Alkyl halide | 1

Exercise - 1 Objective Problems | JEE Main

Preparation Methods Of Alkyl halide 6. The best reagent for converting ethanol to
1. In reaction chloroethane is -
C2H5OH + HX ZnX (A) PCl3 (B) PCl5
2  C2H5X + H2O
(C) SOCl2 (D) HCl + ZnCl2
the order of reactivity of HX is -
(A) HBr > HI > HCl
7. In Hunsdiecker reaction -
(B) HI > HCl > HBr
(A) A sodium salt of an acid reacts with bromine
(C) HCl > HBr > HI
(B) A calcuim salt of an acid reacts with HBr
(D) HI > HBr > HCl
(C) A silver salt of an acid reacts with bromine
(D) A silver salt of an acid reacts with HBr
2. Which of the following leads to the formation of an
alkyl halide -
Chemical Reaction Of Alkyl Halide
(A) C2H5OH Re
dP  Br2
 8. Finkelstein reaction is -
(B) C2H5OH SOCl (A) 2CH3CH2Cl+ Ag2O (dry) 
2 
CH3CH2OCH2CH3+ 2AgCl
(C) C2H5OH KBr

 Conc.H 2SO 4
 
(B) CH 3 CH 2 Br + NaI Acetone
  CH 3 CH 2 I+
(D) All
NaBr
(C) CH3CH2Br + Ag2O (moist) 
3. Which reaction is termed as Darzen’s Reaction
CH3CH2OH + AgBr
(A) ROH + HCl (B) ROH + PCl5
(D) CH3CH2Cl + NaOCH3 
(C) ROH + SOCl2 (D) ROH + PCl3
CH3 CH2OCH3 + NaCl

4. Silver benzoate reacts with bromine in acetone to

9. The reaction of silver carboxylates with bromine
form -
dissolved in carbon tetrachloride is called
Br COBr (A) Hofmann reaction
(B) Borodine reaction
(A) (B)
(C) Borodine - Hunsdiecker reaction
(D) Hypobromide reaction

COOAg
10. In Finkelstein Reaction, which reactants are used -
(C) (D) (A) NaI + C2H5OH (B) NaCl + acetone
Br (C) NaBr + CH3COCH3 (D) NaI + CH3COCH3

11. C2H5Cl + AgF C2H5F + AgCl

5. The reaction of SOCl2 on alkanols to form alkyl
The above reaction is called -
chlorides gives good yields because -
(A) Hunsdiecker (B) Swart
(A) Alkyl chlorides are immiscible with SOCl2
(C) Strecker (D) Wurtz
(B) The other products of the reaction are gaseous
and escape out
12. Which chloride is the most reactive towards aque-
(C) Alcohol and SOCl2 are soluble in water
ous NaOH in -
(D) The reaction occurs via intermediate formation
(A) Methyl chloride (B) Chlorobenzene
of an alkyl chloro sulphite
(C) Vinyl chloride (D) Benzyl chloride
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13. The SN2 reactivity order for halides :-

CH3–CH–CH–CH3 SN1 / C2H5ONa
(A) R–F > R–Cl > R–Br > R–I 19. Ether
CH3 Br Williamson Re action
(B) R–I > R–Br > R–Cl > R–F
Ether is -
(C) R–Br > R–l > R–Cl > R–F
(D) R–Cl > R–Br > R–F > R–I OC2H5
CH3–CH–CH–CH3
(A) CH3–C–CH2–CH3 (B)
CH3 OC2H5
14. In SN1 reaction, the first step involves the forma- CH3

tion of - (C) Both correct (D) None is correct

(A) Free radical (B) Carbanion
(C) Carbocation (D) Final product (A) Cl (B) aq  (C)
20. .KOH

2 

(
O)
 CH3CHO, Identify A, B & C -
15. The rate law for the reaction, RCl + Na (a)
 ROH + NaCl is given by, rate = K1 [RCl]. The (A) Ethylalcohol Ethyl chloride & Ethane
rate of the reaction will be - (B) Ethane, Ethylchloride & CH3–CH2–OH
(C) Propane, Propylchloride & CH3–CH2–CH2–OH
(A) Doubled on doubling the concentration of so-
(D) All the above
dium hydroxide
(B) Halved on reducing the concentration of alkyl
21. An alkyl halide reacted with a metal cyanide to give
halide to half
an alkanenitrile. The metal cyanide is -
(C) Decreased on increasing the temperature of
(A) AgCN (B) KCN
the reaction (C) Cu2(CN)2 (D) Ba(CN)2
(D) Unaffected by increasing the temperature of
the reaction 22. A strong solution of alcoholic alkali will preferen-
tially promote alkyl halide into an alkene by
16. Chlorobenzene is - (A) Addition (B) Elimination
(A) More reactive than ethyl bromide (C) Polymerisation (D) Substitution
(B) More reactive than isopropyl chloride
(C) As reactive as methyl chloride 23. When ethyl bromide is treated with moist Ag2O the
(D) Less reactive than benzyl chloride product is -
(A) Ethyl ether (B) Ethanol
17. Vinylic halides are unreactive towards nucleophilic (C) Ethoxy ethane (D) All of the above
substitution because of the following except -
(A) C - halogen bond is strong 24 A carbon compound A forms B with sodium metal
(B) The halogen is bonded to sp2 carbon and again A forms C with PCl5 but B and C form
diethylether. Therefore A, B & C are -
(C) A double bond character is developed in the
(A) C2H5OH, C2H5 ONa, C2H5Cl
carbon-halogen bond by reasonance
(B) C2H5Cl, C2H5 ONa, C2H5 OH
(D) Halide ions are not good leaving groups
(C) C2H5OH, C2H6, C2H5Cl
(D) C2H5OH, C2H5 Cl, C2H5ONa
18. When an alkyl halide reacts with an alkoxide, the
product is- 25. Action of alcoholic AgNO3 on chlorobenzene is
(A) Ether (B) Ester similar to the action on -
(C) Hydrocarbon (D) Alcohol (A) Allyl chloride (B) Vinyl chloride
(C) Isopropyl chloride (D) Benzyl chloride
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26. The number of steps involved in SN1 and SN 2 32. Reaction of ethyl bromide and silver acetate gives –
mechanisms are given by the set - (A) Ethyl ethanoate
(A) 1,2 (B) 3,1 (B) Methyl ethanoate
(C) 2,1 (D) 2,2 (C) Ethanoic anhydride
(D) 2-Butanone

