Introduction to General and

Organic Chemistry II

Chapter 3

Structure and Stereochemistry

of Alkanes

Dr. David P. Brown

Department of Chemistry
 Hydrocarbons
Hydrocarbons are molecules that are made of
carbon and hydrogen ONLY.

Chapter 3 2
 Alkanes

The alkanes belong to the group of

saturated hydrocarbons.
General Formula: CnH2n+2

H H H
C H H C C H
H H H H

Methane CH4 Ethane C2H6

b.p. -160oC - 89oC
Chapter 3 3
Shapes of Alkanes

Chapter 3 4
 The Butanes

H
H H H H
H C H
H C C C C H
H H
H H H H H C C C H
Butane, C 4H10 H H H

Isobutane, C 4H10

Chapter 3 5
 Common Names

Isobutane, isomer of butane

Isopentane, isohexane, etc., methyl
branch on next-to-last carbon in chain.
Neopentane, most highly branched
Five possible isomers of hexane,
18 isomers of octane and 75 for
decane!

Chapter 3 6
 Pentanes
H
H H H H H H C H
H C C C C C H H H H
H H H H H H C C C C H
H H H H
n-pentane, C 5H12
isopentane, C 5H12
CH3
H3C C CH3
CH3
neopentane, C 5H12
Chapter 3 7
 IUPAC Names

Find the longest continuous carbon chain.

Number the carbons, starting closest to
the first branch.
Name the groups attached to the chain,
using the carbon number as the locator.
Alphabetize substituents.
Use di-, tri-, etc., for multiples of same
substituent. *go up to ten for the course*
Chapter 3 8
 Longest Chain

The number of carbons in the longest chain

determines the base name: ethane, hexane.
(Listed in Table 3.2)
If there are two possible chains with the same
number of carbons, use the chain with the
most substituents.
H3C
CH CH2 CH3
CH3
H3C CH2 C CH CH2 CH2 CH3
CH3
9
 Main Chain

Two longest chains of equal length: use the chain with the
greatest number of substituents.
Chapter 3 10
 Number the Carbons
Start at the end closest to the first attached
group.
If two substituents are equidistant, look for
the next closest group.
2,6 DIMETHYL
3 ETHYL
HEPTANE
3 - ETHYL 2, 6 - DIMETHYLHEPTANE

CH3 CH3
1 3 4 5
H3C CH CH CH2 CH2 CH CH3
2 6 7
CH2CH3

Chapter 3 11
 Name Alkyl Groups

CH3-, methyl

C
H
3C
H CH C
H
CH3

CHC
HCH C
HH
CC H
CH3CH2-, ethyl

iso
p
ro
p
y 3
l sec-butyl tert-butyl
CH3 CH CH2

33 2 33 3
CH3CH2CH2-, n-propyl isobutyl

CH3CH2CH2CH2-, n-butyl

Chapter 3 12
 Propyl Groups

H H H H H H

H C C C H H C C C H

H H H H H H

n-propyl isopropyl

H removed from primary H removed from secondary

carbon carbon

Chapter 3 13
 Butyl Groups

H H H H H H H H
H C C C C H H C C C C H
H H H H H H H H

n-butyl sec-butyl

A primary carbon A secondary carbon

Chapter 3 14
 Isobutyl Groups

H H
H
H C H
C H H H
H H
H C C C H
H C C C H
H H H H H
H

isobutyl tert-butyl

A primary carbon A tertiary carbon

Chapter 3 15
 CH C
H
Alphabetizing

H
3CC
H
3 C
HC
H3C
H
Alphabetize substituents by name.

22 3
Ignore di-, tri-, etc. for alphabetizing.

233-ethyl-2,6-dimethylheptane
Chapter 3 16
 Question
The IUPAC name for the compound
below:
*ALWAYS TRY TO GO TO THE ONE WITH THE LOWEST NUMBER

A. 6-Ethyl-3,4-dimethylheptane
B. 2-Ethyl-4,5-dimethylheptane
C. 3,4,6-Trimethyloctane *
D. 3,5,6-Trimethyloctane
E. 2-(1-Methylpropyl)-4-methylhexane
17
 Complex Substituents

If the branch has a branch, number the

carbons from the point of attachment.
Name the branch off the branch using a
locator number.
Parentheses are used around the
complex branch name.

