1.

Revision of GOC-I
The electron displacement in an organic molecule may take place under the influence of an atom or a
substituent group or in the presence of an appropriate attacking reagent.
Classification :

Comparision between Electronic effects:

Inductive effect Mesomeric effect Hyperconjugative effect
(1) It is found in saturated and (1) It is found in unsaturated (1) It is found in carbocation,
unsaturated compounds. compounds especially having carbon free radical and
conjugated system. unsaturated compounds.
(2) It involves partial shifting of (2) It involves complete shifting (2) It involves partial shifting
sigma electrons. of pi-electrons of pi-bonds or of sigma-electrons into
lone pair of electrons. adjacent p-orbital.
(3) The electron pair is slightly (3) The electron pair is (3) The electron pair is
displaced from its position and completely transferred and partially transferred.
thus partial charges are thus full positive and negative
developed. charges are developed.
(4) It is transmitted over a quite (4) It is transmitted from one (4) It is transmitted from one
short distance. The effect end to other end of the chain end to other end of the chain
becomes negligible after third provided conjugation is provided conjugation is
atom in the chain (distance present. It is distance present. It is distance
dependent). independent. independent.

Important points :
(a) If any group has more than one  bond in conjugation, then only one  bond will take part in delocalisation.
CH2  CH – C  CH

Out of two  bonds only one  bond will take part in delocalisation.
(b) If any conjugate position has more than one lone pair then only one lone pair will take part in the
delocalisation.
..
CH 2 = CH – .O. – CH 3

Out of the two lone pair ’s only one will take part in delocalisation.
(c) If any conjugate position has  bond and any of the positive charge, negative charge, odd electron,
lone pair electrons then only  bond will take part in delocalisation on priority.

.N.

Nitrogen has  bond as well as lone pair, but only  bond of nitrogen will take part in delocalisation.

ANIRUDDH SINHA - 9930991983

 (d) Electrons of negative charge or lone pair behave as 2 electrons if it is in conjugation to bond.

; ;

Electromeric effects :
It is a temporary effect. The organic compound having a multiple bond ( double or triple bond) show this effect
in the presence of an attacking reagent only. It is defined as the complete transfer of a shared pair of -
electrons to one of the atoms joined by a multiple bond on the demand of an attacking reagent. It is represented
by E and the shifting of the electrons is shown by a curved arrow. There are two types of eletromeric effect.
(i) +E effect : In this effect -electron of the multiple bond are transferred to that atom to which the reagent
gets attached.

– CH2 – E
(ii) – E effect : In this effect the -electron of the multiple bond are transferred to that atom to which the
attacking reagent does not get attached

+ NC
Note : When inductive and electromeric effects operate in opposite directions then the electromeric effect
dominates

2. Applications of electronic effects

(a) Stability of reaction intermediates :
(i) Stability of carbocation  + M, + I groups, hyperconjugation.
(ii) Stability of carbon free radical  + I groups, hyperconjugation.
(iii) Stability of carbanion  – M, – I groups.

(b) Stability of Alkene :

More substituted (Branched) Alkenes are more stable due to hyperconjugation.
Note : Resonance effect or delocalisation of electrons increases the stability of over all system.
For example carbocation, carbon free radical, carbanion & Alkenes.

(c) Acidic & Basic Strength :

(i) Acidity (Ka)  – M, –I groups.
(ii) Basicity (Kb)  + M, +I groups and solvation effect in aqueous solution.
3. Reaction Intermediates
Reactive, shortlived, high energy, unstable species, those are formed in the course of organic reactions are
called reaction intermediates.
Reaction intermediates generally formed after bond breaking and before bond formation.
A covalent bond can get cleaved either by :
(i) Heterolytic cleavage, or (ii) Homolytic cleavage.

Homolysis fission of Covalent Bonds

The bond may break in such a way that each fragment takes away one of the electrons of the bond. This
process called homolysis, produces fragments with unpaired electrons called radicals.

ANIRUDDH SINHA - 9930991983

 Heterolytic fission of Covalent Bonds
The bond may break in such a way that one fragment takes away both electrons of the bond, leaving the
other fragment with an empty orbital. This kind of cleavage is called heterolysis, produces charged fragments
or ions.

Heterolysis of a bond normally requires that the bond be polarised.

