Carbocations and Carbanions- MCQ

Dr.A.SHUNMUGASUNDARAM
Head, Department of Chemistry (Retd.)
VHNSN College,
Virudhunagar.

Carbocations :

A carbocation is a positively charged carbon species in which the carbon atom has six electrons
in its valence shell.
The state of hybridization of a carbocation is sp².
The geometry of a carbocation is trigonal planar.
The bond angle between the three substituents is 120°.
Carbocations act as electrophiles and Lewis acids

Stability of Carbocations :

1. Inductive Effect :
Electron-releasing (+I) groups increase the stability of the carbocation.
Electron-withdrawing (-I) groups destabilise the carbocation.

2. Resonance Effect :
The +M effect (electron-donating resonance effect) of substituents increases stability.
The -M effect (electron-withdrawing resonance effect) decreases stability.

3. Hyperconjugation :
Overlap of adjacent C-H sigma electrons with the empty p-orbital of the carbocation stabilises it.

4. Aromaticity:
If the positive charge is part of an aromatic system with (4n+2) π electrons, the carbocation is
stabilised.

Reactions Involving Carbocations :

1. SN1 Reactions
Examples: Hydrolysis of alkyl halides.
Solvolysis of alkyl halides in polar protic solvents

2. Electrophilic Addition Reactions

Examples: Addition of HBr to alkenes.
Addition of bromine to alkene
3. Electrophilic Aromatic Substitution Reactions
Examples: Nitration
Friedel-Crafts reaction
Halogenation

4. Rearrangement Reactions
Examples: Wagner-Meerwein rearrangement
Pinacol-Pinacolone rearrangement

5. E1 Elimination Reactions
Examples: Dehydrohalogenation of alkyl halides in the presence of alcoholic KOH
Acid catalised dehydration of alcohol

Carbanions

A carbanion is a negatively charged carbon species in which the carbon atom has an extra pair
of electrons.
The state of hybridization of a carbanion is sp³.
The geometry of a carbanion is trigonal pyramidal.
Carbanions are conjugate bases of carbon acids.
Carbanions act as nucleophiles and bases.

Stability of Carbanions :

1. Inductive Effect:
The +I effect of substituents decreases stability.
The -I effect of substituents increases stability.

2. Resonance Effect:
Resonance stabilises carbanions. More resonance structures of carbanion can stabilise it.

3. Aromaticity:
If the negative charge is part of an aromatic system, the carbanion is stabilised.

4. Hybridization:
Greater the s-character of the negatively charged atom, the more stable the carbanion:
sp > sp² > sp³
Reactions Involving Carbanions :

1. Nucleophilic Substitution Reactions

Examples : Grignard reactions with alkyl halides
Reaction of enolates with alkyl halides

2. Addition Reactions
Examples: Aldol condensation
Michael addition
Grignard addition to carbonyl compounds

3. E1cB Elimination Reactions

Examples: Aldol condensation
Elimination of alkenyl halides to give alkynes

4. Rearrangement Reactions
Examples: Favorskii rearrangement.
Benzilic acid rearrangement
[1,2]-Wittig rearrangement

MULTIPLE CHOICE QUESTIONS

1. The shape of carbocations is

1) tetrahedral 2) trigonal planar
3) pyramidal 4) linear

2. Which among the following factors influence the stability of carbocations?

a) Hyperconjugation b) Inductive effect
c) Mesomeric effect d) van der Waals forces

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

3. Which of the following statements is false?

1) Electron withdrawing groups destabilise the carbocations.
2) The stability of the carbocations is in the order tertiary> secondary> primary
3) Mesomeric effect increases the stability of carbocations.
4) More s-character on the carbon of the carbocation increases its stability
4. The nature of hybridisation in ethyl carbocation is
1) sp3
2) sp2
3) sp
4) dsp2

5. Which of the following statements about the reactions of carbocation is not true?
1) Carbocation can react with a nucleophile to give SN2 product
2) Carbocation can lose a proton to give E1 product
3) Carbocation can react with an unsaturated compound to give addition product
4) Carbocation can undergo rearrangement to give another carbocation

6. Which among the following statements about carbocations is not true?

1) The positive charge is localised on the carbon in the absence of conjugation.
2) The positive charge is delocalised by resonance involving lone pair of electrons.
3) The positive charge is delocalised by a double or triple bond in the allylic position.
4) The positive charge at bridgehead position of smaller bicyclic compounds is stabilised
more than a normal tertiary carbocation.

