Hydrocarbon 1081
Chapter
Aliphatic Hydrocarbon
Organic compounds composed of only carbon and hydrogen are
called hydrocarbons. Hydrocarbons are two types
(1) Aliphatic Hydrocarbon (Alkanes, Alkenes and Alkynes).
(2) Aromatic Hydrocarbon (Arenes)
(1) Sources of aliphatic hydrocarbon
Mineral oil or crude oil, petroleum [Petra  rock; oleum  oil] is
the dark colour oily liquid with offensive odour found at various depths in
many regions below the surface of the earth. It is generally found under the
rocks of earth’s crust and often floats over salted water.
(2) Composition
(i) Alkanes : found 30 to 70% contain upto 40 carbon atom. Alkanes
are mostly straight chain but some are branched chain isomers.
(ii) Cycloalkanes : Found 16 to 64% cycloalkanes present in
petroleum are; cyclohexane, methyl cyclopentane etc. cycloalkanes rich oil is
called asphaltic oil.
(iii) Aromatic hydrocarbon : found 8 to 15% compound present in
petroleum are; Benzene, Toluene, Xylene, Naphthalene etc.
(iv) Sulphur, nitrogen and oxygen compound : Sulphur compound
present to the extent of 6% include mercaptans [R-SH] and sulphides [R-S-
R]. The unpleasant smell of petroleum is due to sulphur compounds.
Nitrogenous compounds are pyridines, quinolines and pyrroles. Oxygen
compounds present in petroleum are. Alcohols, Phenols and resins.
Compounds like chlorophyll, haemin are also present in it.
(v) Natural gas : It is a mixture of Methane (80%), Ethane (13%),
Propane (3%), Butane (1%), Vapours of low boiling pentanes and hexanes
Table : 24.1
Fraction Boiling range ( C)
o
Approximate composition
Uncondensed gases Upto room temperature
24
Hydrocarbon
(0.5%) and Nitrogen (1.3%). L.P.G. Contain butanes and pentanes and used
as cooking gas. It is highly inflammable. This contain, methane, nitrogen and
ethane.
(vi) C.N.G. : When natural gas compressed at very high pressure is
called compressed natural gas (CNG). Natural gas has octane rating of 130 it
consists, mainly of methane and may contain, small amount of ethane and
propane.
(3) Theories of origin of petroleum : Theories must explain the
following characteristics associated with petroleum,
Its association with brine (sodium chloride solution). The presence
of nitrogen and sulphur compounds in it. The presence of chlorophyll and
haemin in it. Its optically active nature. Three important theories are as
follows.
(i) Mendeleeff’s carbide theory or inorganic theory
(ii) Engler’s theory or organic theory
(iii) Modern theory
(4) Mining of petroleum : Petroleum deposits occurs at varying
depth at different places ranging from 500 to 15000 feet. This is brought to
the surface by artificial drilling.
(5) Petroleum refining : Separation of useful fractions by fractional
distillation is called petroleum refining.
Uses
C–C
1 4
Fuel gases: refrigerants; production of carbon black,
hydrogen; synthesis of organic chemicals.
 1082 Hydrocarbon
Crude naphtha on refractionation 30 – 150 o
C –C
5 10

yields,
(i) Petroleum ether 30 – 70o
C –C
5 6
Solvent
(ii) Petrol or gasoline 70 – 120 o
C –C
6 8
Motor fuel; drycleaning; petrol gas.
(iii) Benzene derivatives 120 – 150 o
C –C
8 10
Solvent; drycleaning
Kerosene oil 150 – 250 o
C –C
11 16
Fuel; illuminant; oil gas
Heavy oil 250 – 400 o
C –C
15 18
As fuel for diesel engines; converted to gasoline by
cracking.
Refractionation gives,
(i) Gas oil, (ii) Fuel oil,
(iii) Diesel oil
Residual oil on fractionation by Above 400 o
C –C
17 40

vacuum distillation gives,

(i) Lubricating oil C –C
17 20
Lubrication
(ii) Paraffin wax C –C
20 30
Candles; boot polish; wax paper; etc
(iii) Vaseline C –C
20 30
Toilets; ointments; lubrication.
(iv) Pitch C –C
30 40
Paints, road surfacing
Petroleum coke As fuel.
(on redistilling tar)

(6) Purification (a) Bergius process : This method was invented by Bergius in
(i) Treatment with concentrated sulphuric acid : The gasoline or Germany during first world war.
kerosene oil fraction is shaken with sulphuric acid to remove aromatic
Coal  H 2  o Mix. Of hydrocarbons or crude oil
Fe2 O3
compounds like thiophene and other sulphur compound with impart 450 500 C
offensive odour to gasoline and kerosene and also make them corrosive. 250 atm

(ii) Doctor sweetening process : (b) Fischer- tropsch process : The overall yield of this method is
slightly higher than Bergius process.
2 RSH  Na 2 PbO2  S  RSSR  PbS  2 NaOH
Mercaptan Disulphide s o
H 2 O  C   CO  H 2
1200 C

(iii) Treatment with adsorbents : Various fractions are passed over
adsorbents like alumina, silica or clay etc, when the undesirable compounds
get adsorbed.
(7) Artificial method for manufacture of Petrol or gasoline
(i) Cracking, (ii) Synthesis
(i) Cracking : It is a process in which high boiling fractions
consisting of higher hydrocarbons are heated strongly to decompose them
into lower hydrocarbons with low boiling points. Cracking is carried out in
two different ways.
(a) Liquid phase cracking : In this process, the heavy oil or residual
oil is cracked at a high temperature (475 – 530 C) under high pressure (7
o
to 70 atmospheric pressure). The high pressure keeps the reaction product
in liquid state. The conversion is approximately 70% and the resulting
petrol has the octane number in the range 65 to 70.
The cracking can be done in presence of some catalysts like silica,
zinc oxide, titanium oxide, ferric oxide and alumina. The yields of petrol are
generally high when catalyst is used.
(b) Vapour phase cracking : In this process, kerosene oil or gas oil
is cracked in vapour phase. The temperature is kept 600 – 800 C and the
pressure is about 3.5 to 10.5 atmospheres. The cracking is facilitated by use
of a suitable catalyst. The yields are about 70%.
(ii) Synthesis : Two methods are applicable for synthesis.
Watergas
xCO  yH 2  Mix. Of hydrocarbon  H 2 O .
The best catalyst for this process is a mixture of cobalt (100 parts),
thoria, (5 parts), magnesia (8 parts) and kieselguhr (200 parts).
Characteristics of hydrocarbons
(1) Knocking : The metallic sound during working of an internal
combustion engine is termed as knocking.
“The greater the compression greater will be efficiency of engine.”
The fuel which has minimum knocking property is always preferred.
The tendency to knock falls off in the following order : Straight
chain alkanes > branched chain alkanes > olefins > cyclo alkanes > aromatic
hydrocarbons.
(2) Octane number : It is used for measuring the knocking
character of fuel used in petrol engine. The octane number of a given
sample may be defined as the percentage by volume of iso-octane present in
a mixture of iso-octane and n-heptane which has the same knocking
performance as the fuel itself.
o
CH 3  CH 2  CH 2  CH 2  CH 2  CH 2  CH 3
n-heptane; octane no. = 0
 Hydrocarbon 1083

CH 3 CH 3  By increasing the proportion of branched chain or cyclic alkanes.

| |
CH 3  C  CH 2  C  CH 3 ; Octane no. = 100  By addition of aromatic hydrocarbons Benzene, Toluene and
| Xylene (BTX).
CH 3
 By addition of methanol or ethanol.
2, 2, 4-Trimethyl pentane or Iso-octane.
For example : a given sample has the knocking performance  By additon of tetraethyl lead (C2 H 5 )4 Pb
equivalent to a mixture containing 60% iso-octane and 40% heptane. The
octane number of the gasoline is, therefore, 60. (5) Cetane number : It is used for grading the diesel oils.
Presence of following types of compounds increases the octane CH 3  (CH 2 )14  CH 3 Cetane  cetane no. = 100
number of gasoline.
(i) In case of straight chain hydrocarbons octane number decreases CH 3

with increase in the length of the chain.

(ii) Branching of chain increases the value of octane number
(iii) Introduction of double bond or triple bond increases the value
of octane number.
(iv) Cyclic alkanes have relatively higher value of octane number.
(v) The octane number of aromatic hydrocarbons are exceptionally
high
(vi) By adding gasoline additives (eg TEL)
(3) Antiknock compounds : To reduce the knocking property or to
improve the octane number of a fuel certain chemicals are added to it.
These are called antiknock compounds. One such compound, which is
extensively used, is tetraethyl lead (TEL). TEL is used in the form of
following mixture,
TEL = 63%, Ethylene bromide = 26%, Ethylene chloride = 9% and a
Cetane no. = 0
-Methyl naphthalene
The cetane number of a diesel oil is the percentage of cetane
(hexadecane) by volume in a mixture of cetane and  -methyl naphthalene
which has the same ignition property as the fuel oil under consideration.
(6) Flash point : The lowest temperature at which an oil gives
sufficient vapours to form an explosive mixture with air is referred to as
flash point of the oil.
The flash point in India is fixed at 44 o C , in France it is fixed at
35 C, and in England at 22.8 C. The flash point of an oil is usually
o o

determined by means of “Abel’s apparatus”.

dye = 2%.
Chemists have prepared some hydrocarbons with octane number
However, there is a disadvantage that the lead is deposited in the even less than zero (e.g., n-nonane has octane number – 45) as well as
engine. To remove the free lead, the ethylene halides are added which hydrocarbon with octane number greater than 100 (e.g., 2, 2, 3 trimethyl-
combine with lead to form volatile lead halides. butane. has octane number of 124).
(7) Petrochemicals : All such chemicals which are derived from
Pb  Br  CH 2  CH 2  Br  PbBr2  CH 2  CH 2 petroleum or natural gas called petrochemicals. Some chemicals which are
Ethylene bromide Volatile Ethylene
obtained from petroleum are summarised in table :
However, use of TEL in petrol is facing a serious problem of Lead Table : 24.2
pollution, to avoid this a new compound cyclopenta dienyl manganese Hydrocarbons Compounds derived
carbonyl (called as AK-33-X) is used in developed countries as antiknocking Methane Methyl chloride, chloroform, methanol, formaldehyde,
compound. formic acid, freon, hydrogen for synthesis of ammonia.
(4) Other methods of improving octane number of hydrocarbon. Ethane Ethyl chloride, ethyl bromide, acetic acid, acetaldehyde,
ethylene, ethyl acetate, nitroethane, acetic anhydride.
(i) Isomerisation [Reforming] : By passing an alkane over AlCl3 at Ethylene Ethanol, ethylene oxide, glycol, vinyl chloride, glyoxal,
o polyethene, styrene, butadiene, acetic acid.
200 C .
Propane Propanol, propionic acid, isopropyl ether, acetone,
CH 3 nitromethane, nitroethane, nitropropane.
| Propylene Glycerol, allyl alcohol, isopropyl alcohol, acrolein,
CH 3 CH 2 CH 2 CH 2 CH 3  
AlCl3
o
 CH 3 CHC H 2 CH 3 nitroglycerine, dodecylbenzene, cumene, bakelite.
Pentane 200 C Isopentane
(Octane number  62)
Hexane Benzene, DDT, gammexane.
(Octane number  90 )
Heptane Toluene
(ii) Alkylation : Cycloalkanes Benzene, toluene, xylenes, adipic acid.
CH 3 CH 3 CH 3 CH 3 Benzene Ethyl benzene, styrene, phenol, BHC (insecticide), adipic
| | | | acid, nylon, cyclohexane, ABS detergents.
H SO 4
CH 3 CH  CH 2  C CH 3 2  CH 3 CCH 2 CHCH 3 Toluene Benzoic acid, TNT benzaldehyde, saccharin, chloramine-
| Isobutylene | T, benzyl chloride, benzal chloride.
CH 3 CH 3
Isobutane Iso - octane Alkanes [Paraffines]
(Octane number  100)
“Alkanes are saturated hydrocarbon containing only carbon-carbon
(iii) Aromatisation : single bond in their molecules.”
CH 3 Alkanes are less reactive so called paraffins; because under normal
conditions alkanes do not react with acids, bases, oxidising agents and
CH 3 (CH 2 )5 CH 3 o 
 Pt / Al2O3
 4H2
Heptane 500 C reducing agent.

