1

2
Preface

We are immensely happy in bringing this Book ‘Organic Synthesis’ for the students of B.Sc.
Fifth Semester of U.P. State Universities.
This book provides;
(i) Synthesis and chemical properties of aliphatic & aromatic hydrocarbon.
(ii) Synthesis and chemical properties of alcohols, halides carbonyl compounds, carboxylic
acids and esters.

(iii) Industrial important of compounds, inter conversion of functional groups, many name
reactions, Baeyer’ strain theory conquered system.
(iv) Conversion of aliphatic and aromatic hydrocarbons in to industrially important materials.
(v) Inter conversion of functional groups.
Many examples have been given to explain, clarity, and concept of aromatic compounds.
This book not only covers the entire course objective of this course but give a clear idea of
the concept as well. This book will be help to students to acquire.

Quality is never an accident

It is always the result of intelligent effort
There must be a will to produce it.

Authors
Dr. Renu Agarwal
Dr. Surbhi Arya
Dr. Paresh Kumar

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 Contents of the Book

Unit-I No. of Lectures Allotted - 8

Chemistry of Alkanes and Cycloalkanes

1.1Alkanes: Classification of carbon atom in alkanes.

1.2 General methods of preparation
1.3 physical and chemical properties of alkanes: Wurtz Reaction
1.4 Wurtz-Fittig Reactions
1.5 Free radical substitutions: Halogenation -relative reactivity and selectivity
1.6 Cycloalkanes: Nomenclature
1.7 methods of formation
1.8chemical reactions
1.9 Baeyer's strain theory and its limitations. Chair
1.10 Boat and Twist boat forms of cyclohexane with energy diagrams ring strain in small rings
1.11Theory of strain less rings. The case of cyclopropane ring
1.12 Banana bonds.

Unit-II No. of Lectures Allotted - 12

Chemistry of Alkenes
2.1 Methods of formation of alkenes
2.2 Addition to C=C: mechanism (with evidence wherever applicable)
2.3reactivity
2.4 regioselectivity (Markownikoff and anti-Markownikoff additions)
2.5 Stereoselectivity reactions: hydrogenation, halogenation
2.6 hydrohalogenation
2.7 hydration
2.8 oxymercuration demercuration
2.9 hydroboration-oxidation
2.10 epoxidation
2.11 syn and anti-hydroxylation
2.12 ozonolysis
2.13 addition of singlet and triplet carbenes
2.14 Simmons-Smith cyclo propanation reaction
2.16 electrophilic
2.17 Addition to diene (conjugated di enes and allene)
2.18 radical addition: HBr addition
2.19 mechanism of allylic and benzylic bromination in competition with bromination across C=C use of
NBS
2.20 interconversion of E- and Z- alkenes
2.21 contra-thermodynamic isomerization of internal alkenes

Unit-III
Chemistry of Alkynes No. of Lectures Allotted - 6
4
3.1 Nomenclature of Alkynes
3.2 Physical properties of alkynes
3.3 Methods of formation of alkynes
3.4 Addition to C≡C
3.5 Oxymercuration, demercuration of alkynes
3.6 Oxidation of Alkynes
3.7 Dissolving metal reduction of alkynes (Birch)
3.8 Isomerization -Inter conversion of terminal and non- terminal alkynes
3.9 Polymerization
3.10 Formation of alkali metal acetylides

Unit-IV
Aromaticity and Chemistry of Arenes No. of Lectures Allotted - 10

4.1 Nomenclature of benzene derivatives

4.2 MO picture of benzene
4.3 Aromaticity: Hückel’s rule
4.4 Aromatic character of arenes
4.5 Cyclic carbocations/carbanions
4.6 Electrophilic aromatic substitution: halogenations
4.7 Nitration
4.8 Sulphonation and Friedel-Craft’s alkylation/acylation with their Mechanism
4.9 Directing effects of the groups. Birch reduction
4.10 Methods of formation and chemical reactions of
4.11 Alkyl benzenes
4.12 Alkyl benzenes and biphenyl
4.13 Naphthalene and anthracene

Unit-V
Chemistry of Alcohols No. of Lectures Allotted - 8

5.1 Classification and nomenclature

5.2 Monohydric alcohols – nomenclature
5.3 methods of formation by reduction of Aldehydes, Ketones
5.4 Carboxylic acids and Esters
5.5 Hydrogen bonding
5.6 Acidic nature
5.7 Reactions of alcohols
5.8 Dihydric alcohols nomenclature
5.9 Methods of formation
5.10 Chemical reactions of vicinal glycols,
5.11 Oxidative cleavage [Pb(OAc)4 and HIO4] and pinacol pinacolone rearrangement.
5.12 Trihydric alcohols - nomenclature,
5.13 Methods of formation,
5.14 Chemical reactions of glycerol.
Unit-VI
Chemistry of Phenols No. of Lectures Allotted - 6

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 6.1 Nomenclature
6.2Structure and bonding
6.3preparation of phenols
6.4Physical properties and acidic character
6.5Comparative acidic strengths of alcohols and phenols
6.6 Resonance stabilization of phenoxide ion
6.7Reactions of phenols – electrophilic aromatic substitution
6.8Acylation and carboxylation
6.9Mechanisms of Fries-rearrangement
6.10 Claisen rearrangement, Gatterman syntheis
6.11 Hauben Hoesch reaction
6.12 Lederer-Manasse reaction and Reimer-Tiemann reaction

Unit-VII
Chemistry of Ethers and Epoxides No. of Lectures Allotted - 5

7.1 Nomenclature of ethers

7.2 Methods of formation of ethers
7.3 General physical properties
7.4 Chemical reactions – cleavage and autoxidation
7.5 Ziesel's method
7.6 Synthesis of epoxides
7.7 Preparation of epoxides
7.8 Reactions of epoxides- Acid and base-catalyzed ring opening of epoxides
7.9 Orientation of epoxide ring opening
7.10 Reactions of Grignard and Organo-lithium reagents with epoxides

Unit-VIII
Chemistry of Organic Halides No. of Lectures Allotted - 5

8.1 Nomenclature and classes of alkyl halides

8.2 Methods of formation
8.3 Chemical reactions
8.4 Mechanisms of nucleophilic substitution reactions of alkyl halides
8.5 SN2 and SN1 reactions with energy profile diagrams
8.6 Polyhalogen compounds: Chloroform
8.7 Carbon tetra chloride
8.8 Methods of formation of aryl halides
8.8 Nuclear and side chain reactions
8.9 The addition-elimination and the elimination-addition mechanisms of nucleophilic aromatic
substitution reactions
8.10 Relative reactivities of alkyl halides vs allyl vinyl and aryl halides

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 Unit -1
Alkanes
That consist of alkanes are organic compounds atoms. The formula for alkanes is CrH2m+2. It is
divided in to three parts:

(a) Chain alkanes

(b) Cycloalkanes
(c) Branched alkanes

When carbon and hydrogen atoms joined with single covalent bonds are known as alkanes or
saturated hydrocarbons.

General formula of alkanes = CnH2n+2

• Simplest family of hydrocarbons are alkanes.

• Each carbon has four valency
• Each hydrogen atom. Forms one bond.
• The simple alkane is CH4 which has one carbon and 4 hydrogen bonded by single
covalent bond.
• Molecular formula of methane is CH4

Methane

• In a long chain alkane molecule additional carbon atoms are attached to each other by
single covalent bond.
• Long chain structure is known as octane which has eight carbon alkane has a molecular
formula C8H18
Structural formula is

Octane

7
S.N List of Molecula Structure
o Alkane r formula

1. Methane CH4

2. Ethane C2H6

3. Propane C3H8

4. Butane C4H10

5. Pantance C5H12

6. Hexane C6H14

7. Heptane C7H16

8. Bctanc C8H18

9. Nonane C9H20

8
10. Decan C10H22

1.1 CLASSIFICATION OF ALKANES

Any family of compounds in which adjacent members differ from each other by a definite factor
a CH2 group is called homologous series alkanes are based on the classified number of carbon-
carbon bonds are formed:

• Primary carbon atom; one carbon neighbor

• Secondary carbon atom; two carbon neighbors
• Tetiary carbon atom; three carbon neighbors
• Quaternary carbon atom; four carbon neighnors

1 Carbon 2 Carbon 3 Carbon 4 Carbon

Figure 1.2 Classification of carbon atoms

In this figure in primary carbon is bonded to one carbon atom, secondary carbon atom is bonded
to two carbon atom, tertiary carbon is bonded to three carbons atom and quaternary carbon is
bonded to four carbon.

Figure1. Classification of carbon atom within a molecule

1.2 GENERAL METHODS OF PREPARATIONS;

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1) From alkenes and alkynes (Sabatier and Sandrens reaction) or (By hydrogenation of alkenes
and alkynes): Alkenes and alkynes on catalytic hydrogenation give alkanes.

Alkene

Alkyne

Catalyst:

(a) Pd/Pt at ordinary temperature and pressure

(b) Ni, 200-300° C (Sabatier)
(c) Raney Nickel at room temp.
(d) Methane can not be prepared by this method

2) From alkyl Halides (By reduction):

Catalyst:

(i) Zn + HCl (ii) Zn + CH3 COOH (iii) Zn—Cu couple in C2H5OH

(iv) Red P + HI (v) Al — HG + ethanol

3) From alkyl halide (By Wurtz reaction): A solution of alkyl halide in ether on heating with
sodium Gives alkane.

(a) Two moles of alkyl halide are treated with Na in presence of dry ether. If ether is wet
then we obtain alcohol.

Methanol
(b) Methane can not be prepared by this method. The alkane produced is higher and
symmetrical i.e. It contains double the number of carbon atoms present in the alkyl
halide taken.
10
 (c) Two different alkyl halides, on wurtz reaction give all possible alkanes.
(d) The separation of mixture into individual members is not easy because their B.P. are near
each other and thus wurtz reaction is not suitable for the synthesis of alkanes containing
of number of carbon atom.

4) From Frankland Reagent:

Frankland reagent

4) From Carboxylic Acid (By decarboxylation): Sodium salt of saturated monocarboxylic acid
on dry distillation with sodalime give alkane.

Note:-
Sodalime

5) From carboxylic acid (By Kolbe’s electrolysis process): Alkanes are formed on
electrolysis of concentrated aqueous solution of sodium or potassium salt of saturated
monocarboxylic acid.

6) From alkanol, alkanas, Alkanone and alkanoic acid (By reduction): The reduction of
either of the above compound in presence of red P and H gives corresponding alkan.

11
In the above reaction I2 is formed which may react with alkane to form alkyl halide. So red P is
added in the reaction to remove I2 formed in the reaction.

7) From alkanones (By Clemmensen’s method): Carbonyl compound may also be reduced
with Zinc amalgam and concentrated HCL (Zn-Hg/hcL), this reaction is called clemmensen
reduction.

8) From alkanals and alkanones (By Wolf Kishner reaction):

9) From G.R. :
(a) Formation of alkanes with same number of C atoms: Grignard reagent reacts with the
compounds having active hydrogen to form alkane.

This reaction is used to determine the number of active H-atoms in the compound this is
known as Zerewitnoff’s method.

(b) G.R. react with alkyl halide to give higher alkanes:

10) Corey-House Synthesls: This method is suitable for the preparation of unsymmetrical
alkanes i.e. those of type R—R’

12
 Note: In Corey-house reaction symmetrical and unsymmetrical alkane both can be formed.

11) From metal carbide (By hydrolysis):

Only CH4 can be obtained by the hydrolysis of Be or Al carbides

1.3 PHYSICAL & CHEMICAL PROPERTIES OF ALKANES

(i) The Solubility of Alkanes

• Alkanes are generally non-polar molecules due to very little diference of electron
gratuity between carbon and hydrogen and covalent nature of C-C bond or C-H bond
• Polar molecules are soluble in polar solvent as water and non-polar molecules are
soluble in non-polar solvents.
• Alkanes are insoluble in water so are called hydrophobic (water hating).
• Alkanes are soluble in organic solvents.
(ii) The Boiling Point of Alkanes
• Intermolecular vander waals is directly proponial to size of molecular or the surface
area of molecules.
• The boiling point of alkanes increaser with creasing molecular weight.
• The straight chain alkanes are observed to have a higher boiling point than branched
chain alkanes due to lesser surface area in branched chain alkanes.
(iii) The Melting Point of Alkanes
• M.P. of alkanes do not regular treat even number of carbon atoms have higher M.P.
than their old number of carbon atoms of alkanes.
• Even number of carbon atom alkane the end carbon atom on opposite side and odd
number of carbon atom alkane the end carbon atom on same side.

Odd number of carbon first Even number of carbon

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1.3.1 CHEMICAL PROPERTIES: Akanes are low reactive because:
(i) They are non-polar because electronegative difference between carbon and hydrogen.
(ii) They have inert towards strong sigma (σ) bond.
(iii)They do not give acids, bases, oxidizing and reducing agents.

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1.3.2 COMBUSTION:- In the presence of air or dioxygen alkanes are oxidized to caron
dioxide and water with the huge amount of heat.

∆𝐻𝑐 = −2875.84 𝐾𝐽 𝑚𝑜𝑙 −1

The general combustion equation

3(𝑛 + 1)
𝐶𝑛 𝐻2𝑛+2 + 𝑂2 → 𝑛𝐶𝑂2 + (𝑛 + 1)𝐻2 𝑂
2
*Alkanes are used as fuel due to evolution of large amount of energy.

* Due to incomplete combustion (less amount of oxygen) of alkanes carbon black is

formed which is used in the manufacture of ink, printer ink

𝑖𝑛𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑒
𝐶𝐻4(𝑔) + 𝑂2(𝑔) 𝐶(𝑠) + 2𝐻2 𝑂
⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗
𝐶𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛
Carbon black

1.3.3 ISOMERISATION:- n Hexane reacts with an hydrous aluminium chloride with

hydrogen chloride gas isomerise into branched chain alkanes.

2 Methyl pertane

(Major product)
Product is major due to tertiary carbocations

1.3.4 COONTROLLED OXIDATION:- Alkanes on heating with a supply of dioxygen

or air at high pressure and in the presence of copper give methanol, methanoic acid

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 1.3.5 PYROLYRISE:- Higher alkanes decompose into power alkanes on heating higher
temperature

1.3.6 REACTION WITH STEAM:- Methane reacts with water or steam at 1273 in the
presence of nickel catalyst to produce carbon mono oxide and hydrogen

1.3.7 AROMATIZATION:- On heating at temperature 773K at 10-20 atomospheric

pressure in the presence of of Catalysis oxides of vanadium molybdenum or
chromium n-alkanes having six or more carbon atoms get dehydrogenated and
cyclized to benzene. This is known as aromatization.

N haxane

1.4 WURTZ FITTING REACTION:-

• It is substituted aromatic reactions
• It is discover by Wertz in 1885.
• Reactant product may be aryl halides, sodium, metal and dry ether.
• It involves two alkyl halides to produce a new carbon-carbon bond.
• It is coupling reaction.

16
 Mechanism (The organo- Alkali mechanism)
• When the aryl haliele is reacted with sodium metal.
• Homolysis of the C-x bond in Aryl halid to give phenyl radical.

Phenyl Radical

• Organo-alkali is strong nucleophile.

• Breaking of heterolysis of C-Na and C-x bond and Na+ and x combine to farm a salt.
• Phenyl benzene is formed

Application of Wurtz fitting reactions

It is not used in industry because side reactions like elimination and rearrangement are
occur.
Use of this reactions in coupling of various aromatic rings.
It is used in the lab preparation of organo silicon compound.

1.5 Free radical reaction

SUBSTITUATION REACTIONS: When one or more hydrogen atoms of alkanes are
replaced by other group like halogens, nitro group and sulphuric acid group are called
substitution reactions.
Halogenation:- It take place under higher temperature 573 - 773 and presence of sunlight or
ultraviolet light lower alkanes do not under so nitration and sulphonation.
All four hydrogen of methane are replaced by four chlorine atoms

17
 Chloromethane

Ri chloromethane

Tri chloromethane

Carbon Tetrachloride

Rate of reactions of alkanes with halogens is F2Cl27Br27I2 Rate of replacement of hydrogens

of alkanes is 3° 72° 71°
Halogenation is carried out by free radical chain mechanism.

Mechanism
(i) Initiation:- Cl-Cl bond is weaker than C-C bond so that is broken in to free radical by
hemolysis.

(ii) Propagation:- Chlorine free radical attacks the methane molecule.

(a)

CH3 (The methyl radical) attacks on the second molecule of chlorine to give methyl
chloride and free chlorine (Cl)

(b)
Chlorine free radical
This free chlorine atom react with methyl chloride to give more highly halogenated
products are formed.

(iii)Terminations:- The reactions stops after some time

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(a)
(b)
(c)
(Chlorination of methan give ethane as a by product.
* Iodination is very slow and reversible research

It is carried out in present of HIO3 or HNO3 as oxidizing agent.

1.6 Cycloalkane : Nomenclature

When three or more carbon atom arranged in a ring, are called Cycloalkane.

• The general molecular formula of cycloalkane is CnH2n

• There are saturated carbon atom so it is joint by single bonded to other atom
• In cyclic ring, each carbon has two hydrogen
The rules of cycloalkanes are similar to straight chain alkanes

• The parent ring is the largest ring in the molecular

• Cycle prefix is added in the name of alkane
• Identify the substituents and there location by numbering.
• Substituent are arranged by alphabetically

Parent Cyclo alkane Substituents

1- Propyl, 2- Methyl, 4- Ethyl Cyclo hexane

Arranged alphabetically

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 4- ethyl, 2-methyl, 4-propyl cyclo hexance

1.7 methods of formation

Wurtz Reactions when dihalogen is react with zink or sodium

• When calcium or barium salt of dicarboxylic acid is distlled is petore in formed

1.8. Chemical Reaction

Addition reaction

Cycloalkane behave like alkene and alkanes in their chemical properties .cycloalkane
under goes addition reaction.

