Chapter 4 – Cycloalkanes

Goals
• To name cycloalkanes.
• To understand cis-trans isomerism in cycloalkanes.
• To understand the nature of ring strain.
• To understand conformations of cyclic alkanes.
• To understand the conformations of polycyclic molecules.

Why?
Understanding how to language of chemistry is important, so we will begin by naming
cycloalkanes. The conformations of cyclic alkanes are very important in terms of reactivity and
stereochemistry also discussed in chapter 9. Ring strain also helps us understand reactivity as we
start reactions in upcoming chapters.

Additional Resources
Practice problems on Florida Online

Terms
Cis-trans isomerism.

Nomenclature of Cycloalkanes

1. The prefix cyclo- is added to the name of the alkane with the same number of carbons
2. When one substituent is present it is assumed to be at position one and is not numbered
3. When two alkyl substituents are present the one with alphabetical priority is given
position 1
4. Numbering continues to give the other substituent the lowest number
5. If a long chain is attached to a ring with fewer carbons, the cycloalkane is considered the
substituent

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Ring Strain-Why?

Heats of combustion per CH2 unit reveal cyclohexane has no ring strain and other cycloalkanes
have some ring strain.

Angle strain is caused by bond angles different from 109.5. Tortional strain is caused by
eclipsing C-H bonds on adjacent carbons.
Cyclopropane has both high angle and tortional strain, where cyclobutane has considerable angle
strain. It bends to relieve some tortional strain, and cyclopentane has little angle strain in the
planar form but bends to relieve some tortional strain.

Cyclohexane is the perfect scenario. Why?

All bond angles are 109.5º and all C-H bonds are perfectly staggered!

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Conformations of Cyclohexane - Axial and Equatorial Hydrogen Atoms

Axial hydrogens are perpendicular to the average plane of the ring, and so called equatorial
hydrogens lie around the perimeter of the ring. The C-C bonds and equatorial C-H bonds are all
drawn in sets of parallel lines, and the axial hydrogens are drawn straight up and down.

The so called “chair” can flip, that is the “headrest” can become the
footrest and vice versa. When this occurs, whatever is axial becomes
equatorial and whatever is equatorial becomes axial.

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In this case we have hydrogen both axial and equatorial, but the implications of this reversal can
be very significant, that is, will the energy of an axial substituent be the same as that of an
equatorial?

The answer is no, due to so called 1,3 diaxial interactions. Notice in the Newman projection the
two methyl groups are gauche to each other, just like we saw in the analysis of butane. Even if
you change your perspective you will still have a so called 1,3 diaxial interaction (figure b).

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If we have the methyl group equatorial we would have the following:

And since this is anti it is more favorable to have the methyl group equatorial, so a flip of the
chair conformation can have significant implications. The more substitutents on a ring, the more
one has to analyze the steric effects imposed by such a flip.

Cis/Trans Isomerism in Cycloalkanes - Disubstitued Cycloalkanes

Can exist as pairs of cis-trans stereoisomers.

Cis: groups on same side of ring, Trans: groups on opposite side of ring. The following are not
chair conformations as we have drawn them, just another way of representing a ring to
emphasize cis/trans isomerism.

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So how do we convert the following into a chair representation?
CH 3

CH3

Practice: Draw the following in a two dimensional form.

a) b) c) d) e)

Now let’s draw cis-1,3-dimethylcyclohexane and consider what is the most stable chair?

And trans-1,3-dimethylcyclohexane?

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Sometimes a conformation can be “locked”. That is, the most stable form predominates over any
other form. An example is tert-butylcyclohexane.

So which is the most stable in the following?

a) b) c) d) e)

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There are other molecules that are “locked” in a certain conformation. Decalin is an example.

Draw these as in the chair form. Hint, start with trans-decalin.

What are the relative geometries of ring fusions (starting from the left) for the steroid shown
below?
H3 C R
H3 C
H

H H

1. cis, cis, cis

2. cis, cis, trans
3. cis, trans, trans
4. trans. cis, cis
5. trans, trans, cis