Polarisation of a bond usually result from different electronegatives of the atoms joined by the bond. The
greater the difference in electronegativity, the greater the polarisation. In the given instance, atom B is more
electronegative than A.

(A) Carbocation :
Definition : A carbon intermediate which contain three bond pair & a positive charge on it is called carbocation.
Hybridisation : Carbocation may be sp2 & sp hybridised
Hybridisation Example

sp2 , , ,

sp H2C = , HC 

Carbocations are electron deficient. They have only six electrons in their valence shell, and because of this,
carbocations act as Lewis acids. Most of the carbocations are short-lived and highly reactive, they occur as
intermediates in some organic reactions. Carbocations react with Lewis bases or ions that can donate the
electron pair, that they need to achieve a stable octet of electrons (i.e., the electronic configuration of a noble
gas):

Because carbocations are electron seeking reagents, chemists call them electrophiles. All Lewis acids,
including protons, are electrophiles. By accepting an electron pair, a proton achieves the valence shell
configuration of helium; carbocations achieve the valence shell configuration of neon.
Stability : Carbocations are stabilised by
(i) + I effect (ii) + m effect (iii) Hyperconjugation (iv) delocalisation of charge
General stability order :

> > > >

> > >

Ex. > >

t-Butyl carbocation has +I effect of three Me–groups and also Hyperconjugation effect which makes it most
stable.
ANIRUDDH SINHA - 9930991983
Ex. > >

In Benzyl cation, Extensive Resonance is seen which stabilises .

In Ethyl carbocation + I and Hyperconjugation of Me – group stabilizes carbocation.
In vinyl carbocation stability decreases rapidly since carbon of (CH2) is sp2 hybridized which is slightly more
electronegative hence acts as – I group which increases (+) charge density.
Rearrangement :
Whenever an Intermediate carbocation is formed in reaction it may rearranges.
Only those carbocation will rearrange which can produce more stable species. It can be done either by
(i) Shifting of H, alkyl, aryl, bond (1, 2 shifting)
(ii) Ring expansion (more strained ring to less strained ring)
(iii) Ring contraction
(i) Shifting of H, alkyl, aryl

1,2 H
(A) 

Shifting

1,2 Me
(B) 
Shifting

1,2 Ph
(C) 
Shifting

+
CH2
–

1,2 Bond
(ii) Ring expansion :  
Shifting

1,2 Bond
(iii) Ring contraction :  
Shifting

Note : The unique stabilisation of cyclopropyl methyl carbocation due to  electrons overlapping with vacant p-
orbital of carbocation carbon is seen.

(more stable than Benzyl)

cyclopropyl methyl carbocation

Q. Rearrange (if applicable) the following carbocations into more stable form :-
CH3
+
(a) CH3 – CH2 – CH2 (b) (c) CH3 – C – CH – CH3
+
CH3

CH3 CH3
–
––

(d) CH3 (e) (f)

+ +

ANIRUDDH SINHA - 9930991983

Ans. For students only (f)

(B) Carbanion
Definition : A carbon intermediate which contain three bond pair and a negative charge on it, is called
carbanion.
Hybridisation : Hybridisation of carbanion may be sp3, sp2 & sp.
Hybridisation Example

sp3 , CH3– , , ,

sp2 H2C= , CH2=CH– ,

sp HC 

Stability of carbanion : Carbanions are stabilised by electron withdrawing effect as

(i) – I effect (ii) – m effect (iii) Delocalisation of charge
Carbanions are Lewis bases. In their reactions they seek a proton or some other positive centre to which
they can donate their electron pair and thereby neutralize their negative charge.

Example of stability order :

Ex. (a) CH3 CH3 CH2 CH 3 CH2 CH3 CH3 C CH3 (Stability order : 1 > 2 > 3 > 4)

CH3

(b) CH  C .. (Stability order : 1 > 2 > 3)

1
.. .. ..
CH2
(c) (Stability order :1 > 2 > 3)

1 2 3
  
••
(d) CH2  CH – C H2 C 6H5 – C H2 ( C 6H5 ) 3 C (Stability order : 1 < 2 < 3)
1 2 3

Rearrangement :
Generally carbanions do not undergo rearrangement.
(C) Free Radicals
Homolysis of covalent bond results into free radical intermediates possessing the unpaired electrons.

