3.

40 | Organic Chemistry Module I

50. In allene (C3H4), the type(s) of hybridisation of the Cl
carbon atoms, is (are) [ITT Adv. 2012]
(1) sp ad sp 3
(2) sp and sp2 Br CH3
3
(3) only sp (4) sp2 and sp3 Br Cl
51. The hyperconjugative stabilities of tert-butyl cation
and 2-butene, respectively, are due to [IIT-2013]
CH3
(1) p(empty) and * electron delocalisa-
tions 54. Hydrogen bonding plays a central role in the follow-
(2) * and electron delocalisations ing phenomena: [JEE Adv-2014 (MCQ)]
(3) p (filled) and electron delocalisa- (1) Ice floats in water
tions (2) higher lewis basicity of primary amines than
(4) p(filled) * electron delocalisations tertiary amines in aqueous solutions
52. Among P, Q, R and S, the aromatic compound(s) is/ (3) Formic acid is more acidic than acetic acid
are [IIT Adv. 2013 (MCQ)]
55. The correct order of acidity for the following com-
Cl pounds is [JEE(Adv)-2016]

AlCl3 NaH
P Q
O O
O
(NH4)2CO3
R HCl S
100-115°C

(1) P (2) Q
(3) R (4) S
53. The total number(s) of stable conformers with non-
zero dipole moment for the following compound is
(are) [JEE(Adv)-2014]

(1) I > II > III > IV (2) III > I > II > IV
(3) III > IV > II > I (4) I > III > IV > II

ANSWER KEY

EXERCISE # 1 EXERCISE # 2
1. (4) 2. (4) 3. (2) 4. (4) 5. (3)
6. (3) 7. (1) 8. (3) 9. (2) 10. (1)
11. (3) 12. (1) 13. (3) 14. * 15. (3)
 General Organic Chemistry | 3.41

EXERCISE # 3 CH3 CH COOH

1. (1,2,3) 2. (2,3,4) 3. (3) 4. (1,4) NO2
5. (1,3) 6. (1,2,3) 7. (1,2) 8. (2,3,4) (–I)
9. (3,4) 10. (1,2) 11. (1,2,3,4)
12. (2,3,4) 13. (2,3) 14. (1,3,4) 15. (1,2,4) –I group present
CH2 CH2 COOH at same distance
16. (2,3) 17. (1,2,3) 18. (4) 19. (4) 20. (3) from COOH
21. (4) 22. (3) 23. (1) 24. (4) 25. (4) NO2
26. (1) 27. (2) 28. (4) 29. (2) 30. (3)
Then number
31. (4) 32. (4) 33. (4) 34. (3) 35. (5)
Cl preferred over
36. (6) 37. (8) 38. (4) 39. (6) 40. (3) power
CH3 CH COOH
EXERCISE # 4
NO2 Cl –I (More effective)

For – I (Preferable order)

1
________ 1
____
Acidic strength – I Power
+ I power PKa
Cl
CH3 C COOH
Cl
Most + effective – I most Acidic least PKa
HINT AND SOLUTION Between number and strength, number dominates in
the groups having –I effect.
EXERCISE # 1 5. [3]
1. [4] Nuclophile having two nucleophilic site (e––denating
site) is ambident nucleophle.
sp
2
sp
3 6. [3]
Bond-1 Bond-2 Bond-3
sp3-sp3 sp-sp sp2-sp2
2 4 6
1
% s E.N bond strength
3 5
sp (1) < (3) < (2)
sp
2
3 7. [1]
sp sp
– NR3 > – NO2 > – CN > – COOH
______________________________
2 3
Hence, C2 and C3 are sp -and sp -hybridised
2. [4] m-directing strength
e-deficient species are electrophile 8. [3]
3. [2] (I) Structure non polar (most stable)
1
Acid strength – I __ (II) Structure Incomplete octet
+I (III) Structure Complete octet
Also –I power increases as the distance from source (I) > (III) > (II)
group decreases 9. [2]
4. [4]
3.42 | Organic Chemistry Module I
1° 1° O– +
CH3 CH3 +
C C
CH3 (iii) (iv)
CH3
1° 1° 4n + 6 = 2, n = 0
C 4n + 2 = 6, n = 1 Aromatic
Aromatic
CH3 CH3 16. [4]
1° 1°

All 1°C attach with 4°C so 1°H are identical CH3–CH–CH=CH–C C–H
(1) (1) (3)
10. [1]
sp2 sp2 sp
O O– O– O
17. [1]
–
O O O O Removal of most acidic H takes place, according to
(i) > (ii) > (iii) > (iv)
size factor, Acidic strength size
non polar complete octet More E.N –ve More E.N +ve OH OH
Incomplete octet C CH C CH
–H
11. [3]
NaNH2
(1 mole)
SH SNa
(1) (2)
18. [2]
4 –H 6 –H
Resonance bond length of double bond
19. [3]
+ x H
H z
(3) (4) H w
H
7 – H (Most stable) 4 –H H yH
12. [1]
–x (H effect only)
CHCl3 CCl3 Most stable, due to p -d bonc CH2–CH2–CH=CH–CH3
Most acidic –y
CH3–CH–CH=CH–CH3 (R + H) effect
CHF3 CF3 EWG stabilised anion –w More EN caries radical
CH3–CH2–C=CH–CH3
– (like +ve) unstable
CH3–CH3 CH3 CH2 –z CH –CH –CH=CH–CH Only R effect
3 2 2
ERG, destabilised anion Bond dissociation energy
Stability of anion Acid strength of conjugate
13. [3] 1
__________________________
(a)NH2 O stability of carbon free radical
20. [4]
NH(b) e-density of benzene ring E.R.G Power
Thus –NHCOCH3 > –OCOEt > –CH3 > COOEt
21. [3]
CH2–NH 2
(c) In reasonating structures atoms always at same
position only migration of e– takes place.
c > a > b
l.p localised less de-localised more de-localised 22. [3]
(due to cross conjugation) –
. conjugation dominant (– ve) is not in
14. [2]
conjugation
15. [3] 23. [4]
+
(i) (ii) Ph–C–Ph > CH3–C–CH3
4n = 4, n = 1 4n = 4, n = 1 Ph CH3
Anti aromatic Anti aromatic Resonance stable
 General Organic Chemistry | 3.43

