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Organic compounds
Organic chemistry deals with carbon compounds and their properties. Carbon has a unique property called
catenation due to which it forms covalent bonds with atoms of other elements and with its own atoms. First
synthesised organic compound is urea by Wohler, from NH4CNO – ammonium cyanate.
Heat
NH4CNO NH2CONH2
Tetravalency of carbon : Shapes. Carbon is tetravalent and forms covalent bonds. This is explained on the basis of
configuration and hybridisation of ‘s’ and ‘p’ orbitals in CH4( C – sp3), in C2H2(C – sp) and in C2H4(C – sp2).
Hybridization influences the bond length and bond enthalpy of organic compounds. sp hybrid orbital contains more
‘s’ character and closer to its nucleus. So the bonds are shorter and stronger than sp3 hybrid orbital. sp2 is
intermediate in character than sp and sp3. So the length and enthalpy is also intermediate between sp and sp3.
Structural representations :
Covalent bonds are represented by ‘– ‘ (dash). A ‘ – ‘ represents a single bond.
‘ = ‘ represents a double bond.
Condensed structural formula : Eg : CH3CH3 or C2H6(Ethane), H2C = CH2 or C2H4(Ethene), HC = CH or C2H2(Ethyne)
Such structural representations are condensed structural formula.
Complete structural formula :

Bond line structural representation

Here C – C bonds are drawn in a zig – zag way. Only Chlorine, Bromine etc are specified. The terminals denote –CH3
group. The line junction represents carbon with appropriate number of hydrogen atoms to satisfy the valancy of
carbon.

2 Bromo butane

Classification of organic compounds : Organic compounds are broadly classified as follows.

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Acyclic or open chain compounds : They are also called aliphatic.

They contain open chain of carbon atoms. Eg:
Cyclic compounds or closed chain compounds: They
are ring compounds where carbon atoms are joined in
the form of a ring. Eg :

Aromatic compounds : These include benzene and other related ring compounds.

Benzenoid aromatic compounds

Non Benzenoid compounds

Hetrocyclic aromatic compounds

Three dimensional representation of Organic compounds: 3D

structure of organic molecules are represented by Wedge formula.
- Solid Wedge  Bonds projecting out of paper, towards the
observer.
- Dashed Wedge.  Shows bonds projecting out of the plane,
away from the observer. – shows the bonds in t he plane of the paper.
Homologous series : A group or a series of organic compounds each containing a characteristic functional group
forms a homologous series. The members of a homologous series can be represented by a general molecular formula
and the successive members differ from each other by a -CH2 unit. Examples are alkanes, alkenes, haloalkanes,
alkanols, alkanals, alkanones etc.
Nomenclature: A systematic method of naming has
been developed to identify millions of organic
compounds and is known as nomenclature(IUPAC
system of nomenclature). Before the IUPAC system
of nomenclature common names were used. Some
common names are followed even today. They are
also called trivial names.

Functional group: A functional group may be defined as an atom or group of atoms joined in a specific manner which
is responsible for the characteristic chemical properties of the organic compounds. Examples are –OH, -CHO etc.
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Nomenclature: The name of the carbon chain is called word root and suffix is added to the word root to indicate the
saturation or unsaturation.
Eg : C5  Word Root Suffix Suffix
0
ane, ene or yne 1 20
Pent
ane, ene or yne Functional group(last)
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Rules for naming:

1. Longest chain rule : Select the longest continuous chain of carbon atoms as the parent chain. If the carbon atom
contain multiple bond, the main chain should contain that carbon atom. The alkyl radical is represented by removing
ane from the name and putting ‘yl’. The carbon atom which are not included in the parent chain are considered as
alkyl substituent and determine the prefixes.
Eg: Prefix : Methyl Word root : Hept Prim.Suffix : ane

If two chains are possible, the chain with maximum substituents are taken as the parent chain.

Lowest Number Rule : The numbering is done in such a way that the subtituent carbon atom has the lowest possible
number.

