Organic Chemistry

HYDROCARBON

In One Shot Om Pandey, IIT Delhi

Topics
1 Solvent , Electrophile , Nucleophile

Formation of Carbocation , Carbanion ,

2
Radicals ( Reactions with Metals )

3 Acid Base Reaction

4 Reactions of Alkane , Alkene , Alkyne & Benzene

5 Stereo-chemistry of Reactions of Alkene

6 Physical Properties
Non-polar Solvent Solvent Polar Solvent

Carbon Tetrachloride Water

Ethyl Alcohol
Benzene

Acetone
Cyclohexane
Tetrahydrofuran
 Solvents Polar Protic Aprotic
CH3 CH3
S
O
Dimethyl sulphoxide

CH3
H—C—N
O CH3
Dimethyl formamide

CH3
CH3 — C — N
O CH3
Dimethyl acetamide
Electrophile

Electron deficient species. BH3

Having vacant orbital with incomplete octet . BF3

Species having complete or partial ve charge on central atom. AlCl3

   ZnCl2
NO2 N=O X R–C=O
FeCl3

O O O O Cl
O C O
S C P R C Cl C
O O R R Cl Cl Cl Cl
Cl Cl
Nucleophile
ve charge loving species

Charged : R– H– Cl– Br– SH– OH– R — O–

Neutral : H — O R—O NH3 R — NH2

H
H

R— CH CH — R R—C C—R
Formation of Carbocation BF3 / BCl3 / AlCl3 / SbCl5

HI / HCl / H2SO4 / HNO3

Cl + SbCl5

CH3
|
CH3 —C —Cl + AlCl3
|
CH3

O
||
R —C —Cl + AlCl3
 |
H+
—C — O
|
H

CH AgNO3 (aq.)

Br
 Acid - base reaction

NaOH

NaOEt

NaH

NaNH2

Na

NaHCO3
 Formation of Carbanion

NaH

H H

H
| NaNH2
O2N —CH —CH2
|
F

Na
R—C C—H
20 July, 2021 (Shift-II)

Metallic sodium does not react normally with :

A Gaseous ammonia

B Tert-butyl alcohol

C But-2-ene

D Ethyne
 Reactions With Metal

Mg
CH3 — Br
ether

Li
CH3 — Br
ether

Zn
CH3 — Br

Zn
CH3 — Br
HCl
27 Aug, 2021 (Shift-I)

Cl
dry ethanol
+ Mg [A] P
ether

CH2CH3 O – CH2CH3
A B

C D
 M + R–X

Na
Wurtz Reaction : CH3 – Br
Dry ether

Cl
Na
Fitting Reaction : ether

Cl
Wurtz-Fitting Reaction : CH3 – Cl + Na
ether

Frankland Reaction : Zn
I 

I
Ullmann Reaction : Cu

Preparation of Alkane
Na
Wurtz reaction R — Cl Dry ether

Cl Cl

Cl Cl

Cl

Cl
 Na
Br – CH2 – CH2 – CH2 – Br
ether

Cl
Zn
H – Cl

Zn/Cu couple
CH3 – I Ethanol

OH
Br Na
Elimination Reaction

Addition Reaction
Alkene

Electrophilic Addition Reaction

Reactivity of an Alkene :
 CH2 CH2
Type - iii H + / D+

Cl+ / NO+

Hg2+ / Hg+ X
Hydrohalogenation of Alkene Markovnikov’s Rule : Electrophile
adds to the less substituted carbon

CH3 — CH CH2
HI

EDG — CH CH2
HI

EWG — CH CH2
HI
08 April, 2019 (Shift-II)

Which one of the following alkenes when treated with HCl yields majorly an anti
Markovnikov product ?