Toluene General formula : Cn H 2n 2

The octane no. of petrol can thus be improved. Examples are CH 4 , C2 H 6 , C3 H 8 ,
 1084 Hydrocarbon
(1) General Methods of preparation  
2 R  C  O   2e   2 R  C  O  2 R  2CO 2
(i) By catalytic hydrogenation of alkenes and alkynes (Sabatie and || ||
sanderen’s reaction) O O

Cn H 2n  H 2 
Ni
Cn H 2n  2 ; C n H 2n2  2 H 2 
Ni
Cn H 2n 2 2 R  R  R (alkane)
Alkene heat Alkane Alkyne heat Alkane
At cathode [Reduction] :
 Methane is not prepared by this method
2 Na   2e   2 Na   2 NaOH  H 2 (  )
2 H 2O
(ii) Birch reduction :
R  CH  CH 2 
3
 R  CH 2  CH 3
1 . Na / NH  Both ionic and free radical mechanism are involved in this
2. CH 3 OH reaction.
(iii) From alkyl halide (c) Reduction of carboxylic acid :
(a) By reduction : RX  H 2   RH  HX
Zn / HCl
CH 3 COOH  6 HI    CH 3 CH 3  2 H 2O  3 I2
Re duction
(b) With hydrogen in presence of pt/pd : Aceticacid p Ethane

RX  H 2  RH  HX
Pd orPt .
(x) By reduction of alcohols, aldehyde, ketones or acid derivatives
(c) With HI in presence of Red phosphorus :
CH 3 OH  2 HI   CH 4  H 2 O  I2
Red P
RBr  2 HI  RH  HBr  I2 Methanol 150 o C Methane
Purpose of Red P is to remove I2 in the form of PI3 (Methyl alcohol)

(iv) By Zn-Cu couple :

CH 3 CHO  4 HI   C2 H 6  H 2 O  2 I2
Red P
2CH 3 CH 2 OH  Zn 
 (CH 3 CH 2 O)2 Zn  2 H
Cu
Acetaldehyde 150 o C Ethane
Zn-Cu couple Zincethoxide (Ethanal)

RX  2 H  RH  HX CH 3 COCH 3  4 HI   CH 3 CH 2 CH 3  H 2 O  2 I2
Red P
(v) Wurtz reaction : Acetone 150 o C Propane

R X  2 Na  X R  
(Propanone )
 R  R  2 NaX
Dry ether

Alkyl halide Alkyl halide Alkane O

||
 R  Br or RI preferred in this reaction. The net result in this CH 3  C  Cl  6 HI   CH 3  CH 3  H 2 O  HCl  3 I2
Red P
reaction is the formation of even no. of carbon atoms in molecules. Acetyl chloride 200 o C Ethane
(Ethanoyl chloride)
(vi) Frankland’s reaction :
2 RX  Zn  R  R  ZnX 2 O
||
(vii) Corey-house synthesis CH 3  C  NH 2  6 HI   CH 3  CH 3  H 2 O  NH 3  3 I2
Red P

1. Li CH  CH Cl Acetamide 200 o C Ethane

CH 3  CH 2  Cl (CH 3  CH 2 )2 LiCu 
3

2

 (Ethanamide)
2. CuI
 Aldehyde and ketones when reduced with amalgamated zinc and
CH 3  CH 2  CH 2  CH 3
conc. HCl also yield alkanes.
 Reaction is suitable for odd number of Alkanes.
Clemmenson reduction :
(viii) From Grignard reagent
Zn  Hg
(a) By action of acidic ‘H’ : CH 3 CHO  4 H    CH 3  CH 3  H 2 O
Acetaldehyde HCl Ethane
RMgX  HOH  RH  Mg(OH )X (Ethanal)
Alkylmagnesium Water Alkane
Zn  Hg
halide CH 3 COCH 3  4 H    CH 3 CH 2 CH 3  H 2 O
HCl
(b) By reaction with alkyl halide : Acetone
(Propanone )
Propane

R  X  RMgX  R  R  MgX2  Aldehydes and ketones ( C  O) can be reduced to

(ix) From carboxylic acids hydrocarbon in presence of excess of hydrazine and sodium alkoxide on
heating.
(a) Laboratory method [Decarboxylation reaction or Duma reaction]
Wolff-kishner reduction :
R R R
R COONa  NaOH   R  H  Na 2 CO 3
heat
C  O 

H 2 NNH 2
C  NNH 2 

C 2 H 5 ONa
CH 2
CaO Alkane H 2O 180 o C ,  N 2
R R R
 NaOH and CaO is in the ratio of 3 : 1. (Sodalime)
(xi) Hydroboration of alkenes
(b) Kolbe’s synthesis :
(a) On treatment with acetic acid
O
Electrolysis || R  CH  CH 2 2 

6
 (R  CH 2  CH 2 )3 B 
B H 3

CH COOH
R  C  O  Na  Ionization
R  C  O   Na  Alkene Trialkyl borane
||
O R  CH 2  CH 3
Alkane
At anode [Oxidation] :
(b) Coupling of alkyl boranes by means of silver nitrate
 Hydrocarbon 1085
o (b) Sulphonation : Free radical mechanism
6[R  CH  CH 2 ]   [2 R  CH 2  CH 2 ]3 B 
2 B2 H 6
 
AgNO3 25 C
NaOH
R  H  HOSO 3 H 
 R  SO 3 H  H 2 O
SO 3
Prolonged heating
3[RCH 2 CH 2  CH 2 CH 2 R]
(2) Physical Properties  Lower alkanes particularly methane, ethane, do not give this
reaction.
(i) Physical state : Alkanes are colourless, odourless and tasteless.
Alkanes State (iii) Oxidation

C1  C4 Gaseous state (a) Complete Oxidation or combustion :

C5  C17  3n  1 
Liquid state [Except neo pentane which is gas] Cn H 2 n  2   O 2  nCO 2  (n  1)H 2 O  Q
 2 
C18 and above Solid like waxes
 This is exothermic reaction.
(ii) Density : Alkanes are lighter than water.
(iii) Solubility : Insoluble in water, soluble in organic solvents, (b) Incomplete combustion or oxidation

solubility 
1 2CH 4  3O2   2CO  4 H 2 O
Burn

Molecular mass
(iv) Boiling points and Melting points : Melting points and boiling CH 4  O2  C 2 H 2 O
1
points.  Molecular mass  Cu  tube
(c) Catalytic Oxidation : CH 4  [O]  o CH 3 OH
No. of branches 100 atm / 200 C

Alkane : C3 H 8 C4 H10 C5 H12 C6 H14 C7 H16 C8 H18 This is the industrial method for the manufacture of methyl alcohol.
M.P.(K) : 85.9 138 143.3 179 182.5 216.2  Higher alkanes are oxidised to fatty acids in presence of
 Melting points of even > Odd no. of carbon atoms, this is manganese stearate.
because, the alkanes with even number of carbon atoms have more CH 3 (CH 2 )n CH 3 

O2
CH 3 (CH 2 )n COOH
symmetrical structure and result in closer packing in the crystal structure as o
100 160 C
compared to alkanes with odd number of carbon atoms. (d) Chemical oxidation :

C C C C C C (CH 3 )3 CH   (CH 3 )3 .C.OH

KMnO 4

Isobutane Tertiary butyl alcohol

C C C C (iv) Thermal decomposition or cracking or pyrolysis or

C C C
Even no. of carbons fragmentation
Odd no. of Carbons
(3) Chemical properties o
CH 4   C  2H 2
1000 C
(i) Substitution reactions of Alkanes Methane

(a) Halogenation : R  H  X  X  R  X  HX o

C 2 H 6   CH 2  CH 2  H 2
500 C

The reactivity of halogen is : F2  Cl 2  Br2  I2 Ethane Cr2 O3  Al2 O3 Ethylene

 Fluorine can react in dark Cl 2 , Br2 require light energy. I 2 C 3 H 8  C 2 H 4  CH 4 or C 3 H 6  H 2

doesnot show any reaction at room temperature, but on heating it shows
iodination.  This reaction is of great importance to petroleum industry.
 Iodination of methane is done in presence of oxidising agent (v) Isomerisation :
such as HNO 3 / HIO3 / HgO which neutralises HI .
CH 3
 Chlorination of methane : AlCl3  HCl
|
CH 3 CH 2 CH 2 CH 3  o
    CH 3 CHCH 3
CH 4  2Cl  Cl   CH 2  Cl 2  
u. v. light 2 u. v . light, Cl n - Butane 200 C , 35 atm Isobutane
 2 HCl  HCl

AlCl3  HCl
 HCl
CHCl 3   CCl 4   
Cl 2 2-Methyl pentane heat
2,3 Dimethyl
(ii) Reaction based on free radical mechanism butane
(a) Nitration : R  H  HONO 2   R  NO 2  H 2 O
High
Alkane temp . Nitroalkane (vi) Aromatisation :
CH3
Nitrating mixture : (i) (Con. HNO 3  Con. H 2 SO 4 ) at 250 o C
H2C CH3
(ii) (HNO 3 vapour at 400  500 C) . o o  
o

Cr2 O3 / Al 2 O3
+4H2
CH2 600 C / 15 atm
H2C
CH2 Benzene
n-Hexane CH3 CH3

H2
  
Cr2O3 / Al 2 O3
o

600 C

n-Heptane Methyl cyclo Toluene

Hexane
 1086 Hydrocarbon
(b) It is lighter than air. Its density at NTP is 0.71 g/L.
(c) It is slightly soluble in water but is fairly soluble in ether,
alcohol and acetone.
(d) Its melting point is  182.5 o C and boiling point is
 161.5 o C .
(vii) Step up reaction (iii) Uses
(a) In the manufacture of compounds like methyl alcohol,
(a) Reaction with CH 2 N 2 (Diazo methane) : formaldehyde, methyl chloride, chloroform, carbon tetrachloride, etc.
(b) In the manufacture of hydrogen, used for making ammonia.
R  CH 2  H  CH 2 N 2 
hv
 R  CH 2  CH 2  H (c) In the preparation of carbon black which is used for making
printing ink, black paints and as a filler in rubber vulcanisation.
(b) Reaction with CHCl 3 / NaOH : (d) As a fuel and illuminant.
(2) Ethane

R  CH 2  H  
CHCl 3 / OH
 R  CH 2  CHCl 2 (i) Methods of preparation
: CCl 2 (a) Laboratory method of preparation :
Zn  Cu couple
(c) Reaction with CH 2  C : C 2 H 5 I  2 H    C 2 H 6  HI
Ethyl iodide C2 H 5 OH Ethane
||
(b) Industrial method of preparation :
O
CH 2  CH 2  H 2 

Ni
CH 3  CH 3
O Ethylene 300 o C Ethane
||
(ethene)
CH 2  C/ 
R  CH 2  H  R  CH 2  CH 3 (ii) Physical properties
:CH 2 /  CO
(a) It is a colourless, odourless, tasteless and non-poisonous gas.
(viii) HCN formation : (b) It is very slightly soluble in water but fairly soluble in alcohol,
acetone, ether, etc.
2CH 4   2 HCN  3 H 2 or
N 2 / electricarc
(c) Its density at NTP is 1.34 g/L
(d) It boils at – 89 C. Its melting point is –172 C.
o o

