2 II Pu Chem Vol-2 2019 Briks (3)

CHAPTER: 10
HALOALKANES AND HALOARENES

Introduction:
Haloalkanes and haloarenes are obtained by replacing one or more number of hydrogen
atom(s) in a aliphatic / aromatic hydrocarbon by halogen atom(s). [X = F, Cl, Br, I (Group-
17 elements)].
Importance:
1. Many halogen containing organic compounds occur in nature, some of them are clinically
useful.
 Chlorine containing antibiotic, chloramphenicol, produced by soil microorganisms is
very effective for the treatment of typhoid fever.
 Our body produces iodine containing hormone thyroxine, the deficiency of which
causes a disease called goiter.
 Synthetic halogen compounds, viz. chloroquine is used for the treatment of malaria;
halothane is used as an anaesthetic during surgery.
 Certain fully fluorinated compounds are being considered as potential blood
substitutes in surgery.
2. These classes of compounds find wide applications in industry as well as in day-to-day life.
3. They are used as solvents for relatively non-polar compounds and as starting materials
for the synthesis of wide range of organic compounds.
In this Unit, you will study the important methods of preparation, physical and
chemical properties and uses of organohalogen compounds.
Classification:
I) On the Basis of Number of Halogen Atoms:

They are classified as mono, di, or polyhalogen (tri, tetra, etc.) compounds depending on
whether they contain one, two or more halogen atoms in their structures.
Example:
CH2 X
CH2 X CH X
CH3 X CH2 X CH2 X
Mono haloalkane di haloalkane poly haloalkane
(Tri haloalkane)
X X X
X X
X
Mono haloarene di haloarene poly haloarene
(Tri haloarene)
Note: Dihaloalkanes are of two types namely:
BRIKS ACADEMY 1 Prepared by Maruthi.R

a) Geminal dihaloalkane: If two halogen atoms are bonded to the same C- atom then they
are said to be geminal dihalides.(Gemini = twins)
CH CH3
X
Geminal di haloalkane
b) Vicinal dihaloalkane: If two halogen atoms are bonded to the neighbouring C- atoms
then they are said to be vicinal dihalides. (Vicinal = neighbours)
CH2 CH2
X X
Vicinal di haloalkane
II) Classification of monohalo compounds on the Basis of hybridisation of the

carbon atom to which the halogen atom is bonded:
Monohalo compounds may further be classified according to the hybridisation of the carbon
atom to which the halogen is bonded.
i. Compounds containing sp3 C—X Bond (X= F, Cl, Br, I);
a) Monohaloalkanes OR Alkyl halides:

Mono halogen derivatives of alkanes are called haloalkanes. They form a homologous
series represented by CnH2n+1X (G.F).
They are generally represented as R-X or R-CH2-X or R-CH2-CH2-X.
They are further classified as primary, secondary and tertiary alkylhalides based
on the nature of carbon atom to which halogen is bonded.
Example:
H R'' R''
b) Allylic halides: These are R' C X R' C X R' C X
the compounds in which the H H R'''
halogen atom is bonded to primary secondary tertiary
0 0 0
an sp3-hybridised carbon ( (2 ) (3 )
1
)
atom next to carbon-carbon double bond (C=C) i.e. to an allylic carbon.
Example: X
Benzylic halides: CH2 X

These are the compounds in which the
halogen atom is bonded to an sp -hybridised carbon atom next to an aromatic ring i.e to a
3
benzylic carbon

Example:
X
R'
CH2X
R''
0
R' = CH3, R'' = H (2 )
0
R' = R'' = CH3 (3 )
ii. Compounds containing sp2 C—X Bond (X= F, Cl, Br, I):
a) Vinylic halides: These are the compounds in which the halogen atom is bonded to an
sp2-hybridised carbon atom of a carbon-carbon double bond (C=C).
Example:
X
b) Aryl halides: These are the compounds in which the halogen atom is bonded to an sp2-
hybridised carbon atom of an aromatic ring.
X X
Example:
CH3
Nomenclature:
1. Monohaloalkanes:
Trivial system: They are named as alkylhalides.
IUPAC system: They are named as haloalkanes.
Example:
CH3 CH CH3 CH3
CH3CH2CH2Br CH3 CH CH2 Cl
Cl
1-Bromopropane 2-Chloropropane 1- chloro-2-methylpropane
(n-Propyl bromide) (Isopropyl chloride) (Isobutyl chloride)
2. Dihaloalkanes:
Trivial system:
i) Geminal dihalides are named as alkylidene dihalides or alkylidene halides
Example:
X CH3
I
C X CH3CHCl CH3CH2CH2Cl2 CH3 C Cl
2
I
Cl
gem dihalides 1,1-dichloroethane 1,1-dichloropropane 2,2-dichloropropane
(Ethylidene dichloride) (propylidene (Iso-propylidene dichloride)
dichloride)
ii) Vicinal dihalides are named as alkylene dihalides or alkylene halides.

Example:
X X CH3
Cl Cl Cl Cl
C C CH3 C CH2
CH2 CH3
CH2
CH
CH2
Br Br
vicinal dihalides 1,2-dichloroethane 1,2-dichloropropane 1,2-dibromo-2-methylpropane
(Ethylene dichloride) (propylene dichloride) (Isobutylene dibromide)
iii) Polymethylene dihalides (terminal dihalides) are the dihalo compounds

containing halogen atoms at the terminal ends of the chain and are named as
polymethylene dihalides.
IUPAC system: They are named as dihaloalkanes (with appropriate locants according
to lowest sum rule).
Example: BrCH2CH2CH2Br ClCH2CH2CH2CH2Cl
1,3-dibromopropane
1,4-dichlorobutane
(Trimethylene dibromide) (Tetramethylene dichloride)
3. Polyhaloalkanes:
Trivial system: They are named as haloforms
IUPAC system: They are named as polyhaloalkanes
Example:
CHCl 3 CHI 3 CCl4
(chloroform) (Iodoform) (carbon tetrachloride)
Trichloromethane Triiodomethane Tetrachloromethane
Note: Fully halogenated compounds are called perhalohydrocarbons, which

are obtained by replacing all the H- atoms of a hydrocarbon by halogen atoms.
Example:
CF3 CF2 CF3
octafluoropropane
(perfluoropropane)
4. Haloarenes: Haloarenes or aryl halides are named by adding the prefix halo (fluro,
Chloro, bromo, iodo) before the name of the aromatic hydrocarbon.
In case of disubstituted compounds, the relative positions of the substituents 1, 2; 1,3
and 1,4 are indicated by the prefixes ortho(o-), meta(m-), para(p-) respectively.
Monohaloarenes: They are named as halobenzene.
Example:
Cl Br

chlorobenzene
Iodobenzene

CH3 CH3 CH3
Cl
Cl
Cl
1-methylchlorobenzene 3- methyl chlorobenzene 4- methyl chlorobenzene
(o-chlorotoluene) (m-chlorotoulene) (p-chlorotoluene)
Dihaloarenes: They are named as dihalobenzene. .
Example: Cl Cl
Cl
Cl
1,2-dichlorobenzene1,4-dichlorobenzene
(o-Dichlorobenzene)(p-Dichlorobenzene)
Trihaloarenes: They are named as Trihalobenzene.
Example: Br
Br Br
1,3,5-tribromobenzene (sym-Tribromobenzene)
Isomerism in haloalkanes and haloarenes:
Haloalkanes show two types of isomerism.

Structural Isomerism: Two or more compounds have same molecular formula but different structural form
Chain Isomerism: The haloalkanes containing four or more carbon atoms exhibit chain isomerism in which
Example:
CH3 CH3
CH CH2 Br Br
CH3CH2CH2CH2Br CH3 CH3 C
CH3
1- Bromobutane 1-Bromo-2-methylpropane 2-Bromo-2-methylpropane
b) Position Isomerism: The haloalkanes containing three or more carbon atoms exhibit position isomerism
Example:
CH3CH2CH2I CH3 CH CH3

I
1-Iodopropane2-Iodopropane

2) Stereo Isomerism:
Two or more compounds have same molecular formula and structural formula but
differ in the spatial arrangement of atoms or group of atoms and exhibit different
physical and chemical properties are called stereo isomers and the phenomenon is
called stereo isomerism.
There are two types of stereo isomerism namely:
a) Geometrical isomerism b)Optical isomerism
Optical isomerism:
Compounds having same molecular formula and structural formula but differ in the
direction of rotation of plane polarized light are called optical isomers and the
phenomenon is called as optical isomerism.
Conditions for a molecule to exhibit optical isomerism:

1. The molecule should contain atleast one chiral C-atom.
2. The molecule should not contain any plane of symmetry.
Plane polarized light:

The light which vibrates in only one plane is called a plane polarized light.
Ordinary light consists of waves vibrating in different plane. When this light is passed through
nicol prism made of CaCO3, plane polarized light is obtained.
----
----
----
----
----
----
---- OR
----
Source Nicol prism Plane polarised light
Sample Dextro rotatory laevo rotatory Polarimeter
OR OR
Clockwise anticlockwise
d/+ l/-
Dextro isomer: If the compound rotates plane polarized light in clockwise direction then it is
called dextro isomer.
It is represented by writing + or d before the name of compound.
Example:
CH
I 3
H *C Br
I
C2 H5
(+)-2-Bromo-butane
Laevo isomer: If compound rotate plane polarized light in anticlockwise direction is called
laevo rotatory.
It is represented by writing – or l before the name of compound.

Example:
CH3
*I
Br CI
C2 H5
(-)-2-Bromo-butane
Chiral C-atom / asymmetric C-atom / Chirality Centre:

The carbon atom bonded to four different atoms or group of atoms in a molecule is called as
a chiral C-atom / asymmetric C-atom / chirality centre.
Example:
CHI3 Chirality center
*
Br OR
C asymmetric center
H
I
C2H5
(-)-2-Bromo-butane
If the molecule contains only one chirality centre, then it is optically active.
If the molecule contains 2 or more chirality centers, then it is need not be optically active.
Optically activity depends only on the absence of plane of symmetry when a molecule
contains 2 or more chirality centers.
Plane of symmetry or mirror plane or sigma plane:

It is an imaginary line which divides the molecules into two identical halves which are
mirror images of each other.
Example:
CH3
*I Plane of symmetry
H C Br
I
H C
* Br
I
CH3
Meso-2,3-dibromobutane
One half of the molecule rotate plane polarized light in clockwise direction and another half
rotate plane polarized light in anti clockwise direction. Both the halves rotates plane polarized
light to the same extent but in opposite direction hence the net rotation becomes zero. This
type of compensation of specific rotation is called internal compensation.
The compounds containing plane of symmetry are optically inactive.
Optical activity:
The property of some organic compounds to rotate plane polarized light in clockwise
or anticlockwise direction in their solution state is called optical activity.

The substances which rotate plane polarized light in clockwise or in anticlockwise direction in
solution state are called optically active substances.
The optical activity of a substance is determined by using an instrument called polarimeter.

The optical activity is expressed in terms of specific rotation.
Specific rotation:
The rotation produced by a solution of length 1 dm (decimeter) having unit
concentration for a plane polarized light of given wavelength at a given temperature is
called specific rotation.
It is given by

  lxc
t
Where, α = angle of rotation
t = given temperature, λ = wave length of light
l = length of polarimeter tube, c = concentration of solution of substance in g/cm2.
Chiral molecules:
Molecules which are non-super imposable mirror images of each other are called as
chiral molecules.
 All chiral molecules are optically active because they do not contain any plane of symmetry.
 The molecules having super imposable mirror images are called achiral molecules.
 All achiral molecules are optically inactive.
Racemic mixture:
Equimolar mixture of d and l isomers is called as a racemic mixture.
It is optically inactive because the rotations produced by d and l isomers are equal
and opposite. Hence the net rotation becomes zero. This type of compensation of rotation of
plane polarized light is called external compensation.
Ex: (±) 2 – Bromobutane.
Enantiomers: The optically active isomers which are non-super imposable mirror
images of each other are called enantiomers.
CH3 CH3
I
Example: H *I
C Br Br * H
I C
I
C 2H 5 C 2H 5
(+)-2-Bromo-butane Mirror (-)-2-Bromo-butane
Note:
Vant Hoff’s rule: The total no. of possible optical isomers for a molecule containing ‘n’ no. of
chirality centre is given by 2n.

Diasteromers:
Stero isomers which are non-superimposable non mirror images of each other are called as diaste
Meso compounds:
Organic compounds having more than one chiral C-atom but are optically in active due to presenc
CH3
*I
H C Br
* I Br
HC
I
CH3
Meso-1,2-dibromobutane
Methods of Preparation:
Preparation of Haloalkanes: (alkyl halides)
1) From Alcohols: Alkyl halides are best prepared from alcohols, which are easily
accessible. The hydroxyl group of an alcohol (-OH) is replaced by halogen (-X) on
reaction with concentrated halogen acids/phosphorus halides/thionyl chloride.
a) Using Hydrogen halides (HX) (Halogen acids):

Alcohols upon treatment with halogen acids respective alkyl halides are obtained
i) On passing through hydrogen chloride gas through 10 and 20 alcohols in presence of
anhydrous ZnCl2 respective chloroalkanes (alkyl chlorides) are obtained.
anhy. ZnCl2
General reaction: R-OH + (g) R-Cl + H2O (Grooves process)
HCl
Chloroalkane
Example: CH -CH -OH + HCl anhy. ZnCl2 CH3-CH2-Cl + H O (Grooves process)

3 2 (g) 2
Chloroethane
(Ethyl chloride)
Note:
1) Order of reactivity of alcohols is 30 >20 >10
2) 30 alcohols react with HCl (g) at room temperature itself and in absence of anhydrous
ZnCl2.
2) Mixture of HCl + anhy.ZnCl2 is called Lucas reagent.
ii) When alcohols are refluxed with Hydrobromic acid in presence of conc.H2SO4
respective bromoalkanes (alkyl bromides) are obtained.
conc. H2SO4
General reaction: R-OH + H-Br R-Br + H2O
Heat
Bromoalkane
Example: CH -CH -OH +H-Br conc. H2SO4 CH3-CH2-Br + H2 O

3 2 Heat
Bromoethane
(Ethyl bromide)

HBr can also be generated in situ (during the reaction) by the action of bromide salts like
KBr or NaBr with conc.H2SO4.
General reaction: R-OH + NaBr + Heat

H2SO4 R-Br + NaHSO 4 H2 O
+
Bromoalkane
Example: Hea
R-OH+ KBr + H2SO4 t R-Br + KHSO + H2 O
4
Bromoalkane
iii) When alcohols are heated with Hydroiodic acid (57%) respective iodoalkanes (alkyl
iodides) are obtained.
General reaction: Reflux
R-OH + H-I R-I + H2 O
Iodoalkane
Reflux
Example: CH -CH -OH + H-I CH3-CH2-I + H2O
3 2
Iodoethane
(Ethyl iodide)
HI is also generated in situ (during the reaction) by the action of 95% phosphoric acid on
KI.
Heat
General reaction: R-OH + KI + H3PO4 R-I + KH2PO4 + H2O
Phosphoric acid Iodoalkane Potassium dihydrogen
Phosphate
Example:
Heat
CH3-CH2-OH + KI H3PO4 CH3-CH2-I + KH2PO4 + H2O
+
Ethanol Phosphoric acid Iodoethane Potassium dihydrogen
(ethyl alcohol) Ethyl iodide Phosphate
b) Using Phosphorous halides (PX3/PX5): Haloalkanes are prepared by the action of

phosphorous halides on alcohols.
General reaction: R-OH + PCl5 R-Cl + POCl3 + HCl
Alcohol Phosphorous Chloroalkane
penta chloride (Alkyl chloride)
3 R-OH +
3 R-X + (X=Cl,Br,I)
PX3
H3PO3
Alcohol Phosphorous
trihalide
3 R-OH Red P/ X 2 3 R-X

X = Br2, I2
Alcohol
Note: Since PBr3 and PI3 are not very stable compounds these are prepared insitu (with
in the reaction) by the action of red phosphorous on Br2 and I2 respectively.
c) Using Thionyl chloride (SOCl2) (Darzens process): Chloroalkanes are best prepared
from alcohols by refluxing alcohols with thionyl chloride in presence of pyridine.
General reaction: Reflux
R-OH + SOCl2 + HCl
R-Cl + SO2
C5 H5 N
Reflux
Example: CH3-CH2-OH + SOCl2 CH3-CH2-Cl+ + HCl
C 5H 5N
SO2
Chloroethane
(Ethyl chloride)

Note:
1. This method is the best method to prepare pure alkyl chlorides because the other two by
products obtained are escapable gases.
2. In this process pyridine is used to neutralise the HCl formed during the course of the
reaction and make the reaction to proceed in the forward direction.
2) From Alkenes:
a) Using hydrogen halides:
Alkenes upon treatment with hydrogen halides (HX) X= F, Cl, Br, I, hydrohalogenation
takes place according to Markownikoff’s rule leading to the formation of alkyl halides.
General reaction: R-CH-CH2

R-CH=CH2 + HX
alkene X H
Halo alkane
(Alkyl halide)
Example: CH3-CH-
CH3-CH=CH2 + HCl + CH3-CH2-CH2-Cl
Propene
CH 3
Cl
2-Chloropropane 1-Chloropropane
(Iso-propyl chloride) (Propyl chloride)
Major Minor
b) Using halogens:
Alkenes upon treatment with halogens such as Br2 in presence of CCl4 at room
temperature addition reaction takes place to form vicinal dibromo alkane and the
orange red colour of bromine is discharged. Hence this reaction is used as a test for
unsaturated compounds.
CCl4
General reaction: R-CH=CH2 + Br2 R-C H-CH2
Room temperature
alkene Br Br
Vicinal dibromoalkane
Example
: CH -CH=CH +
Br
CCl4 CH -CH-CH
3 2 Room temperature 3 2
2 Br Br
Propene
1,2- Dibromopropane
3) Halogen Exchange:
a) Finkelstein Reaction:
Alkyl chlorides or alkyl bromides up on reaction with NaI in dry acetone form respective
alkyl iodides. This reaction is called Finkelstein reaction.
Dry acetone
General reaction: R- + NaI R-I + NaX
Reflux
X
Halo alkane Iodoalkane
(Alkyl iodide)
Bro ethane bromide)
mo (Ethyl
Example: CH3-CH2-Br
+ NaI Dry acetone
C + NaBr
Reflux
H3
-
C
H2
-I
I
o
d
o
e
t
h
a
n
e
(
E
t
h
y
l
i
o
d
i
d
e
)

Note: NaX formed during the reaction gets precipitated in dry acetone as NaX insoluble in
organic solvent; this facilitates the reaction to proceed forward according to Le chatelier’s
principle.
b) Swarts reaction:
Alkyl chlorides or alkyl bromides up on heating in presence of a metallic fluoride such as
AgF/Hg2F2/CoF2/SbF3 alkyl fluorides are obtained. This reaction is called Swarts reaction.
General reaction: R-X + AgF R-F + AgX
Halo alkane Fluroalkane
(Alkyl fluoride)
Example:
CH3-CH2-Br + CH3-CH2-F + AgBr
Bromo ethane AgF Fluroethane
(Ethyl bromide) (Ethyl Fluoride)
Preparation of Haloarenes: (aryl halides)
1) By Electrophilic substitution reaction:

Aryl chlorides or aryl bromides are prepared by reaction of arenes with halogens (X2=Cl2,
Br2) in presence of lewis acid as catalyst such as FeCl3/FeBr3/AlCl3.
X
Anhy. FeCl 3
General reaction: + X 2 + HX
Benzene Halobenzene
Cl
Anhy. FeCl
Example: + Cl
3 2 + HCl
Benzene Chlorobenzene
CH3 CH3 CH3
Br
Example: 2 Anhy. FeBr

+ 2 Br 2
+ + 2 HBr
3
Br
Toulene o-B romo toulene p-Bromo toulene
Note:
 Iodination is reversible require an oxidizing reagent like HNO3/HIO3 to oxidize the HI
formed during the reaction.

Fluro compounds are not prepared by this method due to high reactivity of fluorine.
2) Sand meyer’s Reaction:

When an aromatic primary amine such as aniline is dissolved in a mineral acid (HX) and
then treated with sodium nitrite at 00C to 50C Benzene diazonium halide is obtained which

upon treating with cuprous chloride (Cu2Cl2) or cuprous Bromide (Cu2Br2), Bromo
benzene/chloro benzene is obtained respectively.
NH2 +-
N2X
0 0
General reaction: 0 C-5 C

+ NaNO 2 2H
+ X + NaX + 2 H2O
Aniline Benzene diazonium halide

+ -
N2X X
X = Cl,Br
Cu2X2 / HX
+ N2
Halobenzene (Aryl halide)
Note: Iodobenzene is just obtained by adding Benzene diazonium halide salt to aqueous
solution of potassium iodide and shaking/warming. This is the best method to introduce
iodine to benzene ring.
+-
N 2X I
warm
Example: + KI
+ N2 + KX
Benzene diazonium halide Iodobenzene
Physical Properties:
1. Appearance: Alkyl halides are colourless when pure. However, bromides and iodides
develop colour when exposed to light.
2. Odour: Many volatile halogen compounds have sweet smell.
3. Physical state: Methyl chloride, methyl bromide, ethyl chloride and some
chlorofluoromethanes are gases at room temperature. Higher members are liquids or
solids.
4. Melting and boiling points:

 Haloalkanes/ Haloarenes have considerably higher M.P and B.P than those of the
hydrocarbons of comparable molecular mass.
Reason: Haloalkanes/ Haloarenes are generally polar. Due to greater polarity as well
as higher molecular mass as compared to the parent hydrocarbon, the intermolecular
forces of attraction (dipole-dipole and van der Waals) are stronger in the halogen
derivatives.
 Boiling points of haloalkanes containing the same alkyl group, decrease in the order:
RI> RBr> RCl> RF.

Reason: The attractions get stronger as the molecules get bigger in size and have
more electrons. This is because with the increase in size and mass of halogen atom,
the magnitude of Van der Waal forces of attraction increases as they have more
electrons.
 The boiling points of isomeric haloalkanes decrease with increase in branching
Reason: With increase in branching surface area decreases as a result the magnitude
of Van der Waal forces of attraction decreases.
Example: 2-bromo-2-methylpropane has the lowest boiling point among the three
isomers.
CH
I 3
CH3-CH2-CH2-CH2-Br CH3-CH2-CH-CH3 CH3-C-CH3
BrI Br
B.P in K 375K 364K 346K
 Boiling points of isomeric dihalobenzenes are very nearly the same. However, the
para- isomers have high melting point as compared to their ortho and meta-isomers.
It is due to symmetry of para-isomers that fits in crystal lattice better as compared to
ortho- and meta-isomers.
Cl Cl Cl
Cl
Cl
Cl
B.P in K 453 446 448

M.P in K 256 249 323
5. Density
Bromo, iodo and polychloro derivatives of hydrocarbons are heavier than water. The
density increases with increase in number of carbon atoms, halogen atoms and atomic
mass of the halogen atoms.
6. Solubility: The haloalkanes are only very slightly soluble in water.

Reason: For a haloalkane to dissolve in water, energy is required to overcome the
attractions between the haloalkane molecules and break the hydrogen bonds between
water molecules. Less energy is released when new attractions are set up between the
haloalkane and the water molecules, as these are not as strong as the original hydrogen
bonds in water. As a result, the solubility of haloalkanes in water is low.
However, haloalkanes tend to dissolve in organic solvents because the new
intermolecular attractions between haloalkanes and solvent molecules have much the
same strength as the ones being broken in the separate haloalkane and solvent
molecules.
Nature of C-X Bond:

Since halogen atoms are more electronegative than carbon, the carbon-halogen bond of
alkyl halide is polarised; the carbon atom bears a partial positive charge. (δ+) whereas the
halogen atom bears a partial negative charge.(δ-)
δ+ δ
C X
Since the size of halogen atom increases as we go down the group in the periodic table,
fluorine atom is the smallest and iodine atom, the largest. Consequently the carbon-halogen
bond length also increases from C-F to C-I. Some typical bond lengths, bond enthalpies and
dipole moments are given in following table.
Bond C-X Bond enthalpies( in kJ Dipole moment
Bond
length(pm) mol-1) (Debye)
CH3–F 139 452 1.847
CH3– Cl 178 351 1.860
CH3–Br 193 293 1.830
CH3–I 214 234 1.636
Chemical Properties:
Reactions of Haloalkanes:
1) Elimination reaction:
a) Reaction with alcoholic KOH: (Dehydrohalogination)
When haloalkanes with β-H-atom are heated with alc. KOH solution, elimination of H-atom
takes place at β-carbon atom and halogen from α-carbon atom leading to the formation of
alkenes. Elimination takes places according to Saytzeff’s rule.
General reaction:
R-CH=CH2 + KX +H2O
R-CH2-CH2-X +KOH(alc.)
Halo alkane  alkene
(Alkyl halide)
Example: CH3-CH=CH2 + KCl + H2O

CH3-CH2-CH2-Cl + KOH(alc.)
1- Chloropropane  Propene
(Propyl chloride)
Note:
 This reaction is often called β-elimination because β-H-atom is eliminated.
 If more than one β-H-atom is available for elimination, then the elimination takes place
according to Saytzeff rule.
 Saytzeff rule: In dehydrohalogenation reaction, the preferred product is that alkene
which has the greater number of alkyl groups attached to the doubly bonded C-atoms.
Example: CH3-CH2-CH-CH3 + KOH(alc.)

CH3-CH=CH-CH 3 + CH3-CH2-CH=CH2 + KBr + H2O

Br
-
2 Bromobutane 2- butene 1-butene
(major) (minor)

2) Reaction with metals:
a) Reaction with Sodium (Na) metal: (Wurtz reaction)
Alkyl halides react with Na metal in dry ether medium to give higher alkanes (double the
number of c-atoms present in alkyl group of alkyl halides)
General reaction: Dry ether
R-X + 2Na + R-X R-R + 2NaX
Halo alkane Halo alkane alkane
(Alkyl halide)
(Alkyl halide)
Example: CH Cl 2N
a CH Cl Dry ether CH -CH + 2NaCl
3 + + 3 3 3
Chloromethane Chloromethane Ethane
(Methyl Chloride) (Methyl Chloride)
Note:
 When two different alkyl halides react mixture of three alkanes are obtained.
 30 alkyl halides do not undergo Wurtz reaction instead they undergo dehydrohalogination.
 This reaction is used for ascent in series (i.e. to increase the number of c-atoms).
Dry ether
General reaction: R-X + 2Na + R'-X R-R' + R'-R' + R-R + 2NaX
Dry ether
Example: CH3Cl + 2Na + CH3-CH2-Cl CH3-CH3 + CH3-CH2-CH3 + CH3-CH2-CH2-CH3
Chloromethane Chloroethane Butane
Ethane Propane
b) Reaction with magnesium metal: (preparation of Grignard reagent)

When alkyl halides are treated with Mg metal in presence of dry ether, alkyl magnesium
halides are obtained, they are called as Grignard reagents. They belong to a class of
compounds called as organometallic compounds because they contain C-metal bond.
General reaction: Dry ether

R-X + Mg R-Mg-X
Halo alkane Alkyl magnesium
(Alkyl halide)
halide (Grignard
reagent)
Dry ether
Example: CH3Br + Mg CH3-Mg-Br
Bromomethane Methyl magnesium bromide
(Methyl Bromide)
Note:
 Grignard reagents are highly reactive and react with any source of proton to give
hydrocarbons, even water, alcohol, amines are sufficiently acidic to convert them to
corresponding hydrocarbons. Hence it is necessary to carry out the preparation of RMgX
in absence of moisture.
3) Nucleophile substitution reactions:

In this type of reaction, a nucleophile reacts with haloalkane (the substrate) having a
partial positive charge on the carbon atom bonded to halogen. A substitution reaction
takes place and halogen atom, called leaving group departs as halide ion. Since the
substitution reaction is initiated by a nucleophile, it is called nucleophilic substitution
reaction.

General reaction:
Nu +
- δ- -
δ X Nu + X
+
Nucleophile Halo alkane
Substituted product
(Alkyl halide)
(Reagent) (Substrate)
It is one of the most useful classes of organic reactions of alkyl halides in which halogen
bonded to sp3 hybridised carbon. The products formed by the reaction of haloalkanes with
some common nucleophiles are given below
a) Reaction with Aqueous KOH/NaOH :( substitution by Hydroxyl group)
Haloalkane upon boiling with aqueous alkali such as KOH/NaOH corresponding alcohols are
obtained.
General reaction:
R-CH2-CH2-X +KOH(aq.) R-CH2-CH2-OH+ KX
Halo alkane Alchol
(Alkyl halide)
Example:
CH3-CH2-CH2-Cl + KOH(aq.) CH3-CH2-CH2-OH + KCl
1-Chloropropane Propanol
(Propyl chloride)
b) Reaction with Water: (substitution by Hydroxyl group)

When halo alkanes are boiled with water corresponding alcohols are obtained.
Boil
General reaction: R-X + H 2O R-OH + HX
Halo alkane
Alchol
(Alkyl halide)
Boil
Example: CH3-CH2-Br + H2O CH3-CH2-OH + HBr
Bromoethane Ethanol
(Ethyl bromide) (Ethyl alcohol)
c) Reaction with Sodium alkoxide: (substitution by alkoxy group)

When halo alkanes are heated with sodium or potassium alkoxide corresponding ethers or
alkoxyalkanes are obtained. This reaction is called as Williamson’s ether synthesis.
General reaction: Heat
R-X + R'-O-Na R-O-R' NaX
+
Halo alkane Sod. alkoxide Ether
(Alkyl halide)
Hea
Example: CH3-CH2-Br + CH3-O-Na t CH3-CH2-O-CH3 +NaBr
Bromoethane Sod. methoxide Methoxy ethane
(Ethyl bromide) (Ethyl methyl ether)
c) Reaction with alcoholic Potassium cyanide: (substitution by cyano group)

When halo alkanes react with alcoholic KCN to form alkane nitriles or alkyl cyanides as major

product.

General reaction: R-X +KCN(alc.) R-CN + KX
Halo alkane 
Alkane nitrile
(Alkyl halide) (Alkyl cyanide)
Example: CH3-CH2-Br + KCN(alc.) CH3-CH2-CN + KBr

Bromoethane

Propanenitrile
(Ethyl bromide) (Ethyl cyanide)
Note:
 Isocyanides are also obtained as minor products.
 This reaction is used for ascent in series.
d) Reaction with alcoholic Silver cyanide: (substitution by isocyanide group)

When halo alkanes react with alcoholic AgCN to form alkyl isocyanides or carbylamines
which have extremely unpleasant or foul smell.
General reaction: R-X +AgCN(alc.) R-NC AgX

+
Halo alkane Carbylamine
(Alkyl halide) (Alkyl isocyanide)
Example:
CH3-CH2-Br +AgCN(alc.) CH3-CH2-NC + AgBr
Bromoethane  Ethyl carbylamine
(Ethyl bromide) (Ethyl isocyanide)
Note:
 Ambident Nucleophile: A nucleophile which is capable of attacking through more than
one atom or site is called as ambident nucleophile. Eg: CN-, NO - ….e.t.c..
2
 KCN is predominantly ionic therefore both C and N atoms are free to donate electron pair
because C-C bond is relatively stronger than C-N bond the attack mostly occurs through
the C-atom of the cyanide group to form alkyl cyanides as major product.
 AgCN is predominantly covalent therefore N-atom which is free to donate the electron
pair and hence the attack occurs mostly by the N-atom of cyanide group to form carbyl
amines as major product.
e) Reaction with ammonia: (substitution by amine group)

When halo alkanes are heated with alcoholic ammonia in a sealed glass tube to 110 0C
halogen atom is substituted by –NH2 (amine group) to form primary amine. The primary
amine formed react with haloalkane to form secondary amines, tertiary amines and
Quaternary ammonium halide salts. This reaction is known as Hoffmann ammonolysis
reaction.
1100C
General reaction: R-X + NH3 R-NH + HX
sealed
Halo alkane glass tube 2
0
(Alkyl halide) 1 Amine
R-NH 2 +
R- R2-NH + HX
X  0
2 Amine
R2-NH + X
R- R3-N
0
HX 
+
3 Amine
+ -
R3-N + R- [R4-N] X
X  Quarternary ammonium halide

1100C
Example CH3-Br CH3-NH2 HBr
+ sealed
:
NH3 +
Bromomethane glass tube Methanamine
(Methyl bromide) (Methyl amine)
CH3-NH2 + CH3-Br
 (CH3)2-NH + HBr
N-methyl Methanamine
(Dimethyl amine)
(CH3)2-NH + CH3-Br
 (CH3)3-N + HBr
N,N-dimethyl Methanamine
(Trimethyl amine)
+ -
(CH3)3-N + CH3-Br [(CH3)4-N] Br
 Tetramethyl ammonium bromide
f) Reaction with potassium nitrite: (Substitution by nitrite group)

Haloalkanes upon heating with sodium or potassium nitrite, corresponding alkyl nitrites
are obtained.
General reaction:
R- + KNO R-O-N=O + KX
X 2 
Halo alkane Alkyl nitrite
(Alkyl halide)
Example: CH3-CH2-Br + KNO CH3-CH2-O-N=O + KBr


Bromoethane 2 Ethyl nitrite
(Ethyl bromide)
g) Reaction with silver nitrite: (Substitution by nitro group)

Haloalkanes upon heating with silver nitrite (AgNO2), corresponding nitro alkanes are
obtained.
General reaction: R-X + AgNO 2 R-NO2 + AgX

Halo alkane  Nitro alkanes
(Alkyl halide)
Example: AgBr
CH3-CH2-Br + AgNO CH3-CH2-NO2 +
Bromoethane 2  Nitro ethane
(Ethyl bromide)
h) Reaction with silver salt of carboxylic acid: (Substitution by carboxylic group)

Haloalkanes upon heating with ethonolic solution of silver salt of fatty acid esters are
obtained.
C2H5O
General reaction: R-X + R'-COOAg R'-COO-R + AgX
H
(Alkyl halide)
Halo alkane

 (Alkyl alkanoates)
Ester
Example: C2H5O
CH -CH -Br + CH -COOAg CH -COO-CH -CH + AgBr
H
3 2 3
3 2 3
Bromoethane Silver acetate  Ethyl ethanoate
(Ethyl bromide) (Ethyl acetate)

i) Reaction with Sodium alkynides: (Substitution by alkyl group)
Haloalkanes upon heating with Sodium salt of alkynides (sodium alkynides), higher
alkynes are obtained.
General reaction: _ _
R- + R'-C C-Na R'-C C-R + NaX
X
Halo alkane Sodium alkynide Higher alkyne
(Alkyl halide)
Example: _ _
CH3-CH2-Br + CH C-Na CH C-CH2-CH3 + NaBr
Bromoethane Sodium acetylide 1-Butyne
(Ethyl bromide)
j) Reaction with lithium aluminium hydride: (Substitution by hydride (H -) group)

Haloalkanes on reduction with lithium aluminium hydride gives corresponding hydro
carbons.
General reaction:
4 R-X LiAlH4 4 R-H + LiX + AlX3
Alkane
+
Halo alkane
(Alkyl halide) (Hydrocarbon)
Example: 4 CH3-CH2-Br + LiAlH4 4 CH3-CH3 + LiBr + AlBr 3

Bromoethane Ethane
(Ethyl bromide)
Mechanisms of Nucleophilic substitution reactions:

Alkyl halide undergoes Nucleophilic substitution reactions by the following two different
mechanism.
SN1 mechanism and SN2 mechanism.
a)
SN1 mechanism [Unimolecular reaction]:
Generally tertiary alkyl halide undergoes nucleophilic substitution reaction by SN1
mechanism. It involves 2 steps. The rate of the reaction depends only on the molar
concentration of alkyl halide it does not depend on the molar concentration of nucleophile.
Hence it follows first order kinetics.
Ex: When tertiary butyl bromide is treated with NaOH, t-butyl alcohol is obtained.
CH
I CH
CH -C-Br3 + I 3
3I NaOH CH -C-OH + NaBr
3I
CH3
CH3
t-Butyl bromide t-Butyl alcohol
Mechanism: The mechanism involves the following two steps.

Step 1: Formation of carbocation: t-butyl bromide undergoes ionization to form a t-butyl
carbocation.
CH CH CH3
I 3 Slow I 3
CH -C-Br RDS CH -C
+
3I 3
CH3 +
I

-
Br
t-Butyl bromide t-Butyl carbocation
(planar)
This step is the slowest step hence it is the rate determining step.

Step-2: Attack of nucleophile on the carbocation: The nucleophile OH- can
attack the carbocation either from front side or back side to form t-butyl alcohol.
CH3 CH
I+ Fast I 3
CH -C + OH - CH -C-OH
3I 3I
CH3 CH3
t-Butyl carbocation t-Butyl alcohol
This step is fast.

