CHAPTER 11 :

INTRODUCTION
TO
ORGANIC CHEMISTRY
CHAPTER 11 : INTRODUCTION TO ORGANIC CHEMISTRY

11.1 Introduction
11.2 Empirical molecular and structural formulas
11.3 Functional groups and homologous series
11.4 Classification of carbon atoms in organic molecules
11.5 Isomerism
11.6 Reactions in organic compound
 Organic and Inorganic Compound

Organic compound Inorganic compound

 were defined as  were those that

compounds that came from
could be obtained nonliving sources
from living
organisms
Some examples of carbon compounds in our daily lives :-

CH4 CH3 CHCOOH

NH2
methane
(a component of natural gas) alanine
(amino acid-a protein component)

OCOCH3 CH3
N
CO2CH3
COOH
OCO

Methyl salicylic acid cocaine

(aspirin-a drug) (a pain killer)
11.2 EMPIRICAL, MOLECULAR AND
STRUCTURAL FORMULAE

 Empirical formula is the simplest formula that

shows the relative numbers of the different kinds
of atoms in a molecule.

 Molecular formula is a formula that states the

actual number of each kind of atom found in the
molecule. Example : C2H4 , C2H4O2
Quantitative example :-
A sample of hydrocarbon contains 85.7 % carbon and
14.3 % hydrogen by mass. Its molar mass is 56.
Determine the empirical formula and molecular formula
of the compound.
Solution :-

Element C H
Mass (g) 85.7 14.3
Moles (n) 85.7 14.3
= 7.142 = 14.3
12.0 1.0
Smallest ratio 7.142 14.43
7.142 7.142
=1 =2

 Empirical formula = CH2

n (empirical molar mass)= molar
mass
n ( 12 x 1 + 1 x 2 ) = 56
n = 4
Molecular formula = C4H8
Practice Exercise:
1) A complete combustion of 10.0 g of compound X,
CxHyOz forms 12.0 g H2O and 22.0 g CO2. Its
molar mass is 60.
a) Determine the percentage composition of

C, H and O.
b) Determine the molecular formula of
compound X.
2) A complete combustion of 0.6 g of hydrocarbon,
CxH12 forms 1.98 g CO2. Determine the percentage
of C and H in the hydrocarbon and write the
 Structural formula shows the order in which
atoms are bonded together

Representation of structural formula :-

a) Condensed Structure
b) Expanded Structure

c) Skeletal Structure
d) 3-Dimensional formula
e) Ficher Projection
a) Condensed Structure

 In condensed formulae all the hydrogen atoms

that are attached to a particular carbon are
usually written immediately after that carbon
Example :

CH3CHCH2CH3 or CH3CH(Cl)CH2CH3
C4H9Cl
Cl

Condensed structure
b) Expanded Structure

 Expanded structures indicate the way in which

the atoms are attached to each other and are not
representations of the actual shapes of the
molecules.

Example :
H H H H
H C C C C H
C4H9Cl
H Cl H H

Expanded structure
c) Skeletal Structure

 This structure shows only the carbon skeleton

 The hydrogen atoms that are assumed to be
present, are not written.
Other atoms such as O, Cl, N and etc. are shown

Example :

1. CH3CH(Cl)CH2CH3 =

Cl
2. H2C CH2
=
H2C CH2

3. CH2=CHCH2OH =
OH
Practice Exercise :

Rewrite each of the following structures using skeletal

formula :-

1. CH3CH2CH2C CH3
O

2. (CH3)2CHCH2CH2CH(CH3)CH2CH3

3. CH2= CHCH2CH2CH = CHCH3

4. CH3 CH2 CH ( CH3 ) CH2 C OH

O
d) 3 - Dimensional formula
(wedge - dashed wedge - wedge)

