IIT EASY

GENERAL ORGANIC CHEMISTRY

Organic chemistry, seemingly a

vast area of chemistry, can be made
concise, if the fundamentals are
studied through systematic and correct
approach. Entire concepts of organic
chemistry will be laid down in this
lesson and will serve as the foundation
to master them all. Here, we have
taken all the concepts starting from
basics like bond cleavage, types of
reagents, various effects operating in
compounds and their roles, giving
proper emphasis on IITJEE syllabus.
The concepts studied in this
lesson would be a useful tool in our
hands, which enable us to foretell the
mechanism or product of a given
reaction.

IITJEE Syllabus: Hybridization of carbon; Sigma and pibonds;

Shapes of molecules; IUPAC nomenclature of simple organic compounds
(only hydrocarbons, monofunctional and bifunctional compounds); Inductive and
resonance effects on acidity and basicity of organic acids and bases;
Hyperconjugation; Reactive intermediates produced during homolytic and heterolytic
bond cleavage; Formation, Structure and Stability of carbocations and free radicals.

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 1

 EXERCISE – I
1. Identify the species not capable of acting as an electrophile.
(a) BCl3 (b) AlCl3

(c) NH 4 (d) CO2
2. Which of the following species is a nucleophile but not an electrophile?
 
(a) NH 4 (b) NH 3 OH
(c) H3O (d) CH3CCH3
O
3. Which is the most stable carbocation?

(a) (CH3)2CH+ (b) CH2

(c) CH 2  CH  CH 2 (d) (CH3)3C+

4. Steric inhibition of resonance can be expected in

(a) N (b) N

(c) N (d) N

5. Which free radical is the most stable one?



(a) CH2 (b) CH2

NO2
 
(c) (CH3)3C (d) (CH3)2CH


6. In (tBu)3C, the hybridization of central carbon atom is

(a)Hsp (b) sp2
(c) sp3 (d) none of these

7. Which of the following represents the correct order of acidic strength?

(a) HCO2H > CO2HCO2H (b) CH3CO2H > HCO2H
(c) CO2HCO2H < CO2HCH2CO2H (d) CO2HCO2H > HCO2H
8. A compound/species is antiaromatic when it has
(a) 4n electrons (b) (4n + 1) electrons
(c) (4n + 2) electrons (d) (4n + 3) electrons

9. The cyclopropenyl cation,  is

(a) aromatic (b) antiaromatic

(c) nonaromatic (d) non planar


10. The cyclopentadienyl cation, is

(a) aromatic (b) antiaromatic

(c) nonaromatic (d) none of these

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 29

11. In which of the following molecule, the group attached to benzene donot show any type of resonance
effect?

(a) NH2 (b) NH3

(c) OH (d) Cl

12. Which of the following is correct order regarding the acidity of carboxylic group?
(a) CH3CH2CH(Cl)COOH > CH3CH(Cl)CH2COOH > ClCH2CH2CH2COOH
(b) CH3CH2CH(Cl)COOH < CH3CH(Cl)CH2COOH < ClCH2CH2CH2COOH
(c) CH3CH2CH(Cl)COOH > CH3CH(Cl)CH2COOH < ClCH2CH2CH2COOH
(d) CH3CH2CH(Cl)COOH < CH3CH(Cl)CH2COOH > ClCH2CH2CH2COOH
13. Which of the following is correct order regarding I effect of the substituents?
(a) NH2 > OH > F (b) NH2 < OH < F
(c) NH2 > OH < F (d) NH2 < OH > F
14. Which of the following order is not the correct order regarding I effect of the substituents?

(a) I < Cl < Br < F (b) NR2 <  O R 2

(c) NR2 < OR < F (d) SR < OR <  OR 2
15. Which of the following is correct order regarding the acidity of carboxylic acids?
(a) (CH3)3CCOOH > (CH3)2CHCOOH > CH3CH2COOH
(b) (CH3)3CCOOH > (CH3)2CHCOOH < CH3CH2COOH
(c) (CH3)3CCOOH < (CH3)2CHCOOH > CH3CH2COOH
(d) (CH3)3CCOOH < (CH3)2CHCOOH < CH3CH2COOH
16. Which of the following compound has the highest pKa value?
OH OH
Cl NO2
(a) (b)

OH OH
CH3 OCH3
(c) (d)

17. Which one of the following compound would you expect to be the strongest carbon acid?
O
(a) CH2(COOC2H5)2 (b)

O
O O
(c) CH3COCH2COOC2H5 (d)
18. Which is the most stable singlet carbene among the following?
.. ..
(a) CF2 (b) CCl2
.. ..
(c) CBr2 (d) CI2
19. Which of the following species cannot function as an electrophile?
..
(a) HCl (b) CCl2
(c) SiF4 (d) H3O

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 30

20. Which of the following nitrogenous base is the strongest in water?

(a) (b)
N N
H H

(c) (d)
N N
H
21. In which one of the following compounds delocalisation is not possible?
(a) 2butene (b) 1,3butadiene
(c) 1,3,5hexatriene (d) Benzene
22. Consider the following carbocations:
 
(1) CH3CH2 (2) CH2=CH
 
(3) CH2=CHCH2 (4) C6H5CH2
Stability of these carbocations in decreasing order is
(a) (4) > (3) > (1) > (2) (b) (4) > (3) > (2) > (1)
(c) (3) > (4) > (2) > (1) (d) (3) > (4) > (1) > (2)
23. Which one of the following cation is most acidic?
 
