Unit

Objectives
10
Haloalkanes and
After studying this Unit, you will be
able to
name haloalkanes and haloarenes
Haloar enes
Haloarenes
according to the IUPAC system of
nomenclature from their given
structures; Halogenated compounds persist in the environment due to their
describe the reactions involved in resistance to breakdown by soil bacteria.
the preparation of haloalkanes and
haloarenes and understand
various reactions that they The replacement of hydrogen atom(s) in a
undergo; hydrocarbon, aliphatic or aromatic, by halogen
correlate the structures of atom(s) results in the formation of alkyl halide
haloalkanes and haloarenes with (haloalkane) and aryl halide (haloarene), respectively.
various types of reactions; Haloalkanes contain halogen atom(s) attached to the
use stereochemistry as a tool for sp3 hybridised carbon atom of an alkyl group whereas
understanding the reaction
haloarenes contain halogen atom(s) attached to sp2
mechanism;
hybridised carbon atom(s) of an aryl group. Many
appreciate the applications of
organo-metallic compounds;
halogen containing organic compounds occur in
nature and some of these are clinically useful. These
highlight the environmental effects
of polyhalogen compounds. classes of compounds find wide applications in
industry as well as in day-to-day life. They are used
as solvents for relatively non-polar compounds and
as starting materials for the synthesis of wide range
of organic compounds. Chlorine containing antibiotic,
chloramphenicol, produced by soil microorganisms
is very effective for the treatment of typhoid fever.
Our body produces iodine containing hormone,
thyroxine, the deficiency of which causes a disease
called goiter. Synthetic halogen compounds, viz.
chloroquine is used for the treatment of malaria;
halothane is used as an anaesthetic during surgery.
Certain fully fluorinated compounds are being
considered as potential blood substitutes in surgery.
In this Unit, you will study the important methods
of preparation, physical and chemical properties and
uses of organohalogen compounds.
10.1 Classification Haloalkanes and haloarenes may be classified as follows:

10.1.1 On the These may be classified as mono, di, or polyhalogen (tri-,tetra-, etc.)
Basis of compounds depending on whether they contain one, two or more halogen
Number of atoms in their structures. For example,
Halogen
Atoms

Monohalocompounds may further be classified according to the

hybridisation of the carbon atom to which the halogen is bonded, as
discussed below.
10.1.2 Compounds This class includes
Containing (a) Alkyl halides or haloalkanes (RX)
sp3 CX
Bond (X= F, In alkyl halides, the halogen atom is bonded to an alkyl group (R).
Cl, Br, I) They form a homologous series represented by CnH2n+1X. They are
further classified as primary, secondary or tertiary according to the
nature of carbon to which halogen is attached.

(b) Allylic halides

These are the compounds in which the halogen atom is bonded to an
sp3-hybridised carbon atom next to carbon-carbon double bond (C=C)
i.e. to an allylic carbon.

(c) Benzylic halides

These are the compounds in which the halogen atom is bonded to an
sp3-hybridised carbon atom next to an aromatic ring.

Chemistry 282
10.1.3 Compounds This class includes:
Containing
(a) Vinylic halides
sp2 CX
Bond These are the compounds in which the halogen atom is bonded to
an sp2-hybridised carbon atom of a carbon-carbon double bond
(C = C).

(b) Aryl halides

These are the compounds in which the halogen atom is bonded to
the sp2-hybridised carbon atom of an aromatic ring.

10.2 Nomenclature Having learnt the classification of halogenated compounds, let us now
learn how these are named. The common names of alkyl halides are
derived by naming the alkyl group followed by the halide. Alkyl halides
are named as halosubstituted hydrocarbons in the IUPAC system of
nomenclature. Haloarenes are the common as well as IUPAC names of
aryl halides. For dihalogen derivatives, the prefixes o-, m-, p- are used in
common system but in IUPAC system, the numerals 1,2; 1,3 and 1,4 are
used.

The dihaloalkanes having the same type of halogen atoms are named
as alkylidene or alkylene dihalides. The dihalo-compounds having same
type of halogen atoms are further classified as geminal halides (halogen
atoms are present on the same carbon atom) and vicinal halides (halogen
atoms are present on the adjacent carbon atoms). In common name
system, gem-dihalides are named as alkylidene halides and vic-dihalides

283 Haloalkanes and Haloarenes

 are named as alkylene dihalides. In IUPAC system, they are named as
dihaloalkanes.

Some common examples of halocompounds are mentioned in Table 10.1.

Table 10.1: Common and IUPAC Names of some Halides

Structure Common name IUPAC name

CH3CH2CH(Cl)CH3 sec-Butyl chloride 2-Chlorobutane

(CH3)3CCH2Br neo-Pentyl bromide 1-Bromo-2,2-dimethylpropane

(CH3)3CBr tert-Butyl bromide 2-Bromo-2-methylpropane

CH2 = CHCl Vinyl chloride Chloroethene

CH2 = CHCH2Br Allyl bromide 3-Bromopropene

o-Chlorotoluene 1-Chloro-2-methylbenzene
or
2-Chlorotoluene
Benzyl chloride Chlorophenylmethane

CH2Cl2 Methylene chloride Dichloromethane

CHCl3 Chloroform Trichloromethane

CHBr3 Bromoform Tribromomethane

CCl4 Carbon tetrachloride Tetrachloromethane

CH3CH2CH2F n-Propyl fluoride 1-Fluoropropane

Example 10.1 Draw the structures of all the eight structural isomers that have the
molecular formula C5H11Br. Name each isomer according to IUPAC system
and classify them as primary, secondary or tertiary bromide.
Solution CH3CH2CH2CH2CH2Br 1-Bromopentane (1 )
o

CH3CH2CH2CH(Br)CH3 2-Bromopentane(2o)
CH3CH2CH(Br)CH2CH3 3-Bromopentane (2o)
(CH3)2CHCH2CH2Br 1-Bromo-3-methylbutane (1o)

Chemistry 284
 o
(CH3)2CHCHBrCH3 2-Bromo-3-methylbutane(2 )
o
(CH3)2CBrCH2CH3 2-Bromo-2-methylbutane (3 )
o
CH3CH2CH(CH3)CH2Br 1-Bromo-2-methylbutane(1 )
o
(CH3)3CCH2Br 1-Bromo-2,2-dimethylpropane (1 )

Write IUPAC names of the following: Example 10.2

(i) 4-Bromopent-2-ene (ii) 3-Bromo-2-methylbut-1-ene Solution

(iii) 4-Bromo-3-methylpent-2-ene (iv) 1-Bromo-2-methylbut-2-ene
(v) 1-Bromobut-2-ene (vi) 3-Bromo-2-methylpropene

Intext Question
10.1 Write structures of the following compounds:
(i) 2-Chloro-3-methylpentane
(ii) 1-Chloro-4-ethylcyclohexane
(iii) 4-tert. Butyl-3-iodoheptane
(iv) 1,4-Dibromobut-2-ene
(v) 1-Bromo-4-sec. butyl-2-methylbenzene.