24. [1] 27. [3]

Here (1) is stable because it would not change to Electron deficient molecules are electrophile
other stable carbocation. It can only change 2°C to 28. [2]
2°C . Acidic strength stability of anion
Thus carboxylic acid is more acidic than alcohol due
Me Me Me Me to formation of equal contributor canonical form of
2°C 2°C carboxylate ion.
On the other hand, (2) can change to two 2°C Further in same group
1
structures. Acidic strength – M, – I _______
+M, + 1
1
Me Me Me Me Me Me Acidic strength Ka ____
pKa
Furthermore, (3) is stabilised by 1, 2-Me shift and
(2) is stabilised by 1, 2-H shift. Hence of pKa is (II > I > III > IV)
29. [1]
Me Me Me Ease of hetrolysis Leaving ability of anion
1, 2-H
(3) Me CH2 shift Acidic strength of conjugate
Me acid of anion.
Leaving (anion) OH OAc C l
1°C 3°C Acidic strength order of conjugate acid H 2O
Me Me < ACOH < HCl
(4) Me 1,2-H Me Hence order of case of hetralysis is (I) < (II)
Me Me
H shift < (III)
2°C 3°C 30. [1]
–NO 2 comes out of plane due to ortho effect,
So (1) is most stable.
So (C – N) > (C – N)
25. [1]
(partial double bond character) in (C – N) due to
COOC – –H > HOOC > HOOC Me resonance.
31. [2]
Acidic order: sp > sp2 > sp3(C C > C = C > C – C)
(i) Bond length (C=C bond) Resonance effect
26. [3]
(ii) Bond length (C=C bond) H-effect
Acidic strength stability of conjugate anion
–
C=C bond length is maximum in (III) because of
COOH COO resonance.
In (I) and (II) resonance is same but due to
2 equal contributor Hyperconjugation in (II) C=C bond length is higher
than (I)
–
SO3H SO3 32. [4]
Bond dissociation energy
3 equal contributor 1
______________________ (refer solved example)
stability of C – free radical

33. [4]
Aromatic stable Stability of carbocation + H effect
–
+H power CH3 3 > CT3
34. [1]
–
OH O Heat of hydrogenation reactivity
1
_______________
Only resonance stable Reactivity (Reoetivity)
Stability of alkene
(Less stable in among)
3.44 | Organic Chemistry Module I
1
_______
Stability of alkene number of – H(due to + H) Thus pKa + M, + I
– M, – I
(P) (Q) (R) (S)
–M(–NO2) > –M(–COOH)
1 –H 4 –H 10 –H 7 –H
35. [1] 42. [4]
No –M effect of –NO2 work because of steric hin- Reactivity of aromatic substance towards electrophile
drance (ortho effect) 1
(Ar.SE) ERG _____
36. [1] EWG
The more the s character, the more is the penetration O O CH3
effect of s orbital towards the nucleus, and hence more
_
e-withdrawing effect. So, sp(50% s) > sp2(33% s) > ERG(–O > –NH–C–CH3 > –O–C–CH3 > –CH–CH3)
sp3(25% s). (i) > (iii) > (ii) > (iv)
37. [1]
43. [4]
FeCl3 + Cl2 Cl + FeCl4
38. [1] (I) <
Nucleophilic strength predominantly depends –
upon size Anti aromatic Aromatic
N.S Size of nucleophilic site
39. [2] (II) <

NH2 > R–O > OH > R C O Anti aromatic non Aromatic

EN BS + BS
O – –
No Conjugation Conjugation (III) <
B.S B.S
Aromatic Anti aromatic
Also R — O — OH
+I 44. [2]
Base strength +I power
stabilised is the most favorable
40. [4]
–
– – – + +
–
CH3 3 C CH2 C6H5CH2 CH3 CH2 1 : 2 CH3 shift
+I (Resonance +I More EN
stable) –ve charge less stable more stable stable

(II) > (I) , (III) , (IV) 45. [1]

In option 2, 3, 4 Equal contributed canonical form
E.N. E.N.
will exist hence same bond length between participat-
– –
(C sp )
3
(C sp )
2 ing atom.
46. [4]
(II) > (IV) > (I) , (III)
COOH COOH COOH COOH
Same EN CH3
–
–1 1
stability of —C
+1
CH3
(ortho effect / +H CH No effect
(II) > (IV) > (III) > (I) most acidic) +I 3

