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Compounds containing only two elements carbons & hydrogen are known as hydrocarbons. On
the basis of structure & properties, hydrocarbons are divided into two main classes viz. aliphatic
& aromatic. Aliphatic hydrocarbons are further divided into different families namely alkanes,
alkenes, alkynes and their cyclic analogs (cycloalkanes, cycloakenes and cycloalkynes etc.)

ALKANES
Alkanes are open chain (acyclic) hydrocarbons comprising the homologous series with the
general formula Cn H 2n + 2 where `n’ is an integer. They have only single bonds & therefore are
said to be saturated. Because of their low chemical activity, alkanes are also known as Paraffins.

Nomenclature and Isomerism

According to IUPAC system of nomenclature open chain aliphatic compounds are named as
alkanes. The first three members do not exhibit isomerism, all other members show chain or
nuclear isomerism. The no. of isomerism increase with the increase in the no. of carbon atoms
e.g. butane has 2 isomers, pentane-3, hexane-5, heptane-9, octane-18 and decane 75.

Conformations: Each carbon atom of alkanes is sp3 hybridized and all C—C and C—H
bonds are strong sigma bonds. Since sigma bonded carbon atoms can rotate about the C—C
bonds, a chain of singly bonded carbon atoms can be arranged in any zigzag shape.

C
C C C
C C C
C

Such different arrangements of atoms that can be converted into one another by rotation about
single bonds are called conformations. Since conformations can not be isolated, they are not
isomers. Conformations are of three types as —

Eclipsed (with highest energy, hence least stable)

Staggered (with lowest energy, hence most stable) and the intermediate conformations are called
Skew conformation.

To represent such conformations we often use two kinds of three dimensional formulae: andiron
or sawhorse formulae and Newman projections. The energy required to rotate the ethane
molecule about carbon-carbon bond is called torsional energy.

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H H

H
H H H
H H
H
H H
H Sawhorse Representation
Eclipsed Staggered II

H
H H
H H

Newman
Projection
H H
H H H
H

H
Eclipsed I Staggered II

Nomenclature
CH3

H3C CH3 H3C

H3C CH3
ethane CH3
CH3
propane
2,2-Dimethyl propane
CH3
CH3 H3C
H3C CH3
H3C CH3

H5 C2 CH3 C2 H5
2,2,4,4-tetramethylhexane 3-ethyl-2-methylpentane
CH3

H3C CH3

CH3 CH3
3,4,7-trimethylnonane

Physical Properties

1. Physical Nature

a) State: i) All are colourless and possess no characteristic odour.

ii) Lower alkanes (C1 to C4) are gases, middle one (C5 to C17) are liquids and
highers are solids.

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iii) The boiling point of alkanes increases with increase in molecular weight
due to increase in van der Waals forces with increase in molecular
weight i.e.

Boiling point: pentane < hexane < heptane

iv) Also the branching in alkanes gives a decrease in surface area (as the
shape approaches to spherical) which results in decrease in van der Waals
forces. The boiling point of isomeric alkanes show the order:
pentane > isopentane > neopentane.

v) The melting points of alkanes do not show a regular trend. Alkanes with
even number of carbon atoms have higher melting point than their adjacent
alkanes to odd number of carbon atoms.

Melting order: propane < ethane

( −172.0° C )
< methane
( −182.5° C )
( −187.7° C)

The abnormal trend in melting point is probably due to the fact that
alkanes with odd carbon atoms have their end carbon atom on the same
side of the molecule and with even carbon atom alkane, the end carbon
atom on opposite side. Thus alkanes with even carbon atoms are packed
closely in crystal lattice to permit greater intermolecular attractions.

b) Density: The density of alkanes increases with increase in molecular weight and
becomes constant at 0.76g/ml. Thus all alkanes are lighter than water.

c) Solubility:

i) Alkanes being non polar and thus insoluble in water but soluble in non polar
solvents e.g. C6H6, CCl4, ether etc.

ii) The solubility of alkanes decreases with increase in molecular weight.

iii) Liquid alkanes are themselves good, non polar solvents.

Preparation
1. Reduction

a) Reduction of alkyl halides: (Substitution of halogen by H) Alkyl halide can be

reduced into corresponding alkanes by following reducing agents.

R – X i) LiAlH 4
ii) NaBH 4

→R–H
iii) Bu 3SnH
iv) Pd –C / H 2
v) Na / C2 H5 OH
vi) Zn –Cu − couple/C2 H5 OH
vii) Zn / NaOH
viii) Zn / CH 3COOH
ix ) Hg − Mg / HOH

Note: i) LiAlH 4 with 3° R–X give elimination product as major product.

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ii) NaBH 4 reduces 3° & 2° R–X only.

b) Reduction of alkenes: alkenes are reduced into alkanes by hydrogen in the

presence of catalyst [Pt. Pd, Ni/s. PtO 2 ]
R — CH = CH — R ′ + H 2 
catalyst
→ R — CH 2 — CH 2 — R ′
When catalyst is Ni the reaction is known Sabatier - Sanderen’s reaction.

c) Reduction of alkynes: Alkynes also reduced by hydrogen in presence of catalyst.

R — C ≡ C — R ′ + 2H 2 
catalyst
→ R — CH 2 — CH 2 — R ′
First alkene forms thereafter alkane.

d) Reduction of alcohols: Alcohols can be reduced to corresponding alkane as

P / I2 / ∆
a) R — OH  →R — H
b) R — OH 
TsCl
→ R — O — Ts 
LiAlH 4
→R — H

2. From organo metallic compounds: Grignard reagents and alkyl lithium reacts
with water and other compounds having acidic hydrogen to give hydrocarbon
corresponding to alkyl group of the organo metallic compounds.

R — Mg — X + H — OH 
→R—H
R — Li + H — OH 
→R—H

3. Wurtz Reaction: This reaction in which two molecules of symmetrical and primary
alkyl halide in the presence of sodium and dry ether, then it gives higher even numbered
alkane, is known as Wurtz reaction.

R — X + X — R  Na

dry ether
→ R — R + 2NaX

R — X + R ′ — X 
→ R — R + R′ — R + R′ — R′
CH 4 Cannot be prepared by this method.
3° R—X do not give this reaction
Mechanisms have been proposed for this reaction

Mechanism:
R — X + Na 
→ R + NaX
R + R 
→R—R

4. Corey-House synthesis

R — X + 2Li  
dry ether
→ R — Li + LiX

2R — Li + CuI 
→ R 2 CuLi + LiI

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R 2 CuLi + R ′ — X 
→ R ′ — R + R — Cu + LiX

For good yields, R′X should be a primary halide; the alkyl group R in the organometallic
may be primary for better yield. For example,
CH3

CH 3 − Br 
Li
→ CH 3 − Li →
CuI H3C CuLi
Methyl bromide Methylithium
Lithium dimethylcopper
CH 3 − CH 2 (CH 2 )6 CH 3
n-Nonane

CH 3 (CH 2 )6 CH 2 I
n-Octyl iodine

CH3 Br
H3C 
Li
→ →
CuI (CH3 CH2 CH-)2 CuLi H3C
n-Pentyl bromide
Cl
CH3
sec-Butyl chloride

CH3

CH3

CH3
3-methyloctane

5. Frankland’s reaction

R — X + R — X 
Zn / C2 H5 OH
∆
→ R — R + ZnX 2
CH3 — Br + CH3 — Br 
→ CH3 — CH 3 + ZnBr2

6. Kolbe Electrolysis
O O
R — C — O — K + R — C — O — K 
H 2 O electrolysis
→ R — R + 2CO 2 + H 2 + 2KOH

CH 4 can not be prepared.

O O

O  →R O 
→ R + CO 2
–
–e
R C Anode (Oxidation )
C

R + R 
→R—R

7. Decarboxylation of Acids: Sodium salt of carboxylic acids undergo

decarboxylation when heated with sodalime.

R — COONa 
soda lim e
∆
→ R — H + Na 2 CO3

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O
R — C — ONa 
→ R + CO 2 
HOH
→R — H

Chemical Properties of Alkanes

1. Halogenations: One of the important chemical reactions of alkanes is halogenation
which is defined as the replacement of hydrogen atom of the molecule by halogen atom.
A mixture of alkanes and chlorine remains unaffected in the dark but a vigorous reaction
occurs when it is exposed to light or at a higher temperature.
hv or ∆
R — H + Cl2  → R — Cl + HCl

As pointed above the reactions takes place by free radical chain mechanism which
proceeds in the following three distinct steps.

a) Chain initiations
hv or ∆
Cl — Cl  → 2Cl [∆H = +58 kcal / mole]

b) Chain propagation
Cl + H — CH 3 
→ H — Cl + CH 3 [∆H = –1 kcal / mole]
CH 3 + Cl — Cl 
→ CH 3 — Cl + Cl [∆H = –23 kcal / mole]

c) Chain termination
Cl — Cl 
→ Cl — Cl
CH 3 + Cl 
→ CH 3 — Cl
CH 3 + CH 3 
→ CH 3 — CH 3

The ease of substitution at various carbon atoms is of the order tertiary > secondary >
primary which is the same as the stability of various alkyl radicals.