A F3C – CH = CH2

B Cl – CH = CH2

C CH3O – CH = CH2

D H2N – CH = CH2
06 Sept, 2020 (Shift-I) The major product of the following reaction is :

CH3

2HBr

NO2

CH3 CH3
H3C Br Br CH3
Br Br
A B C D
Br Br
Br Br
NO2 NO2 NO2 NO2
Rearrangement

HBr
Hydrogenation of Alkene

H2
CH3 — CH CH2
Pt
JEE ( Advanced ) - 2015

Compound(s) that on hydrogenation produce(s) optically inactive compound(s) is (are)

H Br
H Br
A B H2C CH3
H3C CH3

H Br
H2C Br H
C D H2C CH3
CH3
Halogenation of Alkene

Br2
CH3 — CH CH2 CCl4

Br2
Ph — CH CH2 H2O
 NOCl
Ph — CH CH2

ICl
CH3 — CH CH2
09 Jan, 2019 (Shift-I) The major product of the following reaction is

Br2
EtOH

OEt OEt
Br
A B

Br OEt
OEt OEt
C D
13 April, 2023 (shift-II) Major product ‘P’ formed in the following reaction is :

OH
Br2
NaHCO3
P
O

Br
Br OH Br O
A B O
O
Br
C Br OH D OH

O O
Hydration of Alkene

Acid Catalysed Hydration

Oxymercuration – Demercuration

Hydroboration – Oxidation

Acid Catalysed Hydration

CH3 — CH CH2 H+ / H O
2
Acid Catalysed Hydration

CH3
H3C
Dil. H2SO4
H
 Oxymercuration – Demercuration

Hg(OAc)2
CH3 CH CH2
H2O

(i) Addition of water by Markovnikov’s Rule

(ii) Formation of cyclo-merquric ion [ Non – classical carbocation ]
(iii) Rearrangement is not possible.
(iv) Attack of H2O as nucleophilic on more substituted partial carbocation.
 Hydroboration – Oxidation
BH3
CH3 CH CH2 THF

(i) Syn-Addition of water by Anti-Markovnikov’s Rule

(ii) Formation of 4 membered transition state
Syn-Dihydroxylation by Baeyer’s Reagent

CH3 CH CH2

R—C C—R
Syn-Dihydroxylation by OsO4

CH3 CH CH2
 Anti-Dihydroxylation by Per Acid

Per-acetic acid Trifluoro peracetic acid Hydrogen Peroxide

RCO3H
CH3 CH CH2
 Stereo-chemistry in Reactions of Alkene

Anti-addition Syn - addition

Br2 / CCl4 H2 / Pd

Br2 / H2O BH3 / THF

H2O2 / OH-
HOBr
Cold and Dil. KMnO4
Hg(OAc)2 / H2O
NaBH4
OsO4

RCO3H
H3O+
Hg(OAc)2 / H2O BH3 THF
NaBH4 H2O2 OH–

D D

RCO3H KMnO4
H3O+ 0°C , OH–

D D

HOCl H2
Pt

D D
Ph H
C Cold dil
NaOH / KMnO4
C
H Ph

Ph H
C Cold dil
Alkaline KMnO4
C
Ph H
 H H
RCO3H
C C
H3O+
CH3 CH3

H CH3
RCO3H
C C
H3O+
CH3 H
 H H
Cl2 Br2
C C
CCl4 H2O
CH3 CH3

H CH3
Cl2 Br2
CCl4
C C H2O
CH3 H
 Kharasch Effect or Peroxide Effect Reagents : HBr / R2O2 , hv

R2O2/hv
R — CH CH2 + HBr

Mechanism :

hv
R—O—O—R

R — O• + H — Br

R — CH CH2 + Br•

•
R — CH — CH2 — Br + H — Br
H2O2 H2O2
HCl
Ph— CH CH2 HBr
 Electrophilic addition reaction of Alkynes
ENu
R— C C —H

Br2
R—C C—H CCl4

Br2
R—C C—H H2O

HBr
R—C C—H

HOBr
R—C C—H

KMnO4
R—C C—H
OH-
Test for Unsaturation

Br2 Br2
R—C C—R H2O R — CH CH — R H2O

Red Brown colour of the solution of bromine water is decolourised due to unsaturation.

Br2 Br2
R—C C—R CCl4 R — CH CH — R CCl4

Reddish orange colour of the solution of bromine in carbon tetrachloride is decolourised.

KMnO4 KMnO4
R—C C—R R — CH CH — R OH-
OH-

Colour changes from Pink purple (Bayer’s reagent) to Brown .

Hydrogenation
H2 / Pd
R—C C—R

H2 / Pd / BaSO4
Lindlar’s Catalyst

R—C C—R

Na / Liq. NH3

Na
R—C C—H
Liq. NH3
16 March, 2021 (Shift-I)

Which of the following is Lindlar catalyst?