41. [4] (I) (II) (III) (IV)

1 1
Acid strength Ka ____ – I, M ______
pKa I, + M
 General Organic Chemistry | 3.45

1
_______ 1
_______
Acid strength – H, – I Basic strength – M, – I
+ H, + I + M, + I
5. [3]
(I) > (IV) > (II) > (III)
47. [2]
CH3–CH2–Br + Na–I CH3–CH2–I + NaBr I I
Lg Nu N
48. [2] O O
Acidity : HBr > MeOH > Me2NH > Me3CH
Basicity and nucleophilicity: position of nitro group.
Br < MeO < Me2N < Me3C –NO2 comes out of plane, due to SIR effect (ortho
i.e., IV > III > II > I effect).
49. [4] 6. [3]
4n + 2 = 6 Resonance Resonance energy
N
n=1 In (III), continuous conjugation Resonance energy
aromatic 7. [3]
NO2
50. [2] 5

Reactivity of R–Br stability of C 1 3

Br
NO2 NO2
Br
AgBr
Out of plane (SIR Effect)
O O
Aromatic stable C1—N & C3—N out of plane due to SIR Effect
C5—N present in resonance
EXERCISE # 2
1
1. [2] Resonance _______________
BL of single bond
O Me CH3 Thus (C1—N = C3—N > C5—N)
N N > N > 8. [1]
Me CH3
O Extended
conjugation N=O
Both Resonance in O
same direction
N N
support each other CH3 (I) (II)
N
CH3 p localised p delocalised also
N=O more basic participate in aromatisation
more stable, least basic
O NH2
Due to SIR effect
Resonance is less NH NH2
2. [2]
Bond strength E.N. % of S character
c > b > a. (III) (IV)
3. [3] Phenyl imidine p delocalised
lp delocalised lp localised most basic less basic

I II III IV 9. [4]
Less More E.N. E.N. Acidity:
delocalised delocalised B.S. B.S. H3O > EtOH2 >MeCOOH > H2O > EtOH
Thus order is IV > III > > I > II Basicity and nucleophilicity:
4. [4] H2O < MeOH < MeCOO < OH < EtO
i.e. V > IV > III > II > I
3.46 | Organic Chemistry Module I
10. [2]
(double bond) in resonance (3) 5 -H
(single bond) in resonance
pure single bond
< < (4)
11. [4] 2 -H

due to Bredt’s rule 14. [2]

12. [1] 15. [1]

(I) Ha sp3 O O sp3

–Ha – Aromatic O O3
3 sp 2 sp2 sp
– sp3 sp sp3
6 e
sp3 sp3
In delocalisation
16. [1]
(II) –Hb Non-aromatic Nucleophilicity Attacking rate of anion
17. [2]
Hb 4 e–
In delocalisation

(III) Hc –Hc – Anti-aromatic 4n + 2 = 5 e 4n + 2 = 4 e 4n + 2 = 6 e 4n + 2 = 14 e

n =1 n =1 n =1 n =3
4 e– Aromatic Anti Aromatic Aromatic Aromatic

In delocalisation 18. [3]

In aqueous solution, amine basically follows the
–Hd order
(IV) – Anti-aromatic
Hd NH3 < tertiary < primary < secondary
8 e– This is due to the combined effected of induction and
In delocalisation stabilization of conjugate acid through H-bonding.
Also, a cyclic amine is more basic (IV) than acyclic
The order of Aromatic stability is: amine (II). If their degrees are same. Hence, the
Aromatic > Non-aromatic > Anti-aromatic overall order is
I > II > IV > III Kb : III(3°) < I (1°) < II (2°, acyclic) < IV (2°, cyclic).
IV has more resonating structures than III, and is 19. [2]
therefore, more stable. ortho effect
Ha in I is more acidic since it will give H faster steric hindrance at ortho
to become a stable aromatic anion. Thus least Pka position
value.
20. [1]
13. [1]

–
O
(1) Resonance + 3 -H Most stable (I) (II) (III)

Partial conjugation 4n + 2 = 2 e
(2) 5 -H non-planer n=1
non-aromatic Aromatic
 General Organic Chemistry | 3.47

(III) Stable by resonance

H
H (IV) negative charge do not participate in resonance
(less stable)
(IV) (V)
29. [1]
4n + 2 = 10 e Non planer due to
repulsion between By the removal of –Cl(C), due formation of aromatic
n=2
adjacent H stable carbocation
Aromatic
30. [1]
21. [4] 1
Base strength +M, + I _______
– M, – I
1
_______________________ 31. [4]
Stability of C – free radical
22. [4] Theory based
1
_________________ 32. [3]
Rule 1 Base strength
p CH3
O C CH3
HO
(I) NHCOCH3 (II) C–NHCH3

