INTRODUCTORY ORGANIC CHEMISTRY

 
(CHM 102)

BY

ABDUL-MUMEEN IDDRISU

 
 Ground rules
• Punctuality
• Mobile phones (on vibration, silence or off)
• Discipline
• Openness (feel free to ask questions)
• Participation
• Hardwork & problem solving
 BASIC CHEMISTRY II (CHM 102)
Introduction: This is an introductory course in organic
chemistry for first-year students who will be pursuing other
related science courses. This course aims to provide a
general understanding of organic chemistry and knowledge
of basic organic reactions. A basic understanding of the
fundamental principles of organic chemistry and the
synthesis and reactivity of the most important functional
groups in organic compounds will be studied.
Objectives
• Students will understand quantitative elemental analysis,
structure and bonding and types of organic reactions.
• Students will be able to draw electron dot structures for
isomers of simple alkanes and write condensed structures
of organic molecules.
Objectives
• Determine the IUPAC name and structure of organic
compounds and write balanced equations for organic
reactions.
• Determine the IUPAC name and structure of an aromatic
compound, predict the products and write balanced
chemical equations for aromatic substitution reactions.
• Classify molecules as alcohols, ethers, or amines. State the
general properties of these classes of molecules.
• Classify molecules as ketones or aldehydes.
• Classify molecules as carboxylic acids, esters, or amides.
State the general properties of these classes of molecules.
• Give systematic names of carboxylic acids, esters, and
amides.
Objectives
• Predict the products and write balanced chemical
equations for carbonyl substitution reaction and reactions
of carboxylic acids, esters, and amides with water.
• Give the formula for a segment of the polymer formed as a
result of an alkene polymerization and a polymerization
involving molecules with two different functional groups.
COURSE CONTENT
• Introduction
• Quantitative elemental analysis
• Structure and bonding- atomic structure, bonding and
hybridisation in carbon
• Functional groups, homologous series, types of organic
formulae, types of organic molecules, types of organic
reactions
• The Hydrocarbons
i. The alkanes
ii. Isomerism
iii. Alkane nomenclature
iv. The properties of alkanes
COURSE CONTENT
• The alkenes and alkynes
i. Alkene nomenclature
ii. The carbon-carbon double bond
iii. Alkene polymerization
iv. Alkynes
• Aromatic hydrocarbons
i. Arene nomenclature
ii. Reaction of aromatic hydrocarbons
Functional groups and biomolecules
• The hydroxyl group
i. Alcohols and ethers
ii. Phenols
COURSE CONTENT
• The carbonyl group
i. Aldehydes and ketones
• The carboxyl group
i. Carboxylic acids
ii. Esters
• Functional groups containing nitrogen
i. Amines
• Polymers
• Pesticides
Recommended Books:
• Morrison RT and Boyd RN. Organic Chemistry, 6th edition
• Hart Harold. Organic Chemistry-A Short Course, 13th edition
• Solomons, T. W. G.Fundamentals of Orgainc Chmistry 3rd
edition, John Wily & Sons.
• McMurry John., Organic Chemistry, 6th Edition.
• Finar, I. L., Organic Chemistry, Vol. 1, 6th Edition. Longman
Scientific & Technical
• Atkins, R. C. and Carey, F.A., Organic Chemistry- A brief
course, 3rd ed, Mc Graw Hill.
METHODS OF INSTRUCTION AND ASSESSMENT
• Instruction: The main method of instruction will be
lectures. Students will be provided with lecture notes
covering the course content and also given references to
read on their own. Students must attend all lectures. They
will be encouraged to read the text in advance for a better
understanding of the lecture and are responsible for
learning the material presented whether they attend or
not.
Assessment:
• Two quizzes 10 marks
• One mid-trim exams 15 marks
• One Final exams 75 marks
Grand total 100 marks
Introduction

what is organic chemistry?

Organic chemistry is the chemistry of the
compounds of carbon.
The study of organic chemistry includes both
natural and synthetic compounds
Importance of organic chemistry
All living organisms are made of organic compounds
• The proteins that make up our hair, skin and muscles
• The DNA that control our genetic heritage
• The food that we eat
• The clothes that we wear
• The medicine that we take
• The fuel we use in our vehicles and the gas used for
domestic cooking
• The plastics, rubbers, insecticides, pesticides and most the
synthetic materials we use are all made of organic
compounds.
Why is carbon special?
• Carbon is a group 4A element and can share four valence
electrons and form four strong covalent bonds.
• Carbon atoms can bond to one another, forming long
chains and rings.
• Another unique property of carbon atoms is their ability to
share electrons not only with different elements but also
with other carbon atoms.
Molecular and Empirical Formulae
• Empirical Formula (EF) of a compound shows the simplest
ratio of elements present in a compound.
• The empirical mass (EM) of a compound refers to the sum
of the atomic masses of the elements present in the
empirical formula.
• The molecular formula (MF) of a substance tells us the
actual number of different atoms present .
• Molecular mass (MM) is the sum of the atomic masses of
all atoms in the molecular formula.
The relationship between MM and MF is given by
MM = n x EF
where n is a positive number
Hybridisation
• Hybridisation: is the phenomenon of mixing up of
different orbitals of same energy level of an atom to
produce equal number of hybrid-orbitals of same
energy and identical properties.
• A hybrid orbital contains maximum two electrons with
opposite spin.
• In hybridisation, only those orbitals take part that have
very little difference of energy.
• Hybridisation takes place in the orbitals of a single
atom.
• Two different atoms cannot produce hybrid orbitals by
overlapping their orbitals.
Types of hybridisation in carbon atom
• There are three categories of hybridisation:
• Sp3-hybridisation: is the process of in which one s-
orbital and three p-orbitals overlap to produce four
hybrid-orbitals.
• The hybrid orbitals are identical in shape and
energy and are at an angle of 109.5o from each
other.
• Sp3-orbital are arranged in tetrahedral fashion.
• An example is the methane molecule
Types of hybridisation in carbon atom
• Sp2- hybridisation: is the process in which one s-
orbital and two p-orbital overlap to produce three
hybrid orbitals.
• These orbital are coplanar and directed towards the
corners of an equilateral triangle at an angle of 120o
from each other.
• The fourth un hybrid Pz-orbital lies at right angle to
the plane of Sp2-orbitals.
• Sp2 can be found in the ethene molecule
Types of hybridisation in carbon atom
• Sp- hybridisation: is the process of in which one s-
orbital and one p-orbital overlap to produce two
hybrid orbitals.
• This type of hybridization is also called diagonal
hybridization.
• These orbitals are at an angle of 180o.
• The remaining Py and Pz un hybrid orbitals lie
perpendicular to the plane of sp-orbital.
• Sp hybridisation can be found in the ethene
molecule
Types of organic compounds
Chemically, most organic compounds can be classified under
• hydrocarbons (only C and H)
• oxygen-containing (epoxides, alcohols, phenols, ethers,
aldehydes, ketones, and carboxylic acids),
• nitrogen-containing (amines, nitrosamines, and nitro
compounds),
• sulfur-containing,
• organohalides (hydrocarbon containing at least one atom
of F, Cl, Br, or I),
• phosphorus-containing compounds,
• or a combinations of these kinds of compounds.
Functional Groups
The atom or group of atoms that defines the structure
of a particular family of organic compounds and, at
the same time, determine their properties.
Compound Functional group G. formula Example
• Alkane -C- C nH2n+2 CH4
• Alkene -C = C- CnH2n CH2 = CH2CH3
• Alkyne - C ≡ C- CnH2n-2 HC ≡ CH
• Alcohols OH group ROH CH3CH2- OH
• Aldehydes CHO group RCHO CH3CHO
• Nitrile -C ≡ N RCN CH3CN
• Ketone CO grp RR’CO CH3COCH3
• Acid COOH grp RCOOH CH3COOH
• Esther COOC grp RCOOR’ CH3COOCH2CH3
• Ether COC grp ROR’ CH3CH2OCH2CH3
Compound Functional group G. formula Example
• Amine NH2 grp RNH2 CH3CH2NH2
• Amide CONH2 RCONH2 CH3CONH2
• Acid chloride COCl grp RCOCl CH3COCl
• Arene Benzene ring C6H6
• Substituted arene, benzene ring plus another functional
group, many examples e.g phenol, chlorobenzene,
phenylamine
 Homologous Series
A homologous series is a series of compounds in
which each member differs from the next by a
constant unit and members of the series are called
homologs.
For example, the family of alkanes form such a
homologous series, the constant difference
between successive members being –CH2
Usually, members of a homologous series have the
same functional group.
Structural formula
The structural formula of an organic compound tells us how
the atoms are arranged in the molecule of the compound.
Example
For the molecular formula C2H6O, only two structural formulas
are possible.
H H H H
H–C–C–O–H and H – C – O – C – H
H H H H

For C4H10 H H H
H H H H and H–C–C–C–H
H–C–C–C–C–H H H
H H H H H C H
Types of structural formulae
a. Electron dot formula
This is where dots are used to show the bonding electrons
about the atoms in a compound i.e Lewis structures.

b. Dash /Line formula

This is where organic compounds have dashes or lines
representing bond electrons about the atoms.
H H H
H–C –H H–C –C– H
H H H
 
c. Condensed formula
This is where carbon-hydrogen and carbon-carbon single
bonds are not shown but instead they are understood.
  CH3CH3CH(CH3)2 , CH3CH2OH, CH3C(CH3)2CH3

d. Bond-line or skeletal formula

In this formula, lines are used to show only carbon atoms and
the intersection of two lines or the end of a line represent a
carbon atom.

n-pentane 2-pentene 2-methylbutane

e. Dimension formula
Here conventions are used to depict geometry
TYPES OF ORGANIC COMPOUNDS
1.Aliphatic hydrocarbons
• These are hydrocarbons that may be open-chain or
cyclic (called alicyclic) compounds.
• The open-chains may be straight chains or branched
chains.
• Depending upon the relative amounts of carbon and
hydrogen, aliphatic hydrocarbons can further be
classified as saturated and unsaturated hydrocarbons.
Examples include the alkanes, alkenes, alkynes and their
derivatives
 2. Alicyclic Compounds
These are organic compounds in which carbon
atoms are linked, to form one or more rings. The
ring system is either single or fused.
Examples
Cyclopropane Cyclohexane
 3. Heterocyclic Compounds
These are organic compounds containing at least
one atom of carbon and at least one element
other than carbon such as sulphur, oxygen or
nitrogen within a ring structure.

