Sunteți pe pagina 1din 90

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 oI Chemistry
Faculty oI 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 oI organic compounds, because they contain
only carbon and hydrogen and they have no Iunctional groups. They also reIerred to as ParaIIins.
Alkanes are the saturated hydrocarbon with general Iormula (C
n
H
2n2
). Alkanes contain only
single covalent carbon-carbon (C-C) and Carbon Hydrogen(C-H) bonds. Each carbon atom oI
alkanes is sp
3
hybridized.



Structure oI Methane Structure oI 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 oI tetrahedral position
oI the Iour bonds oI carbon, the C-C chain is zig-zag and not linear some examples oI 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 oI catalyst (Ni, Pt or Pd) at 200-300
o
C

to give alkanes. (Sabatier and Senderen`s
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 Ior
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 Iunction oI red phosphorous is to remove the iodine Iormed by Iorming 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 Iatty 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 oI 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 oI alkyl halide (RX) condense with sodium metal to give
symmetrical alkane (R-R).

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




II two reacting alkyl halides are diIIerent, mixture oI three alcohols are produced which is
diIIicult to separate. For example methyl iodide and ethyl iodide gives the mixture oI 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:-ThereIore this method is useIul only Ior the preparation of symmetrical alkanes.

v) Corey-House Alkane synthesis: This method is superior to Wurtz synthesis. It involves Iirst
conversion oI 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 Ior 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 oI Carboxylic Acid when heated strongly with
sodalime (NaOHCaO), 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) Kolbe`s Synthesis: Alkane is collected at anode when a concentrated solution oI sodium or
potassium salt oI 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 Ior the preparation of symmetrical alkanes.

Properties of Alkanes:
Physical Properties:
1) First Iour 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 oI normal alkanes boiling points and speciIic gravities increase with rise
in molecular weights. As a rule the boiling points oI alkanes having branched
carbon chain are lower than those oI isomeric normal alkanes.
4) Variation in the melting point oI alkanes is not regular. Alkanes with odd
number oI carbon atoms have lower melting point than the next lower and next
higher alkanes having even number oI carbon atoms. This is due to the greater
inter molecular attraction in even numbered alkanes having end carbon on the
opposite sides oI the molecules.

Chemical properties:
1) Alkanes are extremely stable and inert substances. This is due to the Iact that there is a
small diIIerence in the electro negativity oI 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. ThereIore electrophillc or
nucleophillic reagent Iind no site Ior attack on alkane molecules. Furthermore, the C-H
and C-C bonds are strong bonds. Alkanes due to these types oI strong bonds remain
unaIIected by acids, alkalies and oxidizing agents under ordinary conditions.

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

1) Halogenations: This involves replacement oI hydrogen atom by halogen atom.
a) Chlorination: Alkanes react with chlorine in presence U.V light or diIIused sunlight or at
temperature 300-400
o
C to Iorm the corresponding substituted products.
For example: Methane reacts with chlorine to give mixture oI diIIerent 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 diIIicult to stop this reaction at Iirst step. However, the yield oI CH
3
Cl can be improved by
taking excess oI 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 Iormed during iodination reduces the product
back to reactant hence it must be carried out in the presence oI strong oxidizing agent like iodic
acid or nitric acid which destroys the hydroiodic acid (HI) as it is Iormed.
CH
4
I
2
CH
3
I+ HI +
5HI
HIO
3
3I
2
3H
2
O + +

d)Fluorination: Since Iluorine is most reactive, Iluorination under ordinary condition
accompanies by explosion. Fluoroalkane can however be obtained Irom alkane by action oI
Iluorine diluted with Nitrogen.

2) Nitration: This involves replacement oI hydrogen atom by NO
2
group. Nitration is carried
out by heating mixture oI 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 Iusion also takes place during the
reaction and mixture oI 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 oI hydrogen atom by SO
3
H group. It is carried out
by heating alkanes with Iuming 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 oI compound by heat
is known as pyrolysis. Thermal decomposition when applied to alkanes it is known as Cracking.
This leads to the Iormation oI 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 oI catalyst pyrolysis can be carried out at less higher temperature. This is called
Catalytic Cracking.

5) Isomerisation: Conversion oI 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 oI 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 oI 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) OxidationCombustion]: When burnt in excess oI air or oxygen alkanes Iorm carbon
dioxide and water with the evolution oI 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 oI heat in this reaction Iorms the basis oI the use oI these hydrocarbons as source
oI heat and power.