p delocalised In amide p less

delocalised
33. [1]
O NH2
O (I) Acidic strength ortho effect
C–CH2NH2 (IV) 1
_______
(III) C–CH3 (II) Acidic strength – M, – I
+ M, + I
p localised p delocalised 34. [3]
1
___
Base strength +I
1
_____ –I
Rule 2 Base strength + M, + I
– M, I 1
Nucleophilic strength _____________
23. [4] steric hindrance
3 35. [2]
sp 3 3 3
1 1
CH3 sp sp sp Bond length ___ ___
CN H H %S EN
C=C=C
2 2
H sp sp sp H 36. [1]
NC C=O O
Leaving group ability acid strength of conjugate
24. [1] 1
acid ____________________
Ring expansion takes place Base strength of (anion)
25. [2] 37. [3]
When nucleophilic centre is same then Aromaticity resonance energy
Nucleophility basic strength + M, + I 38. [1]
1
_______ 39. [1]
– M, – I Power of leaving group acid strength of conjugate
26. [2] 1
acid ____
27. [1] pKa
+ CH3–COO– CH3–COOH pKa = 4.5
Stability of C conjugation H-effect ( –H)
C6H5– C6H5 –OH pKa = 10
Note: positive charge at bridge head C de-stabilised C6H5– C6H5–SO3H pKa = 2.6
carbocation due to Bredt’s rule.
40. [1]
28. [4]
(I) Stable by resonance
size (dominating factor)
(II) Stable by p – p bonding
base strength
3.48 | Organic Chemistry Module I

EXERCISE # 3 O

1. [1, 2, 3] (4) H2N–CH2 and CH3–C–CH2

conjugation
acidic than p-chloro phenol 6. [1, 2, 3]
2. [2, 3, 4] Theory based
7. [1, 2]
(1) (2)
N N In same period
O
Nucleophilicity Base strength
Non aromatic 4n + 2 = 6 In same group
non-planar n=1
aromatic Nucleophilicity Size (If Protic solvent, CH3–OH)
So that F– > Cl– > Br– > I– (incorrect)
H
8. [2, 3, 4]
N Reactive intermediates are formed for very small
(3) H–N N (4) time, cannot be isolated practically. The most sta-
B ble reactive intermediate is always formed in larg-
4n + 2 = 6 est amount, hence from the major product. It is the
n=1 4n + 2 = 6 reactive intermediates that leads to several products
aromatic n=1 in a reaction
aromatic
9. [3, 4]
3. [3]
In both option (3) and (4), less substituted, less
Here, the negative charge of conjugate base is sta-
stable alkene is being transformed into more stable
bilized by electron withdrawing resonance effect of
alkene.
–NO2 group.
10. [1, 2]
4. [1, 4] Hydride
Both —NO2 and —CHO exert electron withdrawing (1) shift
+ O +
+ O O
resonance effect but from ortho and para-positions so
3°resonance
decreases basic strength, hence meta-isomer is more
Stabilised
basic. (more stable)
Both —Cl and —OCH3 give electron donating reso-
Hydride +
nance effect from ortho and para-positions, increases + shift +
(2) O O O
basic strength hence, their meta-isomer is less
basic. Stabilised by
5. [1, 3] Resonance
(i) Stability of Carboanion Conjugation favourable shift
1 +
(ii) Stability of Carboanion – I ___ (3) O O +
+I
C I II
3° resonance
H2N–CH2 < CH3–C–CH2
(stabilised more stable)
conjugation However, the above step is resonance delocali-
– –
CF3 < CCl3 sation (I and II are canonical forms) not the
p –d conjugation required rearrangement.
– – +
(1) O2N–CH2 and F–CH2 (4) +
–I(–NO2) > –I(–F)
(2) CF3 and CCl3
p –d conjugation
+
(3) F3C–CH2 and Cl3C–CH2 Less stable than the
–I(CH3) > –I(CCl3) Previous carbonation
 General Organic Chemistry | 3.49

Although the above ring expansion increases 15. [1, 2, 4]

stability of cyclopropyl ring but decreases overall All acidic groups, —SO 3H, —COOH and —OH
stability because of loss of resonance. would be neutralised by NaOH Sulphonic acid is most
11. [1, 2, 3, 4] acidic, would be neutralised first, With NaHCO3,
O F —SO3H and —COOH groups would be neutralised
C requiring 3.0 moles of base. Electron withdrawing
C C
H effect of —SO3H and —COOH increases acidity of
H one another.
C C 16. [2, 3]
=0 C =0
O F Nitrogen labelled-II is the most basic.

Cl Cl H3C + H3C
N N—H N + N—H
Cl Cl H3C H3C
Conjugate acid
Cl Cl I II
Cl Cl Cl
=0
Cl +
=0 H3C CH3
N N—H N N—H
H3C H3C +
12. [2, 3, 4] III IV
Among amines, the order of basic strength in gas
phase is 1° < 2° < 3°. Therefore, the order of Kb will Both I and III have complete valence shell of all
also be the same Since, pKb = – log Kb, the order the atoms. Also, —CH3O, group at position-III of
of pKb would be reverse of the order of Kb, i.e. pKb original base would increase the basic strength as it
3° < 2° < 1°. would stabilise the resonance structure IV by reso-
13. [2, 4] nance effect.
17. [1, 2, 3]

(2) a resonance stabilised free radical.

