Chemistry : Alkyl Halides & Aryl Halides

SECTION - I
SUBJECTIVE TYPE PROBLEMS

Problem 1. Propose a mechanism for the following reactions-

OH
CH3 CH3
H2O
C—Br  CH3

CH3
CH3 CH3 + CH3
Solution : CH3
C—Br  
Br  C+
CH3 CH3 H2O

+
OH2
OH CH3
CH3
H
CH3 
CH3


Problem 2. Suggest the mechanism

OH CH3
HO H H
2 CH3 + OH
H3C CH—CH3
CH3 CH3
Br
H2O

+ CH
  H 3
Br 
Solution : H3C CH—CH3 +
H3C CH—CH3 CH3
Br H2O
+
OH2 CH3
H H +
CH3 +
OH2
CH3 CH3

-H+ -H+
OH CH3
H H
CH3 +
OH
CH3 CH3
 Chemistry : Alkyl Halides & Aryl Halides

Problem 3. Write down the intermediate steps in the following reaction

O

H3C C – OC2H5
O
CH
O
C – OC2H5 –
NaOEt Br (i) HO
CH2 + H3C – CH – C – OH
(ii) H
C – OC2H5
CH2 – C – OH
O
O
O
O H3C C – OC2H5
C – OC2H5 O
– CH
Solution : CH ,
C – OC2H5 C – OC2H5
CH
O C – OC2H5

Problem 4. An organic compound A of molecular formula C5H6 reacted with methyl magnesium bromide
to give B, B reacted with CO2 to give a salt which on hydrolysis gives C. C, subsequently
treated with PCl5 and then with Pd/BaSO4 gives D. B reacted with HCHO and on further
acidification gives B. E where oxidized with P.C.c. gives D. A basic solution of A showed
aromatic character. Find A to E.
Solution : A= B=

MgBr
C= D=

COOH CHO

E=

CH2OH
Chemistry : Alkyl Halides & Aryl Halides

Problem 5. Give the products of the following reactions :

O
Br ||
(a)
 N— O  
?

Br

(b)  SCN  
?

(c) CH3CH 2 Br  S2O32 

?

(d) ClCH 2 CH 2 CH 2 I  CN  (one mole each) 

?

H
(e) H 2 N.CH 2CH 2 CH 2CH 2 Br  ?

Solution : (a) N
O

SCN
(b)

(c) CH3CH2S2O3–
(d) ClCH2CH2CH2CN, because I– is a better leaving group than Cl–

(e) N
H
Problem 6. Arene B (C10H14) has 5 possible monochloro derivatives (C10H13Cl) considering both ring
and side chain halogenation. Vigorous oxidation of B yields an acidic compound C8H6O4
having only one mononitro substitution product C8H5 O4NO2 . Identify B and also draw
structures of 5 monochloro derivatives.
Solution : Since C6H­4(COOH)2 has only one mononitro substitution the COOH’s must be para to
each other. Compound B must therefore be a p-dialkyl benzene.

CH2Cl CH3 CH3 CH3 CH3

Cl

Cl
CH CH CH C–Cl CH
CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH2Cl CH3 CH2Cl
 Chemistry : Alkyl Halides & Aryl Halides

CH3
COOH COOH
NO2
[O ] HNO3 / H
    

CH
COOH COOH
CH3 CH3

Problem 7. Predict the major products in the following reaction with proper mechanism.

NH
Me t Bu 
 O Li

ether

NH
Me
Solution : t BuO Li  
  
H :NH—Me

H 
N  +
shifting N—Me
–
Me
H

So the product is
N

Me
Problem 8. Convert the benzene to p-methylbenzoic acid through formation of a Grignard reagent.
Solution :

Me Me Me Me

MeCl FeBr3 Mg CO2

      
anhydrous Br2 dry ether followed
AlCl3 by accidification
(Maintaining
proper condition Br MgBr COOH
for mono
alkylation)
Chemistry : Alkyl Halides & Aryl Halides

Problem 9. A compound having molecular formula C4H5Cl has two optically active isomers (A) and
(B), one of which gives white ppt in presence of ammonical AgNO3 solution. Now compound
(A) losses its optical activity due to acid catalysed hydration (considering the major product)
and forms optically inactive (C) which is major product. But compound (B) doesn’t losses
its optical activity on acid catalysed hydration and gives (D) as major product. Compound
(D) gives positive response in Tollen’s reagent. Identify (A) to (D) with proper explanation.
Solution : According to the molecular formula of the compound C4H5Cl, the compound has either a
triple bond or two double bond or a cyclic compound with double bond.
One of the compound gives white precipitate in presence of ammonical AgNO3 solution. So
it contains terminal ‘CC’.

