26

Haloalkanes and
Haloarenes
The replacement of hydrogen atom(s) in hydrocarbon, aliphatic or
aromatic, by halogen atom(s) results in the formation of alkyl halide
(haloalkane) and aryl halide (haloarene), respectively.

Classification of Halogen Derivatives

On the basis of number of halogen atoms present, halogen
derivatives are classified as mono, di, tri, tetra, etc., halogen
derivatives, e.g.
X
CH2—X
C 2H 5X CH2—X
monohaloalkane monohaloarene dihaloalkane
CH2—X

CH —X

CH2—X
trihaloalkane
On the basis of the nature of the carbon to which halogen atom
is attached, halogen derivatives are classified as 1°, 2°, 3°, allylic,
benzylic, vinylic and aryl derivatives, e.g.
H R¢ R¢
½ ½ ½
R¢¾ C ¾ X R¢¢ ¾ C ¾ X R¢¢ ¾C ¾ X
½ ½ ½
H H R¢¢¢
primary (1°) secondary (2°) tertiary (3°)
 Haloalkanes and Haloarenes 385
On the basis of hybridisation of carbon atom of C—X bond
X
sp2/sp3 sp3
sp3 CH2X X
sp2
sp2
CH2X
X H3C
benzylic vinylic aryl
allylic

Nature of C¾ X Bond
Due to high electronegativity of halogen ( X ) atom, the C¾ X bond is
polar. This bond of haloarene is less polar than that of haloalkanes.

General Methods of Preparation of Haloalkanes

From Alcohols
HCl + Anhy. ZnCl2
R—Cl + H2O (Groove’s process)
(Lucas reagent)
NaBr + H2SO4
R—Br + H2O
Reflux
R—OH PX3
Alcohol
3R—X + H3PO3 (X = Cl, Br)

PCl5
R—Cl + POCl3 + HCl
Pyridine
R—Cl + SO2­+ HCl­ (Darzen procedure)
SOCl2

In Groove’s method, ZnCl2 is used to weaken the C—OH bond. In case

of 3° alcohols, ZnCl2 is not required.
The reactivity order of halogen acids is HI > HBr > HCl.

Darzen procedure is the best method for preparing alkyl halides from
alcohols since both the byproducts (SO 2 and HCl) are gaseous and
escape easily.
Free Radical Halogenation of Alkanes
Cl 2
CH3CH 2CH 2CH3 ¾¾¾¾¾¾® CH3CH 2CH 2CH 2Cl
UV light or heat Chlorobutane

+ CH3CH 2CH CH3

½
Cl
2-chlorobutane
386 Handbook of Chemistry

Addition of Hydrogen Halides on Alkenes

H H H H
½ ½ ½ ½
H ¾ C ¾ C ==C ¾ H + HBr ¾® H ¾ C ¾ C ¾ C ¾H
½ ½ ½ ½ ½ ½
H H H H Br H
2- bromopropane (major)
H H H H
½ Organic peroxide ½ ½ ½
H ¾ C ¾ C == C ¾ + HBr ¾¾¾¾¾¾® H ¾ C ¾ C ¾ C ¾ Br
½ ½ ½ ½ ½ ½
H H H H H H
1- bromopropane (major)

And from Alkynes

Finkelstein Reaction
Acetone
R ¾ X + NaI ¾¾¾® R ¾ I + NaX
( X = Cl, Br)
Swarts Reaction
H3C ¾ Br + AgF ¾® H3C ¾ F + AgBr
Hg2F2 , CoF2 and SbF3 can also be used as a reagent for Swarts reaction.

Hunsdiecker Reaction
- +
CH3COOAg + Br2 ¾¾® CH3 Br + AgBr + CO2­
CCl 4

Physical Properties of Haloalkanes

1. Boiling point orders
(i) R ¾ I > R ¾ Br > R ¾ Cl > R ¾ F
(ii) CH3 ¾ (CH 2 )2 ¾ CH 2Br > (CH3 )2 CHCH 2Br > (CH3 )3 CBr
(iii) CH3CH 2CH 2X > CH3CH 2X > CH3 X
2. Bond strength of haloalkanes decreases as the size of the
halogen atom increases.
Thus, the order of bond strength is
CH3F > CH3Cl > CH3 Br > CH3I
3. Dipole moment decreases as the electronegativity of the halogen
decreases.
4. Haloalkanes though polar but are insoluble in water as they do
not form hydrogen bonding with water.
 Haloalkanes and Haloarenes 387
5. Density order is
RI > RBr > RCl > RF (for the same alkyl group)
CH3I > C2H5I > C3H7I

