Cyclohexane

Rings containing six carbons, the cyclohexanes, form readily and are widely distributed in nature. Because
they play such an important role in all of organic chemistry, it is important that we examine their structure in
some detail. Despite its seeming complexity, cyclohexane can be analyzed by the conformational model we
have developed for n-butane in Fig 1-17.

First, would we expect all six carbons of cyclohexane to lie in one plane? Not likely. In the first place the
internal angles of a regular hexagon are 120°, rather far from the normal 109.5° tetrahedral angles of
saturated carbons. So we would have to bend the bonds to make cyclohexane planar. Second, we have just
seen with cyclopentane that a planar cyclic molecule has all of its C-C bonds eclipsed; in cyclopentane, with
nearly unstrained 108° bond angles in a planar form, some of these angles are bent to escape eclipsing. So on
two accounts, bond angles and eclipsing, we predict that cyclohexane will not be planar.

Figure 1-26. The carbons of cyclohexane can adopt eight distinct conformations, two low-
energy chair forms and six higher-energy boat forms. These conformations are in rapid
equilibrium with one another.

If we make a molecular model of cyclohexane using only the ring carbon atoms and ignoring for the moment
the hydrogen atoms, we find two types of strainless conformations, two identical chair forms and six
identical boat forms (Fig. 1-26). Only one boat is shown in the figure, but notice that any of the three pairs
of opposite carbons may serve as bow and stern of the boat, and they may be raised above the plane of the
remaining four carbons (as shown) or may be pushed below that plane, making a total of six forms.

These conformations can easily be transformed into one another simply by rotation around carbon-carbon
bonds; specifically, a chair is first converted to one of the boats, and the boat may either return to the original
chair or go to the other. The interconversion is rapid at room temperature, as in the case of n-butane. For
reasons discussed in the following paragraph, the two chair forms, which are identical to one another in an
unsubstituted cyclohexane, are of lower energy than the boat forms. Cyclohexane, therefore, spends most of
its time in one or the other of the two chair forms.

To see why the chair form of cyclohexane is more stable than the boat form, and why cyclohexanes in
general are so common and so stable, let us examine a front view of cyclohexane in the chair and boat forms
(Fig. 1-27).
 Figure 1-27. In the chair form of cyclohexane all C-C bonds are in the energetically favorable
staggered form; in the boat form there are eclipsed conformations that are energetically
unfavorable.

Notice that in the boat form the two CH2 groups along each side, the "gunwales" of a boat, are in the
energetically unfavorable eclipsed conformation, in which the hydrogen atoms are directly opposite one
another. Two carbon atoms (the "bow" and "stern") are also eclipsed. In either chair form all carbons and
hydrogens are staggered; as a consequence these chair forms are of lower energy than the boat form.

Next we examine the hydrogen atoms carefully in one of the chair forms of cyclohexane; they will be seen to
fall into two distinct groups, those six which run horizontally around the circumference of the molecule (the
equatorial hydrogens) and those six which point vertically, nearly at right angles to the first set (the axial
hydrogens). These two sets of hydrogens are shown in molecular models in Fig. 1-28. The distinction is also
clear in the Newman projection formula for the chair form of cyclohexane in Fig. 1-27, where the axial
hydrogens point straight up and down, the equatorial hydrogens more nearly right and left. When one chair
form of cyclohexane converts to the other, those six hydrogens which were axial in the first chair form
become equatorial in the second, and those six which were equatorial become axial. Since the two chair
forms are of equal energy and in rapid equilibrium with one another, each hydrogen spends half of its time in
an axial position, half in an equatorial.

Figure 1-28. The hydrogen atoms on a cyclohexane ring fall into two classes, axial and
equatorial. Conversion of one chair form of cyclohexane to the other converts all axial
hydrogens to equatorial and vice versa.
The distinction between an axial and an equatorial position becomes important in a substituted cyclohexane
because a substituent is more stable in an equatorial position than in an axial position. This is so because
axial substituents bump into the hydrogen atoms in the other axial positions, leading to what is called steric
repulsion. This interference is illustrated in the molecular model of axial-methylcyclohexane in Fig. 1-29. A
substituent in an equatorial position is not as crowded and does not experience as much steric repulsion. This
makes that chair form with the substituent equatorial relatively more stable than the form with the substituent
axial, and the molecule spends more of its time in the more stable conformation. For example,
methylcyclohexane (a commonly used lighter fluid) spends 90 percent of its time in that chair form with the
methyl equatorial, and only 10 percent of its time in the other chair form. During the transformation from
one chair form to the other, it passes briefly through a boat conformation. As the size of the substituent
increases, so does the tendency to remain with the substituent equatorial. In t-butylcyclohexane there is no
detectable amount of axial conformer present.

Figure 1-29. An axial substituent is sterically hindered by hydrogens in the other axial positions,
while an equatorial group is not so hindered. The equilibrium between the two chair forms is
thus displaced toward the form with the equatorial substituent.

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