NH3 NH3

(a) (b)

O
 
NH3 NH3

(c) (d)

NO 2 CH3
24. Which of these species is capable of acting as electrophile?
(a) CO2 (b) CH3CH
O
(c) AlCl3 (d) All of these
25. Decreasing order of stability of given carbocations is


(1) (2) CH2=CHCH2
 
(3) C6H5CH2 (4) CH3CHCH3
(a) (3) > (2) > (4) > (1) (b) (1) > (3) > (4) > (2)
(c) (1) > (3) > (2) > (4) (d) (3) > (2) > (1) > (4)

EXERCISE – II
1. Consider the following amines:
(1) C6H5NH2 (2) oNO2C6H4NH2
(3) mNO2C6H4NH2 (4) pNO2C6H4NH2

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 31

 Arrange these compounds in decreasing order of basicity:
(a) (1) > (2) > (3) > (4) (b) (2) > (1) > (3) > (4)
(c) (1) > (3) > (4) > (2) (d) (1) > (3) > (2) > (4)
2. Weakest base among the following amino compounds is:

(a) NH (b) NH NH

(c) NH2 (d) N

3. In which of the following molecules all the effects namely inductive, mesomeric and hyperconjugation
operate:

(a) Cl (b) COCH3

CH3

(c) CH3 (d) CH3CH=CHCl

CH3
4. W
(a) ? (b) ?
(c) ? (d) ?
5. Most acidic hydrogen is present in:
O O O

(a) (b)

(c) (CH3CO)3CH (d) (CH3)3COH

7. Which nitrogen in Lysergic acid diethylamide (LSD) is most basic?

(1) O
(3)
HN
(2) CN(C2H5)2
N
CH3
(a) 1 (b) 2
(c) 3 (d) All are equally basic
9. Which of the following carbanion is most stable?

CH2 CH2 CH2 CH2

NO2 CN
(a) (b) (c) (d)

NO2 CN
10. Which of the following reaction intermediates are electrophilic in character?
(1) Carbocation (2) Carbanion
(3) nitrenes (4) Carbenes
(a) (2) and (4) (b) (1) and (3)
(c) (3) and (4) (d) (1) and (4)

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 32

11. is more basic than because
..
N
.. N

(a) is a six membered aromatic ring.

N
..

(b) Lone pair of is not taking part in delocalization.

N
..
(c) Lone pair of is taking part in delocalization.
..
N

(d) is an aromatic amine.

..
N
12. Which of the following compound/species is an aromatic species?
O
(a) (b)


O

(c) (d)

13. Which of the following represents right order of acidity?

(a) CHF3 > CHCl3 (b) CHCl3 > CHF3

(c) > (d) >

O O S S S S O O
14. Which one of the following compound is most acidic?
(a) HOCH2COOH (b) O2NCH2COOH
(c) ClCH2COOH (d) NCCH2COOH
15. W
(a) ? (b) ?
(c) ? (d) ?
16. Arrange homolytic bond energies of CH bonds designated by (I), (II), (III), (IV) and (V) in increasing
order.
(II)
(V ) H (I )
H H

(III)
H
CH2H
(IV)

(a) (II) < (V) < (IV) < (III) < (I) (b) (III) < (V) < (IV) < (II) < (I)
(c) (I) < (III) < (IV) < (II) < (V) (d) (II) < (IV) < (V) < (I) < (III)
17. Consider the following three halides
(A) CH3CH2Cl (B) CH2=CHCl (C) HCCCl
Arrange these three compounds in decreasing order of CCl bond length.
(a) (A) > (B) > (C) (b) (C) > (B) > (A)
(c) (B) > (C) > (A) (d) (A) > (C) > (B)
18. Arrange basicity of the given compounds in decreasing order.
(A) CH3CH2NH2 (B) CH2=CHNH2 (C) CHCNH2

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 33

 (a) (A) > (B) > (C) (b) (A) > (C) > (B)
(c) (C) > (B) > (A) (d) (B) > (C) > (A)
19. Which of the following is a nonaromatic compound/species?


(A) (B)

(C) (D)

(a) (A) (b) (B)
(c) (C) (d) (D)
21. Arrange stability of given compounds in decreasing order
(1) C6H6 (2) CH2=CHCH2CH2CH=CH2
(3) CH2=CHCH=CH2 (4) CH2=C=CH2
(a) (3) > (1) > (4) > (2) (b) (1) > (3) > (2) > (4)
(c) (1) > (3) > (4) > (2) (d) (3) > (1) > (2) > (4)
23. The most stable free radical is
Me

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

24. According to the Huckel’s rule, which of the following species will be aromatic?


(I) (II) 
(III) (IV)

(a) (I) (b) (II)

(c) (III) (d) (IV)
25. Arrange the following compounds in decreasing order of their acidic strength.
COOH COOH COOH COOH
CH3 Cl NO2 OCH3

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

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

EXERCISE – III
1. Which one of the following is strongest acid?
(a) 2chloropentanoic acid (b) 3chloropentanoic acid
(c) 5chloropentanoic acid (d) 4chloropentanoic acid
2. Consider the following compound
CH2=CHCH=CH2
1 2 3 4

carboncarbon bond length between C2 and C3 will be

(a) 1.54 Å (b) 1.33 Å
(c) Less than 1.54 Å and greater than 1.33 Å (d) 1.21 Å

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 34

3. Among the following compounds, the strongest base is
O NH
(a) NH2CNH2 (b) NH2CNH2
(c) C6H5NH2 (d) CH3NHCH3
4. Arrange the given compounds in decreasing order of their basicity.
(1) CH3CH2NH2 (2) CH2=CHNH2
(3) CHCNH2
(a) (1) > (2) > (3) (b) (1) > (3) > (2)
(c) (3) > (2) > (1) (d) (2) > (3) > (1)
5. Which of the following compounds give white precipitate with AgNO3?

Cl Cl CH2Cl

(I) (II) (III)

(a) (I) and (II) (b) (II) and (III)
(c) (I) and (III) (d) none of these
6. Consider the following compounds:
NH2 NH2 NH2 NH2

NO2 CN CH3
(1) (2) (3) (4)
Arrange these compounds in decreasing order of their basicity
(a) (4) > (1) > (2) > (3) (b) (1) > (3) > (4) > (2)
(c) (4) > (1) > (3) > (2) (d) (1) > (3) > (2) > (4)
7. Consider the following compounds:
O

N N N N
H H H
(1) (2) (3) (4)

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

a b
8. H3C–N CONH2

PhNHCH2 CH2 NHCOCH3

d c
In the given molecule, the most basic nitrogen atom is
(a) a (b) b
(c) c (d) d
9. Which one of the compounds behaves as an electrophile as well as nucleophile?
(a) Acetone (b) Cyanide ion
(c) Nitrite ion (d) Sulphite ion
10. The compound which gives the most stable carbonium ion on dehydration is
Butan2ol 2methylpropan2ol Butan1ol 2methylpropan1ol
(I) (II) (III) (IV)
(a) (I) (b) (II)

