HYDROCARBON (Organic Chemistry)

Hydrocarbon:
Hydrocarbon Functional group Example
Alkanes none (no double or triple bonds) CH3 − CH2 − CH3 , propane
Alkenes double bond CH2 = CH − CH3 , propene
Alkynes −C ≡ C − triple bond H − C ≡ C − CH3 , propyne

Aromatics benzene ring Ethylbenzene

Introduction: Alkanes 2. From alkene:

(i) The alkanes or the paraffins are the saturated 2.1 By catalytic hydrogenation: Addition of H2 on alkene
hydrocarbons. Many occur naturally, and the chief takes place in cis manner in the presence of Pt or Ni or
source of the alkanes is mineral oil or petroleum, Pd to give alkane.
which occurs in many parts of the world. Ni
e.g. (i) CH2 = CH2 + H2 → CH3 − CH3
(ii) These are also called as 'Paraffins' (Parum + Affinis i.e.
less reactive).
(iii) General formula is Cn H2n+2 .
(iv) Hybridisation state of carbon is sp3 .
(v) Geometry of carbon is tetrahedral.
(ii)
(vi) Bond angle is 109∘ 28′ .
(vii) Number of bond angle in methane are six, while in
ethane are twelve.
(viii) C − C bond length is 1.54Å while C − H bond length is
1.11Å.
Preparation of alkane
1. From aldehydes and ketones:
1.1 Clemmensen Reduction:
The Clemmensen reduction is most commonly used to
convert acylbenzenes to alkylbenzenes, but it also works Note: This reaction is exothermic and heat of hydrogenation
with other ketones and aldehydes that are not depend upon no. of 'α' hydrogen.
sensitive to acid. The carbonyl compound is heated 2.2 By hydroboration followed protolysis
with an excess of amalgamated zinc (zinc treated with (i) CH2 = CH2 + H − BH2 ⟶
mercury) and hydrochloric acid. The actual reduction
occurs by a complex mechanism on the surface of the
zinc.
H−BH2
(ii) CH3 − CH = CH2 → CH3 −

1.2 Wolf-Kishner Reduction.

Compounds that cannot survive treatment with hot (iii) CH3 − CH2 − CH2 − BH2 →
2𝐶𝐻3 −𝐶𝐻=𝐶𝐻2

acid can be deoxygenated using the WolfKishner H2 O/H+

reduction. The ketone or aldehyde is converted to its (CH3 − CH2 − CH2 −)3 B → 3CH3 − CH2 − CH3
hydrazone, which is heated with a strong base such as Note: Long- chain alkane may be possible by the coupling of
KOH or potassium t-butoxide. alkyl boranes.
If (AgNO3 + NaOH) is used instead of H2 O/H +
AgNO3
(R −)3 B → R−R
NaOH

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3. From alkyne - by reduction: For Example:

CH3 − Br + 2Zn + Br − CH3 ⟶
CH3 − Zn − CH3 + ZnBr2
CH3 − Zn − CH3 + CH3 − Br ⟶
CH3 − CH3 + CH3 ZnBr
ethane

4.4 Grignard reagents.

Alkyl halides in ether react with magnesium to form
alkyl magnesium halides or Grignard reagents which,
on treatment with water or dilute acid, are
decomposed to alkanes.
in the above reaction if catalyst palladium or platinum ether H+
(i) RI + Mg → R − Mg − I → RH
is used, it is called simple reduction and if Ni is used, H−O−H
it is called Sabatier - Senderen's reaction (catalytic (ii) CH3 MgBr → CH4
R−O−H
hydrogenation). (iii) CH3 MgBr → CH4
CH3 CO2 H
4. From Alkyl halides: (iv) CH3 MgBr → CH4
4.1 By reduction: When alkyl halide is reduced with Preparation by Wurtz reaction, Kolbe electrolysis
Zn − Cu couple +ROH or Na + EtOH/Na − Hg + H2 O Ullmann, Fitting reaction, Wurtz-Fitting reaction
or LiAlH4 , then we get respective alkane. already discussed in free radical reaction.
Zn−Cu
R − X + 2H → RH + HX 5. From Red P +𝐇𝐈 :
R−OH
CH3 Cl + 2H ⟶ CH4 + HCl It is a powerful reducing agent which will convert,
CH3 I + 2H ⟶ CH4 + HI aldehyde, ketone, alcohol, carboxylic acid to alkanes
with same number of carbon.
4.2 Wurtz's reaction: RedP+HI
When alkyl halide reacts with Sodium in presence of (i) R − CH3 − OH → R − CH3
dry ether then we get higher alkane. Mechanism of the
reaction is based on ionic and free radical both. (ii)
dryether
R − X + 2Na + X − R → R − R + 2NaX
CH3 Cl + 2Na + ClCH3 ⟶ CH3 − CH3 + 2NaCl
Note: Current reaction is not suitable for tertiary alkyl (iii)
halides Red+HI
Mechanism: Two mechanism has been suggested for (iv) R − COOH → R − CH3
Wurtz's reaction. Physical Properties
(i) Via organometallic compound 1. The first four alkanes (from methane to butane) are
⊖ ⊕ CH3 −CH2 −Br
C2 H5 Br + Na → C2 H5 Na → colourless and odourless gases. The next thirteen
−NaBr −NaBr (from pentane to heptadecane) are colourless and
CH3 − CH2 − CH2 − CH3 odourless liquids. And, the rest of higher alkanes
(ii) Via free radical (having 18 carbon atoms or more) are colourless
−2NaBr
2C2 H5 − Br + 2Na → 2C2 H5⦁ ⟶ C2 H5 − C2 H5 solids at ordinary temperature.
(iii) Corey-House Synthesis 2. Alkanes being non-polar molecules, are soluble in
Li CuX non-polar solvents like benzene, ether, and
R−X→ R − Li → R 2 CuLi
Ether chloroform. However, they are insoluble in polar
′
R 2 CuLi + 2R − X → 2R − R′ + LiX + CuX solvents like water. Their solubility decreases with
Linthium diallkyl (should be10)
cuprate increase in their molecular weight.
This method is better than Wurtz and can be used for 3. Melting and boiling points are increases with
preparing symmetrical as well as unsymmetrical molecular mass and decreases with No. of branches.
alkanes (having an odd number of carbon atoms). As far as melting point is concerned the alkane having
even carbons has more M.P. than odd carbons, since
4.3 Frankland's reaction/Method: the intermolecular forces in a crystal depend not only
If alkyl halide is treated with Zn dust in closed tube upon the size of the molecules but also upon how well
then higher symmetrical alkanes will be formed. they fit into a crystal lattice.
2RX + Zn ⟶ R − R + ZnZ2
This is known as Frankland's reaction, in this reaction
first Frankland's reagent (R- Zn − R, dialkyl Zinc) is
formed. Which then react with alkyl halide to give
higher alkanes. [Where R = CH3 ]

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For e.g. Mechanism of Halogenation:

The mechanism involves the following steps:
250−40°C
(i) Chain-initiation step X 2 → 2X ∘
or UV light
(ii) Chain-propagation step
X ⦁ + R − H → H − X + R⦁
M.P. even > odd no. of atoms R⦁ + X 2 → R − X + X ⦁
(iii) Chain-termination step
4. Boiling point decreases with the increment of
X ⦁ + X ⦁ → X2
branches.
R⦁ + X ⦁ → R − X
(n-Pentane is liquid but neo-Pentane is gas due to
R⦁ + R⦁ → R − R
increase in branching, surface area decrease therefore
Radical inhibitors stop chain propagation byreacting
intermolecular forces & Vander Waals forces of
with free radical intermediates.
attraction decreases).
Example:
5. Physical state:
Alkanes
C1 − C4 ⟶ Gaseous state 2. Nitration: Under certain conditions, alkanes react
C5 − C17 ⟶ Liquid state (except neo-pentane) with nitric acid, a hydrogen atom being replaced by a
C18 & above ⟶ Solid like wax nitro-group, NO2 . This process is known as nitration.
6. Alkanes are lighter than water, so it floats over water. Nitration of the alkanes may be carried out in the
vapour phase between 150∘ and 475∘ C, where upon a
Chemical Properties: complex mixture of mononitro alkanes is obtained.
1. Halogenation
Alkanes react with bromine or chlorine in the
presence of sunlight or UV light or in dark at high
temperatures (250∘ C − 400∘ C) forming a mixture of
substituted products. For example,
CH4 →
Cl2 Cl2
CH3 Cl → CH3 Cl2 →
Cl2 Cl2
CHCl3 → CCl4 3. Sulphonation: Sulphonation is the process of
hv hv hv hv replacing a hydrogen atom by a sulphonic acid group,
The yield of monohalogenated product can be SO3 H. Sulphonation of a normal alkane from hexane
increased by using substrate (alkane) in excess. The onwards may be carried out by treating the alkane
reactivity of halogens follows the order: with oleum (fuming sulphuric acid). It has been
F2 > Cl2 > Br2 > I2 . shown that in concentrated sulphuric acid,
Direct fluorination is explosive and can be achieved by hydrocarbons containing a tertiary hydrogen atom
the action of inorganic fluorides on bromo or iodo undergo hydrogen exchange (In gold et. al. 1936). The
derivatives. mechanism is believed to occur via a carbonium ion:
2C2 H5 Br + HgF2 → 2C2 H5 F + HgBr2 R 3 CH + 2H2 SO4 ⟶ R 3 C + + HSO4− + SO2 + 2H2 O
Bromination is slower than chlorination and is carried R 3 C + + R 3 CH ⟶ R 3 CH + R 3 C + ,etc.
out at higher temperatures. This reaction is of particular interest since optically
Iodination is reversible and can be carried out active hydrocarbons have been racemised in
sufficiently in the presence of strong oxidising agents sulphuric acid; e.g., Burwell et. al. (1948) have
like iodic acid (HIO3 ) or nitric acid that destroys shownthatopticallyactive3-methylheptane is racemised
hydroiodic acid (HI) and shifts the equilibrium in sulphuric acid.
towards the right.
CH4 + I2 ⇌ CH3 I + HI
5HI + HIO3 → 3I2 + 3H2 O
Alkyl iodides can be prepared conveniently by
Finkelstein reaction which involves treating chloro Imp. Rate of sulphonation 3∘ > 2∘ > 1∘ .
or bromoderivative with NaI in acetone or methanol
acetone 4. Chlorosulphonation/Reaction with 𝐒𝐎𝟐 & 𝐂𝐥𝟐 :
solution. RCl + NaI → RI + NaCl ↓ The reaction is also called as Reed's reaction. When
Alkyl chlorides or bromides cannot be prepared by propane reacts with SO2 andCl 2 in presence of
this method of halide exchange because NaCl and ultraviolet light then propyl sulphonyl chlorides are
NaBr are insoluble in acetone. formed.
U.V.Light
CH3 − CH2 − CH3 + SO2 + Cl2 → CH3 − CH2
−CH2 + SO2 Cl + HCl
This process is used in the commercial formation of
detergents.
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(ii)

Cr2 O3 −Al2 O3
(iii) n-Octane → O + M + P (xylene)
Δ

(detergent i.e. sodium salt of sulphonic acid) 8. Cracking and Hydrocracking:

5. Isomerisation: Lower alkanes are not isomerised but Cracking of large hydrocarbons at high temperatures
butane or higher number of alkanes if heated with produces smaller hydrocarbons. The cracking process
aluminium chloride at high temperature then they usually operates under conditions that give the
convert into stable isomers by the rearrangement maximum yields of gasoline. In hydrocracking,
reaction. Isomerisation is also held by heating alkane hydrogen is added to give saturated hydrocarbons;
with- (AlX3 + HX; X = Cl, Br, I orAl I2 (SO4)3 + H2 SO4 ) cracking without hydrogen gives mixture of alkanes
at 200∘ C. and alkenes.
Catalytic hydrocracking

If we take n - heptane then it converts intomost stable Catalytic cracking

formTriptane (trivial name).

