Hand-Out Chemistry

Chapter 4 : Haloalkanes & Haloarenes

This particular chapter is divided in the following parts with the exam pont of view.
1.

Reasoning 2. IUPAC Naming 3.Mechanisms 4.Name Reactions 5.Conversions

RE ASONINGS
Q1.

In the following pairs of halogen compound which is faster under going SN2 Rx.
(a)
(d)

, &

(c)

Q2.

, &

(c)

C4H9 Br &

(CH3)3CCl & CH3Cl

Ans. (a)
(b)

, (b)

(1 Alkyl Halide) >

(2 Alkyl Halide)

(bigger size, better leaving group) >

C4H9Br (1) >

(d)

(CH3)3 CCl < CH3Cl (1 Alkyl Halide)

Predict the order of reactivity of the following compounds in SN1 and SN2 Rx.
(a)

Ans. (a)

The four isomeric bromo-butanes

(b)

C6H5 CH2 Br, C6H5 CH (C6H5)Br, C6H5 CH (CH3)Br, C6H5C(CH3)(C6H5)

For SN1 Rx. (Reactivity depends on stability of carbo cation 3 > 2 > 1)
CH3CH2CH2CH2Br < (CH3)2 CHCH2 Br < CH3CH2CH (Br)CH3 < (CH3)3 C. Br
For SN2 Rx ( less steric hindrance more reactive)
CH3CH2CH2CH2Br > (CH3)2CHCH2Br > CH3CH2CH (Br)CH3 > (CH3)3 C. Br

(b)

For SN1 Rx C6H5 C(CH3)(C6H5)Br > C6H5CH(C6H5)Br > C6H5CH (CH3)Br > C6H5CH2Br
For SN2 Rx C6H5CH2Br > C6H5CH (CH3)Br > C6H5CH(C6H5)Br > C6H5C(CH3)(C6H5)Br.

Q3.

Identify chiral and achiral molecules in each of the following pair :-

(a)

(b)

(c)

(d)

Ans. (a) & (c) With four different alkyl group.

Q4.

Although chlorine is an EWG yet it is ortho-para directing in electro plilic aromatic substitution Rx.

Ans. Chlorine shows I effect causing the intermediate carbocation will destabilize but +R effect of Cl stabilizes the intermediate
carbocation. The reactivity is controled by the stronger I effect while orientation is centrolled by weaker reasone effect.
Q5.

Haloalkanes react with KCN to form RCN but with AgCN form RNC?

Ans. CN is an ambidient group (can be attached from both the ends). In KCN, it is ionic bond, the reaction occuss through C since C C
bonds are more stronger while in AgCN (covelent bonding), only N electron pair is availale for bond formation.
Q6.

RCl is hydrolysed to ROH slowly but the reaction is rapid if a catalytic amount of KI is added to the reaction mixture.

Ans. I is stronger nucleoplile so it replace Cl to form RI then RI is more hydrolysed to yield ROH due to Iion is a better leaving group than
Cl.
2012 Vidyamandir Classes Pvt. Ltd.
1
Chemistry/Class XII

Hand-Out Chemistry
Chapter 4 : Haloalkanes & Haloarenes
Q7.

Haloalkanes give nucleophilic substitution while Haloarenes give Electrophilic substitution reactions.

Ans. Haloalkanes are more polar than Haloarenes. so their C has more +ve character so they give nucleophilic substitution while
haloarenes has a benzene ring which shows resonance. haloarenes give electrophilic reaction due to I effect and +R effect.
Q8.

Why is sulphuric acid not used during the reaction of Alcohols with KI.

Ans. Sulphuric acid oxidises KI to I2.

Q9.

Arrange on the basis of increasing Boiling Point. (a)bromomethan , bromoform, Chloromethane, dichloromethane (b)1chloropropane,
isopropyl chloride, 1chlorobutane.

Ans. (a)
(b)

Bromoform > dibromomethane > bromomethane > Chloromethane (BP moleculer wt.)
Isopropyl chloride (side chain) < 1 chloropropane < 1 Chlorobutane (more branching, more surface area less B.P.)