CH------------CH ------Br dark (CCL4)------------BrCH—CH-CHBr

20
 CH
1,3 Dibomopropane

1.9 Baeyer’S Strain THeory and its limitatiiion:-

A delfvon Balyer deeribed that first few cycloalkam were stable.

All cycloalkanes are flat and coplanar

They are two dimensional and exist on one plane

The large ring systems do not exist due to negative strain

Bond angle in cyclohexane, cycloheptane cyclooctane are smaller than 109.50

Methan molecule has 109.5 Angle between H – c--H

LIMITATIONS OF BAEYER’S STRAIN THEORY

• The theory was not able to explain angle strain in parger structures.
• According to him Cyclohersare is less stable than cyclopertane but reality is the oppsite.

21
 • Larger ring system are not planar.
1.10.1 Conformations or conformers or rotamers

Rotation around a C–C single bond is not completely free. It is hindered by a small energy
baser of 1-20 Kjmol-1 due to weak force in known as torsional strain.

Conformation of ethane:- ethane molecule (C2H6) contains a carbon, carbon single bond and
each carbon has three hydrogen atoms. In which one carbon atom stationary and one carbon
rotate gas) like ball and stick modal of ethane. They have infinite number of conformation of
ethane.

(a) Sawhorse Projections: Central C – C bond take as longer straight line. Upper end of a line is
slightly tilted towards right or left hand side. The liner are in clined at an angle of 120° to each
other.

Eeclipsed Staggered

(b) Newman Projection:- Three carbon atoms are nearer to the eye is represented by a point and
three carbon are fronts carbon at angle of 120° to each other. The rear carbon atom away from
the eye is represented by a circle and represented by the shorter line.

Eclipsed Staggered

Relative Stability of Conformations:-

In staggered from of ethane, carbon-hydrogen bonds are as for apart as possible. So repulsive
forem and energy between carbon and hydrogen are minimum and maximum stability of
molecule.

• The staggered form changer in to eclipsed from, carbon and hydrogen are come close to
each other, repulsion in creaser maximum energy & low stability of molecule.
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 • It means staggered form has the least torisional strain and eclipsed form has the
maximum tovsional strain.
• The energy difference between the two extreme form is of the order of 12.5 KJ mol-1
• Thus the rotation about carbon carbon single bond in ethane is almost free.

Parent ring Substituents

(4 cyclo bentyl – 3 cyclopropyl, cyclohex) – 6 – methyl heptane.

Conformation:- The bond angle in methane molecule is 109.5 It has tetrahedral structure

Tetrahedra Triangle Square Cyclopera Haxare

𝑛−2
𝐵𝑜𝑛𝑑 𝑎𝑛𝑔𝑙𝑒 = × 180
𝑛
The 60° angle in equilateral angle in much smaller than optimum 109.5° angle in tedra hedla
carbon atom. This angle strain influence the chemical behavious of the cycloalkane.

But to carbon-carbon sigma bond rotation is possible thi rotation result into different spatial
arrangements of atom in space which can change into one another.

When spital arrangement is converted into one another by rotation around a C – C single
bond are called

1.10 Boat ans Twist theory forms of cyclohexane with energy diagrams ring strain in small
ring

CONFORMATION OF CYCLOHEXAN:-
1
• Angle strin in cyclohexane is 2 (109.28° − 120°)
23
 • It is larger than ideal tetrahedral angle
• Every carbon – hydrogen bond is cyclohexane is eclipsed.
• The resulting angle and eclipsing strain destabilize this structure.

All bonds are eclipsing strain small steric strain

Planar structure

CHAIN CONFORMATION OF CYCLOHEXANE:-

Due to free of ring strain the flexibility of cyclo hexane quern. If the two opposite side carbon of
six membered ring are bent out of place of the ring. The chain conformation has lower energy
(0.125°) The bond angle between carbon carbon is 111° which is very close to 109° Tetrahedral
structure.

• All the bonds are staggered so Torisional strain can be negated

• 6 Carbon in axial forms and 6 carbons in equitral form
• It has no angle strain, noeclising strain, small staric strain.

BOAT CONFORMATION OF CYCLOHEXANE

Boat form is less stable than chain form. It has two reason

• It has no staric hn heractions between a-pair of 1, 4 hydrogen flagpole and close to gather
by 1-83 A°

24
 • The streric hindrance has .12 12 J /mol repulsive energy.
• Reason of higher energy of boat confirmation is the adjacent hydrogen atoms are forced
ino eclipsed formed
Twist Boat conformations:-

Reduce the strain due to ahefting of carbon in opposite directions.

• That’s why It is more stable than boat conformation

• It is less stable than chain conformation by 23 KJ /mol

HALF CHAIN CONFORMATION

It has same strain as planar cyclohexane.

• In planar structure C – C bond angle is 120°.

• All C – H bonds are not fully eclipsed
• It has 45 KS/mol
• It is less stable than chain confirmation.
CONFORMATION CHANGES IN CYCLOHEXANE RINGS FLIPS

• One chain orm can not change in other forms of other chain. It can be possible by higher
energy as transitions.
• At room lemperaluve the energy barrier developed by the half chain confermation for
equilibrium.
Between the two chain conformation

25
1.11.CYCLOPROPANE:-

Three carbon atoms found in an equilateral triangle or cyclopropane. It has 60° angle. The Bond
1
angle between two bonds are compressed to 60° and each is pulled by (109.28° − 60°) =
2
24.75°) This is deviation from the normal tetrahedral direction.

Angle strain in cyclo-propane

CYCLOBUTANE:-

Four carbon atoms are arranged in a square. The C – C – C bounda have 90° angle.
7
The strain is 2 (109.28° − 90°) = 9.44°

• Order of stability
Cycloprapane < Cyclobutan < Cyclopertane
26
1.12. BANANA BOND THEORY

• In Cycloprapane, the smallest cycloalkane. It has highly strained.

• It has sp3 hybridization.
• It has 28 K cal/mol
• C – C bond has 88 K cal/mol
• So ring strain weakers the C – C bonds of the ring.
• So cyclpropane is much more reactive than acqyclic alkane and cyclo hexane and
cyclopertane
• Cycloprapane is planer so C – C bonds are staggered
• Estimate energy in staggered form is a K cal/mol of torisional strain in cyclpropane
• Total ring strain in cycloprapane is about 28 K cal/mol
• The angle strain in cyclopropane C – C – C is to be 60º degrees i.e is equilateral triangle
about 49° degree less than ideal angle.

• This strain is partially overcome by using so called ‘Banana bonds’ where the overlap
between orbitals is no directly viewed by two nuclei.

EXCERCISE

1.12. Very Short Answer Question

1. What is General formula of alkane?

2. What is simplest form of alkane?
3. What isformula of Decan?
4. What is homologous series?
5. What isQuaternary Carbon atom?

27
 6. What ishydrogenation?
7. What is Corey Houre synthesis?
8. What product given by Al4C3?
9. Which has more boiling point chain isomer or?
10. Which is strong sigma bond or Pi bond?
1.12.1 Short Answer Question

1. Give Physical property of Alkane.

2. Explain chemical property of Alkane.
3. What is Wurtz reaction?
4. Explain Sandrens and Sabatier reactions.
5. Explain franpland reactions.
6. What is combustion?
7. What is isomerization?
8. Aromatization explain.s
1.12.2 Long Answer Question

1. Give physical & chemical properties of Alkane.

2. Give preparation of Alkane.
3. Explain substitution reaction in Alkane.
Explain preparation of cycloal

28
 UNIT II

Chemistry of Alkenes
Alkenes are a type of hydrocarbon molecule that contains a carbon-carbon double bond. They
are also known as olefins. The general formula for an alkene is CnH2n, where n is the number of
carbon atoms in the molecule.
Alkenes are unsaturated hydrocarbons, meaning they contain one or more double bonds and can
undergo addition reactions with other compounds. They are used in the production of a wide
range of materials, including plastics, synthetic rubber, and solvents. Some examples of alkenes
include ethene (C2H4), propene (C3H6), and butene (C4H8).

2.1 Methods of formation of alkenes

1. Elimination reactions - Alkenes can be synthesized by elimination of leaving grp from a

substrate. This can occur through various mechanisms, such as dehydrohalogenation,
dehydrations, and beta-elimination.

Conc.H2SO4
C2H5OH H2C CH2
430-440K
2. Dehydrogenation - Alkenes can also be prepared by removal of H-atom from a substrate.
This can be achieved through various methods, such as oxidative dehydrogenation or catalytic
dehydrogenation.
O

C6H5CH2CH3 500C C6H5CH=CH2

3. Reduction of alkynes – By reduction of alkynes, alkenes can be synthesized, using various
reducing agents, such as sodium in liquid ammonia or hydrogen gas with a metal catalyst.
H3C CH3
H2 / Lindlard catalyst
H3C C C CH3 C C
H H
H
H3CCis-2-butene
Na / liq NH3
H3C C C CH3 C C
H CH3
trans-2-butene

29
4. Fron alkyl halides
H H
Heat
H C C H + Alc. KOH H2C CH2 + KBr + H2O
H Br

5. Preparation of ethene by kolbe’s electrolytic method

When electrolysis of potassium succinate takes place, ethane is produced at the anode.

-
H2C COOK Electrolysis H2C COO
+ 2K+
H2C COOK H2C COO-

At anode

H2C COO
- CH2
-
+ CO2 + 2e
H2C COO- CH2
Ethene

Physical properties of alkenes

1. Alkenes are present in three states in nature. From C1 to C3 are in gaseous state, the next
fourteen (C4 to C17) are in liquid state, and higher member of the group are solids.
2. In alkenes weak van der Waal forces exist, so they are water insoluble.
3. They are miscible in organic solvents as acetone and benzene.
4. Bigger is the carbon chain, higher is the boiling point.
5. Polar nature of alkenes depends on functional group present.

Chemical Properties of alkenes

Alkenes are double bond bearing (unsaturated) compounds, so they are highly reactive and
chemical reactions takes place at the C=C double bond, alkenes are more reactive than alkanes.

2.2 Additio to C=C mechanism

2.3 Regioselectivity

30
Regioselectivity refers to the preference of a reaction to occur at a particular site or position of a
molecule. In organic chemistry, there are two types of regioselectivity that are commonly
discussed: Markovnikov and anti-Markovnikov additions.
Markovnikov addition is a type of regioselectivity in which the electrophile (i.e., the molecule
that is being added to the substrate) adds to the double bond C-atom that already has the most
hydrogen atoms attached to it. This rule can be expressed as "the rich becomes richer," meaning
that carbon, that already has most hydrogens attached to it becomes more positively charged and
therefore more attractive to the electrophile. E.g., the addition of HBr to propene produces 2-
bromopropane, with the Br adding to the more substituted carbon. e.g.

H H H Br H
H H H
H C HBr
C H C C H + H C C
H H Br
H H H H
H H H
major product minor product

Anti-Markovnikov addition, on the other hand, is a type of regioselectivity in which the

electrophile adds to carbon atom of double bond that has the least number of hydrogens attached
to it. This rule can be expressed as "the poor get richer," meaning that the carbon that has fewer
hydrogens attached to it becomes more positively charged and therefore more attractive to the
electrophile. This type of addition is often observed in the presence of certain types of reagents,
such as hydrogen peroxide (H2O2) with a catalyst like a radical initiator. For example, the
addition of HBr to propene in the presence of peroxide produces 2-bromopropane, with the Br
adding to the less substituted carbon.
It is important to note that Markovnikov and anti-Markovnikov additions are not absolute rules
and there are many cases where exceptions can occur. However, these principles are still useful
guides for predicting the regioselectivity of certain reactions. e.g.

H H H H Br
H H H
H C HBr
C H C C Br
+ H C C H
H H
H H H H
H H H
major product minor product

31
2.4 Stereoselectivity
Stereoselectivity refers to the preference of a reaction to produce a particular stereoisomer. In
other words, it describes the selectivity of a reaction in terms of stereochemistry of the formed
products. In organic chemistry, stereoisomers are molecules that have the same molecular
formula but differ in spatial arrangement of atoms. There are two main types of stereoisomers:
enantiomers and diastereomers. Enantiomers are stereoisomers that are mirror images of each
other and cannot be superimposed on each other. Diastereomers, on the other hand, are
stereoisomers that are not mirror images of each other and can be distinguished by their physical
properties such as melting point, boiling point, and solubility. Stereoselectivity can be either
absolute or relative. Absolute stereoselectivity means that a reaction produces only one
stereoisomer, while relative stereoselectivity means that a reaction produces a mixture of
stereoisomers, but with a preference for a particular stereoisomer. A reaction that involves the
formation of a chiral center may be stereoselective if the reaction conditions favor the formation
of one stereoisomer over the other. Examples of stereoselectivity reactions are -

Hydrogenation – it is a sterioselective reaction.

Pt
+ H2 +
(1R, 2S)-1,2-dimethylcyclohexane (1R, 2R)-1,2-dimethylcyclohexane

major product minor product

Halogenation – It is a sterioselective reaction.

CH3 Br
CH3
Br CH3
+ Br2
CH3
+ CH3
CH3
Br Br
Anti- product Syn- product
not formed
2.4 Hydration reaction of alkenes –
This is the addition of water in presence of acid (in catalytic amount), produces alcohol, addition
occurs according to Markovnikov rule.
H
H3C C CH2 + H2O H3C C CH3
H 32 OH
 2.5 oxymercuration-demercuration – Acid catalyzed hydration of alkenes occur and gives
Markovnikov product.

OH
1) Hg(OAc)2, H2O, THF
_
2) NaBH4, OH
2.6 Hydroboration-oxidation – Addition of water occurs according to Markovnikov rule.

H2C CH2 + (CH3)2BH CH2-CH2-B(CH3)2

_ _
H 2O 2 + OH C2H5OH + B(OH)4 + CH3OH + H 2O
CH2-CH2-B(CH3)2 +

2.7 Epoxidation - Alkenes reacts with oxygen in presence of Ag and gives cyclic ethers known as
Ag O
H2C CH2 + O2
Heat H2C CH2
epoxide
2.8 Syn and Anti-hydroxylation – Hydoxylation of alkene takes place by two paths, syn and
anti. OH H
O H2O / H+
CH CH H C C
CH3
CH3 OH
Anti-dihydroxylation

H H
C C
CH3 H
-
MnO4 / H2O / PH 8 / Cold C C CH3
OH OH

Syn-dihydroxylation

2.9.Ozonolysis – By ozonolysis, alkenes give alcohos, aldehydes, ketones and acids.

O
O
O3 C C O + O C
C C
C
O Carbonyl products
Ozonide
2.10 Addition of singlet and triplet carbenes –
Addition of singlet carbine to an alkane is a stereospecific reaction. e.g. when addition of CH2 to

33
 H2
+ hv C
+ H 2C N N + N2

Cis Cis

cis-l, 2- di-substituted alkene occurs it gives cis product, and when triplet carbine is added to trans-l,
2-di-substituted alkene it gives trans- product.

H2
+ hv C
+ H2C N N + N2
Trans
Trans

2.11 Simmons-Smith cyclo propanation reaction –

When alkene reacts with iodomethyl zinc iodide and produces cyclopropane in presence of zinc-
copper couple, the reaction is known as Simmons-Smith reaction.
1
H3C CH3 CH2I2 , Zn(Cu) H H
H H (C2H5)2O
H3C CH3
cis-2-butene cis-1,2-dimethylcyclopropane

2.11 Simmons-Smith reaction mechanism –

1. Both the new bonds are formed simultaneously at C=C bond.
2. It is a nucleophilic addition.
3. Electrons from the C-Zn bond, form the C-C bond.

IZn R3 R4
R1 R2
+ CH2
+ ZnI2
R3 R4 R1 R2
I
Alkenes Methylene iodide Cyclopropane

2.12 Electrophilic Addition to conjugated diene -

34
Electrophilic addition to a simple alkene would follow Markovnikov’s rule. On increasing
stability of intermediate, a higher yield will be produced. e.g. Addition of HBr to 1,3-butadiene
gives 1, 2-addition product in a higher yield while 1,4-addition product in a low yield.
Carbocation in 1, 2-addition product is much stable.

_ H H
H H Br
H+ +
+ + Br
More stable less stable 1,2-addition product 1,4-addition product
intermediate intermediate 71% 29%

2.14. Radical addition of HBr –

Radical addition of HBr involves the addition of hydrogen bromide (HBr) to an unsaturated
organic compound through a radical mechanism. The process involves the first step initiation,
second step propagation, and third step termination steps.

Initiation: The reaction is initiated by the homo-lytic bond breaking of a weak bond, usually a
peroxide which generates two highly reactive radicals. e.g.

ROOR 2RO
.
Propagation: The radical generated in the initiation step attacks the unsaturated organic
compound (e.g., an alkene) to form a carbon-centered radical. In the case of HBr addition, the H-
atom from HBr adds to the carbon-centered radical to form a new C-H bond and a new bromine-
centered radical. The bromine radical can then react with another molecule of HBr to form more
Br-centered radicals, which can continue the propagation cycle. For example
H
Br
.
H3C HC CH2 + HBr C CH3 +
H3C
Br
Termination: The reaction is terminated by the combination of two radicals, which results
product.
2RO
. ROOR
.
2 Br Br2

35
Overall, this method can be a useful method for the preparation of alkyl halides from alkenes,
although it can be difficult to control selectivity due to the possibility of multiple products
forming.

