UNIT-X HALOALKANE & HALOARENE ( BY:JITENDER SIR)

These 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. For example,

(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+1 X. 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.

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.

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

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

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Halogenation :( it’s a electrophilic substitution reaction )
Cl

+ CI2 AlCl3 + HCl

chlorobenzene
Br

AlCl3
+ Br Br + HBr

Bromobenzene

2 Conc.HNO3
+ I2 2 + HI

Iodobenzene

Halogenation of Toluene :
CH2Cl

Cl2/ U.V. HCl

+
CH3
Bezylchloride

CH3 CH3
Cl
Toluene Cl2 / Anhyd. AlCl 3

o-Chlorotoluene
Cl

Nitration: Benzene is treated with a mixture of concentrated nitric acid and concentrated sulphuric
acid (catalyst) at a temperature not exceeding 50°C. As temperature increases there is a greater
chance of getting more than one nitro group, -NO2, substituted onto the ring.
NO2
Conc.HNO 3
+ H2O
Conc. H 2SO4
Nitrobenzene
Nitration of bromobenzene : Halobenzene is a ortho/para directing compound so nitro group will
attach on orth and meta position of bromobenzene.
Br Br Br
Br2 / FeCl3 Conc. HNO3 NO2
Conc.H2SO4 +
Bromobenzene o-Nitrobromobenzene NO2
p-Nitrobromobenzene

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Electrophilic Substitution in Haloarene:

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

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Q) What is the effect of nitro group on the reactivity of haloarene?
Ans) The presence of an electron withdrawing group (-NO2) at ortho- and para-positions increases
the reactivity of haloarenes.
Q: why does NO2 group show its effect
only at ortho- and para- positions
and not at meta- position?
Answer: 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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Fittig Reaction: Aryl halides also give analogous compounds when treated with sodium in dry
ether, in whic h two aryl groups are joined together. It is called Fittig reaction.

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
Cl CH3

Na/Dry ether
+ CH3-Cl + Na Cl

Chlorobenzene Toluene

Diazotisation : reaction between phenylamine (also known as aniline and aminobenzene) and
nitrous acid - particularly its reaction at temperatures of less than 5°C to produce diazonium salts.
NH2 N NCl
NaNO2 / dil. HCl
273-278K
Aniline Benzene diazonium chloride

Sandmayer Reaction : The Cl, Br and CN nucleophiles can easily be introduced in the benzene
ring of benzene diazonium salt in the presence of Cu(I) ion.
+
N N Cl X
NH2
Cu2X2
NaNO2/ dil HCl
(where X= Cl or Br )
+ N2
273-278K
Aniline Benzene diazonium Chloride Halobenzene ( Haloarene)

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.
+ I
N N Cl
KI
+ N2

Benzene diazonium Chloride Iodobenzene

Carbylamine Reaction : Aliphatic and aromatic primary amines on heating with chloroform and
ethanolic KOH form isocyanides or carbylamines which are foul smelling substances.
+ −

R-NH 2 + CHC 3 + alc. KOH ⎯⎯ → R- N  C + 3KC +H2O
Alkylisocyanide
NH2
N C

+ CHCl3 + 3KOH + 3KCl + 3H2O

Aniline Phenyl isocyanide

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Conversion of Toluene to Benzyl Alcohol to Benzyl chloride:
CH3 CH2Cl CH2OH CH2CI

Cl2 / hv aq.KOH SOCI2

-HCl -KCl

Bezylchloride Benzyl alcohol BenzylChloride

Toluene

Toluene to 2-Phenylethanoic acid :

CH3 CH2Cl CH2CN CH2COOH
+
alc.KCN H /H2O
Cl2 / hv
Complete
-HCl -KCl hydrolysis

Toluene Bezylchloride 2-Phenylethanenitrile 2-Phenylethanoic acid

Convert the following:

1. Toluene to benzyl alcohol

2. Benzene to 4-bromonitrobenzene
3. Benzyl alcohol to 2-phenylethanoic acid
4. Aniline to chlorobenzene
5. Chlorobenzene to p-nitrophenol
6. Benzene to diphenyl
7. Aniline to phenylisocyanide
8. Benzyl chloride to Benzyl alcohol
9. Phenol to Benzene
10. Chlorobenzene to Toluene
11. Aniline to Iodobenzene
12. Aniline to Phenol
13. Benzene to m-Bromonitrobenzene
14. Benzene to p-Bromonitrobenzene
15. Phenol to Toluene

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Halogenation of Alkane :
CH 4 + C 2 ⎯⎯
hv
→ CH3 -C + HC
Methane Chloromethane

CH 4 + Br2 ⎯⎯
hv
→ CH 3 -Br + HBr
Methane Bromomethane

CH 4 + I2 ⎯⎯⎯⎯→
Conc. HNO3
CH3 -I + HI
Methane Iodomethane
The reaction between alkanes and fluorine is explosive even in the cold and dark, and you tend to
get carbon and hydrogen fluoride produced. It is of no particular interest. For example:

Q) Why we used oxidizing agent in iodination of alkane?