Q10. Which of the following has highest dipole moment CH3Cl, CH2Cl2, CCl4

Cl
CH2Cl2 > CHCl3 > CCl4

H
C

Cl

H
C

>
H

Cl

Cl

Cl
C

>
H

Cl

Cl

Cl

Q11. The dipole moment of chloro benzene lower than cyclohexylchloride.

Ans. Cyclohexylchloride has cyclohexyl as a EDG group. It increase electron density at Cl atom makes it polar while in case chlorobenzene
which has benzene ring as EWG and resonating ring it dipole meoment is lower.
Q12. Alkyl halide though polar not soluble in water.
Ans. Alkyl halide cannot form H-bond with water molecules.
Q13. RMgX should be prepared under anhydrons conditions
Ans. RMgX is very reactive, they react with moisture present in apparatus or the starting material.
Q14. Out of C6H5CH2Cl and C6H5CHCl C6H5 which is Easily hydrolysed by KOH (aq.)
Ans. C6H5CHClC6H5 is 2 alkyl halide which is more reactive under SN1 reaction but under SN2 reaction 1 alkyl halide (C6H5CH2Cl) is
more hydrolysed.
Q15. p-dichlorobenzene has high M.P and low solubility than O-dichlorobenzene.
Ans. p-dichlorobenzene has symmetrical structrre so its MP is high and solubitlity low.
Q16. Why SOCl2 is used for preparation of Alkyl Halide from ROH.
Ans. On reaction between SOCl2 and ROH. we get RCl, HCl(g) and SO2(g) as escapible gases.
Q17. Arrange the following in order of increasing ease towards nucleophile.Rx.
4-Nitrochlorobenzene, chlorobenzene, 2, 4, 6-trinitrochlorobenzene, 2, 4-dinitrochlorobenzene
Ans. 2, 4, 6 trinitrochlorobenzene > 2, 4-dinitrochlorobenzene > 4-nitrochlorobenzene > Chlorobenzene. Among the aromatic compounds
have moleculer formula C7H7Cl how many isomess are possible. Write strictures and name. Identity all the possible monochloro
structural isomess that would be expected to form on free radical chloronation of (CH3)2CH CH2CH3. Differentiate between (a)
chiral and achiral, (b) retentin and inversion.

Chemistry/Class XII

2012 Vidyamandir Classes Pvt. Ltd.

Hand-Out Chemistry
Chapter 4 : Haloalkanes & Haloarenes
Q18. What is enantionmers and racimic mixture.
Q19. Allyl chloride is hydrolysed more radily than n-propyl chloride. Vinyl choloride is hydrolysed more slowly than ethyl chloride
Q20. Explain. reaction between Alkyl halide and KOH(aq) yield Alcohol but with KOH(aq) yield alkenes.
Q21. Which one is better nucleophile Br and I.
Q22. Among the isomeric alkanes of moleculer formula C5H12 Identify the one than on photochemical chlorohation yields (i) A single
monochloride, (ii) three isomeric monochlorides, (iii) Four isomeric monochloride.
Uses
of
freon
12,
DDT,
Carbontetrachloride and Iodeform.

M E CH A N IS M S
H

H
SN2 Mechanism: OH +
H

Cl

HO

Cl
H

HO

(CH3)3 CBr

S r.
No .

Facto rs

Nu mb er or Steps

Step 1

CH3

H3 C

CH3
SN1 Mechanism:

+ Cl

CH3

+ Br ;

H3C

+ OH

CH3

SN 2 Reaction s

Step 2

(CH3)3COH

S N 1 Reaction s

One: R : L Nu R : Nu L

T wo: 1. R : L Slow

R :L

F ast
R : Nu
2. R N u

Reactio n rate and

order

Secon d o rder: Rate [Su bstrate]

[Nu cleophile] or R ate = K 2[ RL] [:Nu]

F irst order: Rate [S u bstrate] or Rate =

1 [ RL]

M olecu larity

Bim olecular

Unim olecular

T S o f slow step

: Nu C : L

: N u C : L Nu :

Reactin g nucleophile

The car bon of th e su bstrate is attacked by

the nucleop hile, exclu sively fro m th e back
sid e.