27. Tertiary butyl halide on boiling with water gives

Chemical Properties & Preparation
tertiary butyl alcohol. The reaction follows -
methods of Diahlides
(A) SE mechanism (B) SNI mechanism
33. A vicinal dihalide is not formed in the reaction-
(C) SN2 mechanism (D) E1 mechanism
(A) HOCH2–CH2OH PBr
3 

28. Inversion of configuration of the product alcohol (B) CH3–CH=CH2 Br


2
during the hydrolysis of an optically active halide is
(C) CHCH HBr
 HBr

an experimental evidence for-
HBr
(A) SN2 mechanism (B) SNi mechanism (D) CH3–CH=CHBr  
Peroxide
(C) SN1 mechanism (D) A carbanion

34. 2,2-dichloropropane on hydrolysis yields -

29. Which one of the following pairs of reaction types
(A) Acetone (B) 2,2-Propane diol
included in the reaction sequence below (C) Isopropyl alcohol (D) Acetaldehyde
CH3CH = CHCH3 + HI (in CH3COOH)
 CH3CH2CHICH3 35. Propylidene chloride when heated with zinc gives -
CH3CH2CHICH3 + NaOH(aq) (A) Ethene (B) Propene
 CH3CH2CH(OH)CH3 (C) 1-Butene (D) 3-Hexene
(A) Electrophilic addition and electrophilic
substitution Chemical Properties & Preparation methods
(B) Electrophilic addition and nucleophilic of Chloroform
substitution 36. CHCl is kept in brown bottles well stoppered and
3
(C) Nucleophilic addition and electrophilic also with 1% alcohol so that it may not form -
(A) CH2Cl2 (B) COCl2
substitution
(C) CCl4 (D) None of these
(D) Nucleophilic addition and free radical
substitution
37. Chloroform can be obtained from -
(A) Methanol (B) Methanal
30. An alkyl isocyanide is prepared by -
(C) Propanol–1 (D) Propanol– 2
(A) Heating an amide with P2O5
(B) Reacting an alcohol with NH3
I H 2SO 4
CH3–C–CH3 
2
(A) Ag   (C)
(C) The action of AgCN on alkyl halide 38. Na 2 CO3   (B)
powder Hg 
O
(D) The action of KCN on alkyl halide
Product A, B & C are -
(A) Iodoform, Acetylene & Acetaldehyde

31. CH3Br AgCN
 A H2O B, [B] is - (B) Tri. iodomethane, Ethyne & Acetone
(A) CH3 NH2 (B) (CH3) NH (C) Iodoform, Ethene & Ethylene glycol
(C) C2H5 NH2 (D) CH3 COOH (D) Ethene, iodoform & Ethylhydrogen sulphate
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39. Which of the following statement is wrong - 47. Pyrene is the commerical name of -
(A) All carbonyl compounds of the general struc- (A) Degreasing agent CHCl3
ture CH3–C–R give a positive iodoform test (B) Fire extinguisher CCl4
O (C) Insecticide CHI3
(B) All secondary alcohols give iodoform reaction (D) Aerosol, propellant, C2Cl4 F2
(C) Alkanols of the structure CH3CH(OH) - R (where
R=H, alkyl or aryl) give iodoform reaction. Physical properties and test of Alkyl halide
(D) The only aldehyde giving iodoform reaction is 48. The yield of alkyl bromide obtained as a result of
acetaldehyde. heating the dry silver salt of carboxyic acid with
bromine what will be the order of formation w.r.t.
40. The oxidation of CHCl3 by air & light is prevented alkyl bromide -
by adding - (A) 1º > 3º > 2º bromides
(A) CH3COOH (B) C2H5OH (B) 1º > 2º > 3º bromides
(C) CH3CHO (D) CH3COOCH3 (C) 3º > 2º > 1º bromides
(D) 3º > 1º > 2º bromides
41. Isocyanide reaction involves the intermediate for-
mation of -
49. True about alkyl halides is/are -
(A) :CCl2 (B) CH3+
(A) Tertiary alkyl halides undergo SN2 substitutions
(C) CH3¯ (D) CCl3
(B) Alkyl iodides on exposure to sunlight gradually
42. Chloroform when treated with aniline and alcoholic darken
KOH forms - (C) Alkyl chlorides do not give beilstein test
(A) Phenyl cyanide (B) Phenyl isocyanide (D) A nucleophilic substitution is most difficult in
(C) Phenyl cyanate (D) Phenyl isocyanate alkyl iodides

43. Iodoform test is not given by : - 50. The correct order of density is -
(A) C6H5COC6H5 (B) CH3COCH3 (A) C2H5I > C2H5Br > C2H5Cl
(C) CH3CH2COCH3 (D) CH3CH2CHOHCH3 (B) C2H5 > C2H5Br > C2H5I
(C) C2H5Cl > C2H5I > C2H5CBr
44. The compound with no dipole moment is - (D) None of these
(A) Methyl chloride
(B) Carbon tetrachloride
51. Ethyl bromide and isopropyl chloride can be
(C) Methylene chloride
distinguished by -
(D) Chloroform
(A) Alcoholic AgNO3
(B) Comparing their colours
45. The hydrogen atom in chloroform is -
(C) Burning the compounds on spatula
(A) Acidic (B) Basic
(C) Neutral (D) None of these (D) Aqueous KOH solution