Ans) Reactions of alkane with iodine are reversible in nature and require the presence of an
oxidising agent (HNO3, HIO4) to oxidise the HI (good reducing agent) formed during iodination.
Fluoro compounds are not prepared by this method due to high reactivity of fluorine.
2HNO3 + 2 HI → I2 + 2NO2 + 2H2O

Wurtz Reaction : in this reaction same kind of alkyl halide react with each other in presence of
sodium metal and dry ether.

H3C Cl + 2Na + Cl CH3 dry ether H3C CH3 + Na Cl

Ethane
2 moles of Chloromethane
dry ether
2 H3C CH2 Cl + Na H3C CH2 CH2 CH3
-NaCl
Chloroethane Butane
dry ether
H3C CH2 CH2 CH2 Cl + Na H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3
-NaCl
1-Chlorobutane Octane

CH3 CH3
Cl Cl
Na + Na
H3C CH CH3 + H3C CH CH3
dry ether
H3C CH CH CH3 Cl

2-chloropropane 2-chloropropane 2,3-dimethylbutane

Function of Aqueous KOH/NaOH:( substitution of halogen and with OH- group )

𝐴𝑞𝑢𝑒𝑜𝑢 𝑠 𝐾𝑂𝐻
CH3 − CH2 − X → CH3 − CH2 − OH + KX Where X= Cℓ , Br , I

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Function of Alcoholic KOH : Dehydrohalogenation: Removal of β- hydrogen
and α- halogen from haloalkane to form alkene or alkynes on heating with alcoholic KOH.
β α
C H3 -C H 2 - X ⎯⎯⎯
alc.KOH
⎯→ CH 2 =CH 2 + H 2O + KBr (X=Cl,Br,I)
Haloalkane Ethene
β α
CH3 -C H 2 -C H 2 - Br ⎯⎯⎯
alc.KOH
⎯→ CH3 -CH=CH 2 + H 2O + KBr
1-Bromopropane Propene

Br
alc.KOH
H3C CH CH3 H3C CH CH2 + K Br + H2O

2-bromopropane prop-1-ene
Br
alc. KOH
H3C CH2 CH CH3 H3C CH CH CH3 + H3C CH2 CH CH2

2-bromobutane Saytzeff `s But-2-ene But-1-ene

rule (80% stable) (20%stable)

Br CH3 CH3 CH2

alc. KOH
+

1-bromo-1-methylcyclohexane 1-methylcyclohex-1-ene
( major)
Br CH3 CH3

CH3 alc. KOH

CH3

1-bromo-1,2-dimethylcyclohexane 1,2-dimethylcyclohex-1-ene
Br Br
alc. KOH HC CH
H2C CH2
NaNH2 Ethyne
1,2-dibromoethane (Acetylene)

Q) 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 aq. Solution ,KOH is almost completely ionized to give OH- ions which being a strong nucleophile
brings about a substitution reaction on alkyl halides to form alcohols .
In contrast , an alcoholic solution of KOH, specially in ethyl alcohol, produce C2H5O─ ions. These ions
are stronger base than OH─ ion. Thus they abstracts the β- hydrogen of alkyl halide to produce alkene.
KOH K + OH RO is a strong nucleophile as well as strong
base, So when it behave as a strong base it will
go for elimination process.
H2O(aq.) H + OH
* OH is only act as a nucleophile so always go
ROH(alc.) H + RO for substitution.