T he nucleo ph ile can attack the carbon o f

the su bstrate fro m both sides. Ho wever,
the attack from the back side
pred ominates.

Stereochemistry

Co mplete inversio n of config ur ation takes

places

In version and reten tion takes place

Reactivity o rd er of
alk yl halides

M eth yl I > 1 > 2 > 3 halides. ( I > Br > Cl

> F)

3 > 2 > 1 > methyl h alides. (I > Br > Cl

> F)

Rear rangem ent

No r ear ranged pr odu ct is fo rm ed ( except fo r

allylic)

Rear rang ed pr oducts can b e fo rm ed.

Nature o f nucleoph iles

Favo ur ed b y s tro ng and high concentration

of nucleop hiles.

Favou red by m ild an d lo w con centration

of nucleoph iles

10

Po larity

Favo ur ed b y s olvents of low p olarity

Favou red by so lvents of high polarity.

11

Reactio n rate
determ ining factor
Cataly sis

By s teric hin drance

By electr on ic facto r (stability o f R)

Not catalysed by any cataly st (ph ase

tran sfer)

Cataly sed by L ewis and Brons ted acid s,

e.g., Aq. ACl 3, Z nCl2 an d stro ng HA.

12

Chemistry/Class XII

2012 Vidyamandir Classes Pvt. Ltd.

Hand-Out Chemistry
Chapter 4 : Haloalkanes & Haloarenes
EtOH H 2O
nBuCN
Write the mechanism of the following reaction: nBuBr KCN

+
+

K CN + CH3 CH2 CH2 CH2 Br

CH3 CH2 CH2 CH2 CN + KBr

n-Butyl bromide

n-Butyl cyanide

NAME REACTIONS
1.

Sandmeyers Reaction:
+

N2X

X
Cu2X2

+ Na

2.

Finkelstein Reaction: RX NaI RI NaX

3.

Swarts Reaction: CH3 Br AgF CH3F AgBr

4.

Wurtz Reaction: RX 2Na RX R R 2NaX

5.

Friedel Crafts Reaction:

Cl

(solvent - Acetone)

Cl

Cl
CH3

+ CH3Cl

Anhyd. AlCl3

1-Chloro-2-methylbenzene
(Minor)

CH3
1-Chloro-4-methylbenzene
(Major)

Cl

Cl

O
+ H3C C Cl

Cl

O
CH3 +

Anhyd. AlCl3

2-Chloroacetophenone
(Minor)

CH3

4-Chloroacetophenone
(Major)

6.

Wurtz Fitting Reaction:

R
+ Na + RX

Chemistry/Class XII

Ether

+ NaX

2012 Vidyamandir Classes Pvt. Ltd.

Hand-Out Chemistry
Chapter 4 : Haloalkanes & Haloarenes
7.

Fitting Reaction:

X
Ether

+ Na + RX

+ 2NaX

CONVERSIONS
Q1.

Identify A, B, C, D, E, R and R1in the following:

dry ether

Br + Mg

(i)

(ii)

dry ether

R Br + Mg

H2O

D 2O

CH3CHCH3
D

CH3 CH3
CH3

(iii)

CH3

Na/ether

R1 X

Mg

H2O

CH3 CH3

Br + Mg

Ans.

dry ether

Bromocydohexane

H2O

MgBr

+ Mg(OH) Br , since D of D2O gets attached to the

Cyclohexylmagnesium
bromide
(A)

Cyclohexane
(B)

CH3CHCH3 . Therefore, the compound RBr is CH3CHCH3

carbon atom to which MgBr is attached, C is

MgBr

Br

Isopropylmagnesium
bromide

2-Bromopropane

CH3
CH3 CHCH3 + Mg

dry ether

Br

CH3CHCH3

D2O

CH3CHCH3 . The halide, R1 "X, CH3 C X . Therefore, compound

MgBr
(C)

CH3
tert-Butylhalide

CH3
CH3 C MgBr
D is

CH3
tert-Butytmagnesiumbromide

Chemistry/Class XII

2012 Vidyamandir Classes Pvt. Ltd.

Hand-Out Chemistry
Chapter 4 : Haloalkanes & Haloarenes
Q2.