Knocking:
Knocking may be defined as the pre-ignition of fuel-
If we take n-octane, iso-octane is formed.
air mixture in the cylinder ahead of the flame. It
reduces the efficiency of the engine and also causes
damage to the cylinder and piston of the engine.
1. The extent of knocking depends on the quality of the
fuel used. In other words, a fuel that produces
minimum knocking is considered as a good-quality
Reaction is used in Petroleum industries, with the fuel
help of this reaction, we can convert unbranched 2. The anti-knocking property or the quality of a fuel is
alkane to branched alkane (i.e. lower octane number usually expressed in terms of the octane number.
alkane to higher octane number alkane) or bad fuel to Octane Number: Octane number is a scale that is used to
good fuel. determine the quality of a fuel.
6. Combustion: Combustion is a rapid oxidation that It may be defined as the percentage of isooctane by
takes place at high temperatures, converting alkanes volume in a mixture of isooctane and nheptane that
to carbon dioxide and water. Little control over the has the same anti-knocking properties as the fuel
reaction is possible, except form oderating the under examination.
temperature and controlling the fuel / air ratio to 1. Straight-chain aliphatic hydrocarbons have a higher
achieve efficient burning. tendency to knock than branched-chain
heat hydrocarbons.
Cn H2n+2 + excess O2 → nCO2 + (n + 1)H2 O 2. Two pure hydrocarbons have been selected as
heat
CH3 CH2 CH3 + 5O2 → 3CO2 + 4H2 O standards:
(a) n-Heptane has poor anti-knocking property,
7. Aromatization: therefore, arbitrarily it has been assigned an octane
number of zero.
(i) (b) 2,2,4-Trimethylpentane (isooctane), a branched-chain
hydrocarbon, has the highest antiknocking property.
Therfore, it has been given the octane number of 100.

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The octane number of nonane is -45 and that of with the radicals produced due to irregular
combustion. As a result, reaction chains are broken
and smooth burning of the fuel occurs. This prevents
2,2,3-trimethylpentane called as knocking.
Heat
Pb(C2 H5 )4 → Pb + 4C2 H5 (Ethylradical)
triptane, is 116. The lead deposited in the cylinder is removed by
adding 1,2-dibromoethane (ethylene bromide) that
n-Heptane, octane number = 0 decomposes into ehene (ethylene) and bromine. The
bromine thus obtained combines with lead to form
lead bromide which, being volatile, is carried of from
2,2,4-Trimethylpentane or
the engine by exhaust gases.
isooctane, octane number = 100 BrCH2 CH2 Br → CH2 = CH2 + Br2
Alkanes Octane number Pb + Br2 → PbBr2 (Volatile)
Cetane Number:
CH4 122 1. Cetane number is a scale that is used to determine
the quality of a diesel fuel.
C2 H6 101 Cetane number is the percentage of cetane by volume
in a mixture of cetane and 𝛼 methylnaphthalene that
C3 H8 96 has the same ignition properties as the diesel under
C4 H10 89 examination in a test engien.
C6 H34 (n-hexadecane), cetane number = 100
3. Straight-chain alkanes have very low octane numbers. (ignites spontaneously)
As the length of the chain increases, the octane
number decreases.
4. Branched-chain alkanes have higher octane number.
As the branching increases, the octane number
increases.
5. Cycloalkanes have higher octane number. As the 𝛼-Methylnapthalene, cetane number = 0
extent of branching increases, octane number further (ignites slowly)
increases. or
6. Unsaturated hydrocarbons, i.e., alkenes and alkynes, 1-Methylnapthalene
have higher octane numbers than the corresponding 2. LPG and CNG: The term LPG (liquefied petroleum gas)
straight-chain alkanes. refers to the mixture of hydrocarbons containing
7. Aromatic hydrocarbons have very high octane three or four C atoms. This includes propane (C3 H8 ),
numbers. propene (C3 H6 ), n-butane (C4 H10 ), isobutene
8. It has been found that gasoline obtained by cracking (methylpropane), and various butanes with a little
has a higher octane number than gasoline obtained by amount of ethane (C2 H6 ). The major sources of LPG
direct distillation. This is because cracked gasoline are natural gas and refining and cracking of
contains higher percentage of alkenes, branched chain petroleum. Alkenes are mainly produced during
aliphatic hydrocarbons, and aromatic hydrocarbons. cracking. LPG is mainly used in the manufacturing of
chemicals, as a fuel for households, and in the petro-
The tendency of knocking decreases in the order: chemical industry.
straight-chain alkane > branched-chain alkane > CNG (compressed natural gas) is a highly compressed
alkenes > cycloalkanes > aromatic hydrocarbon. form of natural gas. Many vehicles are designed to
Anti-knocking agent or Gasoline additives: operate on CNG. Natural gas has an octane rating of
Compounds that are added to gasoline and reduce 130.
knocking are called anti-knocking agents. The
problem of knocking in engines can be checked by
using fuels of high octane number and by addition
certain compounds (anti knocking agents) that
reduce knocking.
The best anti-knocking agent is tetraethyl lead (TEL)
or Pb(C2 H5 )4 . This is added to the extent of 0.001% in
gasoline. Such a gasoline is called ethyl gasoline or
leaded gasoline. In the cylinder of an engine, TEL
decomposes to produce ethyl radicals that combine

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ALKENE (g) C-H bond length is 1.10Å.

1. GENERAL INTRODUCTION (h) C = C bond energy is 143.1kcalmol−1 .
• Hydrocarbons that contain a carbon-carbon double (i) C − H bond energy is 98.69kcalmol−1 .
bond are called alkenes. (j) Alkene shows chain, position, functional (ring chain),
• Each double-bonded carbon of an alkene has three sp2 optical & geometrical isomerism.
orbital of another atom to form a σ bond. Note: Cumulated polyene can exhibit geometrical as well as
• Thus, one of the carbon-carbon bonds in a double optical isomerism. for eg. Isomers of C4 H8 :
bond is a σ bond, formed by the overlap of an sp2
orbital of one carbon with an sp2 orbital of the other (i)
carbon. (ii) Position isomers → CH2 = CH − CH2 − CH3 &
• The second carbon-carbon bond in the double bond CH3 − CH = CH − CH3
(the π bonds) is formed from side-to-side overlap of (iii) Functional isomers (ring chain isomerism)
the remaining p-orbitals on the sp2 carbons. Because
three points determine a plane, each sp2 hybridized
carbon and two of the three atoms bonded to it are in
a plane.
(iv) Geometrical isomers →
• In order to achieve maximum orbital-orbital overlap,
the two p-orbitals must be parallel to each other.
Therefore, all six atoms of the double bond system are
in the same plane. A molecular orbital description of a
carbon-carbon double bond. (v) Optical isomerism →
• It is important to remember that the π bond
represents the cloud of electrons that is above and
below the plane defined by the two sp2 carbons and
the four atoms bonded to them.
3. METHODS OF PREPARATION OF ALKENES
3.1 ELIMINATION REACTIONS
Elimination reactions consist in removing the two
groups (generally one being a proton and other is
leaving group from one or two carbon atoms of a
substrate to for man unsaturated linkage.
• Because the two p orbitals that form the π bond must Elimination reactions are classified under two general
be parallel to one another to achieve maximum categories.
overlap, rotation about a double bond does not occur.
If rotation about a double bond did occur, the two p- TYPES OF ELIMINATION REACTIONS
orbitals would ceases to overlap and the π bond 1. α-Elimination (1,1)
would be destroyed. 2. β-Elimination (1,2)
1. 𝛂-Elimination: When the two atoms or groups are
eliminated from the same carbon, the process is
called 𝛼-Elimination.
2. 𝛃-Elimination: When the two groups or atoms are
removed from the two adjacent carbon atoms, the
process is known as β-Elimination.
SOME IMPORTANT TERMS
(1) Substrate: That molecule or ion which undergoes
change is called substrate. Substrate may be alkyl
halide, alcohol etc.
(2) Base: It is negative ion or neutral molecule which
2. CHARACTERISTICS OF ALKENE: abstract the proton from the substrate.
(a) General formula: Cn H2n . (3) Leaving Group: It is an ion or molecule which leaves
(b) Functional group: in alkenes is > C = C < the substrate with a pair of electron. The tendency of
(c) The double bond is made up of one sigma and one pi leaving group is directly proportional to strength of its
bond. conjugated acid. Leaving group ability of different
(d) The doubly bonded carbon atoms are sp2 hybridized. halide ions follows the sequence I Θ > Br Θ > ClΘ > F Θ
(e) Geometry of unsaturated ' C ' carbon is trigonal planar.
(f) C = C bond length is 1.34Å.

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β-ELIMINATION CAN OCCUR BY THREE DIFFERENT (d) Formation of transition state is the rate determining
MECHANISM step.
(1) E-1 mechanism (e) Rate of reaction depends on the concentration of
(2) E-2 mechanism substrate as well as of base i.e. it follows the second
(3) E-1 CB mechanism order kinetics.
Rate = [ Substrate ][ Base ]
CHARACTERISTICS OF E-1MECHANISM:
(f) E-2 mechanism shows the isotopic effect as the loss of
(a) It is called unimolecular elimination reaction.
hydrogen is a part of R.D.S.
(b) It takes place in two steps. KH 7
𝐈 st Step: Departure of leaving group from a molecule =
to form carbocation. KD 1
(g) E-2 mechanism shows the halogen effect as loss of
leaving group is a part of R.D.S.
∴ Reactivity of different alkyl halides follows the
𝐈𝐈 nd Step: Carbocation formed above loses a proton to sequence
the base and forms the alkene. R − I > R − Br > R − Cl > R − F
Reactivity order of different substrate follows
3∘ > 2∘ > 1∘
(h) The rate of reaction increases with increasing
(c) Ist step of E-1mechanism is the rate determining step strength and concentration of the base.
(R.D.S.) (i) Non-polar solvent favors the E-2 mechanism.
(d) Since in R.D.S. only substrate undergoes covalency (j) Since E-2 mechanism involves the transition state;
change. rearrangement is not possible.
i.e. it follows first order kinetics with respect to E1 CB MECHANISM
substrate (a) In this mechanism, the reaction take place in two
Rate = K[ substrate ] steps.
(e) Since in R.D.S. carbocation is formed as an (i) The first step involves rapid removal of a proton
intermediate so the reactivity order of different from the 𝛼-carbon (carbon adjacent to the carbon
substrate follows the stability of order of carbocation bearing halogen atom) forming a carbanion.
formed. (ii) The carbanion formed then loses the halides ion
Allylic carbocation > Tertiary carbocation > in the second rate determining step.
Secondary carbocation > Primary carbocation
(f) Loss of leaving group is the part of R.D.S. therefore the
order of reactivity of alkyl halide in elimination
reaction is
R − I > R − Br > R − Cl > R − F
Above order is parallel to order of leaving group ability
I Θ > Br Θ > ClΘ > F Θ
(g) E-1mechanism does not show isotopic effect as the (b) The overall rate of the reaction is limited to slower
loss of hydrogen is not the part of R.D.S. second step & hence the rate of reaction depends only
KH on the concentration of carbanion.
=1 (c) Since carbanion is the conjugate base of the alkyl
KD
(h) Since the ionization take place in step I. Therefore halide and rate of reaction depends on concentration
polar solvent favors the E-1mechanism. of carbanion hence the mechanism is designated as
(i) E-1mechanism involves carbocation as an intermediate E1CB mechanism.
so rearrangement of carbocation can take if possible. MECHANISM OF α-ELIMINATION
More stable carbocation forms the major product in 𝛼-elimination does not occur frequently and
the reaction. completes in two stages, the second of which is rate
E-2 MECHANISM determining.
(a) It is known as bimolecular elimination mechanism. for eq.
(b) It take place in single step. CHCl3 + OH − Fast ⊕
CCl3 + H2 O
(c) It involves the formation of transition state Θ
CCl3 + H2 O ⟶: CCl2 + Cl−
dichlorocarbene
Another example of 𝛼-elimination reaction is
formation of diphenyl acetylene from2, 2-diphenyl
vinyl bromide and sodamide.