CH 4  NH 3   HCN  3 H 2
Al2 O3
(iii) Uses
700 o C
(a) As a fuel. (b) For making hexachloroethane which is an artificial
(ix) Chloro sulphonation/Reaction with SO +Cl 2 2
camphor.
(3) Interconversion of Alkanes
CH 3  CH 2  CH 3  SO 2  Cl 2 
 u.v light

Ascent of alkane series,

CH 3  CH 2  CH 2 SO 2 Cl  HCl
(i) Methane to ethane :
This reaction is known as reed’s reaction.
CH 4  CH 3 Cl 
Cl 2
  CH 3  CH 3
Wurtzreaction
 This is used in the commercial formation of detergent. Methane UV Heat with Na in ether Ethane

(x) Action of steam : CH 4  H 2 O  o  CO  3 H 2

Ni / Al2O3 (ii) Butane from ethane :
800 C
C 2 H 6  C 2 H 5 Cl 
Cl 2
  C 2 H 5  C 2 H 5
Wurtz reaction

Ethane UV Ethyl chloride Heat with Na in ether Butane

Individual members of alkanes (excess)

(1) Methane : Known as marsh gas. Descent of alkane series : Use of decarboxylation reaction is made. It
(i) Industrial method of preparation : Mathane gas is obtained on a is a multistep conversion.
large scale from natural gas by liquefaction. It can also be obtained by the Ethane to methane
application of following methods,
(a) From carbon monoxide : A mixture of carbonmonoxide and C 2 H 6  C 2 H 5 Cl 
Cl 2
 C 2 H 5 OH 
Aq . KOH
 CH 3 CHO
[O ]

Ethane UV Ethyl chloride Ethyl alcohol Acetaldehyde

(excess)
hydrogen is passed over a catalyst containing nickel and carbon at 250 o C
when methane is formed. 
 CH 3 COOH 
[O ]
 CH 3 COONa 
NaOH
 CH 4
NaOH / CaO

Ni  C heat
CO  3 H 2 
o
 CH 4  H 2 O Aceticacid Sodium acetate Methane
250 C
Higher 
 Alkyl 
 Alcohol
Cl 2
 Aldehyde
Aq .
[O ] [O ]
(b) Bacterial decomposition of cellulose material present in sewage alkane UV
halide KOH

water : This method is being used in England for production of methane.

Acid 
 Sodium salt of 
NaOH
 Lower alkane
NaOH / CaO
(C6 H10 O5 )n  nH 2 O  3nCH 4  3nCO 2 the acid heat
Cellulose
(c) Synthesis :  By striking an electric arc between carbon Alkenes
electrodes in an atmosphere of hydrogen at 1200 C, methane is formed.
o

o
These are the acyclic hydrocarbon in which carbon-carbon contain
C  2 H 2   CH 4
1200 C
double bond. These are also known as olefins, because lower alkene react
By passing a mixture of hydrogen sulphide and carbon disulphide with halogens to form oily substances. General formula is Cn H 2n .
vapour through red hot copper, methane is formed. Examples, C 2 H 4 , C 3 H 6 , C 4 H 8 .
CS 2  2 H 2 S  8 Cu    CH 4  4 Cu 2 S
High temperatur e
(1) Preparation methods
(ii) Physical properties (i) From Alkynes :
(a) It is a colourless, odourless, tasteless and non-poisonous gas.
 Hydrocarbon 1087

H (ix) Action of copper alkyl on vinyl chloride :

|
H 2 C  CHCl   H 2 C  CHR
2 CuR
R  C  C  R  H 2   R  C  C  R
Lindlar's Catalyst
Vinyl chloride
Pd. BaSO 4 |
H (x) By Grignard reagents :
 Poison’s catalyst such as BaSO4 ,CaCO 3 are used to stop the R
reaction after the formation of alkene. Mg  X  CH  CH 2  MgX2  R  CH  CH 2
(ii) From mono halides : X
H H H (xi) The wittig reaction :
| | |
(Ph)3 P  CH 2  CH  R (Ph)3 P  O  R  CH
R  C  C  H  Alc. KOH  
 HX
 R  C  C H ||
| | | ||
O CH 2
H X H
Alkene
O
 If we use alc. NaOH in place of KOH then trans product is ||
formed in majority because of its stability. According to saytzeff rule. (Ph)3 P  CH  R  CH  R (Ph)3 P  O  R  CH  CH  R
(iii) From dihalides
(a) From Gem dihalides (xii) From  bromo ether [Boord synthesis]
X Zn X Br O  C 2 H 5
| | Br

R – CH + + CH – R  R – CH = CH – R R  CH  CH   R  CH  CH  R  Zn
Zn

 2 ZnX 2 C4 H 9 OH
X Zn X | O  C2 H 5
R
 If we take two different types of gemdihalides then we get three
different types of alkenes . (2) Physical Properties
(i) Alkenes are colourless and odourless.
 Above reaction is used in the formation of symmetrical alkenes
only. (ii) These are insoluble in water and soluble in organic solvents.
(iii) Physical state
(b) From vicinal dihalides :
H H H H C1  C 4  gas
| | | |

R  C  C  H  Zn dust  R  C  C  H  ZnX 2 C4  C16  liquid
| | 300 o C
 C17  solid wax
X X
 Alkene is not formed from 1, 3 dihalides. Cycloalkanes are (iv) B.P. and M.P. decreases with increasing branches in alkene.
formed by dehalogenation of it. (v) The melting points of cis isomers are lower than trans isomers
because cis isomer is less symmetrical than trans. Thus trans packs more
C H 2  CH 2  C H 2  
Zn dust
CH 2  ZnX 2 tightly in the crystal lattice and hence has a higher melting point.
| |
X X (vi) The boiling points of cis isomers are higher than trans isomers
H 2C CH 2 because cis-alkenes has greater polarity (Dipole moment) than trans one.
(iv) By action of NaI on vicinal dihalide : (vii) These are lighter than water.
Br Br I I (viii) Dipole moment : Alkenes are weakly polar. The, -electron’s of
| | | | the double bond. Can be easily polarized. Therefore, their dipole moments
C C 
 NaI
C C  C C
acetone  I2 are higher than those of alkanes.
vic dihalide unstable alkene
(v) From alcohols [Laboratory method] : (3) Chemical properties
(i) Francis experiment : According to Francis electrophile first
CH 3 CH 2 OH   CH 2  CH 2  H 2 O
H 2 SO 4 or H 3 PO4

Ethyl alcohol 443 K Ethene attacks on olefinic bond.

(vi) Kolbe’s reaction :
CH2 = CH2 + Br – Br  CH2 – CH2
CCl4

CH 2 COOK CH 2 | |
|  2 H 2 O   | |
Electrolysis
 2CO 2  H 2  2 KOH Br Br
CH 2 COOK CH 2
Potassium succinate Ethene   CH2 – CH2 + CH2 – CH2
NaCl

(vii) From esters [Pyrolysis of ester] : | | | |

Br Br Br Cl
CH 3  CO  O H CH 3  COOH (ii) Reaction with hydrogen :
Glass wool 450 o
| |   
CH 2  CH 2
liq. N 2
CH 2  CH 2 H H H H
| | | |
(viii) Pyrolysis of quaternary ammonium compounds : R  C  C  R  H 2 

Ni
R  C  C R
  | |
(C2 H 5 )4 N OH  (C2 H 5 )3 N  C2 H 4  H 2 O
heat
H H
Tetraethylammonium Triethylamine Ethene
hydroxide (Tert. amine)
 1088 Hydrocarbon
(iii) Reduction of alkene via hydroboration : Alkene can be H H H H
converted into alkane by protolysis | | | |
H  BH 2
R  C  C  H  X  X  R  C  C  H
CCl 4
RCH  CH 2  (R  CH 2  CH 2 )3 B | |

X X
   R  CH 2  CH 3
H / H 2O Vicinal dihalide
Reactivity of halogen is F2  Cl 2  Br2  I2
Hydroboration : Alkene give addition reaction with diborane which
(vii) Reaction with HX [Hydrohalogenation]
called hydroboration. In this reaction formed trialkylborane, Which is very
important and used for synthesis of different organic compound H
|
3 R  CH  CH 2  BH 3  CC  HX  C  C
|
(R  CH 2  CH 2 )3 B Trialkyl borane alkene
X
Alkylhalide

CH COOH/Zn
3
NaOH/ H O 2 2
HI/H O 2 2
According to markownikoff’s rule and kharasch effect.
H H
R – CH –CH R – CH –CH OH R – CH –CH | |
CH 3  CH  CH 2  HBr  CH 3  C  C  H
2 3 2 2 2 3

The overall result of the above reaction appears to be | |

antimarkownikoff’s addition of water to a double bond. Br H
(iv) By treatment with AgNO + NaOH : This reaction gives 3 According to Anti Markownikoff rule (Based on F.R.M.)
coupling
CH 3  CH  CH 2  HBr  
Peroxide
CH 3
| H H H H
6 CH 3  CH 2  CH 2  C  CH 2  

B2 H 6
| | | |
CH 3  C  C  H  CH 3  C  C  H
CH 3 | | | |
|
Br H H Br
2[CH 3  (CH 2 ) 2  C  CH 2 ] 3 B  
Ag / NO 3 NaOH
(minor) (major)
| (viii) Reaction with hypohalous acids :
H  

CH 3 CH 3 CH 2  CH 2  H O Cl  CH 2 OH .CH 2 Cl
Ethylene Ethylene chlorohydr in
| |
CH 3  CH 2  CH 2  C  CH 2  CH 2  C  CH 2  CH 2  CH 3  In case of unsymmetrical alkenes markownikoff rule is followed.
| | (ix) Reaction with sulphuric acid :
H H CH 2  CH 2  H  HSO 4  CH 3 CH 2 HSO 4
Ethylene Ethyl hydrogen sulphate
(v) Birch reduction : This reaction is believed to proceed via anionic
free radical mechanism. CH 3 CH 2 HSO 4  CH 2  CH 2  H 2 SO 4
 
R  CH  CH 2 
 R  C H  C H 2 
Na
 R  CH  CH 3
Et  O  H  This reaction is used in the seperation of alkene from a gaseous
e 
mixture of alkanes and alkenes.