Alkenes or Olefins
Alkenes are unsaturated hydrocarbons containing carbon-carbon double bond (CC) in their
molecules. General Iormula oI alkene is C
n
H
2n
. They are commonly known as oleIins because
lower members Iorm oil products with chlorine or bromine (Latin OleumOil; Iicane to make).
Ethylene and propylene are the Iirst and second members oI 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 oI one sigma (!) and one pi (") bond. Sigma bond is Iormed by overlapping oI sp
2

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

Orbital Structure oI Ethane
8
Alkanes are more reactive than alkanes this is due to the availability oI 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 oI water is eliminated and alkene is Iormed.
R CH CH
2
H OH
R-CH=CH
2
H
2
O


The ease oI dehydration Iollows the Iollowing order.
3
o
alcohol ~2
o
alcohol ~1
o
alcohol
Dehydration oI unsymmetrical 2
o
or 1
o
alcohol can proceed in two ways and mixture oI alkene
is Iormed Ior example dehydration oI 2-butanol yields mixture oI 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 Saytzeff`s rule. Which states that 'Hydrogen is
preIerentially eliminated Irom the carbon atom with Iewer number oI hydrogen atoms. Thus 2-
butene is the major product in above example. In other words SaytzeII`s rule states that 'Greater
the number oI alkyl groups attached to the double bonded carbon atoms, the more stable is the
Alkene. Hence more substituted alkene is preIerentially Iormed. The ease oI Iormation oI
alkene is ,

R
2
CCR
2
~ R
2
CCHR ~ R
2
CCH
2
~ RCHCHR ~ RCHCH
2

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

The ease oI dehydrogenation oI alkyl halide is
3
o
alkyl halide~2
o


alkyl halide ~1
o
alkyl halide
In case oI dehydrogenation oI 2
o
and 3
o
alkyl halides the major product can be predicted
according to SaytzeII`s 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 Kolbe`s electrolytic method: electrolysis oI aqueous solution oI sodium or potassium
salt oI 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 oI 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: ParaIIins on heating at 500-800!C in absence oI 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 Iirst 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 speciIic gravities rise with increase oI
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 oI cis-alkenes do not Iit 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 oI "-bond.
The " electrons constituting " bond are located much Iarther the carbon nuclei and are easily
available Ior reaction when needed. The overlap oI atomic orbital Iorming "-bond is not as
eIIective as that in ! bonds. Thus " bond is weaker than ! bond and can be easily broken.

Addition reactions are the most important reactions oI the carbon-carbon double bond. "
electrons oI double bond are easily available to the reagent. Thus carbon-carbon double bond
acts as a source oI electrons Ior 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 oI (E-Nu) reagent
E-Nu E

:Nu
-
Electrophile Nucleophile

Step 2: Attack oI 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 oI electrophillic reagents relieves the strain oI CC (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
Carbonium ion
Addition product

Because the addition reactions are initiated by electrophiles, they are reIerred 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 oI hydrogen to alkenes takes place under pressure and in the
presence oI 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 oI inert solvent to give dihalogen
derivative Ior 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 oI Hydrogen halide to
alkene produce alkyl halides. In case oI symmetrical alkene only one alkyl halide is Iormed but
when the oleIin 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 Iound that isopropyl bromide is the major product. In such cases addition is governed
by Markonikov`s 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. Markonikov`s rule can be explained with the
help oI mechanism.

12
Step I: Isomerisation oI reagent to give electrophile (H

) and nulceophile.(Br
-
)
HBr
H
+
Br-
Proton
Bromide ion


Step II: Attack oI electrophile (H) to double bond to Iorm 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 preIerentially Iormed.
Step III: Attack oI 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 oI HBr to propane or other unsymmertrical alkene in presence oI organic peroxide (R-
O-OR) yields mainly n-alkyl bromide(anti markonikov`s product). This eIIect is known as
peroxide eIIect 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 I peroxide the addition takes place via a Iree radical mechanism rather than the
ionic mechanism. This addition oI Iree radical to double bond involves the intermediate
Iormation oI more stable Iree radical.

iv) Addition of Hypohalous acid: In hypohalous acid(HOX) OH is more negative part. They
add to alkene to give halohydrin. In case oI unsymmetrical alkene Markonikov`s rule is
Iollowed.
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 oI H
2
SO
4
or HF. The best example oI this reaction is
addition oI 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 Iorm trialkyl borane. The positive part oI 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 oI hydrogen peroxide are
converted to alcohols.

USE: They are used Ior the synthesis oI 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 Iorm diIIerent compounds under
diIIerent conditions.
i)Oxidation with dilute Cold KMnO
4
: On oxidation with cold alkaline KMnO
4
(Bayers`s
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 oI KMnO
4
disappears during the reaction, Bayers`s reagent is used
as a test Ior detecting the presence oI OleIinic double bond.

ii)Oxidation with Hot KMnO
4
: Alkene on treatment with hot potassium permanganate solution
split at the double bond to Iorm 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
CH CH
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 oI silver catalyst at 250-400
o
C to
Iorm 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 Iorm an ozonide. Ozonide on
warming with zinc and water hydrolysed to yield smaller carbonyl Iragments.

The process oI 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 Ior location the position oI the double bonds in unknown alkene
with the help oI products Iormed.