So (A) and (B) may be as both are optically active,

Cl Cl

and CH3—CH—CCH

but we don’t know which is (A) which is (B)

(A) losses optical activity on acid catalysed hydration but (B) remains optically active in
same condition (considering the major product).

Cl Cl

 (A) is and (B) is CH3—CH—CCH

Cl Cl Cl
+
H 
 or
+

2nd carbocation is more stable as distance from ‘Cl’ atom is larger

(which has -I effect)

Cl
So (C) is (optically inactive)
OH

Cl Cl Cl
|  |  or | 
H CH  C H  CH  C H
CH3  C H  C  CH  CH  C H  C  CH2
3 3

1st carbocation is more stable and gives major product (D)

Cl Cl Cl
|  | |
H2O
CH3 — CH— CH  C H   CH 3 — CH— CH == CH CH3 — CH— CH 3CHO
| (D)
O—H (Optically active and gives Tollen's test)
 Chemistry : Alkyl Halides & Aryl Halides

Cl
Cl Cl
So (A) = |
,
(B)= CH3  C H  C  CH , (C)=
OH

Cl
|
(D) = CH3  C H  CH2CHO

Problem 10. Which of the following will react faster

(i) ClCH2 – OCH2CH3 or CH3O – CH2 – CH2Cl (SN1 path way, in a protic solvent)
(ii) CH3CH2CH2Br + Ph3N  CH3CH2CH2N(Ph)3+ + Br–
(S N2 pathway, in a protic solvent)

CH3CH2CH2Br + Ph3P  CH3CH2CH2P(Ph)3+ + Br–

Solution : (i) ClCH2—OCH2—CH3­ will develop a resonance stablised (SN1 mechanism) carbocation
(+CH2—OCH2—CH3­  CH2=O+CH2CH3) but CH3—OCH2CH2Cl will develop no -
bond resonance stablised carbocation. The former effect is stronger than the latter.
The transition state of ClCH2 – O – CH2 — CH3 will be more stable than the other one
i.e., G of the former  G of the latter and hence ClCH2 — O — CH2 — CH3 will
react faster than CH3O — CH2CH2Cl.

(ii) Ph3P is a stronger nucleophile than triphenylamine (Ph3N) because phosphorous atoms
are larger than nitrogen and so the reaction will take place faster with triphenylphosphine
(Ph3 P).
Chemistry : Alkyl Halides & Aryl Halides

SECTION - II
SINGLE CHOICE PROBLEMS
Problem 1. In the reaction, CH3C C–Na+ + (CH3)2CHCl  , the product formed is :
(a) 4-methyl-2-pentyne (b) Propyne
(c) Propyne and propene (d) None
Solution : (a)
CH3C–  Na+ + (CH3)2CHCl  CH3C  C–CH(CH3)2 + NaCl

Problem 2. Iso butyl magnesium bromide with dry and absolute alcohol gives
(a) CH3.CH.CH2OH and CH3.CH2.MgBr

CH3

(b) CH3.CH.CH2.CH2.CH3 and Mg(OH)Br

CH3

(c) CH3.CH—CH3, CH2=CH2 and Mg(OH)Br

CH3

(d) CH3.CH.CH3 and CH3.CH2.OMgBr

CH3
Solution : (d)
OC2H5
Ether
(CH3)2CH.CH2MgBr + HOC2H5   (CH3)2CHCH3 + Mg
Br
Problem 6. Identify ‘Z’ in the following reaction series,

aq.NaOH 2 3 Al O Cl / H O
CH3.CH2.CH2.Br    X   Y 2 
2
 Z
heat

(a) CH3—CH—CH2 and CH3—CH—CH2 (b) CH3—CH—CH2

Cl Cl OH Cl OH Cl

(c) CH3—CH—CH2 (d) CH3—CH—CH2

Cl OH Cl Cl
Solution : (b)
Al O
NaOH(aq) CH CH CH OH 2
CH3CH2CH2 Br  3
 CH3.CH=CH2
  3 2 2

HOCl CH .CH(OH)—CH Cl
  3 2
 Chemistry : Alkyl Halides & Aryl Halides

Problem 4. A compound ‘A’ forms ‘B’ with sodium metal and again ‘A’ forms ‘C’ with PCl5, but ‘B’
and ‘C’ form diethyl ether. Therefore ‘A’, ‘B’ and ‘C’ are respectively
(a) C2H5OH, C2H5ONa, C2H5Cl (b) C2H5OH , C2H5Cl, C2H4Cl2
(c) C2H5OH, C2H5Cl, C2H4Cl2 (d) C2H5OH, C2H5Cl, C2H5ONa
Solution : (a)

