ELECTRONIC EFFECTS (I & R EFFECTS)

ELECTRONIC EFFECT : The effect which appears due to electronic distribution is called electronic effect.
Types of electronic effect
(1) Inductive Effect
(2) Resonance (Mesomeric effect)
(3) Hyper conjugation
(4) Electromeric effect

(A) Inductive Effect When a sigma covalent bond is formed between two atoms of different electronegativity
atom then the sigma () bond pair electron are shited towards more electronegative atom due to this shifiting
of e– a dipole is created between the two atoms.
Due to this dipole the  bonds e– in the chain are also shifted and the chain becomes polarised this effect of
polorisation in the chain due to a dipole is called inductive effect.

Diagram showing I effect

Features of Inductive effect

(i) Inductive effect is a permanent effect.
(ii) I effect is distance dependent and negligible after three carbon atom in the chain
(iii) Inductive effect is operative only through  bond it does not affect the  bond electron
(iv) The C–H bond is the reference of inductive effect i.e. the electron movement or polarity in the C–H bond
is considered to be neglible and the I effect of Hydrogen is taken to be zero.
Types of inductive effect :
(a) – I Effect : The group which withdraws electron cloud is known as – I group and its effect is called – I effect.
Various groups are listed in their decreasing – I strength as follows.

> – > – > – NO2 > –SO3H > –CN > – CHO > – COOH > – F > – Cl > – Br > – I
> – OR > – OH > – NH2 > – C  CH > – C6H5 > – CH = CH2 > – H.

(b) + I Effect : The group which repel (or release) electron cloud is known as + I group & this effect is + I effect.

> > – C(CH3)3 > – CH (CH3)2 > – CH2 – CH3 > – CH3 > – D > – H

Example- Since – NO2 is – I group it pulls or withdraws e¯ from cyclohexane ring making it e¯ deficient

Example-

Example-
Due to e¯ donating nature of carbon chain has become partially negative but – COOH is – I group
therefore carbon chain has become partially positive.
 Example -

(a) CH3 CH2 CH2 (b)

(c) CH2 CN (d)

(e) (f)

(g) (h)

+ + –
(i) (j) CH 3 CH CH NO2

O
-
- -
(k)
- -

Applications of Inductive effect :

(i) Acidity (ii) Basicity
(iii) Dipole moment (iv) Stability of intermediate
(v) Reactivity of compound in chemical reaction
(a) In deciding acidic strength of Carboxylic acid
– I effect  Acidic strength (presence of – I groups increases acidic character)
+ I effect  Basic strength (presence of + I groups increases basic character)

Example :

(I) H3 C  H2 C  H2 C  CH  COOH (II) CH3  CH2  CH  CH2  COOH

| |
Cl Cl

(III) CH3  CH  CH2  CH2  COOH (IV) CH3 – CH2 – CH2 – CH2 – COOH
|
Cl
Acid strength order : I > II > III > IV

Explanation :
We know that – I effect increases acidic strength. Now morever it is distance based effect so where the – I
group is nearest to – COOH, It makes acid strong.
Example :
(I) O2N – CH2 – COOH (II) F – CH2 – COOH
(III) H3CO – CH2 – COOH (IV) CH3 – CH2 – COOH

Acid strength order : I > II > III > IV

Since NO2 has strong – I effect its influence will make corresponding acid strongest (– I effect  acid
character).
 Example :
Arrange for acidic strength order CH3COOH, ClCH2COOH, Cl2CHCOOH, Cl3CCOOH
Ans. CH3COOH < ClCH2COOH < Cl2CHCOOH < Cl3CCOOH

(b) Stability of alkyl carbocation : Carbocations are electron deficient species and they are stabilised by +
effect and destablised by –  effect. Because +  effect tends to decrease the positive charge and –  effect
tends to increases the positive charge on carbocation

  
Example : Stability : CH3 < CH3 CH2 < (CH3 )2 C H < (CH3 )3 C

(c) Stability of carbon free radical : Carbon free radicals are stabilised by + I effect.
 
Example : Stability : CH3 < CH3 CH2 < CH3 < CH3 CH3

(B) Resonance Effect

The delocalisation of adjacent (parallel) p-orbital electron is called resonance. Through resonance the e–
density in the molecule becomes uniform, due to uniformity of e– density the stability of molecule increases.
Hence the phenomena of a resonance is a stabilising effect.
In resonance only parallel p-orbital e– are involved. To explain the property of actual molecule different lewis
structure are drawn with the movement of p-orbital electrons.
These lewis structures are called resonating structure or canonical structure.


Resonance hybrid
Examples :

(I)

(II)  

(III) 

(IV) 

(V) CH2 = CH –  – CH = CH2

(VI) 

Resonating structure are only hypothetical but they all contribute to a real structure which is called resonance
hybrid. The resonance hybrid is more stable than any resonating structure. The P.E. difference between the
most stable resonating structure and resonance hybride is called resonace energy. The stability of molecule
is directly proportional to resonance energy.