2 methyl butane The carbon atom in which substituent is called locant

Lowest set of locant Rule : If two or more different sets of locants containing same
number of terms are possible, then the two sets of locants are compared term by
term. The set of locants which contains the lowest number on the occasion of first
difference is considered correct for numbering the carbon atoms of parent chain.
In unsaturated hydrocarbon, the carbon atom 3 Methyl but-1-ene
having multiple bonds should have the lowest
Locant-(Prefixes) (word root) (p. suffix)
number.
Rule 3 , Use of prefixes, Di, Tri, etc. : If the compound contains more than one similar alkyl group, their positions are
indicated separately. The name of the substituent is not repeated, but an appropriate numerical prefix di, tri, etc is
added before the name of the substituent. The positions of the substituents are separated by commas.

Rule 4 ; Alphabetical arrangement of prefixes : If there are different alkyl

substituents present in the compounds, their names are written in the
alphabetical order of preference. But Di, Tri etc won’t be considered for this.
3 Ethyl, 4 , 4 dimethyl Heptane
Rule 5 , Naming complex Alkyl substituent : If the alkyl substitent is further branched, it is named as substituted alkyl
group. Here carbon atom of the alkyl group are separately numbered in such a way that the carbon atom directly
attached to the parent chain is given number 1.
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Cyclopropane

Cyclopentane

Cyclohexane

Nomenclature of Organic Compounds having Functional Group(s) : The longest chain of carbon atoms containing
the functional group is numbered in such a way that the functional group is attached at the carbon atom
possessing lowest possible number in the chain.
In the case of polyfunctional compounds, one of the functional groups is chosen as the principal functional group and
the compound is then named on that basis. The remaining functional groups, which are subordinate functional
groups, are named as substituents using the appropriate prefixes. The choice of principal functional group is made on
the basis of order of preference.
The order of decreasing priority for some functional groups is: -COOH, –SO3H, -COOR (R=alkyl group), COCl,
-CONH2, -CN,-HC=O, >C=O, -OH, -NH2, >C=C<, -C≡C- . The –R, C6H5-, halogens (F, Cl, Br, I), –NO2, alkoxy (–OR) etc. are
always prefix substituents. Thus, a compound containing both an alcohol and a keto group is named as
hydroxyalkanone since the keto group is preferred to the hydroxyl group. For example, HOCH2(CH2)3CH2COCH3 will be
named as 7-hydroxyheptan-2-one and not as 2-oxoheptan -7-ol. Similarly, BrCH2CH=CH2 is named as 3-bromoprop-1-
ene and not 1-bromoprop-2-ene.
If more than one functional group of the same type are present, their number is indicated by adding di, tri, etc.
before the class suffix. In such cases the full name of the parent alkane is written before the class suffix. For example
CH2(OH)CH2(OH) is named as ethane–1,2–diol. However, the ending – ne of the parent alkane is dropped in the case
of compounds having more than one double or triple bond; for example, CH2=CH-CH=CH2 is named as buta–1,3–
diene.
Nomenclature of substituted Benzene compounds

If Benzene ring is di substituted, the position of substituents is defined by numbering the carbon atoms of the ring
such that the substituents are located at the lowest numbers possible.

Ortho(1, 2) , Meta(1,3) and Para(1, 4) (In trival system)

So 1,2 Dibromo benzene  Ortho dibromo benzene
1, 3 Dibromo benzene  Meta dibromo benzene
1, 4 Dibromo benzene  Para dibromo benzene
But, for tri substitution – locant rule is used. Substituents are named according to alphabetical order and in some
cases, common names of benzene derivatives are used as base compounds.
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Isomerism: Consider the compounds ethyl alcohol C2H5OH and dimethyl ether CH3OCH3 – They have different
properties, but same molecular formula, C2H6O. They are called isomers. So this is a phenomenon by virtue of which
two or more compounds having same molecular formula can be assigned different molecular structure.

