Midsem 2016

a) Draw and explain by molecular orbital diagram the electronic configuration and
nature of cyclooctatetraene. Write the stable structure of cyclooctatetraene and
predict its aromaticity.
b) Is [10] annulene aromatic? Write all the possible structures of [10] annulenes and
explain each one of them.
c) Write the name of the products formed when graphite is heated under inert
atmosphere. Describe briefly the structure and properties of the products formed.
d) Write atleast four postulates of Molecular Orbital Theory.
e) Draw and explain MOT diagram for Allyl system (cation, free radical and anion).
Predict the order of their stability.

a) Explain the electronic configuration of cyclopropenyl systems (cation, free radical

and anion) and predict their nature based on Huckle’s rule of aromaticity.
b) Define the term torsional strain and angle strain and explain with structural
examples.
c) Draw the Newman projection ofchair and boat conformations of cyclohexane. Which
conformer is stable and why?
d) Draw and explain the stability of methyl cyclohexane conformers. How many
gauche-butane interactions are present in each of the conformers? Which conformer
is more stable and by how much energy compared to the other?
e) Write the structural formulas of two chair conformations of cis-1-isopropyl-4-
methyl cyclohexane. Which conformation is stable and preferred at equilibrium?
How many gauche butane-interactions are present in the unstable conformer.

a) Draw the structural formula of a compound which contains three cylohexane rings
fused together. Why diamond is an insulator and one of the hardest substance
known?
b) Write the synthetic steps of for preparation of 3-butyl-2-heptanone.
c) Write step by step mechanism for the preparation of 2-acetylcyclopentanone.
d) How will you prepare acetoacetic ester from ethylacetate? Explain the significance of
alpha hydrogens in this reaction with stepwise mechanism.
e) Beta keto acids undergo spontaneous decarboxylation. Why? How will you
preparebutan-2-one?
 Midsem 2017
(a) Electron waves are described by a wave equation similar to that of string waves or
standing waves. Solution to wave equation gives rise to various parameters which fully
describes the nature of electron. Explain each parameter and its inference for electron.
(b) Write four postulates of Molecular Orbital Theory developed by Linus Pauling.
(c) Explain the arrangement of π-electrons in cyclopentadienyl system (cation, radical and
anion) as per MOT and predict the order of stability as per Huckle’s theory.
(d) As per Huckle’s theory, cyclopropenyl cation is more stable and aromatic compared to
its
radical and anion counter parts. Explain the arrangement of π- electrons in each system
using MOT and substantiate the above statement.
(e) Draw MOT diagram for arrangement of π-electrons in ethylene and 1,3-butadiene in the
ground as well as excited state as per LCAO.

(a) Predict the stability order of cyclopentadienyl anion, benzene and cycloheptatrienyl
cation by drawing electronic configuration of π electrons and why?
(b)Explain strain theory of ring compounds starting with the smallest possible ring. Which
is the most stable among all the ring compounds and why? Note: You need to draw chemical
structure of ring compounds, define angles and predict kind of strain in each molecule
based on strain theory.
(c)Draw both the conformers of 1-methylcyclohexane. Predict which conformer is stable
and why? Write the concentration ratio of conformers in equilibrium as per Nuclear
Magnetic Resonance studies.
(d)Draw the number of stereoisomers possible in 1,2-dimethyl cyclopropane. Which one of
them is optically active and why? Explain the optical activity based on symmetry elements
present in respective stereoisomers.
(e) How many stereoisomers are possible for 1,2-dimethyl cyclohexane? Draw and explain
their optical activity. How many stereoisomers are isolated in reality and why?

(a) Many molecules do not possess chiral centres but still they are chiral. Write down the
structures of two different families of compounds and explain their chirality based on the
knowledge of symmetry elements.
(b) Explain by drawing 3D chemical structure and hybridization principle why diamond is
insulator whereas graphite is a conductor?
(c) Explain stereoisomerism in cis and trans-1,3-dimethylcyclohexanes. Which one of the
stereoisomers are chiral and why?
(d) Draw and predict the number of gauche-butane interactions present in trans-1-chloro-
4-t-butyl cyclohexane conformers. Which of the conformers are stable and by much how
energy does the least stable conformer possess?
(e) Draw the structure of cis and trans-decalins. Which one is stable and how many gauche
butane interactions are present in cis and trans-decalins. Indicate by drawing thick lines in
the bicyclic rings.

