02 - Alkyl Halide - Aryl Halide (Questions)

CHEMISTRY ALKYLHALIDE &ARYLHALIDES
CONCEPTUAL QUESTIONS
1. Which one of the following compounds most readily undergoes substitution by S N2 mechanism?
CH3
H3C
H3C
(A) (B)
Cl
Cl
Cl CH3
H3C
H3C
(C) (D) Cl
C3H7 H3C
2. Which of the following derivatives of benzene would undergo hydrolysis most readily with aq. KOH
Cl Cl
O 2N NO2
(A) (B)
NO2 NO2
Cl Cl
NO2
(C) NO2
(D)
N
NO2 H3C CH3
3. Which of the following compounds would be hydrolysed most easily ?

(A) C2H5Br (B) CH3Br
(C) CH2 = CH — Br (D) CH2 = CH — CH2Br.
+
Cl ONa
NO2 NO2

Dil. NaOH
→
4.
NO2 NO2
The above transformation proceeds through

(A) Electrophilic-addition (B) benzyne intermediate
(C) Activated nucleophilic substitution (D) Elimination, addition mechanism
5. o-Methoxybromobenzene is treated with sodamide and then with ammonia. The product formed is
(A) o-Methoxyaniline (B) Aniline
(C) Methoxybenzene (D) m-methoxyaniline.
Nishith Multimedia India (Pvt.) Ltd 39

ALKYLHALIDE &ARYLHALIDES CHEMISTRY
6. Which of the following is fast debrominated?

Br Br Br Br
(I) (II) (III) (IV)
(A) IV (B) II
(C) III (D) I
7. The organic compound (P) of the reaction:

Ph
Me H

alc. KOH
∆
→ P is
Br H
Ph
Ph Me Ph Me
(A) (B)
H Ph Ph H
Ph Ph
Me H Me H
(C) H H (D) H OH
Ph Ph
Cl Cl 
t-BuO
A
8. t-BuOH A is
t-BuO
O
(A) (B)
O
Cl O-t-Bu
(C) (D)
O O
40 Nishith Multimedia India (Pvt.) Ltd

Me
9. Ph OH 
SOCl2
in C5H5N
→
H
Which statement is true for the above reaction?
(A) Retention of configuration (B) Inversion of configuration
(C) Inversion and Retention both (D) None
10. On heating diethyl ether with conc. HI, 2 moles of which of the following is formed
(A) Ethanol (B) Iodoform
(C) Ethyl iodide (D) Methyl iodide

SINGLE CORRECT ANSWER TYPE
LEVEL - I
Isomerism
1. How many structural isomers are possible for C4H9Br?

(A) 4 (B) 3 (C) 2 (D) 5
2. How many primary halides are possible for C5H11Br?

(A) 1 (B) 2 (C) 3 (D) 4
3. Which of the following alkyl halides is iso-butyl bromide?

CH3
CH
(A) CH3CH2 | CH3 (B) CH3CH2CH2CH2Br (C) H3C C Br (D)
Br CH3
CH3
H 3C CH CH 2Br
Prepration
4. Which reagent cannot be used to prepare an alkyl chloride from an alcohol?
(A) HCl + anhyd. ZnCl2 (B) NaCl (C) PCl5 (D) SOCl2
5. Benzyl chloride can be prepared by reacting

(A) Toluene with Cl2 in the presence of FeCl3 (B) Benzene with CH3Cl in the presence of
AlCl3
(C) Toluene with Cl2 in the presence of sunlight (D) Benzene with Cl2 in the presence of FeCl3
Physical Properties
6. Which of the following alkyl halides has the maximum density.
(A) C2H5Cl (B) C2H5Br (C) C2H5I (D) C2H5F
Chemical Properties
7. When tert-butyl chloride is made to react with sodium methoxide, the major product is
(A) Dimethyl ether (B) Di-tert butyl ether
(C) Tert-Butyl methyl ether (D) Isobutylene
8. Which of the following compounds would be hydrolysed most easily?
(A) C2H5Br (B) CH3Br (C) CH2 = CH – Br (D) CH2 = CH –
CH2Br
9. Ethylene chloride and ethylidene chloride are isomeric compounds. Identify the statement that
is not applicable to both of them
(A) Both of them are dihalogen derivatives
(B) Both of them give Beilstein test
(C) Both of them react with alc. KOH and give same product
(D) Both of them react with aqueous KOH and give same product

10. Photochemical chlorination of an alkane is initiated by a process of

(A) Pyrolysis (B) Peroxidation (C) Homolysis (D) Rearrangement
11. Allylic bromination of olefins is generally carried out with

(A) Phenyl magnesium bromide (B) Dibromo succinic acid
(C) N-Bromo succinimide (D) Pyridine perbromide
12. Which of the following alkyl halide is neo-pentyl chloride?

CH3 CH3
(A) H3C C CH2 CH2 CH2Cl (B) H3C C CH2 CH2 Cl
CH3 CH3
CH3 CH3
H3C C CH2Cl CH CH2 CH2 Cl
(C) (D) H3C
CH3
13. An alkyl halide may be converted into an alcohol by

(A) Addition (B) Elimination (C) Substitution (D) Hydrogenation
14. For the reaction

C2H5OH + HX → C2H5X + H2O
The order of reactivity is
(A) HCl > HBr > HI (B) HI > HBr > HCl (C) HBr > HCl > HI (D) HI > HCl > HBr
15. Chlorobenzene can be prepared by reacting aniline with

(A) Hydrochloric acid
(B) Cuprous chloride under drastic condition
(C) Chloride in presence of anhydrous aluminium chloride
(D) Nitrous acid
16. Which of the following is called Sandmeyer reaction?

(A) 2HCHO 
NaOH
→ CH3OH + HCOONa
(B) N2Cl
→
CuCl
Cl
CH3
(C) + CH3 Cl 
CuCl
→
OH
OH
 →
(D) CO2
NaOH
COOH

17. Toluene when refluxed with Br2 in the presence of light mainly gives
(A) o-Bromotoluene (B) p-Bromotoluene
(C) Mixture of 0- and p-bromotoluene (D) Benzyl bromide
18. Bromination of toluene gives
(A) Only m-substituted product
(B) Only p-substituted product
(C) Mixture of ortho- and para- substituted products
(D) Mixture of ortho and m-substituted products
19. The decreasing order of reactivity of m-nitrobromobenzene (I) : 2, 4, 6-trinitrobromobenzene (II); p-

nitrobromobenzene (III) ; 2, 4-dinitrobromobenzene (IV), towards OH− ions is
(A) I > II > III > IV (B) II > IV > III > I (C) IV > II > III > I (D) II > IV > I > III
20. Which chloro derivative of benzene among the following would undergo hydrolysis most readily
with aqueous sodium hydroxide to furnish the corresponding hydroxyl derivative?
NO2
(A) O 2N Cl (B) O 2N Cl
NO2
(C) Me2N Cl (D) C6H5Cl
CH Cl
21. 
2
AlCl
2
→ X
3
The product is
(A) Benzyl chloride (B) Benzal chloride (C) Benzo chloride (D) Diphenyl methane
22. When chloroform reacts with benzene in the presence of aluminium chloride, the product formed
is
(A) 1, 1, 1-Trichloroethane (B) Trichlorophenyl methane
(C) Triphenyl methane (D) Triphenyl chloromethane
23. Which of the following groups is an ortho-para directing as well as deactivating group?
(A) — OH (B) — NH2 (C) — CH3 (D) — Cl
alcoholic KOH
24. CH3CH2 CH CH2CH = CH2  → A ( predominant ) ,
Br
A is :
(A) CH3 CH2 CH = CHCH = CH2 (B) CH3 CH = CHCH2 CH = CH2
(C) CH2 = CHCH2 CH2 CH = CH2 (D) CH3 CH2 CH2 CH2 C ≡ CH

