QP CODE: 22001593

M.Sc. Degree (C.S.S) Examination, July 2022

First Semester (2019 Admission onwards)
CH500102- Structural and Molecular Chemistry
(Common to all branches of Chemistry)
SCHEME OF VALUATION

INSTRUCTIONS TO THE EXAMINER

• This scheme is only a guideline for the valuation. Any other attempt which is
equally valid and correct, may be given due credit.
• Some of the answers given in the scheme are elaborate and this is to help the
examiner in their valuation. Please do not expect all those points in the answers
of the students.
• If the answer is complete full credit may be given even if the required
number of valuation points could not be identified.
• The valuation points are set for Regular batch (2020 registration) following the
Covid relaxation order by Mahatma Gandhi University.

Time: 3hr Weightage: 30

Part A(Short Answers)
Answer any five questions. Each question carries weight 1.5
[For supplementary students - Answer any eight questions. Weight 1 each.]
(5 points –A+ grade; 4 – A grade; 3 –B grade; 2 – C grade; 1point –D grade ;)

1.Explain the aromaticity of cycloheptatrienyl cation.

In a cycloheptatrienyl cation, seven carbon atoms are arranged in a cyclic manner so as to give it
a structure similar to a regular heptagonal one. All the carbon atoms are sp 2 hybridized. In a
tropylium ion or a cycloheptatrienyl cation, there are six electrons that take-up the three bonding
pi-molecular orbitals, thus, there are three double bonds present in the structure and the seventh
carbon atom has a positive charge on it. Since it can undergo resonance, its hybrid structure
consists of seven resonating structures in which each carbon atom carries part of the positive
charge.

Any compound is said to be aromatic then it should be:

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 ● Cyclic.
● Planar.
● Conjugation in the system.
● Presence of [4n + 2] π electrons.

It can be seen that cycloheptatrienyl cation obeys Huckel’s rule as it has six electrons that falls
under the category of (4n+2) π-electrons forming an uninterrupted electron cloud. Furthermore, it
is a planar and a cyclic structure. Also, it has got three bonding π-MO (molecular orbitals) which
are fully filled by the six pi electrons. Hence, all of this observations show that the tropylium
cation is an aromatic ion or compound.

The molecular orbital diagram for the 7 p orbitals in the tropylium cation has three bonding
MO's and 4 antibonding MO's. The tropylium cation's 6 pi electrons completely fill the bonding
molecular orbitals which is consistent with the tropylium cation being aromatic and therefore
unusually stable.
Huckels rule 2 point
Structue 1 point
Explanation 2 points
2.What is a Wheland complex.

Wheland complex is a cyclohexadienyl cation that appears as a reactive intermediate in

electrophilic aromatic substitution. The electrophile formed in the reaction reacts with the arene
e.g. benzene to generate a carbocation . The structure of the ionic intermediate after attack by
electrophile is a resonance hybrid of three resonance contribution structures which can be
represented by a single structure showing the delocalization of charge. This wheland complex is
also called sigma complex, since the electrophile is joined to the benzene ring via a new sigma
bond. This sigma complex is not aromatic, since the sp3 hybrid carbon atom interrupts the ring
of P orbitals. (i.e., the cyclic system of pi electrons is interrupted)

Definition -3 points
2 Structure -2 points
3. .Explain the steps involved in the esterification by B AC 2 mechanism.

Bimolecular base catalyzed reaction involving acyl- oxygen fission is the most common
mechanism for the basic hydrolysis of esters. This is kinetically a second order reaction, first
order in ester and first order in hydroxide ion.It is, therefore a bimolecular reaction.

The basic hydrolysis of esters of primary and secondary alcohols takes place by this mechanism.
The B AC 2 mechanism may be explained as follows. Since the carbonyl carbon of the ester (1) is
slightly positively charged due to mesomeric effect, hydroxide ion combines with it to form the
anion (II). The negative charge on the oxygen atom of the anion (II) attacks carbonyl carbon and
the ethoxyl group is expelled as ethoxide ion (IV) to form the acid (III). Finally a proton
exchange takes place from the acid (III) to the ethoxide ion (IV) to form a more stable pair
namely carboxylate ion (V) and ethyl alcohol (VI).

The rate determining step is the initial attack of HO-on the ester and the overall reaction is
irreversible due to the insusceptibility of RCOO to be attacked by EtOH.

The following facts support the BAC 2 mechanism for the hydrolysis of esters: (1) The rate of
hydrolysis α [ester] [ HO- ] and (2) The amyl alcohol obtained by the hydrolysis of n-amyl
acetate in H2O18 contained none of the heavy oxygen showing acyl-oxygen cleavage.

Definition- 2 points
Mechanism - 3 points

4.What is photo Fries rearrangement.?

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Phenolicesters rearrange to ortho and para acyl phenols when heated with anhy.AlCl3 and the
reaction is called Fries Rearrangement.

Fries rearrangement can be carried out with UV light in the absence of a catalyst and the reaction
is called Photo - Fries rearrangement.

Photo - Fries rearrangement is an intramolecular rearrangement. The ester dissociates into

phenoxy and acyl radicals which combine within the solvent cage to give intermediates before
diffusion from the solvent cage. The phenol is produced by phenoxy radicals which escape from
the solvent cage

.
Definition and equation -3 points
Explanation / mechanism -2
points
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5. Unlike ethyl methyl amine, 2-butanamine can be resolved into enantiomers. Why.

Due to their tetrahedral configuration, amines with three different substituents are chiral. The R
and S enantiomeric forms of chiral amines cannot be resolved due to their rapid interconversion
by a process called pyramidal or nitrogen inversion. The N-atom of ethyl methylamine
undergoes fast inversion, so it cannot be resolved under normal conditions.

In 2 butanamine the chirality is due to the presence of chiral carbon atom and therefore
butanamine can be resolved into enantiomers

Ethyl methyl amine structure- 1 point

2 Butanamine structure -1 point
Explanation -3 points
6).Which of the following molecules are chiral? Give reason.

a) Due to the presence of plane of symmetry, the molecule is achiral.

b) Allene is achiral due to presence of plane of symmetry, (end carbon do not possess
different substituents).
c) Not chiral due to the absence of four different substituents in the tetrahedral carbon.
d) Chiral, due to the presence of chiral carbon. 4 correct answers- 4 points
Explanation 1 point

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7.What is prostereoisomerism.

It is the property of some molecules due to which these molecules can be converted into
stereoisomers (enantiomers or diastereomers) by replacing one of the identical atoms or groups
by a different atom or group. If the replacement of such atoms or groups leads the formation of
enantiomers, then atoms or groups are said to be enantiotopic; whereas, if such replacement lead
the formation of diastereomers the atoms or groups are termed as diastereotopic.

e.g.

When a carbon has two hydrogens and two other different groups (Cl & I in this case) the
hydrogens are enantiotopic. Replacement of one of these hydrogen atom with deuterium gives
‘R’ while replacement of the other gives ‘S’ toshow these are enantiotopic.
Definition 3 points
Example 2 points
8. Gauche conformer of 2-chloro ethanol is stabler than its anti. Explain.

In most molecules of the type YCH2-CH2Y and YCH2-CH2X the anti-conformation (dihedral
angle 180o) is the preferred conformation since the anti-conformation is having lower energy due
to least steric strain.

In 2 chloro ethanol also steric strain is lowered in the anti-conformation since the repulsive
interaction caused by the comparatively bulky Cl and the OH groups being forced too far apart.
But molecules containing small electronegative atoms generally prefer gauche conformation.
This is known as gauche effect, i.e. the tendency to adopt the structure which has the maximum
gauche interactions between adjacent polar bonds. Another factor which increase the stability of
gauche conformation is the intramolecular hydrogen bonding between the more electronegative
Cl atom and Hydrogen of the hydroxyl group.

Structure of guache conformation (H bonding) 2 points

Explanation for anti and guache conformations 3 points

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9. Draw the conformations of adamantane and norbornane.

Adamantane

Adamantane molecules consists of three connected cyclohexane rings arranged in the "armchair"

The three condensed cyclohexane rings fused in the chair conformation. The carbon-
carbon bond length is 1.54Å and is almost identical to that of diamond, and the carbon-
hydrogen distance is 1.112 Å.
Although a model of adamantane appears strain-free, the molecule has about 7.6 kcal
/mol. This is more than four times the strain in cyclohexane. In adamantane, the
framework structure constrains the bond angles to be nearly perfectly tetrahedral.
However a C-CH2-C bond angle does not want to be exactly tetrahedral; the optimum
(in propane) is 112.5° and in the slightly strained cyclohexane the angle is 111.5°. It is the
further reduction to 109.5° which causes the additional strain in adamantane.

Norbornane (bicyclo [2.2.1] heptane)

In this compound C1 and C4 of cyclohexane are joined by a methylene bridgeforcing it to

adopt a boat conformation.

Protons with subscripts a and a’ are in boat equatorial orientation and those with subscripts b and
b’ are in boat axial orientation. Substituents in boat equatorial orientation are called exo and
those in boat axial orientation are called endo. Protons with subscripts a and b (and also those
with a’ and b’) are diastereotopic and separate replacements of each by a substituent yield exo

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and endo diastereomers respectively. Protons with subscripts a and a’ (and also with b and b’)
areenantiotopic and separate replacement of each by a substituent yield a pair of enantiomers.
Adamantane conformation 2 points
Norborane conformation 3 points

10. Axial conformer of cyclohexane reacts faster than equatorial. Why?

For mono-substituted cyclohexane, the equatorial-conformer is more stable than the axial-
conformer because of the 1, 3-diaxial interaction. The axial conformation is higher in energy.
The steric strain of the axial isomer is relieved in the transition state. Less activation energy is
needed for the axial substituent than the equatorial and thus the axial reacts faster.

SN1 reactions proceed through the formation of carbocation which relieves the steric strain of
the axial isomer due to 1,3-diaxial interactions. Thus, the SN1 reaction is sterically assisted for
an axial substituent, such type of steric acceleration will not occur with the corresponding
equatorial substituent. E.g.; the acetolysis of cis-4-t-butyl cyclohexyl tosylate, with an axial tosyl
group, is about 3.4 times faster than that of the trans isomer.

SN2 reactions takes place more readily with axial substituent than with equatorial. For example,
the SN2 reaction of the thiophenoxide ion with 4, t-butyl cyclohexyl bromide having an axial Br
takes place about 60 times faster as compared to the equatorial isomer because the attack of the
thiophenoxide ion on the equatorial isomer is hindered by the axial hydrogens.

Correct reasoning 5 points

Part B (Short Essay/Problems)

Answer any five questions, each question carries 2.5 weight.

[For supplementary students, answer any six questions. Weight 2 each]

(5 points –A+ grade; 4 – A grade; 3 –B grade; 2 – C grade; 1point –D grade ;)

11. Illustrate elimination -addition and addition-elimination mechanisms.

There are four principal mechanisms for aromatic nucleophilic substitution which is similar to
that of aliphatic nucleophilic substitution.

SNAr (Addition- Elimination) Mechanism is one among them and involves a resonance-
stabilized anionic intermediate called the Meisenheimer complex. The introduction of electron

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withdrawing groups (EWG) on the aromatic nucleus makes the system susceptible to
nucleophilic attack. The mechanism is similar to that of electrophilic substitution except that an
anion rather than a cation intermediate is involved. The nucleophile adds to the aromatic ring to
afford a delocalized anion from which the leaving group (LG) is eliminated.

The delocalization of the negative charge can occur only when the nucleophile adds to the ortho
or para position with respect to the EWG. Addition to meta position gives an adduct stabilized by
the inductive effect, but not the mesomeric effect. Therefore, towards nucleophiles, EWG are
activating and ortho, para-orienting and, in contrast, electron donating group (EDG) deactivating
and meta directing. Eg:

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Nucleophilic elimination- Addition –The Benzyne

Haloarenes do not undergo simple SN2 or SN1 reactions. However, at high temperature and
pressure nucleophilic substitution can be achieved. Thus with hot sodium hydroxide followed by
neutralizing work-up, chlorobenzene gives phenol. Similarly chlorobenzenereacts with
sodiumamide (a very strong base).Thus unlike the addition-elimination mechanism for
nucleophilic aromatic substitution which depends on strong electron withdrawing substituents on
the aromatic ring, under extreme conditions unactivated halobenzenes react with strong bases.

Direct substitution mechanisms are not operative on these compounds. An interesting feature of
this reaction is that the incoming nucleophile does not necessarily takes the position vacated by
the leaving group. This is called cine substitution. In the presence of other nucleophiles mixed
products are formed. Thus ortho chlorotoluene reacts with sodium amide gives 50:50 mixture of
ortho and meta products.

This reaction proceeds via benzyne (aryne) intermediate and the mechanism is called benzyne
(aryne) mechanism. The benzyne intermediate has a triple bond in benzene ring. The triple bond
in benzyne is unusual as each carbon of the six-member ring is sp2 hybridized, and as a result,
the σ bond and two π bonds of the triple bond are formed with the overlapping orbitals. Although
benzyne has been best described as to having a strained triple bond, a biradical representation is
also useful and describes properties of the system.

The reaction of chlorobenzene (radioactive labelled) with sodium amide gives equal amounts of
aniline labelled in position 1 and in the position 2.Step by step elimination through phenyl anion
intermediate gives a highly strained and reactive species called benzyne or 1,2 dehydrobenzyne.

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The benzyne intermediate is symmetrical and can be attacked by amide ion either at two
positions. This formation of the intermediate benzyne, thus explains why half of the aniline
produced from radioactive chlorobenzene was labelled at the position 2.

In some cases, the aromatic nucleophilic substitution occurs at an adjacent position and is called
cine substitution.it can be attacked at both positions. The favoured position for nucleophilic
attack is the one which leads to more stable carbanion intermediate. Thus, in the case of -I
groups, the more stable carbanion is the one in which negative charge is closer to the electron
withdrawing substituent.
SNAr mechanism with explanation - 2 points
Benzyne mechanism with explanation -3 points

12. State Hammond postulate. Explain the significance of Hammond postulate with examples.

Hammond postulate states that 'If two states, a transition state and an unstable intermediate,
occur consecutively during a reaction process and have nearly the same energy content, their
interconversion will involve only a small reorganization of molecular structure'.

The significance of Hammond postulate is that it permits discussion of TS structure in terms of

the reactants, intermediates, or products in a multistep reaction sequence. The postulate indicates

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that the cases where such comparison is appropriate are those in which the TS energy is close to
that of reactant, intermediate, or product.

Electrophilic aromatic substitution is a situation in which it is useful to discuss TS structure in

terms of a reaction intermediate. The ortho, para, and meta directing effects of aromatic
substituents were among the first structure-reactivity relationships to be developed in organic
chemistry. Certain functional groups activate aromatic rings towards substitution and direct the
entering electrophile to the ortho and para positions, whereas others are deactivating and lead to
substitution in the meta position. Example, the bromination of methoxybenzene (anisole),
benzene, and nitrobenzene.

Potential Energy Diagram for Electrophilic Aromatic Substitution

Reaction

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These reactions are kinetically controlled; that is, there is no isomerization among the ortho,
meta, and para products after they are formed. It is therefore the ΔG values that hold the key to
the connection between the rate effects and the substituent-directing effects. However, to discuss
the effect of substituents on ΔG, we must know about the reaction mechanism and the nature of
the competing TS. Evidence indicates that electrophilic aromatic substitution involves a distinct
intermediate and two less well-defined states. The potential energy diagram is believed to be a
good representation of the energy changes that occur during bromination. By application of the
Hammond postulate, we conclude that the rate-determining step involves formation of a TS that
closely resembles the intermediate, which is called the σ complex .It is therefore appropriate to
discuss the effect of substituents on the TS in terms of the structure of this intermediate.

Postulate 2 points
P E diagram 1 point
Significance with Example 2 point

13. Discuss the photochemistry of Vision.

When light hits the retina special cells called photoreceptors turn the light into electrical signals.
These electrical signals travel from the retina through the optic nerve to the brain. Then the brain
turns the signals into the images we see. The vital parts of the eye are the lens and retina. The
retina is made up of two kinds of light-sensitive (photoreceptor) cells, known as rods and cones.
The rods are more sensitive and are responsible for vision in dim light. The cones are
comparatively less sensitive than the rods and provide colour vision in good light. The part of the
retina that corresponds to the center of the visual field contains only cones. Retinol or Vitamin A
plays a crucial role in Vision.