Et.O  H (x) Reaction with nitrosyl chloride

 R  C H  CH 3 
Na
  R  CH 2  CH 3
e  NO
(vi) Halogenation |
o C  C  NOCl  C  C ( NOCl is called Tillden
CH 3 CH  CH 2  Cl 2   ClCH 2  CH  CH 2  HCl
500 C

Propene Allylchloride |
or 3-Chloro-1- propene Cl
 If NBS [N-bromo succinimide] is a reagent used for the specific reagent)
purpose of brominating alkenes at the allylic position.  If hydrogen is attached to the carbon atom of product, the
CH – CO product changes to more stable oxime.
2

| N – Br NO
CH CH=CH + |
3

CH – CO
2
H
C C ⇌ C  C  NOH
2

Propene NBS | | |
CH – CO Cl Cl
2
Oxime
CH – CH = CH + 2 2
| N–H
| CH – CO C C
2

Br CC  NOCl  C  C (Blue colour)

Succinimide C | | C
Allyl bromide
 In presence of polar medium alkene form vicinal dihalide with NO Cl
halogen. (xi) Oxidation : With alkaline KMnO4 [Bayer’s reagent] : This
reaction is used as a test of unsaturation.
 Hydrocarbon 1089

H H H H (CH 3 ) 3 C  CH  CH 2  Hg   (CH 3 )3 C  CH  CH 3

NaBH 4 / NaOH
THF
| | | | | |
R  C  C  H  [O]  H  OH  R  C  C  H
Alk KMnO 4
OCOCH 3 OH
OH 3 , 3  Dimethyl 2  butanol
| |
HO OH (xvi) Epoxidation
glycol
O
With acidic KMnO4 : 1
(a) By O2 / Ag : CH 2  CH 2  O 2 
 CH 2  CH 2
Ag
H H O 2
| | ||
R  C  C  H  [O]  R  C  O  H  CO 2  H 2 O
acidic (b) Epoxidation by performic acid or perbenzoic acid :
KMnO 4 O
(xii) Hydroxylation |
C–O–O–H
(a) Using per oxy acid : | O
CH 3 CH 3
| | CH 2  CH 2  CH 2  CH 2
H C  
H 2 O2 , HCOOH
H  C  OH
|| or HCO 3 H
| O
H C HO  C  H
O
||
| | H  C O O  H
CH 3  CH  CH 2   CH 3  CH  CH 2
CH 3 CH 3
2 - Butene Trans (racemic) (xvii) Hydroboration


R 3 R  CH  CH 2  BH 3  (R  CH 2  CH 2 )3 B  
H 2 O 2 / OH
H Tri alkyl borane

C R  CH 2  CH 2  OH  B(OH)3
(b) Hydroxylation by OsO : | |  OsO4  NaHSO 4 
4
I
(Anti markownikoff’s rule)
C (xviii) Hydroformylation :
R H H
H R | |
H OH R  CH  CH 2  CO  H 2   R  C  C  H
CoH (CO )4
Trans
HO H | |
H C O
R |
 If per benzoic acid or peroxy acetic acid is used then ()
oxirane are H
formed.  If CO  H 2 O is taken then respective acid is formed.
 H 2O R  CH  CH 2  CO  H 2 O   R  CH 2  CH 2
CoH (CO )4
R  CH  CH  R   R  CH  CH  R 
C6 H 5 CO 3 H

or CH 3 CO 3 H | | |
OH OH COOH
(xix) Addition of formaldehyde
R  CH  CH  R   
H 2 C  O  H [H 2 C  O H  H 2 C  OH ]
O R CH CH 2
 HOH
[Oxirane]   R  C H  CH 2  CH 2  OH 
H2 H
3n C
(xiii) Combustion : Cn H 2n  O 2  nCO 2  nH 2 O
2
R – CH CH2 
They burn with luminous flame and form explosive mixture with air
or oxygen.    R  CH  CH 2  CH 2
HCHO / H

O O | |
(xiv) Ozonolysis C OH OH
H2 1, 3 diol

CC 

O3 Cyclic acetal
(xx) Polymerisation
I
O O O

H H  H H H H
C C    ZnO 
H 2 O / H / Zn
C+C  
II | |  | | | | 
Trace O 2  Catalyst
C  C   C  C  C  C 
O O 1500 o / high pressure  
Ozonide | |  | | | | 
 Application of ozonolysis : This process is quite useful to locate  H H H H
the position of double bond in an alkene molecule. The double bond is H H  n
obtained by Joining the carbon atoms. of the two carbonyl compounds.  If in polymerisation zeigler- natta catalyst
(xv) Oxy – mercuration demercuration : With mercuric acetate (in [(R)3 Al  TiCl4 ] is used then polymerisation is known as zeigler-natta
THF), followed by reduction with NaBH 4 / NaOH is also an example of polymerisation.
hydration of alkene according to markownikoff’s rule. (xxi) Isomerisation :
AlCl3
(CH 3 )3 C  CH  CH 2  (CH 3 COO )2 Hg  CH 3  CH 2  CH 2  CH  CH 2
3,3- dimethyl-1- butene Mercuric acetate
CH 3  CH 2  CH  CH  CH 3
The mechanism proceeds via carbocation.
 1090 Hydrocarbon
(xxii) Addition of HNO :3
(ii) It is insoluble in water but highly soluble in acetone and alcohol.
CH 2  CH 2  HO  NO 2  CH 2 OH .CH 2 NO 2 Acetylene is transported under high pressure in acetone soaked on porous
Ethene 2-Nitroethanol material packed in steel cylinders.
(xxiii) Addition of Acetyl chloride :
(iii) Its boiling point is  84 o C .
CH 2  CH 2  CH 3 COCl  CH 2 ClCH 2 COCH 3
Ethene 4 -Chlorobuta none - 2 (iv) It is lighter than air. It is somewhat poisonous in nature.
(4) Uses (v) It burns with luminous flame and forms explosive mixture with
(i) For the manufacture of polythene – a plastic material; (ii) For air.
artificial ripening of fruits; (iii) As a general anaesthetic; (iv) As a starting
material for a large number of compounds such as glycol, ethyl halides, (3) Chemical reactivity of alkynes : C  C is less reactive than the
ethyl alcohol, ethylene oxide, etc; (v) For making poisonous mustard gas carbon-carbon double bond towards electrophilic addition reaction. This is
(War gas); (vi) For making ethylene-oxygen flame. because in alkyne carbon has more S-character so more strongly will be the
Alkynes attraction for  electrons. Alkyne also undergo nucleophilic addition with
electron rich reagents. Ex. Addition of water, cyanide, carboxylic acid,
These are the acyclic hydrocarbons which contain carbon-carbon
alcohols. Nucleophilic addition can be explained on the basis that alkynes
triple bond are called alkynes. General formula is Cn H 2n2 . Ex. Ethyne form vinylic carbanion which is more stable than alkyl carbanion formed by
CH  CH ; Propyne CH 3  C  CH alkene
(1) General methods of preparation Nu
| 
alc KOH or NaNH  C  C   Nu    C  C 
CH Br – CH Br 2 2
2

CH – CHBr alc KOH, NaNH 2

Vinylic carbanion
3 2
(more stable)
Ag dust(Powder)
CHCl Nu

3

| 
Zn dust  C  C   Nu    C  C 
CHBr – CHBr 2 2

 (alkyl carbanion)
CHBr (less stable)
| Zn
(i) Acidity of alkynes : Acetylene and other terminal alkynes (1-
CHBr alkynes) are weakly acidic in character
alc KOH, NaNH 2
1
CH = CH – Cl 2
CH Ex. CH  CH  NaNH 2  H  C  C Na   H2
2 2

[Acetylene] 2
HC – COONa (Monosodium acetylide)
| Kolbe’s electrolytic synthesis
HC – COONa The acetylenic hydrogen of alkynes can be replaced by copper (I)
and silver (I) ions. They react with ammonical solutions of cuprous chloride
H O (Laboratory method) and silver nitrate to form the corresponding copper and silver alkynides.
CaC 2
2

Electric arc, 1200 C o

CH  CH  2[Cu(NH 3 )2 ]Cl  Cu  C  C  Cu  2 NH 4 Cl  2 NH 3

2C+ H 2

Berthelot’s process Dicopper acetylide (Red ppt)

(i) Na (ii) R-X
CH  CH  2[ Ag(NH 3 )2 ]NO 3  AgC  C  Ag  2 NH 4 NO 3  2 NH 3
CH – C CH
3

(i) CH MgI (ii) R-X Disilver acetylide (white ppt)

CH – CCHIn reaction with gem dihalide, Alc. KOH is not used for
3

elimination in 2 step.
3
nd This reaction can be used to distinguish between 2-alkynes and 1-
alkynes. 1-alkynes will give this test while 2-alkynes, will not give this test.
 In reaction with vicinal dihalide, if the reactant is 2-butylene
chloride then product is 2-butyne as major product. CH 3  C  CH  2[ Ag( NH 3 )2 ] NO 3  CH 3  C  C  Ag
1- propyne
Preparation of higher alkynes (by metal acetylide)
 Acetylene gives salt with NaNH 2 or AgNO 3 (ammonical) CH 3  C  C  CH 3  2[ Ag(NH 3 )2 ]NO 3  No reaction
which react with alkyl halide to give higher alkyne.
Explanation for the acidic character : It explained by sp
 2CH  CH   Na  C  C  Na 
NaNH 2

2 CH 3 I
hybridisation. We know that an electron in s  orbital is more tightly held
than in a p -orbital. In sp hybridisation s -character is more (50%) as
CH 3  C  C  CH 3
Butyne
compared to sp 2 (33%) or sp 3 (25%), due to large s -character the
 CH 3  C  CH  CH 3  Mg  X  carbon atom is quite electronegative.
(ii) Reaction with formaldehyde
RX
CH 3  C  C  Mg  X  CH 4  CH 3  C  C  R  MgX 2
Alkyne HC  CH  2CH 2 O  CH 2  C  C  CH 2  
Li / NH 3

| |
(2) Physical properties
OH OH
(i) Acetylene is a colourless gas. It has a garlic odour. The odour is
due to presence of impurities of phosphorous and hydrogen sulphide. CH 2  CH  CH  CH 2 OH [Trans-product ]
|
However, pure acetylene has pleasant odour.
OH
 Hydrocarbon 1091
(4) Chemical properties of acetylene O
Red hot tube ||
C6 H 6 or  CH 3  C  CH 3 (Acetone)
H 2 SO 4
Benzene HgSO 4
NH 3
C4 H 5 N  H 2 Thus it is useful for preparing aldehyde from terminal alkyne.
 Pyrrole Reduction of Alkyne : Alkynes add on hydrogen in presence of
S/H S suitable catalysts like finely divided Ni, Pd.
2

 C4 H 4 S CH  CH  H 2  
Ni
CH 2  CH 2 
Ni
CH 3  CH 3
Thiophene H2
40% H SO /1%HgSO
2 4 4
If the triple bond is not present at the end of the carbon chain of
CH 3 CHO
80 C o

the molecule, the alkene formed may be cis and trans depending upon the
with CH COOH CH 3 CO choice of reducing agents.
3

CH 3 CHO  O
Hg , 80 C2+ o

Acetaldehyde CH 3 CO With Na / NH 3 or Li / NH 3 in (liquid ammonia) trans alkene is

Acetic anhydride
almost an exclusive product while catalytic reduction at alkyne affords
CH  CH CHCl CHCl mainly cis alkenes.
Acetylene Cl 2
Alc. 2
2
| |
CHCl KOH R R
2
CHCl 2

(Westron) (Westrosol) CC 

H2

 R  C  C  R  
Li / NH 3
Pd. / BaSO 4 / quinoline
ClAsCl
CHCl H H (Lindlarcatalyst)
2
| (Cadet and Busen reaction) cis
AlCl 3
CHAsCl 2

Lewisite R H
CC
CH COOH
CH 2  CHOOCCH 3
3

Hg
H R
 
Li / NH
CC–CC
+2

3
Vinyl acetate Trans

Hg /HCl 2+ Trans
60 C o
CH 2  CHCl
Vinyl chloride

HCN  
Lindlar

Ba(CN)
CH 2  CHCN Catalyst
Cis
2
Vinyl cyanide
Degree of unsaturation : The number of degree of unsaturation in a
Cu Cl , HCl hydrocarbon is given by
2 2

Chloroprene
NH Cl 4
2n1  2  n 2
Cu O , Where n1 is the number of carbon atoms; n 2 is
2
Cuprene 2
the number of hydrogen atoms.
C 2 Cl 6 (Artificial camphor) For example in C 6 H 12 , the degree of unsaturation is
Hexa chloro ethane
2  6  2  12
 1
Lindlar’s
2
C 2 H 4 (Cis) Tests of unsaturation
Catalyst
Ethylene (a) Baeyer’s reagent : It is 1% KMnO4 solution containing sodium
Ni carbonate. It has pink colour. An aqueous solution of the compound, a few
C2 H 6 drops of Baeyer’s reagent are added, the pink colour of the solution
300°C Ethane
disappears. The decolourisation of pink colour indicates the presence of
unsaturation in the compound.
Na
HC  CNa  XR  HC  C  R  Alkene without any hydrogen atom on the carbon forming
Sol. Acetylide Higher alkynes
R R
O /SeO CHO the double bond CC don't show this test.
|
3 2

