ORGANIC CHEMISTRY-I BSCCH-102

UNIT 5: STEREOCHEMISTRY-II

CONTENTS:

5.1 Objectives
5.2 Introduction
5.3 Geometrical isomerism
5.3.1 Determination of configuration of geometrical isomers
5.3.2 E & Z system of nomenclature
5.3.3 Geometrical isomerism in oximes and acyclic compounds
5.4 Conformational analysis of ethane and n- butane
5.4.1 Conformational analysis of ethane
5.4.2 Conformational analysis of n-butane
5.5 Conformation of cyclohexane
5.6 Axial and equatorial bond
5.7 Conformation of mono substituted cyclohexane
5.8 Newman projection and Sawhorse formula
5.9 Fischer and flying wedge formula.
5.10 Difference between configuration and conformation.
5.11 Summary
5.12 Terminal Question

5.1 OBJECTIVES:

By the end of this unit you will be able to

• Learn about the stereoisomerism of those organic compounds which are not
optically active
• Understand the geometrical isomerism shown by olefinic compounds (double
bonded compounds)

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• Understand the conformational isomerism and its representation

• Make a difference between configurational and conformational isomers
• Learn about the conformational analysis of aliphatic and cyclic hydrocarbons
• Learn how to write the Fischer projection formulae, flying wedge formula,
Newman projection formulae and Sawhorse projection formulae for various
conformational and configurational isomers.

5.2 INTRODUCTION

In Unit 4 we have discussed about the isomerism and its type. The difference between
structural and stereoisomerism is also drawn in that Unit. However, more detail discussion on
optical isomerism and its related components is presented in Unit 4. In present unit (UNIT 5)
we will learn more about the isomerism exhibited by the; 1) Molecule with restricted rotation
around carbon-carbon bonds (olefinic and cyclic organic compounds) is known as
geometrical isomerism and; 2) Molecules which are readily interconvertible due to rotation
about single bond is known as conformational isomerism. The geometrical isomerism comes
under stereoisomerism whereas the conformational isomerism comes under structural
isomerism. Partly, we have also discussed about stereoisomerism and structural isomerism in
Unit 4.

5.3 GEOMETRICAL ISOMERISM:

Geometrical isomerism is generally observed in alkenes and cyclic compounds due to

their restricted rotation around carbon- carbon bond. The rotation about a double bond in
alkene or about a single bond in a cyclic/ring like compound is restricted. Double bonded
system consists of a σ (sigma) and a π (pi) bond perpendicular to each other. It is not possible
to rotate the molecule about carbon-carbon bond. The rotation will break the π bond as a
result the molecule will lose its identity. In some cased the rotation about single bond is also
restricted due to steric hindrance. Geometrical isomerism is shown by various groups of

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compounds the major class of compounds that exhibit geometrical isomerism are classified
as:

i. Compounds having double bond;

C=C, C=N, N=N

For example cis- and trans-2-butene have same connection of bond and molecular formulae.

If you observe two similar groups are on the same side of C=C bond this is called
cis- isomer; whereas, if two similar groups are on opposite side of C=C bond this is
known as trans- isomer.

Example 1: cis- and trans- isomerism in 2-butene

H3C CH3 H 3C H

H H H CH3

cis-2-butene trans-2-butene

You can understand that due to the presence of one σ (sigma) and one π (pi) bond
in carbon–carbon double bond, rotation around C=C bond is not possible. The
restricted rotation around C=C bond is responsible for geometrical isomerism in
alkenes.
ii. Cyclic compounds like homocyclic, heterocyclic and fused-ring systems

You can easily observe that rotation around C-C bond is also not possible in cyclic
compounds as the rotation would break the bonds and break the ring. Thus Geometrical
isomerism is also possible in cyclic compounds.

Example 2: cis- and trans- isomers of 1,2-dimethylcyclopropane

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CH3 CH3

H H
CH3 H

H
cis trans CH3

Conditions for geometrical isomerism:

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

Remember: Geometrical isomers are non-mirror image of each other hence they are
called diastereomers. Therefore their physical and chemical properties are different.
Triple bonded molecules do not exhibit any kind of stereoisomerism because such
molecule shows cylindrical symmetry.