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 35

 (c) (III) (d) (IV)
11. Alkenes give electrophilic addition reaction in the presence of polar protic solvent with those reagents
which on dissociation give electrophile and nucleophile. Which reagent will not give addition reaction
with alkenes
(a) HCl (b) H2SO4
(c) HOCl (d) NaCl
12. Acyl cation has two resonating structures (I) and (II):
 
RC=O RCO
(I) (II)
Which statement is correct for (I) and (II)
(a) (I) is more stable than (II).
(b) (II) is more stable than (I).
(c) Stability of (I) and (II) will be the same.
(d) For some time (I) is more stable and for remaining time (II) will be more stable.
13. Consider the following amines
(1) C6H5NH2 (2) oNO2C6H4NH2
(3) mNO2C6H4NH2 (4) pNO2C6H4NH2
Arrange these compounds in decreasing order of basicity
(a) (1) > (2) > (3) > (4) (b) (2) > (1) > (3) > (4)
(c) (1) > (3) < (4) > (2) (d) (1) > (3) > (2) > (4)
14. Arrange basicity of the following compounds in decreasing order
(1) pCH3OC6H4NH2 (2) mCH3OC6H4NH2
(3) oCH3OC6H4NH2 (4) C6H5NH2
(a) (1) > (4) > (3) > (2) (b) (4) > (1) > (2) > (3)
(c) (1) > (4) < (2) > (3) (d) (4) > (2) > (3) > (1)
15. Arrange given compounds in order of decreasing acidity
(1) CH3NO2 (2) NO2CH2NO2
(3) CH3CH2NO2 (4) NO2CHNO2
NO2
(a) (4) > (2) > (1) > (3) (b) (4) > (2) > (3) > (1)
(c) (3) > (1) < (2) > (4) (d) (3) > (1) > (4) > (2)
16. Which one of the following has the highest nucleophilicity?
(a) F (b) OH
(c) CH 3 (d) NH 2
17. Decreasing I power of given groups is
(1) CN (2) NO2
(3) NH3 (4) F
(a) (2) > (1) > (4) > (3) (b) (2) > (3) > (4) > (1)
(c) (3) > (2) < (4) > (1) (d) (3) > (2) > (1) > (4)
18. +R power of the given groups is
(1) O (2) NH2
(3) OH (4) NHCOCH2
(a) (1) > (2) > (3) > (4) (b) (1) > (2) > (3) > (4)
(c) (1) > (3) < (2) > (4) (d) (1) > (4) < (3) > (2)
19. Arrange the following groups in order of decreasing R (or M) power
(1) NO2 (2) SO3H
(3) CF3 (4) CHO
(a) (1) > (3) > (2) > (4) (b) (1) > (2) > (3) > (4)
(c) (1) > (4) < (3) > (2) (d) (4) > (3) > (2) > (1)

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 36

20. The number of delocalised electrons in the given compound is

(a) 4 (b) 6
(c) 8 (d) 2
21. Which one of the following is a secallylic carbocation?
 
(a) CH2CH=CH2 (b) CH3CH=CHCH2
 
(c) C6H5CH=CH (d) CH3CHCH=CH2
22. Which allylic carbocation is most stable carbocation?
 
(a) CH3CH=CHCH2 (b) CH3CH=CHCHCH3

(c) CH3CH=CHCCH3 (d) All have same stability
CH3

23. In pyridine
N
..
Number of conjugated electrons are
(a) 6 (b) 8
(c) zero (d) 5
24. Melting point of which compound is maximum?
(a) Chlorobenzene (b) odichlorobenzene
(c) mdichlorobenzene (d) pdichlorobenzene
25. Which one of the following compound is least soluble in water?
(a) Phenol (b) onitrophenol
(c) mnitrophenol (d) pnitrophenol

EXERCISE – IV
H O O
C
H
1. In , which hydrogen is the most acidic? Explain your choice.
H
H
OH

CH3 CH2 OC2H5 CH3 CH2 CH3

C C C C
2. ,
O O O O
(I) (II)
When (I) and (II) are treated with base, separately carbanion results. Which carbanion will be more stable?

3. The basicity order of the following compounds is N < N .Explain the order.

4. Why do electrophiles attack trichloromethyl benzene at meta position where as they attack benzene ring
at ortho and para position in chloromethyl benzene?
5. CH3Cl + AgCN  Major product + Minor product. Describe the major product with reasoning.
6. CH2=CHCl does not give CH2=CHOH easily on treatment with OH. Explain.
7. CHCH  
HCl
CH2=CHCl
HCl HCl

CH3CHCl2 ClCH2CH2Cl
Possibility1 Possibility2

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 37

 In the above reaction sequence if carbocation formation is the intermediate step, then out of the two
possibilities, which one will be favoured?
.. ..
8. Between, C = C  F and C = C  Cl , which lone pair conjugation will be more preferred?
9. Write the basicity order of NH3, CH3NH2, (CH3)2NH, (CH3)3N in aqueous medium.
10. Arrange the following electrophiles in the decreasing order of electrophilicity?
NO2 OMe NO2
  
N2 N2 N2

(I) (II) (III)

11. Give proper explanation/s for the following:
(a) Compound I has greater dipole moment than compound II.
Ph O
O
Ph Ph
Ph
I II
(b) Which compound has the greater electron density on its nitrogen atom?

or NH
N
H
(c) Species I is more stable than II.

I II
12. Give proper explanation/s for the following:
(a) A methyl group bonded to benzene loses proton more readily than a methyl group bonded to
cyclohexane.
(b) The direction of the dipole moment in fulvene and calcene.

fulvene calcene

(c) Compound I is more stable than the compound II.

I II
13. (a) If the pKa of an acid is 6, what will be the pKb of its conjugate base?
(b) Which of the following hydrocarbon is most acidic?
CH3
(i) (ii) (iii) (iv)

14. (a) Which of the two enols would you expect to be the stronger acid and why?
O O OH
CH2
H3C H3C CH3
OH

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 38

 O
(b) is basic but is not.
NH
N O

(c) O is more acidic than .

OH O OH

(d) is less basic than .