1 0 . 3 Nature of Since halogen atoms are more electronegative than carbon, the carbon-
halogen bond of alkyl halide is polarised; the carbon atom bears a
C-X Bond partial positive charge whereas the halogen atom bears a partial negative
charge.

Since the size of halogen atom increases as we go down the group

in the periodic table, fluorine atom is the smallest and iodine atom, the
largest. Consequently the carbon-halogen bond length also increases
from CF to CI. Some typical bond lengths, bond enthalpies and
dipole moments are given in Table 10.2.

285 Haloalkanes and Haloarenes

 Table 10.2: Carbon-Halogen (CX) Bond Lengths, Bond
Enthalpies and Dipole Moments

Bond Bond length/pm C-X Bond enthalpies/ kJmol-1 Dipole moment/Debye

CH3F 139 452 1.847
CH3 Cl 178 351 1.860
CH3Br 193 293 1.830
CH3I 214 234 1.636

10.4 Methods of 10.4.1 From Alcohols

Preparation Alkyl halides are best prepared from alcohols, which are easily accessible.
The hydroxyl group of an alcohol is replaced by halogen on reaction
with concentrated halogen acids, phosphorus halides or thionyl chloride.
Thionyl chloride is preferred because the other two products are
escapable gases. Hence the reaction gives pure alkyl halides. Phosphorus
tribromide and triiodide are usually generated in situ (produced in the
reaction mixture) by the reaction of red phosphorus with bromine and
iodine respectively. The preparation of alkyl chloride is carried out either
by passing dry hydrogen chloride gas through a solution of alcohol or
by heating a solution of alcohol in concentrated aqueous acid.

The reactions of primary and secondary alcohols with HCl require

the presence of a catalyst, ZnCl2. With tertiary alcohols, the reaction is
conducted by simply shaking with concentrated HCl at room
temperature. Constant boiling with HBr (48%) is used for preparing
alkyl bromide. Good yields of RI may be obtained by heating alcohols
with sodium or potassium iodide in 95% orthophosphoric acid. The
order of reactivity of alcohols with a given haloacid is 3>2>1. The
above methods are not applicable for the preparation of aryl halides
because the carbon-oxygen bond in phenols has a partial double bond
character and is difficult to break being stronger than a single bond
(Unit 11, Class XI).
10.4.2 From (a) By free radical halogenation
Hydrocarbons Free radical chlorination or bromination of alkanes gives a complex
Chemistry 286
 mixture of isomeric mono- and polyhaloalkanes, which is difficult
to separate as pure compounds. Consequently, the yield of any one
compound is low (Unit 13, Class XI).

Identify all the possible monochloro structural isomers expected to be Example 10.3
formed on free radical monochlorination of (CH3)2CHCH2CH3.
In the given molecule, there are four different types of hydrogen atoms. Solution
Replacement of these hydrogen atoms will give the following
(CH3)2CHCH2CH2Cl (CH3)2CHCH(Cl)CH3
(CH3)2C(Cl)CH2CH3 CH3CH(CH2Cl)CH2CH3

(b) By electrophilic substitution

Aryl chlorides and bromides can be easily prepared by electrophilic
substitution of arenes with chlorine and bromine respectively in the
presence of Lewis acid catalysts like iron or iron(III) chloride.

The ortho and para isomers can be easily separated due to large
difference in their melting points. Reactions with iodine are reversible
in nature and require the presence of an oxidising agent (HNO3,
HIO4) to oxidise the HI formed during iodination. Fluoro compounds
are not prepared by this method due to high reactivity of fluorine.
(c) Sandmeyers reaction
When a primary aromatic amine, dissolved or suspended in cold
aqueous mineral acid, is treated with sodium nitrite, a diazonium
salt is formed (Unit 13, Class XII). Mixing the solution of freshly
prepared diazonium salt with cuprous chloride or cuprous bromide
results in the replacement of the diazonium group by Cl or Br.

287 Haloalkanes and Haloarenes

 Replacement of the diazonium group by iodine does not require the
presence of cuprous halide and is done simply by shaking the diazonium
salt with potassium iodide.

(d) From alkenes

(i) Addition of hydrogen halides: An alkene is converted to
corresponding alkyl halide by reaction with hydrogen chloride,
hydrogen bromide or hydrogen iodide.

Propene yields two products, however only one predominates as

per Markovnikovs rule. (Unit 13, Class XI)

(ii) Addition of halogens: In the laboratory, addition of bromine in

CCl4 to an alkene resulting in discharge of reddish brown colour
of bromine constitutes an important method for the detection of
double bond in a molecule. The addition results in the synthesis
of vic-dibromides, which are colourless (Unit 13, Class XI).

Example 10.4 Write the products of the following reactions:

Solution

Chemistry 288
10.4.3 Halogen Alkyl iodides are often prepared by the reaction of alkyl chlorides/
Exchange bromides with NaI in dry acetone. This reaction is known as Finkelstein
reaction.

NaCl or NaBr thus formed is precipitated in dry acetone. It facilitates

the forward reaction according to Le Chateliers Principle.
The synthesis of alkyl fluorides is best accomplished by heating an
alkyl chloride/bromide in the presence of a metallic fluoride such as
AgF, Hg2F2, CoF2 or SbF3. The reaction is termed as Swarts reaction.

Intext Questions
10.2 Why is sulphuric acid not used during the reaction of alcohols with KI?
10.3 Write structures of different dihalogen derivatives of propane.
10.4 Among the isomeric alkanes of molecular formula C5H12, identify the one that
on photochemical chlorination yields
(i) A single monochloride.
(ii) Three isomeric monochlorides.
(iii) Four isomeric monochlorides.
10.5 Draw the structures of major monohalo products in each of the following
reactions:

10.5 Physical Alkyl halides are colourless when pure. However, bromides and iodides
develop colour when exposed to light. Many volatile halogen compounds
Properties have sweet smell.

289 Haloalkanes and Haloarenes

 Melting and boiling points
Methyl chloride, methyl bromide, ethyl chloride and some
chlorofluoromethanes are gases at room temperature. Higher members
are liquids or solids. As we have already learnt, molecules of organic
halogen compounds are generally polar. Due to greater polarity as well
as higher molecular mass as compared to the parent hydrocarbon, the
intermolecular forces of attraction (dipole-dipole and van der Waals)
are stronger in the halogen derivatives. That is why the boiling points
of chlorides, bromides and iodides are considerably higher than those
of the hydrocarbons of comparable molecular mass.
The attractions get stronger as the molecules get bigger in size and
have more electrons. The pattern of variation of boiling points of different
halides is depicted in Fig. 10.1. For the same alkyl group, the boiling
points of alkyl halides decrease in the order: RI> RBr> RCl> RF. This
is because with the increase in size and mass of halogen atom, the
magnitude of van der Waal forces increases.

