Chapter - 4 Alkanes and Cycloalkanes - HJM

4.
1 Alkanes
Hydrocarbons are compounds that are only
composed of hydrogen and carbon.
Which of the molecules above is saturated

with hydrogen atoms?
Copyright 2012 John Wiley &
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4 -1
Klein, Organic Chemistry 1e
4.1 Alkanes
Saturated hydrocarbons do NOT contain any
pi bonds.
When communicating about molecules, each

unique molecule must have a unique name.
The suffix ane is used for saturated hydrocarbons.
How are the above hydrocarbons different?

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4 -2
4.2 Naming Compounds

Alkanes
Many organic compounds have common
names.
Some common names have been used for

hundreds of years and are still frequently
4 -3
used.
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Alkanes
In 1892, as the number of known molecules
grew, chemists decided that a SYSTEMATIC
naming system was needed.
IUPAC (International Union of Pure and Applied
Chemistry) system
We can learn the IUPAC system instead of

having to memorize a common name for
every molecule.

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4 -4

Alkanes
Finding The Parent Chain
The IUPAC system:
1. Find the parent chain, the longest consecutive

chain of carbons.

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Alkanes
1. Find the parent chain, the longest

consecutive chain of carbons.
Use Table 4.1 to look up the prefix that corresponds

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4 -6

Alkanes
Use Table 4.1 to look up the prefix that corresponds

to the number of
carbons in the parent
chain.
4 -7

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Alkanes
Finding The Parent
Chain
1. Find the parent chain,
the longest
consecutive chain of
carbons.

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4 -8
If the parent chain has 9

carbons, the parent
name is nonane.
It would be smart to
memorize the names for
chains 1 to 10 carbons in
length.
Use Table 4.1 to look up
the prefix that
corresponds with the
number of carbons in
the parent chain.

Alkanes

If there is more than one possible parent chain,

choose the one with the most substituents (side
chains) attached .
. What is the parent

name for this
4 -9
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Alkanes Finding The Parent
Chain

If the parent chain is cyclic (a ring of carbons),

add the prefix, cyclo to the beginning of the
parent name.
-10
. Practice with 4SKILLBUILDER
4.1.
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Alkanes

Give the parent name for the following

compounds.
The parent name may NOT include carbons that

4 -11
are both in a ring and outside a ring. Find the

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Alkanes
Identifying Substituents
2. Identify and name substituents (side

chains).
Count the number of carbons in each side group,

and use the terms from Table 4.2 to name the
substituents.
The terms in Table 4.2 are the same as those in
4 -12
Sons, Inc. Table 4.1, except they end in yl instead of

Alkanes

chains).
A ring can be either a parent chain or a

substituent depending on the number of
carbons.

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4 -13

Alkanes

chains).
Name the substituents in the following

molecules.

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4 -14

Alkanes

chains).
Some substituents have complex branches.
How many carbons are in the highlighted

substituent above?
4 -15
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Alkanes

chains).
For substituents with complex branches:

4
2
1
1.
Number the longest carbon chain WITHIN the

substituent. Start with the carbon directly attached to
the main chain.
2. Name the substituent (in this case butyl).
Copyright
Wiley & and number
3.2012 John
Name
the substituentsKlein,
sideOrganic
group
(in this1e
4 -16
Chemistry
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Alkanes

chains).
Some branched substituents have COMMON

names that you may want to memorize, because
they are used more frequently than their IUPAC
names.

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4 -17

Alkanes

chains).

names.

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4 -18

Alkanes

chains).

names.

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Alkanes
Numbering the Parent Chain
3. Number in sequence the consecutive

carbons in the parent chain and assign a
locant to each substituent.
The number or LOCANT is used to communicate

where each substituent is attached to the parent
chain.
. The molecules above are isomers, and they

4 -20
have the same parent name. Their full name
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Alkanes
Guidelines to follow when numbering the

parent chain:
1. If ONE substituent is present, number the parent

chain so that the substituent has the lowest
number possible.

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Alkanes

parent chain:
2. When multiple substituents are present, number

the parent chain to give the first substituent the
lowest number possible.

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Alkanes

parent chain:
3. If there is a tie, then number the parent chain so

that the second locant gets the lowest number
possible.

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4 -23

Alkanes

parent chain:
The same rules apply for cycloalkanes.

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4 -24

Alkanes
The
Entire
Name
Assembling
Guidelines to follow
when
numbering
the
parent chain
4. To assemble the complete name, assign a locant

to each substituent, and list them before the
parent chain name in alphabetical order
5. A prefix is used (di, tri, terta, penta, etc.) if
multiple substituents are identical
6. Prefixes are NOT used for alphabetical purposes,
except for the prefix iso
Name the cycloalkanes:

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Alkanes Summary
1. Identify the parent chain, the longest
chains).
3. Number the parent chain and assign a
locant (and prefix if necessary) to each
substituent.
Give the first substituent the lowest number

possible.
4. List the numbered substituents before the

parent chain name in alphabetical order.
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4 -26
Ignore prefixes
(except iso) when
ordering

Alkanes Summary
Name the following molecule.
Draw the bond-line representation for 1-tertbutyl-2-ethyl-4-methyl-3cyclopentylcyclohexane.

