Chapter 4

Alkanes : Nomenclature,
Conformational Analysis, and an
Introduction to Synthesis
Shapes of Alkanes
"Straight - chain" alkanes have a zig - zag orientation when they are
in their most straight orientation
Straight chain alkanes are also called unbranched alkanes

Propane
CH CH CH or
3 2 3

Butane

CH CH CH CH or
3 2 2 3

Pentane

CH CH CH CH CH or
3 2 2 2 3

Chapter 4 2
Branched alkanes have at least one carbon which is attached to
more that two other carbons
Isobutane
CH CHCH or
3 3

CH
3

Isopentane
CH CHCH CH or
3 2 3

CH
3

Neopentane

CH
3

CH CCH or
3 3

CH
3

Chapter 4 3
 Constitutional isomers have different physical properties (melting
point, boiling point, densities etc.)
Constitutional isomers have the same molecular formula but different connectivity
of atoms
Index of
Molecular Structural mp bp(oC)a Densityb Refractionc
Formula Formula (oC) ( 1 atm ) (g mL -1 ) (n 20o c )
D
CH CH CH CH CH CH
CH 3 2 2 2 2 3 -95 68,7 0.6594 20 1.3748
6 14
CH CHCH CH CH
CH
3 2 2 3 - 153.7 60.3 0.6532 20 1.3714
6 14 CH
3

CH CH CHCH CH
CH 3 2 2 3 - 118 63.3 0.6643 20 1.3765
6 14
CH
3
CH CH CH CHCH
6 14 3 3 -128.8 58 0.6616 20 1.3750
CH CH CH
CH 3 3 3 -98 49.7 0.6492 20 1.3688
6 14 CH C CH CH
3 2 3

CH
3
aUnless otherwise indicated, all boiling points given in this book are at 1 atm or 760 torr

bThe superscript indicates the temperature at which the density was measured

cThe index of refraction is a measure of the abilily of the alkane to bend ( refract ) light rays. The values raported are for light of the D line of
the sodium spectrum (n )
D
Chapter 4 4
 The number of constitutional isomers possible for a give
molecular formula increases rapidly with the number of corbons
Possible Number of
Molecular Formula Constitutional Isomers

CH
4 10 2
CH
5 12 3
CH
6 14 5
CH
7 16 9
CH
8 18 18
CH
9 20 35
C H 75
10 22

C H 4,347
15 32

C H 366,319
20 42

C H 4,111,846,763
30 62

C H 62,481,801,147,34
40 82

1
Chapter 4 5
IUPAC Nomenclature of Alkanes, Alkyl Halides and
Alcohols
Before the end of the 19th century compounds were named using
nonsystematic nomenclatur
These" common" or "tivial" names were often based on the source of
the compound or physical property
The International Union of Pure and Applied Chemistry(IUPAC)
strated devising a systematic approach to nomenclature in 1892
The Fundamental principle in devising the system was that each
different compound should have a unique unambiguous name
The basis for all IUPAC nomenclature is the set of rules used for
maming alkanes

Chapter 4 6
 Nomenclature of Unbranched Alkanes
Number of Number of
Carbon Carbon
Name Structure Name Structure
Atoms Atoms
CH CH (CH ) CH
4
Methane 1 Heptadecane
3 2 15 3

CH CH 17 CH (CH ) CH
Ethane 2
3 3
Octadecane
3 2 16 3

CH CH CH 18 CH (CH ) CH
Propane 3
3 2 3
Nonadecane
3 2 17 3

CH (CH ) CH 19 CH (CH ) CH
Butane 4 3 2 2 3
Eicosane
3 2 18 3

CH (CH ) CH
20 CH (CH ) CH
Pentane 5 3 2 3 3
Heneicosane 3 2 19 3

CH (CH ) CH
21
CH (CH ) CH
Hexane 6 3 2 4 3
Docosane 3 2 20 3
22
CH (CH ) CH CH (CH ) CH
Heptane 7 3 2 5 3
Tricosane 3 2 21 3
23
CH (CH ) CH CH (CH ) CH
Octane 8 3 2 6 3
Triacontane 3 2 28 3
30
CH (CH ) CH CH (CH ) CH
Nonane 9 3 2 7 3
Hentriacontane 3 2 29 3
31
Decane CH (CH ) CH CH (CH ) CH
10 3 2 8 3 Tetracontane 40 3 2 38 3

