PHARMACEUTICAL CHEMISTRY

Alkanes, Alkenes, Alkynes, Alkyl Halides, Alicyclic Hydrocarbons, Alcohols,

Ethers and Epoxides, Aldehydes and Ketones, Carboxylic Acids and their
Functional Derivatives


Sameena Bano
Department of Chemistry
Faculty of Science
Jamia Hamdard
New Delhi-110062


(24.07.2007)

CONTENTS
Alkanes
Alkenes or Olefins
Alkynes
Alkyl Halides
Alicyclic Hydrocarbons or Cyclo Alkanes
Alcohols
Ethers
Epoxides
Aldehydes and Ketones
Carboxylic Acids and Their Functional Derivatives




Keywords
Alkanes, alkenes, alkynes, alkyl halides, alicyclic hydrocarbons, alcohols, ethers, epoxides, aldehydes, ketones and
carboxylic acids




1
Alkanes
The alkanes are simplest and least reactive class of organic compounds, because they contain
only carbon and hydrogen and they have no functional groups. They also referred to as Paraffins.
Alkanes are the saturated hydrocarbon with general formula (C
n
H
2n+2
). Alkanes contain only
single covalent carbon-carbon (C-C) and Carbon Hydrogen(C-H) bonds. Each carbon atom of
alkanes is sp
3
hybridized.



Structure of Methane Structure of Ethane

All C-C and C-H bonds are bonds and every C-H and C-C bond lengths have the value 1.09A
o

and 1.54A
o
respectively. All bond angles are tetrahedral (109.5
o
) because of tetrahedral position
of the four bonds of carbon, the C-C chain is zig-zag and not linear some examples of the
alkanes are
CH
3
-CH
2
-CH
3
CH
3
-CH
2
-CH
2
-CH
3
Ethane [ C
2
H
6
] Propane [C
3
H
8
]
Butane [C
4
H
10
]
Methane [CH
4
]
CH
3
-CH
2
-CH
2
-CH
2
-CH
3
Pentane
C
H
H
H
H C
H
C
H
H
H
H
H

First three members do not exhibit isomerism but the higher members [butane and onwards]
exhibit chain isomerism.
Iso butane[C
4
H
10
] Iso pentane [ C
5
H
12
]
Neo pentane [C
5
H
12
]
C H
3
CH CH
3
CH
3
C H
3
CH CH
2
CH
3
CH
3
C H
3
C CH
3
CH
3
CH
3

Methods of preparations:
i) Hydrogenation of unsaturated hydrocarbons: Alkenes or alkynes react with hydrogen in
presence of catalyst (Ni, Pt or Pd) at 200-300
o
C

to give alkanes. (Sabatier and Senderens
reaction).
2
R-CH=CH
2
H
2
Ni or Pt
R-CH
2
-CH
3
Alkene
Alkane
R-C=CH +2H
2
Ni or Pt
R-CH
2
-CH
3
Alkane
+
Alkyne

ii) Reduction of alkyl halide: Alkyl halide on reduction gives alkanes. Reducing agents used for
reduction are zinc and acetic acid; Zn-Cu couple in ethanol; or LiAlH
4
, H
2
gas and Ni or Pt
catalyst.

R-X 2H R-H HX
+
+

Alkyl iodides are conveniently reduced by heating with HI and red P in sealed tube.

R-I +HI
P
150
o
; pressure
RH +
I
2

The function of red phosphorous is to remove the iodine formed by forming PI
3
otherwise it
would react with alkane to give back alkyl iodide.

iii) Reduction of Alcohols, Aldehydes, Ketones and fatty acids:
a) Alcohols, aldehydes, ketones and fatty acids can be reduced with hot hydroiodic acid and red
phosphorous to give alkanes.
R-OH 2HI
red P
R-H
H
2
O
I
2
R-CHO 4HI R-CH
3
2I
2
R-CO-R
R-CH
2
R
R-COOH
6HI 2H
2
O 3I
2
red P
red P
red P
4HI
R-CH
3

H
2
O
H
2
O 2I
2
+
+
+
+
+
+
+
+
+
+
+
+

b) Aldehydes and ketones can also be reduced to alkanes by means of amalgamated zinc and
Conc. Hydrochloric acid (Clemmensen reduction)
Zn-Hg/HCl
R-CH
3
H
2
O
R-CH
2
R H
2
O
Zn-Hg/HCl
+
+
R C H
O
R C R
O

3
iii) Wurtz Reaction: Higher alkanes are produced by heating an alkyl halide with sodium metal
in dry ether solution. Two molecules of alkyl halide (RX) condense with sodium metal to give
symmetrical alkane (R-R).

R-X 2Na X-R
R-R
2NaX
dry ether
alkane
+
+
+

If two reacting alkyl halides are different, mixture of three alcohols are produced which is
difficult to separate. For example methyl iodide and ethyl iodide gives the mixture of ethane,
propane and butane.

CH
3
-I
2Na I-C
2
H
5
CH
3
-C
2
H
5 2NaI + + +
Propane


CH
3
-I
2Na I-CH
3
CH
3
-CH
3 2NaI + + +
Ethane


C
2
H
5
-I
2Na I-C
2
H
5
C
2
H
5
-C
2
H
5
2NaI + + +
Butane

USE:-Therefore this method is useful only for the preparation of symmetrical alkanes.

v) Corey-House Alkane synthesis: This method is superior to Wurtz synthesis. It involves first
conversion of alkyl halide to lithium dialkyl cuperate, LiR
2
Cu and then coupling between lithium
alkyl cuperate and an alkyl halide.
R-X +2Li RLi +LiX
2RLi +CuI
+LiI
+R'X
R-R' +RCu +LiX
Li(R)
2
Cu
R
2
CuLi
Alkane

USE:-This method is suitable for preparation unsymmetrical alkane.

vi) Hydrolysis of Grignard Reagent: Alkyl magnesium halide which is prepared by treating
alkyl halides with magnesium in dry ether, on hydrolysis yield alkane.
RX +Mg
ether
RMgX
RMgX
+HOH R-H +MgX(OH)
Alkane
Alkylmagnesium halide

vii) Decarboxylation of Carboxylic acids: Salt of Carboxylic Acid when heated strongly with
sodalime (NaOH+CaO), decarboxylate to give alkane.
4
R-COONa +NaOH
CaO
R-H +Na
2
CO
3
CH
3
COONa +NaOH
CaO
CH
4
+
Na
2
CO
3

USE:-The alkane produced has one carbon less in its tsructure as campared to parent.

viii) Kolbes Synthesis: Alkane is collected at anode when a concentrated solution of sodium or
potassium salt of carboxylic acid is electrolyzed using Platinum electrodes.
2 RCOONa +
2H
2
O CO
2
AT ANODE

2NaOH +
H
2
AT CATHODE
R-R + +

USE:-This method is also suitable for the preparation of symmetrical alkanes.

Properties of Alkanes:
Physical Properties:
1) First four members (methane to butane) are colourless, odourles gases , next
thirteen (C
3
to C
17
)are colourless, odourles liquids while higher alkanes are
colourless wax like solids.
2) These are insoluble in water as they are nonpolar compounds but soluble in
organic solvents like ether, benzene and acetone etc. Liquid alkanes are lighter
than water.
3) In case of normal alkanes boiling points and specific gravities increase with rise
in molecular weights. As a rule the boiling points of alkanes having branched
carbon chain are lower than those of isomeric normal alkanes.
4) Variation in the melting point of alkanes is not regular. Alkanes with odd
number of carbon atoms have lower melting point than the next lower and next
higher alkanes having even number of carbon atoms. This is due to the greater
inter molecular attraction in even numbered alkanes having end carbon on the
opposite sides of the molecules.

Chemical properties:
1) Alkanes are extremely stable and inert substances. This is due to the fact that there is a
small difference in the electro negativity of carbon (2.60) and hydrogen (2.10). Thus the
bond electron in C-H bond are practically equally shared between them and the bond is
almost non polar. The C-C bond is completely non polar. Therefore electrophillc or
nucleophillic reagent find no site for attack on alkane molecules. Furthermore, the C-H
and C-C bonds are strong bonds. Alkanes due to these types of strong bonds remain
unaffected by acids, alkalies and oxidizing agents under ordinary conditions.

Lower alkanes undergo two types of reactions:
i) Substitution Reaction
ii) Thermal and catalytic Reactions
5
Some of the important reactions of alkanes are following.

1) Halogenations: This involves replacement of hydrogen atom by halogen atom.
a) Chlorination: Alkanes react with chlorine in presence U.V light or diffused sunlight or at
temperature 300-400
o
C to form the corresponding substituted products.
For example: Methane reacts with chlorine to give mixture of different substituted products.
CH
4
Cl
2
-HCl
CH
3
Cl
methyl chloride
Cl
2
-HCl
CH
2
Cl
2
Cl
2
-HCl
CHCl
3
CCl
4
dichloromethane
Cl
2
-HCl
chloroform
carbon tetra choride

It is difficult to stop this reaction at first step. However, the yield of CH
3
Cl can be improved by
taking excess of methane. Ethane and higher alkanes react with chlorine in a similar way and all
possible substitution products are obtained.

b) Bromination: Bromine reacts with alkanes in a similar way but slowly and at higher
temperature.

c) Iodination: It is reversible. The hydrogen iodide formed during iodination reduces the product
back to reactant hence it must be carried out in the presence of strong oxidizing agent like iodic
acid or nitric acid which destroys the hydroiodic acid (HI) as it is formed.
CH
4
I
2
CH
3
I+HI +
5HI
HIO
3
3I
2
3H
2
O + +

d)Fluorination: Since fluorine is most reactive, fluorination under ordinary condition
accompanies by explosion. Fluoroalkane can however be obtained from alkane by action of
fluorine diluted with Nitrogen.

2) Nitration: This involves replacement of hydrogen atom by NO
2
group. Nitration is carried
out by heating mixture of alkanes and nitric acid vapours at 400-500
o
C. The process is known as
Vapour Phase Nitration.
R-H HO-NO
2 +
400-500
o
C
R-NO
2
H
2
O +

Since the reaction is carried out at high temperature, chain fusion also takes place during the
reaction and mixture of all possible mono nitro derivatives are obtained.
For example,
CH
3
CH
2
CH
3
HNO
3
CH
3
CH
2
CH
2
NO
2
CH
3
-CH-CH
3
C
2
H
5
NO
2
CH
3
NO
2
NO
2
+
+
+
400
o
C

3) Sulphonation: This involves replacement of hydrogen atom by SO
3
H group. It is carried out
by heating alkanes with fuming sulphuric acid or oleum at higher temperature.
6
R-H R-SO
3
H
H
2
O
alkane fuming sulphuric acid alkane sulphonic acid
HO-SO
3
H
+
+

Lower alkanes do not give this reaction.

4) Thermal decomposition [Pyrolisis or Cracking]: The decomposition of compound by heat
is known as pyrolysis. Thermal decomposition when applied to alkanes it is known as Cracking.
This leads to the formation of lower alkanes, alkenes and hydrogen etc. For example
CH
3
CH
3
CH
3
400-600
o
C
CH
2
=CH-CH
3
CH
2
=CH
2 CH
4
CH
4
400-600
o
C
+
+

In presence of catalyst pyrolysis can be carried out at less higher temperature. This is called
Catalytic Cracking.

5) Isomerisation: Conversion of alkanes to its chain isomer is carried out by heating normal
alkane with anhydrous AlCl
3
and HCl at 25
o
C. For example,
CH
3
-CH
2
-CH
2
-CH
3
AlCl
3
/HCl
25
o
C
CH
3
-CH-CH
3
CH
3
n-Butane
Iso butane

6) Aromatisation: Conversion of aliphatic compound to aromatic compounds is known as
aromatisation. Alkanes containing 6-10 carbon atoms are converted into benzene and its
homologous at high temperature and in the presence of catalyst.
For example:
Cr
2
O
3
-Al
2
O
3
600
o
C
4H
2
n-Hexane
Benzene
CH
3
CH
2
CH
2
CH
2
H
2
C
H
2
C
CH
3

CH
CH
C
CH
HC
HC
CH
3
CH
3
CH
2
CH
3
CH
2
CH
2
CH
2
n-Heptane Toluene
Cr
2
O
3
-Al
2
O
3
600
o
C
CH
CH
CH
CH
HC
HC
4H
2 +
+

7) Oxidation[Combustion]: When burnt in excess of air or oxygen alkanes form carbon
dioxide and water with the evolution of heat.

7
For Example:
CH
4
2O
2
CO
2
2H
2
O heat
+ +
+
2C
2
H
6
7O
2
4CO
2
6H
2
O
+ +
heat
+

In general,
n
2n
+
2
C H
3n+1
2
O
2 nCO
2 +
+ (n+1) H
2
O
+heat

The evolution of heat in this reaction forms the basis of the use of these hydrocarbons as source
of heat and power.

Alkenes or Olefins
Alkenes are unsaturated hydrocarbons containing carbon-carbon double bond (C=C) in their
molecules. General formula of alkene is C
n
H
2n
. They are commonly known as olefins because
lower members form oil products with chlorine or bromine (Latin Oleum=Oil; ficane = to make).
Ethylene and propylene are the first and second members of this series respectively.
C C
H H
H H
C C
H H
C H
3
H
or
or
CH
2
=CH
2
CH
3
CH=CH
2
Ethylene ( C
2
H
4
)
Propylene (C
3
H
6
)


Double bonded carbon in alkenes is sp
2
hybridised. The Carbon-Carbon double bond in alkene
consists of one sigma () and one pi () bond. Sigma bond is formed by overlapping of sp
2

hybrid orbital of each carbon and bond is formed by overlapping of unhybridised p-orbitals.
The two carbon atoms which are double bonded in alkanes are held more tightly together than in
alkane with the result C=C bond length in alkene is less (1.34A
o
) than C-C bond length in
alkanes.
For example;

Orbital Structure of Ethane
8
Alkanes are more reactive than alkanes this is due to the availability of more exposed -
electrons.

Methods of Preparations:
1) Dehydration of Alcohols: When an alcohol is heated with concentrated sulphuric acid at
100
o
C or with phosphoric acid at 200
o
C or by passing alcohol vapour over alumina, P
2
O
5

or
anhydrous zinc chloride at 350-400
o
C a molecule of water is eliminated and alkene is formed.
R CH CH
2
H OH
R-CH=CH
2
H
2
O
+

The ease of dehydration follows the following order.
3
o
alcohol >2
o
alcohol >1
o
alcohol
Dehydration of unsymmetrical 2
o
or 1
o
alcohol can proceed in two ways and mixture of alkene
is formed for example dehydration of 2-butanol yields mixture of 2-butene.(major product) and
1-butene (minor product).

C H
3
CH CH CH
H H OH
H
2
SO
4
H
2
SO
4
CH
2
-CH=CH-CH
3
CH
3
-CH
2
-CH=CH
2
2-Butene; 80%
1-Butene ; 20%

In such cases major products can be predicted by Saytzeffs rule. Which states that Hydrogen is
preferentially eliminated from the carbon atom with fewer number of hydrogen atoms. Thus 2-
butene is the major product in above example. In other words Saytzeffs rule states that Greater
the number of alkyl groups attached to the double bonded carbon atoms, the more stable is the
Alkene. Hence more substituted alkene is preferentially formed. The ease of formation of
alkene is ,

R
2
C=CR
2
> R
2
C=CHR > R
2
C=CH
2
> RCH=CHR > RCH=CH
2

This can be explained on the basis of more stability of more substituted carbonium ion formed.
ii) By dehydrogenation of Alkyl halides: when an alkyl halide is heated with alcoholic NaOH
or KOH, one molecule of hydrogen halide (HX) is eliminated to give alkene.
R-CH
2
-CH
2
X
alc.KOH
R-CH=CH
2
+
HX

The ease of dehydrogenation of alkyl halide is
3
o
alkyl halide>2
o


alkyl halide >1
o
alkyl halide
In case of dehydrogenation of 2
o
and 3
o
alkyl halides the major product can be predicted
according to Saytzeffs rule. E.g.

9
C H
3
CH CH
2
CH
3
Br
alc. KOH
CH
2
=CH-CH
2
-CH
3
CH
3
-CH=CH-H
3
+
1-Butene
(minor)
2-Butene
(major)


iii) By Dehydro Halogenation of Vicinal Dihalide: when vicinal dihalides (containing two
halogen atoms at adjacent carbon) are heated with zinc dust in alcohol alkenes are produced.


C H
3
CH CH
2
Br Br
alcohol
R-CH=CH
2
ZnBr
2
Zn
+ +

iv) By Kolbes electrolytic method: electrolysis of aqueous solution of sodium or potassium
salt of saturated dicarboxylic acids yields alkene.

CH
CH
COONa
COONa
R
R
2H
2
O +
electrolysis
CH
CH
R
R
CO
2 2NaOH H
2 + + +
At Cathode
At anode


v) By controlled Hydrogenation of Alkyne: Alkyne is presence of Lindlar Catalyst react with
Hydrogen in controlled manners to give alkene. In Lidlar catalyst Pd is deactivated with CaCO
3

and quinoline.

R C C R +H
2
Pd-CaCO
3
quinoline
R-CH=CH
2
Alkene

vi) Cracking of Alkanes: Paraffins on heating at 500-800C in absence of air get decomposed
to lower molecular weight alkene, alkanes and hydrogen.
CH
4
+
CH
3
-CH
3

C
2
H
4
+
H
2
600 C

Properties of Alkenes:
Physical properties:
1) The first three members are gases at ordinary temperature, next 14 are liquids and the
higher ones are solids. Except ethylene all members are colourless and odorless. Ethylene
is pleasant smelling gas.
2) Alkenes are only slightly soluble in water but soluble in non polar solvents.
3) Generally, their boiling points, melting points and specific gravities rise with increase of
molecular weights. Further like alkanes, the branched chain alkenes have lower boiling
points than the corresponding n-alkenes.
4) Like alkanes, alkenes are generally non polar, but certain alkenes due to their
unsymmetrical structure are weakly polar. Trans alkene has a smaller dipole moment than
cis-isomer because trans isomer is relatively more symmetrical than cis-alkene. Due to
10
poorer symmetry molecules of cis-alkenes do not fit into the crystal lattice so well as in
the trans-isomer with the result cis akenes have generally lower melting points than the
trans.

