Organic Chemistry

1 Chemistry XII
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FUNDAMENTAL PRINCIPLES
OF ORGANIC CHEMISTRY
7.1 INTRODUCTION
(1) Vital Force Theory
In the beginning it was believed that organic compound can not be prepared in
laboratory and industry. Organic compound obtained from plants and animals.
Friedrick Wohler contradicted this idea. He prepared urea in laboratory by ammonium
cyanate.
O
||
NH4CNO NH2 — C — NH2
Later on million of organic compound were prepared in laboratory and industry.

(2) Organic Chemistry
The branch of chemistry which deals with the study of organic compounds is called
Organic chemistry.
(3) Organic Compounds
The compounds which contain carbon as main component are called Organic
compounds.
(4) Homologous Series
A set of similar compounds in which the successive member differ by (-CH 2) group is
called Homologous series
(5) Terms
Number of Carbon Atoms Part of Compound Name
1 Meth-
2 Eth-
3 Prop-
4 But-
5 Pent-
6 Hex-
7 Hept-
8 Oct-
9 Non-
10 Dec-
11 Undec-
Illustrations, Composing, Designing and Processing by: Ghulam Farid

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Fundamental Principles of Organic Chemistry 2
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Methane
H
|
H— C — H
|
H
Ethane
H H
| |
H—C—C—H
| |
H H
Propane
H H H
| | |
H—C—C—C—H
| | |
H H H
Butane
H H H H
| | | |
H—C—C—C—C—H
| | | |
H H H H
Pentane
H H H H H
| | | | |
H — C— C — C — C — C — H
| | | | |
H H H H H
Hexane
H H H H H H
| | | | | |
H—C—C—C—C—C—C—H
| | | | | |
H H H H H H
Heptane
H H H H H H H
| | | | | | |
H—C—C—C—C—C—C—C—H
| | | | | | |
H H H H H H H
Octane
H H H H H H H H
| | | | | | | |
H—C—C—C—C—C—C—C—C—H
| | | | | | | |
H H H H H H H H
Author: M. Nawaz Nasir

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Nonane
H H H H H H H H H
| | | | | | | | |
H—C—C—C—C—C —C—C—C—C—H
| | | | | | | | |
H H H H H H H H H
Decane
H H H H H H H H H H
| | | | | | | | | |
H—C—C—C—C—C—C—C—C—C—C—H
| | | | | | | | | |
H H H H H H H H H H
Undecane
H H H H H H H H H H H
| | | | | | | | | | |
H—C—C—C—C—C—C—C—C—C—C—C—H
| | | | | | | | | | |
H H H H H H H H H H H
7.2 SOME FEATURES OF ORGANIC COMPOUNDS
Following are some features of organic compounds.
(1) Peculiar Behaviour
Carbon atom from large number of compounds. The carbon atom from strong stable
covalent bond with other carbon atoms forming ring, chains of great size. This self
linking property of carbon atom is called catenation. Carbon atoms also form stable
covalent bond with other atoms like nitrogen or sulphur.
(2) Non-ionic Character
Organic compounds are covalent in nature so they do not show ionic reaction.
(3) Rates of Organic Reactions
Organic compound have slow rate of reaction.
(4) Complex Nature
Organic compound are complex in nature. Formula of starch is (C6 H10 O5 ) n . When n
may be several thousand.
(5) Similar Behavior
There exists close relationship between organic compounds, existence of homologous
series.
(6) Solubility
Organic compounds which are soluble in non polar solvents.
(7) Isomerism
Organic compound show isomerism.
7.3 SOURCES OF ORGANIC COMPOUNDS
Petroleum, coal and natural gas are vast reservoirs from which many organic
compounds are obtained.
Coal
Coal is black mineral of veritable origin. It is believed that coal was formed from
remains of free buried inside the earth crust about 500 millions years ago. Due to
bacterial and chemical reaction on wood it changes into peat. As a result of high
temperature and pressure peat changed into coal. The total resources of coal in
Pakistan estimated to be 184 billion tons. It is used to make brick. It is used for
domestic purposes.

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bacterial and high
Wood  chemical
   reactions  temperature
    Peat  high     Lignite  pressure
 pressure     Bituminous coal
Dead pressure
plants
and trees Anthracite
Natural Gas
Natural gas is a mixture of methane, ethane, propane and butane. It is used as fuel and
to produce carbon black and fertilizers.
Petroleum
Petroleum is a mixture of hydrocarbon with small amount of sulphur, nitrogen,
hydrogen and oxygen. It is thick viscous liquid of brown or black color. It is formed
by decomposition of plants and marine animals which buried under the layer of
porous rock for millions years ago.
Main Fraction of Petroleum
i. Refinery Gas
It is a mixture of methane, ethane, propane and butane. It is collected below the 20°C.
It is used as fuel.
ii. Gasoline
Gasoline is mixture of hydrocarbon containing 5-8 carbons. It is collected between
40-180°C. It is used as a motor fuel.
iii. Kerosene Oil
It is mixture of hydrocarbon containing 11 to 12 carbon atoms. It is collected between
160°C-250°C. It is used for heating.
iv. Diesel Oil
It is mixture of hydrocarbon having 12-25 carbon atoms. It is collected between
220°C-350°C. It is used as fuel in diesel engines.
v. Residue
Residue is a mixture of hydrocarbons. The liquid components are obtained by vacuum
distillation.
vi. Oil Refineries in Pakistan
Attock oil refinery (Morgah near Rawalpindi)
Karachi refinery (Karachi)
Pak Arab refinery (Muhmud Kot near Multan)
vii. Fractional Distillation of Petroleum
Suspended solids and dissolved gas are removed from crude oil. Different fraction
have different boiling point. The vapours are allowed to pass through condensers
which change them into liquid.
7.4 CRACKING OF PETROLEUM
The breaking down of bigger molecules which have high boiling points into smaller
molecules which have low boiling points is called cracking. Cracking is generally
carried out in the following ways.
(1) Thermal Cracking
The break down of bigger molecules into simpler molecules by heating is called
thermal cracking.
H H
| | ∆
H— C — C — H H2 + H — C C—H
| | | |
H H H H
Ethane Ethene