Ans.

How will you bring about the following conversions?

(i)

Ethanol to but-1-yne

(ii)

Ethane to bromoethene

(iii)

Propene to 1-nitropropane

(iv)

Toluene to benzyl alcohol

(v)

Propene to propyne

(vi)

Ethanol to ethyl fluoride

(vii)

Bromomethane to propanone

(viii)

But-1-ene to but-2-ene

(ix)

1-Chlorobutane to n-octane

(x)

Benzene to biphenyl.

(i)

SOCl2 , Pyridine
CH 3CH 2OH
CH 3CH 2 Cl SO 2 HCl
Ethanol

Chloroethane

Liq. NH3
HC CH NaNH 2
HC CNa

CH 3CH 2 Cl HC CNa
CH3CH 2C CH NaCl
Chloroethane

But 1 yne

Br / UV light

(ii)

Br / CCl

HBr

2
2
4
CH 3 CH 3
CH 3 CH 2 Br HBr

CH 2 CH 2

BrCH 2 CH 2 Br
or heat
KOH(alc.),

Ethane

vic Dibromide

Bromoethane

CH 2 CHBr
KOH(alc)
Bromoethane

(iii)

Peroxide
AgNO2
CH 3 CH CH 2 HBr
CH3 CH 2 CH 2 Br
AgBr CH3 CH 2 CH 2 NO 2

(iv)

Do yourself.

(v)

Br2 / CCl4
NaNH 2
CH 3 CH CH 2
CH3 CHBr CH 2 Br
CH3 C CH
Liq. NH

(vi)

PCl5
AgF
CH 3 CH 2 OH
CH 3 CH 2 Cl
CH 3 CH 2 F
POCl , HCl

(vii)

CH 3 MgBr
KCN(alc)
Hydrolysis
CH 3 Br
CH 3 CN
CH3 C NMgBr
CH3 C = O

Propene

1-Bromopropane

Propene

1,2-Dibromopropane

Ethanol

Bromoethane

1-Nitropropane

Chloroethane

Propyne

Ethyl fluoride

H3O

Acetonitrile

CH 3

CH3
Propanone

Br
(viii)

(ix)

HBr
HBr
CH 3CH 2 CH CH 2
CH3CH2CHCH3
CH 3CH CHCH 3
(Markovnikov addition )
KOH(alc.),
But-1-ene

2-Bromobutane

2-Bromobutane

dry ether

2CH3 CH 2 CH 2 CH 2 Cl 2Na
CH 3CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3
2 NaCl
1-Chlordrutane

n-Octane

Br
Na

Dry ether

Br2 / Fe

dark

(x)
Benzene

Chemistry/Class XII

+ 2NaBr
Diphenyl

Benzene

2012 Vidyamandir Classes Pvt. Ltd.

Hand-Out Chemistry
Chapter 4 : Haloalkanes & Haloarenes
1.

acetone
CH 3CH 2 CH 2 Cl NaI
CH 3CH 2 CH 2 I NaCl
heat
1-Chloropropane

(CH3 )3 CBr

2.

1 Iodopropane

Finkelstein
reaction

KOH

2-Bromo-2-methylpropane

ethanol

heat

CH3 C = CH2 + KBr + H2 O

(Dehydrohalogenation)

CH3
2-Methylpropene

3.

water

CH 3CH(Br)CH 2CH 3 NaOH CH 3CH(OH)CH 2 CH 3 NaBr

2-Bromobutane

4.

aq. ethanol
CH3CH 2 Br KCN
CH 3CH 2CN KBr
(Nucleophilic
Bromobutane

5.

