Assignment 1

AS/JUN 2018/CHM456
2b) The pKa value of anilium ion C6H5NH3+
and ammonium ion NH4+ are 4.63 and
9.2 respectively. On the basis of this fact,
explain whether aniline, C6H5NH2 is a
stronger or weaker base than ammonia,
NH3.
AS/JAN 2018/CHM456
3b) Arrange the following molecules by increasing
reactivity as a nucleophile. Justify your answer.

AS/JUN 2016/CHM456
4a) Ethyl chloride and propyl chloride have
different melting point. Determine which one
shows higher melting point. Justify your
answer.
CHAPTER 4
Alkanes and
Cycloalkanes
• Alkanes are aliphatic hydrocarbon.

• They contain C-C and C-H only which

linked together by single bonds.

H H
H C C H
H H
• Alkanes are called saturated hydrocarbons
which mean that all of the carbons have
the maximum number of bonds (4).

• Example: Methane, CH4, is made from one

carbon atom bonded to four hydrogen
atoms.
H

H C H

H
• General formula of alkanes is CnH2n+2
Where n is the number of carbon atoms in
the alkane molecule.

• Example: n = 3
C3H2(3)+2 = C3H8

• The name of the alkanes ends with “-ane“.

 Table 2.1: The first ten alkanes
IUPAC Number of prefix Molecular Condensed Structural Formula
name Carbons Formula
Methane 1 Meth- CH4 CH4
Ethane 2 Eth- C2H6 CH3CH3
Propane 3 Prop- C3H8 CH3CH2CH3
butane 4 But- C4H10 CH3CH2CH2CH3
Pentane 5 Pent- C5H12 CH3CH2CH2CH2CH3
Hexane 6 Hex- C6H14 CH3CH2CH2CH2CH2CH3
Heptane 7 Hept- C7H16 CH3CH2CH2CH2CH2CH2CH3
Octane 8 Oct- C8H18 CH3CH2CH2CH2CH2CH2CH2CH3
Nonane 9 Non- C9H20 CH3CH2CH2CH2CH2CH2CH2CH2CH3
decane 10 Dec- C10H22 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3
3 Ways to write the structural formula of
organic compounds:

• Condensed structural formula/ Molecular

formula
• Displayed formula/dashed formula
• Skeletal formula
Example: Butane

CH3CH2CH2CH3
condensed structure/ H H H H
molecular formula
H C C C C H
H H H H
displayed formula
skeletal formula
 Cycloalkanes

• Cycloalkanes contain carbons atoms joined

by single bond in one or more rings.

• It is classified as alicyclic compounds.

• The general molecular formula is CnH2n.

 • Cycloalkanes contain two fewer hydrogen
atoms than the aliphatic alkane with the
same number of carbons.

H2C H2C H2C H2C

CH2 loss of
H2C 2H H2C CH2
CH2 CH2
H2C H2C

H H
Hexane (alkane) cyclohexane (cycloalkane)
CnH2n+2 CnH2n
• Cycloalkanes are named by adding the
prefix “cyclo” to the name of the aliphatic
alkane.
 Table 2.2: Common Cycloalkanes
Name Molecular Formula Structural Formula

Cyclopropane C3H6

Cyclobutane C4H8

Cyclopentane C5H10

Cyclohexane C6H12
 Naming Alkanes
• System used: International Union of Pure
and Applied Chemistry (IUPAC).

The rules:
1) Identify the parents hydrocarbon chain
which indicates the number of carbons in
the longest continuous carbon chain and
number the chain.
2) Identify the prefix (refer to table 2.1).

3) Identify the functional group of the

parent’s structure. The suffix indicates
what functional group is present.
Example:

1 2 3 4 5 6 7
CH3CH2CH2CH2CH2CH2CH3

The compound has 7C. The prefix for 7C is

hept, and because it is an alkane group,
the name is written as heptane with
addition of the suffix “ane” at the end of
the name.
4) Identify the side-chain/substituent.
Different side-chains and functional
groups will be named in alphabetical
order.

If two or more identical substituents are

present, use one of the prefixes, di-----, tri---
--, tetra-----, penta-----, hexa----- and so forth.
The prefixes di-, tri-, tetra-, penta-...etc. are
not taken into consideration for grouping
alphabetically.

Example:

Br CH2CH3
1 2 3 4 5 6 7
CH3CHCHCCH2 CH2CH3

CH3 CH2CH3
 Naming of the Carbon Substituent

• Carbon substituent bonded to the longest

carbon chain are called alkyl groups.

• An alkyl group is formed by removing one

hydrogen from an alkane (change the “–ane”
ending of the parent alkane to “–yl”).

