EXERCISE-01 CHECK YOUR GRASP

SELECT THE CORRECT ALTERNATIVE (ONLY ONE CORRECT ANSWER)

1. Carbanion is a :-
(A) Base (B) Nucleophile (C) Both (A) and (B) (D) None
2. Electrophile is :
(A) H 2O (B) NH 3 (C) AlCl 3 (D) C 2 H 5NH 2
3. Which of the following species has a pyramidal shape-

(A) CH 3 + (B) BF3 (C) CH 3– (D) C H 3
4. Increasing order (least basic first) of basic strength is shown by the set
(A) ClNH 2 , NH 3 , CH 3 NH 2 (B) ClNH 2 , CH 3 NH 2 , NH 3
(C) NH 3 , ClNH 2 , CH 3 NH 2 (D) CH 3 NH 2 , ClNH 2 , NH 3
5. The decreasing order of acid strength indicated by the following sequence of reaction is :-

NaNH2   C2H2 H2O

–C–H –C–Na HC CNa+ Ph3CH HC CH + NaOH

(A) NH 3 > Ph 3 CH > C 2 H 2 > H 2 O (B) H 2 O > HC  CH > Ph 3 CH > NH 3

(C) HC  CH > H 2 O > Ph 3 CH > NH 3 (D) Ph 3 CH > HC  CH > H 2 O > NH 3

6. In which of the following compounds is hydroxylic proton the most acidic -

F O O
I O
(A) O (B) (C) H (D) H
H H F F
7. Correct arrangement of the following acids in correct Ka order is :-

(I) H 3 N  —CH 2 —COOH (II) NC—CH 2 —COOH (III) H 3 C—CH 2 —COOH (IV) OOC —CH 2 —COOH
(A) I > II > III > IV (B) II > I > III > IV (C) I > III > II > IV (D) IV > III > II > I
8. Which of the following orders of acid strength is correct :-
(A) RCOOH > ROH > HOH > HC CH (B) RCOOH > HOH > ROH > HC CH
(C) RCOOH > HOH > HC CH > ROH (D) RCOOH > HC CH > HOH > ROH
9. Which of them is false for order of – I effect
 
(A) –F > –Cl > –Br > I (B) –NR3 > –NH3 > –NO2

(C) –OCH3 > –OH > –NH 2 (D) > –C  CH > H

10. The order of basicity of halides is :

– – – – – –
(A) Cl < Br – < I < F (B) F < I < Br– < Cl
– – – – – –
(C) I < Br – < Cl < F (D) Cl < F < I < Br –
11. Which of the following molecule has longest C=C bond length -

(A) CH 2 =C=CH 2 (B) CH 3 –CH=CH 2

CH3
(C) CH3–C–CH=CH2 (D) CH3–C=CH2
CH3 CH3
H 3O 
12. In the reaction CH 3CN  CH 3COOH
heat

the hybridization state of the functional carbon changes from

(A) sp3 to sp2 (B) sp2 to sp3 (C) sp to sp2 (D) sp2 to sp
13. Most stable carbocation is :-

   
CH2 CH2 CH2 CH2

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

Cl NO2 OCH3

14. Most stable carbanion is :-

(A) HC C (B) C 6 H 5 (C) (CH 3 ) 3 C—CH 2 (D) (CH 3 ) 2C CH 
15. Consider the following carbocations

   
(a) CH3O– –CH2 (b) –CH2 (c) CH3– –CH2 (d) CH 3— C H 2

The relative stabilities of these carbocations are such that :-

(A) d < b < c < a (B) b < d < c < a
(C) d < b < a < c (D) b < d < a < c
16. Among the following, the strongest base is :-
(A) C 6 H 5 NH 2 (B) p–NO 2 –C 6 H 4 NH 2 (C) m–NO 2 –C 6 H 4 NH 2 (D) C 6 H 5 CH 2 NH 2

17. The increasing order of base strength of Cl –, CH 3 COO – , —OH and F — is :

(A) Cl – < F — < CH 3 COO – < —
OH (B) Cl – > F — > CH 3 COO – > —
OH
(C) CH 3 COO – < Cl – < F — < —
OH (D) None of these
18. Formic acid is considered as a hybrid of the four structures


O O O O

H– C–OH  H– C = O H  H–C–O–H  H–C–O–H
 

I II III IV
Which of the following order is correct for the stability of the four contributing structures.
(A) I > II > III > IV (B) I > II > IV > III (C) I > III > II > IV (D) I > IV > III > II
19. Which of the following carbonium ion is most stable
(A) Ph 3 C + (B) (CH 3 ) 3 C + (C) (CH 3 ) 2 CH + (D) CH 2 CH—CH 2+
20. Among the following the aromatic compound is

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

  

21. Match List- I with List- II and select the correct answer using the codes given below -
List-I (Stability) List -II (Reason)

H3C CH3
C
(A) > CH3+ (1) Inductive effect

 Br
(B) H3C–C < CH3– (2) Resonance
CH3

 CH3
(C) H3C–C > H3C–CH2+ (3) Hyperconjugation and resonance
CH3

• H3C •
CH2 CH2
(D) > CH3 (4) Hyperconjugation and inductive effect

Codes :
(A) A - 2 ; B - 3 ; C - 4 ; D - 1 (B) A - 3 ; B - 1 ; C - 4 ; D -2
(C) A - 4 ; B - 3 ; C - 1 ; D - 2 (D) A - 3 ; B - 4 ; C - 2 ; D - 1
22. Which of the following compounds is the strongest base -

(A) NH2 (B) NH2 (C) CH3 NH2 (D) NHCOCH3

23. In which of the following molecule all the effect namely inductive, mesomeric & hyperconjugation operate:

(A) —Cl (B) —CH3 (C) —COCH3 (D)

CH3 CH3

24. Which of the following reaction is possible :

OH ONa

(A) + (B) CH3–C–OH + HCOONa

O
NO2

SO3Na COOH

(C) + (D) H–CC–Na+H 2 O 

 COOH

25. , pK a value of the compound decreases if X is :-

(A) –NO 2 (B) –NH 2 (C) –OH (D) –OCH 3

26. Which one of the following results most stable carbon free radical :
• •
CH3 CH3
(A) (B)

• •
(C) (Ph) 2C = C(Ph) 2 CH3 (D) CH 2 = CH 2 CH3

H

CH3–C–CH2
1,2 shift
27. A (Major) ; Here A is :

CH3
 
CH3–C–CH3 CH–CH2
(A) (B)

H
(C) CH3–C–H2C– (D) CH3–C= CH2

Ph

28. –CH2OH ; On dehydration with conc. H2SO4 forms predominantly :

(A) =CH2 (B) –CH3 (C) –CH3 (D) –CH3

29. Which of the following is incorrect :

CH2CH3 •CHCH3

•
:O 
O O O
Cl + HCl
(A) (B) HO–C–H+ C–H  HO–C–H + H–C–H
H H H

H–CH2 H
   
H shift –
(C) CH3 –C  CH3 –C–CH2 HO
(D) CH 3 CH 2 CHO   CH 3 C HCHO  H 2 O
CH3 H

30. The Ka values of alcohols, water and phenol are of order 10–17, 10–14 and 10–10 respectively. Which of the
following reactions is possible :
(I) C 6 H 5 O  + H 2 O  C 6 H 5 OH + OH  (II) C 2H 5 O  + H 2O  C 6 H 5 OH + OH 
(A) Both I and II (B) only II (C) only I (D) neither of two
31. Most stable carbanion is :

 
CH2 CH2

(A) CH 3 (B) CH 2  CH – CH 2 (C) (D)

NO2
32. Stability of :

CH3
(I) C H 3 – C H = C H – C H 3 (II) CH3– C = C – CH3 (III) CH3– C = CH2 (IV) CH3– C = CH – CH3
CH3 CH3 CH3

in the increasing order is :

(A) I < III < IV < II (B) I < II < III < IV (C) I < IV < III < I (D) II < III < IV < I

H2O
33. –MgBr + CH2—CH2 [A] ; the product (A) is :
O

(A) –CH2OH (B) –CH2CH2OH

(C) —CH—CH2 (D) No reaction

O

34. Spin multiplicity of Triplet nitrene is :

(A) 1 (B) 2 (C) 3 (D) 4
35. The maximum probability of proton loss is in the case of :

H H
  H 
(A) CH 3 – CH 2 (B) CH3– C – CH3 (C) (D) (CH3)2C – CH2
CH3 

36. Select the least stable one :

H3C H3C 

(A) CH3 – CH2 
(B) CH3– CH2– CH2 (C) CH– CH2 (D) 3C C – CH2
H
H3C H3C

37. Which of the following will react fastest with conc. HCl :

(A) –CH2CH2OH (B) –CH(OH)CH3

(C) –OH (D) –CH2OH

38. Consider the following reaction :

OCH3

+ NaNH2 Product
Br
The product (P) and reaction (R) are :

OCH3 OCH3
NH2 NH2
(A) ; addition-elimination (B) ; elimination addition

OCH3 OCH3

(C) ; elimination addition (D) ; cine substitution

NH2 NH2

39. Energy of activation is lower for which reaction :

   
(A) RCH 2 OH 2  R C H 2 (B) R 2 CH OH 2  R 2 C H
 
(C) R 3 C OH 2  R 3 C (D) all have same E act.