Undecane CH (CH ) CH CH (CH ) CH

11 3 2 9 3 Pentacontane 50 3 2 48 3

Dodecane CH (CH ) CH CH (CH ) CH

12 3 2 10 3 Hexacontane 60 3 2 58 3

Tridecane 13 CH (CH ) CH
Heptacontane CH (CH ) CH
3 2 11 3
70 3 2 68 3

Tetracane 14 CH (CH ) CH
Octacontane CH (CH ) CH
3 2 12 3 80 3 2 78 3

Pentacane 15 CH (CH ) CH Nonacontane CH (CH ) CH

3 2 13 3 90 3 2 88 3

Hexadecane 16 CH (CH ) CH Hectane CH (CH ) CH

3 2 14 3 100 3 2 98 3

Chapter 4 7
Nomenclature of Unbranched Alkyl groups
The unbranched alkyl groups are obtained by removing one
hydrogen from the alkane and named by replacing the -ane of the
corresponding alkane with -yl

ALKANE ALKYL GROUP ABBREVIATION

CH - H
3 becomes CH -
3
Methane Methyl Me
CH CH - H
3 2 CH CH - Et
Ethane becomes 3 2
Ethyl
CH CH CH - H Pr
3 2 2 CH CH CH -
Propane becomes 3 2 2
Propyl
CH CH CH CH - H CH CH CH CH - Bu
3 2 2 2 3 2 2 2
Butane becomes Butyl

Chapter 4 8
Nomenclature of Branched - Chain Alkanes (IUPAC)
Locate the longest continuous chain of carbons ; this is the parent
chain and determines the parent name.
CH CH CH CHCH
3 2 2 3

CH
2

CH
3
Number the longest chain beginning with the end of the chain
nearer the substituent
Designate the location of the substituent
CH CH CH CH CHCH CH3CH2CH2CH2CHCH3
3 2 2 2 3

CH CH
3 2
2- Methylhexane 3 - Methyheptane
CH
3
when two or more substituents are present, give each substituent
a number corresponding to its location on the longest chain
Substituents are listed alphabetically

Chapter 4 9
When two or more substituents are identical, use the prefixes di -,
tri -, tetra - etc.
Commas are used to separate numbers from each other
The prefuxes are used in alphabetical prioritization
When two chains of equal length compete to be parent, choose
the chain with the greatest number of substituents
7 CH - 6CH - 5CH - 4CH - 3CH - 2CH - 1CH
3 2 3 2,3,5 - Trimethyl -4- propylheptane
CH (four substituents)
CH CH CH
3 2 3 3

CH
2

CH
3
When branching first occurs at an equal distance from either end
of the parent chain, choose the name that gives the lower number
at the first point of difference
6 CH - 5CH - 4CH - 3CH - 2CH - 1CH
3 2 3
2,3,5 - Trimethylhexane
CH CH CH (not 2,4,5 - trimethylhexane)
3 3 3

Chapter 4 10
 Nomenclature of Branched Alkyl Chains
Two alkyl groups can be derived from propane
Three - Carbon Groups
CH CH CH
3 2 2
Propyl group
CH - CH - CH
3 2 3
Propane CH3 CH

CH
3
1- Methylethyl or isopropyl group
Four groups can be derived from the butane isomers
Four - Carbon Groups CH CH CH CH
3 2 2 2
CH CH CH CH Butyl group
3 2 2 3
Butane
CH CHCH CH CH CH
3 3 3 2