Chemical properties: Alkenes are more reactive than alkanes due to the presence of -bond.
The electrons constituting bond are located much farther the carbon nuclei and are easily
available for reaction when needed. The overlap of atomic orbital forming -bond is not as
effective as that in bonds. Thus bond is weaker than bond and can be easily broken.

Addition reactions are the most important reactions of the carbon-carbon double bond.
electrons of double bond are easily available to the reagent. Thus carbon-carbon double bond
acts as a source of electrons for electrophilic reagents and undergoes electrophilic addition
reaction.

C C
H
H H
H
-bond
-bond
E-Nu
C H
3
C C CH
3
E
Nu
CH
3
CH
3
New - -bond
+


Mechanism of electrophillic addition to Carbon-Carbon double bond:
Step 1: Ionisation of (E-Nu) reagent
E-Nu E
+
+ :Nu
-
Electrophile Nucleophile

Step 2: Attack of electrophile (E+) to Carbon- Carbon double bond.
C C
CH
3
CH
3
C H
3
C H
3
E
+
C H
3
C
E
C H
3
CH
3
CH
3
alkene
+
+

The addition of electrophillic reagents relieves the strain of C=C (bond angle 120
o
) by converting
it to C-C (bond angle 109.5
o
)
Step-3: The nuclephile ( ) attack the carbonium ion to give the addition product.
Nu
-
:
C H
3
C C
E
C H
3
CH
3
CH
3
+
:Nu
+
-
C H
3
C C
E
C H
3
CH
3
CH
3
Nu
Carboniumion
Addition product

Because the addition reactions are initiated by electrophiles, they are referred to as electrophilic addition
reactions.
11
E
+
is usually H
+
, Br
+
or Cl
+
Nu
-
:
is usually Br
-
, Cl
-
,
-
OH or
-
OSO
3
H
Some of the important reactions of alkenes are following:
i) Addition of Hydrogen: Addition of hydrogen to alkenes takes place under pressure and in the
presence of catalyst like Ni, Pt or Pd to produce saturated hydrocarbons. This is called catalytic
hydrogenation.
R-CH=CH
2
H
2
Ni
R-CH
2
-CH
3
Alkene
Alkane
+

ii) Addition of Halogen: Alkenes reacts to halogen in presence of inert solvent to give dihalogen
derivative for example.

R-CH=CH
2
inert solvent
Alkene
+
Br
2
R CH CH
Br Br
Dibromo alkane

iii)Addition of Hydrogen Halide-(Hydro halogenation) : Addition of Hydrogen halide to
alkene produce alkyl halides. In case of symmetrical alkene only one alkyl halide is formed but
when the olefin is unsymmetrical two products are possible.
For Example:
RCH=CHR
HBr
R CH
2
CH
Br
symmetrical
alkene
alkyl halide
RCH=CH
2
HBr R CH CH
3
Br
R CH
2
CH
2
Br
2-Bromoalkane
1-Bromoalkane
CH
3
-CH=CH
2
HBr
C H
3
CH CH
3
Br
CH
3
CH
2
CH
2
Br
Iso propyl bromide Propyl bromide
symmetrical
alkene
+
+
+
+
+

It has been found that isopropyl bromide is the major product. In such cases addition is governed
by Markonikovs rule which states that,
When an unsymmetrical reagent(such as HX, H
2
SO
4
,HOCl etc) adds to an unsymmetrical
alkene, then the negative part of the reagent is added to that carbon atom of the double bond
which bears the least number of hydrogen atoms i.e which bears more substituents and positive
part of the reagent is added to that carbon atoms which bears greatest number of hydrogen
atoms i.e. which bears less substituents.

The reaction take place through ionic mechanism. Markonikovs rule can be explained with the
help of mechanism.

12
Step I: Isomerisation of reagent to give electrophile (H
+
) and nulceophile.(Br
-
)
HBr
H
+
Br-
Proton
Bromide ion
+

Step II: Attack of electrophile (H+) to double bond to form more stable carbocation.
CH
3
CH=CH
2
H
+
CH
3
-CH-CH
3
CH
3
-CH
2
-CH
2
+
I
II
2
o
carbonium ion (more stable)
1
o
carbonium ion (less stable)
+
+

I
II
More stable carbocation is preferentially formed.
Step III: Attack of nucleophile (Br-) to carbonium ion (more stable) to give major product.
CH
3
-CH-CH
3
:Br
+ -
C H
3
CH CH
3
Br
isopropyl bromide
+

Peroxide Effect - Anti markovnikov addition: Kharasch and Mayo 1933) discovered that
addition of HBr to propane or other unsymmertrical alkene in presence of organic peroxide (R-
O-OR) yields mainly n-alkyl bromide(anti markonikovs product). This effect is known as
peroxide effect or Kharasch effect. But it does not apply to addition involving HCl, HI or HF
CH
3
CH=CH
2 HBr
CH
3
CH
2
CH
2
Br
C H
3
CH CH
3
Br
peroxide
no peroxide
Propyl bromide
(Anti markonikov's product)
Iso propyl bromide
(markonikov's product)
+

In presence o f peroxide the addition takes place via a free radical mechanism rather than the
ionic mechanism. This addition of free radical to double bond involves the intermediate
formation of more stable free radical.

iv) Addition of Hypohalous acid: In hypohalous acid(HOX) OH is more negative part. They
add to alkene to give halohydrin. In case of unsymmetrical alkene Markonikovs rule is
followed.
13
C H
2
CH
2
HOCl
H
2
C CH
2
OH Cl
Ethylene
Ethylene chlorohydrin
CH
3
CH=CH
2
HOCl C H
3
CH CH
2
Cl
OH
Propylene
Propylene chlorohydrin
+
+


v) Addition of sulphuric acid: alkenes react with sulphuric acid to produce alkyl hydrogen
sulphates which on hydrolysis yield alcohols.
CH
3
CH=CH
2 C H
3
CH CH
3
OSO
3
H
propylene
Iso propyl hydrogen sulphate
HOSO
3
H
+
-
HOH
C H
3
CH CH
3
OH
+


vi) Addition of Alkene [Alkylation]:
Some alkanes add to alkenes in the presence of H
2
SO
4
or HF. The best example of this reaction is
addition of isobutane to isobutene to give isooctane [2,2,4-Trimethyl pentane]
C H
3
C
CH
3
CH
3
H C H
2
C CH
3
CH
3
C H
3
C CH
2
CH
3
C
CH
3
CH
3
CH
3
CH
3
H
2
SO
4
Iso octane
+

vii)Addition of Diborane [Hydroboration]: Diborane (B
2
H
6
) adds to the double bond as BH
3

to form trialkyl borane. The positive part of BH
3
is the boron, the negative part is hydrogen.
3RCH=CH
2
BH
3 (RCH
2
CH
2
)
3
B
alkene Trialkylborane
+


Try alkyl borane on treatment with alkaline aqueous solution of hydrogen peroxide are
converted to alcohols.

USE: They are used for the synthesis of 1
o
alcohol.
(RCH
2
CH
2
)
3
B H
2
O
2
H
2
O
OH-
3RCH
2
CH
2
OH H
3
BO
3
+ +
1
o
Alcohol

2) Oxidation: Alkane undergo oxidation reaction readily to form different compounds under
different conditions.
i)Oxidation with dilute Cold KMnO
4
: On oxidation with cold alkaline KMnO
4
(Bayerss
Reagent) alkenes give glycols.
14
C C
KMnO
4
H
2
O
C H
3
C C CH
3
CH
3
CH
3
OH OH
MnO
2
KOH
C H
2
CH
2
H
2
C CH
2
OH OH
Ethylene glycol
+ + +

Since the bright purple colour of KMnO
4
disappears during the reaction, Bayerss reagent is used
as a test for detecting the presence of Olefinic double bond.

ii)Oxidation with Hot KMnO
4
: Alkene on treatment with hot potassium permanganate solution
split at the double bond to form ketone and /or acids.
CH
3
-CH=CH
2
hot KMnO
4
[O]
CO
2
H
2
O C H
3
C
O
OH
C H
3
C C CH
3
CH
3
H
hot KMnO
4
[O]
C H
3
C
CH
3
O CH
3
COOH
+ +
+

iii) Oxidation with acidic KMnO
4
or K
2
Cr
2
O
7
: Alkenes when oxidized with these strong
oxidizing agents they are converted to ketones and /or carboxylic acid via glycols. e.g.
C H
3
CH
CH
2
C H
3
CH
H
2
C OH
OH
CH
3
COOH
HCOOH
[O]
[O]
H
2
O
+

C H
3
C
CH
3
CHCH
3
C H
3
C O
CH
3
CH
3
COOH
K
2
Cr
2
O
7
/H
+
or
KMnO
4
/H
+
+

iv) Catalytic oxidation: Alkenes react with oxygen in presence of silver catalyst at 250-400
o
C to
form Epoxides.
RCH=CH
2
O
2
Ag
C H
3
HC CH
2
O
ethylene oxide
+

v) Oxidation with ozone: Ozone adds to an alkene molecule to form an ozonide. Ozonide on
warming with zinc and water hydrolysed to yield smaller carbonyl fragments.

The process of preparing the Ozonide and then decomposing it to get the carbonyl compound is
called Ozonolysis.
15
C C
R
R H
R
O
3 C
O
O
C
O
R R
H
R C O
H
R
O C
R
R
Zn
H
2
O 1
1
1 2
2
2
Carbonyl compounds
+
Ozonide

C CH CH
3
C H
3
C H
3
i) O
3
ii) Zn, H
2
O
C O
C H
3
C H
3
H C CH
3
O
Acetone
Acetaldehyde
+


USE: This is the best method for location the position of the double bonds in unknown alkene
with the help of products formed.

3) Combustion: Alkene are completely burnt in air to form CO
2
and H
2
O
C H
2
CH
2
3O
2
2CO
2
2H
2
O
+ +

2C
n
H
2n
+ 3n O
2
2nCO
2
+2n H
2
O
4) Substitution of Alkenes by Halogens: Alkenes having alkyl group undergo substitution,
when treated Cl
2
or Br
2
at high temperature. One of the allylic hydrogen is replaced by halogen
atom. For example
CH
3
-CH=CH
2
Cl
2
Cl CH
2
-CH=CH
2
HCl
500
o
C
Propene Allyl Chloride
+ +

5) Polymerization: The process in which simple molecule join together to form a large molecule
without the elimination of anything is known as polymerization. Simple alkene molecules
undergo polymerization to form long chain polymers. For example

C H
2
CH
2
polymerization
C H
3
CH
2
CH
2
CH
3
n
polyethylene
nCH
3
-CH=CH
2
polymerization C H
3
CH
2
CH
2
CH
3
n
poly propylene
n

These reactions are catalyzed by HF, H
2
SO
4


or organic peroxide and conditions of high
temperature and pressure are generally required.


16
Alkynes
Alkynes are also unsaturated hydrocarbons but they are more unsaturated than alkenes. Alkynes
are characterized by the presence of carbon-carbon triple bond (CC) in hydrocarbon molecule.
The triple bond of alkynes consists of a strong sigma () two weak pi() bonds. In alkynes triple
bonded carbon atom are sp hybridized. The bond is formed by the overlap of sp- hybrid
orbitals and the bonds are formed by the separated overlap of the two P-orbitals. Carbon-
Carbon distance in acetylene is 1.20A
o
and C-H bond length is 1.06A
o
. As acetylene molecule is
linear, the H-C-C bond angle is 180
o
.
Acetylene and 1-alkynes are acidic in character this is because of more S-character of the C-H
bond thus the electrons of the C-H bond in 1-alkynes are more strongly hold by the carbon
nucleus and hydrogen atom of C-H can be easily removed.

Methods of Preparation:
i) Dehydrogenation of Tetra halides: When Vic tetra halides are heated with zinc dust in
alcohol, alkynes are produced.
alcohol
+ +

R C C R
X
X
X
X
Tetra Halide
2 Zn R CH CH R 2 ZnX
2
Alkyne

ii) Dehydro Halogneation of Vicinal Dihalides: When vicinal dihalides are heated with
alcoholic KOH and then sodium amide (NaNH
2
), alkynes are formed.
alcohol
NaNH
2
NaBr NH
3
Alkyne
+ + +
R C C R
H
Br
Br
H
+
KOH R C C R
H
Br
+
KBr H
2
O
+
Vinyl halide
R C C H
H
Br
R C C H

Vicinal dihalides may be directly treated with NaNH
2
to give alkynes.
iii) By Kolbe electrolytic Method: Electrolyses of sodium or potassium salt of unsaturated
dicarboxylic acid yields alkynes.e.g;
17
H
2
O
2
electrolysis
2
CO
2 2KOH
H
2 + + + +
CH-COOK
CH-COOK
CH
CH

iv) Reaction of Sodium Acetylides with 1
o
Alkyl Halides: This reaction is useful for the
preparation of higher alkynes. Sodiuum acetylides are prepared by treatment of acetylene or 1-
alkynes with sodium in liquid ammonia
C CH R
Na
Liquid
NH
3
C C:Na R
+
1/2
H
2
Sod.acetylide
+ +
-

R C C:Na C
2
H
5
Br
R C C C
2
H
5
NaBr
Ethyl bromide
-
+
+
+

v) Reaction of Calcium Carbide with H
2
O: This method is used for the preparation of
acetylene.
CaC
2
+ H
2
O H-CC-H + Ca(OH)
2
Calcium Carbide Acetylene
Properties of Alkynes:
Physical Properties:
i) The First three members are gases, next eight are liquids, and the higher members are
solids.
ii) Alkynes are colourless and odourless except acetylene which has garlic colour.
iii) They are only slighty soluble in water but dissolve in organic solvents.
iv) Their boiling points, melting points and specific gravities show a regular increase
with the increase in molecular weights.

Chemical Properties: Due to the presenc of pi-electrones alkynes give the same kind of addition
reactions as do alkenes. In addition to electrophyllic additions, alkynes also undergo
nucleophillic additions with electron rich regents.

Other reactions of alkynes result from acidic hydrogen atoms in acetylene and 1-alkynes, which
can be easily removed by means of a strong base and hence acetylenes or 1-alkynes are
considered as weak acids.
R C C
+
:Base :H
-
R C C:
-
+
H-Base

Following are some important general chemical reactions of alkynes,
1) Addition of Hydrogen: In presence of catalyst like finely divided Ni, Pt, or Pd, alkynes add
two molecule of hydrogen to give corresponding alkanes.

18

R-C C-H +H
2
Ni
R-CH=CH
2
Ni
H
2
RCH
2
CH
3

The reaction can be stopped at alkene stage by using Lindlars Catalyst (Pd deactivated by
BaSO
4
+ quinoline)
R-C C-H +H
2
R-CH=CH
2
Pd-BaSO
4
quinoline

2) Addition of Halogen: Halogens add to alkyne to form first dihalide and then tetra halide.
R C C H
+
X
2
R CH C H
X X
R CH C H
X X
X X
X
2
Dihalide
Tetrahalide

3) Addition of Halogen Acids: Two molecule of halogen acids can be added to symmetrical
alkynes in two stages. After addition of one molecule alkyne become unsymmetrical derivative
of alkene so that the addition of a second molecule takes place according to Markonikovs rule .
Thus both the halogens become attached to the same carbon atom.

R C C H HX
R CH C H
X X
R C C H
H X
X H
X
2
+
C C H H
2HBr
R C C H
H Br
Br H

In case of unsymmetrical alkynes addition takes place in accordance with Markonikovs rule.
R C C H
+
R CH C H
X H
R CH C H
X H
X H
HX
HX

4) Addition of Hypo Halous acids: Addition of two molecules of hypohalous acids to alkynes
takes place according to Markonikovs rule.Haloaldehyde or Haloketones are the final products.

R-C-CHX
R-C C-H R-C=C-HX
HOX
OH
HOX
OH
OH
2
-H
2
O
R C
CHX
2
O

For example, Acetylene with HOBr give dibromo acetaldehyde
19
H-C C-H
2HOBr
OH
OH
2
-H
2
O
H-C-CHBr H-C-CHBr
O
2

5) Addition of Hydrogen Cyanide: Alkynes react with hydrogen cyanide in presence of barium
cyanide to give addition product alkenyl cyanide. For example, on addition of HCN acetylene
gives vinyl cyanide or acrylonitrile.
H-C C-H HCN
CH=CH-CN
Vinyl cyanide
+
Ba(CN)
2
pressure

(Acrylonitrile)

USE: Acrylonirile is used for the manufacture of synthetic rubber and synthetic fiber, Orlon.

6) Addition of Water( hydration): Alkyne react with water in presence of sulphuric acid and
mercuric sulphate to form aldehyde or ketones.

R-C C-H+H-OH
HgSO
4
H
2
SO
4
R-C=C-H
OH H
Unstable (enol form)
R-C-CH
3
O

7) Addition of Arsenic Trichloride: Alkyne reacts with AsCl
3
in presence of AlCl
3
and HgCl
2

to form 2-chlorovinyl dichloroarsenic, which is commonly known as Lewisite.
H-CC-H =ClAsCl
2
Cl CH=CHAsCl
2
2-chlorovinyl dichloroarsenic(Lewisite)
NOTE: Lewisite is highly poisonous gas. It is four times active than the mustard gas.
8) Ozonolysis: Alkynes form addition products ozonides, with ozone. These ozonides on
decomposition with water yield diketones, which are oxidized by hydrogen peroxide produced in
the reaction to give carboxylic acids. e.g.
R-C C-R' +O
3
R-C C-R'
H
2
O
-H
2
O
R-C C-R'
O
O O
O O
H
2
O
2
R-COOH +HOOC-R'
Carboxylic acids.