3) Combustion: Alkene are completely burnt in air to Iorm 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 oI 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 Iorm a large molecule
without the elimination oI anything is known as polymerization. Simple alkene molecules
undergo polymerization to Iorm 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 oI 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 oI carbon-carbon triple bond (C#C) in hydrocarbon molecule.
The triple bond oI alkynes consists oI a strong sigma (!) two weak pi(") bonds. In alkynes triple
bonded carbon atom are sp hybridized. The ! bond is Iormed by the overlap oI sp- hybrid
orbitals and the " bonds are Iormed by the separated overlap oI 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 oI more S-character oI the C-H
bond thus the electrons oI the C-H bond in 1-alkynes are more strongly hold by the carbon
nucleus and hydrogen atom oI #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 Iormed.
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 oI sodium or potassium salt oI 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 useIul Ior the
preparation oI higher alkynes. Sodiuum acetylides are prepared by treatment oI 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 Ior the preparation oI
acetylene.
CaC
2
H
2
O H-C#C-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 speciIic gravities show a regular increase
with the increase in molecular weights.

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

Other reactions oI alkynes result Irom acidic hydrogen atoms in acetylene and 1-alkynes, which
can be easily removed by means oI 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 oI alkynes,
1) Addition of Hydrogen: In presence oI catalyst like Iinely divided Ni, Pt, or Pd, alkynes add
two molecule oI 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 Lindlar`s 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 Iorm Iirst 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 oI halogen acids can be added to symmetrical
alkynes in two stages. AIter addition oI one molecule alkyne become unsymmetrical derivative
oI alkene so that the addition oI a second molecule takes place according to Markonikov`s 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 oI unsymmetrical alkynes addition takes place in accordance with Markonikov`s 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 oI two molecules oI hypohalous acids to alkynes
takes place according to Markonikov`s rule.Haloaldehyde or Haloketones are the Iinal 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 oI barium
cyanide to give addition product alkenyl cyanide. For example, on addition oI 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 Ior the manuIacture oI synthetic rubber and synthetic Iiber, Orlon.

6) Addition of Water( hydration): Alkyne react with water in presence oI sulphuric acid and
mercuric sulphate to Iorm 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 oI AlCl
3
and HgCl
2

to Iorm 2-chlorovinyl dichloroarsenic, which is commonly known as Lewisite.
H-C#C-H ClAsCl
2
Cl CHCHAsCl
2
2-chlorovinyl dichloroarsenic(Lewisite)
NOTE: Lewisite is highly poisonous gas. It is Iour times active than the mustard gas.
8) Ozonolysis: Alkynes Iorm 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 oI the triple bond takes place to Iorm carboxylic acids and CO
2
.
R-C#C-H H
2
O 4|H
2
O| R-COOH CO
2
R`-C#C-R 4|O| R`-COOH R-COOH
USE: This reaction is useIul in determination oI structure oI alkynes.
10) Salt formation: As hydrogen in 1-alkyne and acetylene are acidic, they can Iorm salts with
metals by replacement oI acidic hydrogen. These salts are known as Acetylides. For example;
a) Formation oI 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 oI Copper and silver acetylides with ammonical solution oI 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 oI alkali like alc.KOH and NaNH
2
undergo
isomerisation, Ior 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 Iorm aromatic hydrocarbons. For example, three molecules oI 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 oI 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 Irom the saturated hydrocarbons by replacement oI one
oI the hydrogen atom by halogen atom.
R H
-H
R-X
Saturated hydrocarbon
Alkyl halide.

Thus they can be represented by general Iormula 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 oI alkyl group. Thus alkyl halide can
be classiIied as primary (1
o
), secondary(2
o
) or tertiary (3
o
) depending upon whether the halogen
is attached to primary, secondary oI 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 useIul organic compounds.
Methods of preparation:
1) By direct Halogenation of Alkanes: Alkanes when treated with chlorine or bromine in the
presence oI 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 oI oxidizing agents like HIO
3
, HIO
4.
Or
Conc. HNO
3
etc. because HI Iormed during the reaction reduces back alkyl iodide to alkane. But
the products are diIIicult to separate.

2) By addition of Hydrogen Halide to Alkene: When alkenes are treated with hydrogen
halides, addition oI hydrogen halide takes place in accordance with Markonikov`s rule except the
addition oI HBr in presence oI 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 oI HBr to unsymmetrical alkene
a) In absence oI peroxide:

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

b) In presence oI 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 oI 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 oI bromine or iodine with red phosphorus
2P2Br
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 oI pyridine give alkyl chloride. Pyridine acts as scavenger Ior HCl
Iormed.
R-OH SOCl
2
pyridine R-Cl SO
2
HCl
6) By Halogen Exchange Reaction Finkelstein reaction]: This method is suitable Ior the
preparation oI alkyl iodides and Iluorides. This involves the treatment oI alkyl bromide or
chloride with concentrated solution oI sodium iodide in acetone.
CH
3
CH
2
Br
NaI
acetone
CH
3
CH
2
I
NaBr



For the preparation oI alkyl Iluoride alkyl bromides or chlorides are heated with inorganic
Iluorides.
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 Iluoride 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 Iorm hydrogen bonding with
water and to break already existing hydrogen bonding in water molecule.
iii) Their densities decrease in the Iollowing order; Iodide~ bromide~Chloride ~ Iluoride. Alkyl
bromides and iodides are denser than water while alkyl chlorides and Iluorides are lighter than
water.
iv) For a given alkyl group boiling points oI alkyl halides Iollow the Iollowing order.
Alkyl iodide~ Alkyl bromide~ Alkyl Chloride~ Alkyl Iluoride.

