Organic Chemistry, 6th Edition

L. G. Wade, Jr.

Chapter 3
Structure and Stereochemistry
of Alkanes

Jo Blackburn
Richland College, Dallas, TX
Dallas County Community College District
 2006, Prentice Hall
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
H H H
=>
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.

CH3 CH3
1 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

=>

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 60°C bp 58°C bp 50°C
mp -154°C mp -135°C mp -98°C

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)

• 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 =>

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.

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

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
Utilizando  los  datos  de  la  tabla  dada  a  continuación.   
Demuestre  cuantitativamente  que  la  tensión  total  en 
ciclobutano  es  aproximadamente  26.4  kcal/mol.   
Describa  los  factores  que  contribuyen  a  esta  tensión  en 
• 
ciclobutano.
cicloalcano ∆H comb 
o   
Tensión Total 
(kcal/mol) (kcal/mol)
ciclopropano 499.8 27.6
ciclobutano 655.9 26.4
ciclopentano 793.5 6.5
ciclohexano 944.5 0
cicloheptano 1108.3 6.3
ciclooctano 1268.9 9.6

Chapter 3 40
 Cyclopentane
• If planar, angles would be 108°, but all
hydrogens would be eclipsed.
• Puckered conformer reduces torsional strain.

=>
Chapter 3 41
 Cyclohexane
• Combustion data shows it’s 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 42
Chair Conformer

=>
Chapter 3 43
Boat Conformer

=>
Chapter 3 44
Conformational Energy

=>
Chapter 3 45
Axial and Equatorial
Positions

=>

Chapter 3 46
Monosubstituted
Cyclohexanes

=>
Chapter 3 47
1,3-Diaxial Interactions

=>
Chapter 3 48
Disubstituted
Cyclohexanes

=>
Chapter 3 49
 Cis-Trans Isomers
Bonds that are cis, alternate axial-
equatorial around the ring.

CH3

CH3
One axial, one equatorial
=>
Chapter 3 50
 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 51
• 3)  Considere el siguiente ciclohexano sustituído:
H C
3
CH(CH )
3 2

OCH
3

• a)  Dibuje la conformación silla correspondiente. 
• (b)  Haga  la  representación  Newman  correspondiente.   
(Recuerde especificar la perspectiva que representa)
• c) Dibuje  ambas  sillas  (interconversión  de  los 
confórmeros).  Señale la que considere más estable.          
                          
• d) Utilizando  los  valores  de  la  tabla Sust de ∆G∆G
o
 
o
 de 
sustituyentes,  calcule  el  ∆Go  para  el  proceso 
kcal/mol de 
interconversión. CH3 1.74
• e)  Calcule el por ciento de cada confórmero OCH3 0.75
CH(CH3)2 2.61

Chapter 3 52
 Bicyclic Alkanes
• Fused rings share two adjacent carbons.
• Bridged rings share two nonadjacent C’s.

bicyclo[3.1.0]hexane bicyclo[2.2.1]heptane
=>
Chapter 3 53
 Cis- and Trans-Decalin
• Fused cyclohexane chair conformers
• Bridgehead H’s cis, structure more flexible
• Bridgehead H’s trans, no ring flip possible.

H H

H =>
H
cis-decalin trans-decalin
Chapter 3 54
Bicyclo[4.4.0]decane

=>
Chapter 3 55
End of Chapter 3

Chapter 3 56