20
9) Oxidation with KMnO
4
: When alkynes are treated with alkaline KMnO
4
, cleavage at the
site of the triple bond takes place to form carboxylic acids and CO
2
.
R-CC-H +H
2
O + 4[H
2
O] R-COOH +CO
2
R-CC-R+ 4[O] R-COOH +R-COOH
USE: This reaction is useful in determination of structure of alkynes.
10) Salt formation: As hydrogen in 1-alkyne and acetylene are acidic, they can form salts with
metals by replacement of acidic hydrogen. These salts are known as Acetylides. For example;
a) Formation of Copper and silver acetylides with sodium in liquid ammonia or sodium amide
(NaNH
2
)
R-C C-H +Na
liquid NH
3
H
2
-
+
H-C C-H + Na
liquid NH
3 - +
H
2
R-C C:Na +1/2
R-C C:Na +1/2
Copper acetylides
Silver acetylides

b) Formation of Copper and silver acetylides with ammonical solution of cuprous chloride and
silver nitrate.
H-C C-H +2AgNO +2NH OH
2
3
4
AgC CAg +2NH NO +2H O
+ + - -
4
3
2
H-C C-H +CuCl +2NH OH
2 4
+ + - -
Cu C C Cu +2NH Cl +2H O
4
Copper acetylides
Silver acetylides

11) Isomerisation: Alkynes when treated with traces of alkali like alc.KOH and NaNH
2
undergo
isomerisation, for example 1-alkynes on treatment with alkali isomerises to 2-alkyne.
KOH
Alcohol
C H
3
CH
2
C C H C H
3
C C CH
3

On the other hand 2-alkyne with NaNH
2
in inert solvent gives 1-alkyne.
C H
3
C C CH
3
NaNH
2
H
+
/H
2
O
2-Butyne 1-Butyne
C H
3
CH
2
C CNa C H
3
CH
2
C CH

12) Polymerization: Alkynes, when passed through a red hot iron tube, undergo cyclic
polymerization to form aromatic hydrocarbons. For example, three molecules of acetylene
combine to give benzene under these conditions.
CH
CH
C H
CH
C H
CH
Red hot tube
Benzene
Acetylene ( 3 molecules )


21
Under similar condition three molecules of propylene polymerizes to give mesitylene.

CH
CH
C H
CH
C H
CH
C H
3
CH
3 C H
3
Red hot tube
CH
3
3
CH
CH
3
mesitylene mesitylene ( )
Propylene( 3 molecules)
mesitylene
( 1, 3, 5 -Trimethyl benzene)

Acetylene with nickel cyanide under pressure gives cyclo-octa tetraene.

C H CH
4
Ni(CN)
2
Pressure
cycloocta-1,3,5,7-tetraene
Acetylene
cycloocta-1,3,5,7-tetraene

Alkyl Halides
Alkyl halides are the compounds derived from the saturated hydrocarbons by replacement of one
of the hydrogen atom by halogen atom.
R H
-H
R-X
Saturated hydrocarbon
Alkyl halide.

Thus they can be represented by general formula R-X where R= alkyl group; X= Cl, Br, I or F.
Halogen atom may be attached to 1
o
, 2o or 3
o
Carbon atom of alkyl group. Thus alkyl halide can
be classified as primary (1
o
), secondary(2
o
) or tertiary (3
o
) depending upon whether the halogen
is attached to primary, secondary of tertiary carbon atom.
R-C-X
R-C-X R-C-X
H
H
H
R'
R'
R"

1
o

alkyl halide 2
o

alkyl halide 3
o

alkyl halide
Alkyl halides are very useful organic compounds.
Methods of preparation:
1) By direct Halogenation of Alkanes: Alkanes when treated with chlorine or bromine in the
presence of U.V light or at high temperature (400
o
C) gives alkyl chloride or alkyl bromide along
with poly halogen derivatives. For example,
22
CH
4
Cl
2
UV light
CH
3
Cl CH
3
Cl
2
CHCl
3
CCl
4
+ +
+

But iodoalkanes can be prepared only in the presence of oxidizing agents like HIO
3
, HIO
4.
Or
Conc. HNO
3
etc. because HI formed during the reaction reduces back alkyl iodide to alkane. But
the products are difficult to separate.

2) By addition of Hydrogen Halide to Alkene: When alkenes are treated with hydrogen
halides, addition of hydrogen halide takes place in accordance with Markonikovs rule except the
addition of HBr in presence of organic peroxide [R-O-O-R].

HC CH
2
R HX R-CH-CH
3
X
Alkyl Halide
R-CH -CH-R
2
X
Alkyl Halide
+
R-CH=CH-R
+
HX

Addition of HBr to unsymmetrical alkene
a) In absence of peroxide:

2
CH -CH=CH +HBr CH -CH-CH
3
3 3
Br

b) In presence of peroxide:
Peroxide
C H
3
CH CH
2 C H
3
CH
2
CH
2
Br +
HBr

3) By treatment of Alcohol with Halogen Acid: Alcohols react with HBr or HI to give alkyl
bromide or alkyl iodide. They react with HCl in presence of zinc chloride catalyst.
R-OH HBr
RBr H
2
O
+
+


R-OH +HCl
R-Cl H
2
O
ZnCl
2
(dry)
+

4) By treatment of Alcohol with Phosphorous Halides: Alcohols react with phosphorous
halides (PX
5
or PX
3
) to give alkyl halides.
R-OH + PX
5
(or PX
3
) R-X
R-OH + PCl
5
R-Cl +POCl
3
+ H
2
O
3 R-OH + PBr
3
3 R-Br +H
3
PO
3
23
3 R-OH+ PI
3
3R-I + H
3
PO
3
PBr
3
or PI
3
are produced in situ by the reaction of bromine or iodine with red phosphorus
2P+2Br
2
2PBr
3
2P +3I
2
2 PI
3
5) By treatment of Alcohol with Thionyl Chloride: Alcohols when treated with thionyl
chloride in the presence of pyridine give alkyl chloride. Pyridine acts as scavenger for HCl
formed.
R-OH +SOCl
2
pyridine R-Cl +SO
2
+ HCl
6) By Halogen Exchange Reaction [Finkelstein reaction]: This method is suitable for the
preparation of alkyl iodides and fluorides. This involves the treatment of alkyl bromide or
chloride with concentrated solution of sodium iodide in acetone.
CH
3
CH
2
Br
NaI
acetone
CH
3
CH
2
I
NaBr
+
+

For the preparation of alkyl fluoride alkyl bromides or chlorides are heated with inorganic
fluorides.
2CH
3
-Cl Hg
2
F
2
2CH
3
-F Hg
2
Cl
2
+ +

Properties of Alkyl halides:
1) Physical Properties:
i) Methyl chloride, Methyl bromide, Methyl fluoride and Ethyl chloride are gases at room
temperature. Other alkyl halides up to C
18
are colourless liquids and beyond C
18
are colorless
gases.
ii) Although alkyl halides are polar in nature but they are insoluble in water but soluble in
organic solvents. Insolubility in water is due to the inability to form hydrogen bonding with
water and to break already existing hydrogen bonding in water molecule.
iii) Their densities decrease in the following order; Iodide> bromide>Chloride > fluoride. Alkyl
bromides and iodides are denser than water while alkyl chlorides and fluorides are lighter than
water.
iv) For a given alkyl group boiling points of alkyl halides follow the following order.
Alkyl iodide> Alkyl bromide> Alkyl Chloride> Alkyl fluoride.

For a given halogen atom, the boiling points of alkyl halides increase with the increase in the size
of the alkyl group.

Chemical Properties: In alkyl halides (C-X) bond is highly polar because of the high
electronegativity of the halogen atom. Thus alkyl halides are very reactive compounds alkyl
halides can be nearly all types of organic compounds and thus synthetically they are very
important. They undergo substitution, elimination, and reduction reactions.
Substitution Reaction: The (C-X) bond is strongly polarized covalent bond due to the high
electronegativity of halogen atom.
24
C X

+
-

Thus carbon atom of C-X bond is therefore a good site for the attack of nucleophiles (electron
rich species) and the nucleophilic substitution reactions are most common reactions of the alkyl
halides.
C X

+
-
Nu:
-
C Nu
X:
-
nucleophile
alkyl halide
substitution product
+
+

The common nucleophile are

OH,
-
CN,
-
SH, NO
2
-
,
-
NH
2
and OR
-
.
Nucleophilic substitution in alkyl halides takes place in two ways.
1) SN
1
Mechanism( unimolecular nucleophilic substitution ): In this mechanism substitution
takes place in two steps. Let us consider the hydrolysis of bromide by aqueous NaOH.
Step-I: This involves the ionization of alkyl halide to give a planar carbonim ion in which central
positively charged carbonium ion is SP
2
hybridised.
Br
R
R
R
Slow
C
+
R
R
R
+
:Br
-
tert-alkyl bromide

Step-II: This involves the attack of nucleophile on carbonium ion from either side to give the
substitution product.
C
+
R R
R
R
OH
R
R
fast
3
o
Alkyl alcohol
O H
-


Remember that if alkyl halide is optically active then we will get the recemic mixture of two
enatiomers. Tertiary alkyl halides undergo substitution by SN
1
mechanism via formation of
carbonim ion because the attack of the nucleophile on the crowded tertiary alkyl halide i.e.
sterically hindered central carbon atom is difficult. The reactivity order for SN
1
mechanism is
3
o
alkyl halide >2
o
alkyl halide >1
o
alkyl halide
1
o
alkyl halide undergoes substitution by SN
2
mechanism and the 2
o
alkyl halide may undergo
substitution by either SN
2
or SN
1

mechanism depending upon the solvent.
2) SN
2
Mechanism [Bimolecular nucleophilic substitution]: 1
o
alkyl halide halides undergo
substitution by SN
2
mechanism. This is one step process in which the attack of the nucleophile
25
and the ejection of the halide ion takes place simultaneously. 1
o
alkyl halide undergoes
substitution by SN
1
mechanism via formation of transition state. Let us consider the hydrolysis
of methylbromide by aqueous NaOH.

Bulkier the alkyl group, more is the steric hindrance in the formation of transition state and thus
is the reactivity of alkyl halide.

The reactivity order for SN
2
mechanism is,
1
o
alkyl halide>2
o
alkyl halide>3
o
alkyl halide
Some important substitution reactions of alkyl halides are given below:
i) Reaction with aqueous KOH: When alkyl halides react with aq.KOH, halogen is substituted
by OH group to give alcohols.

H
2
O
R-X +KOH R-OH +HX
alkyl
halide
alcohol


For example;
C
2
H
5
Br KOH
H
2
O
C
2
H
5
OH KBr
ethyl alcohol
+
+

ii) Reaction with moist Silver Oxide: Alkyl halides on treatment with moist silver oxide also
gives alcohols.
R-X +AgOH R-OH+ AgX
Example: C
2
H
5
Br +AgOH C
2
H
5
OH+ AgBr
iii) Reaction with sodium Alkoxide: Alkyl halides on treatment with sodium alkoxide give
ethers. This reaction is known as Williamson ether Synthesis.
R-X
-
RONa
+
R-OR NaX
Ether
C
2
H
5
Br NaOC
2
H
5
+
C
2
H
5
-O-C
2
H
5
NaBr
Ethyl bromide Dethyl ether
Sodium ethoxide
-
+
+
+
+

26
iv) Reaction with Dry Silver Oxide: Alkyl halides on heating with dry silver oxide give ethers.
E.g. 2CH
3
I +Ag
2
O CH
3
-O-CH
3
v) Reaction with Sodium or Potassium Cyanide: Alkyl halides react with sodium or potassium
cyanide to give alkyl cyanides which are very important synthetic intermediates. They can be
easily converted to carboxylic acids and primary amines.
R-CN
RCOOH
RCH
2
NH
2
LiAlH
4
hydrolysis
H
2
O
H
+
/
or Na-alcohol
(reduction)

aqueous alcohol
R-X +NaCN
R-CN +NaX

Alkyl halides when react with AgCN, isocyanides are formed.

R-X + AgCN R-NC + AgX
isocyanide
vi) Reaction with AgNO
2
: Alkyl halides react with silver nitrite form nitro alkane. Some Alkyl
nitrites are also formed.
RX + AgNO
2
RNO
2
+ RONO + AgX
nitro alkane alkyl nitrite
e.g. C
2
H
5
Br + AgNO
2
C
2
H
5
NO
2
+ C
2
H
5
ONO + AgBr
Ethyl Bromide Nitro ethane Ethyl nitrite
viii) Reaction with KSH: On treatment with alcoholic potassium hydrosulphide, alkyl halides
yield thiols.

RX KSH
alcohol
R-SH
KX
Ethanethiol
C
2
H
5
I KSH
alcohol
C
2
H
5
SH K X
Ethane thiol
e.g.
+
+
+
+


27
viii) Reaction with K
2
S: Alcohols react with potassium sulphide to form alkyl sulphide
2R-X+K
2
S R-S-R +2KX
e.g. 2C
2
H
5
I +K
2
S C
2
H
5
-S-C
2
H
5
+ 2KI
ix) Reaction with R-COOAg: When alkyl halide reacts with alcoholic solution of silver salt of
carboxylic acid an ester is formed.
e.g
R C OAg
O
+
X-R'
R C OR'
O
+
AgBr
C H
3
C OAg
O
+
BrC
2
H
5
C H
3
C OC
2
H
5
O
+
AgBr

x) Reaction with Acetylides: Alkyl halides with sodium acetylides give higher alkyne.
RX +NaC C-H
R-C C-H +NaX
- +
RX +NaC C-R
R-C C-R +NaX

xi) Reaction with Ammonia: Heating of alkyl halides with alcoholic solution of ammonia in a
sealed tube results a mixture of different classes of amines.

RX NH
3
RNH
2
Br H
RNH
2
1
o
amine
RX R
2
NH HBr
2
o
amine
R
2
NH RX
R
3
NH HBr
3
o
amine
R
3
NH
RX
R
4
NX
+
-
4
o
amine
+
+
+
+
+
+
+

xii) Reaction with alcoholic KOH: When alkyl halides are treated with alc.KOH,
dehydrohalogenation takes place and alkenes are produced.
28
R-CH
2
-CH
2
X
KOH,alcohol
R-CH=CH
2
K X H
2
O
+ +

In alcohol, there is an equilibrium between the solvent and KOH
C
2
H
5
OH
KOH
C
2
H
5
OK H
2
O
- +
+
+
Sod.Ethoxide
Ethanol

Sodium ethoxide is a strong base. It favours elimination more than substitution. The rate of
elimination to substitution product depends on the structure of the alkyl halide and experiment
condition. For example in case of 1
o
alcohol substitution product is also formed but in case of 2o

and 3
o
alcohol elimination product predominates. 1
o
and
2
o
alkyl halides undergo
dehydrohalogenation by E
2
mechanism and 3
o
alkyl halides do so by E
1
mechanism.

Saytzeffs Rule: In case of unsymmetrical alkyl halide dehydro halogenation yield more than
one alkene. One of them, the most highly substituted alkene, is the major product. In such cases
elimination of HX is governed by Saytzeffs rule. According to which the main product is the
most highly substituted alkene. Or in other words Hydrogen is eliminated from the Carbon atom
of alkyl halide which bears the least number of hydrogen atoms.

For example, when 2-bromobutane undergo elimination with alc. KOH, two alkenes are possible
and major one is more substituted alkene. (In accordance with Saytzeffs rule).

CH
3
CH=CH-CH
3
CH
2
=CH-CH
2
CH
3
2-Butene
1-Butene
(80%)
(20%)
alc.KOH
-HBr
-HBr
alc.KOH
H C C C
H
H
Br
H
C
H
H
H
H
H

xiii) Reduction: Alkyl halides are reduced to alkanes by different reducing agents like LiAlH
4
,
Zn/HCl and H
2
/Ni or Pd etc.
R-X
LiAlH
4
H
2
/Ni or Pd
Or Zn/HCl
RH +HX
e.g.
C
2
H
5
Br H
2
Ni or Pd
C
2
H
6
HBr
CH
3
CH
2
CH
2
I 2[H]
Zn/HCl
CH
3
CH
2
CH
3
HI
+
+
+
+

29
xiv) Wurtz Reaction: When alkyl halides react with metallic sodium in dry ether two molecules
join together to give alkane with double number of carbon atoms.
C
2
H
5
Br
2Na Br-C
2
H
5 C
2
H
5
- C
2
H
5
2NaBr
ether
Butane
+ +
+

xv) Raction with Mg and Li: Alkyl halides react with Magnesium in dry ether to give alkyl
magnesium halide, the Grignard reagent.
R-X
Mg
RMgX
ether
alkyl mag.halide.
(Grignard reagent)
+

But with Lithium in dry ether alkyl halides give alkyl Lithium.
R-X
ether
Li
R-Li +LiX
+

Grignard reagent is an important group of organometallic complex which has the great synthetic
utility in organic chemistry. Alkyl Lithium behaves in the same way as Grignard reagent but with
increase reactivity.