6.

7.

Butan-2-ol

Cyanoethane

substitution)

(Williamson synthesis)
C6 H5 ONa C 2 H5 Cl
C6 H 5 O C2 H 5
Sodium phenoxide Chloroethane
Phenetole

NaCl

CH 3CH 2 CH 2 OH SOCl2
CH3 CH 2 CH 2 Cl SO 2 HCl
1-Propanol

1-Chloropropane

Peroxide
CH3CH2 CH CH 2 HBr
CH3CH 2 CH 2CH 2 Br
(Anti-Markovnikov's
But-1-ene

1-Bromobutane

addition)

Br
8.

CH 3CH C(CH 3 ) 2 HBr

CH3 CH2 C CH3

(Markovnikov
2-Methylbut-2-ene

addition)

CH3
2-Bromo-2-methylbutane

Q3.

How the following conversions can be carried out?

(i)

Propene to propan-1-ol

(ii)

Ethanol to but-1-yne

(iii)

1-Bromopropane to 2-bromopropane

(iv)

Toluene to benzyl alcohol

(v)

Benzene to 4-bromonitrobenzene

(vi)

Benzyl alcohol to 2-phenylethanoic acid

(vii)

Ethanol to propanenitrile

(viii)

Aniline to chlorobenzene

(ix)

2-Chlorobutane to 3, 4-dimethylhexane

(x)

2-Methyl-1-propene to 2-chloro-2-methylpropane

(xi)

Ethyl chloride to propanoic acid

(xii)

But-1-ene to n-butyliodide

(xiii)

2-Chloropropane to 1-propanol

(xiv)

Isopropyl alcohol to iodoform

(xv)

Chlorobenzene to p-nitrophenol

(xvi)

2-Bromopropane to 1-bromopropane

(xvii)

Chloroethane to butane

(xviii)

Benzene to diphenyl

(xix)

tert-Butyl bromide to isobutyl bromide

(xx)

Aniline to phenylisocyanide

Chemistry/Class XII

2012 Vidyamandir Classes Pvt. Ltd.

Hand-Out Chemistry
Chapter 4 : Haloalkanes & Haloarenes
(i)

HBr/Peroxide
(Nucleophilic substitution)
CH3 CH CH2
CH3 CH 2 CH2 Br
CH3 CH 2 CH2 OH
(Anti-Markovnikov
aq. KOH/
Propene

1-Bromopropane

addition)

Propan-1-ol

(ii)

red P/Br2
Mg / ether
CH 3CH 2 OH
CH3CH 2 Br
CH 3CH 2 MgBr
Ethanol

H2C CH2 ether

Ethyl magnesium bromide (Grignard reaction)

Ethyl bromide

red P/I

H / H O

2
[CH3CH2 CH2 CH2 OMgBr]

Addition product

KOH (alc) /

(Electrophilic addition)

2
CH 3CH 2 CH 2 CH 2 OH
CH 3CH 2 CH 2 CH 2 I
CH 3CH 2 CH CH 2

(Dehydrohalogenation)
Br / CCl

1-Butanol

Iodobutane

But-1-ene

NaNH 2 , liq. NH3

CH3CH2CH CH
CH3CH2CH CH2
196 K
(Dehydrohalogenation)

Br

But-1-yne

Br

1,2-Dibromobutane

Br
(iii)

KOH(alc) /
HBr
CH 3 CH 2 CH 2 Br
CH3 CH CH 2
CH3 CH CH3
(Dehydrohalogenation)
Markovnikov addition
1-Bromopropane

CH2OH

CH2Cl

CH3

aq. KOH/

(nucleophilic

Cl2 / UV light

or heat

(iv)

substitution)
Benzyl
alcohol

Benzyl
chloride

Toluene

Br

Br
HNO /H SO

Br /FeBr

3 2
4

(Nitration)

2
3

Dark

(v)

2-Bromopropane

Propene

Bromobenzene

Benzene

NO2
4-Bromonitrobenzen

PCl5

POCl , HCl

(vi)