Structural  Isomers have different molecular structures due to different arrangement of atoms in their molecules
Chain isomerism  Different skeleton of carbon atoms .
Eg:

Position isomerism  The positions of functional groups

are different. Eg:

Functional isomerism  Isomers have different

functional groups belonging to different families. Eg:

Metamerism: Differs in structure due to difference in H3C – CH2 – O – CH2 – CH3 H3C– O – CH2 – CH2 – CH3
distribution of carbon atoms about the functional group.Eg: Ethoxy ethane 1 – methoxy propane
Stereo isomerism : Compunds that have the same constitution and sequence of covalent bonds but differ in relative
positions of their atoms or groups in space are called stereo isomers. This special type of isomerism is called as stereo
isomerism and can be classified as geometrical and optical isomerism.
Nucleophile and Electrophile : Nucleophilic and negatively charged or neutral species which are capable of donating
a pair of electrons to some other molecules. They attack the electron deficient centres(Lewis base). Eg : :Cl-, :OR-,
:CN-, :NO2-, OH-
R-  Charged nucleophile.
H2O , ROH, NH3 , ROR, RNH2  uncharged nucleophile
Electrophiles : They are neutral or positively charged molecules which are capable of accepting a pair of electron
from the substrate molecule(Lewis acid). They attack the electron rich centres.
Eg : H+, CL+, Br+, NO2+, R+  charged. BF3, AlCl3, SO3  Neutral electrophile
Electron movement in Organic Reactions : Electron movement in organic reaction is given by curved arrow notation.
Curved arrow starts from the point from where an electron pair is shifted and it ends at a location to which the
electron may more.
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Movement of a single electron is represented by fish hook. ( )

Inductive Effect : Permanent displacement of electrons along a carbon chain when some atom or group of atoms
with different electronegativity than carbon is attached to carbon chain is called inductive effect. Inductive effect is of
two types.
i) Electron withdrawing inductive effect( -I effect)
ii) Electron releasing inductive effect(+I effect)

Eg: ( - I Effect)

Inductive effect is a permanent effect. -I effect - NO2 > - F > - Cl > - Br > -I > - OCH3 > -C6H5
Resonance Structures : This is the case where a molecule is represented by two or more electronic structures but
one of them represent the actual structure of the molecule. The acual structure lies between the structures. The
various structures are called contributing structures.
Actual structure of benzene is a resonance hybrid of the above two structures.
The resonance hybrid is more stable than any of the contributing structures and
Eg:
the difference between energy of the most stable contributing structure and
resonance hybrid is called RE(Resonance Energy)
Carboxylic acid

Resonance effect : Resonance causes displacement of electrons from one part of the system to another part creating
centres of high and low electron density. This is called resonance effect.
Hyper conjugation effect : It is an extension of resonance effect. It involves the delocalization of σ electrons through
overlapping of ‘p’ orbitals of a double bond with σ orbital of the adjacent single bond.
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I II III
I, II and III are called hyperion –H+ conjugative structures. It is also called non bond resonance, since there is no bond
between ‘C’ and hydrogen atoms.
Properties of hydrocarbons – Page 371 of text book.
Boiling points: Boiling point of straight chain alkanes increases regularly with the increase of number of ‘C’
atoms. But boiling point decreases with branching in the case of isomeric forms E.g.: in pentane boiling
point decreases in the order n – pentane > Isopentance > neopentance
Which of the following has highest boiling point? i). 2 – methyl pentane ii). 2 – 3 dimethyl butane
iii) 2, 2 – dimethyl butane.
When branching increases, surface area decreases, so magnitude of Vander Wall’s force decreases and
boiling point decreases. 2, 2, dimethyl butane has lower surface area and hence lower boiling point. And 2
methyl pentane has highest boiling point.
Chemical properties
Halogenation Reaction: Replacement of one or more hydrogen of alkanes by halogens is called
halogenations. It is carried in presence of ultraviolet light. F2 is more reactive.
Chlorination: CH4 + Cl2 CH3Cl + HCl
CH3Cl + Cl2 CH2Cl2 + HCl
CH2Cl2 + Cl2 CHCl3 + HCl
CHCl3 + Cl2 CCl4 + HCl

