Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR

Grade XII
Haloalkanes and Haloarenes
Haloalkanes are aliphatic hydrocarbons where a hydrogen atom is replaced by halogen, while haloarenes are aromatic
hydrocarbons where hydrogen in the benzene ring is replaced with halogen atom. Halogen atom is attached to sp3
hybridised carbon atom in haloalkanes while in haloarenes it is attached to sp2 hybridised carbon atom of the aryl group.

Nature of Bond
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Alkyl Group
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COMMON AND IUPAC NAME OF SOME HALOALKANES AND ITS CLASSIFICATION:-
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Classification of Haloalkanes and haloarenes and IUPAC Naming

These may be classified as mono, di or polyhalogen compounds
On the Basis of Number of Halogen Atoms depending on whether they contain one, two or more halogen atoms
in their structures. For example,
Monohaloalkane Dihaloalkane Trihaloalkane
 Grade XII / IUPAC Naming/HIMANSHU SIR
Compounds Containing sp3 C—X Bond (X= F, Cl, Br, I)
(a) Alkyl halides or haloalkanes (R—X) In alkyl halides, the halogen atom is bonded to an alkyl group (R). 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
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(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 sp3-
hybridised carbon atom next to an aromatic ring.
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Compounds Containing sp2 C—X Bond

(a) Vinylic halides 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
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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
 Grade XII / IUPAC Naming/HIMANSHU SIR
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
Grade XII / IUPAC Naming/HIMANSHU SIR
 Grade XII / IUPAC Naming/HIMANSHU SIR
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.

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Ex 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
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(v) CH3CH(CH3)CH(Br)CH3

(vi) CH3C(C2H5)2CH2Br

(vii) CH3C(Cl)(C2H5)CH2CH3

viii) CH3CH=C(Cl)CH2CH(CH3)2
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(ix) CH3CH=CHC(Br)(CH3)2

(x) p-ClC6H4CH2CH(CH3)2

(xi) m-ClCH2C6H4CH2C(CH3)3

(xii) o-Br-C6H4CH(CH3)CH2CH3
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Ex 10.2
Give the IUPAC names of the following compounds:

(i) CH3CH(Cl)CH(Br)CH3

(ii) CHF2CBrClF

(iii) ClCH2C≡CCH2Br
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(iv) (CCl3)3CCl

(v) CH3C(p-ClC6H4)2CH(Br)CH3

(vi) (CH3)3CCH=C(Cl)C6H4I-p
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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
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(v) 4-tert-Butyl-3-iodoheptane

(vi) 1-Bromo-4-sec-butyl-2-methylbenzene

(vii) 1,4-Dibromobut-2-ene
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Methods of Preparation
1. From Alcohols- Alkyl halides are best prepared from alcohols, 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 HX require the presence of a catalyst, ZnCl2. With tertiary
alcohols, the reaction is conducted by simply shaking with concentrated HCl at room temperature

The order of reactivity of alcohols with a given haloacid is 3°>2°>1°.

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The above method is 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
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2. From Hydrocarbons
(a) By free radical halogenation Free radical chlorination or bromination of alkanes gives a complex mixture of
isomeric mono- and polyhaloalkanes, which is difficult to separate as pure compounds

Eg: 10.3- Identify all the possible monochloro structural isomers expected to be formed on free radical monochlorination of
(CH3)2CHCH2CH3.
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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.
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(b) By electrophilic substitution

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.
(c) Sandmeyer’s reaction
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(d) From alkenes

(i) Addition of hydrogen halides:

(ii) Addition of halogens:

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Finkelstein reaction.
Alkyl iodides are often prepared by the reaction of alkyl chlorides/ 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 Chatelier’s Principle.

Swarts reaction- 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.
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Eg- 10.4 Write the products of the following reactions

Intext 10.5- Draw the structures of major monohalo products in each of the following reactions
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Physical Properties
Melting and boiling points

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.
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Ex. 10.18 p-Dichlorobenzene has higher m.p. and solubility than those of o- and m-isomers. Discuss.