Chemical Reactions of Haloalkanes

Nucleophilic Substitution Reactions (S N reactions)
– ½ d+ d - ½
General reaction : Nu + ¾ C ¾ X ¾® ¾ C ¾ Nu + X -
½ ½
KOH (aq)
C2H5OH + KBr
(ethyl alcohol)
NH3
C2H5NH2, (C2H5)2NH, (C2H5)3N
(C2H5)4N+Br– (Hofmann ammonolysis)
KCN
C2H5CN + KBr
(ethyl cyanide)
AgCN
C2H5NC + AgBr
(ethyl isocyanide)
KNO2
C2H5—Br C2H5—ONO + KBr
ethyl nitrite
AgNO2
C2H5NO2 + AgBr
nitroethane
(Williamson’s synthesis)
R¢ONa, D
C2H5—O—R¢ + NaBr
Na—C C—H, D
C2H5—C CH + NaBr
but-1-yne
O
R¢COOAg, D
C2H5—O—C—R¢ + AgBr

KCN is predominantly ionic and provides cyanide ions in solution,

which is ambident nucleophile and bind with carbon side to form
cyanide as the major product, while AgCN is covalent and form
isocyanide as the major product.
Like KCN, KNO2 form R—ONO as K—O bond is ionic while AgNO2
produces R ¾ NO2 as product because Ag—O bond is covalent in
nature. Vinyl chloride is less reactive towards nucleophilic substitution
reactions due to resonance.
388 Handbook of Chemistry

Nucleophilic substitution reactions are of two types :

(a) S N 1 type (Unimolecular nucleophilic substitution)
These reactions proceed in two steps:
CH3
½ Step 1 + CH3 Step 2
CH3 ¾ C ¾ X ¾¾¾¾®
- ( Slow)
CH 3 ¾ C ¾¾¾¾®
- -
CH3 + Nu ( Fast)
½ X
CH3 planar carbocation
alkyl halide
CH3
½
CH3 ¾ C ¾ Nu
½
CH3
substitution product
Rate, r = k [RX ]. It is a first order reaction.
Rate of SN 1 reaction depends upon the stability of carbocation
formed.
Reactivity order of alkyl halide towards SN 1 mechanism
3° > 2° > 1°
Polar solvents, low concentration of nucleophiles and weak
nucleophiles favours SN 1 mechanism.
In SN 1 reactions, partial racemisation occurs due to the possibility
of frontal as well as backside attack on planar carbocation.

R1 R2 R2 R2
Nu– + Nu–
C R1—C—Nu + Nu—C—R1
backside frontal R3 R3
attack R3 attack
retention inversion product
product (enantiomeric forms)
racemisation
planar carbocation

(b) S N 2 type (Bimolecular nucleophilic substitution) These reactions

proceed in one step and is a second order reaction with
-
r = k[RX ] [Nu].
During SN 2 reaction, inversion of configuration occurs
(Walden inversion) i.e. starting with dextrorotatory halide a laevo
product is obtained and vice-versa, e.g.,
 Haloalkanes and Haloarenes 389
H R1 H – H
– d– d– –X
Nu + R1 C—X Nu C X Nu—C R1
R2 R2
R2
inverted product
transition state
Reactivity of alkyl halides toward SN 2 mechanism is 1° > 2° > 3°
Rate of reaction in SN 2 mechanism depends on the strength of the
attacking nucleophile. Strength of some common nucleophiles is
-
-
·
· CN > ·· I- > ·· OR - > ·· OH - > CH3COO ·· > H 2O > F -
Non-polar solvents, strong nucleophiles and high concentration of
nucleophiles favour SN 2 mechanism.
Relative rates of some alkyl halides in SN 1 and SN 2 reactions are in
the order
SN 1 : (CH3 )3 CX > C6H5 ¾ CH 2 ¾ X > CH 2 ==CH ¾ CH 2X
> (CH3 )2CHX > CH3CH 2X > CH3 X
SN 2 : C6H5CH 2X > CH 2 ==CH ¾ CH 2X > CH3 X
1444444 424444444 3
resonance stabilised

> CH3CH 2X > (CH3 )2CHX > (CH3 )3 CX

Resonating structures of benzyl carbocations and allylic carbocation
are
+
CH2Br CH2 CH2 CH2

(–Br–)
+
+
CH2 CH2

+ +
H2C==C—CH2 ¬¾® H2C — C—CH
— 2

H H
Relative reactivity of alkyl halides having same alkyl group is
RI > RBr > RCl > RF
390 Handbook of Chemistry

Elimination Reactions
Dehydrohalogenation is a b-elimination reaction in which halogen is
lost from a-carbon atom and the hydrogen from the b-carbon according
to Saytzeff rule, e.g.
Br
½ Alc. KOH
CH3 ¾ CH 2 ¾ CH ¾ CH3 ¾¾¾¾¾® CH3 ¾ CH==CH ¾ CH3
2- bromobutane – KBr, – H2O but-2-ene
(major)

+ CH3 CH 2 CH==CH 2
but-1-ene ( minor)