Chapter 3 18
 Example 1
3 CH 3

CH 3 2 HC CH 3

CH 2 1 HC CH 2CH 3

CH 3 CH 2 CH CH 2 CH CH 2 CH 2 CH 2 CH 3

1 2 3 4 5 6 7 8 9

3-Ethyl-5-(1-ethyl-2-methylpropyl)nonane

Chapter 3 19
 Example 2

1 1 3
2
3 2

1-(1,2-dimethylpropyl)-3-methylcyclohexane

Chapter 3 20
 Example 3

3 1 3
2
1 2

1,1-dimethyl-3-(1,2-dimethylpropyl)cyclohexane

Chapter 3 21
 Physical Properties

Solubility: hydrophobic
Density: less than 1 g/mL
Boiling points increase with increasing
carbons (little less for branched chains).
Melting points increase with
increasing carbons (less for odd-
number of carbons).

Chapter 3 22
 Boiling Points of Alkanes

Branched alkanes have less surface area

contact, so weaker intermolecular forces.

23
 Melting Points of Alkanes
Branched alkanes pack more efficiently into
a crystalline structure, so have higher m.p.

24
 Branched Alkanes

Lower b.p. with increased branching

Higher m.p. with increased branching
Examples:
CH3
CH3 C CH2 CH3
CH3 CH3 CH3
CH CH2 CH2 CH3 CH CH CH3
CH3 CH3 CH3
bp 60C bp 58C bp 50C
mp -154C mp -135C mp -98C

Chapter 3 25
 Major Uses of Alkanes

C1-C2: gases (natural gas 70% CH4)

C3-C4: liquified petroleum (LPG)
C5-C8: gasoline
C9-C16: diesel, kerosene, jet fuel
C17-up: lubricating oils, heating oil
Origin: petroleum refining

Chapter 3 26
2C
H C
H C
H
3223+ CH 1
3O2 81h
ea
t CO2+0 H
2O
Reactions of Alkanes

lon
g-ch
ain
alkescatlyst sh
an
Combustion

h
ea
t
or
l
i
ght or
t
er-
c
ha
in
a
l
kane
s
Cracking and hydrocracking (industrial)

C
H4+ Cl2 C
Halogenation

H
3C
l+C
Chapter 3
H
2C
l2+CH
C
l3+Cl4
27
 Methane Representations

Tetrahedral *RING STRAIN EXCESS ENERGY; THIS CASE DUE TO ANGLE COMPRESSION
sp3 hybrid carbon with angles of 109.5.
Chapter 3 28
 Ethane Representations

Two sp3 hybrid carbons.

Rotation about the CC sigma bond.
Conformations are different arrangements of
atoms caused by rotation about a single bond.
Chapter 3 29
 Conformers of Alkanes

Structures resulting from the free

rotation of a C-C single bond
May differ in energy. The lowest-energy
conformer is most prevalent.
An infinite number of conformations are
possible through slight changes in the
angle , the Dihedral Angle.

Chapter 3 30
 Conformations of Ethane

Pure conformers cannot be isolated in most cases, because the molecules are
constantly rotating through all the possible conformations.
31
 Newman Projections

The Newman projection is the best way to judge the

stability of the different conformations of a molecule.
Chapter 3 32
 Ethane Conformers
Staggered conformer has lowest energy
(most stable).
Dihedral angle = 60 degrees
H
H H

H H
H
Newman sawhorse
model projection
Chapter 3 33
 Ethane Conformers (2)
Eclipsed conformer has highest energy
(least stable)
Dihedral angle = 0 degrees

Chapter 3 34
 Conformational Analysis
Torsional strain: resistance to
rotation.
Torsional energy required. For
ethane, only 3.0 kcal/mol

Chapter 3 35
 Propane Conformations

Propane is shown here as a perspective drawing and as

a Newman projection looking down the C1C2 bond.