The most stable resonating structure contribute maximum to the resonance hybrid and less stable resonating
structure contribute minimum to resonance hybrid.
 Rules for writing resonating structure :
(i) In resonating structure only p-orbitals electron are shifted,  bond electron are not involved in resonance,
therefore the  bond skeleton will remain same in two resonating structures.
(ii) The atoms are not moved
(iii) The no. of paired e– are same and no. of unpaired electron are same in two resonating structure.
(iv) The octet rule is not violated (for second period element)
(v) High energy structure are rejected as resonating structure or their contribution to the resonance hybrid is
least.
Opposite charge on adjacent atoms and similar charge on adjacent atoms are cases of high energy. They
are not accepted as resonating structures.
e.g.
1. CH2 = CH – CH = CH2

2. CH2 = CH – CH = CH2 CH3 – CH = C = CH2

3. CH2 = CH –

4. CH2 = CH – CH = CH2

5. CH2 = CH – CH = CH2

Condition for resonance :

1. All atoms participating in resonance must be sp or sp2 hybridised.
2. The parallel p-orbitals overlap to each other.
3. Molecule should have conjugated system (parallel p-orbitals systems are called conjugate system)
e.g.
1. CH2 = CH – C  CH (Show resonance)
2. CH2 = CH – CH2 – CH = CH2 (Not show resonance)

3. (Show resonance)

4. (Not show resonance)

5. CH2 = C = CH2 (Not show resonance)

Types of Conjugation:-
1. CH2 = CH – CH = CH2 (Conjugation between C = C and C = C)
+
2. CH 2 = CH – CH 2 (Conjugation between +ve charge and C = C)
..
3. CH 2 = CH – NH 2 (Conjugation between lone pair and C = C)

4. CH2 = CH – CH2 (Conjugation between odd electron and C = C)
–
5. CH2 = CH – CH = CH – CH2 (Conjugation between negative charge and C = C)
Q. Write resonating structure for each of the following molecules :

O
||
(a) CH3  CH  CH  C  CH3 (a)
..
(b) H 2 N CH  CH  C  N (b)

(c) (c)

(d) CH3 – O – CH = CH – (d)

(e) (e)

 ..
(f) CH3  C  O : (f)

(g) (g)

(h) (h)

(i) (i)

(j) (j)

+ +
(k) (k)
+

..  
..

(l) CH2 = C = O (l) CH 2 = C = O C H2 – C  O

–2 
(m) (m)
N– N  N
Rules for stability of resonating structure :
(1) The resonating structure without any charge separation is more stable.
e.g.
1. CH2 = CH – CH = O
I II
Stability order I > II

2.

Stability order I > II

(2) The resonating structure with more no. of  bonds is more stable.

(3) Structure with complete octet of each atom is more stable.

e.g.

Stability order II > I.

(4) Negative charge on more electronegative atom and positive charge on less electronegative atom are more
stable.
e.g.

1.

Stability order II > I.

2.

Stability order II > I.

Note : The rule of electronegativity and rule of octet is are contradictory to each other then priority is given
to the octet rule.

Stability order II > I.

Stability order II > III > I .

(5) Two different compounds in which one compound has more conjugation is more stable (provided nature of
bonding is same).
CH2 = CH – CH = CH – CH2 – CH = CH2 CH2 = CH – CH = CH – CH = CH – CH3
I II
Stability order II > I.
(6) In two compounds if one is aromatic and another is non aromatic and conjugation is equal in both the
compounds then aromatic compound is more stable (nature of bonding is same)

(cyclic and conjugate)

Stability order . II

(7) Structure with linear conjugation is more stable than cross conjugation (nature of bonding is same).
Cross conjugation : If two groups are in conjugation with a particular group but not conjugated with each other
then the system is called cross conjugation.

CH2= CH–CH = CH – CH = CH2 >

linear conjugation

Mesomeric Effect :
When a group releases or withdraw  orbital electron in any conjugated system then it is called M effect
group and effect is known as mesomeric effect.

(a) +M group :
Electron releasing group : A group which first atom bears -ve charge or lone pair always shows
+M effect.

Relative order of +M group :

– >– > > – NR2 > –OH > –OR > – NHCOR > – OCOR > – Ph > – F > –Cl > –Br > –I > –NO > –NC

e.g.

1.

2.

3.

4.

(b) – M group : Electron withdrawing group

Relative order of –M group :

– NO2 > –SO3H > –CN > –CHO > > –COX > > > –COOH > –CONH2
 e.g. 1.

– + . .– – + . .–
– + O – N – .O:
. – + .–. – + ..
O – N = .O:
. O – N – .O:
. O – N – .O:
. O – N = O:
+ +
2.
+

+ –
3. H 2C = CH – C N: H 2C – CH = C = .N:.