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Remember: PossibilityofE1 increases with increasing

stability of carbocation. Similarly possibility of E2
increases with decreasing stability of expected
3.2 From Alkynes carbocation.
3.4 From Dihalides
3.4.1 From gem dihalides: When gem dihalide is heated
with Na in ether then higher alkenes are formed.
poison of catalyst such as BaSO4 , CaCO3 are used to
stop the reaction after the formation of alkene,
otherwise alkanes are formed.
Mechanism
(i) The reaction takes place at the surface of Pd, that is
why it is cis addition and the product is cis form eg.

Conclusion- If we take two different types of gem

dihalides then we obtain three different types of
(ii) Alkyne can be reduced to trans alkene by using
alkenes.
Na + NH3 , or LiAlH4
Note: The above reaction is used in the formation of symm.
alkenes only, because if we take two different types of
halides then mixture of alkenes is obtained so the
Terminal alkynes are not reduced by the Na − NH3 yield of an individual alkene is reduced and it is
untill presence of (NH4 )2 SO4 . improper to separate each alkene from the mixture
3.3 From mono halides because the difference of boiling points in alkenes is
When mono halide react with alcoholic KOH or NaOH very less.
then respective alkenes are formed 3.4.2 From vicinal dihalides:
When vicinal dihalides are heated with Zn dust,
(i) alkene of same no. of carbon is obtained.

(ii)

Note: CH3 − CH2 CHX − CH3 ⟶ CH3 − CH2 −

CH = CH2 ⟶ CH3 − CH = CH − CH3
Minor Major
CH3 − CH = CH − CH3 (Trans) is the major product
because it is more stable as having six ' α ' Hydrogen Note: Alkene is not formed from1,3 dihalides. Cyclo alkanes
in the comparison to CH3 − CH2 − CH = CH2 having are formed by dehalogenation of it.
only two ' α ' hydrogen. For example:
This is in accordance with the saytzeff rule.
Mechanism: E2 and E1 are possible.
E2 Mechanism:

3.5 From Alcohols

When alcohol is heated with conc. H2 SO4 at about
160∘ C, alkenes are formed after dehydration.

As molecularity of slowest step is two i.e. E2 mechanism.

E1 Mechanism:

As molecularity of slowest step is one. That is why it is

termed as E1.

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Δ
CH3 CH2 CH2 CH2 OH + H2 SO4 → CH3 − CH2 − CH = CH2 + CH3 − CH = CH − CH3
160°C 1-butene 2-butene
(majorproduct)

Mechanism:

Note: Since the mechanism proceeds via- C + ion therefore rearrangement is also possible:

Mechanism:

Characteristics of dehydration of alcohol

(1) Since the carbocation is formed as an intermediate in the R.D.S. of dehydration of alcohol The relative reactivity of alcohols
decreases in the order.
Tertiary > Secondary > Primary
(2) Since the R.D.S. is reversible it is necessary to remove the H2 O molecule produced in the reaction. Therefore in
experimental condition conc. H2 SO4 is added in a regular interval.
(3) For dehydration, different dehydrating agent like Al2 O3 , ThO2 can also be employed.
(4) Rearrangement of carbocation can take place.
(5) −OH is not a good leaving group, in alcohols so turn it into a good leaving group, it is converted into −H2 O+ by protonation
(6) −H2 O⊕ is a good leaving group.

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Rearrangement in Alcohol Dehydration

(1) Some alcohols undergo dehydration to form alkene 3.6 Kolbe's Synthesis
having carbon skeleton different from those of the When aqueous solution of K or Na succinate is
starting alcohol. electrolysed, ethylene is released at anode.
(2) This is due to rearrangement of carbocation formed in
the reaction to more stable carbocation.
(3) An example of alcohol dehydration that is accompanied
by rearrangement is.

(4) Percent yield of alkenes formed from rearranged

carbocation is greater than the percent yield of alkene
obtained from unrearranged carbocation.
(5) Rearrangement of carbocations can also lead to a Note- If we use methyl succinic acid as reactant then
change in ring size, as the following example shows propylene is formed.
3.7 From Esters
When esters are heated in presence of liq. N2 and glass
wool, then alkyl part of ester converts into respective
alkene while alkanoate part of ester is converted into
respective acid.

CH3 − COOH + CH2 = CH2

The reaction is called as 'Pyrolysis of Ester'.
Regioselectivity in alcohol dehydration: Mechanism:
1. In alcohols such as 2-methyl-2-butanol, dehydration Pyrolysis of Ester is a type of E1 elimination which
can occur in two different directions to give alkenes proceed via cyclic T.S. that is why the product becomes
that are constitutional isomers. 'cis'
2. More substituted alkene forms the major product and
is called Saytzeff alkene or Zaitsev alkene.
3. Less substituted forms the minor product and is called
Hofmann's alkene.

• It is interesting to note that, in this case major product

is 1- alkene in the comparision to 2alkene.

CH3 − CH2 − CH = CH2 + CH3 − CH = CH − CH3

(Major) (Minor)

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(vii) The increase in branching in carbon chain decreases

3.8 From quaternary ammonium hydroxide the boiling point among isomeric alkenes.
When quaternary ammonium hydroxide is heated
5. CHEMICAL PROPERTIES
strongly it decomposes to give alkene. eg.
The main reactions of alkene are electrophilic
(i) addition reaction and the mechanismis based on ionic.
It was proved by Francis.

(ii)

This elimination is called Hoffman's elimination. It is Thus the electrophilic addition on alkene is trans
markable that in this reaction more acidic H is addition.
preferably eliminated.
6. FRANCIS EXPERIMENT
3.9 The Wittig reaction According to Francis first attacks electrophile on the
In this reaction methylene triphenyl phosphorane is olefinic bond
reacted with carbonyl compound to give alkene.
e.g.:
(i)

(ii)
3.10 The Cope Elimination:
Tertiary amine oxide undergoes the elimination of a
dialkylhydroxyamine when they are heated. This
reaction is called the Cope elimination. 7. CHEMICAL REACTIONS
7.1 Reaction with Hydrogen–

Mechanism:
Mechanism: The reaction takes place at the surface of
Ni, therefore the addition is cis addition.

eg:
4. PHYSICALPROPERTIES
(i) From C2 − C4 they are colourless, odourless gases,
from C5 − C17 they are colourless liquids, C18 onwards
alkenes are solids.
(ii) Alkenes are practically insoluble in water because
they cannot form hydrogen bonds with H2 O molecule.
They dissolve freely in organic solvents like benzene,
chloroform, CCl4 petroleum ether, etc. (Like dissolves like)
(iii) B.P and M.P. decreases with increasing branches in
alkene.
(iv) The melting points of cis isomers are lower than trans Note: Hydrogenation (catalytic hydrogenation) of alkene is
isomers because cis isomer is less symmetrical than a cis addition and is an exothermic reaction. Thus the
trans. Thus trans packs more tightly in the crystal heat evolved decreases with increasing stability of
lattice and hence has a higher melting point. alkene.
(v) The boiling points of cis isomers are higher than trans Remember, Stability of alkene depends upon
isomers because cis-alkenes has greater polarity hyperconjugation and type of geometrical isomerism
(Dipole moment) than trans one.
7.2 Reduction of alkene via hydroboration
(vi) These are lighter than water.
(i) Alkene can be converted in to alkane by hydroboration
followed by protolysis
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This reaction is also represented as

H−BH2 H+ /H2 O
RCH = CH2 → (R − CH2 − CH2 )3 B →
3R − CH2 − CH3 + H3 BO3
(ii) Alkene can be converted into alkane by hydroboration Note: For suitable condition
followed by treatment with AgNO3 + NaOH. This (i) Cis addition on cis form results meso
method gives coupling. (ii) Cis addition on trans form results ( ± )
(iii) Trans addition on cis form results ( ± )
(iv) Trans addition on trans form results meso
7.5 Reaction with HX (Hydro halogenation) –

7.5.1 Markovnikoff's Rule

When an unsaturated unsymmetrical hydrocarbon
reacts with HX then halogen goes on that unsaturated
carbon which has minimum number of hydrogen
7.3 Birch Reduction
atom. Mechanism of the reaction is based on .
A terminal double bond may be reduced by sodium in
liq. NH3 in the presence of alcohol. This method is
known as the Birch Reduction and is believed to
proceed Via an anionic free radical
Na Et−O−H
̅ H2 → Mechanism:
R − CH = CH2 → R − ĊH − C
e
Na Et−O−H
R − ĊH − CH3 → R − C̅H − CH3 → R − CH2 − CH3
e

7.4 Halogenation -
In presence of polar medium alkene form vicinal
dihalide with halogen.

(i) Formation of Carbocation is Rate determining step.

(ii) Rearrangement of carbocation to more stable carbocation
can occur to form a more stable product.
(iii) Regiochemistry - Markownikoff's Addition of HX.
Order of reactivity of halogens is: F2 > Cl2 > Br2 > I2 Addition of HX on unsymmetrical alkenes
Mechanism: It is an electrophilic addition by (R − CH = CH2 ) takes place according to
molecular attack in which the addition takes place in Markownikoff"s rule which states that, "the negative
transmanner. part of abbendum is added on the carbon atom
carrying lesser number of hydrogen atoms".
(iv) Reactivity order of different hydrogen halide towards
addition HI > HBr > HCl > HF
7.5.2 Anti Markownikoff's Principle / Kharasch Effect /
Peroxide Effect -
To understand antimarkownikoff's principle let us
that is why- consider the following reactions

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7.7 Reaction with H2 SO4 −

(a) With conc. H2 SO4 (Elimination)

(b) With dil. H2 SO4 (Substitution)

It is based on free radical mechanism.

(a) Mechanism Concept - Mechanism:
(i) R − O − O − R ⟶ RO⦁ + ⦁ OR
Peroxide
(ii) RO⦁ + H − Br ⟶ ROH + x Br

(iii)

(iv)
• The hydration of alkene is not stereoselective, as in the
case of HCl addition. This fact can be explained on the
(v) ⦁
Br + ⦁ Br ⟶ Br2
basis of classical carbon cation formation.
Note: It is interesting to note that antimarkovnikov addition
• Since hydration proceeds via carbocation intermediate
in the presence of peroxide is not applicable for HCl
therefore rearrangement is always probable.
andHI
(i) In the case of H − Cl, the step

is endothermic (as ΔH ∙ = +12.6KJmol−1 )

(ii) In the case of H − I, the step

endothermic (as ΔH = +46KJmol−1 )

But in the case of HBr both of the steps are exothermic,
which results spontaneous reaction.
• CCl4 , CBrCl3 etc. can also be added to alkene in anti
markovnikov manner.
7.6 Reaction with Hypohalous Acid –
• Rearrangement, however, may be avoided by
treatment of alkene by
oxymercurationdemercuration method
(i) When chlorine water or bromine water is used.