Chapter 3 36
 Propane Conformers
Note slight increase in torsional strain
due to the more bulky methyl group.

Chapter 3 37
 Butane Conformations

Butane has two different staggered conformations: gauche (60 between the
methyl groups) and anti (180 between the methyl groups).
The eclipsed conformation where the dihedral angle between the methyl
groups is 0 is referred to as totally eclipsed.
Chapter 3 38
 Butane Conformers C2-C3

Highest energy has methyl groups eclipsed

(totally eclipsed).
~ 5.0 kcal above the anti conformer.
Dihedral angle = 0 degrees

totally eclipsed 39
 Butane Conformers (2)
Lowest energy, has methyl groups anti.
Dihedral angle = 180 degrees

anti

Chapter 3 40
 Butane Conformers (3)

Methyl groups eclipsed with hydrogens

Higher energy than staggered
conformer
Dihedral angle = 120 degrees

eclipsed
Chapter 3 41
 Butane Conformers (4)
Gauche, other staggered conformer
Methyls closer than in anti conformer
Dihedral angle = 60 degrees

gauche
42
Conformational Analysis

Chapter 3 43
 Steric Strain

The totally eclipsed conformation is higher in energy

because it forces the two end methyl groups so
close together that their electron clouds experience
a strong repulsion.
This kind of interference between two bulky groups
is called steric strain or steric hindrance.
Chapter 3 44
 Question
The most stable conformation of
1,2-diphenylethane is: 3*

Chapter 3 45
 Cycloalkanes

Rings of carbon atoms (CH2 groups)

General Formula: CnH2n
Nonpolar, insoluble in water
Compact shape
Melting and boiling points similar to
branched alkanes with same number of
carbons

Chapter 3 46
 Cycloalkanes (2)
The simplest cycloalkane is cyclo-propane,
C3H6.
Cycloalkanes are usually represented by
geometric structures.

H2
C

H2C CH 2

Cyclopropane Cyclooctane

Chapter 3 47
 Substituted Cycloalkanes

The Cycloalkane is usually the base

compound
Number carbons in ring if there are more
than one substituents.
First in alphabet gets lowest number.
In some cases, the cycloalkane ring is
better considered as a substituent.

Chapter 3 48
 C
H
3 C
H
C
H
2
3
Substituted Cycloalkanes

2
3
1,1-Diethyl-3-methylcyclopentane

2-Cyclopentylheptane

Chapter 3 49
 Cis-Trans Isomerism

Cis: like groups on same side of ring

Trans: like groups on opposite sides of ring

Chapter 3 50
 Cycloalkane Stability

Rings may possess a certain amount of

instability measured as ring strain.
Ring strain results from; 1) Angle strain
(Baeyer Strain), and 2) Torsional Strain.
Angle (Baeyer) strain deviations from the
tetrahedral bond angle (109.50).
Torsional strain due to eclipsing interactions
between groups or atoms.
Ring strain is measured by heats of
combustion per -CH2 -

Chapter 3 51
 Heats of Combustion
Alkane + O2 CO2 + H2O
697.1 686.1
664.0 662.4 663.6 kJ/mol
658.6 kJ 658.6

Long-chain
Chapter 3 52
 Total Ring Strain (kJ)

Heat of combustion per CH2 = 697.1

Reference heat of comb. = 658.6
Ring strain per CH2 = 38.5
Total molar ring strain = 3 x 38.5

= 115.5 kJ for Cyclopropane

Chapter 3 53
 Cyclopropane
Large ring strain (115.5 kJ) due to
angle compression
Very reactive, weak bonds

Chapter 3 54
 Cyclopropane (2)

Torsional strain because of eclipsed

hydrogens

Chapter 3 55
 Cyclobutane
Total ring strain = 110 kJ/mol
Angle strain due to compression
Torsional strain partially relieved by ring-
puckering

Chapter 3 56
 Cyclopentane
Total ring strain = 27 kJ/mol
If planar, angles would be 108, but all
hydrogens would be eclipsed.
Puckered conformer reduces torsional strain.