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 Role of Br2 water with CCl4 : Addition of bromine on multiple bonded carbon ( help in detection of
unsaturated compound) reddish brown colour of bromine change to colourless with alkene/alkyes.
Br Br
Br2/CCl4
CH2=CH2 CH2 CH2

Alkane to alkyne : (i) Cℓ2/hv ii. Alcoholic KOH iii) Br2/CCℓ4 iv) alcoholic KOH

CH 3 − CH 3 ⎯⎯⎯
Cl2 / hv
→ CH 3 − CH 2 − Cl ⎯⎯⎯⎯
alc. KOH
→ CH 2 = CH 2 ⎯⎯⎯⎯
Br2 water
→ Br − CH 2 − CH 2 − Br ⎯⎯⎯⎯
alc. KOH
NaNH 2
→ CH  CH
Ethane Chloroethane Ethene 1,2 -Dibromoethane Ethyne

Q) WhyThionyl chloride is more preferred over concentrated halogen acid for the formation of
alkyl halide from alcohol ?
Ans) Thionyl chloride is preferred because the other two products are escapable gases. Hence the
reaction gives pure alkyl halides
SOCl2
H3C CH2 OH H3C CH2 Cl + SO2 + HCl

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 the alcohol with concentrated HCl at room temperature.
Constant boiling with HBr (48%) is used for preparing alkyl bromide. Good yields of R—I 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°. 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.

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.
NaI
CH3CH 2 -C ⎯⎯⎯⎯⎯⎯
dry Acetone→ CH 3CH 2 -I + NaC
Chloroethane Iodoethane
CH3CH 2 -Br ⎯⎯⎯⎯⎯⎯NaI
dry Acetone→ CH3CH 2 -I + NaBr
NaCl or NaBr thus formed is precipitated in dry acetone. It facilitates the forward reaction according to
Le Chatelier’s Principle. The Dry Acetone in the medium doesn't allow NaX to dissolve because
NaX is a polar compound whereas Acetone is an important organic non-polar solvent, which
results in precipitation of NaX in Acetone which facilitates reaction in forward direction.

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 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.
AgF
CH 3CH 2 -C ⎯⎯⎯
→ CH 3CH 2 -F + AgC
Chloroethane Fluoroethane
AgF
CH 3CH 2 -Br ⎯⎯⎯
→ CH 3CH 2 -F + AgBr
Bromoethane Fluoroethane

Markownikov`s rule :
According to this rule negative part of any addendum ( like HBr , HCℓ ,HI or H2O etc) Goes to that part
of alkene which carry less number of hydrogen and vice versa.
Br
H3C CH CH3
-
H3C CH CH2 + H -Br+
Absence of Peroxide⎯
⎯⎯⎯⎯⎯⎯⎯⎯⎯ → 2-bromopropane

Cl
H3C CH CH3
-
H3C CH CH2 + H+-Cl Absence of Peroxide⎯
⎯⎯⎯⎯⎯⎯⎯⎯⎯ → 2-chloropropane

OH
+
H3C CH CH2 + H+-OH
- H H3C CH CH3
prop-1-ene propan-2-ol

Antimarkownikov`s rule : According to this rule the negative part of the addendum goes to that carbon
of the multiple bond which contains more number of hydrogen carbon atom and vice versa in the
presence of peroxides . ( Peroxide effect )
-
Peroxide
H3C CH CH2 + H+-Br H3C CH2 CH2 Br
1-bromopropane
Reaction with HCl
The reaction with HCl is unfavourable because the H-Cl bond is much stronger than the H-Br bond.
Step 1 is endothermic, and the reaction becomes too slow to be useful.
Reaction with HI
Step 1 is favourable, because the H-I bond is relatively weak.
But Step 2, addition of I─ to the alkene, is unfavourable and endothermic because of the bulk of the
iodine radical.
So, the iodine radicals combine to form I2.

Formation of haloalakne through free radical halogination of alkane is not a suitalbe process bcos we
will get a mixture of haloalakne which is not easy to separate.

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 Formation of isomers: (i)Alcoholic KOH ii) Markownikov`s / Antimarkownikov`s rule
Br
alc. KOH HBr
HC CH CH Br H3C CH CH2 H3C CH CH3
3 2 2 Markownikov`s rule

1-Bromopropane prop-1-ene 2-Bromopropane

Br
alc. KOH HBr
H3C CH CH3 H3C CH CH2 H3C CH2 CH2 Br
anti Markownikov`s

2-bromopropane prop-1-ene rule 1-bromopropane

Function of alcoholic KCN , AgCN and KNO2 and AgNO2 :

alc. KCN
CH
CH33CH
CH22-CN
-CN
Propane nitrile
alc. AgCN
CH3CH2-NC
CH3CH2-X Ethyl isocyanide
( where asX= Cl, Br) alc. AgNO2
CH3CH2-NO2
Nitroethane
alc. KNO2
CH3CH2-ONO
Ethyl nitrite

Q)What do you mean by ambidentate Nucleophiles?