EXAMPLES
Pyridine, piperidine-(CH2)5NH, furan, pyrole
4. Aromatic Compounds
These are cyclic compounds with delocalized
pi electron systems. Typical examples are
benzene and toluene. Bonds inside the ring
system represent the pi electrons.
EXAMPLES
Benzene Toluene
 TYPES OF ORGANIC REACTIONS
1. Addition Reactions
These are reactions in which two small molecules bond and
form one larger one. Only compounds with multiple
bonded atoms can react this way. There are three types of
addition reactions, called electrophilic, nucleophilic, and
free radical.
Examples
H H H H
H-C=C–H + H – Br H – C –C - H
H Br
(addition pdt)
2. Elimination reactions
These are reactions in in which two substituents are removed
from a molecule in either a one or two-step mechanism or
when a single reactant splits into two. Elimination reactions
are in a sense the opposite of addition reactions
Example
H Br Base H H
H–C–C–H C=C + HBr
H H H H
(H and Br are eliminated)
3. Substitution Reaction
These are reactions where two reactants exchange parts to
give two new products. A typical example is the reaction of
an alkane with Cl2 in the presence of light to yield an alkyl
chloride. A Cl atom from Cl2 substitutes for an H atom of
the alkane, and two new products result.
Examples
  H light H
H – C – H + Cl – Cl H – C – Cl + H – Cl
H H
4. Rearrangement Reactions
This occurs when a single reactant undergoes a
reorganisation of bonds and atoms to yield an isomeric
product.
Example
CH3CH2 H H3C H
C=C Acid catalyst C=C
H H H CH3
5. Hydrolysis
Hydrolysis is any reaction which splits apart a
compound with the addition of water. They are
often catalysed by the addition of acids or
alkalis.
Example

H O H O
H–C–C +H2O H- C – C + CH3-OH
H O CH3 OH H
Organic Reactions Mechanisms
• A mechanism describes in detail exactly what takes
place at each stage of a chemical transformation.
• It is a step-by-step description of the bond-breaking
and bond-making processes that occur when reagents
react to form products.
• A complete mechanism must account for all reactants
used, all products formed and the amount of each.
• Curved arrows indicate breaking and forming of bonds
 Arrow Formalism
Arrows in chemical drawings have
specific meanings.
1. Curved arrows are used to show
how electrons are moved in
resonance structures and in
reactions. Therefore, curved
arrows always start at the initial
position of electrons and end at
their final position.
• A curved arrow with half a head is
called a fishhook. This kind of
arrow is used to indicate the
movement of a single electron.
There are two ways of breaking of a covalent bond:
a) Homolytic
b) Heterolytic
1. Homolytic fission
• It is a symmetrical cleavage
• Each product gets one electron from the bond
• Results in the formation of free radicals

homolytic fission free radicals

A radical is a specie with an odd number of unshared
electrons or unpaired electrons.
2. Heterolytic fission
• It is an unsymmetrical cleavage
• Both electrons from the bond that is broken
become associated with one resulting fragment
• Results in the formation of a cation and anion

A–B A+ + B-
 Heterolysis of Bonds to Carbon: Carbocations and
Carbanions
• Heterolysis of a bond to a
carbon atom can lead to either
of two ions: either to an ion with
a positive charge- carbocation,
or to an ion with a negatively
charged carbon- carbanion:
• Carbocations are electron
deficient. They have only six
electrons in their valence shell,
and because of this,
carbocations are Lewis acids.
• Carbanions are electron rich.
They are anions and have an
unshared electron pair.
Carbanions, therefore, are Lewis
bases and react accordingly.
Bond forming
The formation of a covalent bond may be:
a)Homogenic
b) Heterogenic
a) Homogenic:
• It is a symmetrical formation
• One electron comes from each fragment
• No electronic charges are involved
2. Heterogenic: Reaction of an electron pair donor
with an electron pair acceptor.
• It is an unsymmetrical formation
• One fragment supplies two electrons
• One fragment supplies no electrons
• Combination can involve electronic charges

A+ + :B- A:B
 Reactive species in organic chemistry
1. Electrophile
An Electrophile is a chemical species
that is electron-deficient. It will seek
out an electron-rich site in an
organic molecule.
• All Lewis acids are electrophiles.
• Most electrophiles are positively
charged, have an atom that carries a
partial positive charge, or have an
atom that does not have an octet of
electrons.
• H+, NO+ ,HCl, alkyl halides, acyl
halides, and carbonyl compounds,
Cl2, Br2, B2O3, AlCl3, H+, Cl+, Br+, I+,
NO2+, CH3+, CH3CO+, C6H5N2+.
 Reactive species in organic chemistry
2. Nucleophile:
• A Nucleophile is a chemical
species that is electron-rich.
It will seek out an electron-
deficient site in an organic
molecule.
• A nucleophile is a Lewis base
that seeks a positive center
such as a positively charged
carbon atom.
• The more available the
electrons, the more
nucleophilic a system.
H2O, NH3, OH-, F-, Cl-, Br-, CN- I-,
HS-, RS- , Br-, RO-, NC-,
- -
 Reactive species in organic chemistry
3. Free Radicals
• These are species with
unpaired electrons.
• They are produced by
homolytic cleavage of bonds
using free radical initiators
like light, heat, organic
peroxides etc. Examples are
H., Cl., CH3., CH3CH2..
 How to Use Curved Arrows in Illustrating Reactions
Curved arrows
• show the direction of electron flow
in a reaction mechanism.
• point from the source of an
electron pair to the atom receiving
the pair. (Curved arrows can also
show the movement of single
electrons.
• always show the flow of electrons
from a site of higher electron
density to a site of lower electron
density.
• never show the movement of
atoms. Atoms are assumed to
follow the flow of the electrons.
 The Effect of Delocalization & Inductive Effect
• Delocalization of the
negative charge is
possible in a
carboxylate anion, but it
is not possible in an
alkoxide ion.
• Resonance structures
leads to the distribution
of the negative charge
to both oxygen atoms of
the carboxylate group,
thereby stabilizing the
charge.
 The Effect of Delocalization & Inductive Effect
• This is a delocalization effect (by
resonance).
• A rule to keep in mind is that
charge delocalization is always a
stabilizing factor.
• The electronegativity of these
oxygen atoms further helps to
stabilize the charge, by what is
called an inductive electron-
withdrawing effect. A
carboxylate ion has two oxygen
atoms whose combined
electronegativity stabilizes the
charge more than in an alkoxide
ion, which has only a single
electronegative oxygen atom.
 Nucleophilic Substitution Mechanisms
There are two main
nucleophilic
substitution
mechanisms-SN2 and
SN1.
The SN2 mechanism is a
one-step process,
represented by the
following equation:
2 means the reaction is
bimolecular
 Nucleophilic Substitution Mechanisms
The SN1 mechanism is a two-
step process.
The first step is the bond
breaking process which is
slow and leads to the
formation of a carbocation.
The second step is fast which,
the carbocation combine
with a nucleophile to give
the product.
 Elimination Reactions
• There are two main
mechanisms for
elimination reactions, E2
and E1.
• The E2 is a one-step
process which leads to the
elimination of HX and the
formation of C = C bond.
 Elimination Reactions
The E1mechanism is a two-
step process.
The first step is the bond
breaking process which is
slow and leads to the
formation of a carbocation.
The second step is fast, the
carbocation combine with a
nucleophile (SN1 process)
or may lose a proton
(hydrogen) to form an
alkene (E1 process).
ISOMERISM
Isomerism is the phenomenon of exhibiting two or more
compounds with same molecular formula but different
physical and chemical properties due to different structural
formulae.
Isomers are different compounds which have the same
molecular formula.
The isomerism in organic compounds can be classified broadly
into:
1. Structural isomerism (Constitutional isomerism):
Constitutional Isomers are Isomers which differ in
"connectivity"
2. Stereoisomerism: Stereoisomers are Isomers which have
the same connectivity.
1. structural Isomerism
The structural isomerism or constitutional isomerism
arises when atoms within a molecule are arranged
in different orders. The structural isomers have the
same molecular formula but different structural
formulae.
Isomers have different structures:
1. Owing to arrangement of carbon skeleton
2. Owing to position of functional group
3. Owing to different functional groups
• The structural isomers usually show different
physical and chemical properties.
• The structural isomerism is further divided
into:
a. Chain Isomerism
b. Position Isomerism
c. Functional Isomerism
d. Metamerism
e. Tautomerism
 a. Chain Isomerism
This arises due to different arrangements of
carbon atoms leading to linear and branched
chains. The chain isomers have same molecular
formula but different types of chains i.e., linear
and branched.
Linear Branched
CH3 – CH2 – CH2 – CH3 CH3 – CH – CH3
CH3
Butane isobutane or 2-methylpropane
 b. Position Isomerism
This arises due to different positions of side chains,
substituents, functional groups, double bonds,
triple bonds etc., on the parent chain.
CH3 – CH2 – CH2 – Cl and CH3 – CH – CH3
Cl
(1-chloropropane) (2-chloropropane)
CH2= CHCH2CH3 and CH3CH = CHCH3
(1-butene) (2-butene)

CH3-CH2-CH2-OH and CH3-CH-CH3

OH
(propan-1-ol) (propan-2-ol)
C. Functional Isomerism
The functional isomerism arises due to presence
of different functional groups. The functional
isomers have the same molecular formula but
possess different functional groups.
CH3- O – CH3 and CH3CH2-OH
(dimethyl ether) (ethanol)
CH3CH2COOH and CH3COOCH3
(propanoic acid)
O
H3C-CH2-CHO and
propanal H3C-C-CH3
(propan-2-one)
d. Metamerism
This arises when different alkyl groups are attached
to same functional group.
Examples
H3C-CH2-O-CH2-CH3 H3C-O-CH2-CH2-CH3 H3C-O-CH(CH3)2
Diethyl ether methyl propyl ether isopropyl methyl ether
or or or
ethoxyethane 1-methoxypropane 2-methoxypropane
Tautomerism
This refers to the dynamic equilibrium between
two compounds with same molecular formula.
• It is most often a special case of functional group
isomerism. In general, the tautomers have
different functional groups and exist in dynamic
equilibrium with each other due to a rapid
interconversion from one form to another.
• It is very important to note that the tautomers
are not the resonance structures of same
compound.
 2. STEREOISOMERISM
Stereoisomerism deals with molecules that have the
same order of attachment of the atoms, but different
arrangement of the atoms in space.
There are basically two types:
a. Geometric isomerism: involves a double bond, usually
C=C, that does not allow free rotation.
b. Optical isomerism: involves an atom, usually carbon
bonded to four different atoms or groups
• There are two types of stereoisomers: enantiomers
(mirror images) and diastereomers (not mirror images).

 
Geometric isomerism
This is the phenomenon in which compounds have the same
molecular formula, the same connectivity between atoms,
but differ in the arrangement of groups attached to the
double bond. They are not superimposable.
The essential requirement for geometric isomerism is that
each carbon of the double bond must have two different
substituent groups (one may be hydrogen).
No geometric Geometric isomerism exists
isomerism
Geometric isomerism
Examples:
H3C CH2CH3 H3C H
C=C C=C
H H H CH2CH3
cis-2-pentene trans-2-pentene

H3C CH3 H3C H

C=C C=C
H H H CH3
cis-2-butene trans-2-butene
 b. Optical isomerism
In this type of isomerism, the two compounds differ only
in the direction in which they rotate polarised light. The
two isomers rotate plane polarised light in opposite
direction
• Involves an atom, usually carbon, bonded to four
different atoms or groups of atoms.
• They exist in pairs, in which one isomer is the mirror
image of the other. . They are non-superimposable.
• These isomers are referred to as enantiomers
• Enantiomers have identical physical constants, such as
melting points and boiling points
Example