Boiling points of isomeric dihalobenzenes are

very nearly the same. However, the para-
isomers are high melting as compared to their
orthoand meta-isomers. It is due to
symmetry of para-isomers that fits in
crystal lattice better as compared to
ortho- and meta-isomers
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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
Intext -10.6 Arrange each set of compounds in order of increasing B Pt.
(i) Bromomethane, Bromoform, Chloromethane, Dibromomethane.

(ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.

Solubility Ex 10.12- (ii) alkyl halides, though polar, are immiscible with water?
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.
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Chemical Reactions of Haloalkanes
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 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.
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Ambident nucleophiles
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
[-C≡N :C=N-], 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

Q. Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms isocyanides as the chief product.
Explain. KCN is predominantly ionic and provides cyanide ions in 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 C—C bond is more stable than C—N bond. However, AgCN is mainly covalent in nature
and nitrogen is free to donate electron pair forming isocyanide as the main product.
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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

This can be represented

diagrammatically as
shown in
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It depicts a bimolecular nucleophilic displacement (SN2) reaction; the incoming nucleophile interacts with alkyl halide
causing the carbonhalide bond to break while forming a new carbon-OH bond. These two processes take place
simultaneously in a single step and no intermediate is formed. As the reaction progresses and the bond between the
nucleophile and the carbon atom starts forming, the bond between carbon atom and leaving group weakens. As this
happens, the 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.
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Of the simple alkyl halides, methyl halides react
most rapidly in SN2 reactions 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

(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
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
It occurs in two steps. In step I, the polarised C—Br 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.

Step I is the slowest and reversible. It involves the C–Br 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 very fast because of the high stability of 30 carbocations
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR

For a given alkyl group, the reactivity of the halide, R-X, follows the same order in both the mechanisms
R–I > R–Br > R–Cl >> R–F.
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Q- allylic and benzylic halides undergo nucleophilic reaction using SN1 reaction mechanism. Give reason?
Ans: Allyl and benzyl carbocations are stable due to resonance, because of the high stability of allyl and benzyl
carbocation, allylic and benzylic halides show high reactivity towards the SN1 reaction.
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Eg-10.7 Q- Predict the order of reactivity of the following compounds in S N1 and SN2 reactions:
(i) The four isomeric bromobutanes
(ii) C6H5CH2Br, C6H5CH(C6H5)Br, C6H5CH(CH3)Br, C6H5C(CH3)(C6H5)Br
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10.17 Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous KOH.

In Polar protic Solvent like water , the reaction follows SN1 mechanism, In SN1 mechanism the reactivity depends upon
the stability of the carbocations formed which is a reaction intermediate. The greater the stability of the carbocations ,
more easily it will be formed and faster will be th reaction. The stability decreases in the order Tert Carbocation > Sec
Carbocation > Primary Carbocation > CH3+. Further benzene ring also gives stability. The more the benzene ring ,
the more will the +ve charge get delocalized. From the above discussion it is clear that in SN1 reaction the positive
charge is delocalized over two C6H5 rings in C6H5CHClC6H5 is more stable than the carbocation formed by C6H5CH2Cl
since the +ve charge is delocalized over only one C6H5 rings. Therefore in SN1 reaction C6H5CHClC6H5 is more easiliy
hydrolysed.

In SN2 the reactivity depends on steric hinderance also. C6H5CHClC6H5 is more bulkier than C6H5CH2Cl .Therefore in SN2
reaction C6H5CH2Cl will get more easiliy hydrolysed.
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Ex- 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

(iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methylbutane, 1-Bromo-3-methylbutane.