Ans) Groups like cyanides and nitrites possess two nucleophilic centres and are called ambident
nucleophiles. Eg : [–CN →:CN–], i.e., linking through carbon atom resulting in alkyl cyanides and
through nitrogen atom leading to isocyanides.
other eg : [– NO2 → ONO– ] 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.
Ans) 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

Conversion of Ethanol to But-1-yne

Red P/ I2 CH CH
CH3-CH2-I H3C CH2 C CH
CH3-CH2-OH NaNH2
Iodoethane But-1-yne
Ethanol

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 Complete the following:
OH

(i) + SOCl2

CH2CH3 Br2 / hv
(ii)
O2N

CH2OH
(iii) HCl
HO
+

CH3
(iv) + HI

hv
(v) + Br Br

Example10.4: Complete the following:

H H

Absence of peroxide
(i) H + HBr

(ii) H3C CH2 CH CH2 + HCl

H presence of peroxide
(iii) H + HBr

(iv) ( CH3 )3 C-Br ethanol

+ KOH ⎯⎯⎯⎯
heat →

(v) CH3 -CH(Br)-CH 2 -CH3 + KOH Water →

⎯⎯⎯⎯
(vi) C6 H5ONa + C2 H5C ⎯⎯
→
Br MgBr

Mg / dry ether H+/ H2O

(vii) + Mg(OH)Br

Bromocyclohexane Cyclhexylmagnesiumbromide Cyclohexane

Br2/ hv
(Viii) CH3-CH=CH2

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 10.7 Write the equations for the preparation of 1-iodobutane from

(i) 1-butanol (ii) 1-chlorobutane (iii) but-1-ene.

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) Propene to propyne (v) Ethanol to ethyl fluoride (vi) Bromomethane to propanone

(vii) But-1-ene to but-2-ene (viii) 1-Chlorobutane to n-octane (ix) Benzene to biphenyl.

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) Chlorobenzene to p-nitrophenol (xv) 2-Bromopropane to 1-bromopropane

(xvi) Chloroethane to butane (xvii) Benzene to diphenyl

(xviii) tert-Butyl bromide to isobutyl bromide (xx) Aniline to phenylisocyanide

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?

10.21Primary 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.

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 Physical properties of Haloalkane and Haloarene
1. Nature: Alkyl halides are colourless when pure. However, bromides and iodides develop colour
when exposed to light. Many volatile halogen compounds have sweet smell.
2. Melting and boiling point:
Methyl chloride, methyl bromide, ethyl chloride and some chlorofluoromethanes are gases at room
temperature.
Q. Why is the boiling points of chlorides, bromides and iodides are considerably higher than
those of the hydrocarbons of comparable molecular mass?
Ans 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.
The boiling points of alkyl halides decrease in the order: RI > RBr > RCl > RF. because with the
increase in size and mass of halogen atom, the magnitude of van der Waal forces increases.
Q. Why the boiling point of 1-Bromobutane is higher than other isomeric haloalkane?

Ans The boiling points of isomeric haloalkanes decrease with increase in branching because with
branching surface area will decrease. So, 2-bromo-2-methylpropane has the lowest b.pt.
Boiling and melting point for haloarenes:

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.
Q. p-Dichlorobenzene has higher m.p. and solubility than those of o- and m-isomer.
Ans p-Dichlorobenzene is symmetrical, therefore having a close packing in its crystal lattice and has
higher m.pt. Its higher solubility is due to its symmetrical structure and more force of attraction
with the solvent.
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.
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.

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 Chemical properties:
1. Reactions of Haloalkanes:
The reactions of haloalkanes may be divided into the following categories:
1. Nucleophilic substitution (All reactions are on previous page 18)
2. Elimination reactions (β-elimination: Haloalkane to alkene or alkyne)
3. Reaction with metals. (a) Formation of Grignard reaction R-Mg-X (b) Wurtz reaction
2. Reactions of Haloarenes:
1. Nucleophilic substitution (Chlorobenzene to Phenol)
2. Electrophilic substitution reactions(Alkylation/acylation, Nitration, Sulphonation etc.
3. Reaction with metals (a) Formation of Grignard reaction (b) Fittig and wurtz fittig Rx.