CHE CK Y OU R G R ASP ANSWER KEY E XE R CISE -1

Qu e. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans . C C C A B D A B D C D C C A A
Qu e. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Ans . D A A A A B B C D A C A B C B
Qu e. 31 32 33 34 35 36 37 38 39
Ans . D A B C C D B C C
EXERCISE–02 BRAIN TEASERS
SELECT THE CORRECT ALTERNATIVES (ONE OR MORE THEN ONE CORRECT ANSWERS)
1. The correct order of decreasing basic strength is :

NH2

N N N
H H
I II III IV
(A) I > II > III > IV (B) II > III > I > IV (C) II > IV > I > III (D) II > III > IV > I
2. The correct order of increasing dissociation constant of the following compound is :-

OH OH OH OH
NO2 NO2 NO2

NO2
NO2
NO2 NO2

I II III IV
(A) II < IV < I < III (B) IV < III < I < II (C) IV < II < I < III (D) IV < I < II < III
3. In the following arrange the H (numbered) for their ease of displacement during acid base reaction :
(2)
(3) OH
HO
H NaNH2(liquid NH3)
(1) 2 equivalent

(A) 1 > 2 > 3 (B) 3 > 2 > 1 (C) 3 > 1 > 2 (D) 2 > 3 > 1
4. Which one of the following is the strongest base in aqueous medium :-
(A) (C 2 H 5 ) 3 N (B) C 2 H 5 NH 2 (C) NH 3 (D) (C 2 H 5 ) 2 NH
5. The correct order of acid strength of the following compound is -

(I) CH3–C–CH3 (II) CH3–C–C–CH3 (III) CH3–C–CH2–C–CH3

O OO O O
(A) III > II > I (B) III > I > II (C) II > I > III (D) I > II > III
6. Which of the following shows the correct order of decreasing basicity in aqueous medium -
(A) (CH 3 ) 3 N > (CH 3 ) 2 NH > CH 3 NH 2 > NH 3 (B) (CH 3 ) 2 NH > (CH 3 ) 3 N > CH 3 NH 2 > NH 3
(C) (CH 3 ) 2 NH > CH 3 NH 2 > (CH 3 ) 3 N > NH 3 (D) (CH 3 ) 2 NH > CH 3 NH 2 > NH 3 > (CH 3 ) 3 N
7. For the compounds

N N N

H H
I II III
the order of basicity is -
(A) III > II > I (B) II > III > I (C) I > II > III (D) II > I > III
8. Which of the following shows the correct order of decreasing acidity-
(A) PhCO 2 H > PhSO 3 H > PhCH 2 OH > PhOH
(B) PhSO 3 H > PhOH > PhCO 2 H > PhCH 2 OH
(C) PhCO 2 H > PhOH > PhCH 2 OH > PhSO 3 H
(D) PhSO 3 H > PhCO 2 H > PhOH > PhCH 2 OH
7 9. Give the correct order of increasing acidity of the following compounds-

OH OH COOH CCH

I II III IV
(A) II < I < III < IV (B) IV < II < I < III (C) I < II < IV < III (D) IV < I < II < III
10. Which of the following is the most acidic
(A) CH 2 = CH 2 (B) HC  CH

(C) CH 2 =CHCH 2 CH=CH 2 (D)

11. Which of the following substituents will increase the acidity of phenol -
(A) –NO 2 (B) –CN (C) –CHO (D) – CH 3

12. (I) (II) (III)

Compare carbon-carbon bond rotation across I, II, III.

(A) I > II > III (B) I > III > II (C) II > I > III (D) II > III > I
13. Which of the following s-bonds participate in hyperconjugation :

I V
H
H CH3
II
H IV
III
(A) I and II (B) I and V (C) I and V (D) III and IV

14. NH, N–H, N

O
(x) (y) (z)

The correct order of decreasing basic strengths of x, y and z is :

(A) x > y > z (B) x > z > y (C) y > x > z (D) y > z > x
15. Set the following in increasing order of their p K a values:

O O

(x) CH3—S—O—H (y) CH3—C—O—H (z) CH3—OH

O
(A) y > x > z (B) x < y < z (C) y > z > x (D) x < z < y
16. Rank the following alkenes in order of decreasing heats of hydrogenation (largest first):

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

(A) II > III > IV > I (B) II > IV > III > I (C) I > III > IV > II (D) I > IV > III > II
17. Which of the following molecules has all the effects : inductive, mesomeric and Baker Nathan effect ?
(A) C 2 H 5 Cl (B) CH 3 –CH=CH 2

(C) CH 2 =CH–CH=CH 2 (D) CH 3 –CH=CH –C–CH 3

O

18. Which nitorgen in LSD (Lysergic acid diethylamide) is more basic :

O
I III
H–N –C–N(C2H5)2
II
N
CH3
(A) I (B) II (C) III (D) all are equally basic
19. Which of the following substituted carboxylic acids has the highest K a value :

(A) CH 3 —CH 2 —CH— COOH (B) CH 3 —CH— CH 2 —COOH

Cl Cl
(C) CH2— CH 2 —CH 2 —COOH (D) CH 3 —CH— CH 2 —COOH
Cl Br
SELECT THE CORRECT ALTERNATIVES (ONE OR MORE THEN ONE CORRECT ANSWERS)

20. Which of the following compounds yield most stable carbanion after rupture of (C 1 –C 2 ) bond :

O O
(A) CH3—C—CCl3 (B) CH3—C—CBr3
1 2 1 2

O
(C) CH3—CH2—C—CI3 (D) None of these
1 2
 N N
21.
H NH2
pyrrole (I) pyridine (II) aniline (III)

Which is/are correct statements ?

(A) I is more basic than II (B) II is more basic than I and III
(C) III is more basic than II (D) all are aromatic bases
22. Following is true for stability between the two structures :


O O
(A) CH3–CH–CH=CH2 > CH3–C=CH–CH3

CH2
•
(B) CH 2=CH–CH=CH–CH 2• > CH2–C–CH–CH3

CH3
 
(C) CH2=C–CH2 > CH 3 –CH=CH– CH 2

O
(D) —O < CH3–C–O

23. Which have acidic hydrogen :

O
(A) CH 3 COOH (B) —OH (C) CH3—C—CH2—CN (D) NaNH2

24. C—C and C=C bond lengths are unequal in :

(A) Benzene (B) 1,3 buta-di-ene
(C) 1, 3 cyclohexa-di-ene (D) None
25. The acid strength of substituted carboxylic acids is known to be dependent on the nature and position of
the substituent. In the following examples, an attempt has been made to arrange the acids in order of acid
strength, the strongest first. One of the series is incorrect-which one :
(A) CH 3 .CH 2 CH(Cl).COOH > CH 3 .CH(Cl).CH 2 COOH > CH 3 .CH 2 .CH 2 .COOH
(B) NO 2 .CH 2 .COOH > HOCH 2 . COOH > CH 3 .COOH
(C) Cl 3 C.COOH > BrCH 2 .COOH > FCH 2 .COOH
(D) CH 3 . COOH > CH 3 .CH 2 .COOH > (CH 3 ) 3 C.COOH
26. Which species is not aromatic :

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

N N
:
27. Select the correct option :
(A) carbonic acid is weaker acid than acetic acid
(B) the boiling points of acids are higher than corresponding alcohols
(C) chloroacetic acid is stronger acid than acetic acid
(D) phenol is more acidic than ethanol
28. Which reacts with AgNO 3 to give ppt. :

