Nucleophilicities t Basicities

(3) In a group of nucleophiles in which the nucleophilic atom is the same and the category of anion is also same
then,
1
Nucleohilicities t _____________
steric hindrance

(4) In a group of nucleophiles in which the nucleophilic atom is the different, then nucleophilicities are depends upon
nature of solvent:

(i) In Polar Protic Solvents Nucleophilicities t Size

1
(ii) In Polar Aprotic Solvents Nucleohilicities t ____
Size

Relative Nucleophilicity in Protic solvents:

SH – > CN – > I – > OH – > N –3 > Br– > CH3 CO3– > Cl – > F – > H2O
Leaving Groups(or nucleofuge): In alkyl halides the leaving group is the halogen substituent – it leaves as a halide ion.
To be a good leaving group the substituent must be able to leave as a relatively stable, weakly basic molecule or ion.
Nu:– + R – L m R – Nu + :L–

SOLVED EXAMPLE

1. Which of the following compounds easily undergoes (1) CN– and NH3 (2) AlCl3 and Cl–
+
homolytic bond fission? (3) H and H2O (4) Br+ and Cl2
(1) CH3–Cl (2) CH3–CH=O Sol. [1]
(3) H–O–O–H (4) NH2–CH3 e-rich species are nucleophile (refer key concept.)
Sol. [3] 5. The decreasing order of –1 effect of the following
H–O–O–H is:
$UE ,EAST %. DIFFERENCE I. H3N„ II. NO2
2. Which of the following represents the mode of III. CN IV. COOH
hybridisation sp2–sp2–sp–sp from left to right? (1) I > II > III > IV (2) II > I > III > IV
(1) CH2=CH–CyN (2) HCyC–CyCH (3) I > II > III > IV (4) II > I > IV > III
(3) CH2=C=C=CH2 (4) CH2=CH–CH=CH2 Sol. [1]
Sol. [1] – NH+3 > –NO2 > –CN > –COOH
CH2=CH–CyN cation (refer key concept.)
n – I effect
sp2 sp2 sp sp 6. Which of the following has highest Ka value?
3. Which of the following is an electron deficient F
molecule?
F
(1) CH3CH3 (2) BH3 (1) CO2H (2) CO2H
(3) SiH4 (4) PH3
Sol. [2]
F
H H (3) CO2H (4) CO2H
B 6e–
e-deficient
F
H
Sol. [4]
4. One of the following pairs represents a set of
nucleophile: Acidic strength t – I Power t Ka
Also – I power decresed as distance increses
 7. Which of following has lowest pKa value? (1) the formate ion HCOO– is obtained by the
removal of a proton from HCOOH
(1) Cl–CH2–CO2H (2) Cl–CH–CO2H
(2) the carbon atom in HCOO– is sp2 hybridised
Cl (3) the formate ion is a tautomeric mixture of
(3) Cl3C–CO2H (4) CH3–CO2H O
Sol. [3] –
–
1 H C O and O C OH
Acidic strength t
– I t Ka t ____
pKa (4) the formate ion is a resonance hybrid of
As number of –I group increases, –I power further the two equivalent resonance structures
increases hence pKa value decreases. –
O O
8. Arrange the following compound in order of decreas- –
ing acidity H C O and H C O
„ Sol. [4]
CH3–CH2–OH (B); CH3–CH3–OH2(C); CH3–O–CH3 (H) –
O O
(1) B > C > H (2) C > B > H –
H–C–O H–C=O
(3) H > C > B (4) B > H > C
(Resonance)
Sol. [2]
Equal contributor
–
Cation > Alcohol > ether
_____________________
OE
acid Strength n –
Resonating hybrid  H C OE
9. Amongst the amines C6H5NH2 (I), CH3NH2 (II),
(CH3)2NH (III) and (CH3)3N (IV) the order of basic- 12. The hybridisation states of the nitrogen atoms at in
ity (in aqueous medium) is– pyridine, piperidine and pyrrole are respectively:
(1) I < IV < II < III (2) IV < III < II < I
(3) I < II < III < IV (4) II < III < IV < I
N N N
Sol. [1]
H H
C6H5–NH2(I) CH2–NH2(II) (CH3)2 NH(III) (CH3)3N(IV) Pyridine Piperidine Pyrrole
p delocalised (1°) (2°) (3°)
p-localised more basic (1) sp2, sp3 and sp2 (2) sp2, sp3 and sp3
least basic
(3) sp3, sp3 and sp3 (4) sp2, sp2 and sp2
Also as per N.C.E.R.T result if R = –CH3
Sol. [1]
Basic strength 2° > 1° > 3°
Hence order of basic strength in aqueous solution
(I) < (IV) < (II) < (III) N N N
10. The order of decreasing stability of the anions H H
(CH3)3C– (CH3)2CH– CH3CH–2 C6H5CH–2 is– Pyridine Piperidine Pyrrole
2 3 2
I II III IV sp sp sp
(1) I > II > III > IV (2) IV > III > II > I (p delocalised)
(3) IV > I > II > III (4) I > II > IV > III
Sol. [2] 13.
(IV) > (III) > (II) > (I)

Resonance +I Power
Stability
Stability of Carbanion n The least stable canonical structure among these is:
O (1) I (2) II
– (3) III (4) all are equally stable
11. In the formate ion (H C O ), the two carbon-ox-
Sol. [2]
ygen bonds are found to be equal. This is because
m In (II) Str., more EN atom carries positive charge,
less stable
14. Which one of the following is most stable? CH2–H

(1) (2) Y CH2–H

CH2–H
Z
X
(3) (4)
(1) Y > Z > X (2) X > Z > Y
(3) X > Y > Z (4) Z > X > Y
Sol. [3]
Sol. [3]
1
Bond energy t __________________
stablity of free radical

No resonance
Resonance & 3B – H(+H Effect)
most stable
15. Pyridine is less basic than triethyl amine because: CH2–H CH2
(1) Pyridine has aromatic character CH2
CH2–H
(2) Nitrogen in pyridine is sp2 hybridised
Cross
(3) Pyridine is a cyclic system
conjugation
(4) Lone pair of nitrogen is delocalised in pyridine
Sol. [4]
less basic than triethyl amine. Continuous
conjugation
16. Which is an aromatic compound? CH2–H CH2
(Most Stable)
– „
(1) (2) 19. The correct order of decreasing acidity of the
compounds is:
OH OH COOH COOH
(3) (4)

Sol. [2]
– „
4n=8 4n + 2 = 6 Cl CH3
Anti Aromatic ; Aromatic ;
I II III IV
Non planar ; non planar (1) III > IV > II > I (2) IV > III > I > II
non aromatic non aromatic (3) III > II > I > IV (4) II > III > IV > I
Sol. [1]
17. Which of the following is the strongest
nucleophile? O O
2 –
(1) EtO2 (2) O H R—C—OH R—C—O
2 equal contributor
(3) C N (4) I2 more stable
Sol. [1] –
Ph—OH Ph—O
Nucleophilicity is parallel to basicity unequal contributor
Acidity : HI > HCN > H2O > EtOH less stable

Basicity and nucleophilicity:

Acidic strength t stability of anion
2 2
I2 < C N < O H < EtO2 Thus R—COOH > Ph–OH (Acid strength)
18. Which of the following is the correct order for bond when functional group (source group) is same
1
energy for C–H bonds in these compounds? Acid strength t EWG t _____
ERG
Hence III > IV > II > I
20. Compare heat of hydrogenation of the following: COOH COOH
(1) (2)
O2N
(i) (ii) (iii)
O2N COOH COOH
(3) (4)
(1) i > ii > iii (2) iii > ii > i NO2
(3) ii > i > iii (4) ii > iii > i Sol. [1]
Sol. [2] When functional. group (–COOH) same
1
%H Heat of hydrogenation Acidic strength t EWG t ____
pKa
1
1 1
t ________________ t ____________ Acid strength t Ka t ____
sterbility of alkene number B – H pKa
COOH COOH
21. Compare rate of EAS
– „
O Na OH NH2
no effect
NO2
lessAcidiC –M
(a) (b) (c) (d) pKA –I dist.
(EWG)2
(1) a > b > c > d (2) a > c > b > d
(3) c > a > b > d (4) c > b > a > d COOH COOH
Sol. [2] NO2
Rate of Ar – SE t ERG
ERG power (–O2 > – NH2 > –OH) NO2
22. Which among the following statements are –Mda
Meta
incorrect? position only –I dist.
(1) CF2 is more stable than CCl2 –I (EWG)3 (EWG)1
(2) CCl2 is more stable than CBr2
25. Least stable carbocation amongst following is:
(3) singlet CH2 is more stable than triplet CH2
(4) Singlet CH2 has planar geometry
(1) (2)
Sol. [3]
„ „
:CF2 > :CCl2 > :CBr2 > :Cl2 Stability
Triplet CH2 is more stable than singlet CH2. Hence (3) (4)
it is incorrect.
„ „
23. Identify the correct order of the ease of dehydration
Sol. [3]
of the following compounds.