2.15 Mechanism of allylic and benzylic bromination in competition with bromination

across
C=C by use of NBS -
Allylic and benzylic bromination reactions occur when a bromine atom is added to the C-atom
adjacent to a double bond or aromatic ring, respectively. The use of N-bromosuccinimide (NBS)
as a source of bromine is a common method for achieving these types of selective bromination
reactions.
The mechanism of bromination of allylic and benzylic compounds with NBS involves the
following steps -
(i) Formation of a bromonium ion intermediate –
Alkene or aromatic compound reacts with molecular bromine to form a cyclic bromonium ion
intermediate where NBS and light or heat act as catalyst. This intermediate is highly reactive and
can be attacked by a nucleophile, such as bromide ion, to form the final product.

Br2 2 Br
.
(ii) Nucleophilic attack by bromide ion –
Bromide ion attacks the cyclic bromonium ion intermediate at the carbon atom adjacent to the
double bond or aromatic ring, resulting in the formation of a new Carbon-Br bond.Termination –
Recombination of radicals occur and product formation takes place.
CH3 CH3
C H Br
. C . + HBr
CH3 CH3

CH3 CH3
C. +
.
Br C Br
CH3 CH3

The selectivity of reaction depends on several factors, as stability of the intermediate radical,
reactivity of Br radical, and steric hindrance around the reaction center.
36
In general, allylic and benzylic radicals show more stability than alkyl radicals due to resonance
stabilization. Therefore, the intermediate radical formed from elimination of a hydrogen atom at
the allylic/benzylic position is more stable than that formed by elimination of a hydrogen atom at
the C=C double bond.
Additionally, bromine radicals are more reactive than chlorine or iodine radicals, and thus more
likely to attack the intermediate radical at the allylic/benzylic position. This reactivity preference
is further enhanced by steric hindrance around the C=C double bond, which makes it more
difficult for the bromine radical to approach and attack the double bond.
Overall, the combination of resonance stabilization of the allylic/benzylic radical intermediate
and the reactivity preference of the bromine radical results in preferential bromination at the
allylic/benzylic position over bromination across the C=C bond. However, the selectivity can be
influenced by reaction conditions such as temperature, solvent, and concentration of reactants,
and sometimes bromination across the C=C bond can be prioritized over allylic or benzylic
bromination.

2.16 Inter-conversion of E- and Z- alkenes -

E- and Z-alkenes are stereoisomers to one another, meaning they are the same inn terms of
molecular formula, but different in their spatial arrangement.

Interconversion of E- and Z-alkenes can be achieved through a process known as

stereoisomerization. There are a few ways to accomplish this:
1. Thermal isomerization - This method involves heating the E-alkene or Z-alkene to a high
temperature (usually around 200-250°C) with a catalyst such as Pt or Pd. Double bond undergoes
a rotation, resulting in the formation of the other stereoisomer.
2. Chemical isomerization - Chemical isomerization involves the use of reagents to promote the
conversion of one stereoisomer to the other. For example, use of a strong base like NaOH or
KOH in a solvent as ethanol or methanol can be used to isomerize an E-alkene to a Z-alkene, or
vice versa.
3. Photoisomerization - This method involves irradiating the E-alkene or Z-alkene with
ultraviolet light, which can promote the isomerization of the double bond.

37
Overall, the specific method used to interconvert E- and Z-alkenes will depend on factors such as
the starting materials, the desired products, and the conditions available for reaction.

2.17 Contra-thermodynamic isomerization of internal alkenes -

The contra-thermodynamic isomerization of internal alkenes involves the conversion of a less

stable alkene isomer (usually the Z-isomer) to a more stable alkene isomer (usually the E-isomer)
under thermodynamically unfavorable conditions. This process is referred to as "contra-
thermodynamic" because it occurs in the opposite direction of the more favorable
thermodynamic equilibrium. This isomerization can be achieved by using different reagents, as
transition metal catalysts (e.g. ruthenium or osmium), peroxides, or radical initiators. The general
mechanism involves the formation of a transient intermediate with a radical or carbocationic
character, followed by rearrangement to the more stable alkene isomer.
One common example of a contra-thermodynamic isomerization reaction is the conversion of a
terminal Z-alkene to an E-alkene using a transition metal catalyst, such as the Crabtree catalyst
([(Ph3P)2IrCl]2). The reaction proceeds through a radical intermediate, which can rearrange to
form the E-alkene.
Overall, the contra-thermodynamic isomerization of internal alkenes is a useful synthetic tool for
the preparation of more stable alkene isomers, which may be useful in various applications such
as pharmaceutical synthesis or material science.
Questions for practice –

Very short answer type questions -

1. What are alkenes? Give one example.
2. General formula for an alkene is?
3. Write one method of preparation of alkene. Only reaction.
4. What will be the stereochemistry of product if an alkyne gives alkene by reduction in presence
of Lindlard’s catalyst.
5. What will be the product at anode in Kolbe’s synthesis?
6. Write any 2 chemical properties of alkenes.

38
7. What will be the stereochemistry of product if an alkyne gives alkene by reduction in presence
of Na/ liq NH3.
8. What will be the product when ethyl bromide reacts with alc. KOH?
9. Show an example of regioselectivity. Only reaction.
10. Give an example of seterioselectivity. Only reaction.
Short answer type questions –
1. Write down Simmons-Smith reaction and explain its mechanism.
2. Explain addition reaction of singlet with an alkene.
3. Explain regioselectivity with an example.
4. What will be the product when hydroxylation of an alkene takes place?
5. Explain radial addition of HBr with alkene.
6. Explain sterioselectivity with an example.
7. Explain benzylic bromination across C=C by using NBS.
8. Explain allylic bromination across CC by using NBS.
9. How will you convert E-alkene in to Z-alkene.
10. What is contra-thermodynamic isomerisation of internal alkene? Explain.
Long answer type questions –
1. Give 2 methods of preparation of alkenes and its 6 chemical reactions.
2. Explain mechanism of Simmons-Smith reaction and contra-thermodynamic isomerisation.
3. Write down electrophilic addition of conjugated diene, give a suitable reason for the formation
of major and minor product.
4. Explain mechanism of benzylic bromination with the help of NBS.
5. Give some methods for the conversion of E-alkene in to a Z-alkene.

39
 Unit-III
Chemistry of Alkynes
The alkynes are unsaturated hydrocarbons similar to alkenes, comprise a carbon – carbon
triple bond. The molecular formula of alkynes CnH2n-2. Acetylene is the first member of alkynes,
HC ≡ CH and the class as a whole is referred to acetylenes. Monosubstituted acetylene are called
terminal whereas disubstituted acetylene are called non-terminal alkynes. acetylene has sp
hybridized carbon atoms. The end on overlap by the sp hybrid carbon atom formed σ bond and
π-bond formed by 2py and 2pz orbitals. The distance between carbon – carbon bond is 1.20A°
related to ethylene or ethane. Acetylene is a linear molecule having a bond angle of 180°.

1.20A° 1.10A°
H C C H
180°

3.1Nomenclature of Alkynes -
Acctylene, the common name of ethyne. The suffix – yne is used in the nomenclature and its
position is given by a number.
1 2 3 4
2-Butyne (But–2–yne)
CH3 C C CH3
CH3 -C ≡ C-CH(CH3)2 4-Methyl–2–pentyne

3.2 Physical properties of Alkynes-

The boiling point increases with carbon content however low boiling point possess by
substituted acetylenes . Alkynes similar to alkanes and alkenes are non-polar and soluble in
ether, benzene and carbon tetrachloride but insoluble in water or ethanol.

3.3 Methods of formation of Alkynes-

Acetylene is manufactured by methane by partial combustion.

40
 2CH4 (g) + 11⁄2 O2(g) →C2H2 (g) +3H2O (l)

In laboratory- acetylene can be prepared from calcium carbide, CaCl2, by the action of water.
A mixture of quick lime (Cao) and coke (carbon) on heating at high temperature yield CaCl2.
Acetylene prepared from this method is not pure.

CaCO3 Δ
CaO +CO2
Lime stone Quick lime

Cao + 3C → CaC2 + CO
Coke Calcium Carbide

CaC2 + 2H2O → HC≡CH +

Ca(OH)2
Calcium Carbide Acetylene
Hydrated ime

(i) Dehydrohalogenation of dihalides – acetylene formed by dehydrohalogenation of

vicinal dihalides on reacting with alc. potassium hydroxide solution

CH3CHCH + 2KOH CH3C CH + 2 KBr + 2H2O

Br Br
1, 2 – Dibromo propane 1 – Propyne

(ii) Displacement reaction: Terminal hydrogen containing Acetylene is acidic in nature,

can be transformed into its sodium salt. Which quickly take part displacement
reaction of SN2 type .
NaNH2 - + CH3I
CH CH HC CNa HC CCH3 + NaI
Acetylene 1 – Propyne

(iii) From tetrahalides – The tetrahalides yield an alkyne by eliminate ZnCl2 in the
presence of metallic zinc
Cl Cl
2Zn
HC CH HC CH + 2ZnCl2

Cl Cl
1, 1, 2, 2 – Tetrachloroethane Acetylene

41
 (iv) Combustion reaction – Acetylene is burn in presence of oxygen by enormously heat-
releasing manner to form CO2 & H2O

Acetylene takes on addition reactions (hydrogen, halogens and hydrogen halides) with a lot of
reagents as analogous to alkenes. Beside addition alkynes undergo certain reactions that are due
to the acidity of a hydrogen atom attached with triply-bonded carbon

3.4 Addition to C≡C

(i) Addition of Hydrogen – Alkynes hydrogenated to the corresponding alkanes in the
presence catalyst Nickel .

The Lindlar catalyst permits to add only one molecule of hydrogen to the triple
bond.The reduction consists of the syn addition of hydrogen on the triple bond
CH CH3
3

CH3 - C C - CH3 + H2OPd/BaSO4 C=C

Pyridine
H H
Cis-alkene

(ii) Addition of Halogens – Alkynes undertake the identical kind of addition reactions
with chloride and bromine that alkene undergo. Two moles of halogens react with
Alkynes to form tetra halo derivatives while 1 mole of halogen leads to dihalied of
trans- structure

The reaction of addition of halogen to an alkyne can be represent as follows –

42
 (iii) Addition of Hydrogen halides – Alkynes yielding a gem–dihalide by the addition of
Hydrogen halides

2, 2 – Dichloropropane

1, 1 – Diiodoethane

After the initial formation of a vinyl cation, addition will takes place. As per
MarkowniKoff rule addition of second mole will take place.

Vinyl cation

In the presence of free radical initiators such as peroxide, anti MarkowniKoff addition
of HBr to alkynes take place –

1–Bromo–1-butene

3.5 Oxymercuration Demercuration of Alkynes-

(i)Addition of water – Acetylene is a low-priced raw material for the manufacturing

of acetaldehyde. This is obtained by the adding water in the presence of catalyst,
sulfuric acid and mercuric sulfate.

43
 Aldehyde

Since this reaction follows MarkoniKoff rule, acetylene i is the only alkyne that under
goes hydration to give an aldehyde while other alkynes form ketones.

If the unsymmetrical alkyne is terminate addition occurs in accordance with

MarkowniKoff’s rule –

Unstable Propanone (Acetone)

However, if the unsymmetrical alkyne is nonterminal, a mixture of two isomeric

ketone is obtained

2- Pentanone (minor) 3 – Pentanone (Major)

(iv) Addition of HCN: HCN do not react quickly to alkene but in the presence of a CuCl
in HCl as a catalyst can be added to triple bond of acetylene and monomer
acrylonitrile is obtained

Acetlene Acrylonitrile

(v) Formation of acid or salt or ester – In the presence of nickel carbonyl catalyst
carbon monoxide and H2O or NaOH or CH2OH adds to acetylene to form acrylic acid
or sodium acrylate or methyl acrylate

Acrylic acid

Sod. Acrylate

44
 Methyl acrylate

(vi) Addition of Acetic acid –Acetic acid reacts with alkynes making an enol ester and
then gem diester, In the presence of mercuric ions

Enol ester A gem diester

(vii) Addition of hydroboration (oxidation) – Diborane adds to alkynes only once that
have an internal triple bond

The resulting tri vinyl boranes react with a number of reagents. on oxidation of vinyl
borane in alkaline H2O2 , C–B bond is broken and the initial product is vinyl alcohol
which on rearrangement convert into corresponding aldehyde or ketone

Methyl Ethyle Ketone

The reaction stops after addition of a simple molecule of the diborane derivative.
Oxidation of the resulting borane obtained from a terminal alkyne yields an aldehyde
while an internal alkyne yields a Ketone.

45
 The Tri vinyl boranes also undergo protonolysis to give cis – alkenes.

2 – Butyne Cis – butene

(viii) Acetylides formation with alkali metals formation – organometallic derivatives are
formed when 1 – alkynes react with sodium, silver or copper (I).

(from tollens reagents)

Silver acetylide (white ppt.)

(from AuCl)

gold acetylide
(golden colored precipitate)

(From Fehling Solution)

Copper acetylides
(Brown colored precipitate)

Unlike alkali metal acetylides, silver, gold and copper acetylides are not decomposed
by water. They can, however, be decomposed with minerals acids to regenerate the
original alkynes

this reaction can be used for the separation of terminal and non–terminal alkynes
from a mixture. If a mixture of 1-butyne and 2-butyne for example is passed through
ammoniacal silver nitrate solution then 1-butyne forms an in soluble white precipitate
while 2–butyne remains unaffected. The silver acetylide is separated and treated with
acid to generate 1- butyne.

46
 (ix) Formation of Alkynyl Grignard reagent – Terminal alkynes react with Grignand
reagent to form the corresponding alkynyl Grignard reagent

It is an example of transmetallation: in which a metal is transformed from one carbon

to another.
3.6 OXIDATION OF ALKYNES
Alkyne undergo two types of oxidation reactions

(i) Without cleavage –

(a) Baeyer’s Reagent - Alkyne on oxidation with Baeyer’s reagent yield vicinal Di
carbonyl compound

Acetylene Oxalic
acid

(b) With SeO2 → SeO2 converts alkyne into vic dicarbonyl compound

(ii) Oxidative cleavage –

Alkyne undergo cleavage with hot KMnO4 in basic medium. In this reaction triple
bond breaks and both carbons ( triply bonded) change to carboxylic group
47
Terminal alkynes transform into formic acid as one of the product which on further
oxidizes into CO2. Thus, it indicates that alkyne is terminal due to loss of a carbon

(iii)Addition of ozone: Triple bond between carbon – carbon cleavage on

ozonolysis which produces two molecules of carboxylic acids

2, 4 – Butanedione

While – having a terminal carbon it is oxidized to an acid and carbon dioxide

If an alkyne is treated with cold and neutral KMNO4 a diketone results –

2, 3 – Pentanedione

Under vigorous conditions potassium permanganate cleave the carbon – carbon triple
bond to yield the carbonylic acid

3.7 Dissolving metal reduction of alkynes (Birch)

Alkynes are similarly reduced by sodium or lithium in liquid ammonia. But it
produces trans. Alkene rather than cis. Alkene
CH3 H
Na / NH3
CH3 C C (CH2)4CH3 C=C

H (CH2)4CH3

48
 Trans-2-octene
In this reaction, it involves the reduction of the triple bond with two electrons from
sodium atom. The first electron transfer to an antibonding π orbital forming a radical
anion. This strongly basic species is protonated by ammonia to form a vinyl radical
which is reduced by other electron to give a vinyl anion than yield trans alkene and
amide ion.

+
NH3 Na NH3.e + Na
Solvated electron

Simple alkene does not reduce by sodium or potassium in liquid ammonia, so it is

easy to reduce an alkyne to a trans alkene. The stereochemistry of this reaction
suggest that the trans anion is more stable than the cis anion because of non-bonded
interactions.

49
3.8 Isomerization-Inter conversion of terminal and non- terminal alkynes.

Alkyne under goes isomerization in the presence of alc KOH in C6H12 or NaNH2 in
C6H12

(a) Non- terminal alkyne converts into terminal alkyne

(b) Terminal alkyne with α -CH2 group isomerizes into non-terminal alkyne and
conjugated diene.

3.9 Polymersisation of Acetylene –acetylene form a dimer, trimer or tetramer

with appropriate experimental condition as shown

(i) Dimerization – acetylene when goes through a solution of CuCl in NH4Cl at

70°C, from vinyl acetylene

(ii) Acetylene trimerizes when passed through red hot iron tube or in the presence
of catalyst Di carbonyl di(tri phenyl phosphine) nickel to give benzene
Benzene

(iii) Tetramerization – Acetylene tetramerizes to form cyclo octate traene (COT) in

the presence of Ni (CN)2
50
 Cyclooctatetraene (COT)

3.10 Formation of alkali metal acetylides –

Reaction due to the acidic hydrogen is give by acetylene and terminal alkynes. Acetylene
and terminal alkynes on treatment with heated sodium evolve hydrogen and form acetylides.
Sodium acetylides can also be formed by treating such alkynes with sodamide

3.11. Exercise

3.11.1 Very short answer type questions:

1. Write the general formula of alkynes.

2. Why do alkynes not show geometrical isomerism?
3. What is Lindlar’s catalyst?
4. Which gas is produced when 1,1-dibromoethane is heated with alcoholic solution of potash.
5. Which can distinguish propyne from propene?
6. Describe a chemical test for distinguishing terminal alkynes from internal ones.
7. Name the compound which results when pen-1-yne treated with sodium in liquid ammonia.
8. Why are terminal alkynes more acidic than other hydrocarbons?
9. Mejor product of below give reaction

10. How many distinct alkynes exist with a molecular formula of C4H6?
11. Name the compound which result when pent–2– yne is subject to catalytic hydrogenation
using a platinum catalyst.

