ORGANIC CHEMISTRY

DPP Topic - Carbanion,Free Radical,

TARGET
JEE/NEET
DAILY PRACTICE PROBLEMS Carbene, Nitrene,Benzyne

Subjective Questions
Direction : These questionss are subjective in nature, need to be solved completely on notebook.

1. Order the following carbanions in increasing stability.

2. Arrange the following in increasing order of acidic strength for the most acidic hydrogen.
O O
|| ||
i. — — ii. — — —

O O O O
|| || || ||
iii. — — — — iv. — — — —

3. C—H H homolytic bond fission gives free radi

radical
cal intermediate. Considering homolytic
ho
fission of all C—HH bond, one at a time, compare the relative stability of free radicals
formed from the following.

4. Carbene (: )is
is a reactive intermediate that exist in two structural form, in one form, it
is linear and paramagnetic while in other form, it is angular and diamagnetic, explain.

5. Predict
ct whether the equilibrium constants of the following reactions are less than or
greater than unity?
 i. ℎ + ⇋ ℎ +

ii.

iii.
iv. + ⇋ +
· ·
v. — = — + — ⇋ — = — + —

6. Arrange the following carbanions in increasing order of stability -

(A) CH3, CH3 – CH2,
(I) (II)
 
CH3 – CH – CH3, CH3 – C–CH3
CH3
(III) (IV)
Cl

(B) CH3 –CH2, CH2 –CH2
(I) (II)
Cl Cl
 
Cl–CH–CH2 Cl–C–CH2
Cl
(III) (IV)

(C) CH3 , CH3–CH2,

(I) (II)

CH2 = CH , CHC
(III) (IV)
(D) CCl3 – CH2 , NO2 –CH = CH – CH2,


(I) (II)

CH2

CH–CH3

NO2
(III) (IV)

7. Suggest the hybridisation of the following arrow headed carbanions.

 
CH2

(A) CH3–CH2 (B) CCl3–CH2 CH2

(C) CH2=CH–CH (D)


(E) (F)  (G) 

Only One Option Correct Type

Direction : Each question has four choices (a), (b), (c) and (d), out of which ONLY ONE is
correct.

8. Which is the most stable carbanion?

(a) ̅ (b) ̅

(c) (d)

9. What is the decreasing order of acidic strength of the following compounds for their most
acidic hydrogen?
— ( ), — ( ), — = ( )
(a) I > II > III (b) II > I > III (c) III > I > II (d) III > II > I

10. In which of the following reaction, carbene is not formed?

(a) + → (b) + →
(c) = = + → (d) + →

11. Which of the following reaction gives carbene ((: ) as one of the product?
(a) ⎯⎯⎯⎯ (b) ⎯⎯⎯
O
||
(c) = — ⎯
⎯⎯⎯⎯ (d) ⎯⎯⎯⎯⎯⎯⎯
|

12. Which of the following

ng has most acidic hydrogen?

(a) (b)
 (c) (d)

13. Arrange the following carbanions in decreasing order of stability.

(a) I > III > II > IV (b) III > IV > II > I
(c) IV > III > I > II (d) II > I > III > IV

14. Which of the following reaction would be most exothermic?

·
(a) · +( ) → +( ) · (b) — →2
· · ·
(c) + — → + — (d) 2 → — — —

15. Which of the following free radicals would be expected to be most selective?
· · · ·
(a) H— C ≡ C (b) (c) (d) = —
16. Nitrene is a/an -
(a) Nucleophile (b) Electrophile
lectrophile (c) Charged specie (d)
(d Free atom
17. Nitrenes are -
(a) Paramagnetic (b) Diamagnetic (c) a & b (d) Ferromagnetic
18. Benzyne is -
(a) Aromatic (b) Non aromatic (c) Antiaromatic (d) All

19. Which of the following statement is correct about arrow headed 'C' of

(a)) Negative charge is delocalised due to sp2 hybridisation

(b) sp2 hybridised but (–)
( ve charge is localised.
3
(c) sp hybridised and ((–) ve charge is not delocalised.
(d) sp3 hybridised and (–)
( ve charge is delocalised.
20. The most stable free radical among the following is
• 2
(a) C6H5CH2CH • – CH3
(b) CH3 – CH • 3
(c) C6H5CHCH •2
(d) CH3CH
 
CH2 CH2

21. is more stable than because

NO2
NO2
(I) (II)

(a) 180º location of NO2 and CH2 in I (b) – NO2 operate both –I and – M in I.
(c) – I in II is weaker than I (d) Due to steric repulsion