25. The reactivity of halogens towards of alkanes decreases in order :

(A) F2 > Cl2 > Br2 > I2 (B) I2 > Br2 > Cl2 > F2
(C) Cl2 > F2 > I2 > Br2 (D) F2 > Br2 > I2 > Cl2
LEVEL - II
Reactivity
26: Alkyl halide reacts with an alcoholic solution of ammonia to give a mixture of:
(A) 1° and 2° amine (B) 1°, 2°, 3° & quaternary
(C) 1°, 2° & 3° amines (D) 1° & 3° amine
Chemical Properties
27: Product – I ←

aq KOH
 C2H5Br 
alc KOH
→ Product – II, the correct statement is
(A) Product - I is obtained by the elimination reaction

(B) Product - II is obtained by the substitution reaction
(C) The molecular formula of Product - I is C2H4, while the molecular formula of Product - II is
C2H6O
(D) Product-I is the isomer of dimethyl ether, while Product-II is the dehydrated compound of
Product-I
28: F NO2 

(CH3 )2 NH
→ X 
H 2 / Pd
→Y ; Y is :
DMF / ∆
CH3
(A) H2N N (B) H NH2
CH3
NH2
H3 C
(C) H3C N (D)
N NO2
H3 C
CH3
CH3 NaF NaF H

+
(X) ; CH3 CHCl (Y) ; (X)+ (Y) (Z)
Br
H3C H2O
29: S O
CH3
H3C (DMS)
Compound (X) and (Z) are respectively

CH3 CH3
CH3
(a) (b) CH3 and
F
and
OCHMe2 OCHMe2
CH3
(d) CH3 and CH3
(c) CH2 and
OCHMe 2 OCHMe 2

30: Chlorobenzene towards hydrolysis is,

(A) Less reactive than benzyl chloride (B) More reactive than ethyl bromide
(C) Nearly as reactive as methyl chloride (D) More reactive than isopropyl chloride
31: Following equation illustrates

200 − 2500 C
C6H5Cl + 2NaOH 
200 atm
→ C6H5ONa + NaCl + H 2O
(A) Dow’s process (B) Kolbe’s process
(C) Carbylamine test (D) Haloform reaction
32: Alkyl halide on heating with alc. NH3 in a sealed tube results
(A) 10 amine (B) 20 amine (C) 30 amine (D) all of these
33: Carbylamine is liberated when . . . . is heated with chloroform and alcoholic potash
(A) An aldehyde (B) A primary amine
(C) A secondary amine (D) A phenol
34. End product of following sequence of reaction is :
NH O /H O
Br 
3
→ A 
3 2
→ B 
BaO
∆
→C
(A) O (B) OH (C) O (D)

HOOC COOH
35. CH2CH CH2 

NBS
→X

Br /Fe
2
→Y

Br water
2
→Z
X, Y and Z, respectively are :
(A) X: CH2 CH CH2; Y: CH HC CH2

Br Br Br
Z: CH2CHCH2
Br
(B) X: CHCH CH2; Y: CH2CH CH2

Br

Z: CH2 CH CH2
Br Br
(C) in all cases X of (A)

(D) in all cases Y of (A)
36. CH2 = CHCH2CH = CH2 

NBS
→ A , A is
H2C CH CH CH CH2
(A) (B) CH2 = CHCH2 CH = CHBr
Br
(C) CH2 = CHCH2 CH = CHBr (D) H2C CHCH2 C CH

Br
CH 3
CH CH OH
Br →
CH CH ONa
37. B ←
3 2
 CH3 C 3 2
A
(major ) ( CH CH OH )
3 2 (major )
CH 3
A and B are :
CH3 CH3
(A) CH3 C OCH2CH3 in both cases (B) CH3 C CH2 in both cases
CH3
CH3 CH3 CH3 CH3
(C) CH3 C OCH2CH3 and CH3 C (D) CH3 C and CH3 C OCH2CH3
CH3 CH2 CH2 CH3
H3C CH3
Cl FeCl
38.  3
CH NO , 0°C
→ A; A is :
3 2
CH3
CH3 H3C CH3

CH3
(A) (B)
CH2CH3
CH3
(C) Both are correct (D) None is correct

39. When an alkylhalide is dissolved in ethanol the following reaction begins to occur.
S 2 Mechanism
R – X + EtOH  N
→ R − O − Et + HCl
The overall order of reaction is.
(A) One (B) Two (C) Three (D) Zero
40. Major product of the following SN1 reaction is :
−
H3C CH CH CH3 + O C2H5 →
Br CH3
CH3
H3C CH CH2CH2OC2H5
(A) H3C CH CH CH3 (B)
OC2H5 CH3
CH3
CH3CH2 CCH3
(C) (D) None is correct
OC2H5
41. Ethylene reacts with bromine to form
(A) Chloroethane (B) Ethylene dibromide
(C) Cyclohexane (D) 1-bromo propane
42. The reactivities of methyl chloride, propyl chloride and chlorobenzene towards solvolysis are in
the order
(A) Methyl chloride > propyl chloride > chlorobenzene
(B) Propyl chloride > methyl chloride > chlorobenzene
(C) Methyl chloride > chlorobenzne > propyl chloride
(D) Chlorobenzene > propyl chloride > methyl chloride
LEVEL - III
43: An alkyl halide of formula C6H13Cl on treatment with potassium t-butoxide gives two isomeric
alkenes (C6H12). Both alkenes on hydrogenation give 2, 3, dimethyl butane. Isomeric alkenes are
H3C H3C
CH3 CH3
(A) H2C and H3C
CH3 CH3
H3C
H3C
CH3
(B) H2C and

CH3
CH3

H3C CH3
CH3 and
(C) H C
3
H3C CH3
H3C CH3
CH3
(D) H2C and H2C
CH3 CH3
Br
44:  i)  → A  CH
alc. KOH
ii) NaNH
  → B. A and B
NaNH 2
CH Cl
2 3 2
Br
CH 2 CH 3
(A) A≡ B≡
CH 2 CH 3
(B) A≡ B≡
CH
(C) A ≡
B ≡ CH 3
(D) None of these

Br
On treatment with aqueous KOH gives

45:
H 3C CH 3
OH OH
CH3 CH3
(A) (B)
H3C CH3 H3C CH3
OH
CH3
(C) CH3 (D)

H3C OH CH3
46: 3-methyl -2-pentene on reaction with HOCl gives

(A) 3-chloro-3-methyl pentanol-2
(B) 2,3-dichloro-3-methyl pentane
(C) 2-chloro-3-methyl pentanol -3
(D) 2,3-dimethyl butanol-2

47: Silver benzoate reacts with bromine in acetone to form
COOAg
Br
(A) (B) (C) (D)

Br
Br
48: The reaction described below is
CH3(CH2)5
−
Br → CH (CH ) CH = CH - CH
Conc. OH
H3C
3 2 4 3
H
(A) SE1 (B) E2 (C) SN1 (D) SE2
49: Which of the following ether will give always SN2 mechanism in acidic as well as basic conditions?
O
(A) H C CH3 (B) C6 H5 CH2 O CH3
3
H3C
(C) (D) All of these
O
50: Order of hydrolysis of the following in increasing order is
Br , Br , Br , (CH3)3CBr
(I) (II) (III) (IV)

(A) I < II < III < IV (B) I < IV < II < III
(C) IV < III < II < I (D) I < II < IV < III
51: The addition of HBr is easiest with
(A) CH2 = CHCl (B) ClCH = CHCl
(C) CH3 – CH = CH2 (D) (CH3)2C = CH2
52. Which one of the following will produce a primary alcohol by reacting with CH3MgI ?
(A) Acetone (B) Methyl cyanide
(C) Ethylene oxide (D) Ethyl acetate
53. Identify the set of reagent and reaction conditions ‘X’ and ‘Y’ in the following set of transformations,
CH3 CH2 CH2Br

X Y
Product CH3 CH CH3
Br
(A) X = Dilute aqueous NaOH, 20 C, Y = HBr/acetic acid, 200C
0
(B) X = Concentrated alcoholic NaOH, 800C, Y = HBr/acetic acid, 200C

(C) X = concentrated alchololic NaOH, 800 C, Y = HBr / in presence of H2O2
(D) X = Dilute agueous NaOH, 200 C, Y = HBr / in presence of H 2O2

MULTIPLE CORRECT TYPE QUESTIONS

LEVEL - I
1. Which of the following chloro derivatives, on further chlorination can yield three dichloro derivatives?
(A) 1-Chloropropane (B) 2-Chloropropane
(C) Chlorobenzene (D) Chlorocyclohexane
2. Which of the following statements are correct?