• e.g. CH4 (methane) becomes CH3 (methyl)

Example: 1 2
CH3CH2
3 4
CH3CHCHCH2CH3
5 6 7
CH2CH2CH3
4-ethyl-3-methylheptane
suffix

Substituent & location Parent name/preffix

Example:
Start numbering
CH3 Parent name
5 4 3 2 1 suffix
CH3CH2CH2CCH3
Subtituent & location
CH3

The name of the compound is

2,2-dimethylpentane
• If two different chains of equal length
are present, choose one with the most
number of alkyl groups attached to the
main carbon chain.
Example:
CH3CHCH3
2 3 4 5 6 7
A 1
CH3CH2CHCH2CH2CH2CH3

2 1
CH3CHCH3
B
3 4 5 6 7
CH3CH2CHCH2CH2CH2CH3
Two alky group

2 1
CH3CHCH3
3 4 5 6 7
CH3CH2CHCH2CH2CH2CH3
Using of iso, sec-,
tert- in Naming
Alkanes
 “iso”

• Compounds which have the same molecular

formula but differ in the connection of
atoms are called constitutional isomers.

• For example; isobutane is an “iso” mer of

butane.
• Isobutane is a four carbon-alkane with an
“iso” structural unit.

• In isobutane structure, a carbon bonded to

a hydrogen and two CH3 groups.

H H H H
H C C C H CH3CCH3
H H H CH3
butane isobutane isobutane
 “sec- and tert-”
• There are four alkyl groups contain in four
carbon atoms.
A hydrogen removed from a primary carbon.

CH3CH2CH2CH2 CH3CHCH2
a butyl group CH3
an isobutyl group
• A sec-butyl group has a hydrogen removed
from a secondary carbon.

• A tert-butyl group has a hydrogen removed

from a tertiary carbon.

CH3
CH3CH2CH CH3C
CH3 CH3
a sec-butyl group a tert-butyl group
Summary: Names of Some Alkyl Groups
Name Structure
methyl CH3

ethyl CH3CH2

propyl CH3CH2CH2

CH3CH
isopropyl
CH3
 Name Structure
butyl CH3CH2CH2CH2

CH3CHCH2
isobutyl
CH3
CH3CH2CH
sec-butyl
CH3
CH3
tert-butyl CH 3C
CH3
 Naming Cycloalkanes
Step 1: Find the parents cycloalkane.
• Count the number of C atoms in the ring
and name the parent’s structure.
• How many carbons are in the ring?
NO2
Cl

Br
CH3
 NO2
6C Cl 3C

Br
CH3
• 6 carbons is hexane; 3 carbons is propane.

• Add the prefix “cyclo-” and the suffix “–ane”

to the parent name.

• The parent’s name are cyclohexane and

cyclopropane.
Step 2: Name and number the substituent
• No number is needed to indicate the
location of a single substituent or
monosubstituted cycloalkanes

Example:

CH3

Methylcyclohexane
• What happen to the rings with more than
one substituent?

CH3

H3C
• Begin numbering at one substituent and
proceed around the ring clockwise or
counter wise to give the lowest position
number.
Numbering clockwise counterclockwise

5 6 3 2
1 1
4 CH3 4 CH3
3 2 5 6
H3C H3C

1,3-dimethylcyclohexane 1,5-dimethylcyclohexane
(wrong name)
• What happen to the rings with two or three
different substituents?

• If two different substituents, number from

the substituent of lower alphabetical order.

• If three or more substituents, number to

give them the lowest set of numbers and
then list substituents in alphabetical order
when writing the name.
 How to name the following compound?

CH3CH2
1

2
3

CH3

Find the parent name.

Numbering the compound (where to start?)
Name the substituent & state the location.
 Draw the structure of the
following compounds.

a) 3,3,4,4-tetramethylheptane
b) 5-isopropyl-2-methyloctane
c) 1-methyl-2-propylcyclopentane
d) 4-isopropyl-2,4,5-trimethylheptane
e) 4-chloro-2-fluoro-1-methylcyclohexane
f) 4-tert-butylheptane
g) sec-butylcyclopentane
 Bond Rotation and Conformational
Analysis of Butane
• There are three rotation of butane to be
consider. Two CH3 groups (C1 and C4) in the
eclipsed position. This is the highest energy
conformation for butane, due to what is called
‘Van der Waals repulsion’, or ‘steric repulsion’,
between the two rather bulky methyl groups.
• Rotate the front, (blue) carbon by 60°clockwise,
the butane molecule is now in a staggered
conformation or always referred as gauche
conformation.