It is generated in presence of Sun light, Peroxides or High temperature

ANIRUDDH SINHA - 9930991983

 Free Radical : An uncharged intermediate which has three bond pair and an unpaired electron on carbon
atom.

Note : (i) It is Neutral species with odd e¯

(ii) It is paramagnetic in nature due to odd e¯
(iii) No rearrangement is observed generally.
(iv) Carbon atom having odd electron is in sp2 hybridised state
(v) Any reaction if it is carried out in the presence of sunlight, peroxide or high temperature it generally
proceeds via free radical intermediate.
 Stability of free radical : It is stabilised by resonance, hyperconjugation and + I groups.

CH3
  
Ex. H3C–C > H3 C – C H – CH3  H3C – C H2  C H3 (Stability order)
CH3

  
Ex. (C 6H5 )3 C > (C6H5 )2 C H > C6H5 – C H2 > CH2  CH – C– CH3 (Stability order)
|
CH3

(D) Carbenes (Divalent Carbon intermediates) :

Definition : There is a group of intermediates in which carbon forms only two bonds. These neutral divalent
carbon species are called carbenes. Most carbenes are highly unstable that are capable of only fleeting
existence. Soon after carbenes are formed, they usually react with another molecules.

Methods of preparation of carbene :

CHCl3 + : CCl2 CH2I2 + Zn : CH2

CH2N2 N2  + : CH2 CH2 = C = O : CH2 + CO

Types of carbene Singlet Triplet

Shape Bent Linear

2
Hybridisation sp sp
Nature of reaction stereospecific None
State Excited state Ground state
Magnetic Diamagnetic Paramagnetic
Nature Paired electrons Diradical

ANIRUDDH SINHA - 9930991983

(E) Nitrenes
The nitrogen analog of carbenes are nitrenes. They are very much reactive since in them octet of N is
incomplete.
In nitrenes only one valencies of N are satisfied.

(F) Benzyne
The benzene ring has one extra C – C  bond in benzyne

Clearly, we can see that the newly formed  bond cannot enter in resonance with other  orbitals of ring. since
it is in perpendicular plane.
It is also important to note that hybridisation of each carbon involved in 'Benzynic bond' is sp2 since the
overlap between these sp2 hybrid orbitals is not so much effective.

4. Tautomerism :
Definition :
Tautomerism is a phenomenon by which a single compound exists in two or more readily interconvertible
structures that differ in the relative positions of at least one atomic nucleus, generally hydrogen.
These two isomers remain in dynamic equilibrium and can be isolated also give different lab test.
Conditions :
1. Usually present in the following functional groups

2. Basic need for its existence is attachment of these groups with the sp3 hybridised C-atom having
atleast one hydrogen atom as –

To get tautomer of above structures -hydrogen atom is shifting to more electronegative atom attached
to double bond (i.e. hydrogen atom from 1st atom to 3rd atom) and double bond is developed between
1,2-atom from 2,3-atom. This can be represented as :

These two forms (remain in equilibrium) are called tautomers of each other. The interconvertibility of
tautomers is a chemical reaction which involves making and breaking of bonds.
O OH
|| |
Ex. (a) CH3  C  CH3 CH2  C  CH3 (b)
( I) ( II)

(c) (d)

ANIRUDDH SINHA - 9930991983

Keto-enol Tautomerisation :
(A) Base-catalyzed enolization

Protonation of the carbanion by water on the -carbon gives back the carbonyl compound. Protonation on
oxygen gives the enol. Notice that the enolate ion is the conjugate base of both the carbonyl compound and
the enol.

(B) Acid-catalyzed enolization

Involves the conjugate acid of the carbonyl compound. Recall that this ion has carbocation characteristics.
Loss of the proton from oxygen gives back the starting carbonyl compound ; loss of the proton from the -
carbon gives the enol. Notice that an enol and its carbonyl isomer have the same conjugate acid.

% Enol content in the carbonyl compounds :

(a) For monocarbonyl % Enol is very less
(b) Enol content increases with increase in the stability of enol by resonance, hyperconjugation, hydrogen
bonding etc.