A red pigment called rhodopsin or visual purple is the photosensitive pigment in the rod cells of
the retina. Rhodopsin absorb light in the visible spectrum at 400 - 800 nm.Rhodopsin is madeup
of a protein called opsin, and the highly conjugated aldehyde, 11-cis-retinal.11--retinal is derived
by the oxidation of vitamin A -retinal), Complexation between opsin and 11-cis-retinal takes
place by imine formation between the primary amino group of the lysine in the side chain of the
protein (opsin) and the aldehyde group of 11-cs-retinal to form rhodopsin. This protein-retinal
complex absorbs light energy of a visible photon and undergoes stereo mutation of the 11- cis
C=C to 11-trans C=C. This change in the molecular geometry of the retinal separates from the
protein surface, since the all-trans structure of the retinal cannot be sterically accommodated on
the opsin surface. This detachment of the two components of the complex is called bleaching of
rhodopsin and this causes an electrical signal to the brain, where it is translated into visual image.

The photosensitive pigment in the cone cells is called iodopsin. The protein part is photopsin.
The three different kinds of cone cells in man responds to three different wavelengths. Each

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contains 11-cis-retinal and photopsin. The photons of these three wavelengths cause change in
the configuration of the 11-cis-retinal form to all-trans form of retinal in each type of cone cell,
causing an electrical signal to the brain which translates into the respective colours. The time
taken for all these processes are in the picosecond range.

Explanation 3 points
Reaction 2 points

14. Write a brief note on Akamptisomerism.

Akamptisomerism is shown by molecules of the type M1-X-M2, where the central atom X
exhibits a bent geometry and M1 and M2, are any atoms or groups.

For example consider the molecule methoxyethane

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The bond angle inversion (BAI) of the akamptisomer 1 of the ether gives akamptisomer 2 .BAI
is similar to the pyramidal inversion in ammonia and amines and in this case involves the
pushing of oxygen atom above and below C-O-C moiety. In this case the isomer 2 is a slightly
higher energy structure. However torsional motions about the two C-O bonds regenerate the
original structure. Since the torsional motions are low energy processes the two isomers cannot
be separated. The two akamptisomers of methoxy ethane are conformational isomers which
interconvert readily at room temperature. Akamptisomers can only be separated if the torsional
motion is prevented. Thus to observe akamptisomerism, external restraints must be introduced
that prevent torsional motions about single bonds.

Akamptisomers have been separated by encapsulating B-0-B as (BF)O(BF), inside a porphyrin

macrocycle. In this compound the two enantiomers have been resolved.

In this case the torsional transitions between akamptisomers is a higher energy process compared
to BAI and hence cannot cause the interconversion of isomers at ordinary temperature.

The BAI also requires high energy and the two isomers cannot interconvert readily. The two
Isomers (enantiomers) are termed as parvo and amplo.In short, akamptisomerism is a type of
optical isomerism shown by molecules of the type M1-X-M2, with bent geometry and the
torsional motions with respect to M1X and XM2 bonds are restricted.
Definition 3 points
Example 2 points

15. Briefly discuss geometrical isomerism and methods for the determination of configuration of
geometrical isomers.

Two isomers which have the same structural formula but differ in the spatial arrangement of
atoms or groups around a double bond due to restricted rotation about the double bond are called
geometrical isomers and the phenomenon is called geometrical isomerism. In short, geometrical

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isomerism is the type of stereoisomerism which arises due to restricted rotation about double
bonds.

Geometrical isomers are non-mirror image of each other hence they are called diastereomers.
Therefore their physical and chemical properties are different.

Following two conditions are necessary for any compounds to show geometrical isomerism

a) There should be restricted (not allowed) rotation about a bond in a molecule.

b) Both substituent/atoms on each carbon about which rotation is not allowed should (restricted)
be different.

Thus, molecules like abC-Cab, abC-Cad, etc. show geometrical isomerism whereas a2C-Ca2, a2C-
Cab, etc. do not show geometrical isomerism.Triple bonded molecules do not exhibit any kind of
stereoisomerism because such molecule shows cylindrical symmetry.

Cis Trans isomers

The geometrical isomer with similar groups on the same side of the double bond called the cis
isomer while the one with similar groups on opposite sides of the double band is called the trans
isomer. Hence, geometrical isomerism is also referred to as cis-trans isomerism.

In but-2-ene the two methyl groups can lie either on the same side or on opposite sides of the
double bond. Compound 1 is cis-but-2-ene and compound 2 is trans-but-2-e.

E- Z Nomenclature for Geometrical Isomers

According to the E-Z nomenclature the groups at both doubly bonded carbon atom are
arranged according to the sequence rule. If the higher priority groups are on the same side
that isomer is called Z-isomer and if the higher priority groups are on the opposite side
that isomer is called E-isomer. Some examples are given below.

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Geometrical isomerism in oximes and cyclic compounds
Nitrogen containing compounds like >C=N- as well as –N=N- bond also exhibit
geometrical isomerism. The important classes of compounds thatexhibit
geometricalisomerism due to >C=N- bond are:
(a) Oximes

(b) Nitrones

(c) Semicarbazones

(d) Hydrazones

Oximes are the most common compounds among all above classes. Both carbon and nitrogen
atom in oxime are sp2 hybridized the C=N bond of oxime consists a sigma (σ) and a pi (π) bond.
Therefore, there is no free rotation possible around C=N bond; hence, oximes of aldehydes
andketones (unsymmetrical) exhibit geometrical isomerism. The configuration of such
compounds is also based on priority of the groups/atoms attached to the double bonded carbon
and nitrogen. Lone pair of the nitrogen always considered to be the lowest priority group. If the
higher priority groups/atom on double bonded carbon and nitrogen are on same side of the
double bond the isomer is considered as Z- isomer, whereas if the higher priority groups/atoms
are on opposite side the isomer is considered as E- isomer.

Examples of E/Z isomers of oximes

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Geometrical isomerism is usually arises due to restricted rotation about a bond. Since, there is no
rotation possible about the carbon-carbon bond in a cyclic compound or cycloalkanes like
cyclopropane, cyclobutane, cyclopantane, cyclohexane, etc. Hence, such molecule also exhibit
geometrical isomerism, and can be designated as cis- and trans- isomer. In a disubstituted
cycloalkanes, where the two atoms/groups are bonded on different carbons, can be represented in
to two geometrical isomers. The isomer in which the two atoms/groups are located on the same
side of the ring is called cis-isomer; whereas, the isomer in which the two atoms/groups are
located on the opposite side of the ring is called trans-isomer

Examples: Geometrical isomers of disubstituted cyclopropane, cyclobutane

Methods of Determining Geometrical Isomers

i)Dipole Moments
In a compound of the type abC=Cab, generally the cis isomer has a finite dipole moment
and dipole moment of the trans isomer is zero. In a compound of the type abC=Cad, the
dipole moment of the cis isomer is generally greater than that of the trans isomer. When
one of the substituents on the ethylenic system is electron donating and the other is
electron withdrawing, the dipoles are additive. In such cases the trans isomer has the
highest dipole moment. An example is 1-chloro-1-propene.
ii) Melting Point and Solubilty
Since the trans isomer has greater symmetry than the cis, it fits into the crystal lattice
more easily and therefore generally has a higher melting point. For example melting point
of maleic acid is 130°C and that of fumaric acid is 300°C. Along with this goes the higher
solubility of cis isomer over trans isomer
iii)Method of cyclisation
(a) Of the two acids maleic and fumaric, only the former readily forms a cyclic anhydride
when heated; the latter does not form an anhydride of its own, but when strongly heated,
gives maleic anhydride. Thus I is maleic acid, and II is fumaric acid.

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In a number of cases it is possible to determine the configurations of pairs of geometrical
isomers by converting them into compounds the configurations of which are already
known. As an example of this type let us consider the two forms of crotonic acid, one of
which is known as crotonic acid (m.p. 72°), and the other as isocrotonic acid (m.p. 15.5°).
Now there are two trichlorocrotonic acids, III and IV, one of which can be hydrolysed to
fumaric acid. Therefore this trichlorocrotonic acid must be the transisomer, III;
consequently the other is the cis-isomer IV. Both these tri-chlorocrotonic acids may be
reduced by sodium amalgam and water, or by zinc and acetic acid, to the crotonic acids,
III giving crotonic acid, V, and IV giving isocrotonic acid, VI. Thus crotonic acid is the
trans-isomer, and isocrotonic the cis.

• Definition 1 point
• Cis trans,E-Z, Syn –Anti oximes, Examples 2 points
• Methods of determination (any two) 2 points

16. What are the major products of dehydrohalogenation of trans-1-chloro-2-methylcyclohexane

under E2 conditions? Explain with structures.

The stereoelectronic requirement for an E2 elimination reaction is that the leaving groups should
be in the anticonformation. In cyclohexyl systems the anti-relationship occurs as when the

19
substituent on the two adjacent carbon atoms are in the axialposition. The two
chairconformations of trans-1-chloro-2-methylcyclohexane are shown below:

Among the two conformations, the diaxial conformation D, reacts faster than the diequatorial C

In the diequatorial conformation chlorine is equatorial and cannot be anti periplanar with
hydrogens on C2 or C6.Thus to react by E2 mechanism it must undergo a ring flip, when along
with chlorine the CH3 also in the axial position - a strained situation and thus least stable .Even
though the diaxial conformer is a minor component of the equilibrium mixture, it indeed is the
only chair conformer from which elimination can occur. The diaxial conformer has Chlorine in
the axial position and one hydrogen in the C6 position has anti-coplanar arrangement to give the
least stable Hofmann product.

Stereoelectronic Requirement 1 point

Cis and trans conformations 1 point
Explanation of elimination 2 points
Product 1 point

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17. Predict the product of the given reaction and explain.

The chlorination of 1-chloro-3-nitrobenzene gives 1, 4-dichloro-3-nitrobenzene (1) as the

major product, 1, 2-dichloro-3-nitrobenzene (2) as a minor product.

If chlorine electrophile attacks at C-4 or C-6, the resulting intermediate is stabilized by an

extra resonating structure, lowering the energy of this intermediate. Hence electrophilic
aromatic substitution takes place. But when a meta directing group is meta to an Ortho-
Para directinggroup, the incoming group primarily goes Ortho to the meta directing
group rather than Para. This is called Ortho Effect. So 1, 4-dichloro-3-nitrobenzene will
be the major product.

Products with correct mechanism 5 points

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18.Predict the product and mechanism of the following photochemical reactions.

a) The carbon monoxide in thujone is eliminated more frequently in gas- phase reactions
than in liquid phase reactions. When it is eliminated, a relief of ring strain often appears
to be the driving force for the formation of diene as the product.

b) Barton reaction

The Barton reaction, also known as the Barton nitrite ester reaction, is a photochemical
reaction that involves the photolysis of an alkyl nitrite to form a δ-nitroso alcohol. The
nitroso alcohol may rearrange into an oxime.

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a) Product 1 point
Mechanism 1 point
b) Product 1 point
Mechanism 2 points

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 Part C (Essay Type Questions)

Can answer any three questions. Each question carries a weight of 5.

Maximum WGP is 50.

[For supplementary students, answer any two questions. Weight 5 each}

(5 points –A+ grade; 4 – A grade; 3 –B grade; 2 – C grade; 1point –D grade ;)

19. Write a note on various electron displacement effects in organic compounds and their
applications.

Inductive effect -1 point

Definition, different types, examples, any two applications
Electromeric effect- 1 point
Definition, different types, examples, any two applications
Mesomeric Effect- 1 point
Definition, different types, examples, any two applications
Hyper conjugation- 1 point
Definition, different types, examples, any two applications
Characteristics of the above effect or concept of resonance with example -1 point

20.Discuss the concept of hard / soft acids and bases and its applications in organic Chemistry?

Lewis acids are the Chemical Species which have empty orbitals and are able to accept election
pains from Lewis bases.
Lewis bases are the chemical Species which have a highly localized HOMO and have the ability
to donate an electron pall to a given Lewis acids.

The concept of hardness or softness of acids and bases was put forward by Ralph.G.Person. He
classified the Lewis acids and bases into two groups designated as Hard and Soft. The hardness
of an acid or base is generally characterized by several factors Such as Small atomic radius, high
effective nuclear charge and low polarizability. Person suggested a rule called The Principle of
Hard and Soft Acids and Bases (the HSAB Principle) to rationalize chemical reactions.

Soft Base

A soft base is one in which the valence electrons are easily distorted or removed. The word
"soft" signifies the looseness with which they hold their valence electrons.

24
The donor atoms are of low electronegativity and high polarizability and are easy to oxidize.
e.g.: I-,H- ,CN- R- ,CO,C2H4etc.

Hard Base

A hard base has opposite properties, i.e., it holds on its valence electrons very tightly. The donor
electrons are of high electronegativity and low polarizability and are hard to oxidise.
e.g.: H2O,HO-,F-,CI-,CH3COO-,RO- etc.

Borderline Bases

They are intermediate between hard and soft bases. They tend to be larger and less
electronegative than hard bases, smaller and more electronegative than soft bases.
Since fluoride and chloride ions are very electronegative, they are hard bases. While iodide ion is
a soft base, the bromide ion is a borderline base.
e.g.: NH3,RCl, Pyridine etc.

Soft Acid

A soft acid is one in which the acceptor atom is of large size, of low positive charge or has
several valence electrons that are easily removed. They have high polarizability and low
electronegativity.
e.g.: cu+,Ag+, Au+, Hg+,RCH2X etc.

Hard Acid

A hard acid is one in which the acceptor atom is of small size, of high positive charge and with
no valence electrons that are easily removed. They have low polarizability and high
electronegativity.
e.g.: H+,Li+ Na+,K + RCO+etc

Borderline Acids

They are intermediate between hard and soft acids. Thus they tend to have lower charge and
somewhat larger size than hard acids, and higher change and somewhat smaller size than soft
acids.
e.g.: Fe2+,Co2+,Ni2+ ,Cu 2+

Applications of the HSAB Principle

25
"Hard acids prefer to bond to hard bases, and soft acids prefer to bond to soft bases".
This rule states that the product A-B will have extra stability if both A and B are hard or if both
are soft.

Another rule is that a soft Lewis acid and a soft Lewis base tend to form a covalent bond, while a
hard acid and a hard base tend to form ionic bonds.

Some important applications in organic chemistry are given below:

1)Prediction about stabilities of Electron Donor Acceptor (EDA) complexes.
One application of the HSAB rule is found in FDA complexes between alkenes or aromatic
compounds and metal ions.

Alkenes and aromatic rings are soft bases and should prefer to complex with soft acids .The Ag+
Pt 2+and Hg 2+ complexes are common soft acids.

2) Prediction about reactivity of thiol esters.

The HSAB principle predicts that the equilibrium should be to the right, because the hard acid
CH3CO+ should have a greater affinity for the hand base RO- than for the soft base RS- indeed,
thiol esters are easily cleaved by RO- or hydrolyzed by dilute base.

3) Explanation for order of halide nucleophilicity.

All nucleophiles are bases but the nucleophilicity of a reagent is its ability to donate an electron
pair to an electron deficient carbon atom whereas basicity is its ability to donate an electron pair
to a proton .Nucleophilicity is a Kinetic property i.e., is a measure of the rate of reaction whereas
basicity is a thermodynamic property i.e., is a measure of the value of the equilibrium constant.

26
All the strong bases need not be good nucleophiles and vice versa.EtO -and HO- are strong bases
as well as good nucleophiles. I- is a good nucleophile but it is a very weak base.

Going down the periodic table, nucleophilicity increases, although basicity decreases.
.Thus the usual order of halide nucleophilicity is I-> Br-> CI -> F -.The main reason for this
distinction between basicity and nucleophilicity is that the smaller negatively charged
nucleophiles are more solvated by the usual polar protic solvents. That is because the negative
charge of CI - is more concentrated than the charge of I-, the former is more tightly surrounded by
a shell of solvent molecules that constitute a barrier between it and the alkyl substrate. This is
most important for protic polar solventsin which the solvent may hydrogen bond to small
nucleophiles .But in DMF an aprotic solvent, the order of nucieophilicity was CI -> Br -, I-.

The proton is a hard acid; but an alkyl substrate is softer. According to the HSAB principle the
alkyl group prefers softer nucleophiles than the proton does. Thus the larger, more polarizable
(softer) nucleophiles have a greater attraction toward an alkyl carbon than toward a proton.

4) Application to the problem of competition between nucleophilic substitution and

elimination.

The HSAB concept can also be applied to the problem of competition between nucleophilic
substitution and elimination in the reaction of anions with alkyl halides. The sp 3 carbon is a soft
electrophile whereas the proton is a hard electrophile. Thus, according to the HSAB theory a soft
anion should act primarily as a nucleophile, giving the substitution product, whereas a hard anion
abstract a proton, giving the elimination product.

