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UNDERSTANDING WHICH ARE

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EXAM
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 Chapter - 1
ALKYL HALIDES & ARYL HALIDES
Introduction
Alkyl halides have the general formula R – X, in which ‘R’ is an alkyl or substituted alkyl group.

The characteristic feature of alkyl halide structure is halogen atom – X and the characteristic reactions
of alkyl halides are those that take place at the halogen atom.

Classification and Nomenclature

A carbon atom is classified as primary, secondary, or tertiary, according to the number of other carbon
atoms attached to it. Similarly an alkyl halide is classified according to the kind of carbon atom that bears
the halogen
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H R R H
| | | |
R  C|  X R  C|  X R  C|  X H  C|  X
H H R H
1 alkylhalide 2 alkylhalide 3 alkylhalide super 1 alkylhalid e
ES

The different classes of alkylhalides undergo same kinds of reaction as they have the same functional group
but only their reactivity differs.

Some of the common name and IUPAC name of some simpler alkyl halides are given below:
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Formula Common Name IUPAC Name

CH3CH2Cl Ethyl Chloride Chloro Ethane

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CH3 – CH CH3 Isopropyl Chloride 2–Chloro Propane

|
Cl
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CH
| 3
CH 3 CH 2  C  CH 3 Tertiary Pentyl Iodide 2–Iodo–2–Methyl–Butane
|
I

Depending upon the number of halogen atoms attached to one carbon atom, halo alkanes can also be classified
as mono, di, tri, or tetrahalogen derivatives.

Physical Properties

1. Halo-alkanes have considerably higher boiling point than their corresponding alkanes having the
same number of carbon atoms.

2. Lower members of alkyl halides are gases while higher haloalkanes are liquids.

3. Alkyl halides are polar in nature and have low dipole moment. The dipole moment order is

R – Cl > R – F > R – Br > R – I

[1]
Alkyl Halides & Aryl Halides

Though fluorine is more electronegative than chlorine yet the dipole moment of R – Cl is greater
than that of R – F because the dipole moment is a vector quantity and vector is a product of charge
and distance.
D = e × d
and bond length of C – Cl bond is greater than C – F bond.

4. Alkyl chlorides are generally lighter than water but alkyl bromides and alkyl iodides are heavier
than water. The order of the relative densities with same alkyl group is

R – I > R – Br > R – Cl

5. The boiling point order of alkyl halides follows the order

R – I > R – Br > R – Cl

6. Inspite of their moderate polarity, alkyhalides are insoluble in water due to their inability to from
hydrogen bonds with H2O, but are soluble in organic solvents of low polarity e.g., benzene, ether,
chloroform, etc.
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1.1 Preparations of Alkyl Halides (Mono halogen Derivative)

1. From Alcohols: When alcohols are reacted with halogen acids in the presence of H 2SO4
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or anhydrous ZnCl2 then alkyl halides are produced.

(a) Preparation of alkyl chlorides: [Groove’s Process]

Alcohols when treated with HCl(g) in the presence of anhydrous ZnCl2 give alkyl chlorides.
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anhydrous
R  OH  HCl 
 R  Cl  H 2 O
ZnCl /Δ
2
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anhydrous ZnCl
(i) CH 3 CH 2 – OH  HCl (g)      2  CH 3 CH 2  Cl  H 2 O

CH3 anhydrous CH3

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(ii) CH – OH + HCl(g)   
 CH – Cl + H 2O
Zn Cl2
CH3 CH3

CH3 CH3
warm
(iii) CH3 – C – OH + HCl(g)   CH3 – C – Cl + H2O
CH3 CH3

Note : Tertiary alcohols react with HCl(g) even in the absence of anhydrous ZnCl2 .

(b) Preparation of alkyl bromides

conc. H SO
R  OH  HBr   
2
4  R  Br  H 2 O
reflux
conc. H SO
(i) CH 3 CH 2  OH  HBr    4  CH 3 CH 2 – Br  H 2 O
2
reflux

Note: This method is not usually used for the preparation, of alkyl bromides.

Instead of HBr, NaBr is used to prepare HBr in-situ.

[2]
Alkyl Halides & Aryl Halides

(c) Preparation of alkyl iodides

reflux
R  OH  HI 57%  R  I  H 2 O
reflux
CH 3 CH 2  OH  HI 57%  CH 3 CH 2  I  H 2 O

2. From alcohols using PX 3 or PX 5

3R – OH + PCl3  3R – Cl + H3PO3
3R – OH + PBr 3  3R – Br + H3PO3
R – OH + PCl5  R – Cl + POCl3 + HCl

Use of PX3 or PX5 is better than the use of H2SO4 because in former, no dehydration takes
place.

3. From alcohols using SOCl2 (Thionyl chloride) (Darzen’s Procedure)

Pyridine
R – OH + SOCl2   R–Cl + SO (g) + HCl(g)
reflux 2
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Memory aid
R–O–H Pyridine
  R  Cl  SO 2  HCl
Cl SO Cl reflux
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This method is the best method to prepare alkyl chlorides because here the side products obtained
are SO2 and HCl which are gases.

As SOBr2 and SOI2 does not exist, this method is not applicable for the preparation of RBr
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and RI.

4. From Alkanes (The reaction occurs by free Radical Substitution Reaction)

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hv
CH 4  Cl 2 
 CH 3  Cl  HCl

Here mono substituted products, disubstituted or polysubstituted products can be prepared, using
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excess of Cl2 .

e.g., hv
CH 3 Cl  Cl 2 
 CH 2 Cl 2  HCl

hv
CH2Cl2 + Cl2  CHCl3 + HCl
hv
CHCl3 + Cl2  CCl4 + HCl

Similar reactions can be performed on ethane, propane and butane, etc.

hv
CH3CH3 + Cl2  CH3CH2 Cl + HCl
hv
CH 3 CH 2 CH 3  Cl 2  CH 3CH 2 CH 2 Cl  CH 3 CH  CH 2
45% |
Cl
55%

The above reactions can be carried out thermally at 520 K to 670 K. The thermal chlorination
of alkanes is called Hass and Mc BEE Reaction.

