Haloalkanes and haloarenes

Classification:
I Classification based on number of halogens:
On the basis of number of halogen (-X) atoms in a molecule, they are classified into monohalo,
dihalo and trihalo alkanes or arenes. Eg.,

CH3-CH2-X CH2-CH2 CH2-CH-CH2

X X X X X
Monohaloalkane Dihaloalkane Trihaloalkane
X
X X X

X X
Monohaloarene Dihaloarene Trihaloarene
II Classification based on the hybridization of carbon containing halogen atom:
(I) Halogen connected to sp3 carbon:
(i) Alkyl halide: Halogen is connected to alkyl carbon. Alkyl carbon is sp3 carbon connected to
another sp3carbon.
Eg., CH3-CH2-Cl Ethyl chloride
(ii) Allyl halide (or) Allylic halide: Halogen is connected to allylic carbon. Allylic carbon is sp3
carbon connected to sp2 carbon.
Eg., CH2=CH-CH2-Cl Allyl chloride
(iii) Benzyl halide (or) Benzylic halide: Halogen is connected to benzylic carbon. Benzylic carbon
is sp3 carbon connected to benzene.

CH2-Cl
Benzyl chloride

Alkyl, allyl and benzyl halides are further classified into primary (10), secondary (20) and tertiary (30)
halides depending on whether the halogen is attached to primary (10), secondary (20) and tertiary (30)
carbon atoms.
(II) Halogen connected to sp2 carbon:
(i) Vinyl halide (or) Vinylic halide: Halogen is connected to vinylic carbon. sp2 carbon is vinylic
carbon.
CH2=CH-Cl Vinyl chloride
(ii) Aryl halide or phenyl halide: Halogen is connected to benzene ring. Carbon atom in benzene
ring is aryl carbon or phenyl carbon.
Cl
Phenyl chloride

1
Nomenclature
Common names have the format ‘Alkyl halide’
The prefixes n, iso, sec, tert, neo, allyl, vinyl, phenyl and benzyl are used in common names.
Prefix n (from normal) is used when (i) all carbon atoms are in straight chain with no branching
(ii) functional group is in the first carbon (iii) there are minimum of three carbons.
E.g., CH3-CH2-CH2-CH2- CH2-Br n-pentyl bromide
Prefix iso (from isomer) is used when (i) there is a carbon connected to two CH3 groups (ii) functional
group is in the primary carbon (iii) minimum of three carbons.
E.g. CH3-CH-CH2-CH2-Br isopentyl bromide
CH3
Prefix sec (from secondary) is used when (i) all carbon atoms are in straight chain with no branching
(ii) functional group is in the second carbon (iii) there are minimum of four carbons.
E.g., CH3-CH2-CH2-CH- CH3 sec-pentyl bromide
Br
Prefix tert (from tertiary) is used when (i) the functional group is connected to a tertiary carbon (ii)
there are minimum of four carbons.
CH3
CH3- CH2 - C – Br tert-pentyl bromide
CH3
Prefix neo (neo from new) is used when (i) there is a quaternary carbon, a carbon connected to four
carbons and out of four carbons three are CH3 groups (ii) functional group is in the primary carbon
(iii) minimum of five carbons.
CH3
CH3- C - CH2 – Br neopentyl bromide
CH3
Allyl group is CH2= CH- CH2 – E.g., CH2= CH- CH2 – Br allyl bromide
Vinyl group is CH2= CH – E.g., CH2= CH– Br vinyl bromide
Phenyl/aryl group is C6H5- E.g., C6H5- Br Phenyl bromide (or) aryl bromide
Benzyl group is C6H5- CH2 – E.g., C6H5- CH2 –Br benzyl bromide
n, iso and neo are always used for primary halides except isopropyl halide which is secondary.
Compound Common name IUPAC name
CH3-Cl Methyl chloride Chloromethane
CH3-CH2-Cl Ethyl chloride Chloroethane
CH3-CH2-CH2-Cl n-propyl chloride 1-Chloropropane
CH3-CH-Cl
isopropyl chloride 2-Chloropropane
CH3
CH3-CH2-CH2-CH2-Br n-butyl bromide 1-Bromobutane
CH3-CH-CH2-Br
isobutyl bromide 1-Bromo-2-Methylpropane
CH3

2
CH3-CH-CH2-CH3
sec-butyl bromide 2-Bromobutane
Br
CH3
CH3-C-Br tert-butyl bromide 2-Bromo-2-Methylpropane
CH3
CH3
CH3-C-CH2-Br neopentyl bromide 1-Bromo-2,2-Dimethylpropane
CH3
CH2 CH2
Cl Cl Ethylene dichloride 1,2-Dichloroethane
Vicinal (Vic) dihalide
CH3 CHCl2
Ethylidene dichloride 1,1-Dichloroethane
Geminal (Gem) dihalide
Cl
Cyclohexyl chloride Chlorocyclohexane

C6H5Cl Phenyl chloride Chlorobenzene

C6H5CH2Cl Benzyl chloride Chlorophenylmethane
C6H5CHCl2 Benzal chloride Dichlorophenylmethane
C6H5CCl3 Benzo chloride Trichlorophenylmethane
Cl
Cl o-Dichlorobenzene 1,2-Dichlorobenzene

Cl
CH3 2-Chlorotoluene (or)
o-Chlorotoluene
1-Chloro-2-methylbenzene

Br
3-Bromotoluene (or)
m-Bromotoluene
1-Bromo-3-methylbenzene
CH3
Cl
4-Chlorotoluene (or)
p-Chlorotoluene
1-Chloro-4-methylbenzene

CH3
3
 Br
Sym-Tribromobenzene 1,3,5-Tribromobenzene

Br Br

Preparation:
1) From alcohols:
(i) Chloroalkanes from alcohols:
Anhyd.ZnCl2
CH3-CH2-OH + HCl CH3-CH2-Cl + H2O
3CH3-CH2-OH + PCl3 → 3CH3-CH2-Cl + H3PO3
CH3-CH2-OH + PCl5 → CH3-CH2-Cl + HCl + POCl3
CH3-CH2-OH + SOCl2 → CH3-CH2-Cl + HCl + SO2
(ii) Bromoalkanes from alcohols:
CH3-CH2-OH + NaBr + H2SO4 → CH3-CH2-Br + NaHSO4 + H2O
Red P4/ Br2
CH3-CH2-OH CH3-CH2-Br
(ii) Iodoalkanes from alcohols:
CH3-CH2-OH + NaI + H3PO4 → CH3-CH2-I + NaH2PO4
Red P4/ I2
CH3-CH2-OH CH3-CH2-I
Q. Thionyl chloride is the best reagent for converting alcohols to chloroalkanes. Why?
The side products are gases hence they escape leaving the chloroalkanes in pure state.
Q. Sulphuric acid cannot be used with NaI or KI to prepare iodoalkanes from alcohols. Why?
Sulphuric acid converts KI to HI and then oxidises HI to I2 hence iodoalkane will not be formed.
Q. Phosphoric acid, H3PO4 is used with NaI or KI to prepare iodoalkanes from alcohols. Why?
Phosphoric acid converts KI to HI which reacts with alcohols to give iodoalkanes. Unlike sulphuric
acid it will not oxidise HI to I2.
Q. Aryl halides cannot be prepared from phenols using this method. Why?
Due to resonance, the carbon-oxygen bond in phenol has partial double bond character which is
stronger and difficult to break. For example
HCl HO- -CH2-Cl
HO- -CH2-OH + H2O
Heat
Q. What is the role of anhydrous ZnCl2 in converting alcohols to chloroalkanes?
It removes the side product (water) and pushes the equilibrium in forward direction.
Q. The order of reactivity of alcohols towards HX is 30 > 20 > 10. Explain.
This is due to decrease in stabilities of respective carbocations.