51
12. Name the compound which results when pent–2– yne is treated with sodium in liquid
ammonia.
3.11.2 Short answer type questions:

1. Prepare trans–pent–2–ene from propyne.

2. Draw the product that results when CH3CCl is reacts with CH3CH2COCH2CH3 followed by
addition of H2O.
3. Why alkynes are more stable than alkenes?
4. How to distinguish between 1–Butyne and 2–Butyne.
5. Explain why the hydrogen atoms in acetylene are replaceable with metals?
6. Write a note on the industrial importance of acetylene.
7. Give IUPAC name of the following compounds –

(i) (iii)

(ii) (iv)

8. Explain why acetylene in acidic in nature?

9. How is the following pair distinguished? Give one reaction –

And
10. Write the structural formula for –
(a) 4–Methylpentyne (b) 3, 4, 4 – Trimethyl–1–pentyne

11. Give the structure of the product obtained when 1–pentyne reacts with:
(a) One mole of Br2 (b) One mole of HBr and peroxide

12. Explain why CH3C ≡ 𝐶𝐻 has only one acidic hydrogen.

52
 3.11.3 Long Answer type Question
1. How are alkynes are prepared? Discuss any three methods of their preparation.
2. Discuss the acidity of acetylene and also discuss the relative stabilities of ethane, ethylene
and acetylene.
3. Discuss the electrophilic and nucleophilic addition on acetylene.
4. Acetylene reacts with dil H2SO4 in the presence of Hg++ to give acetaldehyde but with dil
HCl under similar condition it gives vinyl chloride. Explain.
5. An alkyne A with molecular formula C5H8 reacts neither with sodamide nor with ammonical
cuprous chloride. Assign a structural formula to A.
6. Complete the following reactions with full equation
(i) 2–Butyne + Ozone folloed by hydrolysis.
(ii) 2–Pentyne and KMNO4.
7. Starts from acetylene how will you obtain each of the following compounds –
(i) Acetaldehyde (ii) Vinyl chloride.
8. How will you convert acetylene into –
(a) Trans–2–pentene (b) 1, 3–butadiene.

53
UNIT 4
Aromatically & Chemistry of Arenas

Aromatic Compounds have benzene structure.

● Molecular formula of Benzene is C6H6.

● Carbon atoms in benzene joined as ring.
● It has alternate (π) Pi bond
● It has chain & boat form
● Isomers of benzene structures are following

Fis – 1 Isomers of benzene

4.1 Nomenclature of benzene derivatives

4.2.1 When one mono substitution on benzene We add prefiz the name of substituent group to the
word.

Chlorobenzene Bromo Propyl Nithno

Iodo benzene
benzene benzene benzene

● Some derivatives have special name when one substituent prsenct on benzene ring.

Methyl benzene Benzok Acid Methoxy Amino benzene Phenol

54
(Tolvene) (Anisole) benzene (Anilines))

Benzene Sulphonic Acid Benz nitrile Styrenc

Benz aldehyde Acetophenone Benzyl Chloride Benzyl Alcohol

● If two group are substituted to the benzene ring numbering of the carbon atoms of the ring such
that substituent has lowest no. and names ortho, meta, para as (- O , - M , - P) etc.

1, 2 Ribromo benzene or 1, 3 dibromo benzene or 1, 4 Rbromo benzene

O-Ribnomo benzene M-dibromo benzene P-dibromobenzen

● Name as alphabetically prese

P bromo iodo benzene M-chloro nitro benzene P – chloro benzene sulphonic

55
 acid

O-xylene M-xylene P-xylene M-nitro benzoic

When three or more Substituents on benzene numbering start where substituents get lowest

3, 4, didromo T.N.T Tri Nitro 2, 4, 5 Tri bromo

5 nitro, 2 propyl aniline
phenol Toulem Aniline

Poly nuclear aromatic hydro carbon where two or more aromatic ring attached

Napthaler Anthracer phenanthrane

4.2 Molecular Orbital (M.O) of Benzene

● Molecular formula of Benzene is C6H6.

● Each carbon has sp2 hybridized.
● sp2 hybridized mean π (pi) bond is between carbon carbon
● π (pi) is decolised form i.e π bond is shifted
● r is aromatic in nature i.e r has 6π electrons
● It is planar structure
● Valancy of carbon is four
56
● Configuration of carbon is 1r22r22p2

57
 Ground state

Excessed state

● P2 is unhyridized i.e p2 is vacant or not participated in hybridization.

● First draw all C – C bond
● Each carbon has sp2 hybridized i.e one s orbital which is spherical and 2-p orbital which is dumb-
hell shaped
● One unhybdrized p2 orbetal is shown by dolled C- - - ) line
● Angle between C – C – C is 126°
● Lengh C – C is .39A°
● Lenth C – H is 1.90 A°
● First join upper unbridized orbital.

4.3. Aromatically: Huckle rule - Best example of aromatic compound is aromatic which have following
characteristic

● They are planar or flat structure i.e all atoms lie in the same plane
● They have cyclic ring. It may be five, six or seven membered ring.
● Each carbon has sp2 hybridized and one ps has unhybridized
● Due to unsaturation (double bond present), They give electrophilic substation reaction like
nutration, sulphonation, halogenation, friedal craft alkylation, acylation.
● It does not give addition reaction
● The total number of π electrons or ion in the molecule should be (4n +2) where n = 0, 1, 2, 3, 4..
● The unhyridized p2 orbital should give continuous ring with upper i.b and lower i.b
● The reason of lowering of energy is delocalization of π(pi) electrons in the ring.

The huckel Rule (4n +2) Compounds have only decoloized is not property for aromatic character.
They have one more property is called Huckel Rule. In which compound must be cyclic, planar and have
(4n+<) π system where n=0, 1, 2, 3, 4, It anti aromatic compounds have 4n system. It may be neutral,
Cationic, Anionic.

58
4.4 Aromatic character of arenes:

4𝑛 + 2 (𝑛 = 1)
(a) 4 + 2 = 6𝑒
3 𝜋 = 6𝑒

4𝑛 + 2 (𝑛 = 2)
(b) 4 × 2 + 2 = 10𝑒
5 𝜋 = 10𝑒

4𝑛 + 2 (𝑛 = 3)
(c) 4 × 3 + 2 = 14𝑒
7 𝜋 = 14𝑒

4.5 CATIONIC OR ANIONIC AROMATIC COMPOUND

4𝑛 + 2 = 6 𝜋
2𝜋 = 4𝑒
𝑜𝑛𝑒 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝑐ℎ𝑎𝑟𝑔𝑒 = 2𝑒
𝐴𝑟𝑜𝑚𝑎𝑡𝑖𝑐

Cyclopentadiengle

Tropylium
2 π electrons
Ion cyclic conjugated Aromatic
Cyclic conjugalid Aromats
6πe

Some move ex of Aromate compounds

59
Phenol Pyrrole

4.6.. ELECTROPHILIC AROMATIC SUBSTIUENT

1. May be by electrophilis nucleophilic or free radical.

2. Arenium ion intermediali is occer in the electrophilic aromatic substation electrophilic susbtituetion
take place by two steps

Step-1

● Electrophilic attack on benzene ring give electrophile have positive charge. It is resonance
stabilized arenium ion.

Arenium
ion

Step-2

● Arenium ion is not stable as benzene due to pass of aromaticity.

● Arenium ion or wheland remove a proton by base and give stable electrophile substituent
product.

4.7. NITRATION:-

● Nintro group (NO2) introduced in to benzene ring, is called nitration.

● Electrophile (𝑁𝑂2+ ) is produced by mixture of co nitric acid and concentration sulphuric acid?

60
Mechanism:-

Step-1 Formation of Electrophile

𝐻𝑂 − 𝑁𝑂2 + 𝐻2 𝑆𝑂4 → 𝐻2 𝑂 + 𝑁𝑂2+ + 𝐻𝑆𝑂4−

𝐻2 𝑂 + 𝐻2 𝑆𝑂4 → 𝐻3 𝑂 + + 𝐻𝑆𝑂4−

Overall

2𝐻2 𝑆𝑂4 + 𝐻𝑁𝑂3 ⇌ 𝑁𝑂2+ + 𝐻3 𝑂+ + 𝐻𝑆𝑂4−

Slow

Intermediate

Electrophil attack on benzene ring and give unstable intermediate

Step-2 Removal of H+ ion or Proton from the intermediate by base give nitro benzene

4.8 Sulphonation of benzene:- 𝑆𝑜3+ is attacked to benzene ring give benzene

sulphuric acid

Mechanism

Step – 1 In first step generate he electrophile2𝐻2 𝑆𝑂4 ⇌ 𝐻3 𝑂+ + 𝐻𝑆𝑂4 + 𝑆𝑂3

Step – 2 Electrophile attack on benzene to give arenium ion intermediate

61
 Arenium i.Q

Step – 3

Benzene Sulphonic acid

Halogenation of benzene:-

Halogen is attacked to the benzne ring give chloro benzne in acidic medium

Step-1

Generation of electrophile

𝐶𝑙 − 𝐶𝑙 + 𝐹𝑒𝐶𝑙3 → 𝐶𝑙 + + 𝐹𝑒𝐶𝑙4+

Step-2

Slow Step electophile attack on the benzene rings

Benzene rings

62
 Chloro
(Intermediate) Arenium
ion
Step-3

It is fast reaction deportation from the benzene

Chloro benzene

FRIEDAL CRAFTS ALKYLATION When alkyl group is introduced in the benzene ring in the
presence of Lewis acid is known as friedal Gafl alkylation

● Carbocation is intermediate in there reaction

● Stabality of carbocation is tertiary 7 secondary 7 primary

Mechanism

Step-1

𝑅 − 𝐶𝑙 + 𝐴𝑙𝐶𝑙3 ⇌ 𝑅 − 𝐶𝑙 + − 𝐴𝑙𝐶𝑙3 ⇌ 𝑅+ + 𝐴𝑙𝐶𝑙4−

Carbocation
Step-2 Generate Carbocation and attack on the benzene ring.

Arenium ion

Step-3 Peprotanation from the arenium ion

63
LIMITATION OF FRIEDAL CRAFTS ALKYLATION:-
● Rearrangement is possible due to intermediate is carbocation most stable carbocation is
favorable.
● Polysubstitution is possible i.e move than on substituent.
● Aryl halide can not be used in place of alkyl holidE
● The activative group like OH, NH2, or do not facilitate friedal craft alkylation.

FRIEDAL CRAFT ACYLATION:- Acyl group introduced in the benzene rings in the presence of
lewis acid catalyst produced mono acylated Product is known as Friedal Craft Acylation.

Mechanism:-

Step-1 Introduction of Acyl intermediate

A celium ion

Step-2 Acelium ion introduced in benzene ring give introduction

Step-3 Deprotonation from the intermediate

64
4.9 Directing effects of the Groups
(a) Groups are divided into two parts first electron donating groups (CDW), which donate the electron to
the benzene ring at ortho & Para posction. Decreasing order of reactivity of orho & para group.

(b) Second electron withraw groups (C W G) which accept the electron from the benzene ring and
default the meta position.

−𝑁𝑂2 > −𝑁(𝐶𝐻3 )+

3 > −𝐶𝑁 > −𝐶𝑂𝑂𝐻 > −𝑆𝑂3 𝐻 > −𝐶𝑆𝐾

(c) Deactivate orhto & para position

−𝐹 > −𝐶𝑙−> 𝐵𝑟 > −𝑍

(a) When two substituents present on benzene ring substituenst are reinjorces introduce new
substituents.

CH3 – O EP
SO3H (Meta)
NO2 – M NHCOCH3 – OC-P
E NO2
Deactivate

(b) When both groups are opposen to each other than coming groups is difficult to introduced in
benzene ring. However it has two principle

(i) Strongly activating group

65
Birch reduction:-
Reduction of benzene by lithium (or kor na ) in liqammonia 8 known as birch reduction intermediate
between reactant & Product radical anion

1, 4 dihydrobenzene

Mechanism
Step-1 Metal transfer one electron to aromatic ring produce radical an ion which is stablised by
resonance

Step-2 e accept by benzene rings

Stablised by
resonance

Step-3 Reduction of the radical to give anion by electron

Radical Electro Anion

66
Step-4 Protonation of the anion by by alcohol

1, 4 dihydrobenznen

Substituent Effects in the Birch Reduction

Electron with drawing group (EWG) facilate the aromatic ring so reaction is faster ex COOH

Protonation

Electron donating group (EDG) like (OCH3), slow the reaction rate due to intornation on adjacent carbon

4.10 Methods of preparation of alkyl benzene

(a) Friedal Craft Alkylation:- alkyl halide reacts with benzene in presence of lewis acid give alkyl
benzene.

67
(b) Clemmensen Resuction:- Acyl benzene is converted to alkyl benzene in the presence of Zn-Hg C
aqueous HCl. Zn-Hg is zinc amalygam.

HCl Alkyl benzene

(c) Wol-Kishner Reduction:- When by benzaldehyde is converted in to alkyl benzene in presence of

hydringe (NH2 – NH2/KOH)

𝐶6 𝐻5 𝐶𝐻𝑂 𝑁𝐻2 /𝐾𝑂𝐻 ⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗

455 − 475𝐾 𝐶6 𝐻5 𝐶𝐻3 + 𝐻2 𝑂 + 𝑁𝐶

Mechanism

Tolunen

4.11. Alkyl benzene

Alkyl Benzene When direct alkyl group attack to the aromatic ring is known as alkyl benzene.
Rearrangement occur due to intermediate carbocation.

(a) Benzylic oxidation alkyl benzene is converted into benzoic acid is the presence of KMnO 4 (Potassium
permanganate)

68
 (b) Alkyl benzene is converted in to benzylic halide in the presence of N-bromosu cinimidy

With the help of

Radical

4.12 Biphenyl

Methods of preparation of Biphenyl

(a) From Grignard Reagent:- Grignand Reagent is react with alkyl halide in the presence of nickyl
𝑅′ 𝑀𝑔𝐵𝑟 + 𝑅′′𝐵𝑟𝑁𝑖𝐶𝑙2 → 𝑅′ − 𝑅′′ + 𝑀𝑔𝐵𝑟2 Chlorid

Mechanism

Grignard Reagert

(b) Fitting Reaction:- Take two mole of Bromo benzene with sodium in presence of Dry ethen

69
 (c) UL Mann Rection:- In this reaction the taken cupper in place of sodium

Chemical Reaction of Biphenyl:-

(a) Electrophic Subsitution Biphynyl

Para Stable

(b) Nitration

4 4’ dinitro piphenyc

(c) Friedal Craft Reaction

CH3 group is introduced in place of No2 group. Final product is:-

70
4.13.Naphthalane:-

● It is polycyclic compounds due to fused two aromatic rings.

● It is aromatic due to 10π system, cyclic, and planar.
● Benzene ring fused at the ortho position

or

● It follow Huckle rule

● It has one α derivative and β derivative

● Preparation of napthalane:-

(a) From Decalin

Dehydrogenation of Decalin in the presence of pt catalyst at iovc to give napthalane

(b) From furan:-

Furan reacts with benzene to give Dicls-Alder product and on dehydrogenation in the presence of H2/Ni

Furan Benzene Ricls Alder Adduet Napthalane

Properties It give electrophilic substituents

71
1. Nitration on nitration with con NNO3 8 H2HO4 give nitro napthelane

Nitronapthole

2. Friedal Craft Acylation:- on a ceytalation give a acyl naphthalene in presence of lewis acidic.

Acyl napthlen

3. Reduction remove the hydrogen from the benzene ring in the presence of Na(C 2H5OH)

1, 4 di hydro napthelne

4. Oxidation:- oxidation in the presence of cromic acid Cr2O3 in CH3COOH

1, 4 naptho quinola

4.15 .1 Anthracene:-

72
 ● It is aromatic >π = 14e system
● It has sp2 hybridize
● It is cycleic , planer
● It show reasonace.

Prepration:-
1. From Benzyl Chloride:- union of two moleculer of Benzyl chloride give

Benzyl Chloride Benzyl Chlorid ISO dehydro

Anthrocem
anthracone

2. With 1 .1, 2.2 tetrabroethanes in the presence of AlCl3

Anthracem
CHEMICAL PROPERTIES:-

(a) Nitration in the reaction nitration occeir in the presence of acitic an hydride

73
 a nitro anthracem

(b) Halogenation:- It react with Halogen

9, 10 Broma Anthracem

(c) Friedal Crafrt Acyclation:- Acylation in the presence of acetyle chloride and Aluminum
chloride

A Acetyl anthracem

(d) Reduction It is fresence of Na/C2HSOH Addita of H2

9, 10 di hydro anthracene

(e) Oxidation:- in the presence of sodium di chromate

74
 9, 10 anthraqunon

4.16 Exerxise

4.16.1 Very Short Question

1. What is molecular formula of benzene?
2. Give the structure of Anisole.
3. Full name of TNT.
4. What is hybridization of each carbon in benzene?