CH2CN

CH2Cl

CH2OH

H / H 2O

Benzyl
cyanide

Benzyl
alcohol

(vii)

(Hydrolysis)

KCN, aq.ethanol

KCl

CH2COOH

2-Phenylethanoic acid

red P/Br2
KCN, aq. ethanol
CH 3 CH 2 OH
CH3 CH 2 Br
CH 3 CH 2 CN
Ethanol

Bromoethane

NH2

Propanenitrile

N2Cl

Cl

NaNO2 2HCl,

273278 K

NaCl, 2H O

(viii)

Cu 2Cl2

Aniline

Chemistry/Class XII

Benzenediazonium
chloride

+ N2
Chlorobenzene

2012 Vidyamandir Classes Pvt. Ltd.

Hand-Out Chemistry
Chapter 4 : Haloalkanes & Haloarenes
CH3 CH3

Cl
(ix)

2Na / dry ether

CH3 CH2 CH CH CH2 CH3 + 2NaCl
2CH3 CH CH2 CH3
(woody reaction )
3,4-dimethylhexane

2-Chlorobutane

CH3

CH3
(x)

HCl

CH3 C CH3
CH3 C = CH2
(Markovnikov
2-Methyl-1-propene

addition)

Cl

2-chloro-2-methylpropane

(xi)

KCN. aq. ethanol

Hydrolysis
CH 3 CH 2 Cl
CH 3 CH 2 CN KCl

CH3 CH 2 COOH

(nucleophilic substitution)

(xii)

HBr / Peroxide
Finkelstein reaction
CH3 CH 2 CH CH 2
CH3 CH2 CH 2 CH 2 Br
CH3 CH 2 CH 2 CH2 I
(Anti-Markovnikov
NaI, dry acetone

Ethylchloride

But-1-ene

H / H 2O

Propanenitrile

Propanoic acid

1-Bromobutane

addition)

n Butyliodide

Cl
(xiii)

KOH(alc) /
HBr / Peroxide
CH 3 CH CH 2 HCl

CH3 CH 2 CH 2 Br
CH3 C CH3
(Dehydrohalogenation)
(Anti-Markovnikov addition )
1-Bromopropane

Propene

2-Chloropropane

aq. KOH/

CH 3 CH 2 CH 2 OH
(Nucleophilic substitution)
1-Propanol

OH
(xiv)

CrO 3
NaOI
CH3 C CH3
CH3 C ONa + CHI3
CH3 C CH3
(oxidation )
(Iodoform reaction)

Isopropyl alcohol

Iodoform

Propanone

Cl

Cl

Cl

Cl
NO2

HNO3 / H 2SO 4

(Nitration )

(xv)

+
NO2

Chlorobenzene

m-Chloronitrobenzene

NO2

o-Chloronitrobenzene

p-Chloronitrobenzene
(Major product)

Br
(xvi)

KOH(alc.) /
(Anti-Markovnikov addition)
CH3 CH CH3

CH3 CH CH 2 HBr

CH3 CH 2 CH 2 Br
Dehydrohalogenation
HBr / Peroxides

2-Bromopropane

(xvii)

Propene

1-Bromopropane

2Na/dry ether
CH 3 CH 2 Cl
CH 3 CH 2 CH 2 CH 3 2NaCl
(Wurtz reaction)
Butane

Br
Br2 / FeBr3

(xviii)
Benzene

Chemistry/Class XII

2Na / dry ether

(Fitting reaction )

+ 2NaBr
Biphenyl

2012 Vidyamandir Classes Pvt. Ltd.

Hand-Out Chemistry
Chapter 4 : Haloalkanes & Haloarenes
CH3

Br
(xix)

CH3

KOH(alc) /
HBr / Peroxide
CH3 C = CH2
CH3 CH CH2 Br
CH3 C CH3
(Dehydrohalogenation)
(Anti-Markovnikov

2-Methylpropene

addition)

Isobutyl bromide

Br

Tert-Butylbromide

NC

NH2
CHCl3 , 3KOH,

(Carbylamine reaction)

(xx)

Phenylisocyanide

Aniline

Q4.