For example, species that exhibit high nucleophilicity toward alkyl bromides include soft bases
like CN-,I-and C6H6S- .
• Hard acid and Soft acid
Definition, Example -1 pt.
• Hard base and Soft base
Definition, Example -1 pt.
• Any three applications- 3point
27
pts
21. Discuss briefly the Norrish Type and Barton reactions.

Norrish type reactions are the photochemical reactions taking place in ketones and aldehydes.
There are two main routes for the photolysis of aldehydes and ketones. The first, referred to as
Norrish type I process - Cleavage of the bond α to the Carbonyl group is known as α cleavage or
Norrish type I cleavage and the Second is Norrish type II process- Cleavage of a bond β to the
carbonyl group followed by intramolecular molecular hydrogen abstraction is known as β
cleavage or Norrish Type II cleavage.

Norrish Type I

The Norrish type I reaction is the photochemical cleavage or homolysis of aldehydes and ketones
into two free radical intermediates. The carbonyl group accepts a photon and is excited to a
photochemical singlet state. Through intersystem crossing the triplet state can be obtained.On
cleavage of the α-carbon carbon bond from either state, two radical fragments are obtained.

Several secondary reaction modes are open to these fragments depending on the exact molecular
structure.

● The fragments can simply recombine to the original carbonyl compound (path A).
● By extrusion of carbon monoxide in path B two organic residues can recombine with
formation of a new carbon carbon bond
● When the carbon fragment has an α-proton available it gets abstracted forming
a ketene and a saturated hydrocarbon in path C.
● When the alkyl fragment contains a β-proton it gets abstracted with formation of
an aldehyde and an alkene.

28
29
 Applications
1)

2)

Norrish Type II

In the Norrish type II reaction, the photochemical intramolecular abstraction of γ-hydrogen by

the excited carbonyl compound forms a 1,4-biradical as a major photoproduct. The resulting
biradical undergoes secondary reactions such as fragmentation to form an enol and an alkene or
undergo intramolecular recombination of the two radicals to a substituted cyclobutane.

30
Primary proccess

Absorption of light in the range of 230-330nm causes n to π* excitation to form an excited

singlet state an excited triplet state by ISC (Inter System Crossing).

Secondary process

31
Applications

1).

2.)

Barton Reaction

The Barton reaction, also known as the Barton nitrite ester reaction, is a photochemical reaction
that involves the photolysis of an alkyl nitrite to form a δ-nitroso alcohol. The nitroso alcohol
may rearrange into an oxime.

The Barton reaction involves a homolytic RO–NO cleavage, followed by δ-hydrogen

abstraction, free radical recombination, and tautomerization to form an oxime. The nitroso and
oxime compounds can be transformed into other functional derivatives such as carbonyl

32
compounds,cyano compounds and amino compounds. The geometry of the 6-membered radical
intermediates accounts for the selectivity of the δ-hydrogen. Often, the site of hydrogen atom
abstraction can be easily predicted. This allows the regio- and stereoselective introduction of
functionality into complicated molecules with high yield. Due to its unique property at the time
to change otherwise inert substrates, Barton used this reaction extensively to create a number of
unnatural steroid analogues.

Applications

Corticosterone acetate react with nitrosyl chloride in dry pyridine yields the nitrite.
Subsequently, irradiation under inert atmosphere followed by treatment with aqueous sodium
nitrite selectively gives the desired oxime. The oxime is then acetylated and hydrolyzed to yield
tthe natural product hemiacetal

33
 Norish type 1 2 points
(Reaction, mechanism,examples -any 2)
Norish type 2 1 points
(Reaction, mechanism,examples -any 2)
Barton 2 points
Reaction,mechanism,examples -any 2)

22. Discuss the stereochemistry and chirality of allenes and biphenyls and explain their
configurational assignment taking suitable example.

Axial chirality is the chirality resulting from the nonplanar arrangement of four groups about an
axis. The axis is called a chiral axis. Suitably substituted allenes, biphenyls,spiranes
alkylidenecycloalkanes can possess chiral axis.

The central carbon atom in allene is sp hybridized and linear, and the two outer carbon atoms are
sp hybridized and trigonal. The whole molecule does not lies in a plane. The central, sp hybrid
carbon atom must use different p orbitals to form the pi bonds with the two outer carbon atoms.
The two unhybridized p orbitals on a sp hybrid carbon atom are perpendicular, therefore two pi
bonds must also be perpendicular.

34
Allene itself is achiral, however, in 2,3-pentadiene C-3 is the sp hybrid allene carbon. The C-2
and C-4 are both sp² and planar, but their planes are perpendicular to each other. This
arrangement places the four ligands in the positions of an elongated tetrahedron. As a result 2,3-
pendatiene is chiral .
In fact the allenes of the type ABC-C-CAB (AB) are chiral. Note that none of the carbon atoms
is attached to four different atoms and therefore, in a chiral allene there is no stereocenter.

In simple alkenes the four groups lie in one plane and such compounds show cis-trans
isomerism. Similarly if there are odd numbers of cumulative double bonds, then the four groups
at the ends lie in one plane and such compounds show cis-trans isomerism. But if there are even
numbers of cumulative double bonds, the groups at the two ends will be in perpendicular planes
and in such cases optical activity is possible.

Stereochemistry of Biphenyls

Stereoisomers obtained due to the restricted rotation about carbon-carbon single bond are called
atropisomers and the phenomenon is called atropisomerism. Such compounds also have the
chirality due to the axis.

35
Suitably substituted biphenyls exhibit enantiomerism due to the presence of chiral axis. This
enantiomerism arises due to atropisomerism i.e. restricted rotation around C-C bond between two
phenyl rings. This steric hindrance of substituents at ortho- position of the each ring is
responsible for such restricted rotation. To maintain the maximum stability, molecule orients
itself in such a manner so that both the ortho- substituted phenyl rings lie in different plane.

Biphenyl shows the enantiomerism when the molecule has the following properties.
a) Each ring must be unsymmetrically substituted. Each of the rings should not contain any kind
of symmetry element.

b) Suitable substitution (at least one substitution) at ortho- position must be there at each rings.
c) othro- substituents must be larger in size (-Cl, -Br, -I, -COOH, -NO2, -NHCOCH3, - SO3H, -
R groups etc.). The smaller groups at othro- position make the compounds planar in nature and
thus do not exhibit atropisomerism.
d) It is not always necessary that four large ortho groups should be present for rotation to be
prevented. The presence of large groups, if large enough can prevent the rotation and can
therefore exist as enantiomers as in the case of biphenyl -2,2 bisulphonic acid

36
CONFIGURATIONAL NOMENCLATURE OF COMPOUNDS WITH AXIAL CHIRALITY PLANAR
CHIRALITY AND HELICITY.

The compounds which have axial chirality include allenes, spiranes, adamantanes, biphenyls,
binaphthyls etc.To determine the absolute configuration of chiral allenes.

Some of the principles here follow about the Cahn-Ingold-Prelog rules in for determining the R
and S absolute configuration. We need to prioritize the atoms/groups and determine the
configuration based on the direction of the arrow.

Let’s, as an example, determine the configuration of allene C where different groups are
connected to each carbon:

First, pick a direction to look through the C=C=C axis. In this case, we will look from the left
side (there is no rule or difference for picking the direction):

To place the groups on the front and back carbon, draw a circle just like you did when drawing
Newman projections and draw a line over the circle. Again, this line is going to show the groups
connected to the front carbon:

37
To add the groups on the back carbon, draw a horizontal line behind the circle:

Next, we put the groups. For the front carbon, Cl is on the top and Br on the bottom:

On the back carbon, CH3 and H are on the right and left sides respectively:

Once we have the structure, groups are prioritized according to the atomic numbers.
Importantly, the groups on the front carbon are assigned first regardless if there is a higher
priority group on the back carbon.

38
The groups on the back carbon are assigned as priority 3 and 4.

The arrow goes 1-2-3 – just like in the regular R and S configuration:

Alternatively, you can simply go from 2 to 3 to make a shorter arrow:

39
At the end, we can prove that the absolute configuration does not/should not depend on the
direction we are looking from. So, this time, let’s look through the C=C=C axis from the right
side. This time the horizontal line is going to be in the front:

The last step is assigning the priorities and determining the configuration based on the direction
of the arrow:

Notice again, that the groups on the front carbon are assigned first even though, in this case,
the ones in the back have higher atomic numbers.

40
Configuration can be assigned to biphenyls in a similar fashion. Thus the following biphenyl
has
S configuration.

Stereochemistry of allenes 2 points

Stereochemistry of biphenyls 2 points
Configurational assignment (R/S)
with example 1 point

41
 Question Paper Code :18002219

I sem M.Sc. DEGREE (CSS) EXAMINATION, DECEMBER 2018

AN 1C 02/AP 1C 02/CH 1C 02/PH 1C 02/POH 1C 02–STRUCTURAL AND
MOLECULAR ORGANIC CHEMISTRY
(Common to all Branches of Chemistry)
(2012 Admission)
SCHEME OF VALUATION

INSTRUCTION TO THE EXAMINERS

This is only a guideline for valuation. If you find any other attempt which is equally
valid and correct, full credit may be given to the students.

Section A
(Answer any Ten questions. Each question carries a weight of 1)
1. What do you understand by the term resonance? Give two examples.

Resonance is a way of describing bonding in certain molecules or ions by the combination of

several contributing structures or canonical structures into a resonance hybrid. Here the
bonding cannot be expressed by one single Lewis structure.

In benzene the two cyclohexatriene Kekulé structures are taken together as contributing
structures to represent the total structure.

In furan a lone pair of the oxygen atom interacts with the π orbitals of the carbon atoms.
The curved arrows depict the permutation of delocalized π electrons, which results in different
contributor.

Or any example
(Correct explanation with 2 examples –A, Correct explanation with 1 example-
B,Explanation only –C, Example only –D)

2. What are graphenes? Give its importance.

Graphenes can be described as one atom thick layer of graphite. It is the basic structural
element of other allotropes of carbon including graphite, charcoal, carbon nanotube, fullerene
and diamond. I graphene, a number of benzene rings are fused together to form a honey comb
array which physically act as a 2-dimensional sheet like structure like material.

Properties of graphene: Good conductor of electricity, Perfect thermal conductor, Opaque,

Soft, Lubricant.

1
Applications:

 Used as amembrane for efficient separation of gases.

 Used in chemical sensors for detecting explosives.
 Used as an efficient lubricant.
 Used to harden rubber.
 Widely used as fuels and as reducing agents in metallurgy.
(Correct explanation with 2 Applications –A, Correct explanation with 1 Applicaton-B,
Explanation only –C, Application only –D)

3. Explain Benzyne mechanism with suitable example.

1,2 dehydrobenzenes and its derivatives are called benzynes. It is highly reactive species.

Some aromatic substitution occurs on aryl halide which had no activating group. Here
strong bases are required than those normally use The incoming group does not always take
the position vacant by the leaving group. This type mechanism is called benzyne or
elimination – addition mechanism.

When C6H5Cl is treated with strong base like NaNH2 in liquid NH3 at-330C . It is
converted to aniline.

Mechanism : Step I: Elimination step; cis elimination of H – X from the vicinal position
and the formation of benzyne
Cl Cl

NH2
- NH3 Cl
H

Step II : Addition of base to the benzyne intermediate.

NH3 NH2

A
NH3

NH3 NH2

B
2
(Correct explanation of mechanism of two steps wth equations–A, only equation of
mechanism -B, Explanation of mechanism only –C, reaction only –D)

4. 1,3-butadiene adds one mole of bromine to give 1,2 adduct as the major product
at a lower temperature, but forms 1,4 adduct at higher temperature. Give
reason.

(Correct reason wth equations–A, only equation -B, only reasons –C, about
kinetic/thermodynamic control –D)

5. Explain BAL1 Mechanism with suitable example.

B AL 1 MECHANISM : is for the hydrolysis of esters of 30 alcohol & those 20 alcohol
that yield more stable carbocations. The B AL 1 mechanism occurs only in neutral or
weakly basic solutions, where the rate of attack by OH- slow. B AL 1 mechanism for
the hydrolysis of esters may be explained as follows. Since, the methyl group
increases the electron availability on the 30 carbon atom the ester is ionized to give the
carboxylate ion & stable 30 butyl carbocation. The 30 butyl carbocation react with a
nucleophile reagent H2O to form the protonated 30 butyl alcohol. The carboxylate ion
abstract a proton to yield 30 butyl alcohol and the acid.

3
(Correct explanation of mechanism wth equations–A, only equation of mechanism -B,
Explanation of mechanism only –C, reaction only –D)

6. What type of photochemical process takes place in hexan-2-one. Give equation.

Norrish Type II Process: This type of process occurs in long chain aliphatic ketones having 𝛾
hydrogen atom. On photolyis, a six membered transitive state results. when hydrogen atom in
the alkyl group can enter into the formation of six membered cyclic transition state involving
the oxygen atom as one member of the ring, 𝛾-hydrogen abstraction and fission of a molecule
occur to give an alkene and a ketone. example 2-Hexanone on photo irradiation gives acetone
and propene as the major products.

(Correct explanation of mechanism wth equations–A, only equation of mechanism -B,

Explanation of mechanism only –C, reaction only –D)
7. What are cyclophanes. How it exhibit optical activity.
A cyclophane is a hydrocarbon consisting of an aromatic unit and an aliphatic
chain that forms a bridge between two non-adjacent positions of the aromatic ring.. If
two aromatic rings are joined together by bridging the para position to give para
cyclophane or the metaposition to give meta cyclophane.

In complex paracyclophane, 2 benzene rings are arranged one above the other and the
substituent –COOH cannot make a full turn if the chains are small. To have enantiomerism at

4
 least one of the ring must be dissymmetrically substituted or in the case of metacyclophane
the two chain must be non-equivalent.

(Correct definition with with an example and optical activity–A, only definition with with an
example -B, optical activity only –C, example only –D)
8.

Question incorrect. If CH3 instead of H3 the configuration is S.

9. Explain why alkyne derivatives do not exhibit cis-trans isomerism.

Alkynes cannot exhibit cis / trans isomerism.

Exists only in C=C system. alkynes are linear molecules .
(Correct definition of cis trans isomerism and explanation–A, only explanation-B, only
definition of cis trans isomerism –C, onlyexample –D)
10. State Curtin-Hammet principle.

Curtin Hammet Principle

 The relationship between the conformation and chemical reactivity is the concept of
Curtin Hammet Principle.
 It corelates the product distribution with the transition state energy.
 Applied to system in which different products are formed from a substrate and whole can
exist in two different forms and are in equilibrium in each other.
 According to Curtin Hammet Principle if one product (PA) formed from one coordinated
isomer(A*)and another product(PB) is formed from another conformational isomer(B*),
and the two conformers A* and B* are rapidly interconvertable. But the products PA and
PB formed are not inter convertable. The product components are not dependent on the
relative proportions of the conformational isomers in the substrate.
 The product ratio is controlled by the difference in standard Gibbs free energy of the
respective transition state.
(four points-A, three points-B, 2 points –C, one point –D)

11. Explain the conformation of congrassane.

5
 (four points with structure-A, three points-B, 2 points –C, one point –D)
12. Cis-cyclohexane-1,2-diol is oxidized by periodic acid more rapidly than the
corresponding trans isomer .Give reason.

The ability of the diol to form an intermediate cyclic diester with periodic acid is critical for
the successful cleavage of vicinal diols. Cis- as well as trans-1,2-cyclohexanediol can form
such an intermediate.

6
 Periodic acid cleaves vicinal diols(to carbonyls) via a cyclic intermediate.
Due to the cyclic intermediate, it needs a syn configuration for the −OH−OH groups for the
reaction.
(explanation with equation-A, explanation only-B, equation only –C, –D)

13. Draw the geometrical isomers of the compound C4H4O4. How it inter converted?

(Correct structure of isomer–A, only equation of mechanism -B, Explanation of mechanism

only –C, reaction only –D)

SECTION B

(Answer any Five questions by attempting not more than three questions from each bunch.
Each question carries a weight of 2)
Bunch I

7
(b)

8
 SNAr reaction mechanism
The following is the reaction mechanism of a nucleophilic aromatic substitution of 2,4-
dinitrochlorobenzene in a basic aqueous solution.