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Bicyclic Compounds
There are many compounds with two fused

rings called bicyclic compounds.
To name a bicyclic compound, include the

prefix bicyclo in front of the normal name
ending in -ane. For example, the
compounds below could both be named,
bicycloheptane.
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4 -28

Bicyclic Compounds
We know that if two molecules are not

identical, they cannot have the same exact
name.
What is the difference between the two
compounds below?
The number of carbons connecting the

bridgeheads is different. Count them.

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Bicyclic Compounds
1. To number the bicyclo parent chain, start at
a bridgehead carbon and number the
longest carbon chain connecters first.
What numbering would result if we started from

the other bridgehead?
2. Without violating rule 1 above, give the

substituents the lowest numbers possible.
. Practice with 4SKILLBUILDER
4.5.
-30
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Larger Molecules
For molecules that are large and complex,

there are MANY more rules to follow using
the IUPAC system.
Just pronouncing the name of this molecule is

difficult.
Often trade names

are used for
the sake of
4 -31

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4.3 Constitutional Isomers
Recall that isomers are different structures

made from the same atoms.
Constitutional isomers differ in connectivity.
Isomers are NOT identical, but they have the

same formula.
Consider two of the five constitutional isomers
for hexane.
Draw the other three C6H14 constitutional

4 -32
isomers.

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The number of different

possible ways to connect
atoms increases
dramatically when there
are more atoms.
Consider Table 4.4.

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How can you recognize if two molecules are

isomers?
Are these two structures

isomers? Do they have
the same formula?
If they have the same formula, they may be
isomers, or they may be identical.
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.
4 -34
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2. Name them. If they have the same name, they

methods:
1. Flip one of the molecules in
3D space and rotate around
its single bonds until it is
superimposable on the other
molecule.

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4 -35

methods:
2. Name them. If they have the same name, they
are identical.
Which method for testing whether

molecules are4 -36
identical is probably
more
Klein, Organic
Chemistry 1e

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4.4 Relative Stability of

Isomers
To rationalize and predict the outcomes of

chemical reactions, it is helpful to assess
the stability of compounds.
Remember:
Stable = low potential energy = low reactivity =

little energy will be released upon reacting
If you drove a car today, what chemical

reaction with alkanes did you perform?
What is the general reaction equation for a
combustion?
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4.4 Relative Stability of

Isomers
Compare the heats of combustion for three
octane isomers.
Which is most stable? Which is the best fuel?

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4 -38
4.5 Sources and Uses of

Alkanes
Petroleum, which literally means rock oil is

the main source of alkanes.
Petroleum is a mixture of hundreds of
hydrocarbons, mostly alkanes, with varying
numbers of carbons and varying degrees of
branching.
The alkanes in petroleum with 5 to 12
carbons per molecule are most valuable,
and they can be separated from the rest of
the oil by distillation.
HOW does distillation work?

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Alkanes
Table 4.5 shows the various components of

petroleum.
The gasoline fraction of crude oil only

4 -40
Organic Chemistry 1e
makes up about
19%, which isKlein,
not
enough

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Alkanes
Gasoline is a mixture of straight, branched,

and aromatic hydrocarbons (512 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.
2012
After
using
these
processes, theKlein,
yield
of gasoline
Copyright
John Wiley
&
4 -41
Organic
Chemistry 1e
Sons, Inc.

Alkanes
At room temperature:
Small alkanes with 14 carbons are gasses.

Medium size alkanes with 512 carbons are
liquids.
Large alkanes with 1320 carbons are oils.
Extra large alkanes with 20100 carbons are
solids like tar and wax.
Supersized alkanes called polymers can have
thousands or millions of carbon atoms in each
molecule.
What type of properties would you expect

such polymers to possess?

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4.6 Newman Projections
We know that single bonds in molecules can

rotate.
Different rotational states are called

CONFORMATIONS.
3D rotational conformations are difficult to

represent on a 2D paper. Its useful to make
a molecular model to help you visualize the
structures.
Here are three ways to represent ethane.

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4 -43
Look directly down the CC single bond axis.

This is where it is especially helpful to have
a model.
The front carbon should eclipse the single bond

and the carbon behind it.
Show the front carbon as a point and the back
carbon as a large circle behind it.

