89
CHAPTER 3
CONFORMATIONS OF ALKANES
AND CYCLOALKANES
H
ydrogen peroxide is formed in the cells of plants and animals but is toxic to them.
Consequently, living systems have developed mechanisms to rid themselves of
hydrogen peroxide, usually by enzyme-catalyzed reduction to water. An under-
standing of how reactions take place, be they reactions in living systems or reactions in
test tubes, begins with a thorough knowledge of the structure of the reactants, products,
and catalysts. Even a simple molecule such as hydrogen peroxide may be structurally
more complicated than you think. Suppose we wanted to write the structural formula for
H
2
O
2
in enough detail to show the positions of the atoms relative to one another. We
could write two different planar geometries A and B that differ by a 180° rotation about
the O±O bond. We could also write an infinite number of nonplanar structures, of which
C is but one example, that differ from one another by tiny increments of rotation about
the O±O bond.
Structures A, B, and C represent different conformations of hydrogen peroxide.
Conformations are different spatial arrangements of a molecule that are generated by
rotation about single bonds. Although we can’t tell from simply looking at these struc-
tures, we now know from experimental studies that C is the most stable conformation.
A B C
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In this chapter we’ll examine the conformations of various alkanes and cycloal-
kanes, focusing most of our attention on three of them: ethane, butane, and cyclohexane.
A detailed study of even these three will take us a long way toward understanding the
main ideas of conformational analysis.
The conformation of a molecule affects many of its properties. Conformational
analysis is a tool used not only by chemists but also by researchers in the life sciences
as they attempt to develop a clearer picture of how molecules—as simple as hydrogen
peroxide or as complicated as DNA—behave in biological processes.
3.1 CONFORMATIONAL ANALYSIS OF ETHANE
Ethane is the simplest hydrocarbon that can have distinct conformations. Two, the
staggered conformation and the eclipsed conformation, deserve special attention and
are illustrated in Figure 3.1. The C±H bonds in the staggered conformation are arranged
so that each one bisects the angle made by a pair of C±H bonds on the adjacent car-
bon. In the eclipsed conformation each C±H bond is aligned with a C±H bond on the
adjacent carbon. The staggered and eclipsed conformations interconvert by rotation
around the carbon–carbon bond. Different conformations of the same molecule are some-
times called conformers or rotamers.
Among the various ways in which the staggered and eclipsed forms are portrayed,
wedge-and-dash, sawhorse, and Newman projection drawings are especially useful.
These are shown for the staggered conformation of ethane in Figure 3.2 and for the
eclipsed conformation in Figure 3.3.
We used wedge-and-dash drawings in earlier chapters, and so Figures 3.2a and
3.3a are familiar to us. A sawhorse drawing (Figures 3.2b and 3.3b) shows the
conformation of a molecule without having to resort to different styles of bonds. In a
Newman projection (Figures 3.2c and 3.3c), we sight down the C±C bond, and repre-
sent the front carbon by a point and the back carbon by a circle. Each carbon has three
substituents that are placed symmetrically around it.
90 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
Eclipsed conformation of ethane
Staggered conformation of ethane
FIGURE 3.1 The stag-
gered and eclipsed confor-
mations of ethane shown as
ball-and-spoke models (left)
and as space-filling models
(right).
Newman projections were
devised by Professor Melvin
S. Newman of Ohio State
University in the 1950s.
Learning By Modeling
contains an animation showing
the rotation about the O±O
bond in hydrogen peroxide.
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PROBLEM 3.1 Identify the alkanes corresponding to each of the drawings
shown.
(a) (c)
(b) (d)
SAMPLE SOLUTION (a) The Newman projection of this alkane resembles that
of ethane except one of the hydrogens has been replaced by a methyl group. The
drawing is a Newman projection of propane, CH
3
CH
2
CH
3
.
The structural feature that Figures 3.2 and 3.3 illustrate is the spatial relationship
between atoms on adjacent carbon atoms. Each H±C±C±H unit in ethane is charac-
terized by a torsion angle or dihedral angle, which is the angle between the H±C±C
CH
2
CH
3
CH
2
CH
3
CH
3
H
H
H
CH
3
H
CH
3
H H
H
H
H
H
CH
3
CH
3
CH
3
H
H
H
H
H
CH
3
3.1 Conformational Analysis of Ethane 91
H
H
H
H
H
H
(a) Wedge-and-dash
H
H
H
H
H
H
(b) Sawhorse
H
HH
H
H
H
(c) Newman projection
H
H
H
H
H
(a) Wedge-and-dash
H
HH
(b) Sawhorse
H
H
H
H
H
(c) Newman projection
H
H
H
HH
FIGURE 3.2 Some commonly used rep-
resentations of the staggered conforma-
tion of ethane.
FIGURE 3.3 Some commonly used rep-
resentations of the eclipsed conformation
of ethane.
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plane and the C±C±H plane. The torsion angle is easily seen in a Newman projection
of ethane as the angle between C±H bonds of adjacent carbons.
Eclipsed bonds are characterized by a torsion angle of 0°. When the torsion angle is
approximately 60°, we say that the spatial relationship is gauche; and when it is 180°
we say that it is anti. Staggered conformations have only gauche or anti relationships
between bonds on adjacent atoms.
Of the two conformations of ethane, the staggered is more stable than the eclipsed.
The measured difference in potential energy between them is 12 kJ/mol (2.9 kcal/mol).
A simple explanation has echoes of VSEPR (Section 1.10). The staggered conformation
allows the electron pairs in the C±H bonds of one carbon to be farther away from the
electron pairs in the C±H bonds of the other than the eclipsed conformation allows.
Electron-pair repulsions on adjacent carbons govern the relative stability of staggered
and eclipsed conformations in much the same way that electron-pair repulsions influence
the bond angles at a central atom.
The destabilization that comes from eclipsed bonds on adjacent atoms is called
torsional strain. Torsional strain is one of several structural features resulting from its
three-dimensional makeup that destabilize a molecule. The total strain of all of the spa-
tially dependent features is often called steric strain. Because three pairs of eclipsed
bonds produce 12 kJ/mol (2.9 kcal/mol) of torsional strain in ethane, it is reasonable to
assign an “energy cost” of 4 kJ/mol (1 kcal/mol) to each pair of eclipsed bonds.
In principle there are an infinite number of conformations of ethane, differing by
only tiny increments in their torsion angles. Not only is the staggered conformation more
stable than the eclipsed, it is the most stable of all of the conformations; the eclipsed is
the least stable. Figure 3.4 shows how the potential energy of ethane changes for a 360°
rotation about the carbon–carbon bond. Three equivalent eclipsed conformations and
three equivalent staggered conformations occur during the 360° rotation; the eclipsed
conformations appear at the highest points on the curve (potential energy maxima), the
staggered ones at the lowest (potential energy minima).
PROBLEM 3.2 Find the conformations in Figure 3.4 in which the red circles are
(a) gauche and (b) anti.
Diagrams such as Figure 3.4 can be quite helpful for understanding how the poten-
tial energy of a system changes during a process. The process can be a simple one such
as the one described here—rotation around a carbon–carbon bond. Or it might be more
complicated—a chemical reaction, for example. We will see applications of potential
energy diagrams to a variety of processes throughout the text.
Let’s focus our attention on a portion of Figure 3.4. The region that lies between
a torsion angle of 60° and 180° tracks the conversion of one staggered conformation of
Torsion angle H11005 180°
Anti
H
H
180°
Torsion angle H11005 60°
Gauche
H
H
60°
Torsion angle H11005 0°
Eclipsed
HH
0°
92 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
Steric is derived from the
Greek word stereos for
“solid” and refers to the
three-dimensional or spatial
aspects of chemistry.
The animation on the
Learning By Modeling CD shows
rotation about the C±C bond in
ethane.
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ethane to the next one. Both staggered conformations are equivalent and equal in energy,
but for one staggered conformation to get to the next, it must first pass through an
eclipsed conformation and needs to gain 12 kJ/mol (2.9 kcal/mol) of energy to reach it.
This amount of energy is the activation energy (E
act
) for the process. Molecules must
become energized in order to undergo a chemical reaction or, as in this case, to undergo
rotation around a carbon–carbon bond. Kinetic (thermal) energy is absorbed by a mole-
cule from collisions with other molecules and is transformed into potential energy. When
the potential energy exceeds E
act
, the unstable arrangement of atoms that exists at that
instant can relax to a more stable structure, giving off its excess potential energy in col-
lisions with other molecules or with the walls of a container. The point of maximum
potential energy encountered by the reactants as they proceed to products is called the
transition state. The eclipsed conformation is the transition state for the conversion of
one staggered conformation of ethane to another.
Rotation around carbon–carbon bonds is one of the fastest processes in chemistry.
Among the ways that we can describe the rate of a process is by its half-life, which is
the length of time it takes for one half of the molecules to react. It takes less than 10
H110026
seconds for half of the molecules in a sample of ethane to go from one staggered con-
formation to another at 25°C. At any instant, almost all of the molecules are in staggered
conformations; hardly any are in eclipsed conformations.