5.3.1 Determination of the configuration of geometrical isomers:

Unlike stereoisomerism of chiral compounds there is no general method for

determining the configuration of geometrical isomers. You can find several methods for
determination of configuration of geometrical isomers. Depending on the nature of
compounds you can apply one or more methods for determination of configuration of
geometrical isomers. The most commonly used methods are as follows:

1) Physical method
2) Cyclization method
3) Method of conversion into compound of known configuration

1) Physical method for determination of configuration:

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The geometrical isomers are non-mirror image of each other hence are called diastereomers.
We have discussed in Unit 4 that diastereomers have different physical and chemical
properties. Based on this fact, we can determine the configuration of geometrical isomers by
comparing their physical properties. For example the melting point and absorption intensity
of the cis-isomer are lower than the trans-isomer. Similarly the boiling point, solubility, heat
of hydrogenation, density, refractive index, dipole moment and dissociation constant of cis-
isomer is greater than the trans-isomer.
Thus if you have a set of geometrical isomers, then by comparing their above mentioned
physical properties you can assign their configuration (means you can identify the cis- and
trans-isomers).

Example 3: Diethyl maleate and diethyl fumarate are the cis- and trans- form to each other.
The configuration of these can be determined by comparing their dipole moment. The dipole
moment of diethyl maleate is 2.54D whereas the dipole moment of diethyl fumarate is 2.38D.
Based on the fact that the dipole moment of trans- form of an isomer is lower than that of
cis- form, you can easily predict the cis- and trans- form for diethyl maleate and diethyl
fumarate.

H COOC2H5 H COOC2H5
C C

C C
H COOC2H5 C2H5OOC H
diethyl maleate diethyl fumarate
dipole moment = 2.54D dipole moment = 2.38D

Example 4: cis- and trans- form of crotonic acid can be differentiated on the basis of their
melting points. cis- isomer have lower melting point in comparison to trans- isomer.

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H CH3 H CH3
C C

C C
H COOH HOOC H
cis-crotonic acid trans-crotonic acid
melting point = 15.5oC meltig point = 72oC

Example 5: Ethylbutenoate exists in cis- and trans- isomeric forms. Both, the forms can also
be differentiated based on their melting points.

H CH3 H CH3
C C

C C
H COOC2H5 C2H5OOC H
cis-ethylbutenoate trans-ethybutenoate
boiling point = 56oC/10mm boiling point = 61oC/10mm

Example 6: cis- and trans- isomer can also be identified on the basis of their absorption
intensities. The UV absorption intensity (λmax) of cis-stilbene is lower than that of trans-
stilbene.

2) Cyclization method: Cyclization within a molecule (intramolecular) is usually depends

upon the distance of two associating groups of a molecule. In other words if the reacting
groups are closer to each other than the intramolecular cyclization takes place more
effectively. This principal is also helps to identify the configuration of geometrical isomers.

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Let us take an example of two geometrical isomer of Butenedioic acid (i.e. Maleic acid and
Fumaric acid) can be differentiated by possibility of formation of anhydride. Maleic acid
which is cis- form of Butenedioic acid can only give the respective anhydride on heating;
whereas, the trans- form of Butenedioic acid (i.e. Fumaric acid) does not give its anhydride
on heating. If the Fumaric acid is strongly heated it get converted into Maleic acid.

Example 7: Cyclization of Maleic acid to Maleic anhydride. Fumaric acid does not give the
anhydride on heating.

O
H COOH H C H COOH
C Heat C C Heat
-H2O O No anhydried
C C C formation
H COOH H C HOOC H
O
Maleic acid Maleic anhydried Fumaric acid
cis- isomer trans- isomer

3) Method of conversion into compound of known configuration: The configuration of

geometrical isomers can also be determined by converting them in to a compound of
known configuration. For example, there are two trichlorocrotonic acid (cis- and trans-),
one of which can be hydrolyzed to Fumaric acid. Therefore this isomer must be trans-
isomer of trichlorocrotonic acid. The cis- isomer does not undergo hydrolysis.

Example 8: Determination of configuration of two isomers of trichlorocrotonic acid by

hydrolysis method.