(xvi) Friedel Crafts Reaction: Alkyl halides react with Arenes in the presence of anhydrous
AlCl
3
to form alkyl benzene.
RX
amhydrous AlCl
3
R
HX
Bnzene
Alkyl benzene
+
+

Alicyclic Hydrocarbons or Cyclo Alkanes
Alicyclic Hydrocarbons are those carboxylic compounds in which the carbon atoms are joined
together to form a ring. In this carbon atoms are joined together to form a ring. In saturated
alicyclic hydrocarbons methylene groups joined together to form a cyclic structure, hence they
are also known as polymethylene. According to IUPAC system, they are named as cycloalkanes
or cycloparaffins. They resemble with the aliphatic compound in their properties. Some example
of cyclo alkanes are,
CH
2
CH
2
H
2
C
H
2
C
CH
2
CH
2
CH
2
CH
2
H
2
C
CH
2
CH
2
H
2
C
CH
2
CH
2
CH
2
CH
2
H
2
C
H
2
C
cyclo propane
cyclopentane
cyclohexane
cyclobutane



30
Methods of preparation:
1) From Dihalides: The reaction is an extension of Wurtz reaction in which terminal dihalides
are treated with sodium or zinc to give cycloalkanes. Three to six membered cycloalkanes can be
prepared by this reaction by using appropriate dihalide:
e.g:
H
2
C
CH
2
Cl
CH
2
Cl
2Na
CH
2
CH
2
H
2
C
2NaCl
Cyclopropane
H
2
C
CH
2
Br
CH
2
Br
H
2
C
2Zn
H
2
C
CH
2
CH
2
H
2
C
ZnBr
2
cyclobutane
+
+
+
+

2) From Calcium salts of Dicarboxilic Acids: When the calcium salts of Dicarboxylic acids are
heated one carbon less cyclic ketones are formed, which can be readily converted into the
corresponding cycloaokanes by Clemmensen reduction.
For Example:
H
2
C
H
2
C CH
2
CH
2
C
C
O
O
Ca
2
+
O
O
-CaCO
3
CH
2
C
H
2
C
CH
2
CH
2
O
Zn/Hg
HCl
CH
2
CH
2
H
2
C
CH
2
CH
2
Calcium Adipate
Cyclopentanone
Cyclopentane

3) From the Esters of Dicarboxylic acids [Dieckmann Reaction]: When ester of Dicarboxylic
acids are leaked with sodium intermolecular condensation takes place to give -keto esters.
keto esters are first hydrolysed to give -keto acid and then decarboxylated to give cyclic keone.
Cyclic ketones on Clemmensen reduction give cyclo alkanes.
For example:

H
2
C
H
2
C
CH
2
C
CH H
COOC
2
H
5
O
OC
2
H
5
Na
-C
2
H
5
OH
C
HC
CH
2
H
2
C
H
2
C
O
COOC
2
H
5
H
2
O
H
+
C
HC
CH
2
H
2
C
H
2
C
O
COOH


31
C
CH
2
CH
2
H
2
C
H
2
C
O
Zn/Hg
HCl
CH
2
CH
2
CH
2
H
2
C
H
2
C
Cyclopentane


C
CH
2
CH
2
H
2
C
H
2
C
O
Zn/Hg
HCl
CH
2
CH
2
CH
2
H
2
C
H
2
C
Cyclopentane


iv) From Aromatic Hydrocarbons: Benzene and its derivatives on catalytic reduction are
converted to six membered cycloalkanes.
E.g.
3H
2
Ni,
pressure
cyclohexane
+

v) From Alkenes: [preparation of cycloproparne derivatives]: Alkene when treated with
methylene iodide in presence of Zn-Cu couple in ether, give cyclopropane derivatives.(
Simmons-Smith Reaction )

R HC CH R
CH
2
I
2
Zn-Cu
ether
R HC CH R
CH
2
Dialkyl cyclo propane
+

Properties:
Physical Properties:
1) Cycloalkanes are liquids at room temperature except cyclopropane and cyclobutane which are
gases at room temperature.
2) Their melting and boiling points are gradually increase with increase in molecular weights.

Compound bp
o
C mp
o
C
Cyclopropane -32.8 -127.4
Cyclobutane 12.5 -90.7
Cyclopentane 49.3 -13.9
Cyclohexane 80.7 6.6
3) Cycloalkanes are insoluble in water but soluble in ethanol and ether.
32
Chemical Properties: Cycloalkanes resemble with alkanes in several chemical properties. But
the lower members, cyclopropene and cyclobutene are the exceptions. They form addition
compounds with the ring fusion. Thus cycloalkanes behave both like alkanes as well as alkenes.

Important Reactions of Cycloalkanes are described below:
1) Substitution with Cl
2
and Br
2
: In presence of UV light cycloalkane react with Cl
2
or Br
2
to
give substitution products.
For example:
Cl
2
UV light
Cl
Cl H
cyclohexane chlorocyclohexane
+
+

2) Addition of Cl
2
and Br
2
: Cyclopropane reacts with Cl
2
or Br
2
indark and in CCl
4
as a
solvent to give addition product with the opening of ring.
Br
2
CCl
4
dark
H
2
C
CH
2
CH
2
Br
Br
1,3-dibromopropane
```` +

Cyclo butane and other higher members do not give this reaction.
3) Addition of Hydrogen: Cyclopropane and Cyclobutane react with Hydrogen in the presence
of Ni Catalyst to give corresponding normal alkanes .i.e. propane and n-butane.
Ni
````
H
2
80
o
C
C H
3
CH
2
CH
3
propane
````
H
2
Ni
200
o
C
C H
3
CH
2
CH
2
CH
3
butane
n-
+
+

4) Addition of HBr and HI: Cyclopropane gives open chain addition product with concentrated
HBr and HI.
````
C H
3
CH
2
CH
2
Br Br H
1-bromopropane
+

Higher members do not give this reaction.
5) Oxidation: Cyclo alkanes when treated with hot alkaline KMnO
4
yield dicarboxylic acid with
the cleavage of ring.
e.g.
33


`
`
`
`
[O]
KMnO
4
COOH
COOH
pentanedioic acid
1,5-
+

Alcohols
Alcohols are the hydroxyl derivatives of saturated hydrocarbon in which hydroxyl(-OH) group is
attached to saturated carbon atom. All the chemical properties of alcohols are due to the presence
of OH group thus hydroxyl group is the functional group of alcohols. Alcohols can be
represented by the general formula R-OH.

Alcohols can be classified as mono, di, tri and polyhydric alcohols depending on the number of
hydroxyl groups (1, 2, 3 or more) present in a molecule. For example
C H
3
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
CHOH
CH
2
OH
CH
3
(CHOH)
4
CH
3
ethanol
ethylene glycol
(Mono hydric)
(Dihidric)
glycerol
[[Trihydric]
Sorbitol
[Poly hydric]

Monohydric alcohols [R-OH] are further subdivided into 1
o
, 2
o
and 3
o
alcohols depending upon
the nature of carbon atom to which OH group is attached.
C OH
H
R
H
C OH
H
R
R'
C OH
R"
R
R'
1
o
Carbon
2
o
Carbon
3
o
Carbon
Primary Alcohol
secondary Alcohol
Tertiary Alcohol

General Methods of preparation:
1) By the Hydrolysis of alkyl halides: Alkyl halides react with aq. KOH or moist silver oxide
to give alcohols.
R-X +KOH(aq)
R-X +AgOH
R-OH +KX
R-OH +AgX

2) By hydration of olefins: Alkenes react with Sulphuric acid (98%) to give first addition
product, alkyl hydrogen sulphates which on hydrolysis give alcohols.

In case on unsymmetrical alkenes for addition, Markonikovs rule is followed.
34
R CH CH
2
HOSO
3
H
R CH CH
3
OSO
3
H
R CH CH
3
OSO
3
H
O H
H
R CH CH
3
OH
H
2
SO
4
Alkyl hydrogen sulhate
2
o
alcohol
+
+
+

Except ethyl alcohols primary alcohols cannot be prepared by this method. Overall reaction is
the Markonikovs addition of water to a double bond. e.g.
C H
3
CH CH
2
O H
2
H
+
C H
3
CH CH
3
OH
+
Propylene
Iso propyl alcohol

3)Hydroboration-Oxidation of Alkenes: When alkenes are treated with diborane, trialkyl
boranes are formed. In this reaction diborane adds as borane (BH
3
). The positive part of BH
3
is
boron and negative part is hydrogen. e.g.
R C CH
2
1/
2
B
2
H
6
(RCH
2
CH
2
)
3
B 3 +

Trialkyl borane on treatment with alkaline aqueous solution of hydrogen peroxide gives
1
o
alcohols.
(RCH
2
CH
2
)
3
B
H
2
O
2
-OH
3RCH
2
CH
2
OH
H
3
BO
3
1
o
Alcohol
+ +

The overall reaction of hydroboration-oxidation results anti- Markonikovs addition of water to
double bond. e.g.
CH
3
CH=CH
2
I)B
2
H
6
II) H
2
O/-OH
CH
3
CH
2
CH
2
OH
Propylene
n-propylalcohol

4) Hydrolysis of Esters: Acid hydrolysis of esters yield alcohols. e.g
C H
3
C CH
3
O
O H
2
H
+
RCOOH R'OH
+ +

5)By catalytic Reduction of Carbonyl Compounds: Aldehydes on reduction give 1
o
alcohols
and ketones give 2
o
alcohols. 3
o
Alcohols cant be prepared by this method.
i) Reduction by using alcoholic sodium[Bouveoult-Blanc reduction]:

R C H
O
Na/C
2
H
5
OH
R-CH
2
OH
R C R'
O
Na/C
2
H
5
OH
R CH R'
OH
1
o
alcohol
Ketone
Aldehyde
2
o
alcohol

35
ii) Reduction by using LiAlH
4

or NaBH
4

:
R C H
O
R-CH
2
OH
R C R'
O
R CH R'
OH
1
o
alcohol
Ketone
Aldehyde
Li AlH
4
or
NaBH
4
Li AlH
4
or
NaBH
4
2
o
alcohol

,-unsaturated carbonyl compounds may also be reduced by LiAlH
4
or NaBH
4
to give
corresponding alcohols.

iii)Reduction with H
2
/Ni:
R C H
O
R-CH
2
OH
R C R'
O
R CH R'
OH
1
o
alcohol
Ketone
Aldehyde
H
2
/Ni
H
2
/Ni
2
o
alcohol

6) From Grignard Reagent: Grignard Reagent (RMgX) first react with carbonyl compound to
give the addition product which on acid-hydrolysis gives corresponding alcohol.

C H
3
C CH
3
O
R-MgX C H
3
C CH
3
OMgX
R
H
+
/H
2
O
C H
3
C CH
3
OH
R

+
-
+
Addition product
Unstable

Grignard reagent with formaldehyde, aldehydes other than formaldehyde and ketones leads to
the formation of 1
o
, 2
o
and 3
o
alcohols respectively. For example,
H C H
O
RMgX
H C H
OMgX
R
H
+
/H
2
O
R-CH
2
OH
1
o
alcohol
R' C H
O
RMgX
R' C H
OMgX
R
H
+
/H
2
O
R' C H
OH
R
2
o
alcohol
R' C R'
O
RMgX
R' C R'
OMgX
R
H
+
/H
2
O
R' C R'
OH
R
3
o
alcohol
+
+
+

36
7) By the reaction of aliphatic primary amine with nitrous acid: Primary aliphatic amines
react with nitrous acid to give alcohols.
RCH
2
NH
2
HONO
RCH
2
OH N
2
H
2
O
+
+
+

8) By Fermentation: Fermentation is the slow decomposition of complex organic compounds
into simple compound in the presence of enzymes obtained from microorganism. Fermentation
of starch and sugars under the influence of suitable microorganism gives alcohols.
For example:

C
6
H
12
O
6 2C
2
H
5
OH 2CO
2
Glucose Ethyl alcohol
Zymase
yeast
(C
6
H
10
O
5
)n
Fermentation
CH
3
CH
2
CH
2
CH
2
OH C H
3
C CH
3
O
Starch n-Butyl alocohol
+
+

Properties:
Physical properties:
1) Lower alcohols are colourless, toxic liquids while higher having more than 12 carbon are
solids. They have characteristic sweet alcoholic odour and burning taste.
2) Lower alcohols are easily soluble in water but solubility decreases with increase in molecular
weight.
Solubility of lower alcohols in water is due to the Hydrogen bonding between highly polarized
OH groups present both in water and alcohols.


H O
H
H O
R
H O
H

| | || || | | | | | | | | | |

+

-
+
-
+
-


Figure-5: Hydrogen bonding between alcohol and water molecules.

But Higher alocohols have less tendency to form hydrogen bonds with water molecule because
of the presence of non polar long hydrocarbon chain and hence the solubility in water decreases.
3) Boiling points of alcohol increase with the increase in number of carbon atoms but their
boiling points are much higher than those of the corresponding alknaes. This is again because of
intermolecular hydrogen bonding. Highly polar OH groups of different alcohol molecule and
partially negative oxygen in another alcohol molecule.
H O
H
H O
R
H O
H

| | || || | | | | | | | | | |

+

-
+
-
+
-

4) Among isomeric alcohols boiling and melting points decreases with branching.
Primary> Secondary>Tertiary.
37
Chemical Properties:
Alcohols are chemically reactive compounds this is due to the presence of reactive functional
group, -OH group, which is polar in nature. Because of the high electronegativity of oxygen
atom both and

+ -
-C-O

+
-
-O-H
bonds in alcohols are polar bonds.
Alcohols undergo following reactions.
1) Reactions involving only the hydrogen atom of the OH group:
These reactions involve cleavage of oxygen and hydrogen bond.
i) Reaction with alkali metals: Alcohols react with sodium or potassium to form alkoxides with
the liberation of hydrogen gas.
2ROH +2Na
2RONa +H

2
Sod.alkoxide

Their reaction shows the acidic nature of alcohols. Primary alcohols are more acidic than
secondary, which in turn is more acidic than tertiary thus order of acidic nature is as follows.
1
o
alcohols>2
o
alohols>3
o
alcohols
This is because of the +I effect of the alkyl groups attached. It would be maximum in tertiary
alcohols.

2)Reaction with carboxylic Acids: Alcohols react with carboxylic acids in presence of
concentrated sulphuric acid as a catalyst to give ester. The process is known as esterification.
The reaction is reversible.
O H C R'
O
H
+
R'O C R
O
H
2
O
Ester
Alcohol Carboxylic acid
C
2
H
5
OH O H C CH
3
O
H
+
H
5
C
2
-O C CH
3
O
H
2
O
Ethyl alcohol Acetic acid
Ethyl acetate
+
+
+
R'OH
+


3) Reaction with Acid halides and Acid anhydrides: Alcohols can more easily esterified by
the action of acid Chloride or acid anhydride.
R C Cl
O
R C OR'
O
HCl
R C O
O
R C
O
R C OR'
O
RCOOH
Ester
Carboxylic acid
Acid anhydride
+
+
+ +
HOR'
HOR'
Ester

38
4) Reaction with Grignard Reagent: Alcohols react with Grignard reagent to give alkanes.
This reaction is used for the estimation of alcoholic group [Zerewitnoff reaction]
R'OH RMgX
RH
R'OMgX
Alcohols
alkyl magnesium
halides
Alkane
Alkoxy mag.halide
C
2
H
5
OH
CH
3
MgI
CH
4
C
2
H
5
OMgBr
methane
Ethoxy mag.bromide
+
+
+
+

(B) Reaction involving OH group: These reaction involve cleavage of Carbon-oxygen bond
-C--OH
`
`
`
`
`
`


5) Reaction with phosphorous Halides: When alcohols react with phosphorous penta
halide[PX
5
] or phosphorous halide [PX
3
], replacement of OH group by halogen atom take place
and alkyl halides are formed.
R-OH PX
5
R-X POX
3
HX
C
2
H
5
OH PCl
5
C
2
H
5
Cl POCl
3
HCl
+
+
+
+
+
+

3-R-OH PX
3
3-R-X H
3
PO
3
3C
2
H
5
OH PX
3 3C
2
H
5
Br H
3
PO
3
+
+
+ +

PBr
3
and PI
3
are usually prepared in situ.
6) Reaction with thionyl chloride: This involves replacement of OH group by chlorine atom.
R CH
3
R Cl
C
2
H
5
CH
3
C
2
H
5
Cl
SOCl
2
SO
2
HCl
SO
2
HCl
+ +
+ +
SOCl
2
+
+

7) Reaction with halogen acids: Alcohols react with halogen acid to give corresponding alkyl
halides.
R OH
R X
+
+
HX
O H
2

The reactivity of halogen acids are in the order,
HI >HBr >HCl
No catalyst is required in case of HI and HBr but HCl reacts only in presence of anhydrous
ZnCl
2
catalyst.
39
C
2
H
5
OH H
5
C
2
Cl
+
+
O H
2
Cl H
anhydrous ZnCl
2

Mechanism: Primary alcohols follow SN
1
mechanism for the substitution of OH group by
halogen atom.
Step 1: Protonation of Alcohol
H
3
CH
2
C O H
+
H
+
..
..
H
3
CH
2
C O
+
H
H
..

Step 2: Attach of nucleophile [X
-
]
H
3
CH
2
C O
+
H
H
+
X
..
-
CH
3
-CH
2
-X
+
O H
2

2
o
and 3
o
alcohols follow SN
2
mechanism.
8) Reaction with sulphuric acid: The action of concentrated sulphuric acid is of great interest
as it gives different products under different conditions.
i) At room temperature, ethyl alcohol reacts with concentrated sulphuric acid to give ethyl
hydrogen sulphate.
H
5
C
2
OH HOSO
3
H
Room Temperature
C
2
H
5
OSO
3
H
+
Ethyl hydrogen sulphate

ii) When alcohols heated with concentrated H
2
SO
4
, dehydration takes place to give alkenes. For
example
H
5
C
2
OH
H
2
SO
4
170
o
C
C H
2
CH
2
+
O H
2
Ethyl alcohol
Ethylene

Mechanism: Mechanism involve formation of carbocation.
Step 1: Protonation of alcohol.
C H
3
CH
2
O H
+
H
+
C H
3
CH
2
O
+
H
H

Step 2: Elimination of water molecule to give carbocation.
C H
3
CH
2
O
+
H
H
C H
3
CH
2
+
+
O H
2
..

Step 3: Removal of proton from carbocation:
40
C C
H
H
H
H
H
+
C H
2
CH
2
Ethylene

The ease of dehydration of alcohols follow the following order
3
o
>2
o
>1
o
This is also the order of stability of carbocation.
With secondary and tertiary alcohols, dehydration may occur in two ways, e.g.:
C H
3
CH
2
CH CH
3
OH
-H
2
O
CH
3
CH
2
CH=CH
2
1-Butene
CH
3
CH=CHCH
3
2-Butene

According to Saytzeffs rule more substituted alkene is the major product.
iii) When excess of ethyl alcohol is heated with concentrated sulphuric acid at 140
o
C, diethyl
ether is formed.
C
2
H
5
OH
+
OHC
2
H
5
con H
2
SO
4
C
2
H
5
-O-C
2
H
5
Diethyl ether
140
o
C

Mechanism: Mechanism involves the following steps.
Step 1: Protonation of one Molecule.

