Chapter 2

Alkanes AND CYCLOALKANES

1
 Learning objectives Alkane and Cycloalkanes
Upon completion of this course, students will be able to:

Explain basic concepts of physical properties, sources and uses of alkane and
cycloalkanes.

Name and draw structures of alkane and cycloalkanes according to their IUPAC
and trivial names

Discuss the method preparation and reaction for alkanes and cycloalkanes

Discuss the Baeyer Strain Theory

List the uses of alkanes

 Overview Alkane and Cycloalkanes

2.1 General formula: CnH2n+2

2.2 Structure and Nomenclature: IUPAC and common

names

2.3 Methods of preparation:

2.3.1 Hydrogenation of alkenes
2.3.2 Reduction of alkyl halides
2.3.3 Hydrolysis of Grignard reagent
2.4 Reactions of alkanes
2.4.1 Halogenation (discuss mechanism)
2.4.2 Combustion
2.4.3 Ring opening reactions : cyclopropane

2.5 Baeyer Strain Theory

2.6 Uses of alkanes
 General Formula

Structure

Sources & uses & Nomenclature

Reaction of Method of
Alkanes Preparation
 GENERAL FORMULA
• Acyclic alkane (alkane without ring) have the general formula CnH2n+2.

• Cycloalkane (carbon atom arranged in a ring) containing a single ring have

two fewer hydrogen atoms, general formula CnH2n.

• Given the number of carbon atoms in an alkane, it is easy to determine the

number of hydrogens in the molecules & also its molecular formula.

• Exp : Decane with 10 carbon atoms must have (2x10) + 2 =22 hydrogen atoms
& a molecular formula of C10H22.
 STRUCTURE
• Shape
– tetrahedral about carbon
– all bond angles are approximately 109.5°

• Representing Alkanes

Ball-an d-stick
mo del

Line-ang le
fo rm ula
Stru ctural CH3 CH2 CH2 CH3 CH3 CH2 CH2 CH2 CH3
fo rm ula Pen tane
Butane
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 NOMENCLATURE
International Union of Pure and Applied Chemistry (IUPAC)

Alkane IUPAC Name

Prefix + parent + suffix CH4 methane
C2H6 ethane
C3H8 propane
Name & Name & C4H10 butane
location of location of
substituent functional C5H12 pentane
group C6H14 hexane
C7H16 heptane
Longest
carbon C8H18 octane
chain C9H20 nonane
C10H22 decane
 ➢ Method
Parent chain Numbering
→Longest carbon →Branch lowest
chain carbon number

Arrange
Locate and name
→Alphabetical branch
order
 ➢ Rule 1
• Find the longest carbon chain
✓ Not necessarily straight
✓ Write the parent name

CH3-CH-CH2-CH3 CH3-CH-CH2-CH2-CH3
CH3 CH2-CH3

BUTANE HEXANE
 ✓ CONTINUE..
• If have more than one possible longest carbon chain
✓ Choose parent chain with more substituent

2 1
CH3-CH-CH3 1
CH3-CH-CH3
2 3 4 5 6 7
3 4 5 6 7

CH3-CH2-CH-CH2-CH2-CH2-CH3 CH3-CH2-CH-CH2-CH2-CH2-CH3
2 substituents 1 substituent
 ➢RULE 2
• Numbering the parent chain
✓ Circle the substituent group atom
✓ Do numbering to give substituent at lowest carbon number
✓ Numbering must be continuous

1 2 3 4 3 4 5 6
CH3-CH-CH2-CH3 CH3-CH-CH2-CH2-CH3
CH3 CH2-CH3
methyl methyl 2 1
C2 C3
 Example…
✓ 1st substituent must be at lowest carbon number

1st substituent: C2 1st substituent: C3

 ➢ Example..
✓ If two possible lowest substituent

❖Choose according to alphabetical order

1 2 3 4 5 6 7

✓ So, Cl (Chloro)should be at lowest carbon number compare to CH3 (Methyl)

 ➢RULE 3
• Name and locate branch
1 2 3 4
CH3-CH-CH2-CH3
CH3
2-methyl
4-isopropyl

CH3CHCH3
1 2 3 4 5 6 7 8 9
CH3CHCH2CHCH2CHCH2CH2CH3
CH3 CH2CH3

2-methyl 6-ethyl
 ➢ EXAMPLE..
• Use prefix
✓ If more than one same substituents
✓ Prefix excluded from alphabetical order except ~iso compound
H H
No. of Prefix
1 2 3 4
substituent used
H3C C C CH3
2 di
CH3 CH3 3 tri
4 tetra
2-methyl 3-methyl 5 penta
6 hexa
2,3-dimethyl
 ➢EXAMPLE
• Alkanes can have many different types of substituent groups