Fig. 10.1: Comparison of boiling points of some alkyl halides

The boiling points of isomeric haloalkanes decrease with increase in

branching (Unit 12, Class XI). For example, 2-bromo-2-methylpropane
has the lowest boiling point among the three isomers.

Boiling points of isomeric dihalobenzenes are very nearly the same.

However, the para-isomers are high melting as compared to their ortho-
and meta-isomers. It is due to symmetry of para-isomers that fits in
crystal lattice better as compared to ortho- and meta-isomers.

Chemistry 290
 Density
Bromo, iodo and polychloro derivatives of hydrocarbons are heavier than
water. The density increases with increase in number of carbon atoms,
halogen atoms and atomic mass of the halogen atoms (Table 10.3).

Table 10.3: Density of Some Haloalkanes

Compound Density (g/mL) Compound Density (g/mL)

nC3H7Cl 0.89 CH2Cl2 1.336

nC3H7Br 1.335 CHCl3 1.489
n-C3H7I 1.747 CCl4 1.595

Solubility
The haloalkanes are only very slightly soluble in water. In order for a
haloalkane to dissolve in water, energy is required to overcome the
attractions between the haloalkane molecules and break the hydrogen
bonds between water molecules. Less energy is released when new
attractions are set up between the haloalkane and the water molecules
as these are not as strong as the original hydrogen bonds in water. As a
result, the solubility of haloalkanes in water is low. However, haloalkanes
tend to dissolve in organic solvents because the new intermolecular
attractions between haloalkanes and solvent molecules have much the
same strength as the ones being broken in the separate haloalkane and
solvent molecules.

Intext Question
10.6 Arrange each set of compounds in order of increasing boiling points.
(i) Bromomethane, Bromoform, Chloromethane, Dibromomethane.
(ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.

10.6 Chemical 10.6.1 Reactions of Haloalkanes

Reactions The reactions of haloalkanes may be divided into the following categories:
(i) Nucleophilic substitution
(ii) Elimination reactions
(iii) Reaction with metals.
(i) Nucleophilic substitution reactions
In this type of reaction, a nucleophile reacts with haloalkane (the
substrate) having a partial positive charge on the carbon atom bonded
291 Haloalkanes and Haloarenes
 to halogen. A substitution reaction takes place and halogen atom,
called leaving group departs as halide ion. Since the substitution
reaction is initiated by a nucleophile, it is called nucleophilic
substitution reaction.

It is one of the most useful classes of organic reactions of alkyl

halides in which halogen is bonded to sp3 hybridised carbon. The
products formed by the reaction of haloalkanes with some common
nucleophiles are given in Table 10.4.

Table 10.4: Nucleophilic Substitution of Alkyl Halides (RX)

Reagent Nucleophile Substitution Class of main

(Nu) product RNu product
NaOH (KOH) HO ROH Alcohol
H2O H2O ROH Alcohol

NaOR RO ROR Ether

NaI I RI Alkyl iodide
NH3 NH3 RNH2 Primary amine
RNH2 RNH2 RNHR Sec. amine
RRNH RRNH RNRR Tert. amine
KCN RCN Nitrile
(cyanide)
AgCN Ag-CN: RNC Isonitrile
(isocyanide)
KNO2 O=NO RON=O Alkyl nitrite
AgNO2 AgN=O RNO2 Nitroalkane
RCOOAg RCOO
RCOOR Ester
LiAlH4 H RH Hydrocarbon
R M+ R RR Alkane

Groups like cyanides and nitrites possess two nucleophilic centres

and are called ambident nucleophiles. Actually cyanide group is a
hybrid of two contributing structures and therefore can act as a
nucleophile in two different ways [VCN :C=NV], i.e., linking through
carbon atom resulting in alkyl cyanides and through nitrogen atom
leading to isocyanides. Similarly nitrite ion also represents an ambident
nucleophile with two different points of linkage [O N =O]. The linkage
through oxygen results in alkyl nitrites while through nitrogen atom,
it leads to nitroalkanes.
Chemistry 292
 Haloalkanes react with KCN to form alkyl cyanides as main product Example 10.5
while AgCN forms isocyanides as the chief product. Explain.
KCN is predominantly ionic and provides cyanide ions in solution. Solution
Although both carbon and nitrogen atoms are in a position to donate
electron pairs, the attack takes place mainly through carbon atom and
not through nitrogen atom since CC bond is more stable than CN
bond. However, AgCN is mainly covalent in nature and nitrogen is free
to donate electron pair forming isocyanide as the main product.

Mechanism: This reaction has been found to proceed by two different

mechanims which are described below:
(a) Substitution nucleophilic bimolecular (SN2)
The reaction between CH3Cl and hydroxide ion to yield methanol and
chloride ion follows a second order kinetics, i.e., the rate depends
upon the concentration of both the reactants.

As you have already learnt in Section 12.3.2 of Class XI, the solid wedge represents the
bond coming out of the paper, dashed line going down the paper and a straight line
representing bond in the plane of the paper.

This can be represented diagrammatically as shown in Fig. 10.2.

Fig. 10.2: Red dot represents the incoming hydroxide ion and green dot represents the
outgoing halide ion

It depicts a bimolecular nucleophilic displacement (SN2) reaction;

the incoming nucleophile interacts with alkyl halide causing the carbon-
halide bond to break while forming a new carbon-OH bond. These two
In the year 1937,
processes take place simultaneously in a single step and no intermediate
Edward Davies Hughes
and Sir Christopher
is formed. As the reaction progresses and the bond between the
Ingold proposed a nucleophile and the carbon atom starts forming, the bond between
mechanism for an SN2 carbon atom and leaving group weakens. As this happens, the
reaction. configuration of carbon atom under attack inverts in much the same
way as an umbrella is turned inside out when caught in a strong wind,
while the leaving group is pushed away. This process is called as
inversion of configuration. In the transition state, the carbon atom is
simultaneously bonded to incoming nucleophile and the outgoing leaving

293 Haloalkanes and Haloarenes

 group and such structures are unstable and cannot be isolated. This
is because the carbon atom in the transition state is simultaneously
bonded to five atoms and therefore is unstable.
Since this reaction requires the approach of the nucleophile to the
carbon bearing the leaving group, the presence of bulky substituents
Hughes worked under
Ingold and earned a
on or near the carbon atom have a dramatic inhibiting effect. Of the
D.Sc. degree from the simple alkyl halides, methyl halides react most rapidly in SN2 reactions
University of London. because there are only three small hydrogen atoms. Tertiary halides are
the least reactive because bulky groups hinder the approaching
nucleophiles. Thus the order of reactivity followed is:
Primary halide > Secondary halide > Tertiary halide.