Since the nitro group is an activator toward nucleophilic substitution, and a meta director, it
allows the benzene carbon to which it is bonded to have a negative charge. In
the Meisenheimer complex, the nonbonded electrons of the carbanion become bonded to the
aromatic pi system which allows the ipso carbon to temporarily bond with
the hydroxyl group. In order to return to a lower energy state, either the hydroxyl group
leaves, or the chloride leaves. In solution both processes happen. A small percentage of the
intermediate loses the chloride to become the product (2,4-dinitrophenol), while the rest
return to the reactant. Since 2,4-dinitrophenol is in a lower energy state it will not return to
form the reactant, so after some time has passed, the reaction reaches chemical
equilibrium that favors the 2,4-dinitrophenol.
(two reactions, explanations, mechanisms –A, two mechanisms -B, one reaction,
explanation, mechanism only –C, two reaction only –D)

9
 (a) Norrish type I reaction

(b) Norrish type I reaction

Mechanism

(two reaction names, mechanisms –A, two mechanisms -B, one reaction name, mechanism
only –C, two reactions only –D)

10
(two reaction names, mechanisms –A, two mechanisms -B, one reaction name, mechanism
only –C, two reactions only –D)

11
 (a) 2S, 3S

(b) 2R, 3S

(c) 2S, 3R

(d) R

(correct four answers –A, correct three answers -B, correct two answers –C, correct one
answer only –D)

Bunch II

18. What are the evidences of an arenium ion mechanism in aromatic

electrophilic substitutions?

Evidence for mechanism .

1) The compound A & B are demonstrated by the reaction of I- C14 with KNH2 . it was
found that in half of the aniline obtained. the NH2 grp was hold by C14 b & the
other was held by adjacent carbon.

2) Another evidence for the reaction is the aryl halide contain two ortho substituent the
reaction could not be able to occur. Since no H atom ortho to the halogen is available
for elimination.

12
 Cl

H3C CH3
NH2
No reaction

(correct two points with equations –A, correct two points -B, correct one point with equation
–C, correct one point only –D)

19. State Taft equation and explain the terms. Write note on the application of
Taft equation.
The Taft equation is a linear free energy relationship (LFER) used in physical
organic chemistry in the study of reaction mechanisms and in the development of
quantitative structure activity relationships for organic compounds.
It was developed by Robert W. Taft in 1952 as a modification to the Hammett
equation. While the Hammett equation accounts for how field, inductive, and
resonance effects influence reaction rates, the Taft equation also describes the
steric effects of a substituent.
The Taft equation is written as:

where log(ks/kCH3) is the ratio of the rate of the substituted reaction compared to
the reference reaction, σ* is the polar substituent constant that describes the field
and inductive effects of the substituent, Es is the steric substituent constant, ρ* is
the sensitivity factor for the reaction to polar effects, and δ is the sensitivity factor
for the reaction to steric effects.

 Taft modified the LFER to aliphatic systems and ortho substituted benzene ne
derivatives by considering the difference in ρ values for hydrolysis of o-
substituted benzoate esters under acidic conditions (ρ=0) and basic conditions
(ρ=2.5).

 He showed that in the hydrolysis of carboxylic esters steric and resonance

(conjugative) effects will be the same whether the hydrolysis is catalyzed by acid
or base.

 The TS for acid catalyzed hydrolysis (a) has a greater positive charge than the TS
for base catalyzed hydrolysis (b) as shown below.

13
 (Equation and explanation- 1 wt, application -1 wt )

20. Write a note on optical isomerism of nitrogen and sulphur compounds.

Nitrogen compounds

Elements other than carbon atoms can also act as the centre of chirality. A nitrogen atom with
three different substituents exist in a pyramidal arrangement. Considering the lone pair of
electron to be a fourth group yields tetrahedral arrangement and is chiral.

Eg:-Ethyl methyl amine

Pyramidal inversion-explanation

This amine can’t be resolved into separate enantiomers because of the rapid inversion at
nitrogen that proceeds through a planar sp2 arrangement. This process converts one
enantiomer into other so rapidly that it is impossible to obtain amines in optically active form.

Resolution has been carried out with the substituted amines of the type ArNR 1R2. The optical
activity of this compound is due to the asymmetry of molecule as a whole arising from
restricted rotation about the nitrogen aryl carbon bond. Although nitrogen atom is in a state of
oscillation there is always restricted rotation the relative positions of ArR1 and R2 remain
unchanged throughout these oscillations.

Quaternary ammonium ions with four different substituents are chiral and can be resolved
into individual enantiomers. If one of the substituent is hydrogen atom a rapid sequence
involving deprotonation , inversion of tertiary centre and reprotonation will convert a single
enantiomer in such a salt into a racemic mixture. Thus quaternary ammonium salts can be
obtained in optically active form when none of the substituents is a hydrogen atom.

When the nitrogen atom forms a part of the ring system pyramidal inversion is not possible
without bond cleavage. With proper substitution the tri coordinate nitrogen becomes a stable
centre of chirality. Eg:-Trogers Base

Optical stability is a measure of resistance of pure enantiomer towards racemisation under a

given set of conditions. Rate of inversion is low when a nitrogen atom is in a three membered
ring and connected to another atom with unshared pair of electron. Thus two isomers of n-
chloro-2-methyl aziridine do not interconvert at room temperature.

14
Tertiary amine oxide:-In this the nitrogen atom is joined to four different groups and the
configuration is tetrahedral. It should be resolvable.

Sulphur compounds

Various types of sulphur compounds have been obtained in optically active form. They
belong to sulphonium salts, sulphoxides, sulphonic esters, sulphide imines and sulphides.

Sulphonium salts:- carboxy methyl ethyl methyl sulphonium bromide .

Sulphoxides: of the type RSOR’ have also be resolved.

(stereochemistry of N with examples – 1 wt.& stereochemistry of S with examples - 1wt )

21.Discuss the conformation of bicyclic systems with suitable examples.

Compounds with two rings fused together are known as bicycles. Bicyclic systems can be
either fused or bridged bycyclic. Fused rings share two adjacent carbon atoms while the
bridged rings shared two non-adjacent carbon atoms (called the bridgehead carbons) with one
or more carbon atoms between them

Decalins are examples of fused ring systems. In fused ring systems, two rings share an
edge. Decalins contain ten carbons total, but the ten carbons are divided into two rings, each
of which is six carbons around.

Trans decaline has a centre of symmetry, so optically inactive. In cis form, the flipping or
chair inversion converts the molecule to its mirror image. So it is a non resolvable dl pair.

Adamantane: Refer Qn. No.25

Congressane: Refer Qn. No.11

Tropinone decalin, norbornane, spiropentane are other examples.

(Conformation of 4 examples-A, Conformation of 3 examples-B, Conformation of 2

examples-C, Conformation of 1 example-D)

15
 SECTION C
Answer any two questions
22. What are anti and homo aromatic systems? Describe the applications of NMR
spectroscopy as a tool for distinguishing these compounds.
Conditions for aromaticity:-

 The structure must be cyclic.

 The ring must be planar.
 Each of the atoms in the ring must be sp2 hybridised and have unhybridised p orbital.
 The total number of 𝜋 electron in the molecule pr ion should be 4n+2 where n=0,1,2,.
Anti aromatic compounds are planar, cyclic, conjugated systems with an even number of
pairs of electrons.
An aromatic compound is more stable compared to an analogous cyclic compound with
localized electrons, where as an anti aromatic compound is less stable compared to an
analogous cyclic compound with localized electrons. Eg: Cyclobutadiene contains 4 electrons
(4n, n = 1) Cyclic, planar, uninterrupted ring of p orbital bearing atoms (conjugation), so Anti
aromatic. Being anti aromatic, cyclobutadiene is unstable. It can be isolated only under
controlled conditions such as in Argon matrix or using trapping agents such as dienes.
Studies show that it has a rectangular structure rather than a square, with C-C bond length of
1.567 Å and C=C bond length of 1.346 Å. Other examples are,

Homoaromaticity If a stabilized cyclic conjugated system (4n+2 e s) can be formed by

bypassing one saturated atom, that lead to homoaromaticity. Compared to true aromatic
systems, the net stabilization here may be low due to poorer overlap of orbitals.
Cyclooctatrienyl cation (homotropylium ion) formed when cyclooctatetraene is dissolved in
concentrated sulfuric acid is the best example to demonstrate homoaromaticity. Here, six
electrons are spread over seven carbon atoms as in Tropylium cation. Electron delocalization
in this case is pictorially represented below

NMR tool for aromaticity:-

In benzene 𝜋 electron are delocalised cyclically over the aromatic ring. These loops of
electrons are induced to circulate in the presence of the applied field B 0 producing a
induced electric current called ring current.

16
 Anisotropic shielding and deshielding associated with the ring current:-The induced
current is diamagnetic(opposing the applied field) in the centre of the ring and is
paramagnetic outside the ring. Thus the aromatic proton experiences a magnetic field
greater than the applied field. Such proton are said to be deshielded and hence smaller
applied field(higher value of 𝛿) will be required to bring them to resonance.

Protons held above and below the plane of the ring resonate at low value. From NMR
spectrum we can decide whether a particular compound has substantial aromatic character
in it or not.

In alkynes electronic circulation around triple bond takes place in such a way that the
proton experience diamagnetic shielding effect. When the axis of alkyne group lies
parallel to the direction of applied field. The 𝜋 electron are induced to circulate around
the axis in such a way taht the induced field opposes the applied field. Thus the proton
feel smaller field strength(shielding) and hence resonance occurs at higher applied

field(low 𝛿 value).

An example of shielding and deshielding by ring current is given by [18]annulene.

It sustains a ring current so that the protons outside the ring are
strongly deshielded and those inside the ring are strongly shielded.

(anti & homo aromaticity- 2wt, nmr as tool of aromaticity -3 wt.)

23. Give an account of the different mechanism of ester hydrolysis with experimental
evidences.

17
Ester hydrolysis

Hydrolysis of esters may be carried out by the refluxing them either with dilute acid or with
dilute alkali. Natural esters of higher fatty acids form soap and glycerol through the base
catalysed process. Soaps are sodium or potassium salts of higher fatty acids.

RCOOR’ + HOH →RCOOH + R’OH

RCOOR’→RCOO - + R’OH

Esterification as well as hydrolysis reaction can be carried out in two different ways.

1. Acyl oxygen fission.( AAC1,AAC2, BAC1, BAC2)

2. Alkyl oxygen fission.( AAL1,AAL2, BAL1, BAL2)

Here A stands for acid catalysed hydrolysis, B for base catalysed mechanism, Ac for acyl-
oxygen bond fission AL for oxygen-alkyl bond fission where 1 and 2 for unimolecularity and
bimolecularity of reactions. Some of them are:-

AAC1 mechanism

Acid catalysed acyl oxygen bond cleavage, unimolecular in this mechanism the protonated
ester decomposes without being attacked by water or alcohol. In the case of 2,4,6-trimethyl
benzoate gives mesiotic acid.

The ester decomposed to give a cation during hydrolysis is a solution of mesitoic acid ester in
sulphuric acid is poured into ice cold water, the acid obtained in quantitative yield.

This type mechanism occur only in esters having high +I groups and they reduced the
positive character on the carbonyl carbon of the acyl cation by hyperconjugation effect and
thus stabilised the acylcarbo cation . The methyl group helps in the complete ionisation of the
compound in H2SO4 solution to the acyl carbocation. This type of mechanism is possible only
in strongly acidic and highly polar solids. Due to steric hinderance the rate is very slow and
hence only traces of mesitoic acid are obtained.

AAC2 mechanism

Acid catalysed acyl oxygen bond cleavage bimolecular.This is the most common mechanism
for esterification and hydrolysis occurs frequently when primary or secondary alcohol are
involved during the reaction. The first step consists of the rapid protonation of the ester which
is then solvalyzed by water molecule leading to the formation of a protonised acid and an
alcohol.

Note that all steps are reversible hence the reverse mechanism constitutes the mechanism of
esterification. Hence microscopic reversibility is applied to draw the mechanism pathway of
ester hydrolysis. The formation of optically active alcohol an ester with asymmetric R’ group
and formation R’OH in the presence of H2O18 support this mechanism.

18
BAC2 mechanism

Base catalysed acyl oxygen bond cleavage bimolecular. This is the most common type of
mechanism of ester hydrolysis by aqueous base. In this reaction nucleophilic attack of
hydroxyl ion on the carbonyl group of ester followed by rapid elimination of alkoxy ion.
Then the transference of a proton from the carboxylic acid to the alkoxide.

19
(Any 5 ester hydrolysis mechanism with explanation –A, 4 mech.-B, 3 mech.-C, 2 mech.-D)

24. Explain stereochemistry of:

(a)Allenes:-Allenes are the compounds which have general formula

Allenes exhibit geometric isomerism if the two groups attached to each terminal carbon
atoms are different.

The groups a and b at one end of system lie in a plane at right angles to those at the other end.
Space formula of allenes show that the molecule and its mirror image are not super
imposable, they are enantiomers.

In allenes the two terminal carbon atoms are in a state of trigonal hybridisation sp2 and the
central carbon atom is in the trigonal sate sp. The central carbon atom forms two 𝜋 bonds
which are perpendicular to each other. In the trigonal state the 𝜋 bond is perpendicular to the

plane containing the three 𝜎 bonds.

(b)Biphenyls:-In biphenyl two phenyl groups are joined by a single bond called pivotal bond.
In biphenyl, the two benzene rings are co-axial. Two conditions are necessary for biphenyl
compound to exhibit optical activity.

 Neither ring must have a vertical plane of symmetry.

 The substituents in ortho position must have a larger size.

20
In optically active biphenyl derivatives the rings are inclined to each other due to the steric
and repulsive effect of group in the ortho position.The actual angle of inclination of the two
rings depends on the nature of the substituents but usually the rings tend to be approximately
perpendicular to each other. In order to exhibit optical activity the substituents group in the
ortho position must be larger enough to prevent the two rings from becoming co-planar. If the
molecule possess a plane plane or centre of symmetry, it is not optically active.

(c)Spirans:-When both the double bonds of allenes are replaced by the rings, the resulting
systems are known as spirocompounds or spiranes.

The two terminal methylene plane are perpendicular to each other as in allenes and if the
substituents a and b are not equivalent the compound would exhibit enantiomerism. The
optical activity of hemispiranes and spiranes are due to the asymmetry of the molecule as a
whole. The method of specifying absolute configuration of alkalidine cyclo alkane and
soirane are similar to that of allenes.

(stereochemistry of allenes-2 wt, stereochemistry of biphenyles-1.5 wt., stereochemistry of

spiranes-1.5 wt)

25.Discuss the conformational studies of:

(a)Cyclohexane

21
The internal angles of a flat regular hexagon are 120°, while the preferred angle between
successive bonds in a carbon chain is about 109.5°, the tetrahedral angle. Therefore, the
cyclohexane ring tends to assume certain non-planar conformations, which have all angles
closer to 109.5° and therefore a lower strain energy than the flat hexagonal shape. The most
important shapes are called chair, half-chair, boat, and twist-boat. The molecule can easily
switch between these conformations, and only two of them—chairand twist-boat—can be
isolated in pure form.

(b)Adamantane (tricycle[3,3,1,1]decane)

With a formula C10H16, Adamantane molecules consists of three connected cyclohexane rings
arranged in the "armchair" configuration. It is unique in that it is both rigid and virtually
stress-free. Adamantane is the most stable among all the isomers with formula C10H16, which
include the somewhat similar twistane. The spatial arrangement of carbon atoms in the
adamantane molecule is the same as in the diamond crystal.

(c)Ethane: Conformations of Ethane

While there are an infinite number of conformations about any sigma bond, in ethane two
particular conformers are noteworthy and have special names. In the eclipsed conformation,
the C-H bonds on the front and back carbons are aligned with each other with dihedral angles
of 0 degrees. In the staggered conformation, the C-H bonds on the rear carbon lie between
those on the front carbon with dihedral angles of 60 degrees.
Conformations of Ethane

22
Figure: The eclipsed and staggered conformations of ethane.

The eclipsed conformation of ethane is less stable than the staggered conformation by 3
kcal/mol. The staggered conformation is the most stable of all possible conformations of
ethane, since the angles between C-H bonds on the front and rear carbons are maximized at
60 degrees. In the eclipsed form, the electron densities on the C-H bonds are closer together
than they are in the staggered form. When two C-H bonds are brought into a dihedral angle of
zero degrees, their electron clouds experience repulsion, which raises the energy of the
molecule. The eclipsed conformation of ethane has three such C-H eclipsing interactions, so
we can infer that each eclipsed C-H "costs" roughly 1 kcal/mol.
The most stable (low energy) conformation is the one in which all six C–H bonds are as far
away from each other as possible (staggered ). The least stable (high energy) conformation
is the one in which the six carbon–hydrogen bonds are as close as possible (eclipsed). All
other conformations lie between these two limits.

The 12 kJ/mol of extra energy in the eclipsed conformation of ethane is called torsional strain
The torsional strain is thought to be due to the slight repulsion between electron clouds in
the eclipsed bonds.