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

Ans.
O
||
(a) – NH – C – CH3 (+ m group)

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

(b) –C–CH3 (–m effect group)

O

CH3 O CH3
O CH3 O O CH3
C C C
C

Note:
1. When a +m group and –m group are at meta-positions with respect to each other then they are not in
conjugation with each other, but conjugation with benzene ring exists.

etc.
2. +M group increases electron density in benzene ring while –M group decreases electron density in the
benzene ring.
Q. Write electron density order in the following compound.

(a)

Ans. III > I > II > IV

(b)

Ans. I > II > III > IV

(c)

Ans. IV > I > III > II

(C) Hyper conjugation :

When a sigma C–H bond of sp3 hybridised carbon is in conjugation with  bond at p-orbital, half filled
p-orbital or vacant p-orbital, then the bond pair e– of sigma C–H bond overlap with adjacent p-orbital. This
phenomena is called hyperconjugation.
Like resonance hyperconjugation is also a stabilising effect but the effect of resonance is more
dominating than hyperconjugation, since in resonance only p-orbital e– overlap while in hyperconjugation 
molecule orbitals overlap with - molecule orbital.
* Hyperconjugation is also called no bond resonance.

Condition : There must be at least one hydrogen at sp3 hybridised -carbon.

Hyperconjugation in alkene

Hyperconjugation in carbocation

Hyperconjugation in radical
H •
• H
CH 2 – C H2 CH 2 = CH2
 Hyperconjugation in toluene

Applications of hyperconjugation
(a) Stability of Alkenes:- Hyperconjugation explains the stability of certain alkenes over other alkenes.
1
Stability of alkenes no. of hyperconjugative structures 
HHydrogenat ion
Stability of alkenes  Number of alpha hydrogens and Number of resonating structures

H3C CH3 H3C H3C

C=C C = CH – CH3 C = CH2
H3C CH3 H3C H3C
Example :
Stability in decreasing order

(b) Heat of hydrogenation : Greater the number of  hydrogen results greater stability of alkene. Thus
greater extent of hyperconjugation results lower value of heat of hydrogenation

Example : CH2 = CH2 < CH3 – CH = CH2 < CH3 – CH = CH – CH3 (Heat of Hydrogenation)
(c) Bond Length : Bond length is also affected by hyperconjugation

Example : 

(i) Bond length of C(II) – C(III) bond is less than expected

(ii) Bond length of C(II) – C(I) bond is more than expected
(iii) C – H bond is longer than expected
(d) Stability of carbocation : Greater number of ‘’ hydrogen results greater stability of carbocations.

Example : (a) < CH3 < CH3 CH3 < (CH3)3

CH3
(b) CH3 – > CH3 – CH2 – CH2 – > – > CH3 C –
CH3
(due to resultant of inductive effect and hyperconjugation)
(e) Stability of free radical : Greater the number of -hydrogen results greater stability of carbon free radical

Example : (a) < CH3 – < CH3 – – CH3 < CH3 –

(b) CH3 – > CH3 – CH2 – > >

(due to resultant of inductive effect and hyperconjugation)

(D) Electromeric effects

(i) Electromeric effect is a temporary effect in which a shared pair of electrons (-electron pair) is completely
transfered from a double or a triple bond to one of the atoms joined by the bond at the requirement of
attacking species.

– CH2 – E

(ii) If the attacking reagent or species is removed, charges disappear and substrate attains its original form.
Thus this effect is reversible and temporary.

(iii) The electromeric effect may be supported or opposed by other permanent effects in various conditions as
follows.

Case I : Electromeric effect may be supported or opposed by I effect as :

(A) CH3  CH3 – –

(B) CH3 –  CH3 – –

In the condition of (A) E effect is supported by + I effect similarly in the case of (B) E effect is opposed by
+ I effect. That is why (A) is easily possible in comparison to (B).

Case II : In the case of vinyl bromide :

 
E E
(A)  – CH = (B) CH2 – Br  – – Br

(A) is the condition of E effect supported by +m effect and opposed by – I effect,

(B) is the condition of E effect opposed by + m effect and supported by - I effect.
Since + m > – I effect, so the (A) is valid case.

Case III : If the multiple bond is present between two different atoms, the electron shift will take place in the
direction of the more electronegative atom.

(a) (b)

+E and – E effect : The electromeric effect is represented by symbol E, and is said to be + E when the
displacement of  electrons is away from the atom or group, and – E when displacement of  electrons is
towards the atom or group.

+ E effect + NC

– E effect +
Relative acidic strength of Organic Acids :
(a) Definition :
(1) Arrhenius Acid : The compounds which furnish H+ ion in aqueous solution are called Arrhenius acids.
Ex. H2SO4, HNO3, HCl, HClO4 etc.
(2) Bronsted Acids : The species which are H+ ion donors are called Bronsted acids.
Ex. NH4+ , H3O+, etc. All Arrhenius acids are Bronsted acids.
(3) Lewis Acids : The lone pair acceptors are known as lewis acids. They have vacant p or d orbitals.
Ex. BX3, AlX3, ZnX2 etc.