(A) Alkyl chlorides are lighter than water
(B) Tetrachloromethane is heavier than water
(C) Alkyl chlorides undergo nucleophilic substitution more easily than alkyl bromides
(D) Fluorobenzene can be prepapred by Sandmeyer’s reaction
3. Which of the following compounds do not respond to silver nitrate test?

(A) Vinyl chloride (B) Allyl chloride
(C) Chlorocyclohexane (D) Chlorobenzene
4. Which of the following compounds would yield chloroform on warming with bleaching powder
paste?
(A) 1-Propanol (B) Propanone (C) Ethanol (D) Propanal
5. Which of the following statements are not correct?

(A) Chlorobenzene is more reactive than benzene towards electrophilic subsititution reactions
(B) C—Cl bond in chlorobenzene is less polar than in CH3Cl
(C) Chlorobenzene is less reactive than CH3Cl towards nucleophilic substitution reactions
(D) In chlorobenzene further substitution take place at meta position
6. Which of the following reactions result in a product with more number of carbon atoms than the
starting compound?
(A) Fitting reaction (B) Gattermann reaction
(C) Wurtz reaction (D) Balz-Shiemenn reaction
7. Which of the following favour SN1 mechanism

(A) Strong nucleophile (B) 3° alkyl halide
(C) Non-polar solvent (D) Low conc. Of nucleophile
8. Which of the following reactions take place via carbocations are intermediates?
(A) CH4 + Cl2 → CH3Cl + HCl
(B) CH3CH = CH2 + Br2 → BrCH2 – CH = CH2 + HBr

800K
(C) CH2 = CH2 + Br2 → BrCH2 – CH2Br
CH
(D) CH3CH = CH2 + HBr → CH3 | CH3
Br

9. Which of the following reagents, on reaction with ethyl bromide, would yield diethyl ether as the
major product?
(A) Aqueous KOH (B) Alcoholic KOH
(C) Silver oxide (D) Sodium ethoxide
10. Which of the following reagents on reaction with 2-bromopropane would yield iso-propyl alcohol as
the major product?
(A) Aqueous KOH (B) Alcoholic KOH
(C) Silver oxide (D) Sodium ethoxide
11. Benzene yields dephenyl methane on reaction with . . . in the presence of anhydrous AlCl3. The
missing items can be
(A) CH2Cl2 (B) CH2Cl
(C) CHCl3 (D) CHCl2
12. Which of the following alkyl halides is / are primary?

(A) neo-Pentyl chloride (B) n-Pentyl chloride
(C) sec-Pentyl chloride (D) iso-Propyl chloride
13. Which of the following chloro derivatives on further chlorination would yield two dichloro derivatives?
(A) 1-Chloropropane (B) 2-Chloropropane
(C) 1-Chloro-2, 2-dimethylpropane (D) 1-Chloro-2-methylpropane
14. Which of the following conditions favour SN2 mechanism?
(A) Strong nucleophile (B) High conc. Of nucleophile
(C) 3°Halide (D) Polar solvent
15. Which of the following processes occur during the formation of iodoform from ethanol?
(A) Oxidation (B) Reduction (C) Iodination (D) Hydrolysis
LEVEL - II
16. Which of the following substrate(s) upon treating with a base at higher temperature will yield
predominantly Hoffmann’s product
(A) CH3 CH2 CH2 CHCH3 (B) CH3 CH2 CH2 CHCH3
| |
F I
(C) (D) CH3 − C H − C H − CH3

| |
Ph Br

17. Which of the following (s) aryl halide will react with sodamide / liquid ammonia leading to sustitution
via bezyne mechanism
(A) (B)
(C) (D)
18. The correct statement(s) regarding a nucleophillic substitution reaction is

(A) During SN1 and SN2 mechanism both electron deficient carbon must attain planar geometry
(B) SN1 reaction are always accompanied by complete recemisation

(C) SN2 reactions are accompanied by inversion of configuration and the leaving group and the
incoming group donot differ in priority
(D) Aprotic polar solvent promote SN1 reaction
19. Which of the following compounds do not respond to silver nitrate test?
(A) 1-Chloropropane (B) 1-Chloropropene
(C) 2-Chloropropene (D) 3-Chloroprop-1-ene
O
18
20. Br 
−
HO C CH2 CH2 CH2 dil OH
→
Product of the above reaction
18
O O
18
(A) C (B) O
O
O
(C) (D) none of these
O C CH2 CH2 CH2 OH

LEVEL - III
21: Which of the following compound will be least reactive towards NaOH.
Cl
(A) CH3Cl (B) (C) (D) H3C Cl
22: Which one of the following compounds give SN1 and SN2 mechanism?
(A) H C Br (B) H3C Br (C) H5C6 Br (D) H C Cl

3 2
23: In the given reaction
H3C I 
HOH
→[X]
[X] will be
HO
(A) H3C OH (B) H C

3
CH3
(C) (D) H3C
HO
24: In the given reaction
C6H5 − CH = CH − CH2 − Br 

HOH
→ [X] + [Y]
[X] and [Y] are

OH
(A) H C (B) CH2
5 6 OH H5 C6
CH2
(C) (D) H5 C6
OH
25: Rate of S N1 reaction is increased based on following factors because:
(A) good leaving groups (more stable anions) lower the energy of the transition state leading to
carbocation formation thus increasing the reaction rate
(B) a nonbasic nucleophile (like H2O) will prevent a competitive E2 reaction
(C) polar solvents stabilize the carbocation intermediate by solvation, thereby increasing the
reaction rate
(D) none of the above

COMPREHENSION TYPE QUESTIONS

Comprehension - I
Nucleophilic substitution reactions generally expressed as
Nu− + R — L → R — Nu + L−
where Nu– is Nucleophile
R — L is substrate
L is leaving group
The best leaving groups are those that become the most stable ions after they depart. Since most
leaving groups leave as a negative ion, the best leaving groups are those ions that stabilize a
negative charge most effectively. A good leaving group should be
i) electron-withdrawing to polarize the carbon atom
ii) stable once it has left (not a strong base)
iii) polarisable – to maintain partial bonding with the carbon in the transition state (both SN1 and
SN2). This bonding helps to stabilise the transition state and reduces the activation energy.
1: Among the following which is feasible?
(A) X– + CH3—CH2—H → CH3—CH2—X + H– (B) X– + CH3—OH → CH3 —X + OH
−
(C) X + H3C OH 
→ CH 3 — X + H 2 O (D) X− +CH3—CH3 → CH3—X+ CH3
H
2: Among the following which is false statement?
(A) The weaker the base after the group departs, the better the leaving group.
(B) A reactive leaving group would raise the energy of the product, driving the equilibrium towards
the reactants.
(C) Relative leaving group ability may vary with change of solvent.
(D) Better leaving group only increases SN2 rate, not SN1.
3: CH3Br CH3F CH3OH CH3OSO2CF3

I II III IV
The correct order of decreasing reactivity above compounds towards CH3O– in an SN2 reaction is
(A) I > IV > II > III (B) IV > I > II > III
(C) IV > I > III > II (D) IV > II > I > III
4: Cl− , CH3 O− , CH3 S− , I−

I II III IV
The correct order of increasing leaving group capability of above compound is

(A) III < IV < II < I (B) II < III < I < IV
(C) II < IV < III < I (D) I < III < II < IV
Comprehension - II
An organic compound A has molecular formula C10H17Br and it is non-resolvable. A does not
decolourize brown colour of bromine water solution. A on treatement with (CH3)2COK/(CH3)3COH
yields B as major product. B on treatement with H 2/Pt yields (C10H18) which on treatement with Cl2/
h υ yields three monochloro derivative. Also B on boiling with acidic permanganate solution yields
C(C10H16O3). C on heating with sodalime yields D (C9H16O). D on reducing with LiAlH4 followed by
heating the product with concentrated H2SO4 yields E (C9H16) as major product. E on treatement
with ozone followed by work-up with Zn- H2O yields 6-Ketononanal

5: Compound A is
Br
Br
(A) (B)
Br
(C) (D) None of these
6: Compound B is
(A) (B)
(C) (D)
7: Compound C is
COOH
O O
CH2
(A) (B)
CH2 O
CH2
O COOH
H CH2
(C)
O (D)
O C == C
H
8: Compound D is
O O
(A) (B)
COOH CH3
O
CH3
(C) (D)

Comprehension III
Nucleophilic substitution reaction is given by those compounds which has nucleophilic group as a
good leaving group is a electron withdrawing group, it should be stable after leaving with bonding
pair of electrons and it should have high polarisability.
9: Which of the following compound will give nucleophlic substitution reactions?