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4 -44

Practice with SKILLBUILDER 4.7.
Draw a Newman projection for the following

molecule.
How would it look if the observer were

viewing it from the opposite direction?
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4 -45
4.7 Rotational Conformations
What is the angle between H atoms on the

same carbon? In the Newman projection it
looks like 120.
Does the angle affect stability? WHY? Think

about VSEPR theory.
The angle between H atoms on

adjacent carbons is called a dihedral
or TORSIONAL angle. It is 60 in the
molecule to the right.
Would you expect VSEPR theory to be useful
when considering the stability of rotational
4 -46 HOW?
conformations?

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If the ethane molecule were to rotate 60

about the
CC bond, the Newman projection would
show that the H atoms on adjacent carbons
eclipse one another.
Compare the stability of the eclipsed and
staggered conformations based on VSEPR
theory.

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4 -47
Consider a complete 360 rotation about

the CC bond.

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4 -48
The difference in energy between the

staggered and eclipsed conformations is
called TORSIONAL STRAIN.
With a difference of 12kJ/mol in stability, at
room temperature, 99% of the molecules
will be in the staggered conformation.
How would the

4 -49ratio change at
a Organic
higher
Klein,
Chemistry 1e

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TORSIONAL STRAIN can be explained using

VSEPR theory or molecular orbital theory.
In the staggered conformation, the bonding
and antibonding MOs of neighboring
carbons overlap.

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4 -50
The analysis of TORSIONAL STRAIN for

propane shows a very similar situation.

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The torsional strain for propane is 14kJ/mol,

which is 2kJ/mol more than for ethane.
To calculate the contribution of a CH3H
eclipsing interaction:
If each HH eclipsing interaction costs 4kJ/mol of

stability, that total can be subtracted from the
torsional strain of 14kJ/mol.
Practice with CONCEPTUAL CHECKPOINT

4.19.

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4 -52

Butanes Conformations
The analysis of torsional strain for butane

shows more variation.
Note that there are multiple staggered

conformations and multiple eclipsed
4 -53
conformations.

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The stability of the different staggered

conformations differs by 3.8 kJ/mol.
The anti conformation has less steric

hindrance.
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The least stable conformation results when

the methyl groups eclipse one another.
Each CH3CH3 torsional interaction accounts

for 11kJ/mol of energy.
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The values
in Table 4.6
can be used
to predict
relative
energies for
various
conformatio
ns.
Practice with
SKILLBUILDE
Klein,
ROrganic
4.8.Chemistry 1e
Draw a Newman projection for the highest

and lowest energy conformations for
2,2,3,5,5pentamethylhexane.
View the Newman projection down the C3C4
axis.

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4.9 Cyclic Alkanes
Carbon atoms in alkanes are sp3 hybridized.

What bond angles are optimal for such
carbons?
If cycloalkanes were flat, what bond angles
would be expected?
To optimize the bond angles, most

4 -58
cycloalkanes are NOT flat in their
most

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4.9 Cyclic Alkanes

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4 -59
Why are
heats of
combustion
reported per
CH2 group?
Considering
the data in
Table 4.7,
which ring
has the
least RING
Klein,
Organic Chemistry 1e
STRAIN?
4.9 Cyclic Alkanes
Why does it make a molecule less stable to

have angles less than 109.5?
Why does it make a molecule less stable to

have angles greater than 109.5?
RING STRAIN results from more than just

angle strain. 4 -60

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4.9 Cyclic Alkanes

Cyclopropane
Cyclopropane is
44kJ/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:

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4 -61
Eclipsing CH bonds all
4.9 Cyclic Alkanes

Cyclobutane
Cyclobutane is 27kJ/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
CH bonds are neither fully eclipsed nor fully
staggered.

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4.9 Cyclic Alkanes

Cyclopentane
Cyclopentane is only 5kJ/mol less stable

than cyclohexane per CH2 group:
1. Angles are close to the optimal value.
2. Identify the minimal but significant torsional
strain in the structure. It is very helpful to use a
handheld model.
4 -63
Why does it adopt
the envelope

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4.10 Cyclic Alkanes

Cyclohexane
Cyclohexane is considered to have ZERO

ring strain in its optimal conformation, the
CHAIR:
1. No angle strainangles must be 109.5.

2. No torsional strainall adjacent CH bonds must
be staggered.
It helps to make a model as a visual aid!

4 -64
WHY is this called the CHAIR?

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4.10 Cyclic Alkanes

Cyclohexane
Other conformations of hexane exist but are

a bit less stable. Consider THE BOAT.
1. No angle strainangles are 109.5.
2. Torsional strain:
Use a molecular model to identify all four pairs of

eclipsing CH bonds
Draw a Newman projection that illustrates the torsional
strain
3. Steric strainflagpole interactions. WHERE?
Why is this conformation called the BOAT?