[3]
Alkyl Halides & Aryl Halides

5. Borodine Hunsdiecker Reaction : (The Reaction occurs by free Radical Mechanism)

CCl
RCOO Ag  Br2 4  R  Br  CO 2  AgBr
reflux

Mechanism
– +
RCOOAg R– C– O + Ag
O
– –
Step–1: R–C–O Br – Br R– C– O – Br + Br
O O
. .
Step–2: R–C– OBr R– C – O + Br Initiation
O O
.
Step–3: R C–O R+ CO2 Propagation
O
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. .
Step–4: R + R – C – O – Br R Br + R COO Propagation
O
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Step–5: Termination :
. .
(a) R – COO + R R– COOR (side product)

(b) If ethyl free radical then

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CH3CH·2 CH2 = CH2 + H·

H + CH3 CH·2 CH3CH3

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H· + Br · HBr
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6. Finkelstein Reaction
acetone
R  Cl  NaI  R  I  NaC l R  Br  NaI  
 R  I  NaBr
acetone

The reverse reactions is not possible because NaCl and NaBr are insoluble in CH3OH or
acetone.

Illustration 1: Explain the formation of the products in the following reaction:

H3 C CH3 H3C
 H 2O
C CH  Ag 
 H3C C CH  C CH
H3 C CH2 Cl OH CH2 H3C CH2 OH
85% 13%

Solution: Both products are derived from the allylic cation which has two resonance forms and the
product can be formed by attack of water at either electron deficient carbon. The major
product (85%) is formed from the more stable tertiary cation.

[4]
Alkyl Halides & Aryl Halides

Illustration 2: In the following reaction the relative rate is 3,300 times faster when X = F than I. Explain.

X N
NO2 NO2
  X
N
NO2 H NO2

Solution: The faster rate with fluoride is attributed to a very large electronegativity of fluorine, it
makes the attack of a nucleophile easier at the site of reaction.

Illustration 3: When CH3Br is treated with CN–, the major product is CH3CN, but some CH3NC is also
formed. Explain.

Solution: The CN– ion can be described by two resonance structures C  C N in which
N 
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case a formal negative charge is placed on either C or N atom, to give rise to a mixture
of products.
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SAMPLE PROBLEMS 1.1 (MCQ)

Problem 1: Consider the following reaction:
H3C CH3
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 Br X  HBr
D CH3

Identify the structure of the major intermediate product X.

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H3C CH2 H3C CH3

C
(a) (b)
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D CH3 D CH3

H3C CH3 H3C CH3

C CH2
(c) (d)
D CH3 CH3

Solution: (b) It is a tertiary stable free radical intermediate.

H3C

Problem 2: CH3 obtained by chlorination of n-butane will be

Cl

(a) Racemic mixture (b) meso

(c) d-form (d) l-form

Solution: (a) Mixture of d and l products would be formed.

[5]
Alkyl Halides & Aryl Halides

1.2 Chemical Reactions of Alkyl Halides

Reaction of alkyl halide can be grouped as :

I. Nucleophillic Substitution Reaction II. Elimination Reaction

III. Miscellaneous Reaction

I. Nucleophillic Substitution Reaction :

–
R – X + :Z R – Z + :X–
Nucleophile

R – X + :OH– R – OH + :X–
+ H2 O: R – OH + HX
–
+ R – O: R – O – R + :X–
ether
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+ :C–  CR R – C  C – R + :X–

alkane
– +
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+ R – M R – R + MX
+ :I– R – I + :X–
–
+ :CN R – CN + :X –
Nitrile
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+ :NC – R – NC + :X–
Isonitrile
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+ R'C – O– R – O – C – R + :X–
O O

ester
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–
+ :SH R – SH + :X–
Thiol

–
+ :SR R – S – R + :X–
Thioether

– COOC2H5 COOC2H5
+ CH R – CH –
COOC2H5 COOC2H5 + :X

O
– C – CH3 COCH3
+ CH R – CH
COOC2H5 COOC2H5

[6]
Alkyl Halides & Aryl Halides

In all such nucleophillic substitution reactions the nucleophile can be provided in the form of
sodium salts or potassium salts or silver salts, etc., in their aqueous solutions.

e.g., R – Cl + aq.KOH R – OH + KCl

R – Br + NaC  CH R – C  CH + NaBr

R – Cl + AgOH R – OH + AgCl

If the nucleophile is not ambident in nature (i.e. a species having two centres to attack as
a nucleophile) then the nucleophile can be provided in Na or Ag salt form.

If the nucleophile is ambident then the ratio of products formed differ when the potassium
salt or silver salt are used.

e.g. R – Cl + aq.KCN R – CN + R – NC
Major Minor

whereas when
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R – Cl + aq.AgCN R – CN + R – NC
Minor Major
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This is because AgCN is more covalent whereas KCN is more ionic.

KCN being more ionic dissociates freely in water whereas, AgCN being more covalent does
not freely dissociate in water to give free CN– ions.
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The reactions of R – X with KNO2 or AgNO2 is also an example of above type of reactions.

R – X + NH3 R – NH2 + HX
excess
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+ R' NH2 R – NH – R + HX

excess
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+ R' NHR" R – N – R' + HX

excess
R"

 –
+(C6 H5 )3 P R : P(C6H5)3 X
Triphenyl phosphine Phosphonium salt

II. Elimination Reactions:

Dehydrohalogenation Reactions:

—C—C— Base
—C C—
H X

In these reactions generally hydrogen atoms are lost from the –carbon atom, therefore, this
reaction is also called –elimination reaction.
[7]
Alkyl Halides & Aryl Halides

H H
 
H — C — C — H + alc.KOH 
CH2 = CH2 + KCl + H2 O
Base
H Cl

CH3 – CH2 – CH2 – Cl + alc.KOH CH3 – CH = CH2 + KCl + H2 O


CH3 – CH2 – CH – CH3 + alc.KOH CH3 – CH = CH – CH3 +
Saytzeff's Product (80%)
Cl

CH3 – CH2 – CH = CH2

Minor Hoffmann's product (20%)

Saytzeff’s Rule: In dehydrohalogenation of haloalkanes, the product formed preferentially is

the one in which maximum number of alkyl groups are attached with double bonded carbon
atoms.