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7.8 Addition of Nitrosyl halide -

Alkene with nitrosyl bromide or nitrosyl chloride
(Tillden reagent) react according to Markovinikoff's
rule to give alkene nitrosobromide and alkene
nitrosochloride respectively.

Similarly

7.9.3 Hydroxylation by 𝐎𝐬𝐎𝟒 :

7.9 Oxidation
Oxidation is completed by the following ways.
7.9.1 With Acidic KMnO4 /HotKMnO4
(Strong oxidising agent)

7.9.4 Ozonolysis:
This is the two step reaction
(i) Ozonide formation
(ii) decomposition of ozonide (reductive hydrolysis)
e.g:

Remember: Ozonolysis gives oxidative cleavage of

alkene to form two carbonyl group for each
> C = C <. Whether it is in acyclic or cyclic or in
aromatic compound.
eg:
Ozonolysis
(a) CH2 = CH − CH = CH2 →

(b)

7.9.2 With alkaline 𝐊𝐌𝐧𝐎𝟒 / Bayer's reagent

7.9.5 Epoxidation by 𝐎𝟐 /𝐀𝐠

(i)
Mechanism: Hydroxylation by alkaline KMnO4
(Bayer's reagent) is cis addition and the mechanism is (ii)
cyclic.

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7.9.6 Epoxidation by performic acid or perbenzoic acid 7.12 Addition of formaldehyde: In the presence of dil.
mineral acids alkene react with formaldehyde to give
1, 3-diol or cyclic acetal. Mechanism, can be given as
follows:
⊕ ⊕ ⊕
(i) H2 C = O + H → [H2 C = OH ⟷ H2 C − OH]
R–CH CH2
→ R − CH − CH2 − CH2 − OH
(ii)

It is observed that is an excellent

reagent for epoxidation

(iii)
HCHO/H3 O⊕
7.10 Hydroboration CH2 = CH2 →
Alkene with borane hydride form an important
compound called trialkyl borane.
3R − CH = CH2 + BH3 ⟶ (R − CH2 − CH2 )3 B
(a) Trialkyl borane is an important compound because it
gives respective alkane on acidic hydrolysis.

7.13 Polymerisation of Alkene

(a) Mechanism is based on ionic or free radicals both.
(b) In alkene polymer name of polymer is given on the
3R − CH2 − CH3 + B(OH)3 basis of name of monomer, only 'Poly' prefix is used.
(b) It gives respective alcohol on alkaline hydrolysis (c) If in polymerisation Zeigler-Natta catalyst (trialkyl
[Hydroboration oxidation (HBO)] aluminium + Titanium tetrachloride
(C2 H5 )3 Al + TiCl4 .) is used than polymerisation is
named as Ziegler-Natta Polymerisation.

3RCH2 CH2 + B(OH)3 e.g.

(c)

Note:
⟶ 3R − CH2 CH2 NH2 + 3NaCl + H3 BO3 (i) If propelene is reacted then polypropelene is formed
(d) its commercial name is 'Koylene'.
(ii) By the use of vinyl chloride polyvinyl chloride is
formed.
(iii) By the use of Vinyl cyanide (Acrylonitrile), polyacrylonitrile
or orlon is formed.
3R − CH2 − CH2 − CH2 − CH2 − R (iv) Zeigler-Natta catalyst is used in addition polymerisation.
(e) In the overall hydroboration-oxidation reaction, three
moles of alkene react with one mole of BH3 to form 7.14 Substitution reaction -
three moles of alcohol. (a) Except ethene other higher alkene having allyl
(f) Because carbocation intermediates are not formed in hydrogen when treated with chlorine or bromine 'α' H
the reaction carbocation rearrangement do not occur. is substituted.
(g) Regiochemistry Anti-markownikoff'sAddition of water.
(h) Alkyl boranes undergo coupling by means of silver
nitrate in the presence of NaOH at 25∘ C. Higher
alkanes are the products of this reaction.
500−600°C
CH3 − CH = CH2 + Cl2 → Cl − CH2
−CH = CH2 + HCl allyl chloride (3-chloropropene)

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(b) Allylic bromination can be easily done by NBS (N- 7.15 Isomerisation: Alkenes isomerises when heated at
bromo succinamide) high temperature or at lower temperature in the
presence of various catalysts as AlCl3
eg:
AlCl3
(i) CH3 − CH2 − CH2 − CH = CH2
CH3 − CH2 − CH = CH − CH3

(ii)
The mechanism proceeds through carbocation

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ALKYNE The elimination of one molecule of hydrogen halide

1. GENERAL INTRODUCTION: yields vinyl halide which is very unreactive. Under
(1) The chemistry of the carbon-carbon triple bond is mild conditions, the dehydrohalogenation stops at
similar to that of the double bond. In this chapter, we vinylic halide stage but more vigorous conditions- like
see that alkynes undergo most of the reactions of the use of a stronger base like amide ion (NH2− )-are
alkenes, especially the additions and the oxidations. required for alkyne formation.
We also consider reactions that are specific to alkynes: 2.3 From Tetrahaloalkanes (Dehalogenation):
some that depend on the unique characteristics of the
C ≡ C triple bond, and others that depend on the
unusual acidity of the acetylenic carbon - bond.
(2) Alkynes are hydrocarbons that contain carbon-carbon
triple bonds. Alkynes are also called acetylenes In the above reaction it is necessary that the four
because they are derivatives of acetylene, the simplest halogen atoms must be attached at vicinal carbons. If
alkyne. they are attached at the two ends then the product
(3) Alkynes are not as common in nature as alkenes, but cyclo alkene is obtained.
some plants do use alkynes to protect themselves
2.4 From Kolbe's Synthesis:
against disease or predators. Cicutoxin is a toxic
compound found in water hemlock, and capillin
protects a plant against fungal diseases. The alkyne
functional group is not common in drugs, but
parsalmide is used as an analgesic, and ethynyl
estradiol (a synthetic female hormone) is a common
ingredient in birth control pills.
(4) Acetylene is by far the most important commercial
alkyne. Acetylene is an important industrial feedstock,
but its largest use is as the fuel for the oxyacetylene
welding torch. Acetylene is a colourless, foul-smelling
gas that burns in air with a yellow, sooty flame. When
the flame is supplied with pure oxygen, however, the
color turns to light blue, and flame temperature At Cathode:
increases dramatically. 2 K + + 2e− ⟶ 2 K ⦁
(5) Bond angle in alkyne is 180∘ . 2 K ⦁ + 2H2 O ⟶ 2KOH + H2 ↑
(6) Their general formula is Cn H2n−2
(7) C − C triple bond length is 1.20Å. 2.5 Laboratory method of preparation of Acetylene:
(a) In laboratory acetylene is prepared by hydrolysis of
(8) C − H bond length is 1.08Å.
calcium carbide.
2. METHODS OF PREPARATION
2.1 From Gem Dihalides (Dehydrohalogenation):
(b) It can also be prepared from CHCl3 with Ag dust.

2.6 From Alkynes: (To form higher Alkynes)

Note: Alc. KOH is not used for elimination in second step 2.6.1 With Na: When acetylene or 1- alkyne react with Na
because in this case elimination takes place from in presence of liq. NH3 then an intermediate
doubly bonded carbon atom which is stable due to compound sodium acetylide or sodium alkynide is
resonance so strong base NaNH2 is used for formed which gives higher alkyne with alkyl halide.
elimination of HX.
2.2 From vicinal dihalides:

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2.6.2 With GR: When acetyline or 1-alkyne react with GR

(i)
then alkane and unsaturated GR is formed which
further react with alkyl halide and form higher alkyne.
H − C ≡ CH + R − Mg − X → HC ≡ C − MgX (ii)
−RH
XR
→ H−C≡C−R Mechanism:
−MgX2
acetylene
R − C ≡ C − H + R − Mg − X → R − C ≡ C − MgX
−RH
R′−X
→ R − C ≡ C − R′
3. PHYSICAL PROPERTIES
(a) Alkynes are colourless, odourless and tasteless.
(b) Lower alkynes are partially soluble in H2 O. (It is due
to its polarisibility).
(c) Higher alkynes are insoluble in water due to more %
of covalent character. 4.1.3 Hydrogenation by 𝐋𝐢𝐀𝐥𝐇𝟒 :-
(d) Completely soluble in organic solvents. Addition upto alkene takes place in trans manner by
(e) Melting point and boiling point increases with LiAlH4 also.
molecular mass and decreases with number of
branches.
(f) Upto C4 alkynes are gaseous. C5 − C11 are liquid, C12 & 4.1.4 Reduction with the help of 𝐁𝟐 𝐇𝟔 :
above are solids. Alkyne is first reacted with B2 H6 and is follwed by
(g) Acetylene & 1-alkyne are acidic in nature. It is due to acidic hydrolysis, cis alkene is obtained.
greater electronegativity of sp hybridised 'C'.
4. CHEMICAL PROPERTIES
The chemical behaviour of alkynes is similar to that of
alkenes. Alkynes form addition products with two or 4.2 Halogenation:
four univalent atoms or groups. They are generally In presence of Lewis acid as a catalyst alkyne form
less reactive than alkenes towards electrophilic tetrahaloderivative with halogen.
addition reactions even though 𝜋 electron density is
higher in alkynes. This is because on moving from
alkene to alkyne, the C − H bond has more of s
character ( 33% in alkenes as compared to 50% in Example:
alkynes). Therefore, the 𝜋-electrons are more firmly
held by carbon nuclei in alkynes and are thus less
reactive to an electrophile.
4.1 Hydrogenation
Alkynes add two molecules of Br2 in CCl4 and
decolourisation of bromine water is used to detect the
presence of a double or triple bond.
4.3 Reaction with HX (Hydrohalogenation):
The above reaction is called as Sabatier Senderson's Alkyne form gem dihalide with HX because reaction
reaction. follows markownikoff's I st and II nd rule both.
4.1.1 Hydrogenation in the presence of Lindlar Catalyst: R − C ≡ C − H + H − X → 2+
Hg
Addition up to alkene takes place in cis manner.
(i)

(ii)
Note: (i) First step is faster than the second step among
4.1.2 Hydrogenation by 𝐍𝐚 + 𝐍𝐇𝟑 (liq.) addition of two HX on alkyne.
(Birch reduction):
Addition upto alkene takes place in trans manner

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Slower rate of addition of 2 nd molecule is caused by

lower electron cloud density on C = C, due to −I effect
of 'Cl'.
(ii) peroxide give same effect as in alkene

(ii) With dialkyl acetylenes, the product of hydrolysis is

cis-alkene and that of oxidation is a ketone.

4.4 Reaction with Hypochlorous acid or Chlorine water:

⊖⊕
Hypochlorous acid is broken into HO C l & ions & give
addb. according to markovnikov rule.