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

Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Stereochemical aspects of nucleophilic substitution reactions
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 light through Nicol prism) when it is
passed through their solutions. Such compounds are called optically active 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 laevorotatory 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: Louis Pasteur (1848) demonstrated that aqueous solutions of both
types of crystals of certain compounds showed optical rotation, equal in magnitude (for solution of equal concentration)
but opposite in direction. He believed that this difference in optical activity was associated with the three dimensional
arrangements of atoms (configurations) in two types of crystals. Dutch scientist, J. Van’t Hoff and French scientist, C. Le
Bel in the same year (1874), independently argued that the spatial arrangement of four groups (valencies) around a
central carbon is tetrahedral and if all the substituents attached to that carbon are different, such a carbon is called
asymmetric carbon or 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.
Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
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The objects which are nonsuperimposable 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 stereoisomers related to each
other as nonsuperimposable mirror images are called enantiomers .

Enantiomers possess identical physical properties namely, melting point, boiling point, solubility, 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

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.
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(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

(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
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Now let us have a fresh look at SN1 and SN2 mechanisms by taking examples of optically active alkyl halides.

STEREOCHEMISTRY in SN2 rections

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STEREOCHEMISTRY in SN1 rections
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
An optically active compound having molecular formula C7H15Br react with aqueous KOH to give a racemic
mixture of products. Write the mechanism in this reaction.
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Elimination reactions When a haloalkane with β-hydrogen atom is heated with alcoholic solution of potassium
hydroxide, there is elimination of hydrogen atom from β-carbon and a halogen atom from the
α-carbon atom. As a result, an alkene is formed as a product. Since β-hydrogen atom is
involved in elimination, it is often called β -elimination.

If there is possibility of formation of more than one alkene due to the availability of more than one α-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)
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Saytzeff rule
“in dehydrohalogenation reactions, the preferred product is that alkene which has the greater number of alkyl
groups attached to the doubly bonded carbon atoms.”

Ex 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.
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR

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
Ans: In an aqueous solution, KOH almost completely ionizes to give OH - ions. OH - ion is a strong nucleophile, which leads
the alkyl chloride to undergo a substitution reaction to form alcohol.

On the other hand, an alcoholic solution of KOH contains alkoxide (RO - ) ion, which is a strong base. It prefers elimination
over substitution Thus, it can abstract a hydrogen from the β-carbon of the alkyl chloride and form an alkene by eliminating
a molecule of HCl.

OH - ion is a much weaker base than RO - ion. Also, OH - ion is highly solvated in an aqueous solution and as a result, the
basic character of OH - ion decreases. Therefore, it cannot abstract a hydrogen from the β-carbon.
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3.Reaction with metals Compounds containing carbon-metal bonds 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.

Nature of bonds in RMgX 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.
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Ex -10.12 Explain why (iii) Grignard reagents should be prepared under anhydrous conditions?
Grignard reagents are highly reactive and react with any source of proton like water ( alcohols amines etc) to give
hydrocarbons. As in presence of water RMgX converts in to alkane , it is prepared under anhydrous conditions

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.
Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Q. Aryl halides are less reactive towards nucleophilic substitution reactions. Give reason
Aryl halides are extremely less reactive towards nucleophilic substitution reactions due to the following four reasons:
(i) Resonance effect : In haloarenes, C—Cl 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

(ii) Difference in hybridisation of carbon atom in C—X bond:

 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
The sp2 hybridised carbon with a greater s-character is more electronegative and can hold the electron pair of C—X
bond more tightly than sp3-hybridised carbon in haloalkane with less s-chararcter. Thus, C—Cl bond length in
haloalkane is shorter than in haloarene and difficult to break, 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 - The presence of an electron withdrawing group (-NO2) at ortho- and para-
positions increases the reactivity of haloarenes.
The effect is pronounced when (-NO2) group is introduced at orthoand para- positions. However, no effect on reactivity
of haloarenes is observed by the presence of electron withdrawing group at meta-position

Reason - 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.
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Q- Write the mechanism of the following reactions -

i)- Reaction of p- nitro cholorobenzene with aq NaOH
i)- Reaction of o- nitro cholorobenzene with aq NaOH
i)- Reaction of m- nitro cholorobenzene with aq NaOH
Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Electrophilic substitution reactions Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
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. Due to resonance, the electron density increases more at ortho- and
para-positions than at meta-positions.