The reactions discussed above may come to a halt if two of the same or different free radicals combine
amongst themselves.
Cl· + Cl· Cl – Cl
CH3• + Cl• CH3 – Cl
Combustion: On heating alkanes readily burns in air giving CO2 and H2O
CH4(g) + 2O2(g) Co2(g) + 2H2O(l) ∆Hc - 890 K/mol
Due to evolution of large amount of heat alkanes are used as fuels.
Controlled oxidation : Heating with regulated supply of O2, at high pressure and in presence of suitable catalyst,
variety of products are formed.
Cu/523K
2CH4 + O2 2CH3OH (methanol)
MnO2
CH4 + O2 HCHO + H2O
(methanol)
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Isomerisation : n – alkanes on heating in presence of anhydrous AlCl3 and HCl gas, isomerises to branched chain
alkanes.
CH3(CH2)4CH3 An. AlCl3/HCl H3C – CH – (CH2)2 – CH3
n – hexane CH3 (2 Methyl pentane)
Aromatization (Reforming): n – alkanes having 6 or more ‘C’ atoms on heating to 773K at 10 – 20 at. pressure, in
presence of oxides of vanadium, gets dehydrogenated and cyclised to benzene.

V2O5 Dehydrogenation
773K
(Cyclization) -H2 Cyclohexane Benzene

Reaction with steam : Methane reacts with steam at 1273K in presence of Ni to form CO and H2. This method is
used to prepare dihydrogen industrially.
CH4 + H2O Ni CO + 3H2
Pyrolysis : Decomposition of a compound by the application of heat is called pyrolysis.
Cracking : Pyrolysis of higher alkanes to a mixture of lower alkanes is called cracking. This is done by heating to a
higher temperature(773 – 973K) and 6 – 7 atmosphere pressure, in the absence of a catalyst.
Stereoisomerism: Isomers having same structural formula but have different relative arrangement of atoms or
groups in space is called stereoisomers. Stereoisomerisms is of the following types
a) Conformational isomerism
b) Optical isomerism
c) Geometrical isomerism
Confirmations of alkanes : The single bond in alkanes allows freedom of rotation about it and the rotation of C – C
bond give different spatial arrangements of atoms or groups. The spatial arrangement of atoms which arise due to
the free rotation of around a C – C single bond are called conformers of rotamers. The molecular geometry
corresponding to a conformer is known as conformation. Out of infinite number of possible conformations of ethane,
two confirmations represent the extremes. They are a) staggered confirmation and b) eclipsed confirmation.
Staggered : The hydrogen atoms of the two ‘C’ atoms are oriented in such a way so that they lie far apart from one
another.
Eclipsed : The hydrogen atoms of one ‘C’ are lying directly behind the ‘H’ atoms of the other. Confirmations can be
represented by Sawhorse projection formulae or Newman projection formulae. In Sawhorse projection, the molecule
is viewed by the molecular axis. The central C – C bond represented by a straight line.

In Newman projection the molecule is visualised from front

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Staggered conformation is relatively more stable than other confirmations, because energy content of the
molecule changes as it gets converted from one arrangement to the other. Staggered conformation is
associated with minimum energy, because repulsive interactions between the electron clouds of C – H
bonds are minimum.
Eclipsed confirmation is associated with maximum energy because the repulsive interactions between
electron clouds of C – H bonds are maximum.
The repulsive interactions between electron clouds of σ bonds of the two adjacent carbon atoms which
affect the stability of the confirmation is called torsional strain.
The magnitude of torsional strain depend upon the angle of rotation about C – C bond. This angle is called
Torsional angle.
ALKENES
ISOMERISM IN ALKENES-GEOMETRICAL ISOMERISM
The stereo isomerism exhibited by alkenes due to the difference in the spatial arrangements of groups
about the double bonded carbon atom is called geometrical isomerism. In alkene it is cis-trans isomerism.

Such isomers are called geometrical isomers. Such isomers with similar groups on same side are called cis
and isomers which have similar group on opposite sides are called Trans isomers.

Why alkenes are easily attacked by electrophiles?

