Chapter 4

Organic
Compounds:
Cycloalkanes and Their
Stereochemistry

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 Organic Compounds can be
Open-Chained or Cyclic
We have discussed open-chained compounds up to this point
Many organic compounds contain rings of carbon atoms
e.g.
- Prostaglandins

- Steroids

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 Naming Cycloalkanes
Cycloalkanes are saturated cyclic hydrocarbons
Have the general formula (CnH2n)

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Mono-Substituted Cycloalkanes

A number is not needed.

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Naming Di-substituted Cycloalkanes
1) Find the parent. # of carbons in the ring.
2) Name and number the substituents.

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 Di-Substituted Cycloalkanes

Substituents are stated in alphabetical order.

Preference is to give #1 to first-listed
substituent. But ..
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 Number Substituents to Achieve
Lowest Possible Numbers

If more than one name has the same low number,

choose the name with the next lowest number.
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More Examples with Substituents

List substituents alphabetically using smallest

numbers.

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Examples with Functional Groups

Functional group gets lowest number. Listed

as a suffix. Substituents on amines prefixed
by N.
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 Cis-Trans Isomerism in
Cycloalkanes
Cycloalkanes are less flexible than open-chain
alkanes
Much less conformational freedom in
cycloalkanes

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 Cis-Trans Isomerism in
Cycloalkanes (Continued)
Because of their cyclic structure, cycloalkanes have 2 faces as viewed
edge-on
top face bottom face
- Therefore, isomerism is possible in substituted cycloalkanes
- There are two different 1,2-dimethylcyclopropane isomers

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 Cis-Trans Isomerism in
Cycloalkanes (Continued)
Stereoisomerism
Compounds which have their atoms
connected in the same order but differ in 3-D
orientation

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 CisTrans Isomers

Cistrans isomers result from restricted rotation.

Cyclic structures restrict rotation.

Cis: The substituents are on the same side of the ring.

Trans: The substituents are on opposite sides of the ring. CHE2201, Chapter 4
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Bond Angles in Planar Cyclic Alkanes

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 Stability of Cycloalkanes:
Ring Strain
Rings larger than 3 atoms are not flat
Cyclic molecules can assume nonplanar conformations to
minimize angle strain and torsional strain by ring-puckering
Larger rings have many more possible conformations than
smaller rings and are more difficult to analyze

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 Stability of Cycloalkanes: The
Baeyer Strain Theory
Baeyer (1885): since carbon prefers to have bond angles of
approximately 109, ring sizes other than five and six may be
too strained to exist.
Rings from 3 to 30 Cs do exist but are strained due to bond
bending distortions and steric interactions

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Types of Strain That Contribute to Overall
Energy of a Cycloalkane
Angle strain - expansion or compression of bond angles
away from most stable
Torsional strain - eclipsing of bonds on neighboring atoms
Steric strain - repulsive interactions between nonbonded
atoms in close proximity

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A Staggered Conformer is More Stable
Than an Eclipsed Conformer

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 Angle Strain

tetrahedral bond angle = 109.5 bond angle < 109.5

Angle strain results from poor orbitalorbital overlap because

bonds have to deviate from the ideal (109.5) bond angle.

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 Conformations of
Cycloalkanes
Cyclopropane
3-membered ring must have planar structure
Symmetrical with CCC bond angles of 60
Requires that sp3 based bonds are bent (and weakened)
All C-H bonds are eclipsed

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Cyclopropane

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 Bent Bonds of Cyclopropane
In cyclopropane, the C-C bond is displaced
outward from internuclear axis

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 Cyclobutane
Cyclobutane has less angle strain than cyclopropane but more torsional
strain because of its larger number of ring hydrogens, and their proximity
to each other
Cyclobutane is slightly bent out of plane - one carbon atom is about 25
above
The bend increases angle strain but decreases torsional strain

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 Cyclobutane

Molecules twist out of a planar arrangement

to minimize the number of eclipsed hydrogens.
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 Cyclopentane
Planar cyclopentane would have no angle strain but very high
torsional strain
Actual conformations of cyclopentane are nonplanar,
reducing torsional strain
Four carbon atoms are in a plane
The fifth carbon atom is above or below the plane looks like
an envelope

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 Cyclopentane

Molecules twist out of a planar arrangement to

minimize angle strain and the number of eclipsed hydrogens.
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 Conformations of Cyclohexane
Substituted cyclohexanes occur widely in nature
The cyclohexane ring is free of angle strain and torsional
strain
The conformation has alternating atoms in a common plane
and tetrahedral angles between all carbons
This is called a chair conformation

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Chair Conformer of Cyclohexane

The chair conformer of cyclohexane is completely free of strain.

All bond angles are 111and all adjacent bonds are eclipsed.
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CHE2201, Chapter 4
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 How to Draw Cyclohexane

Step 1 Draw two parallel lines, slanted downward

and slightly offset from each other. This
means that four of the cyclohexane carbons
lie in a plane.