Mechanism for Nucleophilic substitution of haloalkanes

SN1 Mechanism :
CH3
CH3
Step-1
H3C C Br C
+
+ Br
H3C CH3
CH3
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.
CH3
CH3 CH3
Step-2
C
+
+
OH H3C C OH or HO C CH3
H3C CH3 CH3 CH3

SN2 Mechanism:
H
H H H
- -
HO + H C Br
HO C Br
HO C H + Br

H H weaker
H nucleophile
Bromomethane Methanol
(dextrorotary) (leavorotatory)
allylic and benzylic halides show high reactivity towards the SN1 reaction. The carbocation thus formed
gets stabilised through resonance as shown below:

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 Q) What is the difference between Retention and inversion?

CH3 CH3 CH3

-
OH
OH-
H3C C OH H3C C Br HO C CH3
Retention Inversion
CH3 CH3 CH3

Retention: Retention of configuration of the spatial arrangement of bonds to an asymmetric centre during
a chemical reaction. It means configuration of molecule remain same after the reaction.
Inversion: If the configuration of molecule do not remain same after the reaction and the leaving group is
pushed away. This process is called as inversion of configuration. SN2 reactions of optically active
halides are accompanied by inversion of configuration

Q) What do you mean by Racemic mixture?

Ans) 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
.The process of conversion of enantiomer into a racemic mixture is known as racemisation.

10.17. Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous KOH?
Ans) Hydrolysis by aqueous KOH proceeds through the formation of carbocation. If carbocation is
stable, then the compound is easily hydrolyzed by aqueous KOH. Now, C6H5CH2+ forms 1°-carbocation,
while C6H5CH+C6H5 forms 2°-carbocation, which is more stable than 1°-carbocation. Hence,
C6H5CHClC6H5 is hydrolyzed more easily than C6H5CH2Cl by aqueous KOH

Q. Why benzylic halides show high reactivity toward SN1 reaction.

Ans: Because benzylic carbocation formed is highly stable through resonance.

SN1 SN2
1. It is a first order reaction It is a second order reaction
2 It occurs in two steps. It occurs in one step only
3 The rate of reaction depends only on the The rate of reaction depends upon concentration
concentration of alkyl halide and not on the of alkyl halide and nucleophile
concentration of nucleophile. Rate of reaction = k [R-X] [Nu:]
Rate of reaction = k [R-X]
4. Retention as well as inversion takes place means Only Inversion takes place
racemisation takes place
5. Reactivity order depend upon stability of Reactivity order of R-X:
carbocation of R-X = 30 > 20 > 10 30 < 20 <10
Allylic and benzylic halides show high reactivity
towards the SN1 reaction. (Due to resonance they
have stable carbocation)

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 Q)What is the reactivity in SN2 and SN1 ?
SN2 : Primary halide > Secondary halide > Tertiary halide.
SN1 : Primary halide < Secondary halide < Tertiary halide.
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–C l > R–F.

Q. Predict the order of reactivity of the following compounds in SN1 and SN2 Rx:
(i) C6H5CH2Br (ii)C6H5CH(C6H5)Br (iii)C6H5CH(CH3)Br (iv) C6H5C(CH3)(C6H5)Br
Ans: SN2 (i) > (iii) > (ii) > (iv)
(b) CH3CH2CH2CH2Br , (CH3)3CBr , (CH3)2CHCH2Br , CH3CH2CH(Br)CH3
i)CH3CH2CH2CH2Br < (CH3)2CHCH2Br < CH3CH2CH(Br)CH3 < (CH3)3CBr (SN1)
ii)CH3CH2CH2CH2Br > (CH3)2CHCH2Br > CH3CH2CH(Br)CH3 > (CH3)3CBr (SN2)

10.7. In the following pairs, which compound undergoes faster SN1 reaction?
Br
(i) H3C CH2 CH2 CH2 Br or H3C CH2 CH CH3 Ans:
(A) (B)
Br CH3
H3C CH2 CH CH3 or
(ii) H3C C Br Ans:
(A) CH3
(B)
(iii) H3C CH CH2 CH2 Br or H3C CH2 CH CH2 Br
CH3
CH3

10.8. In the following pairs, which compound undergoes faster SN1 reaction?
Cl
(i) or Cl
Ans:

(A) (B)
Cl
(ii) or Cl
Ans:
(A) (B)

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, 3-Bromo-2-methylbutane
Ans: (i)
(ii)