4-isopropyl

CH3CHCH3
1 2 3 4 5 6 7 8 9
CH3CHCH2CHCH2CHCH2CH2CH3
Cl NO2

2-chloro 6-nitro
 ➢RULE 4
• Arrange according to alphabetical order

CH2 CH3 4-ethyl

CH3 CH2 CH2 CH CH CH2 CH3

7 6 5 4 3 2 1

CH3 3-methyl

4-ethyl-3-methylheptane
 ✓ Example..
4-tert- butyl

C(CH3)3
1 2 3 4 5 6 7 8 9
CH3CH2CHCHCH2CHCH2CH2CH3
CH3 CH3CHCH3

6-isopropyl @
3-methyl
6-sec-propyl
4-tert-butyl-6-isopropyl-3-methylnonane
@
4-tert-butyl-3-methyl-6-sec-propylnonane
 ➢Exercises
• Give the IUPAC name for the following compounds
 ➢ DRAWING ALKANE STRUCTURE

Place the Complete the

Draw the substituents structure of
parent chain Number the at the parent parent chain
of carbon parent chain chain with suitable
atoms indicated by number of
the numbers hydrogen
✓Example..

CH3
1 2 3 4 5 6
CH3CHCH2CHCH2CH3
CH3
 EXERCISE
a. CH3CH2CH2C(CH3)3 b. CH3C(CH3)2CH(CH3)2

c. d.

e. f.
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 ……CONT EXERCISE
Write the skeletal structure for each following compound
a. 4-tertbutyl-3-methylheptane
b. 4-chloro-2,3-dimethylnonane
c. 1,4-dichloropentane
d. Sec-butylbromide
e. 2,2-dimethyl-4-propyloctane
f. 1-bromo-1-chloro-2-methylpropane
g. 5-isopropyl-6-tert-butyl-2,2-diiodo-3-methylnonane

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 INTRODUCTION
 Cyclic compound: A compound in which a
series of atoms is connected to form a loop or
ring.
 Cycloalkanes: Alkanes that contain rings of
carbon atoms.
 Examples:

H H
H
H
C
C C
H H
C C H
H
C
H H
H H
cyclobutane cyclohexane
 NOMENCLATURE
Parent chain
→Longest carbon Arrange
chain →Alphabetical order
→ cyclic / acyclic

Numbering
→SUBSTITUENTS Locate and name
must at lowest carbon substituents
number
 CYCLOALKANES
1. Named like acyclic (noncyclic) alkanes, with the prefix
cyclo- indicating the presence of a ring.

2. If there is just one substituent, no numbering is needed.

For examples:
 CONTINUE..
3. If there are two or more substituents on the ring, the ring
carbons are numbered to give the lowest possible numbers for the
substituted carbons.

4. In the name, the substituents are listed in alphabetical order.

5. When the numbering could begin with either of two alkyl

groups (as in disubstituted cycloalkanes), begin with the one
that is alphabetically first.
 EXAMPLES..
1
CH3 CORRECT

4 32 1-ethyl-3-methylcyclohexane
5 1
6
CH2CH3 (lowest possible numbers of
substituents)
CH3
INCORRECT
45 6
32 1
1-ethyl-5-methylcyclohexane
CH2CH3

INCORRECT
CH3
3-ethyl-1-methylcyclohexane
6 12
5 3
4
CH2CH3 (begin with the one that is
alphabetically first)
 EXAMPLES..
2 CH3 CH3 1,1,3-trimethylcyclopentane
1 (carbon 1 = carbon that attached to
5 2 many substituents)
3
4
CH3
3
CH3
6
1 2 Br CORRECT
3
2-bromo-4-chloro-1-methylcyclohexane
5
4 (lowest possible numbers of substituents)
Cl

CH3
4 Br
5
3 INCORRECT
6
3-bromo-1-chloro-4-methylcyclohexane
2
1
Cl
 CONTINUE..
6. If longest carbon chain: Acyclic > cyclic
Or
➢ Acyclic contain an important functional group

So, the CYCLIC PORTION will be the substituent group and name
as cycloalkyl group.