Such products are favorable if the base used is small. However, when a larger base is used,
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then the product so formed is Hoffmann’s product.

Types of Elimination Reactions

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Elimination reactions are of two types :

1. Unimolecular (E 1 type):

This reaction proceeds in two steps.

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CH3
CH3 
C — CH3 + Cl-
Step–1. CH3 C – Cl
CH3
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CH3

CH 3 CH3

H
Step–2. C— C— H C = CH2
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H
CH 3 Base CH3

Rate of E1 reaction = K[(CH3 )3C – Cl]

2. Bimolecular (E 2 type):

This reaction proceeds in one steps

— C— C— X C=C + KX + H2 O
H
–
OH (from alc.K OH)

Rate of E2 reaction = K[R – X] [Base]

[8]
Alkyl Halides & Aryl Halides

Reactivity Order of Alkyl Halides towards E1 or E2 is 3º > 2º > 1º.

This is because ease of dehydrohalogenation depends upon the stability of alkene formed,
because in both types, the 3º alkyl halides give the maximum substituted alkene which is the
most stable.

Mechanism of Nucleophillic Substitution Reaction.

The compounds required for a nucleophillic substitution reactions are :

(i) Substrate : The compound on which substitution reactions take place.

(ii) Nucleophile : Species (anion or neutral) which are electron rich.

(iii) Solvent : Medium in which reaction is carried out.

The substrate consists of two parts, alkyl groups and leaving groups,

Alkyl group Leaving

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–
R—L + :Nu– Solvent
R – Nu + :L
(Substrate) Nucleophile
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Looking at the reaction it becomes clear that both nucleophiles and leaving groups are bases and
hence basicity plays an important role in understanding them.

A rough correlation between degree of basicity on one hand and nucleophillic power/leaving group on
the other hand is as follows: Stronger of the two bases is often more powerful nucleophile and the
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weaker of the two bases is a better leaving group. But this holds true for very closely related sets of
nucleophiles or sets of leaving groups. There are many exceptions to such a correlation and basicity
is the only one factor which governs them.
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Types of Nucleophillic Substitution Reaction

The different types of nucleophillic substitution reactions are :

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I. Substitution by Ionization : S N1Mechanism

II. Synchronous Substitution : S N2 Mechanism

I. Substitution by Ionization : S N1 Mechanism

a. Mechanism – SN 1 process :
Slow
R– L R+ + L – Step–1 (Ionization)
Fast
R+ + Nu– R – Nu Step–2 (Combination)
The slowest step being the rate determining step suggests that
Rate of SN1 reaction = K[R – L]

b. The effect of structure of substrate on S N1 reactions :

The SN1 reaction involves the formation of carbocation. This suggests that the substrate
which forms a stable carbocation will be the most reactive towards nucleophilic substitution

[9]
Alkyl Halides & Aryl Halides

reactions by SN1 mechanism. Thus the major structural feature necessary for a substrate
to undergo SN1 substitution is the presence of substituents which stabilize the carbocation
derived from it. There are some substituents which have +I and / or +M effect. Among
the alkyl halides, the reactivity towards nucleophilic substitution reactions by S N1
mechanism is

3º > 2º > 1º > CH3

For that matter, any tertiary compound would undergo nucleophilic substitution reaction by
SN1 mechanism.

Allylic and benzylic halides can also react by SN1 mechanism since these can form relatively
stable carbocation.

+ 
CH2 = CH – CH2 CH2 – CH = CH2

+
CH2 CH2 CH2 CH2 CH2+
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+ +

+
ES

Steric hindrance are also observed in many substrates and these effect the rate of SN
reactions. e.g. when in a tertiary alkyl halide (R3CX) one or more alkyl groups are highly
branched like a tertiary butyl group, the ionization is facilitated by relief in steric crowding
in going from a tetrahedral ground state to the carbocation.
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CH3

CH3 C X
CH3 CH3
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
C C CH3
sp 3 CH3
CH3 C CH3
hybridized tetrahedral
CH3 CH3 structure
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sp2hybridization
(Steric strain relieved)

(Steric strain maximum)

Thus, the carbocation stability order of compounds for SN1 reactions are:

Benzyl > allyl > tertiary > secondary > primary > methyl halides. (on the basis of electron
releasing factor)

c. Nucleophilicity and S N1 reactions:

The rate of SN1 reactions are independent of the nature of the nucleophile since it does
not participate in the rate determining step.

d. Effect of nature of leaving groups on S N1 reaction:

When the leaving group is a good leaving group, then the activation energy for the formation
of carbocation will be less and the reactivity of alkyl halide for the reaction by S N1
mechanism would be maximum. The leaving group order is I– > Br– > Cl– > F– .
[ 10 ]
Alkyl Halides & Aryl Halides

e . Stereochemistry of SN1 reactions:

The structure of carbocation is trigonal planar which is flat. Hence the nuclephile can attack
the carbocation carbon from either of two directions (i) front side and (ii) back side.

Nu–
Frontal Nu R2 R1 R2
R1 
C R3 C +
R2 C
R2 R3
– R1 Nu
Nu Backside

50%(+) or d 50% (–) or l

(R1, R2, R3 any alkyl group for SN1 mechanism)

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Thus we expect a complete racemization but the side of the leaving group is to some extent
hindered so the attack from this side is less when compared to attack from backside.
Therefore, there is going to be a partial racemization.
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II. Synchronous Substitution : SN2 Mechanism

R1
an

–
Nu C H +L
slow fast
Rate determing
step
H
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The transition state of SN2 consists of central carbon atom which is sp4 hybridised.
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a. Structure and Reactivity of Substrate

SN2 reaction mechanism requires an approach by nucleophile to a distance within bonding

range of the carbon atom bearing the leaving group. Thus, bulky substituents on or near
that carbon atom will have a dramatic inhibiting effect. They cause the potential energy
of the required transition state to be increased and consequently they increase the frequency
of activation for the reaction. The relative rates of R–X in SN2 reactions are.