CHO R R
Glyoxal
(b) Bromine- carbon tetrachloride test : The compound is dissolved
KMnO COOH in carbon tetrachloride or chloroform and then a few drops of 5% bromine
4

| solution in carbon tetrachloride are added to it, the colour of bromine

Oxidation
COOH disappears. It indicates the presence of unsaturation.
Oxalic acid
Oxidative–Hydroboration : Alkynes react with BH 3 (in THF) and  This test also fails in the case of alkene of the
finally converted into carbonyl compounds. R R
3 CH 3  C  CH  (CH 3  CH  CH )3 B 2
 
BH / THF H O
3 2
CC .
Propyne OH 
R R
CH 3  CH  CHOH    CH 3 CH 2 CHO
Tautomeris es

(Propanal) (5) Uses

 1092 Hydrocarbon
(i) Acetylene is used as an illuminant. CH 3 CH 2 OH    CH 2  CH 2
H 2 SO 4
(ii) It is used for the production of oxy-acetylene flame. The Ethanol
o
170 C Ethene
o
temperature of the flame is above 3000 C . Is is employed for cutting and (vii) Acetylene into propyne (methyl acetylene) : (Ascent)
welding of metals.
(iii) Acetylene is used for artificial ripening of fruits. CH  CH 
 CH  CNa 
Na
 CH  C  CH 3
CH 3 I
Acetylene Monosodium Propyne
(iv) It is used as a general anaesthetic under the name naracylene. acetylide

(v) Acetylene has synthetic applications. It serves as a starting (viii) Propyne into acetylene : (Descent)
material for the manufacture of a large variety of substances.
(vi) On electrical decomposition acetylene produces finely divided CH 3 C  CH   CH 3 CH  CH 2 3 2
Lindlar's catalyst O /H O

carbon and hydrogen. Hydrogen is used in airships. Propyne Propylene

C2 H 2  2C  H 2
CH 3 CHO   CH 3 CHCl 2 
PCl5
 CH  CH
Alc.
KOH Acetylene
(6) Interconversion Acetaldehyde Ethylidene
chloride
(i) Conversion of ethane into ethene : (Alkane into alkene)
(ix) 1-Butyne into 2-pentyne : (Ascent)
CH 3  CH 3  C 2 H 5 Br 
Br2
 CH 2  CH 2
Alc.

Ethane hv Ethyl bromide KOH Ethene

CH 3 CH 2 C  CH   CH 3 CH 2 C  C  Na  
2 NaNH 3 CH I
(ii) Ethene into ethane : (Alkene into alkane) 1  Butyne

CH 2  CH 2 
o CH 3  CH 3
H2
CH 3 CH 2  C  CCH 3
Ethene Ni, 300 C Ethane
2  Pentyne
(iii) Ethane into ethyne (acetylene) : i.e., alkane into alkyne
(x) 1-Butyne into 2-pentanone : (Not more than three steps)
CH 3  CH 3  CH 3 CH 2 Br 
Br2
 CH 2  CH 2 
Alc.

Br2
hv KOH CCl 4
Ethane Ethene
CH 3 CH 2 C  CH   CH 3 CH 2 C  CNa 
NaNH 2

CH 3 I

CH 2 Br  CH 2 Br   CH  CH
Alc. KOH 1 - Butyne ( Liq . NH 3 )

1, 2-Dibromoeth ane or NaNH 2 Ethyne

O
(iv) Ethyne into ethane : (Alkyne into alkane) ||
CH  CH 
o CH 2  CH 2 
H2
o CH 3  CH 3
H2
CH 3 CH 2 C  CCH 3   CH 3 CH 2 CH 2 C CH 3
H 2O , H 2 SO 4
Ethyne Ni, 300 C Ethene Ni, 300 C Ethane 2  Pentyne HgSO 4 2  Pentanone
(v) Ethene into propene : Ascending in alkene series
Separation of alkane, alkene and alkyne
CH 2  CH 2 
 CH 3 CH 2 I 
HI
 CH 3 CH 2 CN 
KCN

[H ]
Reduction
Ethene Iodoethane Propane nitrile The gaseous mixture is passed through ammonical cuprous chloride
(Ethyl cyanide)
solution. The alkyne (acetylene) reacts with Cu 2Cl 2 and forms a red
CH 3 CH 2 CH 2 NH 2   CH 3 CH 2 CH 2 OH
HNO 2
precipitate. It is filtered. The alkyne or acetylene is recovered by
1- Aminopropa ne 1Propanol
decomposition of the precipitate with an acid.
CH 3 CH  CH 2 
 CH 3 CH 2 CH 2 Br 
Alc.

PBr3

Propene KOH 1  Bromopropa ne C2 H 2  Cu 2Cl 2  2 NH 4 OH  C2Cu 2  2 NH 4 Cl  2 H 2O

(Red ppt.)
or CH 2  CH 2 
 CH 3 CH 2 I 32  CH 3 CH 2 CH 3
HI Li (CH ) Cu

Ethene Iodoethane Propane C2Cu 2  2 HNO3  C2 H 2  Cu 2 (NO3 )2


  CH 3 CH 2CH 2Cl  CH 3 CH  CH 2
Cl Alc.
2
The remaining gaseous mixture is passed through concentrated
hv 1- Chloro propane KOH Propene
H 2 SO 4 . Alkene is absorbed. The Hydrogen sulphate derivatives is heated
or CH 2  CH 2 
 CH 3 CH 2 I 
HI
 CH 3 CH 2 CH 3
CH 3 I / Na
at 170 C to regenerate ethene.
o

Propane

C2 H 4  H 2 SO 4  C2 H 5 HSO 4  C2 H 4  H 2 SO 4

  CH 3 CH 2CH 2Cl  CH 3 CH  CH 2
2Cl Alc. 170 o C
hv 1- Chloro propane KOH Propene
The methane or ethane is left behind unreacted.
(vi) Propene into ethene : Descending an alkene series

CH 3  CH  CH 2 3 2 CH 3 CHO 

O /H O
[H ]

Propene Ethanal LiAlH4

Distinction between alkanes, Alkenes and Alkynes

Table : 24.3
Property Alkane (Ethane) Alkene (Ethene) Alkyne (Ethyne)
Molecular formula CnH2n+2(C2H6) CnH2n(C2H4) CnH2n–2(C2H2)
Nature Saturated Unsaturated Unsaturated
Single bond between carbon atoms. Double bond between two carbon atoms. Triple bond between two carbon atoms both
Each carbon atom is sp3-hybridized Both carbon atoms are sp2-hybridized carbon atoms are sp-hybridized
C–C C=C –CC–
Bond length 1.54 Å 1.34 Å 1.20 Å
 Hydrocarbon 1093

Bond energy : 83 Kcal mol–1 146 Kcal mol–1 200 Kcal mol–1
Burning Burns with nonluminous flame Burns with luminous flame Burns with smoky flame
C2H6+7/2O2  2CO2+3H2O C2H4+3O2  2CO2+2H2O C2H2+5/2O2  2CO2+H2O
Reaction with H2 – Forms alkane Forms alkene and alkane
CnH2n + H2 
Ni CnH2n+2 CnH2n + H2 
Ni CnH2n+2
o o
300 C 300 C Alkane
Alkane
C2H4 + H2  C2H6 CnH2n–2 + H2 
Ni CnH2n
o
300 C Alkene
Reation with conc. H2SO4 and – Addition Addition
hydrolysis
C2H4+H2SO4  C2H5HSO4 C2H2 CH3CH(HSO4)2  
H 2O

  C2H5OH
H 2O CH3CHO
Alcohol Aldehyde
Br2/CCl4 – Decolourises Decolourises
Dibromo derivative, Tetrabromo derivative,
C2H4 + Br2  C2H4Br2 C2H2Br4
Baeyer’s reagent (Alk. KMnO4) – Decolourises Decolourises
Glycol is formed Oxalic acid is formed
CH 2 CH 2 OH CH COOH
||  H 2O  O | |||  4 O |
CH 2 CH 2 OH CH COOH
Ammonical Cu2Cl2 – – Red precipitate
CH CCu
| | |  Cu 2 Cl 2  2 NH 4 OH  | | |
CH CCu
(Red)

+ 2NH4Cl + 2H2O
Ammonical silver nitrate – – White precipitate
CH C  Ag
| | |  2 AgNO 3  2 NH 4 OH  | | |
CH C  Ag
+ 2NH4Cl + 2H2O

Cycloalkane (iii) Their boiling points show a gradual increase with increase of
molecular mass. Their boiling points are higher than those of isomeric
(1) Methods of preparation
alkenes or corresponding alkanes.
(i) From dihalogen compounds (Freund reaction): (iv) Their density increase gradually with increase of molecular
mass.
CH Cl CH (3) Chemical properties : Cycloalkanes behave both like alkenes and
+2NaCl
2 2

heat
CH 2
+2Na alkanes in their chemical properties. All cycloalkanes undergo substitution
CH Cl
2
HC
2
CH 2 reaction with halogen in the presence of light (like alkane). All cycloalkane
1,3 Dichloropropane Cyclopropane (lower members) undergo addition reaction (ex. Addition of H 2 , HX , X 2 ).
Further the tendency of forming addition compounds decreases with
(ii) From alkenes : increase in size of ring cyclopropane > Cyclobutane > Cyclopentane.
Zn Cu alloy Relative ring opening of ring is explained by Baeyer strain theory.
CH 3  CH  CH 2  CH 2 I 2   CH 3  CH  CH 2
Propene (i) Addition in spiro cycloalkane : If two cycloalkane fused with one
CH 2 another then addition take place in small ring
Methyl cyclopropane

(iii) From Aromatic compounds + H2

o
+ 3H2  
Ni, 200 C Spiro compound
under pres sure Because small ring is more unstable than large ring
Benzene
(2) Physical properties Cyclohexane Higher cycloalkanes do not give addition due to more stability.
(i) First two members are gases, next three members are liquids (ii) Free radical substitution with Cl2

and higher ones are solids.

(ii) They are insoluble in water but soluble in alcohol and ether.
 1094 Hydrocarbon

CH 2  CH 2  Cl 2 

hv
CH 2  CH Cl  HCl (1) Conjugated dienes : Double bonds are seperated by one single
bond.
CH 2 CH 2 Ex : CH 2  CH  CH  CH 2 (1, 3-butadiene)
Cyclopropa ne Chlorocyclopropane
(2) Cumulative dienes : Double bonds are adjacent to each other.
(iii) Addition reaction
Ex : CH 2  C  CH 2 Propadiene [allene]
Br BrH C – CH – CH Br
2

2 2 2
(3) Isolated or Non-conjugated : Double bonds are separated by
(CCl ) dark 4 1, 3-Dibromopropane more than one single bond.
HBr Ex : CH 2  CH  CH 2  CH  CH 2 (1, 4 pentadiene)
H C – CH CH – CH – CH Br
3 2 2
2 2

1-Bromopropane The general formula is Cn H 2n2 . The predominant member of

CH this class is 1, 3-butadiene.
(i) Conc. H SO
2

CH – CH – CH OH (1) Method of preparation

Cyclopropane 2 4

(ii) H O
3 2 2
(i) From acetylene :
2 1-Propanol
H , Ni 2 HC  CH   HC  C  CH  CH 2 
Cu 2 Cl 2

H2
2
CH – CH – CH NH 4 Cl Vinyl acetylene Pd / BaSO 4
80 C
3 2 3
o

Propane
(iv) Oxidation CH 2  CH  CH  CH 2
1, 3 -Butadiene
CH
(ii) From 1, 4-dichlorobutane :
2

HC CH CH CH COOH
2 2 Cl Cl
2 2

+ 5[O] 

Alk | |
CH 2 CH 2 CH 2 CH 2    CH 2  CH  CH  CH 2
Alc. KOH
HC CH
KMnO4 CH CH COOH
2 2
1,4 -Dichlorobu tane 1, 3 -Butadiene
2 2