5. Tropylicim is aromatic prove.

6. What is intermediate in electro phallic substitution reaction?

7. What is electrophile in nitration?
8. What is product of Birch reduction?
9. Alkyl benzene is conveted into Benzylic halide give reagents.
10. Give preparation of Naphthalene
4.16.2 Short Questions
1. What is aromaticity?
2. Napthalene is aromatic prove it.
3. Explain Huckil rule
4. What is Electrophile aromatic substation reaction.
5. Give Limitation of friedal Craft Alkylation.
6. EDG & ERG effect on Birch reduction.
7. Explain clemmenser reduction.
8. Explain Wolf Kishner reduction.
4.16.3 Long Questions
1. Explain Electrophilic aromatic substitution reaction with example.
2. Explain friedal crast Alkylation with mechanism.
3. Explain friedal Crast A Cylation with mechanism.
4. Explain Birch reduction.

75
UNIT V
Alcohols
Formation of alcohols occur when a hydrogen atom is replaced by hydroxyl group (-OH) in a
aliphatic, aromatic and hydrocarbons. These compounds have wide industrial applications and
have many uses in our day-to-day life. According to IUPAC they are known as alkanols and
represented by R-OH.
5.1 Classification – Alcohols may be classified as mono, di, tri or polyhydric compounds,
depending upon the number of hydroxyl group present in the molecule.
CH2OH
CH2OH
CH3OH CHOH
CH2OH
Monohydric CH2OH
Dihydric Trihydric

Monohydric alcohols may classified further as – primary, secondary and tertiary alcohols depend
up on the nature of carbon atom to which hydroxyl group is attached. Some examples are –

CH2 OH CH OH C OH
O
Primary (1 ) Secondary (2 )
O
O
Tertary (3 )
Allylic alcohols – The –OH group is attached to a sp3 hybridized carbon atom and adjacent to
this carbon atom one double bond is present. e.g.-
CH3
H
H2C CH CH2 OH H2C CH C OH H2C CH C OH
Primary H3C CH3
Secondary
Tertiary
Benzylic alcohols – When –OH group is attached to a sp3 hybridized carbon atom which is
present next to the aromatic ring.
CH3
H
CH2 OH C OH C OH
H3C CH3
Primary
Secondary Tertiary

76
Vinylic alcohols - The –OH group is attached to a sp2 hybridized carbon atom and adjacent to
this carbon atom one double bond is present. e.g.-

H2C CH OH
5.2 Nomenclature of monohydric alcohol – For IUPAC naming of a alcohol following
steps need to be followed
1. Name of alcohol is based on the parent hydrocarbon where “e” in the name will be replaced by
suffix “ol”.
2. Select longest and continuous carbon chain, bearing –OH group.
3. Position of –OH group will be mentioned with a number and this number should be the lowest
number. Some examples are -

OH
2 5 3 1
OH 4 4
1 2 3 2 OH
3 1
1-Propanol 2-Butanol 4-methyl-1-pentanol

5.3. By reduction of aldehydes and ketones –

On reduction aldehydes and ketones give corresponding alcohols when hydrogen is added in
presence of catalyst. Generally platinum, palladium and nickel are catalysts.

RCHO + H2 Pt
RCH2OH

NaBH4 H
RCOR' R C R'
OH
5.4. By reduction of carboxylic acids and esters –
When reduction of carboxylic acid takes place in presence of LiAlH 4, it gives primary alcohol in
a good yield.

(i) LiAlH4
RCOOH RCH2OH
(ii) H2O

77
LiAlH4 is an expensive chemical so commercially first acids will be converted in to esters and
then reduction in presence of catalyst takes place.

R'OH H2
RCOOH RCOOR'
Catalyst
RCH2OH + R'OH
+
H

5.5 Hydrogen bonding in alcohols –

Alcohols are –OH group containing organic compounds and they tend to form hydrogen bonds
with each other or with the other molecules. Hydrogen bonding in alcohols occur due to the
partial positive charge on H-atom and partial negative charge on O-atom. This charge separation
with in the molecule creates dipole due to which this molecule form hydrogen bond with other
molecule. The strength of hydrogen bonding increases on increasing the number of bonding sites
and number of hydroxy (-OH) groups present.
Due to the hydrogen bonding physical and chemical properties of alcohols changes, such as
boiling point, due to stronger hydrogen bonding boiling point becomes higher.

H H
O
O H H
H H O
Hydrogen bonds
O
H H
Hydrogen bonding in water
Alcohols are weak acids due to the presence of –OH group. O-H bond is polar because of
electronegativity difference so alcohols can donate H + ion in solution. Acidity of alcohols depend
up on the stability of formed carbanion (alkoxide).

Generally primary alcohols are less acidic than secondary and tertiary alcohols, because he
alkoxide of a primary alcohol is less stable.

An electron releasing group increases the electron density over O-atom due to which polarity of
O-H bond decreases and acidic strength of alcohol decreases.

R R
R CH2OH CHOH R C OH
R R
Primary Secondary 78 Tertiary
Additionally, the electron-withdrawing effect of nearby functional groups or substituents can
increase the acidity of an alcohol by stabilizing the conjugate base. For example, alcohols with
electron-withdrawing groups such as carboxylic acid or sulfonic acid groups adjacent to the
hydroxyl group are more acidic than alcohols without such groups.

Overall, while alcohols are weak acids, their acidity can be influenced by factors such as the
degree of substitution, steric hindrance, and electron-withdrawing effects of nearby functional
groups.

5.7 Reactions of monohydric alcohols

1. Metal salt formation

Alcohols are weak acids than water. When ethanol with sodium metal it produces sodium
ethoxide and hydrogen gas.

CH3 C OH Na
+
CH3 C ONa -
+ + H2
H2 H2

2. Alkyl halide formation

Alcohols give alkyl halides by SN1 and SN2 reactions.

CH3CH2OH + HCl CH3CH2Cl + H2 O

CH3 CH3
H3C C OH + HCl H3C C Cl + H2O
CH3 CH3

3. Reaction with thionyl chloride (SOCl2)

This reaction is more efficient to produce alkyl halide.

Heat
CH3CH2OH + SOCl2 CH3CH2Cl + SO2 + HCl

4. Ester formation
On reacting with acids, alcohols will produce ester.
79
 O O
CH3CH2OH + H3C C OH H3C C O CH2CH3 + H2O
Ethanol Acetic acid Ethyl acetate

5. Formation of carboxylic acid

(a) Oxidation of alcohol with a strong oxidising agent like acidic KMnO4 gives acid.
O
KMnO4
CH3CH2OH H3C C OH
O
H2SO4 /100
(b) CrO3 in anhydrous medium is used to isolate aldehyde from alcohols.

O
CrO3
CH3CH2OH H3C C H
O
H2SO4 /100

(c) Pyridinium chlorochromate (PCC) is a better reagent for the formation of an aldehyde from
an alcohol.
PCC CH3 CH CH CHO
CH3 CH CH CH OH
2

5.8. Dihydric alcohols nomenclature -

Dihydric alcohols are dihydroxy derivatives of alkanes and contain two hydroxy (-OH) groups.
IUPAC naming rules are the same as for primary alcohols, the number of –OH groups is
indicated by adding prefix, di, tri etc. before “ol”. Examples –

OH-CH2-CH2-OH HO-CH2-CH2-CH2-OH
Ethane-1, 2 diol Propane-1,3 triol

5.9 Methods of formation

1. From ethylene –

When ethylene reacts with icy dilute alkaline solution of Bayer’s reagent.
(i) dil KMnO4 H H
H3C C C CH3
H H (ii) OH - OH OH
H3C C C CH3
H OH
RCOOH OH / H
H3C C C CH3
80 OH H
O
2. With O2 in presence of Ag
CH2 Catalyst H2O HC OH
CH2 + 1/2 O2 O
Dil HCl HC OH
Ag / 200-400
O
3. With HOCl
CH2 HC OH H2C OH
NaHCO3
CH2 + HOCl + NaCl + CO2
HC Cl H2C OH
4. From 1, 2 dibromo ethane
H2C Br H2C OH
+ Na2CO3 + H2O + 2NaBr + CO2
H2C Br H2C OH

Physical properties
1. It is a colourless, sweet, viscous liquid with boiling point is 197°C, melting point -11.50C
2. It is soluble in water and ethanol but insoluble in organic solvents.
3. If taken orally it is toxic.
4. Widely used as an antifreeze agent.

5.10 Chemical reactions of glycol

1. Reaction with Na metal
On reacting with Na metal at higher temperature, gives mono and dialkoxide.
O + O
+
H2C OH 50 C H2C ONa 160 C H2C ONa
+ Na + Na +
H2C OH H2C OH H2C ONa

2. Reaction with HCl

At elevated temperature, ethylene dichloride is formed in two steps.
O
H2C OH 160 C H2C Cl
+ HCl + H2O
H2C OH H2C OH

3. Action with phosphorus halides

H2C OH O

160 C H2C Br
3 + PBr3 3 + 2 H3PO4
H2C OH H2C Br

81
When PI3 reacts with ethylene glycol it produces ethylene di-iodide, It is not stable and further
split into I2 and ethylene.
H2C OH H2C I CH2
+ PI3 + I2
H2C OH H2C I CH2

4. Reaction with carboxylic acid

When reacts with acetic acid it gives monoacetate and when reacts in excess it gives diacetate.

H2C OH H2SO4 H2C OCOCH3 CH3COOH H2C OCOCH3

+ CH3COOH
H2C OH H2C OH Excess H2C OCOCH3
Glycol monoacetate Glycol diacetate

5. Reaction with aldehyde and ketones

On reacting with aldehydes and ketones it gives acetals and ketals. Which further reacts with
HIO4 and produces aldehyde and ketone.

H2C OH R O R
+ O C C + H2O
H2C OH H O H

H2C OH R O R
+ O C C + H2O
H2C OH R O R

O R R
HIO4 2 CHCO + O C
C
O R R

6. Oxidation with KMnO4 or K2Cr2O7

H2C OH KMnO4 O
2
H2C OH K2Cr2O7 H OH

Oxidation with Pb (OCOCH3)4 or HIO4

H2C OH Pb(OCOCH3)4 O
2
H2C OH HIO4 H OH

7. Dehydration -
(a) Heating with ZnCl2 gives acetaldehyde
H2C OH ZnCl2
CH3CHO + H2O
H2C OH
82
(b) On heating at 5000°C, it gives ethylene oxide.
H2C OH Heat
+ H2O
H2C OH
O

(c) On heated with conc. H2SO4 dioxane is obtained

H2
HO-CH2-CH2-OH C
H2SO4 H 2C O
+ + H2O
HO-CH2-CH2-OH O CH2
C
H2

5.11. Pinacol Pinacolone Rearrangement –

Pinacol is a compound in which two hydroxy groups are present at vicinal carbon atoms. It is a
white solid.
CH3 CH3 CH3 O
H+
H3C C C CH3 H3C C C CH3
Acid
OH OH CH3
Pinacol Pinacolone

Mechanism –
Step 1- The reaction is occurring in an acidic medium, the -OH group of the pinacol is
protonated.
Step 2- Water is removed from the compound, which produce a carbocation. This carbocation is
tertiary and stable.
Step 3- Rearrangement of methyl group occurs.
Step 4- Deprotonation of doubly bonded O-atom occurs and formation of pinacolone takes place.
H
+
H H
O+
H H H H O
O O O
H3C CH3 H3C CH3 H3C + CH3

H3C CH3 H3C CH3 H3C CH3

Removal of water Rearrangement

Protonation

H
H3C O
H3C O
H3C CH3
H3C CH3 +
H3C H3C
Deprotonation
83
5.12. Trihydric alcohols – nomenclature –

Trihydric alcohols are trihydroxy derivatives of alkanes and contain three hydroxy (-OH) groups.
IUPAC naming rules are the same as for primary and secondary alcohols, the number of –OH
groups is indicated by adding prefix, di, tri etc. before “ol”. Examples –
CH2OH
CHOH
CH2OH
Propae 1, 2, 3 triol

5.13 Preparation
1. From oils and fats

CH2OOCR CH2OH
CHOOCR 3H2O CHOH + 3RCOOH
+
Steam Fatty acids
CH2OOCR CH2OH
Oil or Fat

CH2OOCR CH2OH
CHOOCR + 3NaOH CHOH + 3RCOONa
CH2OOCR CH2OH Sodium salt of
higher Fatty acids
Oil or Fat

2. By fermentation of sugar
Yeast C3H8O3 + CH3CHO + CO2
C6H12O6
Na2SO3

3. From propene
CH3 CH2 Cl CH2 OH CH2 OH CH2 OH
Cl2
CH O
CH NaOH (dil) CH HOCl CH aq. NaOH HC OH
CH2 600C CH2 H2C OH
CH2 CH2
Propene Allyl chloride Allyl alcohol Monochloro Glycerol
cyanohydri
4. From propenal
H2 H2O2 / OH
H2C CH CHO H2C CH CH2OH CH2OH-CHOH-CH2OH
Catalyst 84
Physical properties
1. Glycerol is a viscous, colourless, odourless ad hygroscopic liquid.
2. Boilig point is 290°C. Higher viscosity and higher boiling point is due to hydrogen bonding.
3. Miscible in water, ethanol and immiscible in organic solvents.
4. It taste sweetened and nature wise non-toxic.

5.14. Chemical reactions of glycerol

1. Reaction with sodium
CH2OH CH2ONa CH2ONa
Na Na
CHOH CHOH CHOH
Room temp. Room temp.
CH2OH CH2OH CH2ONa
Mono Disodium
sodiumglycerol glycerolate

2. Reaction with PCl5, PBr3 and PI3

CH2OH CH2Cl
CHOH + 3PCl5 CHCl + 3POCl3 + 3HCl
CH2OH CH2Cl
Glyceral trichloride

CH2OH CH2Br
CHOH + 3PBr3 CHBr + H3PO4

CH2OH CH2Br
1, 2, 3 tribromo
propane

CH2OH CH2I CH2

CHOH + 3PI3 CHI CH + I2
CH2OH CH2I CH2I
unstale Allyliodide
3. Reaction with HI

CH2OH CH2I CH2

warm
CHOH + 3HI CHI CH + I2
CH2OH CH2I CH2I
unstale Allyliodide
85
 CH2 CH3 CH3 CH3
HI
CH + HI CHI CH CHI
-I2
CH2I CH2I CH2 CH3
Allyliodide unstale Propene Isopropyliodide

4. Reaction with oxalic acid

O
CH2OH CH2OOC COOH CH2O CH CH2OH
O
COOH 100-110C H2O
CHOH + CHOH CHOH CHOH + HCOOH
COOH -H2O -CO2 Formic acid
CH2OH CH2OH CH2OH CH2OH
Glycerol Glycerol Glycerol
mono-oxalate mono-formate

CH2OH O
CH2OOC CH2
COOH 260C CH
CHOH + CHOO C
COOH -2H2O -2CO2 CH2OH
CH2OH CH2OH
Allyalcohol

5. Dehydration
CH2OH CH2
Conc H2SO4 / P2O5 / KHSO4
CHOH CH + 2H2O
Heat
CH2OH CHO

6. Oxidation
CHO COOH COOH
[O] [O] [O]
CHOH CHOH CHOH
dil HNO3
CH2OH CH2OH COOH
Glyceraldehyde Glyceric acid Tartronic acid

CHO CH2OH
Fenton's C=O
reagent
CHOH +
CH2OH
CH2OH CH2OH
CHOH Glyceraldehyde Dihydroxyacetone
CH2OH COOH
CH2OH CH2OH
[O] [O] [O] COOH [O]
[O]
C=O C=O C=O CO2 + H2O
KMnO4 COOH
CH2OH COOH COOH Oxalic acid
Dihydroxyacetone Hydroxy Mesoxalic acid
Pyruvic acid

2HIO4 2CH2O + HCOOH + 2HIO3 + H2O

Heat
86
7. Reaction with nitric acid

CH2OH CH2ONO2
Conc. H2SO4
CHOH + 3HNO3 CHONO2 + 3H2O
CH2OH CH2ONO2
Glyceral
trinitrate
Dynamite is prepared from TNG

5.12. Exercise
5.12.1 Very short question–
1. What are alcohols? Give one example.
2. General formula for an alcohol is?
3. Write one method of preparation of dihydric alcohol. Only reaction.
4. Give one example of allylic alcohol and benzylic alcohol.
5. What will be the product when ethyl alcohol reacts with acetic acid?
6. Write any 2 chemical properties of alcohols.
7. What will be the product when ethyl alcohol reacts with CrO3.
8. What will be the product when a dihydroxy alcohol reacts with KMnO4?
9. Give product when two mole of a dihydroxy alcohol reacts in the presence of H 2SO4.
10. Give Pinacol Pinacolone rearrangement. Only reaction.

5.12.2 Short answer type questions –

1. Write down the methods of preparation of monohydric alcohols and its physical properties.
2. Give at least 6 chemical properties of monohydric alcohol.
3. Write down the products when a trihydric alcohol reacts with Fenton’s reagent, HIO4/heat,
oxidation in presence of dil HNO3, oxidation in presence of KMnO4.
4. Write down the methods of preparation of dihydric alcohol and its physical properties.
5. Give at least 6 chemical properties of dihydric alcohol.
6. Write down the preparation of TNG.
7. Give a complete reaction when glycerol reacts with oxalic acid.