Describes how the atoms of a molecule are arranged

in space

Example : Br
Indication :-
bonds that lie in the
(Bromoethane) H plane of the page
C H bonds that lie behind
the plane
H
bonds that project out
of the plane of the
paper
Br H H
OR OR
C C C
H H H Br H H
H H Br
e) Fischer Projection

 Vertical lines represent bonds that project behind

the plane of paper

 Horizontal lines represent bonds that project out of

the plane of paper

 The intersection of vertical and horizontal lines

represent a carbon atom, that is stereocentre
Example :

2 – butanol , CH3CH(OH)CH2CH3

CH3 CH3

HO H OR H OH

CH2CH3 CH2CH3
 11.3 FUNCTIONAL GROUPS AND
HOMOLOGOUS SERIES

 A functional group is an atom or group of

atoms in an organic molecule which characterized
the molecule and enables the molecule to react
in specific ways (determines its chemical properties)
Some important functional groups in organic
compounds :-

Homologous Functional General IUPAC Example

Series Group Formula nomenclature
Prefix- -suffix
alkane none CnH2n+2 -ane CH4
methane
alkene C=C CnH2n -ene CH2=CH2
(double
bond) ethene
alkynes CC CnH2n-2 -yne CH  CH
(triple
bond) ethyne
Homologous Functional General IUPAC Example
Series Group Formula nomenclature
Prefix- -suffix
arene CnH2n-6 -benzene CH3

aromatic
ring methylbenzene

alcohol –OH CnH2n+1OH alkanol CH3CH2OH

(hydroxyl) ethanol
ether –OR CnH2n+2O alkoxyalkane CH3OCH3
(alkoxy) methoxymethane

haloalkane –X CnH2n+1X haloalkane CH3CH2Cl

(halogen) chloroethane
Homologous Functional General IUPAC Example
Series Group Formula nomenclature
Prefix- -suffix

aldehyde O CnH2nO alkanal CH3C=O

C H
H
carbonyl ethanal
ketone O CnH2nO alkanone CH3C=O
C
CH3
carbonyl propanone
carboxylic O CnH2nO2 alkanoic acid CH3C=O
acid C OH
OH
carboxyl ethanoic
acid
Homologous Functional General IUPAC Example
Series Group Formula nomenclature
Prefix- -suffix

acyl O CnH2n+1 alkanoyl CH3C=O

chloride C Cl COCl chloride
Cl
acyl
ethanoyl
chloride
O
ester CnH2nO2 alkyl CH3COOCH3
C O C ethyl
alkanoate ethanoate
ester
O
amide CnH2n+1 -amide CH3CONH2
C NH2 CONH2 ethanamide
amide

amine -NH2 CnH2n+1 -amine CH3NH2

amino NH2 methanamine
11.4 CLASSIFICATION OF CARBON AND
HYDROGEN ATOMS IN ORGANIC
MOLECULES

 Carbon atom classified primary (1o)

secondary (2o)
tertiary (3o)
quarternary (4o)

depending on the
number of carbon
atoms bonded to it
 A primary carbon – directly bonded to one other
carbon atom
(has 1 adjacent carbon atom)

Example :
1o H

H C H

CH3

1o carbon
 A secondary carbon – directly bonded to two other
carbon atoms
(has 2 adjacent carbon atoms)

Example :
2o H
H

H C CH3

CH3

2o carbon
 A tertiary carbon – directly bonded to three other
carbon atoms
(has 3 adjacent carbon atoms)

Example :

CH3

3o H H C CH3

CH3

3o carbon
 A quarternary carbon – directly bonded to four other
carbon atoms
(has 4 adjacent carbon atoms)

Example :

CH3

H3C C CH3

CH3

4o carbon
 Similarly, a hydrogen atom is also classified as
primary, secondary or tertiary depending on the
type of carbon to which it is bonded.

1° hydrogen atom bonded to a 1° C atom

2° hydrogen atom bonded to a 2° C atom
3° hydrogen atom bonded to a 3° C atom
 Classification of haloalkanes (alkyl halides)

 Alkyl halides are classified based on the carbon atom

to which the halogen is directly attached.

