SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I
1. How do you convert p-chlorobenzoic acid from p-chloronitrobenzene?
2. The alkylation of aniline with alkyl halide in presence of AlCl3 gives poor yields. Explain.
3. Write the products:
(a) Toluene Cl2 (A)
Boiling condition
(b) Toluene Cl2 (B) (C)
CH3
4. conc.lHNO3 –conc.H2SO4
OMe
In the above reaction which is the major product and why?
CH3
5. conc.HNO3 –conc. H2SO4
NO2
In the above reaction which pr
SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I
1. How do you convert p-chlorobenzoic acid from p-chloronitrobenzene?
2. The alkylation of aniline with alkyl halide in presence of AlCl3 gives poor yields. Explain.
3. Write the products:
(a) Toluene Cl2 (A)
Boiling condition
(b) Toluene Cl2 (B) (C)
CH3
4. conc.lHNO3 –conc.H2SO4
OMe
In the above reaction which is the major product and why?
CH3
5. conc.HNO3 –conc. H2SO4
NO2
In the above reaction which pr
SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I
1. How do you convert p-chlorobenzoic acid from p-chloronitrobenzene?
2. The alkylation of aniline with alkyl halide in presence of AlCl3 gives poor yields. Explain.
3. Write the products:
(a) Toluene Cl2 (A)
Boiling condition
(b) Toluene Cl2 (B) (C)
CH3
4. conc.lHNO3 –conc.H2SO4
OMe
In the above reaction which is the major product and why?
CH3
5. conc.HNO3 –conc. H2SO4
NO2
In the above reaction which pr
SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I
1. How do you convert p-chlorobenzoic acid from p-chloronitrobenzene?
2. The alkylation of aniline with alkyl halide in presence of AlCl3 gives poor yields. Explain.
3. Write the products:
(a) Toluene Cl2 (A)
Boiling condition
(b) Toluene Cl2 (B) (C)
CH3
4. conc.lHNO3 –conc.H2SO4
OMe
In the above reaction which is the major product and why?
CH3
5. conc.HNO3 –conc. H2SO4
NO2
In the above reaction which pr
SECTION - I SUBJECTIVE QUESTIONS LEVEL - I 1. How do you convert p-chlorobenzoic acid from p-chloronitrobenzene? 2. The alkylation of aniline with alkyl halide in presence of AlCl3 gives poor yields. Explain. 3. Write the products: Cl2 (a) Toluene Boiling condition (A)
Cl (b) Toluene 2 Fe (B) (C)
CH3
conc.lHNO3 –conc.H 2SO 4
4.
OMe In the above reaction which is the major product and why? CH3
conc. HNO3 – conc. H 2SO4
5. NO2 In the above reaction which product is most likely to be formed? 6. Pyrridine is more basic than pyrrole, why? 7. Identify the compounds from A to D Nitric acid Sn / HCl HNO 2 (D) (A) Sulfuric acid p nitro Toluene (B) HCl, 5 C (C) p-flouro Toluene
8. What are the signs of the –I and +R effects for the following groups attached to the benzene ring. –NO 2 , — NH 2 , — Br , —COMe, — N Me, —SO3 H , —OMe? When in opposition,which effect is greater? 9. What happens when benzene is treated with methyl chloride in presence of anhydrous AlCl3 and the product is treated with excess of chlorine in presence of UV light? 10. Ortho & Para product of the electrophilic substitution of diphenyl ring ( ) is major, but the meta product is minor, why? Chemistry : Electrophilic Aromatic Substitution
LEVEL - II 1. Predict the major product in the following reactions: H 2SO 4 (i) C6 H 6 (CH3 ) 2 CHCH 2OH ? 1. Br2 , heat , light (ii) C6 H 5 CH 2 CH 3 2. NaCN ?