Fig.10.3: Steric effects in SN2 reaction. The relative rate of SN2 reaction is given in parenthesis

(b) Substitution nucleophilic unimolecular (SN1)

SN1 reactions are generally carried out in polar protic solvents (like
water, alcohol, acetic acid, etc.). The reaction between tert-butyl
bromide and hydroxide ion yields tert-butyl alcohol and follows
the first order kinetics, i.e., the rate of reaction depends upon the
concentration of only one reactant, which is tert- butyl bromide.

It occurs in two steps. In step I, the polarised CBr bond undergoes

slow cleavage to produce a carbocation and a bromide ion. The
carbocation thus formed is then attacked by nucleophile in step II
to complete the substitution reaction.

Chemistry 294
 Step I is the slowest and reversible. It involves the CBr bond breaking for which the
energy is obtained through solvation of halide ion with the proton of protic solvent. Since
the rate of reaction depends upon the slowest step, the rate of reaction depends only on the
concentration of alkyl halide and not on the concentration of hydroxide ion. Further, greater
the stability of carbocation, greater will be its ease of formation from alkyl halide and faster
will be the rate of reaction. In case of alkyl halides, 30 alkyl halides undergo SN1 reaction
0
very fast because of the high stability of 3 carbocations. We can sum up the order of reactivity
of alkyl halides towards S N1 and SN2 reactions as follows:

For the same reasons, allylic and benzylic halides show high reactivity towards the SN1
reaction. The carbocation thus formed gets stabilised through resonance (Unit 12, Class XI) as
shown below:
+ +
H2C C CH2 H2C C CH2
H H

For a given alkyl group, the reactivity of the halide, R-X, follows the same order in both the
mechanisms RI> RBr>RCl>>RF.

In the following pairs of halogen compounds, which would undergo Example 10.6
SN2 reaction faster?

It is primary halide and therefore undergoes SN2 Solution

reaction faster.

As iodine is a better leaving group because of its

large size, it will be released at a faster rate in the
presence of incoming nucleophile.

Predict the order of reactivity of the following compounds in SN1 and Example 10.7
SN2 reactions:
(i) The four isomeric bromobutanes
(ii) C6H5CH2Br, C6H5CH(C6H5)Br, C6H5CH(CH3)Br, C6H5C(CH3)(C6H5)Br

295 Haloalkanes and Haloarenes

 Solution (i) CH3CH2CH2CH2Br < (CH3)2CHCH2Br < CH3CH2CH(Br)CH3 < (CH3)3CBr (SN1)
CH3CH2CH2CH2Br > (CH3)2CHCH2Br > CH3CH2CH(Br)CH3 > (CH3)3CBr (SN2)
Of the two primary bromides, the carbocation intermediate derived from
(CH3)2CHCH2Br is more stable than derived from CH3CH2CH2CH2Br because
of greater electron donating inductive effect of (CH3)2CH- group. Therefore,
(CH3)2CHCH2Br is more reactive than CH3CH2CH2CH2Br in SN1 reactions.
CH3CH2CH(Br)CH3 is a secondary bromide and (CH3)3CBr is a tertiary
bromide. Hence the above order is followed in SN1. The reactivity in SN2
reactions follows the reverse order as the steric hinderance around the
electrophilic carbon increases in that order.
(ii) C6H5C(CH3)(C6H5)Br > C6H5CH(C6H5)Br > C6H5CH(CH3)Br > C6H5CH2Br (SN1)
C6H5C(CH3)(C6H5)Br < C6H5CH(C6H5)Br < C6H5CH(CH3)Br < C6H5CH2Br (SN2)
Of the two secondary bromides, the carbocation intermediate obtained
from C6H5CH(C6H5)Br is more stable than obtained from C6H5CH(CH3)Br
because it is stabilised by two phenyl groups due to resonance. Therefore,
the former bromide is more reactive than the latter in SN1 reactions. A
phenyl group is bulkier than a methyl group. Therefore, C6H5CH(C6H5)Br
is less reactive than C6H5CH(CH3)Br in SN2 reactions.

(c) Stereochemical aspects of nucleophilic substitution reactions

A SN2 reaction proceeds with complete stereochemical inversion while
a SN1 reaction proceeds with racemisation.
In order to understand this concept, we need to learn some basic
stereochemical principles and notations (optical activity, chirality,
retention, inversion, racemisation, etc.).
(i) Plane polarised light and optical activity: Certain compounds
rotate the plane polarised light (produced by passing ordinary
William Nicol (1768- light through Nicol prism) when it is passed through their
1851) developed the first
solutions. Such compounds are called optically active
prism that produced
plane polarised light.
compounds. The angle by which the plane polarised light is
rotated is measured by an instrument called polarimeter. If the
compound rotates the plane polarised light to the right, i.e.,
clockwise direction, it is called dextrorotatory (Greek for right
rotating) or the d-form and is indicated by placing a positive (+)
sign before the degree of rotation. If the light is rotated towards
left (anticlockwise direction), the compound is said to be laevo-
rotatory or the l-form and a negative () sign is placed before
the degree of rotation. Such (+) and () isomers of a compound
are called optical isomers and the phenomenon is termed as
optical isomerism.
(ii) Molecular asymmetry, chirality and enantiomers: The
observation of Louis Pasteur (1848) that crystals of certain
compounds exist in the form of mirror images laid the
foundation of modern stereochemistry. He demonstrated that
aqueous solutions of both types of crystals showed optical
rotation, equal in magnitude (for solution of equal concentration)
but opposite in direction. He believed that this difference in
Chemistry 296
 optical activity was associated with the three dimensional
arrangements of atoms (configurations) in two types of crystals.
Jacobus Hendricus
Dutch scientist, J. Vant Hoff and French scientist, C. Le Bel in
Vant Hoff (1852-1911) the same year (1874), independently argued that the spatial
received the first Nobel arrangement of four groups (valencies) around a central carbon
Prize in Chemistry in is tetrahedral and if all the substituents attached to that carbon
1901 for his work on are different, such a carbon is called asymmetric carbon or
solutions. stereocentre. The resulting molecule would lack symmetry and
is referred to as asymmetric molecule. The asymmetry of the
molecule is responsible for the optical activity in such organic
compounds.
The symmetry and asymmetry are also observed in many day to day
objects: a sphere, a cube, a cone, are all identical to their mirror images
and can be superimposed. However, many
objects are non superimposable on their
mirror images. For example, your left and
right hand look similar but if you put your
left hand on your right hand, they do not
coincide. The objects which are non-
superimposable on their mirror image (like
a pair of hands) are said to be chiral and
this property is known as chirality. While
the objects, which are, superimposable on
their mirror images are called achiral.
The above test of molecular chirality
can be applied to organic molecules by
constructing models and its mirror images
or by drawing three dimensional structures
and attempting to superimpose them in our
minds. There are other aids, however, that
can assist us in recognising chiral molecules.
One such aid is the presence of a single
asymmetric carbon atom. Let us consider
Fig 10.4: Some common examples of chiral and two simple molecules propan-2-ol and
achiral objects butan-2-ol and their mirror images.