Bromination of alkanes has close similarities to chlorination except the rate of

reaction is slow.

Fluorination of alkane is so violent that it results in the cleavage of C—C as well as

C—H bonds.

∴ Reactivity of X 2 : F2 > Cl2 > Br2 > I 2 [I 2 does not react.]

The potential energy curve for the halogenation (chlorination) of alkane is shown as

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E act
R • + Cl 2
R − H + Cl•

Potential energy
R − Cl + Cl•

Progress of reaction

Illustration 1: How many monochlorinated products are obtained by the chlorination of

isopentane and what is the percentage of each assuming the reactivity ratio of
3°H : 2°H : 1°H = 5 : 3.8 : 1.

Solution: Isopentane on chlorination in presence of sun light gives five different

monochlorinated products.

CH 3 – CH – CH 2 – CH3 + Cl 2 
hv
→ CH 2 Cl – CH – CH 2 – CH 3 +
CH3 CH3 (A)

CH3 — CCl — CH 2 — CH 3 + CH3 — CH — CHCl — CH3

CH3 (B) CH3 (C)

CH3 — CH — CHCl — CH 3 + CH3 — CH — CH 2 — CH 2 Cl

CH3 (D) CH3 (E)
Product Reactivity × Probability = Number Percentage
Factor factor of parts
(A) 1 × 6 = 6 20.6%
(B) 5 × 1 = 5 17.1%
(C) 3.8 × 2 = 7.6 26.0%
(D) 3.8 × 2 = 7.6 26.0%
(E) 1 × 3 = 3 10.3%
Total number of parts = 29.2

BRAIN TEASER
When 2-methylbutane is chlorinated, the percentage of (CH 3 ) 2 – CH – CH 2 – CH 2 Cl is……….
Assuming reactivity ratio of 3°H : 2°H : 1°H for chlorination = 5 : 3. 8 : 1.

2. Nitration: The displacement of an atom of hydrogen by a nitro group ( – NO2 ) is called

nitration. Alkanes can be nitrated with nitric acid in the gas phase generally at 400–
500°C.
400–500° C
R — H + HO — NO 2  → R — NO2 + H 2 O

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CH 3 — CH 2 — CH 2 — NO 2 + CH3 — CH — CH 3

NO2
CH 3 — CH 2 — CH 3 
HNO 2
400–500° C
→

CH 3 — CH 2 — NO2 + CH 3 — NO 2

3. Sulphonation: Sulphonation of a hydrogen atom of the alkane by sulphuric acid

group (–SO3 H) is called sulphonation. The ease of substitution is tertiary ≥ secondary >
primary.
CH3 CH3
H3C H + H 2SO 4 
→ H3C SO3H + H 2O
CH3 CH3

4. Isomerisation: Heating of straight chain alkanes with anhydrous aluminum chloride

(lewis acid) affords branched chain hydrocarbons. This process is termed isomerisation.

CH3
AlCl3 ∆
CH3 — CH 2 — CH 2 — CH 3  → H3C CH3
H

The process of isomerisation has been of immense utility in petroleum industry for raising
the octane number of a particular petroleum fraction.

Example

AlCl3 (RCl)
25° C

Rearrangement of alkanes are thermodynamically controlled

Reactivity Selectivity Principle

1. Probability factor: The factor is based on the number of each kind of H atom in the
molecule.

For example is CH3 — CH 2 — CH 2 — CH3 there are six equivalent 1° H’s and four
equivalent 2° H’s.

The probability of abstracting 1° H’s to 2°H’s is 6 to 4. i.e., 3 to 2.

2. Reactivity of halogen free radical: The more reactive chlorine free radical is less selective
and more influenced by the probability factor. On the other hand, the less reactive Br
radical is more selective and less influenced by the probability factor (Reactivity
selectivity principle).

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3. Reactivity of alkanes (ease of abstraction of `H’ atoms): Since the rate determining step in
halogenations is abstraction of hydrogen by a halogen atom be the formation of alkyl
radical, halogenation of alkanes follows order of stability of free radical is 3° > 2° > 1° >
CH3

The above order of stability of radicals is due to the ease of their formation from the
corresponding alkane which in turn is due to difference in the value of ∆H .

CH 3 — H 
→ CH 3 + H ∆H = 104 kcal
CH 3 — CH 2 — H 
→ CH 3 — CH 2 + H ∆H = 98 kcal
CH 3 — CH — CH 3 
→ CH 3 — CH — CH 3 + H ∆H = 104 kcal
H
Reactivity of any H-atom ∝ number of H atoms of that kind × reactivity of that H
CH3 CH3

CH 3 — C — CH 3 
→ CH 3 — C — CH 3 + H ∆H = 104 kcal

Thus the amount of energy required to form the various classes of radicals’ decreases in
the order CH 3 > 1° > 2° > 3° i.e. it is easiest to form 3° radical and it is most difficult to
form CH.3 . We can also interpret this in an alternative way the case of abstraction of H
atoms from hydrocarbon follows the sequence 3° > 2° > 1° CH 4 which should also be the
case of formation of free radicals.

The above order of stability is in accordance with the stability of free radicals on the basis
of delocalization of odd electron. Order of stability of free radical is

Allyl > benzyl > 3° > 2° > 1° > methyl, vinyl.

ALKENES

Alkenes are unsaturated hydrocarbons having carbon-carbon double bonds. The general
molecular formula for alkene is Cn H 2n .

Alkenes and cycloalkanes are isomeric compounds because both have same general molecular
formula.

Nomenclature
The IUPAC names of alkenes are given by replacing the –ane ending of the corresponding alkane
with –ene. The two simplest alkene ethene and propene.

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H C = CH
2 2 CH 3 — CH = CH 2
IUPAC − Ethene IUPAC : propene
Commen Name: ethylene Commen Name: Pr opylene

1 2 3 4 6 5 4 3 2 1
H 2 C = C H — C H 2 — C H3 C H3 — C H2 — C H2 — C H = C H — C H3
1− Butene 2 Hexene
(not 1− 2 butene) (not 4 − hexene)

4 3 2 1 6 5 4 3
C H3 — C H — C H = C H2 C H 2 — C H 2 — C H 2 — C H — CH 2 — CH 2 — CH 3

CH3 Br 2 1
C H = C H2
3-methyl-1-butene
6-Bromo-3-propyl-1-hexene

Structure and Bonding in Alkenes

134 pm

H H
117.2°
110 pm
H 121.4° H

Ethylene is planar, each carbon is sp2 hybridized and the double bond is considered to have a σ
component and π component. The σ component arises from overlap of sp 2 hybrid orbital along
a line connecting the two carbon atoms, the π component via a side by side overlap of two p
orbital. Regions of high electron density attributed to π electrons, appear above and below the
plane of the molecule and are clearly evident in the electrostatic potential map.

Isomerism in Alkenes
Naming stereo isomeric alkenes by the E–Z: When the groups on either end of a double bond are
the same and are structurally similar to each other it is simple matter to describe the configuration
of double bond as cis and trans.

The term cis and trans are ambiguous however when it is not obvious which substituents on the
carbon is similar to a reference substituents on the other. A completely unambiguous system for
specifying double bond stereochemistry has been developed based on an atomic number criterian
for ranking substituents on the doubly bonded carbon. When atoms of higher atomic number are
on the same side of the double bond then that double bond has Z configuration where Z stands
for Zusammen meaning together. When atoms of higher atomic weight are on opposite side of
the double bond that double bond is with E configuration E stands for entegen means opposite.
Higher Cl Br ←
 Higher 
→ Cl F ←
 Lower

Lower H F ←
 Lower 
→ H Br ←
 Higher
Z E

Physical Properties of Alkene

a) All are colouress and have no characteristic odour. Ethene has pleasant smell.

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b) Lower members (C2 to C4) are gases, middle one (C5 to C17) are liquids, highers are
solids.
c) The boiling points, melting points, and specific gravities show a regular increase with
increase in molecular weight, however less volatile than corresponding alkanes.
d) A cis isomer has high boiling and melting point than trans because of more polar nature.
e) Like alkanes, these too are soluble in non polar solvents.
f) Alkenes are weak polar. The polaritiy of cis isomer is more than trans which are either
non polar or less polar.(e.g. trans butane-2- is non polar; trans pentene-2-is weakly polar).

Relative Stabilities of Alkene

The stabilities of alkene are governed by —
a) Degree of substitution: Double bonds can be classified as monosubstituted, disubstituted,
trisubstituted and tetrasubstituted. According to the number of carbon atoms directly
attached to the C=C structural unit.
Alkenes with more highly substituted double bonds are more stable than isomers with less
substituted double bond.
b) Vander Waal’s strain: Alkenes are more stable when large substituents are trans to each
other than when they are cis.