Methyl 1º 2º 3º
Decrease
30 1 0.02 ~0

b. Effect of concentration and Strength of Nucleophile

The kinetics for the SN2 mechanism as described above suggests that

Rate  [R – L][Nu– ]

[ 11 ]
Alkyl Halides & Aryl Halides

Hence, the rate of reaction depends upon the concentration and the strength of the
nucleophile.

A strong Nucleophile reacts rapidly with the substrate while a poor (weak) nucleophile
reacts slowly with the substrate. This can also be termed as nucleophilicity. The two
structural features are:

(i) Negatively charged nucleophile is more reactive than its conjugate neutral form,
e.g., nucleophilicity of OH– > H2 O and that of RO– > ROH.

(ii) More easily the nucleophile is polarizable greater is its nucleophilicity.

e.g., I– > Br– > Cl– > F– .

(iii) In a group of nucleophile in which electron rich atom is same, nucleophilicity parallels
basicity e.g. R – O– > OH– >>> RCO2– > ROH > H2 O

c. Leaving Group Ability

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The leaving group ability effect is just the same as for SN1 reactions.

MISCELLANEOUS REACTIONS
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1. Wurtz Reaction

Dry ether
2 R – X + 2Na   2NaX + R – R

2. Formation of Grignard Reagent

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R – X + Mg ether
 R MgX
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When a solution of an alkyl halide in dry ether is allowed to stand over turnings of metallic
magnesium, a vigorous reaction takes place the solution turns cloudy, begin to boil, and
magnesium metal gradually disappears. This resulting solution is known as Grignard’s reagent.
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The carbon magnesium bond is covalent but highly polar. Grignard reagent is an Organometallic
compound which own their usefulness chiefly to one common quality, i.e., they serve as
Carbanions which are strong nucleophiles.

Grignard’s Reagent being highly reactive reacts with many organic or inorganic compounds
including H2O, CO2, and oxygen.

3. Reaction with Active Metals

R – I + 2 Li  RLi + LiI.

Dry ether
CH3 CH2 – I + 2 Li   CH3CH2Li + LiI.

Dry ether
4 CH3CH2 – Br + 4 Pb. Na   3Pb + 4 NaBr + (C2H5)4 Pb

alloy

[ 12 ]
Alkyl Halides & Aryl Halides

4. Corey House Reaction

Dry ether
R2 Cu Li + R´ X   R – R´ + R Cu + LiX

R2 Cu Li is prepared as follows :

Dry ether
(i) R – Br + 2Li   LiBr + RLi

Dry ether
(ii) 2RLi + CuI   R2CuLi + LiI

5. Friedal Crafts Reaction

+ R – X Anhyd

AlCl3

 + HX
Δ
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6. Isomerisation
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AlCl3
CH3CH2CH2 – Cl CH3 – CH – CH3
573 K
Cl
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7. Reduction Reactions
Ni
(a) R – Cl + H2  R – H + HCl
Pt or Pd
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(b) R – I + HI Re
dP
R – H + I2

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Zn  Cu/alloy
(c) R – Cl + 2 [H]   R – H + HCl
(d) R – Cl + LiAlH4 — R – H + LiCl + AlCl3

SAMPLE PROBLEMS 1.2 (MCQ)

Problem 1: The order of reactivity of the following alkyl halides in SN2 reaction is
(a) RF > RCl > RBr > RI (b) RF > RBr > RCl > RI
(c) RCl > RBr > RF > RI (d) RI > RBr > RCl > RF

Solution: (d) I is a better leaving group than other halides.

Problem 2: Which of the following will react with water?

(a) CCl4 (b) CHCl3
(c) CCl3CHO (d) ClCH2CH2Cl

Solution: (c) The hydrated compound is stable.

[ 13 ]
Alkyl Halides & Aryl Halides

Problem 3: Chlorine (Cl2) reacts with CS2 in the presence of I2 to give

(a) CCl4 (b) CHCl2
(c) CH3I (d) C2H5Cl

Solution: (a) Lactral

Problem 4: In the following groups:

O O
- -
OAc  OCH 3 F3 C S O H3C S O

O O
I II III IV
The increasing order of leaving tendency is
(a) I > II > III > IV (b) III > IV > I > II
(c) III > II > I > IV (d) II > III > III > I
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Solution: (b)

Problem 5: Which has the highest nucleophilicity?

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(a) F– (b) OH–

(c) CH 3 (d) NH 2

Solution: (c)
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Problem 6: Benzoyl chloride is prepared from benzoic acid by

(a) Cl2, h (b) Cl2, H2O
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(c) SO2Cl2 (d) SOCl2

Solution: (d)
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Problem 7: In the reaction of p-chlorotoluene with KNH2/NH3, the major product is:
(a) o-Toluidine (b) m-Toluidine
(c) p-Toluidine (d) p-Chloroaniline

Solution: (b)

Problem 8: An unknown alkyl halide A reacts with alc. KOH to produce a hydrocarbon B, C4H8.
Ozonolysis of B affords one mole of proponal and one mole of formaldehyde. Suggest which
structure among the following is the correct structure of A.
(a) CH3(CH2)3Br (b) Br(CH2)4Br
(c) CH3CH2CHBrCH3 (d) CH3CHBrCHBrCH3

alc. KOH O
Solution: (a) CH 3 CH 2 CH 2 CH 2 Br   CH 3 CH 2 CH  CH 2   CH 3 CH 2 CHO  HCHO
3

[ 14 ]
Alkyl Halides & Aryl Halides

ARYL HALIDES
Introduction
Aryl halides are compounds containing halogen attached directly to an aromatic ring. They have the general
formula ArX, where Ar is phenyl or a group derived from some other aromatic system

e.g.,
Br Cl I COOH
Cl

NO2
CH3

An aryl halide is not any halogen compound containing an aromatic ring that is why C6H5 – CH2 – Cl is
not an aryl halide since halogen is not attached to the benzene ring directly.
JE

The properties of aryl halides are entirely different from that of Alkyl halides.