(A) R – Br (B) R – N3
+
(C) R − OH (D) all of these
2
10: Leaving power of which leaving group will be maximum

O O
O O
(A) H3C S
C2H5
(B) H3C S
CH3
O O
O
O F O O
H3C S H3C
(C) (D)
O F CH3
F
11: Nucleophilic substituion reaction with greater ease, is given by
(A) R – NH2 (B) R – OH
(C) R – OR (D) R – Br

MATRIX-MATCH TYPE
1. MATRIX MATCHING:
LIST-I LIST-II
(A) p) E2
(B) q) E1CB
CH3 H CH3
C CD CH3 C CD CH3
(C) Br 
Strong base
∆
→ r) order =1
(D) s) E 1
2: Match List – I with List – II and select the correct answer from the codes given below the lists:
List – I List – II
Br
(A)
H3C + HOH 
→ (p) Ether
CH3 CH3
CH3
(B)
H3C O + CH 3 − Br (q) Sec alcohol
CH3 Na
Br
(C) (r) Tert alcohol

H3C CH3 + NaOH (aq )
OH
+
H3C CH3 
H
∆
→
(D) (s) Alkene
CH3

3: Match the following

List – I (Substrate) List–II
(Relative rate of solvolysis in 50% aqueous ethanol at 450C)
(A) Cl (p) 7700
(B) Cl (q) 1
H3C
(C) (r) 91
H3C Cl
(D) Ph Cl (s) 1,30,000
4: Match: A student studied the rate of SN2 reaction of many organic halide (given in column I) with NaI
in acetone solvent and measured the relative rates in each case (given in column II). Now, match
column I with column II to get meaningful result.
List – I (Substrate) List–II
((Relative rate of solvolysis in 50% aqueous ethanol at 450C)
Me
(A) O Cl
(p) 80
Cl
(B) (q) 105
H2C
(C) (r) 103
Cl
O
Cl
(D) (s) 200

ASSERTION REASONING TYPE QUESTIONS
1. Assertion : n-Butyl chloride has higher boiling point than tert-butyl chloride.
Reason : C —Cl bond in n-butyl chloride is more polar than in tert-butyl chloride.
2. Assertion : iso-Butyl bromide is a secondary halide.

Reason : neo-Pentyl chloride is a primary halide.
3. Assertion : Alkyl halides undergo nucleophilic substitution reactions radily.

Reason : Halide ion is a very weak base and hence can be easily replaced by the attacking
nucleophile.
4. Assertion : C — X bond in aryl halides is less polar than the C — X bond in alkyl halides.
Reason : sp2 hybridized carbon is more electronegative than sp3 hybridized carbon atom.
5. Assertion : Alkyl chlorides are more reactive than alkyl bromides.

Reason : C — Cl bond is more polar than C — Br bond.

INTEGER TYPE QUESTIONS
1. Number of possible isomers for C2H2 Cl2
2. Total number of isomers formed when 2-methyl butane is subjected to monochlorination

3. When 3- bromo-2,2-dimethyl butane is treated with alcoholic potassium the number of possible
alkene isomers formed is
4. The number of substitution products formed when metabromo anisole is treated with KNH2 / NH3
5. During the preparation of chloroform from ethanal by treating with Cl2 / base , the number of base
molecules consumed is.
CH3
6. How many structoral isomers can be obtained by monochlonation of ?
7. is on treating with excess AgNO3 . The
number of moles of AgCl formed is

8. The number electrons p orbitals of carbon present in Benzyne is
9. When m-dichorobenzene is chlorinated the number of possible products are
10. When 3,3-dimethyl -2-butanol is treated with HBr the number of 3 0 carbons present in the major
product formed is

SUBJECTIVE TYPE QUESTIONS

1: What would be the major product in each of the following reactions?
CH3 Cl
i) + H3C 
AlCl3
→
CH3
Cl
H3C 
alc.KOH
→
ii)
CH3 CH3
H3C
Cl 
boil
→
iii) alkali
Cl
C 6H5
CH3   → ?   →?
alcoholic HBr
iv) KOH,∆
Br
v) H5C 6 C 2H5  

1.Br2 ,Heat, Light
2.NaCN
→
Cl
Cl Cl
vi)

Cl2 / Fe
→
H3C
vii) 
AgCN
→
Br
Ph H
A
viii) + KNH 2 
→−−−−−−
Ph Br
B
ix) Me I +Cu + heat 
→−−−−−−
H
x) + CHBr3 + t − BuOK 
→−−−−−−
2: Give reasons for the following:

i) Methane does not react with chlorine in the dark.
ii) Propene react with HBr to give isopropyl bromide but does not give n-propyl bromide.
iii) Toluene reacts with bromine in the presence of light to give benzyl bromide while in presence
of FeBr3 it gives p-bromotoluene. Give explanation for the above observati
3. Suggest the mechanism

CH3
CH3 
aq. AgNO3
→ OH
CH2Cl

4: Write the structure of all the possible isomers of dichloroethane. Which of them will have zero
dipole moment?
5: Identify, B (C4H8) which adds on HBr in the presence and in the absence of peroxide to give the
same product, C4H9Br.
6: Draw the stereochemical structures of the products in the following reactions:
C 2H 5
H 
NaOH
→
i)
Br SN 2 ii) R − C ≡ C − R  H2
Lindlar catalyst
→
CH3
7: 1,4-Pentadiene reacts with excess of HCl in the presence of benzoyl peroxide to give compound X
which upon reaction with excess of Mg in dry ether forms Y. Compound Y on treatment with ethyl
acetate followed by dilute acid yields Z. Identify the structures of compound X, Y and Z.
8: Give the structures of the major organic products from 3-ethyl-2-pentene under each of the following
reaction conditions.
a) HBr in the presence of peroxide
b) Br2/H2O
c) Hg(OAc)2/H2O; NaBH4
9: What would be the major product in each of the following reactions?
F
CH 3 Ph
  
→   →
NaOCH 3 base
H 3C 
C 2 H 5 OH
∆
→ ∆
O
i) ii) iii)
CH 3 Br Br
NO 2
10: An organic compound A, C6H10O, on reaction with CH3MgBr followed by acid treatment gives
compound B. The compound B on ozonolysis gives compound C, which in presence of a base gives
1-acetyl cyclopentene D. The compound B on reaction with HBr gives compound E. Write the
structures of A, B, C and E. Show how D is formed from C.
11: Explain briefly the formation of the products giving the structures of the intermediates.
+
OH → H2C + etc.
HCl
H2C Cl
Cl
CH3 CH3
→
HCl
only
H2C OH H2C Cl
12: Optically active 2-iodobutane on treatment with Nal in acetone gives a product which does not show
optical activity. Explain why ?
13: (W) and (X) are optically active isomers of C5H9Cl. (W) on treatment with one mole of H2 is converted
to an optically inactive compound (Y), but (X) gives an optically active compound (Z) under the same
conditions. Give structure of (Y) and configuration of (W), (X) and (Z) in Fischer projections.
14: A white precipitate was formed slowly when AgNO3 was added to a compound (A) with molecular
formula C6H13Cl. compound (A) on treatment with hot alcoholic KOH gave a mixture of two isomeric
alkenes (B) and (C) having formula C6H12. The mixture of (B) and (C) on ozonolysis furnished four
compounds.
i) CH3CHO; ii) C2H5CHO; iii) CH3COCH3; iv) (CH3)2CH.CHO.
What are (A), (B) and (C)?
15: An organic compound (X) on analysis gives 24.24% C, 4.04% H. Further sodium extract of 1.0 g of
(X) gives 2.90 g of AgCl with acidified AgNO3 solution. The compound (X) may be represented by two
isomeric structures (Y) and (Z). (Y) on treatment with aqueous KOH solution gives a dihydroxy
compound, while (Z) on similar treatment gives ethanal. Find out (X), (Y) and (Z).