87
8. Write down the methods of preparation of trihydric alcohol and its physical properties.
9. Give at least 6 chemical properties of trihydric alcohol.
10. Give products when glycerol reacts with PBr3, PI3 and HI.

5.12.3 Long answer type questions –

1. What do you understand by monohydric word, give methods of preparation of monohydric
alcohol and its chemical reactions?
2. Explain mechanism of Pinacol-Pinacolon reaction and contra-thermodynamic isomerisation.
3. Write down the methods of preparation of glycerol, its physical and chemical properties.
4. Give an example of dihydric alcohol, write down its preparation methods, physical and
chemical properties.
5. Explain acidic nature of alcohols and give chemical properties of a monohydric alcohols.

88
UNIT VI
Phenols

Introduction;
Phenols are first surgical anti septic general formula of alcohols are R-OH when alkyl group is removed
by aromatic nuclear as As-OH is called Phenols.

6.1 Nomenclature:
(i) Monohydric Phenols

1. When one OH group is attached to the Benzene ring:

Phenol o-Chlorophenol p-Cholrophenol m-nitrophenol

(2-Chlorophenol) 4 Chlorophenol 3 nitrophenol

p-nitrophenol 2-napthol p-hydro benzene

4-nitrophel β napthol acid

2. Most of the phenols are known as specific name, e.g.

89
o-cresol m-cresol p-cresol
3. When two op-OH group are present on benzene ring:

Catechol Rescrinol Hydro quinone

O-dihydroxy benzene M-dihydroxy benzene p-dihydroxy benzene
2 hydroxy phenol 3 hydroxy phenol 4 hydroxy phenol

4.When are OH group and two substitutes are present :

4 Chloro-2 methyl 3, 5 dichloro phenol 4 cheloro 3, 5 dinitrophenol

phenol 2 nitrophenol

5. When three –OH group are present on aromatic ring:

90
Pyrogallol Phloro gluicinol

91
 6.2. Structure and Bonding
The chemical formula of phenol is C6H6O It is an aromatic compound. It is also known as carbolic acid

C6H5OH OR

2D structure Phenoxide iQ 3D structure

Bonding in Phenol Inter Hydrogen bonding is present in phenols e.g.

6.3 Methods of Preparation;

(i) From benzene diazonium Chloride;
Followed by reduction to give aniline, aniline and nitrous acid (NaNo2+HCl) give diazonium chloride.
This diazonium chloride warmed with water or diluto acids give phenol. This is laboratory method.

Nitro
Bengen 323K Bengen Anilire Diagotisation Phenol

(ii) From Fusion of benzene sulphonic acid;

Sulphonated with oleum (Fuming H2So4) to form benzene sulphonic acid, When sulphonic acid react
with sodium hydroxide at 573-623K. Sodium pheroxide on treatment with dilute acid or Carbon dioxide
yields phenol

92
 Benzene
Sodium bengene
Bengene Sulphonic Sodium phenoxid phenol
sulphonate
acid

This is Laboratory Method

P Toluene Fuse
P Cresol
Sulphuric acid

(iii)From Grignard Reagent

When Bromo benzene or chloro benzene is react with magnesium in presence of ether, phenyl
magnesium bromide is formed and it is react with oxygen presence of dry ether to give phenoxy
magnesium bromide which give phenol on hydrolysis by mineral acid

Bromo Benzene Phenol Phenoxy Phenol

Magnesium Magnisum
bromide Bromide

93
 (iv) Dow’s Methods

Aryl Halide heated with NaOH at high temperature and pressure give phenol it elimination reaction
via benzyne intermediate

Benzyne

(v) From Salicylic Acid;

Salicylic acid react with soda lime (NaOH + Cao) to give phenol

(vi) Oxidation of
isopropyl
benzene
(Cumene)

Salicylic Acid

Cumen is oxidized in the presence of air in to cumene hydro peroxide in presence of catalyst after that is
decomposed by dilute suplhuric acid into phenol and acetone

Benzene Propene Isoproyl Cumene phenol

benzene hydroperoxide

94
6.4 Physical Properties and acidic character
(i) Pure Phenols are colourless liquids or low melting solids. They tern pink or red on exposure to air and
light due to oxidiation

Phenol (Pink)
Para benzoquinone

(ii) It is characteristic smell

(iii) Phenols have high boiling point due to presence of inter molecular hydrogen bonding

Associated Moluculer

(iv) They are soluble in water due to H-bonding but due to presence of benzene ring solubility is less
alcohols.

(v) Phenols are poisonous in nature but act as disinfectant and antiseptic.

Acidic strengths of phenols

Cleavage of (O -: H) bond support the acidic natureof phenols.

(i) Reaction with active metals: alkali metal (Na arK) to form Phenoxide with evolution of hydrogen gas,

Phenol Sodium Phenoxide

95
(ii) Phenols changer blue litmus to re:

Phenols are weaker acid due to presence of poler O-H group in them

Phenoxide ion (Stable)

(iii) Reaction with alkalis : Phenols react with alkali to give phenoxide. They do not react with carbonate
or bicarbonate

Phenol Sod. Phenoxide

6.5. Comparative acidic strength of alcohols and Phenols
If Compound can donate the proton, It is called acidic.

When phenol is dissolved in water, it give phenoxide ion and proton. This phenoxide ion is very
stable due to reasonance. Oxygen atom has 3 lone pair and a negative charge due to loss of
proton. The negative charge on oxygen atom is transferred to benzene ring. Five reasonance
structure are formed by reasonance. So phenoxid is very stable.

Phenoxide Ion
In case of alcohols, alkyl group is attached to the oxygen atom. Oxygen is electron releasing in
nature due to +i effect so oxygen has partial positive character and can lose hydrogen in alcohol.
So it is less acidic than phenol

Alcohols are less acidic than phenol due to alcohols have electron donating group.

Formula Ka
96
Phenols Ar-OH 10-19
Alcahols R-OH 10-18
Carboxylic Acid R-CooH 10-5
Carbonic Acid H2CO3 10-7

*Due to Acidic nature of phenol, can tern blue litmus red

*Phenols are weaker acid than carboxylic acid

Due to electron withdraw of benzene benzene is more acidic due to reasonance than hydroxyl
group to alcohol oxygen acquire a +ve charge which weakens the oxygen –hydrogen bond and
proton will be release.

Phenoxide D table due due to reasonance negative charge localiged in the benzene ring but in
alcohol negative charge in localzed in single oxygen atom that why phenol is more acidic then
alcohols

Methoxide ion due to + I effect of alkyl group alcohol is less acidic

Effect of Substituents on Acidity

Group one is electron – Withdrawing substituents and electron releasing gp. E.W.S

(i) are – No2, -Cl, -CN, - CHO, -COOH on aromatic ring is facilitate the acidic character. They provide
more election towards benzene ring and stabilized phenoxide.

Ex. –P netrophenol is more acidic than phenol

97
P nitrophenol p nitrophenoxid ion

Electron rich position is ortho & Para poision at para position reasonace is acid than ortho nitro phenol.
So acidic character is

No of netro groups are increasing acidity increasing

2, 4, 6 Tri 2, 4, di 4 nitro 2 nitro phenol

Nitro phenol Nitro phenol Phenol

Effect of Electron Releasing Substitution

E.R.S.
Groups are –CH3, -OCH3, - NH2) on the aromatic ring, weak acidic character.

Acidity of Cresols

Methyl group is electron donating group to the benzene Q. Thus O, M, P issomers of cresols are less
acidic than phenol M gesol is the strongest acid due to hyper conjugation

98
O – Gesol M – Cresol P Cresol

O – Cresol

Anion is destablised Unstable due to

by like charger
+ I of Methyl group

Acidity of O-Cresol is decreased due to + I effert or hyper conjugation

p-Cresol

99
ET effect [ Audity of p gesol is do cresol due to + I effect and hyper conjugation

100
6.7 Resonance staiblizatiom of phenoxide ion
If Compound can donate the proton, It is called acidic.

When phenol is dissolved in water, it give phenoxide ion and proton. This phenoxide ion is very stable
due to reasonance. Oxygen atom has 3 lone pair and a negative charge due to loss of proton. The negative
charge on oxygen atom is transferred to benzene ring. Five reasonance structure are formed by
reasonance. So phenoxid is very stable.

Phenoxide Ion
In case of alcohols, alkyl group is attached to the oxygen atom. Oxygen is electron releasing in nature due
to +i effect so oxygen has partial positive character and can lose hydrogen in alcohol. So it is less acidic
than phenol

6.7. Reactions of phenols – Electrophilic aromatic Substitution Reaction

Phenols give highly electrophilic substitution reaction due to election rich benzene ring, so electrophile
attack on benzene ring where electron density is high

6.8 Acylation The acylation of phenol is an important reaction in organic synthesis, as it allows
for the introduction of various functional groups onto the phenolic compound. The resulting
acylated phenols can be used as intermediates in the synthesis of pharmaceuticals, dyes,
fragrances, and other organic compounds. Additionally, the acylation reaction can be used to
modify the reactivity and properties of phenolic compounds for specific applications

101
Carboxylation;

When phenoxide is heated with carbon dioxide under pressure, a carboxylic group is attach on orhto
position to the –OH group.

This reaction is known as Kolbe – Schmitt reaction

Carboxylic Anion

At lower temp (up to 140°) the ortho isomer dominate and above 140° para isomers is dominate

Mechanism;

Salicylic Acid
6.9 fires rearrangement

6.10.Claisen Rearrangement;

When phenol is treated with allyl bromide in the presence of NaOH formation of aryl allyl ether take
place

Allylphenyl ether
(Allyl ether of phenol)
102
Allyl ether of phenol, rearrange to O-allyl phenol when heated at 200°C

O – allyl-phenol

H O position is occupied than p position is dominate.

4 – Allyl 2, 6, dimethyl phenol

Mechanism;

(i)

Ortho-Poisition

(ii)

Para poisition
Gatterman synthesis

103
6.11 Houben – Hoesh – Reaction
This is the extension of Gatterm ann Synthesis, in this phenol is heated with a mixture of hydrogen
cyaride, hydrogen chloride and anhydrous chloride. An aldehyde group is introduced in the para position
to –OH group

If para poision is occupied than ortho poision is favorable in Houben – Hoesch Reaction, polyhydric
phenols is treated with an alkyl cyanide, hydrogen chloride an the presence of anhydrous ZnCl 2 or ACl3.
Ketimine hydrochloride is formed:

Acyl derivative of phenol

Mechanism;

Step – I

(Intermediate – I)

Step – II Acetaldimminium ion attach on poly phenol

104
Phloroglucinol 1,3,5 Ketimine intermediate
Trihydroxyl benzene

Step – III

Phloroacetophenone

6.12 Reimer Tiemann Reaction

When Phenol react with chloroform in aqueous sodium hydroxide followed by acid hydrolysis
product is solicylaldehyde If carbon tetra chloride is used, solicyclic is formed

Phenol Salicylaldehde

Salicylicacid
– CHO and – COOH group as are present on ortho position.

Mechanism;

105
Step-I Choloro form is react with sodium hydroxide to produce richloro carbine

Dichloro Carben

Step-II Dichloro carbene is electron deficient and react with sodium phenol oxide to form dihalide

Step- III The ortho dichloromethyl phenoxide ion on hydrolyris gives salicyalclohyde (o-hydroxy benzal
dehydroxy)

Salicylaldehyde

6.11. Exercise
6.11.1 Very Short Answer
1) Explain Tulene has low b.P Than Phenol.
2) Give the method of preparation of Picric acid.
3) Explain following example

106
 4) Explain Phenol is not react with sodium bicarbon ate.
5) Phenol is a strong acid than
(a) O-Cresol (b) Carbonic acid (c) O-nitrophenol.
6) Arrange the following compounds in order to increasing acidity.
Phenol, Cyclohexanol, p-bromophenol, p-methox Phenol
7) Why 2,6, di-terti butlphenol is much weaper acid than phenol.
8) Explain conversion of Phenol into Quinol.
9) Give the reagert to convert Phenol into
(i) Salicyladehyde (ii) Phenol thallic
10) Increasing order of solublity in water
𝐶6 𝐻5 𝐶𝐻2 𝑂𝐻 , 𝐶2 𝐻5 𝑂𝐻 , 𝐶6 𝐻5 𝑂𝐻

6.11..2 Short Answer

1) When Phenol is treated with bromine water, a white precipitate is obtained, Give the name & st of
comp.
2) What happended when benzene dizonium chloride is heated with water.
3) Arrange increasing order of acidity 𝐻2 𝑂 , 𝑅𝑂𝐻, 𝐶2 𝐻2
4) Explain why the OH group in phenol is more strongly held as compared to –OH group in alcohol.
5) Explain Electrophile substitute react.
6) Explain Gatterman Reaction.
6.11.4.Long Question
1) Explain Claiser rearrangement.
2) Explaination of kolble-schemitt Reaction.
3) Give Reimer Tiemann Reaction with mechanism.
Give the preparation proportion of phenol

107
 Unit-VII
Chemistry of ethers

to exhibits ethers. Ethers also be regard R– O – R is the general molecular formula ed as

dialkyl derivatives of water and we obtained by replacing its hydrogen atoms by alkyl groups.

H–O–H R–O–R
Water Ether (di alkyl derivative of water)

Simple ether (R – O – R) have same alkyl groups attached to the oxygen atom

e.g. 𝐶𝐻3 − 𝑂 − 𝐶𝐻3 (𝑑𝑖𝑚𝑒𝑡ℎ𝑦𝑙 𝑒𝑡ℎ𝑒𝑟)

Mixed ether (R – O – R’) have different alkyl groups attached to the oxygen atom

e.g 𝐶𝐻3 − 𝑂 − 𝐶2 𝐻5 (𝑒𝑡ℎ𝑦𝑙𝑚𝑒𝑡ℎ𝑦𝑙 𝑒𝑡ℎ𝑒𝑟)

7.1. Nomenclature of ethers
The ethers are termed according to the alkyl groups involved with oxygen atom.

Ether Common name

𝐶𝐻3 − 𝑂 − 𝐶𝐻3 Dimethyl ether

𝐶2 𝐻5 − 𝑂 − 𝐶2 𝐻5 Diethyl ether
𝐶𝐻3 − 𝑂 − 𝐶2 𝐻5 Ethyl methyl ether
IUPAC System – Ethers are named as the alkoxy derivative of alkanes. Ethers are termed as
alkoxy alkanes. Out of these two alkyl groups the larger one chosen as the alkane and the smaller
one as the alkoxy group.

𝐶𝐻3 − 𝑂 − 𝐶2 𝐻5 Methoxy ethane

𝐶2 𝐻5 − 𝑂 − 𝐶2 𝐻5 Ethoxy ethane
Ethoxy propane
𝐶2 𝐻5 − 𝑂 − 𝐶3 𝐻5
Two Isomeric ethoxy propane are

𝐶𝐻3 𝐶𝐻2 𝐶𝐻2𝑂𝐶2 𝐻5 1- Ethoxy propane

𝐶𝐻3 𝐶𝐻𝐶𝐻3
2- Ethoxy propane
𝑂𝐶2 𝐻5
108
7.2 Methods of formation of ethers-
(i) By dehydration of alcohols: alcohol on excess hearting with concentrated sulphuric acid
lost water molecule for every pair of alcohol molecules

At around 180°c, alcohols undergo dehydration. Secondary and tertiary alcohols undergo
dehydration predominantly. While in case of a mixture of alcohols, one alcohol is tertiary and
the other primary or secondary , a tertiary carbocation is formed readily to yield unsymmetrical
ethers

t – Butyl alcohol
isopropyl alcohol t – Butyl isopropyl ether
(ii)By William Son’s Synthesis: heating sodium or potassium alkoxide with an alkyl
halide

Sodium
Alkyl halide Ether Sodium halide
alkoxide

Sodium
Diethyl ether
ethoxide

Potassium
Ethyl methyl ether
methoxide
Williamson’s synthesis is useful for preparing simple and mixed ethers and it is best
to use the alkoxide of the secondary and tertiary alcohols and then react it with a primary alkyl
halide. However, the method fails when tertiary alkyl halides are used since being powerful
nucleophiles and bases, alkoxide ions bring dehydrohalogenation of tertiary alkyl halides to
produce alkene preferentially.

The mechanism of the reaction is possibly-

Alkyl Ether
Alkoxide ion
halide
109
 (iii) alkyl halides heating with silver oxide: Ethers may also be prepared by heating
an alkyl halide or a mixture of two alkyl halides with dry silver oxide.
2𝑅𝑋 + 𝐴𝑔2 𝑂 → 𝑅𝑂𝑅 + 2𝐴𝑔𝑋
Alkyl halide ether
𝑅𝑋 + 𝐴𝑔2 𝑂 + 𝑅′ 𝑋 → 𝑅𝑂𝑅′ + 2𝐴𝑔 𝑋
Mixed ether

Ethyl methyl ether

(iv)By Grignard Reagents: By the action of a Grignard reagent on a halogenated ether

𝑅𝑂𝐶𝐻2 𝐶𝑙 + 𝑋𝑀𝑔𝑅 → 𝑅𝑂𝐶𝐻2 𝑅 + 𝑀𝑔. 𝑋. 𝐶𝑙
Grignard Higher ether
Lower chloro ether
reagent

𝐶𝐻3 𝑂𝐶𝐻2 𝐶𝑙 + 𝐵𝑟𝑀𝑔𝐶2 𝐻5 → 𝐶𝐻3 𝑂𝐶𝐻2 𝐶𝐻2 𝐶𝐻3 + 𝑀𝑔𝐵𝑟𝐶𝑙

Methyl Propyl ether

7.3 General physical properties: CH3 – O – CH3 and CH3-O-C2H5 are gases while other
members ethers are colorless good smelling volatile liquids. Their vapors are highly
inflammable.

