EXCEL 2022

GENERAL ORGANIC CHEMISTRY - II

SUBSTITUTION ON AROMATIC RINGS 04J

Marking Scheme : Single Correct (+3,-1) M M: 140 Time : 1 hr 30 min

Single Correct Answer Type

1. Arrange the following compounds in decreasing order of reactivity (most reactive first) towards SArN
reaction.
(I) (II) (III) (a) (I) > (II) > (III)
(b) (III) > (II) > (I)
(c) (I) > (III) > (II)
(d) (III) > (I) > (II)
2. Identify the product.

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

3. Identify the product.

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

4. Identify the product.

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

5. What is true about benzyne intermediate?

(a) Benzyne is the intermediate in all SArN reactions.
(b) Benzyne does not have a formal triple bond.
(c) Strong Lewis acids such as AlCl3 help in the formation of benzyne intermediate.
(d) All of the above.
6. What is true about these two reactions?

(a) KH/KD ratio varies between 7 to 8.

(b) Both the reactions do not progress through intermediate.
(c) Rate of both the reactions is nearly same.
(d) Cleavage of C—H and C—D bond takes place in the rate-determining step.

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7.

The para to ortho product ratio is highest when X is:

(a) NO2+ (b) Cl+ (c) Br+ (d) SO3
8. Identify the product.

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

9. Arrange the following with respect to the reactivity (Least first) towards ring bromination.

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

(a) II < V < IV < III < I (b) II > III > V > IV > I (c) I > III > V > II > IV (d) I > IV > V > II > III
10. An organic compound A when reacted with benzoyl chloride by Friedel Crafts reaction forms B. B reacts
with NH2OH to yield another compound C, which is an oxime. Subjecting C to Beckmann rearrangement
and hydrolysis gives benzoic acid and aniline. Identify A.

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

11. Pick the correct statement.

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

(a) I and II are two different products. (b) III and IV are resonating structures.
(c) III and IV are identical products. (d) III and IV are two different products.

12. (I) (II)

Product(s) of which of the above reaction(s) would incorporate deuterium.

(a) I only (b) II only (c) Both (d) None
13. In which of the following case the benzyne mechanism would not operate?

(a) (b)

(c) (d)

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14. Predict the product for the intramolecular Friedel-Crafts reaction.

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

15.

Predict the product for the given reaction.

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

16. Pick the false statement(s) for the above reaction.

(a) —NO2 groups deactivate the ring towards the reaction.
(b) The reaction takes place through benzyne mechanism.
(c) It is a typical nucleophilic substitution on aromatic ring.
(d) Reaction takes place through elimination-addition sequence.
17. Benzene reacts with 2,5-dibromo-2,5-dimethylhexane in presence of AlBr3 to give:

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

18. Predict the product for the following reaction.

(a) (b)

(c) (d)

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 Multiple Correct Answer Type
19. Which of the following reaction(s) would produce the following product?

(a) (b)

(c) (d)

20. Which ofthe following(s) upon oxidation using hot aq. KMnO4 gives:

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

21. Check the following reaction and pick the correct sentence(s).

(a) One isomer is formed exclusively, no other stereoisomer.

(b) Benzene ring reacts with the three membered ring at the more hindered site.
(c) It is a nucleophilic substitution on aromatic ring.
(d) Benzene is nucleophilic here.
22. Which set of reagent(s) cannot carry out the following conversion.

(a) HBr, peroxide (b) Br2 in CCl4 (c) Br2, FeBr3 (d) KBr

23. In which of the following(s), the C—C bond length is in between that of C—C single bond and double
bond?

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

24. When the following compound is subjected to isomerisation upon treatment with dilute mineral acid,
which of the following is / are not formed?