CH 2
Adipic acid (iii) From 1,4-butanediol :
Cyclohexane OH OH
| |
Cycloalkene CH 2 CH 2 CH 2 CH 2   CH 2  CH  CH  CH 2
H 2 SO 4

1, 4 -Butanediol heat 1, 3 -Butadiene

Carbocyclic compounds with double bonds in the ring are called
cycloalkenes. Some of the common cycloalkenes are (iv) From butane :
CH 3 CH 2 CH 2 CH 3    CH 2  CH  CH  CH 2
Catalyst
6 n -Butane
o
600 C 1, 3-Butadiene
5 1 (Cr O used as catalyst.)
2 3

(v) From cyclohexene :

4 2
3
Cyclobutene Cyclopentene Cyclohexene 1, 4-Cyclohexadiene  CH 2  CH  CH  CH 2  CH 2  CH 2
1, 3-Butadiene Ethene
Cycloalkenes can be easily obtained by Diels-Alder reaction. These
compounds undergo the electrophilic addition reactions which are (2) Physical property : 1,3-butadiene is a gas.
characteristic of alkenes, while the ring remains intact. Cycloalkenes (3) Chemical properties
(i) Addition of halogens :
decolourise the purple colour of dilute cold KMnO4 or red colour of
CH BrCHBrCH=CH
bromine in carbon tetrachloride.
2 2

3,4-Dibromo-1-butene (1, 2-Addition)

predominates (62%) in non-ionising solvent
CH = CHCH = CH + Br (hexane)
+ Br2
2 2 2

Br
4

1, 3-Butadiene
CCl

Cyclopentene CH BrCH=CH.CH Br2 2

Br 1,4-Dibromo-2-butene (1, 4-Addition)

predominates (70%) in an ionising solvent
1, 2-Dibromo
(acetic acid)
cyclopentane (ii) Addition of halogen acids :
CH CHBrCH=CH
3 2

KMnO (aq.) (1, 2-Addition)

+O + H O 4

2
3-Bromo-1-butene
CH =CH–CH=CH +HBr
2 2
(Major yield at low temp.)
OH
Cyclopent-1-ene
OH CH –CH=CH–CH Br
3 2

Cyclopentane 1,2-diol (1, 4-Addition)

1-Bromo-2-butene
CH (Major yield at high temp.)
(iii) Addition of water :
2

O H2 O
+O 3
O CH 2
CHO CH CHOHCH=CH 3 2

O But-3-en-2-ol
CHO CH =CH–CH=CH +H O
(Cyclohexene) CH 2 2 2

Dienes
2

CH 2
CH CH=CHCH OH
These are hydrocarbon with two carbon-carbon double bonds. 3 2

Dienes are of three types (iv) Polymerisation : But –2-en-1-ol

 Hydrocarbon 1095

nCH 2  CHCH  CH 2  [ CH 2 CH  CHCH 2 ]n

Peroxide

1, 3-Butadiene Buna rubber

Diels-alder reaction :
CH CH 2

CH  Coal tar is a mixture of large numbers of arenes.

H–C CH 2
HC 2

200o C
+ 
 (3) Distillation of coal tar : Arenes are isolated by fractional
distillation of coal tar,
H–C CH 2
HC CH 2

Ethene
Table : 24.4
CH CH 2
2
(Dienophile) Name of the fraction Temperature Main constituents
1, 3-Butadiene Cyclohexene
range (K)
Stability of conjugated dienes : It is explained on(Adduct)
the basis of Light oil (or crude oil) Upto 443 Benzene, toluene, xylene
delocalisation of electron cloud between carbon atoms. fraction
The four  electrons of 1, 3-butadiene are delocalised over all the Middle oil fraction 443-503 Phenol, naphthalene, pyridine
four atoms. This delocalisation of the  electrons makes the molecule (Carbolic oil)
more stable. Heavy oil fraction 503-543 Naphthalene, naphthol and
(Creosote oil) cresol
Green oil (Anthracene 543-633 Anthracene, phenanthrene
oil)
Pitch (left as residue) Non-volatile Carbon
C C C C
 The residue left after fractional distillation of coal-tar is called
pitch.
(4) Isolation of benzene
C C C C– Lightoil   Basic impurities removed 
cold H 2 SO 4

NaOH
[Like pyridene]

Phenols removed   Benzene (255 - 257 K )

distillation

[Acidic impurities]
 - Delocalised Toluene (383 K )
electron’s
General characteristics of arenes
(v) Ozonolysis :
(1) All arenes have general formula [Cn H 2n  6 y] . Where y is
CH 2  CHCH  CH 2  2O3   2 HCHO  OHCCHO
Zn / H 2O
number of benzene rings and n is not less than 6.
O 3
(2) Arenes are cyclic and planar. They undergo substitution rather
than addition reactions.
HO 2
(3) Aromaticity or aromatic character : The characteristic behaviour
CH –O–CH – CH–O–CH
2 2
of aromatic compounds is called aromaticity. Aromaticity is due to extensive
delocalisation of -electrons in planar ring system. Huckel (1931) explained
aromaticity on the basis of following rule.
O O O O Huckel rule : For aromaticity the molecule must be planar, cyclic
system having delocalised (4 n  2) electrons where n is an integer equal
(Diozonide) to 0, 1, 2, 3,------.
Aromatic Hydrocarbon Thus, the aromatic compounds have delocalised electron cloud of
2,6,10 or 14  electrons.
(1) Source of Arenes
4
Source of arenes is coal. It contains benzene, xylene, naphthalene etc. Example : 4n  2  6 ; 4n  4 ; n  1
Arenes are obtained by destructive distillation of coal. 4
(2) Distillation of coal
Benzene 6 electrons
COAL n=1
Heated to 1273-1373 K
(Destructive distillation)

Naphthalene 10 electrons Anthracene 14 electrons

n=2
COKE HOT VAPOURS AND GASES Similarly cyclolpentadienyl anion or tropylium ionn are
= 3 also aromatic
(Solid residue nearly 70%). because of containing 6 electrons (n=1).
It is used as a fuel and as Cooled and passed
reducing agent in metallurgy. H H H
through water
H H 
.. H
H
H 
H
Condensed liquid COAL GAS H H
(Mixture of uncondensed H
gases nearly 17%). Cyclopentadienyl anion 6 Tropyllium ion 6  electrons Cyclopropenyl cation
Allowed to settle, It is used as a fuel. electrons
Hetrocyclic (n=61) electrons (n = 1). (n = 0)
(n=1) compounds also have
two layers are separated

Upper layer Lower layer

.. .. ..
N N
AMMONICAL LIQUOR (nearly COAL TAR (nearly 4-5%) O S
8-10%) Black, viscous liquid having H Furan Thiophene Pyridine
It is used for the preparation of unpleasant odour Pyrrole
(NH4)2SO4 to be used as a
fertilizer.
 1096 Hydrocarbon


3CH  CH 

 Benzene gives cyclohexane by reduction with hydrogen.

Molecules do not satisfy huckel rule are not aromatic.
C6 H 6  3 H 2 O 

Ni

H  Cyclohexane
Cyclopentadiene Cyclopentadienyl cation (b) Objections against Kekule's formula
4 electrons 4 electrons  Unusual stability of benzene.
H ..
 According to Kekule, two ortho disubstituted products are
possible. But in practice only one ortho disubstituted product is known.
 Heat of hydrogenation of benzene is 49.8 kcal/mole, whereas
Cyclooctatetraene Cyclopropenyl anion theoretical value of heat of hydrogenation of benzene is 85.8 kcal/mole. It
8 electrons 4 electrons means resonance energy is 36 kcal/mole.
(4) Antiaromaticity : Planar cyclic conjugated species, less stable  C  C bond length in benzene are equal, (although it contains 3
than the corresponding acyclic unsaturated species are called antiaromatic. double bonds and 3 single bonds) and are 1.39 Å.
Molecular orbital calculations have shown that such compounds have 4 n Kekule explained this objection by proposing that double bonds in
electrons. In fact such cyclic compounds which have 4 n electrons are benzene ring were continuously oscillating between two adjacent positions.
called antiaromatic compounds and this characteristic is called
antiaromaticity.
Example : 1,3-Cyclobutadiene, It is extremely unstable antiaromatic
compound because it has 4 n electrons (n  1) and it is less stable than
1,3 butadiene by about 83.6 KJ mol . –1
(2) Methods of preparation of benzene
(i) Laboratory method :
4 COONa
4n  4 ; n 1 CaO
4 + NaOH + Na CO
heat 2 3

Thus, cyclobutanediene shows two equivalent contributing

structures and it has n  1 . Sodium benzoate Benzene
  (ii) From benzene derivatives
(a) From phenol :
OH
Cyclopropenyl anion Cyclopentadienyl
4 electrons + Zn distill + ZnO
 4 electrons

Benzene
Phenol
(b) From chlorobenzene :
Cycloheptatrienyl anion Cycloctatetraene Cl
8 electrons 8 electrons
+ 2H Ni-Al alloy + HCl
Benzene (C6H6)
NaOH
Benzene is the first member of arenes. It was first discovered by
Faraday (1825) from whale oil. Mitscherllich (1833) obtained it by distillating Chlorobenzene Benzene
benzoic acid with lime. Hofmann (1845) obtained it from coal tar, which is (c) By first preparing grignard reagent of chlorobenzene and then
still a commercial source of benzene. hydrolysed
(1) Structure of benzene : Benzene has a special structure, which is
although unsaturated even then it generally behave as a saturated OH
C 6 H 5 Cl 
 C 6 H 5 MgCl 
Mg
 C 6 H 6  Mg
H 2O
compound. Chlorobenz ene dry ether Phenyl magnesium Benzene Cl
chloride
(i) Kekule's structure : According to Kekule, in benzene 6-carbon
atoms placed at corner of hexagon and bonded with hydrogen and double (d) From benzene sulphonic acid :
bond present at alternate position. SO H 3

(a) Evidence in favour of Kekule's structure

+ 150°-200°C +H SO
 Benzene combines with 3 molecules of hydrogen or three HOH 2 4

HCl,pressure
molecules of chlorine. It also combines with 3 molecules of ozone to form Steam
triozonide. These reactions confirm the presence of three double bonds. Benzene sulphonic acid Benzene
 Studies on magnetic rotation and molecular refraction show the (e) From benzene diazonium chloride :
presence of three double bonds and a conjugated system. N Cl
2

 The synthesis of benzene from three molecule of acetylene also

favour's Kekule's structure. SnCl2
+ 2H +N +HCl
NaOH 2

Benzene
 Hydrocarbon 1097

(f) From acetylene :

HC
+
HC CH red hot tube
+
1500-2000°C
HC CH
Benzene
+ Addition of ozone :
HC
O O
Three molecules of acetylene H
 Cyclic polymerisation takes place in this reaction. C CH
O
HC CH O
(g) Aromatisation : C6 H 14    C6 H 6  4 H 2
Cr2O3 / Al2O3
C CH 3H2O
n  Hexane 500 C
at high pressure
Benzene +3O  3
O Zn
C CH
(3) Properties of benzene HC CH O
O C
(i) Physical properties C
O O CHO
H
(a) Benzene is a colourless, mobile and volatile liquid. It's boiling 3 + 3H O
Benzene triozonide 2 2

point is 80°C and freezing point is 5.5°C. It has characteristic odour. Benzene CHO
(b) It is highly inflammable and burns with sooty flame. (b) Substitution reactions : Glyoxal

(c) It is lighter than water. It's specific gravity at 20°C is 0.8788. Nucleophilic substitution :
Unimolecular : Mostly uncommon in aromatic substitution, there is
(d) It is immiscible with water but miscible with organic solvents
only one example which obtain in benzene diazonium dichloride.
such as alcohol and ether.
(e) Benzene itself is a good solvent. Fats, resins, rubber, etc. dissolve Ar  N 2   N 2  Ar 