As you can see very clearly, propan-2-ol does not contain an

asymmetric carbon, as all the four groups attached to the tetrahedral
carbon are not different. Thus it is an achiral molecule.

297 Haloalkanes and Haloarenes

 Butan-2-ol has four different groups attached to
the tetrahedral carbon and as expected is chiral. Some
common examples of chiral molecules such as
2-chlorobutane, 2, 3-dihyroxypropanal, (OHCCHOHCH2OH),
bromochloro-iodomethane (BrClCHI), 2-bromopropanoic
acid (H3CCHBrCOOH), etc.
Fig. 10.5: A chiral molecule The stereoisomers related to each other as non-
and its mirror image superimposable mirror images are called enantiomers
(Fig. 10.5).
Enantiomers possess identical physical properties namely, melting
point, boiling point, refractive index, etc. They only differ with respect
to the rotation of plane polarised light. If one of the enantiomer is
dextro rotatory, the other will be laevo rotatory.

However, the sign of optical rotation is not necessarily related to

the absolute configuration of the molecule.

A mixture containing two enantiomers in equal proportions will

have zero optical rotation, as the rotation due to one isomer will be
cancelled by the rotation due to the other isomer. Such a mixture is
known as racemic mixture or racemic modification. A racemic mixture
is represented by prefixing dl or () before the name, for example
() butan-2-ol. The process of conversion of enantiomer into a racemic
mixture is known as racemisation.

Example 10.8 Identify chiral and achiral molecules in each of the following pair of
compounds. (Wedge and Dash representations according to Class XI,
Fig 12.1).

Chemistry 298
 Solution

(iii) Retention: Retention of configuration is the preservation of integrity

of the spatial arrangement of bonds to an asymmetric centre during
a chemical reaction or transformation. It is also the configurational
correlation when a chemical species XCabc is converted into the
chemical species YCabc having the same relative configuration.

In general, if during a reaction, no bond to the stereocentre is broken,

the product will have the same general configuration of groups
around the stereocentre as that of reactant. Such a reaction is said
to proceed with retention of the configuration. Consider as an
example, the reaction that takes place when ()-2-methylbutan-1-ol
is heated with concentrated hydrochloric acid.

(iv) Inversion, retention and racemisation: There are three outcomes

for a reaction at an asymmetric carbon atom. Consider the
replacement of a group X by Y in the following reaction;

If (A) is the only compound obtained, the process is called retention

of configuration.
If (B) is the only compound obtained, the process is called inversion
of configuration.
If a 50:50 mixture of the above two is obtained then the process is
called racemisation and the product is optically inactive, as one
isomer will rotate light in the direction opposite to another.
299 Haloalkanes and Haloarenes
 Now let us have a fresh look at SN1 and SN2 mechanisms by
taking examples of optically active alkyl halides.
In case of optically active alkyl halides, the product formed as a
result of SN2 mechanism has the inverted configuration as compared
to the reactant. This is because the nucleophile attaches itself on the
side opposite to the one where the halogen atom is present. When
()-2-bromooctane is allowed to react with sodium hydroxide,
(+)-octan-2-ol is formed with the OH group occupying the position
opposite to what bromide had occupied.

Thus, SN2 reactions of optically active halides are accompanied by

inversion of configuration.
In case of optically active alkyl halides, S N1 reactions are
accompanied by racemisation. Can you think of the reason why it
2
happens? Actually the carbocation formed in the slow step being sp
hybridised is planar (achiral). The attack of the nucleophile may be
accomplished from either side resulting in a mixture of products, one
having the same configuration (the OH attaching on the same position
as halide ion) and the other having opposite configuration (the OH
attaching on the side opposite to halide ion). This may be illustrated
by hydrolysis of optically active 2-bromobutane, which results in the
formation of ()-butan-2-ol.

2. Elimination reactions
When a haloalkane with -hydrogen atom is heated with alcoholic
solution of potassium hydroxide, there is elimination of hydrogen
atom from -carbon and a halogen atom from the -carbon atom.
As a result, an alkene is formed as a product. Since -hydrogen
atom is involved in elimination, it is often called -elimination.

Chemistry 300
 If there is possibility of formation of more than one alkene due to
the availability of more than one -hydrogen atoms, usually one alkene
is formed as the major product. These form part of a pattern first
observed by Russian chemist, Alexander Zaitsev (also pronounced as
Saytzeff) who in 1875 formulated a rule which can be summarised as
in dehydrohalogenation reactions, the preferred product is that
alkene which has the greater number of alkyl groups attached to the
doubly bonded carbon atoms. Thus, 2-bromopentane gives
pent-2-ene as the major product.

Elimination versus substitution

A chemical reaction is the result of competition; it is a race that is won by the fastest
runner. A collection of molecules tend to do, by and large, what is easiest for them. An
alkyl halide with -hydrogen atoms when reacted with a base or a nucleophile has two
competing routes: substitution (SN1 and SN2) and elimination. Which route will be taken
up depends upon the nature of alkyl halide, strength and size of base/nucleophile and
reaction conditions. Thus, a bulkier nucleophile will prefer to act as a base and abstracts
a proton rather than approach a tetravalent carbon atom (steric reasons) and vice versa.
Similarly, a primary alkyl halide will prefer a SN2 reaction, a secondary halide- SN2 or
elimination depending upon the strength of base/nucleophile and a tertiary halide- SN1 or
elimination depending upon the stability of carbocation or the more substituted alkene.

3. Reaction with metals

Most organic chlorides, bromides and iodides react with certain
metals to give compounds containing carbon-metal bonds. Such
compounds are known as organo-metallic compounds. An
important class of organo-metallic compounds discovered by Victor
Grignard in 1900 is alkyl magnesium halide, RMgX, referred as
Grignard Reagents. These reagents are obtained by the reaction of
haloalkanes with magnesium metal in dry ether.

301 Haloalkanes and Haloarenes

 Victor Grignard had a strange start in academic life for a chemist - he
took a maths degree. When he eventually switched to chemistry, it was
not to the mathematical province of physical chemistry but to organic
chemistry. While attempting to find an efficient catalyst for the process
of methylation, he noted that Zn in diethyl ether had been used for this
purpose and wondered whether the Mg/ether combination might be
successful. Grignard reagents were first reported in 1900 and Grignard
used this work for his doctoral thesis in 1901. In 1910, Grignard obtained
a professorship at the University of Nancy and in 1912, he was awarded
the Nobel prize for Chemistry which he shared with Paul Sabatier who
had made advances in nickel catalysed hydrogenation.