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

Chemical Properties: In alkyl halides (C-X) bond is highly polar because oI the high
electronegativity oI the halogen atom. Thus alkyl halides are very reactive compounds alkyl
halides can be nearly all types oI 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 oI halogen atom.
24
C X
$
$
+
-

Thus carbon atom oI C-X bond is thereIore a good site Ior the attack oI nucleophiles (electron
rich species) and the nucleophilic substitution reactions are most common reactions oI 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 oI bromide by aqueous NaOH.
Step-I: This involves the ionization oI 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 oI nucleophile on carbonium ion Irom either side to give the
substitution product.
C
+
R R
R
R
OH
R
R
fast
3
o
Alkyl alcohol
O H
-


Remember that iI alkyl halide is optically active then we will get the recemic mixture oI two
enatiomers. Tertiary alkyl halides undergo substitution by SN
1
mechanism via Iormation oI
carbonim ion because the attack oI the nucleophile on the crowded tertiary alkyl halide i.e.
sterically hindered central carbon atom is diIIicult. The reactivity order Ior 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 oI the nucleophile
25
and the ejection oI the halide ion takes place simultaneously. 1
o
alkyl halide undergoes
substitution by SN
1
mechanism via Iormation oI transition state. Let us consider the hydrolysis
oI methylbromide by aqueous NaOH.

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

The reactivity order Ior SN
2
mechanism is,
1
o
alkyl halide~2
o
alkyl halide~3
o
alkyl halide
Some important substitution reactions oI 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 Iormed.

R-X AgCN R-N#C AgX
isocyanide
vi) Reaction with AgNO
2
: Alkyl halides react with silver nitrite Iorm nitro alkane. Some Alkyl
nitrites are also Iormed.
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 Iorm alkyl sulphide
2R-XK
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 oI silver salt oI
carboxylic acid an ester is Iormed.
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 oI alkyl halides with alcoholic solution oI ammonia in a
sealed tube results a mixture oI diIIerent classes oI 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 Iavours elimination more than substitution. The rate oI
elimination to substitution product depends on the structure oI the alkyl halide and experiment
condition. For example in case oI 1
o
alcohol substitution product is also Iormed but in case oI 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.

Saytzeff`s 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 oI HX is governed by SaytzeII`s rule. According to which the main product is the
most highly substituted alkene. Or in other words Hydrogen is eliminated Irom the Carbon atom
oI alkyl halide which bears the least number oI 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 SaytzeII`s 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 diIIerent 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 oI 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 oI 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 oI anhydrous
AlCl
3
to Iorm 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 Iorm a ring. In this carbon atoms are joined together to Iorm a ring. In saturated
alicyclic hydrocarbons methylene groups joined together to Iorm a cyclic structure, hence they
are also known as polymethylene. According to IUPAC system, they are named as cycloalkanes
or cycloparaIIins. They resemble with the aliphatic compound in their properties. Some example
oI 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 oI 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 oI Dicarboxylic acids are
heated one carbon less cyclic ketones are Iormed, 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 oI Dicarboxylic
acids are leaked with sodium intermolecular condensation takes place to give %-keto esters. %
keto esters are Iirst 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 oI cycloproparne derivatives|: Alkene when treated with
methylene iodide in presence oI 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 Iorm addition
compounds with the ring Iusion. 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 oI 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 oI 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
oI 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 oI ring.
e.g.
33


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


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

Alcohols can be classiIied as mono, di, tri and polyhydric alcohols depending on the number oI
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 Iurther subdivided into 1
o
, 2
o
and 3
o
alcohols depending upon
the nature oI 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 Iirst addition
product, alkyl hydrogen sulphates which on hydrolysis give alcohols.