1.3 Preparation of Aryl Halide

ES

1. From Diazonium Salts

+ –
NO2 NH2 NN X
an

Re duction Na NO /HX
2

 
Sn /HCl (0-5°C) diazotisation
ka

diazonium salt

(a) Sandmeyer Reaction

lp

Cl

(i) Cu Cl /HCl
2 2 + N2
 

+ –
N  N Br Br

(ii) CuBr/HBr + N2
 

+ –
NN I I

(iii) CuI
 + N2
KI

[ 15 ]
Alkyl Halides & Aryl Halides

(b) Gattermann Reaction

The Gattermann reaction is a modification over Sandmeyer reaction. In Sandmeyer reaction,

cuprous halide is used which is unstable and difficult to handle. However in Gattermann
reaction copper powder and hydrogen halide are used.
+ –
N  N Cl Cl

(i) Cu/
 HCl
 + N2

+ –
N  N Br Br

(ii) Cu / HBr + N2


(c) Balz Scheiman Reaction (Preparation of fluorobenzene)

JE

+ + –
–
NN X N2 BF4 F
ES

HBF Δ + N2 + BF3

4 

2. By Direct Halogenation of Aromatic Hydrocarbon (By Electrophilic Aromatic

an

Substitution)
Cl

FeCl dark
ka
3
(a) + Cl2    + HCl
310320 K
Br
lp

3 FeBr , dark
(b) + Br2   + HBr
Room Temp.

(c) + I2 + HI.

This reaction is reversible due to the formation of HI which is a strong reducing agent. To get
iodobenzene, HI must be removed from the reaction mixture. To achieve this, some oxidising
agent like HIO3, HNO3 is used.

HIO3 + 5HI  3H2O + 3I2 2HNO3 + 6HI  3I2 + 4H2O + 2NO

3. Raschig Process
Cl

CuCl
2 + 2HCl + O2 
2 2 + 2 H2O.
500 K

[ 16 ]
Alkyl Halides & Aryl Halides

4. From Phenol with PCl5

Phenols can be reacted with PCl5 to get chlorobenzene, however the yields are poor. This is
because phenol reacts with PCl5 to form triphenyl phosphate which is the main product.
OH Cl

+ PCl5  + HCl + POCl3

Physical Properties

1. Aryl halides are colourless liquids and colourless solids with characteristic odour.

2. The boiling point of aryl halide follows the order

Ar I > Ar Br > ArCl > ArF

3. The melting point of p– isomer is more than o– and m– isomer.

JE

Structure and Reactivity of Aryl Halide and Vinyl Halides

Let us look at the structure of chlorobenzene with resonance interpretation.

ES

Chlorobenzene is a resonance hybrid of 5 resonating structures:

       


+Cl


+ +
Cl Cl Cl



Cl

















an

I II III IV V
Contribution by II, III and IV give a double bond character to the carbon-chlorine bond. Hence
ka

C–Cl bond in chlorobenzene is strong. Hence, aryl halides are less reactive than the corresponding
Alkyl halide towards nucleophillic substitution reaction.

Similar is the case with vinyl halildes.

lp

 
– +
CH2 = CH – Cl  CH2 – CH = Cl

 

 
 

(a) Therefore, attempts to convert arylhalides into phenols, ethers, amines with usual nucleophillic
reagents and conditions are unsuccessful.

e.g., R – Cl + aq NaOH R – OH + NaCl

Cl

+ aq. NaOH No reaction

(This could however be achieved under vigorous conditions)

[ 17 ]
Alkyl Halides & Aryl Halides

(b) The carbon–halogen bonds of arylhalides and vinyl halide are usually short.

(c) Dipole moments of aryl and vinyl halides are usually small



Cl  Cl 


–
(d) In chlorobenzene, the chlorine atom is attached to a sp2 hybridized carbon atom where as in
alkyl chloride the chlorine atom is attached to a sp3 hydridized carbon atom.

3
sp
2 Cl sp centre
centre
CH3 – CH2 – Cl
JE

The sp2 hybridized carbon atom is more electronegative than the sp3 hybridized carbon atom
so the release of electrons towards chlorine atom is less in chlorobenzene and more in alkyl
chloride.
ES

(e) The resonating structure of chlorobenzene indicate that the benzene ring carries a –ve charge
at o and p–positions w.r.t. chlorine atom. Thus the benzene ring definitely takes part in
electrophillic substitution reactions.
an

Reactions of Aryl Halides

Reactions of Aryl halides can be grouped as :

ka

I. Nucleophillic substitution reactions.

II. Electrophillic substitution reactions.

lp

III. Miscellaneous reactions.

I. Nucleophillic substitution reactions:

(a) Dow’s Process

– +
Cl OK
573 to 673 K
+ aq. KOH   
 + KCl + H2O
200300 atms.

– +
OK OH

+ dil. HCl + KCl.

Potassium phenoxide Phenol

[ 18 ]
Alkyl Halides & Aryl Halides

The presence of nitro group at ortho or para position w.r.t. chlorine increases its reactivity.
Further as the number of such NO2 groups increase the reactivity is increased.

Cl OH
ONa

15% NaOH dil. HCl

  
  

160C
NO2 NO2
P-nitro chlorobenzene NO2 P-Nitrophenol

Cl OH
NO2 NO 2
(i) Na CO
2
  
3

130C
(ii) dil. HCl
NO2 NO2
JE

Cl
NO2 NO2
2H O warm
 
ES

NO2
Like –NO2, certain other groups have been found to increase the reactivity of chloro benzene
if present at ortho or para position w.r.t. chlorine atom. These groups are,
an


 N (CH 3 ) 3 , –CN, –SO3H, –COOH, –CHO, – C – R .
O
ka

A nitro group at meta position to chlorine has practically no effect on reactivity

Cl NH2

NH , Cu O
lp

(b) 3 
2
 + HCl
200C
2030 atm
Aniline
Here again the presence of NO2 groups at ortho or para position w.r.t. Cl atom increases the
reactivity.