In the Grignard reagent, the carbon-magnesium bond is covalent but

highly polar, with carbon pulling electrons from electropositive
magnesium; the magnesium halogen bond is essentially ionic.

Grignard reagents are highly reactive and react with any source of
proton to give hydrocarbons. Even water, alcohols, amines are sufficiently
acidic to convert them to corresponding hydrocarbons.

It is therefore necessary to avoid even traces of moisture from a Grignard

reagent. On the other hand, this could be considered as one of the
methods for converting halides to hydrocarbons.
Wurtz reaction
Alkyl halides react with sodium in dry ether to give hydrocarbons
containing double the number of carbon atoms present in the halide.
This reaction is known as Wurtz reaction. (Unit 13, Class XI).

10.6.2 Reactions of 1. Nucleophilic substitution

Haloarenes Aryl halides are extremely less reactive towards nucleophilic
substitution reactions due to the following reasons:
(i) Resonance effect : In haloarenes, the electron pairs on halogen
atom are in conjugation with -electrons of the ring and the
following resonating structures are possible.

CCl bond acquires a partial double bond character due to

resonance. As a result, the bond cleavage in haloarene is difficult
than haloalkane and therefore, they are less reactive towards
nucleophilic substitution reaction.

Chemistry 302
 (ii) Difference in hybridisation of carbon atom in CX bond: In
haloalkane, the carbon atom attached to halogen is sp3
hybridised while in case of haloarene, the carbon atom attached
to halogen is sp2-hybridised.

The sp2 hybridised carbon with a greater s-character is more

electronegative and can hold the electron pair of CX bond
more tightly than sp3-hybridised carbon in haloalkane with
less s-chararcter. Thus, CCl bond length in haloalkane is
177pm while in haloarene is 169 pm. Since it is difficult to
break a shorter bond than a longer bond, therefore, haloarenes
are less reactive than haloalkanes towards nucleophilic
substitution reaction.
(iii) Instability of phenyl cation: In case of haloarenes, the phenyl
cation formed as a result of self-ionisation will not be stabilised
by resonance and therefore, SN1 mechanism is ruled out.
(iv) Because of the possible repulsion, it is less likely for the electron
rich nucleophile to approach electron rich arenes.
Replacement by hydroxyl group
Chlorobenzene can be converted into phenol by heating in aqueous
sodium hydroxide solution at a temperature of 623K and a pressure
of 300 atmospheres.

The presence of an electron withdrawing group (-NO2) at ortho- and

para-positions increases the reactivity of haloarenes.

303 Haloalkanes and Haloarenes

 The effect is pronounced when (-NO2) group is introduced at ortho-
and para- positions. However, no effect on reactivity of haloarenes is
observed by the presence of electron withdrawing group at meta-position.
Mechanism of the reaction is as depicted:

Can you think why does NO2 group show its effect only at ortho- and para- positions
and not at meta- position?
As shown, the presence of nitro group at ortho- and para-positions withdraws the
electron density from the benzene ring and thus facilitates the attack of the nucleophile
on haloarene. The carbanion thus formed is stabilised through resonance. The negative
charge appeared at ortho- and para- positions with respect to the halogen substituent is
stabilised by NO2 group while in case of meta-nitrobenzene, none of the resonating
structures bear the negative charge on carbon atom bearing the NO2 group. Therefore,
the presence of nitro group at meta- position does not stabilise the negative charge and
no effect on reactivity is observed by the presence of NO2 group at meta-position.

Chemistry 304
2. Electrophilic substitution reactions
Haloarenes undergo the usual electrophilic reactions of the benzene
ring such as halogenation, nitration, sulphonation and Friedel-Crafts
reactions. Halogen atom besides being slightly deactivating is o, p-
directing; therefore, further substitution occurs at ortho- and para-
positions with respect to the halogen atom. The o, p-directing influence
of halogen atom can be easily understood if we consider the resonating
structures of halobenzene as shown:

Due to resonance, the electron density increases more at ortho- and

para-positions than at meta-positions. Further, the halogen atom
because of its I effect has some tendency to withdraw electrons from
the benzene ring. As a result, the ring gets somewhat deactivated as
compared to benzene and hence the electrophilic substitution reactions
in haloarenes occur slowly and require more drastic conditions as
compared to those in benzene.
(i) Halogenation

(ii) Nitration

(iii) Sulphonation

305 Haloalkanes and Haloarenes

 (iv) Friedel-Crafts reaction

Example 10.9 Although chlorine is an electron withdrawing group, yet it is ortho-,

para- directing in electrophilic aromatic substitution reactions. Why?
Solution Chlorine withdraws electrons through inductive effect and releases
electrons through resonance. Through inductive effect, chlorine
destabilises the intermediate carbocation formed during the electrophilic
substitution.

Through resonance, halogen tends to stabilise the carbocation and

the effect is more pronounced at ortho- and para- positions. The
inductive effect is stronger than resonance and causes net electron
withdrawal and thus causes net deactivation. The resonance effect
tends to oppose the inductive effect for the attack at ortho- and para-
positions and hence makes the deactivation less for ortho- and para-
attack. Reactivity is thus controlled by the stronger inductive effect
and orientation is controlled by resonance effect.

Chemistry 306
 3. Reaction with metals
Wurtz-Fittig reaction
A mixture of an alkyl halide and aryl halide gives an alkylarene when
treated with sodium in dry ether and is called Wurtz-Fittig reaction.

Fittig reaction
Aryl halides also give analogous compounds when treated with sodium
in dry ether, in which two aryl groups are joined together. It is called
Fittig reaction.

Intext Questions
10.7 Which alkyl halide from the following pairs would you expect to react more
rapidly by an SN2 mechanism? Explain your answer.

10.8 In the following pairs of halogen compounds, which compound undergoes faster
SN1 reaction?

1
10.9 Identify A, B, C, D, E, R and R in the following:

307 Haloalkanes and Haloarenes

10.7 Polyhalogen Carbon compounds containing more than one halogen atom are usually
referred to as polyhalogen compounds. Many of these compounds are
Compounds useful in industry and agriculture. Some polyhalogen compounds are
described in this section.
10.7.1 Dichloro- Dichloromethane is widely used as a solvent as a paint remover, as a
methane propellant in aerosols, and as a process solvent in the manufacture of
(Methylene drugs. It is also used as a metal cleaning and finishing solvent.
chloride) Methylene chloride harms the human central nervous system. Exposure
to lower levels of methylene chloride in air can lead to slightly impaired
hearing and vision. Higher levels of methylene chloride in air cause
dizziness, nausea, tingling and numbness in the fingers and toes. In
humans, direct skin contact with methylene chloride causes intense
burning and mild redness of the skin. Direct contact with the eyes can
burn the cornea.
10.7.2 Trichloro- Chemically, chloroform is employed as a solvent for fats, alkaloids,
methane iodine and other substances. The major use of chloroform today is in
(Chloroform) the production of the freon refrigerant R-22. It was once used as a
general anaesthetic in surgery but has been replaced by less toxic,
safer anaesthetics, such as ether. As might be expected from its use as
an anaesthetic, inhaling chloroform vapours depresses the central
nervous system. Breathing about 900 parts of chloroform per million
parts of air (900 parts per million) for a short time can cause dizziness,
fatigue, and headache. Chronic chloroform exposure may cause damage
to the liver (where chloroform is metabolised to phosgene) and to the
kidneys, and some people develop sores when the skin is immersed in
chloroform. Chloroform is slowly oxidised by air in the presence of
light to an extremely poisonous gas, carbonyl chloride, also known as
phosgene. It is therefore stored in closed dark coloured bottles
completely filled so that air is kept out.