As with all chemical processes, the rate of rotation about the carbon–carbon bond
increases with temperature. The reason for this can be seen by inspecting Figure 3.5,
where it can be seen that most of the molecules in a sample have energies that are clus-
tered around some average value; some have less energy, a few have more. Only mole-
cules with a potential energy greater than E
act
, however, are able to go over the transi-
tion state and proceed on to products. The number of these molecules is given by the
shaded areas under the curve in Figure 3.5. The energy distribution curve flattens out at
higher temperatures, and a greater proportion of molecules have energies in excess of
E
act
at T
2
(higher) than at T
1
(lower). The effect of temperature is quite pronounced; an
increase of only 10°C produces a two- to threefold increase in the rate of a typical chem-
ical process.
3.1 Conformational Analysis of Ethane 93
Potential energy, kcal/mol
Potential energy, kJ/mol
0 60 120 180 240 300 360
Torsion angle, H11034
3
2
1
0
12
8
4
0
2.9 kcal/mol 12 kJ/mol
The structure that exists at
the transition state is some-
times referred to as the tran-
sition structure or the
activated complex.
FIGURE 3.4 Potential
energy diagram for rotation
about the carbon–carbon
bond in ethane. Two of the
hydrogens are shown in red
and four in green so as to in-
dicate more clearly the bond
rotation.
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3.2 CONFORMATIONAL ANALYSIS OF BUTANE
The next alkane that we examine is butane. In particular, we consider conforma-
tions related by rotation about the bond between the middle two carbons
(CH
3
CH
2
±CH
2
CH
3
). Unlike ethane, in which the staggered conformations are equiva-
lent, two different staggered conformations occur in butane, shown in Figure 3.6. The
methyl groups are gauche to each other in one, anti in the other. Both conformations are
staggered, so are free of torsional strain, but two of the methyl hydrogens of the gauche
conformation lie within 210 pm of each other. This distance is less than the sum of their
van der Waals radii (240 pm), and there is a repulsive force between them. The desta-
bilization of a molecule that results when two of its atoms are too close to each other is
94 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
Fraction of molecules
having a particular energy
Low
temperature (T
1
)
High
temperature (T
2
)
E
act
Energy
FIGURE 3.5 Distribution of
molecular energies. (a) The
number of molecules with
energy greater than E
act
at
temperature T
1
is shown as
the darker-green shaded
area. (b) At some higher
temperature T
2
, the shape
of the energy distribution
curve is different, and more
molecules have energies in
excess of E
act
.
CH
3
CH
3
H
HH
H
CH
3
CH
3
H
H
H
H
FIGURE 3.6 The
gauche and anti conforma-
tions of butane shown as
ball-and-spoke models (left)
and as Newman projections
(right). The gauche confor-
mation is less stable than the
anti because of the van der
Waals strain between the
methyl groups.
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called van der Waals strain, or steric hindrance and contributes to the total steric
strain. In the case of butane, van der Waals strain makes the gauche conformation approx-
imately 3.2 kJ/mol (0.8 kcal/mol) less stable than the anti.
Figure 3.7 illustrates the potential energy relationships among the various confor-
mations of butane. The staggered conformations are more stable than the eclipsed. At
any instant, almost all the molecules exist in staggered conformations, and more are
present in the anti conformation than in the gauche. The point of maximum potential
energy lies some 25 kJ/mol (6.1 kcal/mol) above the anti conformation. The total strain
in this structure is approximately equally divided between the torsional strain associated
with three pairs of eclipsed bonds (12 kJ/mol; 2.9 kcal/mol) and the van der Waals strain
between the methyl groups.
PROBLEM 3.3 Sketch a potential energy diagram for rotation around a car-
bon–carbon bond in propane. Clearly identify each potential energy maximum
and minimum with a structural formula that shows the conformation of propane
at that point. Does your diagram more closely resemble that of ethane or of
butane? Would you expect the activation energy for bond rotation in propane to
be more than or less than that of ethane? Of butane?
3.2 Conformational Analysis of Butane 95
Potential energy, kcal/mol
3
kJ/mol
6
5
4
3
2
1
0
Potential energy, kJ/mol
25
20
15
10
5
0
0 60 120 180 240 300 360
Torsion angle, H11034
14
kJ/mol
FIGURE 3.7 Potential energy diagram for rotation around the central carbon–carbon bond
in butane.
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96 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
MOLECULAR MECHANICS APPLIED TO ALKANES AND CYCLOALKANES
O
f the numerous applications of computer
technology to chemistry, one that has been
enthusiastically embraced by organic chemists
examines molecular structure from a perspective sim-
ilar to that gained by manipulating molecular models
but with an additional quantitative dimension. Mo-
lecular mechanics is a computational method that
allows us to assess the stability of a molecule by com-
paring selected features of its structure with those of
ideal “unstrained” standards. Molecular mechanics
makes no attempt to explain why the van der Waals
radius of hydrogen is 120 pm, why the bond angles in
methane are 109.5°, why the C±C bond distance in
ethane is 153 pm, or why the staggered conforma-
tion of ethane is 12 kJ/mol more stable than the
eclipsed, but instead uses these and other experi-
mental observations as benchmarks to which the cor-
responding features of other substances are com-
pared.
If we assume that there are certain “ideal” val-
ues for bond angles, bond distances, and so on, it fol-
lows that deviations from these ideal values will
destabilize a particular structure and increase its po-
tential energy. This increase in potential energy is re-
ferred to as the strain energy of the structure. Other
terms include steric energy and steric strain. Arith-
metically, the total strain energy (E
s
) of an alkane or
cycloalkane can be considered as
E
s
H11005 E
bond stretching
H11001 E
angle bending
H11001 E
torsional
H11001
E
van der Waals
where
E
bond stretching
is the strain that results when C±C
and C±H bond distances are distorted from
their ideal values of 153 pm and 111 pm, re-
spectively.
E
angle bending
is the strain that results from the ex-
pansion or contraction of bond angles from the
normal values of 109.5° for sp
3
hybridized
carbon.
E
torsional
is the strain that results from deviation of
torsion angles from their stable staggered rela-
tionship.
E
van der Waals
is the strain that results from “non-
bonded interactions.”
Nonbonded interactions are the forces be-
tween atoms that aren’t bonded to one another;
they may be either attractive or repulsive. It often
happens that the shape of a molecule may cause two
atoms to be close in space even though they are sep-
arated from each other by many bonds. Induced-
dipole/induced-dipole interactions make van der
Waals forces in alkanes weakly attractive at most dis-
tances, but when two atoms are closer to each other
than the sum of their van der Waals radii,
nuclear–nuclear and electron–electron repulsive
forces between them dominate the E
van der Waals
term.
The resulting destabilization is called van der Waals
strain.
At its most basic level, separating the total
strain of a structure into its components is a qualita-
tive exercise. For example, a computer-drawn model
of the eclipsed conformation of butane using ideal
bond angles and bond distances (Figure 3.8) reveals
that two pairs of hydrogens are separated by
a distance of only 175 pm, a value considerably
smaller than the sum of their van der Waals radii
(2 H11003 120 pm H11005 240 pm). Thus, this conformation is
destabilized not only by the torsional strain associ-
ated with its eclipsed bonds, but also by van der
Waals strain.
At a higher level, molecular mechanics is ap-
plied quantitatively to strain energy calculations.
Each component of strain is separately described by a
mathematical expression developed and refined so
that it gives solutions that match experimental obser-
vations for reference molecules. These empirically de-
rived and tested expressions are then used to calcu-
late the most stable structure of a substance. The
various structural features are interdependent; van
der Waals strain, for example, might be decreased at
the expense of introducing some angle strain, tor-
sional strain, or both. The computer program
searches for the combination of bond angles, dis-
tances, torsion angles, and nonbonded interac-
tions that gives the molecule the lowest total strain.
This procedure is called strain energy minimization
and is based on the commonsense notion that the
most stable structure is the one that has the least
strain.
—Cont.
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3.3 Conformations of Higher Alkanes 97
The first widely used molecular mechanics pro-
gram was developed by Professor N. L. Allinger of the
University of Georgia and was known in its various
versions as MM2, MM3, and so on. They have been re-
fined to the extent that many structural features can
be calculated more easily and more accurately than
they can be measured experimentally.
Once requiring minicomputers and worksta-
tions, many molecular mechanics programs are avail-
able for personal computers. The information that
strain energy calculations can provide is so helpful
that molecular mechanics is no longer considered a
novelty but rather as one more tool to be used by the
practicing organic chemist. They have been joined by
programs that calculate the energies of conforma-
tions by molecular orbital methods. The Learning By
Modeling CD that accompanies this text contains
molecular mechanics software that lets you seek out
the most stable conformation of the structures you
assemble. It also contains the most stable conforma-
tions of some molecules as determined by molecular
orbital calculations.
3.3 CONFORMATIONS OF HIGHER ALKANES
Higher alkanes having unbranched carbon chains are, like butane, most stable in their
all-anti conformations. The energy difference between gauche and anti conformations is
similar to that of butane, and appreciable quantities of the gauche conformation are
present in liquid alkanes at 25°C. In depicting the conformations of higher alkanes it is
often more helpful to look at them from the side rather than end-on as in a Newman
projection. Viewed from this perspective, the most stable conformations of pentane and
hexane have their carbon “backbones” arranged in a zigzag fashion, as shown in Figure
3.9. All the bonds are staggered, and the chains are characterized by anti arrangements
of C±C±C±C units.