(Slow )
HOH ArOH
Arenediazonium
in it. cation (Fast) Phenol
X –

(f) It is a non-polar compound and its dipole moment is zero. ArX

(g) It is an extremely poisonous substance. Inhalation of vapours or  Bimolecular : Aryl halide
absorption through skin has a toxic effect.
Z Z
(ii) Chemical properties : Due to the presence of  electron clouds
above and below the plane benzene ring, the ring serves as a source of ..
Y attaches to the positively
electrons and is easily attacked by electrophiles (Electron loving reagents). Y + Y + charged carbon atom (slow)
Hence electrophilic substitution reaction are the characteristic reactions of
aromatic compounds. Y Z Y Z Y Z Y Z Y
Substitution reactions in benzene are prefered rather than addition 
are due to the fact that in the former reactions resonance stabilised benzene  (Fast)
ring system is retained while the addition reactions lead to the destruction or +Z
of benzene ring. Principal reactions of benzene can be studied under three 
heads, (Resonating structure of the
(a) Addition reactions hexadienyl anion)
Example :
(b) Substitution reactions OH Cl
Cl OH
(c) Oxidation reactions
(a) Addition reactions : In which benzene behaves like unsaturated OH+ (Slow) (Fast) + Cl
hydrocarbon.
Addition of hydrogen : Benzene reacts with hydrogen in the Phenol
presence of nickel (or platinum) as catalyst at 150°C under pressure to form  Elimination-addition mechanism (Benzyne mechanism)
cyclohexane. * Cl *
– HCl
NH
Ni H 3

+ 3H or CH
2
150°C,pressure 6 12

(Benzene)
Benzene Cyclohexane

Addition of halogen : * NH * *NH 2
*H
H
3

 +
+  NH
C H

2

NH 3

(47%) (53%)
HC CH
hv  Electrophilic substitution reaction : Benzene undergoes this
+ 3Cl Cl H reaction because it is an electron rich system due to delocalized -
2

HC CH
electrons.
C
C H
H Cl 
H C C E ;
Cl H + (Slow)
Benzene E
H Cl
C C Carbonium ion
Cl H
( - complex)
C
 1098 Hydrocarbon

H
 E
E
 (Fast)
Nu: + H – Nu
+
 H H H Substitution product

E E E
 

Resonance forms of carbonium ion (Arenium ion) Table : 24.5

Electrophile (E) Name Source Name of substitution reaction

Cl  Chloronium Cl 2  AlCl3 or FeCl3 Chlorination

Br  Bromonium Br2  AlBr3 or FeBr3 Bromination

NO 2 Nitronium HNO3  H 2 SO 4 Nitration

SO 3 Sulphur trioxide Conc. H 2 SO 4 , Fuming sulphuric acid Sulphonation

R Alkyl carbonium RX  AlX3 (X  Cl or Br), ROH  H  Friedel-Craft's (Alkylation)

 Acyl carbonium RCOCl  AlCl3 Friedel-Craft's (Acylation)

R C  O

 Free radical aromatic substitution : The aromatic substitution When vapours of benzene and air are passed over vanadium
reactions which follow free radical mechanisms are very few and have pentoxide at 450 – 500°C, maleic anhydride is obtained.
limited synthetic value. But some typical example of these reactions are:

(CH 3 )3 COOC  (CH 3 )3   2(CH 3 )3 C O 
heat
CHCO
C6 H 6  9[O]  | |
V2O5
O  2CO 2  2 H 2 O
450  500 C CHCO

2CH 3  2CH 3 COCH 3 Maleicanhydride

X X X X  Strong oxidising agents converts benzene slowly into CO 2 and

. H water on heating.
+ CH 3 . CH + 3
. + . H (d) Reduction :
CH
o- 3

CH
(x = Cl, OCH3, NO2, CH3 etc.) H CH m-Intermediate 2 +
3

3
+12HI +6I 2

X X Benzene Cyclohexane Methylcyclopentane

X
CH 3
. (iii) Uses : (a) In dry cleaning (b) As a motor fuel when mixed with
+ + + H petrol. (c) As a solvent. (d) In the manufacture of gammexane (As
CH insecticide). (e) In the preparation of nitrobenzene, chlorobenzene, benzene
m
3

O sulphonic acid, aniline, styrene, etc. Many of these are employed for making
The mechanism of chlorination of benzene CH at high temperature is 3
dyes, drugs, plastics, insecticides, etc.
similar to that of the free radical aliphatic substitution
p Directive effect in substituted benzene derivatives
. . (1) Directive effect in mono substituted benzene derivatives : The
Cl 2  Cl  Cl (Chain initiation)
substituent already present on the benzene ring directs the incoming
. . substituent to occupy ortho (2 or 6), meta (3 or 5) or para (4) position.
C6 H 6  Cl  C6 H 5  HCl (H- abstraction) This direction depends on the nature of the first substituent and is called
directive or the orientation effect.
. . The substituent already present can increase or decrease the rate of
C6 H 5  Cl 2  C6 H 5 Cl  Cl (Chain propagation)
further substitution, i.e., it either activates or deactivates the benzene ring
towards further substitution. These effects are called activity effects.
(c) Oxidation : 2C6 H 6  15O2 12CO 2  6 H 2 O
H  6530 kJ/mole
 Hydrocarbon 1099
There are two types of substituents which produce directive effect (ii) Those which direct the incoming group to meta-position only
are, (Neglecting ortho- and para-positions all together).
(i) Those which direct the incoming group to ortho- and para-
positions simultaneously (Neglecting meta all together).

Ortho-para directors Meta directors

.. .. .. .. ..– Moderately deactivating
Strongly activating  NH 2 , NHR , NR 2 , – .OH
. , – .O. : C  N ,SO 3 H , COOH ,COOR, CHO, COR
.. .. .. .. Strongly deactivating  NO 2 , NR 3  ,CF3 ,CCl 3
Moderately activating  NHCOCH 3 ,  NHCOR , –. OCH
. , – .OR
3 .
Weakly activating CH 3 ,C2 H5 ,R,C6 H5
.. .. .. ..
Weakly deactivating – . F.: , – .Cl. : , – .Br. : , –. I. : ,

Theory of ortho – para directing group (2) Directive effect in disubstituted benzene
:S S S S (i) If the directive effects of two substituents reinforce, then a single
:S
product is formed.
.. .. Example :
,i.e.,
CH 3 CH 3
CH 3

NO
.. 2

 S Ortho attack S S ; Nitration

Ortho
E +NO
 
2


+ E + NO 2
(m) NO 2
NO 2

Thus, both (CH 3 , NO 2 ) direct further substitution to the same

 Ortho product
E position (Ortho with respect to CH ). 3

Para attack Para product (ii) If the directing effect of two groups oppose each other strongly
The above mechanism is followed when S is
activating groups win over deactivating or weakly activating group. The
OH,  NH 2 ,Cl,  Br,I,OR, NR 2 , NHCOR etc. sequence of directing power is
CH 3
CH 3
CH 3
CH 3
 NH 2  OH  OCH 3   NHCOCH 3  C6 H 5  CH 3  meta
.. .. directors
OH
OH OH Directs
(Powerful
Directs
activator)
 Example :
In methyl or alkyl group, the +I effect .of. the methyl group or alkyl
group initiates the resonance effect.
Thus, methyl or alkyl group directs all electrophiles to ortho and CH 3
CH 3
CH 3

para positions. Directs Directs

OH OH
Theory of meta directing group : The substituent, S withdraws
electrons from ortho and para positions. Thus, m-position becomes a point Br
of relatively high electron density and further substitution by electrophile Br 2

occurs at meta position. For example,  NO 2 group is a meta directing FeBr 3

(Electron withdrawing). Its mechanism can be explained as :

CH 3
CH 3

(iii) There is normally little substitution when the two groups are
meta to each other. Aromatic rings with three adjacent substituents are
O 
O O  O O  O generally prepared by same other routes.
N N N
CH 3
Too hindered position

O  O O  O
N N
 Cl
..

Toluene, methyl benzene or phenyl methane
All meta-directing groups have either a partial positive charge or a
full positive charge on the atom directly attached to the ring.
 1100 Hydrocarbon
Toluene is the simplest homolouge of benzene. It was first obtained
by dry distillation of tolubalsam and hence named toluene. It is
commercially known as tolual.
(1) Methods of preparation
(i) From benzene [Friedel-craft's reaction] :
CH 3

(2) Physical properties

AlCl + HCl (i) It is a colourless mobile liquid having characteristic aromatic
+CH Cl 3
3

odour.
 Alkyl halide employed may undergo anToluene
Benzene isomeric change (ii) It is lighter than water (sp. gr. 0.867 at 20°C).
CH 3 (iii) It is insoluble in water but miscible with alcohol and ether in
C6 H 6  ClCH 2 CH 2 CH 3  C6 H 5 CH  HCl
AlCl3
all proportions.
n  Propyl chloride CH 3
Isopropyl benzene (65 70%) (iv) Its vapours are inflammable. It boils at 110°C and freezes at –
(Cumene) 96°C.
 Catalysts can be used in place of anhydrous AlCl3 are, (v) It is a good solvent for many organic compounds.
AlCl3  SbCl 3  SnCl 4  BF3  ZnCl 2  HgCl2 (vi) It is a weak polar compound having dipole moment 0.4D.
(ii) Wurtz fitting reaction : (3) Chemical properties : Toluene shows the behaviour of both an
alipatic and an aromatic compound.
Br+2Na+BrCH Ether CH
CH +2NaBr 3

Side chain (Aliphatic)

3 3

Bromobenzene Methyl bromide Toluene

(iii) Decarboxylation : Benzene ring (Aromatic)
CH 3
C6 H 4  NaOH    C6 H 5 CH 3  Na 2 CO 3
Soda lime
(i) Electrophilic substitution reactions : Aromatic character (More
COONa Toluene
(o-,m- or p- )
reactive than benzene) due to electron releasing nature of methyl group.
Sodium toluate
(iv) From
CHcresol : CH CH CH
3
CH 3
3 3
3

OH E
heat 
+Zn + ZnO + E +
Electrophile
o-Cresol Toluene   
(v) From toluene sulphonic acid : o-Derivative E
 E may be Cl, NO 2 , SO 3 H etc.
+

CH 3 CH 3
p-Derivative
(ii) Reactions of side chain
+HOH Boil +H SO (a) Side chain halogenation : CH Cl
CH
2 4

2
3

SO H Toluene Cl
Cl
2

p-Toluene sulphonic acid

2
UV
(vi) From toluidine : UV
CH CH
3
3
CH 3
Toluene Benzyl chloride
NaNO C H OH
2
2 5

+N +CH CHO+HCl CHCl CCl

HCl 2 3 2 3

NH 2
N Cl2
Toluene Cl
2

p-Toluidine p-Toluene diazonium chloride UV

(vii) From grignard reagent :
MgBr CH 3
Benzal chloride Benzo trichloride
 Benzyl chloride on hydrolysis with aqueous caustic soda forms
+MgBr benzyl alcohol.
+CH Br 3
2

C6 H 5 CH 2 Cl  NaOH  C6 H 5 CH 2 OH  NaCl

Phenyl magnesium bromide Toluene (Benzyl chloride)
(viii) Commercial preparation
From coal tar : The main source of commercial production of  Benzal chloride on hydrolysis forms benzaldehyde.
toluene is the light oil fraction of coal-tar. The light oil fraction is washed C6 H 5 CHCl 2  2 NaOH  C6 H 5 CH (OH )2  2 NaCl
with conc. H 2 SO 4 to remove the bases, then with NaOH to remove (Benzal chloride) 
acidic substances and finally with water. It is subjected to fractional C6 H 5 CHO  H 2 O
distillation. The vapours collected between 80 110C is 90% benzol  Benzo trichloride on hydrolysis forms benzoic acid.
which contains 70  80% benzene and 14  24% toluene. 90% benzol
is again distilled and the portion distilling between 108 110C is C6 H 5 CCl 3  3 NaOH  C6 H 5 C(OH )3  3 NaCl
(Benzotri chloride) 
collected as toluene. C6 H 5 COOH  H 2 O
(ix) From n- heptane and methyl cyclohexane
CH 3
(b) Oxidation :
|  With hot acidic KMnO : 4