4.9 Addition of 𝐇𝐂𝐍:

Addition takes place in the presence of CuCl
CuCl
H − C ≡ C − H + H − CN → CH2 = CH − C ≡ N
4.5 Hydration: Addition of water to alkynes is carried out 770∘
in the presence of acid andmercuric sulphate. 4.10 Addition of 𝐀𝐬𝐂𝐥𝟑 :
Lewisite is obtained

H4 H
CH3 − CH2 − C = CH → 4.11 Oxidation:
HgSO4 ,H2 SO4
4.11.1 With acidic or alkaline KMnO4 alkyne break into two
parts from triply bonded carbon and every part forms
respective acid.

4.6 Addition of alcohol

Exception:
Acetylene forms oxalic acid with alkaline KMnO4
exceptionally.
4.7 Addition of carboxylic acid:
In the presence of Hg 2+ unioxylation of carboxylic
acid takes place.
4.11 Ozonolysis
The ozonolysis of alkynes yields a mixture of carboxylic
acids.
4.8 Addition of Boron Hydride (Hydroboration):
(i) With mono-alkyl acetylene, R 2 BH gives an intermediate
which on hydrolysis gives alkene but on alkaline
oxidation yields aldehyde.

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4.12 Acidic nature of 1- Alkyne or Acetylene (a) Dimerisation: Two mole acetylene reacts with
In 1- alkyne or acetylene, the H which is linked with Cu2 Cl2 & NH4 Cl and forms vinyl acetylene.
sp hybridised carbon is called as acidic or active H. It Note: If acetylene would be in excess then product would be
can easily be substituted by metal or alkaline species. divinyl acetylene and the reaction is called trimerisation.
Hence 1- alkyne or acetylene are acidic in nature. eg.
4.12.1 Reaction with 𝐍𝐚 :
LiqN3 Vinyl acetylene or butenyne
2R − C ≡ C − H + Na → 2R − C ≡ C Θ Na⊕
−H2
(b) Trimerisation: If three mole of acetylene is passed
sodium alkynide
into red hot iron or Cu or quartz tube, then a cyclic
OR
trimer is formed which is called benzene.
2R − C ≡ C − H + NaNH2 → 2R − C ≡ C Θ Na⊕
−NH3
H − C ≡ C − H + Na ⟶ Na C ≡ C Θ Na⊕
⊕ Θ

disodium acetylide
Note: Where this alkynide is treat with alkyl halide higher
alkyne is obtained.
R − C ≡ CNa + X − R′ ⟶ R − C ≡ C − R′ + NaX
NaC ≡ CNa + 2R′ − X ⟶ R′ C ≡ C − R′ + 2NaX
4.12.2 Reaction with Ammonical Silver Nitrate
solution: (Tollen's Reagent)
2R − C ≡ C − H + AgNO3 + NH4 OH
→ 2R − C ≡ C Θ Ag ⊕
−H2 O
silver alkynide (white ppt)
H − C ≡ C − H + AgNO3 + NH4 OH
→ Ag ⊕ C Θ ≡ C Θ Ag ⊕
−H2 O
silver acetylide (white ppt) mesitylene (having 3 − 1∘ , 3 − 2∘ &3 − 3∘ carbons)
4.12.3 Reaction withAmmoniacal Cuprous Important: Mesitylene can also be obtained from acetone by
Chloride solution: condensation polymerisation.
2R − C ≡ C − H + Cu2 Cl2 + NH4 OH (c) Tetramerisation: According to the name four moles
→ 2R − C ≡ C Θ Cu⊕ of acetylene are heated with nickel tetra cyanide, then
−2HCl
cuprous alkynide (red ppt.) acetylene forms a cyclic tetramer cyclooctatetraene.
H − C ≡ C − H + Cu2 Cl2 + NH4 OH 4.13.2 Coupling:
→ Cu⊕ CuΘ ≡ C Θ Cu⊕ (a) Alkyne form respective cuprous alkynide with a
−2HCl
dicuprous acetylide (red ppt.) ammonical cuprous chloride solution. When cuprous
alkynide is reacted with potassium ferri cyanide
4.12.4 Reaction with 𝐍𝐚𝐎𝐂𝐥 : [K 3 Fe(CN)6 ] they converted into conjugated diyne.
Acidic hydrogen is substituted by ‘Cl’ ⊖ ⊕
NaOOCl
(i) H−C≡ C−H→ Cl − C ≡ C − Cl R − C ≡ CH + Cu(NH3 )2 Cl ⟶ R − C ≡ C ⋅ u
NaOOCl cuprous alkynide
(ii) R − C ≡ C −H→ R − C ≡ C − Cl O2
2R − C ≡ C ⋅ Cu R − C ≡ C − C ≡ C − R
Mechanism: Δ
Diyne
(b) Coupling is also done easily by 1-alkyne in the
Note: These (5.12.2) and (5.12.3) both reactions are used in presence of Cu2 Cl2 (cuprous compound) and amine
the test of terminal alkynyl hydrogen. These ppt or (ie. pyridine + air) cuprous alkynide is formed (this
metal acetylide or alkynide are insoluble in solution coupling is known as oxidative coupling or glaser
and in dry condition explode, therefore they are coupling)
destroyed with HNO3 before dryness (they form same 1 Cu2Cl2/NH3
2R − C ≡ CH + O2 →
compound again) 2
R − C ≡ C − C ≡ C − R + H2 O
4.13 Polymerisation Reactions: Alkyne mainly shows Cu2 Cl2 /NH3
addition polymerisation reactions. 2CH3 − C ≡ CH + 1/2O2 →
CH3 − C ≡ C − C ≡ C − CH3 + H2 O
4.13.1 Dimerisation and Cyclization 2,4 − Hexadiyne.

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4.14 Formation of heterocyclic compounds:

(a)

(b)

4.15 Reaction with Formaldehyde

1-Alkyne in the presence of copper react with
methanal to form alkynol.

Note: Acetylene react with two mole of HCHO (methanal) to

give 2-butyne-1,4-diol. This reaction is used in the
formation of 1,3 butadine. Which is used in the
formation of buna rubber.
4.16 Isomerisation:
(a) When 1-alkyne is treated with alcoholic KOH 2-alkyne
is formed.
Alc. KOH
R − CH2 − C ≡ CH → R − C ≡ C − CH3
Δ
1 − alkyne 2 − alkyne
(b) When 2-alkyne is treated with sodamide then it is
converted into 1-alkyne.
−NaNH3
CH3 − C ≡ C − CH3 → CH3 − CH2 − C ≡ CNa
−NH3
−H2 O
→ CH3 − CH2 − C ≡ CH
−NaOH

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EXERCISE – I
Q.1 How many moles of 𝐎𝟐 required for complete
combustion of one mole of propane: (A) (B)
(A) 7 (B) 5 (C) 16 (D) 10
Q.2 How much volume of air will be needed for complete
combustion of 10 lit. of ethane:
(A) 135 lit. (B) 35 lit. (C) (D)
(C) 175 lit. (D) 205 lit.
Q.3 During the preparation of ethane by Kolbe's
Q.10 How many dibromo derivative are obtain on addition
electrolytic method using inert electrodes the 𝐩𝐇 of
of bromine to (3S)-3-Methyl Cyclohexene in
the electrolyte:
1,2-dichloroethane:
(A) Increases progressively as the reaction proceeds
(A) 2 (B) 3 (C) 4 (D) 6
(B) Decreases progressively as the reaction proceeds
(C) Remains constant throughout the reaction
Q.11 (E)-3-bromo-3-hexene when treated with CH3 ONa in
(D) May decrease of the the concentration of the
CH3 OH gives
electrolyte is not very high
(A) 3-hexyne (B) 2-hexyne
Q.4 BrCH2 − CH2 − CH2 Br reacts with Na in the presence (C) 2,3-hexadiene (D) 2,4-hexadiene
of ether at 100∘ C to produce:
(A) BrCH2 − CH = CH2 (B) CH2 = C = CH2
Q.12
(C) (D) All of these

Alkene (P) & (Q) respectively are

Q.5 How many products will be formed excluding stereo
when cis-1,3,5-trimethyl cyclohexene reacts with (A)
NBS?
(A) 3 (B) 4 (C) 5 (D) 6
(B)
Q.6
The structures of (X) and (Y) respectively are (C)
(A)

(B) (D)

Q.13 Ozonolysis of CH3 − CH = C = CH2 will give

(C) (A) Only CH3 CHO
(D) (B) Only HCHO
(C) Only CO2
Q.7 When n-butane is heated in the presence of AlCl3 /HCl (D) Mixture of CH3 CHO, HCHO & CO2
it will be converted into – Q.14 O-xylene on ozonolysis will give
(A) Ethane (B) Propane
(C) Butene (D) Isobutane (A)

Q.8
(B)

(A) (B) (C)

(C) Both correct (D) None is correct

Q.9 Major product obtained from following reaction is: (D)

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Q.15 The reacting species of alc. KOH is: (C)

(A) OH − (B) OR+
(C) OK + (D) RO−
(D) none is correct
Q.16 Anti-Markownikoff's addition of HBr is not observed
in: Q.22 Major products in following reaction is:
(A) Propene (B) But-2-ene
(C) Butene (D) Pent-2-ene
Q.17 Major product in following reaction is:
(A) (B)

(C) (D)

(A) (B) Q.23 Major product A,B,C respectively in following reaction

is:

(C) (D)

Q.18 Which is expected to react most readily with bromine

gas:
(A) CH3 CH2 CH3 (B) CH2 = CH2 (A)
(C) CH ≡ CH (D) CH3 − CH = CH2
Q.19 A and B in following reaction is:
(B)

(A)
(C)

(B)
(D)

(C)

Q.24 Major Product obtained in following Reaction:

(D)

Q.20 Major product in following reaction is: (A) (B)

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

(C) (D) none is correct Q.25 Major product in following reaction is:

Q.21 Major product in following reaction is:

(A) (B)

(A) Br − CH2 − CH = CH − CH2 − CCl3

(B)
(C) (D)

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Q.26 For the ionic reaction of hydrochloric acid with the Q.31 Major product in following reaction is:
following alkenes, predict the correct sequence of
reactivity as measured by reaction rates:
(I) ClCH = CH2 (II) (CH3 )2 . C = CH2
(III) OHC. CH = CH2 (IV) (NC)2 C = C(CN)2
(A) IV > I > III > II (B) I > IV > II > III
(A) (B)
(C) III > II > IV > I (D) II > I > III > IV
Q.27 x in following reaction can be-
x
Cis-2-butene ⟶ Y (non-resolvable)
(A) Br2 water (B) HCO3 H (C) (D) Reaction will not occur
(C) Cold alkaline KMnO4 (D) all of the above
Q.28 R1 and R 2 in following reaction can be respectively:
Q.32 Which alkene on heating with alkaline KMnO4
solution gives acetone and a gas, which turns lime
water milky-
(A) 2-Methyl-2-butene (B) Isobutylene
(A) Cold alkaline KMnO4 , OsO4 /H2 O2 (C) 1-Butene (D) 2-Butene
(B) Cold alkaline KMnO4 , HCO3 H Q.33 A in given reaction can be:
(C) Cold alkaline KMnO4 , CH3 − O − O − CH3
(D) C6 H5 CO3 H, HCO3 H
Q.29 Major product in following reaction is: (A) Conc. H2 SO4 (B) alcoholic KOH
(C) Et 3 N (D) t-BuOK
Q.34 which statement(s) is/are true about major product
of this reaction?