In case on unsymmetrical alkenes Ior addition, Markonikov`s rule is Iollowed.
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 Markonikov`s addition oI 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 Iormed. In this reaction diborane adds as borane (BH
3
). The positive part oI 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 oI 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 oI hydroboration-oxidation results anti- Markonikov`s addition oI 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 oI 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 can`t be prepared by this method.
i) Reduction by using alcoholic sodiumBouveoult-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) Iirst 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 Iormaldehyde, aldehydes other than Iormaldehyde and ketones leads to
the Iormation oI 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 oI complex organic compounds
into simple compound in the presence oI enzymes obtained Irom microorganism. Fermentation
oI starch and sugars under the inIluence oI 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 oI 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 Iorm hydrogen bonds with water molecule because
oI the presence oI non polar long hydrocarbon chain and hence the solubility in water decreases.
3) Boiling points oI alcohol increase with the increase in number oI carbon atoms but their
boiling points are much higher than those oI the corresponding alknaes. This is again because oI
intermolecular hydrogen bonding. Highly polar OH groups oI diIIerent 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 oI reactive Iunctional
group, -OH group, which is polar in nature. Because oI the high electronegativity oI oxygen
atom both and
$ $
+ -
-C-O
$ $
+
-
-O-H
bonds in alcohols are polar bonds.
Alcohols undergo Iollowing reactions.
1) Reactions involving only the hydrogen atom of the -OH group:
These reactions involve cleavage oI oxygen and hydrogen bond.
i) Reaction with alkali metals: Alcohols react with sodium or potassium to Iorm alkoxides with
the liberation oI hydrogen gas.
2ROH + 2Na
2RONa + H

2
Sod.alkoxide

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

2)Reaction with carboxylic Acids: Alcohols react with carboxylic acids in presence oI
concentrated sulphuric acid as a catalyst to give ester. The process is known as esteriIication.
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 esteriIied by
the action oI 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 Ior the estimation oI 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 oI 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 oI OH group by halogen atom take place
and alkyl halides are Iormed.
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 oI 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 oI halogen acids are in the order,
HI ~HBr ~HCl
No catalyst is required in case oI HI and HBr but HCl reacts only in presence oI 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 Iollow SN
1
mechanism Ior the substitution oI OH group by
halogen atom.
Step 1: Protonation oI Alcohol
H
3
CH
2
C O H

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

Step 2: Attach oI 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 Iollow SN
2
mechanism.
8) Reaction with sulphuric acid: The action oI concentrated sulphuric acid is oI great interest
as it gives diIIerent products under diIIerent 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 Iormation oI carbocation.
Step 1: Protonation oI alcohol.
C H
3
CH
2
O H

H
+
C H
3
CH
2
O
+
H
H

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

O H
2
..

Step 3: Removal oI proton Irom carbocation:
40
C C
H
H
H
H
H
+
C H
2
CH
2
Ethylene

The ease oI dehydration oI alcohols Iollow the Iollowing order
3
o
~2
o
~1
o
This is also the order oI stability oI 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 SaytzeII`s rule more substituted alkene is the major product.
iii) When excess oI ethyl alcohol is heated with concentrated sulphuric acid at 140
o
C, diethyl
ether is Iormed.
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 Iollowing steps.
Step 1: Protonation oI one Molecule.

H
3
CH
2
C O H

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

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

O H
2
..

Step 3: Attach oI carbocation to another molecule oI 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 oI proton Irom Oxonium ion leads to the Iormation oI 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 oI 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 oI oxidation products oI alcohols depend upon the nature oI 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 oI 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 oI carbon atoms, but these ketones
can`t be easily oxidized, these undergo oxidation under very drastic conditions to give mixture oI
carboxylic acid with lesser number oI 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 Iirst Iorm ketones and then carboxylic acid both having lesser number oI 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 Iorm
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
Iunctional group is |C-O-C|. II same alkyl groups are attached to central oxygen atom ethers are
classiIied as symmetrical ethers. While ethers containing diIIerent alkyl groups attached with
central oxygen atom are classiIied as unsymmetrical ethers.
R O R
..
..
R O R'
..
..
symmetrical ethers unsymmetrical ethers

43
Ethers may be considered as derivatives oI 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 oI 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 Iormed by the
overlap oI two halI Iilled sp
3
hybrid orbitals oI oxygen atom with the halI Iilled sp
3
hybrid
orbitals oI two carbon atoms oI two alkyl groups. Remaining two sp
3
hybrid orbitals oI oxygen
atoms are occupied by the two unshared pairs oI 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 oI Ether
Methods of preparation:
i) Dehydration of alcohols: By heating excess oI 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 useIul Ior the preparation oI simple ethers only.
3) Williamson Ether Synthesis: This is the most important industrial and laboratory method oI
preparation oI ethers. It involves the treatment oI 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 Ior 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 Iollows SN
2
mechanism. Displacement oI 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 oI primary or
secondary alcohols with diazomethane in presence oI Ilouroboric 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 useIul Ior the preparation oI methyl ethers.
45
Properties:
Physical properties:
1) Ethers are highly volatile and inIlammable 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 oI Iorming inter molecular hydrogen bonds due to the absence oI OH
groups.