2 - Methylpropyl or isobutyl group CH

CH 3
CH CHCH 3
1- Methylproyl or see - butyl group
3 3 CH
3

CH CH C CH
3 3 3
Isobutane
1,1 - Dimethylethyl or tert - butyl group
CH
3
Chapter 4 11
The neopentyl group is common branched alkyl group
CH
3
2,2- Dimethylpropyl or neopenty group
CH C CH
3 2

CH
3

Examples
CH CH CH CHCH CH CH
3 2 2 2 2 3

CH CH
3

CH
3
4-(1 - Methylethyl) heptane or 4 - isopropylheptane

CH CH CH CHCH CH CH CH
3 2 2 2 2 2 3

CH C CH
3 3

CH
3
4-(1,1 - Dimethylethyl) octane or 4 - tert - butyloctane

Chapter 4 12
Classification of Hydrogen Atoms
Hydrogens take their classification from the carbon they are
attached to
1O Hydrogen atoms

CH
3

CH CH CH CH
3 2 3

3O Hydrogen atoms 2O Hydrogen atoms

Chapter 4 13
Nomenclature of Alkyl Halides
In IUPAC nomenclature halides are named as substituents on the
parent chain
Halo and alkyl substituents are considered to be of equal ranking
CH CH
3
3

CH CHCHCH CH CH CHCH CHCH

3 2 3 3 2 3

Cl Cl
2 - Chloro - 3 - methylpentane 2 - Chloro - 4 - methylpentane

In Common nomenclature the simple haloalkanes are named as

alkyl halides
Common nomenclature of simple alkyl halides is accepted by IUPAC and still
used
CH
3

CH CH Cl CH CHCH (CH ) CBr CH CHCH Cl CH CCH Br

3 2 3 3 3 3 3 2 3 2

CH CH
3
3 CH
3
Ethylh Isopropyl tert - Butyl Isobutyl Neopentyl
coloride bromide chloride chloride bromide

Chapter 4 14
IUPAC Substitutive Nomenclature
An IUPAC name may have up to 4 features : locants, prefixes,
parent compound and suffixes
Numbering generally starts from the end of the chain which is
closest to the group named in the suffix
CH CH CHCH CH CH OH
3 2 2 2 2

CH
3
4 - Methyl - 1 - hexanol

Locant Suffix
Locant Parent
Prefix

IUPAC Nomenclature of Alcohols

Select the longest chain containing the hydroxyl and change the
suffix name of the corresponding parent alkane from -ane to -ol
Number the parent to give hydroxyl the lowest possible
number
The other substituents take their locations accordingly
Chapter 4 15
 Examples CH
3

Cl3CH 2CH 1CH OH CH 2CH3CH4 CCH 5

2 2 2 3 2 3

OH CH
3

3-Chloro- 1 - propanol or 4,4-Dimethyl-2-pentanol or

3-chloropropan- 1 - ol 4,4-dimethylpentan-2-ol

Common Names of simple alcohols are still often used and are
approved by IUPAC
CH CH CH OH CH CH CH CH OH CH CH CHCH
3 2 2 3 2 2 2 3 2 3

OH

Propyl alcohol Butyl alcohol sec-Butyl alcohol

CH
3
CH CH
3 3
CH COH
3
CH CHCH OH CH CCH OH
3 2
CH 3 2
3
CH
3

tert-Butyl alcohol Isobutyl alcohol Neopentyl alcohol

Chapter 4 16
Alcohols with two hydroxyls are called diols in IUPAC
nomenclature and glycols in common nomenclature

CH2 CH2 CH CH CH CH CH CH
3 2 2 2 2

Common OH OH OH OH OH OH
Substitutive
Ethylene glycol Propylene glycol Trimethylene glycol
1,2-Ethanediol 1,2-Propanediol 1,3-Propanediol
or ethane-1,2-diol or propane -1,2-diol or propane -1,3-diol