(A) (B)

(A) A is meso 2, 3-butan-di-ol formed by syn addition

(C) (D) (B) A is meso 2, 3-butan-di-ol formed by anti addition
(C) A is a racemic mixture of d and l, 2,3-butan-di-ol
formed by anti addition
(D) A is a racemic mixture of d and l2,3-butan-di-ol
Q.30 Compound (A) on oxidation with hot KMnO4 /NaOH formed by syn addition
gives two compound then A is:
Q.35 (P) in the following reaction is:

(A) (A) (B)

(B) (C) (D)

Q.36 The reaction of cyclooctyne with HgSO4 in the

(C) presence of aq. H2 SO4 gives

(A) (B)
(D)

(C) (D)

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Q.37 Major product in following reaction is: (A) CH3 − CH2 − C ≡ CH and
CH2 = CH − CH = CH2 ;
(B) CH3 − C ≡ C − CH3 and
CH3 − CH = C = CH2 ; CH3 − C ≡ C − CH3
(A) (B) (C) ;

CH2 = CH − CH = CH2
(C) (D) (D) CH3 − C ≡ C − CH3 and
; CH2 = CH − CH = CH2
Q.38 Mixture of one mole each of ethene and propyne on
reaction with Na will form H2 gas at S.T.P. – Q.45 The product of reaction between one mole of
(A) 22.4 L (B) 11.2 L acetylene and two mole of HCHO in the presence of
(C) 33.6 L (D) 44.8 L Cu2 Cl2 :
Q.39 Acetylene may be prepared using Kolbe's electrolytic (A) HOCH2 − C ≡ C − CH2 OH
method employing – (B) H2 C = CH − C ≡ C − CH2 OH
(A) Pot. Acetate (B) Pot. Succinate (C) HC ≡ C − CH2 OH
(C) Pot. Fumarate (D) None of these (D) None of these

Q.40 Correct option about given products is: Q.46 In the presence of strong bases, triple bonds will
Lindlar Na/NH3 migrate within carbon skeletons by the
B ⟵ R−C≡C−R ⟶ A (A) removal of protons
(A) A is trans, B is cis (B) A and B both are cis (B) addition of protons
(C) A and B both are trans (D) A is cis, B is trans (C) removal and readdition of protons
Q.41 A mixture of CH4 , C2 H4 and C2 H2 gaseous are passed (D) addition and removal of protons.
through a Wolf bottle containing ammonical cuprous Q.47 A and B in following reaction is:
chloride. The gas coming out is A
(A) Methane (B) Acetylene CH3 − CH2 − C ≡ CH ⇄ CH3 C ≡ C − CH3
B
(C) Mixture of methane and ethylene (A) alcoholic KOH and NaNH2
(D) original mixture (B) NaNH2 and alcoholic KOH
(C) NaNH2 and Lindlar
Q.42 Major product A and B in following reaction
respectively is: (D) Lindlar and NaNH2
Q.48 Major Product obtained in following reaction

(A)
(A) (B)
(B)
(C) CH3 CH2 CHO (both)
(D) (C) (D)

Q.43 Which of the following reagents cannot be used to Q.49 Major product in following reaction is:
NH4 Cl
locate the position of triple bond in CH3 − C ≡ C − CH3 CH ≡ CH ⟶
(A) Br2 (B) O3 (C) Cu2+
2 (D) KMnO4 Cu2 Cl2
(A) CuC ≡ CCu (B) CH2 = CH − C ≡ CH
Q.44 An organic compound of molecular formula C4 H6 , (A), (C) CH ≡ CCu (D) CuC ≡ CNH4
forms precipitates with ammoniacal silver nitrate and
Q.50 Ethylene forms ethylene chlorohydrin by the action
ammoniacal cuprous chloride. ' A ' has an isomer ' B ',
of-
one mol of which reacts with one mol of Br2 to form 1,
(A) Dry HCl gas
4-dibromo-2-butene. Another isomer of A is ' C ', one
(B) Dry chlorine gas
mole of C reacts with only 1 mol. m2 Br2 to give vicinal
(C) Solution of chlorine gas in water
dibromide. A, B & C are
(D) Dilute hydrochloric acid

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EXERCISE – II
Q.1 The correct statements regarding the following
reactions is: (A) (B)

(A) Q is a meso compound (C) (D)

(B) Q is a racemic compound
(C) P is a racemic compound
(D) P is a meso compound Q.8 Which of the following elimination reactions will
Q.2 occur to give but-1-ene as the major product?
EtOH
(A) CH3 ⋅ CHCl ⋅ CH2 ⋅ CH3 + KOH ⟶
(B)
A could be:
(A) NH2 NH2 , glycol/OH − (B) Zn(Hg)/ conc. HCl
(C) Red P/HI (D) ; Raney Ni
Δ
(C) CH3 ⋅ CH2 ⋅ CHCl ⋅ CH3 + Me3 CO− K + ⟶
(D)CH3 ⋅ CH2 ⋅ CH(OH) ⋅ CH3 +conc.H2 SO4 ⟶
H2 /Pt O3 /H2 O Δ
Q.3 (A) C4 H6 ⟶ (B) C4 H8 ⟶ CH3 COOH Q.9 For the following reaction correct option(s) are
Hence A and B are
(A) CH3 C ≡ CCH3 , CH3 CH = CHCH3
(B) CH2 = CHCH3 = CH2 , CH3 CH = CHCH3
(C) , CH3 CH = CHCH3 (A) Total 8 monocholorinated products will obtained
(B) Total 6 enantiomeric monocholorinated pair will
(D) None obtained
NBS
(C) 5 fractions of monocholorinated products will
Q.4 CH2 = CHCH2 CH = CH2 ⟶ A, A can be obtained on fractional distillation
(A) (D) Total 2 achiral monocholorinated products will
obtained
Q.10 Which of the following hydrocarbon(s) will give same
(B) CH2 = CHCH = CH − CH2 Br product with HBr in presence or absence of peroxide.
(C) CH2 = CHCH2 CH = CHBr (A) Cyclohexene
(D) (B) 1-methylcyclohexene
(C) 1,2-dimethylcyclohexene
(D) 1-butene
Q.5 An alkene on ozonolysis yields only ethanal. There is Q.11 The ionic addition of HCl to which of the following
an isomer of this which on ozonolysis yields: compounds will produces a compound having Cl on
(A) propanone (B) ethanal carbon next to terminal.
(C) methanal (D) Propanal (A) CF3 ⋅ (CH2 )3 ⋅ CH = CH2
Q.6 CH3 − CH = CH − CH3 + CH2 N2 → A A can be (B) CH3 ⋅ CH = CH2
Δ (C) CF3 ⋅ CH = CH2
(A) (B) (D) CH3 ⋅ CH2 CH = CH ⋅ CH3
Q.12 Select true statement(s):
(A) I2 does not react with ethane at room temperature
even though I2 is more easily cleaved homolytically
(C) (D) than the other halogens.
(B) Regiochemical outcome of a free radical addition
and an electrophilic addition reaction on propene is
peroxide identical.
Q.7 𝐏h − CH = CH2 + BrCCl3 ⟶ (C) The rate of bromination of methane is decreased if
Product is: HBr is added to the reaction mixture.
(D) Allylic chloride adds halogens faster than the
corresponding vinylic chloride.

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Q.13 Which is/are true reactions?

(A) Al4 C3 + H2 O ⟶ CH4 (B) CaC2 + H2 O ⟶ C2 H2
H+
(C) Mg 2 C3 + H2 O ⟶ CH3 C ≡ CH (D) Me3 C − H + KMnO4 ⟶ Me3 C − OH
Q.14 Which reagent is the most useful for distinguishing compound I from the rest of the compounds
I CH3 CH2 C ≡ CH II CH3 C ≡ CCH3 III CH3 CH2 CH2 CH3 IV CH3 CH = CH2
(A) alk. KMnO4 (B) Br2 /CCl4
(C) Br2 /CH3 COOH (D) Ammonical AgNO

Q.15

B & C are identical when A is -

Q.16 Match List-I with List-II:

List-I (Reaction) List-II (Reagents)
(A) CH3 − CH = CH2 → CH3 − CHBr − CH3 (P) HBr
(B) CH3 − CH = CH2 → CH3 − CH2 − CH2 Br (Q) Br2
(C) CH3 − CH = CH2 → BrCH2 − CH = CH2 (R) HBr/ Peroxide
(D) CH3 − CH = CH2 → CH3 − CHBr − CH2 Br (S) NBS
Q.17 Match the reactions in column-I with appropriate reagent in column II
Column I Column II

(A) (P) Birch reduction

(B) (Q) Stephen’s reduction

(C) (R) Wolf-Kishner reduction

(D) (S) Clemmensen reduction

Q.18 Match the reaction in column-I with name of reaction in column-II

Column I Column II
electrolysis
(A) RCOONa ⟶ R−R (P) Correy-House reaction
Soda lime
(B) R − CH2 − COOH ⟶ R − CH3 (Q) Kolbe electrolysis
Δ
(i) AgNO3
(C) RCOOH ⟶ R − Cl (R) Oakwood degradration
(ii) Cl2 /Δ
(D) R′ − X + R 2 CuLi ⟶ R − R′ (S) Hunsdiecker reaction
Q.19 Column I (Reactions) Column II (Products)
(A) (P) CH3 − CH2 − CH = CH2

(B) (Q) CH3 − CH = CH − CH3

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(C) (R)

(D) (S)

Q.20 Column I Column II

(A) CH3 − C ≡ C − CH3 ⟶ cis-2-butene (P) Na/NH3 (𝑙)
(B) CH3 − C ≡ C − CH3 ⟶ trans-2-butene (Q) H2 /Pd/BaSO4
(C) CH3 C ≡ C − CH3 ⟶ 1-Butyne (R) alc. KOH, Δ
(D) CH3 − CH3 − C ≡ CH ⟶ 2-Butyne (S) NaNH2 , Δ

Q.21 Chlorination of ethane to ethyl chloride is more Q.25 Propose structures for intermediates & products A to K
practicable than the chlorination of n-pentane to
1-chloropentane.
Q.22 Why n-pentane has higher boiling point than
neopentane?

Q.23 (a) A. Write the structure of A.

Q.26 Identify the following (A to D).

(b) B. Write the structure of

major product A.
Q.24 One of the constituent of turpentine is 𝛼-pinene
having molecular formula C10 H16 . The following
scheme give reaction of α-pinene. Determine the
structure of α-pinene & of the reaction products A
through E.

Q.27 What will be the product in the following reaction

(i)

(ii)

(iii)

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Q.33 Give the structure of A, B and C.

