Organic

Chemistry
Organic chemicals appear in materials like clothing,
fuels, polymers, dyes and medicines.
It is about the compounds present in living organisms.
They all contain carbon.
Organic Chemistry is the Chemistry of Carbon.
In 1828, Wohler (a German chemist) synthesized an
organic compound, urea from an inorganic compound

(Inorganic (Organic
compound) compound)
 Tetravalence Of Carbon
Shapes of Carbon Compounds
The shapes of molecules like
 Methane (CH4) – are explained in terms of the use of sp3

hybridisation
 Ethene (C2H4) - sp2 hybridisation carbon Ethene

 Ethyne (C2H2) - sp hybridisation carbon Ethyne

 Structural Representations Of Organic
Compounds
Complete, Condensed and Bond-line Structural
Formulas:
Complete Structural
Formulas:
Bond-line Structural Formulas:
In this bond-line structural representation of organic
compounds, carbon and hydrogen atoms are not shown
and the lines representing carbon-carbon bonds are
drawn in a zig-zag fashion.
The terminals denote methyl (–)groups.
The line junctions denote carbon atoms bonded to
appropriate number of hydrogens required to satisfy the
valencyof the carbon atoms.
3-Methyloctane can be represented in various
forms as
3-D Representation of Organic Molecules
By using solid ( ) and dashed ( ) wedge formula,
the 3-D image of a molecule from a two-dimensional
picture can be perceived.
The solid-wedge is used to indicate a bond projecting out
of the plane of paper, towards the observer.
The dashed-wedge is used to depict the bond projecting
out of the plane of the paper and away from the observer.
 Classification Of
Organic
Compounds
1.Basing on functional
group
2.Basing on Carbon chain
3.Homologous series
 Carbon chain
Organic
compounds
Acyclic Or Open Chain CompoundsCyclic Or Closed Chain
Compounds

Homocyclic Heterocylic
Compounds Compounds

Alicyclic Compounds Aromatic Compounds

Benzenoid Compounds Non-benzenoid Compound

Acyclic or Open Chain Compounds
These compounds are also called as aliphatic compounds
and consist of straight or branched chain compounds.

Eg:
Alicyclic or Closed Chain or Ring Compounds
Alicyclic (aliphatic cyclic) compounds contain carbon
atoms joined in the form of a ring.
If atoms other than carbon are present in the ring then
they are called Heterocylic compounds.
Aromatic compounds

Aromatic compounds are special types of compounds.

These include benzene and other related ring compounds
(benzenoid).
Like alicyclic compounds, aromatic compounds may also
have hetero atom in the ring. Such compounds are called
Hetrocyclic aromatic compounds.
Benzenoid aromatic compounds

Non-benzenoid compound
Heterocyclic aromatic compounds
 Functional group

Functional group of a carbon

atom is defined as an atom,
bond or group of atoms in its
molecule that responsible for
the characteristic properties
of the compound.
Homologous
Series:
A homologous series is a series of compounds that have
the same functional group, and each member differs from
the next member by a – CH2 – unit in their formulae.

CH4 C2H6 C3H8 C4H10

CH2 CH2 CH2

E.g: alkanes: CnH2n+2 alkanols: CnH2n+1OH

alkenes: CnH2n alkanals: CnH2n+1CHO

alkynes: CnH2n-2 alkanoic acids:

CnH2n+1COOH
 Nomenclature Of Organic
Compounds
The International Union of Pure and Applied Chemistry
(IUPAC) developed a system for naming organic
compounds.
This system eliminated many of the ambiguities that
overwhelmed earlier naming systems
Common names for many substances are still widely
used.
Eg: Buckminsterfullerene is a common name given to
the newly discovered C60 cluster.
A series of prefixes are used to designate the number of
carbon atoms in a carbon chain

meth 1C hex 6C

eth 2C hept 7C

prop 3C oct 8C

but 4C Non 9C

pent 5C Dec 10 C
IUPAC System of Nomenclature
Alkanes are named by a process that uses
Prefix - Parent - Suffix

branching
groups are in longest
chain?

2,3-dimethylpentane
IUPAC Nomenclature of Alkanes
Straight chain alkanes are also called unbranched alkanes
Straight-chain alkanes have a zig-zag orientation when they
are in their most straight orientation
IUPAC Names of Some Unbranched Saturated
Hydrocarbons
Branched alkanes have at least one carbon which is
attached to more than two other carbons
Nomenclature of Branched-Chain Alkanes:
Locate the longest continuous chain of carbons; this is
the parent chain and determines the parent name.

