ANDHERI / BORIVALI / DADAR / CHEMBUR / THANE / MULUND/ NERUL / POWAI

IIT – JEE - 2019 CRASH COURSE (MAIN) MARKS: 90

TIME: 45 MIN. DATE:6/12/18
TOPIC: ALKYL & ARYL HALLIDE, ALCOHOL ETHERS & PHENOLS

SECTION–I (Multiple Choice Questions)

This section contains 30 multiple choice questions. Each question has 4 choices (1), (2), (3) and
(4) for its answer, out which ONLY ONE is correct.

1. Alkyl halides can be prepared by all the following methods except

SO 2 Cl2 .475K
(1) CH 3CH 2 OH  HCl  g  
ZnCl 2
 (2) CH 3  CH  CH 2  
CCl 4 .Re flux
(3) C 2 H 5OH  NaCl  (4) CH3 COOAg  Br2 

2. In the following reaction.

CH3 B
A
H 2 O/H   (minor
CH3 C CH CH2   (major
product) product)
CH3
The major product is

(1) CH3 (2) CH3

CH3 C CH CH3 CH2 C CH2 CH3
OH CH3 OH CH3
(3) CH3 (4) CH3
CH3 C CH CH3 CH3 C CH2 CH2
H3C OH CH3 OH

3.
NH2

NaNO2 /HCl CuBr/ HBr


0o C
P  Q

The compound Q is
(1) bromobenzene (2) chlorobenzene (3) benzyl bromide (4) benzyl chloride

4. In the following sequence of reactions,

CH 3 CH CH3  HNO 2 Oxidation  i  CH3 MgI
 A   B  
 ii  H
C
/H 2 O
NH2
The compound C formed will be
(1) butanol – 1 (2) butanol – 2
(3) 2 – methylpropanol - 1 (4) 2 – methyl-2-propanol
5. Which of the following are arranged in the decreasing order of dipole moment
(1) CH 3Cl, CH 3Br, CH 3F (2) CH 3Cl, CH 3F, CH3Br
(3) CH 3Br, CH 3Cl, CH 3F (4) CH 3Br, CH 3F, CH 3Cl

CENTERS: MUMBAI / DELHI / AKOLA / KOLKATA / LUCKNOW / NASHIK / GOA / PUNE # 1

6. An unknown alcohol is treated with Lucas reagent to determine whether alcohol is primary,
secondary or tertiary. Which alcohol reacts fastest and by what mechanism?
(1) Tertiary alcohol by SN 2 (2) Secondary alcohol by SN1
(3) Tertiary alcohol by SN1 (4) Secondary alcohol by SN 2

7. The decreasing order of nucleophilicity among the nucleophiles

(a) CH 3  C  O  (b) CH 3O 
O
(c) CN  (d) O
-
H3C S O
O
(1)  a  ,  b  ,  c  ,  d  (2)  d  ,  c  ,  b  ,  a  (3)  b  ,  c  ,  a  ,  d  (4)  c  ,  b  ,  a  ,  d 

8. The structure of the compound that gives a tribromo derivative on treatment with bromine water is

(1) CH3 (2) CH3

OH

OH
(3) CH3 (4) CH2OH

OH

9. Arrange the following: CH 3 CH 2 CH 2 CH 2 Cl  I  , CH 3CH 2  CHCl  CH 3  II  ,  CH 3 2 CHCH 2Cl  III 

and  CH 3 3 C  Cl  IV  in order of decreasing tendency towards SN2 reaction
(1) I  III  II  IV (2) III  IV  II  I (3) II  I  III  IV (4) IV  III  II  I

10. The best method to prepare 3-methylbutan-2-ol from 3-methylbut-1-ene is

(1) Addition of H 2O in presence of dil. H 2SO4
(2) Addition of HBr in presence of peroxide followed by hydrolysis with NaOH (aq)
(3) Hydroboration – oxidation reaction
(4) Oxymercuration – oxidation reaction