Ease of dehydrohalogenation among alkyl halides

3° > 2° > 1°
i.e. (CH3 )3 CCl > (CH3 )2CHCl > CH3CH 2Cl

Reduction
Ni, 575 K
C2H5 ¾ Br + H 2 ¾¾¾¾® C2H 6 + HBr
Red P, 420 K
C2H5I + HI ¾¾¾¾¾® C2H 6 + I2

Reaction with Metals

(i) Wurtz reaction
Dry ether
RX + 2Na + XR ¾¾¾¾® R ¾ R ( alkane) + 2NaX
(ii) Reaction with Mg
Dry ether
C2H5 Br + Mg ¾¾¾® C2H5 ¾ Mg ¾ Br
(Grignard' s reagent)

Grignard reagent is never isolated in the solid state as it explodes in

dry state. So it is used in ethereal solution.

Isomerisation
Cl
573 K ½
CH3 CH 2 CH 2 ¾ Cl ¾¾¾¾¾¾® CH3 ¾ CH ¾ CH3
1-chloropropane or anhy. AlCl3 2-chloropropane
 Haloalkanes and Haloarenes 391
General Methods of Preparation of Aryl
Halides (Haloarenes)
By Halogenation of Aromatic Hydrocarbons
Cl

FeCl3 , dark
+ Cl2 + HCl
310–320 K

It is an electrophilic substitution reaction.

By Side Chain Halogenation

CH3 CH2Cl CHCl2

383 K Cl2 Cl2

+ Cl2
Sunlight Sunlight Sunlight
–HCl –HCl –HCl
CCl3

Benzotrichloride
(It involves free radical mechanism.)

From Benzene Diazonium Salt

CuCl/HCl
C6H5Cl + N2
CuBr/HBr Sandmeyer reaction
C6H5Br + N2
+
N2Cl– Cu/HCl
C6H5Cl + N2
Cu/HBr Gattermann reaction
C6H5Br + N2
HBF4 + – D
C6H5N2BF4 C 6H 5F
273 K –N2, –BF3
(Balz Schiemann reaction)
KI, D
C6H5I + N2 +KCl
392 Handbook of Chemistry

From Phenol
OH

+ PCl5 C6H5Cl + HCl + POCl3

Physical Properties of Aryl Halides

1. Aryl halides are colourless liquids or colourless solids with
characteristic odour.
2. Boiling point generally increases with increase in the size of aryl
group or halogen atom. Boiling point order
Ar—I > Ar—Br > Ar—Cl > Ar—F
3. The melting point of p -isomer is more than o- and m-isomer.
This is because of more symmetrical nature of p-isomer.
4. Due to resonance in chlorobenzene, C—Cl bond is shorter and
hence, its dipole moment is less than that of cyclohexylchloride.

Chemical Properties of Aryl Halides

1. Nucleophilic Substitution Reactions
Aryl halides are less reactive towards nucleophilic substitution
reaction. Their low reactivity is attributed due to the following reasons:
(i) Due to resonance, C—X bond has partial double bond character.
(ii) Stabilisation of the molecule by delocalisation of electrons.
(iii) Instability of phenyl carbocation.
However, aryl halides having electron withdrawing groups
(like ¾ NO2 , ¾ SO3H, etc.) at ortho and para positions undergo
nucleophilic substitution reaction easily.
Cl OH

(i) NaOH, 623 K, 300 atm

(ii) H+

Presence of electron withdrawing group ( ¾ NO2 ) increases the

reactivity.
 Haloalkanes and Haloarenes 393

Cl OH

(i) NaOH, 443 K

(ii) H+

NO2 NO2
Cl OH

O2N NO2 O2N NO2

Warm
H2O

NO2 NO2

2. Electrophilic Substitution Reactions

Halogens are deactivating but o, p-directing. Thus, chlorination,
nitration, sulphonation and Friedel Craft’s reaction give a mixture of
o- and p- chloro substituted derivatives.
(i) Halogenation
Cl Cl Cl

Cl
Anhy. FeCl3
+ Cl2 +

1,2-dichlorobenzene
Cl (minor)
1,4-dichlorobenzene
(major)

(ii) Nitration
Cl Cl Cl

NO2
Conc. HNO3
+
Conc. H2SO4

NO2
1-chloro-2-nitrobenzene 1-chloro-4-nitrobenzene
(minor) (major)
394 Handbook of Chemistry

(iii) Sulphonation
Cl Cl Cl

SO3H
Conc. H2SO4
+
D

2-chlorobenzene
SO3H
sulphonic acid
(minor) 4-chlorobenzene
sulphonic acid
(major)
(iv) Friedel-Crafts reaction
Cl Cl Cl