1° alkyl halide – the halogen atom is bonded to a

primary carbon atom

2° alkyl halide – the halogen atom is bonded to a

secondary carbon atom

3° alkyl halide – the halogen atom is bonded to a

tertiary carbon atom
 H H 1° C

H C C Cl

H H 2° C
1° alkyl chloride H H H

H C C C H

3° C H Cl H
H CH3 H
2° alkyl chloride
H C C C H

H Cl H
3° alkyl chloride
 Classification of alcohols

 Alcohols are classified based on the carbon atom

to which the hydroxyl group is directly attached.

1° alcohol – the hydroxyl group is attached to a

1° carbon atom

2° alcohol – the hydroxyl group is attached to a

2° carbon atom

3° alcohol – the hydroxyl group is attached to a

3° carbon atom
 H H 1° C

H C C OH

H H
2° C
1° alcohol
H H H

H C C C H

H OH H
3° C
H CH3 2° alcohol
H

H C C C H

H OH H
3° alcohol
 Classification of amines

 Amines are classified based on the number of alkyl

groups or carbon atoms that are directly attached
to the nitrogen atom

1° amine – N is bonded to one alkyl group

2° amine – N is bonded to two alkyl groups
3° amine – N is bonded to three alkyl groups
 N bonded to
one alkyl group H3 C N H

H3 C N H CH3
N bonded to
two alkyl group
H
A primary (1°) A secondary (2°)
amine amine

H3 C N CH3

CH3 A tertiary (3°)

amine
N bonded to three
alkyl group
ISOMERISM

Isomerism

Structural/Constitutional Isomerism Stereoisomerism

Chain Functional Geometric Optical

isomerism group isomerism isomerism
isomerism
Positional
isomerism
 Isomerism is the existence of different compounds
with the same molecular formula but different
structural formulae

 Isomers – different compounds that have same

molecular formula

structural isomerism
Two types different order of attachment
of of atoms
isomerism
stereoisomerism
different spatial arrangement of
atoms in molecules
 Structural isomers are different compounds with
the same molecular formula but differ in the order
of attachment of atoms

Structural isomerism

Chain/skeletal Positional Functional

isomerism isomerism group
isomerism
a) Chain/skeletal isomerism

 The isomers differ in the carbon skeleton

(different carbon chain)

 They possess the same functional group and

belong to the same homologous series

Example :

CH3CH2CH2CH2CH3
CH3
C5H12 :
CH3CHCH2CH3 CH3-C-CH3

CH3 CH3
b) Positional isomerism
 These isomers have a substituent group in
different positions in the same carbon skeleton

Example :

i) C3H7Cl CH3CH2CH2Cl CH3CHCH3

1-chloropropane Cl
2-chloropropane

ii) C4H8 CH2=CHCH2CH3 CH3CH=CHCH3

1-butene 2-butene
iii) C8H10 CH3
CH3
CH3

1,2-dimethylbenzene

CH3
CH3
1,4-dimethylbenzene
CH3
1,3-dimethylbenzene
c) Functional group isomerism

 These isomers have different functional groups

and belong to different homologous series with
the same general formula

 Different classes of compounds that exhibit

functional group isomerism :-

General formula Classes of compounds

CnH2n+2O alcohol and ether
CnH2nO aldehyde and ketone
CnH2n alkene and cycloalkane
CnH2nO2 carboxylic acid and ester
 Example :

i) C2H6O CH3CH2OH CH3OCH3

ethanol dimethyl ether

ii) C3H6O CH3CH2C-H CH3C-CH3

O O
propanal propanone

iii) C3H6O2 CH3CH2C-OH CH3C-O-CH3

O O
propanoic acid methyl ethanoate
 Stereoisomerism

Geometric Isomerism Optical Isomerism

a) Geometric isomerism

 occurs only in two classes of compounds :