(a) A(C4 H8 ) which adds on HBr in the presence and
(iv) in the absence of peroxide to give the same product
C4 H9 Br.
(b) B(C4 H8 ) which when treated with H2 SO4 /H2 O
give (C4 H10 O) which cannot be resoslved into
optical isomers.
(v)
(c) C(C6 H12 ), an optically active hydrocarbon on
catalytic hydrogenation gives an optically inactive
compound C6 H14 .
Q.34 An alkylhalide, X, of formula C6 H13 Cl on treatment
with potassium tertiary butoxide gives two isomeric
Q.28 Write the structural formula of limonene from the alkenes Y and Z(C6 H12 ). Both alkenes on
following observation: hydrogenation gives 2,3-dimethylbutane predict the
(a) Limonene when treated with excess H2 & Pt structures of X, Y and Z.
catalyst, the product formed is 1 isopropyl 4 methyl
cyclohexane Q.35 A hydrocarbon A, of the formula C8 H10 , on
(b) When it is treated with O3 & then Zn/H2 O the ozonolysis gives compound B(C4 H6 O2 ) only. The
products of the reaction are HCHO& following compound B can also be obtained from the
compound alkylbromide (C3 H5 Br) upon treatment with
magnesium in dry ether, followed by carbondioxide
and acidification. Identify A, B and C and also give
equations for the reactions.
Q.36 Compound A(C6 H12 ) is treated with Br2 to form
compound B(C6 H12 Br2 ). On treating B with
alcoholic KOH followed by NaNH2 the compound
Q.29 There are six different alkene A, B, C, D, E and F. Each C(C6 H10 ) is formed. C on treatment with H2 /Pt
on addition of one mole of hydrogen gives G which forms 2-methylpentane. The compound ' C ' does
has the lowest molecular wt hydrocarbon not react with ammonical Cl2 Cl2 or AgNO3 . When A
containing only one asymmetric carbon atom. None is treated with cold KMnO4 solution, a diolD is
of the above alkene give acetone as a product on formed which gives two acids E and F when heated
ozonolysis. Give the structures of A to F. Identify the with KMnO4 solution. Compound E is found to be
alkenes that is likely to give a ketone containing ethanoic acid. Deduce the structures fromA to F.
more than five carbon atoms on treatment with a
warm conc. solution of alkaline KMnO4 . Q.37 A organic compound A having carbon and hydrogen,
adds one mole of H2 in presence of Pt catalyst to
Q.30 3,3-dimethyl-1-butene and HI react to give two form normal hexane. On vigorous oxidation with
products, C6 H13 I. On reaction with alc. KOH one KMnO4 , it gives a simple carboxylic acid containing
isomer, (I) gives back 3,3-dimethyl-1-butene the 3 carbon atoms. Assign the structure to A.
other (J) gives an alkene that is reductively ozonized Q.38 Give the product of
to Me2 C = O. Give the structures of (I) and (J) and
explain the formation of the later. (a)
Q.31 Three isomeric alkenes A, B and C, C5 H10 are
hydrogenated to yield 2-methylbutane A and B gave (b)
the same 3∘ ROH on oxymercuration -
demercuration B and C give different 1∘ ROH 's on
hydroboration -oxidation. Supply the structures of
A, B & C. Q.39 A + B. What are A

Q.32 Two isomeric alkyl bromides A and B(C5 H11 Br) and B?
yield the following results in the laboratory. A on
treatment with alcoholic KOH gives C and D(C5 H10 ). Q.40 Give the structure of the alkene that yields on
C on ozonolysis gives formaldehyde and 2 methyl ozonolysis
propanal B on treatment with alcoholic KOH gives (i) CH3 CH2 CH2 CHO & HCHO
only C(C5 H10 ). Deduce the structures of A, B, C and (ii) C2 H5 COCH3 & CH3 CH(CH3 )CHO
D. Ignore the possibility of geometrical and optical (iii) Only CH3 CO. CH3
isomerism. (iv) CH3 ⋅ CHO&HCHO&OHC CH CH2 ⋅ CHO
(v) Only OHC- CH2 CH2 CH2 − CHO.
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Q.41 What are A to K for the following reactions

ArCH2 Cl Li/NH3
(i) PhC ≡ CH + CH3 MgX ⟶ A ⟶ B ⟶ C. (ix)
(ii) PhCH2 CH2 CH3 +
hv alcoholic cold dil. KMnO4 hot KMnO4
Br2 ⟶ D ⟶ E ⟶ F ⟶ G
KOH

(iii)

(iv)
(x) (a)
HBr
(v) CF3 − CH = CH2 ⟶ J

(vi) (b)

Q.42 Explain the following: Q.44 (a) Outline a stereospecific synthesis of meso 3, 4
(i) 1,2 shift does not take place during dibromohexane from ethyne.
oxymericuration demercuration. Why? (b) Acetylene is acidic but it does not react with NaOH
(ii) Halogneation of alkene is antiaddition but not syn or KOH. Why?
addition. Why? Q.45 A chloro compound (A) showed the following properties:
(iii) Anti markovnikov addition is not applicable for (i) Decolourized bromine in CCl4
HCl. Why? (ii) Absorbed hydrogen catalytically.
(iv) 1,4-addition takes place in butadiene. Why? (iii) Gave a precipitate with ammonical cuprous chloride
Q.43 Conversion: (iv) When vaporised 1.49 g of (A) gave 448 mL of
(i) C2 H2 ⟶ racemic 2, 3 dibromobutane vapours at STP.
(ii) 2-butyne ⟶ 2-pentyne Identify (A) and write down the equations of
(iii) Ethyne ⟶ Acetone reactions.
(iv) cis but 2 ene ⟶ Trans but 2 ene
(v) Ethene ⟶ Propionic Acid
(vi) HC ≡ CH ⟶ CH3 − CH2 − C ≡ C − CH3
⟶ CH3 − CH2 − C ≡ C − CD3

(vii) HC ≡ CH

(vii) HC ≡ CH ⟶ CH2 = C − CH = CH2

⟶ CH3 − CH = CH − CH3
⟶ meso-Butane-2,3-diol
⟶ (±) Butane-2, 3-diol

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EXERCISE - III (JEE-MAIN)

1. The number and type of bonds in C22− ion in CaC2 are: (A) (B)
[JEE MAIN 2014]
(A) Two σ bonds and one π – bond
(B) Two σ bonds and two π – bonds
(C) One σ bond and two π – bonds
(D) One σ bond and one π – bond (C) (D)
2. Which on of the following class of compounds is
obtained by polymerization of acetylene?
[JEE MAIN 2014] 9. Which One of the following alkenes when treated
(A) Poly-ene (B) Poly-yne with HCl yields majorly an anti Markovnikov
(C) Poly-amide (D) Poly-ester product? [JEE MAIN 2019]
3. The gas liberated by the electrolysis of Dipotassium (A) CH3 O − CH = CH2 (B) Cl − CH = CH2
succinate solution is: (JEE MAIN 2014) (C) H2 N − CH = CH2 (D) F3 C − CH = CH2
(A) Ethyne (B) Ethene 10. The major product of the following addition reaction
(C) Propene (D) Ethane Cl2 /H2 O
is H3 C − CH = CH2 → [JEE MAIN 2019]
4. The reagent needed for converting (JEE MAIN 2014) (A) (B)

(A) H2 / Lindlar Cat (B) Cat. Hydrogenation

(C) LiAlH4 (D) Li/NH3
(C) (D)
5. on mercuration -demercuration

11. Consider the following reaction: [JEE MAIN 2019]

produces the major product: - (JEE MAIN 2014)
(A)

(B)
'A' is:
(A) CH ≡ CH (B) CH3 − C ≡ C − CH3
(C) (C) CH3 − C ≡ CH (D) CH2 = CH2
12. The major product in the following reaction is
(D) [JEE MAIN 2020]

6. The major product obtained in the photo catalysed of

2-methylbutane is: (JEE MAIN 2014)
(A) 2-bromo-2-methylbutane
(B) 2 -bromo-3 -methylbutane
(C) 1-bromo-2-methylbutane
(D) l-bromo-3 -methylbutane (A) (B)
7. In the presence of peroxide, HCℓ and HI do not give
anti-Markownikoff s addition to alkenes because
(JEE MAIN 2014)
(A) All the steps are exothermic in HCI and HI
(B) One of the steps is endothermic in HCI and HI (C) (D)
(C) HCl is oxidizing and the HI is reducing
(D) Bbth HCI and HI are strong acids 13. The major aromatic product C in the following
8. Which compound would give 5-keto-2-methyl hexanal reaction sequence will be [JEE MAIN 2020]
upon ozonlysis? (JEE MAIN 2015)

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(D) Statement I is incorrect but Statement II is

correct
(A) (B)
18. Benzene on nitration gives nitrobenzene in presence
of HNO3 and H2 SO4 mixture, where:
[JEE MAIN 2020]
(C) (D) (A) both H2 SO4 and HNO3 act as a bases
(B) HNO3 acts as an acid and H2 SO4 acts as a base
(C) both H2 SO4 and HNO3 act as an acids
14. The increasing order of the boiling points of the (D) HNO3 acts as a base and H2 SO4 acts as an acid
major products A, B and C of the following reactions
will be [JEE MAIN 2020] 19. The major product 'A' of the following given reaction
has ______ sp2 hybridized carbon atoms.
H+
2,7 – Dimethyl 1-2, 6-octadiene ⟶ A
Mojor Product
[JEE MAIN 2022]
20. Two isomers ' A ' and 'B' with molecular formula C4 H8
give different products on oxidation with KMnO4 in
acidic medium. Isomer 'A' on reaction with KMnO4 /
H + results in effervescence of a gas and gives ketone.
The compound ' A ' is [JEE MAIN 2022]
(A) But-1-ene (B) cis-But-2-ene
(A) a < c < b (B) c < a < b (C) trans-But-2ene (D) 2-methyl propene
(C) b < c < a (D) a < b < c 21. In the following given reaction 'A' is
[JEE MAIN 2023]

15.

Identify the reagent(s) ' A ' and condition(s) for the

reaction: [JEE MAIN 2021]
(A) A = HCl; Anhydrous AlCl3 (A) (B)
(B) A = HCl, ZnCl2
(C) A = Cl2 ; UV light
(D) A = Cl2 ; dark, Anhydrous AlCl3
16. An unsaturated hydrocarbon X on ozonolysis gives A. (C) (D)
Compound A when warmed with ammonical silver
nitrate forms a bright sitver mirror along the sides of
the test tube. The unsaturated hydrocarbon X is:
[JEE MAIN 2020] 22. Given below are two statements: [JEE MAIN 2023]
Statement I: under Clemmensen
(A) (B)

(C) HC ≡ C − CH2 − CH3 (D) CH3 − C ≡ C − CH3

reduction conditions will give .
17. Given below are two statements: [JEE MAIN 2020]
Statement-I: 2 -methyl butane on oxidation with
KMnO4 gives 2 -methylbutan- 2 -o1. Statement II: under Wolff-Kishner
Statement-II: n-alkanes can be easily oxidised to
corresponding alcohol with KMnO4 . Choose the
correct option:
(A) Both statement I and statement II are correct reduction condition will give
(B) Both statement I and statement II are incorrect In the light of the above statements, choose the
(C) Statement I is correct but Statement II is correct answer from the options given below:
incorrect

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(A) Statement I is false but Statement II is true (B) A: n-Pentane; B: trans - 2 - butene
(B) Both Statement I and Statement II are false (C) A: 2 - Pentyne; B: Cis -2 - butene
(C) Statement I is true but Statement II is false (D) A: n-Pentane; B: Cis -2 - butene
(D) Both Statement I and Statement II are true
28. Total number of isomeric compounds (including
23. The compound which will have the lowest rate stereoisomers) formed by monochlorination of
towards nucleophilic aromatic substitution on 2 – methylbutane is______. [JEE MAIN 2024]
treatment with OH − is [JEE MAIN 2023]
29. 3-Methylhex-2-ene on reaction with HBr in presence
of peroxide forms an addition product (A). The
number of possible stereoisomers for ' A ' is
[JEE MAIN 2024]
(A) (B) 30. Among the following, total number of meta directing
functional groups is (Integer based)
−OCH3 , −NO2 , −CN, −CH3 − NHCOCH3 , −COR,
−OH, −COOH, −Cl [JEE MAIN 2024]
31. The final product A, formed in the following reaction
sequence is: [JEE MAIN 2024]