OH OH OH
„
I II III
m $UE TO "REDTS RULE VE CHARGE CANNOT BE PLACED
(1) I > II > III (2) III > II > I at the bridgehead carbon.
(3) I > III > II (4) III > I > II 26. Consider the following compounds:
Sol. [2] NH2
NH2
Rate of dehydration t stability of carbocation
24. Which of the following compounds has the highest (I) (II)
pKa value?
NO2
 NH2 NH2 Therefore correct stability after is:
(II) > (I) > (III)
(III) (IV)
29. Arrange 2, 4, 6-trinitrophenol (I); 2, 4-dinitrophenol
CH3 (II); o-nitrophenol (III) and p-nitrophenol (IV) in
CN
order of acidity:
Arrange these compounds in decreasing order of their
(1) I > II > III = IV (2) IV > III > II > I
basicity:
(3) I > II > IV > III (4) III > II > I > IV
(1) I > II > III > IV (2) II > III > I > IV
Sol. [3]
(3) IV > I > III > II (4) IV > I > II > III
Sol. [3]
OH OH
1
Base strength t + M, + I t _______ NO2 NO2
– M, – I NO2
27. Which of the following has highest leaving group
ability?
– – NO2 NO2
(1) NH2 (2) H3C– C –O
(I) (II)
O Intra-molecular
– –
(3) OCH3 (4) I H-bond OH
OH
Sol. [4] NO2
Leaving ability t acid strength of conjugate acid
1
t ___________________
base strength of anion NO2
–
m
HI is most acidic hence I is good leaving (III) (IV)
group

Removal of Proton becomes difficult, so it is
28. What is the decreasing order of stability of the less acidic than para nitrophenol
1
ions? Acidic strength t – M, – I t _______
+ M, + I
+ +
H3C—HC (I) > (II) > (IV) > (III)
(I) H3C—HC (II) O
CH3 CH3 30. Which one of the following substances is aromatic?
+
H3C—HC
(III) CH3 (1) + (2)
O
H H
(1) I > II > III (2) II > III > I
(3) III > I > II (4) II > I > III (3) (4)
Sol. [4]
+ Sol. [4]
CH3–CH—CH3 + +
CH3–CH—OCH3 CH3–CH—C—CH3 4n = 4
Incomplete octet
and less EN car- + O (1) + n=1
CH3–CH=O—CH3 anti aromatic
bon atom car- +
ries +ve charge, Complete octet CH3–CH=C—CH3
O
+ (2) non-planar
Hence more (Most stable)
stable than III (3) non-planar due to repulsion between adjacent
Incomplete octet and
but less stable H-atom
more EN oxygen atom
than II carries +ve charge (4) 4n + 2 = 10
hence less stable n=2
 EXERCISE 1
1. In the compound CH2=CH–CH2–CH2–CyCH, the 7. Arrange the following groups in order of decreasing
+
(C2–C3) bond is of the type: m-directing strength. –NR3, –CN, –NO2, –COOH
+
(1) sp – sp2 (2) sp3 – sp3 (1) –NR3 > –NO2 > –CN > –COOH
+
(3) sp – sp3 (4) sp2 – sp3 (2) –COOH > –CN > –NO2 > –NR3
+
2. Which of the following series contains electrophile (3) –CN > –NO2 > –COOH > –NR3
only? +
„ (4) –NO2 > –CN > –NR3 > –COOH
(1) H2O, SO3, NO2 (2) NH3, H2O, BI3
„ „
8. (I) CH3–O–CH=CH–CH=CH2
(3) ROH, NH3, NO2 (4) AlCl3, SO3, Cl „ „
(II) CH3–O–C H–CH=CH–C H2
3. Give the correct order of increasing acidity of the „ „
following compounds. (III) CH3–O=CH–CH=CH2–C H2
ClCH2COOH CH3CH2COOH Among these three canonical structures (through
I II more are possible) what would be their relative
ClCH2CH2COOH (CH3)2CHCOOH contribution in the hybrid:
III IV (1) I > II > III (2) III > II > I
CH3COOH (3) I > III > II (4) III > I > II
V 9. An organic compound has molecular formula C9H18.
(1) V < II < IV < I < III Its all carbon atoms are sp3 hybridised and its all
hydrogen atoms are identical. Its structural formula
(2) IV < II < V < III < I can be:
(3) III < I < IV < II < V
CH3–CH2–CH–CH–CH2–CH3
(4) V < IV < II < I < III
4. Which of the following acids has lowest pKa CH
value? (1)
CH2
O O
CH2
(1) CH3–CH–C–OH (2) CH2–CH2–C–OH
NO2 NO2 H3C CH3
C C
O Cl O (2) H3C CH3
C
(3) CH2–C–OH (4) CH3–C–C–OH H3C CH3
Cl Cl CH3
5. A nucleophile is called an ambident nucleophile if: CH3
(3) H3C
(1) It is capable of acting as nucleophile as well as
an electrophile H3C
(2) Its attacking atom has two lone pairs CH3
(3) It has two possible electron donating sites
(4) It can act lewis acid (4)
6. Rank the indicated bonds in each compounds in order H3C CH3
of increasing bond strength:
Bond (1) Bond (3) 10. Stability order of the following resonating structure
Bond (2) will be–
–
O O
C C „
(i) O (ii)
O
(1) 1 < 2 < 3 (2) 3 < 1 < 2
(3) 1 < 3 < 2 (4) 2 < 3 < 1
 –
O O„ 16. What is the hybridisation of C1, C2, C3 carbon in the
following compound?
(iii) „
O (iv) –
O „
CH3–CH–CH=CH–C C–H
1 2 3
(1) i > ii > iii > iv (2) ii > i > iii > iv (1) sp3, sp3, sp3 (2) sp3, sp2, sp2
(3) iii > ii > i > iv (4) i > iii > ii > iv (3) sp3, sp2, sp (4) sp2, sp2, sp
11. Which carbocation is the most stable? OH
C CH
(1) „ (2) „ NaNH2
17. (A); Product (A) is:
(1 mole)

„ SH
„
(3) (4) 2„
OH ONa
C CH
C CH
12. Compare acidic strength–
(1) (2)
(i) CHCl3 (ii) CHF3
(iii) CH3–CH3 „
SNa SH
(1) i > ii > iii (2) ii > i > iii
(3) iii > i > ii (4) ii > iii > i 2„
OH 2„
(a)NH2 O
C CNa
(3) (4)
13. NH(b) ; Basic strength order is–

SH
CH2–NH2
(c) 18. Which of the following has longest C – O bond?
(1) a > b > c (2) b > a > c O O
(3) c > a > b (4) c > b > a (1) (2)
„
14. Electrophile NO2 attacks the following:
O O
NO2
(I) (II) (3) (4)

2
CHO O x H
(III) (III) H z
H w
19.
H
H yH
„
In which cases NO2 will attack at meta position
(1) II and IV (2) II and III Arrange the (C–H) bonds x, y and z in decreas-
(3) II and IV (4) I only ing order of their bond dissociation energies in
15. Which of the structures below would be aromatic? homolysis
+ (1) y > x > z > w (2) z > x > w > y
(i) (ii) (3) w > x > z > y (4) y > z > w > x
20. Find the correct order of electron density at benzene
O + ring:
(iii) (iv) COOEt OCOEt CH3 NHCOCH3

(1) i and iv (2) i, iii and iv

(3) iii and iv (4) ii
(I) (II) (III) (IV)
 (1) IV > III > II > I (2) I > II > III > IV 25. The decreasing order of the acidic character is:
(3) IV > II > I > III (4) IV > II > III > I I. COOC– y
–H II. HOOC
21. Which of the following pairs of structure are reso-
nance structure? III. HOOC Me

„
(1) I > II > III (2) III > II > I
CH3– O CH3– O (3) II > I > III (4) III > I > II
(i) CH – „ CH3 CH3
3 C =N
and CH3– C –N 26. Which of the following is least acidic?
CH3 CH3
COOH SO3H
OH OH
(1) (2)
(ii)
and
HO OH HO OH OH

O (3) (4)
OH
and
(iii) N
N N 27. Amongst NO2, CH3, OCH3, Br, CMe3, the decreasing
order of groups or atoms having negative inductive
H effect is:
„
O OH (1) NO2 > Br > OCH3 > CMe3 > CH3
(iv) (C6H5)2CH–N and (C6H5)2C=N – (2) NO2 > OCH3 > Br > CMe3 > CH3
– O
O
(3) NO2 > Br > OCH3 > CH3 > CMe3
(1) (i) and (iv) (2) (ii) and (iii)
(4) Br > NO2 > OCH3 > CH3 > CMe3
(3) (i) and (ii) (4) All of these
28. The correct order of the decreasing pKa values of the
22. Which of the following anions is resonance
compounds is:
destabilised?
OH COOH
– CH3OH HCOOH
(1) (2)
–
I II III IV
–
(3) (4) (1) I > II > III > IV (2) II > I > III > IV
– (3) III > IV > I > II (4) IV > III > I > II
23. In which of the following pairs, 1st is more stable 29. The order of ease of heterolysis of following t-butyl
than 2nd? compound is:
(I) (CH3)3C–OH (II) (CH3)3C–OAc
(1) (2) (III) (CH3)3C–Cl
(1) I < II < III (2) III < II < I
(3) I < III < II (4) II < I < III
(3) (4) Ph3Cs, (CH3)3Cs 30. Compare C–N bond length B, C as indicated:
NO2
24. Which of the following carbocations is most B
CH3 CH3
stable?
„
(1) Me Me (2) Me „ Me C

Me NO2

„ Me „ (1) B > C (2) B = C

(3) Me CH2 (4) Me (3) B < C (4) can’t be predicted
Me
31. The decreasing order of bond length of C=C in the
Me following compounds is:
 H3C 36. The decreasing order of –I effect of the orbitals is:
I. sp II. sp2
H3C III. sp3
I II III IV
(1) I > II > III (2) III > II > I
(1) II > I > IV > III (2) III > II > I > IV (3) I > III > II (4) II > III > I
(3) II > III > I > IV (4) IV > I > II > III 37. Electrophile in the case of chlorination of benzene in
32. C1–H, C2–H, C3–H and C4–H the homolytic bond the presence of FeCl3 is:
dissociation energy is in the order: (1) Cl+ (2) Cl–
H (3) Cl (4) FeCl3
H
2 3 4 38. Identify the strongest nucleophile.
CH3—C—CH—CH=CH–H (1) CH3CH2SH (2) CH3COO2
2
1CH2–H (3) CH3NH2 (4) NC–CH2
39. Among the following the correct order of basicity
(1) C2–H > C3–H > C4–H > C1–H is:
(2) C1–H > C4–H > C2–H > C3–H – – – –
(1) NH2 > OH > RO > RCOO
(3) C2–H > C3–H > C1–H > C4–H – –
– –
(4) C4–H > C1–H > C3–H > C2–H (2) NH2 > RO > OH > RCOO
– – – –
33. Arrange the following cation in increasing order of (3) RCOO > NH2 > RO > OH
stability – – – –
„ „ „ (4) RCOO > RO > NH2 > OH
CH2 CH2 CH2 40. Identify the correct order of stability among the fol-
lowing carbanions
– – – –
(CH3)3C—CH2 C6H5CH2 CH3CH2 C6H5
CD3 CT3 (I) (II) (III) (IV)
CH3
(A) (B) (C)
(1) I > III > IV > II (2) I > IV > III > II
(1) A < B < C (2) A < C < B (3) II > III > IV > I (4) II > IV > III > I
(3) C < A < B (4) C < B < A 41. Value of pKa will be minimum for:
34. Arrange the following alkenes in increasing order of
OH OH
their enthalpy of hydrogenation (– %H):