Pentane Hexane
FIGURE 3.8 Ball-and-spoke and space-filling models of methyl-methyl eclipsed conformation of butane.
FIGURE 3.9 Ball-and-spoke models of pentane and hexane in their all-anti (zigzag) con-
formations.
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3.4 THE SHAPES OF CYCLOALKANES: PLANAR OR NONPLANAR?
During the nineteenth century it was widely believed—incorrectly, as we’ll soon see—
that cycloalkane rings are planar. A leading advocate of this view was the German
chemist Adolf von Baeyer. He noted that compounds containing rings other than those
based on cyclopentane and cyclohexane were rarely encountered naturally and were dif-
ficult to synthesize. Baeyer connected both observations with cycloalkane stability, which
he suggested was related to how closely the angles of planar rings match the tetrahedral
value of 109.5°. For example, the 60° bond angle of cyclopropane and the 90° bond
angles of a planar cyclobutane ring are much smaller than the tetrahedral angle of 109.5°.
Baeyer suggested that three- and four-membered rings suffer from what we now call
angle strain. Angle strain is the strain a molecule has because one or more of its bond
angles deviate from the ideal value; in the case of alkanes the ideal value is 109.5°.
According to Baeyer, cyclopentane should be the most stable of all the cycloal-
kanes because the ring angles of a planar pentagon, 108°, are closer to the tetrahedral
angle than those of any other cycloalkane. A prediction of the Baeyer strain theory is
that the cycloalkanes beyond cyclopentane should become increasingly strained and cor-
respondingly less stable. The angles of a regular hexagon are 120°, and the angles of
larger polygons deviate more and more from the ideal tetrahedral angle.
Some of the inconsistencies in the Baeyer strain theory will become evident as we
use heats of combustion (Table 3.1) to probe the relative energies of cycloalkanes. The
most important column in the table is the heat of combustion per methylene (CH
2
) group.
Since all of the cycloalkanes have molecular formulas of the type C
n
H
2n,
dividing the
heat of combustion by n allows direct comparison of ring size and potential energy.
Cyclopropane has the highest heat of combustion per methylene group, which is con-
sistent with the idea that its potential energy is raised by angle strain. Cyclobutane has
less angle strain at each of its carbon atoms and a lower heat of combustion per meth-
ylene group. Cyclopentane, as expected, has a lower value still. Notice, however, that
contrary to the prediction of the Baeyer strain theory, cyclohexane has a smaller heat of
combustion per methylene group than cyclopentane. If bond angle distortion were greater
in cyclohexane than in cyclopentane, the opposite would have been observed.
98 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
TABLE 3.1 Heats of Combustion (H11002H9004H°) of Cycloalkanes
Heat of combustion
per CH
2
group
Cycloalkane
Cyclopropane
Cyclobutane
Cyclopentane
Cyclohexane
Cycloheptane
Cyclooctane
Cyclononane
Cyclodecane
Cycloundecane
Cyclododecane
Cyclotetradecane
Cyclohexadecane
Number of
CH
2
groups
3
4
5
6
7
8
9
10
11
12
14
16
Heat of combustion
kJ/mol
2,091
2,721
3,291
3,920
4,599
5,267
5,933
6,587
7,237
7,845
9,139
10,466
(kcal/mol)
(499.8)
(650.3)
(786.6)
(936.8)
(1099.2)
(1258.8)
(1418.0)
(1574.3)
(1729.8)
(1875.1)
(2184.2)
(2501.4)
kJ/mol
697
681
658
653
657
658
659
659
658
654
653
654
(kcal/mol)
(166.6)
(162.7)
(157.3)
(156.0)
(157.0)
(157.3)
(157.5)
(157.5)
(157.3)
(156.3)
(156.0)
(156.3)
Although better known now
for his incorrect theory that
cycloalkanes were planar,
Baeyer was responsible for
notable advances in the
chemistry of organic dyes
such as indigo and was
awarded the 1905 Nobel
Prize in chemistry for his
work in that area.
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Furthermore, the heats of combustion per methylene group of the very large rings
are all about the same and similar to that of cyclohexane. Rather than rising because of
increasing angle strain in large rings, the heat of combustion per methylene group
remains constant at approximately 653 kJ/mol (156 kcal/mol), the value cited in Section
2.15 as the difference between successive members of a homologous series of alkanes.
We conclude, therefore, that the bond angles of large cycloalkanes are not much differ-
ent from the bond angles of alkanes themselves. The prediction of the Baeyer strain the-
ory that angle strain increases steadily with ring size is contradicted by experimental fact.
The Baeyer strain theory is useful to us in identifying angle strain as a destabiliz-
ing effect. Its fundamental flaw is its assumption that the rings of cycloalkanes are pla-
nar. With the exception of cyclopropane, cycloalkanes are nonplanar. Sections 3.5–3.11
describe the shapes of cycloalkanes. Six-membered rings rank as the most important ring
size among organic compounds; thus let us begin with cyclohexane to examine the forces
that determine the shapes of cycloalkanes.
3.5 CONFORMATIONS OF CYCLOHEXANE
Experimental evidence indicating that six-membered rings are nonplanar began to accu-
mulate in the 1920s. Eventually, Odd Hassel of the University of Oslo established that
the most stable conformation of cyclohexane has the shape shown in Figure 3.10. This
is called the chair conformation. With C±C±C bond angles of 111°, the chair con-
formation is nearly free of angle strain. All its bonds are staggered, making it free of
torsional strain as well. The staggered arrangement of bonds in the chair conformation
of cyclohexane is apparent in a Newman-style projection.
A second, but much less stable, nonplanar conformation called the boat is shown
in Figure 3.11. Like the chair, the boat conformation has bond angles that are approxi-
mately tetrahedral and is relatively free of angle strain. As noted in Figure 3.11, how-
ever, the boat is destabilized by van der Waals strain involving its two “flagpole” hydro-
gens, which are within 180 pm of each other. An even greater contribution to the
H
H CH
2
H
CH
2
H
H
H
H
H
Staggered arrangement of
bonds in chair conformation
of cyclohexane
3.5 Conformations of Cyclohexane 99
Hassel shared the 1969 Nobel
Prize in chemistry with Sir
Derek Barton of Imperial
College (London), now at
Texas A&M University. Bar-
ton demonstrated how Has-
sel’s structural results could
be extended to an analysis of
conformational effects on
chemical reactivity.
(a)(b)
FIGURE 3.10 (a) A
ball-and-spoke model and
(b) a space-filling model of
the chair conformation of
cyclohexane.
Make a molecular model
of the chair conformation of cy-
clohexane, and turn it so that
you can look down one of the
C±C bonds.
Recall from Section 3.2 that
the sum of the van der Waals
radii of two hydrogen atoms
is 240 pm.
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estimated 27 kJ/mol (6.4 kcal/mol) energy difference between the chair and the boat is
the torsional strain associated with eclipsed bonds on four of the carbons in the boat.
Figure 3.12 depicts the eclipsed bonds and demonstrates how the associated torsional
strain may be reduced by rotation about the carbon–carbon bonds to give the slightly
more stable twist boat, or skew boat, conformation. The same bond rotations that reduce
the torsional strain also reduce the van der Waals strain by increasing the distance
between the two flagpole hydrogens.
The various conformations of cyclohexane are in rapid equilibrium with one
another, but at any moment almost all of the molecules exist in the chair conformation.
Not more than one or two molecules per thousand are present in the higher energy skew
boat and boat conformations. Thus, the discussion of cyclohexane conformational analy-
sis that follows focuses exclusively on the chair conformation.
3.6 AXIAL AND EQUATORIAL BONDS IN CYCLOHEXANE
One of the most important findings to come from conformational studies of cyclohexane
is that its 12 hydrogen atoms are not all identical but are divided into two groups, as
shown in Figure 3.13. Six of the hydrogens, called axial hydrogens, have their bonds
parallel to a vertical axis that passes through the ring’s center. These axial bonds alter-
100 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
(a)(b)
(a)(b)
FIGURE 3.12 (a) The boat and (b) skew boat conformations of cyclohexane. A portion of
the torsional strain in the boat is relieved by rotation about C±C bonds in the skew boat. Bond
rotation is accompanied by movement of flagpole hydrogens away from each other, which re-
duces the van der Waals strain between them.
FIGURE 3.11 (a) A
ball-and-spoke model and
(b) a space-filling model of
the boat conformation of
cyclohexane. The close ap-
proach of the two upper-
most hydrogen substituents
is clearly evident in the
space-filling model.
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3.6 Axial and Equatorial Bonds in Cyclohexane 101
H
H
H
H
H
H
Axial C±H bonds
H
H
H
H
H
H
Equatorial C±H bonds Axial and equatorial
bonds together
H
H
H
H
H
H
H
H
H
H
H
H
nately are directed up and down on adjacent carbons. The second set of six hydrogens,
called equatorial hydrogens, are located approximately along the equator of the mole-
cule. Notice that the four bonds to each carbon are arranged tetrahedrally, consistent with
an sp
3
hybridization of carbon.
The conformational features of six-membered rings are fundamental to organic
chemistry, so it is essential that you have a clear understanding of the directional prop-
erties of axial and equatorial bonds and be able to represent them accurately. Figure 3.14
offers some guidance on the drawing of chair cyclohexane rings.
