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
Shapes of Carbon 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:
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 Cyclic Or Closed Chain

Compounds Compounds

Homocyclic Compounds Heterocylic

Compounds

Alicyclic Aromatic
Compounds Compounds

Benzenoid Non-benzenoid
Compounds 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” halohydrocarbo Fluoro, bromo, chloro
ns 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
 ISOMERIS
The phenomenon of Mexistence of two or more compounds
possessing the same molecular formula but different properties is
known as isomerism. Such compounds are called as isomers.
Two forms of isomerism
● Structural isomerism
● Stereoisomerism

Structural isomerism
● Same empirical formula but different atom-to-atom
connections.
Stereo isomerism
● Same atom-to-atom connections but different arrangement
 ISOMERISM

Structural Stereo
Isomerism isomerism

Functional
Chain Position Geometrical Optical
Isomerism Isomerism
Group Metamerism Isomerism Isomerism
Isomerism
 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 methoxypropan
ethane e
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 distinguished

by D,L configurations.
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
The general organic reaction is depicted as
follows :
Organic Attacking reagent
Molecule [Intermediate]
Products
(Substrate)
Byproducts
A sequential account of each step, describing details of 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.

Eg:
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:
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 effect or polarisability effect.
Inductive Effect
1. Permanent effect in saturated 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 , C2 H5
– I Effect Effect – Electron Withdrawing 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 ( ).
Positive Electromeric Effect (+E
effect)
π−electrons of the multiple bond are transferred to that atom to
which the reagent gets attached.

Negative 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 energy.

Rules for writing resonance

structures:
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.

Positive 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.
• The organic compound should not react with the solvent.
 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 Compounds
Detection of Carbon and 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.
 

• 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.
 
 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.
• A yellow colouration
  or precipitate indicates the presence of

  phosphorus.

Ammonium
molybdate

Ammonium
phosphomolybdat
e
 Quantitative
Carbon andAnalysis
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 respectively.
CxHy+ (x + y/4) O2 → x CO2+ (y/2) H2O
 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.

2NaO
Organic compound + H2SO4 → (NH4)2SO4 H → 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). It is
filtered, washed, dried and weighed
 Sulphu
r
• 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.
Phosphor
us
 Oxyge
 n