CH 2
CH COOH
CH 3
3

HC CH
2 3

Cr O / Al O KMnO / H +

2 3 2 3
4

+ HO
3[O]
2

500-550°C
HC CH 150 atms
2 2
Toluene Benzoic acid
Toluene
CH 2

n-Heptane
 Hydrocarbon 1101
 TNT is also used as a mixture of aluminium nitrate, alumina and
charcoal under the name ammonal.
T.N.B. (Tri-nitro benzene)
Preparation :
 With acidic manganese or chromyl chloride (Etards reaction) : CH 3
CH 3

CH 3
CHO ON NO
2 2

H SO
2 4
K Cr O
2 2 7

CrO C
+ 2[O]
2 2

+H O2 HNO 3
H SO2 4

Toluene Benzaldehyde Toluene

NO
 All alkyl benzenes on oxidation with hot acidic KMnO4 or COOH 2

ON NO ON NO
Na 2 Cr2 O7 form benzoic acid. The length of the side chain does not 2 2 2
2

Soda
matter. lime
(c) Hydrogenation :
R R NO 2
NO 2

T.N.B.
+ 3H 2
Na / liquid NH – C H OH 3 2 5
Properties and uses: It is colourless solid (M.P. = 122°C). It is more
Birch reduction explosive than T.N.T. and used for making explosive.
Alkyl benzene Alkyl cyclohexane Xylenes (Dimethyl benzene) C6H4(CH3)2
(d) Combustion : C6 H 5 CH 3  9 O2  7 CO 2  4 H 2 O
(e) Ozonolysis : The molecular formula, C 8 H 10 represents four isomers.
O O CH 3
CH CH CH
H 3
3 2 5

CH CH
C O 3

HC CH O
C CH Zn
+3O  O
3

CH HOH
CH C O CH
HC 3

C O C o-Xylene m-Xylene CH Ethyl benzene

3

H O O p-Xylene
These are produced along with benzene, toluene and ethylbenzene
Toluene
Triozonide
CH –C=O CHO when aromatisation of C 6  C 8 fraction of petroleum naphtha is done.
3

+2 + 3H O 2 2
The xylenes are isolated from the resulting mixture (BTX) by fractional
H – C=O CHO distillation.
(4) Uses Methyl glyoxal Glyoxal These can be prepared by Wurtz – Fittig reaction. A mixture of
(i) In the manufacture of benzyl chloride, benzal chloride, benzyl bromotoluene and methylbromide is treated with sodium in dry ethereal
alcohol, benzaldehyde, benzoic acid, saccharin, etc. solution to form the desired xylene.
(ii) In the manufacture of trinitrotoluene (TNT), a highly explosive CH 3
CH 3

substance. Br
CH 3

(iii) As an industrial solvent and in drycleaning. + 2Na + BrCH 3 + 2NaBr

(iv) As a petrol substitute.
(v) In the manufacture of certain dyes and drugs. o-Bromotoluene
o-Xylene
T.N.T. (Tri-nitro toluene) CH 3
CH 3

CH 3

Preparation : + 2Na + BrCH + 2NaBr

3

+ 3HNO H SO
3
2 4

Br CH 3

Fuming m-Bromotoluene m-Xylene

Toluene CH CH 3
CH 3

ON NO
2 2
+ 2Na + BrCH 3
+ 2NaBr
+ 3H O 2

Br CH
Properties : It is pale yellow crystalline solid NO
3

(M.P. = 81°C). p-Xylene

p-Bromotoluene
2

These can also be obtained by Friedel – craft's synthesis,

Uses :  It is used as an explosive in shells, bombs and torpedoes
 m-Xylene can be obtained from mesitylene.
under the name trotyl.
Xylenes are colourless liquids having characteristic odour. The
 When mixed with 80% ammonium nitrate it forms the explosive boiling points of three isomers are,
amatol.
o-Xylene=144°C; m-Xylene=139°C; p-Xylene=138°C.
 1102 Hydrocarbon
Xylenes undergo electrophilic substitution reactions in the same chain (Electrophilic addition). However, the side chain double bond is more
manner as toluene. Upon oxidation with KMnO4 or K 2 Cr2 O7 , Xylenes susceptible to electrophilic attack as compared to benzene ring.
At lower temperature and pressure, it reacts with hydrogen to
form corresponding dicarboxylic acids. produce ethylbenzene and at higher temperature and pressure, it is
COOH COOH converted into ethyl cyclohexane.
COOH CH = CH2 CH CH3 CH CH3
2 2

, ,
H / Ni H / Ni
COOH
2 2

COOH 20°C, 3 atm 125°C, 110 atm

Phthalic acid Isophthalic acid
Xylenes are used in the manufacture of lacquers and asCOOH
solvent for
Terephthalic acid Styrene Ethyl benzene Ethyl cyclohexane
rubber. o-Xylene is used for the manufacture of phthalic anhydride. With bromine, it gives the dibromide.
Ethyl benzene (C6H5C2H5)
CH = CH CHBr.CH Br
It can be prepared by the following reactions, 2 2

(1) By Wurtz-Fittig reaction :

+ Br 2

C 6 H 5 Br  2 Na  BrC2 H 5  C 6 H 5 C 2 H 5  2 NaBr

Styrene Styrene dibromide
(2) By Friedel-craft's reaction : Halogen acids add to the side chain.

C 6 H 5 H  BrC2 H 5   C 6 H 5 C 2 H 5  HBr

AlCl3 C 6 H 5 CH  CH 2  HX  C 6 H 5 CHXCH 3
Preparation of ring substituted styrenes is not done by direct
(3) By catalytic reduction of styrene :
halogenation but through indirect route.
CH CH3 CH CH3
C 6 H 5 CH  CH 2  H 2  C 6 H 5 CH 2 CH 3 2 2

(4) By alkyl benzene synthesis : FeCl3 Cl2

+ Cl
2

hv
C 6 H 5 H  H 2 C  CH 2    C 6 H 5 CH 2 CH 3
AlCl3 , HCl
95 C ,Pressure
CHClCH CH = CH
It undergoes electrophilic substitution reactions in the same way as
3

Cl 2

toluene. When oxidised with dil. HNO 3 or alkaline KMnO4 or chromic Alc.. KOH
acid it forms benzoic acid. Heat

C 6 H 5 C 2 H 5 
 C 6 H 5 COOH
[O ]

When oxidised underCldrastic conditions, the side chain

Cl is completely
Styrene (C6H5CH=CH2) oxidised to a carboxyl group.
It is present in storax balsam and coal-tar in traces.
CH = CH2 COOH
(1) Preparation
(i) Dehydrogenation of side chain of ethylbenzene : [O]
CH CH2 3
CH = CH 2
KMnO 4

AlCl 600°C In presenceStyrene Benzoic acidfree radical

of peroxides, styrene undergoes
+ CH = CH
2 2
3

Cr O / Al O polymerisation resulting in the formation of polystyrene – an industrially

2 3 2 3

important plastic.
Benzene Ethylbenzene Styrene  
(ii) Decarboxylation of cinnamic acid : This is the laboratory  
preparation and involves heating of cinnamic acid with a small amount of nC 6 H 5 CH  CH 2   CH  CH 2 
Peroxide

quinol.  | 
 C6 H 5 
C 6 H 5 CH  CHCOOH   C 6 H 5 CH  CH 2  CO 2
Quinol
 n
(iii) Dehydration of 1-phenyl ethanol with H SO : 2 4
Co-polymers of styrene with butadiene and other substances are also
important since many of them are industrially useful products such as SBR
C 6 H 5 CHOHCH 3   C 6 H 5 CH  CH 2
H 2 SO 4
( A rubber substitute).
 H 2O
(iv) Dehydration of 2-phenyl ethanol with ZnCl 2
: Bi-phenyl (C6H5 – C6H5)
C 6 H 5 CH 2 CH 2 OH   C 6 H 5 CH  CH 2
ZnCl 2 , heat
 H 2O It occurs in coal-tar. It is the simplest example of an aromatic
(v) Dehydrohalogenation of 1-phenyl-1-chloro ethane : On heating hydrocarbon in which two benzene rings are directly linked to each other.
with alcoholic potassium hydroxide, a molecule of hydrogen chloride is (1) Methods of formation
eliminated by the chloroderivative. (i) Fittig reaction : It consists heating of an ethereal solution of
C 6 H 5 CHClCH 3   C 6 H 5 CH  CH 2
Alc.KOH
bromobenzene with metallic sodium.
Heat
(2) Properties : It is a colourless liquid, boiling point 145°C. On
Br +2Na + Br + 2NaBr
keeping, it gradually changes into a solid polymer called metastyrene. The
polymerisation is rapid in sunlight or when treated with sodium. It shows
properties of benzene ring (Electrophilic substitution) and unsaturated side
 Hydrocarbon 1103
(ii) Ullmann biaryl synthesis : Iodobenzene, on heating with copper common functional groups such as C=O, NO and C  N remain
2

in a sealed tube, forms biphenyl. The reaction is facilitated if a strong unaffected,

electron withdrawing group is present in ortho or para position.
 The order of reactivity of primary (1 ), secondary (2 ) and tertiary
o o

I+ 2Cu + I + 2CuI (3 ) hydrogens in alkanes follows the sequence : 3 > 2 > 1 .

o o o o

(iii) Grignard reaction : Phenyl magnesium bromide reacts with

bromo benzene in presence of CoCl 2 .

MgBr + Br CoCl 2

+ MgBr 2

(2) Properties : It is a colourless solid, melting point 71°C. It

undergoes usual electrophilic substitution reactions. Since aryl groups are
electron withdrawing , they should have deactivating and m-orientating
effect. But, it has been experimentally shown that presence of one benzene
ring activates the other for electrophilic substitution and directs the
incoming group to o- and p- positions. It has been shown that
monosubstitution in the bi-phenyl results in the formation of para isomer as
the major product.
Another special feature of the biphenyl is the behaviour towards
second substitution in a monosubstituted biphenyl. The second substituent
invariably enters the unsubstituted ring in the ortho and para position no
matter what is the nature of substituent already present.
HNO / H SO
3 2 4

NO 2

HNO / H SO
3 2 4

ON 2
NO
2

 Octane number may be less than zero (e.g., n-Nonane has an

octane number-45) and higher than 100 (e.g., Triptane or 2, 3, 3-
Trimethylbutane has an octane number of 124).
 To avoid lead pollution, a new compound cyclopentadienyl manganese
carbonyl
CO
– Mn CO
CO
(called as AK-33-X) is used as antiknock now a days in developed countries
(unleaded pertol).
 Acetylene has a garlic odour when impure due to impurities of
phosphine and hydrogen sulphide.
 Fluorination is a violent reaction and can be controlled by diluting
fluorine with nitrogen.
 The relative acidic character of water, alcohols acetylene, ammonia,
ethylene and ethane follows the order :
H O > ROH> HC  CH >CH > CH = CH > CH –CH .
2 3 2 2 3 3

Obviously, the basic character of their conjugate bases follows the

reverse order, i.e.,
CH CH >CH = CH > NH > HC  C >RO > HO .
3
–

2 2
– –

2
– – –

 Wilkinson’s catalyst : (Triphenylphosphine) rhodium, (PPh ) RhCl is 3 3

called wilkinson’s catalyst. It reduces alkenes and alkynes while other