Conformations of Cyclic and Acyclic Molecules-1

Conformations of alkanes and
Cycloalkanes
In 1874, Van’t Hoff and Le Bell independently proposed that the four valencies of
carbon are directed toward the corners of a tetrahedron with the carbon atom at its center
Configuration of a molecule denotes three-dimensional arrangement of atoms in space.
The infinite number of different arrangements of atoms in space that is a result of rotation
about a single bond is called conformational isomers, conformers or conformations or
rotamers
It is often said that a rotation about a single bond is ‘‘free’’.
The statement is not meant to imply that there is no energy barrier to a rotation,
but that rotation is spontaneous at room temperature.
Thus, conformations are not actual isomers as they cannot be separated and isolated.
They are different shapes of the same molecule.

Conformational analysis is the study of kinetic and thermodynamic properties of molecules
that are conformation dependent such as the existence of a preferred conformation,
energies and populations of different conformational arrangements, and
chemical consequences of it.
One of the simplest organic compounds that exists in different conformations is ethane.
Different conformations of ethane are a result of rotation about the carbon–carbon bond.
There is an infinite number of such conformations.
Fortunately, to carry out conformational analysis of ethane one needs to consider

only the two extreme conformations—staggered and eclipsed.
In the eclipsed conformation, each of the carbon–hydrogen bonds

is in the same plane as the carbon–hydrogen bonds on the neighbouring carbon.
In a staggered conformation, each of the carbon–hydrogen bonds

is in between the two carbon–hydrogen bonds on the neighbouring carbon atom.
Configuration of an organic compound is usually represented by a perspective formula

For the purpose of conformational analysis, the Newman projection and the
sawhorse formula are frequently more suitable.
Ethane molecule Newmann Projection formula Sawhorse formula
In a Newman projection formula one observes the molecule along the bond joining
the two atoms, in this case the carbon–carbon bond of ethane . As a convention, the
carbon nearest to the eye is labeled as carbon 1 and farthest from the eye carbon 2.
The closer carbon atom is represented as a dot and the remaining three substituents
are represented as attached to it with the angles between the substituents of 120.
The back carbon is represented as a circle and its substituents are shown as
appearing over the horizon of that atom.
In Sawhorse formula one draws an elongated bond connecting these two atoms and,
again similar to the Newman projection formula, the substituents on each carbon
atom are represented as if the angle between them was 120—resembling a letter Y
or an inverted letter Y.
Dihedral angle (also called torsion angle), h, is the angle between two planes.
Each plane is defined by three atoms C–C–X and C–C–Y as shown above
In the case of ethane, the dihedral angle is the angle between the carbon–
hydrogen bonds on the two carbon atoms.
The change in energy due to rotation from a staggered conformation to an

eclipsed is called torsional strain or rotational strain.
Conformations in between staggered and eclipsed conformations are called as

skewed conformations.
Skewed conformations are important for cyclic molecules like cyclohexane.

The stability of staggered conformation is due to steric reasons as well as due to the
Facile delocalisation of electrons from the bonding C-H orbital which acts as a donor to
the vacant anti-bonding C-H orbital which acts as an acceptor.
Hyperconjugation is special phenomenon where electron-density from a sigma bond can
overlap with an empty or anti-bonding orbital, sharing that electron density and
leading to increased stability.
Conformational analysis of propane:
the energy difference between the staggered and the eclipsed conformation
of propane is only 0.5 kcal mol−1 higher compared to ethane
steric hindrance raises the energy of the staggered conformation.
To relieve steric strain, the C–C–C angle in propane increases from the
ideal tetrahedral angle of 109.5° to 111.7°
Conformational analysis of butane:
As can be seen from the above diagram, there are three staggered conformations of which
two are guache and one is anti. Hence based on entropy and based on probability
the gauche conformation is favoured. Based on entropy mixture of conformations is more
favoured than a single conformation as mixture has greater entropy than a single
Conformation.
Types of strain:
Conformational analysis of simple alkanes revealed two types of strain
1. Torsional strain
2. Steric strain
According to Hendrickson and Allinger the total strain of a conformation is the
sum of:
3. Bond strain—stretching or compression of chemical bonds.
This type of strain is rather severe and is not encountered very often in organic
compounds. To minimize bond strain, a molecule adopts conformations that have
other, less energy-demanding, types of strain.
2. Torsional strain (eclipsing strain, Pfitzer strain) is caused by eclipsing interactions.
Torsional strain is considerably higher compared to steric or angle strain.
3. Steric strain (Van der Waals strain, Prelog strain) is caused by atoms forced too
close to each other. Transannular strain (Prelog strain) is a form of steric strain
characteristic of medium rings.
4. Angle strain (Bayer strain, classical strain) is a result of deviation from the ideal
bond angle. Compared to other types of strain, increase in energy of a conformation
caused by angle strain is relatively low. As a result, a molecule can accommodate
relatively large deviation from an ideal bond angle and still be stable.
Cyclohexane is the smallest ring that exhibits no strain and types of bonds and
conformations of cyclohexane form the basis of conformational analysis of other rings
Cyclohexane is not planar and the bond angle is not 120o as initially thought by Von Bayer.
Instead, cyclohexane ring is puckered to relieve both the torsional and the angle strain.
In fact, one of the resulting puckered cyclohexane conformations has no strain at all.
The two extreme conformations of cyclohexane are chair and boat.
Chair conformation is the one without strain
In a chair conformation all of the bond angles are tetrahedral angles and all of the
C–H bonds are in staggered conformations.
The ideal bond angle for a tetrahedral molecule is 109.5o. This is seen when the four
Substituents are same. Ex: CH4 or CCl4. But when the substrates /atoms are different the
Bond angle deviates from the ideal bond angle in order to accommodate the steric strain
Ex: in propane the C–C–C bond angle is 111.7.
Comparison of cyclohexane to propane is appropriate as in each molecule carbon
atoms have identical sets of four substituents—two Carbons and two Hydrogens.
In a chair conformation of cyclohexane twisting of the ring results in a bond angle of

111.5, which is very close to that of propane and, therefore, cyclohexane does not
exhibit an angle strain.
The chair conformation flips from one chair form to the other. It has to go through all
the other conformations like half chair, twist boat and boat forms to change to the other
Chair form. The half chair form can be considered as transition state which leads to the
Twist boat form.
This happens continuously at room temperature. The two chair forms are
Same in energy and are mirror images of each other.

Conformations of Cyclic and Acyclic Molecules-1

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Conformations of alkanes and

Configuration of a molecule denotes three-dimensional arrangement of atoms in space.

They are different shapes of the same molecule.

There is an infinite number of such conformations.

Fortunately, to carry out conformational analysis of ethane one needs to consider

In the eclipsed conformation, each of the carbon–hydrogen bonds

In a staggered conformation, each of the carbon–hydrogen bonds

Configuration of an organic compound is usually represented by a perspective formula

The change in energy due to rotation from a staggered conformation to an

Conformations in between staggered and eclipsed conformations are called as

Skewed conformations are important for cyclic molecules like cyclohexane.

In a chair conformation of cyclohexane twisting of the ring results in a bond angle of

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