Examples:

H C C CH2 CH2 CH2

4-cyclopropyl-3-methyloctane 5-cyclobutyl-1-pentyne
 CIS / TRANS
✓ Less flexible than their open-chain
✓ Two isomers:
i) cis – two substituents point toward the same direction.
ii) trans - two substituents point toward opposite direction.
✓ Example:
 Exercises
a) d) j)

g)

k)
b) h)

e)
i) l)
c) f)
m) o) r)

n) u)
p)
s)
q)
t)
 CLASSIFICATION OF CARBONS
 Primary (1°): a C bonded to one other carbon
 Secondary (2°): a C bonded to two other carbons
 Tertiary (3°): a C bonded to three other carbons
 Quaternary (4°): a C bonded to four other carbons
a 2° carb on
a 4° carb on
a 3° carb on
CH3
CH3 -C- CH2 - CH-CH3
a 1° carb on CH3 CH3 a 1° carb on

2,2,4-Trimeth ylp entane

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 Method of
Preparation

Hydrolysis of
Hydrogenation Reduction of
Grignard
of alkenes alkyl halides
Reagent
 HYDROGENATION OF ALKENES
• Alkenes & alkynes reacts with H2 in the presence of metal catalyst (Ni/Pd/Pt) to
produce alkanes. Usually carried out at 25°C and 50 atm.

R R' R R'
H 2 /Pt
C C CH CH
R R' R R'

H H
H 2 /Pt
R C C R' R C C R'
H H

Example:
Pt /Pd /Ni
+ H2
C2H5OH

25°C. 50 atm
cyclohexane
cyclohexene
• Margarine manufacture
• Some margarine is made by hydrogenating
carbon-carbon double bonds in animal or
vegetable fats and oils.
• You can recognize the presence of this in foods
because the ingredients list will include words
showing that it contains "hydrogenated
vegetable oils" or "hydrogenated fats".
 REDUCTION ALKYL HALIDES

• Alkyl halides reduction can occur via lithium aluminium hydride

(LiAlH4) and via acid/zn to produce an alkanes
H H H
+
LiAlH 4 Zn/H
R C R' R C R' R C R'
ether
X H X

• Example;
CH3CH2CHCH3 Zn/HCl CH3CH2CHCH3

Br H
2-bromobutane butane
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 HYDROLYSIS GRIGNARD REAGENTS
• alkyl halide reacts with dry ethyl ether and metallic Mg to produce Grignard Reagent (R-C-Mg-X)
• The Grignard Reagent is very highly reactive reacts with H2O and form an alkane

Mg
R C X R C Mg X
ether

an alkyl halide a Grignard reagent

R C Mg X R C H + Mg(OH) X
H 2O

alkane
H2 H2O
C + Mg H2 H2
C C + HOMgBr
H3C Br dry ether H3C MgBr H3C H 39
 EXERCISE
1. Suggest a suitable starting material and condition to prepare 2-methylbutane by
hydrolysis of Grignard Reagent.
2. Specify the missing compounds/reagents in each of the following syntheses. (More
than 1 step may be necessary in some cases)
a) ?
b)

c)

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REACTION OF ALKANES

Combustion

Ring opening
reaction : Halogenation
cyclopropane
 ➢Combustion
• Alkanes burn in plentiful supply of air or oxygen to produce water
and carbon dioxide only
✓ C3H8 + 5O2 3CO2 + 4H2O
• In a limited supply of air, combustion of alkanes produces carbon
monoxide and water
✓ C2H6 + 5/2 O2 2CO + 3H2O
• In a very limited supply of air, alkanes burn to form carbon and
water
✓ C2H6 + 3/2 O2 2C + 3H20
 ➢ Halogenation
• At room temperature (RT), alkanes do not react with chlorine or
bromine.
• At high temperature (300-400 ⁰C) or irradiated by UV light, the H
atoms in the alkane are replaced by halogen to produce a mixture
of haloalkanes and a hydrogen halide.
• This reaction is a free radical substitution reaction- halogenation
 ✓ Continue…
• Equation for reaction of methane with chlorine

✓ Equation 1: reaction with limited supply of chlorine and excess

of methane. The major product is chloromethane.
✓ Equation 2: reaction with the excess of chlorine and limited of
methane. The major product is tetrachloromethane.
 ✓ Continue…
• This reaction is called a substitution reaction (an atom or a group atom in
an organic compound is replaced by another atom or a group of atoms).
✓ Involves a halogen - called halogenation
✓ If the halogen is chlorine – called chlorination.
✓ If the halogen is bromine – called bromination.

