Organic Chemistry, 6th Edition

L. G. Wade, Jr.

Chapter 3
Structure and Stereochemistry
of Alkanes
Classification Review

Chapter 3 2
 Alkane Formulas
All C-C single bonds
Saturated with hydrogens
Ratio: CnH2n+2
Alkane homologs: CH3(CH2)nCH3
Same ratio for branched alkanes
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, C4H10 H H H
Isobutane, C4H10 =>
Chapter 3 3
 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 4
Alkane Examples

=>

Chapter 3 5
 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. =>

Chapter 3 6
 Longest Chain
The number of carbons in the longest
chain determines the base name:
ethane, hexane. (Listed in Table 3.2,
page 82.)
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
Chapter 3
=>
7
 Number the Carbons
Start at the end closest to the first
attached group.
If two substituents are equidistant, look
for the next closest group.

1
CH3 CH3
3 4 5
H3C CH CH CH2 CH2 CH CH3
2 6 7
CH2CH3
=>
Chapter 3 8
 Name Alkyl Groups
CH3-, methyl
CH3
CH3CH2-, ethyl
CH3 CH CH2
CH3CH2CH2-, n-propyl isobutyl
CH3CH2CH2CH2-, n-butyl CH3
C H3 C H C H3 CH3 CH CH2 CH3 H3C C CH3
isopropyl sec-butyl tert-butyl
=>

Chapter 3 9
 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

A primary carbon A secondary carbon

=>

Chapter 3 10
 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 11
 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 12
 Alphabetize
Alphabetize substituents by name.
Ignore di-, tri-, etc. for alphabetizing.
CH3 CH3
H3C CH CH CH2 CH2 CH CH3
CH2CH3

3-ethyl-2,6-dimethylheptane
=>
Chapter 3 13
 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.
1
2

3
1-methyl-3-(1,2-dimethylpropyl)cyclohexane =>
Chapter 3 14
 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 15
 Boiling Points of Alkanes
Branched alkanes have less surface area contact,
so weaker intermolecular forces.

=>

Chapter 3 16
Melting Points of Alkanes
Branched alkanes pack more efficiently into
a crystalline structure, so have higher m.p.

=>

Chapter 3 17
 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 18
=>
 Major Uses of Alkanes
C1-C2: gases (natural gas)
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 19
 Reactions of Alkanes
Combustion
heat
2 CH3CH2CH2CH3 + 13 O2 8 CO2 + 10 H2O

Cracking and hydrocracking (industrial)

catalyst
long-chain alkanes shorter-chain alkanes

Halogenation
heat or light
CH4 + Cl2 CH3Cl + CH2Cl2 + CHCl3 + CCl4

=>
Chapter 3 20
 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.
Molecules constantly rotate through all
the possible conformations.
=>

Chapter 3 21
 Ethane Conformers
Staggered conformer has lowest energy.
Dihedral angle = 60 degrees
H
H H

H H =>
H
Newman sawhorse
model projection
Chapter 3 22
 Ethane Conformers (2)
Eclipsed conformer has highest energy
Dihedral angle = 0 degrees

=>
Chapter 3 23
Conformational Analysis
Torsional strain: resistance to rotation.
For ethane, only 12.6 kJ/mol

=>
Chapter 3 24
 Propane Conformers
Note slight increase in torsional strain
due to the more bulky methyl group.

=>
Chapter 3 25
Butane Conformers C2-C3
Highest energy has methyl groups eclipsed.
Steric hindrance
Dihedral angle = 0 degrees

totally eclipsed =>

Chapter 3 26
 Butane Conformers (2)
Lowest energy has methyl groups anti.
Dihedral angle = 180 degrees

anti
=>
Chapter 3 27
 Butane Conformers (3)
Methyl groups eclipsed with hydrogens
Higher energy than staggered
conformer
Dihedral angle = 120 degrees

eclipsed =>
Chapter 3 28
 Butane Conformers (4)
Gauche, staggered conformer
Methyls closer than in anti conformer
Dihedral angle = 60 degrees

gauche =>
Chapter 3 29
Conformational Analysis

=>
Chapter 3 30
 Higher Alkanes
Anti conformation is lowest in energy.
Straight chain actually is zigzag.

CH3CH2CH2CH2CH3

H H H H H H
C C C
H C C H
H H H H
=>
Chapter 3 31
 Cycloalkanes
Rings of carbon atoms (-CH2- groups)
Formula: CnH2n
Nonpolar, insoluble in water
Compact shape
Melting and boiling points similar to
branched alkanes with same number of
carbons =>

Chapter 3 32
 Naming Cycloalkanes
Cycloalkane usually base compound
Number carbons in ring if >1 substituent.
First in alphabet gets lowest number.
May be cycloalkyl attachment to chain.
CH2CH3
CH2CH3
CH3 =>

Chapter 3 33
 Cis-Trans Isomerism

Cis: like groups on same side of ring

Trans: like groups on opposite sides of ring

Chapter 3 34
 Cycloalkane Stability

5- and 6-membered rings most stable

Bond angle closest to 109.5
Angle (Baeyer) strain
Measured by heats of combustion
per -CH2 -

Chapter 3 35
Heats of Combustion/CH2
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 36
 Cyclopropane
Large ring strain due to angle compression
Very reactive, weak bonds

Chapter 3 37
 Cyclopropane (2)
Torsional strain because of eclipsed
hydrogens

=>
Chapter 3 38
 Cyclobutane
Angle strain due to compression
Torsional strain partially relieved by
ring-puckering

Chapter 3 39
 Cyclopentane
If planar, angles would be 108, but all
hydrogens would be eclipsed.
Puckered conformer reduces torsional strain.

Chapter 3 40
 Cyclohexane

Combustion data shows its unstrained.

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 41
Chair Conformer

Chapter 3 42
Boat Conformer

Chapter 3 43
Conformational Energy

Chapter 3 44
Axial and Equatorial
Positions

Chapter 3 45
Monosubstituted
Cyclohexanes

Chapter 3 46
1,3-Diaxial Interactions

Chapter 3 47
Disubstituted
Cyclohexanes

Chapter 3 48
 Cis-Trans Isomers
Bonds that are cis, alternate axial-
equatorial around the ring.

CH3

CH3
One axial, one equatorial

Chapter 3 49
 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 50
 Bicyclic Alkanes
Fused rings share two adjacent carbons.
Bridged rings share two nonadjacent Cs.

bicyclo[3.1.0]hexane bicyclo[2.2.1]heptane
Chapter 3 51
 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 52
Bicyclo[4.4.0]decane

Chapter 3 53