Rate  [t-butyl bromide]1 [OH-]0
 Order = 1
Note:
1.
The order of reactivity of different alkyl halides towards SN1 mechanism is tertiary >
secondary > primary alkyl halides.
2.
It is favoured by weak nucleophile and polar solvents.
3.
SN1 mechanism is a unimolecular reaction.
4.
The product obtained is a racemic mixture if the reaction is carried at an asymmetric C-
atom.
b)
SN2 mechanism [Bimolecular reaction]:
Generally primary alkyl halides undergo Nucleophilic substitution reaction by SN2
mechanism. This involves only one step. The rate depends on molar concentrations of both
alkyl halide and nucleophile. Hence it follows a second order kinetics.
Ex: When methyl bromide is treated with NaOH sodium hydroxide, methanol is obtained
CH3 – Br + NaOH  CH3OH + NaBr
Mechanism of SN2 mechanism:

The mechanism of above reaction involves the following step. The nucleophile OH- of NaOH
attack carbon atom of methyl bromide exactly from the opposite side to that of Br to form a
transition state. The transition state involves the formation of a partial C-OH bond and
cleavage of C-Br bond. The transition state attains stability by loosing Br- to form methanol.
H H H H
- -
OH + H C Br HO C IIIIIIIIIIIIIII Br HO H + Br
IIIIIIIIIIIIIII
H
H
CH
Nucleophile Methanol
Methyl bromide Transition state
 rate  [CH3Br]1 [OH-]1

 Order = 2
Note:
1. The reactivity of different alkyl halides towards SN2 mechanism is as follows:
Primary > Secondary > tertiary alkyl halides

2.
It is favoured by strong nucleophile and non polar solvents.

3. SN2 mechanism is a bimolecular reaction.
4.
The product obtained has inverse configuration to that of alkyl halide if the reaction is
carried at an asymmetric C-atom.
Differences between SN1 mechanism and SN2 mechanism:

SN1 mechanism SN2 mechanism
a) It involves 2 steps It involves only one step
b) It follows first order kinetics It follows second order kinetics
c) Rate depends only on alkyl halide Rate depends on both nucleophile and
alkyl halide
d) The order of reactivity of different alkyl The order of reactivity of different alkyl
halides is 3o > 2o > 1o alkyl halides halides is 1o > 2o > 3o alkyl halides.
e) It is favoured by polar solvent and by It is favoured by non polar solvents and by
weak nucleophile strong nucleophile
f) The product is racemic The product obtained has inverse
configuration to that of alkyl halides.
Stereochemical aspects of nucleophilic substitution reactions:

If in a reaction, no bond to the stereocentre is broken, the product will have the same general
configuration of groups around the stereocentre as that of reactant. Such a reaction is said to
proceed with retention of the configuration.
Retention: Retention of configuration is the preservation of integrity of the spatial

arrangement of bonds at an asymmetric centre during a chemical reaction or
transformation.
OR
It is the configurational correlation when a chemical species XCabc is converted into
the chemical species YCabc having the same relative configuration.
c c
-
Y
b X b
Ya a
Example: The reaction that takes place when (–)-2-methylbutan-1-ol is heated with
concentrated hydrochloric acid.
CH3 CH3
H CH2-OH H CH2-Cl
Heat
+ HCl + H 2O
CH2 CH2
CH3 CH3
(-)-2-Methylbutan-1-ol (-)-1-Chloro-2-methylbutane

If the nucleophilic substitution reaction is carried for an optically active alkyl halide at the
1 2
stereo center then SN reaction proceeds with racemisation and a SN reaction proceeds with
complete stereochemical inversion.
Inversion, retention and racemisation: There are three outcomes for the reaction that
takes place at an asymmetric carbon atom.
Consider the replacement of a group X by Y in the following reaction;
 If (A) is the only compound obtained, the process is called retention of configuration.
 If (B) is the only compound obtained, the process is called inversion of configuration.
 If a 50:50 mixture of the above two is obtained then the process is called racemisation
and the product is optically inactive, as one isomer will rotate light in the direction
opposite to another.
C2H5 C2H5
C2H5
Y Y
H Y Y H
X H
CH3 CH3
CH3
B A
Inversion Retention
Y
A+B
50:50
Racemisation
Now let us have a fresh look at SN1 and SN2 mechanisms by taking examples of
optically active alkyl halides.
SN1 mechanism at an asymmetric C-atom:

In case of optically active alkyl halides, SN1 reactions are accompanied by racemisation.
Because the carbocation formed in the slow step (first step) being sp 2 hybridised is planar
(achiral). The attack of the nucleophile on the carbocation may be accomplished from either
side resulting in a mixture of products, one having the same configuration i.e the –OH
attaching on the same position as halide ion and the other having opposite configuration i.e
the –OH attaching on the side opposite to halide ion.
Example:
In the hydrolysis of optically active 2-bromobutane, which results in the formation of (±)-butan-2-ol.
Step-I: Formation of carbocation:

H CH3
H3C
Br -
+ + Br
H3C-H2C H
CH2-CH3
2-Bromo butane Carbocation

Step-II: Attack of nucleophile on the carbocation:
CH2-CH3 H C H CH3
- 3 -
HO OH OH OH
H +
+
CH2-CH3 H3C-H2C
H3 C H +
(+)-2-Butanol Carbocation (-)-2-Butanol
SN2 mechanism at an asymmetric C-atom:

In case of optically active alkyl halides, the product formed as a result of S N2 mechanism has
the inverted configuration as compared to the reactant. This is because the nucleophile
attaches itself on the side opposite to the one where the halogen atom is present.
Example: When (-)-2-bromooctane is allowed to react with sodium hydroxide, (+)-octan-2-ol

is formed with the –OH group occupying the position opposite to what bromide had occupied.
Thus, SN2 reactions of optically active halides are accompanied by inversion of configuration.
CH3 CH3
H Br + NaOH HO H + NaBr
C6H13 C6H13
(-)-2-Bromooctane (+)-Octan-2-ol
Reactions of Haloarenes /Halo benzene:

1) Reaction with metals:
a) Wurtz Fittig reaction: When a mixture of alkyl halide and aryl halide are heated with
sodium metal in presence of dry ether alkyl arene or alkyl benzene is obtained. This reaction
is called Wurtz Fittig reaction.
R
X
General reaction: + Dry ether

2Na + R-X + 2NaX

Haloarene
Halo alkane Alkyl benzene
(Aryl halide)
(Alkyl halide) (Alkyl arene)
Cl CH3
Dry ether
+ 2Na +CH3-Cl + 2NaCl
Example: 
Chlorobenzene
Chloro methane Methyl benzene
(Methyl chloride) (Toluene)

CH3-CH-CH3
Cl
CH3-CH-CH3 Dry ether

+ 2Na I + 2NaCl
Example: 
+ Cl
Chlorobenzene 2-Chloro propane Isopropyl benzene
(Isoproplyl chloride) (Cumene)
b) Fittig reaction:
When aryl halides or haloarenes are heated with sodium metal in presence of dry ether
diphenyl is obtained. This reaction is called Fittig reaction.
Cl
Dry ether
+ 2Na + 2NaCl
Example: 2 
Chlorobenzene
Diphenyl
2) Nucleophilic reactions:
Aryl halides are extremely less reactive towards nucleophilic substitution reactions due to
the following reasons:
(i) Resonance effect: In haloarenes, the lone pair of electrons on halogen atom are in
conjugation with -electrons of the ring and the following resonating structures are
possible.
..
:Cl: Cl
+
Cl
+
Cl
+
Cl
As a result C-Cl bond acquires a partial double bond character due to resonance.
As a result, the bond cleavage in haloarene is difficult than haloalkane and therefore,
they are less reactive towards nucleophilic substitution reaction.
(ii) Difference in hybridisation of carbon atom in C—X bond: In haloalkane, the carbon
atom attached to halogen is sp3 hybridised while in case of haloarene, the carbon atom
attached to halogen is sp2-hybridised. The sp2 hybridised carbon with a greater s-
character is more electronegative and can hold the electron pair of C—X bond more
tightly than sp3-hybridised carbon in haloalkane with less s-chararcter. Thus, C—Cl bond
length in haloalkane is 177pm while in haloarene is 169 pm. Since it is difficult to break
a shorter bond than a longer bond, therefore, haloarenes are less reactive than
haloalkanes towards nucleophilic substitution reaction.

X
X
2
sp hybridised
3
sp hybridised
Instability of phenyl cation: In case of haloarenes, the phenyl cation formed as a result of
self-ionisation will not be stabilized by resonance and therefore, SN1 mechanism is ruled out.
(iii) Because of the possible repulsion, it is less likely for the electron rich nucleophile to
approach electron rich arenes.
Example:
1) Replacement by hydroxyl group (formation of phenol): Dow’s process

On heating aryl halides (Chlorobenzene) with aqueous solution sodium hydroxide at a
temperature of 623K under a pressure of 300 atmospheres the halogen atom is replaced by
an hydroxyl group leading to the formation of phenol.
ONa OH
Cl
+ 623K, 300atm
NaOH + HCl + NaCl

Chlorobenzene
Sodium phenate Phenol
The presence of an electron withdrawing group (-NO2) at ortho- and para-positions

increases the reactivity of haloarenes.
Cl ONa OH
443K
+ NaOH + NaCl
+ HCl

NO2 NO2 NO2

4-Nitrochlorobenzene 4-Nitrophenol
ONa OH
Cl
NO2 NO2
NO2
368K
+ + HCl + NaCl
NaOH

NO2 NO2
NO2
2,4-Dinitrochlorobenzene 2,4-Dinitrophenol
The effect is pronounced when (-NO2) group is introduced at ortho and para- positions.
However, no effect on reactivity of haloarenes is observed by the presence of electron

withdrawing group at meta-position.

Mechanism of the reaction is as depicted:
3) Electrophilic reactions:
Haloarenes undergo the usual electrophilic substitution reactions of the benzene ring such as
halogenation, nitration, sulphonation and Friedel-Crafts reactions. Halogen atom besides
being slightly deactivating is o, p directing; therefore, further substitution occurs at ortho- and
para positions with respect to the halogen atom.
The o, p-directing influence of halogen atom can be easily understood if we consider the
resonating structures of halobenzene as shown:
Due to resonance, the electron density increases more at ortho- and para-positions than at
meta-positions. Further, the halogen atom exhibits -I effect as a result some electron cloud is
withdrawn from the benzene ring. As a result, the ring gets somewhat deactivated as
compared to benzene and hence the electrophilic substitution reactions in haloarenes occur
slowly and require more drastic conditions as compared to those in benzene.
i. Halogenation:
When haloarenes are treated with halogens In presence of a lewis acid catalyst which
also acts as a halogen carrier such as ferric salts halogenation takes place leading to the
formation of a mixture of o- dihalobenzene and p- dihalobenzene.

Cl
Cl
Cl
Cl
anhy.FeCl 3
2 + 2Cl2 + + 2HCl
Cl
Chlorobenzene 1,2-Dichlorobenzene 1,4-Dichlorobenzene
(o-Dichlorobenzene) (p-Dichlorobenzene)
ii. Nitration
When haloarenes are heated with conc. Nitric acid in presence of conc.H2SO4 a mixture
of o-nitrohalobenzene and p-nitrohalobenzene are obtained.
Cl
Cl
Cl
NO 2
conc.H 2SO4
2 +2HNO + + 2H2O

3
NO
2
Chlorobenzene
1-chloro,2-nitrobenzene 1-chloro,4-nitrobenzene
(o-nitrochlorobenzene) (p-nitrochlorobenzene)
iii. Sulphonation
When haloarenes are heated with conc.H2SO4 a mixture of o-Chlorosulphonicacid and p-

Chlorosulphonicacid are obtained.
Cl Cl
Cl SO3H
+ 2H2SO4 conc.H 2SO4

2 + + 2H2O

SO3H
Chlorobenzene 4-chlorobenzene sulphonic acid
2-chlorobenzene sulphonic
acid
iv. Friedel-Crafts alkylation

When haloarenes are heated with Alkyl halides such as methyl chloride in presence of
anhydrous aluminium chloride catalyst a mixture of o-Chlorotoluene and p- Chlorotoluene
are obtained.
Cl Cl
Cl CH3
+ 2CH3Cl Anhy.AlCl 3
2 + + 2HCl

CH3
Chlorobenzene

1-chloro-2- 1- chloro-4-methylbenzene
methylbenzene

v. Friedel-Crafts acylation
When haloarenes are heated with Acyl halides such as ethonyl chloride or acetyl chloride
in presence of anhydrous aluminium chloride catalyst a mixture of o-Chloroacetophenone
and p- Chloroacetophenone are obtained.
Cl Cl
Cl O
O
2 + 2 H3C Anhy.AlCl 3 CH3

Cl + + 2HCl

Chlorobenzene
Acetylchloride
H3C O
2-chloroacetophenone 4-chloroacetophenone
Polyhalogen Compounds:
Carbon compounds containing two or more halogen atoms are usually referred to as
polyhalogen compounds. These compounds are useful in industry and agriculture.
Some commercially important polyhalogen compounds are:
1)
Dichloromethane (Methylene chloride), CH2Cl2:
Uses:
Dichloromethane is widely used.
1. As a solvent for paint remover, metal cleaning, finishing solvent and in the in the
manufacture of drugs.
2. As a propellant in aerosols,
Harm full effects:

1. Methylene chloride harms the human central nervous system. Exposure to lower levels of
methylene chloride in air can lead to slightly impaired hearing and vision.
2. Higher levels of methylene chloride in air cause dizziness, nausea, tingling and
numbness in the fingers and toes.
3. In humans, direct skin contact with methylene chloride causes intense burning and mild
redness of the skin. Direct contact with the eyes can burn the cornea.
2)
Trichloromethane (Chloroform), CHCl3:
Uses:
1. In industry, chloroform is used as a solvent for fats, alkaloids, iodine and other substances.
2. It is used the production of the Freon refrigerant R-22.
3. It is used as general anesthetics in surgery. But has been replaced by less toxic, safer
anesthetics, such as ether.
Harm full effects:

1. Chronic chloroform exposure may cause damage to the liver (where chloroform is
metabolised to phosgene) and to the kidneys, and some people develop sores when the
skin is immersed in chloroform.

2. Chloroform is slowly oxidised by air in the presence of light and release extremely
poisonous gas i.e carbonyl chloride, also known as phosgene (COCl2). (Therefore it is
stored in closed dark coloured bottles completely filled so that air is kept out).
2 CHCl3 + O2 2 COCl2 + 2 HCl
Note: Chloroform was used as a general anesthetic in surgery. This is because inhaling
chloroform vapours depresses the central nervous system. Breathing about 900 parts of
chloroform per million parts of air (900 parts per million) for a short time can cause
dizziness, fatigue, and headache.
3)
Triiodomethane (Iodoform),CHI3:
Uses:
1. It was earlier used as an antiseptic but the antiseptic properties are due to the
liberation of free iodine and not due to Iodoform itself. Due to its unpleasant smell, it
has been replaced by other formulations containing iodine.
2. It is used in the manufacture of pharmaceuticals.
4)
Tetrachloromethane (Carbontetrachloride),CCl4:
Uses:
1. It is produced in large quantities for use in the manufacture of refrigerants and
propellants for aerosol cans.
2. It is also used as feedstock in the synthesis of chlorofluorocarbons and other
chemicals, pharmaceutical manufacturing, and general solvent use.
3. Until the mid 1960’s it was widely used as a cleaning fluid, both in industry, as a
degreasing agent, and in the home, as a spot remover and as fire extinguisher.
Harm full effects:

1. There is some evidence that exposure to carbon tetrachloride causes liver cancer in
humans. The most common effects are dizziness, light headedness, nausea and
vomiting, which can cause permanent damage to nerve cells. In severe cases, these
effects can lead rapidly to stupor, coma, unconsciousness or death. Exposure to CCl 4
can make the heart beat irregularly or stop. The chemical may irritate the eyes on
contact.
2. When carbon tetrachloride is released into the air, it rises to the atmosphere and
depletes the ozone layer. Depletion of the ozone layer is believed to increase human
exposure to ultraviolet rays, leading to increased skin cancer, eye diseases and
disorders, and possible disruption of the immune system.
5)
Freons:
Definition: The chlorofluorocarbon compounds of methane and ethane are collectively
known as freons.
Example: Freon 12 (CCl2F2). (It is one of the most common freons in industrial use)
Preparation: Freon 12 is manufactured by the action of antimony fluoride on

tetrachloromethane in the presence of antimony pentachloride by Swarts reaction.

Physical properties: They are extremely stable, unreactive, non-toxic, non-corrosive
and easily liquefiable gases.
Uses of Freon 12 (CCl2F2):

1. These are usually produced for aerosol propellants, refrigeration and air conditioning
purposes.
Harm full effects:

1. Freon are used in refrigeration, eventually makes its way into the atmosphere where it
diffuses unchanged into the stratosphere. In stratosphere, freon is able to initiate radical
chain reactions that can upset the natural ozone balance.
2. By 1974, total freon production in the world was about 2 billion pounds annually.
6)
p,p’-Dichlorodiphenyltrichloroethane(DDT):
DDT is the first chlorinated organic insecticides.
Uses:
1. The use of DDT increased enormously on a worldwide basis after World War II, primarily
because of its effectiveness against the mosquito that spreads malaria and lice that carry
typhus.
Harm full effects:

However, problems related to extensive use of DDT began to appear in the late 1940s. Many
species of insects developed resistance to DDT, and it was also discovered to have a high
toxicity towards fish. The chemical stability of DDT and its fat solubility compounded the
problem. DDT is not metabolised very rapidly by animals; instead, it is deposited and stored
in the fatty tissues. If ingestion continues at a steady rate, DDT builds up within the animal
over time.
Structure of DDT:
Cl
Cl
Cl Cl
Cl H
DDT
Note:
1. DDT was first prepared in 1873, but it was not until 1939 that Paul Muller of Geigy
Pharmaceuticals in Switzerland discovered the effectiveness of DDT as an insecticide.
Paul Muller was awarded the Nobel Prize in Medicine and Physiology in 1948 for this
discovery.
2. IUPAC name for DDT is 2, 2-bis (p-chlorophenyl)-1,1,1 trichloroethane.
3. The use of DDT was banned in the United States in 1973, although it is still in use in some
other parts of the world.

*********

CHAPTER: 11
ALCOHOLS, PHENOLS AND ETHERS
ALCOHOLS
Introduction:
Alcohols are the compounds containing Hydroxyl group (-OH) attached to the alkyl group.
Therefore they are regarded as hydroxy derivatives of aliphatic hydrocarbons.
Examples:
CH3 OH CH3 CH2 OH CH3 CH2 CH2 OH
Methyl alcohol Ethyl alcohol Propyl alcohol
Classification:
On the basis of number of hydroxyl group present per molecule of alcohol, alcohols are
classified as follows:
1) Monohydric alcohols 2) Dihydric alcohols, 3) Trihydric alcohols and 4) polyhydric
alcohols depending up on one, two, three and more hydroxyl groups present in there
molecules.
CH2 OH CH2 OH
CH2 OH CH OH (C OH)4
H
Examples: CH3 CH2 OH CH2 OH CH2 OH CH2 OH
Ethanol Ethan-1,2-diol Propan-1,2,3-triol Hexan-1,2,3,4,5,6-hexol
(Ethyl alcohol) (Glycol) (Glycerol) (Sorbitol)
(Monohydric)
(dihydric) (Trihydric (polyhydric)
)
Classification of Monohydric alcohols:
On the basis of hybridisation of the carbon atom to which the hydroxyl group (-OH) is attached
monohydric alcohols may be classified as follows.
1. Compounds containing sp3 C-OH bond:
a) Alkyl alcohols or Alkanols: In these alcohols the hydroxy group (-OH) is directly
attached to an sp3 hybridised carbon atom of an alkyl group. They form a homologous
series which can be represented by a general formula CnH2n+1OH and are generally
represented as R-OH where R is any alkyl group .
They are further classified as primary (10), secondary (20) and tertiary alcohols (30)
depending up on the nature of carbon atom to which the hydroxyl group is bonded.

H R'' R''
General representation: R' C OH R' C OH R' C OH
H 0 R'''
0 H
primary (1 ) secondary (2 ) tertiary(3 )0
H CH3 CH3
Examples: CH3 C OH
CH3 C OH CH3 C OH
H H CH3
Ethanol propan-2-ol 2- methyl-2-propanol
(Ethyl alcohol) (Isopropyl alcohol) (Tertiary butyl alcohol)
b) Allylic alcohols: In these alcohols the hydroxy group is attached to sp3 hybridised
carbon next to carbon-carbon double bond (known as allylic carbon)
These alcohols can also be classified as primary, secondary and tertiary allylic alcohols.
H R
Examples: CH2 CH CH2 OH CH2 CH C OH CH2 CH C OH

2-Propenol R R
0
primary (1 0 0
tertiary(3 )
secondary ( 2 )
)
c) Benzylic alcohols: In these alcohols the hydroxy group is attached to sp3 hybridised
carbon next to aromatic ring.
These alcohols can also be classified as primary, secondary and tertiary allylic alcohols.
H R
CH2 OH R C OH R C OH
Examples:
Benzyl alcohol 0 0
0
( ) tertiary(3 )
primary (1 ) secondary 2
2. Compounds containing sp2 C-OH bond:

The hydroxy group (-OH) is attached to a carbon-carbon double bond.
a) Vinylic alcohols: In these alcohols the hydroxy group is attached to sp2 hybridised carbon
of a carbon-carbon double bond. These alcohols are called vinyl alcohols.
Example: CH2 CH OH
(Vinyl alcohol)
Ethenol
b) Phenols: In these alcohols the hydroxy group is attached to sp2 hybridised carbon of a
carbon atom of benzene ring.
OH
Example:
Phenol
(Hydroxy benzene)

Nomenclature of Monohydric alcohols:
In Trivial system they are named as Alkyl alcohols
In IUPAC system they are named as Alkanols
Monohydric cyclic alcohols are named as Cycloalkanols
OH OH
CH3
Examples:
Cyclohexanol 2- methyl Cyclopentanol
Isomerism in Monohydric alcohols:

Structural isomerism:
Chain isomerism: Monohydric alcohols containing four or more carbon atoms

exhibit chain isomerism in which the isomers differ in the number of carbon atoms in the parent chain.
CH3 CH3
CH
Examples: CH3-CH2-CH2-CH2-OH CH3 CH2 OH CH3 C OH
CH3
1-Butanol 2-methyl-1-propanol 2-methyl-2-propanol
(Isobutylacohol) (Tertiarybutylacohol)
(Butylacohol)
b) Position isomerism: Monohydric alcohols containing three or more carbon atoms exhibit pos
–OH group in the parent chain.
OH
Examples: CH3-CH2-CH2-OH CH3 CH CH3

1-Propanol (Propylacohol)
2-Propanol
(Isopropylacohol)
c) Functional isomerism: Monohydric alcohols containing two or more carbon atoms exhibit functio
Example
(Eth
2. Stereoisomerism:
a) Optical isomerism: Unsubstituted alcohols containing four or more carbon atoms with a stereo cent
C 2H 5
Examples:CH3- CH-OH*
2-Butanol (sec.butylalcohol)

Methods of preparation of alcohols:
1. From alkenes:
i) By acid catalysed hydration:
Alkenes reacts with water in presence of Conc. H2SO4 to give alcohols. The addition of
water takes place according to Markownikoff’s rule.
conc.H2SO4
General reaction: R CH CH + H O R CH CH
2 2 3
OH
Alkene Alcohol
Example: conc.H2SO4
CH3 CH CH 2+ H 2O CH3 CH CH3
OH
propene propan-2-ol
Mechanism:
Step-1: Protonation of H2O followed by electrophilic attack of hydronium ion on alkene.
..
+
H + H2 O . . . .
H3 O
+
+ ..
CH3
CH CH2 + 3. CH3 CH CH3 + H2O ..
H.
Propene Hydronium ion Carbocation
Water reacts with Conc. H2SO4 forming hydronium ion. This hydronium ion attacks the -
electrons of alkene forming the most stable carbocation.
Step-2: Nucleophilic attack by H2O on carbocation to form protonated alcohol.

+ .. CH CH CH
CH3 CH CH3 3 3
+.O.H2
+H2.O.
Carbocation Protonated alcohol
Lone pair of electrons of water molecule makes a nucleophilic attack on the carbocation
forming protonated alcohol.
Step-3: Deprotonation to form alcohol.

.. +
CH3 CH CH CH3 CH CH3 + H3O..
+ H 2. O. 3
+ . O. H 2
:.O.H
Protonated alcohol propan-2-ol

Protonated alcohol loses a proton to water molecule forming respective alcohols and
hydronium ion.

ii) By Hydroboration – Oxidation:
Alkenes react with diborane (B2H6) or (BH3)2 to form trialkylborane which upon treatment with
alkaline H2O2 give respective alcohols. (The addition of borane to the double bond takes
place in such a manner that the boron atom gets attached to the sp 2 hybridised carbon
carrying greater number of hydrogen atoms). This reaction involves the addition of water to a
double bond against Markovnikov’s rule. This involves two reactions, addition of borane
(BH3)2 to double bond called Hydroboration-oxidation and Hydrolysis.
General reaction:
H BH2
I I 2 R-CH=CH2 2 R-CH=CH2
2 R-CH=CH2 + (H-BH2)2 2 R CH CH2 2 (R-CH2-CH2)2BH 2 (R-CH2-CH2)3B
Diborane Alkyl borane Dialkyl
Trialkyl borane
borane
-
(R-CH -CH ) B + 3 H O OH /H2O 3 R-CH -CH -OH + B(OH)
2 2 3 2 2 2 2 3
Trialkyl borane Alcohol Boric acid
Example:
H BH2
I I
CH3-CH=CH2 + (H-BH2)2 CH2 CH3-CH=CH 2 CH3-CH=CH 2
(CH3-CH2-CH2)3B
CH3 CH (CH -CH -CH ) BH
3 2
Diborane Alkyl borane Dialkyl borane Trialkyl borane
-
(CH -CH -CH ) B + 3 H OH /H 3 CH -CH -CH -OH + B(OH)
O 2O
3 2 2 3 2 2 3 2 2 3
Trialkyl borane Alcohol Boric acid
2. From Carbonyl compounds:

i) By reduction of aldehydes and ketones:
Aldehydes and ketones are reduced to corresponding 1 0 and 20 alcohols respectively by
using the following suitable reducing agents such as hydrogen gas in presence of
catalyst such as finely divided Pt, Pd, Ni and Ru. Na/EtOH, Zn/Dil.HCl, Fe/Dil.HCl,
LiAlH4, NaBH4….etc.
O
General reaction: Pd
R C H + H2 R CH2 OH
0
Aldehyde 1 Alcohol
O
Example:
CH3 C H + H2 CH3 CH2 OH
Pd
Acetaldehyde Ethyl alcohol
O OH
General reaction: Pd
C R' + H2
R Ketone R CH R'
0
2 Alcohol
O OH
Example: Pd
CH3 C CH 3+ H2
CH3 CH CH3
Acetone 2-propanol

ii) By reduction of carboxylic acids and esters:
carboxylic acids are reduced to primary alcohols in the presence of strong reducing agents,
lithium aluminium hydride.
O
LiAlH4
General reaction: R OH + 4 [H] R CH 2
OH+ H O
2
C
0
Carboxylic acids
1
O
Example: LiAlH4
CH3 C OH + 4 [H] CH3 CH2 OH + H2O
Ethanoic acid Ethyl alcohol
Esters also gives alcohols and give a mixture of two alcohols, one from the acyl group (RCO-)
and the other from the alkoxy (-OR’) group.
O
General reaction: Ni
R C O R' + 2H R CH2 OH+ R' OH
2
Ester 1 0Alcohols
0
1 Alcohols
O
Example: Ni
CH3 C O CH CH + 2H2 2 CH2 OH
3
CH3
2
Ethylethanoate Ethyl alcohol
Note: LAH reduces only carbonyl group (-CO-) without reducing olefinic linkages(C=C).
1. From Grignard Reagents:

Aldehydes and Ketones react with Grignard reagents (R-Mg-X) to form addition compound
(adduct) which on hydrolysis gives Corresponding 10, 20 and 30 alcohols.
O dry OMgX
II OH
I + I X
General reaction: R Mg X + H C + Mg
C ether C + H2O I
I OH
R R
Alkyl magnesium Aldehyde/ Adduct Alcohol
halide Ketone
i) Grignard reagent reacts with formaldehyde to form the adduct which on hydrolysis gives
primary alcohols.
O H H
+ I
II dry I H I
Example: CH3 Mg I + H C H CH3 C OMgI+ H2O CH3 C OH + Mg
ether I I
H H OH
Methyl magnesium Formaldehyde Ethylalcohol
Iodide 0
(1 alcohol)
ii) All aldehydes (other than formaldehyde) reacts with Grignard reagent to form the adduct
which on hydrolysis gives secondary alcohols.
O H H
II dry I + I I
Example: CH3 Mg I + H CH3 C OMgI + H O H CH3 C OH + Mg
CH3 C ether I 2 I OH

Methyl magnesium CH3 CH3
Iodide Acetaldehyde Propan-2-ol
0
(2 alcohol)

iii) Ketones reacts with Grignard reagent to form the adduct which on hydrolysis gives tertiary
alcohols.
O CH3 CH3
Example: II dry I + I I
CH3 Mg I + CH3 C CH3 CH3 C OMgI+ H2O H CH3 C OH + Mg
ether I I OH
CH3 CH3
Methyl magnesium propanone 2-methylpropan-2-ol
Iodide 0
(3 alcohol)
Note: In this reaction first step is a nucleophilic addition followed by hydrolysis.
Physical properties:
Alcohols consist of two parts namely an alkyl group and a hydroxyl group. The properties of
alcohols is mainly due to the hydroxyl group. The nature of alkyl groups modify these
properties.
1. Physical state: Lower members up to 4 C-atoms are liquids where as higher members
are solids.
2. Solubility: Lower members of alcohols are soluble in water in all proportions, due to their
ability to form hydrogen bonds with water molecules.
 The solubility of alcohols decreases with increase in size of alkyl (hydrophobic) groups.
 Solubility increases with increase in branching.
3. Boiling point: Boiling points of alcohols are higher in comparison to other classes of
compounds, like hydrocarbons, ethers, haloalkanes and haloarenes of comparable
molecular masses.
For example: Ethanol and propane have comparable molecular masses but their boiling
points differ widely. The boiling point of methoxy methane is intermediate of the two
boiling points.
C2H5-OH CH3-O-CH3 CH3-CH2-CH3
Ethanol Methoxy methane Propane
Molecular mass 46 46 44
Boiling point 351K 248K 231K
-- ---H
O O O O O- - - - -
--------- --------- --------- ---------
H H H H R
R R R R
Inter molecular H-bonding in alcohols
 The high boiling points of alcohols are mainly due to the presence of intermolecular
hydrogen bonding in them which is lacking in ethers and hydrocarbons.
 The boiling points of alcohols increase with increase in the number of carbon atoms
as Vander Waals forces increases.
 In alcohols the boiling points decrease with increase of branching in carbon chain
because of decrease in Vander Waals forces with decrease in surface area.

Structure of Functional Group:
In alcohols, the oxygen of the –OH group is attached to carbon by a sigma () bond formed
by the overlap of a sp3 hybridised orbital of carbon with a sp3 hybridised orbital of oxygen.
142pm
96pm
..
H :O H
0
H C 108.9
H
Methanol
The bond angle in alcohols is slightly less than the tetrahedral angle (109°-28′). It is due to
the repulsion between the lone pair of electrons of oxygen.
As O- atom of the Hydroxyl group is more electronegative then H- atom it acquires a partial
negative charge and H- atom acquires a partial positive charge as a result alcohols become
polar
Chemical Properties: Alcohols are versatile compounds. They act both as nucleophiles as
well as electrophiles.
i) As Nucleophiles: Alcohols act as nucleophiles when the bond between oxygen and
hydrogen (O-H) is broken as shown below.
.. +
R-.O.-H +
H
+ .. +
C R-O .. R-.O. +H
C -C
Alcohols Carbocation
ii) As Electrophiles: Alcohols act as electrophiles when the bond between carbon and
oxygen (C-O) is broken as shown below.
The reactions are carried out in the presence of acid to form protonated alcohol, these
protonated alcohols acts as electrophiles.
.. + +
R-CH2-.O.H + H +
H
. .
R-CH2- O H2
Protonated alcohol
Alcohol
..
- +
Br + R-CH2 O ..H2 R-CH2-Br + H2 O . .
On the basis of cleavage of different bonds the reactions of alcohols can be classified in to
three types.
I. Reactions involving the cleavage of oxygen-hydrogen bond.

II. Reactions involving the cleavage of carbon-oxygen bond.
III. Reactions involving both the alkyl and the hydroxyl groups.

I. Reactions involving the cleavage of oxygen-hydrogen bond:
i. Acidic Nature:
a) Reactions with metals:
Alcohols react with active metals such as sodium, potassium and aluminium forming
respective metal alkoxides along with liberation of hydrogen gas.
General reaction: 2 R-OH 2Na 2 R-ONa + H2

+
Alcohol Sodium alkoxide
Example: 2 C2H5-ONa + H2
2 C2H5-OH +
2Na
Ethanol Sodium ethoxide
CH3 CH3
6 CH3 2 CH3 C O Al + 3H2

C OH + 2 Al
CH3 CH3
3
2-methyl-2-propanol Aluminium tertiary butoxide
(Tertiary butyl alcohol)
b) Acidity of alcohols:
Reactions of alcohols with alkali metals shows that they are acidic in nature. In fact, alcohols
are Bronsted acids as they can donate a proton to a stronger base (B:).
B:
- + .. ..-
Base H- O . . B-H
Conjugate acid
+ R-O ..
Conjugate Base
-R
Acid
(Alcohol) (Alkoxide ion)
The acidic character of alcohols is due to the polar nature of O–H bond. Presence of an
electron-releasing group (–CH3, –C2H5) increases electron density on oxygen atom there by
decrease the polarity of O-H bond. This decreases the acid strength. Due to this reason, the
acid strength of alcohols decreases in the following order:
R R
R CH2OH > CHOH > C-OH

R
R R
0 0 0
1 2 3
Alcohols are, however, weaker acids than water. This can be illustrated by the reaction of
water with an alkoxide.
..- .. .. -
R- + R-O-H +
Conjugate acid
.O.-H
Conjugate Base
O ..: . Acid
H- O -H.
Base
(Alkoxide ion)
(Water) (Alcohol) (Hydroxide ion)
This reaction shows that water is a better proton donor i.e., stronger acid than alcohols. Also,
in the above reaction, we can see that an alkoxide ion is a better proton acceptor than
hydroxide ion, which suggests that alkoxides are stronger bases i.e. sodium ethoxide is a
stronger base than sodium hydroxide.
Therefore, Alcohols act as Bronsted bases as well. It is due to the presence of unshared
electron pairs on oxygen atom, which makes them proton acceptors.

Esterification reaction:
Alcohols react with carboxylic acids/ Acid chlorides /acid anhydrides in the presence of a
catalyst, to form esters. This reaction is called esterification reaction
i) Alcohols react with carboxylic acids in the presence of concentrated sulphuric acid as
catalyst which acts as a dehydrating agent, to form esters.
O
O
General reaction: R C OH + Conc.H2SO 4
HO R'  R C OR' + H2O
Carboxylic acid Alcohol Ester
O O
Example: Conc.H2SO 4
CH3 C OH + HO  CH3 C OC2H5 + H2O
C 2H 5
Ethanoic acid Ethyl alcohol Ethyl acetate
ii) Alcohols react with Acid chlorides in the presence of bases like pyridine or dimethyl aniline
as catalyst, to form esters.
O O
Pyridine
General reaction: R C Cl+ HO R' R C OR' + HCl
Acid chloride Alcohol Ester
O O
Example: Pyridine
CH3 C Cl + HO C2H5 CH3 C OC2H5 + HCl
Acetyl chloride Ethyl alcohol Ethyl acetate
Note: Pyridine is a organic base which neutralises the HCl formed during the reaction and
helps the reaction to proceed in forward direction
iii) Alcohols react with Acid anhydrides in the presence of concentrated sulphuric acid as
catalyst; to form esters
O O O O
+
General reaction: H
R' + R' C O R + R' C OH
R' C O C HO R
Acid anhydride Alcohol Ester Carboxylic acid
O O O O
+
H
Example: CH3 C O C CH3 + HO C2H5 CH3 C O C2H5 + CH3 C OH
Acetic anhydride Ethyl alcohol Ethyl acetate Ethanoic acid
Note: Esters consists of two groups namely Acyl group (R’CO-) and alkoxy group (-O-R).
Acyl group comes from carboxylic acids / acid chlorides/acid anhydrides, where as alkoxy
group comes from alcohol.
R' C O R
Acyl Alkoxy

(Acid part) (Alcohol part)

Reactions involving the cleavage of carbon-oxygen bond:
Alcohols undergo a number of reactions involving the cleavage of carbon-oxygen(C-OH)

bond. In these reactions the order of reactivity of alcohol is Tertiary > Secondary > Primary
alcohols.
1) Reaction with Hydrogen Halides:
Alcohols upon treating with halogen acids respective alkyl halides are obtained
General reaction:
R-OH + HX R-X + H 2O
Alcohol Hydrogen halide Alkyl halide
Example: CH -CH -OH + HC anhy. ZnCl2 CH -CH -Cl + H O

l 2
3 2 (Grooves process) 3 2
Ethanol Chloroethane
(Ethyl alcohol) (Ethyl chloride)
On passing through hydrogen chloride gas through ethanol in presence of anhydrous ZnCl2
ethyl chloride is obtained.
HCl + Anhy.ZnCl2 is called Lucas reagent. This reagent is used for differentiating 10, 20,
and 30 alcohols and the test is known as Lucas test.
Experiment Observation Inference
a) Turbidity appears immediately, Tertiary alcohol.
Alcohol + conc. HCl + b) Turbidity appears with in five

Secondary alcohol
Anhy.ZnCl2 minutes
c) Turbidity appears only upon
Primary alcohol.
heating
Appearance of turbidity indicates the formation of alkyl chlorides.
R-OH + HCl anhyd.ZnCl2
R-Cl + H2O
The order of reactivity of hydrogen halides is HI > HBr > HCl> HF.
The order of reactivity of alcohols is Tertiary > Secondary > Primary alcohols.
Note: Tertiary alcohols react in the absence of catalyst at room temperature only to give
haloalkanes.
2) Reaction with Phosphorus trihalides:

Alcohols react with phosphorus trihalides such as PCl3, PBr3 or PI3 (Red P./I2) react with
alcohol to form corresponding haloalkanes.
General reaction:
3R-OH + PX3 3 R-X + H3PO3
Example: 3 CH3-CH2-OH+ PCl3 3 CH3-CH2-Cl+ H3PO3

Ethylalcohol Ethylchloride

Note: Since PBr3 and PI3 are not very stable compounds these are prepared insitu by the
action of red phosphorous on Br2 and I2 respectively.
III. Reactions involving both alkyl and Hydroxyl group:

a) Dehydration:
Alcohols on heating with conc.H2SO4 or H3PO4 or P2O5 or anhyd. ZnCl2 and alumina (Al2O3)
undergo dehydration to give alkenes.
General reaction: conc.H2SO4
R-CH-CH2 R-CH=CH2 + H2O
I I 
H OH
Alcohol Alkene
Example: conc.H2SO4
CH3 CH2 O 443K
CH2 CH2 + H 2O
Ethyl alcohol Ethene
Secondary and tertiary alcohols can be dehydrated under milder conditions.
CH -CH-CH 85% H3PO4 CH -CH=CH + H2O
3 2
3 3 440K
I
OH
Isopropyl alcohol Propene
CH3 CH3
I I
20%H3PO4 +H O
CH3-C-OH CH3-C=CH2 2
I 358K
CH3
Tert-Butyl alcohol 2-methyl propene
The rate of dehydration for different alcohols is in the following order 30 > 20 > 10.
Mechanism of Dehydration:
It involves the following steps.
Step-1: Protonation of alcohol: Alcohol combines with a proton to form a protonated alcohol.
H H
.. H H H
+ Fast +
H C C . H+ H H C C .O. H
O
.
H H H H
Ethanol Proton Protonated alcohol
(Ethyl oxonium ion)
Step-2: Formation of carbocation: The protonated alcohol loses a water molecule to form
a carbocation.
H H H H H
+ slow ..
H C C . O. H H C C+ + H2O..
H H H H
Carbocation
Step-3: Elimination of a proton: The carbocation then eliminates a proton and undergoes
rearrangement of electrons to form the alkene.
H H H H
H C C+ C

+
C + H
H H H H
Ethene Proton

Dehydrogenation:
When vapours of primary alcohols, secondary alcohols and tertiary alcohols are passed over
heated copper catalyst at 573K dehydrogenation takes place forming aldehydes, ketones
and alkenes respectively.
i) When vapours of primary alcohols are passed over copper catalyst at 573K
dehydrogenation takes place and aldehydes are formed.
General reaction:
R-CH -OH R-CHO + H
Cu
2 573 2
0
1 Alcohol K Aldehyde
CH -CH -OH CH3-CHO + H2

Cu
3 2
573K
Ethylalcohol Ethanal
ii) When vapours of secondary alcohol are passed over copper catalyst at 573K, ketones are
formed.
OH O
I Cu
General reaction: R-CH-R' R-C-R' + H2
0 573K Ketone
2 Alcohol
O
Example: Cu
CH3-CH-CH3 CH -C-CH + H
3 3 2
I 573K
OH
Propan-2-ol Propanone
iii) When vapours of tertiary alcohol are passed over copper catalyst at 573K, alkenes are
formed.
Example: CH3 CH3

I I
CH3-C-OH Cu
CH3-C=CH2 + H2O
I 573K
CH3
Tert-Butyl alcohol 2-methylpropene
b) Oxidation:
i) Oxidation Primary alcohols:
Primary alcohols upon treating with strong oxidising agents like alkaline or acidified KMnO 4,
acidified Na2Cr2O7 or K2Cr2O7 undergo oxidation forming aldehydes containing same number
of C-atoms, which undergo further oxidation to form carboxylic acids containing same
number of C-atoms.
General reaction: K2Cr2O7 / K2Cr2O7 /H2SO4

R-CH2-OH + H2SO4 R-CHO + [O] R-COOH
0
Alcohol (1 ) [O] -H2O Aldehyde Carboxylic acid
Example: CH
+ -CH -OH K2Cr2O7 /H2SO4 CH -CHO + [O] K2Cr2O7 / CH -COOH
[O] H SO
2 4
3 2 -H2O 3 3
0

Note: Ethyl alcohol ) Acetaldehyde Acetic acid
(1
Strong oxidising agents such as acidified potassium dichromate convert alcohols to

carboxylic acids directly. However oxidation can be stopped at aldehyde stage itself by using
anhydrous chromic trioxide /chromic anhydride (CrO 3) or Pyridinium chloro chromate
(PCC) or Pyridinium dichromate (PDC).