(Conformation of cyclohexane-2 wt, Conformation of adamentane-1 wt, Conformation of

ethane-2 wt)

23
24
 MSc DEGREE (CSS) EXAMINATION FEBRUARY 2016
FIRST SEMESTER
AN IC 02/AP IC 02/CH IC 02/ PH IC 02/ POH IC 02- STRUCTURAL AND MOLECULAR ORGANIC CHEMISTRY

(Common to all branches of Chemistry)(2012 Admission onwards)

Section A
(Answer any 10 questions. Each carries a weight of 1)
1. Cyclo-octatetraene is non-aromatic. But when it is reduced by alkali metals it becomes aromatic.
How?
Cyclo-octatetraene is an acyclic, tub shaped, nonplanar compound contains eight pi electrons, it does
not obey the Huckel’s rule. So it is a non aromatic compound. when cyclo-octatetraene react with alkali
metal, one molecule of cyclo-octatetraene takes up two electrons from two alkali metal and produce a
salt which is cyclic, planar, and have ten delocalized pi electrons, that is a (4n+2) system and is an
aromatic compound.
2. Explain inductive effect with suitable examples.
Inductive effect is a permanent effect which involves the displacement of shared pair of electrons in a
carbon chain towards the more electronegative group.
For example, in a C-Cl bond, the electron pair displaced towards the Chlorine atom due to much greater
electronegativity of Chlorine than Carbon. Thus the chlorine acquires a small negative charge and
Carbon acquires a small positive charge. This effect is known as inductive effect.
When the group withdraws the electrons from the carbon chain towards itself, it is said to have-I effect.
Example- F, Cl, CN, NO2 etc.
When the group donate the electrons to the carbon chain. It is said to have + I effect.
Example- CH3, C2H5 etc.
Chloroacetic acid is stronger than acetic acid because of the -I effect; the electron displacement effect
stabilizes the carboxylate ion and hence the acidity increases.
3. Explain why a nitro group in the para position is more effective in increasing the acidity of phenol
that of benzoic acid.
Since phenol is planar,resonance effect in phenol is more effective with respect to nitro group(electron
withdrawing group). Moreover, the distance between the negative charge on the carboxylate ion and
the electron withdrawing group(nitro) is more as compared to that distance in phenoxide ion. Hence the
– I effect of nitro group is more effective in phenol.
4. Explain the mechanism of the Photo- Fries rearrangement.
Phenol esters in solution on photolysis give a mixture of ortho and para acyl phenols. In photo-fries
rearrangement such product is formed in the absence of catalyst and is predominantly an
intermolecular free radical process.

(Wrong question give full credit if attempted)

5. Give the mechanism of the following reaction.
Wrong question. Give full credit.

6. Explain kinetic isotopic effect with suitable example.

 The kinetic isotopic effect is a change of a rate that occurs upon isotopic substitution and is
generally expressed as the ratio of the rate constants (klight/Khevy).
 Primary isotopic effect is one which results from the making or breaking of a bond to an
isotopically substituted atom and this must occur in rate determining step.
 Secondary isotopic effect is due to isotopic substitution of an atom not involved in bond making
or bond breaking in the rate determining step.
 Example- Elimination of HBr from 1-bromo-2-phenylethane: - When the rate constant(KH)for
elimination of HBr from 1-bromo-2-phenylethane at 300 is compared with the rate constant(KD)
for elimination of DBr from 2-bromo-1,1-diduterio-1-phenyethane determinate at the same
temperature. KH is found to be 7.1 times KD. The difference in the reaction rate is due to the
difference in energy required to break C-H bond compared to C-D bond.
(Definition with relevant example-Give Full credit)

7. What is meant by (a) Chirality (b) Diastereomers.

a) A chiral molecule is a type of molecule that has a non-superimposable mirror image.
The cause of chirality in molecule is the presence of an asymmetric carbon atom.
Chirality is a necessary and sufficient condition for the occurrence of enantiomerism.
All molecules belonging to the point group C1, Cn and Dn , show chirality.
Example -tartaric acid, biphenyl etc.
(b) Diastereomers are stereomers that are not mirror images of each other that is, Diastereomers are
not enantiomers.
Diastereomers have different physical properties like melting point, boiling point, solubility etc.
Diastereomeric and enantiomeric relationships are mutually exclusive.
Standard techniques like crystallization, distillation or chromatography can therefore, be used to
separate diastereomeric mixture.
(Any four points- Give full credit)

8. Draw the conformations of cyclohexane derivatives.

 Cyclohexane is a least strained structure of all ring sizes. It has neither torsional strain nor angle
strain.
 The most stable conformation of cyclohexane is chair conformation

(Any four conformation- Give full credit)

9. Assign R/S configuration for the following:

C1- S configuration, C2- R configuration

(Wrong question- Give full credit if attempted)

10. What is meant by topicity? Explain with example.

It is a sterochemical relationship between substituents and the structure to which they are attached.
Depending on the relationship, such groups can be heterotopic, homotopic,enantiotopic,
or diastereotopic.

Homotopic groups in a chemical compound are equivalent groups. Two groups A and B are homotopic if
the molecule remains the same when the groups are interchanged with the remaining parts of the
molecule fixed.

The stereochemical term enantiotopic refers to the relationship between two groups in a molecule in
which, if one or the other were replaced, would generate a chiral compound. The two possible
compounds resulting from that replacement would be enantiomers. For example, two hydrogen atoms
attached to the second carbon in butane is enantiotopic.

The stereochemical term diastereotopic refers to the relationship between two groups in a molecule in
which, if replaced would generate compounds that are diastereomers. For example,the two hydrogen
atoms of the CH2 moiety in (S)-2-bromobutane are diastereotopic.

11. Explain Curtin Hammett principle.

According to Curtin Hammett principle- In a chemical reaction that yields one product from one
conformational isomer and a different product from another conformational isomer, the product
composition is not solely dependent on relative proportions of the conformational isomer in the
substrate; it is controlled by the difference in standard Gibbs energy of their respective transition state.
This equation shows that the product ratio solely depends on the difference in energy of two transition
state and is completely independent on the difference in ground state stability of the reacting
conformer.

12. Name the following compounds as E, Z or syn or anti.

The highest priority groups are on the opposite side in (a) and so it is the E isomer. The highest priority
group and hydroxyl group are on the opposite in (b) and so it is the anti-isomer.

13. A solution of optically active 1-phenyl ethanol, C6H5 CH(OH)- CH3 in aqueous solvent containing H+
slowly racemizes. Account.

The slow racemisation is due to the formation of intermediate carbonium ion(planar

carbocation) and that on further reaction with a molecule of water to form an equimolar mixture of d
and l form.

(Any relevant explanation- Give full credit)

Section B

14. Predict the products in the following reaction. Indicate the stereochemistry if any:

(a) &(b) are out of syllabus. Give full credit.

16 b)

Mechanism
Ph Ph Ph
Ph
CO
O O

Ph
Ph Ph Ph

17 a)

Mechanism
 17.(b) Predict the product and explain the mechanism

18. Explain Hofmann elimination with examples.

The Regioselectivity of elimination reactions can explain the formation of structural isomers which have
the double bond in different positions.

In acyclic systems anti elimination is preferred particularly with good leaving groups such as Cl, Br etc
but syn elimination is not uncommon and may be the preferred mode with bulky and poor leaving
groups such as onium (poor leaving groups relative to halides and tosylates).

Interestingly, syn eliminations give predominantly the trans olefins while the cis olefins are obtained
exclusively through anti elimination.

Then the orientation of double bonds are governed by two rules; the Hofmann and the Saytzeff rule.

According to Hofmann’s rule the olefins formed from onium salts(t.s. is primary carbanion) is least
substituted.The Hofmann’s rule also deals with the orientation of C-C double and triple bonds in β-
elimination reactions.

In β-elimination reactions, the least substituted alkene will be formed predominantly and the usual
mechanisms are E2 and E1cB. E2 reactions involving bulky positively charged leaving groups follow this
rule .eg:- NR3+,SMe2+ etc.
The bulkier leaving groups and bases increases the yield of Hofmann’s product.Acidity of the β-H and the
steric strain on the β-C determine the direction of the formation of the double bond.

Example:- Elimination of quarternary ammonium salts;

The reaction gives less substituted alkene ie.Hofmann product as the major product due to the relatively
poor leaving group property of amine.

Another eg:- Alkyl fluorides give Hofmann product as the major product but chlorides, bromides and
iodides give Saytzeff product as the major product ie. the fluoride ion has less tendency to leave
compared to other halide ions and the carbanion T.S. is stabilized by the strongly electron withdrawing
fluoride.(Any relevant eight points- Give full credit)

19. Explain with example how NMR used to distinguish enantiotopic/ diascoreotopic ligands.
(correction :- it is diastereotopic ligand)

Enantiotopic ligands :- The steriochemical term enantiotopic refers to the relationship between two
groups in a molecule which, if one or the other were replaced, would generate a chiral compound. The
two possible compounds resulting from the replacement should be enantiomers.

For example:- The two hydrogen atoms attached to the second carbon atom in butane are
enantiotopic.Replacement of one hydrogen atom with a bromine atom will produce (R) -2-
bromobutane. Replaccement of the other hydrogen atom with a bromine atom will produce the
enantiomer (S)-2-bromobutane.

Diaasteriotopicligands :- The steriochemical term diasteriotopic refers to the relationship between the
two groups in a molecule which, if replaced would generate compounds that are diasteriomers.
Diasteriotopic groups are often but not always, identical groups attached to the same atom in a
molecule contain at least one chiral center.

For example:- The two hydrogen atoms of the CH2 moiety in (S)-2-bromobutane are diasteriotopic.
Replacement of one hydrogen atom with a bromine atom will produce (2S,3R) -2,3-dibromobutane.
Replacement of the other hydrogen atom with a bromine atom will produce the diasteriomer (2S,3S)-
2,3-dibromobutane.
NMR identification

Enantiotopic ligands:- Enantiotopic nuclei are related by a plane of symmetry. Enantiotopic protons are
isochronous since their geometrical environment remain identical. The enantiotopic protons however
become chemical shift non- equivalent when the molecule is placed in a chiral environment and then
these can be distinguished. Such an environment is created by using an optically active solvent or by
placing the material in the active site of an enzyme.

Example:- In CH3SOCH3, dimethyl sulphoxide, the two CH3 groups are enantiotopic and isochronous. But
the spectrum of optically active PhCHOHCF3 and CH3SOCH3 the two methyl groups are seen as a doublet
separated by 0.02 ppm (due to association of them). Chiral solvents and chiral shift reagents are thus
widely used to differentiate between enantiomers.

Diasteriotopicligands:-Diasteriotopic ligands are not symmetry equivalent, that is non interchangeable

by any symmetry operation. Diasteriotopic proton reside in different environments and always show
chemical shift differences, that is they are anisochronous. The anisochrony, that is the chemical shifts, is
however often very small(1ppm or less) and only increase with 13C-NMR,1H-NMR,change of solvents
etc.Diasteriotopic ligands can be distinguished by 13C-NMR or by higher fields.

Example 1:- In methyl ester of 2,3-dibromo-2-methyl propionic acid, the protons HA and HB are
chemically nonequivalent and so anisochronous , and appear in the NMR spectrum as an AB quartet,
JAB=10 Hz. They are not symmetry related.

Example 2:- In 2-chloropropenic acid, the two terminal hydrogens are anisochronous and form an AB
quartet with chemical shift difference 0.85ppm. .(Any relevant eight points- Give full credit)

20. What are hard and soft acids? How HSAB principle used to distinguish them?

A Lewis acid is any species with a vacant orbital.Eg:-AlCl3,BF3,SnCl4,SO3 etc.

Pearson in 1963 suggested an important concept to rationalize chemical reactions. According to him a
chemical bond is made up of an acid-base combination. Thus properties of molecules can be explained
by dividing them into acid and base componenets.

Pearson classified the Lewis acids and bases into two groups designated as ‘Hard’ and ‘Soft’. The
hardness of an acid or base is generally characterized by several factors such as small atomic radius, high
effective nuclear charge and low polarizability.

Hard and soft acids:-

Light metal ions with lesser number of d- electrons like alkali metal ions, alkaline earth metal ions etc or
metal ions in higher oxidation states are classified as ‘hard acids’.

“The acceptor atoms of hard acids are small, have high positive charge and contain unshared pair of
electron in their valence shells. They have low polarizability and high electronegativity.” ie. Their
electronic configurations are such that their outer electron charge clouds cannot be easily distorted.
Heavier metal ions with nearly full d-electrons or metal ions in lower oxidation states or metal ions with
bigger size, are classified as ‘soft acids’.

“Hence the acceptor atoms are large, have low positive charge and contain unshared pair of electrons(in
p or d) in their valence shell”. They have high polarizability and low electronegativity. Metals in zero
oxidation state are also classified as soft acids.

Hence soft acids possess opposite characteristics of hard acids.

HSAB principle:-The chemical reactivity of molecules and ions can be rationalized on the basis of the
hard and soft acids and bases and is called HSAB principle.”According to this HSAB principle, hard acids
prefer to associate and react with hard bases and soft acids with soft bases”.

Since hard acids have generally vacant d-orbitals,they can accept electrons from hard bases so that the
bonding between hard acids and hard bases is predominantly ionic. Interaction between soft acids and
soft bases occurs mostly though π- bonding so that the bonding between soft acids and soft bases is
largely covalent.

This principle doesnot state, however that hard-soft or soft-hard combinations cannot exist. It only state
that if there is a choice, a hard-hard or soft-soft combination would be preferred to a hard-soft or soft-
hard combination. The complex A-B will have extra stability if A and B are hard or if both are soft.

(Any relevant eight points- Give full credit)

21. Write a note on Fullerenes and Graphene.

A fullerene is a molecule of carbon in the form of a hollow sphere, ellipsoid, tube, and many other
shapes. Spherical fullerenes are also called Buckminsterfullerene (buckyballs), and they resemble the
balls used in football (soccer). Cylindrical ones are called carbon nanotubes or buckytubes. Fullerenes
are similar in structure to graphite, which is composed of stacked graphene sheets of linked hexagonal
rings; but they may also contain pentagonal (or sometimes heptagonal) rings.

The first fullerene molecule to be discovered, and the family's namesake, buckminsterfullerene (C60),
was prepared in 1985 by Richard Smalley, Robert Curl, James Heath, Sean O'Brien, and Harold
Kroto at Rice University. It contains 12 pentagonal and 20 hexagonal rings. Fullerenes have since been
found to occur in nature. More recently, fullerenes have been detected in outer space.

Examples include:

 Buckyball clusters: smallest member is C20 (unsaturated version of dodecahedrane) and the most
common is C60
 Nanotubes: hollow tubes of very small dimensions, having single or multiple walls; potential
applications in electronics industry;
 Megatubes: larger in diameter than nanotubes and prepared with walls of different thickness;
potentially used for the transport of a variety of molecules of different sizes;
 polymers: chain, two-dimensional and three-dimensional polymers are formed under high-pressure
high-temperature conditions; single-strand polymers are formed using the Atom Transfer Radical
Addition Polymerization (ATRAP) route;
 nano"onions": spherical particles based on multiple carbon layers surrounding a buckyball
core; proposed for lubricants;
 linked "ball-and-chain" dimers: two buckyballs linked by a carbon chain;

 Fullerenes are divided into two classes:- Exohedral fullerens with substituents outside the cage and
endohedral fullerens with trapped molecules inside the cage.

 A spherical fullerene of n carbon atoms has n pi-bonding electrons, free to delocalize. These should
try to delocalize over the whole molecule. The quantum mechanics of such an arrangement should
be like one shell only of the well-known quantum mechanical structure of a single atom, with a
stable filled shell for n = 2, 8, 18, 32, 50, 72, 98, 128, etc.; i.e. twice a perfect square number; but this
series does not include 60. This 2(N + 1)2 rule (with N integer) for spherical aromaticity is the three-
dimensional analogue of Hückel's rule. The 10+ cation would satisfy this rule, and should be
aromatic. This has been shown to be the case using quantum chemical modelling, which showed the
existence of strong diamagnetic sphere currents in the cation.

 Fullerenes are stable, but not totally unreactive. The sp2-hybridized carbon atoms, which are at their
energy minimum in planar graphite, must be bent to form the closed sphere or tube, which
produces angle strain. The characteristic reaction of fullerenes is electrophilic addition at 6,6-double
bonds, which reduces angle strain by changing sp2-hybridized carbons into sp3-hybridized ones. The
change in hybridized orbitals causes the bond angles to decrease from about 120° in the sp2 orbitals
to about 109.5° in the sp3 orbitals. This decrease in bond angles allows for the bonds to bend less
when closing the sphere or tube, and thus, the molecule becomes more stable.