CH3
Anhy. AlCl3
+ CH3Cl +

1-chloro-2-methyl
CH3
benzene
1-chloro-4-methyl
benzene
Cl Cl Cl
O Anhy.
COCH3
AlCl3
+ H3C—C—Cl +

2-chloroacetophenone
COCH3
4-chloroacetophenone

3. Reaction with Metals

(i) Wurtz Fittig reaction
X

R
Ether
+ 2Na + RX + 2NaX

(ii) Fittig reaction

X

Ether
2 + 2Na + 2NaX

Diphenyl
 Haloalkanes and Haloarenes 395
(iii) Ullmann reaction
I

+ Cu powder

iodobenzene biphenyl

Dihalogen Derivatives
Cl
CH3 ¾ CH 2 ¾ CH ¾ CH 2 CH3 CH 2 CH
½ ½ Cl
Cl Cl (Gem or geminal-dihalide)
(Vic or vicinal-dihalide)

ClCH 2 ¾ CH 2 ¾ CH 2 ¾ CH 2 ¾ Cl
(Isolated dihalides)
Dichloromethane (CH 2Cl2 ) is widely used as a solvent, as a propellant
in aerosols. Direct contact of dichloromethane in humans causes
intense burning and mild redness of the skin.

Trihalogen Derivatives
1. Chloroform [Trichloromethane, CHCl 3 ]
Methods of preparation
Sunlight
(i) CH 4 + 3Cl2 ¾¾¾¾¾¾¾¾® CHCl3 + 3HCl
Controlled chlorination
(ii) Haloform reaction
C2H5OH + Cl2 ¾® CH3CHO + 2HCl [Oxidation]
CH3CHO + 3Cl2 ¾® CCl3 × CHO + 3HCl [Chlorination]
2CCl3 × CHO + Ca(OH)2 ¾® 2CHCl3 + (HCOO)2Ca
[Hydrolysis]

Properties
(i) Oxidation of CHCl3 gives poisonous gas phosgene (carbonyl
chloride).
Light
2CHCl3 + O2 ¾¾® 2COCl2 + 2HCl
phosgene
To avoid this oxidation, CHCl3 is stored in dark brown bottles
and filled to the brim. 1% ethanol is added to chloroform which
converts harmful phosgene gas into diethyl carbonate.
396 Handbook of Chemistry

(ii) CHCl3 is widely used in the production of freon refrigerant R—22.

(iii) On nitration, it gives tear producing insecticide substance
chloropicrin.
CHCl3 + HONO2 (conc. ) ¾® NO2 × CCl3 + H 2O
chloropicrin
(iv) On dehalogenation, it gives C2H 2 (acetylene).
CHCl3 + 6Ag + CHCl3 ¾® CH ººCH + 6AgCl
D
(v) When subjected to hydrolysis, it gives formate.
OH
- +
CHCl3 + 3NaOH ¾® HC OH —® HCOON a
- 2H 2O
OH

2. Iodoform (tri-iodomethane, CHI 3 )

Iodoform is prepared by iodoform reaction.
CH3COCH3 + 3I2 + 4NaOH ¾®
CHI3 ¯ + 3NaI + CH3COONa + 3H 2O
Compounds containing either CH3CO ¾ or CH3CH(OH) group form
yellow coloured iodoform with I2 and NaOH.
Iodoform when comes in contact with organic matter, decomposes
easily to free iodine, an antiseptic. Due to its objectionable smell, it has
been replaced by other formulations containing iodine.

Polyhalogen Derivatives
1. Tetrachloromethane (Carbon Tetrachloride, CCl4 )
Preparation
Sunlight
(i) CH 4 + 4Cl2 ¾¾¾® CCl4 + 4HCl
hn
(ii) CHCl3 + Cl2 ¾® CCl4 + 2HCl
CCl4 is a colourless, non-inflammable, poisonous liquid, soluble in
alcohol and ether.
Uses
Carbon tetrachloride is used
(i) as a solvent for oils, fats, resins
(ii) in dry cleaning
(iii) as fire extinguisher under the name ‘pyrene’.
 Haloalkanes and Haloarenes 397
2. Freons
The chlorofluorocarbon compounds of methane and ethane are
collectively known as freons. These are usually produced for aerosol
propellants, refrigeration and air conditioning purposes. Carbon tetra
chloride when reacts with antimony trifluoride in the presence of SbCl5
as catalyst, dichlorofluromethane (freon) is obtained.

3. DDT (p, p¢-Dichlorodiphenyltrichloroethane)

Cl

Cl
Cl Cl
Cl H
2,2- bis (4-chlorophenyl) -1,1,1- trichloroethane

DDT is the first chlorinated organic insecticide. Its stability and fat
solubility is a great problem.
It is prepared from chloral and chlorobenzene in the presence of conc.
H 2SO4.

4. Perchloroethane (C 2Cl 6 )
It is used as moth repellant and is also known as artificial camphor.