It is no accident that sections of our chair cyclohexane drawings resemble sawhorse
projections of staggered conformations of alkanes. The same spatial relationships seen
in alkanes carry over to substituents on a six-membered ring. In the structure
substituents A and B are anti to each other, and the other relationships—A and Y, X and
Y, and X and B—are gauche.
PROBLEM 3.4 Given the following partial structure, add a substituent X to C-1
so that it satisfies the indicated stereochemical requirement. You may find it help-
ful to build a molecular model for reference.
(a) Anti to A (c) Anti to C-3
(b) Gauche to A (d) Gauche to C-3
SAMPLE SOLUTION (a) In order to be anti to A, substituent X must be axial.
The blue lines in the drawing show the A±C±C±X torsion angle to be 180°.
A
1
X
A
3
1
A
X
Y
B
A
X
Y
B
(The substituted carbons
have the spatial
arrangement shown)
FIGURE 3.13 Axial and equatorial bonds in cyclohexane.
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102 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
(1) Begin with the chair conformation of cyclohexane.
(2) Draw the axial bonds before the equatorial ones, alternating their direction
on adjacent atoms. Always start by placing an axial bond “up” on the
uppermost carbon or “down” on the lowest carbon.
(4) Practice drawing cyclohexane chairs oriented in either direction.
Following this pattern gives the complete set of equatorial bonds.
Start here
or start here
Then alternate to give
in which all the axial
bonds are parallel to
one another
4
5
23
6 1
Place equatorial bond
at C-1 so that it is
parallel to the bonds
between C-2 and C-3
and between C-5 and
C-6.
4
5
23
6
1
and
(3) Place the equatorial bonds so as to approximate a tetrahedral arrangement of
the bonds to each carbon. The equatorial bond of each carbon should be
parallel to the ring bonds of its two nearest neighbor carbons.
FIGURE 3.14 A guide to representing the orientations of the bonds in the chair conforma-
tion of cyclohexane.
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3.7 CONFORMATIONAL INVERSION (RING FLIPPING) IN
CYCLOHEXANE
We have seen that alkanes are not locked into a single conformation. Rotation around
the central carbon–carbon bond in butane occurs rapidly, interconverting anti and gauche
conformations. Cyclohexane, too, is conformationally mobile. Through a process known
as ring inversion, chair–chair interconversion, or, more simply, ring flipping, one
chair conformation is converted to another chair.
The activation energy for cyclohexane ring inversion is 45 kJ/mol (10.8 kcal/mol).
It is a very rapid process with a half-life of about 10
-5
s at 25°C.
A potential energy diagram for ring inversion in cyclohexane is shown in Figure
3.15. In the first step the chair conformation is converted to a skew boat, which then
proceeds to the inverted chair in the second step. The skew boat conformation is an inter-
mediate in the process of ring inversion. Unlike a transition state, an intermediate is not
a potential energy maximum but is a local minimum on the potential energy profile.
The most important result of ring inversion is that any substituent that is axial in the
original chair conformation becomes equatorial in the ring-flipped form and vice versa.
The consequences of this point are developed for a number of monosubstituted cyclo-
hexane derivatives in the following section, beginning with methylcyclohexane.
very
fast
4
5
6
1
2
3
X
Y
X axial; Y equatorial
X
Y
1
6
5
4
3
2
X equatorial; Y axial
1
6
5
4
3
2
1
6
5
4
3
2
3.7 Conformational Inversion (Ring Flipping) in Cyclohexane 103
A more detailed discussion
of cyclohexane ring inversion
can be found in the July
1997 issue of the Journal of
Chemical Education,
pp. 813–814.
Skew boat
Energy
Half-chair Half-chair
Chair Chair
45 kJ/mol
23 kJ/mol
FIGURE 3.15 Energy dia-
gram showing interconver-
sion of various conforma-
tions of cyclohexane. In
order to simplify the dia-
gram, the boat conforma-
tion has been omitted. The
boat is a transition state for
the interconversion of skew
boat conformations.
The best way to under-
stand ring flipping in cyclo-
hexane is to view the animation
of Figure 3.15 in Learning By
Modeling.
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3.8 CONFORMATIONAL ANALYSIS OF MONOSUBSTITUTED
CYCLOHEXANES
Ring inversion in methylcyclohexane differs from that of cyclohexane in that the two
chair conformations are not equivalent. In one chair the methyl group is axial; in the
other it is equatorial. At room temperature approximately 95% of the molecules of
methylcyclohexane are in the chair conformation that has an equatorial methyl group
whereas only 5% of the molecules have an axial methyl group.
When two conformations of a molecule are in equilibrium with each other, the one
with the lower free energy predominates. Why is equatorial methylcyclohexane more sta-
ble than axial methylcyclohexane?
A methyl group is less crowded when it is equatorial than when it is axial. One of
the hydrogens of an axial methyl group is within 190–200 pm of the axial hydrogens at
C-3 and C-5. This distance is less than the sum of the van der Waals radii of two hydro-
gens (240 pm) and causes van der Waals strain in the axial conformation. When the
methyl group is equatorial, it experiences no significant crowding.
The greater stability of an equatorial methyl group, compared with an axial one,
is another example of a steric effect (Section 3.2). An axial substituent is said to be
crowded because of 1,3-diaxial repulsions between itself and the other two axial sub-
stituents located on the same side of the ring.
PROBLEM 3.5 The following questions relate to a cyclohexane ring depicted in
the chair conformation shown.
(a) Is a methyl group at C-6 that is “down” axial or equatorial?
(b) Is a methyl group that is “up” at C-1 more or less stable
than a methyl group that is up at C-4?
(c) Place a methyl group at C-3 in its most stable orientation.
Is it up or down?
3
1
6
5
42
Van der Waals strain
between hydrogen of axial
CH
3
and axial hydrogens
at C-3 and C-5
H
H
H
1
2
3
4
5
6
H
H
C
H H
H
Smaller van der Waals
strain between hydrogen
at C-1 and axial hydrogens
at C-3 and C-5
C
H
H
H
H
H
H
H
4
5
6
1
2
3
H
very
fast
5% 95%
CH
3
H
CH
3
H
104 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
See the box entitled “En-
thalpy, Free Energy, and
Equilibrium Constant” ac-
companying this section for
a discussion of these rela-
tionships.
Make a molecular model
of each chair conformation of
methylcyclohexane, and com-
pare their energies.
See Learning By Model-
ing for an animation of this
process.
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3.8 Conformational Analysis of Monosubstituted Cyclohexanes 105
SAMPLE SOLUTION (a) First indicate the directional properties of the bonds to
the ring carbons. A substituent is down if it is below the other substituent on the
same carbon atom. A methyl group that is down at C-6 is therefore axial.
Other substituted cyclohexanes are similar to methylcyclohexane. Two chair con-
formations exist in rapid equilibrium, and the one in which the substituent is equatorial
is more stable. The relative amounts of the two conformations depend on the effective
size of the substituent. The size of a substituent, in the context of cyclohexane confor-
mations, is related to the degree of branching at its point of connection to the ring. A
single atom, such as a halogen substituent, does not take up much space, and its prefer-
ence for an equatorial orientation is less pronounced than that of a methyl group.
A branched alkyl group such as isopropyl exhibits a greater preference for the equator-
ial orientation than does methyl.
A tert-butyl group is so large that tert-butylcyclohexane exists almost entirely in the con-
formation in which the tert-butyl group is equatorial. The amount of axial tert-butylcy-
clohexane present is too small to measure.
PROBLEM 3.6 Draw or construct a molecular model of the most stable confor-
mation of 1-tert-butyl-1-methylcyclohexane.
Greater than 99.99%
(Decreased
van der Waals strain)
C(CH
3
)
3
H
Less than 0.01%
(Serious 1,3-diaxial repulsions
involving tert-butyl group)
H
H
H
C
CH
3
CH
3
CH
3
CH(CH
3
)
2
H
3% 97%
CH(CH
3
)
2
H
F
H
40% 60%
F
H
4
5
6
1
2
3
6
H
CH
3
up
down
The halogens F, Cl, Br, and I
do not differ much in their
preference for the equatorial
position. As the atomic ra-
dius increases in the order
F H11021 Cl H11021 Br H11021 I, so does the
carbon–halogen bond dis-
tance, and the two effects
tend to cancel.
Highly branched groups such
as tert-butyl are commonly
described as “bulky.”
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3.9 SMALL RINGS: CYCLOPROPANE AND CYCLOBUTANE
Conformational analysis is far simpler in cyclopropane than in any other cycloalkane.
Cyclopropane’s three carbon atoms are, of geometric necessity, coplanar, and rotation
about its carbon–carbon bonds is impossible. You saw in Section 3.4 how angle strain
in cyclopropane leads to an abnormally large heat of combustion. Let’s now look at
cyclopropane in more detail to see how our orbital hybridization bonding model may be
adapted to molecules of unusual geometry.
Strong sp
3
–sp
3
H9268 bonds are not possible for cyclopropane, because the 60° bond
angles of the ring do not permit the orbitals to be properly aligned for effective overlap
(Figure 3.16). The less effective overlap that does occur leads to what chemists refer to
106 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
ENTHALPY, FREE ENERGY, AND EQUILIBRIUM CONSTANT
O
ne of the fundamental equations of thermo-
dynamics concerns systems at equilibrium and
relates the equilibrium constant K to the dif-
ference in free energy (H9004G°) between the products
and the reactants.