(1) (2)
P Q R S
OCH3
(1) R < S < Q < P (2) R < S < P < Q
OH OH
(3) P < Q < R < S (4) P < Q < S < R
35. Which of the following effects of —NO2 group oper-
ates on —NH2 group in this molecule? (3) (4)
NH2
COOH NO2
42. The order of reactivity of the compounds
H3C CH3 2 H
O
NO2
O N
(1) Only –I effect
O O
(2) Only – M effect
(3) Both –I and –M effect (I) (II) (III) (IV)
(4) Only + M effect Towards substitution with a given electrophile is:
 (1) IV > III > II > I (2) I > II > III > IV 47. In the given ionic reaction, designate the nucleophile
(3) III > II > I > IV (4) I > III >II > IV and the leaving group
43. In which pair second ion is less stable than first? CH3–CH2–Br + NaI CH3–CH2–I + NaBr
2 2 2 2
(1) Nu = Br , L = I
„ –
(2) Nu2 = I2, L2 = Br2
2
–
(3) Nu2 = I2, L2 = CH3C H2
„ 2
I
„
II
„
III (4) Nu2 = CH3C H2, L2 = Br2
48. The decreasing order of nucleophilicities of the fol-
(1) (I) and (II) (2) (II) and (III) lowing is
(3) only (II) (4) only (III) I. Br2 II. MeO2
2
44. Which of the following carbocation will undergo III. Me2N IV. Me3C2
favourable rearrangement? (1) I > II > III > IV (2) IV > III > II > I
(3) IV > III > I > II (4) II > I > III > IV
+ + 49. Which of the following is best classified as hetero-
(1) (2)
cyclic aromatic compound?

(1) N–H (2) N

(3) + (4)
+
N
45. In which of the following, all C–O bonds are not of (3) (4)
N
equal length?

– 50. Among the following which is more reactive toward

(1) O O (2) CH3–COO– AgNO3?
Br
(3) CO32 – (4) NO2–
(1) (2)
46. Arrange o-toluic acid (I), m-toluic acid (II), p-toluic O Br
acid (III) and benzoic acid (IV) in order of decreasing O
acid strength. Br
Br
(1) I > II > III > IV (2) I > II > IV> III
(3) III > IV> I > II (4) I > IV > II > III (3) (4)

EXERCISE 2
1. The correct order of resonance energy in the follow- a b
ing is: c
CH3–N N
O2N NMe2 NMe2 H C N

O2N (1) a > b > c (2) c > b > a

(3) b > c > a (4) c > a > b
NMe2 3. The correct order of basicity of the compounds is-

NO2

(1) II > I > III (2) I > II > III N N N N

H H H
(3) III > II > I (4) II > III > I I II III IV
2. Rank the indicated bond in the given compound in
(1) IV > III > II > I (2) III > IV > I > II
order of decreasing bond strength:
(3) IV> III > I > II (4) III > IV > II > I
4. The weakest base amongst the following is: 8. The decreasing order of basic characters of the
following is:
(1) (2)
N N I. II. N
H N
NO2 O2N NO2 H
NH2
(3) (4) NH2
N III. NH IV.
N
H H
5. In which of the following molecules, – NO2 group is (1) III > I > IV > II (2) II > I > IV > II
not coplanar with phenyl ring? (3) IV > III > II > I (4) I > II > III > IV
CH3 CH3 9. The decreasing order of nucleophilicities of the
following is:
(1) (2) I. H2O II. EtOH
2
2
N III. MeCOO IV. O H
N
O O V. EtO2
O O
(1) I > II > III > V > IV
(2) I > II > III > IV > V
(3) IV > V > III > II > I
(3) I I (4) (4) V > IV > III > II > I
N N=O 10. B, C and H are three (C–O) bonds in methyl acetate;
O O O O
B
6. Among these compounds, which one has maximum CH3–C–O–CH3
resonance energy? C H

O O O O the bond lengths are in the order:

(1) B > C > H (2) B < C < H
(3) B = C = H (4) B < C = H
(I) (II) (III) (IV) 11. Which of the following carbonium ion is the most
(1) I (2) II stable?
(3) III (4) IV „
„
7. Which of the following statements would be true (1) (2)
about this compound? CH3 CH3
NO2
5 (3) „ (4) „
CH3 CH3
1 3
NO2 12. Which of the following will have the lowest pKa
NO2
value?
Br
Ha
(1) All three C–N bonds are of same length
(1) (2)
(2) Cl–N and C3–N bonds are of same length but
Hb
shorter than C5–N bond
(3) Cl–N and C3–N bonds are of same length but
(3) Hc (4)
longer than C5–N bond
Hd
(4) Cl–N and C3–N bonds are of different length but
both are longer than C5–N bond 13. The most stable carbocation is:
 „ „ 19. Arrange in increasing order of pKb value of given
(1) (2) substance:

COOH COOH COOH

„ „ Me
Me Me Me Me Me
(3) (4) Me

14. Which of the following is most stable cation? (I) (II) (III)
O O
(1) I < II < III (2) III < I < II
(1) (2)
„ (3) II < I < III (4) II < III < I
+
O O 20. Which of the following compounds are aromatic?
„
(3) (4) „
„ H
–
H
15. A synthetic cockroach repellent has following O „
structure, (I) (II) (III) (IV) (V)
O O
O O (1) III and IV (2) I and II
(3) II, III and IV (4) III, IV and V
21. Arrange them in increasing bond dissociation energy
The compound contains: of C–H bond:
(1) sp3 and sp2-hybridised carbon atom H 4
(2) Only sp2-hybridised carbon atom H1
(3) sp, sp2 and sp3-hybridised carbon atom
(4) Only sp3-hybridised carbon atom H
2
H3
16. The correct order of increasing nucleophilicity in
protic solvent is: (1) 1 > 2 > 3 > 4 (2) 4 > 3 > 2 > 1
2 2 2 2
(1) SH > CN > I > OH > N2
3
(3) 4 > 1 > 3 > 2 (4) 3 > 2 > 1 > 4
(2) N2 > OH2 > I2 > CN2 > SH 2 22. The correct order of basic strength of the following
3
is:
(3) CN2 > SH2 > I2 > OH2 > N2
3 O
(4) OH2 > CN2 > SH2 > I2 > N2 3 (I) NHCOCH3 (II) C–NHCH3
17. Which of the following is anti aromatic?
(1) Cyclopentadienyl anion
O NH2
(2) Cyclopentadienyl cation
(III) C–CH2NH2 (IV)
(3) Cycloheptatrienyl cation COCH3
(4) Anthracene
18. What is the increasing order of basic strength of the (1) I > II > III > IV (2) IV > II > III > I
following compounds in aqueous solution? (3) III > IV > II > I (4) III > II > IV > I
H 23. Which of the following molecules does not contain
sp3 hybridised carbon atoms?
N
(I) NH2 (II) CH3
H CN
(1) (2)
N NC C
N O
(III) (IV)
H H
(3) C=C=C (4)
(1) I < II < III < IV (2) I < II < IV < III O H H
(3) III < I < II < IV (4) III < I < IV < II 24. Following carbocation rearranges to from:
 NH2 (1) IV > I > III > II (2) IV > III > I > II
(3) I > IV > III > II (4) I > III > IV > II
28. The most unstable carbanion among the following
„
is:
CH2 2 2
(1) H5C6 – H2 (2) CCl3
__
(3) H2C (4) :C6H5
OH
CHO
NH2 NH2 29. Which Cl will eliminate with fastest rate in the form
of Cl2 to form AgCl?
Cl(c)
(1) „ (2)
O
„
OH OH AgNO3
Cl(b) AgCls
NH2
NH2

Cl(d)
Cl(a)
(3) (4)
„ (1) Cl(c) (2) Cl(b)
„
(3) Cl(a) (4) Cl(d)
OH HO
30. The correct order of increasing basic nature for the
25. The correct nucleophilicity order is: following compounds is:
ONa ONa ONa ONa NH2 CH3 CN

