Organic Chemistry ABCT2423: Alkanes

Organic Chemistry
ABCT2423
Alkanes
Dr. Chau Ming SO
Office: Y843
Email: bccmso@polyu.edu.hk
1
Handout for “ALKANES”
IUPAC Nomenclature of Alkanes

Conformational Analysis of Ethane
Conformational Analysis of Butane
Conformations of Higher Alkanes
Conformational Analysis of Cycloalkanes
Conformational Analysis of Monosubstituted
Cyclohexanes
2
IUPAC Nomenclature of Branched Alkanes
• Step 1) Find the longest continuous carbon chain

and use the IUPAC name of the unbranched alkane
as the basis.
• Step 2) Add name of substituent as a prefix.
• Step 3) Number the chain from the end nearest

the substituent, and identify the carbon to
which the substituent is attached by number.
3
C6H14 Isomers
(CH3)2CHCH2CH2CH3
2-Methylpentane
(CH3CH2)2CHCH3
3-Methylpentane
4
C6H14 Isomers
(CH3)2CHCH(CH3)2
2,3-Dimethylbutane
(CH3)3CCH2CH3
2,2-Dimethylbutane
• Use replicating prefixes (di-, tri-, tetra-, etc.)

according to the number of identical substituents
5
attached to the main chain.
Branched Alkanes
Octane 4-Ethyloctane
4-Ethyl-3-methyloctane
List substituents in alphabetical order.

6
Branched Alkanes
4-Ethyl-3,5-dimethyloctane
• List substituents in alphabetical order.

• But don't alphabetize di-, tri-, tetra-, etc.
7
First Point of Difference Rule
2 4 6 8 7 5 3 1
3 5 7 6 4 2
1 8
What is the correct name?

2,3,3,7,7-Pentamethyloctane
2,2,6,6,7-Pentamethyloctane
• The chain is numbered in the direction that

gives the lower locant to the substituent at the
first point of difference in the names.
8
Cycloalkanes
• Cycloalkanes are alkanes that contain a ring of

three or more carbons.
• Count the number of carbons in the ring, and
add the prefix cyclo to the IUPAC name of
the unbranched alkane that has that number
of carbons.
Cyclopentane Cyclohexane 9
Cycloalkanes
CH2CH3
Ethylcyclopentane H3C CH3
CH2CH3
3-Ethyl-1,1-dimethylcyclohexane
10

Cyclohexanes
11
• Conformations are different spatial

arrangements of a molecule that are
generated by rotation about single bonds.
12
Eclipsed
Conformation
Staggered
Conformation
13
Projection Formulas of the Staggered
Conformation of Ethane
H H
H H
H H
H H
H H
H H
Newman Sawhorse
14
Anti Relationships
H H
H H
H H
180° H H
H H
H H
Two bonds are anti when the angle

between them is 180°.
15
Gauche Relationships
H 60° H
H H
H H
H H
H H
H H
• Two bonds are gauche when the angle between

them is 60°. Two bonds are skewed when the
angle other then 60°
• The terms anti, gauche and skewed apply only to
bonds (or groups) on adjacent carbons, and only
to staggered conformations. 16
eclipsed
12 kJ/mol
0° 60° 120° 180° 240° 300° 360°
gauche anti gauche 17

Torsional Strain
• The eclipsed conformation of ethane is 12
kJ/mol less stable than the staggered.
• The eclipsed conformation is destabilized by
torsional strain.
• Conformations in which the torsion angles
between adjacent bonds are other than 60o
are said to have torsional strain.
• Torsional strain is the destabilization that
results from eclipsed bonds.
18

Cyclohexanes
19
eclipsed
14 kJ/mol
3 kJ/mol
0° 60° 120° 180° 240° 300° 360°
gauche anti gauche 20

van der Waals Strain
gauche anti
• The gauche conformation of butane is 3 kJ/mol
less stable than the anti.
• The gauche conformation is destabilized by
van der Waals strain (also called steric strain).
• van der Waals strain is the destabilization that
results from atoms being too close together.
21
van der Waals Strain
eclipsed
• The conformation of butane in which the two

methyl groups are eclipsed with each other is
the least stable of all the conformations.
• It is destabilized by both torsional strain
(eclipsed bonds) and van der Waals strain.
22

Cyclohexanes
23
Unbranched Alkanes
Hexane
• The most stable conformation of unbranched
alkanes has anti relationships between carbons.
24

Cyclohexanes
25
Types of Strain
• Torsional strain
strain that results from eclipsed bonds
• van der Waals strain (steric strain)
strain that results from atoms being too
close together
• Angle strain
strain that results from distortion of bond
angles from normal values
26
Cyclopropane
Sources of strain
torsional strain
angle strain 27
Cyclobutane
Nonplanar conformation relieves some torsional strain
angle strain present

28
Cyclopentane
All bonds are eclipsed in planar conformation

Planar conformation destabilized
by torsional strain 29
Nonplanar Conformations of Cyclopentane
Envelope Half-chair
• Relieve some, but not all, of the torsional strain.