N N

15. The phenols shown below have approximate pKa values of 4, 7, 9, 10 and 11.Suggest with explanations,
which pKa value belongs to which phenol?
OH
OH OH OH OH

O2N NO2 O2N

OH

ANSWERS TO EXERCISE – I

1. (c) 2. (b) 3. (d) 4. (c) 5. (a)

6. (b) 7. (d) 8. (a) 9. (a) 10. (b)
11. (b) 12. (a) 13. (b) 14. (a) 15. (d)
16. (d) 17. (b) 18. (a) 19. (d) 20. (d)
21. (a) 22. (a) 23. (c) 24. (d) 25. (c)

ANSWERS TO EXERCISE – II

1. (c) 2. (d) 3. (b) 4. (d) 5. (c)

6. (b) 7. (b) 8. (d) 9. (a) 10. (c)
11. (b) 12. (d) 13. (d) 14. (b) 15. (c)
16. (a) 17. (a) 18. (a) 19. (d) 20. (b)
21. (b) 22. (a) 23. (d) 24. (b) 25. (d)

ANSWERS TO EXERCISE – III

1. (a) 2. (c) 3. (b) 4. (a) 5. (c)

6. (c) 7. (d) 8. (a) 9. (a) 10. (b)
11. (d) 12. (b) 13. (c) 14. (a) 15. (a)
16. (c) 17. (a) 18. (a) 19. (a) 20. (b)
21. (d) 22. (c) 23. (a) 24. (d) 25. (b)

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 39

 ANSWERS TO EXERCISE – IV
1. COOH always shows stronger acidity as compared to other functional groups (except SO3H).
2. Carbanion from (II) will be formed because of more thermodynamic stability due to greater resonance
(as COR group is more electron withdrawing than CO2R group).

3. The basicity in the present case is influenced by solvation effect more than the availability of electron pair
on nitrogen atom.

4. Participation of chlorine atoms in H (Hyperconjugation).

5. CH3NC. This is because of hard acidhard base interaction (nitrogen atom is a harder acid than carbon).

6. This is because of lone pairp conjugation in CH2=CHCl increases the bond order between CCl
bond. Thus, CCl bond is not broken easily under milder conditions.

7. Possibility 1 will exist because CH2=CHCl on taking H+ from HCl form CH3CHCl , while in possibility II
  
the carbocation formed is CH2CH2Cl . The carbocation CH3CHCl is more stable than CH2CH2Cl
because the former has +I effect of CH3, +R effect of Cl and I effect of Cl whereas the latter has I

effect of CH2Cl. Thus, CH3CHCl is attacked latter by Cl to form CH3CHCl2 as the major product.

8. Lone pairp conjugation between fluorine and carbon will be more effective than between chlorine and
carbon (as Cl and C belong to 3rd and 2nd period respectively and F and C, both belong to 2nd period).

9. (CH3)2NH > CH3NH2 > (CH3)3N > NH3

10. (III) is the strongest electrophile because of R effect of nitro group is also operative along with its I
effect but (I) has a greater +R effect (lesser I effect) and NO2 from meta position will only show I
effect. Thus, the decreasing order of electrophilicity is (III) > (I) > (II).
O O O


11. (a)

I The +ve charge is resonance

Highly strained ring
stabilized.
O O 

C C
II
Greater charge separation in I assigns it a higher dipole moment than II.

..

(b) .. 
N N
H H

In N H ; no such resonance is possible. Hence, electron density is more over nitrogen atom.

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 40

 (c)  is aromatic as it involves cyclic delocalization and follows Huckel’s (4n + 2)  e rule.

(I)

is not aromatic and hence is less stable.

(II)
CH3
CH3
12. (a) In , the CH bond is more polar than the CH bond in due to e shift by

hyperconjugative effect. Moreover, the loss of H+ gives benzyl carbanion PhCH2 , which is
resonance stabilized but not so in the anion of methyl cyclohexane.


(b) CH2 CH2
fulvene aromatic

aromatic
calcene aromatic

Since both the charges have greater separation in calcene, so it has more dipole moment than fulvene.

(c) The sp2 hybridised carbon is in a sixmembered ring where the angle strain will be less as

(I)

compared to that in where there is a fourmembered ring, which is more strained. Thus,

(II)
compound (I) is more stable than compound (II).

13. (a) pKa = 6, pKb of its conjugate base = 14  6 = 8.

(b) Cyclopentadiene is most acidic as the loss of proton in it gives a carbanion, which is stabilized by
aromaticity.
..

(i) + H+
Most stable (aromatic)
..

(ii) + H+

CH3 .. CH2

(iii) + H+

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 41

 ..
(iv) + H+

In case (i), the equilibrium is shifted most in the forward direction, hence compound (i) is most acidic.
O O
CH2 CH3
14. (a) H3C H3C
OH O
O
Both C and OH groups are in trans position and so no hydrogen bonding exists and can easily
tautomerise and it is more polar.
H
O O O
O

CH3 H3C CH3

H3C
Here, intramolecular hydrogen bonding exists and is less polar. This compound is more acidic than
the former as its carbanion is more resonance stabilized.
O
(b) is basic but is not because in the first case, the lone pair on nitrogen
NH
N O
donot participate in resonance with O since it will generate a double bond on bridgehead position
while in the second case it does participate in resonance, decreasing its basicity.
O O
.. 
NH NH

(c) O is more acidic than because its conjugate base is more resonance
OH O OH
stabilized.

..
..
O O O O
 ..
O O O O

O

(d) The lone pair on nitrogen of participates in resonance with phenyl ring, so it becomes
N

less basic. This doesnot happens in .

N

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 42

 OH
O OH OH OH
H
15. O
NO2 N NO2
O OH (v)
(i) (ii) (iii) (iv)

(i) pKa = 4 (ii) pKa = 7 (iii) pKa = 11 (iv) pKa = 10 (v) pKa = 9
NO2 groups exerts I and R effect from ortho and para position. OH group exerts only I effect from
meta position. Me group exerts +I and +H effect from ortho and para position while it exerts only +I
effect from meta position.