—Br
(A) —Br (B) –CH=CH–CH2Br (C) (D) —Br

29. Which statement is ture :

– –
(A) NH2
is stronger base than OH

(B) NH 2–OH is less basic than NH 3

(C) CH 3 –NH 2 is weaker base than N(CH 3 ) 3 in (aq) medium

NH2 CH2–NH2

(D) is weaker base than

30. Which is less acidic than phenol :

OH OH

—CH3 —NH2
(A) (B) CH 3 –OH (C) (D) H 2 O

31. The precursor carbocation to the product in the following reaction is :

H

C6H5 H C6H5
OH H


(A) C6H5 (B) C6H5  (C) either of the two (D) none of the two

32. Which of the following ion is formed in the following reaction :

H
OH O



(A) 
(B)
OH OH


CH2
(C) (D) All of three
OH
 OD
D NaOH
33. [Intermediate] P. Product is :
CO2 D

OD OD
HOOC D DOOC D
(A) (B)

OH
DOOC D
(C) (D) Reaction not possible

34. Predict the nature of A in the following reaction :

O
+ ClCH2COOC2H5 Base
(A)

Cl
O
CCOOC2H5
(A) (B)
CH2COOC2H5

O O
(C) CHCOOC2H5 (D) CHCOOC2H5

35. Which of the following intermediate is most likely to be formed during addition of HBr on crotonic acid :

CH 3 CH = CHCOOH + HBr(g)  CH 3 CH–CH 2 COOH :

Br
 
(A) CH 3 CH 2 – C HCOOH (B) CH 3 CH – CH 2COOH
OH
(C) CH3CH=CH–C–OH (D) none of these


36. Which will give most stable cation upon strong heating :

CH2–Cl Cl
CH2
(A) (B) (Ph) 3C–Cl (C) (D) CH
CH2–Cl

Cl
37. (A); Here (A) is :
—Cl
H


(A) (B) (C) 

(D)


 F

–F
38. Cl – C – C – F [X] ; Here [X] is :
Cl F

F F F F
(A) Cl – C = C – F (B) Cl – C = C – Cl (C) Cl – C = C – F (D) C l – C = C – F
Cl F Cl F

H3C CH3
H3C CH3 CHCl3
C C KOH
39. H H the reaction proceeds via :
H H

(A) carbene (B) Carbon free radical (C) Carbocation (D) Carbanion

Cl
:C Cl
40. (A) ; Here A is :
••
N
H
Cl
Cl
(A) (B) Cl
 (C) (D)
N N N
N
H
41. Which of the following can give benzyne :

Cl Cl
(A) NaNH2 (B)  (C) NaNH2 (D) All
H N2 Br

42. Dehydration of the following in increasing order is :

(I) –OH (II) –OH (III) –OH (IV) –OH

(A) I < II < III < IV (B) II < III < IV < I (C) I < III < IV < II (D) I < IV < II < III
43. Increasing tendency for SN1 and SN2 reaction is :

CH3
(I) CH 3 CH 2 CH 2 CH 2 Cl (II) CH3CH2CH – CH3 (III) CH3CHCH2 – Cl (IV) CH3–C – Cl
Cl CH3 CH3

(A) SN1 ; I < III < II < I V (B) SN2 ; IV < II < III < I
(C) (A) and (B) both are correct (D) Both incorrect
44. Cyclopentyl ethyl ether can be obtained by :

(A) –ONa+CH3CH2Br (B) –Br+CHCH

3 2ONa

(C) –OH+CH3CH2Cl (D) none is correct

45. Major product in the following reaction is :

–Br + KOCH2CH3 Product

(A) –OCH2CH3 (B) (C) —Br (D)

OCH2CH3

46. Mechanism of insertion reaction is of :

(A) One step for triplet carbene (B) Two step for singlet carbene
(C) One step for singlet carbene (D) Two step for both
H3C
1 
6 2 NH2
47. (P) . The most probable structure of intermediate P is :
5 –Cl
3
4

OCH3 OCH3 OCH3 OCH3

1 1 1 1
6 2 6 2 6 2 6 2
(A) (B) (C) (D)
5 3 5 3 5 3 5 3
4 4 4 4

CH3
1 
6 2 NH2
48. (A). The most probable structure of intermediate A is :
5 –Cl
3
4

CH3 CH3 CH3 CH3

1 1 1 1
6 2 6 2 6 2 6 2
(A) (B) (C) (D)
5 3 5 3 5 3 5 3
4 4 4 4

49. Hybridisation of arrow headed 'C' is

(A) sp 2 sp 3 (B) sp 3 sp 3 (C) sp 2 sp 2 (D) sp 3 sp 3 d

50. Which of the following is most strongest electrophile :

•• ••
(A) singlet H – N
•
• (B) triplet H – N
•
• (C) singlet –C (D) triplet –C–

51. In benzyne two external unshared electronic orbital :

(A) do not overlap to form a  bond (B) can overlap to form a complete  bond
(C) poorly overlap to form a ver y weak bond (D) contribute in benzene ring
52. Which of the following is aromatic intermediate :

•
•
(A) carbene (B) (C) Benzyne (D)
•
53. In which of the following case 'H' shift is more preferable than 'CH 3 ' shift :

CH3 CH3 H
 
(A) CH3–C–CH2 (B) CH3–C– CH–C–H
H CH3 H

CH3

(C) CH3–C–CH–CH3 (D) all
Ph

54. Which of the following will not give 1, 2, shift :

2
Hg

OH
(A) (CH 3 )3 C — C H 2 (B) (CH3)3C CH—CH2 (C) 
(D) all

55. Which of the following reactions is wrong :

 
(A) CH3CH2CHO OH
CH3 – CH – CHO

•
CH2CH3 CHCH3 + HCl
(B) Cl•

O O O O
(C) HO–C–H+ H– C–H  HO– C–H + H–C–H
H H

CH3
(D) CH3 –C 
Hydride
shifting
CH3 –CH–CH2
CH3 CH3

56. Methyl benzylic carbonium ion is the most stable one, hence it will react fastest consider the following
reaction :
Br CH3 SN2
+ OH (P) ; product (P) will be :
H H

H CH3 HO CH3
(A) (B)
HO H H H

OH
H CH3 CH3
H
(C) (D)
H H H H
OH
57. Consider the following reaction -
R – CH = CH2+ IN3  A , A is :

(A) R – CH – CH2N3 (B) R – CH – CH2I

I N3

(C) R – CH – CH2 (D) R – CH– CH

N N
I

58. + CHBr3 1 BuOK product ; product will be :

Br Br Br
(A) Br (B) Br
Br

Br
(C) (D)
Br

CH2

59. HBr major product will be :

Me CH2Br CH2Br CH3

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

CH3
O OH
60.  Product ; major product of the reaction can be :
O
CH3

O O O O

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

( i ) Zn
61. CH3COCH3 + BrCH2COOEt 
( ii ) H 2 O / H 
 (A) ; the product (A) is :

OCH3 OH
CH3
(A) C (B) CH3–C–CH2COOEt
CH3 Br
CH3

CH3 OH CH3 OCH2COOEt

(C) C (D) C
CH3 COOEt CH3 Br
 OH

62. Which carbocation is more likely to be formed in the dehydration of H :


 
(A) (B) (C) (D)


63. The most probable structure for (P) in the following reaction is :

conc H2SO4
2 (P)

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

64. Which of the following alcohols is dehydrated most readily with conc. H2SO4 ?

CHOHCH3 CHOHCH3 CHOHCH3 CHOHCH3

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

OCH3 NO2 Cl

65. Dehydration of alcohols by conc. H2SO4 takes palce according to following steps :

CH3 CH3 CH3

•• H  –H2O 
CH3–C–CHOH
2 •• step -I CH3–C–CHOH
2 2 step -II CH3–C–CH2
H H H


CH3 CH3
1,2–H shift –H
step -III CH3–C–CH3 step -IV CH2=C–CH3


the slowest and fastest steps in the above reaction are :

(A) step I is slowest, while III is fastest
(B) step II is slowest, while III is fastest
(C) step II is slowest, while IV is fastest
(D) all step proceed at equal rate
66. Pyrrole is treated with alkaline chloroform to form two products A and B ?

Cl
+ CHCl3 KOH +
N N CHO N
H H
(A) (B)

Which of the following intermediate is likely to be formed ?

Cl
C 
H Cl
(I)  (II)  (III) ••
(IV)
N CCl2 N N N
H
(A) I and IV (B) I and III (C) III and IV (D) I, III and IV

conc. H2SO4
67. Major product is :

OH

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

BRAIN TEASER S ANSWER KEY E XE R CISE -2

Qu e. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
An s . D C B D A C D D B D A ,B,C C B B B
Qu e. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
An s . D D B A A B,D A ,C A ,B,C C C B A ,B,C ,D B,D A ,D A ,B,D
Qu e. 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45
An s . A B C D C C C A A D D A A A B
Qu e. 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
An s . C A B C B C C A B D A B C A B
Qu e. 61 62 63 64 65 66 67
An s . B C C B C B C
EXERCISE–03 MISCELLANEOUS TYPE QUESTIONS
TRUE OR FAL SE :
1. In benzene, carbon uses all the three p-orbitals for hybridization.
2. All the carbon atoms in bicyclbutane are sp 2-hybridized.
3. Allene (CH 2 =C=CH 2 ) is a planar molecule.
4. The greater stability of trans-but-2-ene over cis-but-2-ene can be explained on the basis of hyperconjugation
effect.
5. In a two step reaction, the rate determining step has the lowest energy of activation.