H CCl3 H COOH H CCl3

C H 2O C C H 2O No Reaction
C C C
HOOC H HOOC H H COOH
trans- cis-
trichlorocrotonic Fumarc acid trichlorocrotonic
acid acid

Example 9: Reduction of trans-crotonaldehyde in to trans-crotyl alcohol

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H CH3 H CH3 H CH3

C LiAlH4 C C LiAlH 4 No Reaction
C reduction reduction
C C
OHC H HOH2C H H CHO
trans- trans-crotyl alcohol cis-crotonaldehyde
crotonaldehyde

5.3.2 E & Z system of nomenclature:

We have already discussed about the cis- and trans- nomenclature of geometrical
isomerism. The cis- and trans- nomenclature is the oldest and most fundamental
nomenclature system for geometrical isomerism. The cis- and trans- nomenclature system is
applicable only for those geometrical isomers in which at least one identical atoms/groups is
bonded with each double bonded carbon. If both the identical groups/atoms are on same side
of double bond the isomer is called as cis- isomer; whereas, if both identical groups/atoms
are on opposite side of the double bond the isomer is called as trans- isomer (see example 1
of this unit).

The cis- and trans- nomenclature method is limited to the molecule in which identical
groups/atoms are attached to double bonded carbon. If all the atoms/groups on double
bonded carbon are different then the configuration of such molecule could not be assigned as
cis- and trans- nomenclature. A more general nomenclature (i.e. E/Z nomenclature) was
introduced which was based on Cahn-Ingold-Prelog system. In E/Z system the configuration
is specified by the relative positions of two highest priority groups/atoms on the two carbons
of the double bond.

Let us understand the E/Z nomenclature system by considering an example which we have
already discussed in the beginning of this Unit (example 1).

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H3C CH3 H 3C H

C C C C

H H H CH3
cis-2-butene trans-2-butene

You can easily identify which one is cis- isomer and which one is trans- just by looking the
position of similar atoms/groups. It is a simple and visual way of telling the two isomers
apart. So why do we need another system?

Now consider one another example in which we will change all the atoms/groups in above
example by replacing one CH3- by Br, other CH3- by Cl, and one H- by F. Now try to predict
the nomenclature of these two isomers of 2-bromo-1-chloro-1-fluoroethene (I and II). Could
you name these isomers using cis- and trans- nomenclature? The simplest answer is ‘NO’.

Br Cl Br F

C C C C

H F H Cl
I II

Because everything attached to the carbon-carbon double bond is different, there are not so
simple so that you can predict them as cis- and trans- to each other. The E/Z system of
nomenclature provides the most appropriate solution to above problem. This system is based
on the priority of the attached atoms/groups on each double bonded carbon. The priority of
the atoms/groups can be assigned as per the ‘Sequence Rule’ or ‘CIP Rule’ given by Cahn-
Ingold-Prelog. We have already discussed the detail about ‘Sequence Rule’ in Unit 4. Now
assign priority to atoms/groups attached to each double bonded carbon in above example.

1 1 1 2
Br Cl Br F

C C C C
2 2 2 1
H F H Cl
Molecular Plane
I II

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We can easily observe that the both higher priority atoms/groups on each double bonded
carbon of isomer I are on same side; whereas, the higher priority atoms/groups on each
double bonded carbon of isomer II are on opposite side. If the two groups with the higher
priorities are on the same side of the double bond, such isomer is designated as the (Z)-
isomer. So you would write it as (Z)-name of compound. The symbol Z comes from a
German word ZUSAMMEN, which means together. If the two groups with the higher
priorities are on opposite sides of the double bond, then such isomer is designated as (E)-
isomer. E comes from the German ENTGEGEN, which means opposite. Thus in given
example the isomer I is having both higher priority groups/atoms are on same side of double
bond, hence it is Z- isomer; whereas, the isomer II is having both higher priority
groups/atoms are on opposite side of the double bond, hence it is E- isomer.

1 1 1 2
Br Cl Br F

C C C C
2 2 2 1
H F H Cl
Molecular Plane
I II
(Z)-2-bromo-1-chloro-1-fluoroethene (E)-2-bromo-1-chloro-1-fluoroethene

Example 10: Some other examples of geometrical isomers with E and Z configuration

1 2 1 2
H 3C F D F 1 1
H 3C C 2H 5
C C C C
2 1 2 1 C C
H Cl H Cl 2 2
H CH3
(E)-1-chloro-1- (E)-Deuterated1-chloro-1-
(Z)-3-methylpent-2-ene
fluoroprop-1-ene fluoroprop-1-ene

1 1 1 2 2 2
H3C OCH3 H 3C CH2OH H 3C CH2CH3

C C C C C C
2 2 2 1 1 1
H OH H CHO C2 H 5 CH CH2
(Z)-3-ethyl-4-
(Z)-1-methoxyprop-1-en-1-ol (E)-2-(hydroxymethyl)but-2-enal
methylhexa-1,3-diene