H9004G° H11005 G°
products
H11002 G°
reactants
H11005H11002RTlnK
where T is the absolute temperature in kelvins and
the constant R equals 8.314 J/mol H11080 K (1.99 cal/mol H11080 K).
For the equilibrium between the axial and
equatorial conformations of a monosubstituted cy-
clohexane,
the equilibrium constant is given by the expression
K H11005
[products]
[reactants]
X
X
K
Inserting the appropriate values for R, T (298 K), and
K gives the values of H9004G° listed in the table (page
107) for the various substituents discussed in Section
3.8.
The relationship between H9004G° and K is plotted
in Figure 3.17. A larger value of K is associated with
a more negative H9004G°.
Free energy and enthalpy are related by the ex-
pression
H9004G° H11005 H9004H° H11002 TH9004S°
where H9004S° is the difference in entropy between the
products and reactants. A positive H9004S° is accompa-
nied by an increase in the disorder of a system. A pos-
itive TH9004S° term leads to a H9004G° that is more negative
than H9004H° and a larger K than expected on the basis of
enthalpy considerations alone. Conversely, a negative
H9004S° gives a smaller K than expected. In the case of
conformational equilibration between the chair
forms of a substituted cyclohexane, H9004S° is close to
zero and H9004G° and H9004H° are approximately equal.
—Cont.
H
H
H
H
H
C
H
CC
FIGURE 3.16 “Bent bonds”
in cyclopropane. The orbitals
involved in carbon–carbon
bond formation overlap in a
region that is displaced from
the internuclear axis. Orbital
overlap is less effective than
in a normal carbon–carbon H9268
bond, and the carbon–car-
bon bond is weaker.
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as “bent” bonds. The electron density in the carbon–carbon bonds of cyclopropane does
not lie along the internuclear axis but is distributed along an arc between the two carbon
atoms. The ring bonds of cyclopropane are weaker than other carbon–carbon H9268 bonds.
In addition to angle strain, cyclopropane is destabilized by torsional strain. Each
C±H bond of cyclopropane is eclipsed with two others.
Cyclobutane has less angle strain than cyclopropane and can reduce the torsional
strain that goes with a planar geometry by adopting the nonplanar “puckered” confor-
mation shown in Figure 3.18.
PROBLEM 3.7 The heats of combustion of ethylcyclopropane and methylcy-
clobutane have been measured as 3352 and 3384 kJ/mol (801.2 and 808.8 kcal/mol),
respectively. Assign the correct heat of combustion to each isomer.
All adjacent pairs
of bonds are eclipsed
3.9 Small Rings: Cyclopropane and Cyclobutane 107
1 2 3 4 5 67
0 5 10 15 20 25 30
Percent major component at equilibrium, 25
H11034
C 100
90
80
70
60
50
40
Free energy difference (?GH11034), kcal/mol
Free energy difference (?GH11034), kJ/mol
FIGURE 3.17 Distribution of two products at equilibrium plotted as a function of the difference in free energy (H9004G°) at
25°C between them.
H9004GH11543
298 K
Substituent X
±F
±CH
3
±CH(CH
3
)
2
±C(CH
3
)
3
Percent
axial
40
5
3
H110210.01
Percent
equatorial
60
95
97
H1102299.99
K
1.5
19
32.3
H110229999
kJ/mol
H110021.0
H110027.3
H110028.6
H1100222.8
(kcal/mol)
(H110020.24)
(H110021.7)
(H110022.1)
(H110025.5)
In keeping with the
“bent-bond” description of Fig-
ure 3.16, the carbon–carbon
bond distance in cyclopropane
(151 pm) is slightly shorter than
that of ethane (153 pm) and cy-
clohexane (154 pm). The calcu-
lated values from molecular
models (see Learning By Model-
ing) reproduce these experimen-
tal values.
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3.10 CYCLOPENTANE
Angle strain in the planar conformation of cyclopentane is relatively small because the
108° angles of a regular pentagon are not much different from the normal 109.5° bond
angles of sp
3
hybridized carbon. The torsional strain, however, is substantial, since five
bonds are eclipsed on the top face of the ring, and another set of five are eclipsed on
the bottom face (Figure 3.19a). Some, but not all, of this torsional strain is relieved in
nonplanar conformations. Two nonplanar conformations of cyclopentane, the envelope
(Figure 3.19b) and the half-chair (Figure 3.19c) are of similar energy.
In the envelope conformation four of the carbon atoms are coplanar. The fifth car-
bon is out of the plane of the other four. There are three coplanar carbons in the half-
chair conformation, with one carbon atom displaced above that plane and another below
it. In both the envelope and the half-chair conformations, in-plane and out-of-plane car-
bons exchange positions rapidly. Equilibration between conformations of cyclopentane
occurs at rates that are comparable with the rate of rotation about the carbon–carbon
bond of ethane.
3.11 MEDIUM AND LARGE RINGS
Beginning with cycloheptane, which has four conformations of similar energy, confor-
mational analysis of cycloalkanes becomes more complicated. The same fundamental
principles apply to medium and large rings as apply to smaller ones—there are simply
more atoms and more bonds to consider and more conformational possibilities.
3.12 DISUBSTITUTED CYCLOALKANES: STEREOISOMERS
When a cycloalkane bears two substituents on different carbons—methyl groups, for
example—these substituents may be on the same or on opposite sides of the ring. When
substituents are on the same side, we say they are cis to each other; if they are on oppo-
108 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
FIGURE 3.18 Non-
planar (“puckered”) confor-
mation of cyclobutane. The
nonplanar conformation is
more stable because it avoids
the eclipsing of bonds on
adjacent carbons that char-
acterizes the planar confor-
mation.
(a) Planar (b) Envelope (c) Half-Chair
FIGURE 3.19 The
(a) planar, (b) envelope, and
(c) half-chair conformations
of cyclopentane.
Neighboring C±H bonds are
eclipsed in any planar cy-
cloalkane. Thus all planar
conformations are destabi-
lized by torsional strain.
In 1978, a German-Swiss
team of organic chemists re-
ported the synthesis of a cy-
cloalkane with 96 carbons in
its ring (cyclo-C
96
H
192
).
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site sides, they are trans to each other. Both terms come from the Latin, in which cis
means “on this side” and trans means “across.”
PROBLEM 3.8 Exclusive of compounds with double bonds, four hydrocarbons
are constitutional isomers of cis- and trans-1,2-dimethylcyclopropane. Identify
these compounds.
The cis and trans forms of 1,2-dimethylcyclopropane are stereoisomers.
Stereoisomers are isomers that have their atoms bonded in the same order—that is, they
have the same constitution, but they differ in the arrangement of atoms in space.
Stereoisomers of the cis–trans type are sometimes referred to as geometric isomers. You
learned in Section 2.15 that constitutional isomers could differ in stability. What about
stereoisomers?
We can measure the energy difference between cis- and trans-1,2-dimethylcyclo-
propane by comparing their heats of combustion. As illustrated in Figure 3.20, the two
compounds are isomers, and so the difference in their heats of combustion is a direct
measure of the difference in their energies. Because the heat of combustion of trans-
1,2-dimethylcyclopropane is 5 kJ/mol (1.2 kcal/mol) less than that of its cis stereoisomer,
it follows that trans-1,2-dimethylcyclopropane is 5 kJ/mol (1.2 kcal/mol) more stable
than cis-1,2-dimethylcyclopropane.
H H
H
3
CCH
3
cis-1,2-Dimethylcyclopropane trans-1,2-Dimethylcyclopropane
H
H
3
C
CH
3
H
3.12 Distributed Cycloalkanes: Stereoisomers 109
The prefix stereo- is derived
from the Greek word
stereos, meaning “solid.”
Stereochemistry is the term
applied to the three-
dimensional aspects of
molecular structure and
reactivity.
H
H H
H
H
H
H
H
H
H
H
H H
H
H
cis-1,2-Dimethylcyclopropane trans-1,2-Dimethylcyclopropane
5 kJ/mol
(1.2 kcal/mol)
3371 kJ/mol
(805.7 kcal/mol)
3366 kJ/mol
(804.5 kcal/mol)
5CO
2
H11001 5H
2
O
H
15
H11001 O
2
2
15
H11001 O
2
2
FIGURE 3.20 The enthalpy
difference between cis- and
trans-1,2-dimethylcyclo-
propane can be determined
from their heats of combus-
tion. Van der Waals strain
between methyl groups on
the same side of the ring
makes the cis isomer less sta-
ble than the trans.
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In this case, the relationship between stability and stereochemistry is easily
explained on the basis of van der Waals strain. The methyl groups on the same side of
the ring in cis-1,2-dimethylcyclopropane crowd each other and increase the potential
energy of this stereoisomer. Steric hindrance between methyl groups is absent in trans-
1,2-dimethylcyclopropane.
Disubstituted cyclopropanes exemplify one of the simplest cases involving stabil-
ity differences between stereoisomers. A three-membered ring has no conformational
mobility, and there is no way the ring can adjust to reduce the van der Waals strain
between cis substituents on adjacent carbons. The situation is different in disubstituted
derivatives of cyclohexane.
