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Unit – 12 & 13
ORGANIC CHEMISTRY
Preparation of Alkanes

i. Wurtz Reaction
Alkyl halides on treating with sodium metal in presence of dry
ether, a higher alkane containing twice the number of carbon atoms
present in the alkyl halide is formed. This reaction is called Wurtz
Reaction.
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
𝐶𝐻3 − 𝐵𝑟 + 2𝑁𝑎 + 𝐵𝑟 − 𝐶𝐻3 → 𝐶𝐻3 − 𝐶𝐻3 + 2𝑁𝑎𝐵𝑟
(Bromomethane Or Methyl bromide) (Ethane)
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
𝐶𝐻3 − 𝐶𝐻2 − 𝐵𝑟 + 2𝑁𝑎 + 𝐵𝑟 − 𝐶𝐻2 − 𝐶𝐻3 → 𝐶𝐻3 − 𝐶𝐻2 − 𝐶𝐻2 − 𝐶𝐻3 + 2𝑁𝑎𝐵𝑟
(Bromoethane Or Ethyl bromide) (Butane)
Previous HSE Questions
𝑸𝟏 . Complete the reaction
𝒅𝒓𝒚 𝒆𝒕𝒉𝒆𝒓
𝑪𝑯𝟑 − 𝑪𝑯𝟐 − 𝑩𝒓 + 𝑵𝒂 → ………… + …………
𝑸𝟐 . Complete the reaction
𝒅𝒓𝒚 𝒆𝒕𝒉𝒆𝒓
𝑪𝑯𝟑 − 𝑩𝒓 + 𝑵𝒂 → ………… + …………
𝒅𝒓𝒚 𝒆𝒕𝒉𝒆𝒓
𝑸𝟑 . 𝟐𝑪𝑯𝟑 − 𝑪𝒍 + 𝑵𝒂 → 𝑩, 𝑰𝒅𝒆𝒏𝒕𝒊𝒇𝒚 𝑩?
𝑨𝒏𝒔: 𝑪𝑯𝟑 − 𝑪𝑯𝟑 (Ethane)
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
𝐶𝐻3 − 𝐶𝑙 + 2𝑁𝑎 + 𝐶𝑙 − 𝐶𝐻3 → 𝐶𝐻3 − 𝐶𝐻3 + 2𝑁𝑎𝐶𝑙
(Ethane)
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𝑸𝟒 .Explain the reaction between sodium metal and

bromomethane in dry ether?
𝑸𝟓 . What is Wurtz reaction ? Give an example ?
ii. Kolbe’s Electrolytic Method
An aqueous solution of sodium or potassium salt of a carboxylic
acid on electrolysis gives alkane containing even number of carbon
atoms at the anode.
𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑠𝑖𝑠
2𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎 + 2𝐻2 𝑂 → 𝐶𝐻3 − 𝐶𝐻3 +2𝐶𝑂2 + 2𝑁𝑎𝑂𝐻 + 𝐻2
2[H – OH] (ethane – At anode)
Previous HSE Questions
𝑸𝟏 . How will you prepare ethane by Kolbe’s electrolytic
method?
𝑸𝟐 . Complete the reaction?
𝑬𝒍𝒆𝒄𝒕𝒓𝒐𝒍𝒚𝒔𝒊𝒔
𝑪𝑯𝟑 𝑪𝑯𝟐 𝑪𝑶𝑶𝑲 → …………
Ans : 𝐶𝐻3 − 𝐶𝐻2 − 𝐶𝐻2 − 𝐶𝐻3 (𝐵𝑢𝑡𝑎𝑛𝑒)
The reaction is Kolbe’s electrolysis
𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑠𝑖𝑠
2𝐶𝐻3 − 𝐶𝐻2 − 𝐶𝑂𝑂𝐾 +2𝐻2 𝑂 → 𝐶𝐻3 − 𝐶𝐻2 − 𝐶𝐻2 − 𝐶𝐻3 + 2𝐶𝑂2 + 2𝐾𝑂𝐻 + 𝐻2
2[H - OH] (Butane)
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Conformations

The different spatial arrangements of atoms in a molecule which

arise due to free rotation about carbon – carbon single bond are called
conformations or conformers or rotamers.

