Chemsitry –BTCH-101-18

CHAPTER - 6
STEREOCHEMISTRY
NOTES
CONFORMATIONAL ANALYSIS:
In alkanes, the distribution of electrons in sigma molecular orbital is
symmetrical around the internuclear axis of the C-C bond. Thus, it permits the
possibility of free rotation about the C-C single bond. Due to this rotation, different
spatial arrangements of carbon atoms in space are observed which can change into
one another. Such spatial arrangement of carbon, hydrogen atoms which can be
converted into one another by rotation around a C-C single bond is called
confirmation or conformer or rotamer. Alkanes can thus have an infinite number
of conformations by rotation around C-C single bonds. However, this rotation is
not completely free due to repulsive interactions between the electron clouds of C-
H bonds. This repulsive interaction is termed as torsional strain.
The different spatial arrangements of atoms in a molecule which are readily
inter convertible by rotation about single bonds are called conformations.
The terms conformation and configuration are related to energy barrier for
interconversions of different spatial arrangements of atoms in a molecule. If the
energy barrier for conversion of different spatial arrangements is between > 0.6
and < 16 kcal/mol they are conformations (i.e., conformers), and if it is): 16
kcals/mol, they are configurations (i.e., stereoisomers). If the energy barrier is 0.6
kcal/mol or less at room temperature, the rotation would be free because this
amount of energy can be readily provided by the thermal energy of the molecule.
*0.6 Kcal/mole = 2.5 KJ/mol and 0.6 Kcal/mole = 70 KJ/mol
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The study of the existence of preferred conformations in molecules, and the

relating of physical and chemical properties of a molecule to its preferred
conformation is known as conformational analysis.
Conformations of ethane:
When an ethane molecule rotates about its carbon-carbon single bond, two
extreme conformations can result: the staggered conformation and the eclipsed
conformation. An infinite number of conformations between these two extreme
conformations is also possible. These are called skew conformations. There are
various ways to represent the three-dimensional conformations on the paper.
Sawhorse Formula:
The sawhorse formula indicates the spatial arrangement of all the atoms or groups
on two adjacent carbon atoms. The bond between the adjacent carbon atoms is
represented by a diagonal line, usually from lower left to upper right, the left hand
bottom end representing the atom nearest to the observer and the right hand top
end the atom that is farther away. Two of the remaining bonds to the two atoms are
drawn vertically and the other four at 120º angles to these two as shown below:

Newman Projection: It is useful in alkane stereochemistry; it visualizes the

conformation of a chemical bond from front to back, with the front atom
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represented by a dot and the back carbon as a circle. The front carbon atom is
called proximal, while the back atom is called distal.
Staggered conformation: A conformation with a 60° dihedral (torsional) angle is
known as staggered conformation. The angle between the atoms attached to the
front and the rear carbon atoms is called the torsional angle.
Eclipsed conformation: A conformation with a 0° torsional angle is known as
eclipsed conformation.
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The Dihedral Angle (Or Torsion Angle)

he dihedral angle [also: torsion angle] is defined as the angle made between
the four atoms A-B-C-D when looking along the B-C bond.

Torsional Strain:
Torsional strain is the repulsion that arises between atoms or group of atoms
when a molecule is rotated around a sigma bond. Torsional strain occurs when
bond electrons pass by each other when the molecule is rotating.
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Energy and Stability. The low energy staggered conformation of ethane is more
stable than its high energy eclipsed conformation. It is important for you to
understand the relationship between stability and energy. The more stable (or more
favorable) staggered conformation is lower in energy than the less stable (or less
favorable) eclipsed conformation. When comparing two or more molecules, or
conformations of molecules, that with lowest energy is most stable while that with
highest energy is least stable.
least stable = least favorable = highest energy
most stable = most favorable = lowest energy
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Conformations of Propane:
Similar to ethane, propane also has the following two extreme conformations:

Eclipsing Interactions in Propane

In propane there is a CH3-H repulsive interaction that is not present in ethane.

The CH3 group is in relatively close proximity to the C-H bond, and the electron
clouds around each group repel each other. This is known as Van der Waals or
steric repulsion.
Since CH3 is bigger than H, we would expect this repulsive interaction to be much
larger.
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The energy diagram showing these staggered and eclipsed propane conformations
looks identical to the one we showed for ethane except that the eclipsed
conformation of propane has an energy 14 kJ/mol higher than its staggered
conformation. This is 2 kJ/mol greater than the energy difference for eclipsed and
staggered ethane (12 kJ/mol). The most stable conformation is the staggered
conformation although it can freely change into the eclipsed conformation and vice
versa.
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Conformations of n-butane:
Butane has three carbon-carbon single bonds and the molecule can rotate about
each of them. If the rotation will be about C2 and C3 bond then conformations will
be symmetrical.

For conformational analysis butane may be treated as the of ethane where one
hydrogen on each carbon is replaced by a methyl group. Different conformations
of butane can be obtained by rotation about its middle carbon-carbon bond (i.e.,
between C2 and C3 bond) as shown below:

Butane has three staggered conformers (I, III and V). Conformer III, in which the
two methyl groups are as far apart as possible is more stable than the other two
staggered conformers I and V. The most stable of the staggered conformers (III) is
called the anti-conformer and the other two staggered conformers (I and V) are
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called gauche conformers (anti is Greek for "opposite of', gauche is French for
"left.")
In the anti-conformer the largest substituents are opposite to each other; in the
gauche conformer, they are adjacent. The two gauche conformers have the same
energy, but each is 3.8 kJ/mol less stable than the anti-conformer.

“Steric Interactions” In Butane

Steric Strain: Steric strain is the repulsion between two atoms or groups of atoms
when the distance between them is decreased.
The strain of the C2-C3 syn conformation is about 18.4 KJ/mol higher than the C2-
C3 anti conformation.

Why so high?
When electron clouds surrounding the hydrogens on the CH3 groups are brought
too close together, there are electron-electron repulsions (like charges repel, after
all), and this is destabilizing; their natural inclination is to “push away” from each
Chemsitry –BTCH-101-18

other, much like two magnets of the same polarity push apart when brought close
together.

This interaction in butane is often called the CH3 – CH3 “eclipsing” interaction. It’s
an example of what we often call a “steric interaction”.
The CH3-CH3 Eclipsing Interaction in Butane “Costs” About 11 KJ/mol

Two More Eclipsed Conformations Of Butane

The two other eclipsed conformations, where the dihedral angle between the
methyl groups is at 120° and 240° respectively. (14.6 KJ/mol)

Not All Staggered Conformations Are Equal – The Gauche Conformation of

Butane
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The two other “staggered” conformations of butane, those with a dihedral angle
between methyl groups of 60° and 300° respectively.
Since the substituents on C2 are staggered with respect to the three groups on
C3, you might initially think the strain in these conformations is zero. That’s
not quite true.
The two conformations have a torsional strain of about 3.8 KJ/mol relative to
the anti-conformation.
As it turns out these methyl groups are not so far apart. The calculated distance
between the two methyl groups is about 3.1 Å, which is not far from the distance
of 2.9 Å in the syn orientation, meaning they are still quite close together.
This minor steric interaction has come to be known as the “gauche” conformation
– gauche meaning, “awkward”.
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Thus, the relative stabilities of the six conformers of n-butane in decreasing order
is as follows:
Anti > gauche > eclipsed > fully eclipsed
III I and V II and IV VI
Molecules with carbon-carbon single bonds have many interconvertible
conformers. Conformers cannot be separated because they rapidly interconvert.