EXERCISE – I
CBSE PROBLEMS
1. What is the shape of following compounds?
(a) H2C=O (b) CH3F (c) HCN
2. Find out the number of  and bonds in the following compound.
(CN)2C=C=C(CN)2
 
3. Among the structures RCO and RC=O of acylium ion, which one is more stable?
4. Which of the following acids has the least strength?
CH3CHFCOOH, BrCH2CH2COOH, FCH2CH2COOH and CH3CHBrCOOH
5. Why is ethyl amine a stronger base than ammonia?
6. Draw the resonance structures of the following compounds.
HOC=O OCH3

(a) (b)

7. Explain why alkyl group acts as electron donor when attached to a -bonded system?
8. Arrange the following radicals according to the increasing order of stability.
 
(a) CH3 O— — C H2 (b) NO2— — C H2

 
(c) CH3 — — C H2 (d) — C H2

9. Higher alkyl substituted alkene is formed in greater proportion than the lower alkyl substituted alkene.
Justify the statement.
10. Among the following compounds which one is/are aromatic?
O + +
+ O
(a) (b) (c) (d) (e)

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 43

 EXERCISE – II
AIEEE-SINGLE CHOICE CORRECT

1. Consider the following amines:

(1) C6H5NH2 (2) oNO2C6H4NH2
(3) mNO2C6H4NH2 (4) pNO2C6H4NH2
Arrange these compounds in decreasing order of basicity:
(a) (1) > (2) > (3) > (4) (b) (2) > (1) > (3) > (4)
(c) (1) > (3) > (4) > (2) (d) (1) > (3) > (2) > (4)
2. Weakest base among the following amino compounds is:

(a) NH (b) NH NH

(c) NH2 (d) N

3. Most acidic hydrogen is present in:

O O O

(a) (b)

(c) (CH3CO)3CH (d) (CH3)3COH

4. Which nitrogen in Lysergic acid diethylamide (LSD) is most basic?

(1) O
(3)
HN
(2) CN(C2H5)2
N
CH3
(a) 1 (b) 2
(c) 3 (d) All are equally basic
5. Which of the following carbanion is most stable?

CH2 CH2 CH2 CH2

NO2 CN
(a) (b) (c) (d)

NO2 CN
6. Which one of the following compound is most acidic?
(a) HOCH2COOH (b) O2NCH2COOH
(c) ClCH2COOH (d) NCCH2COOH
7. Arrange homolytic bond energies of CH bonds designated by (I), (II), (III), (IV) and (V) in increasing
order.
(II)
(V ) H (I )
H H

(III)
H
CH2H
(IV)

(a) (II) < (V) < (IV) < (III) < (I) (b) (III) < (V) < (IV) < (II) < (I)

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 44

 (c) (I) < (III) < (IV) < (II) < (V) (d) (II) < (IV) < (V) < (I) < (III)
8. Consider the following three halides
(A) CH3CH2Cl (B) CH2=CHCl (C) HCCCl
Arrange these three compounds in decreasing order of CCl bond length.
(a) (A) > (B) > (C) (b) (C) > (B) > (A)
(c) (B) > (C) > (A) (d) (A) > (C) > (B)
9. Arrange basicity of the given compounds in decreasing order.
(A) CH3CH2NH2 (B) CH2=CHNH2 (C) CHCNH2
(a) (A) > (B) > (C) (b) (A) > (C) > (B)
(c) (C) > (B) > (A) (d) (B) > (C) > (A)
10. Which of the following is a nonaromatic compound/species?


(A) (B)

(C) (D)

(a) (A) (b) (B)
(c) (C) (d) (D)
11. Arrange stability of given compounds in decreasing order
(1) C6H6 (2) CH2=CHCH2CH2CH=CH2
(3) CH2=CHCH=CH2 (4) CH2=C=CH2
(a) (3) > (1) > (4) > (2) (b) (1) > (3) > (2) > (4)
(c) (1) > (3) > (4) > (2) (d) (3) > (1) > (2) > (4)
12. The most stable free radical is
Me

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

13. According to the Huckel’s rule, which of the following species will be aromatic?


(I) (II) 
(III) (IV)

(a) (I) (b) (II)

(c) (III) (d) (IV)
14. Which of the following compound is most acidic?
OH OH OH
NO2
(a) OH (b) (c) (d)
NO2
NO 2
15. Which of the following carbocation is most stable?
 
(a) (CH 3 ) 2 CH (b) (CH 3 ) 3 C
 
(c) Ph  CH  CH3 (d) Ph  CH2

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 45

 EXERCISE – III
IIT-JEE- SINGLE CHOICE CORRECT
1. Identify the species not capable of acting as an electrophile.
(a) BCl3 (b) AlCl3

(c) NH 4 (d) CO2
2. Which of the following species is a nucleophile but not an electrophile?
 
(a) NH 4 (b) NH 3 OH
(c) H3O (d) CH3CCH3
O
3. Which is the most stable carbocation?

(a) (CH3)2CH+ (b) CH2

(c) CH 2  CH  CH 2 (d) (CH3)3C+

4. Steric inhibition of resonance can be expected in

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

5. Which free radical is the most stable one?



(a) CH2 (b) CH2

CH3
 
(c) (CH3)3C (d) (CH3)2CH


6. In (tBu)3C, the hybridization of central carbon atom is

(a)Hsp (b) sp2
(c) sp3 (d) none of these
7. Which of the following represents the correct order of acidic strength?
(a) HCO2H > CO2HCO2H (b) CH3CO2H > HCO2H
(c) CO2HCO2H < CO2HCH2CO2H (d) CO2HCO2H > HCO2H
8. A compound/species is antiaromatic when it has
(a) 4n electrons (b) (4n + 1) electrons
(c) (4n + 2) electrons (d) (4n + 3) electrons

9. The cyclopropenyl cation,  is

(a) aromatic (b) antiaromatic

(c) nonaromatic (d) non planar


10. The cyclopentadienyl cation, is

(a) aromatic (b) antiaromatic

(c) nonaromatic (d) none of these
11. In which of the following molecule, the group attached to benzene does not show any type of resonance
effect?

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 46

 
(a) NH2 (b) NH3

(c) OH (d) Cl

12. Which of the following is correct order regarding the acidity of carboxylic group?
(a) CH3CH2CH(Cl)COOH > CH3CH(Cl)CH2COOH > ClCH2CH2CH2COOH
(b) CH3CH2CH(Cl)COOH < CH3CH(Cl)CH2COOH < ClCH2CH2CH2COOH
(c) CH3CH2CH(Cl)COOH > CH3CH(Cl)CH2COOH < ClCH2CH2CH2COOH
(d) CH3CH2CH(Cl)COOH < CH3CH(Cl)CH2COOH > ClCH2CH2CH2COOH
13. Which of the following is correct order regarding I effect of the substituents?
(a) NH2 > OH > F (b) NH2 < OH < F
(c) NH2 > OH < F (d) NH2 < OH > F
14. Which of the following order is not the correct order regarding I effect of the substituents?