• Envelope and half-chair are of similar stability
and interconvert rapidly.
30
Chair is the most stable conformation of
cyclohexane
• All of the bonds are staggered and the bond

angles at carbon are close to tetrahedral.
31
Boat conformation is less stable than the
chair
180 pm
• All of the bond angles are close to tetrahedral

but close contact between flagpole hydrogens
causes van der Waals strain in boat.
32
Boat conformation is less stable than the
chair
• Eclipsed bonds give torsional strain to

boat.
33
Skew boat is slightly more stable than boat
Boat Skew boat
• Less van der Waals strain and

less torsional strain in skew boat.
34
Generalization
The chair conformation of cyclohexane is the

most stable conformation and derivatives
of cyclohexane almost always exist in the
chair conformation
35
Axial and Equatorial Bonds in Cyclohexane
• The 12 bonds to the ring can be

divided into two sets of 6. 36
6 Bonds are axial
Axial bonds point "north and south"

37
6 Bonds are Equatorial
Equatorial bonds lie along the equator
38
Axial and Equatorial Bonds in Cyclohexane
39
Conformational Inversion
• Chair-chair interconversion (ring-flipping)

• Rapid process (activation energy = 45 kJ/mol)
• All axial bonds become equatorial and vice versa
40
Half-
chair
Skew
boat
Chair Chair
41
45 45
kJ/mol kJ/mol
23
kJ/mol
42
Conformational Inversion
43
44

Cyclohexanes
45
Conformational Analysis of
Monosubstituted Cyclohexanes
The Most stable conformation is chair

Substituent is more stable when equatorial
46
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.
47
Methylcyclohexane
5% 95%
• Source of crowding is close approach to axial

hydrogens on same side of ring.
• Crowding is called a "1,3-diaxial repulsion" and
is a type of van der Waals strain.
48
Methylcyclohexane
49
Fluorocyclohexane
40% 60%
• Crowding is less pronounced with a "small"

substituent such as fluorine.
• Size of substituent is related to its branching.
50
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.
51
tert-Butylcyclohexane
van der Waals

strain due to
1,3-diaxial
repulsions
52
Alkanes
1. Able to name the alkanes from a given compounds.

2. Able to show the different isomers from a given
organic compounds.
3. Understanding of the conformational different of
alkanes.
4. Able to recognize the types of strain from a give
molecule.
5. Able to draw different conformers of
cycloalkanes.
6. Able to recognize the most stable conformers
from a given molecule.
53

Organic Chemistry ABCT2423: Alkanes

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Organic Chemistry

IUPAC Nomenclature of Alkanes

• Step 1) Find the longest continuous carbon chain

• Step 2) Add name of substituent as a prefix.

• Step 3) Number the chain from the end nearest

• Use replicating prefixes (di-, tri-, tetra-, etc.)

List substituents in alphabetical order.

• List substituents in alphabetical order.

What is the correct name?

• The chain is numbered in the direction that

• Cycloalkanes are alkanes that contain a ring of

Ethylcyclopentane H3C CH3

IUPAC Nomenclature of Alkanes

• Conformations are different spatial

Two bonds are anti when the angle

• Two bonds are gauche when the angle between

0° 60° 120° 180° 240° 300° 360°

gauche anti gauche 17

IUPAC Nomenclature of Alkanes

gauche anti gauche 20

• The conformation of butane in which the two

IUPAC Nomenclature of Alkanes

IUPAC Nomenclature of Alkanes

Nonplanar conformation relieves some torsional strain

angle strain present

All bonds are eclipsed in planar conformation

• Relieve some, but not all, of the torsional strain.

• All of the bonds are staggered and the bond

• All of the bond angles are close to tetrahedral

• Eclipsed bonds give torsional strain to

Boat Skew boat

• Less van der Waals strain and

The chair conformation of cyclohexane is the

• The 12 bonds to the ring can be

Axial bonds point "north and south"

Equatorial bonds lie along the equator

• Chair-chair interconversion (ring-flipping)

IUPAC Nomenclature of Alkanes

The Most stable conformation is chair

• Chair-chair interconversion occurs, but at any

• Source of crowding is close approach to axial

• Crowding is less pronounced with a "small"

Less than 0.01% Greater than 99.99%

• Crowding is more pronounced with a

van der Waals

1. Able to name the alkanes from a given compounds.

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