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H H H H H H
| | | | ∆ 550°C | |
H—C—C—C—C—H H—C C—C—C—H+
| | | | | | | |
H H H H H H H H
n Butane 1 Butene
H H H H
| | | |
H—C—C C—C—H
| |
H H
2 Butene
(2) Catalytic Cracking
The breaking down of bigger molecules into simpler molecules in the presence of
catalyst is called catalytic cracking.
Al2O3
C16H34 C8H16 + C8H18
Alkane Alkene
(3) Steam Cracking
The process in which hydrocarbon in vapour phase mixed with steam and heat in
short time above 400°C is used for production of smaller unsaturated hydrocarbons.
Application of Cracking
It produces large number of by products which are used for manufacture of drug,
plastics, ethanol, fertilizer and synthetic fiber.
7.5 REFORMING OF PETROLEUM
The conversion of straight chain alkane into branched chain in the absence of oxygen
and in presence of catalyst is called reforming of petroleum. When n octane is heated
in the presence of catalyst, it converts into 2, 2, 4-trimethyl pentane.
CH3 CH3
Heat | |
CH3 ― (CH2)6 ― CH3 CH3 ― C ― CH2 ― CH ― CH3
n-Octane catalyst |
CH3
2, 2, 4-Trimethylpentane
Octane Number
The percentage of iso-octane in mixture of iso-octane and n-heptane is called octane
number. Octane number of branched chain is higher.
7.6 CLASSIFICATION OF ORGANIC COMPOUNDS
The organic compounds are classified into two types.
1. Open Chain or Acyclic Compounds
2. Closed Chain or Cyclic Compounds
(1) Open Chain or Acyclic Compounds
The organic compound in which there are open chain of carbon atom. e.g.
H H H H
| | | |
| | | |
H H H H
n Butane

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H H H
| | |
H— C — C — C — H
| | |
H CH3 H
2-Methylpropane
There are two types of open chain organic compounds.
Straight Chain Compounds
The organic compound which contains straight chain of carbon atoms.
H H H H
| | | |
| | | |
H H H H
n Butane
Branched Chain Compounds
The organic compound which contains branch chain of carbon atoms are called
branched chain compounds.
H H H
| | |
H—C—C—C—H
| | |
H CH3 H
2-Methyl Propane
(2) Closed Chain Compounds or Cyclic Compounds
The organic compounds in which there are closed chain of carbon atoms.
H H
| | OH
H—C—C—H |
| |
H—C—C—H
| |
H H
Benzene Cyclo Butane Phenol
There are two types of closed chain organic compound
Homocyclic or Carbocycilc Compounds
The organic compound in which ring contains carbon atoms.
H H
| | CH3
H— C — C ─ H |
| |
H─C—C─H
| |
H H
Benzene Cyclo Butane Toluene
Homocyclic are of two types.
Alicyclic Compounds
The organic compounds which do not contain benzene ring are called alicyclic
compounds.

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H H H H
| | | |
H—C—C─H H—C—C—H
| |
H─C—C─H C
| | Cyclo Propane
H H
Cyclo Butane
Aromatic
The organic compounds which contain at least one benzene ring are called aromatic
compounds.
OH CH3
| |
Phenol Toluene
Heterocyclic Compounds
The organic compounds in which ring contain different kind of atoms. e.g.
.. ..
N
..S O
..
Pyridine Thiophene Furan
7.7 FUNCTIONAL GROUP

The atoms or group of atoms which confer the characteristic properties of compound
called functional group.
Types of Compounds on the basis of Functional Group
(1) Alkyl Halide
The organic compound which obtains by replacing H-atoms of alkane by halogen
atom (Cl, Br, I, F) is called alkyl halide.
H H H H H
| | | | |
H — C — C — Cl H — C — C — C — Br
| | | | |
H H H H H
Ethyl Chloride Propyl Bromide
(2) Alcohol
Organic compound in which hydroxyl group (-OH) directly linked with carbon of
open chain compound.
H H H H H
| | | | |
H — C — C — OH H — C — C — C — OH
| | | | |
H H H H H
Ethyl Alcohol Propyl Alcohol