Ethers are sparingly soluble in water since their oxygen atom is not capable oI Iorming H-bond
with hydrogen with hydrogen atom oI 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 preIerentially 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 oI 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 oI 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 Irom ethyl bromide and to distinguish Irom 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 Iorm 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
puriIied beIore distillation. When ethers that contains peroxide is distilled, at the end oI
46
distillation residual peroxide may explode. Because oI 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 oI mixed ethers the halogen atom attacks to the smaller alkyl groups, due to the sterric
eIIect. e.g.
H
5
C
6
O C
2
H
5

C
6
H
5
-OH
HI
C
2
H
5
I

The order oI reactivity oI halogen acid is
HI~HBr~HCl
With the excess oI 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
Iorm three membered ring. i.e. oxiran (oxirane) ring. Epoxy compound contain oxirane ring.
Oxiran compounds are also reIerred 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 oI this group.
Method of preparation: Epoxides may, in general, be prepared by epoxidation oI 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, Ilammable 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 oI various compounds to Iorm 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 Iunctional
group oI aldehydes is CHO. This group occurs at the end oI a chain. In ketones carbonyl
carbon, on both sides attack to carbon atoms, thus the Iunctional 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 oI one ! and one " bond. Carbonyl carbon is in a state oI sp
2
hybridization. The
carbon oxygen ! bond is Iormed by the overlap oI sp
2
orbital oI carbon with sp
2
- orbital oI
oxygen atom. On the other hand the carbon oxygen " bond is Iormed by side wise overlap oI
unhybridised p-orbital oI both atoms. Two unshared pairs oI electron occupy the sp-hybrid
orbitals oI oxygen. since three !-bond oI 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 oI
the electronegativity . Due to the high electronegativity oI oxygen atom, the " electron cloud is
pulled more Iorward 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 oI dipole moments oI aldehydes and ketones can`t be accounted only
by inductive eIIect but also by the resonance eIIect. Following resonance structures are possible.
.
C
.
O
.
C
.
O
- +

Carboxyl group is resonance hybrid oI above two structures.
Methods of Preparation:
Both Aldehydes and ketones may be prepared by the Iollowing methods.
1) Oxidation of alcohols: Aldehydes are Iormed by the oxidation oI 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 oI 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 Iurther. Ketones can also be obtained by Oppenauer oxidation
oI secondary alcohols, which involves reIluxing oI second alcohol with acetone in the presence
oI 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 oI calcium
salt oI Iatty acid with Calcium Iormate. While calcium Iormate alone on heating gives
Iormaldehyde.

53

Ketones are obtained by heating calcium salt oI Iatty acid other than calcium Iormate.

4) Hydration of alkynes: Aldehydes and ketones can be prepared by reactions oI alkynes with
the water in presence oI 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 oI 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 oI 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 oI 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 oI acid chloride in the presence oI 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 Iinal product.
Ketones cannot be prepared by this method.
8) From Grignard Reagent: Aldehydes can be prepared Irom 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 Irom 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 Iormed, may Iurther react with excess oI the Grignard reagents to give
alcohols.

9) Oxo process: This method is industrially important Ior the preparation oI aldehydes. It
involves the treatment oI an alkene with carbon monoxide and hydrogen in the presence oI
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 oI alkene with acidiIied aqueous
solution oI 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 oI Iorming hydrogen
bonds with water molecules. But higher members containing more than Iive 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 oI Iorming
intermolecular hydrogen bonds. Their boiling points are lower than corresponding
alcohols.
4) Density oI aldehydes and ketones are lesser than that oI water.

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

Carbonyl carbon is electron deIicient and carbonyl oxygen is electron rich. The electron deIicient
carbon is readily attacked by electron rich nucleophiles and electron rich oxygen is attacked by
electron deIicient electrophiles. The typical reaction oI aldehydes and ketones is nucleophilic
addition. They undergo nucleophilic addition reaction by Iollowing 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 oI nucleophile at carbonyl carbon to Iorm new !-bond.
.
.
O
Nu
.
O
-
Nu:
..
:
:
..
..

Step 2: Attack oI 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 oI carbonyl group.
.
.
O
:
..
..
+ H
+
.
.
O
+
H
..
.
.
O H
..
..
+
Resonance stabilised protonated carbonyl group

Step 2: Attack oI 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 oI the carbonyl group towards the nucleophilic addition reactions depends upon
the magnitude oI the positive charge on the carbonyl carbon and also on crowding around the
carbonyl carbon. (Steric Iactor). Alkyl groups oI other electron donating that decreases the
positive charge on the carbonyl carbon will decrease its reactivity towards the nucleophilic
addition Iollows the Iollowing 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 Iact that carbonion Iormed the normal
oI 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 oI enolate ion act as a nucleophile. All condensation reaction
involved Iormation oI 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 oI HCN give
cyanohydrins. Reaction is carried out in the presence oI basic catalyst. HCN is produced in situ
by the action oI 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 Iirst give the
addition product which can be hydrolysed with dilute acid to yield alcohol. Only Iormaldehyde
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 oI sodium bisulphate, a solid addition compound is Iormed.
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, thereIore this process oI Iormation and decomposition oI bisulphite is used Ior the
puriIication and separation oI carbonyl compounds Irom mixtures.