(a) I < Cl < Br < F (b) NR2 <  O R 2

(c) NR2 < OR < F (d) SR < OR <  OR 2
15. Which of the following is correct order regarding the acidity of carboxylic acids?
(a) (CH3)3CCOOH > (CH3)2CHCOOH > CH3CH2COOH
(b) (CH3)3CCOOH > (CH3)2CHCOOH < CH3CH2COOH
(c) (CH3)3CCOOH < (CH3)2CHCOOH > CH3CH2COOH
(d) (CH3)3CCOOH < (CH3)2CHCOOH < CH3CH2COOH
16. Which of the following compound has the highest pKa value?
OH OH
Cl NO2
(a) (b)

OH OH
CH3 OCH3
(c) (d)

17. Which one of the following compound would you expect to be the strongest carbon acid?
O
(a) CH2(COOC2H5)2 (b)

O
O O
(c) CH3COCH2COOC2H5 (d)

18. Which is the most stable singlet carbene among the following?
.. ..
(a) CF2 (b) CCl2
.. ..
(c) CBr2 (d) CI2
19. Which of the following species cannot function as an electrophile?
..
(a) H3C (b) CCl2
(c) SiF4 (d) H3O
20. Which of the following nitrogenous base is the strongest in water?

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 47

 (a) (b)
N N
H H

(c) (d)
N N
H
21. In which one of the following compounds delocalisation is not possible?
(a) 2butene (b) 1,3butadiene
(c) 1,3,5hexatriene (d) Benzene
22. Consider the following carbocations:
 
(1) CH3CH2 (2) CH2=CH
 
(3) CH2=CHCH2 (4) C6H5CH2
Stability of these carbocations in decreasing order is
(a) (4) > (3) > (1) > (2) (b) (4) > (3) > (2) > (1)
(c) (3) > (4) > (2) > (1) (d) (3) > (4) > (1) > (2)
23. Which one of the following cation is most acidic?
 
NH3 NH3

(a) (b)

OH
 
NH3 NH3

(c) (d)

NO 2 CH3
24. Which of these species is capable of acting as electrophile?
(a) CO2 (b) CH3CH
O
(c) AlCl3 (d) All of these
25. Decreasing order of stability of given carbocations is


(1) (2) CH2=CHCH2
 
(3) C6H5CH2 (4) CH3CHCH3
(a) (3) > (2) > (4) > (1) (b) (1) > (3) > (4) > (2)
(c) (1) > (3) > (2) > (4) (d) (3) > (2) > (1) > (4)

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 48

 EXERCISE – IV
ONE OR MORE THAN ONE CHOICE CORRECT

1. The correct order of the stability of the given resonating structures

 
CH2CHCH=CHOCH3 CH2CH=CHCH=OCH3
(I) (II)
 
CH2=CHCHCHOCH3 CH2=CHCHCH=OCH3
(III) (IV)
(a) (IV) > (II) > (I) > (III) (b) (IV) < (II) < (III) < (I)
(c) (III) < (I) < (II) < (IV) (d) (I) > (III) > (II) > (IV)
2. Which of the following compound shows +R effect on benzene ring?
O
NHCCH3 OCH3 C(CH3)3 O

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

3. Which of the following reaction leads to the formation of carbocation as an intermediate?


C N; polar h
(a) RCl   ? (b) RH + X2  ?
protic solvent

(c) RCH=CH2 + H  ? (d) CH3NO2 + B  ?

4. Which of the following are aromatic species?

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

.. ..
 .. 

(a) (b)
HO2C CO2H
5. The correct acidity order of the indicated groups in the following compound is

NH3
(c)
(a) (b) > (a) > (c) (b) (a) < (b) < (c)
(c) (c) > (b) > (a) (d) (c) < (a) < (b)
6. Which of the following is true about carbenes?
(a) Carbenes can be formed by elimination of CHCl3.
(b) Carbenes can do nucleophilic attack.
(c) Among alkylated carbenes, singlet form is more stable than triplet form.
(d) Carbenes can undergo addition to double bond to give cyclopropyl systems.
7. In which of the following molecules all the effects namely inductive, mesomeric and hyperconjugation
operate:

(a) Cl (b) COCH3

CH3

(c) CH3 (d) CH3CH=CHCl

CH3
8. Which of the following reaction intermediates are electrophilic in character?
(1) Carbocation (2) Carbanion

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 49

 (3) nitrenes (4) Carbenes
(a) (2) and (4) (b) (1) and (3)
(c) (3) and (4) (d) (1) and (4)

9. is more basic than because

..
N
.. N
H

(a) is a six membered aromatic ring.

N
..

(b) Lone pair of is not taking part in delocalization.

N
..

(c) Lone pair of is taking part in delocalization.

..
N
H

(d) is an aromatic amine.

..
N
H
10. Which of the following compound/species is/are aromatic species?
O
(a) (b)


O

(c) (d)

11. Which of the following represent(s) correct order of acidity?

(a) CHF3 > CHCl3 (b) CHCl3 > CHF3

(c) > (d) >

O O S S S S O O
12. Which of the following intermediate(s) is/are electrically neutral?
(a) Carbanion (b) Benzyne (c) Carbene (d) Carbocation
13. Which of the following intermediate is aromatic in nature?
CH3

 :
(a) (b) (c) (d) (singlet)
..
14. Which of the following is/are correct statement(s)?
(a) Aniline shows stronger resonance than phenol.
(b) 2,6dimethyl4nitrophenol is more acidic than 3,5dimethyl4nitrophenol.
. .
(c) CH2CH=CHCH2 is a valid resonance structure of CH2=CHCH=CH2.
(d) Benzyl free radical is more stable than tbutyl free radical.
15. In which of the following pairs, first member is more stable than the second?
  .
(a) (C6H5 )3 C , (C6H5 ) 2 C CH 3 (b) :CH2, CH2
.
 