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(3) ETHER
Organic compound in which oxygen atom directly linked with two carbon atoms is
called ether.
H H
| |
H—C—O—C—H
| |
H H
Ethyl Methyl Ether
(4) Aldehyde
Organic compound in which carbon of carbonyl group is linked with at least one
hydrogen atom is called aldehyde.
O
||
CH3 — C — H
Ethanal
(5) Ketone
Organic compound in which carbon of carbonyl group is linked with two carbon
atoms is called ketone.
O O
|| ||
CH3 — C — CH3 CH3 — C — CH2 — CH3
Di-methyl Ketone Ethyl Methyl Ketone
(6) Carboxylic acid
Organic compound which contains carboxylic group (─COOH) is called carboxylic
acid.
H O O
| || ||
H — C — C — OH CH3 — CH2 — CH2 — C — OH
|
H
Ethanoic Acid Butanoic Acid
(7) Acid Chloride
Organic compound which obtains by replacing (-OH) of carboxylic acid by chlorine
atom is called acid chloride.
H O
| ||
H — C — C — Cl
|
H
Acetyl Chloride
(8) Acid Amide
Organic compound which obtains by replacing (-OH) of carboxylic acid by amino
group (NH2) is called acid amide.
H O
| ||
H — C — C — NH2
|
H
Acet amide

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(9) Ester
Organic compound which obtains by replacing H-atoms of carboxylic acid by alkyl
group is called ester.
O
||
CH3 — C — OCH3
Methyl Acetate
(10) Phenol
OH
|
Phenol
7.8 HYBRIDIZATION
The process of intermixing of orbitals having different shapes and energy to form new
orbitals having same shapes and energy is called hybridization.
Types
(1) sp3 - Hybridization
(3) sp - Hybridization
The process of intermixing one s and three p orbitals to form equivalent hybrid
orbitals is called sp3 -hybridization. When carbon atoms linked with four other atoms
then sp3 - hybridization takes place.
H
|
H—C—H
|
H
Methane
In methane carbon atoms linked with four hydrogen atoms. So on carbon sp3 -
hybridization takes place. Electronic configuration of C
1s2, 2s2, 2px1, 2py1, 2pz0
1s2, 2s1, 2p1x, 2p1y, 2p1z
Suppose 2s, 2px, 2py, 2pz orbitals intermix to form four equivalent sp3 hybrid orbitals.
2s1, 2p1x, 2p1y, 2p1z = 4sp3
In sp3 25% s and 75% p character presents.
The angle between two sp3 - hybrid orbitals is 109.28°
The geometry of sp3 is tetrahedral.

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H H
Four sigma bonds formed due to sp3 -1s overlapping.

The process of intermixing one s and two p orbitals to form three equivalent hybrid
orbitals is called sp2 - hybridization. When carbon atom linked with three other atoms
then sp2 - hybridization takes place.
H H
| |
H—C C—H
Ethene
In ethene carbon atom linked with three other atoms (one carbon two hydrogen), so
on carbon sp2- hybridization takes place. Electronic configuration of C
1s2, 2s2, 2p1x, 2p1y, 2p0z
1s2, 2s1, 2p1x, 2p1y, 2p1z
Suppose 2s, 2px and 2py orbitals intermix to form three equivalent sp2 - hybrid
orbitals.
2s1, 2p1x, 2p1y, 2p1z = 3sp2
In sp2 33% s and 67% p character presents.
The angle between sp2 hybrid orbitals is 120°
The geometry of sp2 hybridization in ethene is trigonal planer.
The pz orbital of one carbon atom overlaps with pz orbital of other carbon atom to
form π- bond. Five sigma bonds formed one due to sp2 - sp2 overlapping and four due
to sp2 -1s overlapping.
(3) sp - Hybridization
The process of intermixing one s and one p orbitals to form two equivalent hybrid
orbitals is called sp hybridization. When carbon atom linked with two other atoms the
sp – hybridization takes place. In ethyne carbon atom linked with two other atoms, so
on carbon atom sp-hybridization takes place.
H ― C ≡≡ C ― H
Electronic configuration of carbon is
1s2, 2s2, 2p1x, 2p1y, 2p0z
1s2, 2s1, 2p1x, 2p1y, 2p1z
Suppose 2s and 2px orbitals intermix to form two equivalent sp-hybrid orbitals.
2s2, 2p1x = 2sp
In sp hybridization 50% s and 50% p character presents.