Number the longest chain. The numbering is done in

such a way that the branched carbon atoms get the
lowest possible numbers.
The names of alkyl groups attached as a branch are
then prefixed to the name of the parent alkane and
position of the substituents is indicated by the
appropriate numbers.
When two or more substituents are identical, use the
prefixes di-, tri-, tetra- etc.
When two chains of equal length compete to be parent,
choose the chain with the greatest number of
substituents

When branching first occurs at an equal distance from

either end of the parent chain, choose the name that
gives the lower number at the first point of difference
Cyclic Compounds:

A saturated monocyclic compound is named by prefixing

‘cyclo’ to the corresponding straight chain alkane.
Cycloalkanes generally are shown as skeletal structures.
 Nomenclature of Organic
Compounds having Functional
Group
Various functional groups have unique suffixes that
designate the functional group.
The functional group takes precedence in numbering
the carbon chain.
Branches to the carbon chain are named in the usual
manner.
alcohols “ol” Amides “amide”
Aldehydes “al” Amines “amine” or amino as a prefix
Ketones “one” Ethers Ethoxy as prefix
Acids “oic” halohydrocarbons Fluoro, bromo, chloro or iodo
Esters “oate”
Nomenclature of Benzene Derivatives
Benzene is the parent name for some monosubstituted
benzenes; the substituent name is added as a prefix

For other monosubstituted benzenes, the presence of

the substituent results in a new parent name
When two substituents are present their position may be
indicated by the prefixes ortho, meta, and para (o, m and
p) or by the corresponding numerical positions
Dimethyl substituted benzenes are called
xylenes
Numbers must be used as locants when more than two
substituents are present
The lowest possible set of numbers should be given to the
substituents
The substituents should be listed in alphabetical order
If one of the substituents defines a parent other than
benzene, this substituent defines the parent name and
should be designated position 1
 ISOMERISM
The phenomenon of existence of two or more compounds
possessing the same molecular formula but different
properties is known as isomerism. Such compounds are
Two forms
called of isomerism
as isomers.
 Structural isomerism
 Stereoisomerism
Structural isomerism
 Same empirical formula but different atom-to-atom
connections.
Stereo isomerism
 Same atom-to-atom connections but different
 ISOMERISM

Structura Stereo
l
Isomeris
isomeris
m m
Function
Position Geometric Optical
Chain al Group Metameris
Isomeris al Isomeris
Isomerism
m
Isomeris m Isomerism m
m
 Chain isomerism:
When two or more compounds have similar molecular
formula but different carbon skeletons, these are
referred to as chain isomers and the phenomenon is
termed as chain isomerism.
Eg:
 Position isomerism:
When two or more compounds differ in the position of
substituent atom or functional group on the carbon
skeleton, they are called position isomers and this
phenomenon is termed as position isomerism.

Eg:
Functional group isomerism

Two or more compounds having the same molecular

formula but different functional groups are called
functional isomers and this phenomenon is termed as
functional group isomerism.
Metamerism:

It arises due to different alkyl chains on either side of the

functional group in the molecule.

Ethoxy ethane methoxypropane

Geometrical Isomerism

Compounds with same molecular formulae and

have different spatial arrangement exhibits
geometrical isomerism.
E- Higher atomic
number elements on
same side of double
bond.
Z- Higher atomic
number elements on
opposite side of
double bond.
Cis- Higher atomic number
elements on same side of
double bond.
Trans- Higher atomic
number elements on
opposite side of double
bond.
 Optical isomerism
 Molecules with non
superimposable mirror
images are called
chiral .

 The non
superimposable mirror
images and
stereoisomers are called
enantiomers.

 There are
D,L – system of configuration

D refers to an
arrangement about a
centre of chirality such
that OH on the right side
of Fischer’s projection
formula.