11. Which of the following compounds undergo nucleophilic substitution reaction most readily?

(1) (2)

(3) (4)

CENTERS: MUMBAI / DELHI / AKOLA / KOLKATA / LUCKNOW / NASHIK / GOA / PUNE # 2

12. (I) 1, 2-Dihydroxybenzene
(II) 1, 3-Dihydroxybenzene
(III) 1, 4-Dihydroxybenzene
(IV) Hydroxybenzene
The increasing order of boiling points of above mentioned phenols is
(1) I  II  III  IV (2) I  II  IV  III (3) IV  I  II  III (4) IV  II  I  III

13. Consider the following reaction,

Product X formed is

(1) (2)

(3) (4)

14. When diethyl ether is treated with excess of Cl2 in the presence of sunlight, then the product formed
is
(1) CH 3CHCl  O  CH 2CH 3 (2) CH3CHCl  O  CHClCH 3
(3) CCl3  CCl2  O  CCl 2  CCl3 (4) CH3CCl2  O  CHClCH 3

15. Arrange the following compounds in order of decreasing acidity.

(1) IV  III  II  I (2) II  IV  I  III (3) I  II  III  IV (4) III  I  II  IV

16. Chlorination of toluene in presence of light and heat followed by treatment with aqueous NaOH
gives
(1) o-cresol (2) p-cresol
(3) mixture of o-cresol and p-cresol (4) benzoic acid

17. Hydroboration oxidation of 3, 3-dimethylbut-1-ene gives

(1) 2, 3-dimethylbutan-2-ol (2) 3, 3-dimethylbutan-1-ol
(3) 3, 3-dimethylbutan-2-ol (4) 2, 3-dimethylbutan-1-ol

18. Among the following derivatives of ethane, the one having the highest boiling point is
(1) C2 H 5F (2) C2 H 5Cl (3) C2 H5 Br (4) C 2 H 5I

19. In which of the following reactions, H2 gas will not be evolved?

Na Mg
(1) CH 3OH   (2) C 2 H 5 OH  
CH 3MgBr
(3)  CH 3 2 CHOH 
Al
 (4)  CH 3 3 COH  

CENTERS: MUMBAI / DELHI / AKOLA / KOLKATA / LUCKNOW / NASHIK / GOA / PUNE # 3

20. The structure of the major product formed in the following reaction is

(1) (2)

(3) (4)

21. The following reaction is an

(1) Nucleophilic substitution reaction

(2) Electrophilic substitution reaction
(3) Nucleophilic addition reaction
(4) Electrophilic addition reaction

22. Consider the following nucleophilies.

CF3  SO3 C6 H 5SO3 C6 H 5O  CH 3CO 2
(I) (II) (III) (IV)
3
When attached to sp  hybridized carbon their leaving group ability in nucleophilic substitution
reactions decreases in the order:
(1) II  I  III  IV (2) I  II  IV  III (3) IV  I  II  III (4) III  I  IV  II

23. In the reaction

The products are

(1) (2)

(3) (4)

CENTERS: MUMBAI / DELHI / AKOLA / KOLKATA / LUCKNOW / NASHIK / GOA / PUNE # 4

24. The major product formed in the following reaction is

(1) (2)

(3) (4)

25. Acid – catalyzed hydration of alkenes except ethene leads to the formation of
(1) Primary alcohol
(2) Secondary or tertiary alcohol
(3) Mixture of primary and secondary alcohols
(4) Mixture of secondary and tertiary alcohols

26.

A (predominantly) is

(1) (2)

(3) (4)

27. CH3OC2 H5 and  CH 3 3 COCH 3 are treated with hydriodic acid. The fragments after reaction
obtained are:
(1) CH 3 I  HOC 2 H 5 ;  CH 3 3 C  I  HOCH 3
(2) CH 3OH  C2 H 5 I;  CH 3 3 C  I  HOCH 3
(3) CH 3 OH  C 2 H 5 I;  CH 3 3 C  OH  CH 3 I
(4) CH 3 I  HOC 2 H 5 ; CH 3 I   CH 3 3 C  OH \

28. (R)-2-Bromobutane is allowed to react with aqueous KOH. Identify the product formed.