Decreasing order of enol content for above carbonyl compounds is : 3 > 2 > 1.
(c) For a carbonyl compound having active methylene group percentage of enol content will be more
because enolic form has intramolecular H-bonding and also it will be stabilised by resonance.

ANIRUDDH SINHA - 9930991983

 (d) If active methylene group is more acidic then enol content will be more.

For example in acetyl acetone enolic content is 75–76% while it is 7–8% in

acetoacetic ester because ester group shows less electron withdrawing nature than keto group.
(e) Percentage of enol content is more in non-polar media while % of keto form is more in polar media.

Racemisation and D-exchange :

Exchange of -hydrogen from deuterium as well as racemization at the -carbon are catalyzed not only by
bases but also by acids due to the phenomenon of tautomerisation.

1. (D-exchange)

2.

3.

Other examples of Tautomers

Lactam-Lactim system :
O
O

N O
| N OH
H

O OH
|| |
C C
NH N
SO2 SO2
Nitro-Acinitro system :
The acidic nature of the nitro compounds gives rise to the belief that the nitro compounds exist in two forms,
a more stable or normal nitro form and the less stable acinitro form.
R – CH2 R – CH
| ||
N N
O O HO O
Nitroform Acinitroform

ANIRUDDH SINHA - 9930991983

 The stability of the nitro form is more as compared to the acinitro form because it is stabilised by resonance.
O OH
C6H5 – CH2 – N C 6H 5 – CH = N
Nitroform O Acinitroform O

Nitroso-Isonitroso system :
Like primary and secondary nitro compounds, primary and secondary nitroso compounds also exhibit
tautomerism with their more stable isonitroso or oxime form.
NO
|
, CH3 – C – CH3
CH3 – CH – CH3 ||
2-Nitrosopropane NOH
Acetoneoxime
Imine - Enamine system :
R 2CH – CR = NR
Imine
Among these two tautomers, enamines are stable only when there is no hydrogen on the nitrogen, otherwise
the imine form predominates.

5. Bases
(a) Arhenius base : A base is a substance that can donate (or loose) OH– ions in H2O.
(b) The Bronsted - Lowry definition of acids and bases
An acid is a substance that can donate (or loose) a proton, and a base is a substance that can accept a
proton.
Let us consider, an example of this concept, the reaction that occurs when gaseous hydrogen chloride
dissolves in water :

(c) The Lewis definition of acids and bases

Lewis proposed that acids are electron pair acceptors and bases are electron pair donors. For example
aluminiumchloride, reacts with ammonia in the same way that a proton donor does. Using curved arrows to
show the donation of the electron pair of ammonia (the Lewis base), we have the following examples:

Cl¯ + H –

(d) Basicity (Kb) :

ANIRUDDH SINHA - 9930991983

 [NH4  ] [OH ]
Kb =
[NH3 ]
pKb = – log Kb

Basicity order in periodic table :

(1) Basic strength decreases down the group, (2) Basic strength decreases along the period because electron
neagativity increases so electron donor tendency decreases.

Aliphatic bases
(1) On the basis of + I effect basic strength of amines should be 3º > 2º > 1º > NH3
But this order is applicable only when the amines are in gaseous state or in case of non-polar aprotic solvent.
In aqueous medium, stability of conjugate acid (by hydrogen bonding) is also considered.
(2) Basic strength of nitrogeneous compound depends upon the hybridised state of nitrogen
R–CH2 –CH2 –NH2 > R –CH2 –CH = NH > R–CH = CH–NH2 > R–CN
   
sp3 (localised) sp2 (localised) sp2 (delocalised) sp
(3) More electronegative atom (–I group) will decrease the basic strength
CH3–CH2–CH2–NH2 > CH2=CH–CH2–NH2 > H–CC–CH2–NH2
(4) Cyclic amines are more basic than acyclic amines of same nature

>

(5) Amidines are more basic in nature because their conjugate acid are more stable due to resonance.

 
 
H Nitrogen (X) is more basic than nitrogen (Y).

..
Aromatic amines (Ph – NH2) or Anilines :
Aniline is less basic than Ammonia because presence of lone pair of electron at nitrogen atom conjugate
with -electron of benzene ring and as a result electron density at nitrogen atom is decreased and hence the
basic character is also decreased.