Cl NH2
NO2 NO2
NH 170C
3

NO2 NO 2

Cl CN

(c) + Cu CN 
 + CuCl
475 K

[ 19 ]
Alkyl Halides & Aryl Halides

Cl OCH 3

(d) + NaOCH3 Cu

salt
 + NaCl
220C

Mechanism

The nucleophilic aromatic substitution (NAS) reaction can be well explained by a bimolecular
mechanism (SN2 mechanism)
Cl : Nu– Cl Nu

slow
Step-1 (Intermediate)

Cl Nu Nu
. .–
+ :Cl:
..
Step-2
Product
JE

The intermediate carbanian ion is stabilized due to resonance.

ES

Resonance hybrid.
an

The stability of such a carbanian can be further increased by – R or – M groups at ortho or para
positions.
ka

Elimination - Addition Reaction

Reactions with Sodamide
NH2
lp

Cl
NaNH /aq NH
3
 2  
196 K
H
Benzyne
This reaction is an elimination – addition mechanism for nucleophillic substitution.
Mechanism

X
X X
NH2 +X
+ NH3 –
H – Benzyne
Addition

NH2 NH 2

[ 20 ]
Alkyl Halides & Aryl Halides

NH2 NH2
+
+ H – NH2 –
+ NH2

II. Electrophillic Substitution Reaction

Halogens are unusual in their effect on electrophillic substitution reactions : They are electron
withdrawing, but also ortho and para-directing.
To understand the influence of halogens, let us consider the intermediate formed when an
electrophile attacks the halobenzene at ortho, meta and para positions.
JE
ES
an

In A, B, and C, if one considers the inductive effect, i.e., (–I effect) of X, then A and B would
be unstable because the (+) charge comes on the carbon atom carrying the halogen atom X.
The structure C be most stable since (+) charge does not come on the carbon atoms carrying
ka

the halogen atom X.

We should therefore, expect that halogen atoms attached to the benzene ring would be meta.
directing for electrophillic substitution reactions.
lp

The existence of halonium ions have shown that halogen can share a pair of electrons and can
accommodate a positive charge. When this idea is applied to the present problem the carbocations
formed when an electrophile attacks at ortho or para position i.e., (A) and (B) would be stabilized
as below.

(A) charge delocalized

(B) charge delocalized

[ 21 ]
Alkyl Halides & Aryl Halides

Whereas the carbocation formed when the electrophile attacks the meta position on halo
benzene, i.e., C would be destabilized.

The inductive effect causes electron withdrawing deactivation – the resonance effect tends to
oppose the inductive effect for attack at ortho and para position, and hence makes the
deactivation less for ortho and para than for meta. Thus reactivity is controlled by the inductive
effect, and orientation is controlled by resonance effect.

Reactions

Cl Cl Cl
Cl
FeCl dark
3
1. Halogenation + Cl2    +
Δ

Cl
Cl Cl Cl
NO2
JE

H 2SO 4
2. Nitration + HNO3  
60C
+

NO2
ES

Cl Cl Cl
SO3H
Δ
3. Sulphonation + H2SO4 
 +
an

SO3H
4. Friedel Crafts Reactions

Cl Cl Cl
R
ka
anhyd.
(a) Alkylation with Alkyl halide + R – X Al
Cl
3
Δ +

(b) Acylation with Acetyl Chloride or Acetic anhydride

lp

Cl Cl O Cl
C – CH3
anhyd. AlCl
+ CH3COCl or CH3 C  O  C CH 3   3  +
Δ
|| ||
O O C=O
(c) Benzoylation with Benzoyl chloride or Benzoic anhydride CH3

Cl O Cl
Cl
C – C 6H 5
AlCl3
+ C6H5COCl or C6H5 – C – O – C – C6H5  +
Δ
O O
C=O
C 6H5
[ 22 ]
Alkyl Halides & Aryl Halides

III. Miscellaneous Reactions

(a) Fittig Reaction

2 dry ether
Cl + 2Na  + 2NaCl



(b) Wurtz-Fittig Reaction

ether
Cl + R – Cl + 2Na  R + 2NaCl

Here side products like R – R and are also formed.

(c) Ullmann’s Reaction

JE

Cu powder
ES



Δ

Biphenyl
Chlorobenzene does not undergo Ullmann’s reaction whereas if a ring deactivating group
an

is attached to chlorobenzene then the substituted chloro benzene can take part in Ullmann’s
reaction.
ka

Cl NO 2
NO2
Cu powder NO 2
  NO2
Δ
lp

NO2
NO2

(d) Formation of Grignard’s reagent

+ Mg Dry

ether
 MgI

(e) Reduction

Cl

Ni Al/NaOH
   + HCl

[ 23 ]
Alkyl Halides & Aryl Halides

Polyhalogen Compounds
I. Alkyl Dihalides :

When the two halogen atoms are attached to the same carbon atom, i.e., they are said to be in
the geminal (gem.) position and these derivatives are called alkylidene halides, e.g., CH3CHBr2
(Ethylidene bromide); CH3CCl2CH3 (Isopropylidene chloride).

When the two halogen atoms are on adjacent carbon atoms, i.e., they are said to be in vicinal
positions and then are named as alkylene halides –

e.g., CH2  CH2 CH3 – CH –CH2

Br Br Cl Cl
(ethylene bromide) (propylene chloride)

Preparation
1. Vicinal Dihalides
JE

(a) CH2 = CH2 + Br2  Br – CH2 – CH2 – Br 1, 2 Dibromo ethane.

CH3 – CH = CH2 + Br2  CH3 – CH – CH2 1, 2 Dibromo propane
ES

Br Br

(b) From Glycols

HO – CH2 – CH2 – OH + 2PCl5  CH2 – CH2

an

Cl Cl
2. Alkylidene Halides (Gem-Dihalides)
Cl
ka

(a) CH3 – CHO + PCl5  CH3 – CH + POCl3

Cl
Cl
lp

(b) CH3 – C – CH3 + PCl5  CH3 – C – CH3 + POCl3

O Cl

Here we can use SOCl2, PCl3, or PX3

Br
(c) CH  CH + 2 HBr  CH3 – CH
Br
Properties :
(i) Lower members are colourless, oily liquids with sweet smell.
(ii) The reactivity of gem dihalides is less than alkyl halides, which might be due to the fact that in
the presence of one halogen atom (with a strong attracting effect, i.e., –I effect), vic. dihalides
have same order of reactivity as alkyl halides. Thus reactivity order is vic. dihalides > gem.
dihalides.
[ 24 ]
Alkyl Halides & Aryl Halides

(iii) Some of the important reactions of dihalides are given below :

(a) Action of alcohlic KOH.