(1) (2)

(3) Equimolar amounts of (1) and (2) (4) Slight excess of (1)

CENTERS: MUMBAI / DELHI / AKOLA / KOLKATA / LUCKNOW / NASHIK / GOA / PUNE # 5

29. Phenol when it first reacts with concentrated sulphuric acid and then with concentrated nitric acid
gives
(1) p-nitrophenol (2) nitrobenzene
(3) 2, 4, 6-trinitrobenzene (4) o-nitrophenol

30. Bottles containing C6 H 5 I and C6 H 5CH 2 I lost their original labels. They were labeled A and B for
testing. A and B were separately taken in test tubes and boiled with NaOH solution. The end solution
in each tube was made acidic with dilute HNO3 and some AgNO3 solution added. Solution B gave a
yellow precipitate. Which one of the following statements is true for the experiment?
(1) Addition of HNO3 was unnecessary (2) A was C6 H 5I
(3) A was C 6 H5CH 2 I (4) B was C 6 H 5 I

CENTERS: MUMBAI / DELHI / AKOLA / KOLKATA / LUCKNOW / NASHIK / GOA / PUNE # 6

 ANDHERI / BORIVALI / DADAR / CHEMBUR / THANE / MULUND/ NERUL / POWAI
IIT – JEE - 2019 CRASH COURSE (MAIN)
TOPIC: ALKYL & ARYL HALLIDE, ALCOHOL ETHERS & PHENOLS DATE: / /18

1. (3)
Cl  ion being a weak nucleophile cannot displace OH ion which is a stronger nucleophile.
Na  Cl  C 2 H 5 OH  No reaction.
2. (1)
3. (1)
Diazonium salts react with CuBr/HBr (Sandmeyer reaction) to form bromobenzene.
4. (4)
HNO 2
CH 3  CH  CH 3   CH 3  CH  CH3

NH 2 OH
 
O  3 i CH MgI
 ii  H /H O 
  CH 3  C  CH 3   CH 3 3 COH
2

2-Methyl
O
B 2-propanol

5. (2)
Due to much smaller size of F than Cl, the dipole moment (i.e., product of charge and distance) of
CH 3 F is lower than that of CH3Cl . Thus, option (2) is correct
6. (3)
Tertiary alcohols react with the Lucas reagent at the fastest rate since the reaction occurs through
intermediate formation of most stable 3o carbocations. Further since carbocations are the
intermediates, the reaction occurs by SN1 mechanism. Thus, option (3) is correct.
7. (4)
Because of lower electronegativity of C over O, CN  is a better nucleophile than methoxide ion.
Among acetate ion and p-toluene-sulphonate ion, because of smaller resonance stabilization,
CH 3COO  is a better nucleophile than p-toluenesulphonate ion. Thus, option (4) is correct.
8. (3)
Only 3 – methylphenol has two ortho and one para position free w.r.t. OH group and hence gives
tribromo derivative.
CH3 CH3
Br Br
Br2 /H 2 O


OH OH
3-Methylphenol
Br
2,4,6-Tribromo-
3-methylphenol
9. (1)
As the steric hindrance increases at the   carbon atom holding the halogen, the reactivity towards
SN 2 mechanism decreases, i.e., I  II  II  IV .
10. (4)
11. (A)
Electron – withdrawing groups (i.e., NO2 , CO2 R, etc.) increase the reactivity of aryl halides towards
nucleophilic substitution reactions by stabilizing the intermediate carbanion.
CENTERS: MUMBAI / DELHI / AKOLA / KOLKATA / LUCKNOW / NASHIK / GOA / PUNE # 7
12. (3)
13. (4)
Reaction occurs by SNi mechanism with retention of configuration