L refers to an
arrangement about a
centre of chirality such
that OH on the left side
of Fischer’s projection
formula.
 Organic Reaction Mechanism
he general organic reaction is depicted as follows :

Organic Attacking reagent

Molecule [Intermediate]
Products

(Substrate)
A sequential account of each step, describing details of
Byproducts
electron movement, energetics during bond cleavage and
bond formation, and the rates of transformation of
reactants into products is referred to as Reaction
Mechanism.
Fission of a Covalent Bond

A covalent bond can get cleaved by:

• Heterolytic cleavage
• Homolytic cleavage.
Homolytic Fission:
When the cleavage of covalent bond between two
atoms enables each atom to retain one electron of the
shared pair instead of electron pair, it is known as
homolytic fission.
The free radicals are denoted by dot over the symbol of
atom or group of atoms.
. .
homolytic fission B
A:B A +
Eg:

free radicals
Heterolytic fission:

Heterolytic fission is unsymmetrical wherein the bond

breaks and shared pair of electron remains with one of
the fragments
This results into two charged particles as:
heterolytic fission B
A:B A +

Nucleophile, Nu Electrophile, E
Nucleophile, Nu-:
A reagent that brings an electron pair is called a
nucleophile Nucleophile or nucleus seeker or anion is a
species that donate an electron pair to a positive ion.
All molecules or ions with a free pair of electrons or at
least one pi bond can act as nucleophiles.
Because nucleophiles donate electrons, they are by
definition Lewis bases.
Eg: OH-, CN-, Cl-, Br-, I-, NO3-, SO42-, H2O, NH3 ………. etc.
Electrophile, E+:

A reagent that takes away an electron pair is called

Electrophile. Electrophiles or electrons seekers or
cations are positively charged species that accept
electron pair.
Because electrophiles accept electrons, they are Lewis
acids.
Most electrophiles are positively charged, have an
atom that carries a partial positive charge.
Eg: H+, NH4+, NO2+, SO3H+, RCO+, BF3, AlCl3, FeCl3 ………..
etc.
 Electron Movement in Organic Reactions
The movement of electrons in organic reactions can be
shown by
from π bond to adjacent bond position

from π bond to adjacent atom

from atom to adjacent bond position

Movement of single electron is indicated by a single

barbed ‘fish hooks’
Electron Displacement Effects in Covalent
Bonds
The electron displacement in an organic molecule takes
place either in the ground state under the influence of an
atom or a substituent group or in the presence of an
appropriate attacking reagent.
Inductive effect and resonance effects are examples of
the electron displacements.
The electron displacements due to the influence of an
atom or a substituent group present in the molecule
cause permanent polarlisation of the bond.
Temporary electron displacement effects are seen in a
molecule when a reagent approaches to attack it . This
type of electron displacement is called electromeric
 Inductive
Effect effect in saturated
1. Permanent carbon chain
compounds.
2. Group attached to carbon chain should have
tendency to release or withdraw electrons.
Types of inductive effect

+ I Effect Effect – Electron Donating

Groups
Eg: CH3 ,Withdrawing
– I Effect Effect – Electron C2 H5 Groups
Eg: - NO2 , –CN, - COOH
 Electromeric Effect

Temporary effect which is observed in presence of

reagents involving transfer of electrons of a shared pair
of π-electrons to one of the atoms joined by a multiple
bond on the demand of an attacking reagent.
It is represented by E and the shifting of the electrons is
shown by a curved arrow ( ).
ositive Electromeric Effect (+E effect)

π−electrons of the multiple bond are transferred to that

atom to which the reagent gets attached.

egative Electromeric Effect (-E effect)

π - electrons of the multiple bond are transferred to

that atom to which the attacking reagent does not get
attached.
 Resonance Structure
Structures I and II are equal resonance contributors to
the real structure of benzene
Benzene is particularly stable because it has two
equivalent and important resonance structures
Each carbon-carbon bond distance is 1.39 Å and a
carbon-carbon double bond distance is 1.33 Å
Often the hybrid is represented by a circle in a
hexagon (III)
 The resonance structures (canonical structures or
contributing structures) individually do not characterize
any real molecule
Eg: Consider nitromethane(CH3NO2)

The two N–O bonds of nitromethane are of the same length

(intermediate between a N–O single bond and a N=O
double bond). The actual structure of nitromethane is
therefore a resonance hybrid of the two canonical forms I
and II.
 The energy of actual structure of the molecule (the
resonance hybrid) is lower than that of any of the
canonical structures.
The difference in energy between the actual structure and
the lowest energy resonance structure is called the
Resonance stabilisation energy or simply the resonance
Rules for writing resonance structures:
energy.
The resonance structures have
• the same positions of nuclei
• the same number of unpaired electrons.
 Resonance Effect
The polarity produced in the molecule by the interaction of
two π-bonds or between a π-bond and lone pair of
electrons present on an adjacent atom.

