ORGANIC CHEMISTRY

AROMATIC
COMPOUNDS

CONTENTS
EXERCISE - I
EXERCISE - II
EXRECISE - III
EXRECISE - IV(A)
EXRECISE - IV(B)
ANSWER KEY
 Exercise -I

Q1. + CHCl3 + KOH  + B

un exp ected product

What are A & B? Explain with mechanism.

Q2. PhCH2MgCl + MeCHO  PhCH2CHOH Me + A

A is an isomer of the other product & undergoes the haloform reaction to give o-toluic acid. What is A?
Suggest a mechanism for its formation.

Q3. 2, 4 dinitrophenyl diazonium ion couple with PhOMe whereas 2, 4, 6 compound couple with 2, 4, 6
trimethyl benzene. (mesitylene). Explain.

Q4. If there is kinectic isotope effect what will happen when

(a) C6H6 & C6D6 are allowed to react separately but under identical condition with E+.
(b) a 50 : 50 mixture of C6H6 & C6D6 is allowed to react with a limited amount of reagent.
(c) Anisole & 4D anisole are allowed to react with E+ separately.

1. NaH 1. NaOH
Q5. EtOH
 
 A   B   
 C 1
. SOCl 2
 D
H 2. MeI 2. H 2 . AlCl 3

What are A to D?

Q6. The following diacid undergo intramolecular Fridel Craft acylation with

concentrated H2SO4 to give two products. Give their structures with proper mechanism.

Q7. Mesitylene + HF + BF3  A yellow colored compound (A) where mesitylene : HF : BF3 =1 : 1 : 1.
Give proper reasoning.

Q8. What is the attacking site of diazocoupling of

(i) napthol (ii)  napthol (iii) resorcinol.

Q9. Account for the following facts

(a) why PhNO2 acting as suitable solvent in Fridel Carft Alkylation.
(b) The diazo coupling of phenol is carried out at pH = 9.
(c) Biphenyl is more reactive than benzene towards EAS.

Q10. The nitration of furan with acetyl nitrate proceeds via 2, 5 addition intermediate with the reagent. Suggest
a plausible mechanism for this product formation.
Q11. 4  Product. What type of reaction it is? Give proper mechanism.
HClO

 
Q12. when reacts with N O 2 B F 4 two products & are formed with

 
44% & 56% respectively whereas when treated with N O 2 B F 4 only one product

is formed as sole product. The structure of the products given as follows .

Q13. Iodination of Phenol & 2, 4, 6 trideuterophenol when carried out separately KH/KD ratio is found to be
4. Explain.

Q14. No reaction   CH2O +

furan

What are A & B? What explanation can you give for unreactivity of furan w.r.t. reagents as compared to
2 Me-furan & pyrrole.

Q15. AcCl

 A AcCl  AlCl 3
  B (disubstituted product)
AlCl3

(monosubstituted
product)
What are A & B? Explain with reason.

Q16. Kolbe Schmidt reaction if carried out in presence of soidum phenoxide product will be exclusively
sodium ohydroxy benzoate whereas if reaction is carried out in presenceof K+ OPh–, salt of p acid
becomes major product. Explain.

Q17. Heating acetone with an excess of phenol in presence of HCl produces bisphenol A (C15H16O2) &
reaction involved in its formation are similar to those involved in synthesis of DDT. Explain structure of A
with mechanism.

Q18. When a mixture of N chloro 2, 4 di chloro acetanilide & anisole is dissolved in HCl among the products
isolated are o & p chloroanisole . Discuss.
Q19. What are the products in the following reaction?

+ (AcO)2Hg NaOH
 A NaCl
 B.

What are A & B?

Q20. What are the products in the following reaction?

(a) + MeCO2H ZnCl

2  (b) + NaNO2 
HCl


Br2
(c) Aq
  A AcOH
. NaHCO 3
  B Boil
 in
 C
H O 2

Exercise - II
Q1. Write an equation for the formation form H2SO4 of each of the following sulfonating eletrophiles.
(a) H3SO4+ (b) HSO3+ (c) H2S2O7

Q2. When phenol is treated with D2SO4 in D2O there is formed phenol containing D instead of H at o & p
to the –OH group. Benzene undergo similar exchange but at a much lower rate; under same conditions
PhSO3H does not undergo exchange at all.
(a) Outline a plausible mechanism for H–D exchange in aromatic compounds.
(b) What is the attacking reagents in each case.