CH3—CH—CH CH2 CH3—CH CH—CH2

(4) decreases on increasing bond length. C—H (I)

involves the smaller on sp2 hybridised orbital for
In option 1, 3, unequal contributor is formate other sigma boding, shorter bond than on C—H (II) and
de-localisation C—H (III) which employs bigger sp3 hybridised
14. [1, 3, 4] orbitals for bond formation.
18. [4]
H H H O +
+ +
H H
N N N
O O + O
N
O O O Most stability
H
cis trnas By resonance
(Intramolecular H-bonding) 19. [4]
trans-isomer shown above is slightly more stable NH2 NH3
due to presence of intramolecular H-boding form- Acidic solution
ing six membered ring. The molecule is planar, no
enantiomerism is possible. It’s cis-isomer has greater H
+
relative solubility in water due to free C O and –NH2(+M) group changes in – NH3 (–M) group which
is least reactive towards E
N—H groups capable of intermolecular H-bonding
with water. Also, the molecular is planar and highly 20. [3]
conjugated, has high resonance stabilisation energy.
3.50 | Organic Chemistry Module I
+ 28.[4]
Me CH2 Me — O — CH2
29.[2]
+I +M
Due to resonance 30.[3]
21. [4] Sol.(28 to 30)
+
: CCl2 have vacant d-orbital so it is good In the given amino acid cation, –COOH to – NH3
electrophile is most acidic followed by the second –COOH group
+
22. [3] and – NH3
+
H
– NH3 on a-COOH
+ 31. [4]
N N 2 2 3 3
sp sp sp sp sp sp sp
H H H
CH2 = C = CH – CH2 – C C – CH2 – NH2
p delocalised Anti aromatic 7 6 5 4 3 2 1
less basic C1 sp3
In pyrelle (I) C2 sp
C5 sp2
23. [1]
C6 sp
As distance of –I group increase from source, –I
32. [4]
power decrease,
(A) B A+ + B
So that acid strength decrease.
A Heterolysis (q)
24. [4] +
It is generally true that a tertiary carbocation is more (B) CH3–C H–CH3 carbocation (r)
stable than primary one. However, this does not apply (C) A – A A +A
in the present case because it is less stable than I as Free radical (p)
II has greater angle strain. The favourable rearrange-
2N2 H2 + N2
ment here is ring expansion.
carbene (t)
+ (E) CH3– H Nucleophile (s)
+
CH2 33. [4]
–
Primary Secondary O O O
Less angle strain (i)
CH2 Most stable form
25. [4]
26. [1] (ii) O O
+ + O
27. [2] +
Sol. (25 to 27) Most stable form

O O
– This carbocation is also stabilised by hyper-
conjugation effect. Also the carbocation have
C H C + H deficiency of a pair of electron, act as a strong
H N H N Lewis acid in chemical reaction
H H (iii) It is a free radical, therefore paramagnetic due
IV to unpaired electron. It is also stabilised by
hyperconjugation effect.
I is obtained on protonation of formamide, hence (iv) It is a carbene. It’s triplet form is paramagnetic.
conjugate acid. If has restricted rotation, show geo- It has deficiency of a pair of electron, acts as a
metrical isomerism. strong Lewis acid during the reaction.
HO HO H 34. [3]
C N C N 1
H H Acidic strength – I, – M _______
H + I, + M
II II Acids stronger than phenol are : II, IV, V, VII
cis trans
 General Organic Chemistry | 3.51

In carbene, there are a total of six valence electrons

OH OH OH OH (2 bond pairs + 1 lone pair). In case of triplet carbine,
there are four electrons having same spin direction.

A triplet carbene
CH3 OH
–I –I (meta) C H 4 electrons with up-spin and
Cl OH
I II III IV 2 electrons with down-spin

39. [6]
OH OH OH OH Acids, I, III, IV, VII, VIII and IX are all stronger than
OH OCH3 benzoic acid. I is stronger because of stabilisation of
conjugate base by intramolecular H-bonding.
OCH3 O
–I
OCH3
C –
V VI VII VIII O Intramolecular
OH H H-bonding
O
OH III is stronger because from meta position, —OH
exert only – I-effect, its electron donating resonance
effect has no role on acidic strength.
CH CH—OCH3 IV is stronger acid due to loss of planarity of
IX X —COOH with phenyl ring, hence absence of elec-
tron donating resonance effect as phenyl rings on
35. [5] —COOH increases acidic strength.
(i), (ii), (v), (i) and (vii) have conjugated C=O and VII is stronger because a sulphonic acid is stronger
resonance delocalisation decreases bond order of than a carboxylic acid.
C=O less than 2, hence weaker bond than C—O bond VIII is stronger because electron withdrawing induc-
in acetaldehyde tive effect of one —COOH over other increases acidic
36. [6] strength.
The given carbocation has six-H that can take part IX is stronger due to only – I-effect of methoxy
in hyperconjugation as: group operate from meta position but not its electron
donating resonance effect.
H H 40. [3]
+ Six a-H capable of showing
C C CH3 Antiaromatic substance are unstable at room
hyper conjugation temperature
H C–H H
H EXERCISE # 4

37. [8] 1. [1]

–
Br
When R is attached with benzyl/allyl system + induc-
+ tive effect occurred + I Power branching
Br
Show both geometrical and optical 2. [1]
isomerism, total four isomers As per NCERT result
In aq. solution (when R = –CH3)
– Br
+ Br 2° amine > 1° amine > NH3 (basic strength)
3. [1]
Show both geometrical and optical
isomerism, total four isomers. Rate of SN reaction Leaving tendency Acidic
strength of conjugate acid
38. [4] Since HCl is strongest acid so that Cl– is best leaving
group
3.52 | Organic Chemistry Module I
4. [4] Since, alcohols and cyanides are weaker acid than
Acid strength M, – I (EWG) sulphonic and carboxylic acids. Thus, the order of
1
_______ acidic strength of the given species are
(ERG)
+ M, + I
COOH COOH O
NO2 H3 C S —OH > CH3–C–OH > CH3OH > HCN

