Acidic character

OH

pka = 9.98
I
Acidic Character II >
OH

OH

OH

OH

OH

NO2

Cl

Me

OMe

10.14
IV

10.21

7.15

9.38

II

III

III >

>

IV

>

( - NO2 > - Cl

V
> Phenol > -Me > - OMe )

OH
OH

OH

OH

Me

OMe

N
O

- I of NO2 at p
-R of NO2 at p

Cl

-I of Cl at p
+ R is not considered;
ineffective 2p(C) - 3p ( Cl )
overlap

Standard

+I of Me at p
H.C of Me

-I of Me
+R of OMe
( Net e- donating effect is
more than in IV )

Acidic character
COOH

pka = 4.17

COOH

COOH

COOH

COOH

NO2

Cl

Me

OMe

3.43

3.98

II

III

I
Acidic Character II >

COOH

III

>

>

IV

>

4.37
IV
V

( - NO 2

4.47
V
> - Cl

COOH
COOH

> BA > -Me > - OMe )

COOH

COOH

Me

OMe

N
O

- I of NO2 at p
-R of NO2 at p

Cl

-I of Cl at p
+ R is not considered;
ineffective 2p(C) - 3p ( Cl )
overlap

Standard

+I of Me at p
H.C of Me

-I of Me
+R of OMe
( Net e- donating effect is
more than in IV )

Basic character
NH2

pkb = 9.42

NH2

NH2

NH2

NH2

NO2

Cl

Me

OMe

12.98

I
Basic character V
NH2

9.82

II
>

IV

> I >

III

III
> II

NH2

8.92
IV

8.82
V

(Reverse of acidity )

NH2

NH2

NH2

Me

OMe

N
O

- I of NO2 at p
-R of NO2 at p

Cl

-I of Cl at p
+ R is not considered;
ineffective 2p(C) - 3p ( Cl )
overlap

Standard

+I of Me at p
H.C of Me

( More electron donating group, stronger is the base )

-I of Me
+R of OMe
( Net e- donating effect is
more than in IV )

Acidic character
OH

OH

OH

OH
Br

Br
Br

II

III

pka = 9.98

8.58

9.12

Acidic character

II

>

III

> IV > I

IV
9.48

-I effect of

Br at

o > m > p

Acidic character
COOH

COOH

COOH

COOH
Br

Br
Br

II

III

pka = 4.17

3.1

3.93

Acidic character

II

>

III

> IV > I

-I effect of

IV
4.10
Br at

o > m > p

Basic character
NH2

NH2

NH2

NH2
Br

Br
Br

II

pkb = 9.42

11.4

Basic character

III

IV

10.49

I > IV > III > II

( Aniline >

>

>

10.09
[ Reverse of acidity ]

o )

Acidic character
OH

OH

OH

OH
Me

Me
Me

II

pka = 9.98

10.28

Acidic character
OH

III

>

III

> IV > II
OH

OH

IV
10.14

10.08
( phenol > m > p > o )
OH

Net e-donating effect at o- > p- > mSo Acidic character m- > p- > oStandard

Me

only + I

Me
Me

+ I at p
H.C at p

+I at o- > m- > pH.C at o- and p- same

Acidic character
COOH

COOH

COOH

COOH
Me

Me
Me

I
pka = 4.17
Acidic character

II

III

3.91

4.27

II > I

>

III

> IV

IV
4.37

( o- > BA > m > p )

In II , there is ortho effect, strongest acid.

So o- substitued acid , containg EWG or EDG, is the strongest acid among its isomers ( except in case of o-amino benzoic acid )
Place o-methyl substitued at the strongest position, keeping the rest of the order same as in Me - substitued phenol.

Basic character
NH2

NH2

NH2

NH2
Me

Me
Me

I
pkb = 9.42
Basic character

II

III

9.61

9.31

IV > III

>

> II

IV
8.92

( p- > m- > aniline >

o- )

According to +I and HC effects, ortho isomer (II) should be the strongest base. Due to ortho effect, basic character is decreased.
In this case, ortho effect is due to steric hindrance of (Me) group, over the (NH 2) group; this results in the protonation of ( NH2 )
group becoming more difficult ( solvation effect ), hence the basicity decreases.

NH2

NH3
H2O

Me

HO

Me

In general , basicity order of methyl substitued aromatic amine is reverse of the acidic order of methyl substituted benzoic acid.
NH2

NH2

>

NH2

Me

>

>

Me

+ I of Me at pHC of Me at p-

only +I of Me at m-

standard

NH2

Me

ortho effect

Acidic character
OH

OH

OH

OH
OMe

OMe
OMe

II

III

OH

OH

>

- I of OMe at mNo + R effect at m-

OMe

>

-I at o- & +R at o( +R > - I )

Standard

COOH

OH

OH

>

OMe

IV

COOH

OMe

-I at p- & +R at p( +R at o- & p- equal )

COOH

COOH
OMe

OMe
OMe

II

COOH

III

Me

COOH
OMe

COOH

>
OMe

II

III

IV

>

>

OMe

Due to ortho effect in (II), it is the strongest, rest explanation is same as above.

