All About the Chair Conformation

Background

Before we begin, here are some terms to know:
1. Conformation: the shape that a molecule can adopt due to rotation around one or
more single bonds
2. Angle strain: strain due to deviation from one or more ideal bond angles
3. Torsional strain: strain caused by van der Waals repulsion which can be reduced
or eliminated by rotation around a single bond

Now, whats so special about the chair conformation?

Molecules will try to adopt the most stable conformation that minimizes strain. For
cyclohexane, C
6
H
12
, this would be the chair conformation. Lets see why.







If cyclohexane was planar, its structure would look like the picture to the left. All the
carbons in cyclohexane are sp
3
hybridized, so the ideal bond angle for a tetrahedral
atom would be 109.5 degrees. However, the planarity of the ring would force the
carbons to have bond angles of 120 degrees, which makes it unstable. There would
also be torsional strain, as all 12 carbon-hydrogen bonds would be fully eclipsed.
To gain more stability, cyclohexane adopts the chair conformation instead. The chair
conformation is a six-membered ring in which atoms 2, 3, 5, and 6 lie in the same plane,
atom 1 lies above the plane, and atom 4 lies below the plane. We will examine how to
draw and number the structure later. With this conformation, the bond angles are 110.9
degrees, much closer to the ideal 109.5 degrees. All the carbon-hydrogen bonds are
also fully staggered, eliminating the torsional strain. Together, these features make the
chair conformation very stable.


versus
How to Draw the Chair Conformation


The chair conformation consists of three sets of parallel lines, drawn in one set at a
time. It is important to draw the structure clearly so that the substituents can be placed
correctly on the ring.
Now lets look at axial and equatorial bonds. Axial bonds are parallel to the axis of the
ring, while equatorial bonds are perpendicular to the axis of the ring and lie along the
equator of the chair. Notice that each carbon has one axial and one equatorial bond.




When drawing the bonds, it is important to clearly distinguish between axial and
equatorial. The equatorial bonds should be drawn parallel to the lines representing the
carbon-carbon bonds in the ring. After the equatorial bonds are drawn, fill in the axial
bonds by drawing lines up or down.





Without any other substituents, the final chair conformation would have hydrogen atoms
at the ends of all the axial and equatorial bonds. The structure would look like this:




Now lets number the structure and place substituents on the ring.
The carbons can be numbered any way, as long as you are consistent in counting either
clockwise or counterclockwise. One of the more common ways to number the carbons
is like this:


Now for the substituents. Solid wedges indicate that the bond projects outward towards
the viewer, and broken (dashed) wedges indicate that the bond recedes away from the
viewer. For simplicity in drawing, we will label atoms on solid wedges as being up on
the ring and atoms on dashed wedges as being down on the ring. This makes sense,
because in the chair conformation, each attachment to a carbon will have either an up
or down orientation. It is important to note, however, that there is no correlation between
up/down and axial/equatorial. Lets take a look at an example.




First we number the carbons on the structure to the left. The OH group is on carbon 1.
We see that it is on a solid wedge, so we place it up on carbon 1 on the chair. For the
methyl group on carbon 3, we see that it is on dashed wedge, so we place it on down
on carbon 3 on the chair. In this case, the OH group happens to be axial up and the
methyl group happens to be equatorial down. But there is no relation between our
naming of up/down and axial/equatorial. For example, if the OH was on carbon 2, then it
would be up on the equatorial position instead. It just depends which carbon the
substituent is on.

Flipping the Chair
When the chair is flipped, all the axial positions become equatorial, and all the
equatorial positions become axial. It is also important to note that even after the chair
flips, all the up substituents remain up and all the down substituents remain down.



In this example, the OH on carbon 1 switches from axial to equatorial, but it is still in the
up position. The methyl group on carbon 3 switches from equatorial to axial, but it is
still in the down position.
To draw the flipped conformation, follow the same steps as before, but take note of the
difference in drawing the parallel lines. In the picture before, the difference is indicated
in the color red. Also use the same method to number the carbons as before. This time,
however, the more common way to number the carbons is starting with carbon 1 on the
bottom right corner.


Also take note of the arrow between the conformations that indicate equilibrium. The
cyclohexane structure continuously flips from one chair conformation to the other.
Without any substituents, both forms are equal in energy and are equivalent to each
other. However, once substituents are placed on the ring, the two forms may not be
equal in energy, and the molecule may spend more time in one conformation compared
to the other. The next section will address this difference in stability.

Comparing the Stability of Chairs
Substituents on the chair conformation prefer to be in the equatorial position. The
reason is that when substituents are in the axial position, there tends to be more
unfavorable interactions with other axial atoms on the same side. These unfavorable
interactions are called 1,3-diaxial interactions. When substituents are in the equatorial
position, they are farther away from each other. This increases the stability of the
conformation. In the pictures below, the methyl in the equatorial position is more stable
because it avoids interaction with the hydrogen atoms.




The larger the group is, the more it will tend to remain in the equatorial position.
Therefore, when trying to determine which chair is more stable, place the larger group in
the equatorial position.


Which structure is more stable, the left or the right? The C(CH
3
)
3
group is larger than the
chlorine atom so it will have a tendency to remain in the equatorial position. Therefore,
the structure on the left is more stable.
Also note that when you have two groups and they can be either both axial or both
equatorial, it is more stable when they are both equatorial.




Determining Cis and Trans
Cis means on the same side and trans means on opposite sides. When both
substituents are both up or both down, they are cis to each other. When one group is up
and one group is down, we call them trans to each other. Lets look at three examples.





1) Both substituent groups are on dashed wedges. They are both down. They are cis.
2) The OH group is on a dashed wedge, whereas the methyl group is on a solid wedge.
One is down, while the other is up. They are trans.
3) Both groups are on solid wedges, so they are both up. They are cis.

Works Cited
- Illustrated Glossary on course website
- Professor Lavelles Chem 14B Organic Chemistry course reader
- Google images
versus
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versus
The conformation on the right is
more stable because both
substituents are equatorial.