CHAPTER 2: SATURATED CARBON

2.1 Alkanes
2.2 IUPAC Naming System for Alkanes
2.3 Drawing Structural Formulas
2.4 Haloalkanes
2.5 Cycloalkanes
2.6 Physical Properties of Alkanes and
Cycloalkanes
2.7 Chemical Properties of Alkanes and
Cycloalkanes
 Classification of Hydrocarbons
Hydrocarbons are made up of only hydrogen and carbon.

saturated unsaturated 2
 Haloalkanes
Haloalkanes are also known as Halogenoalkanes or alkyl
halides.

Halogenoalkanes are compounds in which one or more

hydrogen atoms in an alkane have been replaced by halogen
atoms (fluorine, chlorine, bromine or iodine).
The different kinds of halogenoalkanes
Halogenoalkanes fall into different classes depending on how the halogen
atom is positioned on the chain of carbon atoms. There are some
chemical differences between the various types.

Primary halogenoalkanes: In a primary (1°) halogenoalkane, the carbon

which carries the halogen atom is only attached to one other alkyl group.
 CYCLOALKANE NOMENCLATURE

A hydrocarbon that contains carbon atoms joined to form a ring is called

a cyclic hydrocarbon. When all carbons of the ring are saturated, the
hydrocarbon is called a cycloalkane
Cycloalkanes contain two fewer hydrogen atoms than an alkane with the
same number of carbon atoms and have the general formula CnH2n. For
example, compare the molecular formulas of cyclohexane, C6H12, and
hexane, C6H14.
To name a cycloalkane, prefix the name of the corresponding open-chain
alkane with cyclo-, and name each substituent on the ring

Cyclopropane Cyclobutane Cyclopentane Cyclohexane

 Naming of Cycloalkanes
 Name any alkyl groups on the ring in the usual
way.
CH2CH3 Ethylcyclopentane

 List substituents in alphabetical order and count

in the direction that gives the lowest number.

H3C CH3
3-Ethyl- 1,1-dimethylcyclohexane

CH2CH3
 IUPAC Nomenclature of Cycloalkanes

 Named by placing the prefix cyclo to the

corresponding alkanes

Examples

CH2 H2C CH2

H2C CH2 H2C CH2

Cyclopropane Cyclobutane
If only one substituent present : not necessary to
designate its position

Example

suffix
prefix

6C 1 CH3

Methyl cyclo hexane

When 2 substituents present :
i. Numbered the C beginning with
substituent according to the alphabetical
order
ii. Numbered in the way that gives the
next substituent the lowest number
possible
 Example 1 Methyl
CH3
3 2

1-ethyl-2-methyl cyclohexane 4 1
CH2CH3
5 6 Ethyl

CH3
5 6

4 1
CH2CH3
1-ethyl-6-methylcyclohexane
3 2
 Practice Exercise
Give IUPAC names for the following cycloalkanes :

CH3 H3C

H 3C CH3
1,4-dimethylcyclohexane
Isopropylcyclobutane
CH2CH3

1-ethyl-3-methylcyclopentane
CH3
When a single ring is attached to a chain with greater no. of C atoms :
named as cycloalkylalkane

5 C chain parent
C H2 C H2 C H CH CH
3 2 4 2 5 3
1 2

4C
chain 1- cyclo butyl pentane

substituent
When more than 1 ring is attached to a single chain :
also named as cycloalkylalkane

parent
straight chain
CH
1 2CH
2 2CH
3 2

substituent groups
1,3- di cyclo hexyl propane
PHYSICAL PROPERTIES OF ALKANES AND CYCLOALKANES

Physical Properties

Non – polar molecules

Not – soluble in water

Low density
These goes up as the number
Low melting point
of carbons increase

Low boiling point

Physical state: C1 – C4 (gaseous), C5 – C17 (liquid),

>= C18 (solid)
 Properties of Alkanes
• Alkanes is saturated hydrocarbon therefore they do
not react as most chemicals
• Burning in flame produce carbon dioxide and water
• React with chlorine Cl2 in a presence of light to
replace H’s with Cl’s
• Boiling point increases as the number of carbon
increases
• Dispersion forces increases as the molecular size
increases, resulting melting point and boiling point
increases