H
3
CH
2
C O H
+
H
+
..
..
H
3
CH
2
C O
+
H
H
..

Step 2: Elimination of water molecule:
C H
3
CH
2
O
+
H
H
C H
3
CH
2
+
+
O H
2
..

Step 3: Attach of carbocation to another molecule of alcohol.

C H
3
CH
2
+
CH
2
CH
3
O H . .
. .
. .
+
C
2
H
5
-O-C
2
H
5
H
+
Oxonium ion

41
Step 4: Removal of proton from Oxonium ion leads to the formation of ether.
H
5
C
2
O
+
C
2
H
5
H
..
-H
+
H
5
C
2
O C
2
H
5
..
..
Diethyl ether


Alcohols can also be dehydrated by passing the vapours of alcohol over heated aluminia to give
ethers or alkenes e.g.
2C
2
H
5
OH
Al
2
O
3
200
o
C
H
5
C
2
O C
2
H
5
+
O H
2
diethyl ether
..
..

9) Reduction of Alcohols:
Alcohols are reduced to alkanes by concentrated HI and red phosphorous
ROH 2HI RH
I
2
H
2
O
red P
+ + +
alcohol
Alkane
C
2
H
5
OH
2HI
red P
+
C
2
H
6
I
2 H
2
O
+ +
Ethane

10) Oxidation: Nature of oxidation products of alcohols depend upon the nature of alcohols,
oxidizing agent used and reaction conditions. Most commonly used oxidizing agents are acidic
KMnO
4
and acidic Na
2
Cr
2
O
7
.

Primary alcohols are easily oxidized to aldehydes and then to carboxylic acids both with the
same number of carbon atoms as the parent alcohol. E.g.:
CH
3
CH
2
OH
[O]
K
2
Cr
2
O
7
/H
+
C H
3
C H
O
[O]
K
2
Cr
2
O
7
/H
+
CH
3
COOH
Acetic acid
Acetaldehye Ethyl alcohol

Secondary alcohols oxidized to ketone with same number of carbon atoms, but these ketones
cant be easily oxidized, these undergo oxidation under very drastic conditions to give mixture of
carboxylic acid with lesser number of carbon atomes than parent alcohol. Eg:
C H
3
HC CH
3
OH
[O]
K
2
Cr
2
o
7
/H
+
C H
3
C CH
3
O
Isopropyl alcohol
C H
3
CH CH
3
OH
[O]
KMnO
4
/H
+
CH
3
COOH
+
HCOOH
Acetic acid
Formic acid
Acetone

42
Tertiary alcohols are resistant to oxidation under normal conditions but under drastic conditions
they oxidized to first form ketones and then carboxylic acid both having lesser number of carbon
atoms.
C H
3
C OH
CH
3
CH
3
[O]
C H
3
C CH
3
O
t-Butyl alcohol
(one carbon less)
[O]
KMnO
4
/H
+
KMnO
4
/H
+
CH
3
COOH
+
HCOOH
Acetic acid Formic acid
Acetone

USE: The oxidation reaction may also be used to distinguish between primary, secondary
and tertiary alcohols.

11) Reaction with hot Copper: Primary and secondary alcohols dehydrogenated to form
aldehyde and ketones respectively, Tertiary alcohols are not dehydrogenated but they dehydrated
to give alkanes. e.g.
C H
3
CH
2
OH
Cu
300
o
C
C H
3
C H
O
acetaldehyde ethanol
C H
3
CH CH
3
OH
iso propyl alcohol
Cu
300
o
C
C H
3
C CH
3
O
acetone
C H
3
C OH
CH
3
CH
3
Cu
300
o
C
C H
3
C CH
2
CH
3
+
O H
2
t-Butyl alcohol
Isobutene

USE: The dehydrogenation with hot copper may also be used to distinguish between
primary and secondary alcohols.

Ethers
Ethers are the organic compounds in which an oxygen atom is bonded to alkyl groups. The
functional group is [C-O-C]. If same alkyl groups are attached to central oxygen atom ethers are
classified as symmetrical ethers. While ethers containing different alkyl groups attached with
central oxygen atom are classified as unsymmetrical ethers.
R O R
..
..
R O R'
..
..
symmetrical ethers unsymmetrical ethers

43
Ethers may be considered as derivatives of alcohol or water in which hydrogen atom /atoms have
been replaced by alkyl group or groups.
H O H
..
..
R O H
..
..
R O R
..
..
water alcohol
ether

Some common examples of ethers are
H
5
C
2
O CH
3
..
..
H
5
C
2
O C
2
H
5
..
..
ethyl methyl ether
diethyl ether
[methoxy ethane] ethoxy ethane

In ethers central oxygen atom is sp
3
hybridized .Thus two C-O, -bond are formed by the
overlap of two half filled sp
3
hybrid orbitals of oxygen atom with the half filled sp
3
hybrid
orbitals of two carbon atoms of two alkyl groups. Remaining two sp
3
hybrid orbitals of oxygen
atoms are occupied by the two unshared pairs of electrons. Here the C-O-C bond angle is about
110
o
which is quite close to tetrahedral angle [109.5
o
]
R R
R
R
110
o
unshared
pair of
electrons
S
P
3 -
S
P
3 S
P
3
-
S
P
3

Structure of Ether
Methods of preparation:
i) Dehydration of alcohols: By heating excess of alcohol with concentrated sulphuric acid at
140
o
C
R-OH
HO-R
+
Con.H
2
SO
4
140
o
C
R-O-R
+
O H
2
C
2
H
5
OH
+
HO-C
2
H
5
Con.H
2
SO
4
C
2
H
5
-O-C
2
H
5+
O H
2

ii) By passing alcohol vapors over Al
2
O
3
at 250
o
C:
R-OH HO-R
R-O-R H
2
O
Al
2
O
3
+
+

2) By heating alkyl halides with silver oxide: Ethers are obtained by heating alkyl halides with
dry silver oxide.
C
2
H
5
I Ag
2
O IC
2
H
5 + +
C
2
H
5
-O-C
2
H
5
Diethyl ether

44
This method is useful for the preparation of simple ethers only.
3) Williamson Ether Synthesis: This is the most important industrial and laboratory method of
preparation of ethers. It involves the treatment of sodium alkoxide with an alkyl halide. Both
symmetrical unsymmetrical ethers can be prepared by this method.


R-ONa
NaX
+ +
+ -
Alkyl halide Sod. alkoxide Symmetrical ether
R-O-R
X-R

R-ONa R-O-R'
NaX
+ +
unsymmetrical ether
+ -
X-R'
Sod. alkoxide
Alkyl halide

+ +
+
-
C
2
H
5
ONa Br-C
2
H
5
C
2
H
5
-O-C
2
H
5
NaBr
Diethyl ether


+ +
+
-
CH
3
ONa Br-C
2
H
5
CH
3
-O-C
2
H
5
NaBr
Ethyl methyl ether

Tertiary and Secondary alkyl halides undergo elimination reaction with sodium alkoxide [strong
base]. Thus to introduce a tertiary group it will be better to take this group as a base, not as a
tertiary halide. For example
R-ONa
C H
3
C H
3
C H
3
Cl
C H
3
C CH
2
CH
3
+
Cl H

Thus for preparing (CH3)
3
C-O-C
2
H
5
, we should start with
(CH
3
)
3
C-ONa
+ -
and C
2
H
5
Br.

Mechanism: It follows SN
2
mechanism. Displacement of halide ion by alkoxide ion.
R-ONa R X
SN
2
R-O-R NaBr
+ +
+ -

5)Action of Diazomethane on Alcohols: Ethers can be prepared by treatment of primary or
secondary alcohols with diazomethane in presence of flouroboric acid as a catalyst.
R-OH
CH
2
N
2
HBF
4
R-O-CH
3
N
2 +
+
C
2
H
5
-OH CH
2
N
2
+
HBF
4
C
2
H
5
-O-CH
3
N
2
+

But this method is only useful for the preparation of methyl ethers.
45
Properties:
Physical properties:
1) Ethers are highly volatile and inflammable substances.
2) Except dimethyl ether and ethyl methyl ether, which are gases all are pleasant
smelling colourless liquids.
3) Their boiling points gradually increase with the increase in molecular weight. But
ethers have lower boiling points than isomeric alcohols because they are
incapable of forming inter molecular hydrogen bonds due to the absence of OH
groups.

Ethers are sparingly soluble in water since their oxygen atom is not capable of forming H-bond
with hydrogen with hydrogen atom of water molecule.

Chemical Properties:
Ethers are much less reactive compounds because they are quite stable. They do not react with
active metals, strong bases like NaOH, reducing and oxidizing agents.
1) Halogenations: When ethers react with chlorine or bromine substitution preferentially at -
Carbon takes place.
For example:
CH
3
-CH
2
-O-CH
2
-CH
3
Cl
2
dark
CH
3
-CH-O-CH
2
-CH
3 CH
3
-CH-O-CH-CH
3
Cl
2
dark
Cl
Cl
Cl

- Chloro diethyl ether ,
1
-

Dichlorodiethyl ether.

The extent of substitution depends on reaction conditions.
2) Basic Nature: Ethers react with cold concentrated sulphuric acid or HCl to give oxonium salt.
Their basic nature is due to the presence of two lone pairs on oxygen atom.
Cl R O R
..
..
+
Cl H
R O
+
R
H
..
-
oxonium ion
cold

This property is used to separate ethers from ethyl bromide and to distinguish from alkanes.
Since alkanes do not react with acids.

3) Formation of peroxides (Auto oxidation): On standing in contact with air ethers combine
with oxygen to form peroxide which is highly explosive.
H
2
CH
3
C O CH
2
CH
3
+
O
2
long
contact
(CH
3
CH(OOH).OC
2
H
5

These peroxides decompose violently at high temperature. Thus ethers should be always be
purified before distillation. When ethers that contains peroxide is distilled, at the end of
46
distillation residual peroxide may explode. Because of this ether should never be evaporated to
dryness.

4) Hydrolysis: Ethers when treated with dilute sulphuric acid under pressure, they hydrolyse to
give alcohols.
R O R
+
dil H
2
SO
4
2 ROH O H
2
under pressure
H
5
C
2
O C
2
H
5
dil H
2
SO
4
2 C
2
H
5
OH O H
2
under pressure
+
Diethyl ether
Ethyl alcohol

5) Reaction with Phosphorus Penta-chloride: With PCl
5
ether cleave to give alkyl chlorides
R O R
+
R O R'
+
PCl
5 2 R-Cl POCl
3 +
PCl
5
R-Cl
R'Cl
POCl
3
+
+

6) Reaction with HI and HBr: Ethers react with hot concentrated HI or HBr to give an alcohol
and alkyl halide.
R O R'
+ R'Br
+
Br H
R-OH

In case of mixed ethers the halogen atom attacks to the smaller alkyl groups, due to the sterric
effect. e.g.
H
5
C
6
O C
2
H
5
+ +
C
6
H
5
-OH
HI
C
2
H
5
I

The order of reactivity of halogen acid is
HI>HBr>HCl
With the excess of acid, the alcohol initially produced is also converted to alkyl halide. e.g.
H
5
C
2
O C
2
H
5
+
+
2HI
2C
2
H
5
I O H
2
(excess)

7) Reaction with acetyl chloride: Ethers react with acid chloride to give alkyl halides and
esters. For example
H
5
C
2
O C
2
H
5+
C H
3
C Cl
O
C
2
H
5
Cl
+
C H
3
C C
2
H
5
O
Ethyl actate Ethyl chloride Diethyl ether Acetyl chloride
ZnCl
2

47
Epoxide
Epoxides are the cylclic ethers in which ethereal oxygen is linked with two adjacent carbon to
form three membered ring. i.e. oxiran (oxirane) ring. Epoxy compound contain oxirane ring.
Oxiran compounds are also referred to as cyclic ethers or alkene oxides.
C C CH
3
C H
3
O
OH O H
H
2
C CH
2
O
HC CH
2
O
R
epoxide
Ethyleneoxide[ 1, 2 -Epoxyethane]
[ 1, 2 -epoxyalkane]

Epoxy ethane or ethylene oxide (oxiran) is the most important member of this group.
Method of preparation: Epoxides may, in general, be prepared by epoxidation of alkenes with
peroxy acids. Perbenzoic acid C
6
H
5
COO
2
H, monoperphthalic acid, HOOCC
6
H
4
COO
2
H and P-
nitro benzoic acid have been used.
R-CH=CHR'
per acid
R R
O
'
Epoxide
C H
2
CH
2
per acid
H
2
C CH
2
O
Ethylene oxide


Ethylene oxide may be obtained:
i) By Reaction of Chlorohydrin with base:
HO-CH
2
-CH
2
-Cl
+
KOH H
2
C CH
2
O
+
KCl H
2
O
+



48
Possibly the mechanism is:
H O CH
2
CH
2
Cl
fast
-H
2
O
O
-
H
2
C CH
2
Cl
CH
2
H
2
C
O
-
HO
-
-Cl

ii) By oxidation of ethylene with oxygen in the presence of silver catalyst.
2CH
2
=CH
2
+
O
2
Ag
250
0
C
H
2
C C
2
O
H
2

Properties:
Ethylene oxide is toxic, flammable gas having b.p 10.7
o
C.generally epoxides are reactive
compound, this is because to release their strain they have the tendency to open their ring. These
oxygen atoms combine with the reactive hydrogen atom of various compounds to form hydroxyl
group.
H
2
C CH
2
O
H A
+
HO-CH
2
-CH
2
-A

Reaction with HOH

H
2
C CH
2
O
+
O H
2
H
+
H
2
C C
2
OH OH
H
Ethylene glycol

Reaction with alcohols
H
2
C CH
2
O
+
H
2
C CH
2
OH
OR
H-O-R
Alkoxy ethane

Reaction with Ammonia
H
2
C CH
2
O
+
H
2
C CH
2
OH
NH
2
2-Aminoethonal
HNH
2

Reaction with halogenated, HBr:
H
2
C CH
2
O
+
H
2
C CH
2
OH
Br
Br H

49
Reaction with LiAlH
4
H
2
C CH
2
O
+
LiAlH
4
CH
3
CH
2
OH
Ethyl alcohol

Unsymmetrical epoxides give the more highly substituted alcohol with main product.
H
2
C CH
2
O
R LiAlH
4
R-CH-CH
3
RCH
2
CH
2
OH
+
OH
main product


Reaction with HCN:
H
2
C CH
2
O
+
HCN HO-CH
2
-CH
2
-CN
ethylene cyanohydrin

Reaction with Grignard Reagent:
Ethylene oxide reacts with Grignard Reagent to give addition product which on hydrolysis yield
primary alcohol.
H
2
C CH
2
O
+
R-MgX CH
2
-CH
2
-R
OMgX
H
+
/ H
2
O
HO-CH
2
-CH
2
-R

Oxidation:
Epoxides are oxidized with dimethyl sulphoxide to -hydroxy ketones.
HC CH
O
R R
+
Me
2
SO
H
+
R CH C R
O SMe
2
OH H
+
-
R CH C
OH O
R
-Me
2
S

Aldehydes and Ketones
Aldehydes and ketones both contain oxo or carbonyl group ( >=O ). In aldehydes carbonyl
carbon on one side attached to hydrogen atom and to carbon atom on other side, thus functional
group of aldehydes is CHO. This group occurs at the end of a chain. In ketones carbonyl
carbon, on both sides attack to carbon atoms, thus the functional group in ketones occurs within a
chain. (
c c c
O
)
50


Aldehyde and ketones are collectively called carbonyl compounds.


Like carbon-carbon double bond, double bond between carbon and oxygen in carbonyl group is
composed of one and one bond. Carbonyl carbon is in a state of sp
2
hybridization. The
carbon oxygen bond is formed by the overlap of sp
2
orbital of carbon with sp
2
- orbital of
oxygen atom. On the other hand the carbon oxygen bond is formed by side wise overlap of
unhybridised p-orbital of both atoms. Two unshared pairs of electron occupy the sp-hybrid
orbitals of oxygen. since three -bond of carbonyl carbon utilize sp
2
orbitals, they lie in one
plane. The bond angles between the attached atoms are approximately 120
0
.


But here electrons are not equally shared by both carbon and oxygen atoms. This is because of
the electronegativity . Due to the high electronegativity of oxygen atom, the electron cloud is
pulled more forward the oxygen atom. As result bond is polarized, oxygen attains a partial
negative charge and carbon a partial positive charge.
51
.
C
.
O
+ -
polarity due to inductive effect

However the high values of dipole moments of aldehydes and ketones cant be accounted only
by inductive effect but also by the resonance effect. Following resonance structures are possible.
.
C
.
O
.
C
.
O
- +

Carboxyl group is resonance hybrid of above two structures.
Methods of Preparation:
Both Aldehydes and ketones may be prepared by the following methods.
1) Oxidation of alcohols: Aldehydes are formed by the oxidation of primary alcohols.
RCH
2
OH
K
2
Cr
2
O
7
/ H
+
RCHO
Controlled Oxidation
Aldehyde
CH
3
CH
2
OH CH
3
CHO
Controlled Oxidation
1
o
alcohol
+
H
2
O
+
H
2
O
Ethyl alcohol Acetaldehyde

Controlled oxidation can also be carried out by using CrO
3
- pyridine [Collin reagent] Ketones
are prepared by the oxidation of secondary alcohols.
K
2
Cr
2
O
7
/ H
+
R-C-R'
Ketone
2
o
alcohol
R-CHOH
R'
O
C H
3
C CH
3
O
K
2
Cr
2
O
7
/ H
+
C H
3
CH CH
3
OH
+
H
2
O
2-Propanol
Acetone
+ H
2
O

Ketones are not easily oxidized further. Ketones can also be obtained by Oppenauer oxidation
of secondary alcohols, which involves refluxing of second alcohol with acetone in the presence
of aluminium tertiary butoxide, AlOC(CH
3
)
3
, catalyst.
52
R
CHOH
R'
C
C H
3
C H
3
O
AlOC(CH
3
)
3
C
R
R'
O
CHOH
C H
3
C H
3
+
+
Acetone
Ketone Iso propyl alcohol
2o Alcohol

2) Dehydrogenation of alcohols: By passing the alcohol vapours over a copper catalyst heated
to about 300
o
C, aldehydes and ketones are prepared. 1
o
alcohols give aldehydes while 2
o
give
ketones.
RCH
2
OH
Cu
300
o
C
R C H
O
+
H
2

CH
3
CH
2
OH
Cu
300
o
C
C H
3
C H
O
+
H
2
Ethylalcohol
Acetaldehyde
R-CHOH-R'
R C R'
O
+
H
2
2
o
alcohol
Cu
300
o
C
Ketone
C H
3
CH CH
3
OH
Cu
300
o
C
C H
3
CH CH
3
O
+
H
2
Iso propyl alcohol
Acetone

3. Dry distillation of calcium salts of Acids: Aldehydes are prepared by pyrolysis of calcium
salt of fatty acid with Calcium formate. While calcium formate alone on heating gives
formaldehyde.