(c) (C6H5)3C: , :CH3 (d) (C2H5 )3 C, (CH 3 )3 C

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 50

 EXERCISE – V

MATCH THE FOLLOWING

1.
Column I Column II
I. Elimination X
(A) CH3CHCH=CH2 + HX  CH3CCH2–CH3
CH3 CH3
Anhydrous
II. Substitution (B) CH3CH2CH2Cl CH3CHCH3
AlCl3, 
Cl
III. Rearrangement 
(C) CCC XY
C C
X Y C

IV. Addition NO2

(D) H2SO4
+ HNO3 + H2O

2.
Column I Column II
HIO4
I. O (A) Aromatic product

K
II. (B) Non-aromatic product

AgNO3
III. Cl (C) Precipitates are formed

Br AgBF4
IV. (D) No precipitation

3. Match the following pKa values if pKa value of orthonitro aniline is 0.29
Column I Column II
I. Paramethyl aniline (A) 3.98
II. Paramethoxy aniline (B) 5.19
III. Paranitro aniline (C) 1.02
IV. Parachloro aniline (D) 5.29

REASONING TYPE
Directions: Read the following questions and choose
(A) If both the statements are true and statement-2 is the correct explanation of statement-1.
(B) If both the statements are true but statement-2 is not the correct explanation of statement-1.
(C) If statement-1 is True and statement-2 is False.
(D) If statement-1 is False and statement-2 is True.
1. Statement-1: The basic strength of amines in an aqueous solution is (CH3)2NH > CH3NH2 > (CH3)3N >
NH3.
Statement-2: The basic strength of amines in aqueous solution is governed by the availability of electron
pair on nitrogen as well as on the solvation of their conjugate acids.

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 51

 (a) (A) (b) (B) (c) (C) (d) (D)
2. Statement-1: The ohydroxy benzoic acid is a stronger acid than omethoxy benzoic acid.
Statement-2: The ortho effect is more prominent in ohydroxy benzoic acid than in omethoxy benzoic
acid.
(a) (A) (b) (B) (c) (C) (d) (D)
3. Statement-1: Phenoxide ring is more activated than phenol ring towards electrophilic substitution
reaction.
Statement-2: O group shows +I effect while OH group shows I effect. +R effect is shown by O
as well as OH group.
(a) (A) (b) (B) (c) (C) (d) (D)
4. Statement-1: Maleic acid is a weaker acid than fumaric acid towards first ionization.
Statement-2: Conjugate base of maleic acid is stabilized by intramolecular hydrogen bonding but not the
conjugate base of fumaric acid.
(a) (A) (b) (B) (c) (C) (d) (D)
5. Statement-1: 7bromo1,3,5Cycloheptatriene ionizes more readily than
5bromo13cyclopentadiene.
Statement-2: Cycloheptatrienyl cation is more stable than cyclopentadienyl cation due to aromatic
character of the former.
(a) (A) (b) (B) (c) (C) (d) (D)
PASSAGE BASED PROBLEMS
Planar monocyclic rings containing (4n + 2) electrons (where n = 0, 1, 2, 3, and so on), should be

aromatic. This is known as Huckel ' s rule for aromaticity. Applying this rule, benzene and its derivatives have
six delocalised electrons and n = 1.
Thus to be aromatic, a molecule must have 2(n = 0), 6(n = 1), 10(n = 2) etc. electrons in a closed orbital
loop. Another requirement for aromaticity is planarity of the ring. If the ring is not planar, overlap of porbitals is
diminished or prevented, then compound will not be aromatic.
Derivatives of benzene are aromatic as they fulfill both the conditions. Molecules having two or more benzene
rings fused together are called polycyclic benzenoid aromatic hydrocarbons. For example, naphthalene, anthracene etc.
Nonbenzenoid aromatic compounds are those which contain a ring that is not six membered. Examples
of such compounds are cyclopentadienyl anion, cyclopropenium cation, tropylium cation etc. Cyclic conjugated
compounds, which possess only 4n electrons, do not satisfy the Huckel rule and are antiaromatic in nature. In a
reaction the reactant would tend to react with reagents that can result into aromatic products / salts.
1. Which of the following is the correct option regarding the direction of the dipole moment?

(a) (b)

(c) (d)
2. Which of the following is the correct statement?

(a) gives immediate turbidity with aqueous AgNO3.

Br

(b) Br gives an immediate turbidity with aqueous AgNO3.

(c) Both of them give immediate turbidity with aqueous AgNO3.

(d) None of them give any turbidity with aqueous AgNO3.
3. Which of the given statement is correct?

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 52

 (a) is more acidic than CH2=CHCH2CH=CH2 (b) is more acidic than

(c) Both (a) and (b) are correct. (d) None of the given option is correct.
4. Which of the given reaction is correct?
 OH
(a) O + HBr  OH (b) O + HBr 
Br
Br
Ph Ph Ph Ph
+ HClO4   ClO4
(c) (d) Both (a) and (c) are correct.
O OH

EXERCISE – VI

SUBJECTIVE PROBLEMS
H O O
C
H
1. In H , which hydrogen is the most acidic? Explain your choice.
H
OH
CH3 CH2 OC2H5 CH3 CH2 CH3
C C C C
2. ,
O O O O
(I) (II)
When (I) and (II) are treated with base, separately carbanion results. Which carbanion will be more stable?

3. The basicity order of the following compounds is N < N .Explain the order.

4. CH2=CHCl does not give CH2=CHOH easily on treatment with OH. Explain.
5. CHCH  
HCl
CH2=CHCl
HCl HCl

CH3CHCl2 ClCH2CH2Cl
Possibility1 Possibility2

In the above reaction sequence if carbocation formation is the intermediate step, then out of the two
possibilities, which one will be favoured?
.. ..
6. Between, C = C  F and C = C  Cl , which lone pair conjugation will be more preferred?
7. Give proper explanation/s for the following:
(a) Compound I has greater dipole moment than compound II.
Ph O
O
Ph Ph
Ph
I II
(b) Which compound has the greater electron density on its nitrogen atom?

or NH
N
H

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 53

 (c) Species I is more stable than II.