2. Arrange the following five compounds in order of decreasing rate of bromination: benzene, toluene, o-xylene m-xylene, 1, 3, 5 trimethyl benzene (the relative rates are 2 107 , 5 104 , 5 102 , 60 and 1). 3. Below are given two different routes for the preparation of 3-phenylpropane: H2 C CH2 CH3
Write route would you prefer for the actual preparation of 3-phenyl propane? Give reaction. 4. Benzene ring despite of unsaturated ring, undergoes electrophilic substitution rather than electrophilic addition, why?
CH3 5. How will you synthesize from benzene?
H3C CH3 6. A . Identify A and also the electrophile involved in the reaction. HF or BF3
7. Write the structure of the major product (only monosubstitution is involved in each case).
O AlCl3 (i) CH3 C NH CH 3COCl Cs ? 2 OH
Br2 (ii) CH2 CHCl ? 2
(i) KMnO 4 8. C7H7Cl has four isomers A1, A2, A3 and A4. A 4 (ii) Sodalime , Benzene, Identiyf A1, A2 , A3 and A4.
9. What happen when p-xylen is treated with concentrated sulphuric acid and the resultant product is fused with KOH.
CH3
10. How will you synthesize from Benzene.
LEVEL - III 1. Oxidation of toluene by acidic KMnO4 gives poor yield of benzoic acid while oxidation of p-nitrotoluene gives yield of p-nitrobenzoic acid. Why? 2. Phenyl ring is known to exert negative inductive effect. But each phenyl ring in biphenyl (C6H5—C6H5) is more reactive than benzene towards electrophilic substitution. Explain. 3. Give the product (s) obtained from the reaction each of the following compunds with Br2/FeCl3.
6. Predict the structure of the intermediate products in the following reaction sequence.
OMe O O MeO O 1.AlCl3 Zn/Hg/HCl H3PO4 + 2.H O [A] [B] 3
7. Predict the product
Br2 / Fe N (1 aq)
8. Predict the major monosubstituted product in the following cases –
C(CH3)3 OCH3
H 2SO 4 (a) Conc. HNO 3 (b) (CH3 ) 2 C CH 2 conc. H SO 2 4
CH(CH3)2 CH3
Br2 (c) OH CHCl3
9. Compound (A), (B), (C) are three methyl isomeric derivatives of benzene. Identify which is O–, m– or p– from the product of Nitration Conc. HNO3 A H 2SO 4 two mononitro product
Conc. HNO3 B H SO three mononitro products 2 4
Conc. HNO3 C H SO one mononitro product 2 4
10. Describe how mescalcine could be synthesize from toluene.
SECTION - II SINGLE CHOICE QUESTIONS 1. The correct order of reactivity towards electrophilic substitution is (a) benzoic acid > chlorobenzene > benzene > phenol (b) benzoic acid > phenol > benzene > chloro benzene (c) phenol > benzene > chlorobenzene > benzoic acid (d) phenol > chlorobenzene > benzene > benzoic acid HNO3 / H 2SO 4 Zn / HCl NaNO 2 H 2 O / H3 PO 2 2. C6 H 6 A B HCl(0 C) C D The product D is OH Cl
(a) (b)
COOH
(c) (d)
3. Chlorination of toluene in 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 4. Aryl halides are less reactive towards nucleophilic substitution reactions as compared to alkyl halides due to : 1. The formation of less stable carbonium ion 2. Resonance stabilization 3. Longer carbon-halogen bond 4. The inductive effect 5. sp 2 -Hybridized carbon attached to halogen. (a) 1, 2, 3 (b) 2, 4, 5 (c) 2, 5 (d) 4, 5. 5. When nitrobenzene is treated with Br 2 in presence of FeBr 3, the major product formed is m- bromonitrobenzene. The statements which are related to obtain the m-isomer are 1. The electron density on meta carbon is more than at ortho and para-positions. 2. The intermediate carbonium ion formed after initial attack of Br+ at the meta-positions is least destabilized. 3. Loss of aromaticity when Br+ attacks at the ortho and para-positions and not at m-position 4. Easier loss of H+ to regain aromaticity from the meta position than from ortho and para-positions. (a) 1, 2 (b) 1, 3 (c) 1, 3, 4 (d) 1, 4. Chemistry : Electrophilic Aromatic Substitution