14. (3)
Cl2 / h
CH 3CH 2OCH 2CH 3   CCl3CCl 2  O  CCl 2CCl 3
Perchlorodiethylether
15. (4)
Electron – withdrawing groups increase while electron-donating groups decrease the acidity of
phenols. Since NO2 is a stronger electron withdrawing group than Cl, therefore, p-nitrophenol (III) is
a stronger acid than p-chlorophenol (I). Further, OCH 3 is a stronger electron donating group than
CH3 , therefore, p-methoxyphenol (IV) is a weaker acid than p-methylphenol (II). Combining the
two statements, the overall acidity of the four phenols decreases in the order: III > I > II > IV, i.e.,
option (4) is correct.
16. (4)
3Cl2 ,h ,  Aq.NaOH
C 6 H 5 CH 3 
3HCl
 C6 H 5 CCl3 
3NaCl

Toluene

C 6 H5  OH 3 
 H2O
 C 6 H5COOH
Benzoic acid

17. (2)
18. (4)
For the same alkyl group, boiling point increases as the size of halogen increases. Thus, C2 H 5 I has
the highest b.p.
19. (4)
Alcohols react with CH 3MgBr to evolve CH 4 gas.
 CH 3 3 COH  CH 3MgBr  CH 4   CH 3 3 COMgBr
20. (4)
Aralkyl halides are more reactive than aryl halides, therefore, only the halogen in the side chain is
displaced.

21. (2)
Electrophilic substitution reaction.
22. (2)
Stronger the acid, weaker is its conjugate base and hence higher is its leaving group ability.
Now basicity increases in the order : CF3  SO3
 C 6 H5SO3  CH 3COO   C6 H 5O  and hence its leaving group ability decreases in the reverse order,
i.e., CF3  SO3  I  , C 6 H 5SO 3  II   CH 3 COO   IV   C 6 H 5O   III  , i.e., option (2) is correct.

CENTERS: MUMBAI / DELHI / AKOLA / KOLKATA / LUCKNOW / NASHIK / GOA / PUNE # 8

23. (4)
Protonation of anisole gives methyl phenyl oxonium ion (I). In this ion, O  CH3 bond is weaker than
O  C6 H 5 bond since carbon atom of the phenyl group is sp 2 - hybridized and there is partial double
bond character in O  C6 H 5 bond due to resonance. Therefore, attack of the Br  ion exclusively
breaks the weaker O  CH3 bond forming CH3Br and C 6 H5OH . Thus, option (4) is correct.

24. (3)
Although the given alkyl halide is 1o , yet the carbocation which it generates on ionization, rearranges
to form a more stable 3o carbocation which in presence of a strong base  CH 3O   prefers to undergo
elimination rather than substitution to afford 2  methylpropene

25. (2)
Only ethene gives 1o alcohol, i.e., ethanol while other alkenes either give 2o or 3o alcohols.

CENTERS: MUMBAI / DELHI / AKOLA / KOLKATA / LUCKNOW / NASHIK / GOA / PUNE # 9

26. (4)

27. (1)
In CH3OC 2 H5 , attack of I  occurs at CH3 group giving CH 3 I and C 2 H 5OH . In contrast, in
 CH3 3 COCH3 , reaction occurs by SN mechanism and I  iodide attacks the more stable  CH3 3 C 
1

giving  CH 3 3 Cl and CH3OH . Hence, option (1) is correct.

28. (1)

Since in SN2 reactions, inversion of configuration occurs, therefore, option (1) is correct.
29. (4)

30. (2)
Since B gives yellow ppt. with AgNO3 / HNO3 ,
B must be C 6 H5CH 2 I and hence A is C 6 H 5 I .

CENTERS: MUMBAI / DELHI / AKOLA / KOLKATA / LUCKNOW / NASHIK / GOA / PUNE # 10