(a) Pyrrole undergoes electrophilic aromatic substitution reaction. Predict the

regioselectivity of the product and explain the preference of substitution by drawing
resonance structures.
(b) Arrange benzene, nitrobenzene, anisole, and pyridine in the increasing order of
electrophilic aromatic substitution reactions.
(c) pKa1 and pKa2 of glycine are 2.3 and 9.6 respectively. What is the isoelectric point of
glycine?
(d) Write the structure of adenine and 5-methyl uracil.
(e) The sequence of amino acids in a peptide chain is determined chemically by the Edmann
and Sanger methods. Write the chemical structure of reagents used in these methodologies.

(a) Write step by step mechanism for acid catalyzed halogenation of methyl ketones. What
happens to the rate of the reaction if the concentration of methyl ketone is doubled?
(b) Benzaldehyde when treated with 50% alkaline solution undergoes auto-oxidation and
auto-reduction. Explain the reaction mechanism for the formation of product and the effect
of
methoxy and nitro substituents in the rate of the reaction.
(c) Ethyl acetate undergoes self-condensation to form β-keto ester in presence of mild base,
sodium ethoxide. Explain with mechanism how the product formation is favored even
though
every step is an equilibrium step?
(d) How will you prepare 4,6-nonanedione from 2-pentanone? Write the equations with
proper reagents and along with mechanism.
(e) 3-Butyl-2-heptanone is prepared from the condensation product of ethylacetate suing
mild base. Please use appropriate reagents and reactants for the preparation of the 3-Butyl-
2-heptanone in a stepwise manner.

(a) Normally aldehydes undergo addition reactions with nucleophiles. However it is

possible to make carbonyl carbon of aldehydes to react with electrophile which is unusual.
Using this methodology how will you prepare acetophenone?
(b) It is almost impossible to introduce functional groups in cyclobutane. However
cyclobutane carboxylic acid in prepared in ease in laboratory from diethyl malonate using
appropriate reagents and reactants. Explain the steps involved in the preparation of
cyclobutane carboxylic acid.
(c) What happens when 1° or 2° amine is mixed with methanal and acetone in the presence
of mild acid? Explain the formation of product with mechanism.
(d) Treatment of acetoacetic ester with -bromo ethylacetate in the presence of sodium
ethoxide followed by hydrolysis results in the formation of -ketoacid. Explain the
formation of -ketoacid instead of β-ketoacid with reagents and mechanism.
(e) 2-Methylcyclohexane-1,3-dione undergoes addition reaction with MVK followed by
condensation in presence of mild base to form the core structure of steroids. Write the
names of the reactions involved along with the structure of product formed using proper
reagents and mechanism.
 End sen 2019
(a) Explain the arrangement of π-electrons in cyclopentadienyl system (cation, radical and anion)
as per MOT and predict the order of stability as per Huckle’s theory.
(b) As per Huckle’s theory, cyclopropenyl cation is more stable and aromatic compared to its
radical and anion counter parts. Explain the arrangement of π- electrons in each system using
MOT and substantiate the above statement.

(a) Draw the conformers of tert-butylcyclohexane. Predict which conformer is stable and why?
Write the concentration ratio of conformers in equilibrium as per Nuclear Magnetic Resonance
studies.
(b) Draw the number of stereoisomers possible in 1,2-dimethyl cyclopentane. Which one of them
is optically active and why? Explain the optical activity based on symmetry elements present in
respective stereoisomers.

(a) Explain stereoisomerism in cis and trans-1,2-dimethylcyclohexanes. How many

stereoisomers are possible and how many are isolable? Why?
(b) Draw and predict the number of gauche-butane interactions present in trans-1-chloro-4-t-butyl
cyclohexane conformers. Which of the conformers are stable and by much how energy does the
least stable conformer possess?