(C) (D)

24. Which of the following compound will most easily be (A) Ph − CH2 − CH2 − CH3
attacked by an electrophile? [JEE MAIN 2024] (B)

(A) (B)
(C)

(C) (D) (D) Ph − CH2 − CH2 − CH2 − OH

32. The major product (P) in the following reaction is
[JEE MAIN 2024]
25. Given below are two statements: [JEE MAIN 2024]
Statement (I): The NH2 group in Aniline is ortho and
para directing and a powerful activating group.
Statement (II): Aniline does not undergo Friedel
Craft's reaction (alkylation and acylation).
In the light of the above statements, choose the most (A) (B)
appropriate answer from the options given below:
(A) Both Statement I and Statement II are correct
(B) Both Statement I and Statement II are incorrect
(C) Statement I is incorrect but Statement II is correct
(D) Statement I is correct but Statement II is incorrect (C) (D)

26. Total number of deactivating groups in aromatic

electrophilic substitution reaction among the
following is [JEE MAIN 2024] 33. The arenium ion which is not involved in the
bromination of Aniline is [JEE MAIN 2024]

(A) (B)
27. In the given reactions identify A and B.
[JEE MAIN 2024]

Na/ Liquid NH3 (C) (D)

CH3 − C ≡ C − CH3 + H2 → "B"
(A) A: 2-Pentyne; B: trans - 2 - butene
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34. Identify product A and product B:

[JEE MAIN 2024]

(A)

(B)

(C)

(D)

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EXERCISE - IV (JEE ADVANCED)

1. When Phenyl Magnesium Bromide reacts with tert.
butanol, which of the following is formed?
[IIT '2005]
(A) Tert. butyl methyl ether (B) Benzene
(C) Tert. butyl benzene (D) Phenol
2. 1-bromo-3-chlorocyclobutane when treated with two
equivalents of Na, in the presence of ether which of The correct order of their boiling point is
the following will be formed? [IIT '2005] (A) I > II > III (B) III > II > I
(C) II > III > I (D) III > I > II
(A) (B) Paragraph For Question 9 and 10
Schemes 1 and 2 describe sequential transformation
(C) (D) of alkynes M and N. Consider only the major products
formed in each step for both the schemes.
[JEE ADVANCED 2014]
3. CH3 − CH = CH2 + NOCl → P [IIT 2006]
Identify the adduct.
(A) (B)

(C) (D)

4. The number of stereoisomers obtained by

bromination of trans-2-butene is [IIT 2007] 9. The product X is:
(A) 1 (B) 2
(C) 3 (D) 4 (A) (B)
5. The number of structural isomers for C6 H14 is
[IIT 2007]
(A) 3 (B) 4
(C) 5 (D) 6 (C) (D)

6. The reagent(s) for the following conversion,

[IIT 2007]
10. The correct statement with respect to product Y is -
(A) It gives a positive Tollens test and is a functional
is / are isomer of X
(A) alcoholic KOH (B) It gives a positive Tollens test and is a
(B) alcoholic KOH followed by NaNH2 geometrical isomer of X
(C) aqueous KOH followed by NaNH2 (C) It gives a positive Iodoform test and is functional
(D) Zn/CH3 OH isomer of X
(D) It gives a positive Iodoform test and is a
7. The synthesis of 3-octyne is achieved by adding a geometrical isomer of X
bromoalkane into a mixture of sodium amide and an
alkyne. The bromoalkane and alkyne respectively are 11. Compound(s) that on hydrogentation produce(s)
[IIT 2010] optically inactive compound(s) ia (are)
(A) BrCH2 CH2 CH2 CH2 CH3 and CH3 CH2 C ≡ CH
(B) BrCH2 CH2 CH3 and CH3 CH2 CH2 C ≡ CH (A) (B)
(C) BrCH2 CH2 CH2 CH2 CH3 and CH3 C ≡ CH
(D) BrCH2 CH2 CH2 CH3 and CH3 CH2 C ≡ CH
8. Isomers of hexane, based on their branching, can be
divided into three distinct classes as shown in the
figure [JEE ADVANCED 2014] (C) (D)

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Paragraph For Question 12 and 13 15. The number of hydroxyl group(s) in Q is

In the following reactions [JEE ADVANCED 2015] [JEE ADVANCED 2015]

16. The major product formed in the following reaction is:

[JEE ADVANCED 2021]
12. Compound X is: [JEE ADVANCED 2015]

(A)
(A) (B)
(B)
(C)
(C) (D) (D)
17. In the following reactions, P, Q, R and S are the major
13. The major compound Y is: [JEE ADVANCED 2015] products. [JEE ADVANCED 2023]

(A)

(B)

(C)

(D)

The correct statement about P, Q, R, and S is

14. In the following reaction, the major product is: (A) P is a primary alcohol with four carbons.
[JEE ADVANCED 2015] (B) Q undergoes Kolbe's electrolysis to give an eight-
carbon product.
(C) R has six carbons and it undergoes Cannizzaro
reaction.
(D) S is a primary amine with six carbons.

(A) (B) (SUBJECTIVE TYPE)

18. CH2 = CH − is more basic than HC ≡ C −
[JEE ADVANCED 2000]
19. On reaction with 4 N alcoholic KOH at 175∘ C 1-
pentyne is slowly converted into equilibrium mixture
(C) (D)
of 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5%
1,2-pentadiene (C). Give the suitable mechanism of
formation of A, B and C with all intermediates.
[JEE ADVANCED 2001]

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20. A biologically active compound, Bombykol (C16 H30 O) 22. If after complete ozonolysis of one mole of monomer
is obtained from a natural source. The structure of of natural polymer gives two moles of CH2 O and one
the compound is determined by the following
reactions.
mole of Identify the monomer and
(a) On hydrogenation, Bombykol gives a compound
draw the all-cis structure of natural polymer.
A, C16 H34 O, which reacts with acetic anhydride to
[JEE ADVANCED 2005]
give an ester.
(b) Bombykol also reacts with acetic anhydride to
give another ester, which on oxidative ozonolysis 23.
(O3 /H2 O2 ) gives a mixture of butanoic acid, oxalic
acid and 10 -acetoxy decanoic acid.
Identify X and Y. [JEE ADVANCED 2005]
Determine the number of double bonds in
Bombykol. Write the structures of compound Aand
Bombykol. How many geometrical isomers are
possible for Bombykol? [JEE ADVANCED 2002]
21. Identify X, Y and Z in the following synthetic scheme
and write their structures. Is the compound Z
optically active? Justify your answer.
[JEE ADVANCED 2002]
()i NaNH H2 /Pd −BaSO4 alkalineKMnO4
CH3CH2C  C − H ⎯⎯⎯⎯→
( ii) CH3CH2Br X ⎯⎯⎯⎯⎯
2
→ Y ⎯⎯⎯⎯⎯ →Z

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ANSWER KEY
EXERCISE – I
1. B 2. C 3. A 4. C 5. B 6. C 7. D
8. C 9. D 10. C 11. C 12. C 13. D 14. D
15. A 16. B 17. A 18. D 19. D 20. B 21. A
22. B 23. A 24. B 25. C 26. D 27. C 28. B
29. A 30. B 31. B 32. B 33. A 34. A 35. A
36. D 37. C 38. B 39. C 40. A 41. C 42. B
43. A 44. A 45. A 46. C 47. A 48. C 49. B
50. C
EXERCISE – II
1. B,C 2. A,B,C,D 3. A,B 4. A,B 5. A,B,C,D 6. A,B,C,DQ 7. A,C
8. B,C 9. A,C,D 10. A,C 11. A,B,D 12 . A,C,D 13. A,B,C,D 14. D
15. A,C 16. (A) P (B) R (C) S (D) Q 17. (A) S; (B) R; (C) P; (D) R,S
18. (A) Q, (B) R, (C) S, (D) P 19. (A) R (B) S (C) Q (D) P,S
20. (A) Q, (B) P (C) S (D) R
22. n - pentane has larger surface area and hence stronger Vander waal’s forces.

23.

24.

25.

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26.

27.

28.

29.

30.

31.

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32.

33. (a) CH3 − CH = CH − CH3 (A) (b) (B) (c) (C)

34.

35.

36.

37.

38. (a)

39. A & B are two enantiomers

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40.

41. (A) PhC ≡ CMgx, (B) Ph − C ≡ C − CH2 Ar, (C) (D)

(E) Ph − CH = CH − Me trans, (F) (threo mix.), (G) Ph − COOH

(H) cold dil. KMnO4 , (I) HCO3 H, (J) CF3 CH2 CH2 Br, (K)

EXERCISE - III (JEE – MAIN)

1. (C) 2. (B) 3. (B) 4. (D) 5. (A) 6. (A) 7. (B)
8. (D) 9. (D) 10. (B) 11. (C) 12. (C) 13. (A) 14. (C)
15. (C) 16. (C) 17. (C) 18. (D) 19. (2) 20. (D) 21. (D)
22. (C) 23. (D) 24. (D) 25. (A) 26. (2) 27. (A) 28. (6)
29. (4) 30. (4) 31. (D) 32. (D) 33. (C) 34. (D)
EXERCISE - IV (JEE ADVANCED)
1. (B) 2. (D) 3. (A) 4. (A) 5. (C) 6. (B) 7. (D)
8. (B) 9. (A) 10. (C) 11. (BD) 12. (C) 13. (D) 14. (D)
15. (4) 16. (B) 17. (B)
SUBJECTIVE TYPE
18. higher electronegativity of sp carbon

19.

20. Bombykol:- HO − C − C − C − C − C − C − C − C − C − C = C − C = C − C − C − C
(A) 4 geometrical isomers are possible

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21.

22.

23.

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SOLUTION
EXERCISE – III (JEE MAIN) 13.
9.

10.

11. 14.

Boiling point decreases with branching

∴ order of B.P. is A > C > B

15.

For substitution at allylic position in the given

compound, the reagent used is Cl2 /uv light. The
reaction is free radical halogenation.
12.

16.

As (1) compound given positive tollen's test hence it

may consist-CHO (aldehyde group). or it can be
HCOOH So for the given option:

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(3)
20.

and for other compounds (options):

(1) 21.

(2)

Ozonolysis
(4) CH3 − C ≡ C − CH3 ⟶ 2CH3 − COOH 22.
(Does not show tollen's test)

17.

18. Reagent for nitration of Benzene

23. Electron withdrawing groups are highly ineffective

at meta position in nucleophilic aromatic
substitution reactions.
Hence compound will have lowest

rate in nucleophilic aromatic substitution.

24. Higher the electron density in the benzene ring
more easily it will be attacked by an electrophile.
Phenol has the highest electron density amongst all
the given compound.
25. The NH2 group in Aniline is ortho and para directing
19. and a powerful activating group as NH2 has strong
+M effect.
Aniline does not undergo Friedel-Craft's reaction
(alkylation and acylation) as Aniline will form
complex with AlCl3 which will deactivate the
benzene ring.

26.

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33. Since −NH2 group is o/p directing hence arenium

ion will not be formed by attack at meta position i.e.
27. <smiles> Nc1cccc (Br)c1</smiles>
Hence Answer is (3)
34.

28.

29. Hence correct Ans. (D)

30. −NO2 , −C ≡ N, −COR, −COOH are meta directing.

B2 H6 /H2 O2 ,OH−
31. PhCH = CH2 → PhCH2 CH2 OH

32.

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