Na
C2H5OH  C2H5ONa
(A) (B)
C2H5OC2H5
PCl5
C2H5Cl
(C)

PCl
5 Alc. KOH 1. Conc.H SO
Problem 5. Identify Z in the series : Z  
     Y    2 
4
 Z
2. H2O,boil

(a) CH3 .CH2 .CH2 OH (b) CH3—CH—CH3

OH

(c) (C 2 H5 ) 3C—OH (d) CH3 —CH=CH2

Solution : (b)

PCl3 Alc. KOH 

H3 O
CH 3  CHOH  CH 3  
  CH 3  CHCl  CH 3    CH 3  CH  CH 2  CH3–CH–CH3
(Z) ( X) ( Y)
OH
(Z)

Problem 6. The end product in the following sequence of reaction,

PBr3 KCN B H O 
C2H5OH   A  
  3 C
(a) Acetamide (b) Propionic acid
(c) Ethyl amine (d) Acetic acid
Solution : (d)

PBr2 KCN C 2 H5 CN H3 O
C2 H 5OH   C2 H 5Br       C2 H5COOH

Problem 7. Which of the following decolourises aqueous bromine and gives white fumes of HCl on
reaction with PCl5
(a) CH3CH2 .CH2.CH2.CH3 (b) CH3.COCH2.CH=CH2
(c) CH3 .OCH2 .CH2 .CH2 CH2 OH (d) CH3 .CH=CH.CH2.CH2OH
Solution : (d)
Compound must have unsaturation and –OH group
Chemistry : Alkyl Halides & Aryl Halides

Problem 8 : A hydrocarbon (A) having molecular weight 70 gives a single monochloride but three
dichlorides on chlorination in the presence of ultra violet light. The hydrocarbon (A) is
(a) 2-pentene (b) cyclopentane
(c) 2-methyl-2-butene (d) methylcyclobutane
Solution : Since the hydrocarbon (A) gives only a single monochloride, it implies that all the C—H
bonds must be of the same type. So the given hydrocarbon should be cyclopentane.
Cl Cl Cl
Cl Cl
Cl
Cl 2 / uv Cl 2 / uv

light

light + +

Cl
(b)
Problem 9: For the reaction,

CH3CH  CHCH3
NaNH 2
CH3 CH·CH 2 CH3  
|
(X) CH 2  CHCH 2 CH 3

(a) CH3 — CH = CH — CH3 predominates

(b) CH2 = CH — CH2 — CH3 predominates
(c) Both are formed in equal amounts
(d) The product ratio is dependent on the halogen (X)
Solution : When alkyl halide undergoes elimination reaction in presence of base, more substituted
alkene (Saytzeff’s product) will be the major product.
But either in presence of bulky base or the poor leaving group may give rise to the less
substituted alkene (Hoffmann’s product) as the major product.
Since base in a non-bulky strong one, the ratio of product is determined by the halogen atom.
(d)
Me Me Me Me
 
OH OH
Problem 10. HO H 
(H )
 H Cl 
(I)
H OH + HO H

Et Et Et Et
Step (I) and (II) are
(a) both SN1 (b) both SN2
(c) (I) : SN1, (II) : SN2 (d) (I) : SN2, (II) : SN1
Solution : By (I) there is a product with no change in configuration while by (II) there is inversion
hence (I) is SN1 and (II) is SN2.
(c)
 Chemistry : Alkyl Halides & Aryl Halides

SECTION - III
MULTIPLE CHOICE PROBLEMS
Problem 1: Vinyl chloride undergoes
(a) addition reactions (b) elimination reactions
(c) substitution reactions (d) none of these
Solution : (a, b)
Problem 2: Which of these statements are true for the isomeric compounds ethylene chloride and ethylidene
chloride?
(a) Both react with aqueous KOH to give the same product
(b) Both react with alcoholic KOH to give the same product
(c) They are derivatives of ethane
(d) They respond to Beilstein’s test
Solution : (b, c, d)
Problem 3: The reaction of ethyl alcohol and bleaching powder gives
(a) acetaldehyde (b) chloroform
(c) chloral (d) none of these
Solution : (a, b, c)
Problem 4: Which of the following statements are true about chloroform?
(a) It is used as an anaesthetic (b) It is used as a solvent
2
(c) It has sp -hybridized carbon (d) It has a distorted tetrahedral shape
Solution : (a, b, d)
Problem 5: The halogen atom in haloalkanes can be easily replaced by nucelophiles such as
(a) CN – (b) NO 2 —
(c) OR – (d) none of these
Solution : (a, b, c)
Chemistry : Alkyl Halides & Aryl Halides

MISCELLANEOUS PROBLEMS
SECTION - IV
COMPREHENSION TYPE PROBLEMS

Write up – I
When chloroform is treated with an alkoxide base a small amount of its conjugate-base anion is formed.

