Organic Chemistry

Fourth Edition
David Klein

Chapter 4

Alkanes and Cycloalkanes

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Copyright ©2021 John Wiley & Sons, Inc.

4.1 Alkanes

• Hydrocarbons – composed of hydrogen and carbon

• Hydrocarbons are saturated or unsaturated

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 IUPAC Names of Unbranched Alkanes

Latin or Greek prefix for number of carbons + ane suffix

CnH2n+2
4.2 IUPAC Nomenclature – Alkanes

• Found in separate set of slides

Copyright ©2021 John Wiley & Sons, Inc. 4

Skip and will not be covered in the exams:
- Naming Bicyclic Compounds (page 148)
- Relative Stability of Isomeric Alkanes
(Section 4.4, page 153)
- Sources and Uses of Alkanes (Section 4.5
page 154)
 Constitutional Isomers
• How can you recognize if two molecules are isomers or
the same?

3-methylpentane 3-methylpentane

You can test if they are identical using two methods:

1. Flip one of the molecules in 3D space and rotate around
its single bonds until it is superimposable on the other
molecule.
2. Name them. If they have the same name, they
are identical.
Conformations are different spatial arrangements
of the same molecule that are generated by
rotation about single bonds.
4.6 Drawing Newman Projections /
Introduction
• There are various ways to represent the 3-D shape of a
compound

• Newman projections are ideal for comparing the relative

stability of possible conformations resulting from single bond
rotation
Copyright ©2021 John Wiley & Sons, Inc. 8
4.6 Drawing Newman Projections /
Looking Down a Bond
• A Newman projection is the perspective of looking straight
down a particular C—C bond
• Show the front carbon as a point and the back carbon as a large
circle behind it

• Practice with SkillBuilder 4.7 – Drawing Newman Projections.

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4.7 Conformational Analysis – Ethane

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4.7 Conformational Analysis – Propane

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Rotational Conformations –
Butane’s Conformations

The values in
Table 4.6 can be
used to predict
relative energies
for various
conformations.
4.8 Conformational Analysis – Butane

Copyright ©2021 John Wiley & Sons, Inc. 13

 4.9 Cyclic Alkanes
• Carbon atoms in alkanes are sp3 hybridized.
• If cycloalkanes were flat, what bond angles would be
expected?

Angle Strain: the increase in energy associated

with a bond angle that deviates from the
preferred angle of 109.5°
 Cycloalkanes
Heats of combustion: examine the stability of each compound by comparing
the heat of combustion of each per CH2 unit.

Which ring has the most strain? Which ring has the least strain?

To optimize the bond angles, most cycloalkanes are NOT flat in their
most stable conformation. Larger cycloalkanes have
conformations that minimize the total energy.
 Cycloalkanes
What factors affect stability?

Ring Strain: the term applied to the strain of cyclic systems. It is composed of
Angle strain and Torsional strain.

Angle Strain: the increase in energy associated with a bond angle that deviates
from the preferred angle of 109.5°

Torsional Strain: occurs when there are eclipsed interactions (lack of stabilizing
orbital overlap).

Steric Strain: results from the electron-electron repulsion of atoms (or groups of
atoms/bulky groups) that are too close together.
 Cyclopropane
• Cyclopropane is 44 kJ/mol less
stable than cyclohexane per
CH2 group. It is highly strained
and very reactive due to:
1. Angle strain:
• Bond angles of 60° cause
electron pair repulsion in
adjacent bonds
• Inefficient sigma bond overlap
2. Torsional strain:
• Eclipsing C–H bonds all the way
around the ring—see Newman
projection
 Cyclobutane
• Cyclobutane is 27 kJ/mol less stable than cyclohexane per CH2 group. It is
also strained and reactive:
1. Angle strain results from bond angles of 88°, although it is not as severe
as the 60° angles in cyclopropane.
2. Slight torsional strain results because adjacent C–H bonds are neither
fully eclipsed nor fully staggered.

• Why does it adopt a puckered conformation?

Nonplanar conformation relieves some torsional strain
 Cyclopentane
• Cyclopentane is only 5 kJ/mol less stable than
cyclohexane per CH2 group:

1. Angles are close to the optimal value. – no angle strain

2. Minimal torsional strain in the structure.
 Cyclohexane
• Cyclohexane is considered to have ZERO ring strain in
its optimal conformation, the CHAIR conformation:

1. No angle strain—angles must be 109.5°.

2. No torsional strain—all adjacent C–H bonds must be
staggered.
Chair is the most stable conformation of cyclohexane
 Cyclohexane
• Other conformations of hexane exist but are a bit less
stable. Consider the BOAT conformation.