(4) Addition of Ammonia: Aldehydes (except Iormaldehyde) Iorm 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 oI Iormation and decomposition oI these compounds can be used or the separation and
puriIication oI aldehydes.
Formaldehyde and ketones do not Iorm 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 oI Aldehyde and Ketones with ammonia
derivatives are very important and characteristic reactions oI carbonyl compounds. They react
with ammonia derivatives (H
2
N-Y) to Iorm compounds containing carbon-nitrogen double bond
(CN-), with the elimination oI 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 oI the reaction involve Iollowing steps.
Step 1: Attack oI 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 oI water to give the Iinal 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 Iollow the same mechanism. The ammonia derivatives are
hydrazine, phenyl hydrazine, 2,4-dinitrophenyl hydrazine, hydroxylamine, and semicarbazide.

a) Reaction with Hydrazine: Aldehydes and ketones Iorm 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 Iorm phenyl hydrazone with
phenyl hydrazine.

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


d) Reaction with Hydroxylamine: Aldehydes and ketones Iorm 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 oI dry HCl gas to Iorm
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 Iorm ketals with monohydric alcohols, they react with dihydric alcohols to give
cyclic ketals. e.g

(C) Condensation Reactions: These reactions involve Iormation oI enolate ion which attack on
carbonyl carbon oI 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 Iunctional groups. For example two molecules oI acetaldehyde combine in
presence oI dilute NaOH to Iorm 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 oI aldol condensation reaction.
Step 1: Formation oI 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 oI enolate ion (nucleophile) on carbonyl carbon oI another molecule oI
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 oI proton Irom water molecule to give Iinal 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 oI water to Iorm &,%-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 oI acetone condense together in the presence oI barium hydroxide to Iorm 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 oI water to Iorm mesityl oxide.

Mixed Aldol Condensation: Condensation that take place between two diIIerent molecules, one
oI which must have an &-hydrogen, in the presence oI base is known as mixed aldol
condensation. For example condensation oI 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 oI both aldehydes and ketones to alcohols may be eIIected by means oI Merwein-
PonndroI-Verley Reduction which involves the reduction by means oI 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 transIer Irom 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 oI zinc amalgam and hydrochloric acid | Clemensen reduction| or alkaline solution oI
hydrazine.|WolI Kishner Reduction|

Clemmensen Reduction: This involves the use oI 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 oI basic solution oI 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 Tollen`s reagent, Fehling`s
solution and Benedicts solution and thus act as a strong reducing agents.

Tollen`s Reagent:Ammonical Silver nitrate Solution] : When Tollen`s reagent is used to
oxidize an aldehyde, the Silver ion is reduced to metallic Iorm and deposits as a mirror on clean
test tube. This reaction is used as a test oI 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 oI 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 oI 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 Tollen`s 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 Iorm
carboxylic acids with Iewer 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 oI NaOH undergo dis proportionation reaction. One halI oI the aldehydes
are oxidized to carboxylic acid and other halI 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 oI the

OH on the carbonyl group.


H C
O
H

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

Step 2: Hydride transIer:
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 oI aldehydes and ketones with &-bromoester in the
presence oI metallic zinc and ether to give %-hydroxy ester is known as ReIormatsky 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 oI zinc salt oI enol oI 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 oI alkali to give haloIorm. This reaction is known as HaloIorm 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
HaloIorm reaction is used as a diagnostic test Ior detecting the presence oI 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
PCR
2
) to Iorm 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 oI negative carbon oI ylide on carbonyl carbon to Iorm 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, iI reaction is carried out in presence oI aluminum ethoxide. But in such
case, acid and alcohol react together to Iorm ester as the Iinal 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 Iorm diIIerent products under
diIIerent 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 Iormula.
R COOH
Or C H
3
C
O
OH

They are Iurther classiIied as mono, di, tri etc., carboxylic acids, according to the number oI
carboxylic groups present in their molecules. The long chain monocarboxylic acids are also
called Iatty acids because many oI them are obtained Irom Iats.

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 oI carboxylic acids are Iormed 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
Iirst 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 oI Grignard Reagent.

5) By Malonic Ester Synthesis: Alkyl halide react with sodium derivative oI 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 oI starting alkyl halide.

6) By Carboxylation of Alkenes: This is a recent industrial method oI preparation oI carboxylic
acids and is called Koch Reaction. This involves treatment oI 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 Iour members are Ireely 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 oI higher members decreases rapidly with the increase in the size oI the alkyl
group due to increased inIluence oI the non-polar and hydrophobic hydrocarbon chain.

3)Melting points oI 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 oI the carboxylic acids, particularly lower members higher than the alcohols oI
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 Iorm 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 oI carboxylic acids decreases with increase in molecular weight. Formic
acid is strongest oI all Iatty acids.

The acidic character oI carboxylic acid is due to the resonance. The carboxylic ion Iorm by
ionization is stabilized by resonance.