Alkenes & cyclic compound

(because of rigidity in molecules)

 Geometric isomers (also called cis-trans isomers)
are stereoisomers that differ by groups being
on the same side (cis-isomer) or opposite
sides (trans-isomer) of a site of rigidity in a molecule

 The requirements for geometric isomerism :

i) restricted rotation about a C=C,double bond, in

alkenes or a C-C single bond in cyclic compounds

ii) each carbon atom of a site of restricted rotation has

two different groups attached to it
Examples :

i) H3C CH3 H3C H

C=C C=C
H H H CH3

cis-2-butene trans-2-butene

ii) H3C CH2CH3 H3C CH3

C=C C=C
H H CH2CH3
CH3
trans-3-methyl-2-pentene cis-3-methyl-2-pentene
iii)
H H H CH3

CH3 CH3 CH3 H

cis-1,2-dimethylcyclohexane trans-1,2-dimethylcyclohexane

Cl Cl
iv) Cl H
H H
H Cl

cis-1,3-dichlorocyclopentane trans-1,3-dichlorocyclopentane
 If one of the doubly bonded carbons has 2 identical
groups, geometric isomerism is not possible.

Examples :

i) CH3CH2 H ii) H CH3

C=C C= C
H3C H Cl CH3

2-methyl-2-butene 1-chloro-2-methylpropene
 cis-trans isomers have similar chemical properties
but different physical properties

 They differ in melting and boiling points and

solubility due to different polarity of the molecules

cis-isomers polar molecules

trans-isomers non-polar

• Melting point: trans- isomer > cis-isomer

• Boiling point: cis-isomer > trans- isomer
• Stability: trans-isomer > cis-isomer
b) Optical isomerism

 If a beam of light is passed through a piece of

polarizer prism, the emergent light vibrates in a
single plane, hence it is called a plane-polarized
light

 Optically active compounds have the ability to

rotate plane-polarized light

 The angle of rotation can be measured with an

instrument called polarimeter
Schematic representation of a polarimeter containing
an optically active sample :

clockwise rotation – plus sign (+) / dextrorotarory

anticlockwise rotation – minus sign (-) / levorotorary
  The requirements for optical isomerism :-

i) molecule contains a chiral carbon or chiral centre

(carbon atom with 4 different groups attached to it)

ii) molecule is not superimposable with its mirror image

 A representation of a chiral molecule with

3-dimensional formula :-

P
PQRS
C*
Q S *designates chiral centre
R
 Enantiomers are a pair of mirror-image molecules
that are not superimposable (must have one or more
chiral carbons)
Examples :

i) 2-butanol, CH3CHCH2CH3 :-
OH

CH2CH3 CH2CH3
C* C
H3C H CH3
H
OH OH

enantiomers
ii) 2-hydroxypropanoic acid, CH3CHCOOH :-
OH

COOH COOH

H OH HO H

CH3 CH3

enantiomers
 A racemic mixture or racemate is an equimolar
mixture of enantiomers which is optically inactive
because the two components rotate plane-polarized
light equally (same degree of rotation but in opposite
direction– so they can cancel each other’s rotation)

 A pair of enantiomers have identical chemical and

physical properties but differ in the direction of
rotation of plane-polarized light
 A compound with n chiral centers can have a
maximum of 2n stereoisomers

 If a molecule contains two or more chiral centers,

diastereomers may exist

 Diastereomers are stereoisomers that are not

mirror images of each other

 All physical properties of diastereomers are usually

different from one another
Example :
The 4 stereoisomers of 2-amino-3-hydroxybutanoic
acid CH3CH-CHCOOH are shown below using
Fischer projection formula:-
OH NH2