(b) Scale for Measurement of Acid Strength :

Ka 
RCOO H 
 
Where Ka  acid dissociation constant.
RCOOH
A strong acid is defined as the acid which furnish more number of H+ ion in aqueous solution
OR the acid which is more ionised in aqueous solution.
So, a stronger acid has higher value of Ka , or it has lower value of pKa.
pKa = –log Ka

(c) (i) Inorganic acids : The mineral acids are inorganic acids. These are considered as completely ionised
in aqueous solution and are described as strong acids. [H2SO4 > HNO3 > HCl].
(ii) Organic acids : These are weakly ionised in water, so these are weaker acids than mineral acids.
R – SO3H > R – COOH > Ph – OH > ROH.
(d) Prediction of Acid strength :

(i) (Anion/conjugate base of HX)

(ii) (conjugate base)

A stronger acid has more stable anion, so a stronger acid forms a more stable conjugate base.

Factors affecting stability of conjugate base/anion :

(i) Presence of EWG in the alkyl (–R) part of the acid increase stability of anion, and hence increases
acidic strength.

–H

Periodicity in Acid Strength of Hydrides :

(1) Along the period from left to right : As electronegativity increase, Ka 

CH4 < NH3 < H2O < HF. (Ka)

Conjugate base/Anion : (stability)

E.N. dominates over size decrease.

(2) Along the group from up to down : As size increases, Acid Strength 
HF < HCl < HBr < HI

(3) Organic acids :

RSO3H > RCOOH > PhOH > R–OH in acidic character

Explanation :

O O O

|| | ||
H 
(i) RSO3H  R – S — O  R – S  O  R – S  O
|| || |
O O O

(ii) (both of equal stability)

(iii)

Negative charge partially

localised to oxygen.

(iv) ROH

* In sulponate anion three equivalent resonating structure is formed.

* In carboxylate anion two resonating structure are equally stable and are equally contributing to R.Hybrid.

* The phenoxide (C6H5O–) is a less stable anion, although it has five R.S. but three R.S. (II, III, IV) have
negative charge at C-atom, so are less stable and less contributing.

* The alkoxide anion does not have any resonance stabilization, so it is least acidic.

4. Experimental (Ka) Order :

(1) Aliphatic acid

Ex.1

Ans. Ka order : (11) > (2) > (7) > (3) > (6) > (10) > (1) > (4) > (5) > (8) > (9)
Ex.2 CH3COOH < ClCH2COOH < Cl2CHCOOH < Cl3CCOOH

Ex. 3 > >

Ex.4 (a) H–COOH > CH3–COOH

(I = 0) (+I)
(b) CH3 – COOH > CH3–CH2–COOH
(+I) (+I)
(c) C–COOH > C–C–COOH > C–C–C–COOH
Thus, as alkyl size increase, acid strength decreases.
 (e) C–C–C–C–COOH > >

(f) F – CH2 – COOH > Cl – CH2 – COOH > Br – CH2COOH > I – CH2 – COOH

(g)

(h) CH3 – CH2 – COOH < CH2 = CH – COOH < CH  C – COOH

sp3 sp2 sp

(2) Dicarboxylic acids :

1st one is stabilizing, 2nd one destabilizing.

In case of Polybasic acids (compounds having more than one acidic H) , the successive acid dissociation
constant always have order
Ka1 > Ka2 > Ka3 > ...............
In second dissociation H ion is taken out from a negatively charged species, so it is difficult.

(ii)

Ka1  I > II > III > IV ; pKa1  IV > III > II > I
(iii) Maleic acid is stronger acid than fumaric acid.

Ka1 > Ka1' ; Ka2' > Ka2

 Acidic strength in aromatic acid depends upon following factors
(i) Steric effect (steric inhibition of resonance) or Ortho effect
(ii) Electronic effect of substituents
(iii) Intermolecular and intramolecular hydrogen bonding.
Steric effect (ortho effect) : In case of 1,2-disubstituted benzene if the substituents are bulky then due to
steric repulsion (vanderwaal repulsion) the group go out of plane w.r.t. benzene ring. Due to this change in
planarity the conjugation between the substituents on benzene is slightly diminished. This effect is called
steric inhibition of resonance. (ortho effect) In case of ortho substituted benzoic acid due to steric inhibition
of resonance the conjugation between benzene and carboxylic group is diminished and acidity increases
w.r.t. benzoic acid inspite any electronic effect of substituent

O O–H O O
–

C C
G H  G


G may be  – NO2 , – R , – X , – COOR , – COOH

except  – OH , – NH2, – C  N
(COOH group goes out of plane)
Substituted Benzoic Acid :
(1) (G = –m, –I)

COOH
NO2

–H +

O O
C O
+
N

–I, –m

Ka order = ortho > para > meta > benzoic acid

(2) G = (–I) ................. CCl3

Ka order = ortho > meta > para > benzoic acid

(3) G = (–I > +m) – Cl, Br, F, I

Ka order = ortho > meta > para > benzoic acid

(4) G = (+m > –I) ..... OCH3

 Ka order = meta  ortho > benzoic acid > para

(5) G = (+I, H.C.) ........ R (Alkyl group)

Ka order = ortho > benzoic acid > meta > para

Ex. < < < <

Ex. >

Note : In case of different ortho susbstituted benzoic acids the acidity is not decided by the basis of ortho effect but
it is decided by the. electronic effect of substituents.