7. The stability of the carbocations of alkyl groups is in the order

1) primary > secondary > tertiary
2) secondary > primary > tertiary
3) tertiary > secondary > primary
4) tertiary > primary > secondary

8. The order of stability of the following carbocations is

+ + + +
i) CH3 ii) CH3CH2 iii) (CH3)2-CH iv) (CH3)3C

1) I > ii > iii > iv 2) iv > iii > ii > i

3) ii > I > iv > iii 4) iv > iii > I > ii

9. The order of stability of the following carbocations is

+ + +
i) CH2ClCH2 ii) CHCl2CH2 iii) CCl3-CH2

1) I > ii > iii 2) ii > iii > i

3) iii > ii > i 4) iii > I > ii
10. The order of stability of the following carbocations is

1) A > B > D > C 2) C > B > A > D

3) C > A > B > D 4) D > B > C > A

11. The order of stability of carbocations for the following is

1) D > C > B > A 2) A > B > C > D

3) B > A > D > C 4) C > B > D > A

12. The correct order of stability of the following carbocations is

1) D > A > B > C 2) C > A > D > B

3) A > D > C > B 4) D > B > A > C
13. The least and most stable carbocations in the following are respectively

1) D and A 2) B and C 3) C and A 4) D and B

14. Which of the following carbocations is most stable?

15. Among the following carbocations the least stable carbocation is

16. The most stable carbocation in the following is

17. The stability of the following carbocations is in the order

1) C > B > A 2) B > A > C

3) A > B > C 4) A > C > B
18. In the following pairs of carbocations, the least stable carbocations in the pairs are
respectively

1) A’ and B 2) A and B’ 3) A and B 4) A! and B’

19. The stability of the following carbocations is in the order

1) A > B > C 2) C > B > A

3) B > A > C 4) C > A > B
20. In which of the following pairs of carbocations, B ion is less stable than A?
A B

1) i and ii 2) ii and iii 3) i and iii 4) iii and iv

21. Arrange the following carbocations in the decreasing order of stability.

1) A > B > C > D 2) D > C > B > A

3) B > A > C > D 4) C > D > A > B

22. Which of the following statements are true with respect to electronic effect in the stability
of carbocations?
i) The carbocations of cyclic rings with the least angular strain are more stable.
ii) bicyclic systems of smaller rings can not have positive charge at the bridgehead
position.
iii) When the s-character of carbon is more the stability of the carbocation is more.
iv) The +I effect of the substituents destabilises the carbocation.

1) i and ii 2) iii and iv 3) i and iii 4) ii and iv

23. Among the following pairs of ions, which ion is more stable in each pair of ions than the
other?

1) i) A > B ii) A’ > B’ iii) A’’ > B’’

2) i) A > B ii) B’ > A’ iii) A’’ > B’’
3) i) B > A ii) B’ > A’ iii) B’’ > A’’
4) i) B > A ii) A’ > B’ iii) B’’ > A’’

24. In the following pair of carbocations A and B

which of the following statements is true?

1) Both A and B are equally stable.
2) A is more stable than B.
3) B is more stable than A.
4) There is no resonance stabilisation in both A and B.
25. Which carbocation is more stable in each of the following pairs ?

1) A > B and A’ > B’

2) B > A and A’ > B’
3) A > B and B’ > A’
4) B > A and B’ > A’

26. In the following pairs of ions

Assertion: A is more stable than B.

Reason: A is a tertiary carbocation and is therefore more stable than B.

1) Both the assertion and reason are true

2) The assertion is correct and the reason is not true
3) The assertion and reason are true but reason is not the explanation of assertion
4) Both the assertion and reason are false
27. Which among the following is the most stable carbocation and least stable carbocation?

1) D and A 2) B and C 3) D and C 4) B and A

28. The order of stability of the following carbocations is

1) C > B > A 2) A > B > C 3) B > A > C 4) C > A > B

29. The stability of the following carbocations is in the order

1) A > B > C 2) B > C > A 3) A > C > B 4) C > A > B

30. Carbocation intermediate is not involved in one of the following reactions?

1) Nucleophilic substitution by SN1 mechanism
2) Elimination reaction by E2 mechanism
3) Addition of HX molecule or H3O+ ion to alkene
4) Wagner- Meerwein rearrangement reaction
31. Which of the following reaction(s) does/do not involve the formation of carbocation?