S.A.I.S.A.Kadir 16
Properties of Alkanes and Cycloalkanes

S.A.I.S.A.Kadir 17
Properties of Alkanes and Cycloalkanes

S.A.I.S.A.Kadir 18
Practice Exercise

Arrange the following compounds in order of

increasing boiling point
CH3CH2CH3
propane Boiling point
CH3CH2CH2CH2CH3 increases
n-pentane
CH3(CH2)7 CH3
n-nonane
 The synthesis of alkanes
1. Hydrogenation of alkenes
H H H H
Pt / Pd / Ni
C C + H2 H C C H
H H H H
alkene hydrogen alkane

Example:
Ni
C2H4 + H2  C2H6
ethene ethane
 The synthesis of alkanes

2. Hydrolysis of Grignard reagent (alkylmagnesium halide)

H+
RMgX + H2O  RH + Mg(OH)X
alkylmagnesium
alkane
halide

Example:
H+
CH3CH2CH2MgCl + H2O CH3CH2CH3 + Mg(OH)Cl

Propylmagnesium Propane MagnesiumChloride

chloride Hydroxide
 The synthesis of alkanes

3. Wurtz reaction (Reduction of alkyl halide)

2RX + 2Na  R-R + 2NaX

alkyl halide reducing alkane
agent

Example:
2CH3CH2CH2Br + 2Na  CH3CH2CH2CH2CH2CH3 + 2NaBr

bromopropane hexane Sodium Bromide

4. Combustion
5. Halogenation

Light/heat
 Reactions of Alkanes and Cycloalkanes

.. .. .. ..
.. .. .. . + . ..
Cl
.. Cl
.. Cl
.. Cl
..

H H
.. Chlorine radical
H C Cl H C . + . Cl ..
..
H H
Methyl radical
H H
..
+ .
+ . Cl .
H C Cl H C .. .
H H Carbocation
H H
-.
H C H H C. + H+
H H Carbanion 25
 Reactions of Alkanes and Cycloalkanes

• Free Radical Substitution Reaction

• replace H with a halogen atom
• initiated by addition of energy in the form of heat or
ultraviolet light
• to start breaking bonds
• generally get multiple products with multiple
substitutions through chain reactions

H Heat OR H
UV light
H C H + Cl Cl H C Cl + HCl
H H

26
 Reactions of Alkanes and Cycloalkanes

• Chlorination of Methane
• Methane reacts with chlorine in the presence of heat
or light to produce a mixture of products through a
sequence of substitution reactions in which the H
atoms are successively replaced by Cl atoms.

CH4 + Cl2 heat or light CH3Cl + HCl

Cl2
CH2Cl2 + HCl
CH3Cl , chloromethane Cl2
CH2Cl2 , dichloromethane CHCl3 + HCl
CHCl3 , trichloromethane Cl2
CCl4 , tetracloromethane CCl4 + HCl
27
 Free Radical Substitution

• The breaking of a covalent bond so that each atom

retains one of the shared electrons will produce two
free radicals.
• Free radicals are very reactive. They are intermediates
in reaction mechanism.
• The substitution reactions of alkanes follow the free
radical mechanism, which involved three major steps:
1. Initiation: Initial production of free radicals
2. Propagation: Free radicals attack molecules to
produce another free radical
3. Termination: Two free radicals combine to form a
molecule

28
 Mechanism of Free Radical substitution
a) Initiation
Dissociation of a chlorine molecule into two chlorine radicals

b) Chain propagation

The Cl free radical attacks the CH4 molecule to give a methyl free radical

Step 1: Hydrogen atom is removed from methane after attacked by chlorine

radical and produce a methyl free radical

Step 2: Reaction of methyl radical with molecular chlorine

c) Termination
Free radicals combine to produce molecules and reaction stops