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11 Chemistry XII
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The angle between two sp hybrid orbitals is 180°
The geometry of sp hybridization in ethyne is linear.
py orbitals of each carbon atom overlap to form π- bond. Similarly p z orbitals of each
carbon atom overlap to form other π – bond.
Three sigma bonds are formed one due to sp-sp overlapping and two due to sp-1s
overlapping.
7.9 ISOMERISM
Two or more compounds which have same molecular formula but different structural
formula are called isomers and phenomenon is called isomerism.
e.g. C2H6O
H H H H
| | | |
H — C — C — OH H—C—O—C—H
| | | |
H H H H
Ethyl Alcohol Di-methyl Ether
Types
There are four types of isomerism.
1. Functional Group Isomerism
2. Positional Isomerism
3. Chain Isomerism
4. Meta Isomerism
5. Geometrical Isomerism
(1) Functional Group Isomerism
Two or more compounds which have same molecular formula but different functional
group are called functional group isomers and phenomenon is called functional group
isomerism.
H H H H
| | | |
H — C — C — OH H—C—O—C—H
| | | |
H H H H
Ethyl Alcohol Di-methyl Ether
(2) Position Isomerism
Two or more compounds which have same molecular formula and functional group
but differ in position of functional group are called positional isomers and
phenomenon is called positional isomerism
H H H H H H
| | | | | |
H — C — C — C — Cl H—C—C—C—H
| | | | | |
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H H H H H H
1-Chloropropane 2-Chloropropane
(3) Chain Isomerism
Two or more compounds which have same molecular formula but differ in
arrangement of carbon atoms are called chain isomerism.
H H H H H H H
| | | | | | |
H—C—C—C—C—H H—C—C—C—H
| | | | | | |
H H H H H CH3 H
n-Butane 2-Methylpropane
(4) Metamerism
Two or more compounds which have same molecular formula but different alkyl
group attach to polyvalent atom are called metamers and phenomenon is called
metamerism.
CH3 — CH2 — O — CH2 — CH3 CH3 — O — CH2 — CH2 — CH3
Diethyl Ether Methyl Propyl Ether
(5) Geometrical Isomerism
Two or more compounds which have same molecular formula and structural formula
but differ in arrangement of group of atoms are called geometrical isomers and
phenomenon is called geometrical isomerism or Cis-trans isomerism.
H H H CH3
| | | |
C C C C
| | | |
CH3 CH3 CH3 H
Cis-Isomer Trans-Isomer

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ALIPHATIC
HYDROCARBONS
8.1 ALKANES
Alkanes are the simplest organic compounds made up of carbon and hydrogen only.
They have general formula of Cnh2n+2. Each carbon atom in alkanes is sp3 hybridized
and has tetrahedral geometry.
(1) I.U.P.A.C Names of Alkanes
a. Select the longest continuous chain of carbon atom and name it according to number of
carbon atoms in the longest chain.
b. When two chains contain same chain selected which contain greater number of
substituents.
c. Numbering of longest chain of carbon atoms is done from that end from where branch is
near.
d. Two of the same groups are written by word di, three by tri, four by tetra, and five by
penta.
e. Substituents are given number and name.
f. The groups may be written in alphabetical order.
Examples
H H H H
| | | |
H―C―C―C―C―H
| | | |
H H H H
n-Butane
H H H H
| | | |
H―C―C―C―C―H
| | | |
H H H H
2-Methyl Butane
CH3 ― CH ― CH ― CH2 ― CH2 ― CH3
| |
CH3 C2H5
3-Ethyle-2-methylhexane
(2) Preparation of alkanes
i. Hydrogenation of Unsaturated Hydrocarbons (Sabatier-Sender's Reaction)
Alkanes and alkynes react with H2 in the presence of Ni at 200-300C° to given
alkanes.
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H H H H
| | Ni | |
C C + H2 H―C―C―H
| | 200-300°C | |
H H H H
Ni
H ― C ≡≡ ― H + H2 H―C C―H
200-300°C | |
H H
H H H H
| | Ni | |
C C + H2 H―C―C―H
| | 200-300°C | |
H H H H
The hydrogenation can also be carried out with Pt or Pd at room temperature but they
are expensive than Ni. The method is of industrial importance.
ii. From alkyl halide
a. Wurtz Reaction
Two molecules of alkyl halide react with two atoms of sodium in the presence of ether
to give alkanes.
H H H H
| | Ether | |
H ― C ― Cl +Na + Na + Cl ― C ― H 2NaCl + H ― C ― C ― H
| | | |
H H H H
b. By Reduction Of alkyl halide
Alkyl halide can be reduced to alkanes by nearest hydrogen. Nearest hydrogen is
produced by the action of dil.HCl on zinc.
H H
| | Zn + dil.HCl
H ― C ― C ― Br + 2H HBr + CH3 ― CH3
| |
H H
c. By Zn
Alkanes are produced when an alkyl halide reacts with Zn in the presence of an
aqueous acid, HCl.
HCl
2CH3 ― CH2 ― CH ― CH3 + Zn ZnBr2 + 2CH3 ― CH2 ― CH2 ― CH3
|
Br
HCl
2CH3I + Zn ZnI2 + CH3 ― CH3
iv. By dry distillation of sodium salt of carboxylic acid with soda lime
Soda lime is a mixture of NaOH and calcium oxide
CaO
CH3COONa + NaOH Na2CO3 + CH4
O
|| CaO
CH3 ― CH2 ― C ― ONa + NaOH Na2CO3 + CH3 ― CH3
This process is called decarboxylation.
v. Kolbe’s Reaction