Graphene is an allotrope of carbon in the form of a two-dimensional, atomic-scale, honey-comb lattice

in which one atom forms each vertex. It is the basic structural element of other allotropes,
including graphite, charcoal, carbon nanotubes and fullerenes. It can also be considered as an
indefinitely large aromatic molecule, the ultimate case of the family of flat polycyclic aromatic
hydrocarbons.

Graphene and its band structure and Dirac Cones, effect of a grid on doping Graphene has many
extraordinary properties. It is about 100 times stronger than the strongest steel with a hypothetical
thickness of 3.35Å which is equal to the thickness of the graphene sheet. It conducts heat and electricity
efficiently and is nearly transparent. Researchers have identified the bipolar transistor effect, ballistic
transport of charges and large quantum oscillations in the material.
Graphene is a crystalline allotrope of carbon with 2-dimensional properties. Its carbon atoms are
densely packed in a regular atomic-scale chicken wire (hexagonal) pattern.

Each atom has four bonds, one σ bond with each of its three neighbors and one π-bond that is oriented
out of plane. The atoms are about 1.42 Å apart.

Graphene's hexagonal lattice can be regarded as two interleaving triangular lattices. This perspective
was successfully used to calculate the band structure for a single graphite layer using a tight-binding
approximation.
(Any relevant eight points- Give full credit)

Section C
Answer any two questions. (Each question carries a weightage 5.)

22. (a) Explain the mechanism of Barton reaction . What are its synthetic applications?

Barton reaction is also known as Barton Nitrile Ester reaction. It is a photo chemical reaction
that involves the photolysis of an alkyl nitrite to form a ᵟ-nitroso alcohol. The Barton reaction involves
a homolytic RO-NO cleavage, followed by ᵟ-hydrogen abstraction, free radical recombination, and
tautomerisation to form an oxime.
Selectivity for the ᵟ -hydrogen is a result of the conformation of the six membered radical intermediate.
The site of hydrogen atom abstraction can be easily predicted. This allows the region-and stereo
selective introduction of functionality in to complicated molecule. Barton used this reaction extensively
to create a no. of unnatural steroid analogus.

1. Mechanism

The Barton reaction commences with a photo chemically induced cleavage of the nitrite O-N bond, by
using a high pressure mercury lamp. This produces an alkoxyl radical which immediately abstracts a
hydrogen atom from the ᵟ- carbon .In the absence of other radical sources or other reactive groups, the
alkyl radical recombines with the nitrosyl radical. The resultant nitroso compounds undergo
tautomerization to the isolated oxime product.
2. Mechanism

The alcohol on reaction with nitrosyl chloride (NOCl) is first converted to the nitrite, which on photolysis
undergoes hemolytic cleavage to give alkoxy radical. Abstraction of hydrogen atom from a carbon atom
in a ᵟ position to the original hydroxyl group produces nitroso alcohol, which tautomerizes to the oxime.
The transfer of hydrogen to alkoxy free radical take place by a six numbered transition state. Further
the oxime group can be hydrolyzed to aldehyde. Thus, in Barton reaction methyl group ᵟ- position to an
OH group is converted into aldehyde functionality.

For the synthesis of aldosterone from corticosterone

22(b) Outline the mechanism of photo-fries rearrangement. How will you show that the
rearrangement proceed as intramolecularly?

Phenol esters in solution on photolysis give a mixture of ortho and para acyl phenols. In fries
rearrangements such products are formed in the presence of a catalyst. But photo fries reaction does
not need a catalyst and is a predominantly an intramolecular free radical process.

(Qn.22(a) is wrong Explanation with a relevant mechanism of 22(b) give full credit)
23. How do mesomeric ,hyperconjugative and steric effects influence the strength of organic bases ?

The flow of π electrons or displacement of π electrons in a conjugated system (alternate single

and double bond ) is known as resonance effect or mesomeric effect(R or M).There can be +R effect and
– R effect or +M or – M .If a group donate electron to the conjugated system, then it is said to have +M
effect.

eg :Cl, OH, F, Br, I, OR etc.

vinyl chloride has two resonance structures

Groups which withdraws electrons towards themselves show –M effect .ie , groups attract electrons
from the conjugated system.

eg: -CN , - CHO , -COOH , etc.

Basicity of amine can be explained on the basis of resonance. In case of arylamine, due to resonance,
electron pair on nitrogen is less available for sharing with proton. So aryl amines are weaker bases.

If electron withdrawing groups are present at ortho or para positions it will further weakens basicity. So
para nitro aniline is weaker than aniline,phenyl methyl aniline , ammonia, methylamine.

CH3NH2 > > NH3 >

Guanidine is a strongest organic base.

Guanidium cation
Equivalent structures and no charge separation, so stable.

Guanidinium cation more stable stabilized by 3 equivalent structures .While Guanidine has resonance
structures with charge separation.

On comparing 4-nitro aniline and 4-methyl aniline, the methyl group is electron releasing (+R) but the
nitro group is electron withdrawing (-R).

4-nitro aniline 4-methyl aniline

The +R effect of the methyl is transmitted through the aromatic ring, intensifying the electron density on
nitrogen and increasing the basicity.

When the size of the atom or group in an organic molecule influences the rate of a reaction ,
the effect is called steric effect. When steric effect slows down a reaction ,then it is called steric
hindrance and when rate of reaction increases due to steric effect ,it is termed as steric acceleration.

There are two catogeries of steric hindrance around the basic atom that influence relative base strength.

Primary steric effect: Steric impedance to protonation occurs when bulky groups surrounds the basic
centre. When this results in greater strain in the cationic conjugate acid produced up on protonation
than in neutral molecules, the base is weaker.

Secondary steric effect: There is hinderance to solvation and it is base weaking.

The primary steric effect is credited with the greater basicity of aniline relative to 2,6 dimethyl aniline,
due to greater inhibition of reaction with a proton.

ANILINE 2,6-DIMETHYL ANILINE

The secondary effect is responsible for the difference in basicity between N,N –dimethyl aniline and
N,N-diethyl aniline.The two ethyl groups inhibit solvation of the protonated conjugated acid, which is
the ammonium salt.

N,N-dimethyl aniline N,N-diethyl aniline

Solvation varies with the available space around the basic centre, and should be less for pyridine than
for aniline.The diminished basicity of tertiary amines relative to secondary amines in solution has been
attributed to this effect.

N,N-dimethyl aniline and 2,6-dimethy derivative of it

1 2

Structure 2 is more basic than structure 1. Since electron pair on nitrogen is not delocalised and it is
available on nitrogen.

Trimethyl amine and quinuclidine are having comparable base strength. Both of them react with
trimethylborane to form complexes but complex formed by tri methyl amine is unstable.

Trimethyl amine Quinuclidine

Hyperconjugation is the interaction of the electrons in a sigma bond (usually C–H or C–C) with
an adjacent empty (or partially filled) non-bonding p-orbital, antibonding σ or π orbital, or filled π
orbital, to give an extended molecular orbital that increases the stability of the system. Only electrons in
bonds that are β to the positively charged carbon can stabilize a carbocation by hyperconjugation. An
organic Lewis base loses an electron pair and become a positively charged species. As the system is
more alkyl substituted it become more stable. Thus according to hyperconjugative effect tertiary system
is more stable than secondary and which is more stable than primary. Hence the basicity also follows the
same order.

(Any relevant 20 points-Give full credit)

24. Give account of the following:-

(a) Chirality due to helicity

A helix is inherently chiral and is non superimposable on its mirror image. If

moving from one end to the other along the axis, the helix describes a clockwise direction, it is
designated P (Plus) and if it describes an anticlockwise direction, it is designated M (Minus). At the
molecular level, helicity often arises from secondary structure and is conformational in origin. Thus
helical structure has been intensively studied in protein molecules. Molecular overcrowding may lead to
helicity and consequently, chirality in molecules. Hexahelicene provides a good example. The molecule is
normally expected to be planar. However, due to molecular overcrowding, the terminal benzene rings
are forced to remain in different planes. As a result, the molecule assumes a helical shape and exists as
two helical enantiomers.

(b) Prostereo-isomerism

Prochirality is the property of certain molecules due to which these can be converted into stereo
isomers – appropriate replacement of one of the ligands in an achiral molecule leads to chiral products.
If the replacement of one of the pair of enantiotopically related ligand by another group creates a chiral
centre – Then it is said to be prochiral –Such stereoisomerism is known as prostereoisomerism –
Examples

The molecules which have stereoheterotropic ligands possess prostereo isomerism. E.g. Propionic acid
is prochiral molecule. In this molecule the C2 carbon atom is not a stereo centre. The C2 carbon can be
made a stereo centre by replacing one or other of the two apparently identical ligands (two hydrogen
atoms) by a different ligand(OH) to give enantiometric product.
The two (apparently identical) hydrogen atoms of methylene group in propionic acid and the methylene
hydrogen of ethyl group in 2-Butanol are called stereoheteropropic group.

(c) Configuration of Cyclophanic compounds

In the case of molecule with a chiral plane, an exchange of ligands

across the chiral plane leads to enantiomers. This is also a type of atrop isomerism and is exhibited by
ansa compounds, cyclophanes and certain trans cycloalkenes .

The configurational stability arises out of restriction imposed by

steric factor on the out of plane movement of a structural unit.

Cyclophanes

Cyclophanes are basically similar to ansa-compounds. Cyclophanes are compounds in which one or two
aromatic rings are bridged by methylene group in the para position to give paracyclophanes or the meta
position giving the meta cyclophanes .

In paracyclophanes, the planes of the two benzene rings are

approximately parallel, the phenyl ring with a bulky substituent cannot rotate to give the enantiomer. To
have enantiomerism, at least one of the ring must be dissymmetrically substituted or in the case of meta
cyclophanes, the two chains must be non equivalent as shown in the structure below.

(d) Axial chirality

A chiral centre X can be detected in a molecule, when the four

different ligands a , b , c and d of central atom X are located on the corners of a tetrahedron. When this
centre is replaced by a linear grouping such as C-C , C=C=C ,etc. the tetrahedron become elongated
In this elongation of the tetrahedron, the chiral centre is extended to produce a chiral axis (XY) i.e.,a
stereo axis is generated . The condition for chirality in the case of a molecule with chiral axis is a≠b
andc≠d .e.g. biphenyls, allenes , alkylidine cycloalkanes and spiranes.

1) Stereochemistry of allene: An allene is a cumuline with even number of double bonds and
exhibit enantiomerism , thus allenes of the type ab c=c=c ab are chiral provided a≠b. A cumuline
of the type ab c=c=c=c ab (i.e.,with odd number of double bonds ) does not show
enantiomerism because ab and ab will be in the same plane and hence exhibit geometrical
isomerism .

(Examples like Spiranes, biphenyls etc. with explanation- Give full credit)

25. Illustrate the conformational studies of the following compounds.

(a) Congressane

Diamantane C14H20 (also called congressane) is an organic compound that is a member of

the diamondoids . These are cage hydrocarbons with structures similar to a subunit of the diamond
lattice. It is a colorless solid since its discovery in oil and separation from deep natural gas condensates.
Diamondoids such as diamantane exhibit unusual properties, including low surface energies, high
densities, high hydrophobicities, and resistance to oxidation. Diamantanes are formed via the catalytic
rearrangements of polycyclic naphthenic hydrocarbons.
(b) Sucrose

Sucrose is a common, naturally occurring carbohydrate found in many plants and plant parts.
Saccharose is an obsolete name for sugars in general, especially sucrose. The molecule is
a disaccharide combination of the monosaccharides glucose and fructose with the formula C12H22O11.In
sucrose, one of the constituent monosacchrides is in the furanosyl form. There is possibility of variety of
conformations around the glycosidic bonds having one or two hydrogens. Recent NMR studies and
molecular mechanic calculations suggest that the conformation of sucrose is flexible in solution.

(C) Adamantane

 The chair form is fixed in the molecule of adamantine C10H16, first isolated from mineral oil. It is
the smallest unit of diamond lattice.
 Adamantane has high symmetry and is almost spherical. It has four C3 axes, three C2 axes and six
sigma planes.
 The four six membered rings of adamantine are strain free and are identically arranged in chair
forms. In adamantane the carbon frame work forces the bond angles to be perfectly tetrahedral,
but in the C----CH2------C system the bond angle need not be exactly tetrahedral and it is this
further reduction to 109. 50 in adamantine that causes strain in the molecule.
 It is like an expanded tetrahedron and when the four bridgehead positions carry different
groups, the compound becomes chiral.
 The introduction of a double bond in the ring systemof adamantine is sterically
impossible(Bredt’s rule) and Bredt’s rule is applicable to every carbon in adamantine.
 The bridgehead adamantly tosylate does undergoes SN1 reaction but extremely slowly, since a
planar cabocation cannot be formed easily at bridgehead positions. The SN2 reactions at bridge
head positions are totally ruled out. The nucleophile cannot attack from the rear and the
configuration of the carbon cannot be inverted.
 Twistane C10H16 is an isomer of adamantine. It is constructed from the four cyclohexane rings
which are in twist boat form rather than chair form. In twistane, a twist boat form of
cyclohexane is locked.

Adamantane Twistane
F 7739
M.SC DEGREE (CSS) EXAMINATION, FEBRUARY 2014
First semester
ANICO2/APICO2/CHIC02/PHICO2/POH1CO2-STRUCTURAL AND MOLECULAR
ORGANIC CHEMISTRY
(Common to all Branches of Chemistry) (2012 Admission onwards)

INSTRUCTIONS TO THE EXAMINERS

 This is only a guideline for valuation. If you find any other attempt which is equally
valid and correct, full credit may be given to the students.
 Some of the answers, particularly in Section C, given in the scheme are very elaborate
and that is done only to help the evaluator. Please do not expect all those points in the
answers of the students and A Grade may be given to any answer that fulfills the
direction given at the end of each question.
 Questions with number 16 (a) ii is found to be outside the syllabus/bit confusing due to
spelling mistake. Special care should be taken while evaluating these answers so that
the students are not penalized.
Chairman

Section A
(Answer any Ten questions. Each question carries a weight of 1)
1. Arrange the following in the increasing order of their acidity and comment on it- -
chlorobutyric acid, -chlorobutyric acid, -chlorobutyric acid and n-butyric acid.
 Substitution of a Cl on the - of butyric acid give -chlorobutyric acid, causes a 100-fold
increase in Ka
 When Cl is on the -position, Ka increases by only a factor of 7.
 -chlorobutyric acid increases Ka by only a factor of 2.
 Because, inductive effect operates through -bonds and is dependent on distance, the effect of
halogen substitution decreases on the substituent moves farther from the carboxyl.
n-butyric acid-chlorobutyric acid < -chlorobutyric acid-chlorobutyric acid
(Correct order with sufficient reasons- A, correct order with some reasons-B,
Correct order or reasons-C, partially correct order or reasonable attempt-D)

2. Explain the aromatic character of Tropilium ion using Huckel’s rule

 Statement of Huckel’s rule

[1]
 Cycloheptatrienyl cation (tropyliumion) is an aromatic cation.
 It is a planar carbocation with three double bonds and a positive charge contained in a seven-
membered ring.
 Because the tropylium cation has three -bonds and no other nonbonded electron pairs, it
contains six  electrons, thereby satisfying Huckels rule.
(Statement of Huckel’s rule with explanation–A, Huckel’s rule with partial explanation– B,
Huckel’s rule or sufficient explanation-C, reasonable attempt – D)

3. How NMR is used as a tool for aromaticity?

 If a magnetic field is directed perpendicular to the plane of the aromatic system, the circulating π
electrons in the aromatic molecule produce an induced ring current that oppose the applied
magnetic field in NMR.
 This induced field curves around and in the area of the proton is parallel to the external field.
 So the field seen by the aromatic protons is greater.
 So the outside protons are moved downfield (to higher δ) compared to where they would be if
electron density were the only factor.
 Thus ordinary alkene hydrogens are found at ~ 5 – 5.6 δ, while the hydrogens of benzene rings
are located at ~ 7 – 8 δ). Thus if the protons attached to ring are shifted downfield from the
normal olefinic region, then the molecule is diatropic and hence the molecule is aromatic.
 Thus deshielding of external aromatic protons which results from the circulating pi electrons is
best physical evidence to show pi electron delocalization in aromatic rings.