N N N N
CH3 OCH3 Cl (I) (II) (III) (IV)
(1) (2) (3) (4) (1) IV < I < III < II (2) I < II < III < IV
(1) 1 > 2 > 3 > 4 (2) 3 > 2 > 1 > 4 (3) IV < III < II < I (4) II < IV < I < III
(3) 3 > 2 > 4 > 1 (4) 2 > 1 > 3 > 4 31. The compound shown is planar and all the carbon-
26. The correct leaving group ability has been mentioned carbon bond lengths are the same. What can you
in the option deduce about the bonding of boron from these
observations?
2 2
(1) SO2 < COO
B–CH3
(2) CF3SO2
3
> CCl3SO2
3
(3) I2 < 2CN (4) 2NH2 > 2OH (1) The boron is sp2-hybridised and the p-orbital
27. Find out correct stability order in the following contains an unshared pair of electrons
carbocations: (2) The boron is sp2-hybridised and a hybrid orbital
„ contains an unshared pair of electrons
„
(I) (II) (3) The boron is sp2-hybridised and a hybrid orbital
is vacant
„ OH (4) The boron is sp2-hybridised and the p-orbital is
„
(III) (IV) vacant
32. Which of the following cations is the most stable?
 CH3 (1) II < I < III (2) I < III < II
CH3
CH3 (3) III < II < I (4) I = II = III
(1) C CH3 (2) H C C
„
3 37. Arrange these compounds in the increasing order of
H3C „
OH their aromatic character
CH3 CH3
(3) CH3 (4) C O S NH
C
HO „ H3C „ OH
33. The decreasing order of acidic character of the (A) (B) (C)
following is:
COOH COOH (1) C, B, A (2) A, B, C
(I) HO OH (II) OH (3) A, C, B (4) A = B = C
38. Consider the following statement:

COOH COOH OH CH3

(III) (IV)
(I) is more stable than
OH „ „
H NO2 H NO2
(1) I > II > III > IV (2) III > IV > II > I
(3) IV > III > II > I (4) I > II > IV > III NO2 NO2
34. Consider the following nucleophiles (A) and (B)
is more stable than –
CH3 (II)
2 – Cl
(A) H3C–C–O (B) HO2 HO Cl OH
CH3
Select correct statements about (A) and (B) (1) I and II both are correct
(1) A is weaker nucleophile and weaker base (2) I and reverse of II are correct
compared to B which is stronger nuclephile and (3) II and reverse of I are correct
stronger base (4) I and II both are incorrect
(2) A is stronger nucleophile and stronger base 39. Arrange the CH3COO–, C6H5O– and C6H5SO3– anions
compared to B which is weaker nuclephile and as leaving group in the decreasing order if the pKa
weaker base values of their conjugate acids are 4.5, 10 and 2.6
(3) A is weaker nucleophile and stronger base respectively
compared to B which is strong nuclephile and
weaker base (1) C6H5SO–3 > CH3COO– > C6H5O–
(4) None of these (2) C6H5O– > CH3COO– > C6H5SO–3
35. Which of the following is the incorrect order of bond (3) CH3COO– > C6H5SO–3 > C6H5O–
lengths?
(1) C – C > C = C > C y C > C y N (4) CH3COO– > C6H5SO–3 > C6H5O–
(2) C = N > C = O > C = C > C = S 40. The order of decreasing nucleophilicities of the fol-
(3) C = C > C = N > C = O > C y N lowing species is:
(4) C – C > C = C > C y C > C – H
2 2 2
36. Arrange in increasing order of leaving group (1) CH3S > CH3O > CH3COO > CH3OH
ability: 2
2 2
– – – (2) CH3COO > CH3S > CH3O > CH3OH
CO2 CO2 CO2
2 2 2
(3) CH3OH > CH3S > CH3COO > CH3O
2 2 2
(4) CH3O > CH3OH > CH3COO > CH3S
CH3 CF3
(I) (II) (III)
 EXERCISE 3

One and More Than One Option Correct 4. Which of the following is/are more basic than its own
Type Question para-isomer?

1. Among the following which statement is correct? NH2 NH2

(1) 4 nitrophenol is more acidic than 3,5-dimethyl-
4-nitrophenol (1) (2)
(2) Among R2NH, and R–C N weakest base NO2 Cl
is R–C y
N NH2
NH2
(3) Bridge head carbocation is rarely formed
(4) p-fluorophenol is stronger acid than (3) (4)
p-chlorophenol CHO
OCH3
2. Which of the following are aromatic?
5. In which of the following the first anion is more
stable than the second?
(1) N N (2)
O 2 2
„ (1) O2N–CH2 and F–CH2
H
2 2
N (2) CF3 and C Cl3
(3) H– N N (4) 2 2
(3) F3C– CH2 and Cl3C–C H2
B
3. Predict the major product in the following reaction. O
2 2
(4) CH3– C–CH2 and H2N– CH2
HO HO 6. In the vinyl cation, the positively charged carbon is sp
O2N OH 1.0 mol NaOH hybridised. Which statement about the hybridisation
type of the negatively charged carbon in the vinyl
OH carbanion is incorrect?
1.0 mol (1) The carbon is sp hybridised to help to stabilise
–
the orbital with the lone pair
O HO (2) The carbon is sp hybridised to maximise s-char-
acter in the orbital with the lone pair
(1) O2N OH
(3) The carbon is sp hybridised to minimise re-
OH pulsion between the bonding and non-bonding
electrons
HO HO (4) The carbon is sp2 hybridised to minimise angle
strain around pi-bond
(2) O2N OH
7. Which of the following is correct order of nucleo-
O– philicity in CH3OH ?
(1) H3 < H2 – H2
HO O–
O
(3) O2N 2 2 2
OH (2) CH3CH2 O > OH > CH3– C–O
OH (3) F2 > Cl2 > Br2 > I2
HO HO 2 2
(4) H3C–C O > H3CO O
(4) O2N O–
O
OH
 8. What is/are true regarding a reactive intermediate Cl
formed in a reaction?
(1) It is the species present at the maxima of the (4)
activation energy diagram
Cl Cl
(2) It is formed for infinitesimal time only, cannot
be isolated practically 12. Consider the following amines.
(3) The most stable reactive intermediate leads to
CH3—CH2—NH2 CH3—NH—CH3
the formation of major product
(4) It is responsible for more than one product in a (I) (II)
reaction
CH3 CH2 N CH3
9. Which of the following process is/are exothermic?
H3C H3C CH3
(III)
(1)
H3C H3C Which of the following statements is/are correct
regarding their basicity?
H3C H3C (1) In aqueous solution, the increasing basicity
(2) is I < II < III
H3C H3C (2) In gas phase, the basic strength follows the order
I < II < III
H3C H3C
(3) The pKa values of these amines in gas phase is
(3) in the order III < II < I
H3C H3C (4) In aqueous solution, II evolve maximum heat on
H3C H3C the basis of per mol when neutralised by adding
(4) excess of HCl
H3C H3C 13. In which of the following, all C—O bonds are of
equal length?
10. Which of the following carbocation (s) undergo
favourable rearrangement into more stable one? (1) O O– (2) CH3—COO–
+
(1) (2) O
+ O (3) HCO–3 (4) NO–2
+ 14. Consider the molecule indigotin
„
(3) (4)
O
H H
N N
11. Which of the following (s) is/are non-polar?
CHO
O O
(1)
OHC The correct statement (s) regarding the compound
C CF (indigotin) is/are
(1) In exhibit geometrical isomerism and its trans
isomer is more stable
(2) FC C (2) It exhibit enantiomerism
(3) Its ‘CiS’ isomer has greater solubility in water
Cl
Cl than the trans one
(4) It is a planar molecule with very large resonance
(3) stabilisation energy
Cl 15. Which of the following statement applies correctly
Cl regarding acidity of the following acid?
 SO3H (II) + +
(I) HO (1) (2)
COOH (III) O O
+
COOH (IV) (3) (4)
O + O
(1) One mole of acid would require 4.0 mol of
NaOH for complete neutralisation Assertion and Reason Type Question
(2) Proton labelled II will be deprotonated first during
(1) If both Statement-I and Statement-II are correct
neutralisation
and Statement-II is the correct explanation for
(3) On treatment with NaHCO3, its one mole would Statement-I
require two moles of base
(2) If both Statement-I and Statement-II are correct
(4) The acid is stronger than both benzene sulphonic and Statement-II is not the correct explanation
acid and benzoic acid for Statement-I
16. Which of the following deduction regarding follow- (3) If Statement-I is correct and Statement-II is
ing base is/are true? incorrect
H3C (4) If Statement-I is incorrect and Statement-II is
(I) N N(II) correct
H3C 19. Statement-1: In strongly acidic solutions, ani-
(IV) (III)
line becomes more reactive towards electrophilic
(1) Nitrogen I is protonated first during stepwise reagents.
neutralisation Statement-2: The amino group being completely
(2) Nitrogen II is protonated first during stepwise protonated in strongly acidic solution, the lone pair
neutralisation of electrons of the nitrogen is no longer available for
resonance.
(3) Conjugate acid has a resonance structure with „
complete valence shells of all atoms 20. Statement-1: Me–CH2 is more stable than MeO – CH2„
(4) –OCH3 group at IV will increase basic strength Statement-2: Me is a + I group where as MeO is
while the same from positions III will decrease a – I group
basic strength 21. Statement-1: F2 is good electrophile than :CCl2
17. The correct statement(s) concerning the labelled Statement-2: Electronegativity of F is greater than
hydrogens in the following molecule is/are electronegativity of Cl.
22. Statement-1: Pyrrolidine (II) is more basic than
H II pyrrole (I)
III H
H I
N N
(1) II undergo easiest homolytic bond fission in a
chemical reaction H H
(2) Amongst the labelled hydrogens, C—H II has (I) (II)
greatest bond length
Statement-2: Protonated pyrrole has resonance sta-
(3) Amongst the labelled hydrogens C—H I has the bilisation of positive charge in aromatic ring.
shortest bond length
23. Statement-1: The difference between Ka1, and Ka2
(4) Hydrogens labelled I and II take part in
for dicarboxylic acids of type
hyperconjugation
COOH
18. Alkenes on electrophilic attack by H+ forms carboca-
tion. Which is/are the probable carbocation possible (CH2)n decreases as n increases
in this reaction? COOH
Statement-2: On increasing n the – I effect of
H+ – COOH group decreases (Ka1, decreases) also + I
Most stable carbocation
effect of – COO– group decreases (Ka2 increases)
O
 –
24. Statement-I: Following is a favourable rearrange- (1) OCO–CH2CH2–CH–COOH
ment of carbocation:
NH3
Hydride shift +
H + –
+ CH3 (2) HOOC–CH2CH2–CH–COO
CH2
NH3
Statement-II: A tertiary alkyl carbocation is more +
stable than primary alkyl carbocation. (3) HOCO–CH2CH2–CH–COOH

