.
* The p orbitals on carbons contain one electron and p orbtials on the sulphur atom contains a
lone pair of electrons. The lateral overlap of these p orbitals above and below the plane produces
pi molecular orbital containing six electrons.
* Thus it satisfied the Huckel’s rule of aromaticity with (4n+2)π electrons where n=1,
delocalized over a cyclic planar system.
* Thiophene is stabilized due to the following resonace hybrid of the following structures
16. Explain the aromaticity of pyridine (3m)

1. In Pyridine all the ring atoms (five C and one N)are sp2 hybridized.
2. Two of the sp2 orbitals overlap each other to form C-C and C-N sigma bonds. The third sp2
orbital on each carbon overlaps with an s orbital from hydrogen to form the C-H sigma bonds
and the other on nitrogen is occupied by the lone pair of electrons. All the sigma bonds in
pyridine in one plane having the bond angle of 1200.
3. The unhybridized p orbital containing one electron perpendicular to the plane in the axial
position is forming σ bonds. These p orbitals overlap laterally producing the delocalized π
molecular orbital lying above and the other half below the plane of sigma bonds following the
Huckel’s rule of aromaticity [(4n+2) rule, with n=1), it should be noted that the N- having lone
pair of electrons being in sp2 hybrid orbital do not interact with pi molecular orbital.
4. Pyridine contains a planar cyclic structure with six π electrons, but the nitrogen atom is more
electro negative than carbon(n=3, C=2.5), due to this it resembles nitrobenzene in many of its
properties. 5. Pyridine exhibits the following canonical structures showing its resonance stability.
17. How is Indole synthesized by Fischer’s method? Give the equation. (4m)
Phenyl hydrazone of pyruvic acid (CH3COCOOH) is heated with ZnCl2 catalyst, it gives
Indole-2-carboxylic acid which is decarboxylates by heating with soda lime to get Indole.
18. Describe Skraup’s synthesis of Quinoline. (4m)

Aniline is reacted with glycerol, concentrated sulphuric acid, nitrobenzene and ferrous sulphate,
quinoline is obtained. This reaction is called Skraup’s synthesis
19. How is acetylene converted into i) Pyrrole ii) Pyridine (each 2m)
i) Pyrrole: Acetylene and ammonia is passed through red hot tube to get pyrrole
ii) Pyridine: Acetylene and hydrogen cyanide is passed through red hot tube
3HC º CH + HCN---red hot tube--à Pyridine

20. Explain why pyridine is more basic than pyrrole?)(3m)
Basicity is due to the availability of lone pair of electrons on the nitrogen for protonation.
Pyrrole, pyridine and piperidine, all three have an N-atom containing a lone pair of electrons,
they are basic in nature.
Weak basic nature of pyrrole is due to the lone pair of electrons on nitrogen is involved in the
formation of the delocalized pi molecular orbital and is not available for the formation of a new
bond with proton. Furthermore, if proton is added to the N-atom by reaction with an acid, the
resulting structure ceases to be aromatic and the resonance energy is lost.
This makes the pyrrole cation very unstable in comparison to the free pyrrole and indicates why
pyrrole is a weak base.
Pyridine behaves as a base and reacts with acid forming fairly stable salt.
Pyridine is a strong base than pyrrole. This is because the lone pair of electrons on N-atom is not
involved in the formation of the delocalized pi molecular orbital and so readily available for
protonation. Thus it is a stronger base than pyrrole.
21. Compare the basic strengths of pyrrole and pyridine and thiophene..(2m)
Pyridine is more basic than Pyrrole than Thiophene (Pyridine >Pyrrole > Thiophene)
Basicity is compared on the basis of how easily and effectively the base can share its lone pair.
As in pyrrole, the lone pair of N is already involved in the cyclic conjugation and is completely
delocalized over 6 atoms; the lone pair is in available for donation. In pyridine, nitrogen has
already contributed a pie electron and so its lone pair is free for donation. Electron pair
availability indicates the strength of basicity. In this case, pyridine is the stronger base. While
pyridine is an electron deficient specie (inductive effect of nitrogen) and behaves as if it a
nitrobenzene (m), pyrrole is an electron rich specie( lone pair of nitrogen goes into the ring to
make it aromatic) compared to thiophene with sulphur atom which is less electronegative.
22. Compare the basicities of Pyrrole pyridine and piperidine with the help of their pKb values.
The pKbvalues of a base is the measure of the strength of a base, smaller its value stronger be its
basic character. pKb values of the above heterocyclics are:
Piperidine(2.9),Pyridine(8.8),Pyrrole(13.6).
Their basicities follows (decreasing)the order: Piperidine(2.9)>Pyridine(8.8)>Pyrrole(13.6).
In piperidine N atom is in sp3 hybrid orbital where as in pyridine it is in sp 2hybrid order. Due to
this and the percentage of s character, the lone pair of electrons on Nitrogen atom in Piperidine is
readily available compared to pyridine where it is bonded with hydrogen or proton. Hence
Piperidine is more basic compared to the other two heterocyclics.

Ch-03-Hetrocyclic Compounds

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Heterocyclic compounds

3. Explain Chichibabin reaction of pyridine with equation.(2m)

4. Give the method of preparation of Thiophene.(2m)

5. How is pyrrole prepared from ammonium mucate?

6. Explain the Friedel craft’s reaction of thiophene.(2m)

9. How is thiophene prepared from acetylene? Give the chemical equation.(2m)

10. How is Indole converted in to 3-nitro indole? or

13. Explain the aromaticity of pyrrole (3m)

16. Explain the aromaticity of pyridine (3m)

18. Describe Skraup’s synthesis of Quinoline. (4m)

3HC º CH + HCN---red hot tube--à Pyridine

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