• Although they are staggered, the two methyl

groups are not as far apart as they could possibly
be. There is still significant steric repulsion
between the two bulky groups.
• A further rotation of 60° gives a second eclipsed
conformation (B) in which both methyl groups are
lined up with hydrogen atoms.

• Due to steric repulsion between methyl and

hydrogen substituents, this eclipsed
conformation B is higher in energy than the
gauche conformation. However, it is lower in
energy than eclipsed conformation A because
there is no methyl-to-methyl eclipsing.
• One more 60° rotation produces the ‘anti’
conformation, where the two methyl groups are
positioned opposite each other and steric
repulsion is minimized. This is the lowest energy
conformation for butane.
• The relative energies for the various eclipsed,
staggered, and gauche conformations of butane.
 Conformation of Cyclohexane
• There are two conformations of cyclohexane,
the planar and chair conformations.

• In the planar conformation, the bond angle

in the ring is 120o, all 12 C-H bonds are
eclipsed and as a result very unstable.
• In the chair conformation of cyclohexane,
all 12 C-H bonds are staggered and the
bond angle is 109.5° (tetrahedral bond
angle).

• With no angle strain and no torsional

strain, the chair conformer of cyclohexane
is very stable and is the preferred
conformation in which cyclohexane
systems exist in.
Looking at the chair conformation, one can identify a back-rest, a
seat and a leg-rest like that of a chair.
• Boat conformations are also possible with cyclohexane
systems, but they are of higher energy than the chair
conformations.
Of all conformations of cyclohexane, the chair conformations are
of least energy and thus most stable. Chair conformations are
therefore the most realistic representations of cyclohexanes.
There are two types of bonds in cyclohexanes: Equitorial bonds are oriented
towards the rings equator, while axial bonds are on the rings axis.
To ring flip, identify where the substituents are. In one
conformer, push up at C-4 and down at C-1 to obtain the
4C conformer. The other conformer is obtained by
1
pushing up at C-1 and down at C-1 to provide the 1C4
conformer.
• In methylcyclohexane, the methyl group can
be in an equatorial or axial position.
• We might, therefore, expect to find two
conformers of methylcyclohexane.
 Stability of Cyclohexane Conformer
• Although cyclohexane rings rapidly flip
between conformations at room temperature,
the two conformers of a monosubstituted
cyclohexane are not of equal stability.
• In the 1C4 conformer, there is van der Waals
strain between hydrogens of the axial CH3 and
hydrogens at C-3 and C-5, while in the 4C1
conformer, there is a smaller van der Waals
strain between hydrogens at C-1 and
hydrogens at C-3 and C-5.
The investigation of molecular conformations and their relative
energies is called conformational analysis. As a generalization, for
other monosubstituted cycloalkanes: “a substituent is almost always
stable in an equatorial position than in an axial position”.
PHYSICAL PROPERTIES OF
ALKANE
(Reading Assignment)
 Physical Properties
Boiling Point
Alkanes have low bp’s compared to more polar compounds
of comparable size

Bp increases as the number of carbons increases because of

increased surface area & greater London forces
 Physical Properties
Boiling Point
The bp of isomers decreases with branching because of
decreased surface area & weak London forces

As branching increases, the alkane molecule becomes more spherical

in shape & has a smaller surface area
As the surface area ↓, contact between adjacent molecules ↓,
London forces ↓, boiling point ↓
 Physical Properties

Solubility
❑ Alkanes are soluble in nonpolar organic solvents
❑ Alkanes are insoluble in water

Physical state
At room temperature (25°C) and atmosphere pressure
(1 atm)
❖ methane, ethane, propane and butane are gases
❖ the C5-C17 are liquids
❖ C18 and above are solid
Physical Constants of the Hexane Isomers
Branching of the alkane chain lowers the boiling point

1. Boiling points of C6H14: hexane (68.7 °C); 2-methylpentane (60.3 °C); 3-methylpentane (63.3
°C); 2,3-dimethylbutane (58 °C); 2,2-dimethylbutane (49.7 °C).

2. As the molecular weight of unbranched alkanes increases, so too does the molecular size,
and even more importantly molecular surface areas.
1) Increasing surface area ⇒ increasing the van der Waals forces
between molecules ⇒ more energy (a higher temperature) is required
to separate molecules from one another and produce boiling.

3. Chain branching makes a molecule more compact, reducing the surface are~ 21 ~and with it
the strength of the van der Waals forces operating between it and adjacent molecules ⇒
lowering the boiling.
Synthesis of Alkanes
 Hydrogenation of Alkenes

• Hydrogens are added to alkenes in the

presence of alcohol and metal catalysts like
nickel, palladium or platinum.

