Organic Chemistry
Fourth Edition
David Klein
Chapter 4
Alkanes and Cycloalkanes
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4.1 Alkanes
• Hydrocarbons – composed of hydrogen and carbon
• Hydrocarbons are saturated or unsaturated
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4.3 Constitutional Isomers / Introduction
• Isomers
o different structures, same molecular formula
• Constitutional Isomers
o different connectivity of atoms
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4.3 Constitutional Isomers / Many
Isomers Possible
• As the number of carbon Table 4.4 Number of Constitutional
atoms increases, the Isomers for Various Alkanes
Molecular Formula Number of Constitutional
number of constitutional Isomers
isomers increases C3H8 1
C4H10 2
C5H12 3
C6H14 5
C7H16 9
C8H18 18
C9H20 35
C10H22 75
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4.3 Constitutional Isomers / How to
Recognize Them
• Be able to recognize different structures as either being isomers
or being the same compound.
o You can test if structures are the same in two ways:
1. Flip one of the molecules in 3-D space and rotate around its single
bonds until it is superimposable on the other molecule
2. Name them. If they have the same IUPAC name, they are the
same compound
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4.3 Constitutional Isomers / Practice
180° rotation along the C3—C4 bond would make it more obvious
these two compounds are the same
• Following IUPAC rules for naming yields the same name as
well
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SkillBuilder 4.6
Identify whether the following two drawings represent
constitutional isomers or whether they are simply different
representations of the same compound:
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4.4 Relative Stability of Isomeric
Alkanes
• Relative stability of isomers can be determined by measuring
heat of combustion
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4.5 Sources and Uses of Alkanes /
Summary
• Various components of petroleum are separated by distillation
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4.5 Sources and Uses of Alkanes /
Examples
• Gasoline is a mixture of straight, branched, and aromatic
hydrocarbons (5-12 carbons in size)
• Large alkanes can be broken down into smaller molecules by
cracking
• Straight chain alkanes can be converted into branched alkanes
and aromatic compounds through reforming
• After using these processes, the yield of gasoline is about 47%
rather than 19%
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4.6 Drawing Newman Projections /
Introduction
• Single bonds rotate, resulting in multiple 3-D shapes, called
conformations
• 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
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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
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4.6 Drawing Newman Projections /
Example
• Another example
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SkillBuilder 4.7
Draw a Newman projection of the following compound, as viewed
from the angle indicated:
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4.7 Conformational Analysis
• The angle between atoms on adjacent carbons is called a
dihedral angle or torsional angle. It is 60° in the molecule
below
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4.7 Conformational Analysis – Ethane /
Introduction
• Staggered conformations are more stable (lower in energy)
than eclipsed conformations
• The difference in energy between these conformations is due to
torsional strain. Here, the difference in energy is 12 kJ/mol
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4.7 Conformational Analysis – Ethane /
Graphical Representation
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4.7 Conformational Analysis – Ethane /
Energetics
• It’s possible the eclipsed conformation is 12 kJ/mol less stable
because of electron pair repulsion between the eclipsing bonds
(4 kJ/mol for each eclipsing interaction)
• With a difference of 12 kJ/mol in stability, at room temperature,
99% of the molecules will be in the staggered conformation
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4.7 Conformational Analysis – Ethane /
MO Perspective
• The difference in energy can also be rationalized by the
presence of stabilizing interactions in the staggered
conformation
• A filled, bonding MO has side-on-side overlap with an empty
anti-bonding MO.
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4.7 Conformational Analysis –
Propane / Introduction
• The analysis of torsional strain for propane (below) is similar
to ethane
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4.7 Conformational Analysis –
Propane / Energetics
• The barrier to rotation for propane is 14 kJ/mol, which is 2
kJ/mol more than for ethane
• If each H-----H eclipsing interaction costs 4 kJ/mol of stability,
that total can be subtracted from the total 14 kJ/mol to calculate
the contribution of a CH3-----H eclipsing interaction
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4.8 Conformational Analysis – Butane /
Introduction
• The analysis of torsional strain for butane shows more
variation
• Note that there are
multiple staggered
conformations and
multiple eclipsed
conformations
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4.8 Conformational Analysis – Butane /
Steric Strain
• The stability of the different staggered conformations differs by
3.8 kJ/mol
• When the methyl groups are gauche to one another, there is
steric strain, and a higher energy conformation than when they
are anti to one another
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4.8 Conformational Analysis – Butane /
Energetics
• The highest energy conformation for butane results when
the methyl groups eclipse one another
• Each CH3-----CH3 eclipsing interaction accounts for
11 kJ/mol of energy (torsional and steric strain).