46. Iodoform gives a precipitate with AgNO3 on heating 52. The compound C2H4Cl2 has two isomers and they
but chloroform does not because - can be distinguished by the reaction with
(A) Iodoform is ionic (A) Aq. KOH (B) Alc. KOH
(B) Chloroform is covalent (C) Bromine water (D) NaNH2
(C) C–I bond in iodoform is weak and C–Cl bond
in chloroform is strong
(D) None

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Exercise - 2 (Level-I) Objective Problems | JEE Main

Prepration of Alkyl halide Chemical Reaction of Alkyl Halide
1. From each of the following pairs select the
compound that will react faster with sodium iodide Zn—dust
5. (p)
in acetone
(a) 2-Chloropropane or 2-bromopropane compound (p) is
I II
CH3 CH3
(b) 1-Bromobutane or 2-bromobutane
H Br
I II (A) (B) H Br
(A) (a)-I, (b)-I (B) (a)-I, (b)-II H Br Br H
(C) (a)-II, (b)-I (D) (a)-II, (b)-II CH3 CH3

O Br
2.  product are
Ph — C — CH3   PCl5
(C) Br

Cl
| Br
(A) Ph — C — CH3 (B) Ph — CH — CH 2 (D) Br
| | |
Cl Cl Cl

Cl CH3
(C) Ph — CH 2 — CH Zn—dust
H Br
Cl 6. (p). The product (p)
Br H
(D) Ph — CH2 — CH2 — Cl
CH3
3. In the acid catalyzed dehydration of alcohols to
alkenes, the intermediate species formed is is
(A) Free radical
(B) Carbocation (A) (B)
(C) Carbanion
(D) Carbene
(C) (D)
Br
H3C H
4. Anti elimination ? major 7. Which of the following compound will be most
—Br2 reactive for SN1 and SN2 reactions
H CH 3
Br
products is : I Cl
H3C H
O O
(A) (A) (B)

H CH 3

H3C H Cl
Br
(B)
O
H3C H (C) (D)
O
(C) both (A) & (B) (D) none of these

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CH3 CH 3 Br
Zn
11. + ZnBr2
8.
Br
Cl
This reaction is a case of
Total number of SN1 products of given compound (A) -elimination (B) -elimination
are
(C) -elimination (D) none of these
(A) 3 (B) 4
(C) 5 (D) 6
Br
SN2 12.
Nu + C [TS] C + L
9.

Which of the following figures represent correctly The major products obtained when this substrate is
the structure of transition state in this reaction? subjected to E2 reaction will be

C
(A) [ Nu (A) (B)

(C) both (A) and (B) (D) none of these

Nu C
(B) [
13. Which of following cannot undergo an E 2
reaction ?
(C) either (A) or (B) depending upon situation
(D) none of these H3C CH2Br H3C Br CH2Br
CH3 CH3
10. Best method for preparation of
CH3
| (i) (ii) (iii)
CH3— O — C — CH 3 by williamson’s ether
| (A) (i) (B) (ii)
CH3 (C) (iii)
(D) None (all can undergo an E2 reaction)
synthesis is
CH3 14. Which alkylbromide will yield-3-methyl-1-hexene as
| the major product upon treatment with potassium t-
(A) CH 3O + CH 3 — C — Br
| butoxide in t-butyl alcohol (solvent) ?
CH3 Br
(A)
(B) CH 3 — CH — O + CH 3 — CH — Br
| |
CH3 CH3
(B)
CH 3
| Br
(C) CH 3 — C — O + CH 3 — Br
|
CH3 (C)
Br
CH 3
|
(D) CH3 — C| — OH + CH3 — Br (D)
CH 3 Br

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 Alkyl halide | 7

alc. KOH
17. CH 3 — CH2 — CH — CH 3
CH3
Br
15.
X EtONa
;
Br Major CH 3 — CH2 — CH — CH 3
CH3 NMe3
+

Y
The major product obtained when this substrate is Major
subjected to E2 reaction will be
Product (X) and (Y) respectively is
(A) 1-butene, trans-2-butene
CH3 CH2
(B) 1-butene, cis-2-butene
(A) (B)
(C) cis-2-butene, 1-butene
(D) trans-2-butene, 1-butene

CH3 CH3
CH 3

(C) both (A) and (B) (D) none of these 18.

Br
16. If the following E2 reaction proceeds through an CH3
anti-periplaner transition state, what products are
expected ? The major product obtained when this substrate is
CH 3
subjected to E1 reaction will be

CH 3 CH3
Cl
(A) (B)
(A) Only 3-methylcyclohexene
(B) Only 1-methylcyclohexene CH2 CH3
(C) The major product is 3-methylcyclohexene and
the minor product is 1-methyl cyclohexene CH 3
(D) The major products is 1-methylcyclohexene and (C) (D) none of these
the minor product is 3-methyl cyclohexene
CH3

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Exercise - 2 (Level-II) Multiple Correct | JEE Advanced

Comprehension (Q.1 to 7) Paragraph for Question Nos. 8 to 10
(3 questions) :
(A) Cl (B) Cl
Dehydration require an acid catalyst to protonate
(C) (D) CH3–Cl the hydroxy group of the alcohol and convert it into
Cl
good leaving group. Loss of water followed by a
1. Most reactive towards SN1 reaction loss of a proton, given the alkene an equilibrium is
2. Most reactive towards SN2 reaction ? stablished between reactants and products.