General reaction: R-CH2- CrO3
+ [O] R-CHO + H2O
OH
Alcohol Aldehyde
Example:
CrO3
CH3 -CH2 -OH0 + [O] CH3 -CHO + H2O
Ethyl alcohol (1 ) Acetaldehyde
A better reagent for oxidation of primary alcohol to aldehyde in good yield is PCC.
Example: PCC
CH3-CH=CH-CH 2-OH [O] CH3-CH=CH- + H2 O
+ CHO
2-Butenol 2-Butenal
Note: PCC oxidizes only the carbonyl group but not the olefinic linkages(C=C).
ii) Oxidation Secondary alcohols:

Secondary alcohols upon treating with strong oxidising agents like alkaline or acidified
KMnO4, acidified Na2Cr2O7 or K2Cr2O7 undergo oxidation forming ketones containing same
number of C-atoms, which undergo further oxidation to form carboxylic acids containing less
number of C-atoms.
Note:
1. Oxidation of unsymmetrical ketones takes place according to Popoff’s rule.
Popoff’s rule: During oxidation of unsymmetrical ketones carbon-carbon bond cleavage
takes place in such a way that carbonyl group goes with a shorter alkyl chain.
2. Oxidation of symmetrical ketones gives two types of carboxylic acids where as
unsymmetrical ketones gives only one type of carboxylic acids
3. During oxidation of ketones if one of the carboxylic acids obtained is formic acid it further
gets oxidised to CO2 and H2O.
OH O
I K2Cr2O7 / H2SO4 K2Cr2O7 /H2SO4
General reaction: R-CH-R'0 + [O] -H O R-C-R' + 4 [O] R-COOH + R'-COOH
2
Carboxylic acid Carboxylic acid
Alcohol (2 ) Ketone
O
K2Cr2O7 /H2SO4
Example:
CH3-CH-CH3 + [O] CH -C-CH + 4 [O] K2Cr2O7 /
CH3-COOH + H2O + CO2
I 2
-H O 3 H2SO4
OH
Propan-2-ol Propanone Acetic acid
O
K2Cr2O7 / H2SO4
Example: CH -CH-CH -CH
+ [O] CH -C-CH - K2Cr2O7 / 2 CH -COOH
+ SO
H 4 4[O]
CH 2
3 2 3 -H2O 3 2 3 3
I
OH
Butan-2-ol 2-Butanone Acetic acid
Secondary alcohols undergo oxidation using chromic anhydride (CrO3) forming Ketones,
OH O
General reaction: I CrO3
R-CH-R' + [O] R-C-R' + H2O
0
Alcohol (2 ) Ketone
O
Example: CrO3
CH3-CH-CH3 + [O] CH3-C-CH3 + H2O
I
OH
Propan-2-ol Propanone

iii) Oxidation Tertiary alcohols:
Tertiary alcohols are very difficult to oxidise because they do not contain hydrogen on carbon
atom bearing –OH group. Under strong reaction conditions using strong oxidising agents like
alkaline or acidified KMnO4, acidified Na2Cr2O7 or K2Cr2O7 and elevated temperatures,
undergo oxidation forming ketones containing less number of C-atoms, which undergo
further oxidation to form carboxylic acids containing still lesser number of C-atoms.
CH3 O
I K2Cr2O7 /
Example: CH3-C-OH + CH3-C-CH3 + 4
K2Cr2O7 /
CH3-COOH + CO2 + H2O
H2SO4 H2SO4
4[O] -2H O, -CO [O]
I 2 2
CH3
Tert-Butyl alcohol Propanone Acetic acid
Some Commercially Important Alcohols:

Methanol and ethanol are among the two commercially important alcohols.
1. Methanol:
Preparation:
a)
Methanol, CH3OH, also known as ‘wood spirit’, was produced by destructive
distillation of wood.
b)
Most of the methanol is produced by catalytic hydrogenation of carbon monoxide at
high pressure and temperature and in the presence of ZnO-Cr2O3 catalyst.
ZnO-Cr 2O3
CO + 2H2 200-300atm CH3OH
573-673K
Properties:
 Methanol is a colourless liquid and boils at 337 K.
 It is highly poisonous in nature. Ingestion of even small quantities of methanol can cause
blindness and large quantities causes even death.
Uses:
Methanol is used as a solvent in paints, varnishes and chiefly for making formaldehyde.
2. Ethanol:
Preparation:
a)
Ethanol, C2H5OH, is obtained commercially by fermentation, the oldest method is from
sugars. The sugar in molasses, sugarcane or fruits such as grapes is converted to
glucose and fructose, (both of which have the formula C 6H12O6), in the presence of an
enzyme, invertase. Glucose and fructose undergo fermentation in the presence of
another enzyme, zymase, which is found in yeast.
C H O + H O Invertase
C H O +C H O
12 22 11 2 6 12 6 6 12 6
Zymase Glucose Fructose
C H O 2 C H OH + 2 CO
6 12 6 2 5 2

In wine making, grapes are the source of sugars and yeast. As grapes ripen, the quantity of
sugar increases and yeast grows on the outer skin. When grapes are crushed, sugar and the
enzyme come in contact and fermentation starts. Fermentation takes place in anaerobic
conditions i.e. in absence of air. Carbon dioxide is released during fermentation.
The action of zymase is inhibited once the percentage of alcohol formed exceeds 14
percent. If air gets into fermentation mixture, the oxygen of air oxidises ethanol to ethanoic
acid which in turn destroys the taste of alcoholic drinks.
b)
Nowadays, large quantities of ethanol are obtained by hydration of ethene.
Properties:
Ethanol is a colourless liquid with boiling point 351 K.
Uses:
 It is used as a solvent in paint industry and in the preparation of a number of carbon
compounds.
 The commercial alcohol is made unfit for drinking by mixing in it some copper sulphate (to
give it a colour) and pyridine (a foul smelling liquid). It is known as denaturation of
alcohol.
PHENOLS
Phenols are hydroxyl derivatives of aromatic hydrocarbons where the hydroxyl group (-OH) is
directly attached to the carbon atom of the aromatic ring.
Classification of Phenols:
Based on the number of –OH groups present in a phenol they are classified as
a) Monohydric phenols b) Dihydric phenols c) Trihydric phenols
a) Monohydric phenols: Monohydric phenol contains one –OH groups per molecule, which
is directly attached to the benzene ring.
OH OH
OH OH OH OH OH
CH3 NO2
Examples:
CH3 NO2
CH3 NO2
Phenol o-Cresol m-Cresol p-Cresol o-Nitrophenol m-Nitrophenol p-Nitrophenol
b) Dihydric phenols: Dihydric phenol contains two –OH groups per molecule, which is
directly attached to the benzene ring.
OH
OH OH
OH
Examples:
OH
OH
Catechol Resorcinol Quinol

c) Trihydric phenols: Trihydric phenol contains three –OH groups per molecule, which is
directly attached to the benzene ring.
OH
OH OH OH
OH
Examples:
OH OH HO OH
Pyrogallol Hydroxy quinol Phluroglucinol
Methods of preparation of phenols:

Phenols are also known as carbolic acid, first isolated from coal tar. In the laboratory,
phenols are prepared from benzene derivatives by the following methods.
1) From Benzene Sulphonic acid:

Benzene is Sulphonated with Oleum (mixture of H2SO4 and SO3) and benzene sulphonic acid
is formed and it is converted to sodium phenate by heating with molten sodium hydroxide.
This on acidification gives Phenol.
SO3H
SO3Na ONa OH
0
Conc. H2SO4
+ H2SO4 0 + NaOH + 2
NaOH
Fuse 300 C + HCl +NaCl
80 C - Na 2 SO 3-,H2 O
- H2O
Benzene Benzene sulphonicacid Sodium benzene sulphonate Sodium phenate Phenol
2. From Haloarenes: (Dow’s Process)

Chlorobenzene on heating with sodium hydroxide solution to a temperature of 623K under
300 atmosphere pressure forms sodium phenate which on acidification gives phenol. This
method is called Dow’s process.
Cl ONa OH
+ 623K, 300atm
NaOH -NaCl , -H O + +NaCl
2
HCl
Chlorobenzene
Sodium phenate Phenol
3. From diazonium salts:

Aromatic primary amines upon treating with nitrous acid (NaNO2+HCl) at low temperature
273- 278K (0-50C) diazonium salts are obtained. This reaction is called diazotization reaction.
These diazonium salts upon hydrolysis gives phenols.
+ -
NH2 N2Cl OH
0 0
2HCl
2+
+ NaNO 0 C-5 C
warm - NaCl, - H O
2

+ H 2O +
+N2 HCl
Aniline Benzene diazonium chloride Phenol

4. From Cumene:
Phenol is prepared commercially from cumene (Isopropyl benzene).Cumene is oxidised in

the presence of air to cumene hydroperoxide which on hydrolysis with dil H2SO4 gives phenol
and propanone (acetone).
CH3
CH3-CH-CH3 CH3-C-O-O-H OH
0
130 C dil. H 2SO4
+ O2 0
+ CH3COCH3
100 C
Cumene Cumene hydroperoxide Phenol Acetone
(Isopropyl benzene)
1. State and smell: Phenols are colourless crystalline solids with characteristic phenolic
odour. When exposed to air, it develops red colour due to formation of phenoquinone.
2. Solubility: Phenols are sparingly soluble in water because the non-polar aryl group is so
large as a result it masks the polar O-H group, but completely soluble in NaOH, alcohols,
ethers…etc.
3. Boiling point: Boiling points of phenols are higher than the boiling points of aromatic
hydrocarbons and haloarenes of comparable molecular masses due to presence of inter
molecular H-bonding.
-- ---H
O O O O O- - - - -
--------- ---------- --------- ---------
H H H H
Inter molecular H-bonding in Phenols
4. Phenols are corrosive in nature when falls on skin forms blisters.

5. Phenol containing 5% water is called carbolic acid.

In phenols, the –OH group is attached to sp2hybridised carbon of an aromatic ring. The
carbon– oxygen bond length (136 pm) in phenol is slightly less than that in methanol. This is
due to
(i) Partial double bond character on account of the conjugation of unshared electron pair of
oxygen with the aromatic ring.
(ii) sp2 hybridised state of carbon to which oxygen is attached.
.. H
:O 0
136pm 109

Phenol

CHEMICAL PROPERTIES:
1) Acidic nature of phenols:

a) Reaction with metals:
Phenol reacts with active metals like sodium, potassium and aluminium to form
corresponding metal phenoxides along with liberating hydrogen.
OH ONa
Example: 2
+ 2 + H2
2Na
Phenol Sodium phenate
b) Reaction with NaOH:

Phenols react with aqueous sodium hydroxide to form sodium phenate.
OH ONa
Example:
+ NaOH + H 2O
Phenol Sodium phenate
c) Acidity of phenols: The reactions of phenol with metals (e.g., sodium, aluminium)
and sodium hydroxide indicate its acidic nature. The hydroxyl group, in phenol is
directly attached to the sp2 hybridised carbon of benzene ring which acts as an
electron withdrawing group. Due to this, the charge distribution in phenol molecule, as
depicted in its resonance structures, causes the oxygen of –OH group to be positive.
.. .. .. .. ..
:O-H +O-H +O-H +O-H :O-H
The reaction of phenol with aqueous sodium hydroxide indicates that phenols are stronger
acids than alcohols and water. Let us examine how a compound in which hydroxyl group
attached to an aromatic ring is more acidic than the one in which hydroxyl group is attached
to an alkyl group. The ionisation of phenol takes place as follows:
OH -
O
+
+ H
Phenol Phenoxide ion Proton
2
Due to the higher electronegativity of sp hybridised carbon of phenol to which –OH is
attached, electron density decreases on oxygen. This increases the polarity of O–H
bond and results in an increase in ionisation of phenols than that of alcohols. Now let
us examine the stabilities of alkoxide and phenoxide ions. In alkoxide ion, the negative
charge is localised on oxygen while in phenoxide ion, the charge is delocalised.

The delocalisation of negative charge (structures I-V) makes phenoxide ion more stable and
favours the ionisation of phenol. Although there is also charge delocalisation in phenol, its

resonance structures have charge separation due to which the phenol molecule is less stable
than phenoxide ion.
.. .._
_
:O: :O: :O: :O:
:O:
In substituted phenols, the presence of electron withdrawing groups such as nitro group,
enhances the acidic strength of phenol. This effect is more pronounced when such a group is
present at ortho and para positions. It is due to the effective delocalisation of negative charge
in phenoxide ion. On the other hand, electron releasing groups, such as alkyl groups, in
general, do not favour the formation of phenoxide ion resulting in decrease in acid strength.
Cresols, for example, are less acidic than phenol.
2) Esterification reaction:
Phenols react with carboxylic acids/ Acid chlorides /acid anhydrides in the presence of a
catalyst, to form esters. This reaction is called esterification reaction
i) Phenols react with carboxylic acids in the presence of concentrated sulphuric acid as
catalyst which acts as a dehydrating agent, to form esters.
O O
Conc.H2SO 4
General reaction: R C OH + HO Ar  R C OAr+ H2O
Carboxylic acid Ester
O O
Conc.H2SO
Example CH3 C OH + C 6H 5 CH3 C OC6H5 + H2O
4
: HO 
Ethanoic acid Phenol Phenyl acetate
ii) Phenols react with Acid chlorides in the presence of bases like pyridine or dimethyl aniline
as catalyst, to form esters. This reaction is also called Acetylation reaction.
O O
R C Cl+ HO Ar
General reaction: Pyridine R C OAr+ HCl
Acid chloride Phenol Ester

O O
Example: Pyridine
CH3 C Cl + HO C6H5 CH3 C OC6H5 + HCl
Acetyl chloride Phenol Phenyl acetate
Note: Pyridine is a organic base which neutralises the HCl formed during the reaction and
helps the reaction to proceed in forward direction
iii) Phenols react with Acid anhydrides in the presence of concentrated sulphuric acid as
catalyst; to form esters
O O O O
+
General reaction: H
R' + R' C O Ar+ R' C OH
R' C O C HO Ar
Acid anhydride Alcohol Ester Carboxylic acid
O O O O
+
H
Example: CH3 C O C CH3 + HO C6H5 CH3 C O C6H5 + CH3 C OH
Acetic Phenol Phenyl acetate Ethanoic acid
anhydride
Preparation of Aspirin: (acetylation of salicylic acid)
Salicylic acid on acetylation with acetic anhydride in presence of conc. H2SO4 gives acetyl
salicylic acid also called as aspirin which is an analgesic as well as antipyretic.
COOH
COOH
OH
Conc. H SO OCOCH3
2 4
+ (CH3CO)2O + CH3COOH

Salicylic acid Acetic anhydride Acetyl salicyclic acid Acetic acid
(Asprin)
Reactions of Benzene Ring: (Electrophilic Substitution Reaction)
Phenols undergo electrophilic aromatic substitution reaction. The –OH group attached to the
benzene ring activates it towards electrophilic substitution. Also, it directs the incoming
group to ortho and para positions in the ring as these positions become electron rich due
to the resonance effect caused by –OH group. The resonance structures are shown below.
.. .._
_
:O: :O: :O: :O:
:O:
Common electrophilic aromatic substitution reactions taking place in phenol are as follows:
1) Halogenation:
Phenol on treating with bromine water at room temperature, a white precipitate of 2,4,6-
tribromophenol is obtained.
OH
OH
Br Br
Example: + 3Br2 + 3HBr

Br
Phenol 2,4,6-tribromophenol
However, if the reaction is carried out in presence of an inert solvent/ less polar solvents like
carbon disulphide (CS2) or CHCl3, at 00C (273K), a mixture of ortho and para bromophenols
are obtained.

OH
OH OH
Br
CS2
Example: 2 +2Br2 0 0C + + 2HBr
Br
Phenol o-bromophenol p-b romophenol
2) Nitration:
a) Phenol on treating with dil. nitric acid at 200C gives a mixture of ortho and para nitrophenols.
OH
OH OH
NO2
200C 2H2O
Example: 2 + 2HNO +
3
Phenol o-Nitrophenol +
NO2
p-Nitrophenol
The ortho and para isomers can be separated by steam distillation. o-Nitrophenol is steam
volatile due to intramolecular hydrogen bonding while p-nitrophenol is less volatile due to
intermolecular hydrogen bonding which causes the association of molecules.
O O. .
.
N H.
o-Nitrophenol
Intra molecular H-bonding
O
.........HO O
N
O ..........HO N
O.........
p-Nitrophenol
Inter molecular H-
bonding
b) When phenol is treated with concentrated nitric acid and concentrated sulphuric acid
2,4,6-trinitrophenol (picric acid) is obtained.

OH
OH
O2N NO2
Conc.H2SO4
Example: +3HNO + 3H2O
3 NO2
Phenol 2,4,6-trinitrophenol
(picric acid)
3) Kolbe’s Reaction: When phenol is treated with sodium hydroxide gives sodium phenate
which is heated with carbon dioxide to 1400C under 6 -7 atm pressure sodium salicylate
is formed which on acidification with dil hydrochloric acid gives salicylic acid.

OH ONa OH
OH
0 COONa COOH
140 C
+ NaOH - H + 6-7atm + HCl + NaCl
O
2
CO2
Phenol
Sodium phenate Sodium salicylate Salicylicacid
(o-Hydroxy benzoic acid)
4) Reimer –Tiemann reaction:

When phenols are heated with NaOH and chloroform at a temperature of 340K sodium salt
of salicylaldehyde is obtained which on hydrolysis gives salicylaldehyde . This reaction is
called Reimer –Tiemann reaction.
OH ONa ONa ON ONa OH
a
CHCl2 CH(OH)2 CHO CHO
+ NaOH - H + CHCl 3 - + 2 NaOH -  +HCl - NaCl

2 HCl 2NaCl
O
Phenol
Sodium phenate Sodium salt of Salicylaldehyde
Salicylaldehyde
5) Reaction with Zinc dust:

When phenol is heated with zinc dust, phenol is reduced to benzene.
OH

Example: + Zn + ZnO
Phenol Benzene
6) Oxidation:
Phenol undergoes oxidation with chromic acid and produces a conjugated diketone known as
benzoquinone.
OH O
Example
: Na2Cr2O7
H2SO4
O
Phenol Benzoquinone
ETHERS
Introduction:
Ethers are alkoxy derivatives of alkanes obtained by replacing one or more number of H-
atoms by Alkoxy (R-O-) group. Ethers have -O- as the functional group. They are generally
represented as R-O-R’ OR R-O-R .where R and R’ may be any alkyl or aryl group.
Classification: Ethers may be classified as:
1. Aliphatic Ethers: In which the R and R’ are both alkyl groups.
Examples: CH3-O-CH2-CH3
CH3-O-CH3

Dimethyl ether Ethyl methyl ether
2. Aromatic Ethers: In which either one are both R and R’ are aryl groups.

Examples: C6H5-O-C6H5
C6H5-O-CH3
Methyl phenyl ether Diphenyl ether
Aromatic ethers are further classified in to two types:
i) Alkyl aryl ethers: Ethers in which one of the group is aryl while the other is alkyl are
called alkyl aryl ethers.
Examples: C6H5-O-CH3
Methyl phenyl ether
ii) Diaryl ethers: Ethers in which both the diaryl ethers groups are aryl are called diaryl ethers.
Examples: C6H5-O-C6H5
Diphenyl ether
(diaryl ether)
Classification of ethers based on the R-groups on the either side of the O-atom.
1. Symmetrical Ethers: Ethers with two similar alkyl groups are called symmetrical ethers.
Examples: CH3-O-CH3 CH3-CH2-O-CH2-CH3

Dimethyl ether Diethyl ether
2. Unsymmetrical ethers: Ethers with two different alkyl groups are called unsymmetrical ethers.
Examples: CH3-O-C6H5
CH3-O-CH2-CH3
Ethyl methyl ether Methyl phenyl ether
Nomenclature of Ethers:
In Trivial system:
a) Symmetrical Ethers are named as dialkyl ethers
b) Unsymmetrical Ethers are named as alkyl-alkyl ethers. Alkyl group names are written in
the alphabetical order.
In IUPAC system: Ethers are named as alkoxy alkane. Smaller alkyl group is named as
alkoxy and bigger alkyl group is named as alkane.

In ethers, the four electron pairs, i.e., the two bond pairs and two lone pairs of electrons on
oxygen are arranged approximately in a tetrahedral arrangement.
The bond angle is slightly greater than the tetrahedral angle due to the repulsive
interaction between the two bulky (–R) groups. The C–O bond length (141 pm) is almost
the same as in alcohols.
....
141pm
H
H O
C 0 C
111.7
H H
H H
Methoxy methane

Methods of preparation of Ethers:
By dehydration of Alcohols:
Alcohols undergo dehydration in the presence of protic acids (H2SO4, H3PO4). The formation
of the reaction product, alkene or ether depends on the reaction conditions.
If excess of alcohols are heated to a temperature of 413K ethers are obtained. If alcohols are
heated with excess of conc.H2SO4 to a temperature of 443K alkenes are obtained.
Example: When ethanol is heated with conc.sulphuric acid at 443 K ethene is formed as the
major product. However, at 413 K, ethoxyethane is obtained as the main product.
H2SO4
General Reaction: R-OH + HO-R R-O-R + H2O
413K
H2SO4
Example: C2H5-OH + HO-C2H5 C2H5-O-C2H5 + H2O
413K
Ethyl alcohol diethyl ether
Example: H2SO4
C H -OH CH =CH + H O
2 5 2 2 2
443K
Ethyl alcohol Ethene
Note: only Symmetrical Ethers can be prepared by the dehydration of alcohols with conc.
sulphuric acid at 413 K.
Mechanism of Dehydration:
Formation of ether is a nucleophilic bi molecular reaction (SN2) which involves the following
steps.
Step-1: Protonation of alcohol: Alcohol combines with a proton to form a protonated alcohol.
H H
.. H H H
+ Fast +
H C C . H+ H H C C .O. H
O
.
H H H H
Ethanol Proton Protonated alcohol
(Ethyl oxonium ion)
Step-2: Attack of alcohol molecule on a protonated alcohol: Alcohol molecule attacks

the protonated alcohol to form protonated ether.
H H H H H H H H H
.. + .+. ..
.
H + H C C
.O.
O C C H + H2O..
H C C O H H C C
.
H H H H H H H H H
Ethanol
Protonated alcohol Protonated ether

Step-3: Elimination of a proton: protonated ether eliminates a proton and undergoes
rearrangement of electrons to form ether.
HH H H HH H H
. +. .. +
H C C O C C H H C C O.. C H + H
C
H H H H H H H H H
Protonated ether Diethyl ether Proton

Williamson synthesis:
Alkyl halides on heating with sodium alkoxide ethers are obtained. In this method both
symmetrical and unsymmetrical ether can be prepared.
General Reaction: .. ..
R-X + R'-O..- R-O..- + NaX
Alkyl halide Na R'
Sodium alkoxide Ether
Example: C2H5-O-C2H5 + NaCl
C2H5-Cl + C2H5-O-Na
Chloroethane Sodium ethoxide Ethoxyethane
Ethers containing substituted alkyl groups (secondary or tertiary) may also be prepared by
2
this method. The reaction involves SN attack of an alkoxide ion on primary alkyl halide.
CH3 CH3
CH3 C ...- Na+ CH3-Br .. CH3 + NaBr
CH3 O ..
O + C
.
CH3 CH3
Sodium tertiarybutoxide
Methyl bromide 2-methyl-2-methoxypropane
(Tertiarybutyl methyl ether)
Better results are obtained if the alkyl halide is primary. In case of secondary and tertiary
alkyl halides, elimination competes over substitution. If a tertiary alkyl halide is used, an
alkene is the only reaction product and no ether is formed.
Example: In the reaction of CH3ONa with (CH3)3C–Br gives exclusively 2-methylpropene. It is

because alkoxides are not only nucleophiles but strong bases as well. They react with alkyl
halides leading to elimination reactions.
CH3 ..- CH3
CH3 C Br + CH3 + I
CH3-C=CH2 + CH3OH + NaBr
. O.
Na
CH
- - -
2 methyl 2 3
Sodium methoxide 2- methyl propene Methyl alcohol
bromopropane
Phenols are also converted to ethers by this method.

.. .-. +
:OH :.O.Na O-R
General reaction :
+ NaOH + R-X + Nax
Phenol
Sodium phenate Alkoxy benzene

.. .-.
+
:.O.Na O-CH3
:OH
Example :
+ NaOH + CH3-Cl + NaCl
Phenol
Sodium phenate Methoxy benzene
(Anisole)

PHYSICAL PROPERTIES:
1. Dimethyl ether and ethyl methyl ether are gases while other members are liquids which
are highly volatile.
2. Ethers are sparingly soluble in water but completely soluble in organic solvents. The
miscibility of ether in water is due to formation of hydrogen bonding with water.
Clevage of C-O bond in ethers:
Reaction with Hydrogen halides:
Ethers react with hydrogen halides to give a mixture of alkyl halide and an alcohol. In the
product halogen atom is attached to smaller alkyl group.
General reaction R-O-R + HX R-X + R-OH
:
Example : CH3-O- CH2-CH3 + HI CH3-I + CH3-CH2-OH

Ethyl methyl ether Methyl Iodide Ethyl alcohol
In case of alkyl aryl ethers, cleavage of alkyl- oxygen bond takes place giving phenol and
alkyl halide.
.. ..
:O-R :O
H
General reaction : + HX + R-X

Alkoxy benzene Phenol
.. ..
:O-CH3 :OH
Example : CH3-I
+ HI +
Methoxy benzene
(Anisole) Phenol
Electrophilic substitution:
The alkoxy group (-OR) is ortho, para directing and activates the aromatic ring towards
electrophilic substitution in the same way as in phenol.
.. .. .. .. ..
:O-R +O-R +O-R +O-R :O-R

(i) Halogenation: Phenyl alkyl ethers undergo usual halogenations in the benzene ring.
Example: Anisole undergoes bromination with bromine in ethanoic acid even in the
absence of iron (III) bromide (Anhy. FeBr3) catalyst. It is due to the activation of benzene
ring by the methoxy group. Para isomer is obtained in 90% yield.
OCH3 OCH3
OCH3
Br
2 CH3COOH
+ 2 Br2 + + 2 HBr
Br
Anisole o-Bromoanisole (10%) p-Bromoanisole (90%
(ii) Friedel-Crafts reaction: Anisole undergoes Friedel-Crafts alkylation and acylation

reactions in the presence of anhydrous aluminium chloride (a Lewis acid) as catalyst in which
alkyl and acyl groups are introduced at ortho and para positions.
OCH3 OCH3 OCH3
Anhyd.AlCl3 CH3
2 + 2 CH3Cl CS2 ,
+ + 2 HCl
CH3
Anisole 2-methoxy- 4- methoxy-
toluene toluene
OCH3 OCH3 OCH3
COCH
3
2 + 2 CH3COCl Anhy.AlCl3
+ + 2 HCl
COCH3
Anisole Acetylchloride 2-methoxy- 4-methoxy-
acetophenone acetophenone
(iii) Nitration: When Anisole is treated with a mixture of concentrated sulphuric and nitric
acids, a mixture of ortho and para-nitroanisole is obtained.
OCH3 OCH3 OCH3
Conc. H SO
NO2
2 + 2 HNO 3 2 + + 2 H 2O
NO2
Anisole 2-Nitroanisole 4-Nitroanisole
***********

CHAPTER: 12
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
ALDEHYDES AND KETONES
Introduction:
Aldehydes and ketones are the organic compounds containing carbonyl group as the
functional group (>C=O) hence they are called as carbonyl compounds.
Aldehydes: These are the carbonyl compounds containing -CHO as functional group. These
are the first oxidation products of 10 alcohols.
Note: In aldehydes carbonyl group (>C=O) is always present at the terminal end of the
carbon chain/Alkyl chain and one of its valencies is satisfied by H-atom.
Classification of aldehydes:
On the basis of nature of R- group present in Aldehydes, they are classified into two types
namely
1) Aliphatic aldehydes: These are the aldehydes containing aliphatic carbon chain (open / closed).
CHO
Examples: H-CHO CH3-CHO

(Formaldehyde) (Acetaldehyde) Cyclohexanecarbaldehyde
Methanal Ethanal
2) Aromatic aldehydes: These are the aldehydes containing aromatic carbon chain i.e. at
least one benzene ring in them. The functional group may be bonded directly to the C-
atom of the benzene ring or to the side chain of the benzene ring.
CHO CH 2-CHO CHO
Examples:
Br
Benzenecarbaldehyde 2-Phenylethanal
(m-Bromobenzaldehyde)
OR Benzaldehyde  Phenyl acetaldehyde)
3- Bromobenzenecarbaldehyd
OR 3-Bromobenzaldehyde
Nomenclature of aldehydes:
Trivial system: They are named based on the carboxylic acids from which they are
obtained.
 The trivial names of most aldehydes are derived from the common names of the
corresponding carboxylic acids by replacing the ending –ic of acid with aldehyde. The
names reflect the Latin or Greek term for the original source of the acid or aldehyde.
 In substituted aldehydes the location of the substituent group in the carbon chain is
indicated by Greek letters α, β, γ, δ... etc. The α-carbon is that C- atom which directly
linked to the aldehyde group, β-carbon the next one, and so on.
IUPAC system: Aliphatic aldehydes are named as alkanals by replacing the letter -e from
the respective alkane by the suffix –al when the C-atom of the -CHO group is considered in
the parent chain. When the C-atom of the -CHO group is not considered in the parent chain
then they are named as carbaldehydes.

Formula Trivial name IUPAC name
H-CHO Formaldehyde Methanal
CH3-CHO Acetaldehyde Ethanal
CH3-CH2-CHO Propionaldehyde Propanal
CH3-CH2-CH2-CHO Butyraldehyde Butanal
CH3-CH-CHO
Isobutyraldehyde 2-Methylpropanal
CH3
CH3-CH2-CH2-CH2-CHO Valeraldehyde Pentanal
CH2=CH-CHO Acrolein 2-Propenal
CH3-CH2-CH=CH-CHO ------------------- 2-Pentenal
CH3-CH-CH2-CHO
β- Bromobutyraldehyde 3-Bromobutanal
Br
CH3-CH2-CH2-CH-CH-CH 2-
CHO ------------------- 4-Bromo-3-methylheptanal
Br CH3
OHC-CH2-CH-CH2-CHO Propane-1,2,3-
CHO
------------------- tricarbaldehyde
CHO
------------------- Cyclohexanecarbaldehyde
CHO
γ-Methylcyclohexane 3-Methylcyclohexane
carbaldehyde carbaldehyde
CH3
CHO
Benzaldehyde
------------------- OR
Benzenecarbaldehyde
CHO 3-Bromobenzaldehyde
m-Bromobenzaldehyde OR
3-Bromobenzene
Br carbaldehyde
CHO
4-Nitrobenzaldehyde
p-Nitrobenzaldehyde
OR
4-Nitrobenzenecarbaldehyde
NO 2
CH2-CHO
α-Phenyl acetaldehyde 2-Phenylethanal
CH=CH-CHO
Cinnamaldehyde 3-Phenylprop-2-ene-1-al
CH3-CH-CH 2-CHO
β-phenyl butyraldehyde 3-Phenylbutanal
CHO
Phthalaldehyde Benzene-1,2-dicarbaldehyde
CHO

Ketones: These are the carbonyl compounds containing >C=O as functional group. These
are the first oxidation products of 20 alcohols.
Note: In ketones carbonyl group (>C=O) is present in between the carbon chain/Alkyl chain
and the remaining two valencies of carbonyl C-atom is satisfied by other two C-atoms.
Classification of ketones:
I) On the basis of nature of R- group present in ketones, they are classified in to two types
namely:
1. Aliphatic ketones: These are the ketones containing aliphatic carbon chain (open /
closed).
O
Example : CH3-CO-CH3 CH3-CO-CH2-CH3
Propanone
(Di-methyl ketone) 2-Butanone Cyclopentanone
(Ethyl methyl ketone)
2. Aromatic ketones: These are the ketones containing aromatic carbon chain i.e. at least
one benzene ring in them. The functional group may be bonded directly to the C-atom of
the benzene ring or to the side chain of the benzene ring.
O O
Example : C-CH 3 C
1-phenylethan-1-one Benzophenone
(methylphenyl ketone) (Di-phenyl ketone)
II) On the basis of type of R- group present on either side of the carbonyl group ketones are
classified into two types namely:
1) Symmetrical ketones: These are the ketones containing same type of alkyl or aryl group
on either side of the carbonyl group.
O
Example : CH3-CO-CH3 CH3-CH2-CO-CH2-CH3 C
Propanone 3-Pentanone Benzophenone

(Di-methyl ketone) (Di-ethyl ketone) (Di-phenyl ketone)
2) UnSymmetrical ketones: These are the ketones containing different type of alkyl or aryl
group on either side of the carbonyl group.
Example : CH3-CO-CH2-CH3 O
CH3-CO-CH2-CH2-CH3
C CH3
2-Butanone
(Ethyl methyl ketone) 2-Pentanone 1-phenylethan-1-one
(Methyl propyl ketone) (methylphenyl ketone
Nomenclature of ketones:
Trivial system:
 Symmetrical ketones are named as dialkyl ketones or diaryl ketones.
 UnSymmetrical ketones are named as alkylalkyl ketones or alkylaryl ketones. The
two different alkyl or aryl groups are written according to alphabetical order.
 Some historical names (his) are also still retained in the trivial system of
nomenclature.

IUPAC system: Aliphatic ketones are named as alkanones by replacing the letter -e from
the respective alkane by the suffix –one.

CH3-CO-CH3 Dimethyl ketone Propanone
Or Acetone*
CH3-CH2-CO-CH2-CH3 Diethyl ketone 3-Pentanone
CH3-CO-CH2-CH3 Ethyl methyl ketone 2-Butanone
CH3-CH2-CH2-CO-CH2-CH2-CH3 Dipropyl ketone 4-Heptanone
CH3-CO-CH2-CH2-CH3 Methyl propyl ketone 2-pentanone
CH3-CH2-CO-CH2-CH2-CH3 Ethyl propyl ketone 3-Hexanone
(CH3)2-CH-CO-CH-(CH3)2 Diisopropyl ketone 2,4-Dimethylpentan-3-one
(CH3)2-C=CH-CO-CH3 Mesityl oxide 4-Methylpent-3-en-2-one
O
------------------- Cyclopentanone
O
β- Methyl
3-Methylcyclopentanone
cyclopentanone
CH3
O
------------------- Cyclohexanone
CH3
α- Methylcyclohexanone 2-Methylcyclohexanone
O
Methylphenyl ketone
C-CH 3 1-Phenylethan-1-one
Or Acetophenone*
O
Ethylphenyl ketone
C-CH 2-CH 3 1-Phenylpropan-1-one
Or Propiophenone*
O
Diphenyl ketone
C Benzophenone*
Or Benzophenone*
* Historical names
Preference Compound Prefix Suffix

1 Aldehyde Aldo / Formyl -al
2 Ketone Keto / Oxo -one
O
Example : CH3-CH2-C-CH2-CHO
3-Oxopentanal

STRUCTURE OF THE CARBONYL GROUP:
The carbonyl C-atom is sp2 hybridised and forms three sigma (σ) bonds. The fourth valence
electron of C-atom remains in its p-orbital and forms a pi bond (π) with oxygen atom by
overlapping with the p-orbital of oxygen atom. In addition, the oxygen atom also has two non
bonding electron pairs (lone pair of electrons). Thus, the carbonyl C-atom and the three
atoms attached to it lie in the same plane and the p-electron cloud is above and below this
plane. The bond angles are approximately 120° as expected of a trigonal coplanar structure
as shown below.
0
  bond 120
0
.O.:
  bond  120 C
C
C .O.:
bond
.O.:
0
120
Orbital diagram showing the formation of carbonyl group
The carbon-oxygen (>C=O) double bond is polarised due to higher electronegativity of

oxygen atom relative to carbon atom. Hence, the carbonyl carbon is an electrophilic (Lewis
acid), and carbonyl oxygen, a nucleophilic (Lewis base) centre. Carbonyl compounds have
substantial dipole moments and are polar than ethers. The high polarity of the carbonyl group
is explained on the basis of resonance involving a neutral (A) and a dipolar (B) structures as
shown below.
.. ..
O: :O:
+
C C
(A) (B)
METHODS OF PREPARATION OF ALDEHYDES AND KETONES:
1. From Hydrocarbons:
a) By Ozonolysis alkenes: When alkenes are treated with ozone, addition reaction takes
place leading to the formation of ozonide. Which up on further reaction with zinc dust
followed by hydrolysis give mixture of aldehydes or ketones or both depending on the nature
of alkene.
O
O
General Reaction: R-CH=CH-R + R-CH CH-R + H2O Zn 2 R-C-H + H2O2
O3
Alkene Aldehyde
O O
Ozonide
O
O O
Zn
R-CH=CH2 + R-CH CH2 + H2O R-C-H + H-C-H + H2O2
O3
Alkene Aldehyde Formaldehyde
O
O
Ozonide

O O O
Zn
Example: CH -CH -CH=CH + O3 CH3-CH2-CH CH2 + H2O
CH3-CH2-C-H + H-C-H + H2O 2
3 2 2
1- Butene Propanal Formaldehyde
O O
O O
CH -CH=CH-CH + O
CH3-CH CH-CH Zn 2 CH -C-H + H O
3 3 3 + H2O 3 2 2
3 Acetaldehyde
2- Butene
O O
H3C H3C O O O
Zn
CH3-C=CH-CH3 + O3 CH3-C CH-CH3 + H2O CH3-C-CH3 + CH3-C-H + H2O2
2-Methyl-2-butene Acetone Acetaldehyde
O O
H3C CH3
H3C O CH3 O
Zn
CH -C=C-CH + O CH -C C-CH +HO 2 CH -C-CH +H O
3 3 3 3 3 2 3 3 2 2
2,3-Dimethyl-2-butene Acetone
O O
b) By hydration of alkynes:
Alkynes on acid hydrolysis adds on to one molecule of H2O in presence of dilute sulphuric
acid and mercuric sulphate (HgSO4) as catalyst at 343K, hydration takes place to forming
unstable α, β- unsaturated alcohols called alkenols as intermediates which rearranges to give
aldehydes or ketones.
Only ethyne / acetylene gives aldehyde, where as other alkynes upon hydration gives ketones.
Note:
 The addition of water across the triple bond takes place according to Markownikoff’s rule.
 Enols and carbonyl compounds (aldehydes / ketones) are tautomers.
OH O
dil.H2SO4
General Reaction: R C CH+ H2O HgSO4 R-C=CH2 R-C-CH3
Alkyne 343K Enol Ketone
 Unsaturated alcohols
Tautomers
O
dil.H2SO4
Example : CH CH + H2O CH3-C-H
HgSO4
Ethyne 343K Ethanal
(Acetylene) (Acetaldehyde)
O
dil.H2SO4
H3 C C CH + CH3-C-CH3
HgSO4
H 2O Propanone
343K
Propyne (Dimethyl ketone)
2. From alcohols:
a) By the oxidation of alcohols:
When 10 and 20 alcohols are treated with mild and selective oxidising reagents like PCC,
PDC, CrO3 etc they get oxidised to aldehydes and ketones respectively.
However strong oxidising agents like KMnO4/H+, KMnO4/OH- , K2Cr2O7/ H+ ,K2Cr2O7/ OH-
can also be used or controlled oxidation of alcohols to aldehydes and ketones but as soon
as they are formed they must be distilled from the reaction mixture if not they further gets

oxidised to give carboxylic acids as the final products.