Comprehension Type Question NH2

–
Comprehension (Q. 25–27) (4) HOOC–CH2CH2–CH–O
Amide is a conjugated system, exhibit resonance, Following NH3
are formamide and structures that bear some relationship to
the Lewis structure of formamide. 30. If the above amino acid is treated with excess of
H NaOH, what would be formed?
O + OH – –
O (1) OOC–CH2CH2–CH–COO
C H C
C H N NH2
H N H
H N –
H H (2) HOOC–CH2CH2–CH–COO
H
Formamide II
I NH2
– – – –
O O (3) OOC–CH2CH2–CH–COO

C C + H NH2
N N +
H H –
H (4) OOC–CH2CH2–CH–COOH
H
III IV NH2
25. Which is a resonance contributor to formamide?
(1) Only I (2) Only II Column Matching Type Question
(3) Only III (4) Only IV 31. Match the following: (More than one option in col-
26. Which represents a conjugate acid of formamide? umn-II may match with single option in column-I).
(1) Only I (2) Only II Match the hybridisation state of below listed carbon
(3) Only III (4) Only IV atoms.
27. Which is capable of showing stereoisomerism? CH2=C=CH–CH2–CyC–CH2–NH2
(1) Only I (2) Only II Column-I Column-I
(3) Only III (4) Only IV Carbon atoms Hybridization state
Comprehension (Q. 28–30) (A) C1 (P) sp
Consider the following amino acid (protonated) to answer (B) C2 (Q) sp2
the next three questions.
(C) C5 (R) sp3
O
$ #6 (S) dsp2
HO–C–CH2–CH2–CH–COOH (1) A m P; B m Q; C m 2 $ m S
x NH3 Y (2) A m S; B m P; C m 1 $ m R
+
(3) A m R; B m Q; C m 0 $ m S
Z
(4) A m R; B m P; C m 1 $ m P
28. the order of acidic strength of X, Y and Z is 32. Column-I Column-II
(1) X > Y > Z (2) Z > X > Y +
(A) A – B m A + :B–
(p) Free radical
(3) Y > Z > X (4) Y > X > Z „
(B) CH3C H–CH3 (q) Heterolytic cleavage
29. If the amino acid shown above is treated with 1.0 · ·
mole of NaOH, the species formed is (C) A – A m A + A (r) Carbocation
 $ #(2N2 m H2 + N2 (s) Nucleophile 35. In how many of the following, at least one of
(E) CH3 H (t) Carbene the C—O bond is weaker than the C—O bond in
acetaldehyde?
(1) A m q; B m r; C m P $ m s; E m t O O
(2) A m q; B m p; C m R $ m t; E m s
(3) A m r; B m q; C m P $ m t; E m s i. CH3 C OH ii. CH2 CH C H
+ +
(4) A m q; B m r; C m P $ m t; E m s iii. CH3 C O iv. CH2 CH C O
33. Column-I has listed some common reactive interme- O
diates and column-II has listed some of the properties
v. vi. CO2–
3
possessed by these intermediates. Match the quantity
from column-I with the quantities from Column-II
vii. NCO–
Column-I Column-II
36. The total number of contributing structures showing
O hyperconjugation for the following carbocation is
(A) – (p) Has more stable reso- CH3
CH2
nance structure
+
(B) O (q) Paramagnetic CH3
+
37. If the following carbocation is formed in a chemical
(C) (r) Hyperconjugation stabi- reaction that finally bonds with bromide nucleophile,
lises the intermediates how many different bromination products are
$ :CH2 (s) Acts as a strong Lewis expected?
acid
+
(1) A m q; B m p; C m Q S $ m p, r
(2) A m p; B m q; C m R $ m s 38. In carbene (:CH2), what is the maximum num-
(3) A m s; B m r; C m P $ m q ber of valence electrons that may have same spin
(4) A m p; B m p, r, s; C m Q R $ m q, s direction?
39. From the list below how many of them are stronger
Single Digit Integer Type Question acid than benzoic acid
COOH
34. How many of the following are stronger acid than COOH
phenol?
OH HO
OH OH OH OH

I II

CH3 OH COOH COOH

Cl OH CH3
I II III IV
OH
OH OH OH OH III IV
OH OCH3
COOH
OH
OCH3
OCH3
V VI VII VIII O2N
CH3
OH V VI

OH
SO3H COOH

CH CH OCH3 O2N COOH

IX X VII VIII
 COOH N
(a) (b)
COOH N
CH3
OCH3 CH3O
IX X (c) (d)

40. X = N Number of compound unstable at room O

temperature.
(e) (f)
O

EXERCISE 4
1. In the following benzyl/allyl system [AIEEE-2002]
(3) NH2 (4) CH2NH2
R–CH=CH2 or R
CH3
(R is alkyl group) 6. The decreasing order of nucleophilicity among the
Increasing order of inductive effect is- nucleophiles [AIEEE-2005]
– –
(1) (CH3)3C– > (CH3)2CH– > CH3CH2– (a) CH3 C —O (b) CH3O
(2) CH3CH2– > (CH3)2CH– > (CH3)3C–
(3) (CH3)2CH– > CH3CH2– > (CH3)3C– O
(c) CN–
(4) (CH3)3C– > CH3CH2– > (CH3)2CH– O
2. The correct order of increasing basic strength of the (d) H3C –
S—O
bases NH3, CH3NH2 and (CH3)2NH is
O
[AIEEE-2003]
(1) NH3 < CH3NH2 < (CH3)2NH (1) (d) > (c) > (b) > (a) (2) (a) > (b) > (c) > (d)
(2) CH3NH2 < (CH3)2NH < NH3 (3) (c) > (b) > (a) > (d) (4) (b) > (c) > (a) > (d)
(3) CH3NH2 < NH3 < (CH3)2NH 7. Amongst the following the most basic compound is
(4) (CH3)2NH < NH3 < CH3NH2 [AIEEE-2005]
3. Rate of the reaction [AIEEE-2004] (1) Aniline (2) benzylamine
O O (3) p-nitroaniline (4) acetanilide
–
R–C + Nu R–C + Z 8. The increasing order of stability of the following free
Z Nu radicals is–
Is fastest when Z is- [AIEEE-2006]
s s s s
(1) Cl (2) NH2 (1) (C6H5)3C < (C6H5)2CH < (CH3)3C < (CH3)2CH
(3) OC2H5 (4) OCOCH3 s s s s
(2) (C6H5)2CH < (C6H5)3C < (CH3)3C < (CH3)2CH
4. Consider the acidic nature of the carboxylic acids- s s s s
[AIEEE-2004] (3) (CH3)2CH < (CH3)3C < (C6H5)3C < (C6H5)2CH
(a) PhCOOH (b) o–NO2C6H4COOH s s s s
(4) (CH3)2CH < (CH3)3C < (C6H5)2CH < (C6H5)3C
(c) p–NO2C6H4COOH (d) m–NO2C6H4COOH 9. CH3Br + Nu– m CH3 – Nu + Br–
Which of the following order is correct ? The decreasing order of the rate of the above reaction
(1) a > b > c > d (2) b > d > c > a with nucleophiles (Nu– ! TO $ IS ;AIEEE-2006]
(3) b > d > a > c (4) b > c > d > a [Nu– = (A) PhO–, (B) AcO–, (C) HO– $ #(3O–]
5. Which of the following is the strongest base-  $  #  "  !  !  "  #  $
[AIEEE-2004]  "  $  #  !  $  #  !  "
10. Among the following acids, which has the lowest pKa
(1) NH2 (2) NHCH3 value? [AIEEE-2006]
 (1) (CH3)2CH–COOH (2) CH3CH2COOH 17. The correct order of acid strength of the following
(3) CH3COOH (4) HCOOH compounds is: [AIEEE-2011]
11. The correct order of increasing acid strength of the (A) Phenol (B) p-Cresol
compounds- [AIEEE-2006] # M .ITROPHENOL $ P .ITROPHENOL
(A) CH3CO2H (B) MeOCH2CO2H  $  #  !  "  "  $  !  #
Me  !  "  $  #  #  "  !  $
(C) CF3CO2( $ CO2H
Me 18. The non aromatic compound among the following
 "$!#  $!#" is– [AIEEE-2011]
 $!"#  !$#"
12. Which one of the following is the strongest base in (1) (2)
aqueous solution? [AIEEE-2007] S
(1) Trimethylamine (2) Aniline
 $IMETHYLAMINE  -ETHYLAMINE (3) (4)
13. Presence of a nitro group in a benzene ring –

[AIEEE-2007] 19. Ortho-Nitrophenol is less soluble in water than p- and

m-Nitrophenols because– [AIEEE-2012]
(1) activates the ring towards electrophilic
substitution (1) o-Nitrophenol shows intramolecular H-bonding
(2) renders the ring basic (2) o-Nitrophenol shows intermolecular H-bonding
(3) deactivates the ring towards nucleophilic (3) Melting point of o-Nitrophenol is lower than
substitution those of m-and p-isomers.
(4) deactivates the ring towards electrophilic (4) o-Nitrophenol is more volatile in steam than
substitution those of m-and p-isomers
2 2 2
14. Arrange the carbanions, (CH3)C, C Cl3, (CH3)2CH, 20. Which of the following compounds are antiaromatic
2 [AIEEE Online-2012]
C6H5CH2, in order of their decreasing stability-
[AIEEE-2009]
2
2
– 2 (I) (II)
(1) (CH3)2 C H > C Cl3 > C6H5C H2 > (CH3)3C
2
2
2 2
O
(2) C Cl3 > C6H5C H2 > (CH3)2 CH > (CH3)3C
2 2
2
2