In case of substituted anilines electron withdrawing group decreases the basic strength whereas electron
releasing group increases the basic strength.
Note : 1. The base strengthening and base weakening effect is more observed at meta and para positions.

(i) > (ii) < (iii) >

2. Pyridine is more basic than aniline and pyrole.

In aniline and pyrole lone pairs are involved in resonacne therefore these are less basic. But in pyridine lone
pairs are in perpendicular plane of  orbitals therefore not involved in resonance hence more basic.

ANIRUDDH SINHA - 9930991983

 Basicity order : > >

3. Steric effect of ortho-substituted group (ortho effect)

–
+
H2N: H–N–H
G
–

–
H
–

–


(a) Ortho-substituted anilines are mostly weaker bases than aniline itself due to ortho effect to solvation of
anilinium ion).
(b) Ortho-substituent causes steric hinderance to solvation in the product (conjugate acid i.e. cation).
(c) The small groups like –NH2 or –OH do not experience (SIR) due to small size.
General basicity order :

Ex. (a) G = (–M, –); NO2

NH2
–

(Aniline > m > p > o).

(b) G = (–); CCl3

NH2 NH2 NH2 NH2

–

–
–

CCl3
–

(Aniline > p > m > o).

CCl3
–

CCl3
Only (–) decides the order.

(c) G = (– > + m); Cl

NH2 NH2 NH2 NH2

–

–
–

Cl
–

(Aniline > p > m > o)

–

Cl
–

Cl
Only (–) decides the order.

(d) G = (+, HC); If R = –CH3 (Toluidines)

ANIRUDDH SINHA - 9930991983

 NH2 NH2 NH2

–
–
–
CH3

–
+m CH3
+w
HC  more do min ating
(e) G = (+m > –);

Kb order : p > Aniline > o > m

6. Acids
(a) Arhenius acid : An acid is a substance that can donate (or loose) a proton in H2O.
(b) The Bronsted - Lowry definition of acids and bases
An acid is a substance that can donate (or loose) a proton, and a base is a substance that can accept a
proton.
Let us consider, an example of this concept, the reaction that occurs when gaseous hydrogen chloride
dissolves in water :

Hydrogen chloride, a very strong acid, transfers its proton to water. Water acts as a base and accepts the
proton. The products that result from this reaction are a hydronium ion (H3O+) and a chloride ion (Cl–).
The molecule or ion that forms when an acid loses its proton is called the conjugate base of that acid. (The
chloride ion is the conjugate base of HCl). The molecule or ion that is formed when a base accepts a proton
is called the conjugate acid of that base.
(c) The Lewis definition of acids and bases
Lewis proposed that acids are electron pair acceptors and bases are electron pair donors.

(d) Acid dissociation constant (Ka) :

RCOOH + H2O RCOO– + H3O+

[RCOO ] [H3O  ]
Keq =
[RCOOH] [H2O]

[RCOO  ] [H3O  ]
Ka =
[RCOOH]
pKa = – log Ka

ANIRUDDH SINHA - 9930991983

 Relative acidity of hydrocarbons :
Being most electronegative the sp hybridised carbon atom of ethyne polarizes its C–H bond to the greatest
extent causing its H to be most positive therefore ethyne is most acidic hydrocarbon.
HC  CH > H2C = CH2 > H3C – CH3
Acidity of Phenols :
When phenol ionises the phenoxide ion is more stabilised by resonance than the unionised phenol. In phenol
unlike charges are spread and so it is less stable.

Groups which are – I, – m increases acidic character of phenol of effectively dispersing negative charge of
phenoxide ion. Alternatively + I and + m groups decreases acid strength.

Ex.

Ans. acid strength order : I > II > IV > V > III

Sol. Step 1. III will be least acidic as it has no dispersion of negative charge (No delocalisation of negative
charge).
Step 2. since – I, – m group will increase acid strength, Nitrophenol will be most acidic followed by phenol,
Step 3. Amongst cresol and methoxyphenol, methoxyphenol has +m effect of – OCH3 which increases e¯
density hence decrease acidic strength

Ex.

Ans. acid strengh order : I > III > II > IV

Sol. Step 1 : Notice that CH3 have + I effect so all methylphenols (cresols) are less acidic than phenol (I).
Step 2 : Now amongst cresols p- and o- CH3 are increasing the e¯ density due to their hyper conjugation but
ortho isomer has viable + I effect also, which will help in destabilising phenoxide ion therefore o- is least
acidic. Since at meta position only + I works it as least e¯ density amongst the cresol

ANIRUDDH SINHA - 9930991983

Ex.