1) iii 2) i 3) i and ii 4) i and iii

32. Major product of the following reaction is

33. The major product formed in the reaction of 2,2-dimethyl- 1- propanol with concentrated
HBr is

34. Statement 1: Neopentyl alcohol on reaction with conc. H2SO4 gives 2-methylbut-2-ene
as the major product
Statement 2: In this reaction carbocation is formed as an intermediate

1) The statements 1 and 2 are false

2) The statements 1 and 2 are true
3) The statement 1 is true and 2 is false
4) The statement 1 is false and 2 is true

35. The order of stability of the following carbocations is

1) A > B > C > D 2) A > B > D > C

3) B > A > C > D 4) C > D > B > A

36. The carbocation which does not have trigonal planar structure is
37. Assertion: In the addition of HBr to the following alkene R CH =CH2 , the electrophile H+
attacks C1 rather than C2.
Reason: Addition of H+ to C1 gives a more stable carbocation intermediate.

1) Assertion is true and reason is false

2) Assertion is false and reason is true
3) Both assertion and reason are true
4) Both assertion and reason are false

38. In which of the following carbocations, nonclassical carbocation formation is not

possible?

39. The order of stability of the following carbocations is

1) A > C > B > D 2) C > B= D > A

3) B > D > A > C 4) D= B > C > A

40. The order of rate of solvolysis in 80% ethanol at 25OC is

1) A > B > C 2) B > C > A

3) A > C > B 4) C > B > A
41. The reaction of (S)-3-bromo-3-methylhexane and water proceeds through the formation
of carbocation and gives
1) (R)-3-methyl-3-hexanol
2) (S)-3-methyl-3-hexanol
3) Racemic mixture of both R and S-3-methyl-3-hexanol
4) A 75:25 mixture of both R and S-3-methyl-3-hexanol

42. The product of the following reaction which proceeds via the formation of carbocation
intermediate, is

43. The rate of solvolysis of the following compounds (X = tosyl group) is in the order

1) A > B > C
2) B > A > C
3) C > A> B
4) A > C> B
44. The major product formed in the following reaction is

45. The carbanion, CH3 - has the shape

1) bent 2) trigonal planar 3) tetrahedral 4) trigonal pyramidal

-
46. The state of hybridisation of a carbanion R3C is
1) sp3
2) sp2
3) sp
4) dsp2

47. Which of the following statements about carbanions is not true?

1) They are good nucleophiles
2) They are Lewis bases
3) They are the conjugate acids of bases
4) They are stabilized by resonance

48. Which of the following reactions does not give carbanion intermediate?
1) Decarboxylation of carboxylate ion
2) Nucleophile attacking an alkene
3) Reaction of organohalide with lithium metal
4) Dehydration of alcohols in the presence of acid

49. The factors which influence the stability of carbanion are

i) Type of hybridization ii) Resonance
iii) Inductive effect iv) van der Waals force

1) i, ii and iv 2) ii, iii and iv 3) ii and iii 4) i, ii and iii

50. Which of the following statements about the stability of carbanion is not true?
1) Electron withdrawing inductive effect destabilizes the carbanions.
2) An increase in the number of resonance structures increases the stability of
carbanion.
3) The stability is directly proportional to the s-character of the orbitals involved in the
bond.
4) Greater the number of alkyl groups, lesser will be the stability of carbanion.

51. The order of stability of the following carbanions is

52. Arrange the following compounds in the order of stability.

1) A > B > C 2) B > A > C 3) C > B > A 4) A > C > B

53. The order stability of the following carbanions is

54. Arrange the following carbanions in the order of stability.

55. The order of stability of the following carbanions is

1) A > B > C > D 2) B > A > C > D

3) A > B > D > C 4) C > D > B > A
56. In the following the most stable and least stable carbanions are

1) A and D 3) B and C
2) C and A 4) A and C

57. Compare the stability of the following pairs of anions. In each pair identify which ion is
more stable.

1) A> B ; A1 > B1 ; A2 > B2

2) A > B ; B1 > A1 ; A2 > B2
3) B > A ; B1 > A1 ; A2 > B2
4) B > A ; A1 > B1 ; B2 > A2
58. Arrange the following in the decreasing order of stability.

1) C > B>A
2) A > C>B
3) B > A>C
4) C > A>B

59. The correct order of acidity of the following compounds is

1) A > B > C
2) B > C > A
3) C > A > B
4) B > A > C

60. The order of formation of carbanion of the following compounds is

1) A > B > C
2) C > B > A
3) B > A > C
4) A > C > B
61. Assertion: Carbanion A is more stable than B

Reason: Carbanion A is stabilised more than B because of resonance.

1) Both assertion and reason are false.