Ex.

+I +m>–I –I>+m –I,–m

I II III IV V
Ka order = V > IV > I > II > III

Ex.

+I –I –I –I
I II III IV V
Ka order = V > IV > III > I > II
At meta positions only inductive effect is operative and mesomeric / hyperconguative effect is not operative
in substituted benzoic acid.

Ex.
+I –I –I –I
I II III IV V
Ka order = V > IV > II >III > I
 insignificatnt).

Ex.

COOH
–H+

OH

COO

Ortho anion stabilised by intramolecular H-bonding.

Ex.

Ka order : (i) > (ii) > (iii) > (iv).

(4) Acid strength of Phenols (effect of substituents) :

Note: Ortho effect is operative only in o-substituted Benzoic acids and not in o-substituted phenols.

> >

(1) EWG = (–m , –I) (–NO2, CHO, –COR, C  N, etc.)

Ka order = Para > Ortho > Meta > Phenol

(2) EWG = (–I) with no mesomeric effect

> > >

Ka order = Ortho > Meta > Para > Phenol

(3) EWG = (–I > + m) X = F, Cl, Br, I

Ka order = Ortho > Meta > Para > Phenol

(4) G = R (Alkyl group) = + I, H.C.

Ka order : Phenol > Meta > Para > Ortho

(5) G = (+m > –I) (–OH, –NH2, –OR, etc.)

 Ka order : Meta > Phenol > Ortho > Pera

Ex. (1) > > > > >

Ex.

(I) (II) (III) (IV) (V) (VI)

only (–I)
Ka order = I > II > III > VI > IV > V

Ex.

(I) (II) (III) (IV) (V) (VI)

Ka order = I > II > III > IV > V > VI

Ex. > > (No acidic H)

Ex. >
Ex. (picric acid) > >

Reaction of Acids with salts :

(1) NaX + HY  NaY + HX

Strong
Salt of Weak acid Acid

Remark : A stronger acid displaces the weaker acid from any 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.

Ex. 2 NaCl + H2SO4  Na2SO4 + 2HCl

Ex. Na2SO4 + 2HCl  No reaction

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

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

Q. Which of the follwing reaction is possible ?

(A) CH3COOH + HCOONa Not possible (reverse is possible)

OH ONa

(B) +  Not possible

NO2

SO3Na COOH

(C) +  Not possible

(D*) HC  C – Na + H2O  HC  C – H + NaOH

(E) CH3COOH + NaCl  Not possible

(F) Ph–COOH + KBr  Not possible

(G) Picric acid + K2SO4  Not possible

(H*) +  +
 BASIC STRENGTH
(I) DEFINITION:
(a) Arrhenius base: Those compound which furinishes OH - ions in aquous solutions are known as arrhenius
base.
Ex: NaOH, KOH, Ca(OH)2 etc.

 

 

(b) Bronsted base:- e– pair donor or H ion acceptor. :NH3, R N H2, R2 N H, R3 N , H2 O, R O H, R – O – R

(c) Lewis base:- e– pair donor to H ion.


NH 3 + H +


NH4
+
R – O – R + H+
 

R– O –R

–
H
(II) BASICITY:
It is the tendency to accept H ion, or it is the case of acceptance of H ion.
Ex: H3N: + H __________easily..
 

H – O – H + H __________less easily..
Thus, NH3 > H2O in basicity.
Less electronegative atom (N) donates electron pair easily.

(III) SCALE OF BASICITY/BASIC STRENGTH:-

In aq. solution:-
+
R – NH3 + OH -


R – NH 2 + H2O
Base Conjugate Acid (C.A.)


[RNH3 ][OH - ]
Kb = – [where Kb = Base dissociation constant].
[RNH2 ]
pKb = –logKb

Note : A stronger base always has a weaker C.A. and vice versa.

(IV) PERIODICITY IN Kb (BASIC STRENGTH):-

Factors:- (i) E.N. of element__________E.N.  , Kb 
(ii) Size of element__________size  , Kb 

- - -
(a) CH3 > NH2 > OH > F - -------- E.N.
CH - is strongest base in periodic table.
3

- - -
(b) CH3 > P H2 > S H > Cl -------- E.N.