When two or more atoms are close enough in space that a repulsion occurs between them
is one type of steric effect and therefore trans isomers are more stable than cis isomer.

c) Heat of hydrogenation: The additionof hydrogen is called hydrogenation. Hydrogenation

reaction are exothermic (negative ∆H0).
CH3
CH3
CH3
CH3
+ H 2 
Pt / C
→ H3C ∆H 0 = −26.9 kcal/mol
H3C
2-methylbut-2-ene
CH3
CH3
CH3
CH3
+ H 2 
Pt / C
→ H3C ∆H 0 = −28.5 kcal/mol
H2C
2-methylbut-1-ene

CH3
CH3
CH3
CH2
+ H 2 
Pt / C
→ H3C ∆H 0 = −30.3 kcal/mol
H3C
3-methylbut-1-ene
The preceding three catalytic hydrogenation reaction all from the same alkane. So the
energy of the product is the same for the each of three reactions. However, three reactants
must have different energies. The reaction associated with the least negative ∆H0 has the
most stable reactant and the reaction with the most negative has the least stable reactant.

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CH3
CH3
CH2 CH3
H3C CH3
H2C CH3
Potential Energy

H3C

∆H0 = −30.3 kcal/mol ∆H 0 = −28.5 kcal/mol ∆H 0 = −26.9 kcal/mol

The greater the number of alkyl groups attached to the doubly bonded carbon atoms the more
stable the alkene.

Stability of alkenes

R2C = CR2 > R2C = CHR > R2C = CH2 > RCH = CHR > RCH = CH2 > CH2 = CH2

Preparation of Alkenes
1. Dehydration of Alcohols: In the dehydration of alcohol the H and OH are lost from
adjacent carbons an acid catalyst is necessary

+
H — C — C — OH 
H
→ C=C + H2O

Alcohol Alkene

CH 3 — CH 2 — OH 
H 2SO 4
160° C
→ H 2 C = CH 2 + H 2 O
Ethyl alcohol Ethylene

OH

H 2SO 4
140° C
→ + H 2O

CH3 H3C
H3C C CH3 →
H 2SO 4
∆
CH2 + H 2 O
H3C
OH

H 2SO 4 and H 3 PO 4 are the acids most frequently used in alcohol dehydration KHSO 4 is
also often used.

Regioselectivity of Alcohol Dehydration

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OH CH3 H3C
H3C CH3 
H 2SO 4
80° C
→ H2C +
CH3 CH3 H3C CH2
2-Methyl-1-butene 2-Methyl-1-buten
(10%) (90%)

Dehydration of this alcohol is selective in respect to its direction

CH3 CH3 CH3

H3 PO 4
∆
→ +
OH
84% 16%

Regioselectivity of β elimination is governed by Zaitsev’s Rule.

Stereoselectivity in Alcohol Dehydration: In addition to being regioselective,

alcohol dehydration are stereoselective. A stereoselective reaction is one which a single
starting material can yield two or more sterioisomeric products, but give one of them in
greater amount than other.

H3C CH3 H3C CH3 H3 C H


H 2SO 4
∆
→ +
OH H H H CH3
cis-2-pentene (25%) trans-2-pentene (75%)

2. Dehydrohalogenations of Alkyl Halide: Dehydrohalogenation is the loss of

hydrogen and a halogen from an alkene.

H — C — C — X 
→ C=C + HX

The reaction is carried out in presence of strong base such as sodium ethoxide
(NaOC2 H 5 ) in ethyl alcohol as solvent.

H — C — C — X + NaOC2 H5 
→ C=C + C 2 H5 OH + NaX

Cl
H H

→
NaOCH 2 CH3

H H
H
Similarly NaOCH 3 , KOC(CH3 )3 are the preferred bases used in this process.
CH3 – (CH 2 )15 – CH 2 – CH 2 – Cl  
KOC(CH 3 )3
DMSO 25° C
→ CH3 – (CH 2 )15 – CH = CH 2

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The regeoselectivity of dehydrohalogenation of alkyl halide follow zaitesev rule of

elimination predominates the direction.
Br CH3 H3C
H3C 
→ H2C +
CH3 CH3 H3C CH3
H3C
2-methyl-1-butene 2-methyl-2-butene
(29%) (71%)

H H
Br H H

→
KOCH 2 (CH3 )
CH3 —CH 2 —OH + H

(85%) (15%)

Reactions of Alkenes
1. Catalytic Hydrogenation: Alkenes reacts with hydrogen in the presence of
platinum, palladium, rhodium or nickel catalyst to form the corresponding alkane.
R 2 C = CR 2 + H 2  
Pt, Pd, Rh or Ni
→ R 2 — CH — CH — R 2


H2
Pt
→

2. Addition of Hydrogen Halide: A proton and a halogen add to double bond of an

alkene to yield an alkyl halide. Addition proceeds in accordance with Markovnikov’s
rule, hydrogen adds to the carbon that has the greater number of hydrogens.
R
+ HX 
→ R CH3
CH2
X

CH2 + HCl 
→ CH3
Cl

3. Addition of sulphuric Acid: Alkene reacts with sulphuric acid to form alkyl
hydrogen sulphates. A proton and a hydrogen sulphate ion adds to double bond in
accordance with Markovnikov’s rule. Alkene that yield tertiary carbocations on
protonation tend to polymerise in concentrated H 2SO 4 .

R 2 C = CR 2 + HOSO 2 OH 
→ R — CH 2 — CR 2

OSO2 OH

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4. Addition of Halogens: Bromine and chlorine adds to alkenes to form vicinal

dihalide. A cyclic halonium ion is an intermediate stereospecific anti addition is observed.
X R

R 2 C = CR 2 + X 2 
→ R R

R X
H2 C Br CH3
CH3 + Br2 
→

Br
Mechanism

Step 1:
H3C CH3 CH3
H3C CH3
+ Br
H3C CH3 + CH3
Br
δ + Br Bromonium ion Bromide ion

δ – Br

A bromine molecule becomes polarized as it approaches the alkene. The polarized

bromine molecule transfers a positive bromine atom (with six electrons in its valance
shell) to the alkene resulting in the formation of bromonium ion.

Step 2:
H3C CH3
H3C H3C
Br
CH3 H3C
C C + Br 
→ C C
+
Br Br CH3
CH3
Bromonium ion Bromide ion vic-dibromide

A bromide ion attacks at the back side of one carbon (or the other) of the brominium ion
in an SN2 reaction causing the ring to open and resulting in the formation of vic-
dibromide.

5. Halohydrin formation: When treated with bromine or chlorine in aquous solution

alkenes are converted to vicinal halohydrin. A halonium ion is an intermediate. The
halogen adds to the carbon that has the greater number of hydrogens. Addition is anti.
R
R — CH = CR 2 + X 2 + H 2 O 
→ HO X + HX
R R

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CH2 + 
Br2
→ Br
H 2O

OH
Mechanism
→ HO − X + + HX
H 2O + X 2 
H3C CH3 CH3
H3C CH3

→ + X
H3C CH3 CH3
X
δ+
X Halide ion

X δ–

Step 2 & 3
H O H
H 3C CH3 H 3C
H 3C O H H
CH3 H3C
C C + O H 
→ C C
X CH3
X H CH3
Here however a water molecule is a nucleophile and attacks a carbon of the ring causing
the formation of a protonated halohydrin.
H
H3C
O
H3C
+
C C + H O H
X CH3 H
CH3
The protonated halohydrin loses a proton (it is transferred to molecule water). This step
produces the halohydrin and hydronium ion.

6. Epoxidation: Peroxy acids transfer oxygen to the double bond of alkenes to yield
epoxides the reaction is a sterospecific syn addition.
O

R 2 C = CR 2 + R — C — OOH 
→ R 2 C — CR 2 + R — COH
O O

CH3 CH3
+ CH3 — COOOH 
→ O + CH 3COOH

Mechanism

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[Type text]
H3C
H3C CH3 H3C O R
O R C C
C
+ O 
→ O +
C O
C
H O
H3C H
H3C CH3
H3C
Alkene Peroxy acid Epoxide Carboxylic Acid

The peroxy acid transfers an oxygen atom to the alkene in a cyclic single step mechanism.
The result is the syn addition of the oxygen to the alkene, with formation of an epoxide
and a carboxylic acid.

7. Acid-Catalyzed Hydration: Addition of water to the double bond of an alkene

takes place in aquous acid. Addition occurs according to Markovnikov’s rule. A
carbocation is an intermediate and is captured by a molecule of water acting as a
nucleophile.
+
RCH = CR 2 + H 2 O 
H
→ R — CH 2 — CR 2
OH
H+
H 2 C = C(CH 3 ) 2 + H 2 O → (CH 3 )3 COH
+
H 2 C = C(CH 3 )2 + H 2 O 
H
→ H 3C — C(CH 3 )2

OH
Mechanism
Step 1: CH2 H
H H

H3 C CH3 + H O
+
H
slow
H3 C C + O H

CH3
The alkene accepts a proton to form more stable 3° carbocation.

Step 2: CH3
H CH3 H
C +
CH3 + O
fast
H3C H H3C C O H

CH3
The carbocation reacts with a molecule of water to form a protonated alcohol.

Step 3: CH3 H H CH3 H

+
H3C C O
+
H + O H
fast
H3C C O H + H O H

CH3 CH3
A transfer of proton to a molecule of water leads to a product.