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 Plane polarized light: light produced by passing ordinary light through Nicol prism.
optically active compounds: Certain compounds rotate the plane polarised light when it is passed
through their solutions. 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 (indicated by d or (+) sign). If the light is rotated towards
left (anticlockwise direction), the compound is said to be laevorotatory. (indicated by ℓ or (-).
asymmetric carbon or stereocentre : if all the substituents attached to that carbon are different. The
asymmetry of the molecule is responsible for the optical activity.
Those compounds which are nonsuperimposable on their mirror image are said to be chiral and this
property is known as chirality. While those compounds, which are, superimposable on their mirror
images are called achiral.
Enantiomers: Those stereoisomers which are nonsuperimposable on their mirror images.
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.

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.
Butan-2-ol :Butan-2-ol has four different groups attached to the tetrahedral carbon and as expected is
chiral so no possibility for superimposable on each other.

Q. Identify chiral and achiral molecules in each of the following pair of compounds.
(i) CH CH3
3
(ii) C3H7 C2H5
H
H
H OH H OH
Br OH Br Br CH3 C2H5
(i) (ii) (i) (ii)

(iii) (a) CH3-CH2-CH2-CH2-Br (b) CH3-CH-CH2-CH3

Br

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 Q) Why Aryl halides are extremely less reactive towards nucleophilic substitution reactions?

Ans)
X H
sp2 hybrid carbon
sp3 hybrid carbon
C
H3C Cl
H
(i) Resonance effect:
C—Cl bond acquires a partial double bond character ( sp2) due to resonance which is difficult to break
as compared to C—Cl in haloarene.

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

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 therefore, haloarenes are less reactive.

(iii) Instability of phenyl cation: In case of haloarenes, the phenyl cation formed as a result of self-
ionisation will not be stabilized 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.

Q) 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.
Reactivity is thus controlled by the stronger inductive effect and orientation is controlled by resonance
effect.

Q: Chloroform is stored in dark coloured bottles, completely filled upto the brim.
Ans) Chloroform is slowly oxidised by air in the presence of light to a poisonous gas phosgene. It is
therefore stored in dark coloured bottles, completely filled upto the brim so that air is kept out.
CHC 3 + 1 O2 ⎯⎯⎯ sunlight
→ COC 2 + HC
2
* 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.

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 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.
The reactions involved in the question are:
Cl
Cl2 Cl 2
No Reaction
Dark Sunlight

cyclopentane chlorocyclopentane

Q)Why is Sulphuric acid not used during the reaction of alcohols with KI?
Ans)In the presence of sulphuric acid (H2SO4), KI produces HI
2KI + H 2SO4 ⎯⎯
→ 2KHSO 4 + 2HI
Since H2SO4 is an oxidizing agent, it oxidizes HI to I2(produced in the reaction to I2).
2HI + H 2SO4 ⎯⎯
→ I 2 + SO2 + H 2O
As a result, the reaction between alcohol and HI to produce alkyl iodide cannot occur. Therefore,
sulphuric acid is not used during the reaction of alcohols with KI. Instead, a non-oxidizing acid such as
H3PO4 is used.

10.12why the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
Ans) Normally dipole moment depends upon
two factor`s –
(i) Magnitude of the charge
(ii) Distance between bonded atom

• In chlorobenzene, the Cl-atom is linked to a sp2 hybridized carbon atom where as in cyclohexyl
chloride it is linked to a sp3hybridized carbon atom. Now, sp2 hybridized carbon is more
electronegative than sp3. Therefore, the magnitute of charge of C−Cl bond is less in chlorobenzene
than in cydohexyl chloride so the polarity of the C−Cl bond in chlorobenzene decreases.
• Due +Resonance effect of the benzene ring in chlorobenzene double bond character will come so
the C−Cl bond length will decreases.

Q) Grignard reagents (organometallic compound) are very reactive in moisture?

Ans: RMgX + H 2O ⎯⎯ → R-H + Mg(OH)X
Grignard reagent are very reactive .They react with moisture present in the apparatus or the starting
material and give alkanes .

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 Q: Haloalkanes though polar but immiscible with water.
Ans) In order for a haloalkane to dissolve in a 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 attraction forces are created between the haloalkane and the water molecules which
are not sufficient to overcome the older forces.