(a) Benzaldehyde when treated with 50% alkaline solution undergoes auto-oxidation and auto-
reduction. Explain the reaction mechanism for the formation of product and the effect of methoxy
and nitro substituents in the rate of the reaction.
(b) Ethyl acetate undergoes self-condensation to form β-keto ester in presence of mild base,
sodium ethoxide. Explain with mechanism how the product formation is favored even though
every step is an equilibrium step?
(c) 3-Butyl-2-heptanone is prepared from the condensation product of ethylacetate using mild
base. Please use appropriate reagents and reactants for the preparation of the 3-Butyl-2-heptanone
in a stepwise manner.

(a) What is Atropisomerism? Explain with examples. Chirality can be exhibited by molecules that
do not possess chiral center. Explain?
(b) Treatment of acetoacetic ester with -bromo ethylacetate in the presence of sodium ethoxide
followed by hydrolysis results in the formation of -ketoacid. Explain the formation of -
ketoacid instead of β-ketoacid with reagents and mechanism.

(a) EtS-CH2CH2Cl is found to undergo hydrolysis 104 times faster than EtOCH2CH2Cl under
comparable condition. Explain.
(b) Which tosylate is found to undergo 103 times faster solvolysis in acetic acid under comparable
condition? Predict the product(s) and explain with mechanism.

(a) Predict the product(s) for the following reactions and explain with mechanism.

(b) Mention the order of reactivity towards electrophilic substitution reaction of the
following five membered heterocyclic compounds. Explain.
 End sem 2020

(a) Linear combination of atomic orbitals is explained by Molecular Orbital Theory

developed by Linus Pauling. Explain the postulates of MOT.
(b) Explain the arrangement of π-electrons in cyclopentadienyl system (cation, free radical
and anion) as per MOT and predict the order of stability.
(c) Predict the stability order of cyclopentadienyl anion, benzene and cycloheptatrienyl
cation by drawing electronic configuration of π electrons and explain?

(a)Explain strain theory of ring compounds starting with the smallest possible ring. Which
is the most stable among all the ring compounds and why? Note: You need to draw chemical
structure of ring compounds, define angles and predict kind of strain in each molecule
based on strain theory.
(b)Draw the number of stereoisomers possible in 1,2-dimethyl cyclopentane. Which one of
them is optically active and why? Explain the optical activity based on symmetry elements
present in respective stereoisomers.
(c) How many stereoisomers are possible for 1,3-dimethylcyclohexanes? Draw and explain
their optical activity. How many stereoisomers are identified in reality and why?

(a) Draw the structure of cis and trans-decalins. Which one is stable and how many gauche
butane interactions are present in cis and trans-decalins. Indicate by drawing thick lines in
the bicyclic rings.
(b) Explain by drawing 3D structure and hybridization concept why diamond is an insulator
whereas graphite is a conductor?
(c) Draw and predict the number of gauche-butane interactions present in trans-1-chloro-4-
t-butyl cyclohexane conformers. Which of the conformers are stable and by much how
energy does the least stable conformer possess?

(a) Pyridine undergoes electrophilic aromatic substitution reaction. Predict the

regioselectivity of the product and explain the preference of substitution by drawing
resonance structures.
(b) How will you synthesize the dipeptide Ala-Phe using a coupling agent and protected
aminoacids. Explain with step by step mechanism.
(c) One of the methodologies to determine the sequence of amino acids in a peptide chain
was discovered by Sanger. Explain the method with chemical equation for determination of
a tripeptide sequence.

(a) Normally aldehydes undergo addition reactions with nucleophiles. However it is

possible to make carbonyl carbon of aldehydes to react with electrophile which is unusual.
Using this methodology how will you prepare acetophenone?
(b) 2-Methylcyclohexane-1,3-dione undergoes addition reaction with MVK followed by
condensation in presence of mild base to form the core structure of steroids. Write the
names of the reactions involved along with the structure of product formed using proper
reagents and mechanism.