Conformation of ethane (𝑪𝑯𝟑 − 𝑪𝑯𝟑 )

Two extreme conformations of ethane are:-
(i) Eclipsed Conformation
(ii) Staggered Conformation
Eclipsed and staggered conformation can be represented by
Newman and Sawhorse projections.
Newman’s Projections of ethane (𝑪𝑯𝟑 − 𝑪𝑯𝟑 )
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Sawhorse projection of ethane (𝑪𝑯𝟑 − 𝑪𝑯𝟑 )

Eclipsed form

Staggered form

Relative stability of conformations

 In Eclipsed conformation, the hydrogen atoms attached to the two
carbon atoms are close together (minimum distance between
hydrogen atoms) so the repulsive forces are maximum (maximum
torsional strain) and it is less stable.
 In staggered conformation, the hydrogen atoms attached to the two
carbon atoms are far apart (maximum distance between hydrogen
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atoms) so the repulsive forces are minimum (minimum torsional

strain) and it is more stable.
∴ Staggered conformation is more stable than eclipsed
conformation.
Note:-
The repulsive interaction between the adjacent bonds in a
conformation is called torsional strain.
Previous HSE Questions
𝑸𝟏 . Draw Newman’s and Sawhorse projections of the two
conformers of ethane. Which among these is more
stable? Justify?
𝑸𝟐 . The repulsive interaction between the adjacent bonds in
a conformation is called _______
Ans:- torsional strain
𝑸𝟑 . Draw the Sawhorse projections of the eclipsed and
staggered conformations of ethane ?
𝑸𝟒. Draw the Newman projections of the eclipsed and
staggered conformations of ethane molecule?
Markovnikov’s Rule
Markovnikov’s rule states that, when an unsymmetrical
reagent is added to an unsymmetrical alkene, the negative
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part of the reagent gets attached to the carbon atom which

carries lesser number of hydrogen atoms.

3 2 1 3 2 1
𝐶𝐻3 − 𝐶𝐻 = 𝐶𝐻2 + 𝐻 − 𝐵𝑟 → 𝐶𝐻3 − 𝐶𝐻 − 𝐶𝐻3 + 𝐶𝐻3 − 𝐶𝐻2 − 𝐶𝐻2 − 𝐵𝑟
|
𝐵𝑟
(Propene) 2 -bromo propane 1 – bromopropane
(major product) (minor product)
Note:- Addition of hydrogen halides (𝐻𝐶𝑙, 𝐻𝐵𝑟, 𝐻𝐼) to an
unsymmetrical alkenes take place according to Markovnikov’s
Rule.
Previous HSE Questions
𝑸𝟏 . Analyse the following reaction
𝑪𝑯𝟑 − 𝑪𝑯 = 𝑪𝑯𝟐 + 𝑯𝑩𝒓 → 𝑨 + 𝑩
If A is the major product and B is the minor product
a) Identify A and B
b) Name the rule related
Ans: Markovnikov’s rule
𝑸𝟐 . Illustrate Markovnikov’s rule taking example of propene.
𝑸𝟑 . From the following, select the one in which Markovnikov’s rule
is best applicable.
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(i) 𝑪𝟐 𝑯𝟒 + 𝑯𝑪𝒍
(ii) 𝑪𝟑 𝑯𝟔 + 𝑩𝒓𝟐
(iii) 𝑪𝟑 𝑯𝟔 + 𝑯𝑩𝒓
(iv) 𝑪𝟑 𝑯𝟖 + 𝑪𝒍𝟐
Ans:𝑪𝟑 𝑯𝟔 + 𝑯𝑩𝒓 [𝐶3 𝐻6 (Propene) – unsymmetrical alkene, HBr
– unsymmetrical reagent]
Anti-Markovnikov Addition [Peroxide effect or Kharash
effect]
When HBr is added to an unsymmetrical alkene in presence of
an organic peroxide (benzoyl peroxide), addition takes place
against Markovnikov’s rule. This addition reaction is known as
peroxide effect or Kharash effect.
𝑂𝑟𝑔𝑎𝑛𝑖𝑐 𝑝𝑒𝑟𝑜𝑥𝑖𝑑𝑒
𝐶𝐻3 − 𝐶𝐻 = 𝐶𝐻2 + 𝐻𝐵𝑟 → 𝐶𝐻3 − 𝐶𝐻2 − 𝐶𝐻2 − 𝐵𝑟
(𝐶6 𝐻5 𝐶𝑂)2 𝑂2

(Propene) (1 – bromopropane)
(major product)
Previous HSE Questions
𝑸𝟏 . Explain Kharash Effect?
𝑸𝟐 . Predict the major product in the following reaction.
𝑂𝑟𝑔𝑎𝑛𝑖𝑐 𝑝𝑒𝑟𝑜𝑥𝑖𝑑𝑒
𝐶𝐻3 − 𝐶𝐻 = 𝐶𝐻2 + 𝐻𝐵𝑟 → … … … … … … ….