6. Arrange the following in correct activating order towards EAS
O –NHCOCH3 , —O — C — CH3 , — N R 3 , —NH 2 I II III IV
(a) III I II IV (b) IV < I < II < III
(c) III < II < I < IV (d) II < III < I < IV. 7. Among the following which is more difficult to nitrate than benzene? (a) Phenol (b) Toluene (c) Chlorobenzene (d) Aniline. C 2H 5 NO 2 NH 4 HS A 8. NO 2 A and B are C2 H5 C2 H 5 NH 2 NO 2 (a) Both are (b) Both are
NO 2 NH 2
C2 H 5 C2 H5 C2 H 5 C2 H5 NO 2 NH 2 NO 2 NO 2 (c) A is and B is (d) A is and B is
NH 2 NO 2 NO 2 NH 2
O CH 3CN 9. the major product is KOH Ph Ph CN OH Ph Ph (a) (b) Ph Ph Ph NCH 2C
OH OCH 3 Ph Ph (c) (d) Ph Ph NC
KMnO 4 10. OH A So A is
HO OH COOH COOH
(a) (b)
OHC CHO COOH
(c) (d)
HOH NH + R X (CH3 ) 2 CHNH 2 , here R should be 11.
16. For the preparation of the possible reactants are
O2N
anhydrous (a) COCl + NO2 AlCl 3
anhydrous (b) O2N COCl + AlCl 3
O Nitration (c)
(d) Any of these
NH2 HCl 17. HCl NH2 yield
H2N
NH (a) (b) NH 2
(c) (d) :
N H N
Cl * NaOH, H2O 18. o Product 395 C
Product is
OH * * (a) (b) OH
(c) Both (d) none of these
Br2 .Fe 19. A. A is
Br
(a)
(b) Br
(c) Both are correct
(d) None if correct Chemistry : Electrophilic Aromatic Substitution
20. End product of the following reaction is
O O + HBr
(a) O O (b) HO OH
Br Br
Br OH (c) (d) Br OH
HO Br SECTION - III MULTIPLE CHOICE QUESTIONS 1. The reaction HN NH
mineral acid
gives NH2
(a) H2 N NH2 (b) H2 N
NH2
(c) H2 N (d) none of these
2. Which of the following are electrophiles?
(a) BF 3 (b) Cl2C: (c) NH 3 (d) I – 3. Which of the following are true? (a) Benzene tends to undergo substitution rather than addition reactions (b) All hydrogen atoms of benzene are equivalent (a) The carbon–carbon bonds of benzene are alternatively short and long around the ring (d) There can be two o–disubstituted derivatives. 4. Triphenylmethane can be prepared by (a) AlCl AlCl3 (b) Benzene + chloroform Benzene + benzal chloride 3 ZnCl 2 (c) Benzene + benzaldehyde (d) none of these 5. Which of the following are electrophilic substitution reactions?
FeCl3 (a) + Cl2 (b) + fuming H2SO4
UV light (c) + Cl2 (d) all of these Chemistry : Electrophilic Aromatic Substitution
6. The sulphonation of toluene with oleum at 35°C produces
(a) p–toluene sulphonic acid (b) o–toluene sulphonic acid (c) m–toluene sulphonic acid (d) a mixture of (a), (b) and (c) in approximately equal proportions 7. The Friedel–Crafts reaction of benzene with n–butyl chloride at 0°C produces
| CH3 8. The major products formed in the reaction of toluene with chlorine in the presence of ferric chloride are (a) o–chlorotoluene (b) m–chlorotoluene (c) p–chlorotoluene (d) benzyl chloride 9. A Friedel–Crafts reaction of benzene with chloroform produces
Cl | (a) C6 H5 CHCl2 (b) C 6 H 5 —C — C6 H 5 | H
C6H5 | (c) C6 H5 —C — C6 H 5 (d) all of these | H 10. Which of the following represents a Friedel–Crafts reaction? AlCl3 (a) C6 H 5 C 2 H5 Cl C6 H 5C 2 H 5 HCl ZnCl 2 (b) C6 H 5 OH HCl C6 H 5 Cl H 2O AlCl3 (c) C6 H6 CH 3COCl C6 H 6COCH 3 HCl ether (d) C 2 H 5 Br Mg C 2 H 5 MgBr MISCELLANEOUS QUESTIONS SECTION - IV COMPREHENSION TYPE QUESTIONS Write up - I The introduction of alkyl or acyl group into an aromatic ring is called Friedel-Crafts reaction. The introduction of an alkyl group into an aromatic ring is called alkylation. The reaction is usually brought about by alkyl halides, olefins, alcohols and carbonyl compounds in the presence of Lewis acid catalyst