COOH COOH
H NH2 H2N H Four pairs of
A B diastereomers
H OH HO H
are identified :
CH3 CH3
enantiomers A and C ;
A and D ;
COOH COOH B and C ;
H NH2 H2N B and D
H
C HO H H OH
D
CH3 CH3
enantiomers
 Meso compound is a stereoisomer that has more
than one chiral centres and that is superimposable
on its mirror image because of the presence of an
internal plane of symmetry, hence it is optically
inactive (does not cause a rotation of plane-polarized
light)
Example : Tartaric acid , HOOCCH(OH)CH(OH)COOH

COOH COOH
P Q
H OH HO H
plane of symmetry
H OH HO H

COOH COOH
rotate 180o

COOH
identical
H OH
plane of symmetry
H OH

COOH
 At first glance, P and Q are assumed to be enantiomers

 But if compound Q is rotated 180o in the plane of

the paper, it is actually identical to compound P,
therefore P and Q are superimposable mirror images

 P and Q are the same compound

 It is a meso compound
 COOH COOH
R S
H OH HO H
*not a plane of symmetry
OH H H OH

COOH COOH
rotate 180o

COOH
different
HO H
*not a plane of symmetry
H OH

COOH
 R and S are related as mirror images and are not
superimposable even if rotated 180o

 Thus R and S constitute an enantiomeric pair

 There are 2 pairs of diastereomers :

P and R & P and S

 Further examples of meso compounds:

CH3 CHO

Cl H HO H
H OH plane of symmetry
Cl H HO H

CH3 CHO
 11.6 REACTIONS OF ORGANIC COMPOUNDS

11.6.1 Types of Covalent Bond Cleavage/Fission

 All chemical reactions involved bond breaking and

bond making

 Two types of covalent bond cleavage :-

 Homolytic cleavage
 Heterolytic cleavage
a) Homolytic Cleavage

 Occurs in a non-polar bond involving two atoms of

similar electronegativity

 A single bond breaks symmetrically into two equal

parts, leaving each atom with one unpaired electron

 Free radicals are formed in homolytic cleavage

X • X X• + X • ≡ 2X•
•

free radicals
b) Heterolytic Cleavage

 Occurs in a polar bond involving unequal sharing

of electron pair between two atoms of different
electronegativities

 A single bond breaks unsymmetrically and both the

bonding electrons are transferred to the more
electronegative atom

 Cation and anion are formed in heterolytic cleavage

A •• - + B+ A is more
anion cation electronegative
A •• B
A+ + B •• - B is more
cation anion electronegative
 Carbocations and free radicals are intermediates in
organic reactions.

 They are unstable and highly reactive

11.6.2 Reaction Intermediates

a) Carbocation

 Also called carbonium ion

 A very reactive species with a positive charge

on a carbon atom

 Carbocation is formed in heterolytic cleavage

 Example :

 
(CH3)3C — Cl (CH3)3C+ + Cl-
carbocation anion

 Chlorine is more electronegative than carbon and

the C—Cl bond is polar

 The C—Cl bond breaks heterolitically and both the

bonding electrons are transferred to chlorine atom
to form anion and carbocation
b) Free Radical
 A very reactive species with an unpaired electron

 Formed in homolytic cleavage

Example :
free radicals
uv
Cl – Cl Cl • + Cl •

C C C• + •C

H3C H • CH3 + •H
 11.6.3 Relative Stabilities of
Carbocations and Free Radicals

 Carbocation and free radical primary

secondary
tertiary
depending on the number of carbon atoms directly
bonded to the :-

• positively charged carbon atom (for carbocation)

• carbon atom with unpaired electron (for free radical)
 The stability of carbocation increases with the
number of alkyl groups present

 The alkyl groups are electron-releasing relative to

hydrogen, thus help to stabilize the positive charge
on the carbocation
 As the number of alkyl groups attached to the
positively charged carbon atom increases, the
stability of carbocation increases

 Carbocation Stability:

H H R R
H C H < R C H < R C H < R
+ C R
+ + +
methyl primary secondary tertiary
cation (1°) (2°) (3°)

Increasing stability
 Likewise, the stability of free radical increases as
more alkyl groups are attached to the carbon atom
with unpaired electron