FILL IN THE BLANKS :

1. Out of benzene, ethylene and acetylene, the carbon-carbon bond is longest in ...................... .
2. The cyclopentadienyl cation is ...................... while cyclopentadienyl anion is ............... .
3. The type of delocalization involving sigma bond orbitals with  bond or vacant orbital is called ..............
4. Hydroperoxide ion is a stronger ...................... but weaker ................... than hydroxide ion.
5. Catalytic hydrogenation of cis-2, 3-diphenyl-2-butene gives..................... .

MATCH THE COLUMN

1. Match the column I with column II.

Column-I Column-II
(A) —NO2 (p) – m effect
–
(B) —O (q) + m effect
(C) —O—CH3 (r) + I effect
(D) —C  N (s) – I effect

2. Match the column I with column II.

Column-I Column-II

(A) (p) Aromatic

(B) (q) Non-aromatic

(C) + (r) Anti-aromatic

(D) (s) Aliphatic

3. Observe the following compound P and match the column I with column II.

HOOC SO3H

HO CCH

Column-I Column-II
(A) Strongest acidic group in P (p) 1
(B) Weakest acidic group in P (q) 2
(C) Number of Intra molecular (r) 3
H-Bonding in P
(D) Number of mole of hydrogen (s) 4
gas that is liberated on reaction
of 'P' with excess of sodium metal if
one mole of P is used

ASSERTION & RE ASON QUESTION :

These questions contains, Statement-I (assertion) and Statement-II (reason).

(A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I
(B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I
(C) Statement-I is True, Statement-II is False.
(D) Statement-I is False, Statement-II is True.
1. Statement-I : Greater the s-character of the hybrid orbital, the smaller is its size.
Because
Statement-II : Bond formed by the overlap of sp 3-sp 3 hybrid orbital is the longest while the bond formed
by the overlap of sp-sp hybrid orbital is shortest.

   
2. Statement-I : Me 3 C is more stable than Me 2 C H and Me 2 C H is more stable than the Me C H 2 .

Because
Statement-II : Greater the number of hyperconjugative structures, more is the stability of carbocation.
3. Statement-I : Cyclopentadienyl anion is much more stable than allyl anion.
Because
Statement-II : Cyclopentadienyl anion is aromatic in nature.
4. Statement-I : CH 3OCH 3 and C 2 H 5OH have comparable molecular masses but boiling point of C 2 H 5OH
is higher than dimethyl ether.
Because
Statement-II : C 2H5OH forms intermolecular H-bonding while CH3OCH3 forms intramolecular H-bonding.
IV III II I
5. Statement-I : In the compound, C H 3 — C H 2 — C  N , the most electroegative carbon is II.

Because
Statement-II : Carbon atom II has more s-character.
6. Statement-I : pk a1 of fumaric acid is more than maleic acid.
Because
Statement-II : Conjugate base of fumaric acid is stabilised by intramolecular H-bonding.
7. Statement-I : Carbocation (II) is more stable than carbocation (I)
 
CH2 CH2

CH3 CD3
(I) (II)
Because
Statement-II : Carbocation (II) has more positive inductive effect of –CD 3 group as compared to –CH 3
group.
8. Statement-I : Carbon-oxygen bonds are of equal length in acetate ion.
Because
Statement-II : Bond length decreases with the multiplicity of bond between two atoms.
9. Statement-I : The potential energy barrier for rotation about C=C bond in 2-butene is much higher than
that in ethylene.
Because
Statement-II : Hyperconjugation effect decreases the double bond character.
10. Statement-I : Pyrrolidine (II) is more basic than pyrrole (I).

•• ••
N N
H H
(I) (II)

Because
Statement-II : Protonated pyrrole has resonance stabilization of positive charge in aromatic ring.

COMPREHENSION BASED QUESTIONS :

Comprehension # 1
The intramolecular delocalisation of  and /non-bonding electrons without any change in the position of
atoms is called resonance. Delocalisation may occur in conjugated system involving carbon atom and atom
other than the carbon. Delocalisation makes system stable. More is the number of resonating structures,
more is the stability of the system. A conjugated structure is least stable when a higher electronegative atom
has positive charge and when identical charges are present on adjacent atoms.
1. The decreasing order of stability of the following resonating structures :

•• – + +
••–
CH2=CH—Cl  CH2—CH=Cl CH2—CH= Cl is -
(I) (II) (III)
(A) I > II > III (B) II > III > I (C) III > II > I (D) I > III > II
 
2. If A is Ph CH 2 and B is CH 2 =CH— CH 2 , the greater number of resonating structure is of -
(A) A (B) B (C) both A and B (D) None of these
3. Which of the following pairs represent resonance ?
–
(A) CH 2 =CHOH ; CH 3 CHO (B) C H 2 –CHO ; H 2 C=CH–OH

+
O OH OH OH

(C) CH3—C—CH3 ; CH3—C—CH2 (D) CH3—C—CH3 ; CH3—C—CH3

4. Examine the structures I and II for nitromethane and choose the statement correctly :
•• ••–
O O
+ +2
——

—
CH3—N ••–
CH3—N ••–
O O
••
(I) (II)
(A) II is less important because electrons have shifted to oxygen
(B) II is less important because nitrogen has sextet of electrons
(C) II is acceptable and important structure
(D) none of these
5. Examine the following two structures for pyrrole and choose the correct statement given below :

+
•• ••
N N–
O O
(I) (II)
(A) II is not an acceptable resonating structure because carbonium ions is less stable than nitride ion
(B) II is not an acceptable resonating structure because there is charge separation
(C) II is not an acceptable resonating structure because nitrogen has ten valance electrons
(D) II is an acceptable resonating structure
6. Delocalization of electrons increases molecular stability because :
(A) Potential energy of the molecule decreases
(B) Electron-nuclei attraction decreases
(C) Both (A) and (B)
(D) Electron-electron repulsion increases
Comprehension # 2
Carbocation is a group of atoms with positively charged carbon atom having six electrons in the valence
shell after sharing. Carbocations are formed in the heterolysis of a bond and are planar species. Stability of
carbocation is determined by inductive effect, hyperconjugation and resonance effect. Greater the number
of contributing structures, more is the stability of a Carbocation. Electron releasing groups (+I effect) increases
the stability of a carbocation whereas the electron withdrawing groups (–I effect) have an opposite effect.
1. Which of the following is most stable carbocation ?

   +
(A) C H 3 (B) CH 3 — C H — CH 3 (C) CH 3 — C H 2 (D) CH3—C—CH3

CH3
2. The most stable carbocation among the following :

NO2
 
(A) (B) (C) (D) 


3. In which of the following cases, the carbocation (I) is less stable than the carbocation (II) ?

+ +
CH2 CH2
 
(A) C 6 H 5 — C H 2 (I), CH 2 = CH— C H 2 (II) (B) (I), (II)

   
(C) CH 2 = C H (I), CH 3 — C H 2 (II) (D) H 3C— C H 2 (I), CH2— CH2 (II)

 F
 
4. The most stable and the least stable carbocation among (I), CH 2=CH— C H 2 (II), C 6H 5— C H 2 (III)


and CH 3 — C H — CH 3 (IV) are respectively :

(A) II, I (B) III, IV (C) I, II (D) I, IV

5. Most stable carbocation is formed by the heterolysis of :
(A) (CH 3 ) 3 CBr (B) (C 6 H 5) 3 CBr (C) (C 6 H 5) 2 CHBr (D) C 6 H 5CH 2 Br
Comprehension # 3
The most important condition for resonance to occur is that the involved atoms in resonating structure must
be coplanar or nearly coplanar for maximum delocalisation. If this condition does not fulfil, involved orbitals
cannot be parallel to each other and as a consequence delocalisation cannot occcur. Bulky groups present
on adjacent atoms inhibit the of orbitats. This phenomenon is known as steric inhibition of resonance.
Steric inhibition of resonance has profound effect on
(1) Physical properties (2) Acidity and basicity (3) Reactivity of organic compounds
1. Arrange the following in the increasing order of basicity :
NH2
NH2 NH2 NH2

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

NO2
NO2

(A) I > II > III > IV (B) IV > III > II > I (C) II > I > IV > III (D) I > IV > III > II
2. Which of the following is most acidic :

COOH COOH COOH COOH

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

CH3
NO2 CH3
3. Consider the following two structures and choose the correct statements -

:
O + O O + O
N N

(I) (II)
(A) carbon-nitrogen bond length structure I is greater than that in structure II
(B) carbon-nitrogen bond length in structure I is less than in structure II
(C) carbon-nitorogen bond length in both structure is same
(D) It can not be compared
4. Arrange the following carbocation in the increasing order of stability :

  
CH2 CH2 CH2

CH3
CH3–CH CH–CH3
CH3 NO2 CH3 NO2
(I) (II) (III)
(A) I < II < III (B) II < III < I (C) III < II < I (D) III < I < II
Comprehension # 4
1-Butene (A) and 1,3-Butadiene (B) differ not only in the number of  bonds, but (B) also has  and  bonds
at alternate positions. This type of the system is called conjugate system. Following are some of the conjugate
system.