3. Most reactive towards E2 reaction ? OH

4. Most reactive towards E1 reaction ? H
+

5. Consider the given reaction CH3—CH=CH 2

CH3 Mechanism
| NaCN
H — C — OTs CH3CH2CH—CN H
| | + +
(S) OH + H2SO4 O CH3—CH—CH 2
C2H5 CH3 (r.d.s) |
HSO4
Which of following statement are correct for above H H
H2O:
reaction.
(A) Product formation takes place due to the
+
breaking of O— Ts CH 3—CH=CH2 + H 3O
(B) The reaction SN2
(C) The reaction is SN1
8. To improve the yield of above reaction which of
(D) Configuration of product is (R)
following is correct.
6. Which are possible products in following (A) High temperature
moist Ag2O
(B) Distillation
CH 3
CH 2Cl SN1
(C) Addition of H2O
(D) Both (A) and (B)
CH3 OH

CH3 +
H
(A) (B)
CH2OH
9. (i) (A) Major
OH
CH2OH CH3
| |
OH +
(C) (D) H
(ii) (B) Major

OH
7. SN1 & SN2 product are same in (excluding steroisomer)
Cl OH
H
+
H
(A) (B) (C) Major
Cl

Total number of -hydrogen in A + B + C is

(A) 23 (B) 25
(C) (D) Ph — CH — CH — CH 3
| | (C) 37 (D) 29
CH3 Cl

Cl

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 Alkyl halide | 9

10. Which alcohol is most reactive towards dehydration 14. Reaction Reaction rate of reaction
of alcohols in acids catayzed reaction. (A) HO + R — CH2 — I  (P) 1
(B) HO + R — CH2 — Br  (Q) 200
OH OH
(C) HO + R — CH 2 — Cl  (R) 10,000
(D) HO + R — CH2 — F  (S) 30,000
(A) (B)
15. column I Column II
Alkyl-bromide Relative rate of SN1
CH3
OH |
(A) CH3 — C — Br (P) 1
OH |
CH3
(C) (D) (B) CH 3 — CH — Br (Q) 11.6
|
CH3
(C) CH3 — CH2 — Br (R) 1,200,000
Matrix Match
11. Column I Column II 16. column I Column II
Primary alkyl bromide SN2 relative rate Solvent Relative rate of SN1
(A) CH3 — CH2 — Br (P) 10–5 (A) 100% water (P) 1200
(B) Me — CH2 — CH2 — Br (Q) 10–2 (B) 80% water + 20% ethanol (Q) 400
(C) 50% water + 50% ethanol (R) 60
(C) Me — CH — CH 2 — Br (R) 0.8
| (D) 20% water + 80% ethanol (S) 10
Me (E) 100% ethanol (T) 1
Me
|
(D) Me — C — CH2 — Br (S) 1 17. Match List-I with List II for given SN2 reaction &
| select the correct answer from the codes given
Me
below
12.
Z—CH 2Br + CH 3O  Z—CH 2OCH3 + Br
Column I Column II
Alkyl—P—toluene sulfonate Ethanolysis relative List I List II (relative reactivity)
(A) CH3 — CH2 — OTs (P)1010 (A) H— (P) 0.1
(B) H2C = CH — CH2 — OTs (Q) 105 (B) CH3— (Q) 3
(C) Ph — CH2 — OTs. (R) 400 (C) C2H5— (R) 1
(D) Ph — CH — OTs (S) 35 CH 3
| (D) CH— (S) 100
Ph
CH3
(E) Ph3C — OTs. (T) 1

13.
Substrate E2 elimination SN2 — substitution
(A) CH3 – CH2 – Br (P) 1 (W)  0
(B) (CH3)2CH – Br (Q) 80 (X) 20
(C) (CH3)3CBr (R) 100 (Y) 90

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Exercise - 3 | Subjective | JEE Advanced

OCH 3
( X) Conc.HI
8.   
1. Which of the following reaction is not possible 4. A gem dichloride is formed in the reaction except
OCH3
(A) R – OH + NaBr  R – Br + NaOH (A) CH3CHO and PCl5
(B) R – OH + HBr R – Br + H2O (B) CHx3COCH and PCl5
= moles
3 of HI consumed
(C) both reaction are possible
value of x is
(D) both reactions are not possible OH
2PCl5
(C) (A) 2 (B) 4
2. Which of the following compound will not undergo (C) 5 OH (D) 6
acid catalysed hydrolysis ?
9. Consider
O the reaction of HI with the following
(D) PCl 5
O—CH 3
O
I II
(A)
5. O
Which of the following nucleophile will show
minimum reactivity towards SN2 reaction
Which forms di-iodide on reaction with HI(excess)?
(A) Me(A)
3COI and II both
(B) MeO
(B) II only
O—Ph
(C) I only (D) none
H
(B) (C) (D) Me2CHO
CH3 CH 3
O EtOH
10. Ph – CH — C — CH3 (A)
(SN ) 1
O—CH2CH3 Br
6. Which of following compounds will show NGP ?

(C) Major-product (A) is

(A) SPh H (B) H H
CH3 CH 3

(A)
H PhCl
– CH – C – CH3 PhS Cl
O
OEt
(D)

Cl
CH3 CH3

(B) Ph H
– C — CH — CH3 H
(C) (D)
Br OEt
Br Br Cl

3. Ph CH3
(C) OCH3
II III CH3 (x) conc.
CH3 HI
I
7.
OCH 3
SN2 reactivity of these substrate, under identical OEt CH3
conditions, will be in the order as Value of x in above reaction is
(D) Ph – C — C — CH3
(A) I > II > III (B) III > II > I (A) 2 (B) 3
H CH3
(C) III > I > II (D) II > III > I (C) 4 (D) 5
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 Alkyl halide | 11

CH3
SOCl2
11. H OH (A) . Product (A) in

Et

CH3 Et

(A) H Cl (B) H Cl

Et CH3

CH 3

(C) Cl H (D)