Ans. Acid strength order : II > IV > III > I

Sol. Step 1. In nitrophenols – I effect of NO2 will help to increase acidic strength hence phenol is least acidic
amongst all nitrophenols
Step 2. Only – I effect is applicable in meta nitrophenol it will be number three. Now – o, – p have both – I and
– m effect of NO2 group over OH and in this particular case para isomer is more acidic than ortho since

H is trapped by NO2 group.

Acidity of carboxylic acids :

-
R – C – OH R – C – O + H

O O
(I)
(i) Conjugate base of carboxylic acid exists as two equivalent cannonical structures (A) and (B). This ion is
resonance stablised and resonance hybrid structure is (C).

(iii) Electron withdrawing group (–M, –I effect) further stablises the anion and hence, increases acidic nature.
(iv) Electron releasing group (+ M, + I effect) destablises the anion and hence decreases acidic nature.
Ex. (a) F – CH2 – COOH > Cl – CH2COOH > Br – CH2COOH > I – CH2COOH

Cl Cl
(b) Cl – C – COOH > Cl – CH – COOH > Cl – CH2COOH > CH3COOH
Cl

(c) HCOOH > CH3COOH > CH3 – CH2 – COOH

COOH COOH CH2 – COOH

(d) > CH2 >
COOH COOH CH2 – COOH

ANIRUDDH SINHA - 9930991983

 Comparison between two geometrical isomers
Ex. Maleic acid Fumaric acid

Now K1 m > K 1 f
Since the conjugate base is stabilised by intramolecular H bonding.
But K2f > K2m Since in maleate ion, after donation of two groups faces each other and
makes system unstable. In fumarate ion this repulsion is minimised.
Acidic strength of substituted benzoic acid :
Formic acid is more acidic than benzoic acid while phenyl acetic acid is more acidic than acetic acid.

HCOOH > PhCOOH > >

Electron withdrawing group attached to benzene ring will increase the acidic strength while electron releasing
group decreases acidic strength.
If electron donating group present at para position than it is always less acidic than benzoic acid.

> > > >

Also it is less acidic than meta substituted benzoic acid.

> >

On the other hand if e– withdrawing group is present at meta position then it is more acidic than benzoic acid.

> > > >

ANIRUDDH SINHA - 9930991983

 Ortho effect :
It is common observation that generally ortho substituted benzoic acids are more acidic as compared to their
isomers and benzoic acid itself. This is called ortho effect (which is combined effect of steric hindrance,
crowding & electronic effect) in benzoic acid. However exceptions are seen.

Ex. (a)

acid strength order : II > IV > III > I

(b) > > >

(c) > > > >

(d) > > >

(e) > > >

Solvent Effect in bases :

The trend is not regular in the aqueous state as evident by their pKb values given in Table.

Name of amine pKb Name of amine pKb

Methanamine 3.38 N,N-Diethylethanamine 3.25

N-Metheylmethanamine 3.27 Aniline 9.38

N, N-Dimethylmethanamine 4.22 Phenylmethanamine 4.70

Ethanamine 3..29 N-Methylaniline 9.30

N-Ethylethanamine 3.00 N,N-Dimethylaniline 8.92

Table : pKb Values of Amines in Aqueous Phase (Ref. NCERT)

ANIRUDDH SINHA - 9930991983

 In the aqueous phase, the substituted ammonium cations get stabilised not only by electron releasing effect
of the alkyl group (+I) but also by solvation with water molecules. The greater the size of the ion (Alkyl groups
are hydrophobic and inhibits H bonding and solvation.), lesser will be the solvation and the less stabilised the
ion.
The order of solvation of ions are as follows:

R H OH2
+| R
|
+
|
N
R N H OH2

|
| |
|
R H OH2 R

20 30

Greater is the stability of the substituted ammonium cation, stronger should be the corresponding amine as
a base.
On the basis of above two sequences, we can say that the basic strength of amines is the combined effect
of inductive effect, steric hindrance and solvation.
R2NH > RNH2 > R3N > NH3 (if R = CH3) ......... (1)
R2NH > R3NH > RNH2 > NH3 (if R = C2H5) ..........(2)

Reactions of Bases :
(i) Nature of aqueous solution : Amines combine with water to form alkyl ammonium hydroxides. This gives
hydroxide ions in solution, thus the aqueous solution of amines is basic in nature.