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4.8 Conformational Analysis – Butane /
Summary
• The energy costs for eclipsing and gauche interactions can be
used to approximate the energy of a given conformation
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4.8 Conformational Analysis – Butane /
Summary
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SkillBuilder 4.8
Consider the following compound:
(a) Rotating only the C3-C4 bond, identify the lowest energy
conformation.
(b) Rotating only the C3-C4 bond, identify the highest energy
conformation.
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4.9 Cycloalkanes / Angle and
Torsional Strain
• Ideal bond angles for sp3 hybridized carbon is 109.5°.
• If cycloalkanes were flat, each carbon in the ring would
experience angle strain.
• Also, if a ring was flat, then all the C—C bonds would be in
eclipsing rotamers... causing considerable torsional strain.
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4.9 Cycloalkanes / Ring Size
The combustion data for cycloalkanes shows that a 6-member ring
is the most stable ring size (it is lowest in energy per CH2 group)
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4.9 Cyclobutane
• Cyclobutane is 27 kJ/mol less stable than cyclohexane per CH2
group.
1. Angle strain bond angles of 88°
2. Slight torsional strain results because adjacent C—H bonds are
neither fully eclipsed nor fully staggered
Puckered conformation has less torsional strain than a flat
conformation
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4.9 Cyclopentane
• Cyclopentane is only 5 kJ/mol less stable than cyclohexane per
CH2 group
1. Very little angle strain – bond angles are nearly 109.5°
2. Slight torsional strain – adopts an envelope conformation to
avoid most of it
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4.10 Conformations of Cyclohexane /
Many Conformations
• Cyclohexane can adopt a variety of conformations, but it is the
chair conformation that is the most stable
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4.10 Conformations of Cyclohexane /
Chair Conformation
• Cyclohexane has no ring strain in a chair conformation
1. No angle strain – bond angles are approximately 109.5°
2. No torsional strain – all adjacent
The other possible conformations of cyclohexane have some
amount of angle and/or torsional strain (i.e. ring strain)
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4.11 Drawing Chair Conformations /
Five Steps
• Drawing a chair conformation (SkillBuilder 4.9).
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4.11 Drawing Chair Conformations /
Check for Correctness
• If drawn correctly, the chair should contain 3 sets of parallel
lines
• Each carbon in the ring has two substituents: one is in an axial
position and the other in an equatorial position
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4.11 Drawing Chair Conformations /
Axial vs Equatorial
• Adding the axial substituents is easy, as they point straight up
and down, alternating around the ring.
• The equatorial groups are drawn off the ring and they run
parallel to the lines in the chair
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4.12 Monosubstituted Cyclohexane /
Introduction
• When cyclohexane has one substituent, there are two possible
chair conformations
• Ring flipping occurs by rotation of all the C—C bonds in the
ring. Axial substituents become equatorial and vice versa.
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4.12 Monosubstituted Cyclohexane /
Equatorial is More Stable
• Consider methylcyclohexane. The chair conformation where the
methyl group is equatorial is the more stable chair
• At room temperature, methylcyclohexane will be in the more
stable chair 95% of the time.
• In the axial position, the methyl group causes steric
interactions that destabilize the conformation.
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4.12 Monosubstituted Cyclohexane /
1,3-Diaxial Interactions
• The steric strain from a substituent being in the axial position is
the result of 1,3-diaxial interactions
• The 1,3-diaxial interactions are
actually gauche interactions, which
are not present when the methyl
group is equatorial
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4.12 Monosubstituted Cyclohexane /
Summary
• Larger groups will cause more steric crowding in the axial
position.
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4.13 Disubstituted Cyclohexane /
Introduction
• With multiple substituents, solid or dashed wedges are used to
show positioning of the groups on the ring
• Realize the Cl group is up in both possible chair conformations,
and the methyl group is down
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SkillBuilder 4.12
Draw both chair conformations of the following compound:
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SkillBuilder 4.12
Draw the more stable chair conformation of the following
compound:
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4.14 cis-trans Stereoisomerism /
Examples
• When naming a disubstituted cycloalkane, use the prefix cis when
there are two groups on the same side of the ring, and trans when two
substituents are on opposite sides of a ring
• These two compounds are stereoisomers. Since they are 6-member
rings, they are best represented as chair conformations
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4.14 cis-trans Stereoisomerism /
Equilibrium
• Each compound exists as two equilibrating chairs, spending
more time in the more stable chair conformation
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4.15 Polycyclic Systems / Decalin
• Decalin is two 6-member rings fused together
• The decalin substructure is
found in many naturally
occurring compounds, such as
steroids
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4.15 Polycyclic Systems / Additional
Examples
• There are many important structures that result when more than
one ring is fused together (recall bicycloalkanes)
• Camphor and camphene are fragrant natural products isolated
from evergreens
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4.15 Polycyclic Systems / Diamond
• The structure of diamond is a network of 6-membered
rings, fused together.
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