4
2) From Hydrocarbons:
(i) By free radical halogenations:
When alkanes are treated with halogen in the presence of UV light the hydrogen atoms are replaced
by halogen atoms.
Eg., Chlorination of methane
UV or hυ
CH4 + Cl2 CH3-Cl + HCl
Chloromethane (or) Methyl chloride
UV or hυ
CH3-Cl + Cl2 CH2Cl2 + HCl
Dichloromethane (or) Methylene chloride
UV or hυ
CH2Cl2 + Cl2 CHCl3 + HCl
Trichloromethane (or) Chloroform
UV or hυ
CHCl3 + Cl2 CCl4 + HCl
Tetrachloromethane (or) Carbon tetrachloride
Free radical halogenation gives mixture of many products which are difficult to be separated hence
this reaction is not carried out in laboratory to produce pure product.
Eg., Consider free radical chlorination of propane. The reaction gives two monosubstituted products,
four disubstituted products etc.,

UV light
CH3-CH2-CH3 + Cl2 CH3-CH2-CH2-Cl + CH3-CHCl-CH3
CH3 Monochloro substituted products
CH3-CHCl-CH2Cl + CH2Cl-CH2-CH2Cl +
CH3-CH2-CHCl2 + CH3-CCl2-CH3
Dicholoro substituted products
But benzyl and allyl carbons are more reactive than phenyl and vinyl carbons hence compounds
with benzyl and allyl carbons give a major product by either benzylic substitution or allylic
substituition. Eg.,
CH3 CH2Cl

+ Cl2 UV light + HCl (Benzyl substitution)

Heat
CH3
Toluene Benzyl chloride
CH3
UV light
CH2= CH-CH3 + Cl2 CH2= CH-CH2-Cl + HCl (Allyl substitution)
Heat
CH3 Cl
CH3
UV light CH
+ Cl2 (Allyl substitution)
Heat
CH3 3

CH3 5
Iodination is carried out in the presence of an oxidising agent like HNO3 or HIO4
UV/HNO3
CH4 + I2 CH3-I + HI
Iodomethane (or) Methyl iodide
The rate of reaction of halogens towards free radical substitution; F2 > Cl2 > Br2 > I2
The rate of reaction of alkanes; 30 > 20 > 10
The above decreasing trend in reactivity is due to decrease in the stability of free radicals.
(ii) Electrophilic aromatic substitution reactions:
Benzene when heated with halogen in the presence of a Lewis acid catalyst like FeCl3, FeBr3 or
AlCl3 gives halo benzene.
X
Anhyd. FeX3
+ X2 + HCl
Dark
CH3 CH3 CH3
CH3
FeCl3 Cl
+ Cl2 +
Dark
Cl
Toluene o-chlorotoluene p-chlorotoluene

Ortho and para chlorotoluene can be easily separated due to their large difference in their melting
points. Iodination is reversible because the side product, HI is a strong reducing agent. Hence,
iodination is carried out in the presence of oxidizing agents like HNO3 or HIO4.
Q. Iodination is carried out in the presence of oxidizing agents like HNO3 or HIO4. Why?
To oxidize the side product HI to I2 and thus to prevent the backward reaction.
4) From alkenes by addition of hydrogen halides:
CH2 = CH2 + HBr CH3-CH2-Br
Addition of HX to unsymmetrical alkenes follow Markovnikov’s rule. When HX is added to an
unsymmetrical alkene, the hydrogen atom gets attached to that carbon which has more number of
hydrogen atoms. Eg.,
CH3-CH = CH2 + HBr → CH3-CH-CH3 + CH3-CH2-CH2-Br
Br
2-Bromopropane (major product) 1-Bromopropane (minor product)
But when HBr is added to an unsymmetrical alkene in the presence of peroxide, the hydrogen
atom gets attached to that carbon which has lesser number of hydrogen atoms. It is known as peroxide
effect or Kharasch effect or anti-Markovnikov’s addition. Eg.,
(C6H5CO)2O2
CH3-CH = CH2 + HBr CH3-CH2-CH2-Br
1-Bromopropane (major product)
Only HBr shows peroxide effect. HCl and HI follow only Markovnikov’s addition.
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3) From aniline:
(i) Diazotisation:
When aniline is treated with a mixture of NaNO2 and HCl (or HNO2), benzene diazonium
chloride is formed and the reaction is known as diazotisation.
NH2 N2Cl
NaNO2 /HCl
0 -5O C

Aniline Benzene diazonium chloride

(ii) Sandmeyer’s reaction:

Diazonium chloride when treated with cuprous chloride and HCl gives chloro benzene and
when treated with cuprous bromide and HBr gives bromobenzene. These reactions are Sandmeyer’s
reactions.
N2Cl Cl
Cu2Cl2
+ N2

Diazonium chloride Chlorobenzene

N2Cl Br
Cu2Br2
+ N2

Diazonium chloride Bromobenzene

(iii) When diazonium salt is treated with KI, iodobenzene is formed.

N2Cl I
KI
+ N2

Diazonium chloride Iodobenzene

5) Addition of halogens:
Halogens add to alkenes to give vicinal dihalides. Eg.,
Bromine adds to ethene in the presence of CCl4 solvent to give 1,2-dibromoethane.

CCl4
CH2 = CH2 + Br2 CH2Br-CH2Br
During addition of bromine to alkene, the reddish orange colour of bromine is decolourised. Hence
this is used as a test to identify unsaturation and used to distinguish alkenes from alkanes.
6) Halogen exchange reactions:

7
(i) Finkelstein reaction:
Alkyl chlorides and bromides when treated with NaI in dry acetone give alkyl iodides.