(c) F - > Cl - > Br - >  - -------- size

(d) - O H > - S H-------- size



(e) H2 O > H2 S

(f) :NH3 > :PH3

(V) CARBANION BASES (:C - ) :
- -
(i) CH3 – CH2 > CH2 = CH > CH  (E.N.  , Kb  )
- -
(ii) CH3 – CH2 – CH2 >> CH2 = CH – CH2
(delocalised lone pair) due to Resonance
- -
(iii) CH2 = CH – CH2 > CH3 – C – CH2
O
(better resonance due to –ve charge on ‘O’)

-
CH2 -
–

(iv) <
(localised
(Resonance –ve charge)
Stabilisation)

Criteria for deciding basec strengths :-

1. Electronic effect : +I, +m group increases electron density at nitrogen atom and increases is lone pair
donating ability therefore basicity increases.
–I, –m group decreases electron density at nitrogen and hence decreases its lone pair donating ability,
therefore basicity decreases.
2. Hybridisation of Nitrogen atom : The lone pair donating ability of nitrogen atom changes with hybridisation.

Electrongeativity : sp(N) > sp2(N) > sp3(N)

Kb  lone pair donating ability sp3(N) > sp2(N) > sp(N)




Ex. CH3 – CH2 – CH2 – N H2 > CH2 = CH – CH2 – N H2 > CH  C – CH2 – N H2
– –

(VI) NITROGENOUS BASES –N: :-



Classification:- (i) Aliphatic amines (R N H2, R2 N H, R3 N)



(ii) Aromatic amines (Ph – N H2) or Anilines



(iii) Amides R – C – NH2

O


(iv) Amidines R – C – NH2

:NH
Among these, amides are the weakest bases.
(iv) > (i) > (ii) > (iii)
(i) Aliphatic amines :
Consider the following molecules , , ,

By visiting + I effect of methyl in above example we may expect basic nature as

NH3 < MeNH2 < Me2NH < Me3N Which is not true
This is due the fact that basic strength of an amine in water is determined not only by ease of electron
donation (protonation) of N atom but also by the extent to which cation so formed can undergo SOLVATION
and become stabilised by H atom attatched to N atom greater is possibility of solvation via H bonding by
water. Alkyl groups are hydrophobic and inhibits H bond.
H
 H
– –

(1) H – N:   + = O, solvation = max., Steric Hinderance = min.

H
 H
H

– –
(2) R – N:  +, solvation, Steric Hinderance
H
H
H

– –
(3) R – N:  + , solvation, Steric Hinderance
R
R
H
– –
(4) R – N:  +max., solvation min., Steric Hinderance max.
R
In aq. solvation, the general order of basic strength is R2NH > R3N > RNH2 > NH3. (R = Ethyl)
or, in some cases, it is R2NH > RNH2 > R3 N > NH3 (R = Methyl)

Explanation: It will be seen that the introduction of an alkyl group into ammonia increases the basic strength
markedly as expected. The introduction of a second alkyl group further increases the basic strength, but the
net effect of introducing the second alkyl group is very much less marked than with the first. The introduction
of a third alkyl group to yield a tertiary amine, however, actually decreases the basic strength in both the
series quoted. This is due to the fact that the basic strength of an amine in water is determined not only by
electron-availability on the nitrogen atom, but also by the extent to which the cation, formed by uptake of a
proton, can undergo solvation, and so become stabilised. The more hydrogen atoms attached to nitrogen in
the cation, the greater the possibilities of powerful solvation via hydrogen bonding between these and water:

Thus on going along the series, NH3  RNH2  R2NH  R3N, the inductive effect will tend to increase the
basicity, but progressively less stabilisation of the cation by hydrating will occur, which will tend to decrease
the basicity. The net effect of introducing successive alkyl groups thus becomes progessively smaller, and
an actual changover takes place on going from a secondary to a tertiary amine.
Conclusion :
(1) Secondary amines are stronger bases than tertiary amines.
Reason:- Solvation is less in 3º amines and more steric hinderance to H ion.
(2) All alkyl amines (1º, 2º, 3º) are stronger bases than ammonia (due to + effect of ‘R’ group).
(3) In gaseous phase, the basic strength order is 3º > 2º > 1º > NH3 (+ effect of R group).

Ex. (1) – CH2 – NH2 > – CH2 – NH2







(2) : NH3 > NH2 – NH2 > NH2 – O H

Ammonia Hydrazine Hydroxylamine


 

 
 

(3) N H3 > R –– O –– R > R – O – H > H – O – H

(+ ) (+ )

(4) N: > N:

(More compact)
 Cyclic Amine is more basic than acyclic amine (if degree of ‘N’ is same).