RNH2 + HOH R NH3 OH – [RNH3]+ + OH–
1º Amine

R2NH + HOH R 2 NH2OH– [R2NH2]+ + OH–
2º Amine
The aqueous solution of amines behave like NH4OH and gives the precipitate of ferric hydroxide with ferric
chloride.
3RNH3OH + FeCl3  Fe(OH)3 + 3RNH3Cl
Brown ppt.
(ii) Aliphatic and aromatic amines form salt because of their basic nature:
 –
RNH2 + H2O  R N H 3 O H
Alkylammoniumhydroxide
 –
RNH2 + HCI  R N H 3 C I
Alkylammoniumchloride

RNH2 + H2SO4  ( R NH3 )2 SO4–2

Similarly we get
 –
C6H5NH2 + H2O  C6H5 N H 3 O H
Aniliniumhydroxide

ANIRUDDH SINHA - 9930991983

  –
C6H5NH2 + HCI  C 6H 5 N H3 C I or C6H5NH2 : HCI
Aniliniumchloride Anilinehydrochloride
Salts of amines are ionic compounds and hence water soluble.

Reaction of Acids with salts :

(1) NaX + HY  NaY + HX
Salt of Weak acid Strong Acid

Remark : A stronger acid displaces the weaker acid from weak acid metal salt. The weaker acid is
released out as a gas or liquid or precipitates out as a solid. The weaker acid cannot displace the
stronger acid from the salt.

1. 2 NaCl + H2SO4  Na2SO4 + 2HCl

2. Na2SO4 + 2HCl  No reaction

3. CH3COONa + CH3SO3H  CH3COOH + CH3SO3Na (feasible)

4. CH3COONa + PhOH  PhONa + CH3COOH (not feasible)

ANIRUDDH SINHA - 9930991983

 MISCELLANEOUS SOLVED PROBLEMS (MSPS)
1. Arrange for acidic strength order CH3COOH, ClCH2COOH, Cl2CHCOOH, Cl3CCOOH
Sol. CH3COOH < ClCH2COOH < Cl2CHCOOH < Cl3CCOOH
2. Draw resonating structure for following molecules

, CH2 = C = O ,

+ +
Sol.
+

. ..   –2 
CH 2 = C = O C H2 – C  O , N = N = N N– N  N
.

3. By drawing resonating structures of following molecules, Judge whether the group attatched to ring exerts
+m or –m effect.

Sol. (a) –NH – C – CH3 (+M group)

||
O

NH–C–CH3 NH–C–CH3
O O

(b) –C–CH3 (–m effect group)

O
O O CH3
O CH3 O CH3 CH3
C O C
C–CH3 C C

4. Which of them is more basic :

(a) (b)

Sol. is more basic due to lone pair of N atom is not delocalized.

5. Which of them is more basic

(a) (b) (c)

Sol. is more basic due to sp3 hybridized N atom.

ANIRUDDH SINHA - 9930991983

6. In which of the following pairs the first one is the stronger base than second.
(A) , (B) ,

(C) , (D) CH3NH2, CH3OH

Ans. A, C, D

> >

7. Which of the following is least stable ?

(A) (B) (C) (D)

Ans. A
Sol. Is less stable due to bridgehead carbanion.

8. Write tautomer of butanone and cyclohexanone.

Ans. (a) CH3 – C  CH  CH3 , (b)

|
OH

9. Arrange the following carbocation s in stability order-

1. H

2.

+
Ans. (1) CH 2 = CH – CH 2 > >
+

+ +
(2) > >

+
Sol. (1) CH 2 = CH – CH 2 > >
(1º + resonance) (2º + hyperconjugation) (no resonance, no hyperconjugation)
(2) Stability order : 3º > 2º > 1º

10. Arrange the following free radicals in increasing order of stability

Ans. V < III < I < II < IV

Sol. Resonance stabilized free radical is more stable.

ANIRUDDH SINHA - 9930991983