A Partially deactivated palladised charcoal

B Cold dilute solution of KMnO4

C Zinc chloride and HCl

D Sodium and Liquid NH3

JEE Adv. 2021

The major product formed in the following reaction is :

NaNH2
Na
liq. NH2

A B

C D
 D2 / Pd Br2 / CCl4
CH3 — C C — CH3
CaCO3

Na Br2 / CCl4
CH3 — C C — CH3
Liq. NH3
01 Feb, 2023 (Corrected) But-2-yne is reacted separately with one mole of
Hydrogen as shown below :
Na Pd/C
B liq. NH3
CH3 – C  C – CH3  A

Identify the incorrect statements from the options given below:

(A) A is more soluble than B.
(B) The boiling point & melting point of A are higher and lower than B respectively.
(C) A is more polar than B because dipole moment of A is zero.

A (B) , (C) B (B), (C)

C (C) only D (A) and (B)

 Addition of H2O

HgSO4 , H2SO4
Me — C C—H
H2O

BH3
Me — C C—H
THF
24 Feb, 2021 (Shift-I)

Which one of the following carbonyl compound cannot be prepared by addition of

water on an alkyne in the presence of HgSO4 and H2SO4?

O O
A CH3 – CH2 – C – H B CH3 – C – CH2CH3

O O
C
D C – CH3 D CH3 – C – CH3
06 Sept, 2020 (Shift-I)

The major product obtained from the following reaction is :

Hg2+/H+
O2N CC OCH3 H2O

OCH3 OH
O

A B
O
O2 N O 2N
OCH3
OH O

D
C
O O 2N
O2N
 Ozonolysis
Reductive Ozonolysis Oxidative Ozonolysis
i. O3 i. O3

ii. Zn/H2O ii. H2O2

DMS

CH3 CH CH2
 Reductive Ozonolysis Oxidative Ozonolysis

CH3 CH CH2

CH3 CH CH CH3

CH3 — C C — CH3

NOTE : KMnO4 / H+ or alkaline KMnO4 with Heat gives same product as in Oxidative
Ozonolysis with alkene and alkyne
12 April, 2019 (Shift-I)

But-2-ene on reaction with alkaline KMnO4 at elevated temperature followed by

acidification will give :

A One molecule of CH3CHO and one molecule of CH3COOH

B CH3 – CH – CH – CH3

OH OH
C 2 molecules of CH3COOH

D 2 molecules of CH3CHO
12 April, 2023 (Shift-I)

(i) O3
2 – hexene (ii) H2O
Products

The two products formed in above reaction are

A Butanoic acid and acetic acid

B Butanal and acetic acid

C Butanal and acetaldehyde

D Butanoic acid and acetaldehyde

 O3
Zn / H2O

CH3
CH3
O3
Zn / H2O
No of pi Bonds & Hydrogenation
13 Jan, 2023 (Shift-II)

A hydrocarbon ‘X’ with formula C6H8 uses two moles of H2 on catalytic hydrogenation
of its one mole. On ozonolysis, ‘X’ yields tow moles of methane dicarbaldehyde. The
hydrocarbon ‘X’ is:

A Hexa-1, 3 , 5-triene

B 1-methylcyclopenta-1, 4-diene

C Cyclohexa-1, 3-diene

D Cyclohexa-1, 4-diene
 IIT-JEE-2012

The number of optically active products obtained from the complete ozonolysis of the
given compound is :
CH3 H

CH3 – CH = CH – C – CH = CH – C – CH = CH – CH3

H CH3

A 0

B 1

C 2

D 4
 Benzene

Addition Reaction

Substitution Reaction

Cl — Cl AlCl3

R — Cl AlCl3

O
R — C — Cl AlCl3
 Electrophilic substitution reaction
1. Formation of sigma complex.

E+

2 . Loss of a proton gives the substitution product.