Q. A hydrocarbon of molecular mass 72gmol-1 gives a single monochloro derivative and two
dichloro derivatives on photochlorination. Give the structure of the hydrocarbon.
Ans: The hydrocarbon is pentane

CH3 H2C Cl CH3 Cl

H3C C CH2 Cl H3C C CH2 Cl H3C C HC
Cl
CH3 CH3 CH3
Monochloro derivative (i) Dichloro derivatives (ii)

Q. Chloroform contains chlorine but gives no reaction with AgNO3 solution. Why?
Ans: CHCI3 contain chlorine but it is bonded to carbon by covalent bond and therefore, it is not in ionic
forms. Hence, it does not combine with AgNO3 solution.
CHCI3 + AgNO3 → No Reaction

Q. Iodoform gives a precipitate with silver nitrate on heating while chloroform does not.
Ans: Carbon - iodine bond is quite weak as compared to carbon-chlorine bond. Therefore, when
iodoform is heated with AgNO3 solution, C-I bond gets cleaved easily and iodide ions react with AgNO3
solution to give precipitate of AgI. On the other hand, C-CI bond does not get cleaved.

Q. A small amount of ethyl alcohol is usually added to chloroform bottles. Why?

Ans: Alcohol retards the oxidation of chloroform to phosgene and it converts phosgene to harmless ethyl
carbonate.
2C2H5OH + COCI2 → ( C2H5)2CO3 + 2HCI

Q: (i) Allyl chloride is more reactive than n-propyl chloride towards nucleophilic substitution.
Explain why?
Or
(iii) Allyl chloride is hydrolysed more readily than n- propyl chloride.
Ans) (i) Because of greater stabilization of allylic carbocation intermediate formed by resonance.

CH2= CH CH2 CH2-CH=CH2

(ii) Allylic chloride readily undergoes ionization to form resonance stabilized carbocation. Since
carbocations are reactive species, allyl cation readly combines with OH─ ions to form allyl alcohol.
Hoever, n-propyl chloride does not undergo ionization to form n-propyl carbocation and hence it
gets hydrolysed less readily than allyl chloride.

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 Q. Organic halogen compounds used in industry as solvents are chlorides rather than bromides
and iodides. Explain.
Ans : Organic alkyl chlorides are used in industry as solvent because chlorides are more volatile than
bromides and iodides.

Q. Why vinyl chloride less reactive than ethyl chloride?

Ans: In vinyl chloride, the electron pair on chlorine atom conjugates with the Pi electron pair of the
double bond.
CH2= CH-CI CH2-CH=CI
As a result, there is partial double bond character in C-CI and its bond strength increases. Consequently,
it becomes difficult to cleave C-CI bond as compared to the bond in ethyl chloride where no such
conjugation is possible.

Q. The use of chloroform as anesthetic is decreasing. Why?

Ans: Because in some cases, CHCℓ3 causes cardiac and respiratory problems. Therefore, its use as
anesthetic is decreasing.

Q. An alkyl halide with molecular formula C4H9Br is optically active. What is its structure?
Ans: CH3 CH-CH2 - CH3

Br

10.13 Give the uses of freon 12, DDT, carbon tetrachloride and iodoform.( Not for 2020-21)
Uses of Freon − 12
Freon-12 (dichlorodifluoromethane, CF2Cl2) is commonly known as CFC. It is used as a refrigerant in
refrigerators and air conditioners. It is also used in aerosol spray propellants such as body sprays, hair
sprays, etc. However, it damages the ozone layer. Hence, its manufacture was banned in the United
States and many other countries in 1994.
Uses of DDT :
DDT (p, p−dichlorodiphenyltrichloroethane) is one of the best known insecticides. It is very effective
against mosquitoes and lice. But due its harmful effects, it was banned in the United States in 1973.
Uses of carbontetrachloride (CCl4)
(i) It is used for manufacturing refrigerants and propellants for aerosol cans.
(ii) It is used as feedstock in the synthesis of chlorofluorocarbons and other chemicals.
(iii) It is used as a solvent in the manufacture of pharmaceutical products.
(iv) Until the mid 1960’s, carbon tetrachloride was widely used as a cleaning fluid, a degreasing agent in
industries, a spot reamer in homes, and a fire extinguisher.
Uses of iodoform (CHI3)
Iodoform was used earlier as an antiseptic, but now it has been replaced by other formulations-
containing iodine-due to its objectionable smell. The antiseptic property of iodoform is only due to the
liberation of free iodine when it comes in contact with the skin.