General Reaction: PCC
R-CH -OH + [O] R-CHO + H O
2 2
0
1 alcohol Aldehyde
Example PCC
: CH3-CH2-OH + [O] CH3-CHO + H2O
Ethanol Ethanal
(Ethyl alcohol) (Acetaldehyde)
OH O
General Reaction: R-CH-R' + [O]
PCC
0 R-C-R' + H2O
2 alcohol Ketone
OH O
Example: PCC
CH3-CH-CH3 + [O] CH3-C-CH3 + H2O
2-propanol 2-propanone
(Isopropyl alcohol) (Acetone)
Note: The other oxidizing agents which can be used for controlled oxidation are LTA {lead
tetra acetate [(CH3COO)4Pb]}, Manganese dioxide(MnO2), Jones reagent (H2CrO4).
b) By catalytic dehydrogenation:
When vapours of 10 and 20 alcohols are passed over red hot copper catalyst or silver catalyst
at 573K (3000C), dehydrogenation takes place forming aldehydes and ketones respectively.
General reaction: Cu
R-CH -OH R-CHO+ H
2 2
0
573K
1 Alcohol Aldehyde
Example:
Cu
CH -CH -OH CH3-CHO + H2
3 2
573K
General reaction: Ethanol Ethanal

(Ethylalcohol) (Acetaldehyde)
OH O
I Cu
R-CH-R' R-C-R' + H2
0 573K
2 Alcohol Ketone
O
Example: Cu
CH3-CH-CH3 CH -C-CH + H
I 573K 3 3 2
OH
Propan-2-ol
Propanone
(Isopropyl alcohol) (Acetone)
Note: Tertiary alcohols undergo dehydration and gives alkenes.

CH3 CH3
I I
Cu
Example: CH3-C-OH CH3-C=CH2 + H2O
I 573K
CH3
(Tert-Butyl alcohol) 2-methylpropene
2-Methyl-2-Propanol
3) From acyl chlorides or acid chlorides:

a) Preparation of aldehydes: Rosenmund’s reduction.
When acid chlorides or acyl chlorides are treated with hydrogen gas through boiling xylene in
the presence of palladium catalyst supported over barium sulphate they get reduced to
aldehydes. This reaction is called Rosenmund’s reduction.

Note: BaSO4 / S / quinoline acts as catalytic poisions. Partial poisoning is done in order to
avoid further reduction of aldehydes to alcohols.
O O
Pd/BaSO4
General Reaction: R-C-Cl + H2 R-C-H + HCl
Acyl Chloride Aldehyde
O O
Example: Pd/BaSO4
CH3-C-Cl + H2 CH -C-H + HCl
3
Ethanal
Ethanoyl Chloride
(Acetyl Chloride) (Acetaldehyde)
O
C-Cl CHO
Pd/BaSO4
+ H2 + HCl
Benzoyl chloride Benzaldehyde
b) Preparation of Ketones: When acid chlorides or acyl chlorides are treated with dialkyl
cadmium, ketones are obtained. Dialkyl cadmium is prepared by the action of CdCl2
(Cadmium chloride) with Grignard reagent.
Dry ether
General Reaction: CdCl2 + 2 R-Mg-X CdR2 + 2 MgClX
Cadmium chloride Grignard Dialkyl cadmium
reagent O
O
2 R'-C-Cl Dry ether
+ CdR2 2 R'-C-R + CdCl2
Acid chloride Dialkyl cadium Ketone
Cd(CH3)2 + 2 MgClBr
Dry ether
Example: CdCl2 + 2 3- Mg-Br
CH
Cadmium chloride Methyl magnesium bromide Dimethyl cadmium
O O
Dry ether
2 CH3-C-Cl + Cd(CH 3)2 2 CH 3-C-C H + CdCl2
3
Ethanoyl chloride Dimethyl cadium Propanone
(Acetyl chloride) (Acetone)
4) From Alkane nitriles or cyanohydrocarbons or alkyl cyanides:

a) Preparation of aldehydes:
i) Using stannous chloride: Stephen reaction

When alkane nitriles or cyano hydrocarbons or alkyl cyanides are reduced with stannous
chloride (SnCl2) in the presence of hydrochloric acid, an imine is obtained which up on acid
hydrolysis gives corresponding aldehyde. This reaction is called Stephen reaction.
+
O
General Reaction: R + H O
H
HCl
SnCl2 / R-
CH=NH R-C-H + NH
C N + 2 [H]
Alkane nitrile Ether 2 
3
Imin Aldehyde
e
SnCl / HCl
O
Example: CH C N + 2 [H] 2 H+
CH -CH=NH + H O CH -C-H + NH
3 Ether 3 2 3 3
Ethane nitrile Ethane imine  Ethanal
Cyano methane (Acetaldehyde)
(Ethyl cyanide)
ii) Using Diisobutylaluminium hydride (DIBAL-H): When alkane nitriles or cyano
hydrocarbons or alkyl cyanides are treated with diisobutylaluminium hydride, (DIBAL-H)
imines are obtained which up on acid hydrolysis gives respective aldehydes.
Note:
1. The reaction is normally carried at very low temperature of -780C in order to prevent the
reduction of aldehydes to 10 alcohols.
2. DIBAL-H can be used to reduce unsaturated nitriles as the double bond is not reduced.
O
General Reaction: i) DIABL- H
R C N ii) H2O, -780C
R-C-H
Alkane nitrile Aldehyde O
Example: i) DIABL- H
CH3-CH=CH-CH 2-CH2 C ii) H2O, -780C CH3-CH=CH-CH CH2-C-H 2-
N
Hex-4-ene-nitrile Hex-4-ene-1-al
Similarly, Esters are also reduced to aldehydes with DIBAL-H.
O O
Example: CH3-(CH2)9-C-O-C2H5 i) DIABL- H
ii) H2O, -780C
CH3-(CH2)9-C-H
Ethyl Undecanoate Undecanal
iii) Using Grignard reagent from HCN:

When hydrogen cyanide is treated with Grignard reagent followed by acid hydrolysis gives
respective aldehyde.
+ O
Dry ether
H
General Reaction: H C N + R-Mg-X R-CH=N-Mg-X + 2H2O R-C-H + HO-Mg-X + NH3
Hydrogen Grignard Aldehyde
Cyanide Reagent
H+ O
Example: H C N + CH -Mg-Cl Dry ether CH3-CH=N-Mg-Cl + 2 H O CH -C-H + HO-Mg-Cl + NH
3 2 3 3
Hydrogen Methyl magnesium Acetaldehyde
Cyanide chloride
b) Preparation of Ketones:
Using Grignard reagent:
When alkane nitriles or cyano hydrocarbons or alkyl cyanides are treated with Grignard
reagent an addition product is obtained which up on acid hydrolysis gives ketones.
R' H+ O
General Reaction: R C N + R'-Mg-X Dry ether R-C=N-Mg-X + 2 H O R-C-R' + HO-Mg-X + NH
2 3
Alkanenitrile Grignard reagent Addition product Ketone
CH3 + O
Example:
CH C N + CH -Mg-Cl Dry ether H -C=N-Mg-Cl + 2 H O
CH CH -C-CH + HO-Mg-Cl + NH
3 3 2 3 3 3
Methyl nitrile 3 Acetone
Methyl magnesium chloride
Preparation of aromatic aldehydes and ketones from aromatic hydrocarbons:
Preparation of Aldehydes:
a)
Use of chromyl chloride (CrO2Cl2): Etard reaction
Chromyl chloride oxidizes toluene OR any alkyl derivatives of benzene (alkyl Benzene) to
aldehydes in presence of carbon disulphide (CS 2) or CCl4, a chromium complex is formed
which on acid hydrolysis give corresponding aldehyde. This reaction is called Etard
reaction.

The methyl group of the alkyl group gets oxidised to aldehydic group in alkyl benzenes.
Example: When toluene is treated with chromyl chloride in presence of CS2 or CCl4, a
chromium complex is formed which upon hydrolysis gives benzaldehyde.
CH3 CH(OCrCl2OH)2 CHO
CCl4 or CS2 +
+ H +
+ 2 CrO2Cl  H 2O 2 CrCl 2(OH) 2
2
Toulene
Chromium complex Benzaldehyde
CH2-CH3 CH2-CHO
i) CrO2Cl2
+
ii) H O/H
2
Ethyl benzene 2-Phenyl ethanal
Note: Only the terminal methyl group gets oxidised to aldehyde group.
b)
Use of chromic oxide (CrO3):
When toluene or substituted toluene is treated with acetic anhydride in presence chromic
oxide at a temperature of 273-283K a complex compound called benzylidene diacetate (gem-
diacetate) is obtained which up on heating with dilute acids gets hydrolysed to benzaldehyde.
CH3 CHO
CH(OCOCH3)2
+
CrO3 H
+ (CH3CO)2O + 273-283K + H2O + 2 CH3COOH
373
(O) K
Toluene
acetic anhydride Benzylidene diacetate Benzaldehyde acetic acid
(Benzal diacetate)
C) By side chain chlorination followed by hydrolysis:

When boiling toluene is treated with chlorine gas in presence of diffused sunlight the methyl
group of toluene gets chlorinated forming benzal chloride, which upon heating with dilute
acids to a temperature of 373K, acid hydrolysis takes place forming benzaldehyde.
CH3 CHCl2 CH(OH)

CHO
2
h 373K
+ 2 Cl2 - 2 HCl + 2 H 2O - 2 HCl + H 2O
Toluene Benzal chloride Benzaldehyde
Note: This is a commercial method of manufacture of benzaldehyde.

d) By Gatterman – Koch reaction: (Gatterman-Koch reaction)
When benzene or its derivative is treated with carbon monoxide with hydrogen chloride in the
presence of anhydrous aluminium chloride or cuprous chloride as catalyst, benzaldehyde or
substituted benzaldehyde are obtained. This reaction is known as Gatterman-Koch
reaction.
CHO
HCl
+ CO anhyd.AlCl3
or Cu2Cl2
Benzene Benzaldehyde
Preparation of Ketones:
a) From benzene or substituted benzenes: (Friedel-Crafts acylation reaction)
When benzene or substituted benzene is treated with acid chloride or acyl chloride in the
presence of anhydrous aluminium chloride Friedel-Crafts acylation reaction takes place
forming respective aromatic ketones.
O
O
Anhyd. AlCl3 R
General Reaction: + R-C-Cl + HCl
Benzene Acid Chloride Ketone

O
O
Example Anhyd. AlCl3 CH3
: + CH3-C-Cl + HCl
Benzene
Acetyl Chloride Acetophenone
O
O
Cl Anhyd. AlCl3
+ + HCl
Benzene
Benzoyl Chloride Benzophenone
O
O
+ CH -CH -C-Cl Anhyd. AlCl3 CH2-CH3
3 2 +HCl
Benzene Propanoyl Chloride 1- phenyl prophenone
The physical properties of aldehydes and ketones are described as follows.
1. Physical state: Methanal is a gas at room temperature. Ethanal is a volatile liquid. Other
aldehydes and ketones are liquid or solid at room temperature.
2. Boiling point: The boiling points of aldehydes and ketones are higher than hydrocarbons
and ethers of comparable molecular masses. It is due to weak molecular association in

aldehydes and ketones arising out of the dipole-dipole interactions. Also, their boiling

points are lower than those of alcohols of similar molecular masses due to absence of
intermolecular hydrogen bonding.
The following compounds of molecular masses 58 and 60 are ranked in order of
increasing boiling points.
Compound Boiling point (K) Molecular mass (a.m.u)

n-Butane 273 58
Methoxyethane 281 60
Propanal 322 58
Acetone 329 58
Propan-1-ol 370 60
3. Solubility:
 The lower members of aldehydes and ketones such as methanal, ethanal and
propanone are miscible with water in all proportions, because they form hydrogen
bond with water.
 Solubility of aldehydes and ketones decreases rapidly on increasing the length of
alkyl chain.
 All aldehydes and ketones are fairly soluble in organic solvents like benzene, ether,
methanol, chloroform, etc.
R O
R C O- - - - - - -H
H- - - - - - -O C
R R
H-bonding of Aldehydes / Ketones with water
4. Odour:
 The lower aldehydes have sharp pungent odours. As the size of the molecule
increases, the odour becomes less pungent and more fragrant.
 Many naturally occurring aldehydes and ketones are used in the blending of
perfumes and flavouring agents.
Properties of aldehydes and ketones:

I. Nucleophilic addition reactions:
Contrary to electrophilic addition reactions observed in alkenes, aldehydes and ketones
undergo nucleophilic addition reactions.
Mechanism for nucleophile on the carbonyl C-atom:
Step 1: Attack of nucleophile on the carbonyl C-atom.
Nu
- Slow C
C .O.: + Nu
:O. .:
Aldehydes / (Planar)
Ketones

T
e
t
r
a
h
e
d
r
a
l
a
l
k
o
x
i
d
e
i
o
n
(
I
n
t
e
r
m
e
d
i
a
t
e
)

The nucleophile (Nu-) attacks the electrophilic carbon atom of the polar carbonyl group
perpendicularly to the plane of sp2 hybrid orbital’s of carbonyl group. The hybridization of
carbonyl C-atom changes from sp2 to sp3 resulting in the formation of a tetrahedral alkoxide
ion as intermediate.
Step 2: Abstraction of proton by alkoxide ion:
Nu Nu
C Fast C
+
+ H
: O. . : : O. . H
Tetrahedral alkoxide ion
Addition product
(Intermediate)
The alkoxide ion formed captures a proton (H+) from the reaction medium to give the final
neutral addition product.
Reactivity of aldehydes and ketones towards Nucleophilic addition reaction:

Aldehydes are more reactive than ketones towards Nucleophilic addition reaction due to the
following two reasons:
1) Stearic effect:
In aldehydes, the carbonyl carbon atom is one side bonded to alkyl group and other
side with H-atom. Where as in ketones, carbonyl carbon atom is either side bonded
with alkyl groups which hinders the approach of nucleophile.
2) Electronic effect:
Electronically in ketones the carbonyl C-atom loses its electrophilicity due to the
presence of two alkyl groups which are electron donating in nature, where as in
aldehydes the electrophilicity of carbonyl C-atom is relatively high due to the
presence of only one electron donating group.
Hence aldehydes undergo Nucleophilic addition reactions more readily than ketones.
1. Reaction with Hydrogen cyanide:
When aldehydes and ketones are treated with HCN, nucleophilic addition reaction takes place
to form respective cyanohydrins. i.e aldehyde cyanohydrin and ketone cyanohydrin.
H H
General Reaction : R-C=O + HCN R-C-OH
CN
Aldehyd Aldehyde Cyanohydrin
e
R'
R' + HCN R-C-OH
R-C =O
CN
Ketone Cyanohydrin
Ketone

H H
Example CH3-C=O + HCN CH3-C-OH
:
CN
Acetaldehyd Acetaldehyde Cyanohydrin
e
CH3 CH3
CH3-C=O + HCN CH3-C-OH
CN
Acetone Acetone Cyanohydrin
Note:
1. The reaction is slow in presence of pure HCN hence the reaction is catalysed in the presence of
base.
2. These cyanohydrins are useful synthetic intermediates.
2.
Reaction with Sodium bisulphite (NaHSO3):
When aldehydes and ketones are treated with Sodium bisulphite, nucleophilic addition
takes place to form respective bisulphites which are white crystalline solids.
H H
:
General Reaction R-C=O + NaHSO 3 R-C-OH
SO3Na
Aldehyde Aldehyde sodium bisulphite
R' R'
R-C=O + NaHSO R-C-OH
3
SO3Na
Ketone Ketone sodium bisulphite
H H
Example: CH3-C=O + NaHSO 3 CH3-C-OH
SO3Na
Acetaldehyde Acetaldehyde sodium bisulphit
CH3 CH3
CH3-C=O + NaHSO CH3-C-OH
3
SO3Na
Acetone sodium bisulphite
Acetone
3.
Reaction with Grignard reagent (R-Mg-X):
Aldehydes other than formaldehyde react with Grignard reagent to form 20 alcohol, where as
formaldehyde gives 10 alcohol.
O O-Mg-X OH
General Reaction : C
H /H2O
+
R-MgX R C H R C H + HO-Mg-X
R
Grignard R R
H+
Aldehydes reagent Alcohol
O O-Mg-Br OH
Example: H-C-H
+ CH -Mg-Br H+/H2O + HO-Mg-Br
3 H-C-H H-C-H
Formaldehyde Methyl CH3
magnesium CH3
Ethanol
Bromide

O
O-Mg-Br OH
CH3-C-H H+/H2O
+ CH3-Mg-Br CH3-C-H CH3-C-H + HO-Mg-X
Acetaldehyde Methyl magnesium CH3 CH3
Bromide 2-Propanol
Ketone reacts with Grignard reagent to form 30 alcohols.

O  
 O-Mg-X OH
 
General Reaction: R  +
H /H2O
C R+ R-MgX R C R C R + HO-Mg-X
Ketone
Grignard R R
s
reagent Alcohol
O O-Mg-Br OH
Example CH -C-CH + CH -Mg-Br CH -C-CH H+/H2O CH -C-CH + HO-Mg-Br
:
3 3 3 3 3 3 3
Acetone Methyl magnesium CH3 CH3
Bromide tertiarybutyl alcohol
4.
Addition of alcohols:
a) Addition of monohydric alcohol to aldehydes:
Aldehydes react with one equivalent of monohydric alcohol in presence of dry HCl gas to
form alkoxy alcohol called as hemiacetal, which further reacts with another molecule of
alcohol to give gemdialkoxy compound known as acetal.
H H + H
Dry HCl gas H
General Reaction: R-C=O + R'-OH R-C-OH + R'-OH R-C-O-R' + H2O
O-R' O-R'
Aldehyde Alcohol Hemiacetal Acetal
(Alkoxy alcohol) (Gemdialkoxy compound)
H H +
H
Example
: CH -C=O + CH -OH Dry HCl gas
CH -C-OH + CH -OH CH -C-O-CH + H O
H
3 3
3 3 3 3 2
O-CH3 O-CH3
Acetaldehyde Methanol 1-methoxy ethanol 1,1-dimethoxy ethane
b) Addition of dihydric alcohol to ketones:

When ketones are treated with ethylene glycol in presence of dry HCl gas, cyclic compounds
are obtained known as ethylene glycol ketals.
R R
CH2 OH HCl gas O CH2
C O + C + H2O
R CH2 OH Dil. HCl O CH2
R
Ketone Ethylene glycol Ethylene glycol ketal
5.
Addition of ammonia and its derivatives: ( Condensation reactions)
When aldehydes or ketones are treated with ammonia and its derivatives such as hydroxyl
amine, hydrazine, phenyl hydrazine, 2, 4-dinitro phenyl hydrazine, semicarbazide and amine
respective condensation products are obtained. These reactions are reversible and are
catalysed by an acid.
Basically the reactions of aldehyde and Ketones with ammonia and its derivatives is
condensation reaction, it is considered to be the Nucleophilic addition reaction based on the
mechanism path.
OH
C=O
+ NH2-Z C=N-Z + H2O
NH-Z
C
Aldehydes /
Ketones
Intermediate Addition product
NO 2
-NH- -NO2
Z = -H, -R, -OH, -NH2, -NH-C6H5, ,-NH-CO-NH2
a) Reaction with ammonia:
When aldehydes or ketones are treated with ammonia, respective imines are obtained.
H +
General Reaction: H
R-C=O + H2N-H R- + H2O
CH=NH
Aldehyde Ammoni Aldehyde imine
a
H +
Example: CH3-C=O H2N-H H CH3-CH=NH + H2O
+ Ammonia Acetaldehyde imine
Acetaldehyde
+ R'
R'
General Reaction: R-C=O + H2N-H R-C=NH + H2O
Ketone Ketone imine
H
Ammonia
CH3 + CH3
Example: 2 CH3-C=O + 2 H N-H H CH3-C-NH2 + H2O
2
CH2-CO-NH2
Acetone Ammoni Diacetone amine
a
Except formaldehyde all aldehydes react with ammonia to form respective amine. Acetone reacts
with ammonia to give diacetone imine where as all the other ketone reacts to give only imine.

Reaction of formaldehyde with Ammonia:
Formaldehyde reacts with ammonia to form hexamethylene tetramine [(CH2)6N4] which is also called as urotrop
H
Example:6 H-C=O + 4 NH3
(CH2)6N4 + 6 H2O
Formaldehyde Urotropine
Note: Urotropine up on nitration under controlled condition gives RDX (Research development explosive) which is
N
CH2
H 2C N CH2
N CH2 H2C N
CH2
Urotropine

b) Reaction with primary amines:
When aldehydes or ketones, are treated with primary amines respective N-substituted imines
are obtained.
H +
General Reaction: H
R-C=O + H2N- R-CH=N-R' + H2O
Aldehyde R' N - substituted Aldimine
Amine
H +
Example H CH3-CH=N-CH 3 + H2O
: CH3-C=O + H2N-CH3
Acetaldehyde Ammonia N-methyl acetalimine
R' + R'
General Reaction: R-C=O + H2N-R'' H
0 R-C=N-R'' + H2O
Ketone 1 Ammonia N - substituted Ketimine
CH3 + CH3
Example CH3-C=O + H2N-CH3 CH3-C=N- + H2O
:
CH 3
H
Acetone Methyl amine N-methyl acetoneimine
c) Reaction with Hydroxyl amine:

When aldehydes or ketones are treated with hydroxyl amine, respective oximes are obtained.
H +
General Reaction: R-C=O + H N-OH H
2 R-CH=N-OH + H2O
Aldehyde Hydroxyl amine Aldehyde oxime
H +
Example: CH -C=O + H
3 H2N-OH CH3-CH=N-OH + H2O
Acetaldehyde Hydroxyl amine Acetaldehyde oxime
R' + R'
General Reaction: R-C=O + H N-OH H R-C=N-OH + H2O
2
Ketone Hydroxyl amine Ketone oxime
CH3 + CH3
H
Example CH3-C=O + H2N- CH3-C=N-OH + H2O
: OH
Acetone Hydroxyl amine Acetoxime
d) Reaction with
Hydrazine:
When aldehydes or ketones are treated with hydrazine, respective hydrazones are obtained.
H +
General Reaction: R-C=O + H2N-NH H
R-CH=N-NH 2 + H2O
Aldehyde 2 Aldehyde Hydrazone
H Hydrazine
+
Example H
CH3-C=O + H2N-NH 2 CH3-CH=N-NH 2 + H2O
:
Acetaldehyde Hydrazine Acetaldehyde hydrazone
R' + R'
General Reaction: R-C=O + H N-NH H R-C=N-NH 2 + H2O
2 2

Ketone Hydrazine Ketone Hydrazone
CH3 + CH3
Example CH3-C=O + H2N-NH H + H2O
CH3-C=N-NH
: 2
2
Acetone Hydrazine Acetone hydrazone

e) Reaction with Phenyl hydrazine:
When aldehydes or ketones are treated with phenyl hydrazine, respective phenyl hydrazones
are obtained.
H +
General Reaction: R-C=O + H N-NH- H + H 2O
2
R-CH=N-NH-
Aldehyde Phenyl hydrazine Aldehyde Phenyl hydrazone
H +
Example: CH -CH -C=O+ H N-NH- H
3 2 2 CH3-CH2-CH=N-NH- + H 2O
Propionaldehyde
Phenyl hydrazine Propionaldehyde phenylhydrazone
R' R'
+
General Reaction: R-C=O + H2N- H R-C=N-NH- + H 2O
NH-
Ketone Phenyl hydrazine Ketone phenylhydrazone
CH3 CH3
H+
Example: CH3-C=O + H2N- CH3-C=N-NH- + H 2O
NH-
Acetone
Phenyl hydrazine Acetone phenyl hydrazone
f) Reaction with 2,4-dinitro phenyl hydrazine:

When aldehydes or ketones are treated with 2,4-dinitro phenyl hydrazine, respective phenyl
hydrazones are obtained.
NO2 NO2
H +
General Reaction: R-C=O + H2N-NH- -NO2 H R-CH=N-NH- -NO2 + H2O
Aldehyde 2,4-dinitroPhenyl hydrazine Aldehyde 2,4-dinitro Phenyl hydrazone
NO2 NO2
+
Example H H
CH3-CH2-C=O+ H2N-NH- -NO2 CH3-CH2-CH=N-NH- -NO2 + H2O
:
Propionaldehyde 2,4-dinitroPhenyl hydrazine Propionaldehyde 2,4-dinitro phenylhydrazone
NO2 NO2
R' + R'
General Reaction: R-C=O H2N-NH- -NO2 H R-C=N-NH- -NO2 + H2O
+
Ketone 2,4-dinitroPhenyl hydrazine Ketone 2,4-dinitro phenylhydrazone
CH3
NO2 NO2
+ CH3
Example CH3-C=O + H2N-NH- -NO2 H CH3-C=N-NH- -NO2 + H2O
:
Acetone 2,4-dinitroPhenyl hydrazine Acetone 2,4-dinitro phenyl hydrazone

g) Reaction with semi-carbazide:
When aldehydes or ketones are treated with semi-carbazide, respective semi-carbazones
are obtained.

H O O
H+
General Reaction: R-C=O + H2N-NH-C-NH R-CH=N-NH-C-NH 2 + H O
2
Aldehyde2 Aldehyde semi-carbazone
Semi-carbazide O
H +
O
Example: H CH3-CH=N-NH-C-NH 2 + H2O
CH3-C=O + H2N-NH-C-NH 2
Acetaldehyde semi-carbazone
Acetaldehyde Semi-carbazide
R' O O
+ R'
General Reaction: R-C=O + H N-NH-C-NH H
2 2 R-C=N-NH-C-NH 2 + H2O
Ketone Semi-carbazide Ketone semi-carbazone
CH3 O + CH3 O
Example: H
CH3-C=O + H2N-NH-C-NH 2 CH3-C=N-NH-C-NH 2 + H2O
Acetone Semi-carbazide Acetone semi-carbazone
II. Reduction:
a) Reduction to Alcohols:
When aldehydes and ketones are reduced by using LiAlH4 or NaBH4 or by catalytic
hydrogenation they get reduced to primary alcohol and secondary alcohols respectively.
H
LiAlH
General R-C=O + 2 [H] 4 R-CH2-OH
Reaction: Aldehyde 0
1 Alcohol
H
NaBH
4
Example: CH3-C=O + 2 CH3-CH2-OH
[H]
Acetaldehyde Ethanol
R'
LiAl OH
H
General R-C=O 2 [H] 4
R-CH-R'
0
Reaction: +
Ketone 2 Alcohol
CH3 OH
Example: NaBH4
CH3-C=O + 2 [H] CH3-CH-CH3
Acetone Propan-2-ol
b) Reduction to Hydrocarbons:
i) Clemmenson’s reduction:
When aldehydes and ketones are heated with zinc amalgam in presence of Conc.
Hydrochloric acid, they get reduced to respective alkanes. This reaction is called as
Clemmenson’s reduction.
Note: The carbonyl group (>C=O) gets reduced to methylene (-CH2-).
H
General Reaction Zn - Hg
R-C=O + 4 R-CH3 + H2O
: Conc. HCl
[H]
Aldehyde Alkane
H
Example Zn - Hg
CH3-C=O + 4 CH3-CH3 + H2O
: Conc. HCl
[H] Ethane
Acetaldehyde

R'
Zn - Hg
General Reaction R-C=O 4 [H] Conc. HCl R-CH2-R' + H2O
: +
Ketone Alkane
CH3
Example CH3-C=O + 4 [H] Zn - Hg CH -CH -CH + H O
: Conc. HCl 3 2 3 2
Acetone Propane
ii) Wolff – Kishner reduction:

When aldehydes and ketones are treated with hydrazine, respective hydrazones are
obtained. Which up on heating with NaOH/KOH in presence of high boiling liquids like
ethylene glycol, alkanes are obtained along with the liberation of nitrogen gas. This reaction
is called Wolff – Kishner reduction.
H
General Reaction: KOH
R-C=O + H2N-NH 2 -H R-CH=N-NH 2 R-CH3 + N2
O
Aldehyde 2
Ethan-1,2-diol

Hydrazine Aldehyde Hydrazone Alkane
H
KOH
Example: CH -C=O + H2N-NH CH3-CH=N-NH CH3-CH3 + N2
3 -H Ethan-1,2-diol
2O 2
2
Acetaldehyde Hydrazine Acetaldehyde hydrazone  Ethane
R' R'
General Reaction: KOH
R-C=O + H2N-NH 2 R-C=N-NH R-CH2-R + N2
- H 2O Ethan-1,2-diol
2
Ketone Hydrazine Ketone Hydrazone  Alkane
CH3 CH3
Example: CH -C=O + H2N-NH 2 CH3-C=N-NH KOH CH3-CH2-CH3 + N2
2 3 - H 2O Ethan-1,2-diol
Acetone Hydrazine Acetone hydrazone  Propane
III. Oxidation:
a) Oxidation of aldehydes:
Aldehydes gets easily oxidised to carboxylic acid up on treating with either strong oxidising
agents like KMnO4/H+, KMnO4/OH-, K2Cr2O7/H+, K2Cr2O7/ OH- or mild oxidising agents like
Conc. HNO3, Tollen’s reagent and Fehling’s solution to give carboxylic acids containing same
number of C-atoms.
H +
General R- K2Cr2O7 / H
R-C OOH
+ [O]
Reaction: C=O
Aldehyde Carboxylic acid
i) Using Tollen’s reagent:

When aldehydes are warmed with freshly prepared ammonical silver nitrate solution (Tollen’s
reagent) a black colour precipitate or silver mirror is produced due to formation of silver metal
and the aldehydes are oxidised to carboxylate anion.

Note:
1. In this reaction aldehydes gets oxidised to carboxylic acid and Tollen’s reagent gets
reduced, black ppt of silver/ silver mirror is obtained.
2. The reaction is carried out in an alkaline medium.

H + - -
General Reaction: R-C=O + [Ag(NH3)2] + 3 OH R-COO + Ag + 2 NH3 + 2 H2O
Aldehyde Carboxylate anion Black ppt
H
Example: + 2 NH + 2 H O
+ [Ag(NH ) ]++ - CH -
Ag -COO +
CH 3 - 3 OH 3 3 2
Ethanal 3 2 Ethanoate ion Black ppt
(Acetaldehyde) (Acetate ion)
Preparation of Tollen’s reagent: 2-3 ml of AgNO3 solution is taken in a test tube, 2-3 drops
of NaOH is added, a brown ppt. is formed. To this NH 4OH solution is added in dropwise until
the brown ppt. just dissolves.
Generally Tollen’s reagent is ammonical silver nitrate.
ii) Using Fehling’s solution:

When aldehydes containing α- Hydrogen atom are heated with Fehling’s solution they get
oxidised to carboxylate anion and Fehling’s solution is reduced to reddish brown ppt. of
cuprous oxide.
H 2+ - -
General Reaction: R-C=O + R-COO + Cu O +3H O
2 Cu + 5 OH 2 2
Aldehyde Carboxylate ion Reddish Brown ppt
H 2+ - -
Example: CH -C=O + CH -COO + Cu O +3H O
3 2 Cu + 5 OH 3 2 2
Ethana
l Ethanoate ion
(Acetaldehyde) (Acetate ion)
Note: Formaldehyde and aromatic aldehydes containing-CHO group directly bonded to
benzene ring do not answer for Fehling’s test because they do not contain α-H atom instead
they undergo Cannizaro’s reaction.
Generally Fehling’s solution is alkaline CuSO 4 solution containing small amount of Rochell’s
salt (Na/K tartarate)
b) Oxidation of ketones:
Ketones are oxidised only under vigorous conditions only upon treatment with strong
oxidising reagents. Oxidation of ketones involves the cleavage of C-C bond which follows
Popoff’s rule. Hence ketones cannot be oxidised using mild oxidising reagents.
Therefore Tollen’s reagent and Fehling’s solution can be used for distinguishing
between aldehydes and ketones.
Popoff’s rule: During oxidation of unsymmetrical ketones cleavage of C-C bond takes place
in such a way that the carbonyl group (>C=O) goes along with the smaller alkyl chain.
(a)
O
(a) (b) R-COOH + R'-CH2-COOH
General Reaction: R-CH2-C-CH2-R' +3 [O]
(b)
R'-COOH+ R-CH2-COOH

c) Oxidation of both aldehydes and ketones:
i) By Haloform reaction:
Aldehydes and ketones having atleast one methyl group linked to the carbonyl carbon atom
are oxidised by sodium hypohalite (NaOX) to sodium salts of corresponding carboxylic acids
containing one carbon atom less than the corresponding aldehyde or ketone and the methyl
group gets converted to haloform. Hence reaction is called Haloform reaction.
CH3
General Reaction: R-C=O + 3NaOX R-COONa + CHX3 + 2 NaOH
Aldehyde / Sodium salt of
Carboxylic acid Haloform
Ketone
O O
Example: CH3-C-H + 3 NaOCl H-C-ONa + CHCl + 2NaOH
3
Acetaldehyde Sodium hypochlorite Sodium acetate Chloroform
CH3 O
CH3-C=O + 3 CH3-C-ONa + CHI 3 + 2 NaOH
NaOI
Acetone Sodium hypoiodite Sodium acetate Iodoform
H3 C O
H3 C O
CH3-CH=C-C-CH3 + 3 NaOCl + 2NaOH
CH3-CH=C-C-ONa + CHCl
3
3-Methylpent-3-ene-2-one Sodium hypochlorite Sodium 2-methylbut-2-enenoate Chloroform
IV. Reaction involving α-H atom:

a) Acidity of α-H atom:
Aldehydes and ketones undergo a number of special type of reaction due to the acidic nature
of α-H atom. The acidic nature of α-H atoms of carbonyl group is due to the strong electron
withdrawing effect of the carbonyl group and resonance stabilisation of the conjugate base.
O H O H -
O H O
R-C C H + : - R-C C H + B-H R-C
B C H R-C=CH2
H
Acid Base Conjugated base Conjugated acid Resonating structures of carbanion
b) Aldol Condensation reaction:

When aldehydes and ketones containing at least one α-H atom undergoes self-condensation
reaction in presence of dilute alkali such as NaOH/KOH as catalyst to form β- hydroxy
aldehyde called aldol β- hydroxyl ketones called ketols respectively. This reaction is known
as aldol condensation. If this ketols or aldol is heated they readily lose water to form α, β
unsaturated carbonyl compounds.
O H O
O OH O
C NaOH
H + R' CH R-C-CH=C-R' + H2O
General Reaction : R-C C 3
R-C-CH2-C-R'
H CH3 CH3
Aldehyde / Ketone ydroxyaldehyde / ketone Aldehyde / Ketone
O NaOH
O H
H C CH
H-
C-
C
H
O OH H-
C- CH
O H-C-CH=C-H3 + H 2O
Example: H-C C H + 3 2
H CH3
Ethanal 3-Hydroxybutanal 2-Butenal

O H O O OH O
C CH CH3
NaO CH -C-CH -C-CH CH -C-CH=C-CH + H 2O
H 3 2 3 3 3
CH3-C C H + CH3 3
CH3
H
Propanone 4-Hydroxy-4-methyl-2-pentanone 4-Methylpent-3-ene-2-one
Note: This reaction is aldol condensation because the products so obtained contain both
alcoholic functional group and aldehydic functional group but the name holds good for ketol
also.
ii) Cross Aldol Condensation reaction:

When mixture of aldehydes and ketones or mixture of only aldehydes or mixture of only
ketones up on heating with dilute alkali, condensation reaction takes place leading to the
formation of mixture of four products, this reaction is called crossed aldol condensation.
Note: Two products will be self condensed products and other two will be cross condensed
reaction.
CH3-CH=CH-CHO + CH3-CH2-CH=C-CHO
CH3
CH -CHO + CH -CH -CHO 1) NaOH 2-Butenal 2-Methyl pent-2-ene-1-al
3 3 2 2)  (Self condensed products)
Ethanal Propanal
(Acetaldehyde) (Propionaldehyde)
CH3-CH2-CH=CH-CHO + CH3-CH=C-CHO
CH3
2-Pentanal 2-Methyl-But-2-ene-1-al
(Cross condensed products)
Cannizaro Reaction:
When aldehyde not containing α-H atom upon heating with strong alkali like sodium
hydroxide/ potassium hydroxide simultaneous oxidation and reduction takes place leading to
the formation of sodium or potassium salt of carboxylic acids and alcohol respectively.
H
General Reaction: 2 R- + NaOH R-COONa + R-CH2-OH
C=O Sodium salt of
Aldehyde Carboxylic acid Alcohol
H
Example 2 H-C=O + KOH H-COOK + CH3-OH
:
Aldehyde Potasium formate Methanol
CHO COONa CH2-OH
2 + NaOH +
Benzaldehyde Sodium Benzoate Benzylalcohol
ii) Electrophilic substitution reaction: Aromatic aldehydes and ketones undergo

electrophilic substitution at the ring in which the carbonyl group acts as a deactivating and
meta-directing group.
Example: Benzaldehyde on treating with nitrating mixture at a temperature of 273K-283K
nitration takes place forming m-nitro benzaldehyde.

