Organic Chemistry

Haloalkanes & Haloarenes

OM PANDEY
JRF : AIR 13
M.S. : IIT DELHI
B.S. : Gold Medalist
 Classification Compounds Containing sp3 C – X Bond

Alkyl halides or haloalkanes R’ R’

R’ CH2 X R’’ CH X R’’ C X

R’’’

Allylic halides
CH2

CH2
Benzylic halides
Classification Compounds Containing sp2 C – X

Vinylic halides

Aryl halides
H3C

gem-dihalide

vic-dihalide
 Nomenclature
CH3CH2CH2Br H3C — CH — CH3 CH3

Cl H3C — CH — CH2 Cl

Br Br
Br

Br Br Br
 Nomenclature

H3C — CHCl2 H2C — CH2

Cl Cl

H3C H H3C CH3

H H
Br H Br
H H
H3C
Methods of Preparation of Haloalkanes
NaBr
HCl
H2SO4

H
PCl3 | PCl5
R — C — OH
|
H

Red P/Br2
SOCl2
 Methods of Preparation of Haloalkanes
From Hydrocarbons

Cl2 / UV light
CH3CH2CH2CH3
or heat

CH3CH CH2 HI

CH3CH CHCH3 HCl

CH3 CH3
Br2
C C
CCl4
H H
Write the products of the following reactions :–

(i) H
+ HBr
H H

(ii) CH3 — CH2 CH = CH2 + HCl

Peroxide
CH2 — C = CH2 + HBr
(iii)
H
 Halogen Exchange
Finkelstein Reaction Swarts Reaction

NaI AgF Hg2F2

H3C — Br H3C — Br

NaI AgF

NaI
H3C — Cl
 Preparation of Haloarenes
Electrophilic substitution reaction

CH3
Fe
+ X2
dark
 Preparation of Haloarenes
Sandmeyer’s reaction
NH2
NaNO2 + HX
273-278 K

N2X
Cu2X2

N2X
KI
 Physical Properties
Boiling Point RI RBr RCl RF
CH3
CH3CH2CH2 CH2 Br CH3CH2CHCH3
H3C — C — CH3
Br Br

Melting Point

Cl Cl Cl
Cl

Cl
Cl
 Reactions of Alkyl Halide
SN2 Bimolecular Nucleophilic Substitution Reaction

Solvent
Nu + R—X

Mechanism

No. of steps

Nature of solvent
 D
NaSH
H3C I Acetone

Rate of reaction : CH3

CH3 H

CH3 — C — I H3C — C — l H—C—l CH3 — I

CH3 H CH3

CH3 — I CH3 — Br CH3 — Cl CH3 — F

 NaOH

NaOCH3

KCN

CH3 — Br
AgCN

KNO2

AgNO2
 CH3Li

LiAIH4

O
H3C – H2C – C – OAg

CH3 — Br
CH3 — NH2

NH3

NaI / Acetone
 Reactions of Alkyl Halide
SN1 Unimolecular Nucleophilic Substitution Reaction

Solvent
Nu + R—X

Mechanism

Nature of solvent
Rate of SN1 Reaction

CH3 CH3 CH3

CH3 — C — Cl H3C — C — Cl H — C — Cl CH3 — Cl

CH3 H H

F Cl Br I
Which one of the following reaction has incorrect product →

(i) H2O

Br OH

I H2O OH
(ii)

I H2O OH
(iii)
 CD3
H2O
H3C I

Ph

CD3
C2H5OH
H3C I

Ph
 Reactions of Haloarenes
Nucleophilic Substitution Reaction Electrophilic Substitution Reaction

X X

X
 Nucleophilic Substitution Reaction

Cl

Cl
NO2
 Cl

(i) NaOH, 623 K, 300 atm

(ii) H

Cl

(i) NaOH, 443 K

(ii) H

NO2

Cl
O2 N NO2
warm
H2O

NO2
 Electrophilic substitution Reactions
Cl

Anhyd. FeCl3
Halogenation + Cl2

Cl

Nitration HNO3

Conc. H2SO4

Cl

Conc. H2SO4
Sulphonation

Alkylation
Cl
Anhyd. AlCl3
+ CH3Cl

Acylation

Cl
O
Anhyd. AlCl3
+ H3C — C — Cl
 Reaction with Metals
Magnesium Sodium
Mg Na
R—X R—X
Dry ether Dry ether

