HALOALKANES AND HALOARENES (SUBJECTIVE)

GIVE REASONS
1.Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms
isocyanides as the chief product. Explain.
ANS- KCN is ionic and provides cyanide ions in solution. The attack takes place mainly through
carbon atom and not through nitrogen atom since C—C bond is more stable than C—N bond.
Hence form cyanides. AgCN is covalent and the attack takes place through lone pair on N-atom
and thus form isocyanides.
2.Can you think why does -NO2 group show its effect only at ortho- and para- positions and not
at meta position?
ANS-The electron withdrawing –NO2 group when present at ortho and para position helps
stabilizing the carbanion formed but when present at meta position has no effect on reactivity
and does not help stabilizing the carbanion.
3.Although chlorine is an electron withdrawing group , yet it is ortho- ,para- directing in
electrophilic aromatic substitution reactions .Why?
ANS- Chlorine shows +R and -I effect. -I effect is stronger than +R effect. -I effect controls the
reactivity and +R effect controls the orientation. Hence it is an ortho- ,para- directing in
electrophilic aromatic substitution reactions
4.Why the dipolemoment of chlorobenzene is lower than that of cyclohexyl chloride?
ANS- In chlorobenzene the C attached to the –Cl atom is sp2 hybridised, hence is more
electronegative. Thus the polarity of C-Cl bond becomes less which is turn decreases the
dipolemoment.
5.Why alkyl halides , though polar, are immiscible with water but readily dissolves in organic
solvents?
ANS- The newer interactions between alkyl halide and water molecules are weak and does not
release sufficient energy to break the older interactions between the water molecules. Hence
immiscible in water.
6.Grignard’s reagents should be prepared under anhydrous conditions. Justify?
ANS- Grignard’s reagent when comes in contact with water or moisture gets converted to
alkanes. Hence must be prepared under anhydrous conditions.
7. p-Dichlorobenzene has higher m.p and solubility than those of o- and m-isomers . Discuss.
ANS- p-Dichlorobenzene because of symmetry fits into the crystal lattice better and gives a
stable lattice . Hence the m.p of p-dichlorobenzene is higher.
8.Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous KOH.
Justify?
ANS- If carbocation is stable, then the compound is easily hydrolyzed by aqueous KOH. In the
given compounds benzyl chloride forms primary carbocation, while chlorodiphenylmethane
forms secondary carbocation, which is more stable than primary carbocation,
hence C6H5CHClC6H5 is more easily hydrolysed by aqueous KOH.
9.Why n-Butyl bromide has higher boiling point than t-Butyl bromide?
ANS- The surface area of t-Butyl bromide is lesser than n-Butyl bromide due to branching.
Hence the intermolecular force of attraction decreases which in turn decreases the boiling point.
10.Why are racemic mixture optically inactive?
ANS- A racemic mixture is a mixture of equimolar amount of d- and l- form. Hence is optically
inactive.
11.Why the presence of nitro group at o/p positions increases the reactivity of haloarenes
towards nucleophilic substitution reactions?
ANS- Nitro is an electron withdrawing group , it stabilizes the carbanion formed and thus
facilitates the attack of the nucleophile.
12.Why Ethyl iodide undergoes SN2 reaction faster than ethyl bromide?
ANS- Iodides because of its larger atomic size are better leaving groups . Hence ethyl iodide
undergoes SN2 reaction faster.
13. ( + ) 2-Butanol is optically inactive. Justify.
ANS- ( + ) 2-Butanol is a racemic mixture which contains equimolar amount of d – and l- form.
Hence optically inactive.
14.C-X bond length in halobenzene is smaller than C-X bond length in CH 3-X. Give reason.
ANS- Due to resonance (+R effect of X-group) the C-X bond in halobenzene develops a partial
double bond character because of which the bond length is smaller but in CH3-X the C-X bond
is a single bond because of which the bond length is greater.
15. Why Chlorobenzene is extremely less reactive towards a nucleophilic substitution reaction.
Give two reasons for the same.
OR.
Explain why haloalkanes undergo nucleophilic substitution whereas haloarenes undergo
electrophilic substitution?
ANS- Because of the following reasons:-
i) Due to resonance (+R effect of X-group) the C-Cl bond in chlorobenzene develops a partial
double bond character.Hence the bond is difficult to be cleaved.
ii) The phenyl carbocation if formed is not resonance stabilized.
Hence Chlorobenzene is extremely less reactive towards a nucleophilic substitution reaction
16. Why is sulphuric acid not used during the reaction of alcohols with KI?
ANS- Sulfuric acid is an oxidizing agent. On using it the reaction of alcohols with KI converts
KI to corresponding HI and oxidizes the HI. Hence sulfuric acid is not used during the reaction
of alcohols with KI.
17)What is the role of dry acetone in Finkelstein Reaction?
ANS-NaCl or NaBr thus formed is precipitated in dry acetone and thus facilitates the forward
reaction according to Le Chatlier’s Principle.