CHO
CHO
Conc. H2SO4
+ HNO 
+ H 2O
3 273K - NO
283K 2
Benzaldehyde m-Nitrobenzaldehyde
Uses of Aldehydes and Ketones:

 In chemical industry aldehydes and ketones are used as solvents, starting materials and
reagents for the synthesis of other products.
 Formaldehyde is well known as formalin (40%) solution used to preserve biological
specimens and to prepare bakelite (a phenol-formaldehyde resin), urea-formaldehyde
glues and other polymeric products.
 Acetaldehyde is used primarily as a starting material in the manufacture of acetic acid,
ethyl acetate, vinyl acetate, polymers and drugs.
 Benzaldehyde is used in perfumery and in dye industries.
 Acetone and ethyl methyl ketone are common industrial solvents.
 Many aldehydes and ketones, e.g., butyraldehyde, vanillin, acetophenone, camphor are
well known for their odours and flavours.
Carboxylic acids
Carboxylic Acids:
Organic compounds containing a carboxyl functional group (–COOH) are called
carboxylic acids. The carboxyl group consists of a carbonyl group attached to a hydroxyl
group, hence its name carboxyl.
Classification of carboxylic acids:
Based on the type of alkyl group carboxylic acids are classified in to two types namely:
1. Aliphatic carboxylic acids (RCOOH): These are the carboxylic acids containing
aliphatic carbon chain.
2. Aromatic carboxylic acids (ArCOOH): These are the carboxylic acids containing
aromatic carbon chain i.e they contain atleast one benzene ring in them.
Fatty acids: Long chain aliphatic mono carboxylic acids are known as fatty acids,
because they occur in natural oils and fats as esters with glycerol.
Carboxylic acids serve as starting material for several other important organic
compounds such as anhydrides, esters, acid chlorides, amides, etc
Structure of Carboxyl Group:

In carboxylic acids, the bonds to the carboxyl carbon lie in one plane and are separated by
about 120°. The carboxylic carbon is less electrophilic than carbonyl carbon because of the
possible resonance structure shown below:

O
O O
R C R + R C
.. C. . ..
.O. H .O. O
H
+
NOMENCLATURE:
Trial names and IUPAC names of some carboxylic acids:

H-COOH Formic acid Methanoic acid
CH3-COOH Acetic acid Ethanoic acid
CH3-CH2-COOH Propionic acid Propanoic acid
CH3-CH2-CH2-COOH n-Butyric acid Butanoic acid
CH3-CH-COOH
Iso-Butyric acid 2-Methyl Propanoic acid
CH3
HOOC-COOH Oxalic acid Ethan-1,2-dioic acid
HOOC-CH2-COOH Malonic acid Propan-1,3-dioic acid
HOOC-CH2-CH2-COOH Succinic acid Butan-1,4-dioic acid
HOOC-CH2-CH2-CH2-COOH Glutaric acid Pentan-1,5-dioic acid
HOOC-CH2-CH2-CH2-CH2-COOH Adipic acid Hexan-1,6-dioic acid
HOOC-CH2-CH-CH2-COOH Propane-1,2,3-tricarboxylic
-------------
COOH acid
COOH
Benzoic acid Benzene carboxylic acid
CH2-COOH
Phenyl acetic acid 2-Phenyl ethanoic acid
COOH
Benzene-1,2-dicarboxylic
Phthalic acid
acid
COOH
PREPARATION OF CARBOXYLIC ACIDS:
1. From primary alcohols:

When Primary alcohols are heated with strong oxidising agents such as potassium
permanganate (KMnO4) in neutral, acidic or alkaline media or by potassium dichromate
(K2Cr2O7) and chromium trioxide (Cr2O3) in acidic media (Jones reagent), they get readily
oxidised to carboxylic acids containing same number of C-atoms.
+
General reaction: KMnO4 / H

RCOOH + H2O
R- 2OH + 2 (O)
Carboxylic acid
CH
0
1 Alcohol
-
Example:
(O)2
CH -CH -OH + CH -COOH + H O
i) KMnO4 / OH
BRIKS ACADEMY 125

3
Prepared by Maruthi.R
3 + 3 2
ii) H O Ethanoic acid
2
Ethanol

CH3-(CH2)8-CH2-OH + 2 Cr2O3 / H2SO4
CH3-(CH2)8-COOH + H O
(O) 2
1-Decanol Decanoic acid
(Capric acid)
2. From aldehydes:
When aldehydes are heated with mild oxidising agents such as Tollen’s reagent,
Fehling’s solution OR with strong oxidising agents such as potassium permanganate
(KMnO4) in neutral, acidic or alkaline media or by potassium dichromate (K 2Cr2O7) and
chromium trioxide (Cr2O3) in acidic media, they get oxidised to Carboxylic acids
containing same number of C-atoms.
+
KMnO / H
General reaction: R-CHO + (O) RCOOH
Aldehyde 4 Carboxylic acid
R-CHO + + - KMnO4 / H
+
-
[Ag(NH3)2] +3 OH RCOO + Ag + 2 H2O + 2 NH3
Aldehyde Tollen's reagent Carboxylic acid Black PPt. /
Silver mirror
+ - KMnO4 / H + -
R-CHO + 2 Cu + 5 RCOO + Cu2O + 3 H2O
OH
Aldehyde Fehling's reagent Carboxylic acid Red PPt.
+
KMnO4 / H
Example: CH3-CHO + (O) CH3-COOH
Ethanal Ethanoic acid
CH3-CH2-CHO + + - KMnO / H+ -
[Ag(NH3)2] +3 OH 4 CH3-CH2-COO + Ag + 2 H2O + 2 NH3
Propanal Tollen's reagent Propanoic acid
+
+ - KMnO / H -
CH3-CH2-CH2-CHO + 2 + 5 OH 4
CH3-CH2-CH2-COO + + 3 H 2O
Cu Cu2O
Butanal Fehling's reagent Butanoic acid Red PPt.
3. From alkyl benzenes:

When alkyl benzenes like toluene, ethyl benzene, propyl benzene....etc. are subjected
vigorous oxidation by treating with oxidising reagents like acidified or alkaline KMnO 4 or
acidified chromium trioxide (Cr2O3), whatever may be the length of the alkyl chain
attached to the benzene the entire alkyl side chain gets oxidised to –COOH group leading
to the formation of benzoic acid.
R COOH
+
KMnO /H
General reaction: 4 0
(O)  Where R= Any / 2 alkyl group
1 0
Alkyl benzene Benzoic acid
CH3 COOK
COOH
+
KMnO 4/KOH H O
Example: 
3
Toulene Potassium Benzoate Benzoic acid
CH2-CH2-CH3
COOK COOH

+
KMnO 4/KOH H O
 3
Propyl benzene Potassium Benzoate Benzoic acid

Note:
1. Primary and secondary alkyl groups are oxidised in this manner while tertiary group is not
affected i.e If tertiary group is attached it does not gets oxidised to -COOH group.
2. Suitably substituted alkenes are also oxidised to carboxylic acids.
4. From nitriles and amides:

Alkyl cyanides or Nitriles or cyano hydrocarbons upon acid / base hydrolysis gets hydrolysed
to amides which upon heating further gets hydrolysed to carboxylic acids.
Note:
1. Mild reaction conditions are used to stop the reaction at the amide stage.
2. H+ or OH- acts as catalyst.
+
H
General reaction: R-CN + H2O RCONH2 + H2O RCOOH + NH3

Alkane nitrile Amide Carboxylic acid
+
Example CH3-CN + H2O CH3CONH2 + H2O CH3-COOH + NH3
: 
Ethane nitrile Ethanamide Ethanoic acid
H
CN
CONH2 COOH
+
H
+ H 2O + H 2O + NH3

Cyano benzene Benzamide Benzoic acid
5. From Grignard reagents:

Grignard reagents react with solid carbon dioxide (dry ice) to form salts of carboxylic
acids which in turn give corresponding carboxylic acids after acidification with mineral
acid.
O
+
General reaction: Dry ether H
R-Mg-X + O=C=O R-C-O-Mg-X + H2O RCOOH + HO-Mg-X
Alkyl magnesium Dry ice Addition product Carboxylic acid
halide
O
Example: H
CH -Mg-Br Dry ether CH -C-O-Mg-Br + H O + CH -COOH +HO-Mg-Br
3 + O=C=O 3 2 3
Methyl magnesium Dry ice Ethanoic acid
bromide
Note: As we know, the Grignard reagents and nitriles can be prepared from alkyl halides
(refer Unit 10, Class XII). The above methods are useful for converting alkyl halides into
corresponding carboxylic acids having one carbon atom more than that present in alkyl
halides (ascent in series).
6. From acyl halides and anhydrides:
Acid chlorides when hydrolysed with water give carboxylic acids, they are more readily
hydrolysed with aqueous base or aqueous alkali solutions to give carboxylate ions which on
acidification provide corresponding carboxylic acids. Anhydrides on the other hand are

hydrolysed to corresponding acids with water.

+ H 2O RCOOH + HCl
Carboxylic acid
General reaction: R-CO-Cl

- +
Acid chloride OH - H O
-
+ H 2O RCOO + Cl 3 RCOOH
Carboxylic acid
(R-CO)2-O + H2O 2 RCOOH

Acid anhydride Carboxylic acid
+ H 2O CH3COOH + HCl
Ethanoicacid
Example: CH3-CO-Cl
+
Ethanoylchloride - - - H O
OH
+ H 2O CH3COO + Cl CH3COOH
Ethanoicacid
3
(CH3-CO)2-O H 2O
+ 2 CH3COOH
Acetic anhydride
Ethanoicacid
(C6H5-CO)2-O + H2 O
Benzoic anhydride
2 C6H5COOH
Benzoicacid
C6H5COOCOCH3 + H O CH3COOH + C6H5COOH

Benzoic ethanoic anhydride 2
Ethanoicacid Benzoicacid
7. From Esters:
Acidic hydrolysis of esters gives directly carboxylic acids while basic hydrolysis gives
carboxylates (salts of carboxylic acids), which on acidification give corresponding
carboxylic acids.
+
General reaction: H
RCOOR' + H2O 
RCOOH + R'OH
Esters Carboxylic acid Alcohol
+
H
RCOOR' + NaOH RCOONa + R'OH
Esters  Sodium carboxylate Alcohol
H3O+
RCOOH
Carboxylic acid
NaOH
Example CH3CH2CH2COOC2H5 CH3CH2CH2COONa C2H5OH
: + Ethanol
Ethyl butanoate Sodium butanoate
H3O+
CH3CH2CH2COOH
Butanoic acid
COOC2H5 COOH
+
H
+ H2O

Ethyl benzoate

+ C2H5OH
Ethanol

Note:
 During this process alcohols are obtained as by products.
 Base hydrolysis is called saponification.
 Na salts of long chain fatty acids (mono carboxylic acids) are called soaps.
1. Physical state: Aliphatic carboxylic acids upto nine carbon atoms are colourless liquids
at room temperature with unpleasant odours. The higher acids are wax like solids and
are practically odourless due to their low volatility.
2. Boiling point: Carboxylic acids are higher boiling liquids than aldehydes, ketones and
even alcohols of comparable molecular masses. This is due to more extensive
association of carboxylic acid molecules through intermolecular hydrogen bonding. The
hydrogen bonds are not broken completely even in the vapour phase. In fact, most
carboxylic acids exist as dimer in the vapour phase or in the aprotic solvents.
O
C
R O H
O - - - - - - - - - - - -H O R
H O
R C C R C H
O O
O H----------------------O
C O- - - - - - -H H------------O
Dimer R
(In vapour state or aprotic H-bonding of carboxylic acids with water
solvent)
3. Solubility:
 Simple aliphatic carboxylic acids having upto four carbon atoms are miscible in water
due to the formation of hydrogen bonds with water.
 The solubility decreases with increasing number of carbon atoms. Higher carboxylic
acids are practically insoluble in water due to the increased hydrophobic interaction
of hydrocarbon part.
 Benzoic acid, the simplest aromatic carboxylic acid is nearly insoluble in cold water.
Carboxylic acids are also soluble in less polar organic solvents like benzene, ether,
alcohol, chloroform, etc.
Properties of Carboxylic acids:
I. Reactions involving cleavage of O-H bond :

1. Reactions with metals:
Carboxylic acids react with highly reactive and electropositive metals like sodium to form
respective sodium salts of carboxylic acids along with evolution of H2 gas.

General reaction:
2 R-COOH + 2 Na 2 R-COONa + H2
Carboxylic acid Sodium carboxylate
Example:
2 CH3-COOH+ 2 Na 2 CH3-COONa + H2
Ethanoicacid Sodium ethanoate
(Acetic acid) (Sodium acetate)
2. Reactions with alkalis:

Carboxylic acids react with strong alkalis like NaOH, KOH ...etc. forming respective salts
of carboxylic acids along with formation of water.
Similarly carboxylic acids react with weak alkalis like carbonates and carbonates of
Na,K... etc forming respective salts of carboxylic acids along with liberation of CO 2 gas
and formation of H2O.
General reaction:
R-COOH + NaOH R-COONa + H 2O
R-COOH + NaHCO 3 R-COONa + CO2

+ H 2O
Example:
CH3-COOH + NaOH CH3-COONa + H 2O
CH3-COOH + NaHCO 3 CH3-COONa + CO2 + H2O

3. Acidity of carboxylic acids:
Reaction of carboxylic acids with alkali metals and alkalis shows that carboxylic acids are
acidic in nature.
Carboxylic acids are acidic in nature because when dissolved in water they dissociate to form
carboxylate ions and hydronium ion.
O O
- +
R C OH + H2O' R C O + H O
3
Carboxylic acid Carboxylate ion Hydronium ion
The carboxylate ion formed is resonance stabilised the resonating structures are as follows,
O -
- O O
R C O
R C O R C O
Resonance structures Resonance Hybrid
For the above reaction,
[H O]+[RCOO- ] [H3 O]+[RCOO- ]
K = 3  K [H O]= =K
eq
e [H2O][RCOOH] [RCOOH] a
2
Where, Keq is equilibrium constant and Ka is the acid dissociation constant. Strength of acids
are also expressed in terms of pKa values rather than Ka value.
pKa = - log Ka

Note:
1.
Larger the value of Ka stronger is the acid and vice versa.
2.
Smaller the value of pKa stronger is the acid and smaller vice versa.
3.
Stronger acids have pKa values < 1. Acids with pKa values ranging in between 1 and 5
are considered to be moderately stronger acids, acids with pKa values ranging between 5
to 15 are week acids and extremely weak acids have pKa values > 15.
Example:
Compound pKa Compound pKa
HCl -7.0 CH3COOH 4.76
CF3COOH 0.23 C2H5OH 16
C6H5COOH 4.19 C6H5OH 10
4.
Carboxylic acids are weaker acids than mineral acids (Inorganic acids), but they are
stronger acids than alcohols and many simple phenols.
5.
If an acid is strong its conjugate base is weak.
6.
Carboxylic acids are more acidic than phenols because carboxylate ions has two
equivalent resonating structures as shown above, where the –ve charge is on the
electronegative O-atom, Where as in phenoxide ion has non-equivalent resonance
structures in which the negative charge is on the less electronegative C-atom.
Effect of substituents on the acidity of carboxylic acids:

Acidity of carboxylic acids depends upon the stability of carboxylate ion. Greater the stability
of carboxylate ion greater is the acidic strength.
Presence of electron donating groups decreases the stability of carboxylate ion due to
+I effect hence acidic strength decreases, where as presence of electron with drawing
groups increases the stability of carboxylate ion due to -I effect hence acidic strength
increases
The effect of the following groups in increasing acidity order is
Ph < I < Br < Cl < F < CN < NO2 < CF3
Thus, the following acids are arranged in order of decreasing acidity (based on pKa values):
CF3COOH > CCl3COOH > CHCl2COOH > NO2CH2COOH > NC-CH2COOH > FCH2COOH>
ClCH2COOH> BrCH2COOH > HCOOH > ClCH2CH2COOH > C6H5COOH > C6H5CH2COOH
> CH3COOH > CH3CH2COOH
Direct attachment of groups such as phenyl or vinyl to the carboxylic acid, increases the
acidity of corresponding carboxylic acid, contrary to the decrease expected due to resonance
effect shown below:
O -
O
CH2=CH-C-OH +
CH -CH=C-OH
2
This is because of greater electronegativity of sp2 hybridised carbon atom of the carboxylic
group. The presence of electron withdrawing groups on the benzene ring of aromatic
carboxylic acid increases their acidity while electron donating groups decrease their acidity.
COOH COOH COOH
OCH3 NO 2
4-Methoxy benzoic acid Benzoic acid 4-Nitro benzoic
acid (PKa = 4.46) (PKa = 4.19) (PKa = 3.41)
II. Reactions involving cleavage of C-O bond:

1. Reaction with P2O5 and Conc.H2SO4: Formation of anhydride:
Carboxylic acids upon heating with dehydrating agents like mineral acids such as
Conc.H2SO4 and P2O5, they undergo dehydration forming respective anhydrides.
P2O
General reaction: 2 R-COOH (R-CO)2O + H 2O
5
Carboxylic acid Acid anhydride

Example: 2 CH -COOH (CH -CO) O + H O
P2O5
3  3 2 2
Ethanoicacid Ethanoic anhydride
(Acetic acid) (Acetic anhydride)
2. Reaction with alcohols : Formation of esters:

Carboxylic acids upon heating with alcohols / phenols in presence of mineral acid such
as Conc. H2SO4 Or dry HCl gas respective esters are obtained. This process is called
esterification.
O O
Conc.H2SO
General reaction: R C OH + HO R' 4 R C OR' + H2O

Carboxylic acid Ester
O O
Example: Conc.H2SO
CH3 C OH + HO C2H5 CH3 C OC2H5 + H2O
4

Ethanoic acid Ethyl alcohol Ethyl acetate
Note:
 Conc. H2SO4 OR dry HCl gas acts as a catalyst as well as dehydrating agent.

Reactivity of alcohols towards esterification increases in the order 30 < 20 < 10.
 Reactivity of carboxylic acids is R3-C-COOH < R2-CH-COOH < R-CH2-COOH < CH3-
COOH < HCOOH.

During esterification H-atom is lost from alcohol and –OH group from carboxylic acid in
the form of H2O.

In ester acyl group (R-CO-) comes from the carboxylic acid and the alkoxy group (R-O-)
from the alcohol.
3. Reaction with PCl3 ,PCl5 and SOCl2: Formation of acid chlorides:

Carboxylic acids react with PCl3, PCl5 & SOCl2 in presence of pyridine (C5H5N) to form
respective acid chlorides.

Note: SOCl2 is a better reagent for preparation of acid chloride from Carboxylic acid as
HCl and SO2 obtained as by products are gases and hence escape from the reaction
mixture leaving behind pure acid chlorides , so the purification process becomes easier.
General reaction: 3 R-COOH + PCl 3 R-COCl + H3PO3
3
Carboxylic acid Acid chloride Phosphorous acid
R-COOH + PCl5 R-COCl + POCl3 + HCl

Carboxylic acid Acid chloride Phosphorous oxy chloride
C5H5N
R-COOH + SOCl2 R-COCl + SO2 + HCl
Carboxylic acid Acid chloride
Example: 3 CH3-COOH + PCl3 3 CH3-COCl + H3PO3
Ethanoic acid Ethanoyl chloride Phosphorous acid
CH3-COOH
+ PCl5 CH3-COCl + POCl3 + HCl
Ethanoic acid Ethanoyl chloride Phosphorous oxy chloride
CH3-COOH C5H5N
Ethanoic acid + SOCl2 CH3-COCl + SO2 + HCl
Ethanoyl chloride
4. Reaction with ammonia: Formation of amide:

Carboxylic acids being acidic in nature react with ammonia which is a Lewis base to form
respective ammonium salts of Carboxylic acid which upon heating to high temperature
undergo dehydration to form acid amides / amides.
General reaction: - + 
R-COOH + NH3 R-COO NH4 R-CO-NH
Amide 2 + H2O
Carboxylic acid Ammonium salt
Example: - + 
CH3-COOH+ CH3-COO NH4 CH3-CO-NH2 + H2O
NH3
Ethanoic acid Ammonium acetate Acetamide
- +
COOH COO NH CO-NH2
4
+ NH3 
+ H2O
Benzoic acid Ammonium
Benzamide
benzoate
Phthalimide synthesis:
Phthalic acid on reaction with ammonia forms ammonium phthalate which upon heating
looses molecules of H2O forming phthalamide, this upon further strong heating looses a
molecule of NH3 forming phthalimide.
COOH COONH CONH2 CO
4  
+ 2 NH 3 NH
- 2 H2O - NH3
COOH CONH2 CO
COONH
4
Phthalic acid Ammonium phthalate Phthalamide Phthalimide
III. Reactions involving –COOH group:

1. Reduction: When carboxylic acids are treated with reducing agents like lithium
aluminium hydride or diborane, they get reduced to primary alcohols.

General reaction: 1) LiAlH4 /
R-COOH Ether R-CH2-OH
0
Carboxylic acid 2) H3O+ 1 Alcohol
Example:
1) LiAlH4 / Ether CH -CH -OH
CH3-COOH 2) H3O+ 3 2
Ethanoicacid Ethanol
Note:
1. Diborane is the better reducing agents for reduction of carboxylic acid.
2. Diborane does not easily reduce other functional group like ester (-COO-), nitro (-NO2),
halo (-X) etc.
3. Sodium borohydride does not reduce carbonyl group (-CO-).
2. Decarboxylation:
a) Using soda lime: Sodium salts of carboxylic acid on heating with sodalime
(NaOH + CaO) gives alkanes containing one carbon atom less than the corresponding
carboxylic acid. Hence this reaction can be used for descent in series (i.e. decreasing
number of carbon atoms).
Note: Sodalime is mixture of (NaOH + CaO) in a ratio of (3:1)
General reaction: CaO

R-COONa + NaOH  R-H + Na2CO3
Sodium carboxylate Alkane
Example: CaO
CH3-COONa + NaOH CH4 + Na2CO3

Sodium ethanoate Methane
(Sodium acetate)
b) Kolbe’s electrolytic method:

When aqueous solution of sodium or potassium salts of carboxylic acids are electrolysed,
reduction takes forming higher alkanes and liberating CO2 gas at the anode and hydrogen
gas at cathode.
General reaction: Electrolysis
2 R-COONa + 2 R-R + 2 CO2 + 2 NaOH + H2
H2O Alkane
Sodium carboxylate
Mechanism: -
R-COONa R-COO +
Sodium Na
- + +
2 H 2O OH + H
At - R-R + 2 CO 2 -
2 R-COO + 2e
At - -
2 H 2O + 2 e H2 + 2 OH
Example: Electrolysis
2 CH3-COONa + 2 CH3-CH3 + 2 + 2 NaOH + H2
H2O CO2
Sodium ethanoate Alkane
(Sodium acetate)

IV. Substitution reactions in the hydrocarbon part:
1. Halogenation: Hell – Volhard – Zelinsky reaction
Carboxylic acids containing α H- atom on treating with halogens like Chlorine or Bromine
in presence of small amount of red phosphorous , the get halogenated at α –position

forming α -halo carboxylic acids this reaction is known as Hell – Volhard – Zelinsky
reaction.
General reaction: 1) X2 / Red

R-CH2-COOH P R-CH-COOH
Carboxylic acid 2) H2O
X
 halocarboxylicacid
Example: 1) Cl2 / Red P CH -COOH
CH 3-COOH 2) H2O 2
Ethanoic acid Cl
(Acetic acid)
Chloro aceticacid
2. Ring substitution: Aromatic Carboxylic acids undergo electrophilic substitution reactions

forming meta – substituted products since -COOH group is a deactivating meta directing
group
Note: Benzoic acid does not undergo Friedel craft’s alkylation. Since -COOH group is
deactivating group & AlCl3 (Lewis acid) gets bonded to the carbonyl group.
a) Nitration:
Benzoic acid on heating with nitrating mixture forms m-nitrobenzoicacid
COOH COOH
Conc. H2SO4
+ HNO + H 2O

3
NO
2
Benzoic acid m-Nitrobenzoic acid
b) Halogenation:
Benzoicacid on treating with Bromine in presence of FeBr3 gives m- Bromobenzoicacid
COOH COOH
FeBr3
+ Br2 + HBr
Br
Benzoic acid m-bromo benzoic acid
Uses of Carboxylic Acids:

 Methanoic acid is used in rubber, textile, dyeing, leather and electroplating industries.
 Ethanoic acid is used as solvent and as vinegar in food industry.
 Hexanedioic acid is used in the manufacture of nylon-6, 6.
 Esters of benzoicacid are used in perfumery. Sodium benzoate is used as a food
preservative.
 Higher fatty acids are used for the manufacture of soaps and detergents.
***************

CHAPTER: 13
AMINES
Amines are alkyl or aryl or aralkyl derivatives of ammonia. They are obtained by replacing
one or more number of hydrogen atoms of ammonia by these groups.
Classification of amines:
I. Based on the nature of R- group:
1. Aliphatic amines:
Amines containing aliphatic carbon chain (open / closed chain) are called aliphatic
amines.
Example: CH3-NH2 CH3-CH2-NH2 CH3-NH-CH 3
Methanamine Ethanamine N-Methylmethanamine

(Methylamine) (Ethylamine) (Dimethylamine)
CH3
CH3-CH2-NH-CH 2-CH3 CH3-N-CH3
N-Ethylethanamine N,N-dimethylmethanamine
(Diethylamine) (Trimethylamine)
2. Aromatic amines:
Amines containing at least one benzene ring in them are called aromatic amines.
NH2
NH-CH 3 N(CH 3)2
Example:
Benzenamine N-Methylbenzenamine N,N-Dimethylbenzenamine

(Aniline) (N-Methylaniline) (N,N-Dimethylaniline)
II. Based on the number of H-atoms replaced per molecule of ammonia by alkyl / aryl
group:
1. Primary amine: These are obtained by replacement of one hydrogen atom of ammonia
by alkyl / aryl / aralkyl group. They are generally represented as R-NH2.
Example: CH3-NH2 CH3-CH2-NH2 CH3-CH2-CH2-NH2
Methanamin Ethanamine Propanamine
e
(Methylamine) (Ethylamine) (Propylamine)
2. Secondary amines: These are obtained by replacement of two hydrogen atoms of

ammonia by alkyl / aryl/ aralkyl group. They are generally represented as R2-NH.
Example: CH3-NH-CH 3 CH3-CH2-NH-CH 2- CH3-NH-CH 2-CH3
N-Methylmethanamine CH3 N-Methylethanamine
N-Ethylethanamine
(Dimethylamine) (Diethylamine) (Ethylmethylamine)

3. Tertiary amines: These are obtained by replacement of all hydrogen atoms of ammonia
by alkyl / aryl /aralkyl group. They are generally represented as R3-N.
CH3 CH3
Example: CH3-N-CH3 CH3-N-CH2-CH3
N,N-dimethyl methanamine N,N-dimethyl ethanamine
(Triethylamine) (Ethyldimethylamine)
Nomenclature:
Amine Common Name IUPAC Name

CH3-CH2-NH2
Ethyl amine Ethanamine
CH3-CH2-CH2-NH2
n-Propyl amine Propanamine
NH2
CH3-CH-CH3 Isopropylamine Propan-2-amine
CH3-NH-CH 2-CH3
Ethylmethylamine N-Methylethanamine
CH3
N,N-dimethylmethanamine
CH3-N-CH3 Trimethylamine
CH2-CH3
CH3-CH2-N-CH2-CH2-CH2-CH3
Diethylbutylamine N,N-Diethylbutan-1-amine
NH 2-CH2-CH=CH2
Allylamine Prop-2-en-1-amine
NH2-(CH2)6-NH2 Hexamethylenediamine
Hexane-1,6-diamine
NH2
Aniline Benzenamine
NH2
CH3
o-Toluidine 2-Methylaniline
NH2
P-Bromoaniline 4-Bromobenzenamine
Br
N(CH 3)2
N,N-Dimethylbenzenamine
Phenyldimethylamine

PREPARATION OF AMINES:
1. From Nitro hydrocarbons:
Nitro-hydrocarbons upon reduction by catalytic hydrogenation (H2 /Ni, H2 /Pd, H2 / Pt, etc.)
or by using metals in acidic medium like Sn/HCl or Fe / HCl etc. They get reduced to
respective amines.
General Reaction: Ni
R-NO2 + 3 H2 R-NH2 + 2 H2O
Nitroalkane Alkanamine
Example: CH3-NO2 + 6 Sn / HCl
CH3-NH2 + 2 H2O
[H]
Nitro methane Methanamine
NO2
NH
2
Fe / HCl
+ 6 [H] + 2 H 2O
Nitro benzene Aniline

Note:
a. Amine group cannot be directly introduced into the benzene ring. However, nitro group
can be directly introduced in to benzene ring by nitration reaction. Hence during
conversion of benzene to aniline, benzene is first converted to nitrobenzene and then
reduced to aniline.
b. Fe / HCl is the better reducing agent for reduction of nitro compounds. Since, FeCl2
formed during the process gets hydrolysed and releases HCl during the reaction, which
initiates the reaction further. Hence only small amount of HCl is required to initiate the
reaction.
2. From Alkyl halides (Ammonolysis):

When alkyl halides are heated with ammonia to a temperature of 373K in a sealed glass
tube successive alkylation takes place leading to the formation of primary amine,
secondary, tertiary and quaternary ammonium halide.
General Reaction: 
R-X + NH3 R-NH2 + HX
373 K 0
1 amine
R-NH2+ R-X R-NH-R + HX
0
2 amine
R
R-NH-R + R-X R-N-R + HX
0
R 3 amine
+ -
R-N-R + R-X [R4 N] X
Quaternary ammonium
Halide

Example: CH -Cl + NH 
3 3 CH3-NH2 + HCl
Methyl chloride 373 K
Methanamine
CH3-NH2+ CH3-Cl
CH3-NH-CH 3 + HCl
N-Methyl methanamine
CH3
CH3-NH-CH 3+ CH3- CH3-N-CH3 + HCl
Cl N,N'- Dimethyl
Methanamine
CH3 + -
CH3-N-CH3 + CH3-Cl [(CH3)4 N] Cl
Tetramethyl ammonium
chloride
Note:
a. In this method, a mixture of amines is obtained. However, only primary amines can be
obtained when excess of ammonia is taken.
b. In this process, ammonium salt is obtained because hydrohaloacids which are
obtained as by-products reacts with the amines so obtained to form salt since, amines
are basic in nature. They can be converted back to amines by treating it with a
stronger alkali than amine such as KOH/NaOH.
+ -
R-NH + NaOH R-NH2 + NaX + H2O
3
Ammonium salt Amine
c. Cleavage of C-X bond by ammonia molecule is known as ammonolysis. (It is a
Nucleophilic substitution reaction).
d. Only alkyl / aralkyl / amines undergo ammonolysis where as aromatic amines do not
because it is a Nucleophilic substitution reaction.
e. Order of reactivity of halides with amines is RI > RBr > RCl.
3. From Nitriles:
When alkane nitriles or aromatic nitriles are treated with lithium aluminium hydride or
sodium amalgam in presence of ethanol, they get reduced to primary amines.
General Reaction: LiAlH 4

R-CN + 4 [H] R-CH2-NH2
Alkanitrile Amine
Na-Hg / C2H5OH
Example: CH3-CN + 4 [H] CH3-CH2-NH2
Ethyl Nitrile Ethanamine
CN
CH2-NH 2
Pt
+ 2 H2
Cyano benzene
Phenylmethanamine
(Benzyl amine)
Note: This reaction is used in ascent in series.

4. From Amides:
i)
Reduction: When amides are reduced using LiAlH4 they get reduced to respective
amines.
O
LiAlH 4
General Reaction: R-C-NH2 + 4 [H] R-CH -NH + H2O
2 2
Amide Amine
O
Example: CH -C-NH + 4 [H] LiAlH 4 CH -CH -NH + H O
3 2 3 2 2 2
Acetamide Ethanamine
O
C-NH2 CH2-NH2
+ 4 [H] LiAlH 4
+ H 2O
Benzamide
Phenyl methanamine
(Benzyl amine)
ii)
Hoffmann’s Bromamide
Reaction:
When amides are heated with bromine and NaOH / KOH (alcoholic / aqueous)
Hoffmann’s bromamide degradation takes place leading to the formation of amines
containing one carbon atom less than the respective amide.
O

General Reaction: R-C-NH2 + Br2 + 4 NaOH R-NH2 + Na2CO3
+ 2 NaBr + 2 H2O
Amide Amine
O
Example: CH -C-NH + Br + 
CH3-NH2 + Na2CO3 + 2 NaBr + 2 H2O
3 2 2 4 NaOH
Acetamide Methanamine
O
C-NH2 NH2

+ Br2 + 4 NaOH + Na2CO3 + 2 NaBr + 2 H2O
Benzamide Anilin
e
Note: This reaction is used in descent in series (To decrease number of C- atoms).
5. Gabriel phthalimide synthesis:

When phthalimide is treated with alcoholic KOH potassium phthalimide is obtained. That
upon heating with alkyl halide or aralkyl halide, N-alkyl phthalimide or N-aralkyl
phthalimide is obtained which upon alkaline hydrolysis with NaOH gives respective alkyl
amine or aralkyl amine along with formation of sodium salt of phthalic acid.
CO
NH + KOH CO CO COONa
- +
+ R-X N-R + 2 NaOH + R-NH
N -K 2
-H2O
CO CO CO COONa
0

Phthalimide Potassium phthalimide N-Alkylphthalimide Sodium phthalate 1 Amine

Note:
a. Aryl amines or aromatic primary amines cannot be prepared by this method because
aryl halides do not undergo Nucleophilic substitution reaction with phthalimide anion.
b. By this method pure primary amines can be prepared.
1. Physical state and smell:

 The lower aliphatic amines are gases with fishy odour.
 Primary amines with three or more carbon atoms are liquid and still higher ones are solid.
 Aniline and other arylamines are usually colourless but get coloured on storage due to
atmospheric oxidation.
2. Solubility:
Lower aliphatic amines are soluble in water because they can form hydrogen bonds with
water molecules. However, solubility decreases with increase in molar mass of amines
due to increase in size of the hydrophobic alkyl part. Therefore, higher amines containing
six or more carbon atoms are insoluble. Because of their weak hydrogen bonds, the
solubility of amines in water is less than that of alcohols. This is because electronegativity
of nitrogen (3.0) than that of oxygen (3.5) and therefore, amines form weaker hydrogen
bonds as compare to alcohols. Amines are soluble in organic solvents like alcohol, ether
and benzene.
3. Boiling point:
Primary and secondary amines are engaged in intermolecular association due to
hydrogen bonding between nitrogen of one and hydrogen of another molecule. This
intermolecular association is more in primary amines than in secondary amines as there
are two hydrogen atoms available for hydrogen bond formation in it. Tertiary amines do
not have intermolecular association due to the absence of hydrogen atom available for
hydrogen bond formation.
The order of boiling points of isomeric amines is Primary > Secondary > Tertiary.
Intermolecular hydrogen bonding in primary amines is as shown below.
.......H R H.......
R-N-H............N-H..............N-R
H
: H
: Hydrogen bond
.......
H-N-R
H.......
Boiling points of amines, alcohols and alkanes of almost the same molar mass are shown
below.

Compound Molecular mass Boiling point
n-C4H9NH2 73 350.8
(C2H5)2NH 73 329.3
C2H5N(CH3) 73 310.5
C2H5CH(CH3)2 72 300.8
n-C4H9OH 74 390.3
Difference in electronegativity between nitrogen and hydrogen atoms and the
presence of unshared pair of electrons over the nitrogen atom makes amines reactive. The
number of hydrogen atoms attached to nitrogen atom also decides the course of reaction of
amines; that is why primary (R-NH2), secondary (R2-NH) and tertiary amines (R3-N) differ in
many reactions. Moreover, amines behave as nucleophiles due to the presence of unshared
electron pair. Some of the reactions of amines are described below:
1. BASIC CHARACTER OF AMINES:

Amines are basic in nature (Lewis bases) due to the presence of lone pair of electrons on
N-atom of the amine group hence reacts with acids to form salts.
.. + -
R-NH2 + HX R-NH3 X
Salt
.. + -
NH2 NH3 Cl
+ HCl
Aniline Anilinium chloride
Reaction of amines with mineral acids to form ammonium salts shows that these are basic
in nature.
Salts of amines on treatment with a base stronger than amines like NaOH, regenerate the
parent amine back.
+ - -
R-NH X + OH R-NH2 + H2O + X
2
Amine salts are soluble in water but insoluble in organic solvents like ether. This reaction
is the basis for the separation of amines from the non basic organic compounds which are
insoluble in water.
Basic character of amines can be better understood in terms of their K b and pKb values as
explained below:
3 +O
R- + -
2+ H2O R-NH
NH

[RNH + ][OH- ] [RNH + ][OH-
K= K[H2O] = ]
[RNH2 3][H2O] 3
 Kb
[RNH2 ]
pKb= -log Kb
Larger the value of Kb or smaller the value of pKb, stronger is the base.
The pKb values of few amines are given below.
Base pKb value
Methanamine 3.38
N-Methylmethanamine 3.27
N,N-Dimethylmethanamine 4.22
Ethanamine 3.29
N-Ethylethanamine 3.00
N,N-Diethylethanamine 3.25
Benzeneamine 9.38
Phenylmethanamine 4.70
N-Methylaniline 9.30
N,N-Dimethylaniline 8.92
 pKb value of ammonia is 4.75.