O O
(a) (b)
Effect no effect –M, –I Hence, the decreasing order of nucleophilicity of the
given nucleophiles is as follows
–I distance
Not effect no effect (EWG)1 O
– – –
COOH COOH H3C S—O < CH3–C–O– < CN < CH3O
O O
NO2
7. [2]
NO2 1
__________________
Base strength
–M, –I –I
(EWG)2 (EWG)3
NH2 CH2–NH2
(c) (d)

b>c>d>a
5. [4]
1
__________________ Aniline Benzylamine
Base strength
p delocalised p localised
CH2–NH 2 most basic
p localised
benzyl amine NH2 NH–C–CH3
O
6. [4]
Weaker the acid, more stable is their conjugate base
and greater is their nucleophilicity. Thus, nucleophi- NO2 NO2
licity order of the conjugate bases is opposite to their
p-nitroaniline Acetanilide
acidic strength.
p delocalised p delocalised
Conjugate bases Acids
–
CH3–C–O CH3–C–OH 8. [4]
O O Free radicals stability

CH3O– CH3OH C6H5–C–C6H5 >C6H5–CH > CH3–C–CH3 > H3C–C–H

CN– HCN
C6H5 C6H5 CH3 CH3
O O
–
(Highly stable by (9-hyperconjugative
CH3 S —O CH3 S —OH delocalisation of hydrogens and
3 phenyl groups) +/– effect of 3 alkyl groups)
O O
 General Organic Chemistry | 3.53

9. [4] 13. [4]

When nucleophilic centre is same but category of –NO2 group (e with drawing) de-crease e-density of
anion is different, Then N.S B.S benzene ring.
So it deactivates the benzene ring towards electro-
Ph—O Ac—O HO CH3—O philic substitution.
A B C (+1) D
14. [2]
Conjugation No Conjugation –/-effect (e– withdrawing) exerting groups stabilises
B.S N.S B.S N.S carbanion by the dispersal of their negative charge
while +/-effect exerting (e– releasing) groups desta-
C , D > A B bilizes the carbanion by increasing electron density
+I Resonance 2 equal on them.
E.N Same B.S But not equal contributor
I factor apply N.S Contributor On the other hand, resonance stabilized carbanion
R.S Resonance are stable due to the involvement of their lone pair
Base strengh Reso B.S N.S
1 B.S N.S of electron with the delocalisation of -electrons of
+I attached phenyl group.
–l
Thus
D > C > A > B
Cl
10. [4] > –
Cl C CH2 >
pka = – log Ka, Hence, higher the value of Ka, smaller
Cl
pKa. Ka is the measure of acidic strength. It is highest
(3-/-effect exerting (-/-effect of phenyl group
for the strongest acid (d) in given case, therefore has
group of Cl) as as well as delocalisation
lowest pKa value. electrons)
will p -d bond
11. [3] resonance
Acidic strength of the compound depends on the Cl
ease of release of proton –I effect exerting groups CH3 –
> CH3 C
(e– withdrawing increase the acidic strength while CH3 CH
+ I effect exerting group decreases the strength of an CH3
acid. (+I effect of (+I effect of
2–CH3 group) 3–CH3 groups)
O O 15. [4]
Me O O
–
CH C–OH < CH3 C–OH
Me
R–C–O R–C O
[2 + I effect exerting groups, [+I effect group of
increases e – density of on – CH3 group]
O-atom, thus the release on oxygen, is in conjugation with bond thus it
of ease of proton becomes is resonance stabilised.
difficult (least acidic)] C –: Carbon is sp hybridised so its
electronegativity is increased & higher relative
to nitrogen.
F
< MeO CH3–C–OH < F C C–OH __
F N H2: Nitrogen is more electronegative than
O
[–I effect group of [–CF3 exerts more-I effect sp3 hybridised C-atom. From the above discus-
–OCH3 group] than MeO (most acidic)] sion, it is clear that the order of the stability of
conjugated bases is as
__ __ __
12. [3] RCOO– > HC C > NH2 > R
2° amine is more basic in aqueous solution And higher is the stability of conjugated bases,
CH3–NH–CH3 lower will be basic character. Hence, the order
of basic character__is as __ __
RCOO– < HC C – < NH2 < R
3.54 | Organic Chemistry Module I
16. [1]
Nucleophilic strength size (v) non-planar, conjugated, 4n = 4, n = 1
+
1
Basic strength ____ (Anti aromatic)
size
Thus R–S is less basic but more nuelophilic strength (vi) planar, conjugated, 4n = 4, n = 1 (Anti
than R–O
17. [1] aromatic)
Acidic strength M, – I (EWG) 21. [3]
1
____________ +(III) O –I
+ M, + I(ERG)
OH OH OH OH N N N N
2
p Present at sp –N atom
H Which is more EN so that H H
base strength is lesser p
NO2 1 delocalised least basic
In same source (base strength) +I
–I
CH3 NO2
(A) (B) (C) (D) Thus I > III > II > IV
–I 22. [2]
No effect +H, +I (at meta position) –M, –I
Cl
Cl Cl
CH3
18. [4] C=C
Cl CH3
non-planar
Non aromatic =0 0