REACTIVITY ORDER

1.Among the isomeric alkanes of molecular formula C5H12, identify the one that on
photochemical chlorination yields

a)A single monochloride

b)Three isomeric monochlorides

c)Four isomeric monochlorides.

2.Arrange each set of compounds in order of increasing boiling points:-

a)Bromomethane , Bromoform , Chloromethane ,Dibromomethane

ANS- Chloromethane < Bromomethane < Dibromomethane < Bromoform

b)1-Chloropropane , Isopropyl chloride, 1-Chlorobutane

ANS- Isopropyl chloride < 1-Chloropropane < 1- Chlorobutane

REMEMBER:

a) Boiling point increases with increase in molecular mass.

b) Boiling point decreases with branching due to decrease in surface area.

c) B.P of Iodides > Bromides > Chlorides.

3. a)CH3-CH2-CH2-CH2-I and CH3-CH2-CH2-CH2-Cl

ANS- The first one – Iodo butane because Iodide is a better leaving group.

REMEMBER:

Order of Nucleophilic Substitution Reaction:- -Iodides > -Bromides > -Chlorides

b) Which compound amongst the following undergoes S N1 reaction?

ANS- The second one – Benzyl chloride because the benzyl carbocation formed is resonance
stabilized.
REMEMBER FOR SN1:

Stability of carbocation is the deciding factor.

4.Predict the order of reactivity of the following compounds in S N1 and SN2 reactions:

a)The four isomeric bromobutanes.

ANS-

b) C6H5CH2Br, C6H5CH(C6H5)Br, C6H5CH(CH3)Br, C6H5C(CH3)(C6H5)Br

REMEMBER FOR SN2:

i) Order of SN2 is -10>20>30

ii) Carbon carrying the halogen should be less crowded (less steric hindrance)

REMEMBER FOR SN1:

a) Order of SN1 is - 30> 20 >10 alkyl halide

b))Stability of carbocation.

5. Identify chiral and achiral molecules in each of the following pair of compounds:
(NCERT PAGE 298 EXAMPLE 10.8)

ANS-Chiral carbon is asymmetric carbon and is bonded to four different groups.

So (i) – The first one is chiral and second is achiral. (ii)-The first one is chiral and the second one
is achiral. (iii)-The first one is chiral and second one is achiral.

6.Which alkyl halide from the following pairs would you expect to react more rapidly by an S N2
mechanism? Explain your answer.

a)CH3CH2CH2CH2Br OR CH3CH2CH(Br)CH3

ANS- CH3CH2CH2CH2Br (10 alkyl halide)

b)CH3CH2CH(Br)CH3 OR (CH3)3CBr

ANS- CH3CH2CH(Br)CH3 (20 alkyl halide)

c)CH3CH(CH3)CH2CH2Br OR CH3CH2CH(CH3)CH2Br

ANS- Both are 10 alkyl halide so we have to see where the C-X is less branched / crowded /steric
hinderance . So the answer is CH3CH(CH3)CH2CH2Br

REMEMBER FOR SN2

i)Order of SN2 is -10>20>30

ii) Carbon carrying the halogen should be less crowded (less steric hindrance)

7.Arrange the compounds of each set in order of reactivity towards S N2 displacement:

a)2-Bromo-2-methylbutane , 1-Bromopentane, 2-Bromopentane

ANS- 2-Bromo-2-methylbutane < 2-Bromopentane < 1-Bromopentane

b)1-Bromo-3-methylbutane ,2-Bromo-2-methylbutane , 3-Bromo-2-methylbutane

ANS- 2-Bromo-2-methylbutane < 3-Bromo-2-methylbutane < 1-Bromo-3-methylbutane

c)1-Bromobutane,1-Bromo-2,2-dimethylpropane,1-Bromo-2-methylbutane,1-Bromo-3-
methylbutane

ANS- 1-Bromo-2,2-dimethylpropane < 1-Bromo-2-methylbutane < 1-Bromo-3-methylbutane

< 1-Bromobutane.
REMEMBER FOR SN2

i) Order of SN2 is -10>20>30

ii) Carbon carrying the halogen should be less crowded (less steric hindrance)

8.In the following pairs of halogen compounds, which compound undergoes faster S N1 reaction?

ANS- (i) The first one as it is a tertiary alkyl halide.

(ii) The first one as it is a secondary alkyl halide.

REMEMBER FOR SN1

a) Order of SN1 is - 30> 20 >10 alkyl halide

b))Stability of carbocation.

9.Which alkyl halide from the following pairs would you expect to react more rapidly by an S N2
mechanism? Explain your answer.

(NCERT Pg 307 Intext Questions 10.7,10.8)

ANS- The ticked ones in the image is the answer.

REMEMBER FOR SN2

i) Order of SN2 is -10>20>30

ii) Carbon carrying the halogen should be less crowded (less steric hindrance)

10.Which compound amongst the following undergoes S N1 reaction?

a) CH2=CH-CH2-Cl or CH3-CH2-CH2-Cl

b) CH2-Cl or CH2-Cl
ANS- a) CH2=CH-CH2-Cl (Though it is a primary alkyl halide , the allyl carbocation formed is
resonance stabilised)

b)

(Though it is a primary alkyl halide , the benzyl carbocation

is resonance stabilised , since the carbocation is stable it shows S N1 pathway)

REMEMBER FOR SN1 – The stability of carbocation plays an important deciding factor.