C = C bond in alkanes contains one σ bond and one π bond. We know that pi bond is weaker bond due to poor side
ways overlapping of two ‘2p’ orbitals. So the presence of pi bond makes the alkenes behave as a source of loosely
hold mobile electrons. So alkenes are easily attacked by reagents which are in search of electrons.
Preparation of alkenes: On reduction with calculated amount of dihydrogen in presence of palladised charcoal
deactivated partially with poisonous sulphur compounds (Lindlar’s reagent) alkynes give alkenes.
R R’
Pd/C
RC CR’ + H2 C=C
H H cis alkene.
R H
But on reduction with Na and liquid NH3 give Trans isomer. C= C
H R’
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Dehydrohalogenation : Alkyl halide on heating with alcoholic potash, eliminate one molecule of halogen acid to form
alkenes ( β elimination)
H H H H
Al. KOH
H–C–C–H C = C + HX
H X H H
Dehalogenation : (From Vicinal dihalides). Dihalides in which two halogen atoms are attached to two adjacent carbon
atoms are known as vicinal dihalides. Vicinal dihalides on treatment with zinc lose a molecule of ZnX2 to form alkenes.
This reaction is known as dehalogenation.
CH2Br – CH2Br + Zn CH2 = CH2 + ZnBr2
How can you prepare alkenes from alcohols?
When alcohols are treated with concentrated H2SO4(heated) elimination of one molecule of H2O takes place and
alkene is formed.
H H
Con.H2SO4
H – C β – Cα – H CH2 = CH2 + H2O
H OH
Reactions of alkenes
How can you prepare alcohol from alkenes?
In presence of few drops of con. H2SO4, alkenes react with water to give alcohols.
CH3
Al. KOH
H3C – C = CH2 + H2O H3C – C – CH3 (Markonicov addition)
CH3 OH
Give a test for instauration (= or )
Alkenes on treating with aqueous solution of KMNO4 (Baeyer’s reagent), glycols are formed. Pink colour of KNO4 is
decolorized.
Dil. KNO4
H2C = CH2 + H2O + O CH2 – CH2
OH OH (Ethane 1, 2 diol) Glycol
What happens when acidic KNO4 or acidic K2Cr2O7 is treated with alkenes?
(H3C)2C = CH2 KMNo4/H+ (H3C)2C = O + CO2 + H2O
2 Methyl propene Propan 2 – one
Acidic KNO4 or acidic K2Cr2O7 oxidises alkenes to ketones
What is ozonolysis?
This is the addition of ozone molecule to alkenes to form ozonide. This ozonide on cleavage give smaller molecules.
This reaction is useful in detecting the position of double bonds in alkenes.
O
CH3CH = CH2 + O3 CH3 – CH CH2 Zn + H2O CH3CHO + HCHO
Propene O – O Ethanal Methanal
Propene ozonide
Write a short note on polymerisation
Large molecules obtained by the combination of small units (monomers) at high temperature is called
polymerisation.
Eg: n(CH2 = CH2) ( CH2 – CH2 )n
Polymers are used for the manufacture of plastics, dishes, toys, pipes etc.
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Markonicov Rule
Addition reaction of alkenes : Alkenes react with halogen acids to form alkyl halides.
CH2 = CH2 + HCl CH3CH2Cl (Chloro ethane)
If both alkenes and reagent are unsymmetrical then two products are theoretically possible
CH3CH = CH2 + HBr CH3 – CHBr- ClH3 + CH3 – CH2 – CH2Br
Such addition reactions are governed by the empirical rule which was given by Russian chemist Markonicov(1869).
The rule is known as Markonicov ‘s rule.
The rule states that during the addition across the unsymmetrical double bond, the negative part of the attaching
molecule attaches itself to the carbon atom carrying less number of hydrogen atoms.
X
CH3 – CH = CH2+ Hδ+ - Xδ- H3C - CH – CH3

Anti markonikov addition (Peroxide effect or Kharasch effect) : In presence of organic peroxide such as benzoyil
peroxide (C6H5CO – O – O – COC6H5), HBr reacts with alkenes to give the product against Markonicov ‘s rule.
CH3CH = CH2 + HBr CH3CH2CH2 – Br
Propene 1 bromo propane
Markonicov ‘s addition does not occur in case of H – Cl or H – I even in presence of peroxides.
Structure of ethyne : Both ‘C’ atoms are sp hybridised. ‘sp’ hybrid
orbital of one carbon atom overlaps axially with the similar orbital
of the other carbon atom to form C – C sigma bond. The remaining
sp hybrid orbital of each carbon atom overlaps axially with 1s
orbital of each of the two ‘H’ atoms to form two C – H sigma
bonds. H – C – C bond angle is 1800. Each ‘C’ atom also has two
unhybridised p orbitals which are perpendicular to each other and
also to the internuclear axis. These ‘p’ orbitals undergo sideways
overlap to form two pi bonds.