53

Ketones are obtained by heating calcium salt of fatty acid other than calcium formate.

4) Hydration of alkynes: Aldehydes and ketones can be prepared by reactions of alkynes with
the water in presence of mercuric sulphate and sulphuric acid.
C H
3
C C CH
3
+
H OH
HgSO
4
H
2
SO
4
R C C H
H
O H
R C CH
3
O Propyne
Acetone
Unstable

Acetylene give aldehyde under these conditions.
H C C H
+
H OH
HgSO
4
H
2
SO
4
C H
3
C H
O

5) Hydrolysis of gem-Dihalides: Aldehydes are prepared by the hydrolysis of gem dihalides
containing both halogen atom on terminal carbon atom.
R CH Cl
Cl
H
2
O
NaOH R CH OH
OH
H
2
O
R C
O
H
-


54
Ketones are prepared by the hydolysis of gem-dihalides containing both halogen atoms on non
terminal carbon atom.
R C R'
Cl
Cl
H
2
O
NaOH
R C
O
R'

For example
C H
3
CH Cl
Cl
H
2
O
NaOH
CH
3
CHO
Acetaldehyde
C H
3
C CH
3
Cl
Cl
H
2
O
NaOH
C H
3
C CH
3
O

6) Catalytic decomposition of acids: Aldehydes cannot be prepared by this method. Ketones
are prepared by passing vapours of carboxylic acid over heated MnO or ThO
2
. For example,
C H
3
C OH
O
2
MnO
300
o
C
C H
3
C CH
3
O
+
O H
2 +
CO
2
2 molecules of acetic acid Acetone

7) Reduction of Acid Chlorides: [Rosenmund Reduction]: Aldehydes can be prepared by the
reduction of acid chloride in the presence of palladium supported over barium sulphate.
R C Cl
O
R C H
O
+
+
H
2
Pd / BaSO
4
S or quinoline
Cl H

Aldehydes can also be easily reduced to primary alcohol but the catalyst is poisoned by the
sulphur and thus aldehydes are the final product.
Ketones cannot be prepared by this method.
8) From Grignard Reagent: Aldehydes can be prepared from Grignard Reagent (RMgX) in
two ways.
i) From hydrogen cyanide:
RMgX H C N
+
R C NMgX
H
Additin product
H
+
/ H
2
O
R C CH
3
O
MgX(NH
2
)
+

55
ii) From alkyl formates:
H C OR'
O
+
RMgX
H C
O-MgX
R
OR'
H
2
O
H C OH
R
OH
-H
2
O
R C H
O

Ketones can also be prepared from Grignard reagent in two ways,
i) From alkyl cyanide:
R'-MgX
+
R C N
R C
R
NMgBr
H
+
/ H
2
O
R C R'
O
+
MgX

ii) From acid Chlorides:
C H
3
C Cl
O
+
R'MgX R C Cl
OMgX
R'
R C R'
O
+
MgXCl

Aldehyde or ketones so formed, may further react with excess of the Grignard reagents to give
alcohols.

9) Oxo process: This method is industrially important for the preparation of aldehydes. It
involves the treatment of an alkene with carbon monoxide and hydrogen in the presence of
cobalt carbonyl catalyst at high temperature and pressure.
R CH CH
2 +
CO
+
H
2
[Co(CO)
4
R CH
2
CH
2
C CH
3
O
Aldehyde
Alkene

Ketones cannot be prepared by this method.

10) Wacker process: This method involves the treatment of alkene with acidified aqueous
solution of palladium chloride, PdCl
2

and cupric chloride, CuCl
2
.
56
C H
2
CH
2
+ +
CuCl
2
C H
3
C H
O
Alkene
PdCl
2
O H
2
+
Pd
+
2HCl
R CH CH
2+ +
PdCl
2
O H
2
R C CH
3
O
+
Pd
+
2HCl
Ketone
Acetaldehyde

Properties:
1) Formaldehyde is gas at room temperature and other aldehydes and ketones are colourless
liquids.
2) Lower aldehydes and ketones are soluble in water due to capability of forming hydrogen
bonds with water molecules. But higher members containing more than five carbon
atoms are insoluble in water and soluble in organic solvent.
3) Since aldehydes and ketones are polar compounds. Their boiling points are higher than
corresponding non polar compounds. But these molecules are not capable of forming
intermolecular hydrogen bonds. Their boiling points are lower than corresponding
alcohols.
4) Density of aldehydes and ketones are lesser than that of water.

Chemical properties: Both aldehydes and ketones contain highly polar carbonyl group.
.
C
.
O
.
C
+
.
O
-


.
C
.
O
+
-

Carbonyl carbon is electron deficient and carbonyl oxygen is electron rich. The electron deficient
carbon is readily attacked by electron rich nucleophiles and electron rich oxygen is attacked by
electron deficient electrophiles. The typical reaction of aldehydes and ketones is nucleophilic
addition. They undergo nucleophilic addition reaction by following general mechanism.

Nu-H
B
Nu:
B-H +
+
-
Neutral weak nucleophile
Strong nucleophile


A: Base Catalysed Addition: Base convert weak nucleophile to strong one
Step 1: Attack of nucleophile at carbonyl carbon to form new -bond.
.
.
O
Nu
.
O
-
Nu:
..
:
:
..
..

Step 2: Attack of electrophile ( e.g., -H
+
) at negatively charged oxygen to give addition product.
57
Nu
.
O
:
..
..
+H
+
Nu
.
OH
..
..
Addition product
-


B) Acid Catalysed Addition:
Step 1: Protonation of carbonyl group.
.
.
O
:
..
..
+H
+
.
.
O
+
H
..
.
.
O H
..
..
+
Resonance stabilised protonated carbonyl group

Step 2: Attack of nucleophile on protonated carbonyl carbon to give addition product.
.
C
.
O H
..
Nu
.
O H
..
..
Nu :
-

..
+
+
Addition product.

Addition products remains same in both acid and base catalysed reaction.

The reactivity of the carbonyl group towards the nucleophilic addition reactions depends upon
the magnitude of the positive charge on the carbonyl carbon and also on crowding around the
carbonyl carbon. (Steric factor). Alkyl groups of other electron donating that decreases the
positive charge on the carbonyl carbon will decrease its reactivity towards the nucleophilic
addition follows the following order.
H C H
O
R C H
O
R C
O
R
> >
Formaldehyde
Aldehyde Ketone

Acidity of -Hydrogens: A carbon atom next to carbonyl group is -carbon atom and hydrogens
attached to this carbon are known as hydrogens. - hydrogens in aldehydes and ketones are
abstractable by base i.e; acidic in nature. this is due to the fact that carbonion formed the normal
of hydrogen atom is stabilized by resonance. this ion is called Enolate ion.
58
C H
3
C
O
C CH
3
H
CH
3
B
C H
3
C
O
C CH
3
CH
3
C H
3
C
O
C CH
3
CH
3
:
..
-
:
..
:
..
:
..
-
-
Resonance Stabilized
Enolate ion.

The negatively charged carbon of enolate ion act as a nucleophile. All condensation reaction
involved formation of enolate ion and its addition to carbonyl group.

(A) Nucleophilic Addition Reactions of Aldehydes & Ketones
(1) Addition of Hydrogen Cyanide: Aldehydes and Ketones on addition of HCN give
cyanohydrins. Reaction is carried out in the presence of basic catalyst. HCN is produced in situ
by the action of dilute H
2
SO
4
on KCN.

+
HCN C H
3
C CH
3
CN
OH
Cyanohydrin
O
C H
3
CH
3


C H
3
C H
O
+
HCN C H
3
C H
OH
CN
Acetaldehyde cyanohydrin
Acetaldehyde




C H
3
C CH
3
O
HCN C H
3
C CH
3
OH
CN
+
Acetone
Acetone cyanohydrin.

(2) Addition of Grignard reagent: Aldehydes and Ketones with Grignard reagent first give the
addition product which can be hydrolysed with dilute acid to yield alcohol. Only formaldehyde
gives 1
0
alcohols, other aldehydes give 2
0
alcohol and ketones give 3
o
alcohols. For example

H C H
O
RMgX
H C H
OMgX
R
H
+
/ H
2
O
RCH
2
OH
1
o
alcohol Formaldehyde

59
R C H
O
R'MgX
R C H
OMgX
R'
H
+
/ H
2
O
R CH
OH
R'
Aldehyde
2
o
alcohol


R C R
O
R'MgX
R C R
OMgX
R'
H
+
/ H
2
O
R C
OH
R'
R
Ketone
3
o
alcohol

(3) Addition of Sodium bisulphate: Aledehydes and methyl ketones when treated with
saturated aqueous solution of sodium bisulphate, a solid addition compound is formed.
H C H
O
+
NaHSO
4
C H
3
CH
3
SO
3
Na
OH
Bisulphite addition compound

C H
3
C H
O
+
NaHSO
4
C H
3
H
SO
3
Na
OH
Acetaldehyde bisulphite
C H
3
C CH
3
O
+
NaHSO
4
C H
3
H
SO
3
Na
OH
Acetone bisulphite

These bisulphites can be decomposed with dilute acids or bases to regenerate the carbonyl
compound, therefore this process of formation and decomposition of bisulphite is used for the
purification and separation of carbonyl compounds from mixtures.

(4) Addition of Ammonia: Aldehydes (except formaldehyde) form solid addition product,
aldehyde ammonia
R C H
O
+
NH
3
R C H
NH
2
OH
Aldehyde ammonia

Aldehydes can also be regenerated by heating aldehyde ammonias with dilute acids. Thus the
process of formation and decomposition of these compounds can be used or the separation and
purification of aldehydes.
Formaldehyde and ketones do not form addition product with ammonia. They yield complex
condensation product with ammonia. For example
60
H C H
O
+
NH
3 6
4
CH
2
CH
2
CH
2
N
Hexamethylene tetramine.
(Urotropine)
N
N N

Urotropine is used as urinary antiseptic.
C H
3
C CH
3
O
2
+
NH
3 C H
3
C CH
2
C CH
3
NH
2
CH
3
O
Diacetone amine.
Acetone

B) Reactions Involving addition followed by removal of water:
5) Reaction with Ammonia Derivatives: Reactions of Aldehyde and Ketones with ammonia
derivatives are very important and characteristic reactions of carbonyl compounds. They react
with ammonia derivatives (H
2
N-Y) to form compounds containing carbon-nitrogen double bond
(C=N-), with the elimination of water.
C H
3
C H
3
O
N H
2
Y
C H
3
C
C H
3
N Y O H
2
+
+

General mechanism of the reaction involve following steps.
Step 1: Attack of nucleophile on carbonyl carbon to give unstable addition product.
C H
3
C H
3
O
N H
2
Y
C H
3
C
C H
3
NH
+
Y
O
-
H
+
..
H
+
transfer
C H
3
C
C H
3
N Y
OH
H
[ unstable]

+ -

Step 2: Removal of water to give the final product.
C H
3
C
C H
3
N Y
OH
H
-H
2
O
C H
3
C
C H
3
N Y

61
All the ammonia derivatives follow the same mechanism. The ammonia derivatives are
hydrazine, phenyl hydrazine, 2,4-dinitrophenyl hydrazine, hydroxylamine, and semicarbazide.

a) Reaction with Hydrazine: Aldehydes and ketones form hydrazones with hydrazine
(NH
2
NH
2
)
C H
3
C O
H
+
N H
2
NH
2 CH
3
CH=N-NH
2
Acetaldehyde hydrazone
acetaldehyde

C H
3
C O
CH
3
+
H
2
NNH
2
C H
3
C
CH
3
N NH
2
Acetone hydrazone
Acetone

b) Reaction with phenyl hydrazine: Aldehydes and ketones form phenyl hydrazone with
phenyl hydrazine.

c) Reaction with 2,4-Dinitro phenyl hydrazine: Aldehydes and ketones react with 2,4-
dinitrophenyl hydrazine to form 2,4-dinitrophenyl hydrazone.


d) Reaction with Hydroxylamine: Aldehydes and ketones form oxime with
hydroxylamine(NH
2
OH).

62
e) Reaction with Semicarbazide: Aldehydes and ketones give Semicarbazone with
semicarbazide
C H
3
C
H
O
+
H
2
N NH C NH
2
O
C H
3
C
H
NH NH C NH
2
O
+
O H
2
Acetaldehyde oxime.
C H
3
C
CH
3
O
+
H
2
N NH C NH
2
O
C H
3
C
CH
3
NH NH C NH
2
O
+
O H
2
Acetone Semicarbazone.
Acetaldehyde
Acetone

6) Reaction with alcohols: Aldehyde react with alcohol in the presence of dry HCl gas to form
Acetals e.g:
R
C
H
O
+
R'OH
dry HCl
C
R OH
H OR'
R'OH
HCl
C
R OR'
H OR'
Hemi acetal
Acetal

Acetals are readily cleaved by acids to give acetaldehydes, and are stable towards base. Ketones
however, do not form ketals with monohydric alcohols, they react with dihydric alcohols to give
cyclic ketals. e.g

(C) Condensation Reactions: These reactions involve formation of enolate ion which attack on
carbonyl carbon of another molecule to give condensation product.

7) Aldol condensation: Aldehydes containing at least one - hydrogen atom. When treated with
dilute base like NaOH undergo condensation reaction to give products called Aldols. The
reaction is known as aldol condensation. Aldols are the compounds containing both aldehydic
and Alcoholic functional groups. For example two molecules of acetaldehyde combine in
presence of dilute NaOH to form 3-hydroxy butanal.
C H
3
C
O
H
+
H
2
C CHO
H
C H
3
CH CH
2
CHO
OH
2-hydroxy butanal (Aldol)

Mechanism:
Following steps are involved in the mechanism of aldol condensation reaction.
Step 1: Formation of enolate ion
63
H CH
2
C H
O
O H
-
CH
2
C H
O
+
O H
2
:
-
Enolate ion
Acetaldehyde

Step 2: Attack of enolate ion (nucleophile) on carbonyl carbon of another molecule of
acetaldehyde.
C H
3
C H
O
CH
2
C H
O
:
-
+
C H
3
CH CH
2
C H
O O
-

-
+

Step 3: Abstraction of proton from water molecule to give final product Aldol.
C H
3
CH CH
2
C H
O O
-
O H H
C H
3
CH CH
2
C H
O OH
+
Aldol
OH
-

Aldol when heated easily loses a molecule of water to form ,-unsaturated compound. For
example
C H
3
CH CH C H
O OH
H
-H
2
O
C H
3
CH CH C H
O
Crotonaldehyde

Ketones containing -hydrogens also undergo condensation to give ketols. For examples, two
molecule of acetone condense together in the presence of barium hydroxide to form diacetone
alcohol ( Ketol)
C H
3
C CH
3
O
+
H
2
C C CH
3
O H
Ba(OH)
2
C H
3
C CH
2
C CH
3
CH
3
OH
O

Diacetone alcohol on heating loses one molecule of water to form mesityl oxide.

Mixed Aldol Condensation: Condensation that take place between two different molecules, one
of which must have an -hydrogen, in the presence of base is known as mixed aldol
condensation. For example condensation of acetaldehyde with benzaldehyde.
64
C H
O
+
H
2
C C
CH
3
CH
3
H
O H
-
CH
OH
CH
2
C H
O
H
+
or
CH CH C H
O
+
O H
2
Cinnamaldehyde

(D) Reduction Reactions:
8) Reduction to Alcohols: Aldehydes and ketones are reduced to the primary and secondary
alcohols respectively by catalytic hydrogenation (H
2
/ Ni or Pt), nascent hydrogen (Na-Hg or
Na/C
2
H
2
OH), LiAlH
4
or NaBH
4
RCHO
+
H
2
or
2[H]
RCH
2
OH
1
o
alcohol
R C
O
R
+
H
2
or
2[H] R CH
OH
R
Ketone
Aldehyde
2
o
alcohol

Reduction of both aldehydes and ketones to alcohols may be effected by means of Merwein-
Ponndrof-Verley Reduction which involves the reduction by means of aluminum iso propoxide
in isopropanol.
RCHO
+
RCH
2
OH
R C
O
R +
(CH
3
)
2
CHOH
[CH
3
CH-O]
2
Al
(CH
3
)
2
CHOH
[CH
3
CH-O]
2
Al
+
C H
3
C CH
3
O
R CH
OH
R
+
C H
3
C CH
3
O

The reduction occurs by hydride ion transfer from aluminium isopropoxide to the carbonyl
compound via a cyclic transition state.

65
9) Reduction to Alkanes: Aldehydes and ketones are reduced to corresponding alkanes by
means of zinc amalgam and hydrochloric acid [ Clemensen reduction] or alkaline solution of
hydrazine.[Wolf Kishner Reduction]

Clemmensen Reduction: This involves the use of zinc- mercury amalgam in hydrochloric acid
as the reducing agent.