(3) (CH3)3C > (CH3)2 C H > C6H5C H2 > C Cl3 (III) (IV)
2
2 2 2 O
(4) C6H5C H2 > CCl3 > (CH3)3C > (CH3)2CH
15. The correct order of increasing basicity of the given
conjugate bases (R=CH3) is [AIEEE-2010] (V) (VI)
– – – –
(1) RCOO > HC y C > R < N H2 „
__ __ __
(2) R < CH y C < RCOO– < NH2 (1) (III) and (VI) (2) (V) and (VI)
__ __ __
(3) RCOO– < NH2 < CH y C < R (3) (I) and (V) (4) (I) and (IV)
__ __ __
(4) RCOO– < CH y C < N H2 < R 21. In the following compounds:
16. Consider thiol anion (RS2) and alkoxy anion (RO2). [AIEEE Online-2012]
Which of the following statements is correct?
[AIEEE-2011] (1) (II)
(1) RS2 is less basic but more nucleophilic than N N
RO2
H
(2) RS2 is more basic and more nucleophilic than
RO2 O
(III) (IV)
(3) RS2 is more basic but less nucleophilic than
RO2 N N

(4) RS2 is less basic and less nucleophilic than H H

RO2
 The order of basicity is as follows: (1) 1° > 2° > 3° > NH3 (2) 3° > 2° > NH3 > 1°
(1) IV > III > II > I (2) II > III > I > IV (3) 3° > 2° > 1° > NH3 (4) NH3 > 1° > 2° > 3°
(3) I > III > II > IV (4) III > I > II > IV 28. In nucleophilic substitution reaction, order of halo-
22. $IPOLE MOMENT IS SHOWN BY gens as incoming (attacking) nucleophile is should
[AIEEE Online-2012] be-
(1) trans-2, 3-dichloro-2-butene [JEE Main Online-2013]
(2) 1, 2-dichlorobenzene (1) Br– > I– > Cl– (2) I– > Br– > Cl–
– – –
(3) 1, 4-dichlorobenzene (3) Cl > Br > I (4) Cl– > I– < Br–
(4) trans-1, 2-dinitroethene 29. Which one of the following substituents at posi-
tion is most effective in stabilising the phenoxide
23. Which of the following cannot be represented by 2
resonance structures? O
, ion? [JEE Main Online-2014]
[AIEEE Online-2012]
 $IMETHYL ETHER  #ARBOXYLATE ANION (1) –CH3 (2) –OCH3
(3) Toluene (4) Nitrate anion (3) –COCH3 (4) –CH2OH
24. Arrange the following compounds in order of decreas- 30. In which of the following pairs A is more stable than
ing acidity: B?
[JEE Main online-2012] [JEE main Online-2014]
OH OH OH A B
OH A B
(1) (2)

A B
Cl CH3 NO2 OCH3
A B
(I) (II) (III) (IV) (3) (4) Ph3C , (CH3)3C
(1) III > I > II > IV (2) IV > III > I > II
(3) II > IV > I > III (4) I > II > III > IV 31. Considering the basic strength of amines in aqueous
25. The order of stability of the following carbocations solution, which one has the smallest pKb value?
[JEE Main Online-2013] [JEE Main Online-2014]
„
CH2 (1) CH3NH2 (2) (CH3)3N
(3) C6H5NH2 (4) (CH3)2NH
„ „
CH2=CH—CH2;CH3—CH—CH2; is 32. or which of the following molecule significant
N x 0? [JEE Main Online-2014]
(I) (II) (III)
Cl CN
(1) I > II > III (2) III > I > II
(3) III > II > I (4) II > III > I (a) (b)
26. Which one of the following is the most stable?
[JEE Main Online-2013] Cl CN
+
„ OH SH
(1) (2)
Ph (c) (d)
+
„ OH SH
(3) (4)
(1) a and b (2) only c
Ph (3) c and d (4) only a
27. The order of basicity of amines in gaseous state is 33. Arrange the following amines in the order of
[JEE Main Online-2013] increasing basicity
JEE Main Online-2015]
 NH2 NH2 NH2 –
OOC OH
(1) CH3NH2 < < <

(3)
OCH3 NO2
NH2 NH2 NH2
–
H
O
(2) < < < CH3NH2 O2N
–
HOOC O
NO2 OCH3

(4)
(3)
–

OH
O2N
NH2 NH2 NH2 „ „
H 3N NH3
(4) < < < CH3NH2 35. (Z) (Y)
COOH
(X)
OCH3 NO2
Correct order of acidic strength is:
COOH OH [IIT-2004]
(1) x > y > z (2) z > y > x
(3) y > z > x (4) x > z > y
34. 36. For-1-methoxy-1, 3-butadiene, which of the follow-
ing resonating structure is least stable?
H [IIT-2005]
2 „
OH (1) C H2–CH–CH–CH=CH–O–CH3
O2N [IIT-2003] 2 „
When X is made to react with 2 eq. of NaNH2 the (2) CH2–CH=CH–CH–O –CH3
„ 2
product formed will be - (3) CH2=CH–CH=CH–O–CH3
– 2 „
OOC OH (4) CH2=CH–CH–CH=O –CH3
37. Among the following, the least stable resonance
structure is: [IIT-2007]
„ O 2 O
(1)
(1) „ (2) „
„
2 N N
–
O O
OH 2 2
O2N 2
2 O O
– –
OOC O (3) „ (4) „ „
„ N
N

O O
2
2
(2)
38. Statement-1: p-Hydroxybenzoic acid has a lower
boiling point that o-hydroxybenzoic
H
Statement-2: o-Hydroxybenzoic acid has intramo-
OH
O2N lecular hydrogen bonding. [IIT-2007]
 (1) If both Statement-I and Statement-II are correct „ 2 „ 2
H2C=N=N CH2–N=N
and Statement-II is the correct explanation for
Statement-I (I) (II)
2 „ 2 „
(2) If both Statement-I and Statement-II are correct C H2–NyN H2C –N=N
and Statement-II is not the correct explanation
(III) (IV)
for Statement-I
[IIT-2009]
(3) If Statement-I is correct and Statement-II is
incorrect (1) I > II > IV > III (2) I > III > II > IV
(4) If Statement-I is incorrect and Statement-II is (3) II > I > III > IV (4) III > I > IV > II
correct 44. Out of the following the alkene that exhibits optical
isomerism is
39. Hyperconjugation involves overlap of the following
orbitals [IIT-2008 +
(1) T – T (2) T – p H3N—CH2—CH2—CH2—CH2 O
CH—C
(3) p – p (4) Q – Q H2N 2
O
40. The correct stability order for the following species
is- [IIT-2008] [IIT-2010]
„ „
(1) 1 (2) 2
O
(3) 3 (4) 4
(I) (II) 45. The compounds P, Q and S [IIT-2010]
„
O „ COOH OCH3
(III) (IV)
HO H3 C
(1) II > IV > I > III (2) I > II > III > IV
(3) II > I > IV > III (4) I > III > II > IV (P) (Q)
41. The correct acidity order of the following is
[IIT-2009]
C
OH OH COOH COOH O
H3C
(S)

Cl CH3 were separately subjected to nitration using HNO3/

(I) (II) (III) (IV) H2SO4 mixture. The major product formed in each
case respectively, is
(1) III > IV > II > I (2) IV > III > I > II
(3) III > II > I > IV (4) II > III > IV > I
(1) COOH OCH3
42. In the following carbocation, H/CH3 that is most
likely to migrate to the positively charged carbon
is- [IIT-2009] HO H3C
NO2 NO2
H H
1 2 „ 4 5 (Pa) (Qa)
H3—C—C—C—C—CH3
HO H O
(1) CH3 at C – 4 (2) H at C– 4 C
(3) CH3 at C – 2 (4) H at C – 2 O
43. The correct stability order of the following resonance O2N
structures is- (Sa)
 (2) COOH OCH3 (1) 6 (2) 4
(3) 3 (4) 2
HO NO2 H3C 48. Match the column reaction in Column I with appro-
NO2 priate options in Column II. [ITT Adv. 2011]
(Pa) (Qa) Column I Column II
i. p. Racemic
O mixture
N2Cl + OH
C
O
O°C NaOH/H2O
NO2
(Sa)
N N OH
(3) COOH OCH3

NO2 ii. q. Addition

HO H3C OH OH reaction
NO2
H3C C C—CH3
(Pa) (Qa)
CH3 CH3
O NO2 O
H2SO4 CH3
C CH3 C
O C CH3
CH3
(Sa)
iii. O r. Substitution
1. LiAIH4 reaction
(4) COOH OCH3 C +
CH3 2. H3O
NO2 OH
HO H3C
HC
NO2 CH3
(Pa) (Qa)
iv. s. Coupling
Base S reaction
SH Cl
t. Carbocation
O
intermediate
C NO2
O Codes
i ii iii iv
(1) r, s t p, q q
(Sa) (2) p r, s q, s t
46. Among the following compounds, the most acidic (3) r, s p t r, s
is- [IIT-2011] (4) q t p, t q, r
(1) p-nitrophenol 49. Which of the following molecules, in pure form, is
(2) p-hydroxybenzoic acid (are) unstable at room temperature?
(3) o-hydroxybenzoic acid [IIT-2012]
(4) p-toluic acid
(1) (2)
47. The total number of contributing structures showing
hyperconjugation (involving C–H bonds) for the fol-
O O
lowing carbocation is [IIT-2011]
H3C + CH2CH3 (3) (4)
 50. In allene (C3H4), the type(s) of hybridisation of the Cl
carbon atoms, is (are) [ITT Adv. 2012]
(1) sp ad sp3 (2) sp and sp2 Br CH3
(3) only sp3 (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) T m p(empty) and T m Q* electron delocalisa-
tions 54. Hydrogen bonding plays a central role in the follow-
(2) T m
T* and T m Q electron delocalisations ing phenomena: [JEE Adv-2014 (MCQ)]
(3) T
m
p (filled) and T m Q electron delocalisa- (1) Ice floats in water
tions (2) higher lewis basicity of primary amines than
(4) p(filled) m T m Q* 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)]  $IMERISATION OF ACETIC ACID IN BENZENE
55. The correct order of acidity for the following com-
Cl pounds is [JEE(Adv)-2016]