O O
CH2=CH–C–H CH2=CH–C–OH
acrolein acrylic acid benzene
in such systems,  electron shifting takes place consecutively giving permanent polarity on the chain. This
type of -electron shift in the conjugate systems is called mesomeric effect or resonance.
Rule s for re sona nce forms :
(i) Individual resonance forms are imaginary, not real
(ii) Resonance forms differ only in the placement of their  electrons or nonbonding electrons.
(iii) Different resonance forms of a substance don't have to be equivalent.
(iv) Resonance forms must be valid Lewis structures and obey normal rules of valencey.
(v) The resonace hybrid is more stable than any individual resonance.
Rules for stability :
(i) Structures with more covalent bonds are more stable than other structures.
(ii) Structures in which all of the atoms have a complete valence shell of electrons (i.e. the noble gas
structure) are especially stable and make large contribution to the hybrid.
(iii) Stability is decreased by an increase in charge separation.
(iv) Structure that carry negative charge on a more electronegative atom and positive charge on less
electronegative atom are comparatively more stable.
1. In which of the following compound, resonance is not possible :

OH2 O
 
(A) CH 2  CH – N Me 3 (B) (C) (D)
N

:
2. Which of the following statement is incorrect -
(A) In a resonance hybrid all the molecules are the same. A resonance hybrid cannot be expressed by any
single structure.
(B) The value of the resonance energy of any resonance hybrid is not an absolute value
(C) The energy of hybrid structures is always less than that of any resonating structure
(D) Only one individual resonating structure explains all characteristics of the molecule
3. Choose the correct option about stability of resonating structure :

 O O

(A) > (B) <

::

Cl : 
Cl N N


O O 
C O
O O
 
(C) < (D) H–C–O > CH3–C–O

M ISCEL L AN E OU S TYP E Q U ESTION ANSWER KEY E XE R CISE -3

 Tr u e / Fals e
1. F 2. F 3. T 4. F 5. F
 F i ll i n t h e B lanks
1. benzene 2. antiaromatic, aromatic 3. hyperconjucation 4. nucleophile, base
5. 2,3-diphenylbutane (optically inactive, meso)
 Matc h th e C o lu mn
1. (A) p,s ; B q,r ; (C)  q,s ; (D) p,s 2. (A) q ; (B) p ; (C)  p ; (D) r
3. (A) p ; (B) q ; (C)  p ; (D) q
 A s s er ti o n - R eas o n Qu es ti o ns
1. B 2. A 3. A 4. C 5. A
6. C 7. D 8. B 9. D 10. C
 C o mp rehe ns i o n B as ed Qu e st i o ns
C o mp re he ns i o n #1 : 1. (A) 2. (A) 3. (B) 4. (B) 5. (C) 6. (C)
C o mp re he n s i o n #2 : 1. (D) 2. (C) 3. (C) 4. (D) 5. (B)
C o mp re he ns i o n #3 : 1. (C) 2. (B) 3. (B) 4. (B)
C o mp re he ns i o n #4 : 1. (A) 2. (D) 3. (C,D)
EXERCISE–04 [A] CONCEPTUAL SUBJECTIVE EXERCISE

1. Rank the following amines in increasing basic nature :

(a)
N N
NH2 NH2
H
(I) (II) (III) (IV)

NH2 NH2 NH2 CH2NH2

(b)
CH3
CH3 CH3
(I) (II) (III) (IV)
NH2

(c)
N
N
H
(I) (II) (III)
2. Rank the following intermediates according to the stability (most stable first).
   
(a) CH 3 CH 2 CH 2 C H 2 , CH 3 C HCH 2 CH 3 , (CH 3 ) 2 C CH 2 CH 3 , (CH 3 ) 3 C
• • • •
(b) CH 3 CH 2 CH 2 C H 2 , CH 3 C HCH 2 CH 3 , (CH 3 ) 2 C CH 2 CH 3 , (CH 3 ) 3 C

3. Rank the following intermediates according to the stability (most stable first).
— — — —
(a) CH 3 CH 2 CH 2 C H 2 , CH 3 C HCH 2 CH 3 , (CH 3 ) 2 C CH 2 CH 3 , (CH 3 ) 3 C

(b) CH 2 •• , CH 3 CH •• , C 6 H 5 CH •• ,  C 6 H 5 2 C ••

4. Show why the phenolate ion, C 6 H 5O –, has a greater resonance stabilization than phenol, C 6 H 5OH.
5. Is phenol a stronger acid than acetic acid. Explain your answer with proper reasoning.
6. Arrange all these numbered H in order of their decreasing acidic strength.
H
4
O O

H H
1 2

OH
3
 •• ••
7. Between –C=C–F and –C=C-Cl which lone pair- p conjugation will be more preffered.
8. Which is more acidic and why ?

OH OH

9. Arrange the following compound in the correct order of acidity :

COOH SO3H OH
CH2OH
(I) (II) (III) (IV)


10. Why a cation like is not possible.

O
H OH
11. (A) Product.
O


H 3O
12. CH 2=CHCHO + C 2H5MgBr   P ; Here P is :
13. Within each set, select the compound which is more reactive in nucleophilic addition at carbonyl carbon :
(I) CH 3 COCH 2 CH 2 Br or CH 3 COCH 2 Br (II) CH 3 CHO or CH 3 COCH 3
(III) CH 3 COCH 3 or CH 3 –CO–CF 3 (IV) PhCHO or CH 3 CHO
14. Rank of the following compounds in increasing order of electrophilicity :

O CH2 NH
(I) F3C H (II) CH3 H (III) CH3 OH

15. Arrange the followings in increasing order of reactivity towards nucleophile :

O O O O
(A) H3C–C–NH2 ; CH3 –C–Cl ; CH3 –C–OAc; H3C–C–OCH3
(I) (II) (III) (IV)

O O O O
(B) H3C–C–Cl ; CH3CH2 –C–Cl ; (CH3)2CH–C–Cl ; (CH3)3C–C–Cl
(I) (II) (III) (IV)

O O O
(C) CH3 –C–OCH3 ; CH3 –C– OCH2CH3 ; H3C–C–OCH3
(I) (II) (III)
16. Suggest the product of the reactions :

Cl Cl
AlCl3/ AlCl3
(A) CH3–CH2 (B) CH3–C= O

CH3
KOH/Alc. HBr
(C) CH3–C–Cl (D) CH2=CH–CH=CH2 A
40°C
CH3
–80°C
B
O
O–C–CH3 OH
AlCl3 AlCl3
(E) E (F) + CO + HCl G

O

N (CH3)3 C Cl

OH AlCl3
(G) CH3–CH2 –CH–CH3 H (H) O

17. Arrange the following in increasing order of basic character :

(A) Cl  , H 2O, Br  , H 2 S

NH2 NH2 CH3–N–CH3 CH3–N–CH3

CH3 CH3 CH3 CH3
(B) , , ,

NH2 NH2 NH2 NH2

(C) , , ,
F Cl
F Cl

O O
O O
C–O C=O O–H
O C
OH C OH NO2
O
(D) ; ; ;
O–H

18. Heat of hydrogenation of CH 2=CH 2 is greater than CH 3–CH=CH 2. Why ?


N(CH3)3
19. In the case of CH3–CH2–CH–CH3 OH, less stable 1-Butene is obtained. Why ?