R C
O
H
Zn-Hg
HCl
R-CH
3
R C
O
R
Zn-Hg
HCl
R-CH
2
-R


Wolf Kishner Reduction : This involves the use of basic solution of hydrazine as the reducing
agent
R C
O
H R-CH
3
R C
O
R'
NaOH
R-CH
2
-R'
NH
2
-NH
2
NaOH
NH
2
-NH
2

(E) Oxidation Reactions:
10) Aldehydes are easily oxidized to carboxilc acid by acidic Na
2
Cr
2
O
7
or K
2
Cr
2
O
7
or acidic
KMnO
4
.
R-CHO
+
[O]
K
2
Cr
2
O
7
/ H
+
RCOOH

Aldehydes can also be oxidized by another oxidizing agents such as Tollens reagent, Fehlings
solution and Benedicts solution and thus act as a strong reducing agents.

Tollens Reagent:[Ammonical Silver nitrate Solution] : When Tollens reagent is used to
oxidize an aldehyde, the Silver ion is reduced to metallic form and deposits as a mirror on clean
test tube. This reaction is used as a test of aldehyde and known as Silver mirror test.
R C H
O
+
Ag(NH
3
)
2
OH
R C
O
ONH
4+
2Ag
+
O H
2
+ -
+
NH
3
3
silver mirror

Fehling solution: Blue coloured alkaline solution of cupric ion [Fehling Solution A] complexed
with sodium potassium tarterate (Fehling Solution B) is also reduced by Aldehyde. The
complexed cupric ion (deep blue) is reduced to Cuprous oxide.
66
Benedict solution (alkaline solution of cupric ion complexed with citrate ions) reacts in the same
way as Fehling Solution.

Ketones are not oxidized by milder oxidizing agents thus they do not reduce Tollens reagent,
Fehling solution and Benedicts solutions. However, ketones can be oxidized by stronger
oxidizing agents such as acid dichromate, alkaline KMnO
4
and hot con. HNO
3
to form
carboxylic acids with fewer carbon atoms that the original ketones. For example
C H
3
C CH
3
O
K
2
Cr
2
O
7
/ H
+
CH
3
COOH
+
HCOOH
C H
3
CH
2
C CH
3
O
HNO
3
CH
3
CH
2
COOH HCOOH
+

(F) Other important Reactions of Aldehydes and Ketones.
(11) Cannizzaro reaction: Aldehydes which do not have -hydrogen atom, when treated with
concentrated solution of NaOH undergo dis proportionation reaction. One half of the aldehydes
are oxidized to carboxylic acid and other half are reduced to alcohol. This reaction is known as
Cannizzaro reaction.
2HCHO
NaOH
HCOONa CH
3
OH
+
+
Formaldehyde
Sodium formate Methyl alcohol

Mechanism: Following steps are involved
Step 1: Attack of the

OH on the carbonyl group.

H C
O
H
+
O H
-
H C H
OH
O
-

+
-

Step 2: Hydride transfer:
H C H
O
-
OH
H
H
O
+ -
H C
O
OH
+
CH
3
O
-
H
+
transfer
H C O
O
+
CH
3
OH

-

Ketones do not give this reaction.
12) Reformatsky Reaction: Reaction of aldehydes and ketones with -bromoester in the
presence of metallic zinc and ether to give -hydroxy ester is known as Reformatsky reaction.
e.g.
67
C H
3
C
O
H
+
Br-CH
2
COOC
2
H
5
i) Zn.ether
ii) H
2
O / H
+
C H
3
C CH
2
OH
H
COOC
2
H
5
C H
3
C
O
CH
3 +
Br-CH
2
COOC
2
H
5
i) Zn.ether
ii) H
2
O / H
+
C H
3
C CH
2
OH
CH
3
COOC
2
H
5

Mechanism: Three steps are involved.
Step 1: Formation of zinc salt of enol of the ester.
Br CH
2
C
O
OC
2
H
5
H
2
C C
OZnBr
OC
2
H
5

Step 2: The zinc salt reacts with the carbonyl compound.
C H
3
C
O
CH
3
+
C H
2
C
O
OC
2
H
5
ZnBr
C H
3
C
OZnBr
CH
2
H
C
O
OC
2
H
5
+
-

Step 3: Acid hydrolysis
C H
3
C
OZnBr
CH
2
H
C
O
OC
2
H
5
H
+
/ H
2
O
C H
3
C
OH
CH
2
H
C
O
OC
2
H
5


13) Haloform Reaction: Acetaldehyde and methyl ketones react rapidly with halogen(Cl
2
,Br
2
or
I
2
) in the presence of alkali to give haloform. This reaction is known as Haloform reaction.
R C
O
CH
3 +
Br
2
4NaOH CHBr
3
3H
2
O 3NaBr
+
+
+
R
O
ONa
+
+
-
Methyl ketone
Bromoform


The reaction takes place in two steps.
1. R C CH
3
O
+ 3Br
2
3NaOH
+
R C CBr
3
O
+
3H
2
O
+ 3NaBr
R C CBr
3
O
NaOH
+
R C ONa
O
+
2. CHBr
3
Bromoform

68
Haloform reaction is used as a diagnostic test for detecting the presence of COCH
3
group in a
compound. This reaction can also be used to distinguish methyl ketones. Ketone not containing
(-CO-CH
3
) do not give this reaction.

14) Wittig Reaction: Reaction between aldehydes and ketones with triphenyl phosphine
alkylidenes or phosopourous ylide (Ph
3
P=CR
2
) to form alkene is known as Wittig reaction.
Alkene
C H
3
C H
3
O
+
R
2
C-PPh
3
+
-
ylide
C H
3
C H
3
CR
2 O=PPh
3 +

Mechanism: Attack of negative carbon of ylide on carbonyl carbon to form betaine,
C
O
C H
3
CH
3
C
PPh
3
R R
O
-
PPh
3
C H
3
CH
3
R
R
+
+ +
+
-
:
-

Betaine undergo elimination to give the alkene.
O
-
PPh
3
C H
3
CH
3
CH
3
C H
3
+
O PPh
3
C H
3
CH
3
R
R
C H
3
C H
3
CR
2 +
O=PPh
3
Betaine

Example:
C H
3
C
CH
3
O C H
2
-
PPh
3
+
C H
3
C
CH
3
CH
2 +
+ O=P-Ph
3
2-methyl propene


15)Reaction with PCl
5
: Aldehydes and ketones react with PCl
5
to give gem-dihalides.e.g.
R C H
O
PCl
5
R C H
Cl
Cl
+
+
POCl
3
R C R
O
PCl
5
R C R
Cl
Cl
+
+
POCl
3
Gem.dihalide

69
16) Tischenko Reaction: Aldehydes having -hydrogen atom can also be made to undergo
cannizzaro type reaction, if reaction is carried out in presence of aluminum ethoxide. But in such
case, acid and alcohol react together to form ester as the final product.
2CH
3
CHO
Al(OC
2
H
5
)
3
CH
3
COOH CH
3
CH
2
OH
CH
3
COOC
2
H
5
+
Ethyl acetate

17) Polymerization: Lower aldehydes undergo polymerization to form different products under
different conditions. Ketones however, are not much susceptible to polymerization.

Carboxylic Acids and Their Functional Derivatives
Organic compounds containing carboxyl group (-COOH) are known as carboxylic acids. They
can be represented by the general formula.
R COOH
Or C H
3
C
O
OH

They are further classified as mono, di, tri etc., carboxylic acids, according to the number of
carboxylic groups present in their molecules. The long chain monocarboxylic acids are also
called fatty acids because many of them are obtained from fats.

Methods of Preparation
1) By the oxidation of primary alcohols or Aldehydes: Primary alcohols or aldehydes are
oxidized by acidic K
2
Cr
2
O
7
or Na
2
Cr
2
O
7
to give carboxylic acids.
RCH
2
OH
K
2
Cr
2
O
7
/ H
+
RCHO
RCOOH
K
2
Cr
2
O
7
/ H
+
1
o
alcohol
Aldehyde
Carboxylic acid
CH
3
CH
2
OH
[O]
CH
3
CHO
[O]
CH
3
COOH
Ethyl alcohol
Acetaldehyde
Acetic acid

2) By the hydrolysis of alkyl cyanides or nitriles: Alkyl cyanide on acid hydrolysis give
carboxylic acids.
R C N
H
+
/ H
2
O
RCOOH NH
3
+
Alkyl cyanide
carboxylic acid
CH
3
CN
CH
3
COOH NH
3
+
H
+
/ H
2
O
Methyl cyanide
Acetic acid

3) By the Hydrolysis of Ester: When esters are hydrolysed by alkali NaOH or KOH, sodium or
potassium salt of carboxylic acids are formed which on treatment with dil HCl gives the
corresponding carboxylic acids.
70
C H
3
C OC
2
H
5
O
NaOH
+
C H
3
C ONa
O
+
C
2
H
5
OH
Sodium acetate
Ethyl alcohol ethyl acetate
- +
C H
3
C ONa
O
- +
+
Cl H C H
3
C OH
O
+
NaCl

4) By the Reaction of Grignard Reagents with CO
2
: Grignard reagent with CO
2
first give
addition product which on hydrolysis yield carboxylic acid.
R-MgX
+
C O
O
R C
O
OMgX
H
+
/ H
2
O
RCOOH
carboxylic acid
Alkyl
Magnesium halide
C
2
H
5
MgBr
+
C O
O
C
2
H 5 C
O
OMgX
H
+
/ H
2
O
C
2
H
5
-COOH
Ethyl
Magnesium bromide
Propionic acid.

Organo lithium compounds can also be used in place of Grignard Reagent.

5) By Malonic Ester Synthesis: Alkyl halide react with sodium derivative of diethyl malonate
to give substituted malonic ester. This is hydrolysed and decarboxylated to yield an acid.
R X
+
NaHC
COOC
2
H
5
COOC
2
H
5
-NaX
HC
COOC
2
H
5
COOC
2
H
5
R
H
+
/ H
2
O
HC
COOH
COOH
R
-CO
2
RCH
2
COOH
Carboxylic acid

In this method two more carbons are added to alkyl group of starting alkyl halide.

6) By Carboxylation of Alkenes: This is a recent industrial method of preparation of carboxylic
acids and is called Koch Reaction. This involves treatment of alkene with carbon monoxide and
steam under pressure with phosphoric acid, H
3
PO
3
at 400
o
C.
71

C H
2
CH
2 +
CO
+
O H
2
H
3
PO
4
400
o
C
CH
3
CH
2
COOH
Propionic acid

Properties:
1) The lower carboxylic acids ( C
1
to C
10
) are colourless pungent smelling liquids. Higher
members are wax like solids and almost colourless.
2) First four members are freely soluble in water due to hydrogen bonding with water molecule.
IIIIIII IIIIIIII
H O C O
R
H O
H
H O C O
R
H O
H
IIIIIII IIIIIII

But the solubility of higher members decreases rapidly with the increase in the size of the alkyl
group due to increased influence of the non-polar and hydrophobic hydrocarbon chain.

3)Melting points of carboxylic acids increase irregularly with increase in the molecular weight.
The even members have markedly higher boiling points than the odd members.

4) Boiling points of the carboxylic acids, particularly lower members higher than the alcohols of
same molecular weight. e.g.
Acetic acid (CH
3
COOH) MW = 60 b.p. = 118
o
C
1-Propanol(CH
3
CH
2
CH
2
OH) MW = 60 b.p = 97
o
C

This is due to the strong hydrogen bonding in carboxylic acids than those in alcohols.
R C
O
O H
R C
O
O H IIIIIII
IIIIIIII

5) Acidity of Carboxylic Acids: Carboxylic acid are acidic in nature but they are weak acids as
compared to inorganic acids (e.g. HCl or H
2
SO
4
). They can donate a proton and form salts with
strong bases and they are only partially ionized in aqueous solution.
R C
O
OH
+
O H
2 R C
O
O
-
+
O H
3
+

The acidic character of carboxylic acids decreases with increase in molecular weight. Formic
acid is strongest of all fatty acids.

The acidic character of carboxylic acid is due to the resonance. The carboxylic ion form by
ionization is stabilized by resonance.

72
Hence carboxylic ion is more stabilized than the acid itself. The equilibrium of the ionization of
acids shifts to the right hand side. X-ray studies also support the existence of carboxylate ion as
resonance hybrid for example bond lengths of carboxy oxygen have different values in formic
acid. Where as in sodium formate the two carbon-oxygen bond lengths are identical.

The stability of carboxylate ion can also be explained on the basis of its molecular orbital
structure. The carbon atom of carboxyl group in sp
2
hybridised. In carboxylate ion the
unhybridised P orbital of carbon overlaps with P orbital of both oxygen atom to form stable
delocalized molecular orbital.

Effect of substituents on Acidity: Acidic character of carboxylic acid is due to the stabilization
of carboxylate ion. So any factor which can enhance the dispersal of negative charge of the
carboxylate ion will increase the acidity and vise versa. Inductive effect of the substituent on the
-carbon play very important role. Electron withdrawing substitutents like Cl, Br, F, NO
2
, OH,
CN etc. would disperse the negative charge and hence stabilize the carboxylic ion. On the other
hand electron releasing substituents would increase the negative charge destabilizes the
carboxylate ion and thus decrease acidity of the acid.

73
Alkyl groups are electron releasing group thus their presence in the molecule will decrease the
acidity . Longer the lengths of alkyl chain, lower will the acidity of the acid. Since formic acid
has no alkyl group, it is the strongest of all fatty acids. It is ten times stronger than acetic acid.
HCOOH>> CH
3
COOH >CH
3
CH
2
COOH
Similarly Chloroacetic acid is hundred times stronger than acetic acid because of the electron
withdrawing nature of Cl group following order is observed in Chloro acetic acid.
Cl
3
-C-COOH > Cl
2
-CH-COOH >Cl-CH
2
COOH> CH
3
COOH
Trichloroacetic acid is almost as strong as a mineral acid.
Chemical Properties:
A) Reactions involving hydrogen atom of the COOH group
1) Reaction with metals and alkalies: Carboxylic acids react with strongly positive metals with
the liberation of hydrogen and form salt.
RCOOH Na RCOONa 1/
2
H
2
+
+
- +

Carboxylic acids also from salts with metal hydroxides, carbonates and bicarbonates. For
example

2) Reaction with Alcohols: Monocarboxylic acids react with alcohols in the presence of strong
acid catalyst like sulphuric acid to form esters. The reaction is known as Esterification.
R C
O
OH
+
R C
O
OR
O H R
H
+
H
2
O
+
carboxylic acid
C H
3
C
O
OH C H
3
C
O
OC
2
H
5
O H C
2
H
5
H
+
H
2
O
+
+
Ethyl acetate
Ethanol
Acetic acid

Following mechanism is suggested for the esterification
Step 1: Protonation of carboxylic acid.
C H
3
C
O
OH
+
H
+
C H
3
C
+
OH
OH

-
+



74
C H
3
C
+
OH
OH +
H
O C
2
H
5
:
..
C H
3
OH
OH
O
+
H
C
2
H
5

Step III: Hydrogen ion transfer
C H
3
O-C
2
H
5
O
OH
2
+
H
C H
3
O
OH
H
O
+
C
2
H
5
H

Step IV: Elimination of water and proton.

C H
3
O-C
2
H
5
O
OH
2
+
H
C H
3
C O-C
2
H
5
O
+
O H
2 +
H
+

B) Reaction involving OH part of the COOH group
3) Reaction with Phosphorous Halides and ThIonyl Chloride: Carboxylic acids react with
phosphorous halides and thionyl chloride to form acid halides. For example.
R C OH
O
+
3
PCl
3 3 RCOCl H
3
PO
3 +

R C OH
O
+
PCl
5
RCOCl POCl
3
HCl
+ +

R C OH
O
+
SOCl
2
RCOCl SO
2
HCl
+
+

4)Reaction with ammonia: Carboxylic acid react with ammonia to form ammonium salt which
on strong heating give acid amides with the elimination of water.
R C OH
O
+
NH
3
R C ONH
4
O
R C NH
2
O
-H
2
O
Carboxylic acid
Ammonium salt
Acid amide
- +

75
C H
3
C OH
O
+
NH
3
C H
3
C ONH
4
O
C H
3
C NH
2
O
-H
2
O
- +
Acetamide
Ammonium acetate
Acetic acid

5) Dehydration: Carboxylic acid on dehydration with P
2
O
5
(dehydrating agents) give acid
anhydride.


C H
3
C OH
O C H
3
C
O
C C H
3
O
O
+ H
2
O
Acetic anhydride
P
2
O
5
2
Acetic acid

Acid anhydrides can also be prepared by heating sodium salt of acids with halides.
R C ONa
O
Cl C CH
3
O
C H
3
C
O
C C H
3
O
O
+ NaCl
+ -
+

C) Some Other Reactions:
6) Reduction: Reduction of carboxylic acids depends on the nature of reducing agents. On
reduction with LiAlH
4
, carboxylic acid gives primary alcohol.
RCOOH
R CH
2
OH
Carboxylic acid
alcohol
LiAlH
4
1
o

Heating with HI / red Phosphorous, under pressure, or with hydrogen under pressure at elevated
temperature in the presence of a nickel catalyst, produces an alkane.
76
RCOOH
H
2
/ Ni
or
HI / red P
R CH
3
Carboxylic acid Alkane

7) Oxidation: All the acids, except formic acid , are extremely resistant to oxidation, but
prolonged heating with oxidizing agents produces carbon dioxide and water.