ositive Resonance Effect (+R effect)

The transfer of electrons is away from an atom or
substituent group attached to the conjugated system.
Negative Resonance Effect (- R effect)
The transfer of electrons is towards the atom or
substituent group attached to the conjugated system
Hyperconjugation
Partial overlap of the s bonding orbital of an adjacent C-H
bond with the vacant 2p orbital of the cationic carbon
delocalizes the positive charge and also the electrons of
the adjacent s bond
Replacing a C-H bond with a C-C bond increases the
possibility for hyper conjugation.
Types of Organic Reactions and
Mechanisms
Substitution reactions
Addition reactions
Elimination reactions
Rearrangement reactions
Substitution reactions:

The reaction in which hydrogen or any

atom or any functional group is
substituted by another atom or group

Eg:
Addition reactions:

The reaction in which the reagent and

the substrate combine together to
give a single product.

Eg:
Elimination reactions:

The reaction in which two or more

atom of substrate are removed to
form multiple bonds.

Eg:
Rerrangement
reactions:
Molecules in the presence of reagents
undergoes rerrangement.

Eg:
Methods of Purification of
Organic Compounds
Sublimation
Crystallisation
Distillation
Differential extraction
Chromatography
 Filtration
It is used when only one of the compounds is soluble in the
given solvent.
Eg: Urea and Naphthalene
Benzoic acid and anthracene
 Sublimation
Used to separate volatile organic compounds from non
volatile impurities
E.g. Naphthalene, benzoic acid, anthracene, camphor.
 Crystallization
Most common method for purification of solid organic
compounds.
Impurities and organic compound have different solubilities
in the given solvent.
The organic compound should be insoluble or sparingly
soluble in the solvent at room temperature but readily
soluble at high temperature.
The impurities should be insoluble in the solvent even at
high temperature .
The solution is concentrated to get a nearly saturated
solution. On cooling the solution, pure compound
crystallises out and is removed by filtration.
 Distillation
Simple distillation:
Liquids having different boiling points vaporise at different
temperatures.
The vapours are cooled and the liquids so formed are
collected separately.Difference in boiling points of
compounds is more than 40ºC.
Eg: Chloroform (B. P- 334K) and Aniline (B. P- 457K).
Fractional distillation: Used if the difference in boiling
points of compounds is less than 40ºc.
Eg: Acetone (B. P. 329K) and Methyl alcohol (B. P. 338k).
Vacuum distillation: Used for organic compounds which
decompose at or below their boiling points.
Eg: Glycerol.
Steam distillation: Used for organic compounds which are
immiscible with water and are steam volatile.
Eg: Aniline.
 Differential Extraction
Used to extract pure organic compounds from their
aqueous solution by shaking with organic solvent in which
they are highly soluble.
The organic solvent and the aqueous solution should be
immiscible with each other so that they form two distinct
layers which can be separated by separatory funnel.
Eg. Benzoic acid from its aqueous solution using benzene.
 Chromatography
It is an important technique extensively used to separate
mixtures into their components, purify compounds and
also to test the purity of compounds
It is based on selective adsorption or partition between
stationary and mobile phase.

Classification of Chromatography:

Adsorption
Chromatography
Partition Chromatography
 Adsorption Chromatography:

Principle: When a mobile phase is allowed to move over a

stationary phase (adsorbent), the components of the
mixture move by varying distances over the stationary
phase.
Types of chromatographic techniques based on the principle
of differential adsorption are :
Column chromatography
Thin layer chromatography.
Column Chromatography
A liquid or a mixture of
liquids is allowed to flow
down the column slowly.
Depending upon the degree
to which the compounds are
adsorbed, complete
separation takes place.
The most readily adsorbed
substances are retained
near the top and others
come down to various
distances in the column
Thin layer Chromatography
It is based on adsorption, used for quantitative analysis.
It involves separation of substances of a mixture over a
thin layer of an adsorbent coated on glass plate.