IV

NH2

NH2

OMe

>

Basic character

NH2

NH2

>

>

OMe

OMe

-I of -OMe at p+ R of - OMe at p-

NO 2

>

Acidic character

NO 2

-I & - R at o-, -I at o- > pNet e- withdraing is more

than p-, But intramolecular
H-bonding decreases acidity
than p- isomer.

- I effect of NO2 & -R

effect of NO2 at p-

COOH

COOH
NO 2

Acidic character

OH

OH

OH

Only -I effect of -OMe at m-

Ortho effect

Standard

>

>

OH

NO 2

only - I effect

COOH

>

>
Standard

COOH

NO 2

>

NO 2

In this case, ortho isomer is stronger due to ortho effect, rest of the explanation is same as above.

NH2

NH2

NH2

>

Basic character

NH2

>

>

NO2

NO2

NO2

The more the e- withdrawing group, the less basic is the aniline.

m-isomer has only -I effect. Both o- and p- have -I & -R effects, but -I effect at o- > at p-. So o- isomer has more e-withdrawing group thanp-.
Hence, o-isomer is the weakest base
COOH

COOH

>

Acidic character
Cl

>
Br

COOH
OH

>

COOH

>

COOH
HO

Acidic character

COOH

COOH
OH

>

COOH

OH

>

COOH

>
OH

Acid Strength
HCOOH

>

PhCOOH

>

CH 3COOH

CH3COOH > C 2H5COOH > C 3H7COOH

Cl3CCOOH > CHCl2COOH > CH 2ClCOOH

1- Chloro-

>

2- Chloro- >

3-Methyl

>

2-Methyl

Terminal alkyne >

3-Chlorobutanoic acid

> 1- Methylpentanoic acid

Alkene

>

Alkane

Explain Grignard reagents should be prepared under anhydrous conditions.

Grignard reagents are very reactive. These are readily decomposed by compounds containing
acidic hydrogen (Protic solvent i.e. water ) Therefore Grignard reagent is prepared in dry ether
under anhydrous conditions.

RMgX
Grignard reagent

H2O

RH
Alkane

Mg (OH)X

Explain alkyl halides, though polar, are immiscible with water.

In water, the water molecules are held together by H-bonding. Despite the polarity of
alkylhalides, alkylhalides can not form H- bonds with water molecules, so it can not break the
strong H-bonds present between water molecules. Thus alkyl halides,though polar are not
soluble with water.

Explain why dipolemoment of chlorobenzene is lower than that of cyclohexylchloride.

3
Cl SP2 The polarity of CCl bond in chlorobenzene is less than that same bond in SP Cl
cyclohexylchloride because of carbon atom involved in chlorobenzene is
more electronegative ( greater s-character ) as compared to the carbon
atom in case of cyclohexyl chloride ( less s-character ). Therefore , the
dipole moment of chlorobenzene is less than that of cyclohexylchloride.
Also due to resonance in chlorobenzene, the lone pair of electrons on chlorine atom is
delocalised over the benzene ring.
p-Dichlorobenzene has higher m.p and lower solubility than those of o- & m-isomers, discuss.
Cl
Cl
Cl
Due to symmetrical nature of p-dichlorobenzene, in
the crystal, it is more closely packed as compared to
Cl
Cl
the other isomers. As a result , it has a higher melting
ParaMetaOrthopoint .
In p-dichlorobenzene, the net dipolemoment is zero, so it is non-polar, hence has lower
solubility as compared to other isomers.

Cl

Although chlorine is an electron withdrawing group, yet it is ortho-, para- directing in electrophilic
aromatic substitution reactions. Why?
x
x

xx
xCl x
x
x

xx

Cl xx

E+
xx
x Cl x
x
x

xx

x Cl x
x
x

xx
x Cl x
x
x

xx
x Cl x
x
x

Inductive effect destabilises the intermediate

carbocation.

E+

[ Attack at para position ]

[ Attack at ortho position ]
Resonance effect stabilises the intermediate carbocation.

Through resonance, halogen tends to stabilise the carbocation and the effect is more
pronounced at ortho- and para- positions. The inductive effect is stronger than resonance
and causes net electron withdrawal and thus causes net deactivation. The resonance effect
tends to oppose the inductive effect for the attack at ortho- and parapositions and hence
makes the deactivation less for ortho- and paraattack. Reactivity is thus controlled by the
stronger inductive effect and orientation is controlled by resonance effect.
Explain why is ortho nitrophenol more acidic than ortho methoxyphenol ?