3.13 CONFORMATIONAL ANALYSIS OF DISUBSTITUTED
CYCLOHEXANES
We’ll begin with cis- and trans-1,4-dimethylcyclohexane. A conventional method to rep-
resent cis and trans stereoisomers in cyclic systems uses wedge-and-dash descriptions as
shown.
Wedge-and-dash drawings fail to show conformation, and it’s important to remember that
the rings of cis- and trans-1,2-dimethylcyclohexane exist in a chair conformation. This
fact must be taken into consideration when evaluating the relative stabilities of the
stereoisomers.
Their heats of combustion (Table 3.2) reveal that trans-1,4-dimethylcyclohexane is
7 kJ/mol (1.6 kcal/mol) more stable than the cis stereoisomer. It is unrealistic to believe
that van der Waals strain between cis substituents is responsible, because the methyl
groups are too far away from each other. To understand why trans-1,4-dimethylcyclo-
hexane is more stable than cis-1,4-dimethylcyclohexane, we need to examine each
stereoisomer in its most stable conformation.
cis-1,4-Dimethylcyclohexane can adopt either of two equivalent chair conforma-
tions, each having one axial methyl group and one equatorial methyl group. The two are
HH
H
3
CCH
3
cis-1,4-Dimethylcyclohexane trans-1,4-Dimethylcyclohexane
H
HH
3
C
CH
3
110 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
TABLE 3.2 Heats of Combustion of Isomeric Dimethylcyclohexanes
Compound
cis-1,2-Dimethylcyclohexane
trans-1,2-Dimethylcyclohexane
cis-1,3-Dimethylcyclohexane
trans-1,3-Dimethylcyclohexane
cis-1,4-Dimethylcyclohexane
trans-1,4-Dimethylcyclohexane
Orientation of methyl
groups in most stable
conformation
Axial–equatorial
Diequatorial
Diequatorial
Axial–equatorial
Axial–equatorial
Diequatorial
Difference in
heat of
combustion
Heat of
combustion
kJ/mol
5223
5217
5212
5219
5219
5212
(kcal/mol)
(1248.3)
(1246.8)
(1245.7)
(1247.4)
(1247.4)
(1245.7)
kJ/mol
6
7
7
(kcal/mol)
(1.5)
(1.7)
(1.7)
More stable
stereoisomer
trans
cis
trans
Make molecular models of
cis- and trans-1,2-dimethyl-
cyclopropane, and compare their
strain energies.
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in rapid equilibrium with each other by ring flipping. The equatorial methyl group
becomes axial and the axial methyl group becomes equatorial.
The methyl groups are described as cis because both are up relative to the hydrogen
present at each carbon. If both methyl groups were down, they would still be cis to each
other. Notice that ring flipping does not alter the cis relationship between the methyl
groups. Nor does it alter their up-versus-down quality; substituents that are up in one
conformation remain up in the ring-flipped form.
The most stable conformation of trans-1,4-dimethylcyclohexane has both methyl
groups in equatorial orientations. The two chair conformations of trans-1,4-dimethyl-
cyclohexane are not equivalent to each other. One has two equatorial methyl groups; the
other, two axial methyl groups.
The more stable chair—the one with both methyl groups equatorial—is the conforma-
tion adopted by most of the trans-1,4-dimethylcyclohexane molecules.
trans-1,4-Dimethylcyclohexane is more stable than cis-1,4-dimethylcyclohexane
because both methyl groups are equatorial in its most stable conformation. One methyl
group must be axial in the cis stereoisomer. Remember, it is a general rule that any sub-
stituent is more stable in an equatorial orientation than in an axial one. It is worth point-
ing out that the 7 kJ/mol (1.7 kcal/mol) energy difference between cis- and trans-
1,4-dimethylcyclohexane is the same as the energy difference between the axial and
equatorial conformations of methylcyclohexane. There is a simple reason for this: in both
instances the less stable structure has one axial methyl group, and the 7 kJ/mol
(1.6 kcal/mol) energy difference can be considered the “energy cost” of having a methyl
group in an axial rather than an equatorial orientation.
Like the 1,4-dimethyl derivatives, trans-1,2-dimethylcyclohexane has a lower heat
of combustion (see Table 3.2) and is more stable than cis-1,2-dimethylcyclohexane. The
cis stereoisomer has two chair conformations of equal energy, each containing one axial
and one equatorial methyl group.
(One methyl group is up, the other down)
trans-1,4-Dimethylcyclohexane
(Both methyl groups
are axial: less stable
chair conformation)
H
CH
3
CH
3
H
(Both methyl groups are
equatorial: more stable
chair conformation)
CH
3
CH
3
H
H
(Both methyl groups are up)
cis-1,4-Dimethylcyclohexane
(One methyl group is
axial, the other
equatorial)
H
CH
3
CH
3
H
(One methyl group is
axial, the other
equatorial)
CH
3
CH
3
H
H
3.13 Conformational Analysis of Disubstituted Cyclohexanes 111
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Both methyl groups are equatorial in the most stable conformation of trans-1,2-dimethyl-
cyclohexane.
As in the 1,4-dimethylcyclohexanes, the 6 kJ/mol (1.5 kcal/mol) energy difference
between the more stable (trans) and the less stable (cis) stereoisomer is attributed to the
strain associated with the presence of an axial methyl group in the cis isomer.
Probably the most interesting observation in Table 3.2 concerns the 1,3-dimethyl-
cyclohexanes. Unlike the 1,2- and 1,4-dimethylcyclohexanes, in which the trans
stereoisomer is more stable than the cis, we find that cis-1,3-dimethylcyclohexane is
7 kJ/mol (1.7 kcal/mol) more stable than trans-1,3-dimethylcyclohexane. Why?
The most stable conformation of cis-1,3-dimethylcyclohexane has both methyl
groups equatorial.
The two chair conformations of trans-1,3-dimethylcyclohexane are equivalent to each
other. Both contain one axial and one equatorial methyl group.
trans-1,3-Dimethylcyclohexane
(One methyl group is axial,
the other equatorial)
CH
3
CH
3
H
H
(One methyl group is axial,
the other equatorial)
H
CH
3H
CH
3
cis-1,3-Dimethylcyclohexane
(Both methyl groups are
equatorial: more stable
chair conformation)
CH
3
H
CH
3
H
(Both methyl groups
are axial: less stable
chair conformation)
H
CH
3CH
3
H
trans-1,2-Dimethylcyclohexane
(Both methyl groups
are axial: less stable
chair conformation)
H
CH
3
H
CH
3
(Both methyl groups are
equatorial: more stable
chair conformation)
CH
3
H
3
C
H
H
cis-1,2-Dimethylcyclohexane
H
CH
3
CH
3
H
CH
3
H
H
CH
3
112 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
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Thus the trans stereoisomer, with one axial methyl group, is less stable than cis-1,3-
dimethylcyclohexane where both methyl groups are equatorial.
PROBLEM 3.9 Based on what you know about disubstituted cyclohexanes, which
of the following two stereoisomeric 1,3,5-trimethylcyclohexanes would you expect
to be more stable?
If a disubstituted cyclohexane has two different substituents, then the most stable
conformation is the chair that has the larger substituent in an equatorial orientation. This
is most apparent when one of the substituents is a bulky group such as tert-butyl. Thus,
the most stable conformation of cis-1-tert-butyl-2-methylcyclohexane has an equatorial
tert-butyl group and an axial methyl group.
PROBLEM 3.10 Write structural formulas or make molecular models for the
most stable conformation of each of the following compounds:
(a) trans-1-tert-Butyl-3-methylcyclohexane
(b) cis-1-tert-Butyl-3-methylcyclohexane
(c) trans-1-tert-Butyl-4-methylcyclohexane
(d) cis-1-tert-Butyl-4-methylcyclohexane
SAMPLE SOLUTION (a) The most stable conformation is the one that has the
larger substituent, the tert-butyl group, equatorial. Draw a chair conformation of
cyclohexane, and place an equatorial tert-butyl group at one of its carbons. Add
a methyl group at C-3 so that it is trans to the tert-butyl group.
Add methyl group
to axial position at
C-3 so that it is trans
to tert-butyl group
tert-Butyl group
equatorial on
six-membered ring
C(CH
3
)
3
H
trans-1-tert-Butyl-3-
methylcyclohexane
CH
3
C(CH
3
)
3
H
H
cis-1-tert-Butyl-2-methylcyclohexane
(Less stable conformation:
larger group is axial)
H
C(CH
3
)
3
CH
3
H
(More stable conformation:
larger group is equatorial)
C(CH
3
)
3
H
H
CH
3
HH
CH
3
CH
3
H
3
C
H
cis-1,3,5-Trimethylcyclohexane
HH
H
3
C
CH
3
H
3
C
H
trans-1,3,5-Trimethylcyclohexane
3.13 Conformational Analysis of Disubstituted Cyclohexanes 113
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Cyclohexane rings that bear tert-butyl substituents are examples of conformation-
ally biased molecules. A tert-butyl group has such a pronounced preference for the
equatorial orientation that it will strongly bias the equilibrium to favor such conforma-
tions. This does not mean that ring inversion does not occur, however. Ring inversion
does occur, but at any instant only a tiny fraction of the molecules exist in conforma-
tions having axial tert-butyl groups. It is not strictly correct to say that tert-butylcyclo-
hexane and its derivatives are “locked” into a single conformation; conformations related
by ring flipping are in rapid equilibrium with one another, but the distribution between
them strongly favors those in which the tert-butyl group is equatorial.