Chromatogram Being Developed Developed chromatogram

Partition Chromatography
Partition chromatography is based on continuous
differential partitioning of components of a mixture
between stationary and mobile phases.
Paper Chromatography: Based on partition and used for
quantitative and qualitative analysis
 Qualitative Analysis of Organic
Detection of Carbon andCompounds
Hydrogen
Carbon and hydrogen are detected by heating the
organic compound with copper oxide
Carbon present in the compound is oxidised to carbon
dioxide and hydrogen to water
C + 2CuO → 2Cu + CO2

2H + CuO → Cu + H2O

CO2+ Ca(OH)2 → CaCO3↓+ H2O

5H2O + CuSO4 → CuSO4.5H2O

White Blue
Detection of Other Elements
Nitrogen, sulphur, halogens and phosphorus present in an
organic compound are detected by “Lassaigne’s test”

Detection of Nitrogen
Detection of Sulphur

The sodium fusion extract is acidified with acetic acid and

lead acetate is added to it. A black precipitate of lead
sulphide indicates the presence of sulphur.
−2 +2
𝑆 + 𝑃𝑏 → 𝑃𝑏𝑆
On treating sodium fusion extract with sodium
nitroprusside, appearance of a violet colour further
indicates the presence of sulphur.
Detection of Halogens
The sodium fusion extract is acidified with nitric acid and
then treated with silver nitrate.
A white precipitate, soluble in ammonium hydroxide
shows the presence of chlorine
A yellowish precipitate, sparingly soluble in ammonium
hydroxide shows the presence of bromine
A yellow precipitate, insoluble in ammonium hydroxide
shows the presence of iodine.
− + ¿→ 𝐴𝑔𝑋 ¿
𝑋 + 𝐴𝑔
Detection of Phosphorus
The compound is heated with an oxidising agent like
sodium peroxide.
The phosphorus present in the compound is oxidised to
phosphate.
The solution is boiled with nitric acid and then treated
with ammonium molybdate.
𝑁𝑎3 𝑃𝑂4 +3or𝐻𝑁
A yellow colouration 𝑂 3 → 𝐻 3 indicates
precipitate 𝑃𝑂 4 +3 𝑁𝑎𝑁
the𝑂presence
3
of phosphorus.

Ammonium
+12 molybdate

Ammonium
phosphomolybdate
 Quantitative Analysis
Carbon and Hydrogen
A known mass of an organic compound is burnt in the presence
of excess of oxygen and copper(II) oxide. Carbon and hydrogen
in the compound are oxidised to carbon dioxide and water
CxHy+ (x + y/4) O2 → x CO2+ (y/2) H2O
respectively.
 Nitrogen
Dumas Method:
• The nitrogen containing organic compound, when heated
with copper oxide in an atmosphere of carbon dioxide,
yields free nitrogen in addition to carbon dioxide and water.

CxHyNz+ (2x + y/2) CuO → x CO2+ y/2 H2O + z/2 N2+ (2x +
y/2) Cu
Kjeldahl’s Method:

The compound containing nitrogen is heated with

concentrated sulphuric acid. Nitrogen in the compound
gets converted to ammonium sulphate.
The resulting acid mixture is then heated with excess of
sodium hydroxide. The liberated ammonia gas is
absorbed in an excess of standard solution of sulphuric
acid. 2NaOH
Organic compound + H2SO4 → (NH4)2SO4 → Na2SO4 +
2NH3 + 2H2O
2NH3+ H2SO4 → (NH4)2SO4
 Halogens
Carius method:
An organic compound is heated
with fuming nitric acid in the
presence of silver nitrate
contained in a hard glass tube
known as Carius tube in a
furnace.
Carbon and hydrogen present in
the compound are oxidised to
carbon dioxide and water.
The halogen present forms the
corresponding silver halide (AgX).
Sulphur

A known mass of an organic compound is heated in a

Carius tube with sodium peroxide or fuming nitric acid.
Sulphur present in the compound is oxidised to sulphuric
acid. It is precipitated as barium sulphate by adding
excess of barium chloride solution in water.
The precipitate is filtered, washed, dried and weighed.
The percentage of sulphur can be calculated from the
mass of barium sulphate.
Phosphorus
Oxygen
A definite mass of an organic compound is
decomposed by heating in a stream of nitrogen gas.
The mixture of gaseous products containing oxygen is
passed over red-hot coke when all the oxygen is
converted to carbonmonoxide.
This mixture is passed through warm iodine
pentoxide() when carbon monoxide is oxidised to
carbon dioxide producing iodine.

The percentage of oxygen can be derived from the