For aromatic substance molecule most be cyclic| planar Cl

conjugated and obey Huckle rule (4n + 2 = e) H
NO2
Rest other satisfied given condition so they are C=C
H NO2
aromatic
19. [1] Cl
In tramolecular H-bond =0 =0
O
H Less bpt. 23. [1]
N O Less soluble CH3
O More volatile –
–
CH3–O–CH3 R–C–O NO3
20. [2]
No resonance O
(i) planner, conjugated, 4n + 2 = 6, n = Resonance present
O 24. [1]
1
_______
1(aromatic) Acidic strength – M, – I
+ M, + I
(ii) non-planar (non-aromatic) OH OH OH OH

; ; ;
(iii) non-planar (non-aromatic)
Cl CH3 NO2 OCH3
(iv) non-planar (non-aromatic) Over all +M < –I +H, +I –M, –I +M > –I
O effect (EWG)2 (EWG)2 (EWG)1 (EWG)1

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

 General Organic Chemistry | 3.55

Thus III > I > II > IV 31. [4]

25. [2] 6H5– H2, Here p de-localised so it is least
The order of stability of carbocation will be basic
+ As per NCERT
CH2
3)
+ + Basic strength Kb pKb
> CH2 = CH–CH3 > CH3–CH2–CH2
32. [4]
In (iii) and (iv), the dipole vectors O–H and S–H
(III) (I) (II) are in tetrahedral plane, do not cancel, In (i) and (ii)
Benzyl carbocation Alyl carbocation Propyl dipole vectors cancel each other completely as:
(more resonance (resonance carbocation
stabilised) stabilised) (stabilised by
+ I effect) Cl Cl
26. [3]
=0

+ve charge present in conjugation with -bond

N C C N
so it is most stablised.
=0
27. [3]
Theory bosed 33. [2]
28. [2] (i) in CH3–NH2, p localised so that base strength
N.S. size highest
1
If solvent is not given then nucleophilic strength (ii) Base strength + M, + I _______
– M, – I
compared in polar solvent
NH2 NH2 NH2
29. [3]
1
Stability of anion – I, – M _______
+ I, + M
–CH3 –OCH3 –C–CH3 –CH2–OH
+H +M +H no effect OCH3 NO2
O –M
30. [4] (+M > –I) (–M, –I)

A B 34. [3]
2 moles of NaNH2 would neutralise the first two
(1) < more acidic groups. Here, —COOH is most acidic
followed by hydroxyl group of the nitrophenol ring
conjugate
because —NO2 has strong –I as well as –R-effect.
A B 35. [4]
(2) A carboxylic acid is more acidic than ammonium ion,
<
hence X is most acidic. For 2nd most acidic group,
4 -H 7 -H (more hyper conjugation) we need Investigets the conjugate base of given ion
formed after first deprotonation as:
A B + +
H 3N NH3
(3) < + +
+
COOH H + H3N NH3
Minimum
ring strain –
COO
A B Now in conjugate base I, COO– is electron donating,
+
(4) Ph3C > (CH3)3C decreases acidic strength of – NH3 at -position,
more resonance only hyper hence Y is second most acidic followed by Z.
stabilised conjugation
stabilised
3.56 | Organic Chemistry Module I
36. [3] 42. [4]
–
CH2=CH–CH=CH–O–CH3 H at C-2 will migrate giving resonance stabilised
carbocation
Lone pair of oxygen is not the part of this mode of
delocalisation.
H H
37. [1]
+ –
H +
The following structure has like charge on adjacent H3 C C C C CH3 HC C CH3 CH(CH3)2
shift 3
atoms, therefore, least stable
OH H CH3 OH
+
+ O
– N H3C C CH2 CH(CH3)2
–
O + OH

38. [4] 43. [2]

Statement I is incorrect but Statement II is correct. I is most stable because it has more covalent bonds
Intramoelcular H-bonding in ortho-hydroxy benzoic and negative charge on electronegative nitrogen, III is
acid lowers the boiling point. more stable than II and IV due to greater number of
39. [2] covalent bonds. Between II and IV, II is more stable
since, it has negative charge on electronegative atom
H H and positive charge on electropositive atom. Hence,
– overall stability order is
H C CH CH2 H C CH CH2
+
H I > III > II > IV.
H
44. [2]
The -electrons of C—H bond is delocalised with Lysine contains two basic groups, e.g., NH2
p-orbitals of -bond. Biomolecules
40. [4] Basic straight
45. [3]
+ O 3°, has resonance
O
+ stability COOH COOH
(I) HO HO

+ has no resonance –OH controls the NO2

stability but 2° orientation, that is
ortho-para directing
(II)

+ OCH3
2°, has resonance OCH3
O O H3C
+ stability H3C NO2
(III) –OCH3 controls the
orientation
(o/p-directing)
+ 1°, has no
resonance stability
(IV) O
B
O
41. [1] A NO2
O
Ring B is more
OH < Cl OH < activated O
I II O
and –O–C–Ph is
H3C COOH < COOH
(o/p-directing)
IV III
+ I-effect
decreases acidic strength
 General Organic Chemistry | 3.57