Acidity of alkynes: Strong bases, (Na metal or Soda amide) react with alkynes to form sodium acetylide with the
liberation of hydrogen gas. These reactions are shown only by alkynes. This is because carbon atoms in alkynes are
‘sp’ hybridised. So 50% ‘s’ character is there . So the sp hybridised orbitals have great electro negativity. They attack
the shared pair of electrons in the C – H bond to a greater extent and hydrogen atoms are liberated more easily. So
they are more acidic than alkanes and alkenes.

Reactions
Write a short note on addition reaction of alkynes
Addition of ‘H2’ gas takes place according to Markonikov’s rule in case of unsymmetrical alkynes.

How can we use Bromine water to test the presence of triple bond in alkynes?
When bromine water is added to alkynes – decolourises.

Br2 1,1,2,2 Tetra Bromo propane

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What are gem – di halides? How they are formed?

Gem dihalides are compound in which two halogen
atoms are added to the same ‘C’ atom.
Addition of water to alkynes : One molecule of H2O is added to alkyens, on warming with mercuric sulphate and
dilute H2SO4 to form carbonyl compounds( aldehydes or ketons)
isomerisation
Ethanal
Cyclic polymerisation : Ethyne on passing through red
hot iron tube at 873K undergoes cyclic polymerization.
Three molecules polymerises to form benzene.

Aromatic compounds : Aromatic compounds are also called arenes. They have odour. Most of them contain benzene
ring.
Structure of Benzene : Benzene was isolated by Michael Faraday in 1825. Benzene is a stable molecule and it is
found to form a triozonode, which shows the presence of 3 triple bonds. In 1865, Kekule proposed an arrangement of
six carbon atoms with alternate single and double bonds.
Write a short note on Kekule’s structure of Benzene.
He proposed that all carbon atoms in benzene are joined to each other by alternate single and double bonds to form
a hexagonal ring. Each ‘C’ atom is connected to hydrogen atom.
Drawbacks
 Unable to explain stability
 Unable to explain why it undergoes addition
reactions only under certain conditions.

Write a note on structure of benzene based on M O theory

All bond angles in benzene are 1200. All carbon atoms are
sp2 – hybridized. Each ‘C’ atom form two σ bond(C – C) with
neighbouring ‘C’ atoms and one C – H σ bond with hydrogen
atom. All σ bonds lie in one plane.

Each ‘C’ atom is now left with an unhybridized ‘p’ orbital. All six
unhybridised ‘p’ orbitals are parallel to one another and
perpendicular to the plane of σ bonds. The ‘p’
orbitals(unhybridised) are close to each other so that they overlap
sideways to form π bond.

The two possible sideways overlap of six unhybridized p – orbitals

to form three π bonds are shown here.
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Electron clouds lying above and below the plane

of the benzene ring.

Resonance : The phenomenon of resonance structures is

said to occur, if for a molecule, we can write two or more
than two Lewis structures which differ in the position of
electrons and not in the relative position of atoms. The various structures are called canonical or resonance
structures. Real structure is a Resonance hybrid of canonical structures. C – C bond length is 1.39A0(Which lie in
between C = C bond length of 1.34A0 and C – C bond length of 1.54A0). Resonance hybrid is stronger than canonical
structures. The difference in internal energy of the resonance hybrid and that of the most stable canonical form is
called resonance energy.
Preparation of Benzene
From ethyne( Refer notes –ethyne)
Decarboxylation of acids (aromatic) : When sodium salt
of benzoic acid is heated with soda lime it gives benzene.

From phenol : When phenol in its vapour form is passed

into heated zinc dust benzene is produced.

Properties :
 Have aroma
 immiscible with water
 miscible with organic solvents
 Normally shows electrophilic substitution reactions. Also shows addition and oxidation reactions
Electrophilic substitution reactions : The common electrophilic substitution reactions are
a) Nitration c) Sulphonation
b) Halogenation d) Friedel – Craft’s alkylation
e) Friedel – Craft’s acylation rection

Nitration : Nitration means ‘nitro’ group is introduced into the benzene ring.
Benzene is heated with a mixture of Con. H2SO4 and HNO3 (Nitrating mixture)
323 – 333K

Haloganation : Haloganation means introduction of a halogen atom on benzene ring by FeCl3, FeBr3 or AlCl3
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Sulphonation : Sulphonation means introduction of ‘SO3H’ group in benzene ring. It is done by heating benzene with
fuming H2SO4.