8. Hydroboration-Oxidation: The two step sequence achieves hydration of alkene in

a stereospecific syn manner with a regeoselectivity opposite to Markovnikov’s rule. An

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organoborane is formed by electrophilic addition of diborane to an alkene oxidation of

organoborane intermediate with hydrogen peroxide completes the process rearrangement
do not occur.
R — CH = CR 2  B2 H 2
H O , OH –
→ R — CH — CH — CR 2
2 2

OH
(CH 3 ) 2 — CH — CH = CH 2 → (CH 3 ) 2 — CH — CH 2 — CH 2 — OH
H3 B. THF
H 2 O2 . OH –

Mechanism
+
H3C H H3C H H3C δ + H
σ σ
π π
H3C H H3C -
H3C H H B HH
+ δ–
H H H H
H
B B

H H
pi-complex four centered transition state

H3C H H3C H
H H3C H
H3C ← B2 H 2
H 2 O 2 , OH –

H OH H B
H H
Addition takes place through the initial formation of a π complex which changes into a
cyclic four center transition state with the boron atom adding to less hindered carbon
atom. The dashed bonds in the transition state represent bonds that are partially formed or
partially broken.

The transition state posses over to become an alkylborane. The other B—H bonds of
alkylborane can undergo similar additions, leading finally to a tri-alkylborane.
CH3 H
 → 
-
(BH3 )2 H 2 O 2 , OH
→ syn-Addition

H3C H OH
methylcyclopentane trans-2-Methyl-1-cyclopentanol

9. Oxidation of alkene: syn Hydroxylation

CH 2 = CH 2 + KMnO 4 
cold
OH – , H O
→ H 2 C — CH 2
2

OH OH

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[Type text]

−

→ 
OH
H2O
→ + MnO 2
O O OH OH
+
O O Mn
Mn O O

O O

10. Oxidative cleavage of Alkenes

H3C O O
+

CH3  →  → 2H3C

– H
KMnO4 , OH
H2O
2 H3 C
heat

O OH
cis/trans Acetate ion Acetic acid

11. Ozonolysis of Alkenes: Alkene when reacts with ozone it forms ozonoid which
further hydrolysed to carbonyl compounds.
R R' R R'

→ O3
H2O
O + O
H R" H R"
Mechanism
O O
(CH 3 ) — (CH 2 )5 CH = CH 2 
→ CH 3 (CH 2 )5 — C — H + H — C — H
O3
H2O

12. Oxymercuration-demercuration

+ Hg(OAc)2 + H 2 O 
→ 
NaBH 4
→
Mercuric acetate
OH HgOAc OH H
Markovnikov addition


Hg(OAc)2 , H 2 O
→ 
NaBH 4
→

Norbornene
OH
exo-Norborneol

13. Dimerization
H3C H3C
CH3 CH3 CH3
CH3

H3C + H3C →

acid
H3C + H3C

CH2 CH2
H3C H3C

CH3 CH2
2,4,4-trimethylpent-2-ene 2,4,4-trimethylpent-1-ene

ALKYNES

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[Type text]

Introduction: Unsaturated hydrocarbons having a carbon-carbon triple bond are called

alkynes. They correspond to general formula Cn H 2n – 2 i.e. they have smaller proportion of
hydrogen than alkene. Alkynes are isomeric with cycloalkenes and alkadienes.

Nomenclature
HC ≡ C — CH 2 — CH = CH 2
1− Penten − 4 − yne

CH3 Cl
4 2 2 4 CH3
H3C 3 CH H3C 3 5 6
5 1 1
4-methylpent-1-yne 2-chlorohex-3-yne

CH3

CH CH
H3C
Pentylethyne
5-methylhex-1-yne

Physical Properties

i) Lower members (C2 to C4) are gases; middle one (C5 to C12) are liquids; highers are
solids.

ii) The boiling point, melting point and specific gravity of alkynes show a regular increase
with increase in molecular weight; however less volatile than alkene. The order of boiling
point in hydrocarbons has been explained in terms of polarity. Alkynes possess more
polarity and thus have higher boiling point.

Boiling point alkyne > Alkene > Alkane

iii) All are colouress and possess no characteristic odour; however C2H2 has garlic odour due
to the impurities of PH3, H2S etc. Pure C2H2 has ethereal odour.

iv) Soluble in organic solvents like acetone, alcohol and sparingly soluble in water.

v) The boiling point of acetylene is –84°C. Liquid acetylene is dangerously explosive and
therefore storage and transportation of liquid acetylene is prohibited by law. That is why
acetylene is stored and transported by dissolving it in acetone soaked on porous material
like asbestos packed in steel cylinders, under high pressure.

Preparation
1. Dehydrohalogenation of vic dihalides: Vicinal dihalides having hydrogens on
carbon gives alkynes with strong base.

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[Type text]

R — CH — CH — R 
NaNH 2 / ∆
→R — C ≡ C — R
X X

2. Kolbe hydrocarbon synthesis: Potassium salt of maleic acid and its alkyl
derivatives gives alkynes on electrolysis.

R — C — COOK

electrolysis
→ R — C ≡ C — R + 2CO 2 + 2KOH + H 2
R — C — COOK

Chemical Nature
A] Reactions due to Acidic Hydrogen: Relative acidities of some compounds are
as follows in decreasing order

HOH > ROH > CH ≡ CH > NH 3 > CH 2 = CH 2

Alkynes are very weak acid. Reaction due to acidic hydrogen will be given by acetylene
and terminal alkynes.

i) Salt formation
1
R — C ≡ C — H →
NaNH 2
NH3 ( l )
R — C ≡ CNa + H 2
2
ii) Formation of metal alkynide
→
Cu 2 Cl2
NH 4 OH
R — C ≡ C — Cu
R —C≡C—H

AuCl / NH 4 OH
→ R — C ≡ C — Au

1. Reaction with Grignard reagent: These two reagents reacts with terminal alkyne to
form hydrocarbon and new organometallic compound respectively.

CH3 MgBr
→ R — C ≡ C — MgBr + CH 4
R —C≡C—H

CH3 Li
→ R — C ≡ C — Li + CH 4

2. Electrophilic substitution with X 2 / OH or NaOX

R — C ≡ C — H 
NaOCl
→ R — C ≡ C — Cl
H — C ≡ C — H 
NaOCl
→ Cl — C ≡ C — Cl

B] Reactions due to Pi bonds

1. Electrophilic Addtition Reaction

i) Addition of X 2

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[Type text]

R X X X
R — C ≡ C — R + X 2 
→ CCl4

X 2 / CCl 4
→R R
X R X X
Both addition follow Markownikov’s Rule
Reactivity Cl2 > Br2 > I 2

ii) Addition of HX
R X X

R — C ≡ C — R →
HX
→
HX
R CH2 R
H R X
order of reactivity of HX is HI > HBr > HCl

iii) Addition of HOX: Alkyne reacts with HOX to give haloenol. This compound undergo
tautomerism to give ∝ -halocarbonyl compound
O H O
R — C ≡ C — H + HOX 
Markownikov
addition
→ R 
→ R
CHX CH2X

2. Nucleophilic Addition Reaction

iv) O
R — C ≡ C — H + HOH → R
HgSO 4 / H 2SO4

CH3

3. Hydroboration: Addition reaction of alkyne with boron hydride is known as

hydroboration
R — C ≡ C— H + BH 3 
THF
→ (R — CH = CH)3 B
3 eqv.

B — (CH — CH 2 — R) 2
(R — CH = CH)3 B + BH 3 
→ R — CH 2 — CH
B — (CH — CH 2 — R) 2
4. Addition of carbene: Alkene reacts with CH 2 and other carbenes. However since
alkyne have two pi bonds this addition can occure twice.
H H
C
R — C ≡ C — R 
→R R 
→R
: CH 2 : CH 2
C C C C R
2 eqv
C C
H H H H
Bicyclobutane

5. Addition of Hydrogen: Alkynes are more reactive than alkenes towards

hydrogenation, because
sp hybrid carbon of alkyne is less hindered than sp 2 hybrid carbon of alkene.

6. Oxidation by Bayer reagent

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[Type text]

R — C ≡ C — R 
KMnO 4 / OH / HOH
cold
→R — C — C — R
O O
O O
COOH
H — C ≡ C — H →
Bayer
Re agent [ H — C — C — H ] 
[O]
→
COOH
oxalic acid

R — C ≡ C — R ′ 
KMnO 4 / OH
hot
→ R — COOH + R ′COOH

7. Ozonolysis: Ozonolysis leads to cleavage at the carbon-carbon triple bonds. The

products are carboxylic acids.
R — C ≡ C — R  O3
HOH / CH3 COOH
→ R — COOH + R ′COOH

Answer to Brain Teaser

Brain Teaser 1: 14%

Solved Problems
Objective

Problem 1: A hydrocarbon with formula C8H18 gives one monochloroderivative. The

hydrocarbon is:
(a) n-Octane (b) 2-Methylheptane
(c) 2,2,4-Trimethylpentane (d) 2,2,33-Tetramethylbutane

Solution: All – CH3 groups are equivalent in ‘d’.

CH3 CH3 CH3 CH3

H3C CH3 

Cl2
− HCl
→ CH3

CH3 CH3 Cl CH3 CH3

∴ (d)

Problem 2: The addition of HBr is fastest to the alkene

(a) CH2 = CH2 (b) CH3 – CH = CH – CH3
(c) (CH3)2C = CH2 (d) CH3 – CH = CH2

Solution: Because ‘a’ give more stable carbocation.

