CHAPTER 4

Cyclic Alkanes
4-1 Names and Physical Properties of Cycloalkanes
The names of the cycloalkanes follow IUPAC rules.
The general formula of a cyclealkane is: CnH2n.

To name a
cycloalkane,
prefix the alkane
name with
“cyclo”.

Numbering a cycloalkane ring is necessary only when there is

more than one substituent. In nonsubstituted cycloalkanes, the
attached carbon is numbered number 1.
Use the lowest possible numbering sequence for polysubstituted
cycloalkanes. If two identical numbering sequences are possible,
use alphabetical precedence.
Substituted cycloalkanes are sometimes named as cycloalkyl
derivatives. The smaller unit is generally treated as a substituent
to the larger unit.
•Propylcyclopentane (not cyclopentylpropane)
•Cyclohexyloctane (not octylcyclohexane)
Disubstituted cycloalkanes possess stereoisomers.
Disubstituted cycloalkanes having substituents on different
carbons possess cis (same side) / trans (opposite side) isomers.
Cis/trans isomers are examples of stereoisomers. These are non-
superimposable molecules having the same molecular formula
and connectivity.
Conformers are also stereoisomers but can be interconverted by
rotations about C-C bonds.
The properties of the cycloalkanes differ from those
of their straight chain analogs.
Cycloalkanes have higher boiling points, melting points, and
densities than their straight-chain analogs.
•Increased London forces are due to more rigid and
symmetric cyclic systems.
The smaller cycloalkanes with an odd number of carbon atoms
have lower melting points than expected compared to
cycloalkanes with an even number of carbon atoms. This is
attributed to crystal-packing forces between the two types of
cycloalkanes.
4-2 Ring Strain and the Structure of Cycloalkanes
The heats of combustion of the cycloalkanes reveal
the presence of ring strain.
Cyclopropane (60o) and cyclobutane (90o) possess C-C-C bond
angles significantly different from 109.5o and are strained. This is
termed ring strain.
Cyclohexane has essentially no ring strain.
The ring strain in cycloalkanes can be estimated by comparing the
theoretical heats of combustion to the measured heats of
combustion:

Four groupings:
Small (3,4)
Common (5,6,7)
Medium (8-12)
Large (>12)
Strain affects the structures and
conformational function of the smaller
cycloalkanes.
Cyclopropane:
All of the methylene hydrogens are eclipsed
(eclipsing strain)
There is no available bond rotation to
achieve a staggered conformation.
The C-C-C bond angles are 60o, far from the
unstrained value of 109.5o.
The C-C bond energy is about 65 kcal mol-1
The ring of cyclopropane is easily opened,
for instance by hydrogenation:
Cyclobutane:
Cyclobutane is puckered with a bending angle of about 26o.

The bent cyclobutane molecules flips rapidly from one puckered

conformation to another.
The puckered conformation partially relieves the strain caused by the
otherwise eight eclipsing hydrogens.
The C-C bond strength is about 63 kcal mol-1.
Cyclobutane also undergoes ring opening but is less reactive than
cyclopropane.
Cyclopentane:
A regular pentagon has interior angles of 108o (close to
tetrahedral). However, cyclopentane is puckered, not planar.

The puckering in cyclopentane relieves some of the hydrogen

eclipsing, however, it somewhat increases the bond strain.
The observed structures balances these two opposing factors
to achieve a structure of lowest energy.
There are two puckered conformations, the envelope and the
half chair. There is little energy difference between them and
they rapidly interconvert.
4-3 Cyclohexane: A Strain-Free Cycloalkane
The chair conformation of cyclohexane is strain
free.
Cyclohexane has several conformations, one of which is called the
chair conformation.

In the chair conformation, eclipsing of the hydrogens is

completely prevented, the C-C-C bond angles are very nearly
tetrahedral, and the molecule is nearly strain free.
Cyclohexane also has several less stable
conformations.
A second, less stable conformation of cyclohexane is the boat
form, which is less stable than the chair form by 6.9 kcal mol-1.