 Aliphatic amines are stronger bases than ammonia due to +I effect (electron
donating nature) of alkyl groups leading to high electron density on the nitrogen atom.
Their pKb values lie in the range of 3 to 4.22.
 Aromatic amines are weaker bases than ammonia due to -I effect (electron
withdrawing nature) of the aryl group. [+M effect also operates over here]
You may find some discrepancies while trying to interpret the K b values of amines on the
basis of +I or –I effect of the substituent’s present in amines. Besides inductive effect,
there are other effects like solvation effect, steric hinderance, etc., which affect the basic
strength of amines.
STRUCTURE-BASICITY RELATIONSHIP OF AMINES:

Basicity of amines is related to their structure. Basic character of amines depends upon the
ease of formation of the cation by accepting a proton from the acid. The more stable the

cation formed, more basic is the amine. i.e. the basicity of amines depends on the
ease of

donation of lone pair of electrons greater the ease of donation of lone pair of electrons
greater is the basic strength and vice versa.
(a) Alkanamines versus ammonia:

Let us consider the reaction of an alkanamine and ammonia with a proton to compare their
basicity.
H H
+
R-N: + R-N -H
+ H
H H
Amine Amine cation
H H
+
H- + H-N -H
+ H
N: H
H
Ammonia Ammonium ion
Due to the electron releasing nature of alkyl group, the electron density on nitrogen
increases nitrogen and thus the unshared electron pair is more available for sharing with
the proton of the acid. Moreover, the substituted ammonium ion formed from the amine
gets stabilised due to dispersal of the positive charge by the +I effect of the alkyl group.
Hence, alkylamines are stronger bases than ammonia. Thus, the basic nature of
aliphatic amines should increase with increase in the number of alkyl groups. This trend is
followed in the gaseous phase. The order of basicity of amines in the gaseous phase
follows the expected order:
Tertiary amine > Secondary amine> Primary amine > NH3
The trend is not regular in the aqueous state as evident by their pK b values given in the
above table.
In the aqueous phase, the substituted ammonium cations get stabilised not only by
electron releasing effect of the alkyl group (+I) but also by solvation with water
molecules.
Greater the size of the ion, lesser will be the solvation and the less stabilised is the ion.
The order of ions stability is as follows:
OH2
H
R OH R
H 2
R-N+ -H OH2 > N
+
> R N
+
H OH2
R H OH2 R
H
OH2
0 1 Amine
0
2 Amine

Decreasing order of extent of H- bonding in water and order of stability of ions by solvation
Greater is the stability of the substituted ammonium cation, stronger should be the
corresponding amine as a base. Thus, the order of basicity of aliphatic amines should be,
primary amine > secondary amine > tertiary amine, which is opposite to the
inductive effect based order. Secondly, when the alkyl group is small, like –CH 3 group,
there is no steric hindrance to H-bonding. In case the alkyl group is bigger than –CH 3
group, there will be steric hinderance to H-bonding. Therefore, the change of nature of the
alkyl group, e.g., from –CH3 to –C2H5 results in change of the order of basic strength. Thus,
there is a subtle interplay of the inductive effect, solvation effect and steric
hinderance of the alkyl group which decides the basic strength of alkyl amines in
the aqueous state.
The order of basic strength in case of methyl substituted amines and ethyl substituted
amines in aqueous solution is as follows:
(CH3)2NH >CH3NH2 > (CH3)3N >NH3
(C2H5)2NH> (C2H5)3N > C2H5NH2 >NH3
(b) Arylamines versus ammonia:

pKb value of aniline is quite high, since in aniline or other arylamines, the -NH 2 group is
attached directly to the C-atom of the benzene ring, this results in the unshared electron
pair on nitrogen atom to be in conjugation with the benzene ring and thus making it less
available for protonation.
..
+ + ..
+
NH2 NH2 NH2 NH2 NH2
On the other hand, anilinium ion obtained by accepting a proton can have only two
resonating structures.
+ +
NH NH
3 3
Resonating structures of Anilinium ion
Greater the number of resonating structures, greater is the stability. Thus you can infer
that aniline (five resonating structures) is more stable than anilinium ion. Hence, the
proton acceptability or the basic nature of aniline or other aromatic amines would be less

than that of ammonia.

In case of substituted aniline, it is observed that electron releasing groups like –OCH3,
–CH3 increase basic strength whereas electron withdrawing groups like –NO2, –SO3, –
COOH, –X decrease it.
Alkanamines > Ammonia > Aryl amines
2. Alkylation: primary amines on heating with alkyl halides in a sealed glass tube to a
temperature of 1000C (373 K) successive alkylation takes place leading to the formation
of secondary amines, secondary amines and Quaternary ammonium halide.
General Reaction: 373 K

R-NH R-NH-R + HX
0 2+ R-X 0
1 amine 2 amine
373 K R
R-NH-R + R-X R-N-R + HX
0
R 3 amine
R-N-R + R-X 373 K + -
[R4 N] X
Quaternary ammonium
halide
Example: CH3-NH2 + CH3-Cl 373 K CH3-NH-CH 3 + HCl

Methyl chloride N-Methyl methanamine
CH3
373 K
CH3-NH-CH 3 + CH3- CH3-N-CH3 + HCl
Cl N,N'- Dimethyl
Methanamine
CH3 +
373 K -
CH3-N-CH3 + CH3-Cl [(CH3)4 N] Cl
Tetramethyl ammonium
chloride
Note: This reaction is used to distinguish between primary, secondary and tertiary
amines.
Experiment Observation Inference

a) Reacts with three moles of alkyl
halide to form final product a) Primary amine.
quaternary ammonium salt.
b) Reacts with two moles of alkyl

Amine + Alkyl halide, heat halide to form final product b) Secondary amine.
c) Reacts with one mole of alkyl

halide to form final product c) Tertiary amine.

3. Acylation:
When aliphatic / aromatic primary and secondary amines are treated with carboxylic acid
derivatives such as acid chlorides, acid anhydrides and esters in presence of a stronger
base than amine like Pyridine (C5H5N) they react to form N-substituted amides or N,N-
disubstituted amides depending on the nature of the amines.
General C5H5N
Reaction: R-NH + R'COCl R'-CO-NH- + HCl
20 R
1 Amine N-substituted amide
R02-NH C5H5N
+ R'COCl R'-CO-N-R 2 + HCl
2 Amine N,N-disubstituted amide
Example: C5H5N
C2H5-NH2 + CH3COCl CH3-CO-NH-C + HCl
2H 5
Ethanamine Ethanoyl chloride N-Ethylacetamide
(C H ) -NH
+ CH COCl C5H5N CH -CO-N-(C H ) + HCl
2 5 2 3 3 2 5 2
Ethanamine Ethanoyl chloride N,N-Diethylacetamide
NH2 NH-CO-CH 3
C5H5N
+ (CH3CO) 2O + CH3COOH
Aniline Acetic anhydride Acetanilide

(N-Phenylacetamide)
Note:
1.
The reaction is carried out in presence of pyridine (C5H5N) since the HCl formed
during the reaction will be removed by reaction and the equilibrium shifts towards
right side.
2.
30amines do not undergo acylation reaction since they do not contain any H- atom
bonded to N- atom of amine group.
4. Carbylamine reaction:
When aliphatic or aromatic primary amines are heated with a mixture of chloroform and
alcoholic KOH, the foul smelling substance called as alkyl isocyanides or carbylamines
are obtained.
General Reaction:
R-NH2 + CHCl 3 + 3 KOH(alc) R-NC + 3 KCl + 3 H 2O

0
1 amine alkyl Isocyanide
Example:

CH3-NH2 + CHCl 3 + 3
CH3-NC + 3 KCl + 3 H 2O
KOH(alc)
Methanamine (Methylisocyanide)
Ethylcarbylamine
NH2 NC
+ CHCl 3+ 3 KOH(alc)
+ 3 KCl + 3 H2O

Aniline Phenylisocyanide

Note: Secondary and tertiary amines do not undergo carbylamine reaction. Hence this
reaction can be used to test primary amines.
5. Reaction with nitrous acid:

Aliphatic and aromatic primary amines react with nitrous acid in different manner
Aliphatic primary amines on reaction with nitrous acid at a temperature of 00C to 50C
forming aliphatic diazonium salts which being highly unstable gets hydrolysed to alcohols
with liberation of quantitative amount of nitrogen gas.
General Reaction: R- + + 2 HCl [R-N +Cl -] + H O R-OH + N + HCl

NH NaNO
2 2 -NaCl, H2O 2 2 -HCl 2
Aliphatic Aliphatic Alcohol
amine diazonium salt
+ -
Example:
CH3-NH2 + NaNO 2 + 2 -NaCl, H2O [CH3-N2 Cl ] + H2O -HCl
CH3-OH + N2 + HCl
HCl
Methanamine Methyl Methanol
diazonium chloride
Aromatic primary amines like benzene on reaction with nitrous acid at a temperature of
00C to 50C forming benzene diazonium chloride.
NH2 +
N2-Cl
+ NaNO 2 + 2 + NaCl + 2 H2O

HCl
Aniline Benzene diazonium chloride
Note:
1) Benzene diazonium chloride is highly unstable; hence it is used as soon as it is
prepared.
2) 20 and 30 amines react with nitrous acid in different manner.
6. Reaction with aryl sulphonyl chloride:

When primary and secondary amines are treated with aryl sulphonyl chloride such as
benzene sulphonyl chloride (C6H5SO2Cl) which is also known as Hinsberg’s reagent gives
N- substituted benzene sulphonamide and N,N-Disubstituted benzene sulphonamide
respectively.
General reaction:
R-NH2 + C6H5SO2Cl C6H5SO2-NH-R + HCl
Amine Benzene Sulphonyl N-Alkyl benzene
Chloride Sulphonamide
Example:
CH3-CH2-NH2 + C6H5SO2Cl C6H5SO2-NH-CH 2-CH3 HCl
+
Ethanamine Benzene Sulphonyl N-Ethyl benzene
C 2H 5- Chloride Sulp
NH-
C 2H 5 + C 2H

C6H5SO2Cl C6H5SO2-N-C2H5
+ HCl
Diethyl amine Benzene Sulphonyl N,N-Diethyl benzene
Chloride Sulphonamide

Note:
1. N-Ethyl benzene sulphonamide is acidic in nature because the hydrogen bonded to the
nitrogen is easily eliminated as H+ due to the strong electron withdrawing effect of
sulphonyl group. Hence it is soluble in alkali where as N,N-Diethyl benzene sulphonamide
is not acidic because it does not contain any H-atom bonded to nitrogen atom hence it is
insoluble in alkali.
2. Tertiary amines do not react with aryl sulphonyl chloride; hence this reaction can be used
to distinguish between 10, 20 and 30 amines and also for separation of mixture of amines.
3. Now a day’s benzene sulphonyl chloride is replaced by p-toluene sulphonyl chloride.
Electrophilic substitution reaction of Aniline:
Resonating structures of aniline:

.. + + ..
+
NH2 NH2 NH2 NH2 NH2
Looking to the resonating structures of aniline it is seen that the negative charges are
developed at ortho and para positions, therefore –NH2 group is a o, p- directing in nature,
hence aniline upon electrophilic substitution reaction gives o, p- substituted products.
Note: –NH2 group is a o, p- directing and it is an activating group.
1. Bromination: Aniline reacts with bromine water at room temperature forming a white
precipitate of 2,4,6-tribromo aniline.
NH2 NH2
Br Br
Example: + 3 Br2 + 3 HBr
Br
Aniline 2,4,6-tribromo aniline
Since -NH2 group is an activating group; substitution takes place at all the ortho and para
positions. However monosubstituted bromoaniline can be obtained upon protection of the
–NH2 group by acylation. Aniline reacts with acetic anhydride in presence of pyridine to
form acetanilide, which upon reaction with bromine water in presence of acetic acid gives
p-bromoacetanilide as major product; this upon acid hydrolysis gives p-bromoaniline.

O O
.. .. .. ..
NH2 NH-C-CH3 NH-C-CH3 NH2
CH3COOH H2O / H+
+ (CH3-CO)2O C5H5N + Br2 + CH3COOH
- CH3COOH - HBr
Acetic Br Br
Anilin anhydride Acetanilide p-Bromoacetanilide p-Bromoaniline Aceticacid
e
Resonating Structures:
..-
: O: O :
.. :
NH-C-CH3 NH=C-CH 3
Amine group upon protection gives the above mentioned resonating structure of lone pair
of electrons of nitrogen atom. As a result of this, the lone pair of electrons will not be
available for donation to the benzene ring. Therefore –NHCOCH3 group becomes a
deactivating group or less activating group than –NH2 group hence only mono substituted
product is obtained.
Note: In the above reaction p-substituted product is obtained as major product due to the
steric hinderance caused by –NHCOCH3 group. Hence Br+ electrophile cannot approach
o-position. Hence p-Bromo product is obtained as a major product.
2. Nitration:
Aniline on nitration at 288K gives tarry oxidation products (Oxidised products of aniline in
addition to nitro derivative) a mixture of o-Nitroaniline, m-Nitroaniline and p-Nitroaniline.
Note:
i)
The –NH2 group of aniline even though being o, p-directing in nature, in this reaction even
meta products are obtained because in strongly acidic medium, aniline gets protonated
forming anilinium ion which is meta directing in nature.
.. + -
NH NH3 Cl
2
+ HCl
Aniline anilinium ion

ii)
Aniline upon direct nitration gives Tarry products in addition to nitro derivatives.(Tarry
products are oxidised products of aniline)
..
NH2 NH2 NH2 NH2
NO2
Conc. HNO3
3 + 3 HNO + + + 3 H2O
298 K
3 NO2
NO2
Aniline o-nitro aniline m-nitro aniline p-nitro aniline
(2%) (47%) (51%)

However, mononitrated products can be obtained by protecting the amine by acylation group.
O O
.. .. .. ..
NH2 NH-C-CH3 NH-C-CH3 NH2
H2O / H+
+ (CH3-CO)O C5H5N + HNO 3Conc. H2SO4 298 K + CH3COOH
- CH3COOH
Acetic NO2 NO2

Aniline anhydride Acetanilide p-nitro acetanilide p-nitro aniline Acetic acid
3. Sulphonation:
When aniline is treated with conc. H 2SO4 it forms anilinium hydrogen sulphate which upon
heating with concentrated sulphuric acid to a temperature of 453-473K gives p-amino
benzene sulphonic acid as major product which is commonly called as sulphanilic acid.
.. .. + - ..
NH2 NH3 HSO 4 NH2

+ H2SO4 + H 2O
453K - 473
K
SO3H
Aniline anilinium hydrogen p-amino benzene
sulphate sulphonic acid
(sulphanilic acid)
Note: Sulphanilic acid contains both basic –NH 2 group and acidic –SO3H group in the
same molecule hence internal neutralisation takes place leading to the formation of a
zwitter ion.
.. +
NH2 NH3
-
SO3H SO
3
p-amino benzene Zwitter ion
sulphonic acid
4. Acylation:
Note:
Aniline does not undergo Friedel crafts alkylation or acylation because the catalyst used in
this reaction i.e, anhydrous AlCl3 catalyst is acidic in nature (Lewis acid), aniline being basic
in nature reacts with it and hence forms salt with aniline and thus prevent aniline from
undergoing alkylation or acylation reaction because that salt becomes a strongly deactivating
group for further reaction.
Diazonium salts: They are generally represented as RN2+X- where X- is Cl-, Br-, HSO4-, BF4-, etc.
‘R’ may be either alkyl or aryl groups.

Generally, alkyl diazonium halides are highly unstable but aromatic diazonium halides are
stable at a temperature range of 0 0-50C due to the resonating structures of diazonium ion as
shown below.
+ .. ..
+ .. + .. + + ..
NN: N N: N N N: NN:
N:
+ +
+
Resonating structures of diazonium ion
Note: N +2 is called as diazonium group.
Nomenclature of diazonium salts: They are named by suffixing the name diazonium group
to the name of parent hydrocarbon from which they are formed, followed by the name of the
anion such as chloride, bromide, Hydrogen sulphate, fluroborate etc...
Example: + -
C6H5N2 HSO 4 Benzene diazonium hydrogen sulphate
+ -
C6H5N2 BF4 Benzene diazonium fluro borate
+ -
C6H5N2 Cl Benzene diazonium chloride
Preparation of diazonium salts:

Aniline reacts with sodium nitrite in presence of hydrochloric acid at a temperature of 00C to
50C diazotisation reaction takes place leading to the formation of benzene diazonium
chloride.
NH2 +
N2-Cl
+ NaNO 2 + 2 + NaCl + 2 H2O

HCl
Aniline Benzene diazonium chloride
Note: Benzene diazonium chloride is highly unstable; hence it is used as soon as it is

prepared.
Chemical properties of Diazonium salts:

Reactions of diazonium salts are broadly classified in to two categories namely:
I. Reactions involving displacement of Nitrogen
II. Reactions involving retention of diazo-group
III. Reactions involving displacement of Nitrogen:
I. Reactions involving displacement of Nitrogen
1. Sandmeyer’s reaction:
Replacement by Halogens such as Cl2, Br2 and by cyanide ion:

When benzene diazonium chloride is treated with Cu2Cl2/HCl or Cu2Br2/HBr or
CuCN/HCN corresponding haloarenes or cyano benzene is obtained. .This reaction is
known as Sandmeyer’s reaction.
+
N2-Cl Cl
Cu2Cl2 / HCl
+ N2
Benzene diazonium chloride Chloro benzene

+
N2-Cl Br
Cu2Br2 / HBr
+ N 2
Benzene diazonium chloride Bromo benzene

+
N2-Cl CN
CuCN / KCN
+ N 2
Benzene diazonium chloride Cyano benzene
2. Gatterman reaction: Benzene diazonium chloride reacts with halogen acids like HCl and
HBr in presence of copper powder forming respective haloarenes .This reaction is known
as Gatterman reaction.
Note: Good yields of haloarenes are obtained in Sandmeyer’s reaction than Gatterman
reaction.
+
N2-Cl Cl
HCl / Cu
+ N 2+ CuCl
Benzene diazonium chloride Chloro benzene

+
N2-Cl Br
HBr / Cu
+ N2 + CuCl
Benzene diazonium chloride Bromo benzene
Note: Better yields of Diazonium halides are obtained by Sandmeyer reaction than in
Gatterman reaction.
3. Replacement by iodide ion: Benzene diazonium chloride reacts with potassium iodide
to form iodobenzene.

+
N2-Cl I
+ KI + N2 + KCl
Benzene diazonium chloride Iodo benzene
Note: Iodine group cannot be easily introduced to the benzene ring by direct iodination
because the HI obtained during the reaction reduces the iodobenzene back to benzene
hence iodobenzene is prepared easily by this method and by Finkelstein reaction.
4. Replacement by fluoride ion:

Benzene diazonium chloride reacts with fluroboricacid (HBF 4) to form benzene diazonium
fluroborate, which on heating decomposes to give flurobenzene.
+
+
N2-Cl
N2-BF4 F
+ HBF 4 + N2 + BF3
-HCl 
Benzene diazonium chloride
Benzene diazonium Fluro benzene
Fluro borate
5. Replacement by hydrogen: Benzene diazonium chloride upon reaction with mild

reducingreagents like hypophosphorous acid [H3PO2 (Phosphonic acid)] or ethanol it
gets reduced to benzene and reducing agents gets oxidised to phosphorous acid or
ethanal respectively.
+
N2-Cl H
+ H3PO2 + H2O + N2 + H3PO3 + HCl
Benzene diazonium chloride Benzene

+
N2-Cl H
+ CH3-CH2-OH + N2 + CH3-CHO + HCl
Benzene diazonium chloride Benzene
6. Replacement by hydroxyl group:

Benzene diazonium chloride upon hydrolysis at a temperature of 283K gets hydrolysed
to phenol.

+
N2-Cl OH
+ H2O + N2 + HCl
283
K
Benzene diazonium chloride Phenol
7. Replacement by nitro group:

Benzene diazonium chloride reacts with fluroboricacid to form benzene diazonium
fluroborate, which on heating with aqueous solution of sodium nitrite in presence of Cu,
nitrobenzene is obtained.
+
+
N2-Cl NO2
N2-BF4
Cu
+ HBF 4 -HCl + NaNO 2 + N2 + NaBF 4

Benzene diazonium chloride
Benzene diazonium Nitrobenzene
Fluro borate
II. Reactions involving retention of diazo-group:

1. Preparation of p-hydroxy azo benzene (orange dye):
Benzene diazonium chloride reacts with phenol in presence of a base such as NaOH
/KOH, coupling reaction takes place leading to the formation of p-hydroxy azo benzene
an orange dye.
+
N N-Cl + OH + NaOH N N OH + NaCl + H2O
Benzene diazonium chloride Phenol p-Hydroxy azo benzene

(Orange dye)
2. Preparation of p-amino azo benzene (Yellow dye):

Benzene diazonium chloride reacts with aniline in presence of a base such as NaOH
/KOH, coupling reaction takes place leading to the formation of p-amino azo benzene an
yellow dye.
+
N N-Cl + NH2 + NaOH N N NH2 + NaCl + H2O
Benzene diazonium chloride Aniline p-Amino azo benzene

(Yellow dye)
Note: Azo products obtained has an extended conjugation since both the aromatic rings
are joined through –N=N– bond hence they are often coloured and are used as dyes.

IMPORTANCE OF DIAZONIUM SALTS IN SYNTHESIS OF AROMATIC COMPOUNDS:
1. From the above reactions, it is clear that the diazonium salts are very good
intermediates for the introduction of –F, –Cl, –Br, –I, –CN, –OH, –NO 2 groups into the
aromatic ring.
2. Aryl fluorides and iodides cannot be prepared by direct halogenation.
3. The cyano group cannot be introduced to benzene by electrophilic substitution, but
cyanobenzene can be easily obtained from diazonium salt.
Thus, the replacement of diazo group by other groups is helpful in preparing
those substituted aromatic compounds which cannot be prepared by direct substitution in
benzene or substituted benzene.
Conversions:
1. Convert aniline to 1,3,5-Tribromobenzene.
2. 2-methylaniline to 3-Nitrotoluene.
3. 4- Nitrotoluene to 2- Bromobenzoicacid.
**************

CHAPTER: 14
BIOMOLECULES
INTRODUCTION:
A living system grows, sustains and reproduces itself. The most amazing thing about all
living system is that it is composed of non-living atoms and molecules. The pursuit of
knowledge of what goes on chemically within a living system falls in the domain of
biochemistry.
Living systems are made up of various complex biomolecules like
carbohydrates, proteins, nucleic acids, lipids, etc. proteins and carbohydrates are essential
constituents of our food. These biomolecules interact with each other and constitute the
molecular logic of life processes. In addition, some simple molecules like vitamins and
mineral salts also play an important role in the functions of organisms. Structures and
functions of some of these biomolecules are discussed in this Unit.
CARBOHYDRATES
The word Carbohydrate is derived from French word hydrate de carbone which means
hydrates of carbon having the formula Cn(H2O)n. But some carbohydrates do not obey
this formula and carbohydrates do not contain water molecules. Hence the word
Carbohydrate lost its significance.
Carbohydrates are polyhydroxy derivatives of aldehydes or ketones or yield such

compounds on hydrolysis. They have the general formula Cx(H2O)Y.
Ex: Glucose, Maltose, Starch etc.
Note: These are also called as saccharides due to their sweet taste. In Latin Saccharum
means sugar.
Classifications of carbohydrates:
I. Based on the number of simple units present per molecule: They are classified into
the following three types.
1) Monosaccharides 2) Oligosaccharides 3) Polysaccharides
1. Monosaccharides: Simplest carbohydrates which cannot be further hydrolyzed are

called monosaccharides. They have the general formula Cn(H2O)n.
Example: Ribose, glucose, fructose, galactose, mannose etc.
2. Oligosaccharides: Carbohydrates which on hydrolysis yield 2 to 10

monosaccharide units are called as oligosaccharides.
They are further classified as disaccharides, trisaccharides, tetrasaccharides etc.,
depending on the number of monosaccharide units present in them.
a) Disaccharides: Carbohydrates which on hydrolysis give two monosaccharide units

are called as disaccharides. They have the general formula Cn(H2O)n-1

Example:
Disaccharide Composition
Maltose Glucose + Glucose
Sucrose Glucose + fructose
Lactose Glucose + Galactose
b) Trisaccharides: Carbohydrates which on hydrolysis give three monosaccharide units

are called as trisaccharides. They have the general formula Cn(H2O)n-2 .
Example: Raffinose (Glucose + fructose + galactose)
3. Polysaccharides: Carbohydrates which on hydrolysis give a large number of

monosaccharide units (i.e >10 simple units) are called as polysaccharides.
POLYSACCHARIDE FUNCTION
STARCH The storage polysaccharide present in plants.
CELLULOSE The structural polysaccharide present in plants.
GLYCOGEN The storage polysaccharide present in animals.
II. Based on the taste and solubility:

They are classified into the following two types.
1) Sugars
2) Non-sugars
1. Sugars: Carbohydrates which are sweet to taste are called as sugars. They are
crystalline solids and soluble in water.
Example: All monosaccharides and oligosaccharides.
Classifications of sugars: Based on the action of sugars on Tollen’s reagent, Fehling’s

solution and Benedict’s reagent sugars are classified as follows.
a. Reducing sugars
b. Non – reducing sugars.
a. Reducing sugars: The sugars which reduce Fehling’s solution and Benedict’s reagent to
red precipitate of cuprous oxide or Tollen’s reagent into black precipitate of silver are called
reducing sugars.

Reducing sugars contain free aldehydic or ketonic group and hence they exist in α and β form.
Example: All monosaccharides and disaccharides like Maltose, Lactose etc.
b. Non – reducing sugars: The sugars which do not reduce Fehling’s solution and
Benedict’s reagent to red precipitate of cuprous oxide or Tollen’s reagent in to black
precipitate of silver are called non-reducing sugars.
Non-Reducing sugars do not contain free aldehydic or ketonic group and hence they donot
exist in α and β form.
Example: sucrose
2. Non-sugars: Carbohydrates which are not sweet to taste are called as non-sugars. They
are amorphous solids and are insoluble in water.
Example: All polysaccharides.
Classification of monosaccharides:
I. Based on the principal functional group: They are classified into the following two types.
1) Aldoses
2) Ketoses
1. Aldoses: Monosaccharides consisting of aldehyde as principal functional group are
called as Aldoses
Example: Glucose, galactose, ribose….etc.
2. Ketoses: Monosaccharides consisting of ketone as principal functional group are called

as Ketoses
Example: Fructose, sorbose….etc.
II. Based on the number of carbon atoms: They are classified into the following five types.
1) Trioses 2) Tetroses 3) Pentoses 4) Hexoses

5) Heptoses
1. Trioses: Monosaccharides consisting of three carbon atoms per molecule are called as
trioses.
Example: Glyceraldehyde
2. Tetroses: Monosaccharides consisting of four carbon atoms per molecule are called as
tetroses.
Example: Erythrose, threose
3. Pentoses: Monosaccharides consisting of five carbon atoms per molecule are called as
pentoses.
Example: Ribose, arabinose

4. Hexoses: Monosaccharides consisting of six carbon atoms per molecule are called as
Hexoses.
Example: Glucose, fructose, galactose, mannose
5. Heptoses: Monosaccharides consisting of seven carbon atoms per molecule are called
as Heptoses.
Example: Sedoheptulose
GLUCOSE (C6H12O6)
Glucose is a monosaccharide present in plants. It is an aldohexose; generally called as

Grape sugar because it is found in grapes to an extent of 20-30%.It is dextrorotatory hence
also called as dextrose.
Preparation:
1.
From sucrose (Cane sugar): Sucrose on boiling with dilute HCl or H2SO4 in alcoholic
medium, acid hydrolysis takes place forming equal amounts of glucose and fructose.
+
C H O
H O H
+ C H O
12 22 + C6H12O6
11  6 12 6
2
Sucrose Glucose Fructose
2.
From starch:
Starch on boiling with dilute H2SO4 at a temperature of 393K under 2-3 atm pressure, acid
hydrolysis take place forming only glucose.
(C6H O ) + +
10 5 n n H n C6H12O6
H2 O
Starch 393K, 2-3
atm Glucose
Elucidation of open chain structure of Glucose:
1. Molecular formula: From elementary analysis and molecular mass determination, the
molecular formula of glucose is found to be C6H12O6.
2. Parent carbon chain: Glucose on reduction using hydroiodic acid (HI) in presence of
red Phosphorus, n-hexane is obtained. This reaction indicates that all the 6 carbon atoms
in glucose are in a straight chain.
CHO
Red P/ CH -CH -CH CH -CH -CH
(CHOH) 4 HI
 3 2 2 2 2 3
CH2OH
gr up:
3. Functional o
Glucose n- Hexane
a. Aqueous solution of glucose is neutral. This confirms the absence of -COOH group.
b. One mole of glucose adds on to one mole of hydrogen cyanide (HCN) forming
glucose cyanohydrin.

CN
CHO CH-OH
(CHOH) + HCN (CHOH) 4
4 CH2OH
CH2OH
Glucose Glucose cyanohydrin
c. One mole of glucose reacts with one mole of hydroxyl amine (NH2OH) forming
glucose oxime.
CHO CH=N-OH
(CHOH) 4
+ NH2OH (CHOH) + H 2O
CH2OH 4
CH2OH
Glucose Glucose oxime
This reaction indicates the presence of a carbonyl (-CO-) group which means that glucose
contains either aldehyde (-CHO) group or ketone (-CO-) group.
4. Confirmation of aldehyde group:

Glucose on oxidation with mild oxidising agents like bromine water gets oxidised to
gluconic acid containing same number of carbon atoms. This reaction indicates that
glucose contains an aldehyde group.
CHO
COOH
(CHOH) Br2 water
+ (O) (CHOH) 4
CH2OH CH2OH
Glucose Gluconic acid
5. Position of aldehyde group:

Aldehyde group being monovalent in nature hence it should always be present as first
carbon atom.
6. Presence of 5 –OH groups:

Glucose on acetylation with acetic anhydride in presence of pyridine, one mole of glucose
reacts with five moles of acetic anhydride forming glucose penta acetate. This reaction
indicates that glucose contains 5 -OH groups.
CHO
CHO
(CHOH) 4 + 5 (CH CO) O
3 2 (CH-O-CO-CH3)4 + 5 CH3COOH
CH2OH
CH2-O-CO-CH3
Glucose Acetic anhydride Glucose penta acetate Acetic acid

7. Presence of primary –OH groups:
Both glucose and gluconic acid on oxidation with nitric acid gives saccharic acid
containing same number of carbon atoms. This reaction indicates the presence of
primary alcoholic group..
CHO
COOH COOH
HNO3 HNO3
(CHOH) + 3 (O) 2 (O) +
(CHOH) (CHOH) 4
-H2O -H2O
4
4
CH2OH COOH CH2OH

Glucose Saccharic acid Gluconic acid
8. Position of –OH groups: If two –OH groups are present on the same C-atom then
the molecule becomes unstable as it loses a molecule of water but glucose is a stable
molecule hence out of 6 C-atoms one of the C-atom is in the form of aldehydic group
so the remaining five C-atoms should contain one –OH group each.
9. Structure of glucose: Taking into account of all the above facts, Bayer in 1870
suggested the following open chain structure for glucose.
CHO
H OH
HO H
H OH
H OH
CH2OH
Glucose
The IUPAC name of glucose is 2,3,4,5,6 -pentahydroxyhexanal. Later in 1886 Killiani
confirmed the structure of glucose by its synthesis.
Note: The above structure contains 4 asymmetric carbon atoms. Hence 16 optical isomers
are possible. Finally based on the configuration, the following spatial arrangement is given
for glucose molecule.
Structures of Glucose, Gluconic acid and Saccharic acid:

The exact spatial arrangement of different -OH groups in glucose was given by Fischer after
studying many other properties. Its configuration is correctly represented as follows along
with the structures of gluconic acid and saccharic acid.
CHO
COOH COOH
H OH
H OH H OH
HO H
HO H HO H
H OH
H OH H OH
H OH
H OH H OH
CH2OH COOH
CH2OH
Glucose Gluconic acid Saccharic acid

Naming of Glucose:
Glucose is correctly named as D(+)-glucose. ‘D’ before the name of glucose represents
the configuration whereas ‘(+)’ represents dextrorotatory nature of the molecule. It may
be remembered that ‘D’ and ‘L’ have no relation with the optical activity of the
compound.
Meaning of D– and L– notations: The letters ‘D’ or ‘L’ before the name of any compound
indicate the relative configuration of a particular stereoisomer. This refers to their relation
with a particular isomer of glyceraldehyde. Glyceraldehyde contains one asymmetric carbon
atom and exists in two enantiomeric forms as shown below.
CHO CHO
H OH HO H
CH2OH CH2OH
(+) - Glyceraldehyde (-) - Glyceraldehyde
 All those compounds which can be chemically correlated to (+) isomer of glyceraldehyde
are said to have D-configuration
 All those which can be correlated to (-) isomer of glyceraldehyde are said to have L-
configuration.
For assigning the configuration of monosaccharides, it is the lowest asymmetric
carbon atom (as shown below) which is compared. As in (+) glucose, if the -OH on the
lowest asymmetric carbon (highest locant asymmetric C-atom) is on the right side which is
comparable to (+) glyceraldehyde, so it is assigned D-configuration.
CHO
H OH
CHO HO H
H OH
H OH H OH
CH2OH CH2OH
(+) - Glyceraldehyde D-(+)-Glucose
Similarly in (+) glucose, if the -OH on the lowest asymmetric carbon (highest
locant asymmetric C-atom) is on the left side which is comparable to (-) glyceraldehyde, so it
is assigned L-configuration.
CHO
H OH
CHO HO H
H OH
H H HO H
O
CH2OH CH2OH
(-) - Glyceraldehyde L-(+)-Glucose
Note: All naturally occurring carbohydrates are D – conformers.

CYCLIC STRUCTURE OF GLUCOSE:
Glucose containing aldehydic group, the open chain structure of glucose explained most of
the properties of aldehyde like reaction with Tollen’s reagent, Fehling’s solution…etc. but the
following reactions and facts could not be explained by this structure.
1. Glucose despite of having the aldehyde group,
a) It did not give immediate pink colour with Schiff’s reagent.
b) It did not give orange red precipitate with 2,4-DNPH.
c) It did not undergo addition reaction with NaHSO3.
2. The glucose penta acetate does not react with hydroxylamine indicating the absence
of free -CHO group.
3. Glucose is found to exist in two different crystalline forms which are named as α and β.
The α -form of glucose (m.p. 419 K) is obtained by crystallisation from concentrated
solution of glucose at 303 K while the β -form (m.p. 423 K) is obtained by crystallisation
from hot and saturated aqueous solution at 371 K.
This behaviour could not be explained by the open chain structure of glucose. It
was proposed that one of the -OH groups may add to the -CHO group and form a cyclic
hemiacetal structure. It was found that glucose forms a six-membered ring in which the -OH
group at C5 is involved in ring formation. This explains the absence of -CHO group and also
existence of glucose in two forms as shown below. These two cyclic forms exist in
equilibrium with open chain structure.
O
Anomeric C-atom
H C
H OH HO H
H OH H
OHO HO H OH
H H
O
HO HO H
OH H OH H OH
Hemi acetal linkage
H
H H H
CH2OH CH2OH
OH
CH2OH
-D-(+)-Glucose -D-(+)-Glucose
The two cyclic hemiacetal forms of glucose differ only in the configuration of the hydroxyl
group at C1, called anomeric carbon (the aldehyde carbon before cyclisation). Such isomers,
i.e., α- form and β-form, are called anomers.
ANOMERS:
Two carbohydrate molecules differing in the position of the –OH group on the
anomeric C-atom are called as anomers.
Example: α-D-(+)-glucose and β-D-(+)-glucose
Anomeric C-atom: The first C-atom in the ring is called as anomeric C-atom.
The six membered cyclic structure of glucose is called pyranose structure (α– or β–), in

analogy with pyran. Pyran is a cyclic organic compound with one oxygen atom and five
carbon

atoms in the ring. The cyclic structure of glucose is more correctly represented by Haworth
structure as given below.
CH2OH CH2OH
O H
O H H
O OH
H H
OHH OHH
HO OH HO H
H OH H OH
Pyran -D-(+)-Glucopyranose -D-(+)-Glucopyranose
Fructose:
It has the molecular formula C6H12O6. It also called as fruit sugar (... mostly found in fruits), it
is laevorotatory and hence it is called laevulose. It is a ketohexose. The open chain and the
ring structures of fructose are as follows
CH2OH
C O HOH2C OH
H O HO CH2OH
HO H HO HO H O
H OH H OH
H OH
H OH H H
CH2OH CH2OH CH2OH
D-(-)-Fructose
-D-(-)-Fructofuranose -D-(-)-Fructofuranose
The cyclic structures of two anomers of fructose are represented by Haworth structures as
given.
HOH2C O CH2OH HOH2C O OH
H HO H HO
H OH H CH2OH
OH H OH H
-D-(-)-Fructofuranose -D-(-)-Fructofuranose
DISACCHARIDES:
In disaccharides the two monosaccharides are joined together by an oxide linkage formed by
the loss of a water molecule. Such a linkage between two monosaccharide units through
oxygen atom is called glycosidic linkage.
1.
Sucrose: It has the molecular formula C 12H22O11. It also called as cane sugar (... mostly
found in sugar cane). It is a disaccharide of α-D-(+)-Glucopyranose and β-D-(-)-
Fructofuranose. These two monosaccharides are held together by a glycosidic linkage
between C1 of α-D-(+)-Glucopyranose and C2 of β-D-(-)-Fructofuranose.
Since the reducing groups of glucose and fructose are involved in glycosidic bond formation,
sucrose is a non reducing sugar.

CH2OH
H
O H
H
OH H -D-Glucose
HO
H OH Glycosidic
linkage
HOH2C O O
H HO
-D-Fructose
H CH2OH
OH H
SUCROSE
Note: Sucrose is dextrorotatory but after hydrolysis gives dextrorotatory glucose and
laevorotatory fructose. Since the laevorotation of fructose (–92.4°) is more than
dextrorotation of glucose (+ 52.5°), the mixture is laevorotatory. Thus, hydrolysis of sucrose
brings about a change in the sign of rotation, from dextro (+) to laevo (–) and the product is
named as invert sugar, therefore acid hydrolysis of cane sugar i.e sucrose is also called as
inversion of cane sugar.
2.
Maltose: It has the molecular formula C12H22O11. It also called as malt sugar (... mostly
found in malts). It is a disaccharide of α-D-(+)-Glucopyranose and α-D-(+)-
Glucopyranose. These two monosaccharides are held together by a glycosidic linkage
between C1 and C4 of the two α-D-(+)-Glucopyranose.
Since the reducing group of one of the glucose unit is free, maltose is a reducing sugar.
CH2OH
O CH2OH
H H
H
O H
H
H
OH H OH H
O
HO OH
H OH H OH
-D-Glucose -D-Glucose
MALTOSE
3.
Lactose: It has the molecular formula C12H22O11. It also called as milk sugar (... mostly
found in milk). It is a disaccharide of β-D-(+)-Galactopyranose and β-D-(+)-
Glucopyranose. These two monosaccharides are held together by a glycosidic linkage
between C1 of β-D- (+)-Galactopyranose and C4 of β-D-(+)-Glucopyranose.
Since the reducing group on the glucose unit is free, lactose is a reducing sugar.

CH2OH CH2OH
HO O H
O OH
H H
OHH O OHH
HH H
H OH H OH
-D-Galactose -D-Glucose
LACTOSE
POLYSACCHARIDES:
Polysaccharides contain a large number of monosaccharide units joined together by
glycosidic linkages. These are the most commonly encountered carbohydrates in nature.
They mainly act as the food storage or structural materials.
1. Starch: It is the main storage polysaccharide of plants. It is the most important dietary
source for human beings. High content of starch is found in cereals, roots, tubers and
some vegetables. It is a polymer of α-D-(+)-Glucopyranose units and consists of two
components namely:
a) Amylose and b) Amylopectin
a) Amylose: It is a water soluble component which constitutes about 15-20% of starch.

Chemically amylose is a long unbranched chain with 200-1000 α-D-(+)-Glucopyranose
units held by C1-C4 glycosidic linkage.
CH2OH CH2OH CH2OH

O O
H
O H
H H
H H
H H H
OHH
O OH H OH H
O O O
H OH
H OH H OH
- link - link
AMYLOSE
b) Amylopectin: It is a water insoluble component and constitutes about 80- 85% of

starch. It is a branched chain polymer of α-D-(+)-Glucopyranose units in which chain is
formed by C1-C4 glycosidic linkage whereas branching occurs by C1-C6 glycosidic
linkage.