22. Carbanion of CH3 – CH2 has geometry -
(a) Planar (b) Pyramidal (c) Squar bipyramidal (d) Triangular bipyramidal
23. Which of the following can stabilize the carbon free radicals -
(A) +  effect (B) + M effect (C) Hyperconjugation (D) All of these

24. Total number of pi bond present in Benzyne

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

25. Total number of resonating structure of Benzyne

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

26. Benzyne intermediate is not observed in -

OCH3 Cl Cl
H3C N2+
F CH3
(a) (b) (c) (d)
COO–

27. 'pi like' bond of benzyne is formed by overlapping of

(a) p-p orbital (b) sp2-p orbital (c) sp2-sp2 orbital (d) None

One or More than One Options Correct Type

Direction (Q. Nos. 28-31). This section contains 4 (multiple choice questions, Each question has
four choices(a), (b), (c) and (d), out of which ONE or MORE THAN ONE are correct.

28. Which of the following is/are true regarding a free radical?

(a) It is formed by homolytic cleavage of bond
(b) A chemical that is free radical initiator, e.g. peroxide, etc is must for the formation of
other free radicals
(c) It is a Lewis acid
(d) It undergoes disproportionation to some extent during the reaction
29. Which
hich of the following compounds forms salt with KOH in aqueous solution?

(a) (b) — —

(c) (d)

30. Which of the following ng is/are regarding a carbene true?

(a) Carbon is s hybridised
(b) it acts only as an electrophile
(c) it can be both paramagnetic as well as diamagnetic
(d) All atoms lie in the same plane

31. The correct statement(s) regarding acidity of the fol

following
lowing compounds is/are

(a) I is more
ore acidic due to the greater -I effect
(b) II is more acidic due to the resonance effect of −
(c) I is less acidicc due to poor resonance delocali
delocalisation
sation of conjugate base
(d) Both have comparable acidity
ac
 ANSWER KEY

1. The increasing order of stability is (i) < (ii) < (iv) < (iii). Both —NO
NO2 and —Cl have net
electron withdrawing effect on phenyl ring, hence increases stability of carbanions.
Cl is weaker electron withdrawing group than —NO2. When —NO — 2 is at orlho/para
position, it increases stability by resonance effect as well.

2. The increasing order of acid strength is (ii) < (i) < (iv) < (iii).
A stronger acid is one that forms more stable conjugate base. Conjugate base of III is
most stable as:
O O O O O O
|| || | || || |
— — ̅ — — ⎯⎯⎯⎯ — = — — ⎯⎯⎯⎯ — — = —

In (ii) and (iv). the oxygen of methoxy group is also in resonance with carbonyl group, it
decreases the stabilisation of carbanion conjugate base as its resonance is opposed.

Conjugate base of (ii) Opposing resonance decreases

stability of carbanion

However (iv) is more acidic than (i) and (ii) due to greater resonance delocalisation of
negative charge in conjugate base
O O O O O O
|| || | || || |
— — ̅ — — — = — — — — = —

3. The various free radicals formed are

I II III IV V VI
 The order of stability is: III > II > I > IV > V > VI.
Here, I. II and III are resonance stabilised free radicals, more stable than others. Hi is
most stable as its resonance structure is a 3° free radical

IV is least stable due to greater s-character

s s bearing the unpaired electron. IV is slightly
more stable then V due to closeness of CH3— group lo free radical..

4. If the two electrons on carbon remain present in the same hybrid orbital, it must be
paired, diamagnetic and angular as :

Angular, diamagnetic Linear, paramagnetic

(Singlet carbene) (Triplet carbene)

5. (i) > 1. ℎ is highly stabi

stabilised by resonance with three phenyl groups, more stable
than , hence equity favours products.
(ii) K < 1. The productuct carbanion is anti
anti-aromatic, highly unstable, he
hence, equilibrium
favours reactants
reactants.
(iii) K > 1. (1°) is more stable than (2°) carbanion. Hence, the equilibrium favours
product.
(iv) K > 1 is more stable (due to three eiectrcn withdrawing F) than , hence
equilibrium favours product.
(v) K >1. Product free radical is more stable, resonance stabilised than . hence
equilibrium favourr products.

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

CH2
sp2
7. (A) CH3–CH2 (B) CCl3–CH2 (C) CH2=CH–CH2 (D)
sp3 sp2 sp2

(E) (F) (G)

sp3
sp 3 sp2

8. d 9. b 10. d 11. c 12. c 13. c 14. d 15. d 16. b 17. c 18. a

19. b 20. c 21. b 22. b 23. d 24. b 25. a 26. b 27. c

28. a,d 29. a,b,c 30. a,c,d 31. b,c