𝑸𝟑 . Predict the major product in the reaction

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(𝐶6 𝐻5 𝐶𝑂) 𝑂2
2
𝐶𝐻3 − 𝐶𝐻 = 𝐶𝐻2 + 𝐻𝐵𝑟 → ……………………

Lindlar’s Catalyst
Lindlar’s catalyst is Pallabised charcoal (Pd/C)
Previous HSE Question
Q. What is Lindlar’s Catalist?
Ans: Lindlar’s catalyst is Pallabised charcoal (Pd/C)
Reactions of Alkenes
i. Ozonolysis
Ozonolysis of alkenes involves the addition of ozone molecule
(O3 molecule) to alkene to form ozonide and then cleavage of
the ozonide by zinc dust and water to give aldehyde and
ketones.
i. Ozonolysis of Propene
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ii. Ozonolysis of Ethene

Previous HSE Questions

𝑸𝟏 . Give the chemical equations for the steps involved in the
ozonolysis of propene?
Ans:- [Ozonolysis of Propene Refer page 8]
𝑸𝟐 . An alkene on ozonolysis followed by the reduction of the ozonide
by zinc dust and water gives a mixture of ethanal and methanal?
(a) Identify the alkene?
Ans:- Propene [𝐶𝐻3 − 𝐶𝐻 = 𝐶𝐻2]
(b) Illustrate the above reaction using chemical equation?
Ans:- [Refer ozonolysis of propene Page No: 8]
𝑸𝟑 . An alkene ‘A’ on ozonolysis give two molecules of
formaldehyde (ethanal).Write the name of ‘A’ and the chemical
equation of ozonolysis.
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Ans:- ‘A’ is 𝐶𝐻2 = 𝐶𝐻2 (ethene) [Refer Ozonolysis of ethene

Page No: 8]
𝑸𝟒 . Identify A, B and C.
Ans:- [Refer ozonolysis of propene Page No: 8]

ii. Oxidation of Alkenes

Baeyer’s test
Baeyer’s reagent is cold dilute alkaline 𝐾𝑀𝑛𝑂4 solution
Alkenes on oxidation with cold, dilute alkaline 𝐾𝑀𝑛𝑂4 solution
(Baeyer’s reagent) to form glycols or diols.

During glycol formation, the pink colour of 𝐾𝑀𝑛𝑂4 is

discharged (decolourised). Hence this reaction is used as a test for
unsaturation.
Previous HSE Questions
𝑸𝟏 . What is Baeyer’s reagent? Write the chemical equation of it’s
reaction with ethylene (𝑪𝑯𝟐 = 𝑪𝑯𝟐 ).
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𝑸𝟐 . The cold dilute aqueous solution of 𝑲𝑴𝒏𝑶𝟒 is generally known

as ……………..
Ans: Baeyer’s Reagent
Preparation of Alkynes
Preparation of Acetylene or Ethyne [CH CH or 𝑪𝟐 𝑯𝟐 ]
From calcium carbide [𝐶𝑎𝐶2 ]
Acetylene or Ethyne is prepared by treating calcium carbide
(𝐶𝑎𝐶2) with water.

𝐶𝑎𝐶2 + 2𝐻2 𝑂 →𝐶2 𝐻2 + 𝐶𝑎(𝑂𝐻)2

2[𝐻 − 𝑂𝐻 ] [CH ≡ CH]
(Ethyne or Acetylene)

Previous HSE Question

𝑸𝟏 . Which gas is formed when water is added to 𝑪𝒂𝑪𝟐 .
Ans: Ethyne or Acetylene gas
𝑸𝟐 . Complete the reaction
𝑪𝒂𝑪𝟐 + 𝑯𝟐 𝑶 →. . . . +. ..
Acidic Character of Alkynes (1 - alkynes)
Example of 1-alkyne → CH CH (Ethyne or Acetylene)
Reaction showing Acidic Character of Ethyne [1 - Alkyne]
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i. Ethyne (acetylene) reacts with sodium metals to form sodium