1. No angle strain—angles are 109.5°.

2. Torsional strain:
• has two sources of torsional strain
3. Steric strain—flagpole interactions.
 Generalization

The chair conformation of cyclohexane is the

most stable conformation and derivatives of
cyclohexane almost always exist in the chair
conformation.

*It is important to draw the chair conformation

precisely!
 Conformational Inversion: Ring Flip

•chair-chair interconversion (ring-flipping)

•rapid process with a half life of 10-5 s at 25 ºC
 Conformational Analysis of
Monosubstituted Cyclohexanes

most stable conformation is chair

substituent is more stable when equatorial

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 Methylcyclohexane

CH3

CH3

5% 95%

Chair chair interconversion occurs, but at any instant

95% of the molecules have their methyl group
equatorial.

Axial methyl group is more crowded than an equatorial

one.
 Monosubstituted Cyclohexane

5% 95%
Source of crowding is close approach to axial hydrogens on same side of
ring.
Crowding is called a "1,3-diaxial interaction" and is a type of steric strain.
The numbers “1,3” describes the distance between the substituents and
each of the H’s.
 Monosubstituted Cyclohexane
• 1,3-diaxial interactions are equivalent to gauche
interactions.

• When the substituent is in the equatorial position, it is

equivalent to an anti interaction.
 Fluorocyclohexane
F

40% 60%

Crowding is less pronounced with a "small" substituent

such as fluorine.
 tert-Butylcyclohexane

C(CH3)3

C(CH3)3

Less than 0.01% Greater than 99.99%

Crowding is more pronounced with a "bulky" substituent such

as tert-butyl.

tert-Butyl is highly branched.

4.12 Monosubstituted Cyclohexane /
Summary
• Larger groups will cause more steric crowding in the axial
position.

Table 4.8 1,3-Diaxial Interactions for Several Common Substituents

Substituent 1,3-Diaxial Interactions (kJ/mol) Equatorial-Axial Ratio (At Equilibrium)
–Cl 2.0 70 : 30

–OH 4.2 83 : 17

–CH3 7.6 95 : 5

–CH2CH3 8.0 96 : 4

–CH(CH3)2 9.2 97 : 3

–C(CH3)3 22.8 9999 : 1

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 Disubstituted Cycloalkanes:
cis-trans Stereoisomers

Stereoisomers are isomers that have

same molecular formula but different
arrangement of atoms in space
 Isomers

Constitutional isomers Stereoisomers

 1,2-Dimethylcyclopropane

There are two stereoisomers of 1,2-dimethylcyclopropane.

They differ in spatial arrangement of atoms.

 1,2-Dimethylcyclopropane

cis
trans
cis-1,2-Dimethylcyclopropane has methyl groups
on same side of ring.
trans-1,2-Dimethylcyclopropane has methyl groups
on opposite sides.
Which is the more stable (lower energy) isomer?

cis trans
Steric strain makes cis stereoisomer less stable
than trans.
Conformational Analysis of Disubstituted Cyclohexanes

1,4-Dimethylcyclohexane Stereoisomers

H3C CH3 H3C H

H H H CH3
cis trans

less stable more stable

Trans stereoisomer is more stable than cis, but

methyl groups are too far apart to crowd each other.
 Compound Orientation

cis-1,4-dimethyl ax-eq
trans-1,4-dimethyl eq-eq*

*trans is the more stable stereoisomer since it can adopt

a chair conformation in which both methyl groups are in
the equatorial position
 1,3-Dimethylcyclohexane Stereoisomers

CH3 CH3

H H H 3C H
H3C H
cis trans

more stable less stable

cis-1,3 is more stable than trans.

 CH3
Conformational analysis of
cis-1,3-dimethylcyclohexane H H
H3C

CH3
CH3
H
H 3C CH3

H
H H
Two conformations are not equivalent; most stable
conformation has both methyl groups equatorial.
 CH3
Conformational analysis of
trans-1,3-dimethylcyclohexaneH3C H
H

CH3
H
H
H CH3

H 3C
H3C H
Two equivalent conformations; each has one axial
and one equatorial methyl group.
 Compound Orientation

cis-1,3-dimethyl eq-eq*
trans-1,3-dimethyl ax-eq

*cis is the more stable stereoisomer since it can

adopt a chair conformation in which both methyl
groups are in the equatorial position