1. Consider the following statements for Friedel–Crafts reaction.
(1) Rearrangement in alkylating group take place. (2) The entering alkyl group is an activating group, hence polyalkylation occurs frequently. (3) Aromatic compounds containing m–directing groups do not give this reaction. (4) Aryl halides can also be used in place of alkyl halides. Of these statements : (a) 1 and 2 are correct (b) 1, 2 and 3 are correct (c) 2, 3 and 4 are correct (d) 1, 2, 3 and 4 are corret 2. Consider the given conversion
Write up - II Electrophilic substitution reactions takes place by arenium ion mechanism. In this mechanism formation of C-E bond is rate determining step. The second step is the breaking of C-H bond which is fast step. All electrophilic reactions are irreversible except sulphonation. Electrophilic substitution reactions are carried out in the presence of proton acid or Lewis acid as a catalyst.
4. Which of the following reactions are carried out in the presence of proton acid? (1) Nitration (2) Sulphonation (3) Halogenation (4) Friedel–Crafts reaction Select the correct answer from the codes given below : (a) only 1 (b) only 2 (c) 1 and 2 (d) 1, 2, 3 and 4 5. In the given reaction
OCH3 OCH3
HNO3
NO2
The structure of complex is :
OCH3 OCH3
(a) (b)
NO2 NO2
OCH3
(c) (d) all of these
NO2 6. The major product of the given reaction
(i) AlCl3 / CH3 — Cl (ii) H O / H [X] 2
[X] is CH3
(a) CH3 (b)
CH3 CH3
(c) (d)
MULTIPLE MATCHING TYPE QUESTIONS
Match the following
7. Column A Column B (P) —NH 2 (A) Strongly deactivating (Q) —NO 2 (B) Weakly diactivating (R) —R (C) Weakly activating (S) —I (D) Strongly activating (P) (Q) (R) (S) (a) A B C D (b) D C B A (c) D C A B (d) D A C B 8. Column A Column B (P) Ethene (A) Nucliophilic addition (Q) Benzene (B) Electrophilic addition (R) Acetaldehyde (C) Nuclophilic substitution (S) Ellyl chloride (D) Electroplilic substitution (P) (Q) (R) (S) (a) B D A C (b) D B A C (c) D B C A (d) B D C A Chemistry : Electrophilic Aromatic Substitution
ASSERTION-REASON TYPE QUESTIONS
The question given below consist of an ASSERTION and the REASON. Use the following key for the appropriate answers (a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion (b) If both Assertion and Reason are correct and Reason is not the correct explanation for Assertion (c) If Assertion is correct but Reason is not correct. (d) If Assertion is incorrect but Reason is correct. 9. Assertion : Nitrobenzene undergoes Friedel-Crafts reaction. Reason : Electrophile of Friedel-Crafts reaction is carbocation which is very weak electrophile. 10. Assertion : Nitration of aniline can be done by protecting -NH2 group by acetylation. Reason : Aniline is oxidised by conc HNO3. ANSWERS SECTION - I (Subjective Questions)
Answers are given in the separate booklet (Level – I to Level – III)