Identify A, B in the following :

Br dry ether H2O

+ Mg A B
 Reaction with Metals
Wurtz – Reaction
Na
RX
Dry ether

Wurtz – Fittig reaction

X
Na
+ RX Dry ether

Fittig reaction
X
Na
Dry ether
In the following pairs of halogen compounds, which compound
undergoes faster SN1 reaction & SN2 reaction?
Cl Cl
(i) and

Cl
(ii) and
Cl
Organic Chemistry

Alcohol Phenol Ether

 Classification Compounds Containing sp3 C – OH

R’ R’

R’ CH2 R’’ CH R’’ C

R’’’

Allylic alcohol
CH2

CH2
Benzylic alcohol
Classification Compounds Containing sp2 C – OH

Vinylic alcohol

Phenol
 Nomenclature
CH3CH2CH2OH H3C — CH — CH3 CH3

OH H3C — CH — CH2 OH

CH2 — OH
| OH CH3
CH — OH |
| CH2 — CH = C
CH2 — OH
CH3
 Nomenclature

OH CH3 CH3 CH3

OH

OH
OH

OH OH
O2 N NO2

NO2
 Nomenclature of Ethers

CH3 — O — CH3

CH3 — O — CH2 — CH2 — CH3 H3C — CH — CH3

OCH3

OCH2CH3
 Preparation of Alcohols

From Alkenes
H2O / H+

CH3CH = CH2
(i) BH3
(ii) H2O2, OH–
 Preparation of Alcohols
From Carbonyl
H2 / Pd
O

CH3 — C — H
(i) NaBH4
(ii) H2O

H2 / Pd
O

CH3 — C — CH3
(i) NaBH4
(ii) H2O
 Preparation of Alcohols
From Carboxylic Acid & Ester

O
(i) LiAlH4
CH3 — C — OH
(ii) H2O

O
(i) LiAlH4
CH3 — C — OCH3
(ii) H2O
 Preparation of Alcohols
From Grignard Reagent

O
H — C — H + CH3MgBr

O
CH3 — C — H + CH3MgBr

O
CH3 — C — CH3 + CH3MgBr
 Preparation of Phenols
Cl

(i) NaOH, 623 K, 300 atm

(ii) H+

Oleum (i) NaOH

(ii) H+

NH2

NaNO2 H2O
+ HCl Warm
 Preparation of Phenols
Cumene Hydroperoxide method

O2 H+ / H2O
 Physical Properties
Boiling Point
ROH RX ROR’ RR

OH R
 Physical Properties
Solubility in water
ROH

OH
 Reactions of Alcohol

PCC or CrO3

H
| Cu / 300°C
R—C—O
| |
H H

KMnO4 / H+ or
K2Cr2O7 / H+
Esterification
O
CH3CH2 — OH + H — O — C — CH3

O
Pyridine
R — OH + Cl — C — R’

O
COOH ||
O—H CH3 — C
H+
+ O
CH3 — C
||
O
 Phenol

OH
Reactions of Phenol
Dilute
HNO3

OH Conc. HNO3

Br2 in
CS2 / CHCl3

Br2
H2O
Reactions of Phenol
NaOH

NaOH (i) CO2

O—H (ii) H+

CHCl3 / NaOH

Zn / heat
 Na2Cr2O7
H2SO4

OH
Na

O
H — O — C — CH3 / H+
 Formation of Ethers

H2SO4
443 K

CH3CH2OH

H2SO4
413 K
 Williamsons ether synthesis

R — X + R’ — O Na

CH3 — O Na + CH3 — CH2 — Br

CH3

CH3 — C — O Na + CH3 — CH2 — Br

CH3
CH3

CH3 — CH2 — O Na + CH3 — C — Br

CH3
 Williamsons ether synthesis

OH

NaOH CH3 — X
 Anisole

O CH3
 Reactions of Anisole
Br2
Ethanoic acid

CH3 — Cl / AlCl3
OCH3

O
CH3 — C — Cl / AlCl3

Conc. HNO3
Conc. H2SO4
 Reaction of Ether

O — CH3

Hl

CH3
|
HI
CH3 — C — O — CH3
|
CH3
 Lucas Test

R R
R — CH2 — O — H CH — O — H R —C — O — H
R R
 Neutral FeCl3 Test

R — CH2 — O — H

OH