NaI or KI
R-X R-I + NaX ( X = Cl, Br)
Dry acetone

Dry acetone
CH3-CH2-Br + KI CH3-CH2-I + KBr

(ii) Swarts reaction:

Alkyl chlorides and bromides when treated with metal fluorides like AgF, Hg2F2, CoF2 or SbF3
give alkyl fluorides.
AgF
R-X R-F + AgX ( X = Cl, Br)
∆
CH3-CH2-Br + AgF CH3-CH2- F + AgBr
Q. What is the role of dry acetone in Finkelstein reaction?
The side product NaCl/ NaBr is insoluble in dry acetone hence gets precipitated. Therefore use of
dry acetone moves the reaction in forward direction.
Q. Boling points of haloalkanes are higher than the parent hydrocarbons. Why?
Haloalkanes are polar hence have stronger dipole-dipole attractive forces. Moreover the molar
masses of haloalkanes are higher than that of the parent hydrocarbons hence have stronger Van der
waal’s attractive forces.
Q. Boiling points of haloalkanes are higher than the alkanes of similar molar mass. Why?
Haloalkanes are polar hence have stronger dipole-dipole attractive forces whereas alkanes are non-
polar hence have weaker London forces.
Q. For the same alkyl group the boiling point increases in the order RF < RCl < RBr < RI. Explain
This is because with increase in size and molar mass of halogens the magnitude of van der Waal’s
forces increases.
Q. For the same alkyl group the boiling point increases with increase in number of halogens. Explain
This is because with increase in number of halogens the size and molar mass increases hence the
magnitude of van der Waal’s force increases.
Q. For the same halogen the boiling point increases with increase in number of carbon atoms. Why?
With increase in number of carbon atoms the size and molar mass increases hence the magnitude
of Van der Waal’s forces increases.
Q. Among isomeric haloalkanes the boiling point decreases with increase in branching. Why?
Branching reduces the surface area of contact hence reduces the magnitude of Van der Waal’s force
of attraction. For example, the decreasing order in boiling points of the three isomers of butyl
bromides are
n-butyl bromide > sec-butyl bromide > tert-butyl bromide
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Q. The boiling points of three isomeric dichlorobenzenes are almost same (BP; ortho – 453 K,
para – 448 K & meta – 446 K) but the melting point of para-dichlorobenzene is much higher than the
ortho and meta isomers (MP; para – 323 K, ortho – 256 K & meta – 249 K). Why?
The para isomer is symmetrical hence the molecules are packed tightly in the crystal lattice.
Q. Haloalkanes and haloarenes are immiscible with water. Why?
This is because haloalkanes and haloarenes can neither form hydrogen bond with water nor can
break the hydrogen bond existing in water.
Q. Haloalkanes and haloarenes are miscible with organic solvents. Why?
This is because halocompounds and organic solvents have similar polarity hence the attractive
forces between the solvent and solute particles are similar.
Q. The stability of alkyl halides decreases in the order: RF > RCl > RBr > RI. Why?
This is due to decrease in bond enthalpy of C-X bond in the same order.
Q. Iodoalkanes become violet on standing. Why?
This is due to decomposition of alkyl iodides in the presence of light to give iodine.
Reactions of haloalkanes:
(I) Nucleophilic substitution:
Haloalkanes undergo nucleophilic substitution reaction due to the presence of polar C-X bond.
CH3-CH2-Br + aq.NaOH/ KOH → CH3-CH2-OH + aq.NaBr/ KBr
CH3-CH2-Br + H2O → CH3-CH2-OH + HBr
CH3-CH2-Br + CH3ONa → CH3-CH2-OCH3 + NaBr
CH3-CH2-Br + KI → CH3-CH2-I + KBr
CH3-CH2-Br + LiH → CH3-CH3 + LiBr
CH3-CH2-Br + LiAlH4 → CH3-CH3 + LiBr + AlBr3
CH3-CH2-Br + CH3Li → CH3-CH2-CH3 + LiBr
CH3-CH2-Br + CH3CH2M → CH3CH2CH2CH3 + MBr (M is alkali metal)
CH3-CH2-Br + CH3COOAg → CH3COOCH2CH3 + AgBr
Silver acetate Ethyl acetate
CH3-CH2-Br + CH3C CNa → CH3CH2C CCH3 + NaBr
Reaction with ammonia or Ammonolysis:
Haloalkanes react with ammonia in the presence of a base like pyridine to give a mixture of
primary amine, secondary amine, tertiary amine and quaternary ammonium salt. This reaction is
known as ammonolysis.
Base CH3-CH2-Br /Base
CH3-CH2-Br + NH3 CH3-CH2-NH2 (CH3-CH2)2 NH
HBr Ethyl amine (10) HBr Diethyl amine (20)

9
 CH3-CH2-Br /Base CH3-CH2-Br
(CH3-CH2)3 N (CH3-CH2)4 N+ Br—
HBr Triethyl amine (30) Tetraethyl ammonium bromide (40)
Q. Ammonolysis of alkyl halides is carried out in the presence of a strong base like pyridine. Why?
The base removes HX and shifts the equilibrium in forward direction.
Q. What is the limitation (or) disadvantage of ammonolysis reaction?
The reaction gives mixture of primary amine, secondary amine, tertiary amine and quaternary
ammonium salt and it is difficult to separate the products.
Ambident nucleophiles:
Nucleophiles that possess two nucleophilic centres are called ambident nucleophiles. Eg Cyanide
(CN—) and Nitrite (NO2—)
Alkyl halides react with KCN to give cyanides whereas with AgCN give isocyanides.
CH3-CH2-Br + KCN ( K+ CN— ) → CH3-CH2-CN + KBr
Ethyl cyanide or Propanenitrile

CH3-CH2-Br + AgCN ( Ag CN ) → CH3-CH2-NC + AgBr

Ethyl isocyanide or Propaneisonitrile
Similarly, alkyl halides react with KNO2 to give alkyl nitrites whereas with AgNO2 give nitroalkanes.
—
CH3-CH2-Br + KNO2 (K+ O N=O) → CH3-CH2-O N=O + KBr
Ethyl nitrite
CH3-CH2-Br + AgNO2 (Ag O N=O) → CH3-CH2-NO2 + AgBr
Nitroethane
Q. Haloalkanes react with alcoholic KCN to give cyanides whereas with alcoholic AgCN give
isocyanides. Explain.
KCN is ionic and gives free CN— ions hence both carbon and nirogen are free to donate electron
pair. But C-C bond is stronger than C-N bond hence carbon attacks the alkyl halide forming cyanides.
Whereas AgCN is covalent hence only nitrogen atom is free to donate electron pair hence nitrogen
attacks the alkyl halide forming isocyanides.
Q. Haloalkanes react with alcoholic potassium nitrite, KNO2 to give alkyl nitrites whereas with
aloholic silver nitrite, AgNO2 give nitroalkanes. Explain.
KNO2 (K+ — O-N=O) is ionic and gives free — O-N=O ions hence both oxygen and nirogen are
free to donate electron pair. But C-O bond is stronger than C-N bond hence oxygen attacks the alkyl
halide forming nitrites. Whereas AgNO2 (Ag-O- N=O) is covalent hence only nitrogen atom is free to
donate electron pair hence nitrogen attacks the alkyl halide forming nitroalkanes.

