CHAPTER 2
ALKANE &
CYCLOALKANES
LESSON OUTLINE
Introduction
General formula
1.1 Structure & Nomenclature
IUPAC and common names
Drawing Structure
1.2 Method of preparation
Hydrogenation of alkenes
Reduction of alkyl halide
Hydrolysis of Grignard reagent
1.3 Reaction of alkanes
Halogenation (mechanism)
Complete combustion
Ring opening reactions (Cyclopropane)
1.4 Baeyer Strain Theory for cycloalkanes
1.5 Uses
INTRODUCTION
Saturated
hydrocarbon
Source
Contain only C-H &
Crude Oil & Natural C-C single bonds
gas
General formula
CnH2n+2
1.1 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 chain C8H18 octane
C9H20 nonane
C10H22 decane
METHOD
Parent chain
Numbering
→Longest carbon
chain →Branch lowest
carbon number
→ cyclic / acyclic
Arrange Locate and name
→Alphabetical order branch
ALKANES
RULE 1
Find the longest continuous carbon chain
Not necessarily straight
Write the parent name
CH3-CH-CH2-CH3
CH3-CH-CH2-CH2-CH3
CH3
CH2-CH3
BUTANE
HEXANE
RULE 1
■ 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
substituent used
1 2 3 4
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
CYCLOALKANES
1. Use prefix cyclo- indicating the presence of a ring.
2. If there is just one substituent, no numbering is needed.
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.
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
EXAMPLES
CH3
CORRECT
4 32
5 1
6
1-ethyl-3-methylcyclohexane
CH2CH3
CH 3 INCORRECT
4 5 6 1-ethyl-5-methylcyclohexane
3 2 1
C H 2C H 3
C H 3
INCORRECT
4 5 6 3-ethyl-1-methylcyclohexane
3 2 1
C H 2C H 3
EXAMPLES
CH3 CH3
1
5 2 1,1,3-trimethylcyclopentane
3
4
CH3
C H 3
1 2 B r
6 2-bromo-4-chloro-1-methylcyclohexane
3 (lowest possible numbers of substituents)
5
4
C l
C H 3
4 B r
5 3-bromo-1-chloro-4-methylcyclohexane
3
6 2
1
C l
DRAWING STRUCTURE
Complete the
Place the
structure of
Draw the substituents at
Number the parent chain
parent chain of the parent
parent chain with suitable
carbon atoms chain indicated
number of
by the numbers
hydrogen
EXAMPLE
CH3
1 2 3 4 5 6
CH3CHCH2CHCH2CH3
CH3
EXERCISES
Draw the structural formula for each of the following
compounds
1.2 METHOD OF PREPARATION
3. Hydrolysis of
[Link] 2. Reduction of
Grignard
of alkenes alkyl halide
reagent
1. HYDROGENATION OF
ALKENES
Addition of two hydrogen atom to the double bond of alkene
2. REDUCTION OF ALKYL
HALIDE
Alkyl halide react with zinc and aqueous acid to produce an alkane
3. HYDROLYSIS OF GRIGNARD
REAGENT
Also known as alkylmagnesium halide (R-MgX)
R-MgX + H-OH H+ R-H + Mg(OH)X
Alkylmagnesium Alkane
halide
H+
CH3CH2CH2MgCl + H-OH R-H + Mg(OH)Cl
1.3 REACTION OF ALKANES
3. Ring Opening
Reactions
1. Halogenation 2. Combustion
1. 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
1. HALOGENATION
■ 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).
EXAMPLE
Equation for reaction of methane with chlorine
CH4 + Cl2 CH3Cl + HCl ………………. (1)
CH3Cl + Cl2 CH2Cl2 + HCl
CH2Cl2 + Cl2 CHCl3 + HCl
CHCl3 + Cl2 CCl4 + HCl ……………….. (2)
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.
Free Radical Substitution Reaction
( MECHANISM)
A) INITIATION B) PROPAGATION C) TERMINATION
→ 1 STEP → 2 STEPS → 3 STEPS
A) INITIATION STEP
B) 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
C) 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• •
CH3CHCH3 CH3CHCH3 + Br• MAIN PRODUCT
2° alkyl radical
CH3CH2CH3 Br
2-bromopropane
1° 2° 1° Br•
CH3CH2CH2• 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
2. COMPLETE COMBUSTION
■ Alkanes burn in plentiful supply of air or oxygen to produce water
and carbon dioxide only
C3H8 + 5O2 3CO2 + 4H2O
3. Ring Opening Reaction
Cyclopropane
1.4 BAEYER STRAIN THEORY
(Determine the reactivity of cyclic structure)
Increasing in energy when bond angles deviate from the optimum tetrahedral angle of 109.5°.
The optimum bond angle is 109.5°.
If the bond angle deviates from the optimum value, it will introduces angle strain.
Increase angle strain will increase reactivity of cyclic compound.
Bond angle :
cyclopropane < cyclobutane < cyclopentane
Angle strain :
cyclopropane > cyclobutane > cyclopentane
Reactivity :
cyclopropane > cyclobutane > cyclopentane
1.5 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
THE END