PREVIOUS YEAR IIT-JEE TYPE QUESTIONS

1. Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH
gives
(A) o-Cresol (B) p-Cresol [IIT 1990]
(C) 2, 4-Dihydroxytoluene (D) Benzoic acid
2. 1-Chlorobutane on reaction with alcoholic potash gives [IIT 1991]

(A) 1-Butene (B) 1-Butanol
(C) 2-Butene (D) 2-Butanol
4. Butanenitrite may be prepared by heating [IIT 1992]

(A) Propyl alcohol with KCN (B) Butyl chloride with KCN
(C) Butyl alcohol with KCN (D) Propyl chloride with KCN
5. The reaction of toluene with chlorine in presence of ferric chloride give predominantly
(A) Benzoyl chloride (B) m-Chlorotoluene [IIT 1993]
(C) Benzyl chloride (D) o- and p-Chlorotoluene
6. Arrange the following compounds in order of increasing dipole moment : Toluene (I), m-
dichlorobenzene (II), o-dichlorobenzene (III), p-dichlorobenzene (IV) :
[IIT 1996]
(A) I < IV < II < III (B) IV < I < II < III
(C) IV < I < III < II (D) IV < II < I < III
7. In the following groups :

—OAc (I), —OMe (II), —OSO2Me (III), —OSO2CF3 (IV) [IIT 1997]
the order of leaving group ability is
(A) I > II > III > IV (B) IV > III > I > II
(C) III > II > I > IV (D) II > III > IV > I
8. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with [IIT 1998]
(A) SO2Cl2 (I), SOCl2 (II), Cl2 (III), NaOCl (IV)
(A) I, II and III (B) I and III
(C) II and III (D) All the four
9. Which of the following will react with water? [IIT 1998]

(A) CHCl3 (B) CCl3. CHO
(C) CCl4 (D) ClCH2. CH2Cl
10. A solution of (+2)-2-chloro-2-phenylethane in toluene racemises slowly in the presence of small

amount of SbCl5, due to the formation of [IIT 1999]
(A) Carbanion (B) Carbene
(C) Free radical (D) Carbocation
11. The order of reactivities of the following alkyl halides of a S N2 reaction is [IIT 2000]
(A) RF > RCl > RBr > RI (B) RF > RBr > RCl > RI
(C) RCl > RBr > RF > RI (D) RI > RBr > RCl > RF

12. Identify the set of reagent / reaction conditions ‘X’ and ‘Y’ in the following set of transformations :
CH
X Product
CH3 — CH2 — CH2Br → Y CH – | – CH [IIT 2002]
→ 3 3
Br
(A) X = dilute aqueous NaOH, 20°C; Y = HBr / acetic acid, 20°C
(B) X = concentrated alcoholic NaOH, 80°C; Y = HBr / acetic acid, 20°C
(C) X = dilute aqueous NaOH, 20°C; Y = Br2 / CHCl3, 0°C
(D) X = concentrated alcoholic NaOH, 80°C; Y = Br2 / CHCl3, 0°C
CH3
13.
[F] 
+
→ →
H CCl
4
C4H8Br2
−H O
2 1424 3
5such products are possible
H3C OH
How many structures for F are possible? [IIT 2003]
(A) 2 (B) 5
(C) 6 (D) 3
14. On monochlorination of 2-methylbutane, the total number of chiral compounds formed is

(A) 2 (B) 4 [IIT 2004]
(C) 6 (D) 8
15. What would be the product formed when 1-bromo-3-chlorocyclobutane reacts with two
equivalents of metallic sodium in ether? [IIT 2005]
Cl
(A) (B)
Br
(C) (D)
16. The reagent (s) for the following convesion, [IIT 2006]
Br 
?
→ H H
Br
is / are
(A) alcoholic KOH (B) alcoholic KOH followed by NaNH2
(C) aqueous KOH followed by NaNH2 (D) Zn / CH3OH
MULTIPLE CHOICE
16. The products of reaction of alcoholic silver nitrite with ethyl bromide are [IIT 1991]
(A) 1-Butene (B) 1-Butanol
(C) 2-Butene (D) 2-Butanol

KEY & ANSWERS

1. (B) 2. (B) 3. (D) 4. (C)

5. (D) 6. (A) 7. (B) 8. (B)
9. (B) 10. (C)
LEVEL - I
1. (A) 2. (D) 3. (D) 4. (B)
5. (C) 6. (C) 7. (D) 8. (D)
9. (D) 10. (C) 11. (C) 12. (C)
13. (C) 14. (B) 15. (B) 16. (B)
17. (D) 18. (C) 19. (B) 20. (A)
21. (D) 22. (C) 23. (D) 24. (A)
25. (A)
LEVEL - II
26. (B) 27. (D) 28. (A) 29. (B)
30. (A) 31. (A) 32. (D) 33. (B)
34. (C) 35. (B) 36. (B) 37. (C)
38. (B) 39. (B) 40. (C) 41. (B)
42. (A)
LEVEL - III
43. (A) 44. (C) 45. (C) 46. (C)
47. (B) 48. (B) 49. (A) 50. (B)
51. (D) 52. (C) 53. (B)
MULTIPLE CORRECT ANSWER TYPE
LEVEL - I
1. (A), (C) 2. (A), (B) 3. (A), (D) 4. (B), (C)
5. (A), (D) 6. (A), (C) 7. (B), (D) 8. (C), (D)
9. (C), (D) 10. (A), (C) 11. (A), (B) 12. (A), (B)
13. (B), (C) 14. (A), (B) 15. (A), (C), (D)
LEVEL - II
16. (A), (C) 17. (B), (D) 18. (A), (C) 19. (B), (C)
20. (A, B)

LEVEL - III
21. (C), (D) 22. (A), (C) 23. (A), (B) 24. (A), (B)
25. (B), (C)
COMPREHENSION TYPE
1. (C) 2. (D) 3. (B) 4. (B)
5. (A) 6. (C) 7. (A) 8. (C)
9. (D) 10. (C) 11. (D)
MATRIX MATCH TYPE
1. (A - q), (B - p), (C - p), (D - r,s) 2. (A - r), (B - p), (C - q), (D - s)w
3. (A - a), (B - r), (C - s), (D - p) 4. (A - r), (B - s), (C - p), (D - q)
ASSERTION REASONING TYPE
1. (C) 2. (D) 3. (A) 4. (A)
5. (D)
INTEGER TYPE
1. (3) 2. (6) 3. (2) 4. (3)
5. (4) 6. (4) 7. (2) 8. (6)
9. (3) 10. (2)
PREVIOUS YEAR QUESTIONS
1. (D) 2. (A) 3. (D) 4. (D)
5. (B) 6. (B) 7. (B) 8. (B)
9. (D) 10. (D) 11. (B) 12. (D)
13. (B) 14. (D) 15. (B) 16. (C), (D)

HINTS & SOLUTIONS

1. Less hindered carbon follows SN2 mechanism.
∴ (B)
2. – NO2 group increases SNAr because of –R and –I effect.
∴ (B)
3. Allylic halides undergo substitution very easily.
∴ (D)
4. —NO2 groups activate the molecule towards nucleophilic substitution by stabilizing the intermediate
carbanion.
∴ (C)
5. Reaction proceeds through benzyne.
∴ (D)
6. (A) More the stability of the product, faster is debromination of the parent compound.
7. (B)
8. (B)
9. (B)
Walden Inversion.
10. (C)
C2H5 – O – C2H5 + 2HI → 2C2H5I + H2O
LEVEL - I
1. (A)
n-Butyl bromide, iso-butyl bromide, sec-butyl bromide and tert-butyl bromide.
2. (D)
1. CH3CH2CH2CH2CH2Br 2. H3C CH CH2 CH2 Br
CH3
CH3
H3C CH CH2 CH3
3. 4. H3C CH CH2Br
CH2Br CH3
CH
|
3. CH3 – –CH2Br is iso-Butyl bromide.
CH3
4. NaCl canot replace —OH by —Cl.