Friedel Craft’s Reactions : (Important) This reaction involves the substitution of alkyl (R -) group or acyl (RCO - )
group on benzene ring. This is of two types. a) Friedel Craft’s alkylation and b) Friedel Craft’s acylation
Friedel Craft’s Alkylation (R – ) Friedel Craft’s Acylation (RO – )
When benzene is treated with alkyl halide in presence of Benzene is treated with acyl halide or acid unhydride in
anhydroul AlCl3, alkyl benzene is formed. presence of anhydrous AlCl3

Mechanism of electrophilic substitution reactions: According to experimental evidences, SE (S =substitution;

E = electrophilic) reactions are supposed to proceed via the following three steps:
(a) Generation of the eletrophile
(b) Formation of carbocation intermediate
(c) Removal of proton from the carbocation intermediate
(a) Generation of electrophile E⊕: During chlorination, alkylation
and acylation of benzene, anhydrous AlCl3, being a Lewis acid helps
in generation of the elctrophile

respectively by combining with the attacking reagent.

In the case of nitration, the electrophile, nitronium ion, NO2+ is

produced by transfer of a proton (from sulphuric acid) to nitric acid
in the following manner. It happens in two steps

It is interesting to note that in the process of generation of nitronium ion, sulphuric acid serves as an acid and nitric
acid as a base. Thus, it is a simple acid-base equilibrium.
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(b) Formation of Carbocation(arenium ion): Attack of

electrophile results in the formation of σ-complex or
arenium ion in which one of the carbon is sp3 hybridised.

The arenium ion gets stabilised by resonance.

Sigma complex or arenium ion loses its aromatic character because delocalisation of electrons stops at sp3 hybridised
carbon.
(c) Removal of proton: To restore the aromatic
character, σ -complex releases proton from sp3
hybridised carbon on attack by [AlCl4]– (in case of
halogenation, alkylation and acylation) and [HSO4]– (in
case of nitration).

Addition reactions : Under vigorous conditions, i.e., at

high temperature and/ or pressure in the presence of
nickel catalyst, hydrogenation of benzene gives
cyclohexane.
Under ultra-violet light, three chlorine molecules add to
benzene to produce benzene hexachloride, C6H6Cl6 which
is also called gammaxane.

Combustion: When heated in air, benzene burns with sooty flame producinjg CO2 and H2O

General combustion reaction for any hydrocarbon may

be given by the chemical equation
Directive influence of groups in Arenes : In benzene all hydrogen atoms are equivalent. So during the formation of
mono substituted products any of the six position can be occupied. But during the formation of disubstituted
product, the substituent already present in the ring directs the incoming group to a particular position. This is called
directive influence of the group.
 -CH3, -C2H5, -Cl, -OH, -Br, -NH2, -NHR, -NR2, -NHCOCH3, -OCH3, etc  Ortho para directing.
 -NO2, -CN, -CHO, -COR, -COOH, -COOR, -SO3H etc are meta directing.

Methods of purification of organic compounds

Common techniques of purification of organic compounds are
Sublimation: On heating some solid substances change from solid to vapour state without passing through liquid
state. The purification technique based on this principle is known as sublimation.
Crystallisation : Most commonly used technique for the purification of solid organic compounds. This is based on the
difference in the solubility of the compound and the impurities in a suitable solvent. The impure substance is
dissolved in a solvent in which it is sparingly soluble at room temperature but appreciably soluble at high
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temperature. The solution is concentrated to get a nearly saturated solution. On cooling the pure substance
crystallise and is removed by filtration.
Distillation : This method is used to separate (i) volatile
liquids from non volatile impurities and (ii) liquids having
sufficient difference in their boiling point. Liquids having
different boiling points vaporise at different
temperatures. The vapours are cooled and the liquids so
formed are collected separately. Chloroform and aniline
are easily separated by this technique of distillation.
Liquid mixture is taken in a round bottom flask and
heated carefully. On boiling the vapours of lower boiling
point components are formed first. The vapours are
condensed by using a condenser and the liquid is
collected in a receiver. The vapours of higher boiling
point component form later and the liquid can be
collected separately.