Q3. Outlines a likely mechanism for the following reaction.

PhCMe3 + Br2 (AlBr3)  PhBr + HBr + Me2C = CH2

Q4. Treatment of sulfanilic acid (p NH2 C6H4SO3H) with 3 moles of Br2 yields 2, 4, 6 tribromo aniline-
explain.

Q5. Resorcinal when reacts with Phthalic Anhydride in presence of H2SO4 what will be product? Explain
with mechanism.

Q6. Benzene, toluene, xylenes (o, m, p) & mesitylenes dissolved in HBF4 to form salts. Explain the order of
basicity mesitylene > m xylene > o & p xylene > toluene > benzene.

Q7. Synthesize butter yellow from Benzene & N, N dimethyl aniline. Structure is given below.
Ph – N = N – – NMe2.

Q8. Synthesize orange II from Benzene using any other reagent. Structure is given below.
Q9. What will be the products in the following reaction ?
(i) COCl2 + 2 equivalent of PhNMe2  (ii) + 2ICl 

(iii) + NaNO2 + HCl  (iv) + Br2 

(v) + 2ICl  (vi) HNO

3 

Q10. What will be the products in the following reaction

(i) + Ac2O AlCl
 3  (ii) + Br2 

(iii) ArH + SO2Cl2 AlCl

 3  (iv) + Cl SO3H 

(v) PhNH2 + PhSO2Cl  ? NaOH

 ? H
O
? 3


 Me SO 2 4

AlCl 3
(vi) + HCl + HCN  
H 2O

Q11. Synthesize
(i) Napthalene from Benzene (ii) Anthracene from Benzene (iii)  tetralone from Benzene

Q12. Synthesize

(a) from PhOMe (b) from PhOMe

Q13. Conversion

(i) (ii)

(iii)

(iv) o hydroxy acetophenone  2, 5 dihydroxy acetophenone

Q14. Conversion

(i)  (ii) 

Q15. Convert
(i) PhNH2  1, 3, 5 tribromobenzene (ii) PhH 2, 4, 6 tribromo 1, nitrobenzene
(iii) Nitrobenzene  Pentabromobenzene

Q16. Conversion

(i)  (ii)  (iii) 

(iv)  (v) 

(vi) Benzene  trinitrostilbene with the help of benzaldehyde formation.

Q17. Conversion

(i)  (ii) 

(iii)  (iv)  (v) 

Q18. (i)  (ii) 

(iii)  (iv)  (v) 

Q19. Conversion

(i)  (ii) 

(iii)  (iv)  (v) 

Q20. Conversion

(i) 

(ii) 

(iii) 

(iv) Benzene  m cresol

(v) Benzene  m - iodophenol
(vi) Benzene  3, 4, 5 tribromophenol

Exercise - III
Q.1 Which of the following structures correspond to the product expected, when excess of C6H6 reacts with
CH2Cl2 in presence of anhydrous AlCl3:

(A) (B)

(C) (D)

Q.2 In the sulphonation, acetylation and formylation of benzene the group of effective electrophiles would be:
   
(A) SO 3 , CH 3  O, HC O (B) SO 3 , CH 3  C  O, HC O
(C) SO3, CH3CHO, CO + HCl (D) HSO3, CH3CO, HCO

Q.3 In the reaction of p-chlorotoluene with KNH2 in liquid NH3, the major product is:
(A) o-Toluidine (B) m-Toluidine (C) p-Toluidine (D) p-Chloroaniline
Q.4 An aromatic compound 'A' C7H6Cl2, gives AgCl on bonding with alcoholic AgNO3 solution, and yields
C7H7OCl on treatment with sodium hydroxide. 'A' on oxidation gives a mono chlorobenzoic acid which
affords only one mononitro derivative. The compound A is:

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

Q.5 Benzyne intermediate is not observed in:

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

NaNH
Q.6 2  A, major product A and reaction R are:
 

(A) , elimination addition (B) , elimination addition

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

Q.7 Chloral + Cl Conc

 
. H 2SO 4
 product. The product is:
(A) Lindane (B) DDT (C) Tefflon (D) Ethaneperchlorate

Q.8 The reaction of benzene with CO and HCl in the presence of anhydrous AlCl3 gives:
(A) Chlorobenzene (B) Toluene (C) Benzyl chloride (D) Benzaldehyde

Q.9 The highest yield of m-product is possible by the electrophilic substitution of the following:
(A) C6H5CH3 (B) C6H5CH2COOC2H5
(C) C6H5CH(COOC2H5)2 (D) C6H5C(COOC2H5)3

Q.10 Benzene on reaction with 'A' forms which on reaction with 'B' forms

'A' and 'B' are:

(A) Zn(Hg) + conc. HCl, (B) , LiAlH4

(C) , NaBH4 (D) , Zn(Hg) + conc. HCl

Q.11 For the electrophilic substitution reaction involving nitration, which of the following sequence regarding
the rate of reaction is true?
(A) k C6 H6 > k C6 D6 > k C6 T6 (B) k C6 H6 < k C6 D6 < k C6 T6

(C) k C6 H6 = k C6 D6 = k C6 T6 (D) k C6 H6 > k C6 D6 < k C6 T6

Q.12 For the electrophilic substitution reaction involving sulphonation, which of the following sequence
regarding the rate of reaction is true?
(A) k C6 H6 > k C6 D6 > k C6 T6 (B) k C6 H6 < k C6 D6 < k C6 T6

(C) k C6 H6 = k C6 D6 = k C6 T6 (D) k C6 H6 > k C6 D6 < k C6 T6

Q.13 Which of the following is ortho-para directing group?


(A) CF3 (B) CCl3 (C) –CH=CH–COOH (D) – N  C
Q.14 Match the column:
Column A Column B

(A) + CrO3 in CH3COOH  ? (P) Tropylium ion

(B) + Ph3C? (Q) Benzaldehyde

(C) + n-Pr Br + ZnCl2  ? (R) Two types of products

(D) + Br2 ? (S) Cumene

Q.15 Match the following:

Column I Column II

(A) CO2is evolved from (P)

NaHCO3 by the reaction of

(B) Libermann nitroso test is given by (Q)

(C) Compounds gives yellow oily (R)

liquid on reaction with NaNO2 + HCl

(D) Compounds evolve a colourless gas (S)

on reaction with active metals
Q.16 Match the following:
Column I Column II

(A) Compounds which on reaction (P)

with neutral FeCl3 gives

violet / Blue colour are

(B) Compounds which on reaction (Q)

with

gives para red dye.

O
||
(C) Compounds which do not give (R) Ph  CH 2  C  CH 2CH 3
yellow ppt. On reaction with NaOI

(D) Compound which have maximum % (S)

of enol form

Q.17 Match the following:

Column I Column II

(A) Compounds which gives Diels (P)

Elder's reaction in greater extent

with dienophile

(B) Compounds which undergoes (Q)

ArSN reaction are

(C) Compound which has highest (R)

aromatic characters

(D) Strongest Base (S)

Q.18 Write the principal organic product in each of the following reactions:

(i) + C6H5CH2SNa  H (ii) + Mg

,THF

heat
 EXERCISE - IV(A)

Q.1 The chlorination of toluene in presence of ferric chloride gives predominatly:

(A) Benzyl chloride (B) m-chlorotoluene (C) Benzal chloride (D) o-and p-chlorotoluene
Q.2 Aryl halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halide due to
(A) The formation of less stable carbonium ion (B) Resonance stabilization
(C) Longer carbon-halogen bond (D) The inductive effect
Q.3 The most basic compound among the following is:
(A) Benzylamine (B) Aniline (C) Acetaniline (D) p-nitro aniline
Q.4 Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH
gives:
(A ) o-cresol (B) p-cresol
(C) 2,4-dihydroxytoluene (D) Benzoic acid
Q.5 W hen nitrobenzene is treated w ith Br 2 in presence of FeBr3 the major product formed is
m-bromonitrobenzene. Statements which are related obtain the m-isomer are:
(A) The electron density on meta carbon is more than on ortho and para position.
(B) The intermediate carbonium ion formed after initial attack of Br+ attack the meta position is least
destabilized.
(C) Loss of aromaticity when Br+ attacks at the ortho and para positions and not at meta position
(D) Easier loss of H+ to region aromaticity form the meta position than from ortho and para position.
Q.6 Choose the correct statement from the ones given below for two aniline in:

(A) II is not an acceptable canonical structure because carbonium ions are less stable than ammonium
ions
(B) II is not an acceptable canonical structure because it is non aromatic
(C) II is not an acceptable canonical structure because the nitrogen has 10 valence electrons
(D) II is an acceptable canonical structure
Q.7 Most stable carbonium ion is:
(A) p – NO2 – C6H4 – +CH2 (B) C6H5+CH2
(C) p – Cl – C6H4– +CH2 (D) p – CH3O – C6H4 – +CH2
Q.8 Arrange in order of decreasing trend towards SE reactions:
(I) Chlorobenzene (II) Benzene (III) Anilinium chloride (IV) Toluene
(A) II > I > III > IV (B) III > I > II > IV (C) IV > II > I > III (D) I > II > III > IV
Q.9 Among the following statements on the nitration of aromatic compounds, the false one is:
(A) The rate of benzene is almost the same as that of hexadeuterobenzene
(B) The rate of nitration of toluene is greater than that of benzene.
(C) The rate of nitration of benzene is greater than that of hexadeuterobenzene
(D) Nitration is an electrophilic substitution reaction
Q.10 Nitrobenzene can be prepared from benzene by using a mixture of conc. HNO3 and conc. H2SO4. In
the nitrating mixture HNO3 acts as a:
(A) Base (B) Acid (C) Reducing agent (D) Catalyst
Q.11 Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with:
(A) SO2Cl2h (B) SOCl2 (C) Cl2 h (D) NaOCl
Q.12 The most unlikely representation of resonance structure of p-nitrophenoxide ion is:

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

Q.13 A solution of (+) -2-chloro-2-phenylethane in toluene racemises slowly n the presence of small amount
of SbCl5, due to the formation of:
(A) Carbanion (B) Carbene (C) Free-radical (D) Carbocation
Q.14 Toluene, when treated with Br2/Fe, gives p-bromotoluene as the major product, because the CH3 group:
(A) is para directing (B) is meta directing
(C) activates the ring by hyperconjugation (D) deactivates the ring
Q.15 Amongst the following the strongest base is:
(A) C6H5NH2 (B) p-O2NC6H4NH2 (C) m-O2NC6H4NH2 (D) C6H5CH2NH2
Q.16 Identify the correct order of reactivity in electrophilic substitution reactions of the following compounds:

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

(A) I > II > III > IV (B) IV > III > II > I (C) II > I > III > IV (D) II > III > I > IV
( CH ) NH NaNO 2 HCl 05 C
Q.17 F 3 2
NO2    A (i)
     B
DMF (ii) H 2 Catalytic Reduction

(A) O2N NH2 (B) N NH2

(C) N NO2 (D) N NO2

Br
Q.18 2 
Fe

Major product of above reaction is:

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

Q.19 Which of the following is obtained when 4-Methylbenzenesulphonic acid is hydrolysed with excess of
sodium acetate?
—
(A) CH3 CO O N a (B) CH3 + SO3


(C) CH3 SO 3 N a + CH3COOH (D) CH3 SO2O. COCH3 + NaOH

EXERCISE - IV (B)

2( i ) Br ,Heat ,Light
Q.1 C6H5C2H5     
( ii ) NaCN

Q.2 An organic compound (A). C8H6 on treatment with dilute sulphuric acid containing mercuric sulphate
gives a compound (B), which can also be obtained from a reaction of benzene with an acid chloride in
the presence of anhydrous aluminium chloride. The compound (B), when treated with iodine in aqueous
KOH, yields (C) and a yellow compound (D). Identify (A), (B), (C) and (D) with justification. Show
how (B) is formed from (A) ?
Q.3 Toluene reacts with bromine in the presence of light to give benzyl bromine while in presence of FeBr3 it
gives p-bromotoluene. Give explanation for the above observations.