I II
8. Give proper explanation(s) for the following:
(a) A methyl group bonded to benzene loses proton more readily than a methyl group bonded to
cyclohexane.
(b) The direction of the dipole moment in fulvene and calcene.

fulvene calcene

(c) Compound I is more stable than the compound II.

I II
9. (a) Which of the two enols would you expect to be the stronger acid and why?
O O OH
CH2
H3C H3C CH3
OH
O
(b) is more basic than
NH
N O

(c) O is more acidic than .

OH O OH

(d) is less basic than .

N N

10. The phenols shown below have approximate pKa values of 4, 7, 9, 10 and 11. Suggest with
explanations, which pKa value belongs to which phenol?
OH
OH OH OH OH

O2N NO2 O2N

OH

ANSWERS
EXERCISE – I
CBSE PROBLEMS
1. Trigonal planar, Tetrahedral, linear 2. C—C  6, C—N  4, CC  2, CN  8

3. R — C  O is more stable 4. BrCH2CH2COOH

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 54

 EXERCISE – II
AIEEE-SINGLE CHOICE CORRECT
1. (c) 2. (d) 3. (c) 4. (b) 5. (a)
6. (b) 7. (a) 8. (a) 9. (a) 10. (d)
11. (b) 12. (d) 13. (b) 14. (d) 15. (c)

EXERCISE – III
IIT-JEE-SINGLE CHOICE CORRECT
1. (c) 2. (b) 3. (d) 4. (c) 5. (a)
6. (b) 7. (d) 8. (a) 9. (a) 10. (b)
11. (b) 12. (a) 13. (b) 14. (a) 15. (d)
16. (d) 17. (b) 18. (a) 19. (d) 20. (d)
21. (a) 22. (a) 23. (c) 24. (d) 25. (c)

EXERCISE – IV
MORE THAN ONE CHOICE CORRECT
1. (a, c) 2. (a, b, d) 3. (a, c) 4. (a, b, c) 5. (a, d)
6. (a, d) 7. (b, d) 8. (b, c, d) 9. (b, c) 10. (a, b, c)
11. (b, d) 12. (b, c) 13. (a, b) 14. (a, b, d) 15. (a, c)

EXERCISE – V
MATCH THE FOLLOWING
1. I  (C) ; II  (D) ; III  (A), (B) ; IV  (A)
2. I  (A), (D) ; II  (A), (D) ; III  (A), (C) ; IV  (B), (C)
3. I  (B) ; II  (D) ; III  (C) ; IV  (A)
ASSERTION AND REASON

1. (a) 2. (c) 3. (a) 4. (d) 5. (a)

PASSAGE BASED PROBLEMS

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

EXERCISE – VI
SUBJECTIVE PROBLEMS
1. COOH always shows stronger acidity as compared to other functional groups (except SO3H).
2. Carbanion from (II) will be formed because of more thermodynamic stability due to greater resonance
(as COR group is more electron withdrawing than CO2R group).

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 55

3. The basicity in the present case is influenced by solvation effect more than the availability of electron pair
on nitrogen atom.
4. This is because of lone pairp conjugation in CH2=CHCl increases the bond order between CCl
bond. Thus, CCl bond is not broken easily under milder conditions.

5. Possibility 1 will exist because CH2=CHCl on taking H+ from HCl form CH3CHCl , while in possibility II
  
the carbocation formed is CH2CH2Cl . The carbocation CH3CHCl is more stable than CH2CH2Cl
because the former has +I effect of CH3, +R effect of Cl and I effect of Cl whereas the latter has I

effect of CH2Cl. Thus, CH3CHCl is attacked latter by Cl to form CH3CHCl2 as the major product.
6. Lone pairp conjugation between fluorine and carbon will be more effective than between chlorine and
carbon (as Cl and C belong to 3rd and 2nd period respectively and F and C, both belong to 2nd period).
O O O


7. (a)

I The +ve charge is resonance

Highly strained ring
stabilized.
O O 

C C
II
Greater charge separation in I assigns it a higher dipole moment than II.
..

(b) .. 
N N
H H

In N H ; no such resonance is possible. Hence, electron density is more over nitrogen atom.

(c)  is aromatic as it involves cyclic delocalization and follows Huckel’s (4n + 2)  e rule.

(I)

is not aromatic and hence is less stable.

(II)
CH3
CH3
8. (a) In , the CH bond is more polar than the CH bond in due to e shift by

hyperconjugative effect. Moreover, the loss of H+ gives benzyl carbanion PhCH2 , which is
resonance stabilized but not so in the anion of methyl cyclohexane.


(b) CH2 CH2
fulvene aromatic

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 56

 

aromatic
calcene aromatic
Since both the charges have greater separation in calcene, so it has more dipole moment than fulvene.

(c) The sp2 hybridised carbon is in a sixmembered ring where the angle strain will be less as

(I)

compared to that in where there is a fourmembered ring, which is more strained. Thus,

(II)
compound (I) is more stable than compound (II).
O O
CH2 CH3
9. (a) H3C H3C
OH O
O
Both C and OH groups are in trans position and so no hydrogen bonding exists and can easily
tautomerise and it is more polar.
H
O O O
O

CH3 H3C CH3

H3C
Here, intramolecular hydrogen bonding exists and is less polar. This compound is more acidic than
the former as its carbanion is more resonance stabilized.
O
(b) is more basic than because in the first case, the lone pair on nitrogen donot
NH
N O
participate in resonance with O since it will generate a double bond on bridgehead position while
in the second case it does participate in resonance, decreasing its basicity.
O O
.. 
NH NH

(c) O is more acidic than because its conjugate base is more resonance
OH O OH
stabilized.
..
..
O O O O
..
O O O O

IIT Easy-9723143889 GENERAL ORGANIC CHEMISTRY 57

 (d) The lone pair on nitrogen of participates in resonance with phenyl ring, so it becomes
N

less basic. This doesnot happens in .

N
OH
O OH OH OH
H
10. O
NO2 N NO2
O OH (v)
(i) (ii) (iii) (iv)
(i) pKa = 4 (ii) pKa = 7 (iii) pKa = 11 (iv) pKa = 10 (v) pKa = 9
NO2 groups exerts I and R effect from ortho and para position. OH group exerts only
I effect from meta position. Me group exerts +I and +H effect from ortho and para position while it
exerts only +I effect from meta position.

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