H2/Pd
C C C C
ethanol
alkene
H H
alkane
 H2/Pt
CH3CH CHCH3 heat
2-butene

CH3CH CHCH3

H H
butane
 Hydrogenation of Alkynes

• H2 adds to an alkyne in the presence of

metal catalyst such as Pd, Pt or Ni.

• It is difficult to stop the reaction at the

alkene stage because hydrogen readily adds
to alkene in the presence of the efficient
metal catalyst.

• The final product is alkane.

The addition of H2 in the presence of metal catalyst:

H2/Pd
CH3CH2C CH CH3CH2CH CH2
alkyne alkene

H2/Pd

CH3CH2CH2CH3
alkane
 Reduction of Alkyl Halides
• Alkyl halides can be reduced by using
lithium aluminium hydride; LiAlH4 in ether
or by using acid in the presence of Zn.

H H
LiAlH4/ether
R C X R C H
R' R'
 • Example:

Br
Zn/acid

butane
2-bromobutane
 Alkylation of Ethyne and
Terminal Alkynes

• Anion of ethyne and terminal alkynes

behave as nucleophiles and react with
methyl halides and primary alkyl halides
unbranched at second carbon to form
carbon-carbon bonds by nucleophilic
substitution.

• The reactions occur in two stages.

 Ethyne is converted to ethynide by
reaction with sodium amide.
sodium amide
NaNH2
H C C H H C C- Na+ + NH3
NH3 (liq)
ethyne sodium ethynide ammonia

NH3 (liq) R-X

Proceed with
hydrogenation
to get alkane H C C R + NaX
ethyne
(terminal alkyne)
When primary alkyl halide is added to the solution, the
ethynide acts as nucleophile to replace halogen atom from
alkyl halide and forms a new carbon-carbon bond.
 Combustion of Alkanes

• Alkane is oxidized (burned in air) to form

carbon dioxide and water.

CH4 + 2O2 CO2 + 2H2O + heat

Reaction of Alkanes with Halogens
• Halogenation is an example of substitution
reaction.

• The hydrogen of alkane’s is replaced by Cl2

or Br2 in the presence of heat or light.

heat/light
CH3CH3 + Br2 CH3CH2Br + HBr
ethane bromoethane
 Free Radical Reaction of Alkanes

• The bond dissociation energy is the amount

of energy required to break a particular
bond homolytically.

• Example is the reaction between methane

and chlorine gas which can proceeds via a
free radical mechanism and it is involve with
3 steps: initiation, propagation and
termination.
• When sunlight or ultraviolet radiation
shines on a mixture of methane and
chlorine, the chlorine molecules dissociate
to produce chlorine radicals because the
Cl-Cl bond is weaker than C-H bond and
can be broken easily by heat or light.

Remember this!

• The UV-light is absorbed by chlorine NOT

methane.
Initiation Step:

• When initiated by sunlight or ultraviolet

radiation, a chlorine molecule splits into
two chlorine atoms.

• A chlorine atom has an unpaired electron

and acts as a free radical.

hv Cl + Cl
Cl Cl
Propagation Steps:

• Chlorine radicals are highly reactive.

• They react with a methane molecule and

remove hydrogen atoms from methane
to form hydrogen chloride and methyl
radicals.
Example:

H H

H C H + Cl H C + HCl

H H
methane methyl radical

A hydrogen atom is pulled off from methane

leaving a methyl radical.
 • Then, the methyl radical reacts with
another chlorine molecule to form
chloromethane and a chlorine free radical.

H H

H C + Cl-Cl H C Cl + Cl

H H
methyl radical chloromethane

Methyl radical pulls a Cl radical from Cl2

 • In the presence of excess chlorine, similar
propagation steps are repeated to
produce CH2Cl2, CHCl3 and CCl4.

H H
H C Cl + Cl H C Cl + HCl
H
chloromethyl radical
chloromethane
 H H

H C Cl + Cl-Cl H C Cl + Cl

Cl
chloromethyl radical
dichloromethane
Termination Steps:

• The reaction stops when two free radicals

collide and combine.

Cl + Cl Cl-Cl
CH3 + Cl CH3Cl

CH3 + CH3 CH3CH3

 Sources of Alkanes
• The alkanes are isolated from natural
gas and petroleum.

• Natural gas contains methane with smaller

amounts of other low-molecular weight
alkanes.
• Petroleum, which is a complex mixture of
many compounds, is the main source of all
other alkanes.
 Uses of Alkanes/Alkenes

Methane/propane - A solvent in
Natural gas for Lubricating oil paint thinner
heating and cooking
Paraffin wax

Petroleum jelly Fuel/diesel

AS/JUN 2016/CHM456
AS/DEC 2016/CHM456