Et

H 3O
12. CH3 – CH 2 – O – C = CH2 Products
CH 3
are

O
(A) + EtOH

O
(B) + EtOH

OH
(C) + EtOH

OH
(D) + O

H3O
excess X
13.
O O
Structure of X is

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15. Among the bromides I-III given below, the order of

reactivity is SN1 reaction is
(A)
HO HO H O
(I) (II)

Br Br

(B) O
OH H O OH
(III)

Br

(C)
OH (A) III > I > II (B) III > II > I
O OH
(C) II > III > I (D) II > I > III

CH2 — OH
(D) (x)HBr
HO HO HO 16.
OH

14. In the given reaction : Value of (x) is

(A) 1 (B) 2
Cl (C) 3 (D) 4
Cl
CH 3OH
[X]
17. In the given reaction CH3 — CH — CH2 — CH2
O Cl |
OTs

(i) SH (one equivalent)

Cl OCH3 — CH — CH3 [X]
| (ii) KOH
Cl Cl OTs
(A) (B)
, [X] will be :
O OCH 3 O OCH 3

OTs S
| |
(A) CH3 — CH — CH2 — CH2 — CH — CH3
Cl OCH3

OCH3 Cl
(C) (D) S S
| |
O Cl O Cl (B) CH3 — CH — CH2 — CH2 — CH — CH3

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 Alkyl halide | 13

S
CH3 CH3
(C) (C) t-Bu

CH3 CH3
(D) t-Bu
(D) S OAc

Br
| (x) NaNH2 +
20. Ph — CH — CH 2
O |
Br (x = No. of moles of NaNH2)
+
H
18. (B) , Give structure of (B) Value of x is
(A) 1 (B) 2
O (C) 3 (D) 4

21. The energy profile of the given reactions.

(A) (B) O

+
H
CH3 — CH — CH3 CH3 — CH — CH3
| +|
OH O
(C) (D) H H

+ +
O —H
CH3 — CH — CH3 CH3 — CH = CH2

t-Bu +
OTs AcO Na
19. (A)
(A) E (B) E

Major-product (A) is
rxn-coordinate rxn-coordinate

(A) t-Bu
OAc

(C) E (D)
E
OAc

rxn-coordinate
(B) t-Bu rxn-coordinate

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14 | Alkyl halide

CH3 OH
O
+
CH 3 H
22. (x)
OH (C) (D)

Major product (X) is OH

25. Rate of dehydration when given compound is

CH 3
treated with conc. H2SO4.
(A) (B)
CH 3
OH
CH 2OH CH 3

(P) (Q)
(C) (D)

23. Which of the following alcohols would be most likely

OH
to undergo dehydration with rearragement by a OH CH
3 CH 3
process involving a methyl migration (methyl shift (R) (S)
only) ?

OH
(A) (B)
OH (A) P > Q > R > S (B) Q > P > R > S
(C) R > Q > P > S (D) R > Q > S > P
(C) (D)
OH OH

26. HO OH
OH
OH conc. H2SO4
A

H2SO4
24. X, X is Final product A is

(A) HO O

(B) CH2 = C = CH2

OH OH

(C)
(A) (B) O

(D) HO
O

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 Alkyl halide | 15

Total number of products obtained when this

Me
conc. H2SO4 substrate is subjected to E2 reaction will be
27. Me A.
(including streoisomer)
OH OH
(A) 3 (B) 4

Product A is (C) 5 (D) 6

Me Me
(A) (B)
Me Me
O CH3
Br

Me 31. CH3
Me
(C) (D) Me
C—Me
O
O
The major products obtained when this substrate to
Me E2 reaction under the treatment of potassium tert-
H Et alc. KOH butoxide will be
28. major product is :
Br Et

Me CH2 CH3
Me Me
(A) (A) (B)
Et Et CH3 CH3

Me Et (C) both in equal proportions

(B)
Et Me (D) none of these

Me Me
CH 3 CH3
H Et H Et
(C) (D) 32. I II
Me Br
Br
CH3

29. Most reactive towards acid-catalyzed hydrolysis is CH3

OEt III
(A) (B) OEt
OEt Br

(C) EtOEt (D) EtOH

Ease of  -dehydrobromination among these
substrates under the treatment of strong base will

Br
be in the order as
| (A) i > ii > iii (B) iii > ii > i
30. —C — CH2 — CH3
| (C) ii > i > iii (D) ii > iii > i
CH2 — CH2 — CH3

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16 | Alkyl halide

CH3OH Cl
33. CH3O — CH = CH2 product formed is
H+
Cl Cl
(A) Acetal (B) Hemiacetal (C)
(C) Alcohol (D) aldehyde
Cl Cl

Cl
Br
(D) all three are equally reactive
34. CH3 — CH2 — CH2 — C — CH2 — CH3

CH3
37. The nitrogen atom in each of the following tertiary
Total number of SN1 + E1 products obtained will be - amines may be removed as trimethyl amine by
(A) 5 (B) 6 (C) 7 (D) 8 repeated Hofmann eliminations (exhaustive
methylation followed by heating with AgOH).
Which of the amines requires the greater number
CH3
+ of Hofmann sequences to accomplish this ?
35. CH3 — C — CH2 — CH3 H

CH3 OH CH3
N
(A) (B)
N

+
(A) H

N(CH3)2 CH3
OH N
(C) (D)

OH +
(B) H (C)
Br CH3
– SN2
38. + OH A , A is
H H
Stability of product (A), (B), (C) is :
(A) C > B > A (B) A > B > C
HO H
(C) B > C > A (D) C > A > B
(A)
H CH3
36. Which of the following isomeric
hexchlorocyclohexanes is least reactive in (  )-
H CH 3
dehydrochlorination of treatment with strong base (B)
OH H
Cl Cl
Cl Cl Cl Cl

(A) (B)
HO CH 3
Cl Cl Cl Cl (C) both (D)
H H
Cl
Cl
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18
O—CH3 Ph Ph
Conc. HI
39. Product are C=C
(A)