Diagram not necessary (Any four points-A, Any three points-B, Any two points or
diagram–C, Reasonable attempt–D)
4. Which give white precipitate when treated with alcoholic AgNO3 and why-chlorobenzene and
benzyl chloride
 Benzyl chloride gives precipitate with alc.AgNO3- The low reactivity of chlorobenzene is due to
two factors i) delocalization of electrons by resonance and ii) bond energies due to difference in
hybridization. Chlorobenzene is considered to be a hybrid structures I to V


 in which chlorine is joined to carbon by double bond and carries a positive charge (II-IV),
whereas the ortho and para positions of ring bear a negative charge-
 Resonance stabilizes chlorobenzene and the double bond character of the carbon-chlorine bond
makes it stronger than if it were a pure single bond- In benzyl chloride the carbon holding
halogen is sp3 hybridized.
[2]
 In chlorobenzene, carbon is sp2 hybridized; the carbon-halogen bond is shorter and stronger and
the molecule is more stable- Hence removal of halogen from chlorobenzene is difficult.
(Correct answer with explanation –A, Correct answer with partial explanation –B, Correct
answer with any one point-C, only correct answer or reasonable attempt – D)

5. What is secondary kinetic effect?

 The situation in which isotope substitution changes the rate of the reaction is called a kinetic
isotopic effect.
 When hydrogen in reactant molecules is replaced by deuterium, there is often a change in the
rate.
 Such changes are known as deuterium isotope effect and are expressed by the ratio kH/kD.
 When the rate change arises from isotopic substitution remote from the bond undergoing reaction
it is called a secondary isotope effect.
 Secondary isotope effects can be divided into  and  effects. In a  secondary isotope effect,
substitution of deuterium for hydrogen  to the position of bond breaking slows the reaction. An
example is solvolysis of isopropyl bromide.

(CH3)2CHBr + H2O kH (CH3)3CHOH

(CD3)2CHBr + H2O kD (CD3)3CHOH

where kH/kD was found to be 1.34.

 Hyper conjugation is the major cause of  isotope effect.  secondary isotope effect results from
a replacement of hydrogen by deuterium at the carbon containing the leaving group. Here kH/kD
is 0.87-1.26.
(Any 4 points – A, 3 points – B, 2 points- C, reasonable attempt-D)

6. What is Hammond postulates.

Since transition state has zero life times, it is impossible to observe them directly and information
about their geometries must be obtained from inference-Hammond postulate states that for any
single reaction step, the geometry of the transition state for that step resembles the side to which
is closer in free energy-Thus for an exothermic reaction, the transition state resembles the
reactants more than the products and in endothermic steps the products will provide the best
models for the transition states.

(a) Exothermic (b) Endothermic

reaction reaction
In fig (a) the transition state lies much closer in energy to reactants. Therefore its geometry
resembles that of reactants. In fig (b) Hammond postulate says T.S resembles product.
(Any 4 points – A, 3 points – B, 2 points- C, reasonable attempt-D)

[3]
7. Explain the mechanism of ester hyhdrolysis by AAc2 mechanism
AAc2- Acid catalyzed, bimolecular acyl-oxygen fission
The first step is the addition of a proton to carbonyl oxygen to from carbocation - which is
susceptible to nucleophilic attack to form intermediate -exchanges the proton to alkoxy oxygen –
which loses R’OH - loses a proton to form the acid

(Explanation of two steps-A, Explanation of only one step-B,

Example only – C, reasonable attempt –D)
8. What is prostereoisomerism?
Procchirality is the property of certain molecules due to which these can be converted into stereo
isomers – appropriate replacement of one of the ligands in an achiral molecule leads to chiral
products. If the replacement of one of the pair of enatiotopically related ligand by another group
creates a chiral centre- Then it is said to be prochiral- Such stereoisomersm is known as
prostereoisomerism-Examples

(Explanation with an example-A, Partial explanation with one examples-B,

Correct explanation or example – C, reasonable attempt –D)

9. Draw structure of erythro and threo-3-bromo-2-butanol

CH3 CH3 CH3 CH3

H OH OH H HO H H OH

H Br Br H H Br Br H

CH3 CH3 CH3 CH3

(-)-Erythro-3-bromo- (+)-Erythro-3-bromo- (+)-Threo-3-bromo- (-)-Threo-3-bromo-

2-butanol 2-butanol 2-butanol 2-butanol

(Correct structure – A, Give grades B, C and D on reasonable attempt)

10. Give four example each for achiral and chiral objects that’s commonly used in day to day life.
Achiral objects-An object is said to be achiral if it has a plane of symmetry and its mirror image
are superimpossable
Football, plain water glass, piece of chalk, cricket bat, letters like O, H, I, M,T, U etc –
Explanation or Fig.
Chiral objects- An object which has no plane of symmetry and is not superimpossable on its
mirror image - Shoes, gloves, ear, hand, screw, letters like C, F, K E, P etc – Explanation or Fig
(4 Examples each for achiral and chiral objects – A, 3 Examples – B,
2 Examples – C, One example – D)
[4]
11. Mention the factors on which the stability of conformation depends.
a. Steric strain: Any two atoms or groups that are not bonded to each other can interact in several
ways- These non-bonded groups can either attractive or repulsive, they stabilize or destabilize the
conformation- The non-bonded groups are as far apart as the sum of their van der Waals radii
attract each other- If brought closer together, they repel each other-Such crowding is van der
Waals strain or steric strain.
b. Dipole-dipole interactions: Non bonded atoms or groups tend to take positions that result in the
most favourable dipole-dipole interactions. ie. positions that minimize dipole-dipole repulsion
and maximize dipole-dipole attraction.
c. Bond angle strain: For SP3 hybridised carbon atom has a bond angle of 109o 28’-Any deviation
from the normal bond angle is accompanied by bond angle strain
d. Torsional strain: Any deviation from the staggered conformation (eg: ethane) are accompanied
by torsional strain.
e. H-bonding: A particularly powerful attraction results from the special kind of dipole-dipole
interaction is called the H-bonding.
Explanation or examples
(Any 4points or example with any 3 points – A, any 3 points or example with 2 points– B,
any 2 points or example with 1 points– C, Example or 1 point – D)
12. Draw the energy profile diagram of conformational isomers of cyclohexane. Name the each
forms.

(Correct diagram- A, according to the attempt made - B,C or D)

13. Draw and explain the stereochemical relation behind the formation of 2- butane from meso
and dl-2,3-dibromobutane.
CH3 CH3

H Br H Br
H Br Br H

CH3 CH3
meso dl form

[5]
 CH3
CH3

Br H H
H H 3C
C C
- Br2
H CH3
Br H
H
trans-2-butene

CH3 CH3

SER satisfied

CH3 CH3
CH3
H Br Br CH3
H Br 1200

Br H
H Br H Br

CH3 CH3 H
Active SER not satisfied
-Br2

CH3

CH3 CH3
H3C
C C

H H H
cis-2-butene
H

The meso-2, 3-dibromobutane gives trans-2-butene and the dl isomer gives the cis-2-butene-
Reactions of the active isomer involve a les stable transition state compared to meso isomer. So
the debromination of dl isomer is slower than the meso isomer.
(Correct diagram with explanation-A, Correct diagram with partial explanation-B, Correct
diagram or explanation-C, Reasonable attempt –D)

Section B
(Answer any Ten questions. Each question carries a weight of 1)
14. Predicts the products and explain the mechanism of following:
CH3 CH3
CH3

NaNH2
+
Liq. NH3
Br I
II

NH3

CH3 CH3

+
NH2 NH3
III
CH3
CH3
NH2 +
NH3

IV
CH3 CH3 NH3 NH3
NH2 +
NH3 CH3
CH3

VI +
NH3 NH2
V

[6]
 Two benzyne derivatives are possible-The direction of elimination and direction of addition is
controlled by the inductive effect of the substituent- CH3 is ortho-para orienting and is +I-Here
benzyne II is more stable-The preferred direction of addition of NH3 to II is leading to the
formation of V. % of yield- ortho-, para-22, meta-56.
(All Products with explanation of the mechanism-A, All Products with partial explanation of the
mechanism-B, All Products or explanation of the mechanism-C, Reasonable attempt –D)

15. Complete the following reaction.

(a)
h
Sensitise

Mechanism 4

5 3
.
2

6 .
1
II
I

..

III IV
3 4

5 2

6
1

On sensitized irradiation, I is excited to its triplet state, a 1,5-biradical (II) is formed which
rearranges to give the 3,5-biradical (III) and finally vinylcyclopropane analogue viz, dibenzo
semi bull valence(IV)
Known as Di π methane rearrangement

(b)
h

H C H . H C . . H C
Ph Ph
.o Ph
Ph OH
Ph
Ph
Ph o Ph OH
Intramolecular hydrogen abstraction of carbonyl group converts it into hydroxyl group followed
by carbon-carbon bond formation.
(Complete the reactions (a) & (b) with sufficient explanation – A, Complete the reactions
(a) & (b) with partial explanation – B, Complete (a) or (b) – C, Reasonable attempt –D)

16. Assgin R or S configuration of following

a. (i) R (explanation)
(ii) Question not clear
[7]
b. Draw the R and S configuration of trans-cyclootene

(Correct answer [a(i)] and R & S configurations16(b)–A, Correct answer [a(i)] & R or S
configurations –B, Correct answer [a(i)] or R and S configurations –C, Reasonable attempt –D)

17. Predicts the products and explain the mechanism of following

CH3

H3C C
+
N C C CH3  CH2 CH2 + H3C C C N(CH3)2
H2 H2 H2 H2 H2
CH3 OH -
Hofmann rule is applicable to the substrates in which -carbon atom is attached to a positively
charged carbon atom (quaternary ammonium salts)- The rule states that in the elimination
reaction of positively charged species that major product will be the alkene that is least
substituted-The hydrogen atom will go from that -carbon which has more number of hydrogen
atom.
(All Products with explanation of the mechanism-A, All Products with partial explanation of the
mechanism-B, All Products or explanation of the mechanism-C, Reasonable attempt –D)

18. Explain the conditions of aromatic nature of neutral and charged aromatic system with
suitable examples.
For a compound to be aromatic - the structure must be cyclic - the ring must be planar - the total
number of  electrons should be (4 n+2) where n=0, 1,2, 3...... (Huckel (4n+2) rule for
aromaticity)-- molecule will have unusual stability.
Neutral aromatic systems
Benzene is the most common aromatic ring having a single ring- Completely conjugated rings
larger than benzene are also aromatic - Annulenes. eg [14]-annulene, [18]-annulene…
Compounds with more than one ring - naphthalene, anthracene, phenanthrene- are aromatic
Hetrocycles like pyridine, pyrrole, furan, thiophene - are also aromatic. Explanation
Charged aromatic system
Cyclopropenyl cation -aromatic- because it does have an uninterrupted ring of p-orbital-bearing
atoms and the  cloud contains one pair of delocalised  electrons

[8]
 Cyclopentadienyl anion - aromatic- because it is cyclic, planar, completely conjugated and has
six  electrons

Tropylium cation -is completely conjugated because the positively charged carbon is sp2
hybridised and has a vacant p-orbital that overlaps with the six p-orbitals from the carbons of the
three double bonds. Aromatic- because - cyclic, planar, completely conjugated and has a six 
electrons delocalised over the seven atoms of the ring

(Explanation with two examples-A, Explanation with one examples-B,

Correct explanation or examples – C, reasonable attempt –D)

19. Discuss Norrish type I reaction with mechanism.c

Simple ketones when irradiated undergo cleavage at the C-C bond  to the carbonyl group, by
hemolytic fission.
Procedure: -cleavage, decarbonylation, recombination, possibility of H abstraction

O O

CH3 C CH3
h
CH3 C . + .CH
3

O O O

2 CH3 C . CH3 C C CH3

O
.CH + CO
CH3 C. 3

. H3C CH3
2 CH3

[9]
 The product formed depends on temperature.
O
O
. . . .
h Recombination
a - cleavage CO

O O
. .
H abstraction
Aldehyde

NH3

O
O

. C
H .
Ketene

In unsymmetrical ketones, more stable radical is formed

h . .
CH3 CO CH(CH3)2 CH3 CO + CH(CH3)2
After cleavage, decarbonylation, recombination, possibility of H abstraction etc.
(Explanation with two examples-A, Explanation with one examples-B,
Correct explanation or examples – C, reasonable attempt –D)

20. a. Rate of racemization of 3-nitro derivative of following compound is much lower than that of
the 5-nitro derivate. Why?
In order to display optical activity of biphenyl derivatives, the substituents in the ortho positions
must be large enough to prevent the two rings from becoming coplanar-In the planar form the
molecule will possess a plane or centre of symmetry-In addition to the bulk of the ortho
substituents, the nature and position of other substituents in the rings often play some role in
determining the configurational stability of the atropisomers- A bulky group adjacent to an ortho
substituent exerts a buttressing effect. Thus the rate of racemisation 3-nitro derivative (I) is much
lower than that of its 5-nitro derivate (II)- The buttressing effects of some of the groups are in the
following order NO2>Br>Cl>Me which does not exactly correspond to the order of steric
hindrance of these groups.
b. In the case of atropisomers, the enatiomers may be formed if the substituent in one ortho-position
is successful in ‘pushing through’ past the smaller ortho-substituent on the second ring-The
stability of the optical activity of atropisomers serves as a measure of size of the substituents-
Measurements have shown that the sum of the effective radii of two groups in ortho positions in
different rings has to be larger than 2.9A0, in order to prevent the molecule from ooccupying a
symmetrical conformation with its two rings in one plane-The effective radii of H and COOH
groups are 0.94 and 1.56Arespectively. Thus diphenic acid racemizes readily. ie. the
enantiomers are readily interconverted.

[10]
 The process involves squeezing hydrogens past the adjacent carboxyl groups via the planar
conformation-Once they reach the planar conformation the chirality is lost and racemization
results- This transition requires the bending of bonds-The process takes energy and is slow- All
attempts to resolve diphenic acid have failed, the slipping of a small hydrogen past the caboxylic
acid groups is easy and leads to rapid racemization of enantiomers.
(Sufficient explanation for (a) and correct structure for (b) – A, Partial explanation for (a) and
correct structure for (b) – B, Correct explanation for (a) or Correct structure for (b) – C,
Reasonable attempt – D)

21. Draw the chair conformation of cis and trans decalin. Predict and explain which one is chiral
and more stable.

Decalin is considered as a fusion of a four carbon chain ie.-CH2-CH2-CH2-CH2- to the chair form
of cyclohexane-Trans-decalin is fused with this four-carbon chain in equatorial positions while in
cis-decalin this fusion involves equatorial-axial positions-As a result in cis-decalin the two
hydrogens attached at the point of fusion between two rings lie on the same side of the ring while
in trans-decalin, they are on opposite sides-Cis-decalin exists as equilibrium between two
enatiomeric chair conformations which are interconvertible-It is dissymmetric in both
conformations which are non-superimposable mirror images of each other-Because of rapid ring
flipping between these forms the compound is a non-resolvable dl-pair

Trans-decalin has a rigid conformation, inversion of which is not possible, as it would otherwise
afford a highly stained system with one ring attached to the other by two axial bonds. It has a
centre of symmetry and is therefore optically inactive-Decalins resemble the cis-and trans-1,2
disubstituted cyclohexanes-As a result trans-decalin is stabler by about 2.7 Kcals/mole (11.3
KJ/mole) as compared with cis form
(Correct figure, prediction and explanation – A, Correct figure & prediction– B, Correct
figure or prediction with explanation – C, Reasonable attempt – D)

[11]
 Section C
(Answer any Ten questions. Each question carries a weight of 1)

22. (a) Discuss SN1, SN2 and SNAr mechanism with suitable example.
(b) Explain Inductive effect and Hyper conjugation
(a) SN1 Mechanism - the unimolecular nucleophilic substitution reaction consists of two steps.
They are slow ionization to form a carbonium ion intermediate and fast attack of nucleophile
on the intermediate
Step I
slow
R X R+ + X-
Step II
Fast
+
R +Y R Y

The first step is the rate determining step. The ionization of first step is assisted by solvent
molecules and this solvation effect supplies energy required for breaking the bond between
carbon and leaving group.
I Evidences for SN1 mechanism
(i) Kinetic evidence
Rate = k[RX]
(ii) Stereochemical evidences etc.
II. a. Effect of substrate structure
b. Effect of nucleophile
c. Effect of leaving group
d. Effect of nature of the solvent
SN2 Mechanism - Substitution nucleophilic bimolecular can be completed in a single step with
the formation of no intermediate. Since both the substrate and reagent are involved in the same
step it must follow the second order kinetics. The nucleophile attacks the substrate carbon 1800
away from the leaving group, which is regarded as rear side or back side attack resulting in the
inversion of configuration.