butan-2-ol

COOH HOOC
H OH HO H

HO H H OH
COOH HOOC
tartaric acid
 Chirality and Enantiomers
A molecule (or object) is
either chiral or achiral. A
chiral molecule (or object)
is one that exhibits the
property of handedness.
An achiral molecule does
not have this property.
A chiral molecule cannot be
superimposed on the
molecule itself but the
mirror image of an achiral
is superimposable on the
molecule itself.
Illustration
 Stereogenic Centers
• A carbon atom with four
different groups attached to
it is called a stereogenic
carbon atom. This type of
carbon is also called a
stereogenic center because it
gives rise to stereoisomers.
 Plane of Symmetry
• A plane of symmetry is a plane
that passes through a
molecule (or object) in such a
way that what is on one side of
the plane is the exact
reflection of what is on the
other side. Any molecule with
a plane of symmetry is achiral.
Chiral molecules do not have a
plane of symmetry.
• Seeking a plane of symmetry is
usually one quick way to tell
whether a molecule is chiral or
achiral.
Configuration and the R-S Convention
• Enantiomers differ in the
arrangement of the groups
attached to the stereogenic
center. This arrangement of
groups is called the
configuration of the
stereogenic center.
Enantiomers are another type
of configurational isomer;
they are said to have opposite
configurations. A convention
for doing this is known as the
R-S or Cahn–Ingold–Prelog
system.
 Configuration and the R-S Convention
The four groups attached to the stereogenic center are placed in a
priority order The stereogenic center is then observed from the
side opposite the lowest priority group, d. If the remaining
three groups (a : b : c) form a clockwise array, the configuration
is designated R. If they form a counterclockwise array, the
configuration is designated as S.
Rule 1
The atoms directly attached to the stereogenic center are ranked
according to atomic number: the higher the atomic number, the
higher the priority.
Rule 2
If a decision cannot be reached with rule 1 (that is, if two or more
of the directly attached atoms are the same), work outward
from the stereogenic center until a decision is reached.
 The E-Z Convention for Cis–Trans Isomers
Stereogenic centers are
applicable to double-bond
isomers and the priority
rules apply. The two groups
attached to each carbon of
the double bond are
assigned priorities.
If the two higher-priority
groups are on opposite
sides of the double bond,
the prefix E is used. If the
two higher-priority groups
are on the same side of the
double bond, the prefix is Z
 Polarized Light and Optical Activity
A beam of light, AB, initially
vibrating in all directions,
passes
through a polarizing
substance that “strains” the
light so that only the vertical
component emerges.
α is the angle of rotation-If the
analyzer is rotated
clockwise, the optically
active substance is said to
be
dextrorotatory (+) and if it is
rotated counterclockwise,
the substance levorotatory
 Fischer Projection Formulas
• This is a two-dimensional
way of depicting a three-
dimensional arrangements
of groups in a chiral
molecule.
 Diastereomers
• Diastereomers have more
than one chiral centre
• Diastereomers are
stereoisomers that are not
mirror images of one
another.
• They have different
physical and chemical
properties
HYDROCARBONS
• Hydrocarbons are compounds that contain only
carbon and hydrogen.
• There are three main classes of hydrocarbons, based
on the types of carbon-carbon bonds present.
• Saturated Hydrocarbons: these contain carbon-
carbon single bonds, alkanes and cycloalkanes
• Unsaturated hydrocarbons: these contain carbon-
carbon multiple bonds, alkenes & alkynes
• Aromatic hydrocarbons: these are a special class of
cyclic compounds related in structure to benzene
ALKANES (Saturated Hydrocarbons)
• These are compounds which contain carbon-
carbon single bonds. They have the general
formula of CnH2n+2 where n is the number of
carbon atoms.
• Alkanes with carbon chains that are unbranched
are called normal alkanes.
• The series differ from each other by a methylene
group (-CH2-).
• Members of such a series have similar chemical
and physical properties.
Names and formula of the first ten unbranched alkanes
Name No. C M.F S.F No.isomers
Methane 1 CH4 CH4 1

Ethane 2 C2H6 CH3CH3 1

Propane 3 C3H8 CH3CH2CH3 1
Butane 4 C4H10 CH3CH2CH2CH3 2
Pentane 5 C5H12 CH3(CH2)3CH3 3
Hexane 6 C6H14 CH3(CH2)4CH3 5
Heptane 7 C7H16 CH3(CH2)5CH3 9
Octane 8 C8H18 CH3(CH2)6CH3 18
Nonane 9 C9H20 CH3(CH2)7CH3 35
Nomenclature of Alkanes (IUPAC rules)
1. The –ane ending is used for all saturated hydrocarbons
2. Alkanes without branches are named according to the
number of carbon atoms.
3. For alkanes with branches, the root name is that of the
longest continuous chain of carbon atoms.
CH3 CH3 CH3 CH3

CH3 CH CH CH2 CH3 or CH3 CH CH CH2 CH3

4. Groups attached to the main chain are called substituents.
Akyl substituents are named by changing the –ane ending of
alkanes to –yl. Alkyl groups have the general formula of
CnH2n+1
There are two types of propyl groups depending of which
hydrogen is removed
CH3CH2CH2- CH3CHCH3 or i-Pr-

propyl isopropyl or 1-methylethyl

There are four different butyl groups

CH3CH2CH2CH2- CH3CHCH2CH3
butyl sec butyl or 1-methylpropyl
CH3 CH3
CH CH2- CH3- C-
CH3 CH3

isobutyl or 2-methylpropyl tert-butyl or 1,1-dimethylethyl

Alkyl halides are classified as being primary (1°), secondary (2°), or tertiary (3°).
This classification is based on the carbon atom to which the halogen is directly
attached. If the carbon atom that bears the halogen is attached to only one
other carbon, the carbon atom is said to be a primary carbon atom and the alkyl
halide is classified as a primary alkyl halide. If the carbon that bears the halogen
is itself attached to two other carbon atoms, then the carbon is a secondary
carbon and the alkyl halide is a secondary alkyl halide. If the carbon that bears
the halogen is attached to three other carbon atoms, then the carbon is a
tertiary carbon and the alkyl halide is a tertiary alkyl halide. Examples of
primary, secondary, and tertiary alkyl halides are the following:
Halogen substituents are named by changing the –ine ending
of the element to –o.
F- Cl- Br- I-
fluoro- chloro- bromo- iodo-
5. The main chain is numbered in such a way that the first
substituent encountered along the chain receives the
lowest possible number. Each substituent must be named
and numbered. For two or more identical groups, used
prefixes such as di- , tri-, and tetra etc.
CH3 CH3
CH3 – CH – CH – CH2 – CH3
2,3-dimethylpentane
6. If two or more different types of substituent are present,
they are listed alphabetically, except that the prefixes are
7. Punctuations is important in writing IUPAC names. IUPAC
names for hydrocarbons are written as one word.
Numbers are separated from each other by commas and
are separated from letters by hyphens. There is no space
between the last named substituent and the name of the
parent alkane that follows it.

Summary and Illustration

1. Locate the longest continuous carbon chain. This gives the
name of the parent hydrocarbon
C–C C–C
C–C–C–C not C–C–C–C
2. Number the longest chain beginning at the end nearest
to the first branched point.
C C C C
C – C – C – C – C – C not C–C–C–C–C–C
6 5 4 3 2 1 1 2 3 4 5 6
If there are two equally long continuous chains, select the
one with most branches
C 3 4 5 6 C 3 4 5 6
C – C – C – C – C – C not C–C–C–C–C–C
1 2 C–C C–C
2 1
2 branches one branch
If there is a branch equidistant from each end of the
longest chain, begin numbering nearest to a third
branch.
C C C C C C
C – C – C – C – C – C – C not C–C–C–C–C–C–C
1 2 3 4 5 6 7 7 6 5 4 3 2 1
2,3,6-trimethylheptane 2,5,6-trimethylheptane
If there is no third branch, begin numbering nearest to the
substituent whose name has alphabetic priority
C–C C C–C C
C – C – C – C – C – C – C not C–C–C–C–C–C–C
2 2 3 4 5 6 7 7 6 5 4 3 2 1
3-ethyl-5-methylheptane 5-ethyl-3-methylheptane
Naming complex cases: If a substituent on the main chain
has sub-branching, to name the compound fully, the complex
substituent must first be named.
Examples:
CH3
CH3 – C – CH2 – CH2 – CH3 CH3 – CH – CH2 – CH2 – CH3
CH3 CH2 – CH3
2,2-dimethylpentane 3-methylhexane
CH3 CH3
CH3 – C – CH2 – CH – CH3
CH3
2,2,4-trimethylpentane
CH3 CH2CH3
CH3 – CH – CH – CH2 – CH – CH2 – CH2 – CH3
CH3
5-ethyl-2,3-dimethyloctane
Cycloalkanes
These are saturated hydrocarbons that have at least one ring of
carbon atoms. They have the general formula of C nH2n
Cycloalkanes are named by placing the prefix cyclo- before the
alkane name that corresponds to the number of carbon atoms
in the ring.

cyclobutane cyclopentane cyclodecane

Alkyl or halogen substituents attached to the rings are named in
the usual way. No number is required for one substituent but
numbering is required for several substituents
With several substituents, the one with the highest alphabetic
priority is located at carbon 1
Examples
CH3 CH3 CH3
CH3 CH2CH3

(a) (b) (c)

(a) methylcyclopentane
(b) 1,2-dimethylcyclopentane
(c) 1-ethyl-2-methylcyclopentane
Questions
Draw the structural formulas for
a. 1,2,3-trichloropropane c) 1,4-dichlorocyclohexane
b. Ethylcyclobutane d)3-bromo-1,1-dimethylcyclopentane
Questions
1. Write the structural formulas for the following:
a. 4-ethyl-3,3-dimethylhexane b. 2,2,3-trimethylbutane
c. 1,1,3,3-tetrachloropropane d. 2-methylpentane
2. Write expanded formulas for the following compounds, and
name them using the IUPAC system
a. CH3(CH2)3CH3 b. CH3CH2C(CH3)2CH2CH3
d. CH2BrCH(CH3)CH(CH3)2 d. CH2ClCH2Br
3. Give the IUPAC name for the following:
a. b. Br Cl
PHYSICAL PROPERTIES OF ALKANES
1. Physical nature:
(a) State:
i. All alkanes are colourless & possess no characteristic odour.
ii. The lower alkanes (C1 to C4) are gases, middle ones (C3 to
C17) are liquids and higher ones are coloured solids.
iii. The boiling point of alkanes increases with increase in
molecular weight due to increase in van der waals forces
with increase in molecular weight i.e.,
B.pt. order : pentane < hexane < heptanes
iv. Branched chain alkanes have lower boiling points as
compared to straight chain alkanes. Branching leads to a
decrease in surface area which results in decrease in van
der Waals forces. e.g pentane > isopentane > neopentane
v. The melting points of alkanes do not show a regular trend.
Alkanes with even number of carbon atoms have higher m.pt.
than their adjacent of odd number of carbon atoms.
e.g propane < ethane < methane
The abnormal trend in m.pt. is probably due to the fact that
alkanes with odd carbon atoms have their end carbon atom
on the same side of the molecule and in even carbon atom
alkane, the end carbon atom on opposite side. Thus alkanes
with even carbon atoms are packed closely in crystal lattice to
permit greater intermolecular attractions.
(b) Density : The density of alkanes increases with increase in
molecular weight and becomes constant at 0.76 g/ml. For
this reason all alkanes are lighter than water or less dense
than water.
(c) Solubility :
i. Alkanes being non polar are insoluble in water but
soluble in non polar solvents e.g., C6H6, CCI4, ether etc.
ii. The solubility of alkanes decreases with increase in
molecular weight.
iii. Liquid alkanes are themselves good, non polar solvents.
REACTIONS OF ALKANES
• All the bonds in alkanes are single, covalent and
nonpolar
• Alkanes are relatively inert set of organic compounds.
Because they are saturated compounds, alkanes, tend
to show very little reactivity
• However, there are a few reactions that alkanes can
and do undergo under specific conditions.
• These reactions include combustion, substitution and
cracking.
• The reactions of alkanes are very important in everyday
life.
Oxidation and combustion
• The most important use of alkanes is as fuel. With excess
oxygen, alkanes burn to form carbon dioxide and water and
with evolution of a considerable amount of heat
(exothermic reaction).
• This is the reaction that occurs in internal combustion
engines.
The general equation for the reaction is
CxHy + (x + y/4) O2 -----------------> xCO2 + (y/2) H2O + heat
Examples
CH4(g) + 2O2(g) -----------------> CO2(g) + 2H2O(g) + heat
C5H12 + 8O2 -----------------> 5CO2 + 6H2O + heat
Halogenation of Alkanes
• Halogenation of alkanes occur in the presence of light
organic peroxides or at high temperatures. It is a
substitution reaction. A halogen atom is substituted for
hydrogen.
light or heat
R – H + Cl – Cl R – Cl + H – Cl
light or heat
CH4 + Cl – Cl CH3Cl + HCl
• In the presence of excess halogen, the reaction can
continue to give polyhalogenated products.
Cl2 Cl2 Cl2
CH3Cl CH2Cl2 CHCl3 CCl4
Mechanism of Halogenation
Halogenation occurs via a free-radical chain of reactions.
a. Initiation Step
This is the breaking of the halogen molecule into two halogen
atoms by homolytic fission. This leads to the formation of
free radicals.
light or heat
X– X X* + X*
b. Propagation step
X* + RH HX + R*
R* + X2 RX + X*
In each chain-propagating step, a radical (or atom) is
consumed, but another radical (or atom) is formed and
can continue the chain.
b. Termination step
There are three possible chain-terminating steps
Cl* + Cl* Cl – Cl
R* + R* R–R
R* + Cl* R – Cl
No new radicals are formed in these reactions and so the
chain is broken or terminated.
Note: Bromine reacts but less readily than chlorine. Iodine
does not react with alkanes. Fluorine reacts violently.
Halogenation of alkanes leads to the formation of more
reactive species.
Chlorination of methane
light
Cl – Cl Cl* + Cl*
CH4 + Cl* CH3* + HCl
CH3* + Cl2 CH3Cl + Cl*
CH3Cl + Cl* CH2Cl* + HCl
CH2Cl* + Cl2 CH2Cl2 +Cl*
CH2Cl2 + Cl* CHCl2* + HCl
CHCl2* + Cl2 CHCl3 + Cl*
CHCl3 +Cl* CCl3* + HCl
CCl3* + Cl2 CCl4 + Cl*
3. Cracking of alkanes
The decomposition of a compound by the action of heat
alone is known as pyrolysis. The pyrolysis of alkanes when
petroleum is concerned is known as cracking.
In cracking, large alkanes are converted into smaller alkanes,
alkenes and some hydrogen.
Cracking may be thermal (employing only heat) or catalytic
(involving the use of a catalyst).
An example of the cracking of an alkane is:
C15H32(l) ---------------> 2C2H4(g) + C3H6(g) + C8H18(l)
Preparation of Alkanes
1. Hydrogenation of unsaurated hydrocarbons
H2 + Pt, Pd or Ni