acetylide with the liberation of dihydrogen gas.
1
𝐻𝐶 ≡ 𝐶𝐻 + 𝑁𝑎 → 𝐻𝐶 ≡ 𝐶 − 𝑁𝑎 + + 𝐻2
2
(Ethyne or (Sodium metal) (Sodium Acetylide)
Acetylene)
ii. Ethyne (acetylene) reacts with sodamide toform sodium acetylide
and ammonia.
𝐻𝐶 ≡ 𝐶𝐻 + 𝑁𝑎𝑁𝐻2 → 𝐻𝐶 ≡ 𝐶 − 𝑁𝑎+ + 𝑁𝐻3
(Ethyne or (Sodamide) (Sodium Acetylide)
Acetylene)
The above reactions show that ethyne (acetylene) is acidic in nature.
Previous HSE Questions
𝑸𝟏 . 1 – Alkynes are weakly acidic in nature. Give any two reactions
to show the acidic character of ethyne?
𝑸𝟐 . Ethyne is acidic in nature. Explain?
Benzene [𝑪𝟔 𝑯𝟔 ]
 Molecular formula of benzene is 𝐶6 𝐻6
 Structure of Benzene
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Preparation of Benzene
i. From Acetylene or Ethyne [𝑪𝑯 ≡ 𝑪𝑯 𝒐𝒓 𝑪𝟐 𝑯𝟐 ]
When acetylene (ethyne) is passed through red hot iron tube,
acetylene undergoes cyclic polymerisation to form benzene.

Previous HSE Question

𝑸𝟏 . Complete the reaction

𝑸𝟐 . Suggest a method to convert Ethyne to benzene.

ii. From Phenol [By reduction of phenol]
Phenol is reduced to benzene by heating with zinc dust.
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Previous HSE Question

Q. Complete the reaction

Addition reactions of Benzene with chlorine (𝑪𝒍𝟐 )

(i) Addition Reaction of Benzene with Chlorine
Benzene reacts with chlorine in presence of UV light to form
benzene hexa chloride (𝐶6 𝐻6 𝐶𝑙2 )

Previous HSE Questions

𝑸𝟏 . Complete the reaction

𝑸𝟐 . Identify the product A

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𝑸𝟑 . Give the product formed when benzene react with 𝑪𝒍𝟐 / hv.
Ans:- Benzene hexa chloride (𝐶6 𝐻6 𝐶𝑙2 )
Electrophilic substitution reactions of Benzene
i) Chlorination
Benzene reacts with chlorine in presence of Lewis acid like
anhydrous Al𝐶𝑙3 or Fe𝐶𝑙3 to give chlorobenzene.

With excess chlorine, benzene gives hexachlorobenzene [𝐶6 𝐶𝑙6 ]

Previous HSE Question

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𝑸𝟏 . Complete the reaction

𝑸𝟐 . Complete the reaction

ii) Friedel – Crafts alkylation reaction

When benzene is treated with an alkyl halide in presence of
anhydrous Al𝐶𝑙3 ], alkyl benzene is formed.
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Previous HSE Question

𝑸𝟏 .

𝑸𝟐 . Complete the reaction

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𝑸𝟑 . Give the products formed when benzene react with 𝑪𝑯𝟑 Cl /

Al𝑪𝒍𝟑
Ans:- Methyl benzene or toluene
iii) Friedel-Crafts acylation reaction
When benzene is treated with an acylhalide or acid anhydride in
presence of anhydrous AlCl3, acyl benzene is formed.

iv) Nitration
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When benzene is heated with a mixture of concentrated nitric

acid and concentrated sulphuric acid (nitrating mixture),
nitrobenzene is formed.

v) Sulphonation
When benzene is heated with fuming sulphuric acid (oleum),
benzene sulphonic acid is formed.

Previous HSE Questions

Q. Explain any two electrophilic substitution reaction of Benzene
with Chemical Equation.
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Aromaticity – Huckel Rule

Conditions for a molecule to be aromatic are given by Huckel
rule.
i) The molecule should be planar and cyclic.
ii) Complete delocalisation of 𝝅 - electrons in the ring.
iii)Molecule should contain (4n + 2) 𝝅 electrons where ‘n’ is an
integer.
Previous HSE Questions
Q. State Huckel Rule.

Reactions of Alkanes
i) Isomerisation
On heating n-alkanes (straight chain alkanes) in presence of
anhydrous Al𝐶𝑙3 and HCl gas, isomerise to branched chain alkanes.

ii) Aromatisation [Reforming]

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n – Alkanes (straight chain alkanes) containing six or more carbon

atoms when heated under pressure in presence of catalyst like
𝐶𝑟2 𝑂3 or 𝑉2 𝑂5 or 𝑀𝑜2 𝑂3 get converted to aromatic hydrocarbon
(Benzene).

Previous HSE Question

𝑸𝟏 . How would you convert the following compounds in to benzene.
i) Ethyne ii) Hexane
Ans:- Ethyne →Benzene (refer preparation of benzene from
ethyne Page No. 11)
Hexane →Benzene (refer Aromatisation or reforming Page
No:21)