Rate of ESR :
 Reactivity Directing nature
Substituent groups
Effect on rate Effect on orientation
Very strongly
–O– , – NH- , – NHR , – NR2 , – OH Ortho-para directing
activating

Strongly activating Ortho-para directing

–OR , – NH – CO – R , – O – CO – R

–R , – Ar , – CH = CH2 Activating Ortho-para directing

 Reactivity Directing nature
Substituent groups
Effect on rate Effect on orientation

–X , – N = O , – CH2X , –CHX2 Deactivating Ortho-para directing

– CHO , – C – R , – COOH , Strongly

Meta directing
– COOR , – COCl , – C  N , – SO3H deactivating

Very strongly
–NO2 , –N+H3 , –N+R3 , – S+R2 , –CF3 Meta directing
deactivating
15 April, 2023 (Shift-I)

Decreasing order of reactivity towards electrophilic substitution for the following

compounds is :
CH3 OCH3
NMe2

a b CF3
d
c e

A c>b>a>d>e

B e>d>a>b>c

C a>d>e>b>c

D d>a>e>c>b
 Halogenation

(a) Br2 / FeBr3

(b) Br2 / Fe / Δ
(c) Cl2 / ZnCl2
(d) Cl2 / AlCl3

Cl2 / Fe
Heat

CH3

Cl2 / AlCl3
 I2 + AlCl3
Iodonation :

CH3O
Cl2
anhy AlCl3
O 2N
 For following sequence of reactions, the correct
31 Aug, 2021 (Shift-II)
products are :

1. Br2/Fe/
2. Mg/dry ether
3. CH3OH
Products

Br H CH3 OH
A + Mg B + Mg
OCH3 Br

H OCH3 OCH3
C + Mg D + HMgBr
Br
26 Aug, 2021 (Shift-II) Consider the given reaction, the Product A is:

O
Br2 , AlBr3
‘A’
(C2H5)2O (Major Product)

O Br O

A B
Br

O O

C D
Br

Br
Nitration
(a) Conc. HNO3 + Conc. H2SO4

(b) Fuming HNO3 / Conc. HNO3

CH3

Fuming HNO3
20 July, 2021 (Shift-II)

Benzene on nitration gives nitrobenzene in presence of HNO3 and H2SO4 mixture,

where :

A Both H2SO4 and HNO3 act as a bases

B Both H2SO4 and HNO3 act as an acids

C HNO3 acts as base and H2SO4 acts as an acid

D HNO3 acts as an acid and H2SO4 acts as a base

10 Jan, 2019 (Shift-II)

What will be the major product in the following mononitration reaction?

O HNO3
Conc. H2SO4
N
H

O O NO2
A B
N N
H H
NO2
O O2N
C D O
O 2N N N
H H
Sulphonation Conc. H2SO4

Oleum
Friedel Craft Reaction Alkylation :

AlCl3
R — Cl
01 Feb, 2023 (Shift-II)
+ HF X
 Major product

A B

D
C
10 April, 2023 (Shift-II)

The major product ‘P’ formed in the given reaction is:

CH3O Cl anhy
‘P’
AlCl3
(major)
O2N
CH3

CH3O CH3O
A B
O 2N O 2N CH3
CH3 CH3
CH3O NO3 CH3O
C D
O 2N OCH3 O2N
CH3 CH3 CH3
 Friedel Craft Reaction
Acylation :

O
R — C — Cl
AlCl3
Limitations :
(i) Poly alkylation is possible but poly acylation is not possible .
 (ii) Rearranged products may form in the Friedel Craft Alkylation reactions.

(iii) Highly reactive rings like aniline and highly deactivated rings like nitrobenzene ,
cyanobenzene do not give Friedel Craft reactions.
Preparation of benzene
Cyclic polymerisation of ethyne :

CH3 — C CH

Reduction of phenol : OH
Zn
08 Jan, 2020 (Shift-II)

In the following sequence of reactions the maximum number of atoms present in

molecule ‘C’ in one plane is

Red hot CH3Cl (1 eq)

A Cu tube
B Anhydrous AlCl3
C A is a lowest molecular weight alkyne
Addition reactions of benzene

H2 Ni
Heat

Cl2
Benzene hexachloride
500 K
BHC ( gammaxene)

Benzene on treatment with excess of chlorine in the presence of anhydrous AlCl3 can be
chlorinated to hexachlorobenzene (C6Cl6 ) .
Preparation of Alkane
(i) Li
Corey House Synthesis R — Cl
(ii) CuCl
(iii) R’ — Cl
 Soda – Lime Decarboxylation

O
NaOH CaO
CH3 C — OH Heat

O
C — OH

NaOH CaO
Heat
Kolbe Electrolysis

O
NaOH
CH3 C — OH
Electrolysis

NOTE : Methane cannot be prepared by this method

JEE Adv. 2019

Which of the following reactions produce (s) propane as a major product?