The bond angle is not exactly 180° so ethers

are weakly polar. Ether possess a small net
dipole moment (=1.18D) because two C–0
bonds do not cancel each other.
Polar ether molecule
Dipole moments is 1.18D
The boiling point of ethers does not substantially affect due to weak polarity, while the
boiling points are much lower than those of alcohols having hydrogen- bonding of the same
molecular weight. While it is not possible in ether due to absence of H-bonding. Ethers are
soluble in water to some extent.

110
 Water ether

General Chemical Properties: As compared to alcohols ethers are very inert due to the absence of
a any active functional group. Ethers do not react with alkalies even on boiling. They are also not
affected by oxidizing and reducing agents.

7.4 Chemical reactions – cleavage and autoxidation

(i) Autoxidation: Ethers undergo autoxidation i.e. they react with atmospheric oxygen to form
peroxides which is poisonous and explosive in nature.

Diethyl ether Peroxide of diethyl ether

All ethers exposed to the atmosphere for any time usually contain peroxides. Peroxides are
hazardous became they explode violently on heating.

Mechanism

Autoxidation includes the subsequent free radical chain mechanism

(𝐶𝐻3 )2 𝐶𝐻𝑂𝐶𝐻(𝐶𝐻3 )2 + 𝑅̇ → (𝐶𝐻3 )2 𝐶𝐻𝑂(𝐶𝐻3 )2 𝐶̇ + 𝑅𝐻

(𝐶𝐻3 )2𝐶𝐻𝑂(𝐶𝐻3 )2 𝐶̇ + 𝑂2 → (𝐶𝐻3 )2 𝐶𝐻𝑂(𝐶𝐻3 )2 𝐶 − 𝑂 − 𝑂̇

(𝐶𝐻3 )2 𝐶𝐻𝑂(𝐶𝐻3 )2 𝐶 − 𝑂 − 𝑂̇ + (𝐶𝐻3 )2 𝐶𝐻𝑂𝐶𝐻(𝐶𝐻3 )2 → (𝐶𝐻3 )2 𝐶𝐻𝑂(𝐶𝐻3 )2 𝐶𝑂𝑂𝐻 +

(𝐶𝐻3 )2 𝐶𝐻𝑂(𝐶𝐻3 )2 𝐶̇
A hydroperoxide

(ii) Reaction with acids: Ethers are inert to several reagents. They are split by strong acids but
not effected by dilute acids .

(a) Hot conc. HBr: Ether on boiling with HBr forms two molecules of alkyl bromide. A molecule
of alcohol is formed initially which reacts further to form a second molecule of alkyl bromide.
111
 130−140°𝐶
𝐶2 𝐻5 𝑂𝐶2 𝐻5 + 2𝐻𝐵𝑟 → 2𝐶2 𝐻5 𝐵𝑟 + 𝐻2 𝑂

Mechanism

Ether due to its basic nature dissolves in the acid with the formation of an oxonium ion.
Then undergo a SN2 reaction with the bromide and produces ethyl bromide and ethyl alcohol.

Oxonium ion

In the next step the ethyl alcohol reacts with HBr to yield a second molecule of ethyl
bromide

Protonated ether attack by nucleophilic halide ion, with the displacement of the weakly basic
molecule of alcohol:

good leaving group

(Weak base)

Quick displacement of the strongly basic alkoxide ion takes place from the neutral ether.

poor leaving group

112
 (Strong base)

Depending upon conditions and the structure of the ether. SN2 displacement by primary alkyl
group, where as SN1 displacement a tertiary alkyl .

1.

2.

(b) Hot. Conc. H2SO4: Secondary and tertiary ether in hot conc. Sulfuric acid form alkenes.

Methyl t -butyl ether Isobutylene

Reaction with Lewis acids: Because of the unpaired electron on the oxygen atom, ethers form
stable complexes with Lewis acids

Cleavage of alkyl ethers by acids is generally not uses as a procedure for the preparation
of alkyl halides or alcohols since ethers are often prepared from these compounds. Al though
aromatic ethers are cleaved by a rigorous treatment with HI and HBr, they can be cleaved under
milder conditions with boron tribromide (BBr3) a Lewis acid.

(iii) Chlorination – Ether gives substitution products with chlorine, the H atom combined
directly to the carbon atom connect to the oxygen atom is most readily replaced. The amount of
halogenation depends upon the conditions of the reaction e.g. in the dark, diethyl ether reacts
with chlorine to give 1, 1- dichloro ethylether

113
In the presence of light, however the same reaction yield pentachloro diethyl ether.

Ether Pentachloro diethyl

ether.
(iv) Reactions involving cleavage of C – O bonds

(a) Hydrolysis: When boiled with water or treated with steam they from corresponding alcohols
by rupture of one C – O bond

𝑅 − 𝑂 − 𝑅 + 𝐻2 𝑂 → 2𝑅𝑂𝐻
Ether alcohol
The rate of hydrolysis is faster in presence of acids.

(b) Action of PCl5 :on heating with PCl5 both the C – O bonds break to produce alkyl chloride

Alkyl chloride
7.5 Zeisel’s method- The reaction of ether with hydriodic acid is used for detecting and
estimating the alkoxy group in a compound. A Known weight of ether is heated with nearly
57% HI. The alkyl iodide so formed is volatile.

The methyl or ethyl iodide then liberated is absorbed in alcoholic silver nitrate solution. Alkyl
halide react with AgNO3 to forms the precipitate of silver iodide. The precipitate is filtered,
washed, dried weighted

One mole of silver iodide precipitate corresponds to the presence of one methoxy or one ethoxy
groups the case may be. Thus the amount or number of – OR group can be calculated from the
weights of silver iodide and the compound.

114
 Chemistry of Epoxides

Epoxides contains a three membered ring:

Epoxide ring,
(Oxirane ring)

Ethylene oxide Propylene oxide Tetrahydro furane

(1,2–Epoxyethane) (1,2–Epoxypropane) (THF)

Ethylene oxide (oxirane-IUPAC) is a three – membered cyclic epoxide. In the numbering of

these rings the oxygen is always considered position.

2–Ethyle–3–methyl oxirane
Comon epoxides such as tetrahydrofuran and dioxane, because of their inertness, are often
used as a solvent. They can be break by the action of strong acids. Due to strain epoxides are
inimitable chemical reactivity.

Ethylene Ethylene oxide

7.6 Synthesis of epoxides: Reaction of alkene with a peroxycarboxylic acid (RCO3H) in an

inert solvent. Such as CHCl3 or CCl4, yields an epoxide or oxirane.

Peroxybenzoic acid (C6H5CO3H) and m-chloroperoxybenzoic acid are commonly used

peroxy acids.

115
 m-chloro peroxy benzoic Pheryloxirane (95%)
Styrene m-chlorobenzoic acid
acid (m-CPBA) (Styrene oxide)

The reaction path involved transfer of an oxygen from the peroxy acid directly to the alkene in
one step.

Alkene Peroxyacid Epoxide Acid

Epoxides can be synthesis by using halohydrins and prepared by electrophilic addition of
HO – X to alkenes. epoxide is produced by the eliminated of HX .

Trans–2– 1, 2 – Epoxyeyclohexane
Cyclohexane cyclohexanol (73%)

The formation of an epoxide by action of a halohydrin is an intramolecular Williamson ether

synthesis.

A bromohydrin An epoxide

7.7 Preparation of epoxides

116
Epoxides are three – membered ring containing compounds which gives them unusual properties
than ethers.

(1) There are two important commercial processes for the prepared of ethylene oxide.
(a) The simplest epoxide, ethylene oxide is prepared through oxidation of ethylene in the
presence of air, catalyzed by Ag2O.

Ethylene Ethylene oxide

(b) The second method includes the reaction of alkenes with peracids like, peroxybenzoic
acid, or m – chloroperbenzoic acid etc. This method is known as epoxidation.

Ethylene Peroxy benzoic acid Ethylene oxide

Cyclohexene oxide
Cyclohexane

This method is the utmost frequently used for the preparation of epoxides in the
laboratory. Among the various peracid m – chloroperbenzoic acid is preferred and is
commercially available as a colorless crystalline solid.
(2) Epoxides may also be commercially obtain from halohydrins by ring closure in the presence
of a base by an intramolecular displacement reaction.

Ethylene Ethylene halohydrin Ethylene oxide

Propylene Propylene chlorohydrin Propylene oxide

117
The transformation of halohydrin into epoxides by the reaction with base is an adaptation of the
Williamson synthesis because alcohol and halide commences to be a part of the same molecule.

A small proportion of the alcohol occurs as alkoxide in the presence of hydroxide ion. The
alkoxide replace halide ion from another portion of the same molecule to produce the cyclic
ether.

Since halohydrins are obtained from alkenes by combination of halogen and water to the carbon
– carbon double bond, this method change alkene into an epoxide.

7.8 Reactions of epoxides- Acid and base-catalyzed ring opening of epoxides

Ring opening: epoxides are highly reactivity, which is due to the opening of the highly
strained three – membered ring, opening of the ethylene oxide ring releases strain and provides a
driving force for the reaction.
(a) Epoxides easily catalyzed by acid and unlike ordinary ethers can even be cleaved by
bases.
Acid–catalyzed cleavage : Acid cleave the epoxide ring leading to the formation of a trans
1, 2 – glycol.

Ethylene oxide Trans ethylene glycol

Ethylene oxide 1, 2 – Ethanediol

118
 Ethylene bromohydrin
(2 – Bromoethanol)

(b) Base – catalyzed cleavage –

Sodium ethoxide 2–Ethoxyethanol

Ethylene oxide 2 – Aminoethanol

(Ethanol amine)
7.9 Orientation of ring opening of epoxides-
In symmetrical epoxide (ethylene oxide), both carbons are equivalent so either can be suffer
nucleophilic attack but in an unsymmetrical epoxide, the carbon are not same and the yield we
get depends on which one is preferentially attacked. Orientation of cleavage of epoxides depends
on whether the reaction is acid–catalyzed or base–catalyzed. Consider, two reactions of
isobutylene oxide.

Here, in general, the nucleophile attacks the more substituents carbon in acid–catalyzed and the
less substituted carbon in base – catalyzed cleavage. So, both are of the SN2 type.

7.10 Reaction with Grignard reagents or methyllithium – The epoxide ring may be
opened by Grignard reagents resulting in an alcohol formation.

119
 Primary alcohol
Chain has been lengthen by two
carbons

Ethylene 1 - Hexanol
oxide

7.11 Exercise

7.11.1Very short answer type questions

1. What are ethers? Give two examples.

2. What happen when?
(i) Ether is heated with phosphorous pentachloride.
(ii) Ether is heated with concentrated sulphuric acid.
3. Alcohols have higher boiling points than the corresponding isomeric ether?
4. Diethyl ether behaves as a base.
5. What is autoxidation in ether?
6. Write a note on Williamson’s synthesis.
7. Why Zeisel’s method is used?
8. Name the following structures-
(i) (𝐶𝐻3 )2 𝐶𝐻 𝐶𝐻2 − 𝑂 − 𝐶𝐻2 𝐶𝐻(𝐶𝐻3 )2
(ii) 𝐶𝐻3 − 𝑂 − 𝐶𝐻(𝐶𝐻3 )2
(iii) (𝐶𝐻3 )2 𝐶 − 𝑂 − 𝐶𝐻2 𝐶𝐻3
9. Write the structure formula for
(i) 3 – methoxy hexane
(ii) 1, 2 – epoxy pentane
(iii) Cyclohexene oxide.
10. Name the following ethers according to IUPAC rule

120
 (i)

(ii)

7.11.2. Short answer type questions

1. Account for the following-

(i) Presence of acid is necessary for the cleavage of ethers.
(ii) Sometimes explosion occurs during distillation of an ether sample.
2. How would you prepare 𝐶𝐻3 − 𝑂 − 𝐶𝐻(𝐶𝐻3 )2 starting from methanol and 2 - propanol?
3. How would you prepare the following compounds using a Williamson synthesis?
4. Predict the following reaction-

5. Predict the major product of the following reaction-

6. Predict the major product of the following reactions:

7. Write fomulas for:

121
 (i) 2, 2 – diethyloxirane
(ii) Cyclooctene oxide
8. Treat the Grignard reagent with ethylene oxide.
9. Complete the following equation-

(i)

(ii)

(iii)

10. How could you prepare phenyl ether from benzene?

7.11.3. Long Answer type Question

1. What is ethers? Give two examples of ethers. Discuss the formation of ethers.
2. Discuss about the cleavage and autooxidation of ether.
3. What is Ziesel’s method? Discuss with example.
4. What is Williamson ether synthesis? Discuss in detail.
5. Discuss acidic cleavage of ethers. Why HI and HBr are more effective than HCl in
cleaving ethers.
6. What is epoxides. Discuss the difference between ether and epoxide and their reactivity.
7. Discuss the mechanism of acid – catalyzed ring opening reaction of epoxides with
example.
8. Predict the major product of the following reactions-

(a)

122
 (b)

9. Discuss the reaction of Grignard reagent with epoxides with example.

10. Discuss the orientation of epoxide ring opening reaction.

123
 Unit-VIII

Chemistry of Organic Halides

Organic halides or alkyl halides are alkanes containing one or more halogens, also known as
haloalkanes or halogenoalkanes. General formula for alkyl halide is CnH2n+1X.

When one or two hydrogen atoms in an aliphatic hydrocarbon are replaced by one or two
halogen atoms (Fluorine, chlorine, bromine or iodine) then formation of haloalkanes occur. They
can also be synthesized in laboratory by using many organic compounds as starting material,
such as alkanes, alkenes, alcohols and carboxylic acids. Generally haloalkanes contain a halogen
(X) atom which is attached to the sp3 hybridized carbon atom of alkyl (R) group.

The R group may be a straight or branched carbon chain, which may be either saturated
(containing only single bonds) or unsaturated (containing one or more double or triple bonds).
Some examples of haloalkanes are –
I H H
2
H3C C C Br
CH3CH2Cl CH3-CH-CH3
CH3
Chloroethane 2-iodopropane 1-bromo-2-methylpropane

Alkyl halides are commonly used as solvents, intermediates in organic synthesis, and as reagents
in various chemical reactions. The properties of alkyl halides depend on the specific halogen and
alkyl group present, as well as the position of the halogen atom in the alkyl chain.

8.1 Classification of Alkyl Halides

On the basis of different aspects alkyl halide can be classified as -

1. On the basis of number of halogen atoms

(a) Mono haloalkane – When only one halogen atom is present in alkyl group.

e.g. CH3CH2CH2-X (Where X = Cl, F, Br or I)

(b) Di haloalkane – When two halogen atoms are present in alkyl group.

e.g. X CH2CH2CH2-X (Where X = Cl, F, Br or I)

(c) Tri haloalkane – When three halogen atoms are present in alkyl group.
124
e.g. X CH2C-CH2-X (Where X = Cl, F, Br or I)
X

On the bases of position of halogen atom in alkyl group

There are 3 types of alkyl halides o the bases of position of halogen atoms –
(a) Primary alkyhalide
(b) Secondary alkylhalide
(c) Tertiary alkylhalide
Primary (1°) alkyhalide – Those alkylhalides, in which the carbon atom at which halogen atom
is present is attached directly to only one alkyl group.

CH3 H2
e. g. CH3CH2CH2 H3C C C Cl
Br H

Secondary (2°) alkylhalide - Those alkylhalides, in which the carbon atom at which halogen
atom is present is directly bonded to two other alkyl groups.
Cl Cl
e. g. CH3 C CH CH3 C C CH3
3
H H H2

Tertiary (3°) alkylhalide - Those alkylhalides, in which the carbon atom at which halogen atom
is present is directly bonded to three other alkyl groupse.g.
CH3 Cl
CH3 C Br CH3 C CH CH
2 3
CH3
CH3

Nomenclature of alkyl halides -

Generally alkyl halides are named as haloalkanes.

CH3 H2
e.g. CH3CH2CH2 Cl H3C C C Br
H
1-chloropropane 1-bromo-2methylpropane

According to IUPAC naming system for naming compounds following steps need to be followed

125
1. Select the longest carbon chain

2. Start the numbering of carbon atoms, from that side of chain from where halogen atom
carrying C-atom will get lowest number.

3. If double/triple bond are present then numbering of carbon atoms will start from where
double/triple bond will get lowest number.
CH3 H2
e.g. H2C C CH2 I
H3C C C Br H
CH3
3 3
2 1 1 2

1-bromo-2, 2-dimethylpropae 3-iodoprop-1-ene

1. Halogen atom present in arylhalides will be named as “halo” (fluoro, chloro, bromo).

2. If more than one halogen atoms are present in the ring then their position on the ring will be
mentioned by mathematical numbers (1, 2, 3…) or by prefix like ortho, meta and para.

e.g. Br Cl I Cl
Cl

1-bromobennzene 1-chlorobenzene 1-iodobenzene 1, 2-dichlorobenzene

I Br
CH3 H2C Br

I Br
Br
1, 3-diiodobenzene 1, 4-dibromobenzene 3-bromotoluene Phenylbromomethane

8.4. Mechanisms of nucleophilic substitution reactions of alkyl halides

When haloalkanes react with hydroxide ion in aqueous medium they produce alcohols through
SN1 or SN2 reaction. By substitution of haloalkanes and sulfonic ester, alcohols can be prepared
efficiently with a good leaving groups.