5. CH3 + Cl2 

sunlight
→ CH2Cl
Benzyl chloride
6. Density of alkyl halides is in the order
R —I > R—Br > R—Cl > R—F.
7. Tertiary halides on treatment with base, such as sodium methoxide, readily undergo elimination
resulting in the formation of alkenes.
8. Allylic halides undergo substitution very easily.
CH2 CH2

aq. KOH
→ CH2 CH2
9.
Cl Cl OH OH
Ethylene chlorides
Cl
CH3 CH Cl 
aq. KOH
→ H3C CHO
Ethylidene chloride
Thus, the statement (D) is wrong.
hν •
10. Cl• • Cl 
Homolysis
→ 2Cl
[chain initiation step]

11. It is reaction with NBS. This reaction is known as Wohl Zeiglar reaction.
CH3
12. H3C C is Neo condition.

CH3
13. R – X + OH− (aq) → R – OH + X−

14. Reactivity of Haloacid HI, HBr, HCl, HF on the basis of bond dissociation energy.
15. It is Nu– substitution.
16. Factual question.
Br
17. C6H5CH3 
2
hν
→ C6H5CH2Br
18. — CH3 group is ortho-para directing group.
19. Greater the number of —NO2 groups at ortho and para positions to —Br group, greater is the
reactivity of the compound towards OH− ions due to stabilization of intermediate carbanion. (II)
having three —NO2 groups is most reactive while (I) having —NO2 group at meta position is least
reactive.
20. Greater the number of electron withdrawing group at ortho and para position to —Cl, greater is the
reactivity with aqueous sodium hydroxide.

2 +CH2 Cl2 →

3 AlCl
CH2 + 2HCl
21.
AlCl
22. 3 + CHCl3 →
3
H5C6 CH C6H5
C6H5
23. —Cl group is ortho-para directing and deactivating.
LEVEL - II
26. Alcoholic solution of ammonia is heated in a sealed tube at 100°C
RI → RNH2 →

NH3 RI
(R)2NH →
RI
(R)3N →
RI
(R)4 N+I–
1° amine 2° amine 3° amine 4° amine
27. C2H5Br 

aq KOH
→ C2H5OH (Product-I)
(Nucleophilic substitution reaction)
C2H5Br alc KOH
→ C2H4 (Product – II)
(elimination reaction)
C2H5OH (Product-I) isomer is CH3OCH3
C2H5OH 
dehydration
→ C2H4
∴ (D)
H3C
F F N CH3 H3C N CH3 H3C
N
CH3

(CH3 ) 2 NH
→ →
28.
− H+
− F−

H 2 / Pd
→
NO2 NO2 NO2 NH2
CH3
NaF
29 CH3
H3C [via E2 machanism]
Br S O
H3C (X)
NaF
CH3 CHCl
H2 O
CH3 CH OH [F- is solvated ]
CH3 CH3
(Y)
+ CH3
H
CH3 + CH3 CH OH
OCHMe 2
CH3
(Z)
30.

Cl CH2 Cl
Chlorobenzene is less reactive than benzyl chloride
in chlorobenzene the lone pairs present on Cl atom get involved in resonance with π electrons of
benzene due to which C – Cl bond acquires double bond character Hence, reactivity decreases
.. .. ..
: Cl : Cl : + Cl : + Cl : +
.. ..
..
Cl Cl
200 − 250°C
31. + 2NaOH 
200atm
→ + NaCl + H2 O
is Dow’s process
32. RX + Alc. NH3 → RNH2 → R2NH → R3N → R 4 N+ X−
33. Carbylamine means Isocynide
RNH2 + CHCl3 + Alc. KOH → RNC + KCl + H2O
Carbylamine
34. Reaction based question.
CH3
CH 2 CH CH 2 CH CH CH2
35.  NBS

wohlzeiglar reaction
→
H 2C CH CH2

Br2
Fe
→
Br Br
CH 2 CH CH 2

→
Br2 /H2 O

Br
|
36. CH = CH − CH2 − CH = CH2 
NBS
→ CH2 = CH − CH – CH = CH2
CH3 CH3
H3C C Br 
E limination CH3CH2ONa
→ H3C C CH2
37. CH CH OH
3 2
CH3
CH3 CH3
( CH3 CH2OH)
Br 
H3C C
substitution
→ H3C C OCH2CH3
CH3 CH3
39. The concentration of solvent alcohol remains constant hence order w.r.t. alcohol is not one but zero.
CH3 CH3
40. H3C C CH CH3 → H3C CH CH CH3 → H3C CH2 C CH3
Br CH3
OC2H5
CH3
H3C CH2 C CH3

OC2H5
41. When ethylene reacts with bromine, it forms ethylene dibromide.
H2C = CH2 + Br2 → H2 C − C H2

Ethylene Bromine | |
Br Br
42. Chlorobenzene is least reactive due to resonance stablization.

LEVEL - III
43.
44. C6 H 5 − C ≡ C − C − C
45.
CH3 CH3
− +
C C C C C + HO Cl → C C C C CH3
46.
OH Cl
R − C|| − OAg →

B r2 / acetone
RBr + AgBr + CO2
47. Hunds − deic ker reaction
O
48. Saydtzeff rule
49. Primary alkyl groups undergoes SN1 reaction.

50. Based on stability of carbocation
51. Based on stability of carbocation (EAR)
52.

C − C − C − Br 
alc . NaOH
→ C − C = C 
HBr
→ C − C| − C
53.
Br
MULTIPLE CORRECT ANSWER TYPE
LEVEL - I
1. (a) 1, 1-Dichloropropane, 1, 2-dichloropropane and 1, 3-dichloropropane.
(c) 1, 2-Dichlorobenzene, 1, 3-dichloropropane and 1, 4-dichlorobenzene.
2. Statement (c) and (d) are wrong. The cause of nucleophilic substitution is in the order :
R — I > R — Br > R — Cl.
Flurobenzene cannot be prepared by Sandmeyer’s reaction.
3. C — Cl bond in vinyl chloride and chlorobenzene has partial double bone character and hence
is difficult to cleave.
C CH
4. For haloform reaction, the compound should have CH3 — — or CH3 – | — group.
||
O OH
6. Fitting reaction involves combination of two aryl groups while Wurtz reaction involves combination
of two alkyl group
7. Self explanatory answer. Strong nucleophile and non-polar solvent favour SN2.
8. Both these reactions are electrophilic addition reactions and proceed through carbocations as
intermediates.
CH Cl

2 2
→ CH2Cl 
AlCl
3
→
11. AlCl 3 CH 6 6
12. neo-Pentyl chloride and n-pentyl chloride are primary halide
CH3
H3C C CH2Cl
CH3
neo-Pentyl chloride
CH3 − CH2 − CH2 − CH2 − CH2 − Cl

n-Pentyl chloride
13. (b) 2-Chloropropane can yield 1, 2-dichloropropane and 2, 2-dichloropropane.