10
Reaction with KCN is used to increase the number of carbon atoms in conversionn. Eg.,
KCN H2O/H+
CH3-CH2-Br CH3-CH2-CN CH3-CH2-COOH
Bromoethane Propanenitrile Propanoic acid

Mechanisms of nucleophilic substitution:

SN2 mechanism: Substitution nucleophilic bimolecular mechanism.
Consider the reaction:
CH3-CH2-Br + aq.NaOH → CH3-CH2-OH + NaBr
The reactant or substrate is bromoethane, reagent is NaOH, nucleophile is OH—, leaving group is Br—
and the product is ethanol.
This reaction follows SN2 mechanism because the substrate is a primary halide.
CH3
CH3 CH3

OH— + H C Br HO C Br HO C H + Br—

H H H H
Nucleophile Substrate Transition state Product
Characteristics of SN2 mechanism:
o Primary halides undergo substitution by this mechanism.
o The reaction occurs in a single step through transition state.
o The nucleophile attacking the carbon and the halogen leaving the carbon occurs
simultaneously.
o The rate of this reaction depends on the concentration of both substrate and the nucleophile
hence it is known as bimolecular.
o The nuleophile approaches the carbon from backside due to lesser steric repulsion.
o In transition state, carbon atom has valency five with trigonal bipyramidal geometry hence it is
unstable.
Reactivity in SN2 mechanism:
The rate of reaction in SN2 mechanism depends on the steric repulsion at transition state. Greater
the steric repulsion to the approaching nucleophile lesser is the reactivity. Methyl halides are the most
reactive in SN2 mechanism because there are only three small hydrogen atoms hence there is no steric
repulsion. Tertiary halides do not undergo substitution by SN2 mechanism because there are three
bulky alkyl groups at alpha carbon causing greater steric repulsion.
The decreasing order of reactivity in SN2 mechanism:

Methyl halide > Primary halide > Secondary halide > Tertiary halide
CH3-X > CH3-CH2-X > (CH3)2CH-X > (CH3)3C-X
This is due to increasing order of steric repulsion to the approaching nucleophile.

11
SN1 mechanism: Substitution nucleophilic unimolecular mechanism.
Consider the reaction:
(CH3)3C-Br + aq.NaOH → (CH3)3C-OH + NaBr
This reaction follows SN1 mechanism because the substrate is a tertiary halide. The reaction occurs in
two steps.
Step 1: Tertiary halide undergoes heterolytic cleavage to form a carbocation intermediate which is
trigonal planar in geometry.
CH3
CH3
Slow + Br—
C +
CH3 C Br
CH3 CH3
CH3
Step 2: Nucleophile attacks carbocation to give the product.
CH3
CH3
Fast
C+ + OH— CH3 C OH
CH3 CH3 CH3

Characteristics of SN1 mechanism:

o Tertiary halides undergo substitution by this mechanism.
o The reaction occurs in two steps through intermediate.
o In the first step tertiary halide undergoes heterolytic cleavage to form a carbocation
intermediate which is trigonal planar in geometry. In the second step nucleophile attacks
carbocation to give the product.
o The rate of this reaction depends on the concentration of only alkyl halide hence it is known
as unimolecular. Because the first step is slow and it is rate determining step which contains
only the tertiary halide.
o The nuleophile can attack the carbocation from either side.
o This reaction requires polar protic solvents like water, alcohol etc in order to stabilise the
carbocation intermediate.
Reactivity in SN1 mechanism:
(i) The rate of reaction in SN1 mechanism depends on the stability of carbocation intermediate.
Greater the stability of carbocation greater will be the reactivity of the alkyl halide. Tertiary halides
are the most reactive in SN1 mechanism because tertiary carbocation is the most stable and hence it is
readily formed. Methyl and primary halides do not undergo substitution by SN1 mechanism because
the respective carbocations are unstable.

12
 (ii) The decreasing order of reactivity in SN1 mechanism:
Tertiary halide > Secondary halide > Primary halide > Methyl halide
(CH3)3C-X > (CH3)2CH-X > CH3-CH2-X > CH3-X
This is due to decreasing order of carbocation stability.
(iii) Allyl and benzyl halides are more reactive than alkyl halides in SN1 mechanism because the
the respective carbocations i.e. allyl and benzyl carbocations are resonance stabilised.
Resonance stabilisation of allyl carbocation:
+ +
CH2 CH CH2 CH2 CH CH2

Resonance stabilisation of benzyl carbocation:

CH2+ CH2 CH2 CH2 CH2+
+ +

+
(iv) Aryl and vinyl halides are unreactive towards SN reacions.

Reactivity of different halides in SN reaction: (Both SN1 and SN2)

For a given alkyl group the reactivity of halides increase in the following order:
R-F < R-Cl < R-Br < R-I
This is because as the size of halogen increases, the bond enthalpy decreases hence they can be
easily cleaved by the nucleophile. Iodine being the largest halogen, forms very weak bond and it is the
best leaving group among halogens hence iodo alkanes are the most reactive in SN reactions.
Primary halides undergo nucleophilic substitution by SN2 mechanism
Tertiary halides undergo nucleophilic substitution by SN1 mechanism
Secondary halides undergo nucleophilic substitution by either SN1 or SN2 mechanisms
Stereochemical principles
(i) Plane polarised light:
Light having all its oscillations in one plane is known as plane polarised light. It is produced by
passing ordinary light through Nicol prism (Crystalline CaCO3)
(ii) Optically active substance:
Substance that rotates the plane of polarised light is known as optically active substance.
Substance that rotates the plane of polarised light to the right or in clockwise direction is known as
dextrorotatory and is denoted by either d or (+) sign before the name. Eg., (+)-Butan-2-ol
Substance that rotates the plane of polarised light to the left or in anticlockwise direction is known
as laevororotatory and is denoted by either l or (-) sign before the name. Eg., (-)-Butan-2-ol

13
(iii) Optical activity:
The phenomenon of rotation of plane polarised light by an optically active substance is known as
optical activity.
(iv) Polarimeter: Device used to measure the angle of rotation.
(v) Chiral centre (or) Chiral carbon (or) Asymmetric carbon (or) Stereo centre:
It is a carbon attached to four different groups.
(vi) Chiral molecule (or) Asymmetric molecule:
It is a molecule that is non-superimposable on its mirror image. All chiral molecules are optically
active. E.g., 2-Bromobutane
(vii) Chirality (or) Molecular asymmetry:
It is the property in which a molecule is non-superimposable on its mirror image. Chirality is the
essential condition for a substance to be optically active.
Enantiomers:
Stereoisomers that are non-superimposable mirror images of each other are enantiomers. Eg., (+)-
Butan-2-ol and (-)-butan-2-ol are enantiomers because they are mirror images and are non-
superimposable.