H3C H3C
+
CH2 + H + Br − 
→ C CH3
H3C H3C
3° carbocation
(more stable)

In (a) and (d), 2° carbocation while (c) 1° carbocation is formed.

∴ (c)

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[Type text]

Problem 3: Which of the following is most suitable reagent to distinguish compound III from
others?
I. CH3 – C ≡ C – CH3
II. CH3 – CH2 – CH2 – CH3
III. CH3 – CH2 – C ≡ CH
IV. CH3 – CH = CH2
(a) Bromine in CCl4 (b) Ammonical Cu2Cl2
(c) Ammonical AgNO3 (d) Both (a) and (c)

Solution: Only terminal alkynes give white ppt. with ammonical AgNO3 and give red ppt.
with ammonical Cu2Cl2.
∴ (d)

Problem 4:
Ozonolysis of forms

(a) Heptanal (b) 5-Ketoheptanal

(c) 6-Ketoheptanal (d) Mixture of (a) and (b)
Solution: 5 7
6
O 4

ozonolysis
→
O 3 O
CHO
2 1
6-Ketoheptanal

∴ (c)

Problem 5: Addition of I – Br to 2-Methylbut-2-ene would form

(a) 2-Bromo-3-iodobutane (b) 2-Bromo-2-iodobutane
(c) 2-Bromo-3-iodo-2-methylbutane (d) 2-iodo-3-bromo-2-methylbutane

Solution: H3C CH3 CH3

δ+ δ−
I − Br

→ H3C
Markownikov's addition
H3C CH3 Br I
2-bromo-3-iodo-2-methylbutane
∴ (c)

Problem 6: Which of following compounds give benzene on heating with (Ph3P)3RHCl?

(a) C6H5Br (b) C6H5 – CHO
(c) C6H5COCH3 (d) C6H5 – SO3H

Solution: O
H5 C6 
Wilkinson 's catalyst
(Ph 3 P)3 RhCl
→ H5C6 H
H Decarbonylation)
∴ (b)

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[Type text]

Problem 7: When isobutylene reacts with diborane followed by reaction with H2O2, the
product is

(a) (b)
OH OH

(c) OH (d)

Solution: In hydroboration – oxidation (B2H6 followed by H2O2/OH–), the net result is

addition of water which is anti-Markownikoff’s
OH

→ i) B2 H6
ii) H 2 O2 / OH −

∴ (b)

Problem 8: An organic compound A (C5H8) on hydrogenation gives compound B (C5H12).

Compound B on ozonolysis give methanal and 2-Ketopropanal. What is E?
CH3 CH3
H2C H2C
(a) (b)

H2C HC
CH2 H3C
(c) H3C (d)
CH3 H3C CH3

Solution: H CH3
O + O H H3C H3C
H O + O 
→ 
→2H 2

H H2C CH2 H3C CH3

2-Methyl-1,3-butadiene

∴ (a)

Problem 9: OH

In the dehydration of , the products formed are

CH2 CH3

(a) (b)

(c) (d) All the three products are formed

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[Type text]

OH
Solution: +
CH2 CH2
H
+
H
− H2O
→ 
→
(A)
+
CH2


alkyl
shift
→ 
→
H
(C)
+
CH2 CH3 CH3
H
H

Hydride
shift
→ 
→
(B)
∴ (d)

Problem 10: Free radical monochlorination of ter butyl bromide gives

(a) 1-Bromo-1-chloro-2-methylpropane
(b) 2-bromo-1-chloro-2-methylpropane
(c) 1-Bromo-2-chloro-2-methylpropane
(d) None
Solution: CH3 CH3 CH3 CH3

H3C Br Cl °
 → H3C Br 
Re arrangement
→ H3C ° 
Cl2
− Cl °
→ H3C Cl
− HCl

CH3 ° CH2
Br
1° Free radical Br
1° Free radical 1-bromo-2-chloro-2-met
(More stable) hylpropane

∴ (c)

Problem 11: Identify the end product

2CH ≡ CH 
CuCl
NH 4 Cl
→ A  H2
Pt / BaSO4
→ B 
Br2
→ C(Main)

Br H2C Br
(a) Br (b)
Br
Br Br
Br
(c) Br (d) Br
Br Br Br

Solution:
2CH ≡ CH 
CuCl / NH 4 Cl
→ H2C  H2
Pt / BaSO 4
→ H2C 
Br2
→
CH
Br CH2

Br +
Br H2C
1,4-Addition (Main) Br
1,2-Addition (Less)

[Type text]
[Type text]

∴ (a)

Problem 12: When acetylene reacted with hydrochloric acid in presence of HgCl2 the product
obtained is
(a) Methyl chloride (b) Acetaldehyde
(c) Vinyl chloride (d) Methanol.

Solution: CH ≡ CH + HCl 

HgCl2
→ CH 2 = CH — Cl
∴ (c)

Problem 13: When propyne is treated with aqueous H2SO4 in presence of HgSO4, the major
product is
(a) Propanol (b) Propyl hydrogen sulphate
(c) Acetone (d) Propanol.

Solution: CH 3 — C ≡ CH 
H 2SO 4 / H 2SO 4
→ CH 3 — COCH 3
∴ (c)

Problem 14: Which one of the following does not dissolve in conc. H2SO4?
(a) CH3—C ≡ C—CH3 (b) CH3—CH2—C ≡ CH
(c) CH ≡ CH (d) CH2 = CH2.

Solution: If CH ≡ CH is dissolved in H 2SO 4 a bisulphate salt of vinyl carbocation

H 2 C = C + H would be formed. The more s-character in the positively charged `C’
less stable is the carbocation and less likely to be formed.
∴ (c)

Problem 15: Which one of the following compounds will give in the presence of peroxide a
product different from that obtained in the absence of peroxide?
(a) 1-butane HCl (b) 1-butene, HBr
(c) 2-butene, HCl (d) 2-butene, HBr.

Solution: Peroxide effect is observed when unsymmetrical alkene is treated with HBr only
(and not with HCl and Hl).
∴ (b)

Problem 16: Which of the following compounds yields only one product on monobromination?
(a) Neopentane (b) Toluene
(c) Phenol (d) Aniline.

Solution: CH3

H3C CH3

CH3
has twelve equivalent 1°H. Hence H forms only one product on

[Type text]
[Type text]

monobromination.
∴ (a)

Problem 17: CH 3 — C ≡ C — CH 3 

NaNH 2
→ `X ' , What is X
(a) CH3CH2CH = CH2 (b) CH3CH2C ≡ CH
(c) CH3—CH ≡ CH—CH3 (d) CH2=C=CH—CH3.

Solution: Isomerisation occurs, when 2-butyne is treated with NaNH 2 , it converts into
terminal alkyne (1-butyne).
∴ (b)

Problem 18: Identify the compound `Y’ in the following sequence of reaction
HC ≡ CH  i) O3
ii) H 2 O / Zn
→ X 
Zn / CH3COOH
→Y
OH OH
(a) HO (b) O
OAc
(c) H3C (d) CH3COOH.
OAc

Solution: HC ≡ CH 
Ozonolysis
→ O OH
O 
Reduction
→ OH
∴ (a)

Problem 19: Dehydration of 1-butanol gives 2-butene as a major product, by which of the
following intermediate the compound 2-butene obtained.
CH2
CH2 H3C C
(a) H3C (b)
CH3
CH3

(c) +CH 3 (d) H3C

H 3C CH
CH2

Solution: + CH2
OH  → H C
H
H3C ∆ 3

CH3 CH2
←
1,2 hydride

H3C CH Shift H3C
2° 1°
∴ (c)

Problem 20: The principal-organic compound formed in the reaction

CH 2 = CH(CH 2 )COOH + HBr  
Peroxide
→ .... is
CH 3 — CH — (CH 2 )8 COOH CH 2 = CH(CH 2 )8 COBr
(a) (b)
Br

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[Type text]

CH 2 — CH 2 (CH 2 )8 COOH CH 2 = CH(CH 2 )7 — CH — COOH

(c) (d)
Br Br

Solution: Follows the peroxide effect

CH 2 = CH(CH 2 )8 COOH HBr

Peroxide
→ CH 2 — CH 2 (CH 2 )8 COOH
Br
∴ (c)

Subjective

Problem 1: 2-Butyne undergoes following reactions in steps as indicated. Identify A to H.

CH 3C ≡ CCH 3  H2
Ni 2 B(P –2)
→ A 
D 2 / Pt
→B


Na / EtOH
→ C 
D 2 / Pt
→D
 H2
Ni 2 B(P– 2)
→ E 
Br2
→F


Br2
→ G 
H2
Ni
→H

H3C CH3
Solution:
A is obtained by syn addition A=
H H
cis
H H

H3C CH3
B is also obtained by syn addition B=
D D
meso
H CH3

C is obtained by anti addition C=

H3C H

H D

H3C CH3
D is mix of d- and l- (reacemic mixture) D=
D H
d- and l-(racemic)

E is obtained by syn addition E= as A

H Br

H3C CH3
Addition of Br2 is anti F=
Br H
racemic
H3C Br

G=
Br CH3

H= as F

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[Type text]

n − BuC ≡ CMe  →A

Li, NH dil.KMnO 4 / H 2 O
Problem 2: 3(l)


→C
 →B
H2 HCO 3H / H 2 O
Lindlar's catalyst

Identify A, B and C with proper explanation.