3.14 POLYCYCLIC RING SYSTEMS
Organic molecules in which one carbon atom is common to two rings are called
spirocyclic compounds. The simplest spirocyclic hydrocarbon is spiropentane, a product
of laboratory synthesis. More complicated spirocyclic hydrocarbons not only have been
synthesized but also have been isolated from natural sources. H9251-Alaskene, for example,
occurs in the fragrant oil given off by the needles of the Alaskan yellow cedar; one of its
carbon atoms is common to both the six-membered ring and the five-membered ring.
PROBLEM 3.11 Which of the following compounds are isomers of spiropentane?
When two or more atoms are common to more than one ring, the compounds are
called polycyclic ring systems. They are classified as bicyclic, tricyclic, tetracyclic etc.,
according to the minimum number of bond cleavages required to generate a noncyclic
structure. Bicyclobutane is the simplest bicyclic hydrocarbon; its four carbons form 2
three-membered rings that share a common side. Camphene is a naturally occurring
bicyclic hydrocarbon obtained from pine oil. It is best regarded as a six-membered ring
(indicated by blue bonds in the structure shown here) in which two of the carbons (des-
ignated by asterisks) are bridged by a CH
2
group.
Camphene
CH
3
CH
3
CH
2
*
*
Bicyclobutane
±CH?CH
2
± ?CH
2
Spiropentane
CH
3
CH
3
CH
3
CH
3
H
H9251-Alaskene
114 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
Make a molecular model
of spiropentane. What feature
of its geometry is more apparent
from a model than from its
structural formula?
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PROBLEM 3.12 Use the bond-cleavage criterion to verify that bicyclobutane and
camphene are bicyclic.
Bicyclic compounds are named in the IUPAC system by counting the number of
carbons in the ring system, assigning to the structure the base name of the unbranched
alkane having the same number of carbon atoms, and attaching the prefix “bicyclo-.”
The number of atoms in each of the bridges connecting the common atoms is then placed,
in descending order, within brackets.
PROBLEM 3.13 Write structural formulas for each of the following bicyclic
hydrocarbons:
(a) Bicyclo[2.2.1]heptane (c) Bicyclo[3.1.1]heptane
(b) Bicyclo[5.2.0]nonane (d) Bicyclo[3.3.0]octane
SAMPLE SOLUTION (a) The bicyclo[2.2.1]heptane ring system is one of the most
frequently encountered bicyclic structural types. It contains seven carbon atoms,
as indicated by the suffix “-heptane.” The bridging groups contain two, two, and
one carbon, respectively.
Among the most important of the bicyclic hydrocarbons are the two stereoisomeric
bicyclo[4.4.0]decanes, called cis- and trans-decalin. The hydrogen substituents at the ring
junction positions are on the same side in cis-decalin and on opposite sides in trans-
decalin. Both rings adopt the chair conformation in each stereoisomer.
Decalin ring systems appear as structural units in a large number of naturally occur-
ring substances, particularly the steroids. Cholic acid, for example, a steroid present in
bile that promotes digestion, incorporates cis-decalin and trans-decalin units into a rather
complex tetracyclic structure.
trans-Bicyclo[4.4.0]decane
(trans-decalin)
cis-Bicyclo[4.4.0]decane
(cis-decalin)
H
H
H11013 H
H
H
H
H11013
H
H
One-carbon bridge
Bicyclo[2.2.1]heptane
Two-carbon bridgeTwo-carbon bridge
Bicyclo[3.2.0]heptane Bicyclo[3.2.1]octane
3.14 Polycyclic Ring Systems 115
Make models of cis- and
trans-decalin. Which is more
stable?
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3.15 HETEROCYCLIC COMPOUNDS
Not all cyclic compounds are hydrocarbons. Many substances include an atom other than
carbon, called a heteroatom (Section 1.7), as part of a ring. A ring that contains at least
one heteroatom is called a heterocycle, and a substance based on a heterocyclic ring is
a heterocyclic compound. Each of the following heterocyclic ring systems will be
encountered in this text:
The names cited are common names, which have been in widespread use for a long time
and are acceptable in IUPAC nomenclature. We will introduce the systematic nomen-
clature of these ring systems as needed in later chapters.
The shapes of heterocyclic rings are very much like those of their all-carbon
analogs. Thus, six-membered heterocycles such as piperidine exist in a chair conforma-
tion analogous to cyclohexane.
The hydrogen attached to nitrogen can be either axial or equatorial, and both chair con-
formations are approximately equal in stability.
PROBLEM 3.14 Draw or build a molecular model of what you would expect to
be the most stable conformation of the piperidine derivative in which the hydro-
gen bonded to nitrogen has been replaced by methyl.
Sulfur-containing heterocycles are also common. Compounds in which sulfur is the
heteroatom in three-, four-, five-, and six-membered rings, as well as larger rings, are all
well known. Two interesting heterocyclic compounds that contain sulfur–sulfur bonds
are lipoic acid and lenthionine.
H
W
N
N
H±
Ethylene oxide
O
Tetrahydrofuran
O
Pyrrolidine
N
H
Piperidine
N
H
Cholic acid
H
HO OH
H
3
C H
CH
3
CHCH
2
CH
2
CO
2
H
W
CH
3
HO
H H
116 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
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Many heterocyclic systems contain double bonds and are related to arenes. The
most important representatives of this class are described in Sections 11.21 and 11.22.
3.16 SUMMARY
In this chapter we explored the three-dimensional shapes of alkanes and cycloalkanes.
The most important point to be taken from the chapter is that a molecule adopts the
shape that minimizes its total strain. The sources of strain in alkanes and cycloal-
kanes are:
1. Bond length distortion: destabilization of a molecule that results when one or more
of its bond distances are different from the normal values
2. Angle strain: destabilization that results from distortion of bond angles from their
normal values
3. Torsional strain: destabilization that results from the eclipsing of bonds on adja-
cent atoms
4. Van der Waals strain: destabilization that results when atoms or groups on non-
adjacent atoms are too close to one another
The various spatial arrangements available to a molecule by rotation about single
bonds are called conformations, and conformational analysis is the study of the dif-
ferences in stability and properties of the individual conformations. Rotation around car-
bon–carbon single bonds is normally very fast, occurring hundreds of thousands of times
per second at room temperature. Molecules are rarely frozen into a single conformation
but engage in rapid equilibration among the conformations that are energetically
accessible.
Section 3.1 The most stable conformation of ethane is the staggered conformation.
It is approximately 12 kJ/mol (3 kcal/mol) more stable than the eclipsed,
which is the least stable conformation.
Staggered conformation of ethane
(most stable conformation)
Eclipsed conformation of ethane
(least stable conformation)
Lipoic acid: a growth factor required
by a variety of different organisms
S S
CH
2
CH
2
CH
2
CH
2
COH
O
X
Lenthionine: contributes to the
odor of Shiitake mushrooms
SS
S
S
S
3.16 Summary 117
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The difference in energy between the staggered and eclipsed forms is due
almost entirely to the torsional strain in the eclipsed conformation. At any
instant, almost all the molecules of ethane reside in the staggered con-
formation.
Section 3.2 The two staggered conformations of butane are not equivalent. The anti
conformation is more stable than the gauche.
Neither conformation suffers torsional strain, because each has a stag-
gered arrangement of bonds. The gauche conformation is less stable
because of van der Waals strain involving the methyl groups.
Section 3.3 Higher alkanes adopt a zigzag conformation of the carbon chain in which
all the bonds are staggered.
Section 3.4 Cyclopropane is the only cycloalkane in which all the ring carbons lie in
the same plane. In all other cycloalkanes, the ring is nonplanar. A planar
cycloalkane is destabilized by torsional strain and, in most cases, angle
strain.
Section 3.5 Three conformations of cyclohexane have approximately tetrahedral
angles at carbon: the chair, the boat, and the skew boat. The chair is by
Cyclopropane
Octane
Anti conformation of butane Gauche conformation of butane
118 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
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far the most stable; it is free of torsional strain, but the boat and skew
boat are not. When a cyclohexane ring is present in a compound, it almost
always adopts a chair conformation.
Section 3.6 The C—H bonds in the chair conformation of cyclohexane are not all
equivalent but are divided into two sets of six each, called axial and
equatorial.
Section 3.7 Conformational inversion (ring flipping) is rapid in cyclohexane and
causes all axial bonds to become equatorial and vice versa. As a result,
a monosubstituted derivative of cyclohexane adopts the chair conforma-
tion in which the substituent is equatorial (see next section). No bonds
are made or broken in this process.
Section 3.8 A substituent is less crowded and more stable when it is equatorial than
when it is axial on a cyclohexane ring. Ring flipping of a monosubsti-
tuted cyclohexane allows the substituent to become equatorial.
Branched substituents, especially tert-butyl, have an increased preference
for the equatorial position.
Section 3.9 Cyclopropane is planar and strained (angle strain and torsional strain).
Cyclobutane is nonplanar and less strained than cyclopropane.