18 MeO CH3
OH I

18 Ph Ph
(A) + CH3I (B) + CH3OH
(B) MeO C– C=O

OH I

CH3
(C) + CH3I (D) + H2O

Ph

alc. KOH (C) CH3 C — C — Ph

40. CH3 — CH2 — CH — CH3 X (Major)
| O
Br

(A) (B)

(C) (D) None of these

41. Among the given compounds, the correct Ph O

dehydration order is :
(D) Ph — C — C Me

(i) OH (ii) OH

OMe
(iii) OH (iv) OH

(A) i < ii < iii < iv (B) ii < iii < iv < i 43. Which of the following expressions is the
(C) i < iii < iv < ii (D) i < ii < iii = iv
experimentally observed rate law for an E2 reaction
of alkyl halide ?
Ph Ph (A) Rate = k[RX]
C—C
(B) Rate = k [RX]2
42. OH OH
(C) Rate = k[RX][base]
MeO CH3
(D)Rate = k[base]

Conc. H2SO4
A, A is :

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18 | Alkyl halide

Exercise - 4 | Level-I Previous Year | JEE Main

Q.1 The correct order of the thermal stability of Q.9 Consider the following bromides :
hydrogen halides (H – X) is – [AIEEE-2005]
(A) HF > HCl > HBr > HI (i) Me [AIEEE 2010]
Br
(B) HI > HBr > HCl > HF Me
(C) HI > HCl < HF > HBr
(D)HCl < HBr > HBr < HI (ii)
Br

Q.2 Tertiary alkyl halides are practically inert to Me

substitution by SN2 mechanism because of – Me
(iii)
[AIEEE-2005] Br
(A) instability (B) insolubility
The correct order of SN1 reactivity is
(C) steric hindrance (D) inductive effect
(A) (ii) > (iii) > (i) (B) (ii) > (i) > (iii)
(C) (iii) > (ii) > (i) (D) (i) > (ii) > (iii)
Q.3 Alkyl halides react with dialkyl copper reagents to
give [AIEEE-2005]
(A) alkyl copper halides (B) alkenes 10. Which branched chain isomer of the hydrocarbon
(C) alkenyl halides (D) alkanes with molecular mass 72u gives only one isomer of
mono substituted alkyl halide ?
Q.4 Elimination of bromine from 2–bromobutane results [JEE Main 2012]
in the formation of – [AIEEE-2005] (A) Isohexane
(A) predominantly 2–butene (B) Neohexane
(B) equimolar mixture of 1 and 2–butene (C) Tertiary butyl chloride.
(C) predominantly 2–butyne (D) Neopentane
(D) predominantly 1–butene
11. Iodoform can be prepared from all except :
Q.5 Among the following the one that gives positive (A) 3 - Methyl - 2 - butanone [JEE Main 2012]
iodoform upon reaction with I2 and NaOH is – (B) Isobutyl alcohol
(A) C6H5 CH2CH2OH [AIEEE 2006] (C) Ethyl methyl ketone
(D) Isopropyl alcohol
(B) 12. What is DDT among the following
(C) PhCHOHCH3 (A) Biodegradable pollutant [JEE Main 2012]
(D) CH3 CH2CH(OH)CH2CH3 (B) Non-biodegradable possutant
(C) Greenhouse gas
Q.6 Which of the following is the correct order of (D) A fertilizer
decreasing SN2 reactivity ? [AIEEE 2007]
(A) RCH2X > R3CX > R2CHX 13. Compound (A), C8H9Br, gives a white precipitate
(B) RCH2X > R2CHX > R3CX when warmed with alcoholic AgNO3. Oxidation of
(C) R3CX > R2CHX > RCH2X (A) gives an acid (B), C8H6O4. (B) easily forms
(D) R2CHX > R3CX > RCH2X anhydride on heating. identify the compound (A).
(X = a halogen) [JEE Main 2013]
Q.7 The organic chloro compound, which shows CH2Br
complete stereochemical inversion during a SN2 CH2Br
reaction , is [AIEEE 2008]
(A) (CH3)3CCl (B) (CH3)2CHCl (A) (B)
(C) CH3Cl (D) (C2H5)2CHCl CH3
CH3
Q.8 Which of the following on heating with aque
CH2Br
ous KOH, produces acetaldehyde ? C2H5
[AIEEE 2009]
(A) CH3COCl (B CH3CH2Cl (c) (D)
(C) CH2Cl CH2Cl (D) CH3CHCl2 CH3 Br

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 Alkyl halide | 19

14. A solution of (–) –1–chloro–1-phenylethane in 19. Which of the following, upon treatment with tert-
toluene racemizes slowly in the presence of a small BuONa followed by addition of bromine water, fails
amount of SbCl5. due to formation of : to decolourize the colour of bromine ?
[JEE Main 2013] [JEE Main 2017]
(A) carbocation (B) free radical O
C6H 5
(C) carbanion (D) carbene
(A) (B)
15. In SN2 reactions, the correct order of reactivity for Br Br
the following compounds ? [JEE Main 2014] O
CH3Cl, CH3CH2Cl, (CH3)2CHCl and (CH3)3CCl is O
(A) CH3CH2Cl > CH3Cl > (CH3)2CHCl > (CH3)3CCl (C) (D)
(B) (CH3)2CHCl > CH3CH2Cl > CH3Cl > (CH3)3CCl Br
Br
(C) CH3Cl > (CH3)2CHCl > CH3CH2Cl > (CH3)3CCl
(D) CH3Cl> CH3CH2Cl > (CH3)2CHCl > (CH3)3CCl
20. The major product formed in the following reaction
16. The synthesis of alkyl fluorides is best accomplished is: [JEE Main 2018]
by : [JEE Main 2015]
(A) Free radical fluorination
(B) Sandmeyer's reaction
(C) Finkelstein reaction
(D) Swarts reaction