CnH2n CnH2n + 2
Alkene Alkane
2H2 + Pt, Pd or Ni

CnH2n-2 ＋C H2n + 2
n

Alkyne Alkane
Examples:
Pt, Pd or Ni
CH2 = CH2 + H2 CH3- CH3
Pt, Pd or Ni
CH3C ≡ CH + 2H2 CH3 – CH2 – CH3
2. Reduction of alkyl halides
a. Hydrolysis of Grignard reagent
ether H2O

R – X + Mg R – MgX R–H
R – MgX – alkylmagnesium halide
Example: Mg, ether H2O

CH3CH2CHCH3 CH3CH2CHCH3 CH3CH2CHCH3

Br MgBr H
b. Reduction by metal and acid
R – X + Zn + H+ R – H + Zn2+ + X-
Zn + H+
CH3CH2CHCH3 CH3CH2CHCH3
Br H
3.Wurtz reaction
This is when an alkyl halide (usually bromide or iodide) is
treated with sodium in dry ether, a symmetrical alkane
containing both twice the number of carbon atoms of alkyl
halide is obtained.
dry ether
RX + 2Na + XR R-R + 2NaX
dry ether
CH3CH2CH2Br + 2Na + CH3CH2CH2Br
CH3CH2CH2CH2CH2CH3 + 2NaBr
ALKENES AND ALKYNES
• Hydrocarbons that contain a carbon-carbon double bond
are called alkenes and those with a carbon-carbon triple
bond are called alkynes. They are referred to as
unsaturated hydrocarbons. Their general formulas are:
CnH2n – alkenes and CnH2n-2 – alkynes
• Compounds with more than one double bond or triple
bond exist
• If two double bonds are present, the compounds are called
alkadienes or dienes, 3 double bonds are trienes, etc
• Compounds with more than one triple bond, or with a
double and triple bond do exist.
• If two or more double bonds are present in a molecule, it is
useful to classify the structure further
• Cumulated: this is when double bonds are next to each
other.
• Conjugated: this is when multiple bonds alternate with
single bonds
• Isolated or nonconjugated: this is when more than one
single bond comes between multiple bonds
C=C=C C=C–C=C C=C–C=C
C=C=C=C C=C–C≡C C≡C–C–C–C≡C
cumulated conjugated isolated
Nomenclature of Alkenes and Alkynes
The IUPAC rules for naming alkenes and alkynes are similar to
those of alkanes. However, a few must be added for naming
and locating multiple bonds.
1. The ending –ene is used to designate a carbon-carbon
double bond. When more than one double bond is
present, the ending –diene, triene, etc are used
The ending –yne is used for a triple bond (-diyne for 2
triple bonds, etc). Compounds with a double and a triple
bond are –enynes.
2. Select the longest chain that includes both carbons of the
double or triple bond
3. Number the chain from the end nearest the multiple bond,
so that the carbon atoms in the bond have the lowest
possible numbers.
If the double is equidistant from both ends of the chain,
number from the end nearest the first branch point
4. Indicate the position of the multiple bond using the lowest-
numbered carbon atom of the bond.
5. If more than one multiple bond is present, number from
the end nearest the first multiple bond.
If a double and a triple bond are equidistant from the end of
the chain, the double bond receives the lowest numbers.
Examples:
CH2 = CHCH2CH3 CH3CH = CHCH3
1-butene 2-butene
HC ≡ CCH2CH3 CH3C ≡ CCH3
1-butyne 2-butyne
 CH2 = C – CH3 CH2 = CH – CH2CH3
CH3 CH3
methylpropene 2-methyl-1-butene
or isobutylene
CH2– C = CHCH3 CH2 = C – CH = CH2
CH3 CH3
2-methyl-2-butene 2-methyl-1,3-butadiene (isoprene)

CH3 – CH = CH –CH – CH3 CH2 = C – CH2= CH3

CH3 CH2= CH3
HC ≡ CH CH3C ≡ CH CH3CH2C ≡ CH CH3C ≡ CCH3
ethyne propyne 1-butyne 2-butyne
or but-1-yne or but-2-yne
 CH3 CH3
CH3 – CH – CH2 – C ≡ C – CH3 CH3 – CH – C ≡ C – H
5-methyl-2-hexyne 3-methyl-1-butyne
CH3 CH3
CH3 – CH – CH – C ≡ C – CH3 CH3 – C – C ≡ C – CH3
Cl CH3
5-chloro-4-methyl-2-hexyne 4,4-dimetyl-2-pentyne

HC ≡ C – CH2 – CH = CH2 CH3 – CH = CH – C ≡ CH

1-penten-4-yne 3-penten-1-yne

H2C = CH – CH2 – C ≡ C – CH2 – CH2 – CH3

1-octen-4-yne
Naming of cyclic hydrocarbons with multiple bonds
CH3

cyclopentene 3-methyl-cyclopentene 1,3-cyclohexadiene

C ≡ CH cyclohexylethyne
Exercise
1. Give the IUPAC names for the following
a. ClCH = CHCH3 b. (CH3)2C = C(CH3)2 c.CH2 = C(CH3)CH = CH2
d. HC ≡ C(CH2)3CH3 e. CH3CH = C(CH2CH2CH3)2
f. HC ≡ CCH2CH = CHCH3 g. CH2 = CHCH2C ≡ CH
h. i.

2. Write a structural formula for each of the following cpds

a. 1,4-hexadiene b. 3-methyl-1-pentyne
c. 2,3-dimethyl-2-butene d. 1,4-cyclohexadiene
Some common names
CH2 = CH2 HC ≡ CH CH3CH =CH2
ethylene acetylene propylene
(ethene) (ethyne) (propene)

CH2 = CH - CH2 = CH - CH2- HC ≡ C- CH2-

vinyl allyl propargyl
(ethenyl) (3-propenyl) (3-propynyl)

CH2 = CHCl CH2 = CH - CH2-Cl HC ≡ C- CH2-Br

vinyl chloride allyl chloride propargyl bromide
(chloroethene) (3-chloropropene) (3-bromopropyne)
Physical Properties of Alkenes & Alkynes
The unsaturated hydrocarbons have physical properties
similar to those of alkanes
• The compounds with four or fewer carbons are colourless
gases whereas higher homologs are volatile liquids
• They are insoluble in water, but are fairly soluble in organic
solvents such as, alcohol, ether, acetone etc
• They are less dense than water
• The melting and boiling points of unsaturated hydrocarbons
increase with molecular mass
PREPARATION OF ALKENES
1. Dehydrohalogenation of alkyl halides
alcohol
C–C + KOH C=C + KX + H2O
H X
KOH (acl)
CH3CH2Cl CH2 = CH2 + KCl + H2O
2. Dehydration of alcohols
acid
–C – C– –C = C– + H2O
H OH
acid
CH3CH2OH CH2 = CH2 + H2O
3. Dehalogenation of vicinal dihalides

–C – C– + Zn –C = C– + ZnX2
X X
Zn
CH3CHBrCHBrCH3 CH3CHCHCH3 + ZnBr2

4. Reduction of alkynes
R R

C=C cis
R–C≡C–R H H
R H
C=C trans
REACTIVITY OF ALKENES
• Unsaturated hydrocarbons such as alkenes and alkynes are
much more reactive than the parent alkanes.
1. Addition of hydrogen
Pt, Pd or Ni
CH2 = CH2 + H2 CH3–CH3

2. Addition of halogens
CH3CH = CHCH3 + X2 CH3CH – CHCH3 X2 = Cl2, Br2
X X
The addition of bromine can be used as a chemical test for the
presence of unsaturation in an organic compound. When
bromine solution is added to the unsaturated compound, the
bromine colour disappears.
3. Addition of hydrogen halides

–C = C– + HX –C– C– HX = HCl, HBr, HI

H X
CH2 = CH2 + HCl CH3–CH2Cl

4. Addition of water(Hydration)
H+
–C = C– + H – OH –C– C–
H OH
H2O,H+

CH2 = CH2 CH3–CH2OH

Addition of unsymmetric reagents to unsymmetric
alkenes (Markovnikov’s rule)
R H R H R H
C =C +X–Y –C – C– and/or –C – C–
X Y Y X

CH3CHCH3
OH

CH3CH = CH2 + H – OH + H+

CH3CH2CH2–OH
Markonikov’s Rule: When an unsymmetric reagent adds to
an unsymmetric alkene, the electropositive part of the
reagent bonds to the carbon of the double bond that has
the greater number of hydrogen atoms attached to it.
H
H+ + C = C C – C+
carbocation

H H
C – C+ + Nu:- C–C
Nu
The initiating step in these additions is attack by the
electrophile, the whole process is called an electrophilic
addition.
Oxidation of alkenes
a. Oxidation with permanganate: a chemical test
Alkenes react with alkaline potassium permanganate to form
glycols ( compounds with adjacent hydroxyl groups).

