VSK_Chemistry_Organic_EAS_Worksheet_1_Subj

1.

What are electrophiles? Can a proton act as an electrophile? Predict the product obtained from toluene after
treatment with D2SO4.

2.

From each of the following sets, select the most reactive and least reactive substrate towards ring nitration:
(a) Benzene, toluene, nitrobenzene and bromobenzene.
(b) Benzene, aniline, acetophenone and acetanilide
(c) m-Dinitrobenzene, m-nitrotoluene and toluene.
(d) Benzene, mesitylene, m-xylene, p-xylene and toluene.
(e) Chlorobenzene, 2,4-dinitrochlorobenzene, and p-nitrochlorobenzene.

3.

(a) It has been shown that chlorination of activated aromatic substrates can be affected with hypochlorous
acid in presence of a proton catalyst. Suggest a suitable mechanistic scheme showing the role of proton
in this reaction.
(b) Compared to aniline (C6H5NH2), acetanilide (C6H5NHCOCH3) is somewhat deactivated towards
electrophilic aromatic substitution. What explanation do you offer for this observation?

4.

(a) Why are the cyanoanilinium ions (C6H4(CN) N H3) stronger acids than anilinium ions ( C6 H 5 NH 3 )?
(b) Rank the three cyanoanilinium ions (o-,p- and m-) in order of decreasing acidity. Give reasons.

5.

(i) More than 1 equi. of AlCl3 is used in Friedel-Crafts acylation reaction in order to obtain a good yield.
Suggest a reason. How does your answer help explain why multiple acylations are not observed?
(ii) In Friedel-Crafts reactions, nitrobenzene is often used as a solvent. Why does it not compete with the
aromatic substrate for this reaction?

6.

Predict the product(s) and sketch a suitable mechanistic scheme for each one of the following reactions:
FeX 3
..
(i) C6 H 6 HCl

7.

(ii)

BF3
C6 H 6 F CHO

Sketch a suitable mechanism of the following transformation:

AlCl3
C6 H 5C CH 3 Br2
C6 H 5 Br CH 3 2 C CH 2

8.

Pick out the substituents which, are (i) o/p-directing with activation, (ii) o/p-directing with deactivation,
and (iii) m-directing with deactivation: Cl , NH 2 , OH , OCH 3 , NO2 , CHO , COOH
Illustrate your answer with the help of energy profile diagrams.

9.

Predict the major product in each of the following reactions:

(a) Monochlorination of p-cymene,

(b)

(c) Mononitration of p-fluorobromobenzene, (d)

Monobromination of o-cresol,
Mononitration of benzotrichloride,

(e) Mononitration of m-bromochlorobenzene.

10.

Treatment of one of the diethylbenzens with bromine in the presence of AlBr 3 results in the formation of
three isomeric monobromo derivatives of which one is the major product. Suggest structure of the
diethylbenzene and the products obtained. Indicate the major product.

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