OH OH

CH3 H H CH3
C2H5 C2H5
d-Butan-2-ol Mirror l-Butan-2-ol
Enantiomers have identical physical properties like melting point, boiling point etc but differ only
with respect to plane polarised light.
Q. Draw the enantiomers of 2-bromobutane according to wedge and dash representation around the
stereocentre:

d-2-Bromobutane Mirror l-2-Bromobutane

14
Racemic mixture (or) Racemic modification:
It is a mixture of equal proportions of the two enantiomers. Eg., dl-Butan-2-ol
Racemic mixture is optically inactive because the rotation caused by one isomer is cancelled by the
other isomer.
Inversion of configuration:
If the configuration of the product is opposite to that of reactant then the reaction is said to proceed
with inversion of configuration.
Eg., All SN2 reactions proceed with inversion of configuration when the reactant is optically acive.
This is because the nuceophile attacks the chiral carbon from backside.
Q. An optically active halide of molecular formula C4H9Br undergoes substitution by aqueous NaOH
with inversion of configuration. Explain the mechanism.
This reaction follows SN2 mechanism because it proceeds with inversion of configuration.
CH3
CH3 CH3

OH— + H C Br HO C Br HO C H + Br—

C2H5 H C2H5 C2H5

(-)-2-Bromobutane Transition state (+)-Butan-2-ol

Racemisation:
The process of conversion of an optically active enantiomer into optically inactive racemic
mixture of products is known as racemisation.
Eg., All SN1 reactions proceed with racemisation when the reactant is optically active. This is
because the carbocation formed in the first step is planar hence it can be attacked by the nucleophile
from either side with equal probability resulting in the formation of equal proportion of dextro and
laevo isomer.
Q. An optically active halide of molecular formula C4H9Br undergoes substitution by aqueous NaOH
with racemisation. Explain the mechanism.
This reaction follows SN1 mechanism because it proceeds with racemisation. SN1 reaction occurs in
two steps.
Step 1: Formation of carbocation intermediate which is trigonal planar in geometry.
CH3
CH3
Slow C+ + Br—
H C Br
H C2H5
C2H5

15
Step 2: Nucleophile can attack from either side to give both d and l isomer.
CH3
CH3 CH3
Fast
C+ HO C H + H C OH

H C2H5 C2H5 C2H5

(+)-Butan-2-ol (-)-Butan-2-ol
—
OH
Racemic mixture
Retention of configuration:
If the bond at the stereocentre is not broken during a reaction, then the configuration of reactant
and product are same around stereocentre and the reaction is said to proceed with retention of
configuration. (or) It is defined as the preservation of integrity of spatial arrangement of bonds around
a stereocentre during chemical reaction.
CH3 CH3
HCl
H C CH2-OH H C CH2-Cl
Heat
C2H5 C2H5
Inversion, retention and racemisation are the three outcomes if substitution occurs at an
asymmetric carbon.
Consider the replacement of group X by Y in the following reactions:

C2H5 C2H5 C2H5

H Y
Y H H

CH3 Y CH3 Y CH3

X
(B) Y (A)

(A) + (B)
(i) If (A) is the only product, the process is retention of configuration.
(ii) If (B) is the only product, the process is inversion of configuration.
(iii) If (A) and (B) are formed in equal proportions, the process is racemization.

16
(II) Elimination reactions: β-Elimination (or) Dehydrohalogenation:
When alkyl halides containing a β-hydrogen are treated with alcoholic KOH (or) an alkoxide,
alkenes are produced. This reaction is known as β-Elimination because the hydrogen atom removed is
a β-hydrogen.
Eg., Bromoethane when treated with alcoholic KOH/NaOH or alkoxide (NaOR) gives ethene.

Alc. KOH
CH3CH2Br CH2==CH2 + KBr + H2O
Saytzeff rule (or) Zaitsev rule:
In dehydrohalogenation reactions, the major product is that alkene which has greater number of
alkyl groups attached to the double bonded carbon atoms.
Eg., When 2-bromobutane is treated with alc. KOH but-2-ene is formed as major product.
CH -CH -CH-CH Alc. KOH CH -CH== CH-CH + CH -CH -CH== CH
3 2 3 3 3 3 2 2

Br Major Minor
(III) Reactions with metals:
(i) Organometallic compounds and Grignard reagents (RMgX):
These are compounds containing metal-carbon covalent bond. Example for organometallic
compounds are alkyl magnesium halides known as Grignard reagents with general formula RMgX.
Grignard reagents are produced by reacting haloalkanes with magnesium metal in dry ether solvent.
Dry Ether
CH3-Cl + Mg CH3MgCl
Methyl chloride Methyl magnesium chloride
Dry Ether
C6H5-Br + Mg C6H5MgBr
Phenyl bromide Phenyl magnesium bromide

Grignard reagents react with any compound containing proton i.e., water, alcohols, amines, alkynes
etc to give hydrocarbons.
RMgX + H2O → RH + Mg(OH)X
CH3MgBr + H2O → CH4 + Mg(OH)Br
CH3MgBr + NH3 → CH4 + Mg(NH2)Br
CH3MgBr + CH3OH → CH4 + Mg(OCH3)Br
CH3MgBr + NH3 → CH4 + Mg(NH2)Br
CH3MgBr + CH CH → CH4 + Mg(C CH)Br
Q. Grignard reagents must be prepared and stored in the absence of moisture. Why?
Grignard reagents are highly reactive and react with water to form hydrocarbons.
RMgX + H2O → RH + Mg(OH)X
(ii) Wurtz reaction:
Alkyl halides when treated with sodium metal in dry ether give alkanes with double the number of
carbon atoms.
Dry Ether
2 RX + 2 Na R-R + 2 NaX
17
 Dry Ether
2 CH3-Cl + 2 Na CH3 – CH3 + 2 NaCl
Dry Ether
CH3-CH2-Br + 2 Na CH3– CH2- CH2-CH3 + 2NaBr
Reactions of aryl halides:
Q. Haloarenes or arylhalides (C6H5-X) do not undergo nucleophilic substitution under normal
conditions. Explain.
Arylhalides are unreactive towards nucleophilic substitution due to the following reasons.
(i) Due to resonance in aryl halides, the carbon-halogen bond has partial double bond character hence
it is stronger and difficult to break.
(ii) The halogen is connected to sp2 hybridised carbon which is more electronegative hence it forms
shorter and stronger bond which is difficult to break.
(iii) Phenyl carbocation if formed by SN1 reaction is not resonance stabilised hence it is highly
unstable. Therefore SN1 reaction is not possible in aryl halides.
(iv) Due to repulsion between the nucleophile and electron rich benzene ring, the nucleophile cannot
attack arylhalides. Therefore SN2 reaction is also not possible in aryl halides.
Q. Vinyl halides (CH2=CH-X) are less reactive toward nucleophilic substitution. Explain.
Vinylhalides are unreactive towards nucleophilic substitution due to the following reasons.
(i) Due to resonance in vinyl halides, the carbon-halogen bond has partial double bond character
hence it is stronger and difficult to break.
(ii) The halogen is connected to sp2 hybridised carbon which is more electronegative hence it forms
shorter and stronger bond which is difficult to break.
(iii) Vinyl carbocation if formed by SN1 reaction is not resonance stabilised hence it is highly
unstable. Therefore SN1 reaction is not possible in vinyl halides.
Q. Ethyl chloride hydrolyses faster than vinyl and aryl chlorides. Why?
In ethyl chloride, chlorine is connected to sp3 carbon hence the bond can be easily broken by
nucleophile. Whereas in vinyl and aryl chlorides, chlorine is connected to sp2 carbon which is more
electronegative and forms shorter and stronger bond. Also due to resonance, the C-Cl bond has partial
double bond character hence it is stronger and cannot be broken by the nucleophile.
Aryl halides undergo nucleophilic substitution under vigorous conditions. For example,
Chloro benzene is converted to phenol by heating it in aqueous NaOH solution at 623 K and at 300
atm pressure followed by acidification.
Cl OH
(i) NaOH, 623 K, 300 atm
(ii) H+
Chlorobenzene Phenol

18
 The presence of electron withdrawing group like NO2 at ortho and para position increases the
reactivity of arylhalides. NO2 group being electron withdrawing by resonance effect increases the
stability of arenium ion intermediate. For example, nitro substituted chlorobenzene undergoes
substitution under less vigorous conditions.
Cl OH

(i) NaOH, 443 K 4-Nitrophenol

(ii) H+

NO2 NO2

Cl OH
NO2 NO2
(i) NaOH, 368 K 2,4-Dinitrophenol
+
(ii) H

NO2 NO2

Cl OH
O2N NO2 O2N NO2
H2O
2,4,6-Trinitrophenol
Heat
or
NO2 NO2 Picric acid

Mechanism of aryl substitution reaction: SN aryl

The reaction occurs in two steps;
Step 1: Nucleophile attacks aryl halide to form carbanion intermediate which is resonance stabilised.

