CONFORMATIONAL ISOMERISM:

(By: Muneeb Ur Rehman)

https://www.youtube.com/watch?v=MVnzACFSm74
Two groups bonded by only a single bond can undergo rotation about that bond with respect to
each other. The temporary molecular shapes that result from such a rotation are called
conformations of the molecule. Each possible structure is called a conformer or conformational
isomer.”

Conformational Analysis:
An analysis of the energy changes that occur as a molecule undergoes rotations about
single bonds is called a conformational analysis.
1. Conformational analysis of Ethane.
2. Conformational analysis of n-Butane.
3. Conformational analysis of Cyclohexane.

Importance of Conformational Analysis:

 This analysis is important because the structure of a molecule can have a significant
influence on the molecular properties, including dictating the outcome of a reaction.
 Although the ideas of conformational analysis are developed for the simplest functional
groups, the alkanes, the same principles can be expanded and applied to other functional
groups as well.

Newman Projection and Conformational Analysis:

 A representation of a molecule in which the atoms and bonds are viewed along the axis
(containing two atoms bonded to each other) about which rotation occurs is called a
Newman projection.
 Conformational analyses are assisted greatly by a representation of molecules in Newman
projection (a manner different to skeletal structures).
  In a Newman projection, the "substituents" of each atom composing the bond, hydrogen
atoms or functional groups, can be viewed both in front of and behind the carbon-carbon
bond.

Torsional Strain :
 It is the resistance to bond twisting or rotating about some Angle.
 It is Actually increased P.E of a molecule due to repulsion between Groups or Atoms.
 Force that opposes rotation due to the repulsion Force that opposes rotation due to the
repulsion of bonding electrons

Angle Strain / dihedral angle or torsion angle (θ) :

 It is the change in angle of rotamers due to change in torsional strain.
 Specifically, one can observe the angle between a substituent on the front atom and a
substituent on the back
atom in the Newman
projection, which is
called the dihedral
angle or torsion angle
(θ).
 A. Conformational Analysis Of Ethane
The simplest hydrocarbon capable of internal rotational motion is ethane (CH3-CH3).
Ethane has two tetrahedral methyl groups connected by a carbon-carbon sigma bond. These
methyl groups are free to rotate relative to each other. Free rotation around the carbon-carbon
bond in ethane leads to many different structures called conformational isomers, or conformers.
In ethane molecule, the arrangement around each carbon atom is almost tetrahedral with
approximately 109.5° bond angles. It is "approximately" because each carbon atoms doesn't have
four identical things attached. There will be a small amount of distortion because of the
attachment of 3 hydrogens and 1 carbon, rather than 4 hydrogens.
There are two limiting rotational positions for ethane i.e.

1. Eclipsed conformation:

 In which the dihedral angle is 0° and the hydrogen atoms on the first carbon perfectly line
up with or eclipse the hydrogen atoms on the second carbon.
 It is the highest energy conformation of ethane because the electron clouds of the C-H
bonds are as close as they can be, and their repulsions raise the energy of the molecule. It
is the least stable conformation due to torsional strain.

2. Staggered conformation:

 It occurs when the hydrogen atoms on the first carbon are as far away as possible
 from those on the second carbon; this occurs at a dihedral angle of atleast 60°. This is the
lowest energy conformation and thus more stable because the electron clouds of the
bonds are the farthest distance apart, and their repulsions are minimized.
 Thus, ethane spends most of its time in this state.
 B. Conformational Analysis of Butane
In butane, two of the substituents, one on each carbon atom being viewed, is a methyl group.

Methyl groups are much larger than hydrogen atoms. Thus, when eclipsed conformations occur

in butane, the interactions are especially unfavorable.

There are four possible "extreme" conformations of butane:

(1) Fully eclipsed, when the methyl groups eclipse each other;

(2) Gauche Staggered, when the methyl groups are staggered but next to each other;

(3) Eclipsed, when the methyl groups eclipse hydrogen atoms; and

(4) Anti Staggered, when the methyl groups are staggered and as far away from each other as
possible.
 C. Conformational Analysis of Cyclohexane
 Saturated six-membered rings are the most common ring systems in nature
because they present an optimal conformational situation. Carbohydrates,
steroids, plant products, pesticides, and many other important compounds
contain 6-membered rings whose conformations and stereochemistry are
critically important to their stability and reactivity.
 A planar, regular hexagon would have bond angles of 120 degrees (rather
than 109.5degrees) implying some angle strain. A planar ring would also have
torsional strain because the bonds on the adjacent CH2 groups would be
eclipsed. Therefore, the ring cannot be planar.