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

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 Assertion-Reason Type
Instruction: Each question contains statement-1(assertion) and statement-2 (reason). Use the fol-
lowing key to select one appropriate answer:
(a) If statement-1 and 2 are true and statement-2 is a correct explanation for statement-I.
(b) If statement-1 and 2 are true and statement-2 is not correct explanation for statement-1.
(c) If statement-1 is true and statement-2 is false.
(d) If statement-1 is false and statement-2 is true.
25. Statement-1: —Cl is a meta director.
Statement-2: —Cl deactivates all positions but deactivates meta position more than it does the ortho
and para positions.
26. Statement-1: —NO2 is an activator in SArN reaction.
Statement-2: SArN is a two-step reaction.
27. Statement-1: Benzene itself is sulphonated fairly slowly by hot concentrated sulphuric acid but rapidly
by oleum.
Statement-2: Oleum contains dissolved SO3, the electrophile.
28. Statement-1: Bromination of benzene is accelerated when I2 is added to the reaction mixture.
Statement-2: I2 promotes formation of more Br+.
29. Statement-1: Pyridine is less reactive than benzene towards nucleophiles.
Statement-2: Nucleophiles tend to attack pyridine at 2 and 4 positions.
30. Statement-1: Bromobenzene with substituted deuterium at both the ortho positions when reacts with
NH2–, primary isotope effect is noticed.
Statement-2: Rate-determining step involves benzyne formation in which NH2– acts as a strong base
to abstract a proton.
31. Statement-1: Phenol can directly reacts with Br2 even in the absence of catalyst to give monobromo
product.
Statement-2: Such reactions are electrophilic aromatic substitution.
32. Statement-1: Pyrrole, a non-benzoid aromatic compound is more reactive than benzene towards
electrophilic aromatic substitution.
Statement-2: The non-bonding pair on nitrogen is a part of the aromatic sextet.

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 Comprehension Type
Aromatic rings resist addition and undergo substitution because they do not want to give up the stability
they enjoy due to aromatic nature. Electrophilic substitution on disubstituted benzene has been an interesting
area for study. When two substituents act in concert, the outcome of the reaction is relatively easy to
predict. On the other hand, when the two groups are opposing the outcome or they are non-cooperating,
the following generalizations help to predict the product theoretically.
 Activator wins over deactivator.
 A powerful activator wins over a weaker activator.
 When one substituent has a pair of non-bonding electron, it normally extends the product determining
influence.
 Ordinarily an incoming group will not enter between any two groups already present due to steric
reasons. Steric factors always play a key role.
33. Identify the most likely product.

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

34. Identify the most.likely product.

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

35. Identify the most likely product.

(a) (b)

(c) (d)

36. Identify the most expected product.

(a) (b) (c) (d) Both (a) and (b)

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 Match the Columns
37. Column-I Column-II
(i) (ii) (iii) (iv)
(i) —N==O (p) Deactivator and meta director (a) (s) (q) (p) (r)
(ii) —NH2 (q) Activator and o/p-director (b) (s) (p) (q) (r)
(iii) —SO3H (r) Deactivator through —I effect (c) (p) (s) (r) (q)
 (d) (p) (s) (q) (r)
(iv) — NH3 (s) Deactivator and o/p-director
38. Column-I Column-II

(i) (p) Reaction at position-3

(ii) (q) Reaction at position-4

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

(a) (p) (r) (s) (q)
(iii) (r) Reaction at position-2 (b) (q) (s) (r) (p)
(c) (r) (s) (p) (q)
(d) (q) (s) (p) (r)
(iv) (s) SArN2

39. Column-I Column-II

(i) (p) Aromaticity is destroyed

(ii) (q) Nucleophilic substitution

(i) (ii) (iii) (iv)
(a) (r) (s) (p) (q)
(iii) (r) Product contains all
pi-bonds in conjugation (b) (r) (p) (s) (q)
(c) (p) (r) (q) (s)
(iv) (s) All pi-bonds in the product (d) (s) (p) (r) (q)
are not in conjugation

40. Column-I Column-II

(i) (p) Nucleophilic aromatic substitution

(ii) (q) Theoretically two products are possible

(i) (ii) (iii) (iv)
(iii) (r) Nucleophilic aromatic substitution (a) (p) (q) (s) (r)
leading to isomerisation (b) (p) (r) (s) (q)
(c) (r) (s) (p) (q)
(iv) (s) Electrophilic substitution (d) (s) (r) (q) (p)

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All students are advised to solve DPPs within allowed time only.
All discussions are scheduled in every 4th doubt discussion class
–MKA Sir (Guruji)

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