2) Both assertion and reason are true.
3) Assertion is true and reason is false.
4) Assertion is false and reason is true.

62. Among the following the most stable and least stable carbanions are

1) B and A
2) C and D
3) D and B
4) A and C

63. Least stable carbanion among the following is

64. The order of stability of the carbanions is

1) C > B > D > A

2) A > D > C > B
3) C > B > A > D
4) A > C > B > D

65. The decreasing order of stability of the following carbanions is

1) A > B > C
2) B > A > C
3) C > A > B
4) A > C > B

66. The most stable carbanion formed in the reaction of the following with OH- ion is
67. Arrange the following in the order of decreasing tendency to form carbanion with base

1) A > D > B > C

2) D > B > C > A
3) C > B > D > A
4) A > C > B > D

68. The decreasing order of stability of the following carbanion is

1) A > B > C > D

2) D > A > B > C
3) A > B > D > C
4) B > A > D > C

69. Which one of the following compounds does not undergo deprotonation easily to form
carbanion?

70. Which of the following reactions does not involve the formation of carbanion?

1) Aldol condensation
2) Pinacol- pinacolone rearrangement
3) Perkin reaction
4) Claisen condensation
71. The intermediate A and the major product B in the following conversion are

OH-
CH3CHO —--------> A —---------> B

1) A is a carbocation and B is CH3 CHOH CH2 CHO

2) A is a carbocation and B is CH3 CH2 COO CH3
3) A is a carbanion and B is CH3 CHOH CH2 CHO
4) A is a carbanion and B is CH3 COO CH2CH3

72. The major product of the following reaction is

73. The intermediate A and the major product B in the following reaction are

74. Match the following reactions involving carbanion intermediate

1) i- c ; ii- b ; iii- d ; iv- a

2) i- c ; ii- a ; iii- d ; iv- b
3) i- a ; ii- d ; iii- b ; iv- c
4) i- b ; ii- c ; iii- a ; iv- d
75. Applying Huckel’s rule

1) A and C are aromatic and B is anti-aromatic

2) A and C are anti-aromatic and B is aromatic
3) A, B and C are all aromatic
4) A, B and C are all anti-aromatic

76. Which of the following ion(s) is/ are destabilised based on Bredt’s rule?

1) only A
2) only C
3) A and C
4) B and C

77. Statement 1: Bridgehead carbocation of smaller ring systems is less stable than
bridgehead carbanion.
Statement 2: Bridgehead C atom in carbocation is sp2 hybridised and not be planar at
the bridgehead.

1) Statements 1 and 2 are false

2) Statements 1 and 2 are true
3) Statement 1 is true and statement 2 is false
4) Statement 1 is false and statement 2 is true
78. Match the pKa values of some carbon acids with their corresponding conjugate bases.

pKa Conjugate bases (carbanions)

i 44 A. (CH3CO)2 C̅H

ii 13.3 B. C̅H3

iii 6 C. C̅H(NO2)2

iv 4 D. C̅H(COOEt)2

1) i- B ; ii- A ; iii- D ; iv- C

2) i- A ; ii- D ; iii- C ; iv- B
3) i- C ; ii- A ; iii- D ; iv- B
4) i- B ; ii- D ; iii- A ; iv- C

79. The correct match of carbanion involved ( A ) and the major product B in the following
Reimer-Tiemann reaction is
80. Statement 1: Carbanions undergo rapid interconversion between two pyramidal
structures when the energy barrier is low.

Statement 2: Trifluoromethyl carbanion does not easily undergo interconversion because

of its stability and high energy barrier.

1) Statement 1 is true and statement 2 is false.

2) Statement 2 is true and statement 1 is false.
3) Both statements 1 and 2 are true.
4) Both statements 1 and 2 are false.
 Answer Key

1 2 41 3
2 3 42 3
3 4 43 1
4 2 44 4
5 1 45 4
6 4 46 1
7 3 47 3
8 2 48 4
9 1 49 4
10 2 50 1
11 1 51 3
12 2 52 2
13 1 53 1
14 3 54 2
15 4 55 3
16 2 56 1
17 3 57 2
18 4 58 1
19 2 59 2
20 3 60 1
21 1 61 1
22 1 62 4
23 2 63 3
24 2 64 1
25 3 65 1
26 4 66 2
27 1 67 4
28 2 68 3
29 3 69 4
30 2 70 2
31 1 71 3
32 2 72 1
33 1 73 2
34 2 74 1
35 1 75 3
36 2 76 1
37 3 77 2
38 1 78 4
39 4 79 1
40 3 80 3