3 C = C + 2KMnO4- + 4H2O 3–C – C– + 2MnO2 +2KOH

OH OH
In this reaction the purple colour of the permanganate ion is
replaced by the brown precipitate of manganese
dioxide.Because of the colour change, the reaction can be
used as a chemical test to distinguish alkenes from alkanes
which normally do not react.
b. Ozonolysis of alkenes
The net result of this reaction is to break the double bond of
the alkene and to form two carbon-oxygen double bonds
(carbonyl groups), one at each carbon of the original
double bond. Ozonolysis can be used to locate the position
of a double bond.
1. O3

CH2=CHCH2CH3 CH2= O + O =CHCH2CH3

2. Zn, H+
1. O3

CH3CH=CHCH3 2CH3CH=O
2. Zn, H+
Preparation of Alkynes
1. Dehydrohalogenation of alkyl dihalides
H H X2 H H KOH (acl) H NaNH2

–C = C– –C– C– –C = C– –C ≡ C–
X X X
Br2 KOH (acl) NaNH2
CH3CH = CH2 CH3CH – CH2 CH3CH = CHBr CH3C ≡ CH
Br Br
2. Reaction of metal acetylides with primary akyl halides
LiNH2 R must be 1o

–C ≡ C– –C ≡ C:- Li+ + RX –C ≡ C–R + LiX

Example ,
–C ≡ C:-Li+ + CH3CH2CH2CH2Br HC ≡ C–CH2CH2CH2CH3
Reactions of Alkynes
1. Addition of hydrogen-discussed

2. Addition of halogens
X2 X2 X X
–C ≡ C– –C = C– –C – C– X2 = Cl2 , Br2
X X X X

Example X2 X2 Br Br
CH3C ≡ CH CH3–C = CH CH3–C –CH
Br Br Br Br
3. Addition of hydrogen halides
HX HX H X
–C ≡ C– –C = C– –C – C– HX = HCl, HBr, HI
H X H X
Example HCl HI I
CH3C ≡ CH CH3–C = CH2 CH3–C –CH3
Cl Cl
4.Addition of water (hydration)
H2SO4, HgSO4 H
–C ≡ C– + H2O –C = C– –C – C–
H OH H O
CH3C ≡ CH + H2O CH3–C–CH3
H2SO4, HgSO4 O
Acidity of Alkynes
A hydrogen atom on a triply bonded carbon is weakly acidic
and can be removed by a very strong base.
This hydrogen is weakly acidic liquid NH3

R–C ≡ C–H + Na+NH2- R–C ≡ C:-Na+ + NH3

sodium amide a sodium acetylide
This type of reaction occurs easily with a hydrogen adjacent to a
triple bond but with increasing difficulty when the hydrogens
are adjacent to a double or single bond. The reason being that
as the hybridisation at a carbon becomes more s-like and less p-
like, the acidity of the attached hydrogen increases.
AROMATIC COMPOUNDS
• Aromatic compounds are benzene and compounds that
resemble benzene in chemical behaviour.
• A benzene molecule is a ring: a ring of a special type
• Aromatic hydrocarbons are characterised by a tendency to
undergo heterolytic substitution.
• Benzene has the molecular formula C6H6
• Benzene yields only one monosubstitution product, C6H5Y
FeBr3 , catalyst
C6H6 + Br2 C6H5Br + HBr
• Benzene yields three isomeric disubstitution products, C6H4Y2
or C6H4YZ
FeBr3 , catalyst
C H Br + Br C H Br + HBr
Two symbols are used to represent benzene

Kekule delocalised pi cloud

Some common names

CH=CH2 CO2H CH3C=O NH2

styrene benzoic acid acetophenone aniline

Naming of Aromatic Compounds
Monosubstituted benzenes are named as derivatives of
benzene
Br NO2 CH2CH3

bromobenzene nitrobenzene ethylbenzene

When two substituents are present, three isomeric structures
are possible. They are designated by the prefixes ortho-
meta- and para-, are abbreviated as o- , m- and p-.
In this structure, o-groups are next to X, m-groups are
separated from X by one carbon, and p-groups are opposite
 X
o o

m m
p
Examples
Cl CH = CH2 OH
Cl

Cl
Cl
o-dichloro- p-chlorostyrene m-chlorophenol
benzene
When more than two substituents are present, their positions
are designated by numbering the ring.
CH3 CH3
CH3

Cl Cl
CH3
1,2,4-trimethylbenzene 3,5-dichlorotoluene
or 2,4-dimethlytoluene
Aromatic hydocarbons are also known as arenes. The symbol
Ar is used for an aryl group. The phenyl group and the
benzyl group are very common.
C6H5– or C6H5CH2– or –CH2–

phenyl group benzyl group

CH3CHCH2CH2CH3 Ph Ph

Ph
2-phenylpentane 1,3,5-triphenylbenzene
or 2-pentylbenzene
Reaction of Benzenes
Benzene undergoes substitution rather than addition
reactions.
1. Nitration H2SO4

C6H6 + HONO2 C6H5–NO2 + H2O

Nitrobenzene
2. Sulfonation SO3

C6H6 + HOSO3H C6H5–SO3H + H2O

Benzenesulfonic acid
3. Halogenation Fe
C6H6 + Cl2 C6H5–Cl + HCl
Chlorobenzene
4. Friedel-Crafts alkylation
AlCl3

C6H6 + RCl C6H5–R + HCl

An alkylbenzene

C6H6 + CH3CH2Cl C6H5–CH2CH3 + HCl

ethylbenzene
5. Friedel-Crafts acylation
AlCl3

C6H6 + RCOCl C6H5–COR + HCl

A ketone
C6H6 + CH3C=O C6H5–C=OCH3 + HCl
Alcohols and Phenols
• Alcohols are compounds that have the general formula of
CnH2n+1OH or R – OH where R is an alkyl group. They are
structurally similar to water. The functional group is the
hydroxyl group, – OH
• Phenols are compounds that have the hydroxyl group
bonded to aromatic rings ( Ar – OH ).
• Alcohols occur widely in nature and have many industrial
and pharmaceutical applications e.g methanol and ethanol
• Methanol is toxic to humans causing blindness in small
doses and death in larger doses. Ethanol can be obtained
from the fermentation of grains and sugars.
• Phenols also occur widely in nature and serve as
intermediates in the industrial synthesis of products.
Naming Alcohols
Alcohols can be classified as primary (1o), secondary (2o), or
tertiary (3o), depending on the number of organic groups
(R) bonded to the hydroxyl-bearing carbon.
H H R
R – C – OH R – C –OH R – C – OH

H R R
A 1o alcohol A 2o alcohol A 3o alcohol

Simple alcohols are named by the IUPAC systems as

derivatives of the parent alkane, using the suffix –ol.
Rule 1: Select the longest carbon chain containing the
hydroxyl group and derive the parent name by replacing
Rule 2: Number the alkane chain beginning at the end nearer
the hydroxyl group.
Rule 3: Number the substituents according to their position
on the chain, and write the name listing the substituents in
alphabetical order.
Examples OH

CH3OH CH3CH2OH CH3CH2CH2OH CH3CHCH3

methanol ethanol 1-propanol 2-propanol

CH2 = CHCH2OH CH3C ≡ CCH2CH2OH ClCH2CH2OH

2-propen-1-ol 3-pentyne-1-ol 2-chloroethanol

CH3CH(CH3)CH2OH C(CH3)3OH CH3C(CH3)(OH)CH2CH2CH3

Naming Phenols
Phenols are named as derivatives of the parent compounds.
The word phenol is used both as the name of a specific
substance (hydroxybenzene) and as a family name for
hydroxy-substituted aromatic compounds. The hydroxyl
group is name as a substituent when it occurs in the same
molecule with carboxylic acid, aldehyde or ketone
functionalities, which have priority in naming.
OH OH OH
Br Br

Cl Br
Phenol p-chlorophenol 2,4,6-tribromophenol
 COOH CHO OH

OH
OH NO2
m-hydroxybenzoic acid p-hydroxybenzaldehyde p-nitrophenol
Hydrogen bonding in alcohols & phenols
The boiling points of alcohols and phenols are much higher
than those of ethers or hydrocarbons with similar
molecular weights. The reason being that alcohols and
phenols form hydrogen bonds with one another. The O – H
bond is polarised by the high electronegativity of the
oxygen atom. This polarisation places a partial positive
charge on the hydrogen atom and a partial negative charge
on the oxygen atom.
R R R R
O–H + O–H O – H ……O – H
two separate alcohol molecules a hydrogen bond
Two or more alcohol molecules thus become loosely bonded
to one another through hydrogen bonds. The lower-
molecular weight alcohols can readily replace water
molecules in the hydrogen bonded network and this
accounts for the complete miscibility of the lower alcohols
with water. However, as the organic chain lengthens, its
water solubility decreases
Acidity of Alcohols and Phenols
Alcohols and phenols are weak acids. The hydroxyl group can
act as a proton donor and dissociation occurs in a manner
similar to that for water.
RO – H RO- + H+
The conjugate base of an alcohol is the alkoxide ion, RO- (e.g
methoxide for methanol, ethoxide for ethanol, etc)

Phenols are stronger acids than alcohols mainly because the

corresponding phenoxide ions are stabilised by resonance.
ArO – H ArO- + H+
Alkoxide ions dissolve in alcohol, like hydroxide ion in water,
are strong bases. Metal alkoxides are frequently used in
organic chemistry as strong bases. They are prepared by
the reaction of an alcohol with sodium or potassium metal
or with a metal hydride.
2RO – H + 2Na RO-Na+ + H2
RO – H + NaH RO-Na+ + H2
Ordinary treatment of alcohols with sodium hydroxide does
not convert them to their alkoxides. This is because
alkoxides are stronger bases than hydroxide ion, so the
reaction goes in the reverse direction. Phenols, however,
can be converted to phenoxide ions in this way.
RO – H + NaOH RO-Na+ + H2O

–OH + NaOH –O-Na+ + H2O

phenol sodium phenoxide
The Basicity of Alcohols and Phenols
Alcohols and phenols can also function as bases. They have
unshared electron pairs on the oxygen and are therefore
Lewis bases. They can be protonated by strong acids.
H +
R – O – H + H+ R–O–H

Alcohol acting as a base akyloxonium ion

Ar – O – H + H+ ArO+H2
1. Dehydration of Alcohols to Alkenes
Alcohols can be dehydrated by heating them with a strong
acid
H+, 180 oC
H – CH2CH2 – OH CH2 = CH2 + H2O

2. The Reaction of alcohols with Hydrogen Halides

R – OH + H – X R – X + H – OH
Reactivity of HX: HI > HBr > HCl
Reactivity of ROH: allyl > benzyl > 3o > 2o > 1o
CH3CH2CH2CH2OH + H – Cl heat, ZnCl , several hours
2

CH3CH2CH2CH2 – Cl + H – OH
3. The reaction of alcohols with thionyl chloride
ROH + SOCl2 heat RCl + HCl + SO2
This reaction is advantageous because gaseous by-products
are produced leaving behind the desired product (alkyl
halide).

4. Oxidation of Alcohols
Alcohols with at least one hydrogen attached to the hydroxyl-
bearing carbon can be oxidised to carbonyl compounds.
Primary alcohols give aldehydes, which may be further
oxidised to acids. Secondary alcohols give ketones.
Tertiary alcohols do not undergo this type of oxidation.
 H CrO3, H+ H CrO3, H+ OH
R – C – OH R–C=O R–C=O
H acetone acetone
Primary alcohol

R’ CrO3, H+ R’
R – C – OH R–C=O
H acetone
Secondary alcohol ketone

5. Ester formation
Alcohols react with carboxylic acids, acid anhydrides and acid
chlorides to give esters.
Preparation of Alcohols
a. Laboratory Methods
i. Hydrolysis of haloalkanes
Haloalkanes are hydrolysed in aqueous alkali to the
corresponding alcohol
CH3CH2Br + OH- (or H2O) heat CH3CH2OH + Br- (or HBr)

ii. The Grignard method

The reaction of Grignard reagents with methanal yields
primary alcohols; other aldehydes give secodary alcohols
while ketones give tertiary alcohols
H2C = O + RMgX R – CH2 – OMgX H+, H O R – CH2 – OH
2
iii. Reduction of carbonyl compounds
Reduction of aldehydes, ketones, acids and other carbonyl
compounds give alcohols. Reduction of aldehydes and
acids gives primary alcohols while ketones give secondary
alcohols. H
R – C = O + H2 LiAlH
4 R – C – OH
H
R – C = O + 2H2 LiAlH4 R – C – OH + H2O
OH H
R – C = O + H2 LiAlH4 R – C – OH + H2O
R R
Esters are reduced with cleavage of the molecule to produce
two different primary alcohols
 O
R – C – OR’ + 2H2 LiAlH4 R – CH – OH + R’OH

iv. Hydration of alkenes

CH3 – CH = CH + H2O H+ CH3 – CH(OH) – CH3

b) Industrial Methods
i. Methanol: Methanol is manufactured from carbon
monoxide and hydrogen.
ZnO-Cr2O3

CO + 2H2 CH3OH
400oC, 150 atm
ii. Ethanol is manufactured by two main processes-(a) by the
hydration of ethene, b) by the fermentation of
carbohydrates.
a) Hydration of ethene: Ethanol is manufactured from the
acid-catalysed hydration of ethene obtained from the
cracking of petroleum.
CH2 = CH2 + H2O +
H CH3CH2OH
b) Fermentation of carbohydrates
Fermentation of the sugar solutions is effected by various
enzymes in yeast. Sucrose (C12H22O11)-cane sugar is first
hydrolysed to two isomeric sugars-glucose and fructose
by the enzyme invertase. Glucose and fructose are
converted to ethanol.
C6H12O6 yeast 2C2H5OH + 2CO2
Aromatic substitution of phenols
Phenols undergo electrophilic aromatic substitution under
very mild conditions because the hydroxyl group is strong
ring activating.