Both vic and gem. dihalides give the same products.

alc. KOH
CH2 – CH2  CH  CH  2KX + 2H O
Δ 2
X X

X
alc. KOH
CH3 – CH   CH  CH  2KX + 2H2O
Δ
X
(b) Action of Zn dust :

CH 2  CH 2 Zn
dust
 CH2 = CH2 + ZnX2
alcohol
| | Δ
X X
JE

alcohol
2 CH3 – CHX2 + 2Zn   CH3 – CH = CH – CH3 + 2ZnX2

ES

X
| CH3 CH3
2 CH 3  C  CH 3  2Zn alcohol
  C=C + 2 ZnX2
 CH3 CH3
an

|
X
ka

(c) Action of aqueous KOH

CH2 – X CH2 – OH
aq. KOH


lp
CH2 – X Δ CH2 – OH

aq. KOH OH
CH3 – CHX2 Δ
 CH3 – CH 
H2O
 CH 3  C  O
OH |
H

(d) Action of KCN followed by hydrolysis.

CH2 – X CH2 – CN CH2 – COOH

H/H O
KCN
 2

 
CH2 – X CH2 – CN CH2 – COOH

CH3
CH3 CH3 CH3
CN COOH 
KCN H/H O CH2
CHX2  CH 2

  CH –CO2
COOH
CN COOH

[ 25 ]
Alkyl Halides & Aryl Halides

Trihalogen Derivatives
(A) CHLOROFORM

Preparation :
1. By distilling ethanol or propanone with a suspension of bleaching powder in water or with
chlorine and alkali. These reagents serve triple purpose and act as oxidizing, chlorinating and
hydrolysing agents.
H2O + CaOCl2  Cl2 + Ca (OH)2
(i) CH3CH2OH + 4 Cl2  CCl3 CHO + 5 HCl
CCl3CHO + NaOH  CHCl3 + HCOONa

(ii) CH3 – C – CH3 + 3Cl2  CCl3 – C – CH3 + 3HCl

O O

CCl3 – C – CH3 + NaOH  CHCl3 + CH3COONa

JE

2. By Chlorination of methane
ES

diffused
CH4 + 3Cl2   CHCl3 + 3HCl
sunlight

This method is of no practical use as mixture of mono, di and tetrahalogenated products are
also possible.
an

3. By reduction of Carbon tetrachloride

H2O
CCl4 + Fe 
 CHCl3 + HCl
2 [H]
ka

4. Pure Chloroform can be prepared by distillation of chloral hydrate with aqueous alkali.
CCl3 CHO.H2 O
lp

or CCl3CH (OH)2 + NaOH  CHCl3 + HCOONa + H2O

Physical Properties:
(i) It is a clourless liquid with sweet smell.
(ii) Insoluble in H2O but soluble in organic solvents.
(iii) Its vapour produces temporary unconsciousness.
(iv) It is used as good solvent for oils, fats and resins.
Chemical Properties :

(i) Oxidation

When exposed to air and sunlight, it gets oxidized to poisonous carbonyl chloride or phosgene gas.
[O]
CHCl3 + O2  COCl2 + HCl
sunlight

But strong oxidising agents convert it to CO2 and H2O

[ 26 ]
Alkyl Halides & Aryl Halides

Since chloroform is used as an anaesthesia, formation of phosgene gas is highly undesirable. It

is therefore advisable to store it in dark coloured bottles or fill upto the stopper containing 1%
ethyl alcohol. Ethyl alcohol retards the decomposition of CHCl3 to phosgene gas and converts
any phosgene gas formed to harmless diethyl carbonate.

OC2H5
COCl2 + 2C2H5OH  O = C + 2 HCl
OC2H5

(ii) Reduction

HCl
CHCl3 + Zn  CH2Cl2 + HCl


H O
CHCl3 + Zn 
2
CH4 + HCl


CHCl3 + Zn alcohol
  CH3Cl + HCl
JE
HCl

(iii) Chlorination

h
CHCl3 + Cl2 
 CCl4 + HCl
ES

(iv) Nitration

CHCl3 + HNO3  CCl3NO2 + H2O

an
Chloropicrin

(war gas)

Chloropicrin is also used as insecticide.

ka

(v) Hydrolysis

When hydrolysed using potassium hydroxide, chloroform is hydrolysed to give potassium formate

CHCl3 + 3KOH  CH (OH)3 

H2O
 HCOOH KOH
 HCOOK.
lp

(vi) Carbylamine Reaction

When warmed with primary (aliphatic or aromatic amine and alcoholic potassium hydroxide),
chloroform gives offensive smell of carbylamine or isocyanide
 –
R – NH2 + CHCl3 + 3KOH  R – N  C + 3HCl + 3H2O

(vii)Condesation with Ketones

In the presence of alkali, chloroform undergoes condensation with acetone to form chloretone.
OH
KOH
CH3 – C – CH3 + CHCl3 CH3 – C – CCl3
O CH3

Chloretone is used as a hypnotic.

[ 27 ]
Alkyl Halides & Aryl Halides

(viii) Dechlorinations to form Ethyne:


2CHCl3 + 6Ag  CH  CH + 6AgCl

(ix) Reimer Tiemann Reaction:

OH OH
CHO
+ CHCl3 + 3NaOH 
335  345 K
  + 3 NaCl + H2O

(x) Reaction with S-amines :

R R
NH +CHCl3 
Pot. ter. butoxide
   H – C – N
R R

Similar are the preparations and properties of Iodoform but Iodoform does not form any special
product with nitric acid or acetone.
JE

Tetra Halogen Derivatives

CCl4; Carbon Tetrachloride
ES

Preparation

By the action of chlorine on carbon disulphide in the presence of aluminium chloride and FeCl3
which acts as catalyst.
an

CS2 + 3Cl2 h CCl4 + S2Cl2.