20. When carbene attacks cis 2-butene singlet gives cis product while triplet gives trans product. Why ?
CON CEP TUAL SU BJ ECTIVE E X ER CISE ANSWER KEY E XE R CISE -4 (A)

1. (a) I > III > II > IV (b) IV > III > II > I (c) II > I > III
   
2. (a) (CH 3 ) 3 C > (CH 3 ) 2 C CH 2 CH 3 > CH 3 C HCH 2 CH 3 > CH 3 CH 2 CH 2 C H 2

• • • •
(b) (CH 3 ) 3 C > (CH 3 ) 2 C CH 2 CH 3 > CH 3 C HCH 2 CH 3 > CH 3 CH 2 CH 2 C H 2
— — — —
3. (a) CH 3 CH 2 CH 2 C H 2 > CH 3 C HCH 2 CH 3 > (CH 3 ) 2 C CH 2 CH 3 > (CH 3 ) 3 C

(b)  C 6 H 5 2 C •• > C 6 H 5 CH •• > CH 3 CH •• > CH 2 ••

4. Free charge has move reactivity than bound charge.

5. No
Anion of acetic acid is more stabilised by resonance than phenoxide ion.
6. 4 > 3 > 2 >1

••
7. In –C=C–F, lone pair - p conjugation will be more due to more overlaping of orbitals involved in conjugation.

8. Phenol is more acidic as after loss of H+, phenoxide ion is Resonance stabilised. No such resonance is seen
in conjugate base of cyclohexanol.
9. II > I > III > IV
10. Due to the non-planar structure.

O
OH
11. 12. CH2=CH–C–C2H5
H
EXERCISE–04 [B] BRAIN STORMING SUBJECTIVE EXERCISE
1. Rank the following sets of intermediates in increasing order of their stability giving appropriate reasons
for your choice.
• •
(a) •
• CH2, ••C(C6H5)2 , CH3CH•• , C6H5CH•, O2NCH2CH•

+ + +
+ O O O
(b) +
O O O

O O O O
(c) CH2—C—CH3, CH2—C—H, CH2—C—NH2 , CH2—C—CH2—OCH3

2. For the following compounds, arrange the labelled proton in increasing order of their ease of
deprotonation :
1
H
O
3
C C—H 3
H
2
(i) H (ii) CH2
CH2 C

H
1 2 O O
H
3. Benzene sulphonic acid is a stronger acid than benzoic acid, explain.
4. Which is a stronger acid, A or B and why ?

COOH COOH

(I)
NO2 NO2
(A) (B)

H Cl
H Cl O
Cl H O
Cl H
C–OH C–OH
(II)

(A) (B)

5. Descuss the following observations :

(a) C—Cl bond in vinyl chloride is stronger than in chloroethane.
(b) Carbon-carbon bond length in ethene is shorter than in CH 2 = CHOCH 3 .
(c) CH 3SH is stronger acid than CH 3OH.
(d) CH 3CH 2 NH 2 is stronger base than CH 2 =CHNH 2 .
6. Discuss the basic strength of two nitrogens in benzimidazole.
N

N
H
Benzimidazole
7. In each of the following pair of compounds, which is more basic in aqueous solution ? Give an explaination
for your choice :
NH

(i) CH 3 NH 2 or CF 3 NH 2 (ii) CH 3CONH 2 or H2N NH2 (iii) PhNH 2 or CH 3CN

8. Answer the following questions :

(i) Which of the indicated H is abstracted rapidly by bromine radical and why ?
Ph Hc

Hb
Ha
(ii) One of the indicated proton Ha or H b, is approximately 1030 times more acidic than other, which is
more acidic and why ?

H
H
Ha
Hb

9. Explain the following

(i) NC—CH 2 —CN is a stronger acid than CH 3 —CO—C 2 H 5 .

(ii) CH 3 —CO—C 2 H 5 is more acidic than CH 3 —CH=CH 2 .

(iii) CH 3 —CH=CH—OH is more acidic than CH 2 =CH—CH 2 —OH.

10. Compare the bond dissociation energies of C—H bonds in the following

H
(i) H—CH 2 —CH 2 —CH 2 —CH 3 (ii) CH3
(iii) (CH 3 ) 3 C—H
H3C
11. The most stable intermediatry carbocation and major product in following reactions :

H
(i) [C ] Product
OH

(ii) H Product
[C ]
OH

OH
HBr
(iii) O [C ] Product
12. Which one of the following is more basic and why ?

2
N •• CH3 CH3
–N N

••
(a) CH3 (b)
N
••
1
(I) (II)

13. Find the product in following reaction :

Ag
A   

(a) (b) + CH2Cl2 Bu O K B

Br
H

KOH H
(c) + CHCl3 C+ D (d) [E]
••
N
Et Et
H

OD
D
(e) NaOH (i) CO2
[Intermediate] (ii) D
F

14. Write the mechanism of following reaction :

OH
O dil H
(a) + [A]
H HO C5H5

NO2

Me
H Me H–Cl
[A]
(b) –O–O–H [B] (c)
O–H
C2H5
3-Hydroperoxycyclohexene

MeO
Me
O BF3
(d) [B] (e) OTs KI
A+ B
15. Find the major product in the reaction the following :

HNO2 P–Ts–OH
(i) (ii)
 H
HO
HO NH2

OAc

O H HClO4
(iii) (iv) THF
Me H

16. Decreasing order of E.S.R.

O O O H
O NH O N NH O
H–N NH NH

(A) (B) (C)

17. Complete the following equations :

O 
NaOH H3O
(A) H+
O
O

O 
NaOH H3O
+
(B)
CHO
2-equivalent 1-equivalent

NaOH
(C) CHO

18. Suggest the mechanism of the following reaction :

OH
H2SO4 CH3 H
(i) CH3–CH2–CH–CH3 C C
H CH3
trans

CH3 CH2
NaOH
(ii) CH3–C–Br alc.
CH3 –C
CH3 CH3

H OAC
 CH3 CH3
(iii) CH3–CH–CH–CH3 C C
H H
cis
 Br H
–CH –CH2 NaOH –CH= CH2
(iv) alc.

Br H
NaOH Ph H
–CH–CH2–CH3 C= C
(v) alc. H CH3

CH3OH
19. Y H2C—CHCH3 CH3OH X ; Here X and Y respectively are.
CH3ONa H
O

20. COOC2H5 C H ONa

2 5
; the product Z is.
Z
COOC2H5

OH
H3C CH3 14
CH2=CHCH2Cl 200°C
21. P; Here P is.

O
H
22. [X] ; most likely the compound [X] is.

R R
O
O
23. H OH ; the above intermediatory involves.
O
24. Suggest the product of the reactions :
H  

/H N NC
H CHCl3
(A) CH3–CH= CH2 (B) NaOH

CH3 O–H
O O
AlCl3 NaOH
(C) CH3–C–O–C–CH3 + (B) (D) + H–CCl3 C

O 
N2Cl
–C–H NaOH
(E) D (F) F

O2N —— C –CH3
OH H
(G) P (H) NaOH
OH 
Cl N
OH
 BRAIN STOR MIN G SUBJ ECTIVE E X ER CISE ANSWER KEY E XE R CISE -4 (B)

1. (a) O2NCH2CH•• < CH2••< CH3CH•• < C6H5CH••< (C6H5)2 C••

+
(b) + + +
< <
+
O O O O O

O
+

O O O O
(c) CH2—C—NH2 < CH2—C—CH2—OCH3 < CH2—C—CH3 < CH2—C—H

2. (i) 2 < 1 < 3 (ii) 3 < 1 < 2

3. Conjugate base of benzene sulphonic acid has greater resonance stabilization than benzoate ion, hence benzene
sulphonic acid is stronger acid than benzoic acid. PhSO3– has three equivalent resonance structure, so more
stable.but PhCOO – has only two equivalent resonance structure, so less stable.
4. B is stronger base than A. Here basic strength is controlled by –R effect of —NO2. In B, due to steric inhibition
to resonance of —NO 2 by two bulky tertiary butyl group, it is not decreasing basic strenght by —R effect,
hence B is stronger base than Al.
5. (a) Due to resonance in vinyl chloride, C—Cl bond acquire some double bond character while in chloroethane,
C—Cl bond is pure, single sigma covalent bond.
(b) Due to resonance in methyl vinyl ether, bond order of C—C is slightly reduced from two while in ethene
C—C bond order is exactly 2.
(c) Larger size of sulphur compared to oxygen gives greater acidity to CH 3 SH.
(d) Lone-pair of electron in vinyl amine is involved partly in resonance delocalization and less avaiable for donation
to a lewis acid, hence a weaker Lewis base.
:
N Basic
6. Lone pair of the basic nitorgen is fully available with
:

nitrogen, i.e. not involved in delocalization while lone pair N Non-basic

of non-basic nitrogen is part of aromatic delocalization. H
Benzimidazole
7. (i) CH 3NH 2, (ii) H2N—C—NH2 (iii) PhNH 2