–OH + HONO2 O2N– –OH + H2O

Phenol is brominated rapidly with bromine water to produce

2,4,6-tribromophenol
OH OH
Br Br
+ 3Br2 + 3HBr
Br
Ester formation
RCOCl RCO – OAr
ArO – H
Ar’SO2Cl Ar’SO2 – OAr
Example

OH + COCl NaOH O – C–
O
phenol benzyl chloride phenyl benzoate

O2N OH + (CH3CO)2O CH3COONa O2N O – C – CH3

O
p-nitrophenol acetic anhydride p-nitrophenyl acetate
Oxidation of Phenols
Phenols are easily oxidised. Phenols function as antioxidants;
they are oxidised instead of the substances to which they
have been added
OH O
(KSO3)2NO

H2O

phenol O
1,4-benzoquinone
OH O
Na2CrO7

H2SO4, 30oC

OH O
hydroquinone 1,4-benzoquinone
Preparation of Phenols
1. Alkyl fusion of aryl sulfonates
SO3H OH
+ NaOH 300oC + NaHSO3

2. Hydrolysis of diazonium salts

Ar – N2+X- + H2O Ar – OH + N2 + H+

N2+HSO4- OH
H2O, H+ , heat + N2
Cl Cl
Ethers and Epoxides
Ethers are organic compounds that have the general formula
of R – O – R’, where R and R’may be identical or different,
and may be alkyl or aryl groups.
Epoxides are cyclic three-membered ethers.

Naming of Ethers
Two systems of naming ethers are allowed by the IUPAC rules.
1. Simple ethers with no other functional groups are named
by giving the name of each alkyl or aryl group in
alphabetical order , followed by the word ether.
CH3CH2 – O – CH3 CH3CH2 – O – CH2CH3
ethyl methyl ether diethyl ether
2. If other functional groups are present, the ether part is
considered an alkoxy substituent.

CH3CHCH2CH2CH3 CH3O OCH3

OCH3
2-methoxypentane p-dimethoxybenzene
CH3 OCH3
O – C – CH3 CH3O
CH3 OCH3
4-tert-butoxy-1-cyclohexene 1,3,5-trimethoxybenzene

HOCH2CH2
OCH2CH3
Physical properties of ethers
i. Ethers are colourless compounds with characteristic
relative pleasant odours.
ii. They have lower boiling points than alcohols with equal
number of carbon atoms.
iii. They are soluble in water as compared to alcohols of the
same molecular weight. Ethers are soloble in water
because they are capable of forming hydrogen bonds with
water molecules.
Preparation of ethers
1. Williamson synthesis
2ROH + 2Na 2RO-Na+ + H2
RO-Na+ + R’- X ROR’ + NaX X = Cl, Br or I
Yield from R’- X : CH3 > 1o , 2o, 3o
Example
2CH3OH + 2Na CH3O-Na+ + H2
CH3O-Na+ + CH3CH2CH2X CH3OCH2CH2CH3 + NaX

Diethyl ether is prepared from ethanol and sulphuric acid

H2SO4

CH3CH2OH + HOCH2CH3 CH3CH2OCH2CH3 + H2O

140oC
Reactions of ethers
i. Ethers are relatively inert compounds and thus do not
react with dilute acids, dilute bases, or common oxidising
and reducing agents.
ii. Because of their inertness and the fact that most organic
are ether-soluble, makes ethers excellent solvents in
which to carry out organic reactions e.g diethyl ether
iii. Ethers undergo just one kind of reaction, cleavage by
acids.
R – O – R’ + HX R – X + R’ – OH HX R’ – X
Reactivity of HX: HI > HBr > HCl
Example
CH3CH2OCH2(CH3)2 + HI heat CH3CH2I + HOCH2(CH3)2
Epoxides or Cyclic Ethers
Epoxides (or oxiranes) are cyclic ethers with a three-
membered ring containing one oxygen atom.
CH2 – CH2
O ethylene oxide
silver catalyst

CH2 = CH2 + O2 CH2 – CH2

250oC , pressure O
CARBONYL COMPOUNDS
These are compounds which contain the carbonyl group
C = O. This group is present in aldehydes, ketones,
carboxylic acids, esters, acid chlorides, amides and acid
anhydrides.
Aldehydes have at least one hydrogen atom attached to the
carbonyl group
O O O O
– C – H or CHO, H – C – H R–C–H Ar – C – H
aldehyde grp formaldehyde aliphatic aldehyde aromatic aldehyde
In ketones, the carbonyl carbon is attached to two other
carbon atoms
O O O
R–C–R R – C – Ar Ar – C – Ar
Naming Aldehydes and Ketones
1. Aldehydes are named by replacing the terminal –e of the
corresponding alkane name with –al. The parent chain
must contain the –CHO group, and the –CHO carbon is
numbered as carbon 1.
O O CH3 O
CH3CH CH3CH2CH CH3CHCH2CHCH
CH2CH3
Ethanal propanal 2-ethyl-4-methylpentanal

For more complex aldehydes in which the –CHO group is

attached to a ring, the suffix –carbaldehyde is used.
CHO
Naming Ketones
Ketones are named by replacing the terminal –e of the
corresponding alkane with –one. The parent chain is the
longest one that contains the ketone group, and the
numbering begins at the end nearer the carbonyl carbon.
O O
CH3CH2CCH2CH2CH3 CH3CH = CHCH2CCH3
3-hexanone 4-hexen-2-one

O O O
– C– CH3 –C– –C–
Acetophenone benzophenone dicyclopropyl ketone
(methyl phenyl ketone) (diphenyl ketone)
Synthesis of aldehydes and ketones
1. Oxidation of alcohols
H
C oxidising agent C=O
OH (CrO , H , acetone)
3
+

Primary alcohols give aldehydes and secondary alcohols give

ketones.
2. Friedel-Crafts acylation
O
R–C + Ar – H 3 AlCl R – C – Ar + HCl
Cl O
aromatic ketone
Reaction of aldehydes and ketones
1. Oxidation of carbonyl compounds
Aldehydes are more easily oxidised than ketones. Oxidation of
an aldehyde gives an acid with the same number of
carbon atoms.
O oxidising agent O
R–C–H R – C – OH
Oxidising agents include KMnO4, CrO3, Ag2O and peroxyacids

Example
CH3(CH2)5CH = O CrO, H+ CH3(CH2)5CO2H

CHO CO2H
Ag2O
2. Addition of alcohols
Alcohols are oxygen nucleophiles. They can attack the
carbonyl carbon of aldehydes or ketones, resulting in
addition to the C = O bond to form hemiacetal. Hemiacetals
are compounds which contain both alcohol and ether
functional groups on the same carbon.
R’ H+ RO
ROH + C=O R’– C – OH
H H
hemiacetal
In the presence of excess alcohol, acetals are formed
RO H+ RO
R’– C – OH + ROH R’– C – OR + HOH
H H acetal
3. Addition of hydrogen cyanide; cynohydrins
Hydrogen cyanide adds to the carbonyl group of aldehydes
and ketones to form cynohydrins, compounds with a
hydroxyl and a cyano group attached to the same carbon.
OH- CN
C = O + HCN C – OH
Example
O OH- OH
CH3– C – CH3 + HCN CH3– C – CH3
CN
acetone acetone cyanohydrin
Keto-Enol Tautomerism
Aldehydes and ketones may exist as an equilibrium mixture of
two forms known as the keto form and the enol form. The
two forms differ in the location of a proton and a double
bond.
H O OH
–C–C– C=C

keto form enol form

This form of structural isomerism is called tautomerism and
the isomers are called tautomers. Example
O OH
CH3– C – CH3 CH2= C – CH3
keto form enol form
Carboxylic acids and their derivatives
Carboxylic acids are the most important organic acids, and
their functional group is the carbonyl group. The name
carboxylic is a contraction of the parts: the carbonyl and
hydroxyl groups. The general formula for carboxylic acid
can be written as
O O
–C R–C or RCOOH or RCO2H
OH OH
Naming Carboxylic acids
The IUPAC name of a carboxylic acid is obtained by replacing
the –e in the name of the corresponding alkane with the
suffix -oic and the word acid. Substituents on the acids are
named in the usual way and numbered beginning with the
the carbonyl carbon atom.
C. atoms Formula IUPAC name Common name
1 HCOOH methanoic acid formic acid
2 CH3COOH ethanoic acid acetic acid
3 CH3CH2COOH propanoic acid propionic acid
4 CH3(CH2)2COOH butanoic acid butyric acid
10 CH3(CH2)8COOH decanoic acid capric acid

CH3 – CH – CO2H CH2 = CHCO2H CH3CHCH2CO2H

Br OH
2-bromopropanoic acid propenoic acid 3-hydroxybutanoic acid
O O
HC – CH2CO2H CH3CCH2CHCO2H
3-oxopropanoic acid Br 2-bromo-4-oxopentanoic acid
When the carbonyl group is attached to a ring, the ending –
carboxylic acid is added to the parent of the cycloalakane.

– COOH – COOH
Cyclopentanoic acid cyclopropanoic acid

Aromatic acids are named by attaching the suffix –oic acid or

–ic acid.
COOH COOH COOH
CH3

Cl
benzoic acid p-chlorobenzoic acid o-toluic acid
Aliphatic dicarboxylic acids are given the suffix –dioic acid in
the IUPAC system.
HO2C – CH2CH2 – CO2H HO2C – C ≡ C – CO2H
butanedioic acid butynedioic acid
Physical Properties of acids
i. The first members of the carboxylic acids are colourless
liquids.
ii. Carboxylic acids are polar in nature and thus form
hydrogen bonds with themselves or other molecules.
iii. Hydrogen bonding is responsible for the high boiling
points and solubility in water.
O…..H – O
R–C C–R
O – H…..O
Acidity of carboxylic acids
Carboxylic acids dissociate in water, yielding a carboxylate
anion and hydroxonium ion.
O O H
R–C + H2O R–C + H – O+ – H
OH O-
carboxylate ion hydronium ion
Carbioxylic acids are more acidic than alcohols and phenols
because of charge localisation through resonance.
O O-
R–C R–C
O- O
Note: Electron –withdrawing groups enhance acidity and
electron-releasing groups reduce acidity.
Preparation of Acids
1. Oxidation of Primary Alcohols or Aldehydes
H R O
R – C – OH C=O R–C
H H OH
alcohol aldehyde acid
The most commonly used oxidising agents for these purposes are
potassium permangante (KMnO4), chromic acid (CrO3), nitric acid,
and with aldehydes only, silver oxide (Ag2O)
CrO3, H+
CH3(CH2)5CH = O CH3(CH2)5CO2H
CHO CO2H

Ag2O
2. Oxidation of Aromatic Side Chains
Aromatic acids can be prepared by oxidising an alkyl side
chain on an aromatic ring.
KMnO4 O

– CH3 –C
toluene heat benzoic acid OH

– CH2CH2CH3 KMnO4 – CO2H

heat
In this reaction it is the alkyl like methyl group, not the
aromatic ring, that is oxidised.
3. Reaction of Grignard reagents with Carbon dioxide
Grignard reagents add to the carbonyl groups of carbon
dioxide to give acids
O HX O
R – MgX + O = C = O R – C – OMgX R – C – OH + MgX2

