Stereochemistry of

Alkanes and
cycloalkanes

Chapter 5:Alkanes & cycloalkanes 1

 Alkanes
Conformations of Acyclic Alkanes
Conformations are different arrangements of atoms that are
interconverted by rotation about single bonds. A particular
conformation is called a conformer.

Chapter 5:Alkanes & cycloalkanes 2

 Alkanes
Conformations of Acyclic Alkanes
• Rotating the atoms on one carbon by 600 converts an eclipsed
conformation into a staggered conformation, and vice versa.

• The angle that separates a bond on one atom from a bond on an

adjacent atom is called a dihedral angle. For ethane in the
staggered conformation, the dihedral angle for the C—H bonds
is 600. For eclipsed ethane, it is 00.

3
 Alkanes
Conformations of Acyclic Alkanes
• End-on representations for conformations are commonly
drawn using a convention called a Newman projection.
How to Draw a Newman Projection??
Step 1. Look directly down the C—C bond. and draw a circle
with a dot in the center to represent the carbons of the C—C
bond.

Chapter 5:Alkanes & cycloalkanes 4

 Alkanes
Conformations of Acyclic Alkanes
How to Draw a Newman Projection??
Step 2. Draw in the bonds.
Draw the bonds on the front C as three lines meeting at the
center of the circle.
Draw the bonds on the back C as three lines coming out of the
edge of the circle.

Chapter 5:Alkanes & cycloalkanes 5

 Alkanes
Conformations of Acyclic Alkanes
How to Draw a Newman Projection??
Step 3. Add the atoms on each bond.

Chapter 5:Alkanes & cycloalkanes 6

 Alkanes
Conformations of Acyclic Alkanes

Newman projections for the stagerred and

eclipsed conformations of ethane

Chapter 5:Alkanes & cycloalkanes 7

Conformations of Acyclic Alkanes
• The staggered and eclipsed conformations of ethane
interconvert at room temperature, but each conformer is not
equally stable.
• In the eclipsed conformation, the C-H bonds on the front and
back carbons are aligned with each other with dihedral angles of
0 degrees.
• In the staggered conformation, the C-H bonds on the rear carbon
lie between those on the front carbon with dihedral angles of 60
degrees.

8
• The staggered conformations are more stable (lower in energy)
than the eclipsed conformations.
• Electron-electron repulsion between bonds in the eclipsed
conformation increases its energy compared with the staggered
conformation, where the bonding electrons are further apart.

9
 Alkanes
Conformations of Acyclic Alkanes
• The difference in energy between staggered and eclipsed
conformers is ~3 kcal/mol, with each eclipsed C—H bond
contributing 1 kcal/mol. The energy difference between
staggered and eclipsed conformers is called torsional energy.
• Torsional strain is an increase in energy caused by eclipsing
interactions.

Chapter 5:Alkanes & cycloalkanes 10

Converting Propane to Newman Projections

Newman Projections
for the staggered and
eclipsed conformers of
propane
11
 Alkanes
Conformations of Acyclic Alkanes
• An energy minimum and maximum occur every 600 as the
conformation changes from staggered to eclipsed. Conformations
that are neither staggered nor eclipsed are intermediate in energy.
• Butane and higher molecular weight alkanes have several C—C
bonds, all capable of rotation. It takes six 600 rotations to return
to the original conformation.

12
Chapter 5:Alkanes & cycloalkanes
Chapter 5:Alkanes & cycloalkanes 13
 Alkanes
Conformations of Acyclic Alkanes
• A staggered conformation with two larger groups 1800
from each other is called anti.
• A staggered conformation with two larger groups 600
from each other is called gauche.
• The staggered conformations are lower in energy (more
stable) than the eclipsed conformations .
• The relative energies of the individual staggered
conformations depend on their steric strain.
• Steric strain is an increase in energy resulting when
atoms are forced too close to one another.
• Gauche conformations are generally higher in energy
than anti conformations because of steric strain.
Chapter 5:Alkanes & cycloalkanes 14
 Alkanes
Conformations of Acyclic Alkanes

15
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Conformations of Acyclic Alkanes

Chapter 5:Alkanes & cycloalkanes 16

Ring Strain in Cycloalkanes

 ring strain is a type of instability that exists when bonds in a

molecule form angles that are abnormal.
 Ring Strain occurs because the carbons in cycloalkanes are
sp3 hybridized, which means that they do not have the
expected ideal bond angle of 109.5o ; this causes an increase in
the potential energy because of the desire for the carbons to be
at an ideal 109.5o.
 An example of ring strain can be seen in the diagram of
cyclopropane below in which the bond angle is 60o between the
carbons.