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By electrolysis of aqueous solution of Potassium salt of carboxylic acid.
Ionization Reaction
2CH3COOK 2CH3COO- +2K+
At anode
2CH3COO- 2e- +2CO2 +CH3-CH3
At cathode
2K+ +2e- 2K+
2K+ +2H2O 2KOH +H2
vi. By Reduction of Carbonyl Compounds

a. By Clemmensen reduction
This reaction is very useful for direct conversion of carbonyl group in aldehydes and
ketones to methyl group or methylene group. The aldehydes and ketones are
converted into alkanes. The reagent used is zinc amalgam is HCl.
O
|| Zn-Hg/HCl
CH3 ― C ― + 4H CH3 ― CH3 + H2O
H
O
|| Zn-Hg/HCl
CH3 ― C ― CH3 + 4H CH3 ― CH2 ― CH3 + H2O
b. Wolf Kishner's Reduction
This reaction is very useful for direct conversion of carbonyl group in aldehydes and
ketones to methyl group or methylene group. The aldehydes and ketones are
converted into alkanes. The reagent used is hydrazine and KOH in ethylene glycol.
O
|| NH2-NH2/KOH
CH3 ― C ― H + 4H CH3 ― CH3 + H2O
O
||
CH3 ― C ― CH3 + 4H CH3 ― CH2 ― CH3 + H2O
vii. From Grignard's Reagent
Grignard’s reagent can be prepared by treating an alkyl halide with magnesium
turnings in the presence of pure dry ether.
Ether
CH3Br + Mg CH3 ― Mg ― Br
Grignard’s reagent reacts with water to give alkanes.
Br
CH3-δ ― Mg+ δ ― Br + Mg + CH4
OH
(3) Reactions of alkanes
i. Combustion
Burning of alkanes in the presence of oxygen is known as combustion. Complete
combustion of an alkanes yields CO2, H2O and heat.
CH4 + 2O2 CO2 + 2H2O ∆H=-891 kjmol-1
ii. Oxidation
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Oxidation of methane under different condition gives different products.
a. Incomplete Oxidation
Incomplete oxidation results on the formation of carbon mono oxide, water and soot.
3CH4 + 4O2 2CO + 6H2O + C
b. Catalytic Oxidation
Lower alkanes when burnt in the presence of catalysts, at high temperature and
pressure results in the formation of different products.
H H
| Cu |
H ― C ― H + [O] H ― C ― OH
| |
H H
H
| Cu
H ― C ― OH + [O] H―C O + H2O
| |
H H
Cu
H―C O + [O] H―C O
| |
H OH
iii. Nitration
When vapours of alkanes and Conc. HNO3 are passed through the copper tube at 400-
450C° it gives nitroalknes.
H H
| |
H ― C ― H + Conc.HONO2 H ― C ― NO2 + H2O
| |
H H
iv. Halogenation
The process of replacing hydrogen atom from organic compound by halogen atom is
called halogenation.
Alkanes react with halogen (Chlorine) in the presence of ultra violet tight and high
temperature to give alkyl halide. This method is not good because the mixture of
mono, di, tri and tetra compound is formed.
H H
| |
H ― C ― H + Cl ― Cl H ― C ― Cl + HCl
| |
H H
H H
| |
H ― C ― Cl + Cl ― Cl Cl ― C ― Cl + HCl
| |
H H
H Cl
| |
Cl ― C ― Cl + Cl ― Cl Cl ― C ― Cl + HCl
| |
H H

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` Cl Cl
| |
Cl ― C ― Cl + Cl ― Cl Cl ― C ― Cl + HCl
| |
H Cl
Mechanism
hυ
Cl ― Cl Cl. + Cl.
H H
| hυ |
Cl. + H ― C ― H HCl + H ― C.
| |
H H
H H
| |
H ― C. + Cl. H ― C ― Cl
| |
H H
v. Sulphonation
Alkanes react with Conc. H2SO4 at40-50C° to give alkyl sulphonic acid.
H H
| |
H ― C ― H + HOSO3H H ― C ― SO3H + H2O
| |
H H
8.2 ALKENES
(1) I.U.P.A.C. Names Of alkenes
a. Select the longest continuous chain of carbon atoms containing the double bond.
CH3 ― CH2 ― C CH2
|
CH3
b. Numbering of carbon atoms is done from that end from where the double bond is near.
CH3 ― CH2 ― C CH2
|
CH3
c. If a compound contains one double bond, then replace “ane” of alkanes by “ene”.
CH3 ― CH2 ― CH CH2
Butane replaced by butene.
d. If a compound contains two double bonds, then replace “ne” of alkane by “deine”.
H H H H
| | | |
H―C C―C C―H
1, 3 Butadiene
e. If compound contain three double bonds, then replace “ne” of alkanes by “triene”.
f. Write the number of carbon atom to which double bond is linked before the name of
alkenes.
g. Substituents are given number and name.
Examples
CH2 CH2 CH3 ― CH CH ― CH3
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Ethene 2-Butene
CH2 CH ― CH CH2 CH3 ― CH2 ― CH2 ― CH CH2
1-3- Butadiene 1-Pentene
CH3 ― CH ― CH2 ― CH2 ― CH CH2
|
CH3
5-Methyl 1-Hexane
Preparation Of alkene
(1) By dehydroHalogenation of alkyl halide
When alkyl halide reacts with alcoholic KOH removal of halogen atom and hydrogen
atom take place from adjacent carbon atoms and alkene is formed.
HH
| |
H-C -C-Cl+alcoholic KOH KCl+H2O+CH2=CH2
| |
H H
(2) By dehalogenation of vicinal dihalide
A compound having two halogen atoms present on adjacent carbon atom is called
vicinal dihalide.
Such compound on heating with Zn dust to give alkene
Cl Cl
| |
H-C - C-H+Zn ZnCl2+CH2=CH2
| |
H H
(3) By dehydration of alcohol
Alcohol on heating with Conc. H2SO4 is at 180C° gives alkene.
H H
| | Conc. H2SO4
H-C - C-OH H2O+CH2=CH2
180C°
| |
H H
The formation of alkene is easier from tertiary alcohol than primary alcohol and
secondary alcohol
H H
| | 98% H2SO4
H-C - C-OH H2O+CH2=CH2
170-180 C°
| |
H H
H CH3
| | 62% H2SO4
H-C - C-OH CH2=CH-CH3 +H2O
87C°
| |
H H 1 Propene
H CH3
| | 46% H2SO4
H-C - C-OH CH2=C-CH3 +H2O
87C°
| | |
H H 2 Methyl 1 Propene CH3