The hydrolysis of haloalkanes will take place by SN 1 mechanism or SN2 mechanism, it depends

126
up on the structure of substrate, nucleophile, leaving group and solvent.

1. SN1 reaction mechanism

SN1 reaction is known as unimolecular nucleophilic substitution reaction. It is a two-step

mechanism and follows first order kinetics.

Step I

1. Due to the presence of nucleophile (electro rich species), heterolytic fission of carbon-halogen
bond takes place and formation of carbocation occurs.

2. It is slowest and rate determining step, a huge amount of energy is required to break the bond.

3. Due to solvation effect bond is broken in a protic solvent.

4. Rate of reaction depends upon only haloalkane not on nucleophile.

Step II

1. Nucleophile attacks the carbocation and bond formation occurs, resulting the formation of a
new compound.

2. Because of the higher stability of tertiary carbocations, 3° alkyl halides give SN1 reaction very
fast.

3. Allylic and benzylic halides are also very reactive towards SN 1 reactions.

Step-1 Formation of carbocation by heterolytic fission

CH3 CH3
H3C Br H3C C + Br
CH3 CH3
Step-2 Nucleophillic attack
CH3 CH3 H
H3C C + H O H H3C C O
CH3 CH3 H

Step-3 Deprotonation of protonated nucleophile

CH3 H CH3
H3C C O + O H3C OH + H3O
H H
CH3 H 127 CH3
8.5 Steps of SN1 reaction mechanism

2. SN2 reaction mechanism

SN2 reaction is known a bimolecular nucleophilic substitution reaction. It is a one-step

mechanism and follows second order kinetics.

Steps involved in SN2 reaction mechanism are –

1. From the opposite side of the leaving group electron rich species (nucleophile) attacks upon
the substrate.

2. At the time of nucleophilic attack, bond breaking between substrate and leaving group starts.
3. Formation of transition state occurs.

4. Here inversion of configuration occurs which means that configuration of chiral carbon atom
will be changed in product from the starting material.

5. The leaving group departs and nucleophile takes the place of it.

6. This mechanism is possible in aprotic solvents and with strong nucleophiles.

H H H_ H
_
HO
H Cl   H _
+ OH C Cl OH + Cl
H H H
Nu attack from Transition state Inversion of configuration
back side

Steps of SN2 reaction mechanism

8.6.Energy profile diagram of SN1 reaction

SN1 reactions are multiple-step reactions, the energy diagram of SN1 mechanism has two

128
Fig. 8.1 Energy diagram of SN1 reaction

Curves, and one curve shows one step. Step 1 has highest activation energy, so this step is the
slowest step and called as rate-determining step. Formation of intermediate in the step 1 shows
carbocation formation.
Here carbocation is the product of step1 and act as reactant for step 2. Carbocation is having
lower energy comparing to transition state 1 but this cation is still a higher energy product and
very unstable, which is why step 2 will take place and formation of product occurs.
In energy diagram product is having low amount of energy than reactants, which shows that
product is quite stable and reaction is exothermic reaction.

8.7 Energy profile diagram of SN2 reaction

The change in energy during SN2 reaction has been shown in the given Fig. (8.2). SN2 reaction is
a single step mechanism so in energy diagram only one curve is present. Products are having
lower energy than the reactants, so the reaction is exothermic reaction.

129
Fig. 8.2 Energy diagram of SN2 reaction

Transition state: This is the highest point on the energy profile, representing the point at which
the nucleophile and the leaving group are in the process of exchanging positions. At this point,
the energy of the system is at its maximum. The energy required for the reaction to proceed is
determined by the difference in energy between the reactants and the transition state. This energy
is known as the activation energy (Ea).

8.8 Polyhalogen Compounds

Carbon compounds with more than one halogen atom are polyhalogen compounds. These
chemicals are useful in industries and agriculture. Some examples of these compounds are
CHCl3, CH2Cl2 and CHI3.

Chloroform (CHCl3)
130
Chemical formula of chloroform is CHCl3 and its IUPAC designation is trichloromethane. By
the overlapping of sp3 hybrid orbitals of C-atom with 1s orbital of H-atom and 3 partially filled
p-orbitals of Cl-atoms, then formation of CHCl3 occurs. The structure of CHCl3 is tetrahedral.
H

C Cl
Cl
Cl

Fig. 8.3 Structure of CHCl3 (Trichloromethane)

8.9. Methods of preparation of Chloroform

1. Lab Preparation
Chloroform can be prepared by distillation of a mixture of ethanol and CaOCl2.

CaOCl2 + H2O Ca(OH)2 + Cl2

C2H5OH + Cl2 CH3CHO+2HCl

CH3CHO + 3Cl2 Cl3CCHO + 3HCl

2Cl3CHO + Ca(OH)2 2CHCl3 + (HCOO)2Ca

2. By chlorination of methane

hυ CHCl3 + HCl
CH4 + Cl2
Controlled chlorination

8.9.1 Properties of CHCl3

1. It has no colour, sweet smelling liquid.

2. Its density is higher than water.

3. Sparingly soluble in H2O and completely missible in organic solvents like ethanol and ether
etc.

131
4. Its poisonous in nature. After the inhalation of its vapours a person becomes unconscious. So
it is used as an anesthetic.

5. In presence of light it reacts air and produces phosgene a poisonous gas.

CHCl3 + O2 COCl2 + HCl

Phosgene

To avoid this reaction CHCl3 is always stored in a dark coloured bottle and a small amount of
ethanol also added to the bottle because ethanol reacts with phosgene gas if in case it is formed.

2C2H5OH + COCl2 (C2H5O)2 CO + 2HCl

Diethylcarbonate

8.9.3. Its Uses

1. Pharmaceutical industry.

2. Used as reactant in synthesis of chloropicrin, chloretone etc.

3. As solvent in laboratories.

4. It has anaesthetic properties but poisonous in nature.

5. Used as Freon Refrigerants.

8.10 Effects on Environment

1. Nervous system of human body gets irritated on inhaling chloroform vapours.

2. A small amount of chloroform can cause dizziness, weariness, and headaches.

3. If it is in direct contact with skin then causes skin wounds.

4. Its long term exposer damages liver and kidney.

8.11 Carbon tetrachloride (Tetrachloromethane) CCl4

It has no color, it is oily liquid, immiscible in water but miscible in organic solvents. It is a liquid
so its boiling point is 350K and inflammable in nature.
8.11.1 Uses of CCl4
1. Widely used, in the manufacturing of aerosols.
132
2. For the formation of chlorofluorocarbons.

3. Used as solvent in pharmaceutical industry.

4. As solvent in oil, paint and wax industry.

5. For dry cleaning of cloths.

8.12. Harmful effects on humans

1. Its exposer liver cancer, dizziness, nausea, vomiting and damage of nerve cells.

2. An exposer of CCl4 may stop heart beats.

3. It irritate eyes if come in touch with them.

8.12.1. Effect on environment

1. CCl4 vapors cause ozone layer depletion which may lead to skin cancer, eye illness etc.

8.13. Aryl Halides

When one hydrogen atom is substituted with one halogen atom on benzene ring then aryl halide
is formed. They are also known as halobenzene. These are organic compounds with generally
known by the formula RX. Where R is aryl grp and X is halogen atom. For example,
Chlorobenzene, bromobenzene and iodobenzene etc.

Cl Br I

Chlorobenzene iodobenzene bromobenzene

8.14. Preparations of haloalkanes

1. Halogenation of benzene
This is the oldest known method for the synthesis of aryl halides.

Br
AlCl3
+ Br2 + HBr

133
2. Sandmeyer reaction
When diazonium salt reacts with CuBr, CuCl, or KI and gives an aryl halide, this reaction is
known as Sandmeyer reaction.

NH2 + _
N2Br Br
NaNO2/HBr
CuBr
o O
+ N2
0-5 100
Aniline Benzenediazoniumbromide

8.15. Reactions of aryl halides

1. On reacting with Mg in presence of dry ether, aryl halides give Grignard reagents.

Br MgBr
Mg

Dry ether
Grignard reagent
2. Nucleophilic substitution reaction
Halo alkanes are not very reactive toward nucleophilic substitution reactions. Due to the steric
hindrance generated by the benzene ring, aryl halides do not show SN2 reactions. In the same
manner, phenyl cations are unstable, so SN1 reactions are not possible. In aryl halides, due to
double bond character carbon – halogen bond is shorter and elimination of halogen atom from
aryl halides is not an easy step.

Cl Cl + Cl + Cl +

_ _

1. SNAR reactions
Aryl halides show nucleophilic substitution reactions, Carbon atom that is attached to halogen
becomes susceptible for nucleophilic attack due to the electron withdrawing nature of halogen
atom. Some examples are -
134
 Br OH
NO2 _ NaHCO3 NO2
+ OH o
H2O 130
Ortho nitrobromobenzene Ortho nitrophenol

Br Br
O2N NO2 _ O2N NO2
NaHCO3
+ OH
H2O 40 o
NO2 NO2

2, 4, 6 tri- nitrobromobenzene 2, 4, 6 tri- nitrophenol

4 SNAR reaction /addition-elimination reaction mechanism

SNAR reaction is an example of addition-elimination reaction, which is a two-step mechanism.
First step is addition and next step is elimination. This reaction proceeds through carbanion (an
intermediate), stabilizes by delocalization of electrons. Formation of p-nitrobanzene from p-
nitrophenol is the example of this reaction.
First step
Nitro group deactivates the ring and generate partially positive charge on the carbon at which
halogen atom is attached. Now a cation has been generated which acts as a weak nucleus.
I I I I

+
+ +
N N _ N _ N _
O O O O O O O O

Second step
Now hydroxide ion (OH–) will attack on the nucleus.
I
I OH
_
+ + OH _

NO2 NO2
Carbanion

135
Third step
From this carbanion, elimination of iodide ion occurs and formation of phenol takes place.

OH OH
I
_
_
_ + I

NO2 NO2

8.16. Elimination-addition reactions

Aryl halides do not show substitution reactions generally. But, under high temperature and
pressure, these compounds can show substitution reactions. Example of this type of reaction is
formation of sodium phenoxide from chlorobenzene.
_
1.
Cl ONa+
NaOH
+ +
350, pressure

Likely at a low temperature, bromobenzene reacts with KNH 2 and gives aniline.

2.
Br NH2
+
_ _ 40o
+ KNH2 + KBr
NH3
Bromobenzene aniline

8.17. Mechanism for aniline formation

Synthesis of aniline from benzene takes place by the formation benzyne intermediate. When a
benzene contains theoretical triple bond then this molecule is called as benzyne. The structure of
benzyne is –

Benzyne

136
Benzyne structure does not contain a true triple bond. The extra bond formation occurs by the
overlapping of sp2 orbitals on adjacent carbon atoms of the ring. These sp2 orbitals are in the
same plane as the ring and they do not overlap with pi orbitals of the aromatic ring. This bond is
weak and highly unstable so very much reactive.
Step I

1. A base (very strong) will eliminate a weak H+ ion from the carbon atom which is at α-position

from that carbon at which halogen atom is attached.

Br _ Br
+ NH2 _
H

Cl Cl + Cl + Cl +

_ _

_
2. Anionic electrons are stabilized by electronegative halogen atom, elimination of halogen atom
occurs and formation of benzyne takes place.

Br _
_ + Br

Benzyne

3. Highly reactive and unstable benzyne again reacts with amide ion and gives a new cation.

_ NH2
+ NH2 _

4. Newly formed carb-anion abstract a H+ ion from NH3 molecule, an acid-base reaction and
preparation of aniline takes place.

NH2 NH2 _
_ + NH3 + NH2
H

137
 8.18. Relative reactivity order of alkyl halides vs allyl, vinyl and aryl
halides
Reactivity order is Allyl alides > Alkyl halides > Vinyl halides > Aryl halides

CH2-CH CH CH2 Cl CH3 C H2C CH Br Cl

Cl
H2
Allyl halides Alkyl halide Vinyl halide Aryl halides

Explanation –
1. On the bases of stability of carbon-halogen bond-
On the bases of carbon-halogen bond stability, the reactivity order is
aryl > vinyl > allyl > alkyl
Due to the resonance, carbon-halogen bond is more stable in aryl halides while in alkyl halides
there is no resonance so alkyl halide is less stable.

8.18. Resonance in Aryl halides, due to which carbon-halogen bond is stable

1 . On the bases of stability of carbocation-
During SN1 reactions, elimination of halogen leads to the formation of cation and stability of
cation is an important factor for the reactivity. The more stable carbocation, the more reactive
halide. So on the bases of stability of carbocation, the reactivity order is -
allyl > alkyl > vinyl > aryl.

8.19. DDT (Dichloro diphenyl trichloro ethane)

Its IUPAC name is 2, 2 bis (4-chlorophenyl) - 1, 1, 1-trichloroethane and molecular formula is
C14H9Cl5.
Structure
Cl

CH CCl3

Cl
138
Properties – It is a colorless, tasteless, crystalline and odorless compound. Very less soluble in
water and highly soluble in organic solvents. It is a synthetic compound so does not present
naturally.
Preparations – When chloral is heated with chlorobenzene, in presence of conc. H 2SO4 then
DDT is formed.

Cl
Cl
conc H2SO4
+ O CH CCl3 CH CCl3 + H2O
Heat
Cl
Cl

Uses
1. DDT act as pesticides, generally used, for the killing of mosquitoes and other insects.
2. Very effective against malaria causing mosquito (female anopheles).
3. DDT is a cost effective insecticide.
Although DDT has many side effects such as-
It is non-biodegradable. Its traces gets accumulated in the environment and are toxic for living
organisms.

8.19. BHC (Benzene hexachloride)

IUPAC name of BHC is 1, 2, 3, 4, 5, 6 – hexachlorocyclohexane and molecular formulae is
C6Cl6.
H Cl
Structure - Cl H
H Cl
Cl H
H Cl
Cl H

Properties – It is a white crystalline solid, in soluble in water and variably soluble in organic
solvent. Soluble in halogenated solvents such as chloroform, low solubility in ethers and
hydrocarbons and very low solubility in alcohols.
Preparation – By chlorination of benzene in presence of ultraviolet light. It is also called as
Lindane.

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 H Cl
Cl H
UV H Cl
+ 3Cl2
Cl H
H Cl
Cl H

Uses –

1. It has many uses as pesticides in agriculture industry such as, to treat food crops, forestry
products, for seed treatment, soil treatment etc. It has been used for the treatment of lice and
scabies in the form of shampoos and lotions.
It has side effects also, some of them are –
It is a carcinogen for the living beings, may cause cancer of liver, kidney and thyroid.

8.20 Exercise
8.20.1. Very short answer type questions -
1. What are alkyl halides? Give one example.

2. General formula for an alkyl halide is?

3. Write one example of SN1 reaction. Only reaction.

4. What do you understand by inversion of configuration, give one example?

5. Give two preparation methods for alkyl halide.

6. Write one example of SN2 reaction. Only reaction.

7. What will be the product when CHCl3 gets oxidised.

8. Give two uses of CHCl3?

9. Give structure and two uses of BHC.

10. Give structure of DDT and its two uses.

8.20. 2 Short answer type questions –

1. Write down the methods of preparation of CHCl3 and its physical properties.

2. Write down at least 3 methods of preparation of chlorobenzene.

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3. Discuss the mechanism of addition-elimination reaction with an example.

4. Write down the methods of preparation of CCl4 and its physical properties.

5. Discuss the mechanism of elimination-addition reaction with an example.

6. Discuss benzyne mechanism with an example.

7. Explain the reactivity order of vinyl halide and aryl halide.

8. Write down the methods of preparation of DDT and its physical properties.

9. Write down Sandmeyer reaction.

10. Write down the methods of preparation of BHC and its physical properties.

8.20.3 Long answer type questions –

1. What do you understand by alkyl halides, give their methods of preparation and chemical
properties?

2. Explain mechanism of addition-elimination and elimination-addition reactions with example.

3. Write down the methods of preparation of CHCl3 and CCl4, their physical, chemical properties
and uses.

4. Explain energy profile with the help of a diagram of SN1 and SN2 reactions.

5. Explain mechanism of SN1 and SN2 reactions.

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Introduction of Authors

Dr. Renu Agarwal

Dr. Renu Agarwal is currently working as associate professor at IIMT Ganga Nagar Meerut. She
has completed MBA from IGNOU MSc organic chemistry, Ph.D from CCS University Meerut.
She is having 15 years of teaching experience. She got the best teacher award and social scientist
award. She has presented many papers in international conferences. She has published many
research papers in National and international journals. She instills positivity in the students for
their future endeavors.

Dr. Surbhi Arya

Dr. Surbhi Arya is an assistant professor in School of basic science and Technology, IIMT
University Meerut. She has completed her M.Sc. (Organic Chemistry) from C.C.S. University
campus Meerut, qualified NET-JRF (CSIR) and earned her Ph.D. from IIT Roorkee. Author has
6 years of teaching experience. She has published her research work in International journals.

Dr. Paresh Kumar

My self Dr. Paresh Kumar, working as an associate professor at School of Basic Sciences &
Technology (Chemistry) IIMT University, Ganga Nagar, Meerut. I have completed Ph.D.
(Physical Chemistry) from Gurukul Kangri Univeristy, Haridwar. I have 28 Years of teaching
experience. I have publish more than 30 research papers in National & International Journals and
conferences

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