AlCl3 NaH
Q
CO2H
P 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)

 
 
 
 


 
 
 
 


 
 
 
 


 
 
 
 


 
 
 
 


 
 
 
 


 
 
 
 


 
 
 
 


 
 
 
 


 
 
 
 


 
 
 
 


 
 
 
 


 
 
 
 

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)


 
 
 
 
 m
$ISTANCE  .UMBER  0OWER


 
 
 
 

1 1


 
 
 
 
 Acidic strength t
– I Power t ________ t ____



+ 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 t
E.N t
bond strength
3 5
sp (1) < (3) < (2)
2 7. [1]
sp 3
sp sp
– NR3 > – NO2 > – CN > – COOH
______________________________
Hence, C2 and C3 are sp2-and sp3-hybridised n
$E ACTIVATING POWER
2. [4] n m-directing strength
e-deficient species are electrophile 8. [3]
3. [2] (I) Structure m non polar (most stable)
1 (II) Structure m Incomplete octet
Acid strength t – I t __
+I (III) Structure m Complete octet
Also –I power increases as the distance from source = (I) > (III) > (II)
group decreases 9. [2]
4. [4]
 1° 1° O– +
CH3 CH3 +
C C
CH3 (iii) (iv)
CH3
1° 1° 4n + 6 = 2, n = 0
C 4n + 2 = 6, n = 1 Aromatic
Aromatic
CH3 CH3 16. [4]
1° 1°
„
m All 1°C attach with 4°C so 1°H are identical CH3–CH–CH=CH–C C–H
(1) (1) (3)
10. [1] 2 2
sp sp sp
O O– O– O„
„ 17. [1]
„ –
O O O O Removal of most acidic H takes place, according to
(i) > (ii) > (iii) > (iv)
size factor, Acidic strength t
size
non polar complete octet More E.N –ve More E.N +ve OH OH
Incomplete octet C CH C CH
„
–H
11. [3]
NaNH2
(1 mole)
„
„ SH SNa
(1) „ (2) 2
18. [2]
4B–H 6B–H
Resonance t
bond length of double bond
19. [3]
+ x H
„ H z
(3) (4) H w
H
7 B – H (Most stable) 4B–H H yH
12. [1]
2 –x (H effect only)
CHCl3 CCl3 Most stable, due to pQ-dQ bonc CH2–CH2–CH=CH–CH3
Most acidic –y
2
CH3–CH–CH=CH–CH3 (R + H) effect
CHF3 CF3 EWG stabilised anion –w More EN caries radical
CH3–CH2–C=CH–CH3
– (like +ve) unstable
CH3–CH3 CH3 CH2 –z CH –CH –CH=CH–CH Only R effect
3 2 2
ERG, destabilised anion Bond dissociation energy
Stability of anion t Acid strength of conjugate "$%
13. [3] 1
t __________________________
(a)NH2 O stability of carbon free radical
20. [4]
NH(b) e-density of benzene ring t
E.R.G Power
Thus –NHCOCH3 > –OCOEt > –CH3 > COOEt
21. [3]
CH2–NH2
(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) –
Q.Q conjugation dominant (– ve) is not in
14. [2]
$E ACTIVATING GROUP ARE META DIRECTOR 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
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 t 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 t
– M, – I t _______
„
+M, + 1
„
1
Me „ Me Me Me Me Me Acidic strength t Ka t ____
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 2
Me Me Ease of hetrolysis t
Leaving ability of anion
„ 1, 2-H
(3) Me CH2 shift t
Acidic strength of conjugate
„
Me acid of anion.

„
Leaving (anion) m
OH OAc C l
„
1°C 3°C Acidic strength order of conjugate acid m
H2O
„ < ACOH < HCl
Me Me
(4) Me 1,2-H
2
„ Me Hence order of case of hetralysis is (I) < (II)
Me Me
H shift < (III)
„ „
2°C 3°C 30. [1]
B–NO2 comes out of plane due to ortho effect,
So (1) is most stable.
So B(C – N) > C(C – N)
25. [1]
(partial double bond character) in C(C – N) due to
COOC – –H > HOOC > HOOC Me resonance.
31. [2]
Acidic order: sp > sp2 > sp3(C y
C > C = C > C – C)
(i) Bond length (C=C bond) t
Resonance effect
26. [3]
(ii) Bond length (C=C bond) t
H-effect
Acidic strength t 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
t______________________ (refer solved example)
stability of C – free radical

33. [4]
Aromatic stable Stability of carbocation t + H effect
–
+H power CH3  #$3 > CT3
34. [1]
–
OH O Heat of hydrogenation t reactivity
1
Only resonance stable Reactivity t
_______________

(Reoetivity)
Stability of alkene
(Less stable in among)
 1
Stability of alkene t number of B – H(due to + H) Thus pKa t + M, + I t _______
– M, – I
(P) (Q) (R) (S)
–M(–NO2) > –M(–COOH)
1B–H 4B–H 10B–H 7B–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) t ERG t _____
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
_ 2
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„ + FeCl2
4
38. [1] (I) <
m Nucleophilic strength predominantly depends – „
upon size Anti aromatic Aromatic
m N.S t Size of nucleophilic site
39. [2] (II) <
2 2 2 2 „ „
NH2 > R–O > OH > R C O Anti aromatic non Aromatic
m

m
m

EN BS + BS
m

O – –
No Conjugation Conjugation (III) <
m

B.S B.S
m

2 2 Aromatic Anti aromatic

Also R — O — OH
+I 44. [2]
Base strength t +I power s 3UCH REARRANGEMENT IN WHICH CARBOCATION GETS
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
m
m

E.N. E.N.
will exist hence same bond length between participat-
– 3 – 2
(C sp ) (C sp ) ing atom.
46. [4]
(II) > (IV) > (I) , (III)
COOH COOH COOH COOH
Same EN CH3
– 1
stability of —C t –1 t
+1
CH3
(ortho effect/ +H CH No effect
most acidic) +I 3
(II) > (IV) > (III) > (I)
41. [4] (I) (II) (III) (IV)
1 1
Acid strength t Ka t ____ t – I, M t ______
pKa I, + M
 1
1
Acid strength t – H, – I t _______ Basic strength t – M, – I t _______
+ H, + I + M, + I
5. [3]
(I) > (IV) > (II) > (III)
47. [2]
CH3–CH2–Br + Na–I m CH3–CH2–I + NaBr I I
Lg Nu N
48. [2] O O
Acidity : HBr > MeOH > Me2NH > Me3CH m
$UE TO PRESENCE OF  BULKY GROUP AT THE ORTHO
Basicity and nucleophilicity: position of nitro group.
Br2 < MeO2 < Me2N2 < Me3C2 m
–NO2 comes out of plane, due to SIR effect (ortho
i.e., IV > III > II > I effect).
49. [4] 6. [3]
Resonance t Resonance energy
N 4n + 2 = 6
n=1 In (III), continuous conjugation Resonance energy
aromatic 7. [3]
NO2
50. [2] 5
„
Reactivity of R–Br t 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
EXERCISE # 2 C5—N present in resonance
1
1. [2] Resonance t _______________
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 t E.N. t % 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]
mm
mm

Less More E.N. E.N. Acidity:

delocalised 2
delocalised B.S. B.S. H3O„ > EtOH2 >MeCOOH > H2O > EtOH
Thus order is IV > III > > I > II Basicity and nucleophilicity:
2
4. [4] H2O < MeOH < MeCOO2 < OH < EtO2
i.e. V > IV > III > II > I
10. [2] „

B
m
(double bond) in resonance (3) 5B-H

C
m
(single bond) in resonance
H
m
pure single bond „
B
< C < H (4)
11. [4] 2B-H
s POSITIVE CHARGE AT BRIDGE HEAD # CAUSE UNSTABILITY
due to Bredt’s rule 14. [2]
s  CARBOCATION CARBONIUM MOST STABLE $UE TO HIGHER EXTENT OF CONJUGATION
12. [1] 15. [1]

(I) Ha „ 2 sp3 O O sp3

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

„
(III) Hc –Hc 2
– Anti-aromatic 4n + 2 = 5Qe 4n + 2 = 4Qe 4n + 2 = 6Qe 4n + 2 = 14Qe
n =1 n =1 n =1 n =3
4 Qe– Aromatic Anti Aromatic Aromatic Aromatic

In delocalisation 18. [3]

„
In aqueous solution, amine basically follows the
–Hd order
(IV) – Anti-aromatic
2
Hd NH3 < tertiary < primary < secondary
8 Qe– 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. s !CIDIC STRENGTH t ortho effect
= Ha in I is more acidic since it will give H„ faster s /RTHO EFFECT t steric hindrance at ortho
to become a stable aromatic anion. Thus least Pka position
value.
20. [1]
13. [1]
$UE TO RESONANCE AND HYPERCONJUGATION „