C X + Y Y...........C............X Y C + X

transition state
Evidences for SN2 Mechanism
1. Kinetic evidence
2. Stereochemical factors
3. Linearity of the transition state etc.
SNAr mechanism
(Any one of the following is enough for giving full credit under SNAr Mechanism)
They are of three types
a) Unimolecular
b) Bimolecular
c) Elimination-addition (Benzyne)
[12]
i)SN1Ar Mechanism
This type of mechanism is known in the thermal decomposition of diazonium salts in aqueous
solutions
+
N N +
slow
+ N2

OH
+
fast +
+ H2O + H

ii)SN2Ar Mechanism
Aryl halides undergo nucleophilic substitution with difficulty. When powerful electron
withdrawing group present in o- and p- position replacement of halogen by nucleophile becomes
fast
Step I
Cl Cl .. Cl
Cl
Nu Nu Nu
:Nu : :
W W W
W
Step II
Cl Nu

Nu + Cl
:
W W

iii) Benzyne Mechanism

Aryl halides that do not contain an electron-withdrawing group generally do not react with
nucleophiles. Under extreme reaction conditions, however, nucleophilic aromatic substitution
can occur with aryl halides. For example, heating chlorobenzene with NaOH above 300 °C and
170 atmospheres of pressure affords phenol

The mechanism involves formation of a benzyne intermediate (C6H4) by elimination–addition.

Benzyne is a highly reactive, unstable intermediate formed by elimination of HX from an aryl
halide.

[13]
Formation of a benzyne intermediate explains why substituted aryl halides form mixtures of
products.
The triple bond in benzyne is unusual. Each carbon of the six-membered ring is sp2 hybridized,
and as a result, the σ bond and two π bonds of the triple bond are formed with the following
orbitals.
The σ bond is formed by overlap of two sp2 hybrid orbitals.
• One π bond is formed by overlap of two p orbitals perpendicular to the plane of the molecule.
• The second π bond is formed by overlap of two sp2 hybrid orbitals.
Thus, the second π bond of benzyne differs from all other π bonds, because it is formed by the
side-by-side overlap of sp2 hybrid orbitals, not p orbitals. This π bond, located in the plane of the
molecule, is extremely weak.
All the nucleophiles that react in this way\are very basic, and it was suggested that they start the
reaction off by removing a proton ortho to the leaving group
Correct explanation of SN1, SN2 and any one mechanism of SNAr in (a) and correct
explanation of (b) – A, Correct explanation of (b) and any one (SN1, SN2 or SNAr) from (a)
or Correct explanation for (a) and reasonable attempt for (b) – B, Both (a) and (b) are
reasonably attempted or any one is fully attempted – C, Reasonable attempt of nay one – D)

(b). Explain Inductive effect and Hyper conjugation

Inductive effect - is permanent effect operating in polar covalent bonds. I n a C-Cl bond, for
example, the electron pair bonding the carbon and chlorine is displaced towards the chlorine
atom due to much greater electro negativity of chlorine as compared with carbon.

Thus, chlorine atom acquires a small negative charge and the carbon atom a small positive
charge. The effect of this electron displacement gets relayed to other carbon atoms as the chain.
This type of electron displacement along a chain of atoms due to the presence of polar covalent
bond inductive effect or transmission effect. When the electronegative atom attracts the electron
pair to itself it is called –I effect. –I effect groups are NO2, CN, F, COOH, Cl, Br etc.
When the atom or group pushes the electrons away from itself, it exerts a + I effect
Examples of + I effect groups –CH3, -C2H5, -C(CH3)3 etc
The inductive effect of an atom or group of atoms diminishes rapidly with distance.
Applications
1) Acidity of chloroacetic acid and acetic acid

Cl C C OH CH3 C OH
H2
O O
Chloro acetic acid pKa = 2.86 pKa = 4.76

In chloroacetic acid, the electron withdrawing inductive effect of chlorine facilitates the release
of the proton from oxygen atom as compared to acetic acid. Therefore chloroacetic acid is a
stronger acid than acetic acid.

[14]
2) Relative acid strengths of formic acid and acetic acid

H C OH CH3 C OH

O O
pKa = 4.76 pKa = 3.77

Methyl group has + I effect, therefore acetic acid is weaker acid than formic acid
3) Relative reactivity of nitrobenzene and benzene in electrophilic aromatic substitution
reactions, nitrobenzene is less reactive.
NO2

Less reactive
4) Relative stabilities of methyl, ethyl, isopropyl and ter-butyl carbocation
CH3+ < ÇH3–CH2+ < C(CH3)2+ < C(CH3)3+
Hyper conjugation
In propene the delocalization of electrons takes place by the overlapping between a -orbital of
carbon and -orbital of the H of methyl group

This delocalization which involves bond orbitals also is referred to as hyper conjuugation or
 conjugation. In structure II there is no bond between the hydrogen on C3 and C1. Therefore
hyper conjugation is called no-bond resonance.
Relative stabilities of alkyl free radicals
Tertiary> secondary> primary

Ethyl, isopropyl and ter-butyl radicals have 3,6,9 hyper conjugative forms respectively.
Therefore ter-butyl radical should be most stable.
Relative stabilities of simple alkyl cations
The decreasing order of stability is
Tertiary > Secondary > Primary > Methyl
(Explanation of all the things in (a) and (b) with suitable examples – A, Explanation of any
two from (a) and (b) or one with example from (a) and (b) – B, Explanation with suitable
examples for (a) or (b) – C, Reasonable attempt – D)

[15]
23. a) Give a detailed account on AAL1 and BAC2 mechanism of ester hydrolysis with experimental
evidence
AAL1 mechanism: Acid hydrolysis of esters of tertiary alcohols and secondary alcohols that yield
more stable carbocations as +C(CH3), allyl carbocations etc. The formation of carbocation as
intermediate is proved by the formation of other byproducts such as racemised product,
rearranged olefins, ethers, etc. The mechanism for hydrolysis of esters of tertiary alcohols may be
formulated as

Where R’ = –CMe3
It resembles the SN1 mechanism of hydrolysis of ter-alkyl halides- The hydrolysis of above ester
with H2O18 gives ter-butyl alcohol containing O18 showing alkyl oxygen cleavage

R C OC(CH3)3 H2O18 H+ + (CH3)3C O18H

+ R C OH

O O
Esterification of optically active 2-octanol with acetic acid in presence of H2SO4 showed a small
racemisation

H CH3COOH H
CH3 C (CH2)5 CH3 CH3 C (CH2)5 CH3
H2SO4
OH OCOCH3
Recemised product
Acid hydrolysis of t-butyl esters results in the formation of isobutylene because the carbocation
rearranges to alkene
H3C
+
(CH3)3C C CH2 + H+

H3C
Alcoholysis of t-butyl esters resulted ether
Eg: t-Butyl benzoate gave 61% t-butyl methyl ether when boiled in anhydrous methanol in four
days
(CH3)3C+ + H OCH3 (CH3)3C O CH3
+
-H
BAC2 mechanism
This is the most common type of hydrolysis of esters which takes place under alkaline conditions
especially when the alcoholic part involved is primary or secondary

RCOOR’ + OH– RCOO– + R’OH

Rate = [ester][OH-]. Thus the reaction is second order-bimolecular

The reaction takes place through acyl-0oxygen fission, is proved by using water labeled with O18.

H2O18 + O18H– + H2O

[16]
 Rapid transfer of proton
Eg: Hydrolysis of n-pentyl acetate
O

H3C C OC5H11 + CH3COOH* + C5H11O–

18
OH– CH3COO* + C5H11OH
Alkaline hydrolysis of 1-methyl ally acetate gives the following product
CH3 CH3
-
OH - +
CH3COO C C CH2 CH3COO HO HC C CH2
H H H
If the hydrolysis takes place via alkyl-oxygen fission, carbocation mayundergo allylic
rearrangement, it is not observed
CH3 CH3 CH3

+ +
CH3COO C C CH2 HC C CH2 HC C CH2
CH3COO
H H H H

CH3 CH3

HOHC C CH2 HC C CH2OH

H H
+

The mechanism may be formulated as

23. b) Briefly explain photoreactions of dienones and arenes with suitable example
In conjugated dienones, the carbonyl chromophore may occupy either the central or terminal
positions. The former class of molecules is termed cross conjugated dienones, and latter is called
linearly conjugated dienones
O
O O

Nonconjugated Conjugated enones Linearly conjugated Cross- conjugated

enones dienones dienones
In cross conjugated dienones, the requirement for a photochemical reaction is that the system
must contain a cyclohexadienone chromophore. A typical example is the photorearrangement of
4,4-dephenyl cyclo hexa dienone.
O OH OH

Ph
h
+

Ph Ph
Ph Ph
Ph

The cyclohexa dienone shows absorption at about 300nm (n→Chapman has proposed the
following mechanism for the reaction

[17]
 O O * O * O *

ISC +
h
n 
300 nm + +

Ph Ph Ph Ph Ph Ph
Ph Ph
S0 S1 T1 T1

O *
O

+
Relaxation Rearrangement
Ph

Ph Ph Ph
I
S1

As I has still a chromophore, it can undergo further n→excitation to form the following
O O O

h +
n  Ph Ph
Ph

+
Ph Ph Ph
A B
Structure A and B further undergo phenyl migration followed by aromatization yielding II and III
O
OH
O

Ph
Phenyl migration Ph Aromatization

+ Ph
+ Ph
H
Ph
Ph H
II
O
OH
O

+ Ph Ph
Ph
Phenyl migration Aromatization
H

Ph Ph Ph
III
Aromatic compounds undergo many photochemical reactions. The photochemical
rearrangements of simple benzene derivatives provide direct route to several highly strained
molecules. Irradiation of benzene, for eg. gives benzvalene and fulvene.
Benzene derivatives also add to olefins and diens. The addition to simple olefin involves
rearrangement as well as addition

h CH3
+ CH3 C C CH3
H H

CH3

+ h
H
H

[18]
 Naphthalenes and anthracenes and polyacenes undergo photo dimerization
Eg. Two anthracene molecules join at 9,10-position in the demerization

h

10

Or any other example

(Explanation of all the things in (a) and (b) with experimental evidence – A, Explanation of one
from either (a) or (b) and complete answer for the other – B, Explanation for one each from (a)
or (b) or complete answer for either (a) or (b) –C, Reasonable attempt for (a) or (b) – D)

24. Give an account of axial and planar chiral molecules. Explain with suitable example
The presence of a centre of chirality is not a necessary and sufficient condition for molecular
dissymmetry. The overall chirality of a molecule can be factorized into three elements-chiral
centres, chiral axes and chiral planes.
Axial chirality
A chiral centre X can be detected in a moleculewhen the four different ligands a,b,c and d of
central atom X are located on corners of a tetrahedrom (I) . When this centre is replaced by a
linear grouping eg. C-C or C=C=C, the tetrahedron becomes elongated (II).

In this elongation of the tetrahedron the chiral centre is extended to produce a chiral axis, ie. a
stereo axis XY. The condition for chirality is that all the four ligands have to be different. But in
the case of a molecule with chiral axis the condition for chirality is a#b and c#d. Some examples
compounds which may have a chiral axis , depending on the nature of the ligands a,b,c,d are
diphenyls, allenes, alkylidene cycloalkanes, spiranes etc.
a) Optical isomerism in biphenyls
Biphenyl has a coplanar structure in which two phenyl groups are joined by a single bond. In the
crystal form both benzene rings of the biphenyl lie in the same plane. However, in solution and in
vapour phase, two rings are twisted with respect to each other by an angle of 450 due to steric
interactions between the 2,2’ and 6,6’ pairs of hydrogens. This interaction is further enhanced by
the ortho substituents larger than hydrogen. Two important conditions for biphenyls for exhibit
optical isomerism are the following a) Neither of the two rings have a vertical plane of symmetry
b) at least one of the two ortho position in each ring must be substituted by larger groups.
R, S- Nomenclature
[19]
 NO2 O2N NO2 HOOC
SO3H

COOH H NO2 HOOC HO3S

Optically active Optically inactive Optically active

b) Optical isomerism in allenes
Allenes are C=C=C. They are found to be optically active when the two groups attached to each
terminal atoms are different.
a a

C C C
b
b
The necessary and sufficient condition for such allene to be dissymmetric is that a#b. The reason
for dissymmetry is that the groups a&b at one end of the system lie in a plane at right angles to
those at the other end. Allenes of the type Cab=C=Cab (a#b) are chiral and exist as enantiomers
despite the absence of a chiral centre. Thus in allenes, a situation of restricted rotation giving rise
to perpendicular dissymmetric planes. Thus substituted allenes exhibit optical isomerism
R, S- Nomenclature
c) Alkylidene cycloalkanes: Since the replacement of a double bond in allene by a ring does not
alter the basic geometry of the molecule. The suitably substituted compounds, therefore exist in
optically active forms.
a
a
C

b b
where a b
R, S- Nomenclature
d) Optical isomerism in spiranes: When both the double bonds in allenes are replaced by rings
the resulting system is optically active
a a

C C CH
b
b
R, S- Nomenclature
Planar Chirality
As in axial chiral molecules, an exchange of a pair of ligands around the chiral axis leads to an
enantiomer. Isolation of these stereoisomers depends on the bulk of certain groups and size of
the ring. This is also a type of atropisomerism exhibited by ansa compounds, cyclophanes and
certain transcycloalkenes.
i) Ansa compounds: If the two para positions of an aromatic ring are attached to a heteroatom
and they are in turn linked through polymethylene chain, the compounds are called ansa
compounds
(CH2)10

O O

COOH
[20]
The aromatic ring must be unsymmetrical substituted and polymethylene chain is either above or
below the plane and the two hetero atoms giving two enantiomers. The two enantiomers are
resolvable only if the bridge is enough and the phenyl group cannot twist around aliphatic ring.
(CH2)n
X

O O

Y
If X=COOH, Y=Br, n = 10
Then it is resolvable and optically active
If X= Y=Br, n = 10
It is resolvable and optically active
If X=COOH, Y=H, n = 10
It is not resolvable and optically inactive
If X=COOH, Y=H, n = 8
Then it is resolvable and optically active
R,S Nomenclature

ii) Paracyclophanes: In paracyclophanes, the planes of the two benzene rings are approximately
parallel, the phenyl ring with a bulky substituent cannot rotate to give the enantiomer.

Paracyclophane-the carboxy-phenyl ring cannot rotate to give the enantiomer

When each bridge contains four methylene groups, the compound cannot be resolved as the
carboxyphenyl ring can now rotate to give the enantiomer. A simple paracyclophane given below
can be resolved because its benzene ring cannot rotate in such a way that the carboxyl groups
goes through the alicyclic ring.
(CH2)10

COOH

R,S Nomenclature
e) Cycloalkenes: Eg: cyclooctene-Refter Q No. 16 (b)

(At least 6 points for both axial & planar molecules with examples – A, At least 4 points for
both axial & planar molecules with examples – B, At least 2 points for both axial & planar
molecules with examples – C, Reasonable attempt for both or reasonably good attempt of
any one – D)

[21]
25. Illustrate the conformational analysis of cyclic and acyclic systems.
Conformation of cyclic systems (Refer Text book by Kalsi – Fourth edition)
a) Conformation of cyclohexane
Refer Kalsi P. No. 235
b) Conformation of substituted cyclohexanes
Refer Kalsi P. No. 240
c) Conformation of disubstituted cyclohexanes
Refer Kalsi P. No. 245
d) Conformation of cyclohexanone
Refer Kalsi P. No. 251
e) Conformation of fused rings: Decalins
Refer Kalsi P. No. 265 Or refer Q No. 21.
Other related cyclic systems
Conformation of acyclic systems
i) Conformation of ethane, propane, and n-butane
Refer Kalsi P. No. 220
ii) Conformation of other substituted n-butane
Eg. 2-methylbutane, 2,3-dimethylbutane, 2,2,3-trimethylbutane, pentane etc.
iii) Conformation of ethylene glycol
Refer Kalsi P. No. 225
iv) Conformation of ethyl halides, ethylenedihalides,
Refer Kalsi P. No. 227
Other related acyclic systems such as conformation of stilbenedibromide, tetrabromoethane,
2,3-dibromobutane, tartaric acid etc.
(Illustration with at least 4 examples from both cyclic and acyclic systems – A,
Illustration with at least 3 examples from both systems – B,
Illustration with at least 2 examples from both or 4 examples from one system – C,
Illustration with at least 1 example from both cyclic systems or 2 examples from one
system or a reasonable attempt – D)

For further clarification, please contact

Dr. Siby Joseph
St. Joseph’s College, Moolamattom
9447066802, [email protected]

[22]