17. The major product obtained in the following reaction I OH

is : [JEE Main 2017] (A) (B)
Br OH OH
H
tBuOK
C6H5
C6H5 (+) I OH
(C) (D)
(A) C6H5CH = CHC6H5
(B) (+)C6H5CH(OtBu) CH2C6H5 I I
(C) (–)C6H5CH(OtBu)CH 2C6H5
(D) (±)C6H5CH(OtBu)CH 2C6H5

18. The increasing order of the reactivity of the following

halides for the SN1 reaction is : [JEE Main 2017]
CH3CHCH2CH3 CH3CH2CH2Cl p-H3CO–C6H4–CH 2Cl
Cl
(I) (II) (III)
(A) (II) < (I) < (III) (B) (I) < (III) < (II)
(C) (II) < (III) < (I) (D) (III) < (II) < (I)

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20 | Alkyl halide

Exercise - 4 | Level-II Previous Year | JEE Advanced

1. The following compound on hydrolysis in aqueous 5. Match the following : [IIT 2006]
acetone will give : [IIT 2005] Column I
(A) CH3—CHBr—CD3 on treatment with alc.
CH 3 CH3 CH 3 KOH gives CH2 = CH — CD3 as a major product
NO 2
(B) Ph—CHBr—CH 3 reacts faster than Ph—
(K) CHBr—CD 3.
H Cl CH 3 (C) Ph—CH2—CH2Br on treatment with C2H5OD/
C 2H 5O — gives Ph—CD = CH 2 as the
CH 3 CH3 CH 3 product.
(D) PhCH 2CH2Br and PhCD 2CH2Br react with
NO 2 (L) same rate
H OH CH 3
Column II
(P) E1 reaction
KOH gives CH2 = CH — CD3 as a major product
CH 3 CH3 CH 3
(Q) E2 reaction
NO 2 (M) (R) E1 cb reaction gives Ph—CD = CH2 as the
product.
OH H CH 3
(S) First order reaction

CH 3 CH3 CH 3 6. The reagent(s) for the following conversion.

NO 2 Br ?
Br H H
H CH3 OH
is/are [IIT 2007]
(A) mixture of (K) and (L) (A) alcoholic KOH
(B) alcoholic KOH followed by NaNH2
(B) mixture of (K) and (M)
(C) aqueous KOH followed by NaNH2
(C) only (M) (D) Zn/CH3OH
(D) Only (K)
7. The number of stereoisomers obtained by
2. Cyclohexene is best prepared from cyclohexanol bromination of trans-2-butene is [IIT 2007]
by which of the following [IIT ‘2005] (A) 1 (B) 2
(A) conc. H3PO4 (B) conc. HCl/ZnCl2 (C) 3 (D) 4
(C) conc. HCl (D) Conc. HBr
8. The major product of the following reaction is

3. 1–bromo–3–chlorocyclobutane when treated with Me Br

two equivalents of Na, in the presence of ether
which of the following will be formed? F
 
Ph S N a
[IIT ‘2005]     
dim ethyl formamide [IIT 2008]

(A) (B)
NO2

(C) (D) Me SPh Me SPh

F F

(A) (B)
H ,  (i) O3
4.  X     
  Y.
(ii) Zn / CH3COOH

NO2 NO2
Identify X and Y. [IIT 2005]

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 Alkyl halide | 21

Me Br Me SPh O
C
SPh SPh
(A) N—CH2 Br
(C) (D)
C

O
NO2 NO2
O
C
9. The correct stability order for the following species
is [IIT ‘2008] (B) N CH 2Cl
C

O O
(I) (II)
O
C
O
(III) (IV) (C) N
(A) II > IV > I > III (B) I > II > III > IV C
(C) II > I > IV > III (D) I > III > II > IV
O — CH2 Br

10. In the following carbocation, H/CH3 that is most

likely to migrate positively charged carbon is
O
H H
1 2 + 4 5 C
H3C – C – C – C – CH3 (D)
[IIT 2009] N
HO H CH3 C
(A) CH3 at C-4 (B) H at C-4 O CH2Cl
(C) CH3 at C-2 (D) H at C-2

11. The synthesis of 3-octyne is achieved by adding a 14. The total number of alkenes possible
bromoalkane into a mixture of sodium amide and by dehydrobromination of 3-bromo-3-
an alkyne. The bromoalkane and alkyne cyclopentylhexane using alcoholic KOH is :
respectively are – [IIT 2010] [IIT 2011]
(A) BrCH 2CH2CH2CH2CH3 and CH3CH2CCH
(B) BrCH2CH2CH3 and CH3CH2CH2CCH 15. The major product of the following reaction is
(C) BrCH2CH2CH2CH2CH3 and CH3CCH
(D) BrCH2CH2CH2CH3 and CH3CH2CCH RCH2OH
+ [IIT 2011]
1]
H (anhydrous)
12. The bond energy (in kcal mol–1) of a C – C single O
bond is approximately [IIT 2010] (A) a hemiacetal (B) an acetal
(A) 1 (B) 10 (C) an ether (D) an ester
(C) 100 (D) 1000
16. KI in acetone, undergoes SN2 reaction with each
13. The major product of the following reaction is : of P,Q,R and S. The rates of the reaction vary as.
O [IIT 2011] [JEE Adv. 2013]
C O
(i) KOH
NH Cl
H3C—Cl Cl
C
(ii) Br CH 2Cl (A) P>Q>R>S (B) S>P>R>Q
O (C) P>R>Q>S (D) R>P>S>Q
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22 | Alkyl halide