(c) It can yield 1, 1-dichloro-2, 2-dimethyl propane and 1, 3-dichloro-2, 3-dimethylpropane.
14. Self explanatory question.
15. Iodoform reaction.
LEVEL - II
16. Poor leaving group & quaternary amine salts undergoes Hoffmann’s elimination
17. Stronger – M groups favours Ar SN2 rection
18. Conceptual

19. 1-Chloropropene and 2-chloropropene are vinylic chlorides and hence do not undergo substitution
easily.
20.
LEVEL - III
21. In Aryl and vinyl halides C − X bond acquries double bond nature due to resonance hence they are
less reactive.
22. Allyl primary undergoes both SN1 and SN2 due to stability of carbocation.
23. Due to allylic shift.
24. Ph − C = C − CH 2 − Br → Ph − C = C − CH2+ ƒ Ph − C − C = C → Ph − C| − C = C
+
OH
25. Conceptual
COMPREHENSION TYPE
1. H3O+ is weak base can be replaced by X −
2. Conceptual
3. Rate of both SN1 and SN2 depends on leaving group.
4. Leaving ability depends on its conjugate acid strength.
5-8.

Conc.H2SO4
9. Conceptual
10. Trflate ion is better leaving group because it is conjugate base of strong acid
11. Conceptual
MATRIX MATCH TYPE

1. E1 via - carbocation
E1 cb via - carbanion
E2 via - transition state
2. (A) 1o - gives SN2 (B) Williamson’s synthesis (C) 3o alcohol produes alkenes upon treating with
acids.
3. Rate of reaction α stability of carbocation .
4. If ‘ β ’ carbon is planar reate of SN2 tremondously increase so most reactive toward SN2

ASSERTION REASONING TYPE
1. Statement R is wrong C — Cl bond in tert-butyl chloride is more polar.
2. Statement A is wrong iso-Butyl bromide is a primary halide.

3. Self explanatory statements.
4. Self explanatory statements.
5. Statements A is wrong. Alkyl chloride are less reactive than alkyl bromides because C — Cl bond
is stronger than C – Br bond.
INTEGER TYPE
H Cl Cl Cl H Cl
1. C C C C C C
H Cl H H Cl H
C| C|
2. Cl2 / hυ
C − C − C − C → C − C − C − C − Cl
C| *
C − C − C| − C
Cl
C|
C|
Cl − C − C − C − C C − C| − C − C
*
Cl
C| Br|
C| C| C|
3. C − C| − C − C   
ale . KOH
→C −C = C − C + C − C− C = C
C
4.

5.
H2C Cl CH3 CH3 CH3

Cl
Cl
6.
Cl
7. Allyl and Benzyl chlorides are reactive with AgNO3, whereas vinyl and Acyl halide s are less
reactive.
sp 2
−
Only 6π e
8.
sp 2
9.
3 products.
10.

SUBJECTIVE TYPE
CH3
H3C CH3
H3C
1. i) + 
AlCl3
→
H3C Cl
+
Note that the carbocation (CH ) CHCH formed during reaction rearranges to the more stable
3 2 2
+
(CH3 )3 C carbocation and hence the above product is formed.
CH3 C CH CH3
ii)
CH3
H3 C Cl H3C
H3 C
iii) 
→ boil
OH →
( − H 2 O)
alkali CHO
Cl HO
H5C6 H
H3C
iv) CH3 
alc.KOH
∆
→ CH3 
HBr
→ H5C6
Br Br CH3
+
C6H5CH2 CHCH3 and
+
C6H5 CHCH2CH3 carbocations are formed on addition of HBr on C6H5CH = CHCH3, the latter is
stabilized due to resonance and hence Br– adds on it forming C6H5CHBr.CH2CH3 as the final product.
CH3 CH3
v) H5C 6 C2H5 
→ H 5C 6 Br2
∆ , light

→ H5C6
NaCN
(HVZ reaction) CN
Br
2-phenylpropanenitrile
Cl
Cl Cl
vi)
Cl
H3C
vii) N C
(isocyanide)
Ph
viii)
Ph

ix) Me Me
Br
x)
2. i) Chlorination of methane is a free radical substitution reaction. In dark, chlorine is unable to be

converted into free radicals, hence the reaction does not occur.
Cl2 
dark
→ Cl •
ii)Addition of unsymmetrical addendum (HBr in present case) to unsymmetrical olefin (CH3CH=CH2
in present case) takes place according to Markownikoff rule “the negative part of reagent (i.e., Br–)
adds on the carbon atom having minimum number of hydrogen atom”. Hence isopropyl will be
formed in the present case
CH3CH = CH2 + HBr → CH3 .CHBr.CH3
Propene iso −propyl bromide
iii) In present of light, toluene undergoes side chain bromination through a free radical
mechanism.
Br
CH3

Br2
hν
→
Benzyl bromide
In presence of FeBr3, toluene undergoes electrophilic substitution in the benzene ring.
CH3 CH3

Br2
FeBr3
→
Br
p-bromotoluene
3.

4. Dichloroethene exists in three isomeric form
Cl Cl Cl
Cl H H
H Cl H
H H Cl
1,1-dichloroethylene (cis)-1,2-dichloroethylene (trans)-1,2-dichloroethylene
trans-1, 2-dichloroethene has zero dipole moment as shown below.
+
H Cl
Cl H
+
5. Identify, B (C4H8) which adds on HBr in the presence and in the absence of peroxide to give the
same product, C4H9Br. [1993]
C2H5 C 2H 5
Br H 
→ H NaOH
OH
6. i) SN 2
CH3 CH3
R R
ii) R - C C-R C C (cis)
H H
7. Remember that
i) 1,4-pentadiene reacts with HCl in presence of benzoyl peroxide in Markownikoff’s way.
ii)Grignard reagent reacts with ethyl acetate to form ketones or ter-alcohol if Grignard reagent is
taken in excess.
H2C H 3C H3C
excess HCl

→(C 6 H 5 CO) 2 O

→
Mg in dry ether
CH2 Cl CH3 MgCl CH3

Cl MgCl
(X) (Y) CH 3
OH
CH3 C O C
OC 2 H 5 CH3
CH3
H3C H3C Br
8. a) 
→ HBr
Peroxide
H3C CH3 H3C CH3
OH
H3C
H3C Br
b) 
Br2 / H2O
→
H3C
H3C CH3 CH3

H3C OH
H3C Br

Hg(OAc)2 / H2O
NaBh4
→
c) H3C
H3C CH3
CH3
CH3
O
H3C
Ph
9. i) ii) iii) O
H3C CH3
NO2
OMgBr CH3
O
CH3
10.    
→
C H 3M gBr
 H[
OH

H+ ]
→
(A) O (B) O
CH3
CH3
OC CH3
 o   →
z o n o lysis −
 I O H  
ntram o lecular
→
aldol condensation
(D)
(B)
CH3
Br
(E)
CH2 −
11. +
→
Cl
H2C Cl
OH → H2C
H
H2C
or
−
→
Cl
CH2
Cl
CH3
CH3
CH3 → H2C

+ Cl
OH → H2C
H Cl
H2C
(more stable)
12. The C—I bond is broken and reformed to give racemic mixture of 2-iodobutane and thus remains
optically inactive. The presence of I– provides opportunities for the remaking of the C—I bond.
CH 3 CH3 CH3
H−C−I →
Nal
Acetone
H−C−I + I−C−H
C2 H5 C2 H5 C2 H5

13. The given statements suggest that (W) and (X) are as follows :
CH2CH3 CH2CH3 CH 2 CH3

H Cl 
H2
→ H Cl or CHCl
CH=CH2 CH2CH3 CH 2 CH3
(W) Optically (Y) (Structure of
(Inactive) Y)
CH3 CH3
H CH 2Cl 
H2
→ H CH2Cl or
CH=CH 2 CH 2CH3
(X) (Optically active)
(Z)
14. i) (A) on treating with alcoholic KOH gives a mixture of two isomeric alkenes (B) and (C).
C6H13Cl 
alc. KOH
−HCl
→ C6H12 + C6H12 isomers
(B) (C)
ii)Mixture of (B) and (C) on ozonolysis gives four products (i) CH3CHO (ii) C2H5CHO (iii) CH3COCH3
(iv) (CH3)2CH.CHO
iii) Since (B) and (C) are of six carbon atoms each and thus, product formed on ozonolysis
for each alkene must contain in all six carbon atoms. That is why one alkene gives CH3CHO +
(CH3)2CHCHO and other alkene gives C2H5CHO and CH3COCH3.
Thus, alkenes are
CH3
(CH3 )2 CH.CH = CH.CH3 C2 H5 .CH = C
(B)
; CH3
(C)
iv) Since (B) and (C) are formed from halide (A), thus, halide should be
CH 3
CH − CH − CH 2 CH 3
CH 3 Cl
(A)
Reactions:
CH 3 CH 3
CH − CH.CH 2 .CH3 
→ (alc.) KOH CH − CH = CH.CH3
CH 3 CH 3 4 − methylpent −2 − ene
Cl (B)
3− chloro, 2 − methylpen tan e
(A)
CH 3
+ C = CH.CH 2 .CH3
CH 3 2 − methylpent −2 − ene
(C)