NH
8. (i) H c > H a > H b (ii) H a : Conjugate base is aromatic

9. Acidic strength  stability of anion formed after removal of H +  number of e – withdrawing groups.

10. III > II > I

1
B.D.E. 
stability of intermediate formed

19. X : HOCH2 – CHCH3 and Y : CH2 – CHCH3

OCH3 OCH3 OH
 OH
H3C CH3
O
20. 21.
COOC2H5 14
CH2CH=CH2
OH
O
22. 23. H

R O
R
EXERCISE–05(A) PREVIOUS YEARS QUESTIONS

1. In the following benzyl/allyl system

R–CH=CH 2 or R [AIEEE 2002]

(R is alkyl group)
decreasing order of inductive effect is-
(1) (CH 3 ) 3 C– > (CH 3 ) 2 CH– > CH 3 CH 2 –
(2) CH 3 –CH 2 – > (CH 3 ) 2 CH– > (CH 3 ) 3C–
(3) (CH 3 ) 2 CH– > CH 3 CH 2 – > (CH 3 ) 3 CH–
(4) None of these
2. In the anion HCOO– the two carbon-oxygen bonds are found to be of equal length. What is the reason
for it- [AIEEE 2003]
(1) Electronic orbits of carbon atoms are hybridised
(2) The C=O bond is weaker than the C–O bond
(3) The anion HCOO – has two resonating structure
(4) The anion is obtained by removal of a proton form the acid molecule
3. The correct order of increasing basic nature for the bases NH 3, CH 3NH 2 and (CH 3) 2NH is-[AIEEE 2003]
(1) CH 3 NH 2 < NH 3 < (CH 3 ) 2 NH
(2) (CH 3 ) 2 NH < NH 3 < CH 3 NH 2
(3) NH 3 < CH 3 NH 2 < (CH 3 ) 2 NH
(4) CH 3 NH 2 < (CH 3 ) 2 NH < NH
4. Consider the acidity of the carboxylic acids- [AIEEE 2004]
(i) PhCOOH (ii) o–NO 2 C 6 H 4 COOH
(iii) p-NO 2 C 6H 4 COOH (iv) m-NO 2 C 6 H 4 COOH
which of the following order is correct for acidic strength-
(1) i > ii > iii > iv (2) ii > iv > iii > i
(3) ii > iv > i > iii (4) ii > iii > iv > i
5. Which of the following is the strongest base- [AIEEE 2004]

(1) NH2 (2) NHCH3 (3) NH2 (4) CH2NH2

CH3
O O
6. Rate of the reaction R–C + Nu R–C + Z is fastest when Z is [AIEEE 2004]
Z Nu

(1) OCOCH 3 (2) NH 2

(3) OC 2H 5 (4) Cl
2
7. Which one of the following does not have sp hybridised carbon [AIEEE 2004]
(1) Acetamide (2) Acetic acid
(3) Acetonitrile (4) Acetone
8. Due to the presence of an unpaired electron, free radicals are [AIEEE-2005]
(1) Chemically inactive (2) Chemically reactive
(3) Cations (4) Anions
9. The decreasing order of nucleophilicity among the nucleophiles [AIEEE-2005]

(a) CH3–C–O— (b) CH 3 O – (c) CN– (d) H3C S O–is

O O

(1) (d) , (c), (b), (a) (2) (a), (b), (c), (d)
(3) (c), (b), (a), (d) (4) (b), (c), (a), (d)

10. Tertiary alkyl halides are practically inert to substitution by SN 2 mechanism because of [AIEEE-2005]

(1) unstability (2) insolubility

(3) steric hinderance (4) inductive effect
11. Among the following acids which has the lowest pk a value- [AIEEE-2005]
(1) CH 3 CH 2 COOH (2) (CH 3 ) 2 CHCOOH
(3) HCOOH (4) CH 3 COOH
12. Amongest the following the most basic compound is- [AIEEE-2005]
(1) p-nitro aniline (2) Acetanilide
(3) Aniline (4) Benzylamine
13. The increasing order of the rate of HCN addition to compounds A–D is [AIEEE-2006]
(A) HCHO (B) CH 3 COCH 3
(C) PhCOCH 3 (D) PhCOPh
(1) D < B < C < A (2) D < C < B < A
(3) C < D < B < A (4) A < B < C < D
14. The increasing order of stability of the following free radicals is [AIEEE-2006]

   
(1) (C 6 H 5 )3 C  (C 6 H 5 )2 C H  (CH 3 )3 C  (CH 3 )2 C H

   
(2) (C 6 H 5 )2 C H  (C 6 H 5 )3 C  (CH 3 )3 C  (CH 3 )2 C H

   
(3) (CH 3 )2 C H  (CH 3 )3 C  (C 6 H 5 )3 C  (C 6 H 5 )2 C H

   
(4) (CH 3 )2 C H  (CH 3 )3 C  (C 6 H 5 )2 C H  (C 6 H 5 )3 C

15. CH 3 Br + Nu –  CH 3 – Nu + Br –
The decreasing order of the rate of the above reaction with nucleophiles (Nu – ) A to D is [ A I E E E - 2 0 0 6 ]
[Nu – = (A) PhO – , (B) AcO –, (C) HO –, (D) CH 3O – ]
(1) D > C > B > A (2) A > B > C > D
(3) B > D > C > A (4) D > C > A > B
16. The correct order of increasing acid strength of the compounds is [AIEEE-2006]
(a) CH 3 CO 2 H (b) MeOCH 2 CO 2 H

Me
(c) CF 3 CO 2 H (d) CO2 H
Me
(1) d < a < c < b (2) d < a < b < c
(3) a < d < c < b (4) b < d < a < c
 OH
— +
O Na
17. + CHCl 3 + NaOH  
CHO

The electrophile involved in the above reaction is [AIEEE-2006]

(1) dichlorocarbene ( :CCl 2 )

(2) trichloromethyl anion (C Cl 3 )

(3) formyl cation (C HO)

(4) dichloromethyl cation (C HCl 2 )
18. Which one of the following is the strongest base in aqueous solution ? [AIEEE-2007]
(1) Trimethylamine (2) Aniline
(3) Dimethylamine (4) Methylamine

19. T he electrophile, E at tacks the benzene ri ng to generate the i ntermediate  –complex. Of thee
following, which  –complex is of lowest energy? [AIEEE-2008]

NO2 NO2 NO2

H
H
(1) + (2) + E (3) + (4) + H
E
E
H E

20. Arrange the carbanions, (CH 3 ) 3 C , CCl 3 , (CH 3 ) 2 CH , C 6 H 5 CH 2 , in order of their decreasing stability :-

(1) CCl 3  C 6 H 5 CH 2  (CH 3 )2 CH  (CH 3 ) 3 C [AIEEE-2009]

(2) (CH 3 ) 3 C  (CH 3 )2 CH  C 6 H 5 CH 2  CCl 3

(3) C 6 H 5 CH 2  CCl 3   CH 3 3 C  (CH 3 )2 CH

(4)  CH 3 2 CH  CCl 3  C 6 H 5 CH 2   CH 3 3 C
21. The correct order of increasing basicity of the given conjugate base (R=CH 3 ) is :- [ AI E E E- 2 0 10 ]

(1) RCOO < HC  C < NH 2 < R

(2) RCOO < HC  C < R < NH 2

(3) R < HC  C < RCOO < NH 2

(4) RCOO < NH 2 < HC  C < R

22. The strongest acid amongst the following compounds is ? [ AI E E E- 2 0 11 ]

(1) CH 3 CH 2 CH(Cl)CO 2 H
(2) ClCH 2 CH 2 CH 2 COOH
(3) CH 3 COOH
(4) HCOOH
23. Ortho-Nitrophenol is less soluble in water than p– and m– Nitrophenols because :- [ AI E E E- 2 0 12 ]
(1) Melting point of o–Nitrophenol is lower than those of m– and p– isomers
(2) o–Nitrophenol is more volatile in steam than those of m– and p– isomers
(3) o–Nitrophenol shows Intramolecular H–bonding
(4) o–Nitrophenol shows Intermolecular H–bonding
24. Which of the following compounds are antiaromatic :- [AIEEE-2012(Onli ne)]

(I) .. (II) (III)

O
..