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 Assignment
Unit X - Haloalkanes and Haloarenes
S.No. Question Details Marks
1. Chloroform contains chlorine but gives no reaction with silver nitrate solution. Why? 1
2. In the following pair of halogen compounds, which compound undergoes faster SN1 1
mechanism?
(CH3)3CCl or CH3CH2CH2Cl
3. State Saytzeff rule. 1
4. Explain why thionyl chloride method is preferred for preparing alkyl chlorides from 1
alcohols?
5. Illustrate retention of configuration with an example. 1
2
6. a)Arrange the following halides in order of increasing SN reactivity: 2
CH3Cl, CH3Br, CH3CH2Cl, (CH3)2CHCl
b) Arrange each of the following compounds in the order of increasing boiling points:
butane, n-butyl chloride, isobutyl chloride, n-pentylchloride
7. Write the structures of the following compounds and identify them as 10, 20 and 30 2
halides: (a) 2-bromo-2-methyl propane (b) 2-bromo-3-methylbutane
8. An alkyl halide (A) on reaction with Mg in dry ether followed by treatment with ethanol 2
gave 2-Methyl butane. Write all structures of (A).
9. Explain the following with the help of suitable examples: 2
(i) Finkelstein reaction
(ii) Swarts reaction
10. How will you prepare the following from benzene: 2
(a) m-chloronitrobenzene
(b) p-chloronitrobenzene
11. An organic compound A with molecular formula C4H9Br on treatment with alcoholic 3
KOH gave two isomeric compounds B and C. On ozonolysis, B gave only one product
CH3CHO while C gave two different products. Identify the compounds A,B and C.
12. Give reasons: 3
(a) Ethyl chloride is a gas whereas ethyl iodide is a liquid at room temperature.
(b) Haloalkanes react with KNO2 to form alkyl nitrite as main product while AgNO2
forms nitroalkanes as chief product.
(c) The boiling point of alkyl halide is higher than that of the corresponding alkane.
13. An alkyl halide X, of formula C6H13Cℓ on treatment with potassium tertiary butoxide 3
gives the someric alkenes Y and Z ( C6H12). Both alkenes on hydrogenation gives 2,
3-dimethylbutane. Predict the structures of X, Y and Z.
Account for the following: 3
14. (a) Vinyl chloride is unreactive towards nucleophilic substitution reactions
(b) Neopentyl bromide undergoes nucleophilic substitution reaction very slowly.
(c) Allylic and benzylic halides show high reactivity towards the SN1 reaction.
15. With the help of an example, discuss the stereo chemistry involved in S N1 and SN2 3
Mechanism.
16. a) p - nitro chlorobenzene undergoes nucleophilic substitution faster than 3
chlorobenzene. Explain giving the resonating structures as well.
b) An optically active compound (d)/(+) having molecular formula C4H9Cl with
aq.KOH gives (-) alcohol. Write the mechanism of the reaction.
How will you convert the following?

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 17. a) Benzyl alcohol to phenylethanenitrile 3
b) Aniline to Iodobenzene
c) Ethyl chloride to Propane
18. How will you distinguish between the following: 3
a) Chlorobenzene and benzyl chloride.
b) Chloroethane and bromoethane
c) Chlorobenzene and cyclohexyl chloride.
19. Explain why tert-butyl chloride reacts with aqueous sodium hydroxide by SN1 3
mechanism while n-butyl chloride reacts by SN2 mechanism.
20. Give reasons: 3
a) Boiling point of bromoethane is higher than that of chloroethane.
b) Haloarenes are insoluble in water but soluble in benzene.
c) Anti Markovnikov rule or peroxide effect applies to addition of HBr only and
not to the addition of HCl or HI.
21. a) Name the reagent used to convert bromoethane to ethoxyethane. 3
b) Why are haloarenes much less reactive than haloalkanes towards nucleophilic
substitution reactions?
HIGH ORDER THINKING QUESTIONS
22. a) Organic halogen compounds used in industry as solvents are chlorides rather than 3
bromides and iodides. Give reason.
b) Iodoform has antiseptic properties Give one reason to support your answer.
c) How do the polar solvents help in the first step in SN1 mechanism?
23. Optically active 2-Iodooctane with NaI in dry acetone gives a product which does not 2
show optical activity.

Q. Which of the two : 2-cyclopentenol or 3- cyclopentenol has chiral centre.

Ans: (a) H OH H OH

2-Cyclopentenol 3-Cyclopentenol
(a) (b)

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