Mg 1.CO2
(CH3)3CBr (CH3)3CMgBr (CH3)3CCO2H
ether 2. H3O+
4. Hydrolysis of Cyanides (Nitriles)
The carbon-nitrogen triple bond of organic cyanides can be
hydrolysed to a carboxyl group. The overall reaction is as
follows:
H+ O
R – C ≡ N + 2H2O or R–C + NH3
OH- OH
The reaction requires and acid or a base as a catalyst, and the
nitrogen atom of the cyanide is converted to ammonia.
NaCN H2 O
CH3CH2CH2Br CH3CH2CH2CN CH3CH2CH2CO2H + NH4+
H+
Carboxylic Acid Derivatives
Carboxylic acid derivatives are compounds in which the
hydroxyl part of the carbonyl group is replaced by various
other groups. All acid derivatives can be hydrolysed to the
corresponding acid. The general formulas are as follows:
O O O O O
R – C – OR’ R–C–X R – C – O – C – R R – C – NH2
ester acyl halide acid anhydride amide
Esters and amides occur widely in nature. Anhydrides are
uncommon in nature, and acid halides are produced only in
the laboratory.
Esters are derived from acids by replacing the –OH group by
an –OR group. They are named by naming the R of the –OR
group first, followed by the name of the acid, with the –ic
ending changed to –ate.
 O O O
CH3C – OCH3 CH3C – OCH2CH3 CH3CH2CH2C – OCH3
methyl ethanoate ethyl ethanoate methyl butanoate
O O
CH3C – O– – C – OCH3
phenyl ethanoate methyl benzoate

1.Preparation of Esters; Fischer Esterification

O H+ O
R – C – OH + HO – R’ R – C – OR’ + H2O
acid alcohol ester
O H+ O
CH3C – OH + HO – CH3 CH3C – OCH3 + H2O
2. Saponification of Esters
Esters are commonly hydrolysed with base and the general
reaction is as follows:
O heat O
R–C + Na+OH- R–C + R’OH
OR’ H2O O-Na+
ester base salt of an acid alcohol
Example
O heat O
CH3C – OCH3 + NaOH CH3C – ONa + CH3OH
H2 O sodium ethanoate
3. Ammonolysis of Esters
Ammonia converts esters to amides
O O
R–C + NH3 R–C + R’OH
OR’ NH2
ester amide
Example
O O
–C + NH3 ether –C + CH3OH
OCH3 NH2
methyl benzoate benzamide
4. Reaction of Esters with Grignard Reagents
Esters react with two equivalents of a Grignard reagent to
give tertiary alcohols.
O OMgBr H2O OH

R – C – OR’ + 2R”MgBr R – C – R” R – C – R”
R” H+ R”
O
CH3CH2C – OCH3 + 2 CH3CH2MgBr

OMgBr H2O OH
CH3CH2 – C -CH2CH3 CH3CH2 – C -CH2CH3

+
5. Reduction of Esters
Esters can be reduced to alcohols
O LiAlH4
R – C – OR’ RCH2OH + R’OH
ether
Example O LiAlH4
CH3CH2 – C – OCH2CH3 CH3CH2CH2OH + CH3CH2OH
ether
O 1. LiAlH4
CH3CH = CHC – OCH2CH3
ethyl 2-butenoate 2. H2O, H+
CH3CH = CHCH2OH + CH3CH2OH
2-buten-1-ol
Acyl Halides
Acyl halides are among the most reactive of the carboxylic
acid derivatives. They are usually prepared from acids by
the reaction with thionyl chloride or phosphorus
pentachloride.
O O
R–C + SOCl2 R–C + HCl + SO2
OH Cl

O O
R–C + PCl5 R–C + HCl + POCl3
OH Cl
Acyl halides react rapidly with most nucleophiles. E.g they are
rapidly hydrolysed by water
O rapid O
CH3 – C – Cl + H2O CH3 – C – OH + HCl

Acyl halides react rapidly with alcohols to form esters

O O
– C – Cl + CH3OH room temp – C – OCH3 + HCl

Acyl halides react rapidly with ammonia to form amides

O O
CH3 – C – Cl + 2NH3 CH3 – C – NH2 + NH4Cl
This reaction is much more rapid than the ammonolysis of
Acid Anhydrides
Acid anhydrides are derived from acids by removing water
from two carboxyl groups and connecting the fragments.
O O O O
R – C – OH + HO – C – R R – C – O – C – R + H2O
O O

H2O CH3C – OH + CH3C – OH

acid
O O O O
CH3– C – O – C – CH3 RO – H CH3C – OR + CH3C – OH
ester
O O
Amides
Amides are the least reactive of the common carboxylic acid
derivatives. The most important amides are the proteins.
Primary amides have the general formula RCONH2. They can
be prepared by the reaction of ammonia with esters, with
acyl halides, or with acid anhydrides. Amides van also be
prepared by heating the ammonium salts of acids.
O O O
R – C – OH + NH3 R – C – ONH4 heat R – C – NH2 + H2O
ammonium salt amide
Amides are named by replacing the –ic or –oic ending of the
acid name, either the common or the IUPAC name, with
–amide ending.
 O O O

H – C – NH2 CH3 – C – NH2 – C – NH2

methanamide ethanamide benzamide

Amides react with nucleophiles. For example they can be

hydrolysed by water.
O O
R – C – NH2 + H2O H+ or OH- R – C – OH + NH3

Amides can be reduced by lithium aluminium hydride to give

amines
O LiAlH4
R – C – NH2 RCH2NH2
Amines and Related Nitrogen Compounds
Amines are organic relatives of ammonia, derived by replacing
one, two, or all three hydrogens of ammonia with organic
groups. Amines are bases and are the most important type
of organic base that occur in nature.

Classification and Structures of Amines

The relation between ammonia and amines is illustrated by
the following structures:
H–N–H R–N–H R–N–R R–N–R
H H H R
Ammonia 1o amine 2o amine 3o amine
For convenience, amines are classified as primary, secondary,
or tertiary, depending on whether one, two, or three
organic groups are attached to the nitrogen. The R groups in
these structures may be alkyl or aryl, and when two or
more R groups are present, they may be identical to or
different from one another.
Nomenclature of Amines
Amines can be named in several different ways. Commonly,
simple amines are named by specifying the alkyl groups
attached to the nitrogen and adding the suffix –amine.
CH3CH2NH2 (CH3CH2)2NH (CH3CH2)3N
ethylamine diethylamine triethylamine

CH3
H3C – C – NH2 –NH2 H2NCH2CH2CH2CH2NH2
CH3 Cyclohexylamine 1,4-Butanediamine
In the IUPAC system, the amino group, -NH2, is named as a
substituent.
CH3CH2NH2 CH3CHCH2CH2CH3 CH3NHCH2CH2CH3
aminoethane NH2 1-methylamino propane
2-aminopentane
CH2CH3 CH3 CH3
CH3N – CH2CH2CH3 N H2N NH2
1-(ethylmethylamino) propane
H H
dimethylamino cyclohexane cis-1,3-diaminocyclobutane
Chemical Abstracts (CA) introduced a system for naming
amines that is rational and easy to use. In this system,
amines are named as alkanamines.
CH3CH2CH2NH2 CH2CHCH3 CH3CHCH2CH2CH3
NH2 NHCH3
propanamine 2-propanamine N-methyl-2-pentamine

–N(CH3)2 N,N-dimethylcyclohexanamine
When other functional groups are present, the amino group is
named as a substituent.
NH2 O
CH3CHCH2CO2H H2NCH2CH2CCH2CH3 CH3NHCH2CH2OH
3-aminobutanoic acid 1-amino-3-pentanone 2-methylaminoethanol

Aromatic amines are named as derivatives of aniline. In the

CA system, aniline is called benzenamine.
NH2 N(CH3) 2 NHCH3

CH3
Br N,N-dimethylaniline m-methyl-N-methylaniline or
p-bromoaniline (N,N-dimethylbenzenamine) N-methyl-m-toluidine
(4-bromobenzenamine) (N-methyl-3-
Example
Give an acceptable name for the following compounds
a. (CH3)2CHCH2NH2 b. CH3NHCH2CH3
Br
c. –NH2
Br

Solution:
b. Isobutylamine (common); 1-amino-2-methylpropane
(IUPAC); 2-methylpropanamine (CA)
c. Ethylmethylamine (common); methylaminoethane
(IUPAC); N-methylethanamine (CA).
d. 3,5-dibromoaniline (common, IUPAC); 3,5-
dibromobenzenamine.
Physical properties of amines
1. Lower amines are gases or low boiling point liquids and
possess a characteristic ammonia like smell (fishy odour).
Higher members are solids.
2. The boiling points rise gradually with increase of
molecular mass. Amines are polar compounds like NH3
and have comparatively higher boiling points than non-
polar compounds of similar molecular masses. This is due
to the presence of intermolecular hydrogen bonding.
H H H H
H–N----H–N----H–N---H–N----
R R R R
Hydrogen bonding in amines
However, the N – H -----N bonds of amines are weaker than
the O – H ---- O bonds of alcohols. The reason being that
nitrogen is not as electronegative as oxygen.
3. Amines are soluble in water. This is due to hydrogen
bonding between amine and water molecules. Amines are
also soluble in benzene and ether.
H H
H – O ----- H – N ------ H – O ------H – N -------
H R H R
Solubility decreases with increase of molecular mass
Preparation of Amines
1. Alkylation of ammonia and amines
Ammonia reacts with alkyl halides to produce primary amines
NH3 + R – X R – N+H3X- NaOH RNH2 + H2O + NaX
1o amine
Primary, secondary and teriary amines can be alkylated
RNH2 + R – X R2N+H2X- NaOH R2NH
1o amine 2o amine
R2NH + R–X R3N+HX- NaOH R3N
2o amine 3o amine

R3N + R–X R4N+X-

3o amine quatenary ammonium salt
2. Reduction of Nitrogen Compounds
a. The best route to aromatic primary amines is by reduction
of the corresponding nitro compounds.
3H2, Ni catalyst

CH3– – NO2 CH3– – NH2 + 2H2O

p-nitrotoluene SnCl2, HCl p-toluidine

b. Amides can be reduced to amines with lithium aluminium

hydride.
O R R’
R–C–N LiAlH4 RCH2N
R R”
O
c. Reduction of nitriles (cyanides) gives primary amines
LiAlH4

R–C≡N RCH2NH2
or H2, Ni

Examples
CH3CH2CH2CN LiAlH4 CH3CH2CH2CH2NH2
NCCH2CH2CH2CH2CN excess H2, Ni H2N – (CH2)6 – NH2
Both CN groups are reduced
d. Aldehydes and ketones undergo reductive amination when
treated with ammonia, primary, or secondary amines, to
give primary, secondary or tertiary amines, respectively.