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

„ Partial conjugation 4n + 2 = 2Qe

(2) 5B-H non-planer n=1
non-aromatic Aromatic
 (III) Stable by resonance
H
H (IV) negative charge do not participate in resonance
(less stable)
(IV) (V)
29. [1]
4n + 2 = 10Qe 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
"OND DISSOCIATION ENERGY "$% t Base strength t +M, + I t _______
– M, – I
1
_______________________ 31. [4]
Stability of C – free radical
22. [4] Theory based
1 32. [3]
Rule 1 Base strength t _________________
$ELOCALISATION OF p CH3
O C CH3
HO T „
(I) NHCOCH3 (II) C–NHCH3
s POSITIVE
p delocalised In amide p less
delocalised s MOST STABLE
33. [1]
O NH2
O (I) Acidic strength t ortho effect
1
(III) C–CH2NH2 (IV) C–CH3 (II) Acidic strength t – M, – I t _______
+ M, + I
p localised p delocalised 34. [3]
1
Base strength t + I t ___
1 –I
Rule 2 Base strength t + M, + I t _____
– M, I 1
Nucleophilic strength t _____________
23. [4] steric hindrance
3 35. [2]
sp 3 3 3
sp sp 1 1
CN
CH3msp
H H Bond length t ___ t ___
C=C=C %S EN
2 2
H sp sp sp H 36. [1]
NC C=O O
Leaving group ability t acid strength of conjugate
24. [1] 1
acid t ____________________
m Ring expansion takes place Base strength of (anion)
25. [2] 37. [3]
When nucleophilic centre is same then Aromaticity t resonance energy
Nucleophility t basic strength t + M, + I 38. [1]
1 39. [1]
t _______
– M, – I Power of leaving group t acid strength of conjugate
26. [2] 1
acid t ____
27. [1] pKa
+ CH3–COO– CH3–COOH pKa = 4.5
Stability of C t conjugation t H-effect (B–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]
s .EGATIVE CHARGED IONS ARE BETTER NUCLEOPHILE
(I) Stable by resonance
s .3 t size (dominating factor)
(II) Stable by pQ – pQ bonding
s .3 t base strength
EXERCISE # 3 O
2 2
1. [1, 2, 3] (4) H2N–CH2 and CH3–C–CH2
conjugation
$UE TO ( BOND AND P FLUORO PHENOL EXCEPTIONALLY LESS
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 t Base strength
Non aromatic 4n + 2 = 6 In same group
non-planar n=1
aromatic Nucleophilicity t
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 t Conjugation favourable shift
1 +
(ii) Stability of Carboanion t – I t ___ (3) O O +
+I
C I II
2 2 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
pQ–dQ conjugation required rearrangement.
– – +
(1) O2N–CH2 and F–CH2 (4) +
–I(–NO2) > –I(–F)
2 2
(2) CF3 and CCl3
pQ–dQ conjugation
+
(3) F3C–CH2 and Cl3C–CH2 Less stable than the
–I(CH3) > –I(CCl3) Previous carbonation
 Although the above ring expansion increases 15. [1, 2, 4]
stability of cyclopropyl ring but decreases overall All acidic groups, —SO3H, —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]
N=0 C N=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
N=0
Cl +
N=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]
$ISSOCIATION OF #ˆ( )) IS THE EASIEST AS IT PRODUCES
(2) a resonance stabilised free radical.
CH3—CH—CH CH2 CH3—CH CH—CH2
$UE TO HYPERCONJUGATION BOND ORDER OF #ˆ( ))
(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.
 „ + 28.[4]
Me CH2 Me — O — CH2
29.[2]
+I +M
Due to resonance 30.[3]
21. [4] Sol.(28 to 30)
+
: CCl 2 have vacant d-orbital so it is good In the given amino acid cation, –COOH B 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 sp 3

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) m B A+ + B2
So that acid strength decrease.
A m Heterolysis (q)
24. [4] +
It is generally true that a tertiary carbocation is more (B) CH3–C H–CH3 m carbocation (r)
stable than primary one. However, this does not apply (C) A – A As + As
in the present case because it is less stable than I as m Free radical (p)
II has greater angle strain. The favourable rearrange- $ #(2N2 H2 + N 2
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 t – I, – M t _______
H + I, + M
II II Acids stronger than phenol are : II, IV, V, VII
cis trans
 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
EXERCISE # 4
H
37. [8] 1. [1]
–
Br
When R is attached with benzyl/allyl system + induc-
+ tive effect occurred + I Power t 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 t Leaving tendency t Acidic
strength of conjugate acid
38. [4] Since HCl is strongest acid so that Cl– is best leaving
group
4. [4] Since, alcohols and cyanides are weaker acid than
Acid strength t M, – I (EWG) sulphonic and carboxylic acids. Thus, the order of
1 acidic strength of the given species are
t _______ (ERG)
+ M, + I
COOH COOH O
NO2 H 3C S —OH > CH3–C–OH > CH3OH > HCN

O O
(a) (b)
Effect m no effect –M, –I Hence, the decreasing order of nucleophilicity of the
given nucleophiles is as follows
m

m
–I distance
Not effect m no effect (EWG)1 O
– – –
COOH COOH H3C S—O < CH3–C–O– < CN < CH3O
O O
NO2
7. [2]
NO2 1
Base strength t __________________
–M, –I –I $E LOCALISATION OF LP
(EWG)2 (EWG)3
NH2 CH2–NH2
(c) (d)

b>c>d>a
5. [4]
1 Aniline Benzylamine
Base strength t __________________
$E LOCALISATION OF LP p delocalised p localised
CH2–NH2 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

– HCN
CN
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
 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 B.S benzene ring.
2 2 2 2
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

m
carbanion by the dispersal of their negative charge
m

B.S N.S B.S N.S

while +/-effect exerting (e– releasing) groups desta-
C , D > A B bilizes the carbanion by increasing electron density
m

+I Resonance 2 equal on them.

mm

E.N Same B.S But not equal contributor

On the other hand, resonance stabilized carbanion
I factor apply N.S Contributor R.S Resonance l
Base strengh are stable due to the involvement of their lone pair
m

Reso B.S n N.S n of electron with the delocalisation of Q-electrons of

m

1 B.S N.S
B+IB 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 pQ-dQ 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 –
CH C–OH < CH3 C–OH O O
Me
R–C–O R–C O
[2 + I effect exerting groups, [+I effect group of
increases e– density of on –CH3 group] s )N CARBOXYLATE ION THE NEGATIVE CHARGE IS PRESENT
O-atom, thus the release on oxygen, is in conjugation with Q bond thus it
of ease of proton becomes is resonance stabilised.
difficult (least acidic)] s (#yC –: Carbon is sp hybridised so its
electronegativity is increased & higher relative
to nitrogen.
F
< MeO CH3–C–OH < F C C–OH s )F NEGATIVE CHARGE ATOM BELONGS TO SAME PERIOD
__
F s 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
__ __ __
RCOO– > HC y C > NH2 > R
12. [3]
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
$IMETHYL AMINE  AMINE of basic character__is as
__ __
RCOO– < HC y C – < NH2 < R
16. [1]
Nucleophilic strength t
size (v) non-planar, conjugated, 4n = 4, n = 1
+
1
Basic strength t
____

(Anti aromatic)
size
Thus R–S2 is less basic but more nuelophilic strength (vi) planar, conjugated, 4n = 4, n = 1 (Anti
than R–O2
17. [1] aromatic)
Acidic strength t M, – I (EWG) 21. [3]
1 +(III) O
t ____________ –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) t + I t
–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
4HUS $  #  !  " Cl
CH3 Cl
18. [4] C=C
Cl CH3
non-planar
Non aromatic N=0 N
x 0

For aromatic substance molecule most be cyclic| planar Cl

conjugated and obey Huckle rule (4n + 2 = Qe) H
NO2
Rest other satisfied given condition so they are C=C
H NO2
aromatic
19. [1] Cl
In tramolecular H-bond N=0 N=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 t – M, – I t _______
+ 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)

 Thus III > I > II > IV 31. [4]
25. [2] s #6H5– H2, Here p de-localised so it is least
The order of stability of carbocation will be basic
+ As per NCERT
CH2 s )N AQ SOLUTION      IF 2n#(3)
+ + Basic strength lKblpKbn
> 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]
N=0
„

+ve charge present in conjugation with Q-bond

N C C N
so it is most stablised.
N=0
27. [3]
Theory bosed 33. [2]
28. [2] (i) in CH3–NH2, p localised so that base strength
N.S. t size highest
1
If solvent is not given then nucleophilic strength (ii) Base strength t + M, + I t
_______


– M, – I
compared in polar solvent
NH2 NH2 NH2
29. [3]
1
Stability of anion t – I, – M t _______
+ 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,
4B-H 7B-H (more hyper conjugation) we need Investigets the conjugate base of given ion
formed after first deprotonation as:
A B + +
H3N 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 B-position,
more resonance only hyper hence Y is second most acidic followed by Z.
stabilised conjugation
stabilised
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 H3C 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 Q 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 T-electrons of C—H bond is delocalised with Lysine contains two basic groups, e.g., NH2
p-orbitals of Q-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
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 B-H attached to sp2 carbon and they
all can participate in hyperconjugation. Pi(Q) bonds are not formed by hybrid orbitals,
therefore, not counted for hybridisation.
+
+ H
+ H
+
H
HT T T H
+ + C C C TT
HT 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 T 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 sp 2 (planar) bital hence, it is stabilised by T-p (empty)
carbon, generating a chiral centre, hence product hyperconjugation.
will be a racemic mixture.
 „ – Cl CH3 Br
H—
T CH2 CH CH CH3 HCH2 CH CH CH3 Cl Br Br
Q Cl Cl Cl
In 2-butene, stabilisation is due to hyperconjugation
between T – Q* 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) = Q 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 > R3N. 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 CH3
resultant dipole moment. donating group) (Electron donating
group)
Cl Cl
Cl Cl  $IMERISATION OF ACETIC ACID IN BENZENE IS DUE TO
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 N x 0) –OH group displays both kinds of effect:
An electron withdrawing acid-strengthening inductive I > II > III > IV
effect from the meta-position and an electron-releasing E– E– E–
acid weakening resonance effect from the para-posi- O O E+ E+ O E– O E+
tion (at this position, resonance effect overweighs the H H H
C C
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