Solution: n − BuC ≡ CMe
Li, Lindlar's catalyst
NH 3 H2
n - BuC C H n - BuC C H

H CH3 H3C H
A-trans B-cis
(by anti addition) (by syn addition)

KMnO 4 HCO3 H

CH3

HO H

H OH

n-Bu
(C) - and its enantiomer (racemic)

Problem 3: One mole of a hydrocarbon (A) reacts with one mole of bromine giving a dibromo
compound C5 H10 Br2 . Substance (A) on treatment with cold, dilute alkaline
KMnO 4 solution forms a compound C5 H12 O 2 . On ozonolysis (A) gives
equimolar quantities of propanone and ethanal. Deduce the structural formula
of (A).

Solution: A – 
i) O3
ii) H 2
→ Propanone + ethanal

So, A is
H3C

H3C CH3
2-methylbut-2-ene

H3C Br CH3
+ Br2 
→ H3C
H3C CH3 CH3 Br
2-methylbut-2-ene 2,3-dibromo-2-methylbutane

[Type text]
[Type text]

H3C OH OH
+ alk. KMnO4 
→ H3C
H3C CH3 CH3 CH3
2-methylbut-2-ene 2-methylbutane-2,3-diol

Problem 4: An unsaturated hydrocarbon A (C 6 H10 ) readily gives B on treatment with

NaNH 2 in liquid NH 3 . When B is allowed to react with 1-chloropropane a
compound C is obtained. On partial hydrogenation in the presence of Lindlar
catalyst, compound C gives D (C9 H10 ) . On ozonolysis D gives 2, 2-dimethyl
propanal and 1-butanal. With proper reasoning give the structures of
A, B, C and D.
CH3 CH3
Solution:
A= H3C H B= H3C C Na

CH3 CH3
CH3 CH3 CH3

C= H3C D= H3C
CH3 CH3 CH3

Problem 5: A compound (X) when passed through dil H 2SO 4 containing HgSO 4 gives a
compound (Y) which on reaction HI and red phosphorous gives C 2 H 6 . The
compound (X) is?
Solution: The compound (X) is likely to be alkyne which reacts with water in presence of
H 2SO 4 and HgSO 4 as catalyst to form a carbonyl compound. HI and red
phosphorous can reduce a carboxyl compound to alkane having same number of
carbon atoms.
Therefore (Y) is likely to be acetaldehyde which is the hydration product of
ethyne
HC ≡ CH + H 2 O 
H 2SO4
HgSO4
→[CH 2 = CH – OH] CH 3 — CHO
X (Y)

CH 3CHO + 4HI 

red P
→ CH 3CH 3 + 2I 2 + H 2 O

Problem 6: What is the major product by the addition of HCl to 2, 2, 2-trichloropropene?

Solution: CCl3 is a strongly electron withdrawing group. The addition of HCl to >C=C<
double bond of 2, 2, 2-trichloropropene does not follows the Markownikoff’s rule
because intermediate secondary carbonium ion is destabilized by the –1 effect of
CCl3 group.
+
+
CCl3 — CH = CH 2 
H
→ CCl3 — C H — CH 3
Less stable

Instead the addition follows anti markownikoff’s rule because primary carbonium
ion becomes relatively more stable.

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+ +
CCl3 — CH = CH 2  → CCl3 — CH 2 — C H 2 →
–
H Cl
CCl3 — CH 2 — CH 2 Cl
relatively more
stables

Problem 7: Write equation showing how the following compound can be converted to (a) an
epoxide (b) a diol (c) a ketone.

Solution:

C6 H5 CO3 H
→ + C6 H 5COOH
O


Cold KMnO 4
H 2O + [O]
→
OH OH
O

CH3
 O2
PdCl 2 / CuCl 2
→

Problem 8: Identify (A), (B) and (C) in the following reactions

→
HCO3 H
(A)
1 eqv.
CH3  → (B)
CrO3
in AcOH


aq. KMnO4
excess
→(C)

Solution: i) Peroxy formic acid hydroxylates double bond but not triple bond. Therefore,
compound (A) is
CH3
HO
OH
ii) Oxidation of triple bond is very much slower than that of double bond.
Therefore, by using a suitable oxidizing agent it is possible to selectively
oxidize double bond in presence of triple bond. CrO3 in presence of AcOH is
one such oxidizing agent, which oxidizes double bond and not triple bond.
Thus, compound (B) is

HOOC COOH CH3

iii) Aqueous KMnO 4 hydroxylates both the double bond as well as triple bond.
The compound (C) is
O O

C C CH3
HO
OH

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Problem 9: Write down the structures of close homolooguoes of heptane having in their
molecule one quaternary carbon atom and the other having two tertiary carbon
atom.

Solution: Homologuoes of heptane (C7H16) are hexane (C6H14) and octane (C8H18).
Quaternary carbon

CH3 H3C
H3C CH3
H3C
CH3 CH3 CH3
2,2-dimethylbutane 2,2-dimethylhexane
CH3
H3C CH3 H3C
t t t t

H3C CH3 H3C CH3

2,3-dimethylbutane 2,3-dimethylhexane

Problem 10: Which alkane, having a molecular weight of 86, will form only two monobromo
alkanes?

Solution: General formula of alkane is CnH2n+2. Its molecular weight = 86

∴12n + 2n + 2 = 86
n=6
Hence the given alkane is C6H14.
H3C CH3
Its isomer would give two products
H3C CH3
H3C CH3 Br CH3 H3C Br

→
Br2 / UV light
H3C +
H3C CH3 CH3 CH3 H3C CH3

Problem 11: A hydrocarbon (A) was found to have a vapour density of 36. It forms only a
single monochloro product. What is (A)?
Solution: Molecular weight = 2 × VD = 2 × 36 = 72
CnH2n+2; 12n + 2n + 2 = 72, n = 5
The alkane is C5H12; its isomer neopentane has all the four identical H, hence will
give only one monochloro product.
CH3
H3C CH3 ≡
CH3

Problem 12: Write balanced equations, naming all organic products, for the following
reactions;
a) isobutyl bromide + Mg/ether b) t-butyl bromide + Mg/ether
c) product of (a) + H2O d) product of (b) + H2O
Solution: a) CH3 CH3
H3C + Mg 
→ ether H3C
H Br H MgBr

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b) CH3 CH3
H3C Br + Mg 
→ H3Cether
MgBr
CH3 H
c) CH3 H3C
H3C + H 2O 
→ CH3 + Mg(OH)Br
H MgBr H3C
isobutane
CH3
d) H3C
H3C MgBr + H 2 O 
→ CH3 + Mg(OH)Br
H H3C
isobutane

Problem 13: Chlorination of ethane (CH3 – CH3) to ethyl chloride is more practicable than the
chlorination of n-pentane to 1-chloropentane. Why?

Solution: It is because monochlorination of ethane gives only ethyl chloride, whereas

monochlorination of n-pentane gives three isomeric monochloro
hν
CH 3 − CH 3 + Cl 2  → CH 3CH 2 Cl + HCl
Cl

Cl + H3C
CH3  → H3C
Cl
H3C
2 CH3
hν
− HCl
+

H3C CH3
Cl

Problem 14: What products are obtained when 1-bromo-2-methyl propane and 2-bromo-2-
methyl propane are allowed to react with metallic sodium in dry ether? Give their
IUPAC names and name the reaction involved.
Solution: CH3 CH3 CH3
H3C
H3C CH3 H3C CH3
CH3 CH3 H3C
CH3 CH3
2,2,3,3-tetramethylbutane H3C CH3
2,2,4-trimethylpentane 2,5-dimethylhexane

It is Wurtz reaction

Problem 15: A chloro derivative (A) on treatment with Zn-Cu couple gives ahydrocarbon of
five carbon atoms. When (A) is dissolved in dry ether and reacted with Na, the
product is 2,2,5,5-tetramethyl hexane? What is (A)?
CH3
Solution:
H3C ≡
CH3 Cl Cl

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KVPY
1. Saponification of oils gives (2007)
(A) Glycerol and alkali salts of fatty acids (B) Glyceraldehyde and alkali salts of fatty acids
(B) Glyceric acid and long chain alcohols (D) Ethylene glycol and alkali salts of fatty acids

2. In the following reaction sequence

Br
1. Alcoholic KOH 3. HgSO/dil. H2SO4, heat Y
Br
X
2. NaNH2 4. Con. HNO3H2SO
Ph
(A)

(B)

(C)

(D)

3. The expected order of boiling points of I –VI would be (2007)

(II) (III) (IV)
(I)

(A) I < II < IV < III (B) III < IV < II < I (C) IV < III < II < I (D) IV < II < III < I

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4. The number of covalent bonds in C4H7Br2 is (2010)

(A) 12 (B) 10 (C) 13 (D) 11

5. Compound ‘X’ on heating with Zn dust gives compound ‘Y’ which on treatment with O3 followed by
reaction with Zn dust gives propionaldehyde. The structure of ‘X’ is (2013)

(A) (B) (C) (D)

6. A compound X formed after heating coke with lime react with water to give Y which on passing over
red hot iron at 873 produces Z. The compound Z is
(A) (B)

(C) (D)

7. 2, 3-Dimethylbut-2-ene when reacted with bromine forms a compound which upon heating with
alcoholic KOH produce the following major product. (2013)

(A) (B) (C) (D)

8. The major product of the reaction of 2-butene with alkaline KMnO4 solution is (2014)
(A) (B)
O
(C) (D)

9. The species that exhibits the highest Rf value in a thin layer chromatogram using a nonpolar solvent
on a silica gel olate is (2014)
(A) (B)

(C) (D)

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10. Among the compound I–IV, the compound having the lowest boiling point is (2014)

(A) I (B) II (C) III (D) IV

Answer Keys :

1:A 2: A 3:B 4:A

5:C 6:A 7:B 8:D
9:A 10:C

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Assignments
SECTION – I Single Choice Questions

1. On heating CH3COONa with soda lime the gas evolved will be

(a) C2 H 2 (b) CH 4
(c) C2 H 6 (d) C2 H 4 .