Methyl group axial (less stable) Methyl group equatorial (more stable)
ring flipping
Axial bonds to H in cyclohexane Equatorial bonds to H in cyclohexane
Chair Skew boat Boat
3.16 Summary 119
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Section 3.10 Cyclopentane has two nonplanar conformations that are of similar sta-
bility: the envelope and the half-chair.
Section 3.11 Higher cycloalkanes have angles at carbon that are close to tetrahedral
and are sufficiently flexible to adopt conformations that are free of tor-
sional strain. They tend to be populated by several different conforma-
tions of similar stability.
Sections Stereoisomers are isomers that have the same constitution but differ in
3.12–3.13 the arrangement of atoms in space. Cis- and trans-1,3-dimethylcyclo-
hexane are stereoisomers. The cis isomer is more stable than the trans.
Section 3.14 Cyclic hydrocarbons can contain more than one ring. Spirocyclic hydro-
carbons are characterized by the presence of a single carbon that is com-
mon to two rings. Bicyclic alkanes contain two rings that share two or
more atoms.
Section 3.15 Substances that contain one or more atoms other than carbon as part of
a ring are called heterocyclic compounds. Rings in which the heteroatom
is oxygen, nitrogen, or sulfur rank as both the most common and the most
important.
PROBLEMS
3.15 Like hydrogen peroxide, the inorganic substances hydrazine (H
2
NNH
2
) and hydroxylamine
(H
2
NOH) possess conformational mobility. Write structural representations or build molecular
models of two different staggered conformations of (a) hydrazine and (b) hydroxylamine.
6-Aminopenicillanic acid
(bicyclic and heterocyclic)
CH
3
CH
3
±
±
±
?
CO
2
H
H
2
N
O
S
N
Most stable conformation of
cis-1,3-dimethylcyclohexane
(no axial methyl groups)
H
3
C
H
H
CH
3
Most stable conformation of
trans-1,3-dimethylcyclohexane
(one axial methyl group)
H
CH
3
H
CH
3
Half-chair conformation of cyclopentaneEnvelope conformation of cyclopentane
120 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
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3.16 Of the three conformations of propane shown, which one is the most stable? Which one is
the least stable? Why?
3.17 Sight down the C-2±C-3 bond, and draw Newman projection formulas for the
(a) Most stable conformation of 2,2-dimethylbutane
(b) Two most stable conformations of 2-methylbutane
(c) Two most stable conformations of 2,3-dimethylbutane
3.18 One of the staggered conformations of 2-methylbutane in Problem 3.17b is more stable than
the other. Which one is more stable? Why?
3.19 Sketch an approximate potential energy diagram similar to that shown in Figures 3.4 and
3.7 for rotation about the carbon–carbon bond in 2,2-dimethylpropane. Does the form of the poten-
tial energy curve of 2,2-dimethylpropane more closely resemble that of ethane or that of butane?
3.20 Repeat Problem 3.19 for the case of 2-methylbutane.
3.21 One of the C±C±C angles of 2,2,4,4-tetramethylpentane is very much larger than the oth-
ers. Which angle? Why?
3.22 Even though the methyl group occupies an equatorial site, the conformation shown is not
the most stable one for methylcyclohexane. Explain.
3.23 Which of the structures shown for the axial conformation of methylcyclohexane do you
think is more stable, A or B? Why?
AB
(b)(a) (c)
Problems 121
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3.24 Which do you expect to be the more stable conformation of cis-1,3-dimethylcyclobutane, A
or B? Why?
3.25 Determine whether the two structures in each of the following pairs represent constitutional
isomers, different conformations of the same compound, or stereoisomers that cannot be inter-
converted by rotation about single bonds.
(a)
(b)
(c)
(d) cis-1,2-Dimethylcyclopentane and trans-1,3-dimethylcyclopentane
(e)
(f)
(g)
3.26 Excluding compounds that contain methyl or ethyl groups, write structural formulas for all
the bicyclic isomers of (a) C
5
H
8
and (b) C
6
H
10
.
3.27 In each of the following groups of compounds, identify the one with the largest heat of
combustion and the one with the smallest. In which cases can a comparison of heats of combus-
tion be used to assess relative stability?
and
CH
3
H
H
CH
3
CH
3
CH
3
CH
2
CH
3
CH
3
CH
2
and
CH
3
CH
3
CH
2
CH
2
CH
3
CH
3
and
CH
3
CH
3
H
3
C
H
3
C
H
H
H
HH
3
C
H
3
C
CH
3
CH
3
and
and
H
CH
3
H
3
C
H
CH
3
H
H
HH
3
C
H
CH
3
CH
3
and
CH
3
CH
3
HH
AB
CH
3
CH
3
HH
122 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
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(a) Cyclopropane, cyclobutane, cyclopentane
(b) cis-1,2-Dimethylcyclopentane, methylcyclohexane, 1,1,2,2-tetramethylcyclopropane
(c)
(d)
3.28 Write a structural formula for the most stable conformation of each of the following com-
pounds:
(a) 2,2,5,5-Tetramethylhexane (Newman projection of conformation about C-3—C-4
bond)
(b) 2,2,5,5-Tetramethylhexane (zigzag conformation of entire molecule)
(c) cis-1-Isopropyl-3-methylcyclohexane
(d) trans-1-Isopropyl-3-methylcyclohexane
(e) cis-1-tert-Butyl-4-ethylcyclohexane
(f) cis-1,1,3,4-Tetramethylcyclohexane
(g)
3.29 Identify the more stable stereoisomer in each of the following pairs, and give the reason for
your choice:
(a) cis- or trans-1-Isopropyl-2-methylcyclohexane
(b) cis- or trans-1-Isopropyl-3-methylcyclohexane
(c) cis- or trans-1-Isopropyl-4-methylcyclohexane
(d)
(e)
(f)
3.30 One stereoisomer of 1,1,3,5-tetramethylcyclohexane is 15 kJ/mol (3.7 kcal/mol) less stable
than the other. Indicate which isomer is the less stable, and identify the reason for its decreased
stability.
or
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
H
3
C CH
3
CH
3
H
3
C
or
CH
3
CH
3
H
3
C CH
3
CH
3
H
3
C
or
H CH
3
H
CH
3
H
3
C
H
H
H
H
H
H
H
Problems 123
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3.31 One of the following two stereoisomers is 20 kJ/mol (4.9 kcal/mol) less stable than the
other. Indicate which isomer is the less stable, and identify the reason for its decreased stability.
3.32 Cubane (C
8
H
8
) is the common name of a polycyclic hydrocarbon that was first synthesized
in the early 1960s. As its name implies, its structure is that of a cube. How many rings are pres-
ent in cubane?
Cubane
3.33 The following are representations of two forms of glucose. The six-membered ring is known
to exist in a chair conformation in each form. Draw clear representations of the most stable con-
formation of each. Are they two different conformations of the same molecule, or are they
stereoisomers? Which substituents (if any) occupy axial sites?
3.34 A typical steroid skeleton is shown along with the numbering scheme used for this class of
compounds. Specify in each case whether the designated substituent is axial or equatorial.
(a) Substituent at C-1 cis to the methyl groups
(b) Substituent at C-4 cis to the methyl groups
(c) Substituent at C-7 trans to the methyl groups
(d) Substituent at C-11 trans to the methyl groups
(e) Substituent at C-12 cis to the methyl groups
CH
3
CH
3
H
HH
H
7
4
1
11
12
OHHO
O
OHHO
HOH
2
C
OHHO
O
OHHO
HOH
2
C
AB
124 CHAPTER THREE Conformations of Alkanes and Cycloalkanes
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3.35 Repeat Problem 3.34 for the stereoisomeric steroid skeleton having a cis ring fusion between
the first two rings.
3.36 (a) Write Newman projections for the gauche and anti conformations of 1,2-dichloroethane
(ClCH
2
CH
2
Cl).
(b) The measured dipole moment of ClCH
2
CH
2
Cl is 1.12 D. Which one of the following
statements about 1,2-dichloroethane is false?
(1) It may exist entirely in the anti conformation.
(2) It may exist entirely in the gauche conformation.
(3) It may exist as a mixture of anti and gauche conformations.
3.37 Compare the two staggered conformations of 1,1,2,2-tetrafluoroethane on Learning By Mod-
eling. Do they differ in respect to their dipole moments? How?
3.38 The compound 2,2,4,4-tetramethylpentane [(CH
3
)
3
CCH
2
C(CH
3
)
3
] is distinctive because it
has an unusually large C±C±C bond angle. What carbons are involved? How large is the angle?
What steric factor is responsible for increasing the size of this angle? One of the other bond angles
is unusually small. Which one?
3.39 Structural drawings (molecular models, too) can be deceiving. For example, the chlorine
atoms in 1,2-dichlorocyclohexane seem much closer to each other in a drawing of the trans
stereoisomer than in the cis. Make a molecular model of each, and measure the distance between
the chlorines. What do you find?
3.40 Two stereoisomers of bicyclo[3.3.0]octane are possible. Make molecular models of both,
and determine which is more stable.
Bicyclo[3.3.0]octane
Cl
Cl
trans-1,2-Dichlorocyclohexane
Cl
Cl
cis-1,2-Dichlorocyclohexane
CH
3
CH
3
H
H
H
7
4
1
11
12
H
Problems 125
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