15. (1) The compound (X) has two isomers (Y) and (Z).
(2) The compound (X) has C, H and Cl atoms.
35.5 × 2.9
(3) % of Cl in (X) = × 100 = 71.72%
143.5
∴ For empirical formula of (X)
Element %Relative no. of atoms Simplest ratio
C24.24 2.02 1
H4.04 4.04 2
Cl 71.72 2.02 1
∴ Empricial formula of (X) is CH2Cl.
(4) Since (x) has two isomers (Y) and (Z); both reacts with KOH(aq). Since the isomer (Y) of
the compound gives a dihydroxy compound on treatment with aqueous KOH, it follows that the
compound must contain two Cl atoms. Hence the molecular formula of (X) is C2H4Cl2. Its two
CH3 CHCl2 Cl.CH2 .CH2Cl.
isomers are (Z)
and (Y)
(Y) →
KOH (aq.)
Dihydroxy compound
(Z) →
KOH (aq.) CH3CHO i.e., (Z) should have 2 Cl atoms on one C atom
CH3 .CHCl2
Thus, (Z) should be (1, 1− dichloroethane)
CH2Cl.CH2Cl
and (Y) should be (1, 2 − dichloroethane)
Reactions :
CH3CHCl2 →
KOH (aq.)
CH3CH(OH)2 → CH3CHO
(Z) (Ethanal)
CH2Cl.CH2Cl →
KOH (aq.)
CH2OH.CH2OH dihydroxy compound
( Y) ethan −1, 2 − diol or ethylene glycol
PREVIOUS YEAR IIT-JEE PROBLEMS

light NaOH
1. C6H6 − CH3 + 3Cl2  → C6H5CCl3 → C6H5COOH
Hydrolysis
2. β -Elimination
CH3 CH2 CH2 CH2Cl →

alc. KOH
−HCl
CH3 CH2 CH = CH2
Butane nitrile
3. CH3CH2CH2 — Cl + KCN → CH3CH2CH2CN + KCl
4. CH3 — group is ortho and para directing group.
5. p-Dichlorobenzene has zero dipole moment because the two C — Cl bonds are oppositely directed.
o-Dichlorobenzene (III) is more polar than m-Dichlorobenzene (II) because the angle between
the two dipoles is less in it.
Toluene (I) has very small dipole moment which is less than (II). Hence, the order of dipole
moments is IV < I < II < III.

6. Weker bases are better leaving groups. The basic strength of the given groups is in the order
— OMe (II)> — OAc(I)> — OSO 2Me (III) > — OSO2CF3 (IV).
OH
8. CCl3 ⋅ CHO + H2O → CCl3 − CH
OH
9. 2-Chloro-2-phenyletane ionizes slowly to form carbocation. The carbocation is then attacked
equally from both sides forming both the enantiomers resulting in racemization.
10. The alkyl halide having weaker C —X bond ghas greater reactivity. The C — X bond strength is
in the order :
C — I < C — Br < C — Cl < C — F
Hence, the reactivity is in the order
R — I > R — Br > R — Cl > R — F.
11. The first steps corresponds to dehydrohalogenation while the second step involves addition of
HBr according to Markownikoff’s rule.
12.
+
→
H
−H O
H +
2
OH H
Br 2
Br
Br
H
H
+
Br Br
H H
d- and l-forms
+
H
Butene-1
trans-Butene-2
Br 2 Br 2
Br
Br
Br Br
H
d- and l
meso-
So F can have three possible structures.

13. (B)
CH3 CH3 CH3
1 2 3 4
CH3 − CH− CH2 − CH3 
mono
chlorination
→ CH3 CHCHCH3 + CH2 ClCHCH2 CH3
Cl d and l
d and l
(i) Chlorination at C-2 and C-4 produces no chiral compounds.

(ii) Chlorination at C-3 produces a chiral carbon marked with star (d and l form).
(iii) Chlorination at C-1 also produces a chiral carbon marked with star (d and l form).
14. It is an example of intramolecular Wurtz reaction
Cl Cl
→
Na

Na
→ + NaCl
ether
Br
Br − is a better leaving group. In this reaction alkali metal (Na) is electron donor..
NaH
15. BrCH2 − CH2Br 
Alc.KOH
→ CH2 = CHBr →
2
CH ≡ CH
Elimination of HBr from CH2 = CHBr requires a stronger base because here, Br acquires partial
double bond character due to resonance.
16. Both (C) and (D) are formed, however, nitroethane is the major product.

02 - Alkyl Halide - Aryl Halide (Questions)

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CHEMISTRY ALKYLHALIDE &ARYLHALIDES

3. Which of the following compounds would be hydrolysed most easily ?

The above transformation proceeds through

Nishith Multimedia India (Pvt.) Ltd 39

6. Which of the following is fast debrominated?

(I) (II) (III) (IV)

7. The organic compound (P) of the reaction:

40 Nishith Multimedia India (Pvt.) Ltd

Nishith Multimedia India (Pvt.) Ltd 41

SINGLE CORRECT ANSWER TYPE

1. How many structural isomers are possible for C4H9Br?

2. How many primary halides are possible for C5H11Br?

3. Which of the following alkyl halides is iso-butyl bromide?

5. Benzyl chloride can be prepared by reacting

42 Nishith Multimedia India (Pvt.) Ltd

10. Photochemical chlorination of an alkane is initiated by a process of

11. Allylic bromination of olefins is generally carried out with

12. Which of the following alkyl halide is neo-pentyl chloride?

(A) H3C C CH2 CH2 CH2Cl (B) H3C C CH2 CH2 Cl

13. An alkyl halide may be converted into an alcohol by

14. For the reaction

15. Chlorobenzene can be prepared by reacting aniline with

16. Which of the following is called Sandmeyer reaction?

Nishith Multimedia India (Pvt.) Ltd 43

19. The decreasing order of reactivity of m-nitrobromobenzene (I) : 2, 4, 6-trinitrobromobenzene (II); p-

(C) Me2N Cl (D) C6H5Cl

44 Nishith Multimedia India (Pvt.) Ltd

25. The reactivity of halogens towards of alkanes decreases in order :

27: Product – I ←

(A) Product - I is obtained by the elimination reaction

28: F NO2 

CH3 NaF NaF H

Compound (X) and (Z) are respectively

Nishith Multimedia India (Pvt.) Ltd 45

30: Chlorobenzene towards hydrolysis is,

31: Following equation illustrates

34. End product of following sequence of reaction is :

(A) O (B) OH (C) O (D)

35. CH2CH CH2 

X, Y and Z, respectively are :

(A) X: CH2 CH CH2; Y: CH HC CH2

(B) X: CHCH CH2; Y: CH2CH CH2

46 Nishith Multimedia India (Pvt.) Ltd

(C) in all cases X of (A)

36. CH2 = CHCH2CH = CH2 

(C) CH2 = CHCH2 CH = CHBr (D) H2C CHCH2 C CH

CH3 CH3 CH3 CH3

CH3 CH2 CH2 CH3

CH3 H3C CH3

(C) Both are correct (D) None is correct

Nishith Multimedia India (Pvt.) Ltd 47

(A) H2C and H3C

(B) H2C and

48 Nishith Multimedia India (Pvt.) Ltd

(D) None of these

On treatment with aqueous KOH gives

(C) CH3 (D)

46: 3-methyl -2-pentene on reaction with HOCl gives

Nishith Multimedia India (Pvt.) Ltd 49