The higher energy is due to the eclipsing of the 8 hydrogens at

the base of the boat, and the transannular (steric crowding across
a ring) strain between the two hydrogens in the boat framework.
The boat form of cyclohexane is flexible and
actually represents a transition state between
two slightly more stable twist-boat (or skew-
boat) conformations.
The stabilization of the twist forms to the boat
form is about 1.4 kcal mol-1,
The activation energy for interconversion of the
chair form and boat forms is 10.8 kcal mol-1.
Normally cyclohexane exists primarily as the
chair confomer with very small amounts of the
twist boat form and no actual boat form.
Cyclohexane has axial and equatorial hydrogen
atoms.
In the chair form, cyclohexane has two types of hydrogens:
•Axial 6 H parallel to the principle molecular axis
•Equitorial 6 H perpendicular to the principle molecular axis
Two draw chair cyclohexanes, follow these steps:

1.) Draw the carbon chair. 2.) Add the axial hydrogens.

3.) Draw the C1 and C4 equitorial hydrogens.

4.) Draw the remaining equatorial hydrogens.

Conformational flipping interconverts axial and
equatorial hydrogens.
Starting with a chair form having C1 down and C4 up, the boat
form can be reached by flipping C1 up. If in returning to the chair
form, C4 is flipped down, rather than C1, the effect is to
interconvert the axial and equitorial hydrogens on the
cyclohexane molecule:

The energy of activation for this conversion is 10.8 kcal mol-1

which is very low, and at room temperature this interconversion
occurs approximately 100,000 times per second.
When substituents replace one or more hydrogens, one conformer
may be more stable than the other, affecting both
stereochemistry and reactivity.
4-4 Substituted Cyclohexanes
Axial and equatorial methylcyclohexanes are not
equivalent in energy.
In methylcyclohexane, the conformer having the methyl group in
an equatorial position is more stable by about 1.7 kcal mol-1.

The 1,3-diaxial interaction is the same as the result in the gauche

conformation of butane.
Newman projections more clearly show the unfavorable 1,3-
diaxial interactions:

Energy differences for other monosubstituted cyclohexanes:

Substituents compete for equatorial positions.
Consider the following disubstituted cycloalkanes:

Equal energies Equal energies

Diequatorial more stable Large group equitorial more stable.

4-5 Larger Cycloalkanes
Rings larger that cyclohexane have more strain.
•Bond angle distortion
•Partial eclipsing of hydrogens
•Transannular steric repulsions
Medium sized rings adopt several conformations that are very
close in energies, such as cyclodecane:

Strain energy of 14 kcal mol-1.

Large-sized cycloalkanes such as cyclotetradecane are able to

adopt staggered and all-anti conformations similar to straight
chain alkanes and are essentially strain free. Attachment of
substituents, however, usually introduces some strain.
4-5 Polycyclic Alkanes
Polycyclic alkanes may contain fused or bridged
rings.
The fused system, decalin, can be compared to the disubstituted
molecule, 1,2-diethylcyclohexane.

Decalin is an example of a fused bicyclic

ring system.
The shared carbon atoms are called
ring-fusion carbons.
Groups attached to the ring-fusion
carbons are called ring-fusion
substituents.
A second example of ring fusion, norborane, can be compared to
the compound, cis-1,3-dimethylcyclopentane:

Norborane is an example of a bridged bicyclic ring system.

Two non-adjacent carbon atoms belong to both rings and are
called bridgehead carbon atoms.
Bicyclic ring systems can be either cis- or trans-fused:
Do hydrocarbons have strain limits?
Many interesting molecules have been synthesized to examine the
limits of strain in hydrocarbon bonds:

66.5 kcal mol-1

129 kcal mol-1

Unknown

166 kcal mol-1

61 kcal mol-1
4-6 Carbocyclic Products in Nature
Natural products are organic compounds produced by living
organisms.
Four classification schemes are used for natural products:
•Chemical structure
•Physiological activity
•Organism or plant specificity (taxonomy)
•Biochemical origin
Terpenes and steroids have received much attention from organic
chemists.
Terpenes are constructed in plants from isoprene
units.
Terpenes are volatile compounds usually containing 10
(monoterpenes), 15 (sesquiterpenes) , or 20 (ditepenes) carbon
atoms.
Terpenes are synthesized in plants by linking two or more 5
carbon fragments called isoprene (2-methyl-1,3-butadiene).
Examples of terpenes include:
• Chrysanthemic acid
Natural insecticide
• Grandisol
Boll weevil sex attractant
• Menthol
Peppermint oil
• Camphor
Camphor Tree
• -Cadinene
Juniper and ceder trees
• Taxol
Pacific yew tree,
Anti-tumor drug
Steroids are tetracyclic natural products with
powerful physiological activities.
Steroids frequently function as hormones, or regulators of
biological activities.
Synthetic steroids are used in the treatment of cancer, arthritis,
allergies, and in birth control.
Steroids consist of 3 fused cyclohexane rings fused to a
cyclopentane ring. The ring junctions are usually trans.

The rings are labeled A,B,C,D.

Methyl groups at C10 and C13 and
oxygen at C3 and C17 are
common.
Due to the trans ring fusion, an all
chair conformation is assumed
with the ring junction hydrogens
and methyl groups in axial
positions.
Groups attached above the plane of the steroid ring structure are
termed  while those below are termed .
Axial methyl groups are referred to as angular methyls because
they sharply protrude from the framework.
Three common steroids are:

Cholesterol is present in almost all human and animal tissue. It can

precipitate in the arteries, causing arteriosclerosis and heart disease. It
is a precursor for bile acids and steroid hormones.
Cholic acid is a bile acid involved in emulsification, digestion and
absorption of fats.
Cortisone is involved in regulating electrolyte and water balance in the
body, as well as carbohydrate and protein metabolism.
Sex hormones are divided into three types: Male sex hormones
(androgens), female sex hormones (estrogens), and pregnancy
hormones (progestins).
Examples of each are

•Testosterone
Produced by testes. Responsible for masculine characteristics.
•Estradiol
Responsible for secondary female characteristics and participates
in regulation of menstrual cycle.
•Progesterone:
Responsible for preparing the uterus for the implantation of an
egg.
4 Important Concepts

1. Cycloalkane Nomenclature: Derived from that

of the straight chain alkanes.
2. Cycloalkanes exist as two isomers unless
they are 1,1-disubstituted. Cis: both substituents on
the same face of the molecule; Trans: substituents on
opposite faces. These are examples of stereoisomers.
3. Cycloalkanes may be strained.
• Bond angle strain: Distortion about tetrahedral
carbon.
• Torsional strain: Inability to adopt staggered
conformations.
• Transannular strain: Steric repulsion between atoms
across a ring.
4 Important Concepts

4. Bond angle strain in small molecules:

Formation of bent bonds.
5. Strain in cycloalkanes other than
cyclopropane: Deviations from planarity.
6. Ring Strain in Small Cycloalkanes: Reactions
result in ring opening.
7. Deviations from Planarity: Lead to
conformationally mobile structures. For cyclohexane,
chair, boat, and twist-boat conformations lead to an
almost strain-free structure.
8. Chair Cyclohexane: Axial and equatorial
hydrogens are rapidly interconverted at room
temperature by chair-chair interconversion (activation
energy: 10.8 kcal/mol)
4 Important Concepts

9. Monosubstituted Cyclohexanes: Chair-chair

interconversion Go is substituent dependent. Axial
substituents exhibit 1,3-diaxial interactions.
10. More Highly Substituted Cyclohexanes:
Substitutent effects are often additive. Bulkiest
substituents most likely to be equatorial.\
11. Completely Strain Free Cycloalkanes: Adopt
an all-anti conformation and lack transannular
interactions.
12. Bicyclic Ring Systems: May be fused or bridged.
Fusion may be cis or trans.
13. Natural Products: Classified by structure,
physiological activity, taxonomy, and biochemical
origin.
4 Important Concepts

14. Terpenes: Made of of 5 carbon isoprene units.

15. Steroids: Three angularly fused cyclohexanes
(A,B,C rings) attached to a cyclopentane D ring.
• Beta substituents: above the molecular plane.
• Alpha substituents: below the molecular plane.
16. Sex Hormones: Steroids controlling physiological
functions, including fertility.