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5.3.3 Geometrical isomerism in oximes and acyclic compounds:

Nitrogen containing compounds like >C=N- as well as –N=N- bond also exhibit
geometrical isomerism. The important classes of compounds that exhibit geometrical
isomerism due to >C=N- bond are:
(a) Oximes
(b) Nitrones
(c) Semicarbazones
(d) Hydrazones

H Ph H 3C Ph Ph CH3 Ph CH3
C C C C

N N N N
OH O H NH2 NHCONH2
(E)-1-(1- (E)-1-(1-
(Z)-benzaldehyde (E)-nitrone phenylethylidene) phenylethylidene)
oxime hydrazine semicarbazide

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
aldehyde and ketones (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. The priority of the groups/atoms is assigned as per the sequence rule which we have
already discussed in Unit 4. 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.

Example 11: E/Z isomerism is shown by i) benzaldoxime, ii) ethylmethylketoxime and iii)
methylphenylketoxime

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H Ph Ph H H 3C C2 H 5 C2H 5 CH3
C C C C
i) ii)
N N N N
OH OH OH OH
(Z)- (E)-
(Z)-benzaldehyde (E)-benzaldehyde ethylmethyl ethylmethyl
oxime oxime ketoxime ketoxime

Ph CH3 H 3C Ph
C C
iii)
N N
OH OH
(E)-acetophenone oxime (Z)-acetophenone oxime

We have already discussed that the 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.

Example 12: Geometrical isomers of disubstituted cyclopropane, cyclobutane,

cyclopantane and cyclohexane.

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COOH H

CH3 CH3 CH3 H

HOOC H COOH COOH

H H H CH3
cis-1,2- trans-1,2- H cis-cyclobutane-1,3- H trans-cyclobutane-
dimethylcycl dimethylcycl
dicarboxylic acid 1,3-dicarboxylic
opropane opropane
acid

H H H CH3 CHO H H H

Cl CH3 Cl H H CHO CHO CHO

cis-1-chloro-3- trans-1-chloro-3- trans-cyclohexane- cis-cyclohexane-1,4-
methylcyclopentane methylcyclopentan 1,4-dicarbaldehyde dicarbaldehyde
e

5.4 CONFORMATIONAL ANALYSIS OF ETHANE AND N-

BUTANE:

The different spatial arrangements of atoms in a molecule which is readily

interconvertible by rotation about single bonds are called conformations. The study of
various preferred conformations of a molecule and the correlation of physical and chemical
properties to the most preferred conformer is called conformational analysis. Due to rapid
interchange of the spatial positions of groups/atoms these conformers are non-separable
under normal conditions. Since, different conformations arises because of the rotation about
single bonds, hence, they are also called the rotamers. The conformational and
configurational isomerisms are related to energy barrier for interconversions of different
spatial arrangements of atoms in a molecule. If the energy barrier for interconversion of
different spatial arrangements is between 0.6 kcal/mol-16.0 kcal/mol; it result the
conformational isomers or conformers; whereas, if this energy barrier is more than or equal
to 16 kcal/mol than the configurational isomers are obtained.

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5.4.1 Conformational analysis of ethane:

When ethane molecule rotates around carbon-carbon single bond, two extreme
conformations (one is highly stable and other is highly unstable) are obtained. The highly
stable conformation of ethane is called ‘staggered conformation’ and the highly unstable
conformation of ethane is called ‘eclipsed conformation’. In between these two extreme
conformations (i.e. staggered and eclipsed), an infinite number of conformations are also
possible.

5.4.1.1 Staggered conformation: A conformation with a 60° dihedral angle is known as

staggered conformation. The angle between the atoms attached to the front and rear carbon
atom is called dihedral angle.

H 60o
H H

H H
H

Staggered conformation
5.4.1.2 Eclipsed conformation: A conformation with a 0° dihedral angle is known as
eclipsed conformation.
H
H H 0o
H

HH

Eclipsed conformation

In staggered conformation the atoms are located at maximum possible distance from each
other hence they are in their most relaxed spatial arrangement thus the staggered
conformation is considered as the most stable conformation; whereas, in eclipsed
conformation the atoms are located at minimum distance, hence due to repulsion between the
atoms the eclipsed conformation is considered as the least stable (high energy) conformation.
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There are two methods for the representation of staggered and eclipsed conformations, a) the
Sawhorse representation formula and b) the Newman representation formula.