Step 2 Place the topmost carbon atom above and to

the right of the plane of the other four, and
connect bonds.

Step 3 Place the bottommost carbon atom below

and to the left of the plane of the middle four,
and connect the bonds. Note that the bonds
to the bottommost carbon atom a parallel to
the bonds to the topmost carbon.
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Drawing the Chair Conformer

Notice that each equatorial bond is parallel to two ring bonds.

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Axial and Equatorial Bonds

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 Axial and Equatorial Bonds in
Cyclohexane
The chair conformation
has two kinds of positions
for substituents on the
ring: axial positions and
equatorial positions

Chair cyclohexane has six

axial hydrogens
perpendicular to the ring
(parallel to the ring axis)
and six equatorial
hydrogens near the plane
of the ring

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 Axial and Equatorial Positions
Each carbon atom in cyclohexane has one axial and one
equatorial hydrogen
Each face of the ring has three axial and three equatorial
hydrogens in an alternating arrangement

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Conformational Mobility of Cyclohexane

Chair conformations readily interconvert,

resulting in the exchange of axial and
equatorial positions by a ring-flip

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 Ring Flip

Cyclohexane interconverts between two stable chair conformers.

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The Boat Conformer of Cyclohexane

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Steric Strain

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Conformers of Cyclohexane

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Conformers of Monosubstituted
Cyclohexanes

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A Substituent is More Stable in an
Equatorial Position

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1,3-Diaxial Interactions

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 Comparing Conformers

Gauche is 0.9 kcal/mole Axial is 1.8 (2 0.9) kcal/mol

less stable than anti. less stable than equatorial.

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 Relationship to Gauche Butane
Interactions
Gauche butane is less stable than anti butane by 3.8 kJ/mol because of
steric interference between hydrogen atoms on the two methyl groups
The four-carbon fragment of axial methylcyclohexane and gauche butane
have the same steric interaction
In general, equatorial positions give the more stable isomer

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 1,3-Diaxial Interactions
Difference between axial and equatorial conformers is due to
steric strain caused by 1,3-diaxial interactions
Hydrogen atoms of the axial methyl group on C1 are too close
to the axial hydrogens three carbons away on C3 and C5,
resulting in 7.6 kJ/mol of steric strain

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Steric Strain in Monosubstituted
Cyclohexanes

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 Conformations of
Monosubstituted Cyclohexanes
Cyclohexane ring rapidly flips between chair conformations at
room temp.
Two conformations of monosubstituted cyclohexane arent
equally stable.
The equatorial conformer of methyl cyclohexane is more
stable than the axial by 7.6 kJ/mol

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 The larger the substituent,
the more the equatorial-substituted
conformer will be favored.

DG = - RT ln Keq where R = 8.314 J.K-1mol-1

The Only Difference Between Starch and Cotton
is an Equatorial Bond Versus an Axial Bond

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 Conformations of
Disubstituted Cylcohexanes
In disubstituted cyclohexanes the steric effects of both substituents must be taken
into account in both conformations
There are two isomers of 1,2-dimethylcyclohexane. cis and trans
In the cis isomer, both methyl groups are on the same face of the ring, and the
compound can exist in two chair conformations
Consider the sum of all interactions
In cis-1,2, both conformations are equal in energy

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 Trans-1,2-Dimethylcyclohexane
Methyl groups are on opposite faces of the ring
One trans conformation has both methyl groups equatorial and only a gauche
butane interaction between methyls (3.8 kJ/mol) and no 1,3-diaxial interactions
The ring-flipped conformation has both methyl groups axial with four 1,3-diaxial
interactions
Steric strain of 4 3.8 kJ/mol = 15.2 kJ/mol makes the diaxial conformation 11.4
kJ/mol less favorable than the diequatorial conformation
trans-1,2-dimethylcyclohexane will exist almost exclusively (>99%) in the
diequatorial conformation

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cis-1-tert-butyl-3-methylcyclohexane

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trans-1-tert-butyl-3-methylcyclohexane

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Cis and Trans Isomers

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Each Disubstituted Isomer Has
Two Chair Conformers

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 This Chair Conformer
Has Four Diaxial Interactions

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Axial and Equatorial Relationships
in Disubstituted Cyclohexanes

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 Conformations of Polycyclic Molecules
Decalin consists of two cyclohexane rings joined to share two
carbon atoms (the bridgehead carbons, C1 and C6) and a
common bond
Two isomeric forms of decalin: trans fused or cis fused
In cis-decalin hydrogen atoms at the bridgehead carbons are
on the same face of the rings
In trans-decalin, the bridgehead hydrogens are on opposite
faces
Both compounds can be represented using chair cyclohexane
conformations
Flips and rotations do not interconvert cis and trans

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 Rings Can Be
Trans Fused or Cis Fused

trans-decalin cis-decalin

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The Steroid Ring System

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