• Condition of reaction:
✓ light or heat (high temperature) or ultraviolet radiation (provides
energy that is absorbed by reactant molecules to produce free radicals).
 ✓ Mechanism of Free Radical Substitution
Reaction

Initiation
Propagation Termination
→ 1 step
→ 2 steps → 3 steps
→ Need heat or uv
 Initiation step
• The mechanism
 Propagation steps
• Free radical species produce another free radical species
✓ Free radical is highly reactive species
• Methyl radical propagates chain reaction
✓ Methyl radical will react with another chlorine molecule producing
chloromethane and a chlorine free radical

• Chlorine radical produced will then react with another methane

molecule and the cycle is repeated
 Termination steps
• The reaction stops when two free radicals collide and combine.
• Highly exothermic.
 Example..
• Bromination reaction of ethane

• Further propagation steps can take place until CBr3CBr3 is finally produced
 ✓ Example..
 Bromination reaction of propane
•
Br• CH CHCH
3 3 CH3CHCH3 + Br• MAIN PRODUCT
2° alkyl radical
Br
CH3CH2CH3 2-bromopropane
1° 2° 1° Br• CH CH CH •
3 2 2 CH3CH2CH2 + Br•
1° alkyl radical Br
1-bromopropane

• 2-bromopropane is the main product because:

✓ It is easier for halogen free radical to abstract a hydrogen atom from a
secondary carbon atom than primary carbon atom
 ✓ Example..

• The major product is the most stable product which are:

✓ Alkyl halide 3o > 2o > 1o
 EXERCISE

1. 1-chlorobutane is the product of chlorination of butane in UV light.

a) Write a general equation for the chlorination reaction described above.
b) Name the mechanism of this reaction
c) The first step in the mechanism is the initiation step. Write equation for
the initiation step
d) The second step of the mechanism of this reaction is the propagation
step. Write equations for the propagation step until 1- chlorobutane is
obtained
e) Write equation for the termination step

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2. 1-bromocyclopentane is the product of bromination of cyclopentane. Show
the mechanism for the bromination of cyclopentane

3. When a few drops of liquid bromine are added to hexane, a reddish-brown

solution is obtained. When the mixture is exposed to sunlight, a reaction
occur slowly. Write the chemical equation for the reaction between bromine
and hexane.

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➢ Ring Opening Reactions : Cyvlopropane
 BAEYER STRAIN THEORY
✓ Conformations of cycloalkanes are affected by:
➢ torsional strain
➢ steric strain
➢ angle strain
❑ Increasing in energy when bond angles deviate from
the optimum tetrahedral angle of 109.5°.
✓ Determine the reactivity of cyclic structure
 CONTINUE..
✓ The Baeyer strain theory
➢ Suggested : bond angle ideally to have 109. Smaller will be
too strained
➢ was formulated when it was thought that rings were flat.
➢ It states that larger rings would be very highly strained,
➢ So, their bond angles would be very different from the
optimum 109.5°.
✓ Cycloalkanes: > 3 C atoms, NOT flat molecules.
✓ They are puckered to reduce strain.
 CONTINUE..

Three-dimensional structure of some cycloalkanes

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 RING STRAIN

Bond angle :
cyclopropane < cyclobutane < cyclopentane

Angle strain :
cyclopropane > cyclobutane > cyclopentane

Reactivity :
cyclopropane > cyclobutane > cyclopentane
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 PETROLEUM
(NATURAL RESOURCES AND USES)
• Natural gas
✓ Used primarily as a fuel to heat buildings and generate electricity as well as starting
material for the production of fertilizers.
• Petroleum
✓ Composed of crude oil (a complex mixture of alkanes & other hydrocarbon)
✓ The crude oil is separated into fractions in the oil refinery by fractional distillation.
✓ Relies on the differences in boiling points of the different fractions in the crude oil.
✓ Each fraction contains hydrocarbons which boil in a common range of boiling points.
 ✓ Uses
• Fuel for automobiles, aircraft and train
• Provide most of the greases and lubricants required for the
machinery of highly industrialized society
• Petroleum with natural gas provides 90% of organic raw materials
for synthesis and manufacture of
✓ synthetic fibers
✓ Plastics
✓ Detergents
✓ Drugs
✓ dyes
USES