11.Out of C6H5CH2Cl and C6H5CHClC6H5,which is more easily hydrolysed by aqueous

KOH?

ANS-

Note:
Stability of Carbocation:- Benzyl carbocation > allyl carbocation >Tertiary carbocation >
Secondary carbocation > Primary carbocation> methyl carbocation
12. Arrange the following set of compounds in order of increasing melting points:-
1,2-dichlorobenzene , 1,4-dichlorobenzene , 1.3-dichlorobenzene

ANS- 1.3-dichlorobenzene < 1,2-dichlorobenzene <1,4-dichlorobenzene

REMEMBER: p-isomer is symmetrical that leads to stability and hence has higher m.p
DISTINCTION REACTIONS
Give suitable chemical test to distinguish between the following pairs of compounds:-
1.Chlorobenzene and Chlorocyclohexane
Ans- Chlorocyclohexane + Aq.KOH → Cyclohexanol +KCl
KCl + AgNO3 solution → White ppt of AgCl.
Chlorobenzene doesn’t respond to the above test.
2.Carbontetrachloride and Chloroform.
Ans- Carbylamine Test
R-NH2 + CHCl3 +KOH → Isocyanide(foul Smelling)
Carbontetrachloride doesn’t respond to the above test.
WORD PROBLEMS
1.Identify A,B,C,D,E,R and R’ in the following:
SOLUTION:-

2.An optically active compound having molecular formula C7H15Br reacts with aqueous KOH
to give C7H15OH, which is optically inactive. Give mechanism for the reaction.
SOLUTION:- The mechanism followed is SN1(Note: Gives racemic mixture)
3.A hydrocarbon C5H10 does not react with chlorine in dark but gives monochloro compound
C5H9Cl in bright sunlight. Identify the hydrocarbons.
SOLUTION:-

4.Primary alkyl halide A- C4H9Br 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 was reacted with sodium
metal it gave a compound D -C8H18 that was different from the compound when n-butyl
bromide was reacted with sodium. Give structural formula of A and write the equation for all the
reactions involved.
SOLUTION:-

(ii) Since compound (a) when reacted with Na metal gave a compound (d) with molecular
formula C8H18 which was different from die compound obtained when n-butyl bromide was
reacted with Na metal, therefore, (a) must be isobutyl bromide and compound (d) must be
2,3-dimethylhexane.

(iii) If compound (a) is isobutyl bromide, than the compound (b) which it gives on treatment with
alcoholic KOH must be 2-methyl-1-propane.
(iv)The compound (b) on treatment with HBr gives compound (c) in accordance with
Markownikoff rule. Therefore, compound (c) is tert-butyl bromide which is an isomer of
compound (a) ,i.e., isobutyl ‘ bromide.

Thus
(A) is isobutyl bromide, (B) is 2-methyl-1 -propane,
(C) is tert-butylbromide, and (D) is 2,5-dimethylhexane.

MECHANISM:
1.Practice SN1 and SN2 mechanism.

NAME REACTIONS:

1)Finkelstein reaction

2)Swarts reaction
3)Wurtz Reaction

4)WurtzFittig reaction

5)Fittig reaction

6)Sandmeyer’s reaction

7)Friedel Craft’s Alkylation:-

8)Friedel Craft’s Acylation:-

FILL IN THE BLANKS:

1.Draw the structures of major monohalo products in each of the following reactions:
ANSWERS:

2.Write the structure of the major organic product in each of the following reactions:
ANSWERS

3.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.

ANSWERS

CONVERSIONS TO PRACTICE:-

1. Write the equations for the preparation of 1-iodoobutane from

(i)1-butanol (ii)1-chlorobutane (iii) but-l-ene.
2. Propene to 1-nitropropane 3.Toluene to benzyl alcohol
4.Propene to propyne 5.Ethanol to ethyl fluoride
6. But-l-ene to but-2-ene 7.1-Chlorobutane to n-octane
8. Benzene to biphenyl 9. Propene to propan-l-ol
10. l-Bromopropane to 2-bromopropane 11.Toluene to benzyl alcohol
12. Benzene to 4-bromonitrobenzene 13. Ethanol to propanenitrile
14.Aniline to chlorobenzene 15.2-Chlorobutane to 3,4-dimethylhexane
16. 2-Methyl-1 -propene to 2-chloro-2-methylpropane.
17.Ethyl chloride to propanoic acid
18.But-1-ene to n-butyliodide 19.2-Chlropropane to 1-propanol
20. Isopropyl alcohol to iodoform 21.Chlorobenzene to p-nitrophenol
22. 2-Bromopropane to 1-bromopropane 23.Chloroethane to butane
24.Benzene to diphenyl 25.tert-Butyl bromide to isobutyl bromide
26.Aniline to phenylisocyanide