2. Which of the following will have least hindered rotation about carbon-carbon bond ?
(a) Ethane (b) Ethylene
(c) Acetylene (d) hexachloro ethane.

3. A sample of 1.79 mg of a compound of molar mass 90 g mol –1 when treated with

CH3 Mgl releases 1.34 ml of a gas at STP. The number of active hydrogen in the
molecule is
(a) 1 (b) 2
(c) 3 (d) 4.

4. The addition of Br2 to trans-2-butene produces

(a) (+) 2, 3-dibromobutane (b) (–) 2, 3-dibromobutane
(c) rac –2, 3-dibromobutane (d) meso-2, 3-dibromobutane

5. The treatment of CH3C(CH3)= CHCH3 with NalO 4 or boiling KMnO 4 produces

(a) CH3COCH3 + CH 2 O (b) CH3CHO + CH 3CHO
(c) CH3COCH3 + CO 2 (d) CH3COCH 3 + HCOOH .

6. What is the chief product obtained when n-butane is treated with bromine in the presence
of light at 130°C ?
CH3
(a) H3C Br (b) H3C
Br
H3C CH3
Br H3C C CH2 Br
(c) (d)
CH3 CH3

7. The olefin, which on ozonolysis gives CH3CH 2 CHO and CH3CHO .

(a) But-1-ene (b) But-2-ene
(c) Pent-1-ene (d) Pent-2-ene.

8. Addition of halogen acid (HX) is least in

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(a) CH 2 = CHCl (b) CH 2 = CH 2

(c) CH3 — CH = CH 2 (d) (CH 3 ) 2 C = CH 2 .

9. Which of the following alkene will react fastest with H 2 under catalytic hydrogenation
condition?
R R R H
(a) (b)
H H H R
R R R R
(c) (d)
R H R R

10. Products of the reaction,

CH3
+

CH2  →
D2 O / D
H3C

CH3
CH3 CH3 CH3

(a) H3C CH2D (b) H3C CH2D

CH3 OD OD
CH3 H CH3

(c) H3C CH3 (d) H3C CH2

OD D CH3 D OD

11. Point out (A) in the given reaction sequence:

∆
(A) 
O3 / H 2 O
→ (B)  → 2CH 3COOH + CO 2

(a) (b)

(c) (d)

12. End product of the following sequence is:

Hg 2+
CaO + C 
Heat
→ (A) H2 O
→ (C) 
H 2SO 4
→(C)
(a) Ethanol (b) Ethyl hydrogen sulphate
(c) Ethanal (d) Ethylene glycol.

13. Hydrogenation of the compound

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[Type text]

H3 C

Me Me

H
H
H
In the presence of poisoned palladium catalyst gives:
(a) An optically active compound (b) An optically inactive compound
(c) A racemic mixture (d) A diastereomeric mixture.

14. The treatment of C2 H5 Mgl with water produces

(a) Methane (b) Ethane
(c) Ethanal (d) Ethanol.
H3C
15. CH2 + HBr 
→ A. (predominant), A is
CH3
Br
H3C CH Br
H3C CH2
(a) CH3 (b)
CH3
CH3
Br

(c) H3C C CH2 CH3 (d) None of these.

CH3

16. Br
When isobutene is brominated, the percentage of would be
H3C CH3
CH3
(a) 0% (b) 83%
(c) 10% (d) 100%

17. Which of the following is used for aromatization of n-hexane?

(a) AlCl3 (b) Na in liquid NH3
(c) Cr2O3/Al2O3 with heat (d) Wilkinson’s catalyst

18. Identify (B) in the following sequence of reactions.

Cu 2 Cl 2 + NH 4 Cl
CH ≡ CH  → (A) →
HCl
(B)
(a) CH3CH 2 Cl (b) CH 2 = CH — CH 2 CH 2 Cl
HC CH3 Cl
(c) (d)
Cl H2C C CH2

19. Propene can be converted into 1-propanol by oxidation. Which set of the reagents is used
to effect the conversion?
(a) OsO4 – CHCl3 (b) O3/Zn – H2O
(c) Alkaline and cold KMnO4 (d) B2H6 and alk. H2O2.

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20. In the following sequence of reactions, identify the product (D).

CH ≡ CH  
HBr
→ (A) 
HBr
→ (B) 
alk. KOH
→ (C) 
NaNH 2
→ (D)
(a) Ethanol (b) Ethyne
(c) Ethanal (d) Ethene

21. B ←
Lindlar / H
2
 R − C ≡ C − R →
Na / NH
A 3

A and B are geometrical isomers (R — CH = CH — R):

(a) A is cis. B is trans (b) A is trans, B is cis
(c) A and B both are cis (d) A and B both are trans
22. CH3 CH3

H 3C CH3 
NaIO 4 / KmnO 4
→ Pr oducts.
CH3
The products are
O O
(a) (b) H3C
H 3C CH3 , (CH3 )3 C − COOH CH3 , (CH 3 )3 C − CHO
O
(c) H3C (d) None is correct
OH , (CH 3 )3 C − COOH

23. CH3
+ CH3 
AlC3
→ hydrocarbon (X).
H 3C
X is
CH3
CH 2 CH CH3 C CH3
(a) (b)
CH3 CH3

(c) CH 3 CH 2 CH 2 CH3 (d) None is correct

24. The reaction of

H3CHC CH OH

with HBr gives

(a) H3C Br OH (b) H3C CH OH

CH CH 2 CH 2 Br

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(c) H3C CH Br (d) None of these

CH 2 Br

25. A sample of diesel has the same knocking characteristic as a 60 ml mixture of centane
and α-methyl naphthalene mixed in 2 : 1ratio (V/V). What is the cetane number of the
diesel sample?
(a) 56.6 (b) 66.6
(c) 76.6 (d) 86.6

SECTION – II May be more than one choice

1. R H

Br2 / CCl4
→P + Q
H R1
Where P and Q are
(a) enantiomers if R ≠ R′
(b) diastereomers if R ≠R′
(c) Both are meso and hence the same compound if R = R′
(d) An equimolecular mixture of P and Q is a racemic mixture if R ≠ R′
2.
CH3 CH3 CH3 H
C C C C
H H H CH3
per acid per acid

A C
+ +
H /H2O H /H2O

B D
Which of the following statements is/are true :
(a) B is a single compound and optically inactive
(b) D is a single compound and optically inactive
(c) B is an equimolar mixture of two enantiomeric compounds
(d) D is an equimolar mixture of two enantiomeric compounds
3. HgSO4/H2SO4

BH3/THF
A H2O2/OH
B

Hg(OAC)2, H2O
NaBH4
B is identical when A is
(a) CH ≡ CH (b) CH3  C ≡ CH
(c) CH3  C ≡ C  CH3 (d) CH3  CH2  C ≡ CH

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[Type text]

4. Which of the following statements are correct:

(a) Hydrogenation of 2-butyne in presence of Na and liquid ammonia yields trans-2-
butene
(b) Hydrogenation of 2-butyne in presence of Lindlar’s catalyst yields cis-2-butane
(c) Hydrogenation of 2-butyne in presence of Brown’s catalyst gives cis-2-butane
(d) None of these
5. Which of the following statements are correct on the basis of heat of combustion:
(a) Trans-2-hexene has less heat of combustion than 2-methyl-2-pentene
(b) Cis-2-pentene has higher heat of combustion than trans-2-pentene
(c) 1-hexene has higher heat of combustion than trans-2-hexene
(d) 2, 5-dimethyl hexane has higher heat of combustion than octane
6. O

C CH3 CH 2 CH3


→
This change can be carried out using:
(a) NH2 NH2, glycol/OH— (b) Zn.Hg/conc. HCl
(c) P/HI (d) None of these

7. Hydroboration oxidation and acid hydration will yield the same product in case of:

(a) (b)

(c) CH2 = CH2 (d) CH3CH = CHCH3

→
8.