Fractional Distillation : If the difference in boiling

points of two liquids is not much, simple
distillation cannot be used to separate them. The
vapours of such liquids are formed within the
same temperature range and are condensed
simultaneously. The technique of fractional
distillation is used in such case. In this technique,
vapours of a liquid mixture are passed through a
fractionating column before condensation. The
fractionating column is fitted over the mouth of
the round bottom flask. Vapours of liquid with
highest boiling point condense before the
vapours of the liquid with lower boiling point.
The vapours rising up in the fractionising column
become richer in more volatile components, by
the time the vapours reach to the top of the
fractioning column these are rich in more volatile
component. Fractionating column provides many
surfaces for heat exchange between ascending
vapours of condensing liquid. Some liquids re-
vaporises. The vapours become rich in low
boiling point components.
Steam distillation: This method is employed for the purification of a substance from non-volatile impurities provided
the substance itself is volatile from steam and insoluble in water. This method is based on the fact that
1. A liquid boils at temperature when its vapour pressure becomes equal to the atmospheric pressure.
2. The vapour pressure of a mixture of the immiscible liquid is equal to the sum of the vapour pressure of the
individual liquids.
Chromatography : This is the modern technique of separation and purification of organic compounds, developed by
Tswett in 1903. Nowadays various chromatographic methods are used to separate any mixture into its constituents
irrespective of whether it is coloured or colourless. Chromatography may be defined as the technique to separate
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constituents of a mixture by differential movement of individual components through the stationary phase under the
influence of mobile phase. Two important chromatographic techniques are
1. Adsorption chromatography
2. Partition chromatography
Adsorption chromatography : Based on the differential adsorption of various components of the mixture on a
suitable adsorbent. Some components are more strongly adsorbed than others. 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. The technique based on the principal of differential adsorption are
i) column chromatography 2) Thin layer chromatography
Column chromatography : This involves the separation of a mixture over a column of adsorbent(stationary phase)
packed in a glass tube. The column is fitted with a stop cock at its lower end. The mixture adsorbed on adsorbent is
placed on the top of the adsorbent column packed in a glass tube. An appropriate eluant(solvent) which is a liquid or
a mixture of liquids is allowed to flow down the column slowly. The most readily adsorbed substances are retained at
the top and others come down to various distances in the column.
Thin layer chromatography (TLC) : Separation of mixtures over a thin layer of an adsorbent. A TLC plate is prepared
first. Two pencil lines are drawn across the width of the plate about 1cm each from top and bottom end. Lower mark
is the starting line and the upper line is the finishing line. A thin layer of an adsorbent(silica gel) is spread over a glass
plate of suitable size. The plate is called TLC plate. The solution of the mixture to be separated is applied as a small
spot about 2cm from one end of the TLC plate. The glass plate is then placed in a closed jar containing the solvent. As
the solvent in the jar moves up, the components of the mixture move up along the plate to different distances
depending on degree of adsorption and separation takes place. The relative adsorption of each component of the
mixture is expressed in terms of its retention factor –Rf

Rf = Distance moved by the substance from its base line

Distance moved by the solvent from the base line
Spots of coloured components are visible on TLC plate due to its original colour. The spots of colourless components
are visible by putting the plate under ultra violet light. Iodine is also used. Spots of the components which adsorb
iodine will become brown. Sometimes chemicals are used.
Partition Chromatography : Based on continuous differential partitioning of components of a mixture between
stationary and mobile phase. In paper chromatography – a special type of paper is used. In this paper water is
trapped in it, which acts as the stationary phase. A strip of chromatography paper spotted at the base with the
solution of the mixtures is suspended in a suitable solvent or a mixture of solvents. This solvent acts as the mobile
phase. The solvent rise up the paper by capillary action and flows over the spot. The paper selectively retains
different components according to their differing partition in two phases. The paper strip developed is known as
chromatogram.