Ans.

+ 3KCl + 3H2O

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), C8H18which 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.
2Na / dry ether
2CH3CH 2CH 2CH 2 Br
CH 3CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 2NaBr
(Wurtz reaction)
n-Butyl bromide

CH3

n-Octane

CH3

CH3

2Na / dry ether

CH3CHCH2Br
CH3CHCH2CH2CHCH3 + 2NaBr
(Wurtz reaction)
Isobutyl bromide
(a)

CH3

2,5-Dimethylhexane
(d)

Br

HBr
CH3 C = CH2
CH3 C CH3
(Markovnikov addition)

2-Methylpropene
(b)

CH3

2-Bromo-2-methylpropane
(c)
(an isomer of (a))

PREVIOUS YEARS CBSE QUESTIONS

1.
2.

2012
Explain the mechanism of acid catalysed hydration of an alkene to form corrouspounding alcohol.
Answer the following questions:
(i) What is meant by chirality of acompound? Give an Example.
(ii) Which of the following compound is more easily hydrolysed by KOH and why?CH3CHClCH2CH3 or CH3CH2CH2Cl
(iii) Which one undergoes SN2 substitution reaction faster and why?

1.
2.

1.

2011
Write the IUPAC name of the following compound :
(CH3)3CCH2Br
Answer the following :
(i) Haloalkanes easily dissolve in organic solvents, why ?
(ii) What is known as a racemic mixture? Give an example.
(iii) Of the two bromoderivatives, C6H5CH(CH3)Br and C6H5CH(C6H5)Br, which one is more reactive in SN1 substitution reaction and
why?
2010
A solution of KOH hydrolyses CH3CHClCH2CH3 and CH3CH2CH2Cl. Which one of these is more easily hydrolysed?

Chemistry/Class XII

10

2012 Vidyamandir Classes Pvt. Ltd.

Hand-Out Chemistry
Chapter 4 : Haloalkanes & Haloarenes
2.
3.
1.

How are the following conversions carried out?

(i) Benzyl chloride to benzyl alcohol,
(ii) Methyl magnesium bromide to 2-methylpropan-2-ol
State one use each of DDT and iodoform.
2009
Which ones in the following pairs of substances undergoes SN2 substitution reaction faster and why?
(i)

2.

(ii)

(a) How are the following obtained?

(i) Benzoic acid and ethyl benzene. (ii) benzldehyde from toluene
(b) Complete each systhesis by giving the missing material, reagent or products:

(i)

H2
C6 H5 COCl
...........
Pd-BaSO4

(ii)

(iii)

1.

2008
Explain as to why haloarenes are much less reactive than haloalkanes towards nucleophilic substitution reactions.
(2 marks)

Hint:
Aryl halides contain a benzene ring. Typical reactions in this case are electrophilic substitution reactions.
Factors responsible for diminished reactivity of haloarenes towards nucleophilic reactions are:
(a) Resonance effect
(b) Difference in hybridisation of carbon atom in the C-X bond
(c) Instability of phenyl cation
(d) Electronic repulsions
On the other hand, carbon carrying the halogen in haloalkanes is more electron deficient than in haloarenes. As a result haloalkanes
undergo nucleophilic substitutions more readily than haloarenes.
2.
Which compound in each of the following pairs will react faster in SN2 reaction with OH? Why?
(2 marks)
(i) CH3 Br or CH3 I
(ii) (CH3)3 CCl or CH3Cl
Answer:
(i) CH3 I
(ii) CH3Cl
(a) State the IUPAC name of the following compound:
(b) Complete the following chemical equations:
H 2 O2
CH3 CH2 CH == CH2 + HBr Peroxide

Answer:
(a) 1-Bromobut-2-ene
(b) CH3 CH2 CH2CH2Br
3.

===========

Chemistry/Class XII

11

2012 Vidyamandir Classes Pvt. Ltd.