OH
O
OH
NO 2

o-Nitrophenol

NO 2

C.B ( More stable )

OCH 3

o-Methoxyphenol

O
+

OCH 3

C.B ( Less stable )

Conjugate base of o-nitrophenol is stable due to resonance as nitro group is the electron
withdrawing group. Conjugate base of o-methoxyphenol is destabilised due to presence of
electron releasing group i.e. methoxy group, which increases electron density on the
negatively charged oxygen atom.
So o-nitrophenol is more acidic than o-methoxyphenol.

Would you expect benzaldehyde to be more reactive or less reactive in nucleophilic addition
reactions than propanal? Explain your answer.
O

The carbon atom of the carbonyl group of

C
benzaldehyde is less electrophilic than carbon
H
atom of the carbonyl group present in propanal.
The polarity of the carbonyl group is reduced in
+
benzaldehyde due to resonance as shown and hence it is less reactive than propanal.

Why electron withdrawing groups at ortho and para position increases the reactivity of haloarenes ?
Electron withdrawing groups at ortho and para position withdraws the electron density from the
benzene ring and thus facilitates the attack of the nucleophile on haloarenes.
The negative charge appear at ortho and para positions w.r.t the halogen
substituent is stabilised by (- NO2 group) electron withdrawing, while in case of m- nitrobenzene,
none of the resonating structure bear the negative charge on carbon atom bearing the - NO2
group.
Why haloarenes are less reactive towards nucleophilic sustitution reactions ?
* C- Cl bond acquires a partial double bond character due to resonance.
* The SP2 hybridised carbon with more electronegativity hold the electron pair of C- Cl bond more
tightly.
* The phenyl cation will not stabilised by resonance.
The solubility of haloalkanes in water is low but in organic solvent is high. Explain .
* Less energy is released by the interaction of haloalkane and water molecules, as compared to
the energy required to overcome the attraction between haloalkane molecules and to break
hydrogen bonds between water molecules. So haloalkanes are less soluble in water.
* Haloalkanes dissolve in organic solvent easily, because the new inter molecular attractions
between haloalkanes and solvent molecules have much the same strength as the ones being
broken in the separate haloalkanes and solvent molecules.

Why para isomers of dihalobenzene have high M.P as compared to their ortho and meta isomer ?
It is due to symmetry of para isomers that fits in crystal lattice better as compared to ortho and
meta isomers.
Explain the boiling point of isomeric haloalkanes decrease with increase in branching.
The intermolecular froces of attraction ( dipole- dipole and Van der waal's forces ) get stronger
as the molecule get bigger size and have more electrons. With increase of branching the size of
molecule decreases, so the inter molecular forces of attraction decreases.
Explain the boiling point order RI > RBr > RCl > RF
With the increase in size and mass of halogen atom, the magnitude of Van der waal's forces
increases.
Explain the boiling point of haloalkanes are considerably higher than those of the hydrocarbons of
comparable molecular mass ?
Haloalkanes are polar where as hydrocarbons are non polar in nature. Due to greater polarity of
haloalkanes as compared to hydrocarbon of comparable molecular mass, the inter molecular
forces of attraction are stronger in the halogen derivatives.
Why is sulphuric acid not used during the reaction of alcohol with KI ?
As sulphuric acid converts KI to corresponding HI and then oxidises it to I 2

Explain haloalkanes react with KCN to form alkyl cyanide but AgCN forms isocyanide.
KCN is pr edominantly ionic and pr ovides cyanide ions in solution. Although both car bon and
nitr ogen atoms ar e in a position to donate electr on pair s, the attack takes place mainly thr ough
car bon atom and not thr ough nitr ogen atom since CC bond is mor e stable than CN bond.
However , AgCN is mainly covalent in natur e and nitr ogen is fr ee to donate electr on pair for ming
isocyanide as the main pr oduct.
H3C
H3C

Br

AgCN

H3C

Br
NC

H3C

KCN

CN

Cyanide

KBr

KBr

Isocyanide
Write the mechanism of
H3C

CH2 CH2 CH2 Br

H3C

KCN
CH2 CH2 CH2

H3C
Br

CH2 CH2 CH2 CN

SN2

H3C

CH2 CH2 CH2 CN

The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in the
presence of alcoholic KOH, alkenes are major products. Explain.

In aqueous medium, KOH will be completely dissociated to give OH ions. They being strong
nucleophile, will bring about the substitution alkylhalides to form alcohols.
H3C

-OH

Br
H

SN2

Bromoethane
-

CH3
HO
H

Br

Ethanol

At the same time OH ions will be highly hydrated and behave as weak base and elimination
leading to alkenes will not be feasible.
By
Mr. A K SAMAL
PGT (Chemistry) KV No. 2 CRPF Bhubaneswar