❑ Subject – Organic Chemistry

❑ Chapter - Hydrocarbons

ONE SHOT Om Pandey, IIT Delhi

1 Solvent , Electrophile , Nucleophile

2 Alkane , Alkene , Alkyne

3 Benzene
 Solvent
Non-polar Solvent Polar Solvent

H2 O
CCl4
CH3 CH2 OH

CH3 CH3
C
O
 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
  
NO2 N=O X R–C=O
ZnCl2

FeCl3

Partial ve charge having species :

Cl
O O O O
O C O C
S C P R C Cl Cl Cl
O O R R Cl Cl Cl
Cl
Nucleophile Nucleus loving species
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
Ambident Nucleophile Species having more than one nucleophilic site.

CN–

NO2–
Electrophilic Addition Reaction Alkene
H2 / Pd HBr
CH2 CH2
Type - iii Type - i

Type - ii

Br2 CCl4
 Type-i : HX [ HF / HCl / HBr / HI / DCl ]

HI
CH3 — CH CH2

Markovnikov’s Rule : Electrophile adds to the less substituted carbon

 Type-ii : Electrophile having Lone pair

Br2
CH3 — CH CH2
CCl4

Br2
CH3 — CH CH2
H2O

Hg(OAc)2
CH3 — CH CH2
H2O
 ICl
CH3 — CH CH2

Type-iii : Cyclic Transition State

CH3 — CH CH2 H2 / Pd

BH3 / THF
CH3 — CH CH2
 Type-iii : Cyclic Transition State

KMnO4
CH3 — CH CH2
Hydrohalogenation of Alkene

HBr
CH3 — C CH — CH3
CH3
 Rearrangement

CH3
HCl
H3C C CH CH2
H

HBr
 Hydration of Alkene
Acid Catalysed Oxymercuration – Demercuration Hydroboration –
Hydration Oxidation
Acid Catalysed Hydration

H3C
H3O+

CH3
H3C
Dil. H2SO4
H
 Oxymercuration – Demercuration

Hg(OAc)2 NaBH4
CH3 CH CH2
H2O

(i) Addition of water by Markovnikov’s Rule

(ii) Formation of cyclo-merquic 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
 Baeyer’s Reagent [ Cold Dilute Alkaline KMnO4 ]

CH3 CH CH2

KMnO4
R—C C—R

Decolorisation of KMnO4 solution is used as a test for unsaturation.

Reagents : HBr / R2O2 , hv Kharasch Effect or Peroxide Effect

R2O2/hv
R — CH CH2 + HBr

Mechanism :
hv
R—O—O—R

RO• + H — Br

R — CH CH2 + Br•

•
R — CH — CH2 — Br + HBr
 H2O2 H2O2
Ph— CH CH2
HCl HBr

BH3 THF
H2O2 OH–
D D

KMnO4
0°C , OH–
D D
 Per Acid
Per-acetic acid Hydrogen Peroxide

RCO3H H3O+
CH3 CH CH2
 Electrophilic addition reaction of Alkynes

—C C— E+Nu –

Br2
R—C C—R CCl4

Reddish orange colour of the solution of bromine in carbon tetrachloride is decolourised. This is used as a
test for unsaturation.

KMnO4
R—C C—R
OH-
 Hydrogenation

H2 / Pd
R—C C—R

H2 / Pd / CaCO3
Lindlar’s Catalyst

R—C C—R

Na / Liq. NH3
Addition of HOX

HOCl HOCl
R—C C—H

Addition of HX

HX HX
R—C C—H

gem dihalides ( two halogens are

attached to the same carbon atom)
Addition of H2O

HgSO4 , H2SO4
H—C C—H
H2O

HgSO4 , H2SO4
Me — C C—H H2O
Ozonolysis Breaking of C=C & C C on reaction with O3

Reductive Ozonolysis Oxidative Ozonolysis

i. O3 i. O3

ii. Zn/H2O ii. H2O2

CH3 CH CH2

CH3 CH CH2

CH3 CH CH2
CH3 CH CH CH3

CH3 — C C — CH3

KMnO4
CH3 — C C — CH3
H+
 Benzene
Addition Reaction

Substitution Reaction

Cl — Cl AlCl3

R — Cl AlCl3

O
R — C — Cl AlCl3
 Electrophilic substitution reaction
1. Attack of electrophile on benzene ring forms the sigma complex.

E+

2 . Loss of a proton gives the substitution product.

Ortho-para directing and activating groups :

Ortho para directing but deactivating groups :

Meta directing and deactivating groups :
 Halogenation
(a) Br2 / FeBr3
(b) Br2 / Fe / Δ
(c) Cl2 / ZnCl2
(d) Cl2 / AlCl3

X2 + Lewis Acid
Iodonation :

I2 + AlCl3
Nitration (a) Conc. HNO3 + Conc. H2SO4

(b) Fuming HNO3 / Conc. HNO3

CH3
Fuming HNO3
Sulphonation Conc. H2SO4
Alkylation : Friedel Craft Reaction

AlCl3
R — Cl

Acylation :

O
R — C — Cl
AlCl3
 Preparation of benzene
Cyclic polymerisation of ethyne :

Decarboxylation of aromatic acids :

O
C — OH

NaOH CaO
Heat
 Preparation of benzene
Reduction of phenol :

OH
Zn
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 Alkene
Dehalogenation From vicinal dihalides by Zn

From vicinal dihalides

KOH
Heat
 Preparation of Alkyne
From calcium carbide

From vicinal dihalides

KOH NaNH2
Heat

Acidic Nature

CH3 — C C—H
NaNH2
 Preparation of Alkane
Hydrogenation
H2 / Ni
CH3 — C C—H

H2 / Ni
CH3 — CH CH2

From alkyl halides

Zn
R — CH2 — Cl
HCl

Wurtz reaction
Na
R — Cl
Dry ether
 Preparation of Alkane
Decarboxylation

O
NaOH CaO
CH3 C — OH
Heat

Kolbe Electrolysis

O
NaOH
CH3 C — OH Electrolysis
 Free Radical Substitution Reaction of Alkanes

UV Light or temp.
R — H + X2
250° — 400°C

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

(ii) Chain propagation : X• + R – H

R• + X – X

(iii) Chain termination : X• + X•

R• + R•

R• + X•
 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 .