Chapter 4 17
Nomenclature of Cycloalkanes
The prefiz cyclo- is added to the name of the alkane with
the same number of carbons
When one substituent is present it is assumed to be at position
one and is not numbered
When two alkyl substituents are present the one with
alphabetical priority is given position 1
Numbering continues to give the other substituent the lowest
number
Hydroxyl has higher priority that alkyl and is given position 1
If a long chain is attached to a ring with fewer carbons, the
cycloalkane is considered the substituent

Chapter 4 18
 CH CHCH CH CH
3 3 3
3

CH CH
2 3
1
2

3
4
CH CH
2 3
Isopropylcyclohexane
1-Ethyl-3-methylcyclohexane
(not 1-ethyl-5-methyclohexane) Cl
4-Chloro-2-ethyl-1-methylcyclohexane
Cl (not 1-chloro-3-ethyl-4-methylcyclohexane)
OH
CH
3

Chlorocyclopentane 2-Methylcyclohexanol

CH CH CH CH CH
3 2 2 2 3

1-Cyclobutylpentane
1,3-Dicyclohexylpropane

Chapter 4 19
Bicyclic compounds
Bicyloalkanes contain 2 fused or bridged rings
The alkane with the same number of total carbons is used as the
parent and the prefix bicyclo- is used

The number of carbons in each bridge is included in the middle of

the name in square brackets

Chapter 4 20
Nomenclature of Alkenes and Cycloalkenes
Alkenes are named by finding the longest chain containing the
double bond and changing the name of the corresponding parent
alkane from -and to -ene
The compound is numbered too give one of the alkene carbons the
lowest number

1 CH 2 CH3CH 4CH CH CH CHCH CH CH

2 2 3 3 2 2 3

1-Butene 2-Hexene
(not 3-butene) (not 4-hexene)

The double bond of a cylcoalkene must be in position 1 and 2

CH
3
1
1
6 2
5 2
5 3
4 3 CH
HC 4 3
3

1 - Methylcyclopentene 3,5-Dimethylcyclohexene
(not 2-methylcycpentene) (not 4,6-dimethylcylohexene)

Chapter 4 21
Compounds with double and alcohol hydroxyl groups are
called alkenols
The Hydroxyl is the groups with higher priority and must be given the lowest
possible number

Two groups which contain double bonds are the vinyl and the allyl
groups

Chapter 4 22
 If two identical groups occur on the same side of the double bond
the compound is cis
If they are on opposite sides the compound is trans
Cl Cl Cl H
C C C C
H H H Cl

cis-1.2-Dichloroethene trans-1,2-Dichloroethene

Serveral alkenes have common names which are recognized by

IUPAC

CH
3

CH CH CH CH CH CH C CH
2 2 3 2
IUPAC : Ethene Propene 2-Methylpropene2
3

Common : Ethylene Propylene Isobutylene

Chapter 4 23
Physical Properties of Alkanes and Cycloalkanes
Boiling points of unbranched alkanes Increase smoothly with
number of carbons

Melting points increase in an alternating pattern according to whether

the number of carbon of carbon atoms in the chain is even or odd

Chapter 4 24
Sigma Bonds and Bord Rotation
Ethanes has relatively free rotation around the carbon - carbon bond
The staggered conformation has C-H bonds on adjacent carbons
as far apart from each other as possible
The drawing to the right is called a Newman projection

The eclipsed conformation has all C -H bonds on adjacent carbons

directly on top of each other

Chapter 4 25
The Potential energy diagram of the conformations of ethane
shows that the staggrered conformations is more stable that
eclipsed by 12 kJ mol-1

Chapter 4 26
Conformational Analysis of Butane
Rotation around C - C of butane give six important
2 3
conformations
The gauche conformations is less stable that the antil conformation by 3.8 kJ Mol -1
becauses of repulsive van der Waals forces between the two methyls