HgSO / H SO4 2 4


A BH / THF
H O / OH
2
→
3
2
B −



Hg(OAC) ,H O
NaBH → 
2
4
2

B is identical when A is:

(a) CH ≡ CH (b) CH3—C ≡ CH
(c) CH3—C ≡ C—CH3 (d) CH3—CH2 — C ≡ CH

9. A + Br → 2-bromo-2, 3-dimethyl butane. Hence A can be:

CH3 CH3

CH2 CH3
(a) (b) H 3C
H 3C
CH3 CH3OH
CH3
CH3 CH3
(c) CH2 (d)
H 3C H 3C CH3
OH

10. C4 H 6 
H / Ni
2
→ C 4 H8 →
O /H O
CH 3COOH 3 2

(A) ( B)

Hence A and B are:

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[Type text]

(a) CH3—C≡C—CH3, CH3CH=CH—CH3

(b) CH2=CHCH=CH2, CH3CH = CHCH3
(c)
, CH3CH = CHCH3
(d) None of these

11. Ammonical silver nitrate reacts with

(a) ethyne (b) ethylene
(c) butyne-1 (d) butyne-2

12. When nitrobenzene is treated with Br2 in the presence of FeBr3, the major product formed
is m-bromonitrobenzene. Statements whichare related to obtain the m-isomer are
(a) the electron density on meta carbon is more than that on ortho and para positions
(b) the intermediate carbonium ion formed after initial attack of Br+ at the meta position
is least destabilized.
(c) loss of aromaticity when Br+ attacks at theortho and para positions and not at meta
position
(c) easier loss of H+ to regain aromaticity from the meta position than fromortho and para
position

13. Which of the following compounds will show cis-trans isomerism?

(a) (H3C)2C = CH — CH3 (b) H2C = CCl2
(c) C6H5(H)C = CH — CH3 (d) H3C — CH = CBr(CH3)

14. When toluene was treated with CBrCl3 in presence of light which one of the product/s is
formed.
(a) Br2 (b) C6H5CH2Br
(c) C2Cl6 (d) CHCl3

15. Which one of the following has the smallest heat of hydrogenation per mole?
(a) 1-butene (b) trans-2-butene
(c) cis-2-butene (d) 1, 3-butadinene

16. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with
(a) SO2Cl2 (b) SOCl2
(c) Cl2 (d) NaOCl

17. Toluene, when treated with Br2/Fe, gives p-bromotoluene as the major product because
CH3 group
(a) is para directing (b) is meta directing
(c) activates the ring by hyperconjugation (d) deactivates the ring
18. Which is/are true statements/reactions?
(a) Al4C3 + H2O → CH4
(b) CaC2 + H2O → C2H2
(c) Mg2C3 + H2O → CH3C ≡CH
(d) Holme signal uses mixture of Ca3P2 and CaC2

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19. Following are used as anaesthetics in surgical operations:

(a) C2H4 (b) N2O
(c) CHCl3 (d) solid CO2

20.
O 
→

This change can be carried out using:

(a) NH2NH2, glycol/OH– (b) Sn(Hg)/conc. HCl
(c) P/HI (d) NH3/LiAlH4
21. CH4 gas is also called/content of :
(a) CNG (b) Marsh gas
(c) water gas (d) producer gas
22. A 
HgSO / H SO
4 2
→ B 
4 BH / THF
3
H O / OH
2 2
→−

B is identical when A is:

(a) CH ≡ CH (b) CH3—C≡CH
(c) CH3—C≡C—CH3 (d) CH3—CH2—C≡CH

23. Which gases are poisonous?

(a) Lewisite (b) Mustard
(c) Phosgene (d) MIC

SECTION – III Comprehension Type Questions

Write-up I
Chlorination of methane involves three steps: chain-initiating, chain-propagating and
chain-terminating.
Cl2 →
Heat or light
2Cl Chain initiating

CH 4 + Cl 
→ CH 3 + HCl
Chain propagating
CH 3 + Cl2 
→ CH 3 Cl + Cl
When oxygen is passed through the reaction mixture, chlorination of methaneslows down
temporarily

1. Chain-propagating steps
(a) consume reactive species and form another reactive species
(b) do not produce reactive species
(c) absorb energy and produce reactive species
(d) are not always the part of chain-reaction mechanism

2. Chain-terminating step may involve the formation of

(a) Chlorine (b) Methyl chloride
(c) Ethane (d) All the three

3. Although chlorination of methane is an exothermic, the reaction requires high

temperature because
(a) Activation energy is low (b) heat of reaction is negative

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(c) Chain-initiating step is endothermic (d) Chain-terminating step is endothermic

4. Temporary slow down of chlorination of methane in presence of oxygen in due to the
formation of
(a) CH3OO• which is highly unstable and decomposes easily
(b) CH3OO• which is less reactive than •CH3
(c) ClO• which is highly reactive
(d) a diradical ClO•

Write-up I
CH2=CHCH3 
BH 3 / THF
H O , OH −
→B
2 2

↓ NBS
D 
Br2
→ E 
Alc.
KOH
→F

5. In the reaction B is
(a) ethyl alcohol (b) propyl alcohol
(c) Allyl alcohol (d) None of these

6. In this D is
(a) Allyl Bromide (b) Vinyl Bromide
(c) 1, 2 dibromo propane (d) None of these

7. F is
(a) 1, 3-diBromo-1-propene (b) 1, 2-di-Bromo-1-propene
(c) 1, 1-diBromo-1-propene (d) 2, 2-di Bromo-1-propene

8. E is
(a) 1, 2, 3-Tri Bromo propane (b) 1, 1, 3-Tri Bromo Propane
(c) 1, 2, 2-Tri Bromo Propane (d) None of these

Write-up II
1 butene 
A/B
→ C 4 H 9 Br 
C
→ C4 H9 I
Go through above reaction sequence and answer the following question

9. The compound A/B is

(a) H2O2 (b) HBr/ROOR
(c) HI/H2O2 (d) HI

10. The name of the reaction is (second step)

(a) Wurtz reaction (b) Cannizaro reaction
(c) Hoffmann elimation (d) Finkelstein reaction

Write-up V
By virtue of its shape ‘s’ orbitals can attract electron density more than ‘p’ orbitals. More
the ‘s’ character more is the electronegativity of the hybrid orbitals. Order of
electronegativity of hybrid orbitals is sp > sp2 > sp3.

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11. Which is acidic?

(a) H3C—C ≡ C —CH3 (b) CH2 = CH2
(c) H3C — C ≡ C—H (d) C2H6

12. Acetylene reacts with sodium hypochlorite to form

(a) vinyl chloride (b) dichloro acetylene
(c) sodium acetylide (d) chloro ethane

13. Acetylene reacts with sodium and methyl iodide and produces
(a) 2-butyne (b) 1-butyne
(c) 1-pentyne (d) 2-pentyne

14. 1-buyne and 2-butyne can be distinguished by

(a) Br2 in CCl4 (b) Tollen’s reagent
(c) Schiff’s reagent (d) 2, 4-DNP

Write-up VI
CH 2 = CH 2 + Br2 
CCl4
→ A 
AlCo. KOH
NaNH 2 ∆
→ B ← Na liq.
One mole CH 3 − CH 2 Cl

C ←
B2 H 6 / THF
H O / OH −
D 
Al(OEt )3
→E
2 2

15. B with excess amount of NaNH2 followed by treatment with methyl chloride produces
(a) butyne-1 (b) butyne-2
(c) propyne-1 (d) 1, 3 butadiene

16. Hydroboration and oxidation is

(a) cis addition (b) Anti addition
(c) cis and anti addition (d) cis addition and elimination

17. hydride ion migration take place in the following

(a) Tischenko reaction (b) Aldol ondensation
(c) Cannizaro reaction (d) a and c
18. Vicinal dihalide of ethane on treatment with aqueous KOH followed by lead tetra acetate
produces.
H2 C CH2
(a) CO2 + HCHO (b)
OH OH
(c) 2HCHO (d) CH3COOH + H2O

Answers to Assignments
SECTION - I

1. (b) 6. (b) 11. (c) 16. (d) 21. (b)

2. (d) 7. (d) 12. (c) 17. (c) 22. (a)
3. (c) 8. (b) 13. (b) 18. (d) 23. (b)
4. (c) 9. (d) 14. (b) 19. (d) 24. (b)
5. (c) 10. (b) 15. (c) 20. (b) 25. (b)

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SECTION - II

1. (a), (c), (d) 9. (a), (b), d) 17. (a), (c)

2. (b), (c) 10. (a), (b) 18. (a), (b), (c), (d)
3. (a), (c) 11. (a), (c) 19. (a), (b), (c)
4. (a), (b), (c) 12. (a), (d) 20. (a), (b), (c)
5. (a), (b), (c) 13. (c), (d) 21. (a), (b)
6. (a), (b), (c) 14. (b), (c), (d) 22. (a), (c)
7. (b), (c), (d) 15. (b) 23. (a), (b), (c), (d)
8. (a), (c) 16. (c)

SECTION - III

1. (a) 7. (a) 13. (a)

2. (d) 8. (a) 14. (b)
3. (c) 9. (b) 15. (b)
4. (b) 10. (d) 16. (a)
5. (b) 11. (c) 17. (d)
6. (a) 12. (b) 18. (c)

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