___________________________________________________________________________
19 Chemistry XII
___________________________________________________________________________
By Partial Hydrogenation of alkyne

Alkyl reacts with H2 in the presence of Pt or Pd and high temperature to give alkene.
Pt, Pd
H-C≡C-H+H2 H-C=C-H
| |
H H
Ethene
By Kolbe’s Reaction
By electrolysis of aqueous solution of sodium salt of dicarboxylic acid, we get alkene.
Ionization reaction
O
||
CH2-C-ONa CH2-COO- +2Na+
| |
+
CH2-COONa CH2-COO-
Disodium Succinate
At anode
CH2-COO- CH2+2e- +2CO2
| ||
-
CH2-COO CH2
At cathode
2Na+ +2e- 2Na
2Na +2H2O 2NaOH+H2
CHEMICAL REACTIONS OF ALKENE
Hydrogenation (Addition of H2)
Alkene reacts with H2 in the presence of Pt, Pd at room temperature to give alkane.
This process is known as catalytic hydrogenation. The catalysts employed are Pt, Pd and
Raney Nickel.
Raney Nickel is obtain by dissolving nickel Aluminum alloy in NaOH soln.
Ni
+3H2 Ni
+3H
Benzene Cyclohexane
Addition of Halogen acid
Alkenes react with halogen acid to give alkyl halide
H H H H
| | | |
H-C = C-H +HCl H-C-C-Cl
| |
H H
The addition of halogen acid to an alkene takes place in two steps.
1st step.
Alkene accepts the proton of halogen acid to form carbocation
H H
| |
H-C = C-H +HCl H-C-C+-Cl-
| | | |
H H H H
Carbocation
___________________________________________________________________________
________________________________________________________________________
2nd step
Carbocation reacts with halide.
H H H H
| | | |
H-C - C+ +Cl- H-C-C-Cl
| | | |
H H H H
The addition of halogen acid over an unsymmetrical alkene follow Markownikoff’s
rule.
The positive part of adding reagent will attack to that carbon atom containing greater
number of Hydrogen atom. e.g.
H H H HHH
| | | | | |
H-C - C=C-H +HBr H-C-C-C-H
| | | |
H H Br H
1 Propene 2 Bromo Propane
Addition of Halogens
Cl2 and Br2 add to alkenes to give vicinal dichloride or vicinal Bromide respectively.
Cl Cl
| |
CH2=CH2 +Cl-Cl CH2- CH2
CH2=CH2 +Br-Br CH2- CH2
| |
Br Br
Addition of Br2 gives a trans product.
H H H H
C C +Br -
+
|| +Br-Br | Br
C C
H H H H
Bromoniumion
Br- then attacks only from the backside of bromonium ion to form trans addition
product.
H H H H
Br- + C Br-C
+
| Br |
C C -Br
H H H H
Or
Br H
| |
H-C-C-H
| |
H Br
Addition of H2SO4
Alkenes are soluble in Conc. H2SO4 to give alkyl hydrogen sulphate

___________________________________________________________________________
21 Chemistry XII
___________________________________________________________________________
CH2=CH2 +HOSO3H CH3-CH2OSO3H
Ethyl hydrogen sulphate
Alkyl hydrogen sulphate on boiling with water gives alcohol.
CH3=CH2OSO3H+H+ OH- CH3-CH2OH+H2SO4
Hydration of alkene
Ethene reacts with water in the presence of 10%H2SO4+HgSO4 to give alcohol.
CH2=CH2+HOH 10% H2SO4 CH3-CH2OH
HgSO
4
The addition of unsymmetrical alkene follow markownikoff rule.
“The positive part of adding reagent will attack to that carbon atom containing greater
number of Hydrogen atom”
Addition of Ozone (O3)
Alkene reacts with ozone to form ozonide
O+ CH2 ____ CH2
| |
CH2=CH2 + O O O
O-
O
Ethylene ozonide
Ethylene ozonide on heating with zinc dust and water gives formaldehyde
O
||
+ Zn dust +H2O ZnO +2H-C-H
O+
CH3-CH=CH-CH3+ O CH3- -CH3
O-
CH3- -CH3+ Zn dust ||