Chapter 5:Alkanes & cycloalkanes 17

 Alkanes

Three dimensional structure of some

cycloalkanes 18
Chapter 5:Alkanes & cycloalkanes
Chapter 5:Alkanes & cycloalkanes 19
 Alkanes
Conformations of Cyclohexane
The chair forms of cyclohexane are 7 kcal/mol more stable than the
boat forms.
The boat conformer is destabilized by torsional strain because the
hydrogens on the four carbon atoms in the plane are eclipsed.
Additionally, there is steric strain because two hydrogens at either
end of the boat (1, 4), the “flag pole” hydrogens, are forced close to
each other.

Two views of the boat conformer

of cyclohexane 20

Chapter 5:Alkanes & cycloalkanes

 Alkanes
Conformations of Cyclohexane
 In cyclohexane, three C atoms pucker up and three C atoms
pucker down, alternating around the ring.
Each C in cyclohexane has two different kinds of hydrogens:
(1) axial hydrogens are located above and below the ring
(along a perpendicular axis); (2) equatorial hydrogens are
located in the plane of the ring (around the equator).

21
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Conformations of Cyclohexane

22
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Conformations of Cyclohexane

23
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Introduction to Cycloalkanes—Cyclohexane
• An important conformational change in cyclohexane involves
“ring flipping”. Ring flipping is a two-step process.
• As a result of a ring flip, the up carbons become down carbons,
and the down carbons become up carbons.
• Axial and equatorial H atoms are also interconverted during a
ring flip. Axial H atoms become equatorial H atoms, and
equatorial H atoms become axial H atoms.

Chapter 5:Alkanes & cycloalkanes 24

Conformation Changes in Cyclohexane - "Ring Flips"
Cyclohexane is rapidly rotating between the two most stable
conformations known as the chair conformations in what is called
the "ring flip"

Chapter 5:Alkanes & cycloalkanes 25

 Alkanes
Conformations of Cyclohexane

Ring-flipping interconverts axial

and equatorial hydrogens in
cyclohexane

26
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Conformations of Cyclohexane
Note that the equatorial position has more room than the
axial position, so larger substituents are more stable in
the equatorial position.
There are two possible chair conformations of a
monosubstituted cyclohexane, such as methyl
cyclohexane.

Chapter 5:Alkanes & cycloalkanes 27

 Alkanes
Conformations of Cyclohexane
How to draw the conformers of a substituted cyclohexane:

Chapter 5:Alkanes & cycloalkanes 28

 Alkanes
Conformations of Cyclohexane
How to draw the two conformers of a substituted cyclohexane:

Chapter 5:Alkanes & cycloalkanes 29

 Alkanes
Conformations of Cyclohexane
• Note that the two conformers of cyclohexane are different, so
they are not equally stable.
• Larger axial substituents create unfavorable 1,3-diaxial
interactions, destabilizing a cyclohexane conformer.
• In methylcyclohexane, each unfavorable H,CH3 interaction
destabilizes the conformer by 0.9 kcal/mol, so Conformer 2 is
1.8 kcal/mol less stable than Conformer 1.

Chapter 5:Alkanes & cycloalkanes 30

 Alkanes
Conformations of Cyclohexane

Three dimensional representations for the

two conformers of methylcyclohexane

The two conformers of tert-

butycyclohexane
31
Chapter 5:Alkanes & cycloalkanes
 Alkanes

Disubstituted Cycloalkanes
Each of the cis- and trans- isomers of a disubstituted
cyclohexane, such as 1,4-dimethylcyclohexane, has two
possible chair conformations.

Cis- and trans- isomers are named by adding the prefixes cis
and trans- to the name of the cycloalkane. Thus, the cis-
isomer would be named cis-1,4-dimethylcyclopentane, and the
trans- isomer would be named trans-1,4-dimethylcyclopentane.
All disubstituted cycloalkanes with two groups bonded to
different atoms have cis and trans isomers.
32
Chapter 5:Alkanes & cycloalkanes
 Alkanes
Disubstituted Cycloalkanes

Chapter 5:Alkanes & cycloalkanes 33

 Alkanes
Disubstituted Cycloalkanes

Chapter 5:Alkanes & cycloalkanes 34

 Alkanes
Disubstituted Cycloalkanes
• Conformers 1 and 2 are not equally stable. Because conformer 2
has both larger CH3 groups in the roomier equatorial position, it is
lower in energy.
• The cis isomer has two substituents on the same side, either both
on up bonds or both on down bonds.
• A trans isomer has two substituents on opposite sides, one up
and one down.
• Whether substituents are axial or equatorial depends on the
relative location of the two substituents (on carbons 1,2-, 1,3-, or
1,4-).

Chapter 5:Alkanes & cycloalkanes 35

 Alkanes
Disubstituted Cycloalkanes

Chapter 5:Alkanes & cycloalkanes 36

End Chapter 4

4. Alkanes
and
Cycloalkanes

Chapter 5:Alkanes & cycloalkanes 37