46. [3] 49. [2, 3]

A monosubstituted benzoic acid is stronger than
monosubstituted phenol as former being a carboxylic (1) (2)
acid. Among the given substituted benzoic acid,
ortho-hydroxy acid is strongest acid although —OH Aromatic Anti aromatic
causes electron donation by resonance effect which
tends to decrease acid strength. It is due to a very –
O O
high strength of conjugate base by intramolecular +
H-bond which outweight the electron donating
resonance effect of —OH. (3) (4)
O Anti
Aromatic
COOH O
–
+
A H + A Anti aromatic substance also unstable
OH H
O 50. [2]
The overall order of acid-strengthof given four Allene is the name given to propdiene,
acids is ortho-hydroxybenzoic acid (pKa = 2.98) > H2C=C=CH2.
Toluic acid pKa = 4.37) > p-hydroxybenzoic acid Hybridisation of an atom is determined by determining
(pKa = 4.58) > p-nitrophenol (pKa = 7.15) the number of hybrid orbitals at that atom which is
47. [1] equal to the number of sigma (s) bonds plus number
of lone pairs at the concerned atom.
There are total 6 -H attached to sp2 carbon and they
all can participate in hyperconjugation. Pi( ) bonds are not formed by hybrid orbitals,
therefore, not counted for hybridisation.
+
+ H
+ H
+
H
H H
+ + C C C
H H
(Three structures) (Two structures)

48. [1]
Here, the terminal carbons have only three sigma
+
(i) N2 + OH bonds associated with them, therefore, hybridisation
of terminal carbons is sp3. The central carbon has
only two sigma bonds associated, hence hybridisation
N N OH at central carbon is sp.
51. [1]
This is an example of electrophilic substitution Spreading out charge by the overlap of an empty
at para position of phenol, giving a coupling p-orbital with an adjacent bond is called hyper-
product. conjugation. This overlap (the hyperconjugation)
(ii) Pianacol-pinacolone rearrangement, occur delocalises the positive charge on the carbocation,
spreading it over a larger volume, and this stabilises
(iii) the carbocation.

Vacant
p-orbital

CH3 C CH2 H CH3 C CH2 H

CH3 CH3

tertiary butyl carbocation has one vacant p-or-

(iv) Nucleophilic addition occur at sp2 (planar) bital hence, it is stabilised by -p (empty)
carbon, generating a chiral centre, hence product hyperconjugation.
will be a racemic mixture.
3.58 | Organic Chemistry Module I
– Cl CH3 Br
H— CH2 CH CH CH3 HCH2 CH CH CH3 Cl Br Br
Cl Cl Cl
In 2-butene, stabilisation is due to hyperconjugation
between – * electron delocalisation. H3C Br H3C Cl Cl CH3
52. [1, 2, 3, 4] CH3 CH3 CH3
A species is said to have aromatic character if (Me-Me) gauche (Br-Me) gauche (Cl-Me) gauche
(a) ring is planar.
These three have non-zero dipole moment due to
(b) there is complete delocalisation of p electrons. non-cancellation of all dipole moment created by
(c) Huckel rule, i.e. (4n + 2) rule is followed. Where C–Cl and C–Br bond.
n is the number of rings (4n + 2) = electron 54. [1, 2, 4]
delocalised.
This problem can be solved by using concept of
Cl H-bonding and applications of H-bonding.
+ AlCl4
– (1) Ice floats in water due to the low density of
+ AlCl3 ice as compare to water which is due to open
cage like structure (formed by intermolecular
Aromatic H-bonding).
(P)
– (2) Basic strength of RNH2 > R 3N. It is also
explained by hydrogen bonding.
+ NaH + H2
Aromatic H
(Q)
O H
(NH4)2CO3 H
O R N R–N–R
O , 100-115°C H
N R
O
H
Aromatic H H
(R)
–
Two H-bonds are No H-bonding is
O O possible with water possible with water
present in aqueous present in aqueous
HCl solution. solution. (stabilisation
(stabilise by solvation) by salvation is very)

Aromatic
(S) O O

53. [3] (3) C C

This problem can be solved by using concept of H H H3C O–H
conformational analysis of given organic compound. More acidic due to the Less acidic than
To the question draw the stable conformational struc- presence of H. (Due to HCOOH due to
tures of organic compound and determine the net the absence of electron presence of CH 3
resultant dipole moment. donating group) (Electron donating
group)
Cl Cl
Cl Cl
Br CH3 Br CH3 Br Br intermolecular hydrogen bonding.
=
Br Cl Br Cl O H H
H3CCH3 H3C C C H3C
CH3 CH3 O H H
55. [1]
Stable conformer (with 0) –OH group displays both kinds of effect:
 General Organic Chemistry | 3.59

An electron withdrawing acid-strengthening inductive I > II > III > IV

effect from the meta-position and an electron-releasing – – –
–
acid weakening resonance effect from the para-posi- O O + + O O +
tion (at this position, resonance effect overweighs the C H H C H
inductive effect) O
O O
o-hydroxybenzoic acid (II) is far stronger than the
corresponding meta and para isomers as the carboxy-
late ion it stabilised by intramolecular H-bonding
II I
2,6-dihydroxybenzoic acid (I) forms carboxylate (most stable)
ion which is further stabilised by intramoleular
H-bonding, Thus, correct order is