2CH3-C-H +ZnO
+H2O
Oxidation
(a) Epoxidation
Per oxy acids like per oxy acetic acid or per oxy benzoic acid react with alkene to
form epoxide
O O
|| ||
CH2=CH2+C6H5-C-O-OH C6H5-C-OH+CH2 ___ CH2
O
1, 2 epoxide ethane
Epoxide is used for the conversion of lower alcohol to higher alcohols using
grignard’s reagent.
(b) Hydroxylation
___________________________________________________________________________
________________________________________________________________________
The hypothetical addition of hydrogen per oxide to an alkene double bond is called
hydrolation.
CH2=CH2 +H-O-OH CH2-CH2
| |
OH OH
(c) Combustion
Burning of alkenes in the presence of oxygen is known as combustion
Complete combustion of an alkene yields CO2, H2O and heat.
C2H4+3O2 2CO2+2H2O+heat
(d) Polymerization
In this process smaller molecules combine together to form bigger molecules,
polymers
Ether at 400C° and 100atm pressure polymerizes to give polyethylene.
(e) Reaction with Hypohalous acid (HOX)
Alkene reacts with Hypohalous acid to form halo alcohol called Halo hydrin.
H H
| |
H-C=C-H +HOX H-C-C-H
| | | |
H H Cl OH
Chloro hydrin
I.U.P.A.C Names of alkyne
1) Select the longest continuous chain of carbon atoms containing the triple bond.
CH35-CH4-CH23-C2≡C1-H
|
CH3
2) Numbering of longest chain atoms is done from that end from where the triple bond is
near.
3) If a compound contains one triple bond, then replace “ane” of alkane by “yne”.
4) If a compound contains two triple bond, then replace “ne” of alkane by “diyne”.
5) Write the number of carbon atom to which triple bond is linked before the name of
alkyne. CH35-CH24-CH23-C2≡CH1
1 Pentyle
6) Substituents are given number and names.
Examples
1) CH3 1-C2≡C3-CH4-CH35 4 methyl 2 pentyne
|
CH3
2) CH31 -C2 ≡C3 -CH34 2 Butyne
3) CH36 -C5≡C4 -CH23 -C2 ≡C1-H 1, 4 Hexadiyne
4) CH3
|
CH35 -C4 -C3 ≡C2-CH31 4, 4 dimethyl 2
pentyne
|
CH3
5) CH35 -CH4 -CH23 -C2≡CH1
|
CH3 4 Methyl 1 Pentyne

___________________________________________________________________________
23 Chemistry XII
___________________________________________________________________________
Preparation of alkyne
(1) By dehalogenation of vicinal dihalide
Vicinal dihalide on treatment with strong base like alcoholic KOH at 160C°
eliminates two moles of hydrogen halide to form alkynes
Br Br Br
| | |
H-C - C-H+alcoholic KOH H-
C=C-H+KBr+H2O
| | |
H H H
(3) By dehydration of tetra halide
Compound containing two halogens attached to each adjacent carbon atom on heating
with Zinc dust form alkyne.
Br Br
| |
H-C - C-H+2Zn H-C≡C-H+2ZnBr2
| |
Br Br
By Kolbe’s Reaction
By electrolysis method involves electrolysis of aqueous solution of K salts of
unsaturated carboxylic acid
Ionization reaction
O O
|| ||
CH-C-OK CH-C-O- +2K+
O
|| || || ||
CH- C -OK CH- C-O-
At anode
O
||
CH- C -O- 2CO2+2e- +CH
|| O
|| || |||
CH -C-O- CH
Ethyne
At cathode
2K+ +2e- 2K
2K +2H2O 2KOH+H2
Industrial preparation of Ethyne
Ethyne is usually prepared by the action of water on calcium carbide.
CaC2+2HOH Ca(OH)2 +C2H2
Or
H-C≡C-H
Ethyne
Calcium carbide is prepared by heating calcium oxide with carbon.
CaO+3C CaC2+CO
CHEMICAL REACTIONS OF ALKYNE
Addition of water
Acetaldehyde is obtained by the addition of water to ethyne in the process of
10%H2SO4+HgSO4
___________________________________________________________________________
________________________________________________________________________
H OH
| |
H-C≡C-H+HOH H-C=C-H
Vinyl alcohol
H OH HO
| | rearrangement | |
H-C≡C-H H-C-C-H
|
H
Acetaldehyde
Addition of Hydrogen
Alkynes are reduced to alkanes with H2 in the presence of Pt or Pd or nickel as
catalyst
Ni
H-C≡C-H+H2 H-C=C-H
Heat
| |
H H
H H
| |
H-C=C-H+H2 H-C-C-H
| |
H H
Ethane
Addition of Halogen acid
Alkynes react with halogen chloride and hydrogen bromide to form dihalo alkane.
The addition follows markownikoff rule
Br
|
H-C ≡ C-H +HBr H-C=C-H
|
H
Br H Br
| | |
H-C=C-H+HBr H-C-C-H
| | |
H H Br
1, 1 di Bromo ethane
Addition of Halogens
One or two molecules of halogens can be added to alkynes giving dihalide and tetra
halides respectively.
Br Br
| |
H-C≡C-H +Br-Br H- C=C-H
Br Br Br Br
| | | |
` H-C=C-H +Br-Br H- C- C-H
| |
Br Br
Addition of NH3
Ethyne reacts with NH3 in the presence of catalyst at 300C° to give methyl nitride.
H-C≡C-H +NH3 CH3-CH3 -C≡ N+H2

