Strain and Stability in Monocyclic Disubstituted Ring Systems

11 November 2023 10:51

Different Types of Strains:

• Eclipsing/Torsional Strain: Torsional strain is the resistance to bond twisting. It occurs when atoms separated by three bonds are
placed in an eclipsed conformation instead of the more stable staggered conformation.

• Bond Angle Strain: It happens when the bond angles in a cycloalkane deviate from the ideal bond angle of 109.5º, causing rise in P.E

• Steric Strain: It happens when atoms are forced to be too close to each other and try to occupy the same space.

NOTE: Transannular strain exists when there is steric repulsion between atoms.

Cyclobutane:
• If cyclobutane were planar, the C-C-C angles would be 90°. However, the planar conformation produces perfect C-H
eclipsing along the C-C bonds, an unfavourable situation. As a result, the molecule puckers, relieving eclipsing but
reducing the C-C-C angles to about 88°. The angle between the two C-C-C planes is 28°. Inversion of the ring to
interconvert the two puckered forms proceeds over a very small barrier (1.45 kcal/mol), and so in many circumstances
one can think of cyclobutane as effectively planar.

• The C-C bond lengths of cyclobutane are 1.55 Å-slightly elongated. The strain energy
is 26.5 kcal/mol, essentially identical to that of cyclopropane. The strain results primarily
from angle bending, but again residual torsional strain (the eclipsing are not completely relieved by puckering) plays a
role.

Cyclopentane:
• Planar cyclopentane would have a C-C-C angle of 108°, very close to the tetrahedral angle. However, as with
cyclobutane, planar cyclopentane would suffer from a large number of C-H eclipsing interactions, and so the planar form
is not a viable conformation. Again, the molecule puckers, even though the puckering compresses the C-C-C bond angles.
Cyclopentane has 6.2 kcal/mol of strain energy, most of it due to torsional (eclipsing) effects, but some due to angle
strain.

• Cyclopentane can distort from the planar form to relieve eclipsing in two different ways. One way is to move just one
carbon out of the plane, producing the envelope conformation, which retains a mirror plane of symmetry.

• Alternatively, cyclopentane can twist about C-C bonds, producing the half-chair form, which has a two-fold rotation axis.
These two forms are very nearly equal in energy, and they interconvert very rapidly (the barrier is < 2 kcal/mol) by a
process termed pseudorotation.

• The rapid interconversion of envelope and half-chair forms makes all hydrogens (and carbons) equivalent, producing a
time-averaged structure that is equivalent to the planar form. Note that the interconversion of envelope and half-chair
forms does not require passing through the fully planar form, which lies - 5 kcal/mol above these structures. Substituents
can cause a cyclopentane to prefer one conformation over the other, or distort this relatively
flexible ring to intermediate conformations.

Cyclohexane:
• As in other cycles, the different types of hydrogens (axial and equatorial) interconvert by a conformational process. What
is unique about cyclohexane is that the barrier for this process is - 10.8 kcal/ mol, much higher than for other carbocycles.
Thus, in many circumstances, it is important to distinguish between the axial and equatorial positions.

• The path by which the chair forms interconvert has been extensively studied. After passing through a
half-chair transition state, the molecule enters the twist boat conformer. This conformer is
flexible, like cyclobutane and cyclopentane, and undergoes rapid interconversions among
equivalent forms via a boat transition state, a process known as pseudorotation. The boat form is destabilized by, a long
range steric interaction called the flagpole interaction. Eventually, the system escapes the twist boat regime via another
half-chair transition state to the flipped chair. At no time during the chair flip process are all six carbons in one plane, as
this would be a very highly strained structure.

• When two or more groups are attached to a cyclohexane ring, they can either be cis or trans to each other. The definitions
can be seen from a view of a flat cyclohexane ring where the groups are either on the same side of the ring (cis) or on
opposite sides (trans). This usage is distinct from the axial /equatorial terminology. Hence, cis and
trans groups can occupy various axial and equatorial positions depending upon the substitution pattern. A few examples
are given to the right.

• When two substituents are in a cis-1,3 relationship in a cyclohexane, they experience a strong interaction if both are axial.
The energetic consequence of this interaction can be substantial. For the case of the two methyl groups shown, the 1,3-
interaction contributes 3.7 kcal / mol of strain to the diaxial form.

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1,1-Disubstituted Cyclohexanes

• 1,1-dimethylcyclohexane does not have cis or trans isomers, because both methyl groups are on the same carbon. Both
chair conformers have one methyl group in an axial position and one methyl group in an equatorial position giving both
the same relative stability. The steric strain created by the 1,3-diaxial interactions of a methyl group in an axial position
(versus equatorial) is 7.6 kJ/mol, so both conformers will have equal amounts of steric strain. Thus, the equilibrium
between the two conformers does not favor one or the other.

• However, if the two groups are different, as in 1-tert-butyl-1-methylcyclohexane, then the equilibrium favors the
conformer in which the larger group (tert-butyl) is in the more stable equatorial position. The energy cost of having one
tert-butyl group axial (versus equatorial) is approximately 22.8 kJ/mol. The conformer with the tert-butyl group axial is
approximately 15.2 kJ/mol (22.8 kJ/mol - 7.6 kJ/mol) less stable then the conformer with the tert-butyl group equatorial.
This means that 1-tert-butyl-1-methylcyclohexane will spend the majority of its time in the more stable conformation,
with the tert-butyl group in the equatorial position.

Cis and trans stereoisomers of 1,2-dimethylcyclohexane

• In cis-1,2-dimethylcyclohexane, both chair conformations have one methyl group equatorial and one methyl group axial.
As previously discussed, the axial methyl group creates 7.6 kJ/mol of steric strain due to 1,3-diaxial interactions. Overall,
both chair conformations have 11.4 kJ/mol of steric strain and are of equal stability.

• In trans-1,2-dimethylcyclohexane, one chair conformer has both methyl groups axial and the other conformer has both
methyl groups equatorial. The conformer with both methyl groups equatorial has no 1,3-diaxial interactions however
there is till 3.8 kJ/mol of strain created by a gauche interaction. The conformer with both methyl groups axial has four
1,3-Diaxial interactions which creates 2 x 7.6 kJ/mol (15.2 kJ/mol) of steric strain. This conformer is (15.2 kJ/mol -3.8
kJ/mol) 11.4 kJ/mol less stable than the other conformer. The equilibrium will therefore favor the conformer with both
methyl groups in the equatorial position.

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Cis and trans stereoisomers of 1,3-dimethylcyclohexane

• For cis-1,3-dimethylcyclohexane one chair conformation has both methyl groups in axial positions creating 1,3-diaxial
interactions. The other conformer has both methyl groups in equatorial positions thus creating no 1,3-diaxial interaction.
Because the methyl groups are not on adjacent carbons in the cyclohexane rings gauche interactions are not possible.
Even without energy calculations it is simple to determine that the conformer with both methyl groups in the equatorial
position will be the more stable conformer.

• For trans-1,3-dimethylcyclohexane both conformations have one methyl axial and one methyl group equatorial. Each
conformer has one methyl group creating a 1,3-diaxial interaction so both are of equal stability.

SUMMARY

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