10.7.3 Triiodo- It was used earlier as an antiseptic but the antiseptic properties are
methane due to the liberation of free iodine and not due to iodoform itself. Due
(Iodoform) to its objectionable smell, it has been replaced by other formulations
containing iodine.

10.7.4 Tetrachlo- It is produced in large quantities for use in the manufacture of

romethane refrigerants and propellants for aerosol cans. It is also used as
(Carbon feedstock in the synthesis of chlorofluorocarbons and other chemicals,
tetrachloride) pharmaceutical manufacturing, and general solvent use. Until the mid
1960s, it was also widely used as a cleaning fluid, both in industry,
as a degreasing agent, and in the home, as a spot remover and as fire
extinguisher. There is some evidence that exposure to carbon
tetrachloride causes liver cancer in humans. The most common effects
are dizziness, light headedness, nausea and vomiting, which can cause

Chemistry 308
 permanent damage to nerve cells. In severe cases, these effects can lead
rapidly to stupor, coma, unconsciousness or death. Exposure to CCl4
can make the heart beat irregularly or stop. The chemical may irritate
the eyes on contact. When carbon tetrachloride is released into the air,
it rises to the atmosphere and depletes the ozone layer. Depletion of the
ozone layer is believed to increase human exposure to ultraviolet rays,
leading to increased skin cancer, eye diseases and disorders, and
possible disruption of the immune system.
10.7.5 Freons The chlorofluorocarbon compounds of methane and ethane are
collectively known as freons. They are extremely stable, unreactive,
non-toxic, non-corrosive and easily liquefiable gases. Freon 12 (CCl2F2)
is one of the most common freons in industrial use. It is manufactured
from tetrachloromethane by Swarts reaction. These are usually produced
for aerosol propellants, refrigeration and air conditioning purposes. By
1974, total freon production in the world was about 2 billion pounds
annually. Most freon, even that used in refrigeration, eventually makes
its way into the atmosphere where it diffuses unchanged into the
stratosphere. In stratosphere, freon is able to initiate radical chain
reactions that can upset the natural ozone balance (Unit 14, Class XI).
10.7.6 p,p-Dichlo- DDT, the first chlorinated organic insecticides, was originally prepared
rodiphenyl- in 1873, but it was not until 1939 that Paul Muller of Geigy
trichloro- Pharmaceuticals in Switzerland discovered the effectiveness of DDT as
ethane(DDT) an insecticide. Paul Muller was awarded the Nobel Prize in Medicine
and Physiology in 1948 for this discovery. The use of DDT increased
enormously on a worldwide basis after World War II, primarily because
of its effectiveness against the mosquito that spreads malaria and lice
that carry typhus. However, problems related to extensive use of DDT
began to appear in the late 1940s. Many species of insects developed
resistance to DDT, and it was also discovered to have a high toxicity
towards fish. The chemical stability of DDT and its fat solubility
compounded the problem. DDT is not metabolised very rapidly by
animals; instead, it is deposited and stored in the fatty tissues. If
ingestion continues at a steady rate, DDT builds up within the animal
over time. The use of DDT was banned in the United States in 1973,
although it is still in use in some other parts of the world.

309 Haloalkanes and Haloarenes

 Summary
Alkyl/ Aryl halides may be classified as mono, di, or polyhalogen (tri-, tetra-, etc.)
compounds depending on whether they contain one, two or more halogen atoms in
their structures. Since halogen atoms are more electronegative than carbon, the carbon-
halogen bond of alkyl halide is polarised; the carbon atom bears a partial positive
charge, and the halogen atom bears a partial negative charge.
Alkyl halides are prepared by the free radical halogenation of alkanes, addition
of halogen acids to alkenes, replacement of OH group of alcohols with halogens using
phosphorus halides, thionyl chloride or halogen acids. Aryl halides are prepared by
electrophilic substitution to arenes. Fluorides and iodides are best prepared by halogen
exchange method.
The boiling points of organohalogen compounds are comparatively higher than the
corresponding hydrocarbons because of strong dipole-dipole and van der Waals forces
of attraction. These are slightly soluble in water but completely soluble in organic
solvents.
The polarity of carbon-halogen bond of alkyl halides is responsible for their
nucleophilic substitution, elimination and their reaction with metal atoms to form
organometallic compounds. Nucleophilic substitution reactions are categorised into
SN1 and SN2 on the basis of their kinetic properties. Chirality has a profound role in
understanding the reaction mechanisms of SN1 and SN2 reactions. SN2 reactions of
chiral alkyl halides are characterised by the inversion of configuration while SN1 reactions
are characterised by racemisation.
A number of polyhalogen compounds e.g., dichloromethane, chloroform, iodoform,
carbon tetrachloride, freon and DDT have many industrial applications. However,
some of these compounds cannot be easily decomposed and even cause depletion of
ozone layer and are proving environmental hazards.

Exercises
10.1 Name the following halides according to IUPAC system and classify them as
alkyl, allyl, benzyl (primary, secondary, tertiary), vinyl or aryl halides:
(i) (CH3)2CHCH(Cl)CH3 (ii) CH3CH2CH(CH3)CH(C2H5)Cl
(iii) CH3CH2C(CH3)2CH2I (iv) (CH3)3CCH2CH(Br)C6H5
(v) CH3CH(CH3)CH(Br)CH3 (vi) CH3C(C2H5)2CH2Br
(vii) CH3C(Cl)(C2H5)CH2CH3 (viii) CH3CH=C(Cl)CH2CH(CH3)2
(ix) CH3CH=CHC(Br)(CH3)2 (x) p-ClC6H4CH2CH(CH3)2
(xi) m-ClCH2C6H4CH2C(CH3)3 (xii) o-Br-C6H4CH(CH3)CH2CH3
10.2 Give the IUPAC names of the following compounds:
(i) CH3CH(Cl)CH(Br)CH3 (ii) CHF2CBrClF (iii) ClCH2CCCH2Br
(iv) (CCl3)3CCl (v) CH3C(p-ClC6H4)2CH(Br)CH3 (vi) (CH3)3CCH=CClC6H4I-p
10.3 Write the structures of the following organic halogen compounds.
(i) 2-Chloro-3-methylpentane (ii) p-Bromochlorobenzene
(iii) 1-Chloro-4-ethylcyclohexane (iv) 2-(2-Chlorophenyl)-1-iodooctane
(v) 2-Bromobutane (vi) 4-tert-Butyl-3-iodoheptane
(vii) 1-Bromo-4-sec-butyl-2-methylbenzene (viii) 1,4-Dibromobut-2-ene