 Free Radical Stability :

H H R R
H C H < R C H < R C H < R C R

methyl primary secondary tertiary

radical (1°) (2°) (3°)

Increasing stability
11.6.4 Reagents and Sites of Organic Reactions

a) Electrophile (E+)

 Means ‘electron loving’

 An electron-deficient species and electron-pair
acceptor that attacks a part of a molecule where
the electron density is high
 An electrophile can be either neutral or positively
charged
 Examples of electrophiles :-

1. cations such as H+, H3O+, NO2+, Br+ etc.

2. carbocations.
3. Lewis acids such as AlCl3, BF3 etc.
4. oxidizing agents such as Cl2, Br2 and etc

 Examples of electrophilic sites in organic molecules :-

• molecules with low electron density around a

polar bond such as :-

+ - + - + -
C=O C–X C – OH
carbonyl haloalkanes hydroxyl
compound
b) Nucleophile (Nu-)

 Means ‘nucleus loving’

 An electron-rich species and electron-pair donor

that attacks a part of a molecule where the electron
density is low

 A nucleophile can be either neutral or negatively

charged
 Examples of nucleophiles :-

1. anions such as OH-, RO-, Cl-, Cn- etc.

2. carbanions. (species with –ve charge on C atoms)
3. Lewis bases which can donate lone pair electrons
such as NH3, H2O etc.

 Examples of nucleophilic sites in organic molecules :-

molecules with high electron density around the

carbon-carbon multiple bond such as :-

-C=C- (alkenes) , -CC-(alkynes),

(benzene ring) and etc.

 11.6.5 Types of Organic Reactions

 The four main types of organic reactions are:

• Addition
• Substitution
• Elimination
• Rearrangement
 1.Addition reaction

A reaction in which atoms or

groups added to a multiple bond

a) Electrophilic addition b) Nucleophilic addition

a) Electrophilic Addition

 Initiated by an electrophile, which attacks a

nucleophilic site of a molecule

 Typical reaction of unsaturated compounds such

as alkenes and alkynes

Example :

room
CH3CH=CH2 + Br2 CH3CHBrCH2Br
temperature

electrophile
b) Nucleophilic Addition

 Initiated by a nucleophile, which attacks an

electrophilic site of a molecule
 Typical reaction of carbonyl compounds

Example :


O OH
H+ CN-
CH3 C CH 3 + HCN CH3 C CH3
+
CN
 2. Substitution Reaction

A reaction in which an atom or

group in a molecule is replaced by
another atom or group

a) Free-radical b) Electrophilic c) Nucleophilic

Substitution Substitution
Substitution
a) Free-radical Substitution

 Substitution which involves free radicals as

intermediate species

Example :

uv light
CH3CH3 + Cl2 CH3CH2Cl + HCl
b) Electrophilic Substitution

 Typical reaction of aromatic compounds

 The aromatic nucleus has high electron density,

thus it is nucleophilic and is tend to electrophilic
attack

Example :
 
Br Br
Fe
+ Br2 Br + HBr
catalyst
electrophile
c) Nucleophilic Substitution

 Typical reaction of saturated organic compounds

bearing polar bond as functional group, such as
haloalkane and alchohol

Example :

 
CH3CH2Br + OH-(aq) CH3CH2OH + Br-(aq)

nucleophile
 3. Elimination Reaction

 A reaction in which atoms or groups are removed

from adjacent carbon atoms of a molecule to form
a multiple bond (double or triple bond)

 Elimination reaction results in the formation of

unsaturated molecules

Example :

Conc. H2SO4
CH3CH2OH CH2= CH2 + H2O

4. Rearrangement Reaction

 A reaction in which atoms or groups in a molecule

change position

 Occurs when a single reactant reorganizes the

bonds and atoms

Example :

enol keto (more stable)

H
H C C R
H C C R
H OH
tautomerisation H O