a) The Sawhorse representation formula: In sawhorse representation formula the spatial

arrangement of all the atoms/groups on two adjacent carbon atoms. The bond
between adjacent carbon atoms is represented by a diagonal line and rest of the atoms
are located on each carbon at +120° or -120° angles to each other. The sawhorse
representation is shown as:
diagonal line H
H H

H H
OR
120o H H 120o H

viewpoint H
H H viewpoint H

Sawhorse representation formula

b) The Newman representation formula: The Newman representation formula is a planar

representation of the sawhorse formula. The molecule is viewed along the axis of a
carbon-carbon bond. The carbon atom in front of the viewer is represented by a dot
(●), whereas the carbon atom away to the viewer is represented by circle. The rest of
the atoms/groups are located on each carbon atoms at +120° or -120° angles to each
other as shown below:

H H
H H H
H H
Circle carbon
120o

H H
H HH
Ponit Carbon

Newman representation formula

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The different conformations of ethane are not equally stable. The staggered form in which
the hydrogen atoms are ‘perfectly staggered’ (dihedral angle is 60°) is the most stable
conformation. This is because, in this conformation the all carbon hydrogen (C-H) bonds are
located at maximum possible distance to each other, and hence they feel minimum repulsive
energy from each other. In eclipsed conformation of ethane, the hydrogen atoms attached to
each carbon are directly opposing to each other. This result the minimum separation of the
atoms or groups, and hence they feel maximum repulsive energy from each other. The
eclipsed conformation therefore, of highest energy and has the lowest stability. A graph plot
for the energy profile for various conformations of ethane is shown on figure1. The relative
stability of various conformations of ethane is
Staggered >> Eclipsed

Figure 1: Energy profile diagram of conformational isomer of ethane

5.4.2 Conformational analysis of n-butane:

n-Butane (C4H10) has three carbon-carbon single bonds (Figure 2); therefore the molecule
can rotate about each of them. The rotation about C2 and C3 bond will provide the
symmetrical conformations. To study the conformational analysis of n-butane, we must

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consider it as a derivative of ethane molecule, where one hydrogen at each carbon of ethane
is replaced by methyl group (-CH3).
H H
1 4
H3 C C C CH3
2 3
H H

Figure 2: Butane molecule

Various conformation of n-butane can be obtained by rotation about C2 and C3 bond are
shown in figure 3:

Figure 3: Energy profile diagram of conformational isomer of n-butane

From figure 3, we can see that n-butane has three staggered conformations (I, III and V).
Conformer I, in which two methyl groups are as far as possible, and hence is more stable
than other two staggered conformers (i.e. III and V), because conformer I, has minimum
repulsive energy. As you can see from figure 3; in conformer I, both the methyl groups are
located opposite to each other. The most stable conformer of n-butane, in which both the
methyl groups are located opposite to each other is called the anti-conformer, whereas other
two staggered conformers (i.e. III and V) are called gauche conformer. Due to difference in
steric strain (repulsion between dihedral atoms/groups) the repulsive energy of anti and
gauche conformers are also different. Three eclipsed conforms (II, IV and VI in figure 3) are
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also exits for n-butane, in which the dihedral atoms/groups are in front of each other (i.e.
dihedral angle is 0°). The fully eclipsed conformer IV, in which the two methyl groups are
closest to each other, has maximum steric strain; hence it is of higher energy than the other
eclipsed conformers (II and VI). Thus the relative stabilities of the six conformers of n-
butane in their decreasing order is given as follows:

Anti > Gauche > Eclipsed > Fully eclipsed

I III and V IV II and VI

5.5 CONFORMATION OF CYCLOHEXANE:

It is known to you that in cycloalkanes, all the ring carbons are sp3 hybridized, hence must
have tetrahedral geometry with all bond angles of 109.5°. But to sustain its cyclic structure
the cycloalkanes could not be able to maintain the bond angle of 109.5°. As a result there is a
deviation from the normal tetrahedral bond angle. This deviation leads the development of
strain in the molecule. Thus the cycloalkanes exhibit angle strain, due to which cycloalkanes
are not as stable as their non-cyclic homologs. To minimize the angle strain the structure of
cycloalkanes is keep on changing from one cyclic form to another which are readily
interconvertible by rotation about single bond. This is the reason why cyclohexane and larger
rings are non-planar.