CH2OH CH2OH
O H
O H
H H
H H
OHH
O OH H - link
O O
H OH
H Branch at C6
OH
CH2OH CH2 CH2OH
H
O H H
O H H
O H
H H H
OH H OH H OH H
O O O O
H OH H OH H OH
- link - link
AMYLOPECTIN
2. Cellulose: It is the main structural polysaccharide of plants and it is the most abundant
organic substance in plant kingdom. It is a predominant constituent of cell wall of plant
cells.
It is a straight chain polysaccharide composed only of β-D-(+)-Glucopyranose units held
by C1-C4 glycosidic linkage.
CH2OH
H
O O
H
CH2OH OH H
H H O O H
CH OH H OH
2 OH H
H H O O H
H OH
OH H
O
H
CELLULOSE
H OH
3. Glycogen: It is the main storage polysaccharide of animals. It is also known as animal

starch because its structure is similar to amylopectin and is rather more highly branched.
It is present in liver, muscles and brain. When the body needs glucose, enzymes break
the glycogen down to glucose. Glycogen is also found in yeast and fungi.

Importance of Carbohydrates:
Carbohydrates are essential for life in both plants and animals.
1. They form a major portion of our food (source of energy).
Carbohydrate as a source of energy:

Carbohydrates normally consumed in the form of starch, are hydrolysed by the enzymes namely saliva
glucose gets oxidized to carbon dioxide and water with the release of energy.
C6H12O6+6O2 6CO2+6H2O + Energy
This energy is used in muscular activity, cell synthesis and to maintain normal body temperature.
Any excess of glucose is converted into glycogen which is stored in the liver and muscles. Glyco
is hydrolysed into glucose.
2. Honey has been used for a long time as an instant source of energy by ‘Vaids’ in
ayurvedic system of medicine.
3. Carbohydrates are used as storage molecules as starch in plants and glycogen in animals.
4. Cell wall of bacteria and plants is made up of cellulose. We build furniture, etc. from
cellulose in the form of wood and cloth ourselves with cellulose in the form of cotton fibre.
5. They provide raw materials for many important industries like textiles, paper, lacquers
and breweries.
6. Two aldopentoses viz. D-ribose and 2-deoxy-D-ribose are present in nucleic acids.
7. Carbohydrates are found in biosystem in combination with many proteins and lipids.
PROTEINS
Proteins are the complex nitrogenous compounds which are condensation polymers of α–
amino acids having molecular mass greater than 10,000U
Amino Acids: Organic compounds containing both amino and carboxylic acid groups in the
same molecule are called as amino acids.
α- Amino Acids: Amino acids consisting the –NH2 group in the α-position with respect to –
COOH group are called as  - amino acids
These are the building blocks of proteins. There are about 20 naturally occurring  -
amino acids.

 - Amino acids are represented by the general formula
COOH
H2 N H
R
Amino acid
Where ‘R’ is -H, alkyl or a complex group.
Characteristic features of α- amino acids:
 α- amino acids are usually colourless, crystalline solids.

 These are water-soluble, high melting solids and behave like salts rather than simple
amines or carboxylic acids. This behaviour is due to the presence of both acidic
(carboxyl group) and basic (amino group) groups in the same molecule.
 They are amphoteric in nature.
 In  - amino acids, both the amino group and carboxylic acid group are connected to the
same carbon atom
 Except glycine, all other naturally occurring α-amino acids are optically active, since the
α-carbon atom is asymmetric. These exist both in ‘D’ and ‘L’ forms. Most naturally
occurring amino acids have L-configuration. L-Aminoacids are represented by writing
the –NH2 group on left hand side.
 There are totally 20 naturally occurring α- amino acids out of which 10 are essential
α- amino acids and the remaining 10 are non essential α- amino acids
 All α-amino acids have trivial names, which usually reflect the property of that
compound or its source.
Example: Glycine is so named since it has sweet taste (in Greek glykos means sweet)
Tyrosine was first obtained from cheese (in Greek, tyros means cheese.)
 Amino acids are generally represented by a three letter symbol, sometimes one letter
symbol is also used.
SOME IMPORTANT AMINO ACIDS AND THEIR FORMULAS:
Name of the amino Characteristic Three letter One letter

Sl. No
acids features of side chain symbol code
1 Glycine -H Gly G
2 Alanine -CH3 Ala A
3 Valine* (CH3)2-CH- Val V
4 Leucine* (CH3)2-CH-CH2- Leu L

CH3-CH2-CH-
5 Isoleucine* l
Ile I
CH3
HN=C-NH-(CH 2)3-
6 Arginine* l
Arg R
NH2
7 Lysine* H2N-(CH2)4- Lys K
8 Glutamic acid HOOC-CH2-CH2- Glu E
9 Aspartic acid HOOC-CH2- Asp D

O
10 Glutamine ll Gln Q
H2N-C-CH2-CH2-
O
11 Asparagine ll Asn N
H2N-C-CH2-
H3C-CH-
12 Threonine* l Thr T
OH
13 Serine HO-CH2- Ser S
14 Cysteine HS-CH 2- Cys C
15 Methionine* H3C-S-CH2-CH2- Met M
16 phenylalanine* CH2 Phe F
17 Tyrosine HO CH2 Tyr Y
CH2
18 Tryptophan* Trp W
NH
CH2
N
19 Histidine* His H
N
H
HO
20 Proline N Pro P
O H
(entire structures)
* Essential amino acids

CLASSIFICATION OF α- AMINO ACIDS:
I.
Based on the chemical nature: Depending upon the relative number of –NH2 and –COOH
groups, α-amino acids are classified into three types.
1. Neutral Amino Acids: Amino acids containing equal number of -NH2 and -COOH groups
are called as neutral amino acids.
Example: Glycine, Alanine, serine…..etc.

2. Acidic amino acids: Amino acids containing more number of -COOH groups than -NH2
groups are called as acidic amino acids.
Example: Aspartic acid, Glutamic acid…..etc.
3. Basic amino acids: Amino acids containing less number of -COOH groups than -NH2
groups are called as basic amino acids.
Example: Lysine, hystidine…..etc.
II.
Based on the requirement or biological importance: Depending upon the requirement
of α-amino acids to the organisms, they are classified into two types.
1. Essential amino acids: Amino acids which cannot be synthesised by the human body
and hence should be supplied through diet are called as essential amino acids.
Example: Lysine, Leucine, Isoleucine …..etc.
2. Non – essential amino acids: Amino acids which can be synthesised by the human
body are called as non-essential amino acids
Example: Glycine, Alanine, serine …..etc.
III.
Based on the nature of R-group or structure: Depending upon the nature of the R-
group or structure, α-amino acids are classified into three types.
1. Aliphatic amino acids: Amino acids containing aliphatic chain as R-groups are called as
aliphatic amino acids.
Example: Glycine, Alanine, Serine …..etc.
2. Aromatic amino acids: Amino acids containing at least one benzene ring as R-groups
are called as aromatic amino acids.
Example: Tyrosine, Phenyl alanine …..etc.
3. Hetero cyclic amino acids: Amino acids containing heterocyclic ring as R-groups are
called as heterocyclic amino acids.
Example: Histidine, Proline, and tryptophan
PROPERTIES OF AMINO ACIDS:
1. Amphoteric nature: Due the presence of both amino group (basic) and the carboxylic
acid group (Acidic) in the same molecule, they can act both as acid as well as base.
Hence amino acids are amphoteric in nature.
Example:
-
HOOC-CH-NH + HCl + Cl
HOOC-CH-NH
I I 3
2
R R
Amino acid
- +
H N-CH-COOH + NaOH +H O
I
H N-CH-COO Na
2 2 I 2
R R
Amino acid

2. Zwitter ion: At isoelectric point amino acids exists as a dipolar ion due to internal
neutralization .This dipolar ion is called as zwitter ion.
Isoelectric point
H N-CH-COOH -
+
H N-CH-COO
2 I
R 3 I
R
Amino acid Zwitter ion
The neutral molecule and the Zwitter ion are in equilibrium with one another.
3. Iso-electric point: It is a particular PH at which amino acids exists as zwitter ion is called
as isoelectric point.
At this point the amino acids doesn’t move either towards the cathode or anode
OR
The pH at which an amino acid molecule doesn’t move towards the cathode or the
anode in an electric field is called the isoelectric point.
Note: Each amino acid has its own characteristic isoelectric point
Example: For glycine it is 6.1, for Cysteine 5.0 …..etc..
Peptide Bond:
A peptide bond is an amide bond (–CO–NH–) formed between two amino acid
molecules.
Peptide bond
O O
II II O O
II II
H2N-CH-C-OH+
I
H-N-CH-C-OH
I
H2N-CH-C-N-CH-C-OH
I I I I
R H R R H R
Amino acid Amino acid Dipeptide
Polypeptide: Polypeptides are the complex nitrogenous compounds which are condensation
polymers of α–amino acids having molecular mass lesser than 10,000U
Note:
 An n-poly peptide contains (n-1) peptide bonds.
Example: When two amino acid molecules combine together, a Dipeptide is formed. A
dipeptide contains 1 peptide bond.
When three amino acid molecules combine we get a Tripeptide. A Tripeptide contains 2 peptide bonds.
Classification of proteins
I. Based on the molecular shape: Proteins are classified into two types on the basis of their
molecular shape.
(a) Fibrous proteins:

When the polypeptide chains run parallel and are held together by hydrogen and disulphide
bonds, then fibre like structure is formed, are known as fibrous protein. Such proteins are
generally insoluble in water. Some common
Example: keratin (present in hair, wool, silk) Myosin (present in muscles), etc.
(b) Globular proteins:
When the chains of polypeptides coil around to give a spherical shape globular proteins are
obtained. These are usually soluble in water.
Example: Insulin, albumins etc.
Extra:
II. Based on the biological functions: Proteins are classified into five types on the
basis of their
biological functions, as follows
1) Enzymes
2) Transport agents
3) Structural materials
4) Antibodies
5) Hormones
1) Enzymes: These are the proteins which catalyses biochemical reactions taking
place in the biological system. Hence they are also called as biochemical catalysts.
Example: 1) The enzyme Lipase hydrolyses oils and Fats into glycerol and fatty acids.
2) The Enzyme Pancreatic amylase hydrolyses starch into glucose.
Enzymes are specific in their actions they are active at 37oC and become inactive above
65oC.
A Conjugated enzyme consists of a protein part called apoenzyme and a non protein part
called coenzyme.
2)
Transport agents: These are the proteins which carries simple molecules like O 2
from one part of the body to another part of the body.
Example: Hemoglobin of blood is a metal protein which carries oxygen from lungs to
various tissues and it bring back carbon dioxide from tissues to lungs. The metal ion
present in Hemoglobin is Fe2+.
3)
Structural materials: These are the proteins which gives support and stability
for soft tissues.
Example: The protein keratin is present in Hair, nails, skin etc
The protein Collagen is present in cartilages
4)
Antibodies: These are the proteins produced by the WBC of blood. These
destroys the pathogenic micro organisms called antigens causing diseases. Hence
they act as self defence mechanism. The excess antibodies produced remain in the
body, gives resistance to the body.
Example: Gamma globulins

5)
Hormones: These are the proteins which are responsible for the growth and
reproduction. These are secreted by endocrine glands (ductless) after secretion,
they reaches their target and perform biological function. Hence they are called as
biochemical messengers
Example: Insulin, Oxytocin etc.
Insulin is a polypeptide hormone secreted by pancreas gland. It regulates the glucose level
in the blood by converting excess of glucose into glycogen.
Oxytocin is polypeptide hormone secreted by pituitary gland. It helps in the ejection of milk
during lactation; it helps in the contraction of muscles of uterus during the birth of child.
III. Based on the product of hydrolysis: Proteins are classified into three types on the
basis of their
Products of hydrolysis, as follows
1) Simple proteins: Proteins which gives only α-amino acids on hydrolysis are
called as simple proteins.
Example: Keratin, albumin…etc.
2) Conjugated proteins: Proteins which gives α-amino acids and non protein parts
like nucleic acids, lipids, sugars…etc (prosthetic group) on hydrolysis are called
as conjugated protiens.
Example: Nucleoproteins, Lipoprotiens, Glycoprotiens…etc.
3) Derived proteins: These are the proteins obtained by partial hydrolysis of simple
or conjugated proteins.
Example: Boiled egg white, curdling of milk ….etc
Protiens Proteoses Peptones Polypeptides
Structure of proteins:
Structure and shape of proteins is studied at four different levels, they are; primary,
secondary, tertiary and quaternary,
1) Primary structure of proteins: The specific sequence in which the amino acids are
linked to each other in one or more poly peptide chains of a protein is called as primary
structure
Note: Change in this primary structure i.e., the sequence of amino acids creates a different
protein.
2) Secondary structure of proteins:

It refers to the shape in which a long polypeptide chain can exist. These structures arises
due to the regular folding of the backbone of the polypeptide chain due to hydrogen
bonding between –CO– and –NH– groups of the peptide bond.
They are found to exist in two different types of structures namely,

a) -helix :
It is one of the most common ways in which a polypeptide chain forms all possible
hydrogen bonds by twisting into a right handed screw (helix) with the –NH group of
each amino acid residue hydrogen bonded to the _CO_ of an adjacent turn of the helix
as shown in the diagram.
C
.O.:
.........
H .O.:
.N.C
.O.H:
.N.
.........
H
.N.
.........
  Helix structure of protiens
b) β-pleated sheet structure:
H N
H N H N
R C H
R C H R C H
C O
C O C O
H N
H N H N
H C R
H C R H C R
O C
O C O C N
N H N H
R C H
C H R C H
R
C O
C O C O
H N
H N
  pleated sheet structure of proteins

This type of structure arises when all the peptide chains are stretched out to nearly
maximum extension and then laid side by side which are held together by intermolecular
hydrogen bonds. The structure resembles the pleated folds of drapery and therefore is
known as β-pleated sheet.

3) Tertiary structure of proteins: It arises due to over all folding, coiling and bending of
secondary structure producing 3-D structures. It gives rise to two major molecular shapes
namely fibrous and globular.
The main forces which stabilises the 2° and 3° structures of proteins are hydrogen
bonds, disulphide linkages, van der Waals and electrostatic forces of attraction.
4) Quaternary structure of proteins: The proteins are composed of two or more

polypeptide chains referred to as sub-units. The spatial arrangement of these subunits
with respect to each other is known as quaternary structure.
Primary Secondary Tertiary Quarternary

structure structure structure structure
DENATURATION OF PROTEINS:
The loss of physical and biological activity of proteins without affecting the chemical
composition by the action of certain denaturing agents like heat, acid, alkali….etc. is
called as denaturation of proteins.
During denaturation of proteins 20 and 30 structures are destroyed but the 10 structure
remains intact.
Example: Coagulation of egg white on boiling , curdling of milk which is caused due to the
formation of lactic acid by the bacteria present in milk….etc.
Enzymes: These are the proteins which catalyses biochemical reactions taking place in
the biological system. Hence they are also called as biocatalysts. Almost all the enzymes are
globular proteins.
Enzymes are very specific for a particular reaction and for a particular substrate. They
are generally named after the compound or class of compounds upon which they work.
Example: 1) The enzyme maltase catalyses the hydrolysis of maltose into glucose.
2) The enzyme Lipase hydrolyses oils and Fats into glycerol and fatty acids.
3) The Enzyme Pancreatic amylase hydrolyses starch into glucose.

4) Sometimes enzymes are also named after the reaction, where they are used.
The enzymes which catalyse the oxidation of one substrate with simultaneous reduction of
another substrate are named as oxidoreductase enzymes. The ending of the name of an
enzyme is -ase.
Enzymes are specific in their actions they are active at 37oC and become inactive above 65oC.
A Conjugated enzyme consists of a protein part called apoenzyme and a non protein part called
coenzyme.
Mechanism of Enzyme Action:

Small quantities of enzymes are needed for the progress of a reaction. Similar to the action
of chemical catalysts, enzymes are said to reduce the magnitude of activation energy.
Example: Activation energy for acid hydrolysis of sucrose is 6.22 kJ mol–1, but when
hydrolysed by the enzyme sucrase, the activation energy is only 2.15 kJ mol-1.
VITAMINS: (Vita = life in latin)

Organic compounds which are required in small amounts in our daily diet to perform
specific biological function and normal maintenance of normal health and growth of
the organism, but their deficiency causes specific diseases are called as vitamins.
Note:
 Vitamins are designated by alphabets A, B, C, D, E, K, Some of them are further named
as sub-groups e.g. B1, B2, B6, B12, etc.
 Excess of vitamins is also harmful and vitamin pills should not be taken without the
advice of doctor.
 The term “Vitamine” was coined from the word vital + amine since the earlier identified
compounds had amino groups. Later work showed that most of them did not contain
amino groups, so the letter ‘e’ was dropped and the term vitamin is used these days.
Classification of Vitamins:
Vitamins are classified into two groups based on their solubility in water or fat.
1. Fat soluble vitamins: Vitamins which are soluble in oils and fat are called as fat soluble
vitamins.
Example: vitamins A, D, E and K.
They are stored in liver and adipose (fat storing) tissues.
2. Water soluble vitamins: Vitamins which are soluble in water are called as water soluble
vitamins.
Example: B group vitamins and vitamin C are soluble in water so they are grouped
together. Note: Water soluble Vitamins must be supplied regularly in diet because they are
readily excreted in urine and cannot be stored (except vitamin B12) in our body.

Some important vitamins, their sources and diseases caused by their deficiency are
listed below:
Sl. Name of
Sources Deficiency diseases
No. Vitamins
Vitamin A Fish liver oil, carrots, butter Xerophthalmia (hardening of
1
(Retinol) and milk cornea of eye), Night blindness
Vitamin B1 Yeast, milk, green Beri beri (loss of appetite),

2
(Thiamine) vegetables and cereals retarded growth.
Cheilosis (fissuring at corners of
Vitamin B2
3 Milk, eggwhite, liver, kidney mouth and lips), digestive
(Riboflavin)
disorders and burning sensation
of
Vitamin B6 Yeast, milk, egg yolk,
4 Convulsions
(Pyridoxine) cereals and grams
Vitamin B12 Pernicious anaemia (RBC

5 Meat, fish, egg and curd
(Cyanocobalamin) deficient in haemoglobin)
Vitamin C Citrus fruits, amla and

6 Scurvy (bleeding gums)
(Ascorbic acid) green leafy vegetables
Rickets (bone deformities in

Vitamin D Exposure to sunlight, fish
7 children) and osteomalacia (soft
(Calciferol) and egg yolk
bones and joint pain in adults)
Vitamin E Vegetable oils like wheat Increased fragility of RBCs and
8 (Tocopherol) germ oil, sunflower oil, etc. muscular weakness
Vitamin K
9 Green leafy vegetables Increased blood clotting time
(Phyrlloquinone)
NUCLEIC ACIDS:
These are the poly nucleotides which are present in the nucleus of the cell and are
responsible for the transmission of genetic information and are involved in the
synthesis of proteins are called as nucleic acids.
There are mainly two types of nucleic acids,

1) Deoxyribonucleic acid (DNA) 2) Ribonucleic acid (RNA).
CHEMICAL COMPOSITION OF NUCLEIC ACIDS:

Complete hydrolysis of DNA /RNA yields the following
1. A pentose sugar 2. A Heterocyclic nitrogenous base 3. A Phosphoric acid

1. Pentose sugar:
The pentose sugar moiety present in DNA molecule is β-D-2-deoxyribose
HOH2C
O OH
H H H
H
OH H
-D-2-deoxyribose
The pentose sugar moiety present in RNA molecule, it is β-D-ribose.

HOH2C OH
O
H H
H H
OH OH
-D-Ribose
The carbon atoms of sugar are numbered as 1l, 2l, 3l..etc. in order to distinguish these from the bases.
2. Heterocyclic nitrogenous base :

There are two types of heterocyclic nitrogenous bases namely,
a) Purines: They have two heterocyclic fused rings.
NH2
O
N
N N NH
NH N NH N NH2
Adenine (A) Guanine (G)
Pyrimidines: They have a single heterocyclic ring.
NH2 O O
N H3C
NH NH
NH O NH
NH O
O
Cytosine (C) Thymine (T) Uracil (U)
DNA contains four bases i.e. adenine (A), guanine (G), cytosine (C) and thymine (T).
RNA also contains four bases, the first three bases are same as in DNA but the fourth
one is uracil (U).
The carbon atoms of bases are numbered as 1, 2, 3…etc.
3. Phosphoric acid (H3PO4): It forms esters with hydroxy groups of sugars.

O

- -
O P O
-
O

Nucleoside: A unit formed by the attachment of a base to 1l position of sugar is known
as nucleoside.
Base + Sugar = Nucleoside
HOH2C Base
O
H H
H H
OH OH
Nucleoside
Nucleotide: Nucleoside containing phosphoric acid at 5l-position of sugar moiety is

called as nucleotide.
Base + Sugar + phosphate = Nucleotide

O
-
O P O H2C O Base
- H H
O H H
OH OH
Nucleotide
Formation of a dinucleotide:
During the formation of a dinucleotide the –OH groups present on 5’ and 3’ carbon atoms of
the pentose sugar are involved in the ester linkage to form a phosphodiester.
O O
- -
O P H2C O Base O P H2C O Base
- H H - H H
OO OO
H H H Phosphodiester
OH OH H linkage
3'
O OH
-
O P O
+
O O
-
O P H2C O Base H2C5' Base
O
- H H
OO H
H H H
H
H
OH OH OH OH
Nucleotide Dinucleotide
Structure of RNA:
RNA has only single strand of polynucleotide chain. DNA consists of two such polynucleotide
chains held together by hydrogen bonds between the bases.

Structure of DNA: Watson and Crick model of DNA:
According to the model, DNA has the double – stranded, double helix. The structure is
comparable to a twisted ladder with uprights (sides) and rungs (steps). The uprights are
composed of repeating units of sugar and phosphate and the steps are composed of base
pairs. Base pairing is complementary i.e pairing occurs between A and T, G and C.
Nitrogenous bases of one strand are linked to the nitrogenous bases of other strand by
hydrogen bonds. There are two hydrogen bonds between A and T (A=T) and three hydrogen
bonds between G and C (G C).
Difference between RNA and DNA:
Sl.No. RNA DNA

1. It is a polymer of ribonucleotide It is a polymer of deoxyribonucleotide.
Contains ribose as the sugar Contains deoxyribose as the sugar
2.
component. component.
Nitrogen bases present are cytosine, Nitrogen bases present are cytosine,
3.
adenine and guanine( CUAG) thymine, adenine and guanine (CTAG)
4. Pyrimidine base Uracil is present Pyrimidine base Thymine is present
5. Has a shorter chain length Has a longer chain length

6. Has lower molecular weight Has higher molecular weight
7. Has a single Helix Has a double helix
8. Does not replicate. Self replication is possible.

RNA are of 3 types, they control the DNA is one type. It controls the hereditary
9.
synthesis of protein characters.

Biological importance of DNA:
1. DNA controls and directs the synthesis of RNA.
2. DNA controls and directs the synthesis of proteins
3. DNA has capacity to replicate itself. This happens when a cell divides. Hence this
process is responsible for complete reproduction of plant or animal.
4. Gene is a portion of DNA which controls all the characters of organisms. DNA encodes
the organism’s entire hereditary information and controls the growth and division of cells.
In organisms the genetic information is stored in DNA and is transcripted to RNA. This
information is then translated for the synthesis of proteins needed for the cellular
structure and function.
Biological importance of RNA:

The function of RNA is different from those of DNA. There are three types of RNA molecules
in a cell which play important roles in protein synthesis. They are
1. Messenger RNA (m-RNA): This carries the message of DNA for specific protein synthesis
2. Ribosomal RNA(r-RNA): This provides the site for protein synthesis
3. Transfer RNA (t-RNA): These transfer amino acids to the site of protein synthesis. Each
of these is specific for a given amino acid.
Biological Functions of Nucleic Acids:
1. DNA is the chemical basis of heredity (the reserve of genetic information).
2. DNA molecule is capable of self duplication during cell division and identical DNA strands
are transferred to daughter cells.
3. Another important function of nucleic acids is the protein synthesis in the cell.
4. DNA is responsible for maintaining the identity of different species of organisms over
millions of years.
5. DNA controls growth and cell division.
**********

CHAPTER: 15
POLYMERS
Polymers are high molecular mass substances containing large number of repeating
structural units derived from simple molecules.
The word ‘polymer’ is coined from two Greek words, ‘poly’ means many and ‘mer’ means
unit / part.
Polymer: These are macromolecules formed by repeated joining of small structural units
called monomers on a large scale. They have high molecular mass ranging from 103 to 107U.
The repeating structural units are derived from some simple and reactive molecules
and are linked to each other by covalent bonds.
Monomers: Simple and reactive molecules which combine to give polymers are called
monomers.
OR
The simplest repeating unit of a polymer is called a monomer.
Polymerisation: The process by which simple molecules (monomers) are converted

into polymers is called polymerisation.
Examples:
1. Homopolymers:
Polymers formed by only one type of monomers are called Homopolymers.
Examples: Polythene. Polypropylene, Poly vinyl chloride (PVC), Polyisoprene,
Polyacrylonitrile(PAN), Polybutadiene, etc.
Ethene polymerises to give polythene.
n CH
=CH polymerisation ( CH -CH )
2 2 2 2 n
Ethene Polythene
(Homopolymer)
2. Co-Polymer:
Polymers formed by two or more different monomers is called co-polymers or
mixed polymers.
Examples: Nylon-6,6 ,Buna-S, polyesters, Bakelite, melamine, formaldehyde, etc.

Hexamethylene diamine polymerises with adipic acid leading to the formation of Nylon 6, 6
n H2N-(CH2)6-NH2 + polymerisation
n HOOC-(CH2)4-COOH (NH-(CH 2)6-NH-CO-(CH2)4-CO )n + n H2O
Hexamethylene Adipic acid 2. Classification Based on Structure of
diamine
Polymer.
Classification of Polymers:
Polymers are classified in a number of ways:
1. Classification Based on Source.

Nylon-6,6 (Copolymer)

3. Classification Based on Mode of Polymerisation.
4. Classification Based on Molecular Forces.
5. Classification Based on Growth polymerisation.
1. Classification Based on Source of availability:

Based on the source of the polymer, they are classified into three types:
a) Natural Polymers.
b) Synthetic Polymers.
c) Semi synthetic Polymers.
a) Natural Polymers:
Polymers obtained from nature (plants and animals) are called natural polymers.
Examples: Starch, Cellulose, Proteins, Nucleic acids, resins, rubber etc.
b) Synthetic Polymers:
Polymers which are prepared by man in the laboratories are called synthetic
polymers. These are also man-made polymers.
Examples: Polythene, PVC, Nylon, Teflon, Bakelite, Terylene, synthetic fibres (nylon 6,6)
and synthetic rubbers (Buna-S).
c) Semi synthetic Polymers:

Polymers mostly derived from naturally occurring polymers by chemical
modifications are called semi synthetic polymers.
Example: Cellulose derivatives such as cellulose acetate (rayon) and cellulose nitrate, etc.
2. Classification Based on Structure of Polymers:

Based on the structure of the polymer, they are classified into three types:
a) Linear Polymers.
b) Branched chain Polymers.
c) Cross-linked Polymers.
a) Linear Polymers:
Polymers in which monomeric units are linked together to form long and linear
(straight) chains are called linear polymers.
Examples: High density polythene (HDPE), poly vinyl chloride (PVC), etc.
They are represented as:
Linear Polymer

b) Branched chain Polymers:
Polymers in which the monomers are joined to form long and linear (Straight)
chains with side chains or branches of different lengths are called branched chain
polymers.
Examples: Low density polythene (LDPE), Glycogen, Starch, etc
Branched chain Polymer
c) Cross-linked / Network Polymers:

Polymers in which monomer units are cross-linked together to form a three-
dimensional network are called branched Cross linked polymers or network
polymers.
Examples: Bakelite, Melamine, Formaldehyde resin, etc.
Crossed linked / Network Polymer
3. Classification Based on Mode of Polymerisation:

Based on the mode of polymerisation, polymers are classified into two types:
a) Addition Polymers.
b) Condensation Polymers.
a) Addition Polymers:
Polymers formed by repeated addition of monomers containing double or triple
bond without the elimination of any by-product molecules are called as addition
polymers.
Homo polymers example: Polythene, polypropene...etc.

Polythene is obtained by addition of ethene (monomer)
nCH polymerisation ( CH -CH )
=CH
2 2 2 2 n
Ethene Polythene
Copolymers example: Buna-S, Buna-N...etc

Buna-S is obtained by addition of 1,3-butadiene and styrene (vinyl benzene).
copolymerisation
nCH =CH-CH=CH + n CH=CH ( CH -CH=CH-CH -CH -CH )
2 2 2 2 n

Buta-1,3-diene Styrene Butadiene-styrene (co-polymer)
(Buna-S)

b) Condensation polymers:
Polymers formed by condensation of two or more monomers with different bi-
functional or tri-functional groups with the elimination of simple molecules like
water, alcohol, hydrogen chloride, etc. as by products are called as condensation
polymers.
Example: Nylon-6,6, terylene, Bakelite, alkyl resin, etc.

Nylon 6, 6 is obtained by the condensation of hexamethylene diamine with adipic acid with
the loss of water molecule.
O O
nH polymerisation
N-(CH2)6-NH2 + nHOOC-(CH2)4-COOH (NH- 2)6-NH-C-(CH2)4-C + n H2 O
2 (CH )n
Hexamethylene Adipic acid -
Nylon 6,6
diamine
(Copolymer)
4. Classification Based on Molecular Forces:

Applications polymers in different fields depend on their mechanical properties like tensile
strength, elasticity, toughness, etc. These mechanical properties depend on intermolecular
forces like Vander Waals forces, hydrogen bonds ..etc. which bind the polymer chains.
Based on the intermolecular forces, polymers are classified into four types.
a) Elastomers.
b) Fibres.
c) Thermoplastic polymers.
d) Thermosetting polymers.
a) Elastomers:
Polymers consisting of rubber like elastic character are called elastomers.
In these elastomers the polymer chains are held together by weak intermolecular
forces. Because of the presence of weak forces, the polymer can be easily stretched by
applying small stress and regains their original shape when the stress is released. A few
‘crosslinks’ are introduced in between the chains, which help the polymer to retract to its
original position after the force is released as in vulcanised rubber.
Examples: Buna-S, Buna-N, Neoprene, etc.
( CH2-C=CH-CH2)n
Cl
Neoprene
b) Fibres:
Polymers which are thread forming solids which possess high tensile strength and
high modulus are called fibres.
High tensile strength and high modulus of fibres can be attributed to the strong intermolecular
forces like hydrogen bonding. These strong forces also lead to close packing of chains and
thus impart crystalline nature.
Examples: Polyamides (nylon-6, 6), Polyesters (terylene), silk, etc.
( NH-(CH 2)6-NH-CO-(CH2)4-CO)
n
Nylon-6,6

c) Thermoplastics:
Polymers consisting of linear or slightly branched long chain molecules capable of
repeatedly softening on heating and hardens on cooling are called thermoplastics.
These polymers possess intermolecular forces of attraction intermediate between that of
elastomers and fibres.
Examples: polythene, polystyrene, polyvinyls, etc.
Cl
( CH -CH)n
2
PVC
e) Thermosetting polymers:
Polymers consisting of cross linked or heavily branched molecules, which on
heating undergo extensive cross linking in moulds and again become infusible are
called thermosetting polymers.
They cannot be reused.
Examples: Bakelite, urea-formaldehyde resins, etc.
OH OH
CH2 CH2
Bakelite
5. Classification Based on Growth polymerisation:

Depending on the type of polymerisation mechanism they undergo during their formation,
polymers are classified into two types
1. Addition polymerisation or chain growth polymerisation.
2. Condensation polymerisation or step growth polymerisation.
1. Addition polymerisation or chain growth polymerisation:

Polymers formed by repeated addition of unsaturated molecules (e.g., alkenes,
alkadienes and their derivatives) of the same monomer or different monomers on a
large scale to form polymers are called as an addition polymer and the process is
called addition polymerisation.
This mode of polymerisation leads to increase in chain length hence this type of
polymerisation is also called as chain growth polymerisation. This type of polymerisation
can take place through the formation of either free radicals or ionic species.
However, the free radical governed addition or chain growth polymerisation is the
most common mode.
Free radical mechanism
A variety of alkenes or dienes and their derivatives are polymerised in the presence of a
free radical generating initiator (catalyst) like benzoyl peroxide, acetyl peroxide, tert-butyl
peroxide, etc.
Example: Polymerisation of ethene to polythene

Ethene on heating or exposing to light in presence of small amount of benzoyl peroxide
as free radical initiator gives polythene.
Step 1: Chain initiation: Benzoyl peroxide undergoes homolysis generating phenyl free
radical. The phenyl free radical formed adds on to the ethene double bond thus
generating a new and larger free radical.
O O
C6H5-C-O-O-C- 2 C6H5-C-
O
. .
C6 H5 + 2 CO2
C6 H5 O
. Benzoyl peroxide Benzoyl peroxide free radical Phenyl free radical
.
C6 H5 CH2=CH2
.
C6H5-CH2-CH2
.
+
Phenyl free radical Ethene Larger free radical
Step 2: Chain propagation: The larger free radical formed in step 1 reacts with another
molecule of ethene to form another bigger sized radical. This process of addition
continues to form newer and bigger radicals, forming a large chain free radical.
.. . ..
C6H5-CH2- + n CH2=CH2 C6H5-CH2-CH2-CH2- C6H5(-CH2-CH2)-CH2-CH2
CH2 CH2 n
Ethene Bigger larger chain free radical
Larger free radical
Step 3: Chain termination: Ultimately, at some stage large chain free radical thus
formed reacts with another large chain free radical to form the final polymerised product.
. .
C6H5(-CH2-CH2)-CH2- + C6H5(-CH2-CH2)-CH2- C6H5-(CH2-CH2)-CH2-CH2-CH2-CH2-(CH2-CH2)-C6H5
n n
CH2 CH2 Polythene (addition polymer)
n n
Bigger larger chain free radical Bigger larger chain free radical
Preparation some important addition polymers:
1. Polythene or Polyethylene:
There are two types of polythene as given below:
a. Low density polythene (LDP) OR Low density polyethylene (LDPE).
b. High density polythene (HDP) OR High density polyethylene (HDPE).
Both of these are obtained from ethene and have the same repeating structural unit that is –
CH2-CH2- .
a) Low density polythene (LDP) OR Low density polyethylene (LDPE):

Ethene or ethylene on heating to a temperature of 350 K to 570 K under high pressure of
1000- 2000 atm in the presence of traces of dioxygen or a peroxide initiator as catalyst which
initiates polymerisation, addition polymerisation takes place leading to the formation of low
density polythene (LDP) or low density polyethylene (LDPE).
n CH2=CH2 350 - 570K
1000 - 2000 atm

( CH2-CH2)n
L
o
w
d
e
n
s
i
t
y
p
o
l
y
t
h
e
n
e

The low density polythene (LDP) obtained through the free radical addition and H-atom
abstraction consists of highly branched chain molecule.
Properties:
1. Low density polythene is transparent polymer of moderate tensile strength and high
toughness.
2. It is chemically inert slightly flexible and a poor conductor of electricity.
Uses: It is used
1. As a packing material in the form of thin plastic bags.
2. For insulation of electric wires.
3. In the manufacture of squeeze bottles, toys and flexible pipes.
(ii) High density polythene (HDP) OR High density polyethylene (HDPE):

Ethene or ethylene on heating to a temperature of about 333K to 343K in a hydrocarbon
solvent under a pressure of 6 to 7 atmosphere in presence of Ziegler-Natta catalyst
(triethylaluminium and titanium tetrachloride) , addition polymerisation takes place leading to
the formation of high density polythene (HDP) or high density polyethylene (HDPE) is
obtained.
n CH =CH
333 - 343K, 6 - 7 atm ( CH -CH )
2 2 (CH CH ) Al + TiCl 2 2 n
Ethene 3 23 4
High density
(Ethylene) polythene
High density polythene (HDPE) thus produced, consists of linear molecules and has a high
density due to close packing.
Note: G.Natta of Imperia and Karl Ziegler of Germany were awarded noble prize in chemistry
in 1963 for the development of Zeigler Natta catalyst.
Properties:
1. It is chemically inert.
2. Has greater toughness and tensile strength.
Uses: It is used in manufacturing of containers (buckets, tubes and dustbins), house wares,
bottles, pipes, etc.
2. Polytetrafluoroethene (PTFE) or Teflon:

Tetrafluoroethene on heating in presence of peroxide or ammonium persulphate as catalyst
at high pressures, addition polymerisation takes place leading to the formation of
Polytetrafluoroethene (PTFE) or Teflon.
n F C=CF (NH4)2 S2O8 ( F C-CF )
2 2  , High pressure 2 2 n
Tetrafluroethene Polytetrafluroethene
(Teflon)
Note: Teflon coatings undergo decomposition at temperatures above 3000C.
Properties:
1. It is very tough material and is chemically inert.
2. It is resistant to heat and attack by corrosive reagents.
3. It is a bad conductor of electricity.
Uses: It is used
1. For coating articles and cookware utensils to make them non-sticky.
2. For making gaskets and oil seals.
3. Polyacrylonitrile (PAN) or Orlon:

Acrylonitrile heating in presence of peroxide catalyst, addition polymerisation takes place
leading to the formation of Polyacrylonitrile.
CN
Peroxide
Example: nCH 2=CH-CN CH2-CH
n
Vinyl cyanide Polyacrylonitrile
(Acrylonitrile)
Uses: It is used
1. As a substitute for wool in the manufacture of Orlon or Acrilan fibres which are used for
making blankets, sweaters, bathing suits, etc.
2. For making synthetic carpets.
Note: Acrylic fibres have good resistance to stains, chemicals, insects and fungi.
2. Condensation Polymerisation or Step Growth polymerisation:

Condensation polymers are formed by the condensation of two or more bifunctional
monomers with the elimination of simple molecules like water, alcohol, ammonia, etc. and
lead to the formation of high molecular mass condensation polymers.
In these reactions, the product of each step is again a bi-functional species and the
sequence of condensation goes on. Since, each step produces a distinct functionalised
species and is independent of each other; this process is also called as step growth
polymerisation.
Preparation of some important condensation polymers:
1. Polyesters: Polymers containing ester linkages are called polyesters and are prepared by
the condensation polymerisation of dicarboxylic acids with diols.
i) Dacron or Terylene:
On heating a mixture of ethylene glycol (ethane-1, 2-diol) and terephthalic acid (benzene-
1,4-dicarboxylic acid) to a temperature of 420K to 460 K in the presence of zinc acetate-
antimony trioxide catalyst.
O O
Example: n HO-CH -CH -OH+ n HOOC COOH
420 - 460K
O-CH2-CH2-O-C + n H2O
2 2
Zn(OCOCH3)2 + Sb2O3
C
n
Ethylene glycol Terephthalic acid Dacron OR Terylene
Uses:
1. Dacron / terylene fibre is a crease resistant and is used in blending with cotton and wool fibres.
2. As glass reinforcing materials in safety helmets.
3. For making magnetic recording tapes.
2. Polyamides: Polymers which have amide linkages are called polyamides.