Chapter 4 27
 The Relative stabilities of Cycloalkanes : Ring
Strain
Heats of combustion per CH unit reveal cyclohexane has no ring
2
strain and other cycloalkanes have some ring strain
Heat of
Heat of Ring
combustion
Combustion Strain
Cycloalkane (CH ) per CH Group
2 n
n (kJ mol -1 ) 2 (kJ mol-1 )
(kJ mol-1 )
Cyclopropane 3 2091 697.0 115
Cyclobutane 4 2744 686.0 109
Cyclopentane 5 3320 664.0 27
Cyclohexane 6 3952 658.7 0
Cycloheptane 7 4637 662.4 27
Cyclooctane 8 5310 663.8 42
Cyclononane 9 5981 664.6 54
Cyclodecane 10 6636 663.6 50
Cyclopentadecane 15 9885 659.0 6
Unbranched alkane - - 658.6 -

Chapter 4 28
The Origin of Ring Strain in Cyclopropane and
Cyclobutane : Angle Strain an Tortional Strain
Angle Strain is caused by bond angles different from 109,5 o
Tortional strain is caused by eclipsing C -H bonds on adjacent
carbons
Cyclopropane has both hight angle and tortional strain

Cyclobutane has considerable angle strain

It bends to relieve some tortional strain

Cyclopentane has little angle strain in the planar form but bends
to relieve some tortional strain
Chapter 4 29
Conformations of Cyclohexane
The chair conformation has no ring strain
All bond angles are 109,5o and all C -H bonds are perfectly staggered

Chapter 4 30
The boat conformations is less stable because of flagpole
interactions and tortional strain along the bottom of the boat

The twist conformations is intermediate in stability between the

boat and the chair conformation

Chapter 4 31
Substituted Cyclohexanes : Axial and Equatorial
Hydrogen Atoms
Axial hlydrogens are perpendicular to the average plane of the ring
Equatorial hydrogens lie around the perimeter of the ring

The C -C bonds and equatorial C -H bonds are all drawn in sets of

paralllel lines
The axial hydrogens are drawn straight up and down

Chapter 4 32
Methyl cyclohexane is more stable with the methyl equatorial
An axial methyl has a unfavorable 1.3 -dilaxial interaction with axial C -H bonds 2
carbons away
A 1,3 -diaxial interaction is the equivalent or 2 gauche butane interactions

Chapter 4 33
Disubstitued Cycloalkanes
can exist as pairs of cis -trans stereoisomers
Cis : groups on same side of ring
Trans : groups on opposite side of ring

Chapter 4 34
Trans-1,4-dimethylcylohexane prefers a trans-
diequatorial conformation

Chapter 4 35
Cis -1,4-dimethylcycloxane exists in an axial -equatorial
conformation

A very large tert -butyl group is required to be in the more stable

equatorial position

Chapter 4 36
Bicyclic and Polycyclic Alkanes
The bicyclic decalin system exists in non - interconvertible cis and
trans forms

Chapter 4 37
Synthesis of Alkanes and Cycloalkanes
Hydrogenation of Alkenes and Alkynes

Chapter 4 38
 Reduction of Alkyl Halides

R X + Zn + HX R H + ZnX
2
Zn,HX
R X (-Zn,X ) R H
2

2 CH CH CHCH 2CH CH CHCH + ZnBr

3 2 3 3 2 3 2

Br H
sec-Butyl bromide Butane
(2-bromobutane)

Chapter 4 39
Alkylation of Terminal Alkynes
Alkynes can be subsequently hydrogenated to alkanes

Chapter 4 40
 Retrosynthetic Analysis - Planning Organic
Synthesis
The synthetic scheme is formulated working backward from the
target molecule to a simple starting material
Often several schemes are possible
2nd precursors a

1st precursors A
2nd precursors b
2nd precursors c
Target molecule 1st precursors B
2nd precursors d
2nd precursors e
1st precursors C
2nd precursors f
Retrosynthetic Analysis

C C CH CH C C :- C C H
2 3

s-Br S+CH CH
2 3
Chapter 4 41