72
Hence carboxylic ion is more stabilized than the acid itselI. The equilibrium oI the ionization oI
acids shiIts to the right hand side. X-ray studies also support the existence oI carboxylate ion as
resonance hybrid Ior example bond lengths oI carboxy oxygen have diIIerent values in Iormic
acid. Where as in sodium Iormate the two carbon-oxygen bond lengths are identical.

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

Effect of substituents on Acidity: Acidic character oI carboxylic acid is due to the stabilization
oI carboxylate ion. So any Iactor which can enhance the dispersal oI negative charge oI the
carboxylate ion will increase the acidity and vise versa. Inductive eIIect oI 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 oI the acid.

73
Alkyl groups are electron releasing group thus their presence in the molecule will decrease the
acidity . Longer the lengths oI alkyl chain, lower will the acidity oI the acid. Since Iormic acid
has no alkyl group, it is the strongest oI all Iatty 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 oI the electron
withdrawing nature oI Cl group Iollowing 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 oI hydrogen and Iorm salt.
RCOOH Na RCOONa 1/
2
H
2


- +

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

2) Reaction with Alcohols: Monocarboxylic acids react with alcohols in the presence oI strong
acid catalyst like sulphuric acid to Iorm 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 Ior the esteriIication
Step 1: Protonation oI 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 transIer
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 oI 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 Iorm 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 Iorm ammonium salt which
on strong heating give acid amides with the elimination oI 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 oI 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 oI carboxylic acids depends on the nature oI 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 oI 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 Iormic 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 oI phosphorous as a catalyst, substitution oI &-halogenated acids are Iormed.
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 oI carboxylic acid are heated with soda lime
|NaOH CaO| alkanes are Iormed.
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 Iormed.
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 Iormed.
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 oI 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 oI concentrated aqueous solution oI sodium or potassium salts
gives alkanes. (Kolbe`s 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 oI carboxylic acids are heated with
chlorine or bromine, alkyl halides are Iormed. 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 Irom the carboxylic
acids by the replacement oI OH Iunction oI Carboxyl group by another group are known as
acid derivatives. All such derivatives upon hydrolysis generate the parent acid.

DiIIerent 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 oI acids in which the OH Iunction oI carboxyl
group is replaced by a halogen atom. Acid halides are also known as acyl halides. Acid chlorides
are most important oI 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 oI 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 oI 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 oI 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 oI hydrolysis.

Chemical properties: Acid chlorides are very reactive compounds as they are more readily
attacked by nucleophile because oI the electron withdrawing eIIect oI highly electronegative,
chlorine atom attached to carbonyl carbon. This Iurther 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 oI acid chloride are Iollowing.
1)Hydrolysis: The acyl chlorides are readily hydrolysed by water to reIorm 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
) oI acid chloride.

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

b) Reaction with Ammonia (Ammonolysis): Amides are Iormed.
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 Iormed.
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 Iormed.
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 Iormed.
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 oI poisoned Palladium Catalyst, they Iorm 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 Iorm 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 oI
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 Irom an acid by the removal oI one water molecule
Irom two molecule oI the acid are called anhydrides.

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

Anhydrides derived Irom two molecule oI diIIerent acids are called mixed anhydride.
R-CO-O-CO-R'

82
Methods of preparation:
Acid anhydrides may be prepared.
1) By reaction oI 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 oI Carboxylic acids in presence oI 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 oI the slow hydrolysis. They are
soluble in ether and benzene.
iii) They have higher boiling points than the corresponding acids because oI large size oI
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 oI carboxylic acids in which the OH Iunction oI
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 oI 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 Iour derivatives oI acids, only acid amides are capable oI Iorming intermolecular
hydrogen bonds due to which they have sharp melting points that are higher than those oI
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 oI the acid derivatives. Important reactions oI 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 Iorm nitriles.
R C NH
2
O
P
2
O
5
-H
2
O
R C N
Amide
Alkane nitrile
(Alkyl cyanide)

v) Hofmann`s 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 Hoffmann`s rearrangement.
Mechanism: The HoImann`s degradation oI amides involves the Iollowing 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 oI the acid e.g
HCOOC
2
H
5
Ethyl Iormate
CH
3
COO C
2
H
5
Ethyl acetate.
A large number oI esters occur in Ilowers, Iruits oI the plants and provide the Iragrance to
Ilowers and Iruits.

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
(Fischer`sEsterification 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 Iormed 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 oI the strongest chain isomers are higher than those oI branched chain
isomers. The boiling points oI methyl and ethyl esters are lower than those oI
corresponding acid, this is due to their inability to Iorm 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 oI the electron withdrawing eIIect oI 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 oI esters are given below.
1) Hydrolysis:
a) Acid hydrolysis: Esters are hydrolyzed in presence oI 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 oI ester to Iorm sodium or potassium salt oI
carboxylic acid and alcohol is reIerred to as SaponiIication.
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 Iirst gives ketone which on
Iurther reacting with another molecule oI 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
Iorm %-ketoesters, in the presence oI 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

S-ar putea să vă placă și