Cl
Cl OH Cl OH Cl OH

+ OH— Slow

Step 2: Loss of halide ion to give the product.

Cl OH OH

Fast
+ Cl—

19
Q. Presence of electron withdrawing groups (-NO2) at ortho and para position of benzene ring
increases the rate (or) tendency of SN reaction in aryl halides. Explain.
Electron withdrawing groups (-NO2) at ortho and para position increase the stability of carbanion
intermediate through resonance.
Q. Electron withdrawing groups (or nitro group) at the meta position does not influence SN reaction in
aryl halides. Why?
Electron withdrawing groups (-NO2) at meta position cannot stabilise the carbanion intermediate
because none of the resonance has negative charge at meta position.
Reaction of aryl halides with metals:
(i) Fittig reaction:
Aryl halides when treated with sodium metal in dry ether give biaryls or biphenyls in which two
aryl groups are joined together.
Cl
Dry Ether
2 + 2 Na + 2 NaCl

(ii) Wurtz-Fittig reaction:

When a mixture of aryl halide and alkyl halide is treated with sodium metal in dry ether
alkylarene or alkyl benzene is produced.
X R
Na
+ RX + 2 NaX
Dry Ether
Br CH3
Na
+ CH3Br + 2 NaBr
Dry Ether

Electrophilic substitution reactions of aryl halides:

Haloarenes undergo electrophilic substitution reaction due to the presence of 6π electrons in
benzene ring.
Halogens are ortho and para directing but deactivating towards electrophilic substitution reactions.
Due to electron releasing resonance effect (+R effect) halogens increase the electron density at ortho
and para positions hence they are orth and para directing. But by electron withdrawing inductive effect
(-I effect) halogens decrease the overall electron density in benzene ring hence they are deactivating.

(i) Nitration of chlorobenzene:

Chlorobenzene when heated with a mixture of concentrated nitric acid and concentrated sulphuric
acid (Nitrating mixture) gives a mixture of o-chloronitrobenzene and p-chloronitrobenzene.
Para isomer is the major product due to lesser steric hindrance.

20
 Cl
Cl Cl
NO2
Con. H2SO4
+ Con. HNO3 +

NO2
(ii) Chlorination of chlorobenzene:
Chlorobenzene when treated with chlorine in the presence of anhydrous FeCl3 gives a mixture of
o-dichlorobenzene and p-dichlorobenzene. Para isomer is the major product due to lesser steric
hindrance.
Cl
Cl Cl
Cl
Anhyd. FeCl3
+ Cl2 +
Cl
(iii) Sulphonation of chlorobenzene:
Chlorobenzene when heated with concentrated sulphuric acid gives a mixture of o-chlorobenzene
sulphonic acid and p-chlorobenzene sulphonic acid. Para isomer is the major product due to lesser
steric hindrance. Cl
Cl Cl
SO3H
Con. H2SO4
+
SO3H
(iv) Friedel – Crafts alkylation of chlorobenzene:
Chlorobenzene when treated with methyl chloride in the presence of anhydrous AlCl3 gives a
mixture of o-chlorotoluene and p-chlorotoluene. Para isomer is the major product due to lesser steric
hindrance. Cl
Cl Cl
CH3
Anhyd. AlCl3
+ CH3Cl +
CH3
(v) Friedel – Crafts acylation of chlorobenzene:
Chlorobenzene when treated with acetyl chloride (or) ethanoyl chloride in the presence of
anhydrous AlCl3 gives a mixture of o-chloroacetophenone and p-chloroacetophenone. Para isomer is
the major product due to lesser steric hindrance.
Cl
Cl Cl
COCH3
Anhyd. AlCl3
+ CH3COCl +
COCH3

21
Polyhalogen compounds:
(i) Methylene chloride (or) Dichloromethane:
It is produced by chlorination of methane. It is used as a solvent to remove paints, as a propellant
in aerosols, as a solvent in the manufacture of drugs and in metal cleaning.
Harmful effects: It affects human central nervous system and causes dizziness, nausea and skin
inflammation.
(ii) Chloroform (or) Trichloromethane:
It is produced by chlorination of methane.
Chloroform is stored in closed dark coloured bottles completely filled to keep out light and air
because it is oxidised by air in the presence of light to give a poisonous gas, phosgene (or) carbonyl
chloride.
Light
2 CHCl3 + O2 2 COCl2 + 2 HCl
It is used to produce freon refrigerant R-22 and as a solvent.
Harmful effects: Breathing chloroform causes dizziness, headache and fatigue. In body chloroform is
converted to a poisonous gas phogene which damages the liver.
(iii) Iodoform (or) Triiodomethane:
It is produced by iodination of methane. It is used as an antiseptic. The antiseptic property is due
to the liberation of free iodine and not due to iodoform itself.
(iv) Carbon tetrachloride (or) Tetrachloromethane:
It is produced by chlorination of methane. It is used in the manufacture of refrigerants, propellants
for aerosol cans and chlorofluorocarbons. At home, it is used as cleaning fluid, spot remover and as
fire extinguisher.
Harmful effects: It causes dizziness, nausea, vomiting, damages nerve cells and causes liver cancer in
humans. It depletes the ozone layer exposing humans to UV rays leading to skin cancer.
(v) Freons:
Chlorofluorocarbons of methane and ethane are known as freons. Dichlorodifluoromethane
(CCl2F2) is known as freon-12. Freon-12 is produced from CCl4 by swarts reaction.
CCl4 + 2 AgF → CCl2F2 + 2 AgF
Freons are used as aerosol propellants, refrigerants and in air conditioning.
Harmful effects: Freons deplete the ozone layer exposing humans to UV rays leading to skin cancer.
(vi) DDT (or) p,p‫׀‬-Dichlorodiphenyltrichloroethane:
(p-ClC6H4)2CH-CCl3
It is used as an insecticide, used to control malaria and typhus and also as pesticide.
Harmful effects: DDT is highly toxic towards fish. It is harmful to animals and humans because it is
fat soluble and highly stable. It does not metabolise easily hence it gets accumulated in tissues.
Test to distinguish alkyl, allyl and benzyl chlorides from vinyl and phenyl chlorides:
On treatment with aq.KOH followed by dil HNO3 and AgNO3 solution alkyl, allyl and benzyl
chlorides give a curdy white precipitate soluble in ammonium hydroxide whereas vinyl and aryl
chlorides do not answer the test.
22
Test to distinguish alkyl chlorides from alkyl bromides and iodides:
On treatment with aq.KOH followed by dil HNO3 and AgNO3 solution, alkyl chlorides give a curdy
white precipitate soluble in ammonium hydroxide, alkyl bromides give a pale yellow precipitate
partially soluble in ammonium hydroxide and alkyl iodides give a yellow precipitate insoluble in
ammonium hydroxide solution
Q. Alkyl halides produce alcohol (Substitution) when treated with aqueous KOH but produce alkene
(Elimination) when treated with alcoholic KOH. Explain.
KOH dissociates completely in water which is highly polar hence the concentration of OH— ions
are very high. Therefore in aqueous solution OH— acts as a nuleophile leading to substitution
reaction. Whereas in alcoholic solution, KOH reacts with alcohol to form alkoxide (OR—) ions which
are strong bases and they abstract proton leading to elimination reaction.
Q. Arrange the following in decreasing order of polarity (or) dipole moment: Give reason
CH3Cl, CH2Cl2, CHCl3 and CCl4
Answer: CH3Cl > CH2Cl2 > CHCl3 > CCl4
As the number of chlorine atoms increases the dipoles partly get cancelled. In CCl4 all dipoles get
cancelled hence it has zero dipole moment and it is non polar molecule.
Q. The dipole moment of chlorobenzene is lower than that of chlorocyclohexane. Why?
The carbon atom in chlorobenzene is sp2 hybridised and is more electronegative hence forms
shorter bond with chlorine whereas the carbon atom in chlorocyclohexane is sp3 hybridised and is less
electronegative hence forms longer bond. Since dipole moment is the product of charge and distance,
chlorobenzene has lower dipole moment.
(OR)
In chlorocyclohexane, the dipole is due to electron withdrawing effect of chlorine and it acts in
same direction whereas in chlorobenzene, the dipole due to electron withdrawing inductive effect is
opposed by dipole due to electron releasing resonance effect hence the dipole gets partly cancelled.