Chemical Properties
ka

(i) With water vapours

Carbon tetrachloride reacts with water vapours at 770 K to form some phosgene.
lp

CCl4 + H2O  COCl2 + 2HCl.

(ii) Reduction

Moist
CCl4 + 2 [H]   CHCl + HCl
Iron filling 3

(iii) Hydrolysis

CCl4 + 6KOH —————— K2CO3 + 3H2O + 4 KCl

(iv) Reaction with phenol

ONa
COONa
CCl4 + C6H5OH aq
. NaOH


[ 28 ]
Alkyl Halides & Aryl Halides

Illustration 1: Which of the two would you expect to possess a high boiling point, nitrobenzene or
n-propylbenzene?

Solution: Nitrobenzene because it has a higher dipole moment.

Illustration 2: Why is acylation followed by alkylation of napthalene not practical?

O
Solution: Acylation introduces a group and prevents further acylation. Introduction of R group
CR

induces alkylation, an electron donating group.

Illustration 3: What do you understand when one says that the cyclopentadiene anion is aromatic?

Solution: It implies that (i) cyclopentadiene anion is planar (ii) it has (4n + 2) electrons
H
JE

(n = 2) (ii) electrons are delocalised in the entire ring.

Illustration 4: Compound A, C8H7O2N by careful reduction gives B, C8H9O2N. Further reduction with
Sn/HCl gives C, C8H11N. Bromination of C in acid solution gives two isomeric compounds
ES

C8 H10 NBr. Oxidation of A with hot alk. KMnO 4 gives D, C 7H5 O4 N. Compound D
dissolves in NaHCO3 with effervescence. D on heating with soda lime gives E, C6H5O2N.
E can be reduced to aniline with Sn/HCl. Deduce structures of the lettered compounds.
an

NO2

Solution: E, is because on reduction with Sn/HCl it gives aniline.

ka

COOH
NO2
lp

D, is because on heating with soda lime produces E.

A, contains a –NO 2 group and an unsaturation in the side-chain. Therefore it is

CH2

NO2

Illustration 5: An organic compound A, C8H6 on treatment with dil. H2SO4 containing mercuric sulfate
gives a compound B, which can also be obtained from a reaction of benzene with an acid
chloride in the presence of anhydrous aluminium chloride. The compound B, on treatment
with iodine in aqueous KOH, yields C, and a yellow compound D. Identify
A to D with justification.

[ 29 ]
Alkyl Halides & Aryl Halides

Solution: Reaction of A with HgSO4 / H2SO4 shows that it is an acetylenic derivative. Therefore
CH

A is

O
CH

HgSO 4 /H 2SO 4 AlCl3

H 2O
    CH 3COCl

(A) (B)
O COO K 

KOH/I 2
  CHI3
JE

(B) (C)

SAMPLE PROBLEMS 1.3 (MCQ)

ES

Problem 1: The electrophile in aromatic nitration is:

(a) Nitrinium ion (b) Nitronium ion
(c) Nitrite ion (d) Nitrate ion
an


Solution: (b) Nitronium ion (O  N  O)

Problem 2: Which of the following benzoinium ions is expected to be most stable?

ka

CH3 CH3
lp

(a) (b)

H X H X
CH3 CH3

(c) X (d) X
H H
CH3

Solution: (a) positive charge is present on the carbon atom bearing the electron donating

H X
–CH3 group.
[ 30 ]
Alkyl Halides & Aryl Halides

Problem 3: Nitrobenzene can be prepared from benzene by using a mixture of con. HNO3 and con.
H2SO4. In the nitrating mixture, HNO3 acts as
(a) Acid (b) Base
(c) Catalyst (d) Reducing agent

Solution: (c) Base, nitric acid accepts a proton from sulfuric acid.

Problem 4: Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with
(a) SO2Cl2 (b) SOCl2
(c) NaOCl (d) Cl2

CH3 CH2 Cl
hν
Solution: (d) Cl2    HCl

Problem 5: Among the following statements on the nitration of aromatic compounds, the false one is
(a) The rate of nitration of toluene is greater than that of benzene.
JE
(b) Nitration is an electrophilic aromatic substitution reaction.
(c) The rate of nitration of benzene is almost the same as that of hexadeuterobenzene.
(d) The rate of nitration of benzene is greater than that of hexadeuteriobenzene.

Solution: (d) The rate of nitration is almost same. This means the kinetic isotope effect is absent
ES

therefore a C – H bond is not weakened in the slow step. In simple words the mechanism
of electrophilic aromatic substitution does not involve the breakage of a C – H bond in
the rate-determining step.
an

Problem 6: The most reactive among the following towards sulfonation is:
CH3 Cl
ka

(a) (b)

CH3 NO2
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(c) (d)
CH3

Solution: (c) In m-xylene the two –CH3 groups activate the ring.

Problem 7: Identify the correct order of reactivity in electrophilic substitution reactions of the following
compounds:
CH3 Cl NO2

I II III IV
(a) I > II > III > IV (b) IV > III > II > I
(c) II > I > III > IV (d) II > III > I > IV
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Alkyl Halides & Aryl Halides

Solution: (c) –CH3 group is activating while –NO2 group is deactivating.

Problem 8: During the ESR of C6H5R, the major product (>65%) is the m-isomer, so the group R is
(a) –Cl (b) –COOH
(c) –NH 2 (d) –OH

Solution: (b) –COOH is electron withdrawing and hence meta-directing.

Problem 9: In the nitration of the following compounds which will give the largest amount of the
p-isomer.
CH3
CH3

(a) (b)

CH3
H3C CH3
H3C CH3
JE

(c) (d)
ES

Solution: (d) The –C(CH3)3 group being bulky, hinders the attack of the nitronium ion at the ortho
position.

Problem 10: In the following reaction:

an

CHCOOH
ka

FeCl3
 Br2   ? the product obtained is:

CHCOOH
CHBrCHBrCOOH
lp

(a) (b)

CHCOOH CHCOOH CHCOOH

Br

(c) Only (d) Both s

Br Br

Solution: (d) –CH = CHCOOH is ortho and para-directing group.

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