(5)
–

:NH2 :NH2
(ii) > (iii) > (i) > (iv)
 (6)

Kb order : I > II > III

(7)

I II III IV
Sulphonamide Amide Ar. Amine Aliphatic amine

Kb order : IV > III > II > I

CH2 — CH2 — NH2 CH3 — CH — NH2 CH3 — CH2 — NH

(8) | | |
Ph Ph Ph
I II III
Kb order : I > II > III

(9) Ph—NH2 Ph2NH Ph3N

I II III
Kb order : I > II > III

(10)

I II III IV

Kb order : IV > II > III > I



(ii) Aromatic amines (Ph – N H2) or Anilines :

When the lone pair lies in conjugation with a multiple bond, it resides in ‘2p’ atomic orbital, so that it can get
resonance stabilisation.
Aniline is a weaker base than NH3 because it has delocalised lone pair.

Ex. Which of them is stronger base

CH3 – NH2

Since ease of donation of lone pair of N is basicity, CH3 – NH2 is more basic due to + I effect of – CH3 group.
Aryl amines aniline is very less basic since lone pair of N are involved in resonance.
Ex. Which of them is strong base

In pyrole lone pairs are involved in resonacne therefore it is less basic. But in pyridine lone pairs are in
perpendicular plane of  orbitals therefore not involved in resonance

Substituted Anilines:-
(i) G = ERG (+m, HC, +)__________Kb 

(ii) G = EWG (–m, –)__________Kb 

Steric effect of ortho-substituted G (ortho effect) :

H
+ –
H2N: H–N–H
–

–
G G
H
–

–


(a) Ortho-substituted anilines are mostly weaker bases than aniline itself.
(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.

Ex. (1) G = (–m, –); NO2

NH2

–
(a) (b) (c) (d) Kb :
dbc a

(2) G = (–); CCl3

NH2 NH2 NH2 NH2
–

–
–

CCl3
–

(Aniline > p > m > o).

–

CCl3
–

CCl3
(3) G = (– > +m); Cl
NH2 NH2 NH2 NH2
–

–
–

Cl
–

aniline > p > m > o

–

Cl
–

Cl
Only (–) decides the order.

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

NH2 NH2 NH2 NH2

–

–
–
–

CH3
–

CH3
–

O effect, +m CH3

+ +
w

HC HC  more do min ating

 (5) G = (+m > –);

Kb order : P > Aniline > O > M

(iii) Amides : 

In amides lone pair donation atom is oxygen which is more electronegative. so it can hold negative charge
more effectively, so it donation tendency decrease (kb decreases).

(iv) Amidines :
(a) Hybridisation of ‘N’ : sp3 > sp2 > sp

(b)

In case of amidines, the doubly-bonded ‘N’ is more basic in nature. Although, both the ‘N’ are sp2 hybridised.
The lone pair of most basic ‘N’ lies in sp2 hybrid orbital (localised).

x
R
y x R y
–

NH2 – C = NH H2N – C = NH
2 2
(1) sp sp
(2) lone pair in sp2 H.O. lone pair in 2p A.O.
(3) lone pair localised lp delocalised
(4) Basicity y > x.

Strongest organic Nitrogenous base:-

(+m)
  (+m)
NH2 – C – NH2 Guanidine
:NH2

 H  + +
NH2 – C – NH2  :NH2 – C – NH2 :NH2 – C = NH2 NH2 = C – NH2
–

:NH

NH2 NH2 NH2
Heterocyclic Compounds (Nitrogenous base) :
(1) Pyridine (C5H5N:)
 
H – –H 6 e – 

S.F.:- H – N: Aromatic A.O. Diagram:-


N
H–
–
H Stronger  base   2
sp hybrid orbital
(lone pair)
localised
 (2) Pyrrole (C4H5N:):-

6e –
2
Aromatic
S.F.:- :N – H (sp ) Very weak base
Non  aromatic after it donates lone pair

 
 (lp. in 2p A.O.)
A.O. Diagram:- N–H
 
Complete delocalisation of e–

Ex:- 1. > >

– 
N
 N
:NH2

–
H
H H H

+ +
N ––– sp (4e )
–
3
N
–
–

NH3 – H

–
H H
Aromatic Aromatic Non-aromatic

O
2. a>c>b>d
 
N N  
N N
–

H
–

H H
(a) (b) (c) (d)
sp3/2º sp2 localised sp3/2º (–) sp2
  
3. NH2 – C – NH2 ; R – C – NH2 ; R–C–R ;
:NH :NH NH
(1) (2) (3)
2 2
sp sp

Kb order : (1) > (2) > (4) > (3) > (5)

:NH2(x)
–

4. N
 Basicity order:- y > x > z
 N(z)
–

(y) H
 Carbanion
Bond dissociation
1. Dissociation of covalent bond, (Homolysis and Heterolysis)

2. Type of Reaction intermediates formed ( C+, , ,: )

Carbanion
A carbon intermediate which contain three bond pair and a negative charge on it, is called carbanion.

, Methyl carbanion

CH3 – Ethyl carbanion

(CH3)2 Isopropyl carbanion

Hybridisation : Hybridisation of carbanion may be sp3, sp2 & sp.