___________________________________________________________________________
25 Chemistry XII
___________________________________________________________________________
Addition of HCN
Ethyne reacts with HCN in the presence of catalyst to give vinyl cyanide.
Cu2Cl2/NH4Cl
H-C≡C-H+HCN H-C=C-CN
300C°
| |
H H
Addition of alcohol
Alcohol adds to acetylene in the presence of KOH to give alkyl vinyl ether.
H-C≡C-H +CH3OH H-C=C-OCH3
| |
H H
Oxidation of alkyne
a) Combustion
Alkyne burns in air to give CO2 and H2O.
Ethyne (acetylene) burns in air to give CO2 and H2O. Oxyacetylene flame has
temperature of 2800C°. It is used to cut and weld metals.
2CH≡CH+5O2 4CO2+2H2O+heat
b) Oxidation with aqueous KMnO4
Ethyne reacts with alkaline KMnO4 to give oxalic acid
KMnO4
CH +4O COOH
||| |
CH COOH
2 Butyne reacts with 10% aqueous KMnO4 to give two molecules
of acetic acid.
O
||
CH3-C≡C-CH3+3O+H2O 2CH3-C-OH
Acidic nature of alkyne
Hydrogen linked with triply bonded carbons and slightly acidic in nature.
Reaction with sodium
Ethyne reacts with sodium at 110C° to give sodium acetylide
110C°
H-C≡C-H+Na H-C≡C-Na+ +1/2 H2
Reaction with sodium amide
Ethyne reacts with sodium amide to give sodium acetylide acid ammonia
H-C≡C-H+NaH2 H=C≡CNa+NH3
Sodium acetylide can be used for preparing higher alkynes.
H-C≡C-Na+CH3Cl H-C≡C-CH3+NaCl
Reaction with ammonical cuprous chloride
Ethyne reacts with ammonical cuprous chloride to give red precipitate of copper acetylide.
H-C≡C-H+Cu2Cl2+2NH4OH 2NH4Cl+2H2O+Cu-C≡C-Cu
Copper acetylide.
Reaction with ammonical AgNO3
Ethyne reacts with ammonical silver-nitrate to give white ppt of silver acetylide
H-C≡C-H+2AgNO3+2NH4OH 2NH4NO3+2H2O+Ag-C≡C-Ag
Silver acetylide
Silver acetylide reacts with dil. H2SO4 to give regenerate alkynes.
Ag-C≡-C-Ag+dil H2SO4 H-C≡C-H+Ag2SO4
Polymerization of alkyne
___________________________________________________________________________
________________________________________________________________________
Polymerization of acetylene gives different products.
Conversion of acetylene to benzene.
Acetylene when heated to 400C° in the presence of catalyst gives benzene.
C-H
H- C C-H
|||
H-C C-H
||| 
C-H BENZENE
Conversion of acetylene to divinyle acetylene
In the presence of Cu2Cl2+NH4Cl two molecules of acetylene combine to form vinyl
acetylene.
Cu2Cl2+NH4Cl
H-C≡C-H+H-C≡C-H H-C≡C-C=C-H
| |
H H
Vinyl acetylene
Vinyl acetylene again reacts with acetylene in the presence of Cu2Cl2+NH4Cl to form divinyle
acetylene
Cu2Cl2+NH4Cl
H-C=C-C≡C-H+H-C≡C-H H-C=C-C≡-C-C=C-H
| | | | | |
HH H H H H
Formation of chloroprene
Vinyl acethylene form chloroprene on treatment with dilute HCl.
Cl
|
+5 -5
H-C≡C-C=C-H+H Cl H-C=C-C=C-H
| | | | |
H H H H H
Chloroprene
Chloroprene further polymerize to neoprene, used as synthetic rubber
Polymerization
Chloroprene Neoprene

___________________________________________________________________________

Organic Chemistry

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1 Chemistry XII

Later on million of organic compound were prepared in laboratory and industry.

Illustrations, Composing, Designing and Processing by: Ghulam Farid

Author: M. Nawaz Nasir

Illustrations, Composing, Designing and Processing by: Ghulam Farid

Author: M. Nawaz Nasir

Illustrations, Composing, Designing and Processing by: Ghulam Farid

Author: M. Nawaz Nasir

7.7 FUNCTIONAL GROUP

Illustrations, Composing, Designing and Processing by: Ghulam Farid

Author: M. Nawaz Nasir

Illustrations, Composing, Designing and Processing by: Ghulam Farid

Four sigma bonds formed due to sp3 -1s overlapping.

Author: M. Nawaz Nasir

Author: M. Nawaz Nasir

Author: M. Nawaz Nasir

2K+ +2H2O 2KOH +H2

vi. By Reduction of Carbonyl Compounds

CH3-δ ― Mg+ δ ― Br + Mg + CH4

Author: M. Nawaz Nasir

Author: M. Nawaz Nasir

By Partial Hydrogenation of alkyne

Author: M. Nawaz Nasir

CH3-CH=CH-CH3+ O CH3- -CH3

CH3- -CH3+ Zn dust ||

Author: M. Nawaz Nasir

Author: M. Nawaz Nasir

Author: M. Nawaz Nasir

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