(IV) (V) (VI)

– +

(1) (III) and (VI) (2) (II) and (V)

(3) (I) and (V) (4) (V) and (VI)
25. In the following compounds : [AIEEE-2012(Onli ne)]

O
(I) (II) (III) (IV)
N N N N
H H H
the order of basicity is as follows :
(1) IV > III > II > I (2) II > III > I > IV
(3) I > III > II > IV (4) III > I > II > IV
26. Dipole moment is shown by :- [AIEEE-2012(Online)]
(1) trans-2, 3-dichloro- 2-butene (2) 1, 2-dichlorobenzene
(3) 1, 4-dichlorobenzene (4) trans-1, 2-dinitroethene
27. Among the following chloro-compound having the lowest dipole moment is :- [AIEEE-2012(Online)]

Cl Cl Cl H
(1) CH 2 Cl 2 (2) CH 3 Cl (3) C=C (4) C=C
H 3C H H 3C Cl

28. In the below mentioned compounds the decreasing order of reactivity towards electrophilic substitution
is : [AIEEE-2012(Online)]

OCH3 CH3 CF3

(i) (ii) (iii) (iv)

(1) (iii) > (i) > (iv) > (ii) (2) (iv) > (i) > (ii) > (iii)
(3) (ii) > (iii) > (i) > (iv) (4) (i) > (ii) > (iii) > (iv)
29. Among the following the molecule with the lowest dipole moment is :- [AIEEE-2012(Online)]
(1) CHCl 3 (2) CH 2 Cl 2
(3) CCl 4 (4) CH 3 Cl
30. The most basic compound among the following is :- [AIEEE-2012(Online)]
(1) Acetanilide (2) Benzylamine
(3) p-Nitro aniline (4) Aniline
31. Among the following the order of reactivity toward nucleophilic addition is :-[ A I E E E - 2 0 1 2 ( O n l i n e ) ]
(1) HCHO > CH 3 CHO > CH 3 COCH 3
(2) CH 3 CHO > HCHO > CH 3 COCH 3
(3) CH 3 CHO > CH 3 COCH 3 > HCHO
(4) CH 3 COCH 3 > CH 3 CHO > HCHO
32. The order of stability of the following carbocations:

+
CH2
+ +
CH2=CH–CH2 ; CH3–CH2–CH2 ; is :- [JEE(MAIN)-2013]
I II
III

(1) III > II > I (2) II > III > I (3) I > II > III (4) III > I > II
33. Arrange the following compounds in order of decreasing acidity : [JEE(MAIN)-2013]

OH OH OH OH

; ; ;

Cl CH3 NO2 OCH3

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

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

PREVIOUS YEAR QUESTIONS ANSWER KEY EXERCISE-05(A)

Q u e. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans 1 3 3 4 4 4 3 2 4 3 3 4 2 4 4
Q u e. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Ans 2 1 3 2 1 1 1 3 4 3 2 1 4 3 2
Q u e. 31 32 33
Ans 1 4 3
EXERCISE–05(B) PREVIOUS YEARS QUESTIONS

1. Which one of the following has the smallest heat of hydrogenation per mole ? [IIT-93]
(A) 1–Butene (B) trans–2–Butene
(C) cis–2–Butene (D) 1, 3–Butadiene

2. What is the decreasing order of strength of bases OH, NH , HCC, CH –CH [IIT-93]
2 3 2

(A) CH3–CH2 > NH2 > HCC > OH (B) HCC > CH3–CH2 > NH2 > OH

(C) OH > NH2 > HCC > CH3–CH2 (D) NH2 > HCC > OH > CH3–CH2

3. In the following compounds [IIT-96]

OH OH OH OH

NO2
CH3 NO2
I II III IV

The order of acidity is -

(A) III > IV > I > II (B) I > IV > III > II
(C) II > I > III > IV (D) IV > III > I > II

4. The formation of cyanohydrin from a ketone is an examples of - [IIT-98]

(A) Electrophilic addition (B) Nucleophilic addition
(C) Nucleophilic substitution (D) Electrophilic substitution
5. The most unlikely representation of resonance structure of p-nitrophenoxide ion is - [IIT-99]

  
 O=N=O O–N=O
O–N=O O–N–O

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

O O O
O

6. An aromatic molecule will not [IIT-99]

(A) have 4n  electrons (B) have (4n + 2) electrons
(C) be planar (D) be cyclic
7. Amongst the following, the most basic compound is - [IIT-2000]
(A) C 6 H 5NH 2 (B) p–NO 2 –C 6 H 4 NH 2
(C) m–NO 2 –C 6 H 4 NH 2 (D) C 6 H 5 CH 2 NH 2
8. Which of the following alkenes will react fastest with H 2 under catalytic hydrogenation conditions
[IIT-2001]

R R R H R R R R

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

H H R H R H R R

9. The correct order of basicities of the following compounds is : [IIT-2001]

NH O
CH3–C CH3CH2NH2 (CH3)2NH CH3CNH2
NH2 , , ,
1 2 3 4

(A) 2 > 1 > 3 > 4 (B) 1 > 3 > 2 > 4 (C) 3 > 1 > 2 > 4 (D) 1 > 2 > 3 > 4
10. Which of the following is least stable : [IIT -2005]

 
(A) CH3–O=CH–CH–HC=CH2 (B) CH3–O=CH–CH=HC–CH2

 
(C) CH3–O–CH–CH–HC=CH2 (D) CH3–O–CH=CH–HC–CH2

11. Among the following, the least stable resonance structure is - [IIT -2007]


 O  O
(A) N (B)  N

O O

 O  O
(C)  N (D)  N

O O

12. The major product of the following reaction is : [IIT-2008]

Me Br

F PhS Na
dimethylformamide

NO2

Me SPh Me SPh Me Br Me SPh

F F SPh SPh
(A) (B) (C) (D)

NO2 NO2 NO2 NO2

13. The correct stability order for the following species is : [IIT-2008]

  
O O 

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

(A) II > IV > I > III (B) I > II > III > IV (C) II > I > IV > III (D) I > III > II > IV
14. Statement-I : p-Hydroxybenzoic acid has a lower boiling point that o-hydroxybenzoic acid.
Because
Statement-II : o-Hydroxybenzoic acid has intramolecular hydrogen bonding. [IIT 2003]
(A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I
(B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I
(C) Statement-I is True, Statement-II is False.
(D) Statement-I is False, Statement-II is True.
15. Statement-I : Bromobenzene upon reaction with Br 2/Fe gives 1, 4-dibromobenzene as the major product.
Because
Statement-II : In bromobenzene, the inductive effect of the bromo group is more dominant than the mesomeric
effect in directing the incoming electrophile. [IIT 2008]
(A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I
(B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I
(C) Statement-I is True, Statement-II is False.
(D) Statement-I is False, Statement-II is True.
16. Out of anhydrous AlCl3 and hydrous AlCl3 which is more suluble in diethyl ether ? Explain with reason.
[IIT 2003]
17. Match Ka values with suitable acid : [IIT 2003]
Ka Acid

(A) 3.3 × 105 (p) —COOH

(B) 4.2 × 10–5 (q) Me— —COOH

(C) 6.3 × 10–5 (r) Cl— —COOH

(D) 6.4 × 10–5 (s) MeO— —COOH

(E) 30.6 × 10 –5 (t) O2N— —COOH

18. Give resonating structures of following compound. [IIT 2003]

OH

19. Which of the following is more acidic and why ? [IIT 2004]

 
NH3 NH3

F
(I) (II)

20. The compound that does NOT liberate CO 2 , on treatment with aqueous sodium bicarbonate
solution, is - [JEE ADVANCED 2013]
(A) Benzoic acid (B) Benzenesulphonic acid
(C) Salicylic acid (D) Carbolic acid (phenol)
21. The hyperconjugative stbilities of tert-butyl cation and 2-butene, respectively, are due to
(A) p (empty) and * electron delocalisations [JEE ADVANCED 2013]

(B) * and  electron delocalisations

(C) p (filled) and  electron delocalisations
(D) p (filled)* and * electron delocalisations
22. The total number of lone-pairs of electrons in melamine is [JEE ADVANCED 2013]

P RE VIOU S Y EARS QU E STION S ANSWER KEY E XE R CISE -5 (B)

1. (D) 2. (A) 3. (D) 4.(B) 5. (C) 6. (A) 7.(D) 8. (A)

9. (B) 10. (D) 11. (A) 12. (A) 13. (D) 14. (D) 15. (C)
16. A nhydrous AlCl3 is more soluble.
17. A-(s) ; B-(q) ; C-(p) ; D-(r) ; E-(t) ;
19. II is more acidic. 20. (D) 21. (A) 22. (6)