These are prepared by the condensation polymerisation of diamines with dicarboxylic
acids and also from amino acids and their lactams. These polymers are commonly called
as nylons.
(a) Preparation of Nylons:

(i) Nylon 6, 6:
On heating hexamethylenediamine and adipic acid under to a high temperature of 553K and
at high pressure condensation polymerisation takes place forming Nylon-6,6.
O O O O
553K
Example: nH2N-(CH2)6-NH2 + n HO-C-(CH2)4-C-OH NH-(CH 2)6-NH-C-(CH2)4-C + n H2 O
High -
Nylon 6,6 n
pressure
Hexamethylene Adipic acid
diamine
Uses: It is used
1. In making bristles for brushes
2. In textile industry and also making sheets. It is blended with wool to make socks and
sweaters.
(ii) Nylon 6: It is obtained by heating caprolactum with water at a high temperature of 533K
to 543K.
N
H 2C C=O O H
n 533K - 543K
C-(CH2 )5 -N
H 2C CH2 H2O
n
H 2C CH2
Caprolactum Nylon-6
Uses: Nylon 6 is used for the manufacture of tyre cords, fabrics and ropes.
3. Phenol - formaldehyde polymer: (Bakelite and related polymers)
Phenol and formaldehyde on condensation reaction in presence of either an acid or a base

catalyst gives bakelite polymer.
Process: The reaction starts with the initial formation of o / p-hydroxymethylphenol or both
and its derivatives, which further react with phenol to form compounds having rings joined to
each other through methylene (–CH2–) groups. The initial product is linear product called
Novolac used in paints. This on further heating with formaldehyde undergoes cross linkages
to form infusible solid called Bakelite.

Phenol - formaldehyde polymers are the oldest synthetic polymers.
OH OH OH
OH
CH2OH CH2OH HOH2C CH2OH
+ HCHO OH-
+
or H+ +
CH2OH
CH2OH
Phenol o-Hydroxymethylphenol o,p-diHydroxymethylphenol
The condensation of o-Hydroxymethylphenol or p-Hydroxymethylphenol gives linear
polymer.
OH OH OH
CH2OH
polymerisation
n CH2 CH2
n H 2O
Linear polymer n
Novolac
The ortho and para substituted phenols can undergo polymerisation to produce a cross-
linked polymer known as Bakelite. Novolac on heating with formaldehyde undergoes cross
linking to form infusible solid mass called Bakelite.
OH OH OH
H2C CH2 CH2 CH2
OH OH
CH2OH
polymerisation
n + n CH2 CH2 CH2
n H 2O
CH2OH
H2C CH2 CH2 CH2
OH OH OH
Bakelite (Cross-linked polymer)
Uses:
It is used for making combs, phonograph records, electrical switches and handles of various
utensils.
4 Melamine – formaldehyde polymer:

It is obtained by the condensation polymerisation of melamine which is a heterocyclic
triamine with formaldehyde.
NH2 N NH2 NH2 N NH-CH 2-OH NH N NH-CH 2
polymerisation
+ HCHO
N N N N N N
NH2
NH2 NH
n
Melamine (Intermediate) Melamine - formaldehyde polymer
Uses: It is used in making crockery. These are used for making cups and plates which are
quite hard and durable.

Copolymerisation:
When two or more different monomers are allowed to polymerize together, a copolymer is
obtained and the process is called copolymerisation.
The copolymer can be made by chain growth polymerisation as well as step growth
polymerisation. It contains multiple units of each monomer used in the same polymeric chain.
Example: A mixture of 1, 3 – butadiene and styrene can form a copolymer known as
butadiene – styrene copolymer called Buna-S
nCH2=CH-CH=CH 2 + copolymerisation
n CH=CH 2 CH2-CH=CH-CH 2-CH-CH2
n
Buta-1,3-diene Styrene Butadiene-styrene co-polymer
(Vinyl benzene) (Buna-S) .
Copolymers have properties quite different from homopolymers.
Example: butadiene - styrene copolymer is very tough and is a good substitute for natural
rubber. It is used for the manufacture of auto tyres, floor tiles, footwear components, cable
insulation, etc.
Natural Rubber and Synthetic Rubber:

1. Natural Rubber:
Rubber is a naturally occurring polymer and possesses elastic properties. It is also termed as
elastomer and has a variety of uses. It is manufactured from rubber latex which is a colloidal
dispersion of rubber in water. This latex is obtained from the bark of rubber tree and is found
in India, Srilanka, Indonesia, Malaysia and South America.
Natural rubber may be considered as a linear polymer of isoprene (2-methyl-1, 3-butadiene).
CH3
CH2=C-CH=CH2
Isoprene
(2-methylbuta-1,3-diene)
In natural rubber about 11,000 to 20,000 isoprene units are linked together in a chain.
CH3
CH3
n CH2=C-CH=CH2
CH2-C=CH-CH2
Isoprene n
Polyisoprene
(2-methylbuta-1,3-diene)
(Natural rubber)
Natural rubber may be considered as a linear polymer of isoprene (2-methyl-1, 3-butadiene)

and is also called as cis-1,4-polyisoprene.

H 3C H H
H 3C
C=C C=C
H 2C
CH2 H 2C CH2 H 2C CH2
C=C
H 3C H
Natural rubber
Vulcanisation of rubber:
Natural rubber is a thermoplastic since, It becomes soft when it is heated at high temperature
(>335 K) and brittle at low temperatures (<283 K). There are no cross links between the
polymers. It shows high water absorption capacity. It is soluble in non-polar solvents and is
non-resistant to attack by oxidising agents. These properties of natural rubber can be
modified and improved by the process called vulcanisation
Vulcanisation:
The process of heating natural rubber with sulphur to a temperature of 373 to 415K
(1000C to 1400C) to improve its properties is called vulcanisation. On vulcanisation,
sulphur forms cross links at the reactive sites of double bonds and thus the rubber
gets stiffened.
In the manufacture of tyre rubber, 5% of sulphur is used as a crosslinking agent. The
probable structures of vulcanised rubber molecules are as shown below:
CH3
CH3
-CH2-C-CH-CH2-
-CH-C=CH-CH
SS
2 -S
-CH2-C-CH-CH2-
-CH-CH=CH-CH 2-
CH3
Vulcanised rubber
2. Synthetic rubbers:
The Synthetic rubber is any vulcanisable rubber like polymer which is capable of getting
stretched to twice its length. However, it returns to its original shape and size as soon as the
external stretching force is released.
Synthetic rubbers are either homopolymers of 1, 3 - butadiene derivatives or
copolymers of 1, 3 - butadiene or its derivatives with another unsaturated monomer.
Preparation of Synthetic Rubbers:

1. Neoprene or polychloropropene:
Neoprene or polychloroprene is prepared by the free radical addition polymerisation of
chloroprene (2-chlorobuta-1, 3-diene).
Cl Cl
polymerisation
n CH2=C-CH=CH2 CH 2-C=CH-CH 2
Chloroprene Neoprene n
(2-chlorobuta-1,3-diene)
Properties: Neoprene is superior to natural rubber in its stability to aerial oxidation and its
resistance to vegetable and mineral oils.

Uses: It is used for manufacturing conveyor belts, gaskets, shoe heals and hoses.
2. Buna – N or Nitrile rubber:

Buna –N is obtained by the copolymerisation of 1, 3 – butadiene and acrylonitrile in the
presence of a peroxide catalyst.
CN
Example: n CH2=CH-CH=CH 2 + CH2=CH-CN Peroxide CH2-CH=CH-CH 2-CH-CH2
1,3-Butadiene Acrylonitrile Buna-N n
Properties: It is resistant to the action of petrol, lubricating oil and organic solvents.
Uses: It is used in making oil seals, tank lining, etc.
3. Buna – S or Styrene Butadiene Rubber (SBR):
It is obtained by the polymerisation of buta-1, 3-diene and styrene in the ratio of 3:1 in the
presence of sodium.
Example: Sodium
nCH2=CH-CH=CH 2 + n CH2-CH=CH-CH 2-CH-CH2
CH=CH2
- n
Buta-1,3-diene Styrene
Butadiene-styrene co polymer
(Buna-S)
Properties: It is also called as Buna-S, in which Bu stands for butadiene, Na for sodium and
S stands for styrene. It has slightly less tensile strength than natural rubber.
Uses: It is used for making automobile tyres and footwear.
Molecular masses of polymers:
Molecular mass of polymers can be determined by chemical and physical methods but not
accurately, hence it is expressed in terms of average molecular mass.
Reason:
The growth of the polymer chain during their synthesis is dependent upon the availability of
the monomers in the reaction mixture. Thus, the polymer sample contains chains of varying
lengths and hence its molecular mass is always expressed as an average.
Note: Polymer properties are closely related to their molecular mass, size and structure.
Biodegradable Polymers:
A large number of polymers are quite resistant to the environmental degradation processes
and are thus responsible for the accumulation of polymeric solid waste materials. These solid
wastes cause acute environmental problems and remain undegraded for quite a long time.
These polymers are regarded as non-biodegradable polymers.
In view of the general awareness and concern for the problems created by the
polymeric solid wastes, certain new biodegradable synthetic polymers have been designed
and developed.

These are the polymers which are degraded by natural agents like microorganisms
such as bacteria, fungi etc. Within a suitable period of time are called biodegradable
polymers.
These polymers contain functional groups similar to the functional groups present in
biopolymers hence the de graded products do not cause any serious affects on the
environment.
Example: Aliphatic polyesters are one of the important classes of biodegradable polymers.
1. Poly-β-Hydroxybutyrate-co-β-hydroxy Valerate:
It is a copolymer which is obtained by polymerisation of 3-hydroxybutanoic acid and 3-
hydroxypentanoic acid, in which the monomer units are joined by ester linkages.
O O
Example: n HO-CH-CH -COOH + n HO-CH-CH -COOH polymerisation
O-CH-CH -C-O-CH-CH -C + (2n-1)H O
2 2 2 2 2
CH3 CH2-CH3 CH3 CH2-CH3
3-Hydroxybutanoicacid n
3-Hydroxypentanoicacid PHBV
Uses: PHBV is used in speciality packaging, orthopaedic devices and in controlled release of
drugs. When a drug is enclosed in a capsule of PHBV, it is released only when the polymer is
degraded in the body. It also undergoes bacterial degradation in the environment.
2. Nylon-2-Nylon-6:
It is a polyamide copolymer of glycine and amino caproic acid. It is also biodegradable.
O O
Example
n H2N-CH2-COOH+ n H2N-(CH2)5-COOH NH-CH 2-C-NH-(CH 2)5- + (2n-1)H2O
:
C n
Glycine Aminocaproic acid
Nylon-2-nylon-6
Some commercially Important Polymers:
Sl.
Name of the
No Monomer unit Structure Uses
polymer
.
Used in the Manufacture of

CH3-CH=CH2 CH-CH2 ropes, toys, pipes,
1 Polypropene
Propene CH3 n fibres, etc.
CH=CH2 Used as insulator, wrapping

-CH2-CH
material, in the manufacture of
2 Polystyrene toys, radio and television
cabinets.
Styrene n
Used in manufacture of rain

Cl
Poly vinyl CH2=CH-Cl coats, hand bags,
3 CH2-
chloride(PVC) Vinyl chloride vinyl flooring, water pipes.
CH
n

i) NH2-CO-NH2
Urea For making unbreakable cups
Urea NH-CO-NH-CH 2
4 formaldehyde and laminated sheets.
ii)HCHO n
resin
Formaldehyde
i) HO-CH2-CH2-OH
Ethylene glycol
HOOC COOH O-CH2-CH2-OOC CO
ii) Manufacture of paints and
5 Glyptal lacquers.
n
Phthalic acid
i) OH
OH OH
CH2 CH2 For making combs, electrical

6 switches, handles of utensils
Bakelite
and computer discs.
Phenol n
ii) HCHO
Formaldehyde
**************

CHAPTER: 16
CHEMISTRY IN EVERYDAY LIFE
Introduction:
Chemistry influences every sphere of human life. The principles of chemistry have been used
for the benefit of mankind. Some of them are as follows.
Cleanliness: Materials like soaps, detergents, household bleaches, tooth pastes, etc. are
used for maintaining cleanliness.
Clothes: Materials like rayon, terylene, nylon...etc. are used for clothing purposes which are
chemicals of the synthetic fibres used for making clothes.
Food materials: Materials like rice, ragi, wheat, jowar, egg, meat...etc which we have learnt
in the previous chapter Biomolecules.
Drugs: Medicines used to cure sickness and diseases like paracetamol, penicillin...etc are
again chemicals.
Explosives, fuels, rocket propellents, building and electronic materials, etc., are all
chemicals.
Chemistry has influenced our life so much that we do not even realise that we come
across chemicals at every moment that we ourselves are beautiful chemical creations and all
our activities are controlled by chemicals.
In this chapter, we shall learn the application of Chemistry in three important and interesting
areas, namely
 Medicines,
 Food materials
 Cleansing agents.
Drugs and their Classification:
Drugs: These are chemical substances with low molecular masses (~100 – 500U)
which interact with macromolecular targets and produce a biological response.
Medicines: Drugs which produce the biological responses that are therapeutic and useful
are called medicines and are used in diagnosis, prevention and treatment of diseases.
Note: If taken in doses higher than those recommended, most of the drugs used as
medicines are potential poisons.
Chemotherapy: Use of chemicals for therapeutic effect is called chemotherapy.
Classification of Drugs: Drugs can be classified mainly on criteria outlined as follows:
(a) On the basis of pharmacological effect: This classification is based on

pharmacological effect of the drugs. It is useful for doctors because it provides them the
whole range of drugs available for the treatment of a particular type of problem.
Example: Analgesics have pain killing effect; antiseptics kill or arrest the growth of
microorganisms.

(b) On the basis of drug action: It is based on the action of a drug on a particular
biochemical process.
Example: All antihistamines inhibit the action of the compound, histamine which causes
inflammation in the body.
(c) On the basis of chemical structure: It is based on the chemical structure of the drug.
Drugs classified in this way share common structural features and often have similar
pharmacological activity.
Example: sulphonamides have common structural feature as given below.
O
H2N
S-NH-R
O
Structural features of sulphonamides
(d) On the basis of molecular targets: Drugs usually interact with biomolecules such as
carbohydrates, lipids, proteins and nucleic acids. These are called target molecules or drug
targets. Drugs possessing some common structural features may have the same mechanism
of action on targets. The classification based on molecular targets is the most useful
classification for medicinal chemists.
Drug – target Interaction:

Macromolecules of biological origin perform various functions in the body.
 Enzymes: Proteins which perform the role of biological catalysts in the body are called
enzymes.
 Receptors: Those which are crucial to communication system in the body are called
receptors.
 Carrier proteins carry polar molecules across the cell membrane.
 Nucleic acids have coded genetic information for the cell.
 Lipids and carbohydrates are structural parts of the cell membrane
We shall explain the drug-target interaction with the examples of enzymes and receptors.
Enzymes as Drug Targets:
(a) Catalytic action of enzymes: In their catalytic activity, enzymes perform two major
functions:
(i) The first function of an enzyme is to hold the substrate for a chemical reaction. Active sites
of enzymes hold the substrate molecule in a suitable position, so that it can be attacked by
the reagent effectively.
Substrates bind to the active site of the enzyme through a variety of interactions such as
ionic bonding, hydrogen bonding, Vander Waals interaction or dipole-dipole interaction.

(ii) The second function of an enzyme is to provide functional groups that will attack the
substrate and carry out chemical reaction.
(b) Drug-enzyme interaction:

Drugs inhibit any of the above mentioned activities of enzymes. These can block the binding
site of the enzyme and prevent the binding of substrate, or can inhibit the catalytic activity of
the enzyme. Such drugs are called enzyme inhibitors.
Drugs inhibit the attachment of substrate on active site of enzymes in two different ways;
(i) Drugs compete with the natural substrate for their attachment on the active sites of
enzymes. Such drugs are called competitive inhibitors.
(ii) Some drugs do not bind to the enzyme’s active site. These bind to a different site of
enzyme which is called allosteric site. This binding of inhibitor at allosteric site changes the
shape of the active site in such a way that substrate cannot recognise it.

If the bond formed between an enzyme and an inhibitor is a strong covalent bond and cannot
be broken easily, then the enzyme is blocked permanently. The body then degrades the
enzyme-inhibitor complex and synthesises the new enzyme.
Receptors as Drug Targets:

Receptors are proteins that are crucial to body’s communication process. Majority of these
are embedded in cell membranes as shown in the diagram. Receptor proteins are embedded
in the cell membrane in such a way that their small part possessing active site projects out of
the surface of the membrane and opens on the outside region of the cell membrane.
.
Receptor proteins are embedded in the cell membrane, the active site of the receptor
opens on the outside region of the cell.
In the body, message between two neurons and that between neurons to muscles is
communicated through certain chemicals. These chemicals, known as chemical
messengers are received at the binding sites of receptor proteins. To accommodate a
messenger, shape of the receptor site changes.
This brings about the transfer of message into the cell. Thus, chemical messenger gives
message to the cell without entering the cell as shown in the diagram.

There are a large number of different receptors in the body that interact with different
chemical messengers. These receptors show selectivity for one chemical messenger over
the other because their binding sites have different shape, structure and amino acid
composition.
Antagonists: Drugs that bind to the receptor site and inhibit its natural function are
called antagonists. These are useful when blocking of message is required.
Agonists: Drugs that mimic the natural messenger by switching on the receptor, these
are called agonists. These are useful when there is lack of natural chemical messenger.
Therapeutic action of different classes of drugs:
I. Antihistamines: The drugs which interfere with the natural action of histamines by
competing with histamine for binding sites of receptor where histamines exerts its
effect and thus inhibits the action of histamines are called antihistamines.
Example: Antacids and antiallergic drugs are antihistamines.
Histamines: These are potent vasodilator. It has various functions.

 It contracts the smooth muscles in the bronchi and gut and relaxes other muscles, such
as those in the walls of fine blood vessels.
 Histamines are also responsible for the nasal congestion associated with common cold
and allergic response to pollen.
1. Antacids:
Drugs (antihistamines) which reduces or neutralises the over production of acid
(gastric juices) in the stomach that causes irritation and pain and in severe cases,
ulcers in the stomach are called as antacids.
Example: Sodium hydrogen carbonate, mixture of aluminium and magnesium hydroxide

(milk of magnesia), cimetidine (Tegamet), ranitidine (Zantac)...etc.
Note:
 Excessive hydrogen carbonate can make the stomach alkaline and trigger the production of even
more acid.
 Metal hydroxides are better alternatives because of being insoluble, these do not increase the pH
above neutrality.
 These treatments control only symptoms, but not the cause. Therefore, with these metal salts, the
patients cannot be treated easily.
 In advanced stages, ulcers become life threatening and its only treatment is removal of
the affected part of the stomach.
 A major breakthrough in the treatment of hyperacidity came through after the discovery of
a chemical, histamine, which stimulates the secretion of pepsin and hydrochloric acid in
the stomach.
2. Antiallergic:

Drugs (antihistamines) which cure the nasal congestion associated with common
cold and allergic response to pollen are called antiallergic drugs.
Example: Brompheniramine (Dimetapp) and terfenadine (Seldane), cetrazine....etc
Note: Antiallergic and antacid drugs both are antihistamines which work on different receptors.
II. Neurologically Active Drugs:

The drugs which affect the message transfer mechanism from nerve to receptors
are called neurologically active drugs.
Example: Tranquilizers, analgesics and antipyretics are neurologically active drugs.
1. Tranquilizers (psychotherapeutic drugs):

Drugs used in the treatment of anxiety, stress, irritability or excitement, and mild or
even severe mental diseases by inducing a sense of well-being in patients are called
tranquilizers.
Note: They form an essential component of sleeping pills.
Example: Barbiturates (veronal, amytal, nembutal, luminal and seconal), valium, Equanil,
chlordiazepoxide and meprobamate, Iproniazid, phenelzine...etc.
Barbiturates:
Derivatives of barbituric acid are called barbiturates. They are hypnotic, i.e., sleep
producing agents.
Example: veronal, amytal, nembutal, luminal and seconal.
2. Analgesics:
The drug that reduce or relives pain without causing any impairment or reduction of
consciousness, mental confusion, incoordination or paralysis or some other
disturbances of nervous system are called anti analgesics.
Example: Aspirin, paracetamol, Morphine, Heroin, codeine. .etc.

Classification: They are classified as follows:
(a) Non-narcotic (non-addictive) analgesics.
(b) Narcotic drugs.
(a) Non-narcotic (non-addictive) analgesics:

These are the analgesic drugs which do not cause addiction or habit forming are
called as non-narcotic drugs.
These drugs are effective in relieving skeletal pain such as that due to arthritis.
Example: Aspirin, paracetamol
(b) Narcotic analgesics:

These are the analgesic drugs which cause addiction or habit forming are called as
narcotic drugs.

These drugs in small doses are effective in relieving postoperative pain, cardiac pain and
pains of terminal cancer, child birth pain and produce sleep. In poisonous doses (excess),
these produce stupor, coma, convulsions and ultimately death.
Note:
Morphine narcotics are sometimes referred to as opiates, since they are obtained from the
opium poppy.
3. Antipyretics: These are the drugs which lowers the body temperature during high
fever conditions
Example: Aspirin, paracetamol phenacetine......etc.
Note:
 Aspirin acts as both analgesic and antipyretic.
 Aspirin inhibits the synthesis of chemicals known as prostaglandins which stimulate
inflammation in the tissue and cause pain.
 Aspirin has many other effects such as preventing platelet coagulation. Because of its
anti blood clotting action, aspirin finds use in prevention of heart attacks.
III. Antimicrobials:
Drugs used to destroy or prevent development or inhibit the pathogenic action of
microbes such as bacteria (antibacterial drugs), fungi (antifungal agents), virus
(antiviral agents), or other parasites (antiparasitic drugs) selectively are called
antimicrobials.
Example: Antibiotics, antiseptics and disinfectants are antimicrobial drugs.
1. Antibiotics:
These are chemical substances produced by microorganisms such as bacteria,
fungi and moulds that inhibit the growth or even destroy other harmful
microorganisms (bacteria).
Development of synthetic methods has helped in synthesising some of the
compounds that were originally discovered as products of microorganisms. Also, some
purely synthetic compounds have antibacterial activity, and therefore, definition of antibiotic
has been modified. An antibiotic now refers to a substance produced wholly or partly
by chemical synthesis, which in low concentrations inhibits the growth or destroys
other harmful
microorganisms by intervening in their metabolic processes.
Example: Penicillin. etc.
CLASSIFICATION OF ANTIBIOTICS:
a) Based on the killing of inhibiting nature:

There are two types of antibiotics
i. Bactericidal antibiotics:
Antibiotics which kill the other harmful microorganisms are called bactericidal
antibiotics.
Example: Pencillin, Aminoglycosides, ofloxacin. etc.

ii. Bacteriostatic antibiotics:
Antibiotics which inhibit the growth of other harmful microorganisms are called
bacteriostatic antibiotics.
Example: Erythromycin, tetracycline, chloremphenicol.
b) Based on the spectrum of action: The range of bacteria or other microorganisms that
are affected by a certain antibiotic is expressed as its spectrum of action.
i. Broad spectrum antibiotics:
Antibiotics which kill or inhibit a wide range of Gram-positive and Gram-negative
bacteria are said to be broad spectrum antibiotics.
Example: Chloramphenicol, Vancomycin, ofloxacin and synthetic modifications of
penicillins like Ampicillin and Amoxycillin.
ii. Narrow spectrum antibiotics:

Antibiotics which kill or inhibit mainly against Gram-positive or Gram-negative
bacteria are said to be narrow spectrum antibiotics.
Example: Penicillin G
iii. Limited spectrum antibiotics:

Antibiotics which kill or inhibit a single organism or disease causing bacteria,
they are said to be limited spectrum antibiotics.
Example: PAS (p-Amino salicylicacid) [used in the treatment of tuberculosis]
Note:
 It is absolutely essential to test the patients for sensitivity (allergy) to penicillin before it is
administered.
 In India, penicillin is manufactured at the Hindustan Antibiotics in Pimpri and in private sector
industry.
 Chloramphenicol, isolated in 1947, is a broad spectrum antibiotic. It is rapidly absorbed from
the gastrointestinal tract and hence can be given orally in case of typhoid, dysentery, acute
fever, certain form of urinary infections, meningitis and pneumonia.
 The antibiotic dysidazirine is supposed to be toxic towards certain strains of cancer cells.
2. Antiseptics and disinfectants:

Antiseptics and disinfectants are also the chemicals which either kill or prevent the
growth of microorganisms.
Antiseptics:
These are the drugs applied to the living tissues such as wounds, cuts, ulcers and
diseased skin surfaces are called antiseptics.

Example: Furacine, soframicine, Iodine (Its 2-3 per cent solution in alcohol-water mixture is
known as tincture of iodine), Iodoform (CHI 3), Boricacid (in dilute aqueous solution is weak
antiseptic for eyes), KMnO4 ...etc.
Disinfectants:
These are the chemical substances that are applied to inanimate objects such as
floors, drainage system, instruments, etc.
Example: Chlorine in the concentration of 0.2 to 0.4 ppm in aqueous solution and sulphur
dioxide in very low concentrations, are disinfectants.
Note: Some substances can act as an antiseptic as well as disinfectant by varying the
concentration.
Example:
a. 0.2 per cent solution of phenol is an antiseptic while its one percent solution is disinfectant.
b. Dettol (it is a mixture of chloroxylenol and terpineol)
c. Bithionol (the compound is also called bithional)
CH3
OH
Cl OH HO Cl
S
H3C CH3 OH
Cl H3C CH3 Cl Cl
Chloroxylenol Terpineol Bithionol
IV. Antifertility Drugs:

These are the drugs used in control of population or birth are called antifertility
drugs.
Example: Norethindrone, ethynylestradiol (novestrol)...etc.
Chemicals in Food:
Chemicals are added to food for
(i) Preservation (ii) Enhancing their appeal and (iii) Adding nutritive value in them
Main categories of food additives are as follows:

i. Food colours
ii. Flavours and sweeteners
iii. Fat emulsifiers and stabilising agents
iv. Flour improvers – antistaling agents and bleaches
v. Antioxidants
vi. Preservatives
vii. Nutritional supplements such as minerals, vitamins and amino acids.

Except for chemicals of category (vii), none of the above additives have nutritive value and
these are added either to increase the shelf life of stored food or for cosmetic purposes.
Here we will discuss only sweeteners and food preservatives.
Artificial Sweetening Agents:

Artificial sweeteners are compounds which have sweet taste but have low calorific
value.
Introduction:
Natural sweeteners, e.g., sucrose add to calorie intake and therefore many people prefer
to use artificial sweeteners.
Ortho-sulphobenzimide, also called saccharin, is the first popular artificial sweetening
agent. It has been used as a sweetening agent ever since it was discovered in 1879. It is
about 550 times as sweet as cane sugar.
It is excreted from the body in urine unchanged. It appears to be entirely inert and
harmless when taken. Its use is of great value to diabetic persons and people who need to
control intake of calories. Some other commonly marketed artificial sweeteners are given in
following table.
Sweetness value
Artificial
Sl.No. Structural formula in comparission
sweetener
to cane sugar
O O O
HO-C-CH2-CH-C-NH-CH-C-OCH 3
NH2 CH2
Aspartic acid part
1. Aspartame 100
Phenyl alanine
methyl ester part
CO
2. Saccharin NH 550
SO2
CH2OH
H OH
H
OH H
3. Sucrolose OH H 600
Cl O CH2Cl
H HO
H OH
ClH2C O H

CH3 CH3
O O O C
4. Alitame HO-C-CH2-CH-C-NH-CH-C-NH-CH S 2000

NH2 CH3 C
CH3 CH3
 Aspartame is the most successful and widely used artificial sweetener. It is roughly 100
times as sweet as cane sugar. It is methyl ester of dipeptide formed from aspartic
acid and phenylalanine. Use of aspartame is limited to cold foods and soft drinks
because it is unstable at cooking temperature.
 Sucrolose is trichloro derivative of sucrose. Its appearance and taste are like sugar. It
is stable at cooking temperature. It does not provide calories.
 Alitame is high potency sweetener, although it is more stable than aspartame, the control
of sweetness of food is difficult while using it.
Food preservatives:
Chemicals added to food to prevent spoilage of food due to microbial growth are
called food preservatives.
Examples: Table salt, sugar, vegetable oils and sodium benzoate (C 6H5COONa) [Sodium
benzoate is used in limited quantities and is metabolised in the body], BHT (Butylated
hydroxy toulene), BHA (Butylated hydroxy anisole), Salts of sorbic acid and propanoic acid
are also used as preservatives (prevents the growth of yeasts and moulds).
Cleansing Agents:
Chemicals substances used for cleaning purposes are called as cleansing agents.
They are usually called as detergents.
There are two types of detergents namely:

1. Soaps
2. Synthetic detergents.
They improve cleansing properties of water and help in removal of fats which bind other
materials to the fabric or skin.
Soaps:
Soaps are sodium or potassium salts of long chain fatty acids.
Example: Sodium stearate (C17H35COONa), sodium oleate (C17H33COONa) and sodium
palmitate (C15H31COONa).
Preparation: Oils and fats on heating with a solution of sodium hydroxide or potassium
hydroxide, base hydrolysis takes place forming sodium or potassium salts of fatty acids
(soaps) and glycerol. . This reaction is known as saponification.

O
CH2 O C C17H35 CH2 OH
O
CH O C C17H35 + 3 NaOH 3 C17H35COONa CH OH
O +
CH2 O C C H CH2 OH
17 35
Tristearin Sodiumstearate Glycerol
(Glyceryl tristearate) (Glycerine)
Note: The soap obtained remains in colloidal form. It is precipitated from the solution by
adding sodium chloride. The solution left after removing the soap contains glycerol, which
can be recovered by fractional distillation. Only sodium and potassium soaps are soluble in
water and are used for cleaning purposes. Generally potassium soaps are soft to the skin
than sodium soaps. These can be prepared by using potassium hydroxide solution in place
of sodium hydroxide.
Types of soaps:
Basically all soaps are made by boiling fats or oils with suitable soluble hydroxide. Variations
are made by using different raw materials.
1. Toilet soaps: They are prepared by using better grades of fats and oils and care is taken
to remove excess alkali. Colour and perfumes are added to make these more attractive.
These soaps are free from excess alkali and hence give more lather.
2. Floating soaps: They are prepared by beating tiny air bubbles before their hardening
hence these float on water.
3. Transparent soaps: They are prepared by dissolving the soap in ethanol and then
evaporating the excess solvent.
4. Medicated soaps: These are soft soaps containing substances of medicinal value. In
some soaps deodorants are also added.
5. Shaving soaps: These soaps are potassium sodium stearates containing glycerol to
prevent rapid drying. A gum called, rosin is added while making them. It forms sodium
rosinate which lathers well.
6. Laundry soaps: These soaps contain fillers like sodium rosinate, sodium silicate, borax
and sodium carbonate.
7. Soap chips: They are prepared by running a thin sheet of melted soap onto a cool
cylinder and scraping off the soaps in small broken pieces.
8. Soap granules: They are dried miniature soap bubbles.
9. Soap powders and scouring soaps: They contain some soap, a scouring agent
(abrasive) such as powdered pumice or finely divided sand, and builders like sodium
carbonate and trisodium phosphate. Builders make the soaps act more rapidly.

Action of soaps with hard water:
Hard water contains calcium and magnesium ions. These ions form insoluble calcium and
magnesium soaps respectively when sodium or potassium soaps are dissolved in hard
water. These insoluble soaps separate as scum in water and are useless as cleansing agent.
C17H35COONa + CaCl2 (C17H35COO)2Ca + 2 NaCl
Sodium stearate Calcium stearate
(Soluble) (In soluble)
Note:
 In fact these are hinderance to good washing, because the precipitate adheres onto the
fibre of the cloth as gummy mass.
 Hair washed with hard water looks dull because of this sticky precipitate.
 Dye does not absorb evenly on cloth washed with soap using hard water, because of this
gummy mass.
Synthetic Detergents:
These are the cleansing agents which have all the properties of soaps, but which
actually do not contain any soap in them hence they are also called as soap less soap.
These can be used both in soft and hard water as they give foam even in hard water. Some
of the detergents give foam even in ice cold water.
Synthetic detergents are mainly classified into three categories:
(i) Anionic detergents
(ii) Cationic detergents and
(iii) Non-ionic detergents.
(i) Anionic Detergents:

These are sodium salts of sulphonated long chain alcohols or hydrocarbons.
Preparation: long chain alcohols on heating with concentrated sulphuric acid gives alkyl
hydrogensulphates that on neutralisation with alkali gives anionic detergents.
Similarly alkyl benzene sulphonates are obtained by neutralising alkyl
benzene sulphonic acids with alkali.
CH3-(CH2)11-OH Conc. H2SO4 NaOH - +

-H2O
CH3-(CH2)11-OSO3H -H2O CH3-(CH2)11-OSO3 Na
Lauryl alcohol Lauryl hydrogensulphate Sodium laurylsulphate
H C-(H C) Conc. H2SO4 H C-(H C) SO H NaOH H C-(H C) -

SO Na +
3 2 11 - 3 3 2 11 3
3 2 11 -
H2O H2O
Dodecyl benzene
Dodecyl benzene sulphonicacid Sodium dodecylbenzenesulphonate
 In anionic detergents, the anionic part of the molecule is involved in the cleansing action.
 Sodium salts of alkylbenzenesulphonates are an important class of anionic detergents.
 They are mostly used for household work.
 Anionic detergents are also used in toothpastes.
(ii) Cationic Detergents:
Cationic detergents are quarternary ammonium salts of amines with acetates,
chlorides or bromides as anions.
Cationic part possesses a long hydrocarbon chain and a positive charge on nitrogen atom.
Hence, these are called cationic detergents.
Example: Cetyltrimethyl ammonium bromide is a popular cationic detergent. It is used in hair
conditioners.
+
CH3
-
CH3-(CH2)15 N CH3 Br
CH3
Cetyl trimethyl ammonium bromide

 Cationic detergents have germicidal properties and are expensive; therefore, these are of
limited use.
(iii) Non-ionic Detergents:
Detergents not containing any ion in their constitution are called as Non-ionic
detergents.
Preparation: When stearic acid reacts with polyethylene glycol an non-ionic detergent of
ester of stearic acid and poly ethylene glycol is obtained.
CH3-(CH2)16-COOH HO-(CH2-CH2-O)n-CH2-CH2-OH CH3-(CH2)16-COO-(CH2-CH2-O)n-CH2-CH2-OH
-H2O
+
Stearic acid Polyethyleneglycol Stearic acid polyethyleneglycol ester
 Liquid dishwashing detergents are non-ionic type.

 Mechanism of cleansing action of this type of detergents is the same as that of soaps.
 These also remove grease and oil by micelle formation.
Harmful effects of detergents:

Main problem that appears in the use of detergents is that if their hydrocarbon chain is highly
branched, then bacteria cannot degrade this easily. Slow degradation of detergents leads to
their accumulation. Effluents containing such detergents reach the rivers, ponds, etc. These
persist in water even after sewage treatment and cause foaming in rivers, ponds and
streams and their water gets polluted.
These days the branching of the hydrocarbon chain is controlled and kept to
the minimum. Unbranched chains can be biodegraded more easily and hence pollution is
prevented.
**************

-KX

2 II Pu Chem Vol-2 2019 Briks (3)

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2 II Pu Chem Vol-2 2019 Briks (3)

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CHAPTER: 10

HALOALKANES AND HALOARENES

I) On the Basis of Number of Halogen Atoms:

BRIKS ACADEMY 1 Prepared by Maruthi.R

II) Classification of monohalo compounds on the Basis of hybridisation of the

i. Compounds containing sp3 C—X Bond (X= F, Cl, Br, I);

a) Monohaloalkanes OR Alkyl halides:

Benzylic halides: CH2 X

BRIKS ACADEMY 2 Prepared by Maruthi.R

BRIKS ACADEMY 3 Prepared by Maruthi.R

iii) Polymethylene dihalides (terminal dihalides) are the dihalo compounds

Note: Fully halogenated compounds are called perhalohydrocarbons, which

BRIKS ACADEMY 4 Prepared by Maruthi.R

BRIKS ACADEMY 5 Prepared by Maruthi.R

Trihaloarenes: They are named as Trihalobenzene.

Isomerism in haloalkanes and haloarenes:

Haloalkanes show two types of isomerism.

CH3CH2CH2I CH3 CH CH3

BRIKS ACADEMY 6 Prepared by Maruthi.R

Conditions for a molecule to exhibit optical isomerism:

Plane polarized light:

BRIKS ACADEMY 7 Prepared by Maruthi.R

Chiral C-atom / asymmetric C-atom / Chirality Centre:

Plane of symmetry or mirror plane or sigma plane:

BRIKS ACADEMY 8 Prepared by Maruthi.R

The optical activity of a substance is determined by using an instrument called polarimeter.

Ex: (±) 2 – Bromobutane.

BRIKS ACADEMY 9 Prepared by Maruthi.R

a) Using Hydrogen halides (HX) (Halogen acids):

Example: CH -CH -OH + HCl anhy. ZnCl2 CH3-CH2-Cl + H O (Grooves process)

Example: CH -CH -OH +H-Br conc. H2SO4 CH3-CH2-Br + H2 O

BRIKS ACADEMY 10 Prepared by Maruthi.R

General reaction: R-OH + NaBr + Heat

b) Using Phosphorous halides (PX3/PX5): Haloalkanes are prepared by the action of

3 R-OH Red P/ X 2 3 R-X

BRIKS ACADEMY 12 Prepared by Maruthi.R

General reaction: R-CH-CH2

BRIKS ACADEMY 14 Prepared by Maruthi.R

Preparation of Haloarenes: (aryl halides)

1) By Electrophilic substitution reaction:

Example: 2 Anhy. FeBr

2) Sand meyer’s Reaction:

BRIKS ACADEMY 16 Prepared by Maruthi.R

General reaction: 0 C-5 C

Aniline Benzene diazonium halide

Benzene diazonium halide Iodobenzene

4. Melting and boiling points:

BRIKS ACADEMY 17 Prepared by Maruthi.R

B.P in K 453 446 448

6. Solubility: The haloalkanes are only very slightly soluble in water.

Nature of C-X Bond:

Example: CH3-CH=CH2 + KCl + H2O

Example: CH3-CH2-CH-CH3 + KOH(alc.)

BRIKS ACADEMY 19 Prepared by Maruthi.R

b) Reaction with magnesium metal: (preparation of Grignard reagent)

General reaction: Dry ether

3) Nucleophile substitution reactions:

BRIKS ACADEMY 21 Prepared by Maruthi.R

a) Reaction with Aqueous KOH/NaOH :( substitution by Hydroxyl group)

b) Reaction with Water: (substitution by Hydroxyl group)

c) Reaction with Sodium alkoxide: (substitution by alkoxy group)

c) Reaction with alcoholic Potassium cyanide: (substitution by cyano group)

BRIKS ACADEMY 22 Prepared by Maruthi.R

BRIKS ACADEMY 23 Prepared by Maruthi.R