R —O H CCl3 ROH + CCl3

This anion can lose a chloride ion to give a neutral species :CCl2 called carbene-a highly reactive and
unstable species with a divalent carbon atom.

Cl Cl
C Cl C + Cl
Cl Cl
Dichloromethylene
(Carbene)
Carbenes are intermediate in many reactions such as Reimer-Tiemann reaction, carbyl amine reaction
etc.

Problem 1: What will be the major product (P) in the following reaction
CHCl3 + (CH3)2CO– K+ + CH2 = CH2 (P)
(a) Ethylene chloride (b) Ethylidene chloride
(c) 1, 2-Dichloro cyclopropane (d) 1, 1-Dichloro cyclopropane
Solution : (d)
Problem 2: The most suitable reagent for producing dichloro carbene from chloroform is :
(a) sodium acetate (b) Potassium-t-butoxide
(c) triethyl amine (d) Pyridine
Solution : (b)
Problem 3: In the following reaction
OH

OCH3 (i) CHCl , KOH, 


3
(ii) H 

X

The major product ‘X’ is :

 Chemistry : Alkyl Halides & Aryl Halides

OH OH
OCH3 OCH3
(a) (b)
CHO
OH OH

OCH 3 OCH3
(c) (d)
CHO

CHO

Solution : (c)

Write up – II
n-Butane is produced by mono bromination of ethane followed by Wurtz reaction, as follows
Br
(i) CH3CH 3 
2
hv
CH3CH 2 — Br
Na
(ii) CH3CH 2 Br  CH 3CH 2 CH 2CH 3  CH 2  CH 2  CH3 — CH 3  NaBr
Mechanism
Na  Na+ + e–; CH3CH2Na + CH3CH2Br  CH3CH2CH2CH3 + CH2 = CH2 + CH3 —CH3

 CH 3 C H 2  Br 
CH3CH 2 Br 

CH 3 C H 2  e  
 CH 3 CH 2

Problem 4: The amount of ethyl bromide required to prepare 55g of butane would be
(a) 106.72 (b) 206.72
(c) 20.67 (d) 2.067
Solution : (b)
Problem 5 : If the yield of n-butane was 85%, then the actual amount of ethyl bromide required to
produce 55 g of n-butane would be
(a) 2.432 g (b) 24.32 g
(c) 243.2 g (d) 0.2432
Solution : (c)
Problem 6 : The other products which could be formed
(a) CH2=CH2 (b) CH3 CH 2 CH 3

(c) CH 4 (d) CH3 CH2 CH 2—CH2 —CH3

Solution : (a)
Chemistry : Alkyl Halides & Aryl Halides

MATCHING TYPE PROBLEM

7. Match List-I with List-II for the given reaction and select the correct answer from the codes
given below the lists :
Z—CH2—Br + CH3O–  Z—CH2—OCH3 + Br–
List I (Z) List II (relative reactivity)
(A) H— 1. 0.1
(B) CH 3 — 2. 3
(C) C 2 H5 — 3. 1
H3C
(D) CH 4. 100
H3C

(A) (B) (C) (D)

(a) 4 2 3 1
(b) 4 2 1 3
(c) 2 4 3 1
(d) 1 2 3 4
Sol. (c)

ASSERTION-REASON TYPE PROBLEMS

The question given below consist of an ASSERTION and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.
8. Assertion : The boiling point of alkyl chlorides, bromides and iodides are considerably higher than those
of corresponding hydrocarbons.
Reason : Greater polarity of C—X bond as well as higher molecular mass (as compared to the parent
hydrocarbon) the intermolecular forces of attraction are stronger in the halogen derivatives.
Solution : (a)
9. Assertion : Halogenation of vinylic hydrogen is easier than that of allylic hydrogen.
Reason : Allyl radical is stabilised by resonance.
Solution : (d)
10.Assertion : Configuration is retained in SN1 reaction.
Reason : Intermediate is a carbocation and nucleophile attacks the same available side.
Solution : (a)