Q.4 Show the steps to carry out the following transformations:

(a) Ethylbenzene  benzene
(b) Ethylbenzene  2-phenylpropionic acid

Q.5 C6H5CH2CHClC6H5 alcoholic

  KOH ,
heat
 (A) + (B)

( i ) NaNH ( 3.0 equiv )

Q.6 C6H5CH = CH2 Br
2 (A)   2    (B)

( ii ) CH 3I

Q.7 Normally, benzene gives electrophilic substitution reaction rather than thus electrophilic addition reaction
although it has double bonds.

Q.8 How would you synthesis 4 methoxyphenol from bromobenzene in NOT more than five steps? State
clearly the reagents used in each step and show the structures of the intermediate compounds in your
synthetic scheme.

Q.9 Carry out following conversions in 3 or less steps.



Q.10 A compound C9H7O2Cl exists in keto form A and enolic form B. Enolic form B predominates at
equilibrium. On oxidation with KMnO4 t gives m-chlorobenzoic acid gives structures of A and B.

Q.11 7-bromo-1, 3, 5-cycloheptatriene is ionic compound, whereas 5-bromo-1,3-cyclopentadiene can't ionise

even n the presence of Ag, Explain why?
 ANSWER KEY
EXERCISE - III
Q.1 D Q.2 B Q.3 B Q.4 A Q.5 B Q.6 A Q.7 B
Q.8 D Q.9 D Q.10 D Q.11 C Q.12 A Q.13 C
Q.14 (A) Q, (B) P, (C) R, S, (D) R Q.15 (A) Q, (B) P,R,S, (C) R,S, (D) P,Q,R,S
Q.16 (A) P,Q,R,S, (B) Q, (C) P,Q,R,S, (D) Q Q.17 (A) R, (B) S, R, (C) P, (D) S

Q.18 (i) (ii)

EXERCISE - IV(A)
Q.1 D Q.2 B Q.3 A Q.4 D Q.5 A,B Q.6 C Q.7 D
Q.8 C Q.9 C Q.10 A Q.11 A,C Q.12 C Q.13 D Q.14 A,C
Q.15 D Q.16 C Q.17 B Q.18 D Q.19 C
EXERCISE - IV (B)

Br
2 
Q.1  ,h NaCN


Q.2 (A) (B) (C)

Q.3 In presence of FeBr3, Br2 produces Br+(an electrophile) which attacks the benzene ring at o-,p-position
to give p-bromotoluene. In presence of light, side chain is attacked to produce benzyl bromide.
3 H O
Q.4 (a) (i) C6H5CH(OH)CCH  


OH 
C6H5CH=CHCHO C6H5CH=C= CH  C6H5CH=C= C H
|
OH

[
O]
(b) (i) Soda
 lime

2
(ii) X KCN
 HOH

hv

KOH ( alc.)
Q.5 C6H5CH2CH2CHClC6H5    C6H5CH= CHC6H5

(Cis and trans forms)
Br NaNH 3 eq .
Q.6 2
  2
Q.7 Benzene has resonance stabilization due to delocalisation of -electrons. Also during electrophilic addition
reactions, it loses its aromaticity. In electrophilic substitution reaction aromaticity is retained.

NaOH
Q.8   Me
 
SO
conc . H SO
 24  NaOH

 high Pr essure 2 4

3 H O
 

Alternative rout

NaOH H O
conc . H SO
 24  NaOH
 Me
 
SO
  3
 
2 4  high Pr essure

conc . H SO HBF / KHF

Q.9  24  4
  2 
 

Q.10 l

(A) (B)
Keto Enol
Enol form is more stable due to extended conjugation

(A) KMnO
 4 

Q.11 On ionization 7-bromo-1,3,4-cycloheptatriene gives tropolium ion which is aromatic with 6 electrons.

l + Brr

5-bromo-1,3-cyclopentadiene can't ionise as it will in that case give highly unstable antiaromatic cation
with 4  electrons.

+ Brr