(D) Reactions Involving alkyl group of the acid:
(8) -Halogenation: Carboxylic acids containing -hydrogen atoms. When treated with Cl
2
or
Br
2
in the presence of phosphorous as a catalyst, substitution of -halogenated acids are formed.
The reaction is known as the Hell-Volhard Zelinsky (HVZ) reaction.
R CH
2
COOH
+
Cl
2
P
R CH COOH
Cl
+
Cl H
Carboxylic acid
halogenated acid
-

C H
3
COOH
+
Cl
2
P
Cl CH
2
COOH
+
Cl H
Chloro acetic acid Acetic acid

CH
2
COOH C H
3
+
Br
2
P
Cl CH COOH
Br
+
Acetic acid 2-Bromo propionic acid.
Br H

(E) Reacations of salts of carboxylic acids:
(9) Heating of Sodium salt: When sodium salt of carboxylic acid are heated with soda lime
[NaOH + CaO] alkanes are formed.
C H
3
C ONa
O
+ -
+
NaOH
CaO
CH
4 +
Na
2
CO
3
Sod. acetate Methane

10) Heating of Ammonium salt: When ammonium salts are heated, amides are formed.
C H
3
C ONH
4
O
Ammonium acetate
+
-
CH
3
CONH
2
H
2
O
+
Acetamide

When ammonium salts are heated with P
2
O
5
, alkyl nitriles are formed.
C H
3
C ONH
4
O
P
2
O
5
C H
3
C N
+
2 H
2
O
methyl cyanide Ammonium acetate

77
11) Heating of Calcium salt: Calcium salts of carboxylic acids on heating give aldehydes and
ketones.
a) Calcium formate gives formaldehyde.

b)Calcium salt of any carboxylic acid other than formic acid gives ketones.
(R-COO)
2
Ca
2CaCO
3
+
(CH
3
-COO)
2
Ca
R C R
O
2CaCO
3
C H
3
C CH
3
O
+

c) Calcium salt of any carboxylic acid. when heated with calcium formate gives aldehyde.
(R-COO)
2
Ca
+
(HCOO)
2
Ca
2R-CHO 2CaCO
3 +
(CH
3
-COO)
2
Ca
+
(HCOO)
2
Ca
2CH
3
CHO 2CaCO
3 +

12)Electrolysis: Electrolysis of concentrated aqueous solution of sodium or potassium salts
gives alkanes. (Kolbes electrolysis)
2RCOONa
+
2H
2
O R R
+
2CO
2
2NaOH
H
2
+ +
electrolysis
At anode At cathode
2CH
3
COONa
+
2H
2
O C H
3
CH
3
+
2CO
2
2NaOH
H
2
+ +
electrolysis
Sodium acetate
Ethane

13) Reaction of silver salts with halogens: When silver salt of carboxylic acids are heated with
chlorine or bromine, alkyl halides are formed. The reaction is known as Hunsdiecker Reaction.
78
C H
3
C
O
OAg +
Br
2
CH
3
Br
+
2AgBr
+
CO
2
+
-

Carboxylic Acid Derivatives (Acid Derivatives): The compounds derived from the carboxylic
acids by the replacement of OH function of Carboxyl group by another group are known as
acid derivatives. All such derivatives upon hydrolysis generate the parent acid.

Different Acid derivatives are:
R C O
O
R C
O
R C OR
O
Name
Formula
i)
Acid halides
C H
3
C
O
CH
3
X =Cl,Br or I
ii) Acid anhydride
iii) Ester
iv) Amide
R C NH
2
O

1. Acid Halides: Acid halides are the derivatives of acids in which the OH function of carboxyl
group is replaced by a halogen atom. Acid halides are also known as acyl halides. Acid chlorides
are most important of all the acid halides.
They are represented as
R C
O
Cl
, some examples are,
C H
3
C
O
Cl
- Acetyl Chloride(Ethanoyl chloride)
H
5
C
2
C
O
Cl
- Propionyl chloride (Propanoyl chloride)

Methods of Preperation:
1) By the reaction of carboxylic acids with phosphorous halides
R C OH
O
PCl
3
R C Cl
O
H
3
PO
3
+
+
3

R C OH
O
PCl
5
R C Cl
O
POCl
3
+
+
HCl
+

2) By the reaction of Carboxylic acids with thionyl chloride
79
R C OH
O
SOCl
2
R C Cl
O
SO
2
+
+
C H
3
C OH
O
SOCl
2
C H
3
C Cl
O
SO
2
+
+

Properties:
Physical Properties:
i) All simple acid chlorides are pungent smelling colourless liquids of lower boiling points than
the corresponding acid. They also have tear producing property. i.e lachrymators.
ii) They are insoluble in water but slowly start to dissolve in it because of hydrolysis.

Chemical properties: Acid chlorides are very reactive compounds as they are more readily
attacked by nucleophile because of the electron withdrawing effect of highly electronegative,
chlorine atom attached to carbonyl carbon. This further diminishes the electron density on the
carbonyl carbon. Cl atom is replaced by the nucleophile.
R C Cl
O
R C Cl
O
-
+
R C Nu
O
+
:Nu
Cl:
-
..


-
+

Some important reactions of acid chloride are following.
1)Hydrolysis: The acyl chlorides are readily hydrolysed by water to reform the original acid.
R C Cl
O
R C OH
O
+
Cl H
Acid chloride
+
O H
2
C H
3
C Cl
O
C H
3
C OH
O
+
Cl H
+
O H
2
Carboxylic acid
Acetyl chloride Acetic acid

2) Acylation: Acid chlorides are important acylating reagent. Thus usually react rapidly with
compounds containing active hydrogen atoms i.e. hydrogen attached to oxygen, nitrogen or
sulphur. This active hydrogen is replaced by acyl group (
R C .
O
) of acid chloride.

a) Reaction with alcohols (Alcohalysis): Esters are formed
80

b) Reaction with Ammonia (Ammonolysis): Amides are formed.
R C Cl
O
+
R C NH
2
O
+
Cl H H-NH
2
Acid chloride

c) Reaction with Primary and Secondary Amines: N-substituted amides are formed.
R C Cl
O
+
R C NHR'
O
+
R C Cl
O
+
R C NR'
2
O
+
N,N-dialkyl amide
Cl H
Cl H
HNHR'
Acid chloride Primary amine N-Alkyl amide
HNHR'
2

d)Reaction with hydrazine and hydroxylamine: Hydrazides are formed.
R C Cl
O
+
R C NHNH
2
O
+
R C Cl
O
+
R C NHOH
O
+
Acetic anhydride
N H
2
NH
2
Cl H
N H
2
OH Cl H

3)Reaction with salt of carboxylic acids: Anhydrides are formed.
R C Cl
O
NaOOCR
- +
+
R C O C R
O O
NaCl
+
Acid anhydride
C H
3
C Cl
O
-
+
+
NaO C
O
CH
3
C H
3
C O C CH
3
O O
+NaCl
Acetic anhydride

81
4) Reduction:
a) Acyl chlorides may be reduced catalytically to aldehydes or to alcohols.
R C Cl
O
R C H
O
H
2
Aldehyde
Pd
H
2
RCH
2
OH
Alcohol

When reduced in presence of poisoned Palladium Catalyst, they form aldehyde. This reaction is
called Rosenmund Reduction.
R C Cl
O
R C OH
O
C H
3
C Cl
O
C H
3
C H
O
H
2
/ Pd
Aldehyde
H
2
/ Pd
BaSO
4
BaSO
4
Acetaldehyde

b) When reduced with LiAlH
4
, they form primary alcohols.
R C Cl
O
LiAlH
4
R CH
2
OH
C H
3
C Cl
O
LiAlH
4
C H
3
CH
2
OH
Ethanol
1
o
Alcohol

5)Friedel-Craft Acylation: Acyl chlorides react with aromatic hydrocarbon in presence of
AlCl
3
catalyst. The reaction is known as F.C.acylation. e.g.
+
C H
3
Cl
O
AlCl
3
C
CH
3
O
HCl
+
Benzene
Acetophenone

2. Acid Anhydrides: The compound derived from an acid by the removal of one water molecule
from two molecule of the acid are called anhydrides.

2 R-COOH
-H
2
O
R C O C
O
R
O

Anhydrides derived from two molecule of different acids are called mixed anhydride.
R-CO-O-CO-R'

82
Methods of preparation:
Acid anhydrides may be prepared.
1) By reaction of acid halide with carboxylic acid or its Sodium salt.
R C OH
O
+
Cl-CO-R
Pyridine
R-CO-O-CO-R HCl
+
R C ONa
O
+
Cl-CO-R
Pyridine
R-CO-O-CO-R
+
NaCl

2) By dehydration of Carboxylic acids in presence of P
2
O
5
.
R C OH
O
2
P
2
O
5
R-CO-O-CO-R H
2
O
+

Properties:
Physical properties:
i) The lower simple anhydrides are colourless liquids with an irritating smell.
ii) They are in soluble in water but dissolve slowly because of the slow hydrolysis. They are
soluble in ether and benzene.
iii) They have higher boiling points than the corresponding acids because of large size of
molecule and enhanced van der Waals interactions.

Chemical Properties: In anhydrides OCOR group is replaced by nucleophile like acid
chlorides but they are less reactive than acid chlorides because OCOR group is not as
electronegative as Cl atom.
R C O C R
O O
+ R C O
O
-
Nu
C O
O
H :Nu
-
R C Nu
O
R C O
-
O
-

The anhydrides give all the nucleophilic substitution reaction given by acid chlorides but with
less vigour.
i) Hydrolysis:

Acetic anhydride Acetic acid
83
ii) Reaction with Alcohols:

iii) Reaction with Ammonia:
Acetamide Acetic acid


iv) Reaction with Amines:

CH
3
COOH
+
N-Alkylacetamide
Acetic acid

v) Friedel Crafts Reacation:
+
(CH
3
CO)
2
O AlCl
3
+
CH
3
COOH
Acetophenone
Acetic Acid Acetic acid anhydride
Benzene
C CH
3
O

3.Acid Amides: These are the derivatives of carboxylic acids in which the OH function of
carboxylic group is replaced by NH
2
group.
R C
O
OH
R C NH
2
O
Amide
-OH
NH
2
+
Carboxylic acid

84
Functional group of amides is CONH
2
.
H C
O
NH
2
C H
3
C NH
2
O
Acetamide
Formamide

Methods of Preparation: Amides are prepared-
i) By the action of Ammonia on Acid Chlorides:
C H
3
C
O
Cl C H
3
C NH
2
O
+
Acetamide
+
2NH
3
NH
4
Cl

ii) By heating of Ammonia salts of Carboxylic acid:
C H
3
C ONH
4
O
+
-
C H
3
C NH
2
O
+
O H
2
Ammonium acetate
Acetamide

iii) By the action of ammonia on Anhydrides:
(CH
3
CO)
2
O NH
3 +
C H
3
C NH
2
O
+
CH
3
COOH
Acetamide Acetic acid

Properties:
Physical Properties:
i) All amides are white, odourless, crystalline solids.
ii) Among the four derivatives of acids, only acid amides are capable of forming intermolecular
hydrogen bonds due to which they have sharp melting points that are higher than those of
corresponding acids.
iii) Simple amides (up to C
6
) are soluble in water but solubility in water decreases as we ascend
the series.

Chemical Properties: Amides are stabilized by resonance.
R C NH
2
O
R C NH
2
+
O
-
..

Since the electron pair on N-atom is not readily available to an acid amides are less basic than
amines. Amides are least reactive of the acid derivatives. Important reactions of amides are given
below.

85
i) Hydrolysis: Amides are hydrolyzed by acid or alkali on prolonged heating.
C H
3
C NH
2
O
+
O H
2
+
Cl H
C H
3
C OH
O
+
NH
4
Cl
+
-
+
-
C H
3
C NH
2
O
+
NaOH
C H
3
C ONa
O
+
-
+
NH
3

ii) Reaction with Nitrous Acid (HONO): Amides when heated with Nitrous acid (NaNO
2
+
HCl) give carboxylic acids.


iii) Reduction: Amides reduces to amines by LiAlH
4
.
R C NH
2
O
LiAlH
4
R-CH
2
-NH
2
Amide
1
o
amine

iv) Dehydration: When heated with strong dehydrating agent such as phosphorous pentoxide,
they form nitriles.
R C NH
2
O
P
2
O
5
-H
2
O
R C N
Amide
Alkane nitrile
(Alkyl cyanide)

v) Hofmanns Degradation: Amides when treated with bromine and sodium hydroxide, they
produces primary amine, which is one carbon less than the amide.
R C NH
2
O
+
Br
2
+
4NaOH RNH
2
2NaBr Na
2
CO
3
2H
2
O
+ + +
1
o
amine
C H
3
C NH
2
O
+
Br
2
+
4NaOH CH
3
NH
2
2NaBr Na
2
CO
3
2H
2
O
Methyl amine Acetamide
+ + +

This reaction is also called Hoffmanns rearrangement.
Mechanism: The Hofmanns degradation of amides involves the following steps.
86
2NaOH
Br
2
NaOBr
NaBr H
2
O
+
+ +
+
-

R C
O
N
H
H
..
O
-
Br
+

I
R C
O
N
H
Br
+
OH
-

II
-H
2
O
,Br
R C
O
N
..
:
III
R-N=C=O
iso cyanate
NaOH
R-NH
2
Na
2
CO
3 +
1
o
amine

4. Esters: Esters are carboxylic acid derivatives in which the OH group has been replaced by
alkoxy (-OR) group. They can be represented as,
R C
O
OR' Or R-COOR'

They are named as the alkyl salts of the acid e.g
HCOOC
2
H
5
Ethyl formate
CH
3
COO C
2
H
5
Ethyl acetate.
A large number of esters occur in flowers, fruits of the plants and provide the fragrance to
flowers and fruits.

Method of Preparation: Generally esters are prepared by carboxylic acids and their other
derivatives.
i) By the reaction of carboxylic acid with alcohols in presence of acid
(FischersEsterification method).
R C
O
OH
+
HOR' R C OR'
O
+
H
2
O
H
2
SO
4
C H
3
C
O
OH
+
HOC
2
H
5
H
2
SO
4
C H
3
C
O
OC
2
H
5
+
O H
2

ii) By the reaction of Acid Chlorides with Alcohols.

iii) By the reaction of Carboxylic salts with alkyl halide.
87
R C ONa
O
+
XR'
-
+
R C OR'
O
+
NaX
+
-
Ester
Sodium carboxylate

iv) By the reaction of carboxylic acid with Diazomethane.
R C OH
O
+
CH
2
N
2
R C OCH
3
O
+
N
2

But only methyl esters are formed by this method.
v) Transformation.
R C
O
R'
+
R"OH R C OR"
O
+
H
+
R'OH
or OH
-

vi) By the reaction of alkyl halide with silver salt of carboxylic acid.
R-COOAg
+
Br-R'
RCOOR'
+
AgBr

Properties:
Physical Properties:
1) The carboxylic esters are pleasant smelling liquids or solids.
2) The boiling points of the strongest chain isomers are higher than those of branched chain
isomers. The boiling points of methyl and ethyl esters are lower than those of
corresponding acid, this is due to their inability to form intermolecular hydrogen bonds.
3) They are generally insoluble in water and soluble in most organic solvents.

Chemical Properties: Esters give nucleophilic substitution reaction similar to acids halides
because of the electron withdrawing effect of the OR
|
group.
R C OR'
O
R C OR'
O
-
Nu
+
:Nu
-
C H
3
C N
O
u
-OR'
+
-

But esters are also stabilized by resonance thus they undergo nucleophilic substitution less
readily than do acid halides.
88
R C OR'
O
R C O
O
-
R
..
.. +
OH H
+

General reactions of esters are given below.
1) Hydrolysis:
a) Acid hydrolysis: Esters are hydrolyzed in presence of acid catalyst (H
2
SO
4
) or HCl) to give
parent carboxylic acid and alcohol.
R C OR'
O
+ R C OH
O
+
R'OH
Ester
Carboxylic acid
Alcohol
O H
2
H
+
reflux

b) Alkaline hydrolysis: The alkaline hydrolysis of ester to form sodium or potassium salt of
carboxylic acid and alcohol is referred to as Saponification.
R C OR'
O
+ R C ONa
O
+
R'OH
CH
3
COOC
2
H
5
+ C H
3
C ONa
O
+
C
2
H
5
OH
NaOH
NaOH
Ester
Sodium carboxylate
Alcohol
Ethyl acetate Sodium acetate Ethyl alcohol
+ -
- +


2) Reaction with Ammonia:
R C OR'
O
+
NH
2
H
R C NH
2
O
+
R'OH
CH
3
COOC
2
H
5
+
NH
2
H
C H
3
C NH
2
O
+
C
2
H
5
OH
Ester Amide
Alcohol
Ethyl acetate
Acetamide


3) Reduction:

R C OR'
O
LiAlH
4
/ Ether
or
Na / C
2
H
5
OH
R-CH
2
OH
R'OH
+
Alcohols

89

C H
3
C OCH
3
O
LiAlH
4
/ Ether
or
Na / C
2
H
5
OH
CH
3
-CH
2
OH
CH
3
OH
+
Ethyl alcohol Methyl alcohol

4) Reaction with Grignard Reagent: Esters with Grignard reagent first gives ketone which on
further reacting with another molecule of the G.R gives tertiary alcohol.
R C OR'
O
R"-MgX
R C OR'
OMgX
R"
-OR'
R C R"
O
Ketone
R"MgX
R C R"
OMgX
R"
H
2
O
R C R"
OH
R"
3
o
alcohol

5) Claisen Condensation: Esters containing -hydrogen atom undergo condensation reactions to
form -ketoesters, in the presence of strong base. This reaction is known as .
C H
3
C OC
2
H
5
O
+
H
CH
2
C OC
2
H
5
O
C
2
H
5
ONa
-C
2
H
5
OH
C H
3
C
O
CH
2
C OC
2
H
5
O
Ethyl acetoacetate

Mechanism: Following steps are involved.
H
CH
2
C OC
2
H
5
O
C
2
H
5
O
-
H
2
C C OC
2
H
5
O
-
C H
3
C OC
2
H
5
O

C H
3
C
O
-
CH
2
C OC
2
H
5
O
OC
2
H
5
Ethyl acetoacetate
-
C H
3
C
O
CH
2
C OC
2
H
5
O
-C
2
H
5
O

(-keto ester)

Suggested Readings:
Organic Chemistry by I. L. Finar, vol. 1, 6
th
edition
Organic Chemistry by Paula Yurkanis Bruice, 3
rd
edition.
Organic Chemistry by Robert T. Morrison and Robert Neilson Boyd, 6
th
edition.
Organic Chemistry by K. Peter C. Vollhardt and Neil E. Schore, 4
th
edition.
90