Chapter 3 57
 Cyclohexane

The cyclohexane molecule has

Zero ring strain !!
Angles would be 120, if planar.
The chair conformer has 109.5 bond
angles and all hydrogens are
staggered.
No angle strain and no torsional strain.

Chapter 3 58
 Question
Which isomer of C5H10 would you
expect to have the smallest heat of
combustion?

A) Cyclopentane *
B) Methylcyclobutane
C) 1,1-Dimethylcyclopropane
D) cis-1,2-Dimethylcyclopropane
E) trans-1,2-Dimethylcyclopropane

Chapter 3 59
Chair Conformer

=>

Chapter 3 60
 Boat Conformer

The Boat conformer also has bond

angles of 109.50, but suffers from
torsional strain due to eclipsing
interactions.
The molecule adopts a slightly skewed
twist-boat that relieves the torsional
strain.

Chapter 3 61
Boat Conformer

Chapter 3 62
Conformational Energy

Chapter 3 63
 Substituted Cyclohexanes
A substituent will occupy either an Axial
or an Equatorial position on the ring.

Chapter 3 64
 Methylcyclohexane
Less stable More stable

65
 Relative Stabilities

The Axial conformer is higher in energy (less

Stable) due to 1,3-diaxial interactions.

Chapter 3 66
 Disubstituted Cyclohexanes

The ideal arrangement is for both groups to

occupy equatorial positions.

Chapter 3 67
 Disubstituted Cyclohexanes

If both groups cannot be equatorial, the larger

group will be equatorial and the smaller one
axial.

More stable
CH 2CH 3
H
H CH 2CH 3
H

CH 3 H
H3C

trans-1-Ethyl-3-methylcyclohexane
Chapter 3 68
 Cis-Trans Isomers

Bonds that are cis, alternate axial-

equatorial around the ring.

CH3

CH3
One axial, one equatorial

Chapter 3 69
 Question
trans-1,2-Dibromocyclohexane is
represented by structure(s):

A) I D) II and III *
B) II E) I and II
C) III Chapter 3 70
 Bulky Groups
Groups like t-butyl cause a large energy
difference between the axial and equatorial
conformer.
Most stable conformer puts t-butyl equatorial
regardless of other substituents.

Chapter 3 71
 Question

The most stable conformation of cis-1-tert-butyl-4-

methylcyclohexane is the one in which:

A. the tert-butyl group is axial and the methyl group is

equatorial.
B. the methyl group is axial and the tert-butyl group is
equatorial. *
C. both groups are axial.
D. both groups are equatorial.
E. the twist boat conformation is adopted.

Chapter 3 72
Bicyclic Systems

Chapter 3 73
 Bicyclic Alkanes
Fused rings share two adjacent carbons.
Bridged rings share two nonadjacent Cs.

bicyclo[3.1.0]hexane bicyclo[2.2.1]heptane

bicyclo[3.1.0]hexane bicyclo[2.2.1]heptane
74
 Cis- and Trans-Decalin

Fused cyclohexane chair conformers

Bridgehead Hs cis, structure more flexible
Bridgehead Hs trans, no ring flip possible.

H H

H =>

H
cis-decalin trans-decalin
Chapter 3 75
Bicyclo[4.4.0]decane

=>
Chapter 3 76
 Question

Which structure is bicyclo[3.2.2]nonane? *3

Chapter 3 77
 Question
A correct name for the compound
below is:
CH3

A) 2-Methylbicyclo[4.3.0]nonane *
B) 1-Methylbicyclo[4.3.1]nonane
C) 7-Methylbicyclo[4.3.0]nonane
D) 2-Methylbicyclo[4.3.1]nonane
E) 1-Methylbicyclo[4.3.0]nonane
Chapter 3 78
End of Chapter 3

Chapter 3 79