C=O + RNH2 NaBH3(CN) CHNHR

o o
Reactions of Amines
1. Basicity of amines
Amines are basic because of the lone pair of electrons on the
nitrogen. Amine are more basic than water.
–N: + H – OH –N+ – H + OH-
amine ammonium ion hydroxide ion
An amine and its ammonium ion are related as a base and its
conjugate acid. For example, RNH3+ is the conjugate acid of
the primary amine RNH2. Alkyl amines are approximate 10
times as basic as ammonia because alkyl groups are
electron-donating relative to hydrogen. The electron-
donating effect stabilises the ammonium ion (positive
charge) relative to the free amine. In general, electron-
donating groups increase the basicity of amines, and
2. Reaction of amines with strong acids
R – NH2 + HCl RN+H3 Cl-
an alkylammonium chloride
Examples:
H
CH3CH2NH2 + HBr CH3CH2N+ – H Br-
ethylamine H
ethylammonium bromide
(CH3)3N: + HCl (CH3)3N+H Cl -
trimethylamine trimethylammonium chloride

– NH2 + HCl – N+H3 Cl-

phenylamine phenylammonium chloride

3. Acylation of amines with acid derivatives
Amines are nitrogen nucleophiles and they react with the
carbonyl group of acid derivatives ( acyl halides, anhydrides
and esters) by nucleophlic acyl substitution.
O O
R – C – Cl + H2N – R’ R – C – NHR’ + HCl
acyl halide 1o amine 2o amide

O R’ O R’
R – C – Cl + HN R–C–N + HCl
R” R”
acyl halide 2o amine 3o amide
CARBOHYDRATES
Carbohydrates occur in all plants and animals and are
essential for life. Plants are able to use the process of
photosynthesis to convert carbon dioxide to carbohydrates,
mainly cellulose, starch and sugars. Cellulose is the building
block of rigid cell walls and woody tissue in plants, whereas
starch is the chief storage of carbohydrates for later use as
a food or energy source. Some plants (cane and sugar
beets) produce sucrose, ordinary table sugar. Glucose, a
sugar is an essential component of blood. Ribose and
deoxyribose are components of the genetic material RNA
and DNA. Other carbohydrates are essential components of
coenzymes, antibiotics, cartilage, and shells of crustaceans,
and bacterial cell walls.
Definitions and classification
Carbohydrates are polyhydroxyaldehydes,
polyhydroxyketones, or substances that give such
compounds on hydrolysis. The chemistry of carbohydrates
is mainly the combined chemistry of two functional groups:
the hydroxyl group and the carbonyl group.
Carbohydrates are usually classified according to their
structure as monosaccharides, oligosaccharides, or
polysaccharides. The three classes of carbohydrates are
related to each other by hydrolysis.
H2O H 2O

Polysaccharides oligosaccharides monosaccharides

H+ H+
For example, the hydrolysis of starch, a polysaccharide gives
first maltose and then glucose.
 n H2O n H2O

〔 C12H20O10 〕 n n C12H22O11 2n C6H12O6

starch H+ maltose H+ glucose
Monosaccharides or simple sugars are carbohydrates that
cannot be hydrolysed to simpler compounds.
Polysaccharides contain many monosaccharides units-
sometimes hundreds or even thousands. Usually, but not
always, the units are identical. Starch and cellulose contain
the same linked units, glucose.
Oligosaccharides contain at least two and generally no more
than a few linked monosaccharide units. They may be
disaccharides, trisaccharides, and so on, depending on the
number of units, which may be the same or different.
Example, maltose is made up of two glucose units, but
sucrose is made of two different monosaccharides units,
Monosaccharide
Monosaccharides are classified according to the number of
carbon atoms present (triose, tetrose, pentose, hexose, etc)
and according to whether the carbonyl group is present as
an aldehyde (aldose) or as a ketone (ketose). There are only
two trioses: glycealdehyde and dihydroxyacetone.
CH = O CH = O CH = O CH = O CH = O
CHOH CHOH CHOH CHOH CHOH
CH2OH CHOH CHOH CHOH CHOH
triose CH2OH CHOH CHOH CHOH
tetrose CH2OH CHOH CHOH
pentose CH2OH CHOH
hexose CH2OH
CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH
C=O C=O C=O C=O C=O C=O
CH2OH CHOH CHOH CHOH CHOH CHOH
triose CH2OH CHOH CHOH CHOH CHOH
tetrose CH2OH CHOH CHOH CHOH
pentose CH2OH CHOH CHOH
hexose CH2OH CHOH
Ketoses heptose CH2OH
octose

Glyceraldehyde is the simplest aldose and dihydroxyacetone is

the simplest ketose. Other aldoses or ketoses can be
derived from glyceraldehyde or dihydroxyacetone by
Reduction of Monosaccharides
The carbonyl group of aldoses and ketoses can be reduced by
various reagents to form polyols, called alditols.
CH = O CH2OH
H OH H OH
HO H H2, catalyst HO H
H OH or NaBH4 H OH
H OH H OH
CH2OH CH2OH
D-glucose D-glucitol (sorbitol)
Sorbitol is used commercially as a sweetener and sugar substitute.
Oxidation of Monosaccharides
The aldehydes groups can be easily oxidised to acids. The
products are called aldonic acids.
CH = O COOH
H OH H OH
HO H Br2, HO HO H
H OH or Ag+ or Cu+ H OH
H OH H OH
CH2OH CH2OH
D-glucose D-gluconic acid
The oxidation of aldoses is so easy that they react with such
mild oxidising agents as Tollens’reagent (Ag+ in aqueous
ammonia), Fehling’s reagent (Cu2+ complexed with tartrate
ion). With Tollens’reagent, they give a silver mirror test and
with the copper reagents, the blue solution gives a red
precipitate of cuprous oxide, Cu2O.
O
RCH = O + 2Cu2+ + 5OH- RCO- + Cu2O + 3H2O
blue solution red precipitate
Stronger oxidising agents, such as aqueous nitric acid, attack the
aldehyde group and the primary alcohol group producing dicarboxylic
acids called aldaric acids.
CH = O COOH
H OH H OH
HO H HNO3 HO H
H OH H OH
H OH H OH
CH2OH COOH
Disaccharides
In a disaccharide, two monosaccharides are linked by a
glycosidic bond between the anomeric carbon of one
monosaccharide unit and a hydroxyl group on the other
unit.
1. Maltose: is the disaccharide obtained by the partial
hydrolysis of starch. Further hydrolysis of maltose gives
only D-glucose.
2. Cellobiose: is the disaccharide obtained by the partial
hydrolysis of cellulose. Further hydrolysis of cellobiose
gives only D-glucose. Cellobiose is an isomer of maltose.
3. Lactose: is the major sugar in human and cow’s milk.
Hydrolysis of lactose gives equimolar amounts of D-
galactose and D-glucose.
Sucrose (ordinary table sugar): is the most important
commercial disaccharide. It is obtained commercially from
sugar cane and sugar beets. Hydrolysis of sucrose gives
equimolar amounts of D-glucose and D-fructose

Maltose Lactose

Sucrose
Polysaccharides
Polysaccharides contain many linked monosaccharides and
vary in chain length and molecular weight. Most
polysaccharides give a single monosaccharide on complete
hydrolysis. The monosaccharide units may be linked
linearly, or the chains may be branched.
Starch: is the energy-storing carbohydrate of plants. It is a
major component of cereals, potatoes, corn and rice. It is a
form in which glucose is stored by plants for later use. Strch
is made of glucose units joined mainly by 1,4-α-glycosidic
bonds, although the chains may have a number of branches
attached through 1,6-α-glycosidic bonds. Partial hydrolysis
of starch gives maltose, and complete hydrolysis gives only
D-gluocose. Starch can be separated by various solution
and precipitation techniques into two fractions: amylose
and amylopectin
Amylose: constitutes about 20% of starch and the glucose
units (30 to 300) are in continuous chain, with 1,4 linkages.

Amylose
Amylopectin: is highly branched and each molecule may
contain 300 to 5000 glucose units, chains with consecutive
1,4 links average only 20 to 30 units in length. The chains
are connected at branch points by 1,6 linkages. Because of
this highly branched structure, starch granules swell and
eventually form colloidal solutions in water.
 Amylopectin
Glycogen: is the energy-storing carbohydrate of animals. It is
made up of 1,4- and 1,6-linked glucose units. Glycogen has
high molecular weight than starch (about 100,000 glucose
units). Its structure is even more branched than that of
amylopectin with a branch every 8 to 12 glucose units.
Cellulose: is an unbranched polymer of glucose joined by 1,4-
β-glycosidic bonds. The only chemical difference between
starch and cellulose is the stereochemistry of the glycosidic
link.

Cellulose
Chitin: is a nitrogen containing polysaccharide that forms the
shells of crustaceans and the exoskeletons of insects. It is
similar to cellulose, except that the hydroxyl group at C -2
of each glucose unit is replaced by an acetylamino group,
CH3CONH-.

chitin
POLYMERS
• Polymers or macromolecules are large molecules that are
built up by repetitive linking of many smaller units called
monomers.
• Polymers may be natural or synthetic. The most important
natural polymers are carbohydrates, proteins and nucleic
acids (DNA, RNA). Synthetic polymers include polyethylene,
Teflon, Styrofoam, nylon, Dacron, saran and polyurethanes.
Classification of Polymers
Synthetic polymers can be classified into two main types,
depending on how they are formed.
1.Chain-growth polymers(Addition polymers): are made by
the addition of one monomer unit to another in repetitive
manner. A catalyst or initiator is required, and it adds to
carbon-carbon double bond to form a reactive intermediate.
• This intermediate then adds to the double bond of a second
monomer unit to yield a new intermediate. The process
continues until the polymer chain is built up. Eventually, the
process is terminated in some way.
• Chain-growth polymers retain all the atoms of the monomer
units in the polymer. An example of a chain-growth polymer is
polyethylene
polymerisation
nCH2 = CH2 – 〔 CH – CH – 〕 n
ethylene initiator polyethylene
The steps for addition polymerization include:
– Initiation - often through the use of free-radicals.
– Propagation - radicals join to form larger radicals.
– Termination - occurs when a molecule is formed that no
longer has an unpaired electron.
2. Step-growth polymers(Condensation polymers): are
usually formed by a reaction between two different
functional groups, with the loss of some small molecule,
such as water, between them.
• A step-growth polymer does not contain all the atoms
initially present in the monomers; some atoms in the small
molecule that is eliminated.
• In condensation polymerization, a small portion of the
monomer molecule is not incorporated in the final
polymer.
• The monomers are held together by a certain kind of bond
(such as an amide bond) and a molecule is eliminated in
the process (such as a water molecule).
• This is the type of process used to make nylons and
silicones
• The monomer units are usually di- or polyfunctional, and
the monomers usually appear in alternating order in the
polymer chain. An example of a step-growth polymer is
nylon.
O O
H2N(CH2)6NH2 + HOC(CH2)4COH 200 – 300 °C
1,6-diaminohexane hexanedioic acid
(hexamethylenediamine) (adipic acid)
O O

〔– NH(CH2)6NHC(CH2)4C – 〕 n +
2n H2O
nylon, a polyamide
Homopolymer: all monomers are identical
• The most produced/used polymers are homopolymers of
terminal alkenes.
• Produced by radical polymerization
Copolymers: made up of different monomers

Types of Polymers: Polymers (synthetic)

• Polymers can be classified in several different ways-according to
their structures, the types of reactions by which they are
prepared, their physical properties, or their technological uses.
• From the general physical properties, there are three types of
solid polymers: elastomers, thermoplastic polymers, and
thermosetting polymers.
Note: These categories overlap considerably but are nonetheless
helpful in defining general areas of utility and types of
structures.
• The structural characteristics that are most important to
determining the properties of polymers are:
1. the degree of rigidity of the polymer molecules
2. the electrostatic and van der Waals attractive forces between
the chains
3. the degree to which the chains tend to form crystalline
domains
4. the degree of cross-linking between the chains. A cross-link is
a chemical bond between polymer chains other than at the
ends. Cross-links are extremely important in determining
physical properties because they increase the molecular
weight and limit the translational motions of the chainswith
respect to one another.
1. Thermoplastics (plastics) — linear, some cross-
linking can be melted and reformed on heating.
Thermoplastic polymers are hard at room
temperature, but on heating become soft and more
or less fluid and can be molded.
a) Amorphous—no ordered structure
b) Semi-crystalline—composed of microscopic
crystallites— domains of crystalline structure. Can
be ordered. Fibers (nylon, polyester)
2) Elastomers (rubbers) — moderately cross-linked can be
stretched and rapidly recover their original dimension.
Elastomers are rubbers or rubberlike elastic materials.
3) Thermostats—(resins)—massively cross-linked
very rigid; degrade on heating. Thermosetting polymers can
be molded at room temperature or above, but when
heated more strongly become hard and infusible.
4) Dendrimers—multiply branched—multiple consecutive
(regular) branches
Biopolymers
1.Polypeptides—proteins-amino acid heteropolymer
2. Nucleic acids—RNA/DNA
3. Polysaccharides—sugars