Chemistry 310
 10.4 Which one of the following has the highest dipole moment?
(i) CH 2Cl 2 (ii) CHCl3 (iii) CCl4
10.5 A hydrocarbon C5H10 does not react with chlorine in dark but gives a single
monochloro compound C5H9Cl in bright sunlight. Identify the hydrocarbon.
10.6 Write the isomers of the compound having formula C4H9Br.
10.7 Write the equations for the preparation of 1-iodobutane from
(i) 1-butanol (ii) 1-chlorobutane (iii) but-1-ene.
10.8 What are ambident nucleophiles? Explain with an example.
10.9 Which compound in each of the following pairs will react faster in SN2 reaction
with OH?
(i) CH3Br or CH3I (ii) (CH3)3CCl or CH3Cl
10.10 Predict all the alkenes that would be formed by dehydrohalogenation of the
following halides with sodium ethoxide in ethanol and identify the major alkene:
(i) 1-Bromo-1-methylcyclohexane (ii) 2-Chloro-2-methylbutane
(iii) 2,2,3-Trimethyl-3-bromopentane.
10.11 How will you bring about the following conversions?
(i) Ethanol to but-1-yne (ii) Ethane to bromoethene (iii) Propene to
1-nitropropane (iv) Toluene to benzyl alcohol (v) Propene to propyne
(vi) Ethanol to ethyl fluoride (vii) Bromomethane to propanone (viii) But-1-ene
to but-2-ene (ix) 1-Chlorobutane to n-octane (x) Benzene to biphenyl.
10.12 Explain why
(i) the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
(ii) alkyl halides, though polar, are immiscible with water?
(iii) Grignard reagents should be prepared under anhydrous conditions?
10.13 Give the uses of freon 12, DDT, carbon tetrachloride and iodoform.
10.14 Write the structure of the major organic product in each of the following reactions:

(i) CH3CH2CH2Cl + NaI

(ii) (CH3)3CBr + KOH

(iii) CH3CH(Br)CH2CH3 + NaOH

(iv) CH3CH2Br + KCN

(v) C6H5ONa + C2H5Cl
(vi) CH3CH2CH2OH + SOCl2

(vii) CH3CH2CH = CH2 + HBr

(viii) CH3CH = C(CH3)2 + HBr
10.15 Write the mechanism of the following reaction:
nBuBr + KCN nBuCN
10.16 Arrange the compounds of each set in order of reactivity towards SN2
displacement:
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 2-Bromo-3-methylbutane

311 Haloalkanes and Haloarenes

 (iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methylbutane,
1-Bromo-3-methylbutane.
10.17 Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous
KOH.
10.18 p-Dichlorobenzene has higher m.p. than those of o- and m-isomers. Discuss.
10.19 How the following conversions can be carried out?
(i) Propene to propan-1-ol
(ii) Ethanol to but-1-yne
(iii) 1-Bromopropane to 2-bromopropane
(iv) Toluene to benzyl alcohol
(v) Benzene to 4-bromonitrobenzene
(vi) Benzyl alcohol to 2-phenylethanoic acid
(vii) Ethanol to propanenitrile
(viii) Aniline to chlorobenzene
(ix) 2-Chlorobutane to 3, 4-dimethylhexane
(x) 2-Methyl-1-propene to 2-chloro-2-methylpropane
(xi) Ethyl chloride to propanoic acid
(xii) But-1-ene to n-butyliodide
(xiii) 2-Chloropropane to 1-propanol
(xiv) Isopropyl alcohol to iodoform
(xv) Chlorobenzene to p-nitrophenol
(xvi) 2-Bromopropane to 1-bromopropane
(xvii) Chloroethane to butane
(xviii) Benzene to diphenyl
(xix) tert-Butyl bromide to isobutyl bromide
(xx) Aniline to phenylisocyanide
10.20 The treatment of alkyl chlorides with aqueous KOH leads to the formation of
alcohols but in the presence of alcoholic KOH, alkenes are major products. Explain.
10.21 Primary alkyl halide C4H9Br (a) reacted with alcoholic KOH to give compound (b).
Compound (b) is reacted with HBr to give (c) which is an isomer of (a). When
(a) is reacted with sodium metal it gives compound (d), C8H 18 which is different
from the compound formed when n-butyl bromide is reacted with sodium.
Give the structural formula of (a) and write the equations for all the reactions.
10.22 What happens when
(i) n-butyl chloride is treated with alcoholic KOH,
(ii) bromobenzene is treated with Mg in the presence of dry ether,
(iii) chlorobenzene is subjected to hydrolysis,
(iv) ethyl chloride is treated with aqueous KOH,
(v) methyl bromide is treated with sodium in the presence of dry ether,
(vi) methyl chloride is treated with KCN?

Chemistry 312
 Answers to Some Intext Questions

10.1

10.2 (i) H2SO4 cannot be used along with KI in the conversion of an alcohol to
an alkyl iodide as it converts KI to corresponding acid, HI which is then
oxidised by it to I2.
10.3 (i) ClCH2CH2CH2Cl (ii) ClCH2CHClCH3 (iii) Cl2CHCH2CH3 (iv) CH3CCl2CH3

10.4 All the hydrogen atoms are equivalent and replacement

of any hydrogen will give the same product.

The equivalent hydrogens are grouped as a, b and

c. The replacement of equivalent hydrogens will
give the same product.

Similarly the equivalent hydrogens are grouped as

a, b, c and d. Thus, four isomeric products are
possible.

10.5

10.6 (i) Chloromethane, Bromomethane, Dibromomethane, Bromoform. Boiling

point increases with increase in molecular mass.
(ii) Isopropylchloride, 1-Chloropropane, 1-Chlorobutane. Isopropylchloride
being branched has lower b.p. than 1-Chloropropane.
10.7 (i) CH3CH2CH2CH2Br Being primary halide, there wont be any steric
hindrance.
(ii) Secondary halide reacts faster than tertiary halide.

(iii) The presence of methyl group closer to the halide

group will increase the steric hindrance and
decrease the rate.

313 Haloalkanes and Haloarenes

 10.8 (i) Tertiary halide reacts faster than secondary halide
because of the greater stability of tert-carbocation.

(ii) Because of greater stability of secondary carbocation

than primary.

10.9

Chemistry 314