A H3C electrolysis
COONa + H2O

B H3C NaOH, CaO, 

COONa

C Cl Zn, dil. HCl

H3C

Br
Zn
D H3C Cl
Free Radical Substitution Reaction
UV Light or
R — H + X2
250° — 400°C

UV or temp.
(i) Chain initiation : X2 250° — 400°C

(ii) Chain propagation : X• + H – R

R• + X – X

(iii) Chain termination : X• + X•

R• + R•

R• + X•
Free radical allylic and benzylic substitution reaction
NBS = N-Bromosuccinimide

Cl2 / hv
CH3 – CH = CH2

CH3

NBS
10 Jan, 2019 (Shift-I)

Which hydrogen in compound (E) is easily replaceable during bromination reaction in

presence of light?
CH3 – CH2 – CH = CH2
   
A  - hydrogen

B  - hydrogen

C  - hydrogen

D  - hydrogen
26 Feb, 2021 (Shift-I)

For the given reaction :

CH2CH3
Br2
‘A’
UV light (major product)
monobrominated
CN
What is ‘A’?
Br CH3
CH2CH3 CH2CH3 CH CH2CH3
Br
A B C D
CN Br CN CN CN
Br
No of monochloro Products

Cl2
Heat

Cl2
Heat
JEE Mains 2022 / 26 July / Shift - II

Total number of isomers (including stereoisomers) obtained on

monochlorination of methylcyclohexane is __________.
06 April, 2023 (Shift-I)

Number of bromo derivatives obtained on treating ethane with excess of Br2, in

diffused sunlight is ………
 Rate of reaction of alkanes with halogens : F2 > Cl2 > Br2 > I2

Rate of replacement of hydrogens of alkanes : 3° > 2° > 1°

Fluorination is too violent to be controlled.

Iodination is very slow and a reversible reaction. It can be carried out in the presence
of oxidizing agents like HIO3 or HNO3 .
Reactivity Vs Selectivity
 Anhy. AlCl3
Isomerisation CH3(CH2)4CH3 HCl, 

13 April, 2023 (Shift-I) In the following reaction, ‘X’ is

Anhy. AlCl3
A CH3(CH2)4CH2Cl CH3(CH2)4CH3 ‘X’
HCl, 
Major Procut
B Cl – CH2 – (CH2)4 – CH2 – Cl

C CH3CH – (CH2)2 CH3

CH3
D
Aromatisation of Alkane :
25 Feb, 2021 (Shift-I)

Identify A in the given chemical reaction.

CH3 CH3 Mo2O3
773 K, 10-20 atm
‘A’
H2C major product
HC
H2C CH3
CH2

CH3
A B

CH3
C D
 Physical Properties

Boiling point Pentane hexane heptane

Boiling point n–Pentane Isopentane Neopentane

Shape approaches to spherical which results in decrease in vander Waal forces (as surface area decreases)
Melting Point :
Alkanes with odd carbon atoms have their carbon atom on the same side of the
molecule and in 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.

Physical State :
C1 to C4 & Neopentane : Gas

C5 to C17 : Colourless liquids

Above C17 : Waxy solids

06 Sept, 2020 (Shift-II)

The increasing order of the boiling points of the major products A, B and C of the
following reactions will be :
O

(C6H5CO)2
+ HBr A
(A)

(B) + HBr B

(B) + HBr C

A B<C<A B C<A<B

C A<B<C D A<C<B
Heat of Combustion

No of Carbon

Stability
09 Jan, 2020 (Shift-I)

The correct order of heat of combustion :

(a) (b) (c)

A (a) < (b) < (c)

B (a) < (c) < (b)

C (c) < (b) < (a)

D (b) < (c) < (a)

17 March, 2021 (Shift-I)

Mesityl oxide is a common name of : A 2,4-Dimethy lpentan-3 -one

B 3-Methylcyclohexanecarbaldehyde

C 2-Methylcyclohexanone

D 4-Methylpent-3-en-2-one

17 March, 2021 (Shift-II)

The total number of C – C sigma bonds in mesityl oxide (C6H10O) is _________. (Round off
to the nearest integer).