Q. Electrophilic substitution reactions of chlorobenzene are slower and require more drastic conditions as compared to
those in benzene or Toluene – Give reason.
Reason - 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
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Example 10.9- Although chlorine is an electron withdrawing group, yet it is ortho-, para- directing in electrophilic aromatic
substitution reactions. Why?
Ans: 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
parapositions and hence makes the deactivation less for ortho- and
paraattack. Reactivity is thus controlled by the stronger inductive
effect and orientation is controlled by resonance effect.
Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR

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.
Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
POLYHALOGEN COMPOUNDS
DICHLOROMETHANE (METHYLENE CHLORIDE):- It is widely used as a solvent as a paint remover, as a
propellant in aerosols, and as a process solvent in the manufacture of drugs. It is also used as a metal cleaning and finishing
solvent. 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.

TRICHLOROMETHANE (CHLOROFORM):- It is used as a solvent for fats, alkaloids, iodine and other substances.
It is also used in 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.
TRIIODOMETHANE (IODOFORM):- It was used earlier as an antiseptic but the antiseptic properties are due to the
liberation of free iodine and not due to iodoform itself. Due to its objectionable smell, it has been replaced by other
formulations containing iodine.

TETRACHLOROMETHANE (CARBON TETRACHLORIDE):- It is produced in large quantities for use in the

manufacture of refrigerants and propellants for aerosol cans. It is also used as feedstock in the synthesis of
chlorofluorocarbons and other chemicals, 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 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.
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.
p, p’-DICHLORODIPHENYLTRICHLOROETHANE(DDT):- DDT, the first chlorinated organic insecticides, was
originally prepared in 1873, but it was not until 1939 that Paul Muller of Geigy Pharmaceuticals in Switzerland
discovered the effectiveness of DDT as 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.
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
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?

 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
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), C8H18 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.
 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
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

 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR

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

 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
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

 Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR

(xvii) Chloroethane to butane

xviii) Benzene to diphenyl

(xix) tert-Butyl bromide to isobutyl bromide

(xx) Aniline to phenylisocyanide

Grade XII / Haloalkanes and Haloarenes /HIMANSHU SIR
An organic compound 'A' having molecular formula C4H8 on treatment with dil.H2SO4 gives 'B'.However, 'B' on
treatment with conc.HCl and anhydrous ZnCl2 gives 'C' and ‘C’ on treatment with sodium ethoxide gives back
'A'.Identify the compounds 'A' , 'B' and 'C'.Also write the equations involved
 How will you distinguish between chloroethane and bromoethane?

Out of ethyl bromide and ethylaiodiede which has higher boiling point and why?

Which of the following reactions is SN2 and why?

Read the passage given below and answer the following questions: 1. Nucleophilic substitution reactions are of
two types; substitution nucleophilic bimolecular (SN2) and substitution nucleophilic unimolecular (SN1) depending
on molecules taking part in determining the rate of reaction. The reactivity of alkyl halide towards SN1 and SN2
reactions depends on various factors such as steric hindrance, stability of intermediate or transition state, and
polarity of the solvent. SN2 reaction mechanism is favoured mostly by primary alkyl halide or transition state and
polarity of the solvent, SN2 reaction mechanism is favoured mostly by primary alkyl halide then secondary and
then tertiary. This order is reversed in the case of SN1 reactions.
(a) Which of the following is most reactive towards nucleophilic substitution SN1 reaction and why ?
(i)C6H5Cl (ii) CH2 =CHCl iii) ClCH2CH=CH2 (iv) CH3CH = CHCl

(b) Out of SN1 and SN2 by which mechanism tert butyl chloride undergoes hydrolysis and why ?

(c) Why does tertiary alkyl halides are practically inert to substitution by SN2 mechanism ?

(d) Arrange the following is the correct order of decreasing SN2 reactivity? RCH2X , R3CX , R2CHX