Questions:

1 Write all possible isomers of C4H9Cl and give their common and IUPAC names. Also classify
them into primary, secondary and tertiary halides.
2 Draw the structures of all eight isomers of C5H11Br and give their IUPAC names.
3 Classify the following as alkyl, allyl, benzyl, vinyl and aryl halides and also classify as primary,
secondary and tertiary halides:
(i) C6H5CH(CH3)Br (ii) C6H5Cl (iii) C6H5CH2Br (iv) (CH3)3CCH2Br (v) (CH3)3CBr
(vi) CH3-CH=CHCl (vii) CH2=CH-CH(CH3)Br (viii) CH2=CH-C(CH3)2Br
(ix) (C6H5)2C(CH3)Br (x) CH3-CH=CCl-CH3 (xi) CH2=CH-CH(Br)-CH3 (xii) C2H5F

23
4 Give the IUPAC names of the following:
(i) CH3CH(Cl)CH(CH3)CH2CH2CH3 (ii) ClCH2-CH=CH-CH2Br
(iii) (CH3)2CHCH(Br)CH3 (iv) CH3CH2CH(CH3)CH2CH2CH(C2H5)Cl
(v) CH3CH2CH(CH3)CH(I)CH(C2H5)CH2CH2Cl (vi) (CH3)3CCH2CH(Br)C6H5
(vii) isohexyl chloride (viii) neohexyl bromide (ix) Benzyl chloride (x) tert-pentyl iodide
(xi) CH3C(C2H5)2CH2Br (xii) ICH2-CH2-C C-CH2-CH2Br
(xiii) CHF2CBrClF (xiv) CH3-C = C –CH2-CH3 (xv) CH2=CH-CH-(CH2)3-CH3
Br CH3 F
CH=CH2 Cl CH3 CH3

(xvi) CH3-CH2-CH-CH-CH-CH3 (xvii) (xviii)

CH2Cl CH3 Br Cl

(xix) p-ClC6H4CH2CH(CH3)2 (xx) m-ClCH2C6H4CH2C(CH3)3 (xxi) Br CH(CH3)2

(xxii) (CH3)3CCH=C(Cl)C6H4I-p (xxiii) CH3C(p-ClC6H4)2CH(Br)-CH3

H CH3 CH3 CH3

(xxiv) (xxv) H
H
H CH3
Cl
CH3 CH3 Br
5 Write the structures of the following:
(i) 2-Chloro-3-methylpentane (ii) 1-Bromo-4-ethylcyclohexane (iii) 1,4-Dibromobut-2-ene
(iv) 4-tert-Butyl-3-iodoheptane (v) 1-Bromo-4-sec-butyl-2-methylbenzene
(vi) 2-(2-Chlorophenyl)-1-iodooctane (vii) p-Bromochlorobenzene (viii) Difluoroethyne
(ix) 1,4-diisobutylcyclohexane (x) p,p‫׀‬-dibromodiphenylmethane
6 Identify all possible monochloro substituted products formed when butane undergoes free radical
chlorination.
7 Identify all possible dichloro substituted products formed when butane undergoes free radical
chlorination.
8 Identify all possible monochloro substituted products formed when 2-methylbutane undergoes
free radical chlorination.
9 A hydrocarbon of molecular formula C5H10 gives only one monochloro product on free radical
halogenation. Identify the hydrocarbon.
10 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.

24
11 How would you prepare 1-iodobutane from
(i) Butane (ii) Butan-1-ol (iii) 1-Chlorobutane (iv) But-1-ene
12 Complete the following giving the major product in each case:
CH=CH2 OH
(i) + HBr → (ii) + SOCl2 →

CH=CH2 CH3
(C6H5CO)2O2
(iii) + HBr (iv) + HI →

Peroxide
(v) CH3-CH2-CH=CH2 + HCl → (vi) CH3-CH2-CH=CH2 + HBr

CH2-CH3
Heat (or) Heat (or)
(vii) + Cl2 (viii) + Br2
UV light UV light
O2N
CH2-OH
(ix) + HCl Heat (or) (x) CH3-CH2-Br + NaI →
HO

Heat (or)
(xi) C6H5-N2Cl + Cu2Cl2 → (xii) CH3-CH2-CH=CH2 + Cl2
UV light
13 Arrange the following in the increasing order of boiling points:
(i) Bromomethane, bromoform, chloromethane, dibromomethane and iodoform.
(ii) 1-Chlorobutane, isopropylchloride, 1-chloropentane and 1-chloropropane
14 Which one of the following will react faster by SN2? Why?
(i) 1-Chloropentane and 2-chloropentane (ii) n-butyl bromide and isobutyl bromide

(iii) CH2Cl and Cl (iv) Cl and

Cl
(v) I and Cl

15 Which one of the following will react faster by SN1? Why?

(i) 1-Chloropentane and 2-chloropentane (ii) tert-butyl bromide and isobutyl bromide