17. The reactivity of compound Z with different halogens

Me OH
under appropriate conditions is given below :
[JEE Adv. 2014] (A)

mono halo substituted derivative when X2 = l2

OH Me OH
X2
di halo substituted derivative when X2 = Br2
(B)
C(CH3)3
Z
Tri halo substituted derivative when X2 = Cl 2

(C)
Me OH
The observed pattern of electrophilic substitution
can be explaind by :
(A) the steric effect of the halogen
(B) the steric effect of the tert-butyl group (D)
Me OH
(C) the electronic effect of the phenolic group
(D) the electronic effect of the tert-butyl group
21. LIST-I contains reactions and LIST-II contains
18. In the following monobromination reaction, the major products. [JEE Adv. 2018]
number of possible chiral products is: LIST-I
[JEE Adv. 2016]
CH2CH2CH3 P. +
Br2(1.0 mole) ONa Br
H Br
CH3 300°C
(1.0 mole) Q. + HBr
(enantiomerically pure) OMe

R. + NaOMe
19. For the following compounds, the correct Br
statement(s) with respect to nucleophilic substitution
reactions is (are) [JEE Adv. 2017]
S. + MeBr
ONa
Br Br
LIST-II

(I) (II)
1.
CH 3 CH3 OH

H 3C—C—Br Br
2.
CH 3 Br
(III) (IV)
(A) I and II follow SN2 mechanism 3.
(B) Compound IV undergoes iniversion of configuration OMe
(C) The order of reactivity for I, III and IV is : IV 4.
> I > III
(D) I and III follows SN1 mechanism O
5.

20. In the following reaction sequence, the correct Match each reaction in LIST-I with one or more
structure(s) of X is (are) [JEE Adv. 2018] product in LIST-Il and choose the correct option.
Me N3 (A) P  1, 5; Q  2; R  3; S  4
(1) PBr3, Et2O
X (B) P  1, 4; Q  2; R  4; S  3
(2) NaI, Me2CO
(3) NaN3, HCONMe2 (C) P  1, 4; Q  1, 2; R  3, 4; S  4
enantiomerically pure (D) P  4, 5; Q  4; R  4; S  3, 4
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 Alkyl halide | 23

22. Choose the correct option(s) for the following set of reactions [JEE Adv. 2019]

(i) MeMgBr conc. HCl S

C6H 10O Q
(ii) H 2o (major)

20% H3PO4, 360 K

(i) H2, Ni HBr, benzoyl peroxide

T R U
(major) (ii) Br2, hv (major)
(major)

H 3C Cl CH3 CH3 H3C Br

Br Br

(A) (B)
S U U T

CH3 H3C Br H3C Br CH3

Cl Cl

(C) (D)

S T U S

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24 | Alkyl halide

Exercise - 1 Objective Problems | JEE Main

1. D 2. D 3. C 4. A 5. B 6. C 7. C
8. B 9. C 10. D 11. B 12. D 13. B 14. C.
15. B 16. D 17. D 18. A 19. A 20. B 21. B
22. B 23. B 24. A 25. B 26. C 27. B 28. A
29. B 30. C 31. A 32. A 33. C 34. A 35. D
36. B 37. D 38. A 39. B 40. B 41. A 42. B
43. A 44. B 45. A 46. C 47. B 48. B 49. B
50. A 51. A 52. A

Exercise - 2 (Level-I) Objective Problems | JEE Main

1. C 2. A 3. B 4. A 5. A 6. B 7. A
8. B 9. A 10. C 11. B 12. B 13. A 14. D
15. D 16. A 17. D 18. B

Exercise - 2 (Level-II) Multiple Correct | JEE Advanced

1. A 2. D 3. A 4. A 5. (B, D) 6. (A,B) 7. B, C
8. D 9. D 10. A
11. A S ; B R ; C Q ; D P 12. A T ; B S ; C R ; D Q; E P
13. A P, Y ; B Q, X ; C R, W 14. A S ; B R ; C Q ; D P
15. A R ; B Q ; C P ; 16. A P ; B Q ; C R ; D S; E T
17. A S ; B Q ; C R ; D P

Exercise - 3 | Subjective | JEE Advanced

1. A 2. B 3. B 4. C 5. A 6. A 7. A
8. C 9. C 10. B 11. A 12. A 13. B 14. A
15. A 16. A 17. C 18. B 19. B 20. C 21. C
22. A 23. A 24. D 25. C 26. C 27. D 28. B
29. A 30. C 31. A 32. D 33. A 34. C 35. D
36. B 37. A 38. C 39. A 40. A 41. A 42. B
43. C

Exercise - 4 | Level-I Previous Year | JEE Main

1. A 2. C 3. D 4. A 5. C 6. B 7. C
8. D 9. A 10. D 11. B 12. B 13. B
14. A

SbCl5
CH – CH3 CH – CH3
Lewis acid
Carbocation
Cl

15. D
SN2

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 Alkyl halide | 25
18. A
1 Intermediate  Carbocation
2
Reactivity of SN 
Steric hindrance
CH2

Order of reactivity towards SN2. CH3–CH–CH2–CH3 CH3–CH2–CH2

CH3Cl > CH3–CH2–Cl > OCH3

(CH3) 2CH–Cl > (CH3) 3C–Cl +M
(III) > (I) > (II)
16. D
19. D
R–Cl O
AgF/dmF
or R–F + AgCl/AgBr
R – Br
Br
Swart reaction Unable to form alkene
So decolourisation
Can't be possible.
17. A
Due to presence of bulky base product would 20. A
be an alkene.

Exercise - 4 | Level-II Previous Year | JEE Advanced

1. A 2. A 3. D

O
4. (x) (y)
CH3–C–(CH2)4–CHO
CH3

5. AQ ; BQ ; CR,S, ; DR,S,

6. B 7. A 8. A 9. D 10. D 11. D 12. C

13. A 14. 5 15. B 16. B 17. ABC 18. 5 19. A, D
20. B 21. B 22. A,B

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