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4.10 Cyclic Alkanes

Cyclohexane
Why is
the halfchair so
unstable
?
The twist
boat
alleviates
some of the
torsional
strain in the
boat.
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4 -66
Rotate the CC
single bonds
in your
handheld
cyclohexane
model to form
each of the
conformations
and analyze
its energy.
4.11 Drawing Chairs
It is critical to draw a CHAIR properly.
Use three sets of parallel lines.
SIX of the atoms attached to the chair are

axial.
Axial groups point straight up and down

alternating around the ring.

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4.11 Drawing Chairs
The other SIX atoms attached to a chair are

in equatorial positions.
Equatorial substituents are positioned at angles

parallel to the sets of parallel lines making up
the chair itself.
In the chair below, axial groups shown in red,

equatorial groups shown in blue.

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4.12 Monosubstituted
Cyclohexane
The vast majority of cyclohexane molecules

will exist in the chair conformation at any
given moment. WHY?
When energy (45 kJ/mol) is available, it can

flip from one chair form to another. Why is
energy needed?

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Cyclohexane
Flipping a chair is not like flipping a

pancake. Flipping a chair is the result of CC
single bonds rotating ONLY.
The Newman projection below shows how

flipping occurs ONLY through rotating bonds and
how it will affect the axial or equatorial position
of the substituents.
Flipping is MUCH easier to see with a handheld

Copyright 2012
John Wiley & Try it 4
model.
yourself!
-70
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Cyclohexane
If both versions of the CHAIR were equally

stable, you would have a 50/50 mixture of
axial/equatorial.
Consider methylcyclohexane.
Why does the equatorial chair dominate the

equilibrium?
Does the axial substituent cause additional
4 -71
Sons, Inc. angle or torsional strain?
Cyclohexane
The axial substituent causes additional

steric strain.
Such steric crowding is called 1,3-diaxial

strain. WHY?
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4 -72
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.

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4 -73
Cyclohexane
Larger groups will cause more steric

crowding in the axial position. Consider
Table 4.8.
-74
Practice with 4Conceptual
Checkpoint
4.30. 1e
Klein, Organic Chemistry

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4.13 Disubstituted
Cyclohexane
When multiple substituents are present, the

positioning of the groups on the chair must
be shown by using solid or dashed wedges
or by showing the groups in either axial or
equatorial positions.
Convince yourself that all of the molecules

above are identical.
It may help
to use a
4 -75

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4.13 Disubstituted
Cyclohexane
Consider both chair conformations for the

following molecule.
Which is more stable? WHY?

Do the same analysis for this molecule.
Practice with SKILLBUILDER 4.13.

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4.14 Cis-trans Isomerism
When naming a disubstituted cycloalkane,

use the prefix cis when there are two groups
on the same side of the ring.
Use the prefix trans when two substituents
are on opposite sides of a ring.

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4.14 Cis-trans Isomerism
These two structures are NOT constitutional

isomers. WHY?
They are STEREOISOMERS. HOW?
Practice with CONCEPTUAL CHECKPOINTs

4.364.38.
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4 -78

Chapter - 4 Alkanes and Cycloalkanes - HJM

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4.

Which of the molecules above is saturated

Klein, Organic Chemistry 1e

When communicating about molecules, each

How are the above hydrocarbons different?

Klein, Organic Chemistry 1e

4.2 Naming Compounds

Some common names have been used for

4.2 Naming Compounds

We can learn the IUPAC system instead of

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

4.2 Naming Compounds

The IUPAC system:

1. Find the parent chain, the longest consecutive

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

4.2 Naming Compounds

1. Find the parent chain, the longest

Use Table 4.1 to look up the prefix that corresponds

Klein, Organic Chemistry 1e

4.2 Naming Compounds

Use Table 4.1 to look up the prefix that corresponds

Copyright 2012 John Wiley &

4.2 Naming Compounds

Copyright 2012 John Wiley &

If the parent chain has 9

4.2 Naming Compounds

1. Find the parent chain, the longest

If there is more than one possible parent chain,

. What is the parent

4.2 Naming Compounds

1. Find the parent chain, the longest

If the parent chain is cyclic (a ring of carbons),

4.2 Naming Compounds

1. Find the parent chain, the longest

Give the parent name for the following

The parent name may NOT include carbons that

Copyright 2012 John Wiley &

4.2 Naming Compounds

2. Identify and name substituents (side

Count the number of carbons in each side group,

4.2 Naming Compounds

2. Identify and name substituents (side

A ring can be either a parent chain or a

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

4.2 Naming Compounds

2. Identify and name substituents (side

Name the substituents in the following

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

4.2 Naming Compounds

2. Identify and name substituents (side

Some substituents have complex branches.

How many carbons are in the highlighted

Sons, Inc. Why is it improper to name it a PENTYL group?

4.2 Naming Compounds