(iii) CH2Cl and CH(Cl)CH3 (iv) Cl and

Cl
(v) Cl and Br

25
16 Which one of the following will react faster by SN reaction? Why?
(i) 1-Chloropentane and 1-bromopentane (ii) CH3-CH2-Cl and CH2=CH-Cl

(iii) CH2Cl and Cl (iv) CH2=CH-CH2-Cl and CH3-CH2-CH2-Cl

17 Out of C6H5CH2Cl and C6H5CHClC6H5 which is more easily hydrolysed by aqueous KOH?
18 Identify the chiral and achiral molecules in the following:
(i) Butan-1-ol, (ii) butan-2-ol, (iii) 1-bromobutane, (iv) 2-bromobutane, (v) 1-bromo-2-
chloropropane, (vi) 2-chloropentane, (vii) 3-chloropentane, (viii)

(ix) (x) Cl
Bromocholoroiodomethane
Cl

19 Identify the stereocentre in the following molecules and draw the structure according to wedge
and dash representation around the stereocentre:
(i) Pentan-2-ol (ii) 2-chlorohexane (iii) 2-Bromobutan-2-ol
20 Which isomer of molecular formula C7H16 is optically active? Give its IUPAC name.
21 Predict the order of reactivity of the following compounds in SN1 and SN2 reactions:
(i) The four isomeric bromobutanes
(ii) C6H5CH2Br, C6H5CH(C6H5)Br, C6H5CH(CH3)Br and C6H5C(CH3)(C6H5)Br
(iii) 2-Bromo-2-methylbutane, 1-bromopentane and 2-bromopentane
(iv) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane and 2-Bromo-3-methylbutane
(v) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 2-Bromo-2-methylbutane and
1-Bromo-3-methylbutane
22 Write the mechanism of the following reactions:
EtOH-H2O
(i) n-BuBr + KCN n-BuCN + KBr
EtOH-H2O
(ii) tert-BuBr + KCN tert-BuCN + KBr
23 An optically active halide of molecular formula C7H15Br undergoes hydrolysis with racemisation.
Explain the mechanism.
24 An optically active halide of molecular formula C7H15Br undergoes hydrolysis with inversion of
configuration. Explain the mechanism.
25 Predict all possible alkenes that would be formed by dehydrohalogenation of the following alkyl
halides and identify the major product:
(i) 2-Bromo-2-methylbutane (ii) 2-Chloro-2,3-dimethylpentane (iii) 3-Bromo-2,2,3-trimethyl
pentane (iv) 1-Bromo-1-methylcyclohexane (v) 1-Bromo-1,2-dimethylcyclohexane
26 Give a chemical test to distinguish the following:
(i) Benzyl chloride and phenyl chloride (ii) 1-Chloropropene and 3-chloropropene
(iii) Chloroethane and chloroethene (iv) Chlorobenzene and chlorocyclohexane
(v) Chloroethane and bromoethane.
26
27 An organic compound A of molecular formula C4H9Br on reaction with alc. KOH gives
compound B. Compound B when treated with HBr gives compound C which is an isomer of A.
When A is reacted with sodium metal in dry ether solvent it gives D of molecular formula C8H18
which is different from the compound formed when n-butyl bromide is reacted with sodium metal
in dry ether solvent. Identify A, B, C and D and give equations for all the reactions.
28 An alkyl halide A when treated with alcoholic solution of KCN gives a compound B. Compound
B on acidic hydrolysis gives propanoic acid. Identify A and B and explain the reactions involved.
29 Complete the following:
Dry Ether H2O
(i) CH3-CH2-Cl + Mg

Dry Ether C2H5OH

(ii) C6H5Br + Mg
KCN H3O+
(iii) CH3-CH2-Cl
Ethanol
Ethanol
(iv) (CH3)3CBr + KOH
Heat
(v) CH3CH2CH(Br)CH3 + KOH Water

Ethanol
(vi) CH3CH2CH(Br)CH3 + KOH

(vii) + Br2 CCl4

(viii) + Br2 Heat or UV light

CH3
(ix) + Cl2 Fe / Dark

CH3
UV light
(x) + Cl2

Heat
(xi) -OH + HCl
SOCl2
(xii) CH2=CH-CH2-OH
30 Write equations for the following:
(i) Friedel-Craft’s acylation of chlorobenzene.
(ii) Ethyl bromide is treated with excess of ammonia in the presence of a base.
(iii) n-propylbromide is treated with sodium ethoxide.

27
 (iv) Isobutyl bromide is treated with sodium metal in dry ether solvent.
(v) CHCl3 is exposed to air.
(vi) Chlorobenzene is treated with Mg in ether followed by hydrolysis.
(vii) Cylcohexene is treated with Br2 in the presence of UV light
(viii) Bromobenzene is treated with ethyl chloride in the presence of anhydrous AlCl3
(ix) Ethyl benzene is treated with chlorine in the presence of UV light.
(x) 1-Bromobutane is treated with sodium phenoxide.
(xi) Aniline is treated with HNO2
(xii) Cyclohexanol is treated with red phosphorus and I2
31 Carry out the following conversions:
(i) Ethanol to but-1-yne (ii) Ethane to bromoethene (iii) Propene to 1-nitropropane
(iv) Propene to n-propylnitrite (v) Propene to 2-nitropropane (vi) Toluene to benzyl alcohol
(vii) Propene to propyne (viii) Ethanol to ethylfluoride (ix) Bromomethane to propanone
(x) But-1-ene to but-2-ene (xi) 1-Chlorobutane to n-octane (xii) Benzene to biphenyl
(xiii) Propene to propan-1-ol (xiv) Propene to propan-2-ol (xv) Ethanol to bromoethane
(xvi) 1-Bromopropane to 2-bromopropane (xvii) Benzene to 4-bromonitrobenzene
(xviii) Ethanol to propanenitrile (xix) Benzyl alcohol to 2-phenylethanoic acid
(xx) Ethanol to ethylisocyanide (xxi) Aniline to chlorobenzene
(xxii) 1-Chlorobutane to 3,4-dimethylhexane (xxiii) 2-Chlorobutane to 2,3-dichlorobutane
(xxiv) 2-Methylprop-1-ene to 2-chloro-2-methylpropane (xxv) But-1-ene to n-butyl iodide
(xxvi) But-1-ene to sec-butyl fluoride (xxvii) Ethyl chloride to propanoic acid
(xxviii) 2-chloropropane to propan-1-ol (xxix) Aniline to iodobenzene
(xxx) Chlorobenzene to p-nitrophenol (xxxi) 2-bromopropane to 1-bromopropane
(xxxii) tert-butyl bromide to isobutyl bromide (xxxiii) Benzene to p-chloroacetophenone
(xxxiv) 1-Chloro-2-methylpropane to 2-chloro-2-methylpropane
(xxxv) Methyl bromide to acetic acid (xxxvi) Bromobenzene to benzene
(xxxvii) Toluene to 1,2-diphenyl ethane (xxxviii) Ethyl benzene to 2,3-diphenylbutane
(xxxix) isopropyl alcohol to iodoform (xl) Aniline to phenylisocyanide

28