Cyclohexane exists in two readily interconvertible forms which are called the chair and
boat conformations of cyclohexane (Figure 4).
1
4
2 4

3 3
1 6 2 5
5 6
Chair Boat
Conformation of Conformation of
cyclohexane cyclohexane

Figure 4: Two readily interconvertible conformations of cyclohexane

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Both chair and boat forms are free from angle strain. In chair form carbon C1, C3 and
C5 are in one plane and carbon C2, C4 and C6 are in different plane. Similarly, in boat form
carbon C1 and C4 are in one plane and carbon C2, C3, C5 and C6 are in other plane. The
interconversions of chair to boat and boat to chair via various other intermediate
conformations are shown in scheme 1. The chair conformation (I and V scheme 1) is
considered as a rigid conformation of cyclohexane in comparison to boat conformation;
because during interconversion from chair to boat conformation, some angular deformations
are required. These angular deformations usually increase the energy barrier for
interconversion from chair to boat conformation. Therefore the chair conformation of
cyclohexane is the most stable conformation.

I II III IV
Chair Half chair Boat Half chair

V
II A III A Chair
twisted boat Twisted boat

Scheme 1: Conformational analysis of cyclohexane

Chair form on distortion gives half chair (II and IV scheme 1) conformations which are of
highest energy conformations. In comparison to chair conformation, the boat conformation
(III scheme 1) is flexible and can readily distort in to many steps to reduce the C-H bond
eclipsing. The boat conformation can be interconvertible in to twisted boat (IIA and IIIA
scheme 1) conformations, which has comparatively less angular and steric strains. The
twisted boat conformations have lower energy than the boat conformation, hence is more
stable than boat conformation. At room temperature 99.9% cyclohexane molecules exist in
the most stable chair conformation.
The energy profile diagram along with various possible conformations of cyclohexane is
shown in figure 5.

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Figure 5: Energy profile diagram of conformation of cyclohexane

5.6 AXIAL AND EQUATORIAL BOND:

In chair conformation of cyclohexane, there are two different positions occupied by the
12 hydrogen atoms of cyclohexane. Out of total 12 Hydrogen atoms of cyclohexane, six
hydrogen atoms are located towards perpendicular to average plane of the ring; these
perpendicular hydrogen atoms are called axial hydrogens (a), and respective bonds are called
axial bonds. The other six hydrogen atoms are located along with the average plane of the
ring; these hydrogens are called equatorial hydrogens (e), and the respective bonds are called
equatorial bond.
a a
a a
e e
e e
a e e a
a a
e e e e
e e
a a a
a

a = axial; e = equatorial
Cyclohexane is rapidly interconvertible (flips) in to its mirror image chair conformations at
room temperature. During flipping all the axial hydrogens becomes equatorial and all the
equatorial hydrogens becomes axial. The flipping of the cyclohexane is so rapid that it is not

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possible to differentiate between equatorial and axial hydrogens. These hydrogens can be
differentiated at very low temperature (i.e. -80°) and analyzed by 1H NMR spectroscopy.

5.7 CONFORMATION OF MONO SUBSTITUTED

CYCLOHEXANE

If one hydrogen atom of cyclohexane is replaced by a larger atom or group, the

molecule becomes highly hindered. As a result the repulsion between atoms increases. Axial
atoms/groups usually face more repulsive interaction in comparison to equatorial
atoms/groups. Since three axial atoms/groups are located in one side of the average plane of
ring, whereas rest three atoms/groups are located in other side of the average plane of ring.
The repulsive interaction experienced by three axial atoms is called 1,3-diaxial interaction.
To minimize the 1,3-diaxial interaction and resulting repulsive energy, the monosubstituted
cyclohexane acquires a chair conformation in which the substituents occupies an equatorial
position. There are two possible chair conformations for methyl cyclohexane. In one
conformation the methyl group located at axial position (I), whereas in other conformation
the methyl group is located at equatorial position (II). When methyl group is at axial
position, it has 1,3-diaxial interaction with hydrogen atoms at C3 and C5 carbons due to
which the energy of such conformation is very high in comparison to the conformer in which
the methyl group is at equatorial position. The conformer with methyl group at equatorial
position does not have any kind of 1,3-diaxial interaction hence is more stable.
CH3 H
H H
H H3 C
H H

Axial conformer with Equatorial conformer

1,3-diaxial interaction with no 1,3-diaxial
interaction

5.8 NEWMAN PROJECTION AND SAWHORSE FORMULA

The Newman representation formula: Newman Projections are used mainly for
determining conformational relationships. Recall that, conformers are molecules that can be

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