Hybridisation Example

sp3 , CH3 –

sp2 H2 C = , CH2 = CH –

sp HC 

Structure of following carbanions

(a) (b) (c) (d) CH2 = CH –

(e) (f)

[Draw the orbital diagram and mention the type of hybridisation involved in each case]

Stability of carbanion :
Carbanions are stabilised by electron withdrawing effect as
(i) – I effect
(ii) – M effect
(iii) Delocalisation of charge

If -position of a carbanion has a functional group which contains multiple bond (C = C, C = O, C  N, NO2
etc) or carries an electronegative atom, such carbanions are stablised by resonance hence more stable than
simple aryl carbanion.
Example of stability order :

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

1

.. .. ..
CH2
(B) .. (Stability order) : 2 > 1 > 3 > 4
CH  C

1 2 3 4
 ..
.. CH3

–
(C) .. (Stability order) : 2 > 1 > 3 > 4
..

–
CH3

1 2 3 4
.. .. ..

(D) (Stability order) : 3 > 4 > 2 > 1

Br NO2 Cl
1 2 3 4

(E) (Stability order) : 1 > 2 > 3

.. ..
(F) CCl3 CF3 (Stability order) : 1 > 2
1 2

.. ..
(G) Cl – CH2 – CH2 F – CH2 – CH2 – CH2 (Stability order) : 1 > 2 > 4 > 3
1 2

.. ..
CH3 – CH CH3 – CH2 – CH2
–

CH3 4
3

CH  C ..
..
(H) CH2 – NO 2 (Stability order) : 1 > 2 > 3
1 3
.. .. ..
CH2 CH – CH –
– –
–

(I) (Stability order) :

– –
NO2 CHO

1 2 3 4>2>6>3>5>1
.. .. ..
CH – CH – CH –
– – –
+
– +
– –
SMe2 NMe3 CN

4 5 6
.. ..
(J) CH3 – CH2 – CH2 – CH2 CH3 – CH – CH2CH3 a>b>d>c
a b
.. ..
(CH 3)2C – CH 2CH 3 (CH 3)3C
c d

O O O
.. .. .. ..
(k) CH2 – C – CH3 CH2 – C – H CH2 – C – OCH
.. 3 e>b>a>c>d
a b c

O
..
CH2 – C – NH2
d
(L) > > (Stability order)

Reaction in which carbanion intermediates are formed

Li / ether
(a) R – X  

Mg / ether
(b) R – X  (Lot of carbanion like character in R)
 

(c) R – Na / NH3 (  )
C – H   


(d) R – CH2 – – R OH


(e)

(f) CH3 – CH = O

(g) Decarboxylation of alkanoic acid by using sodalime dereasing order of decarboxylation

CH3 – CH2 – CH2 – COOH > CH3  CH  COOH (dereasing order of decarboxylation)
|
CH3
 TAUTOMERISM
(1) Definition : Tautomers are two structural isomers (having different functional groups) which exist in dynamic
equilibrium with each other. The isomers change into each other by shifting of H-atom from one position to
another position and simultaneously the position of  bond also changes.

(2) General formula of compounds showing tautomerism

|
C  X Y H

X=Y can be : C = O C = NH N=O NO


O

(i)

(ii)

(iii)

(iv)

(3) Keto-enol tautomerism

General Expression:-
– –
–

–
–

–C–C=O – C = C – OH
H enol form
Keto form

Condition:- Presence of at least one  – H wrt C = O group.

Ex.-1 Draw enol forms of following carbonyl compounds
(i) CH3 – CH = O CH2 = CH – OH

CH3 CH3
–

(ii) CH3 – C = O CH2 = C – OH

(iii) CH3 – C – CH2 – CH3 CH3 – C = CH – CH3 and CH2 = C – CH2 – CH3
–
–

O OH OH
(4) Comparison of stability of Keto-enol tautomers
Keto form Enol form
| |
CC C  C
| || |
H O OH

The group is more resonance stabilized An alkene is less resonance stabilized

(Positive charge at ‘C’ and negative (Positive charge at ‘O’ and negative
charge at ‘O’ atoms) charge at ‘C’ atoms)

In case of monocarbonyl compounds, the compound mainly exists in Keto form (99%). The enol form is
insignificant (less than 1%)
As stability of alkene increases (due to increase in hyper-conjugation or resonance)
% enol content (alkene content) increases.
The -dicarbonyl (or 1, 3-dicarbonyl) compounds have significant enol contents due to resonance stabiliza-
tion of enol form
H3C – C – CH2 – C – CH3 H3C – C = CH – C – CH3

–
O O OH O
keto form ( 25%) enol form ( 75%)

Compare % enol contents

Ex. 1 Keto form Enol form

I : CH3CH = O CH2 = CH – OH

II : CH3 – CH2 – CH = O CH3 – CH = CH – OH

III :
Sol. III > II > I

CH3
|
Ex. 2 CH3  C  CH3 < CH3  CH2  C  CH3 < CH3  CH  C  CH3 ..... (% enol)
|| || ||
O O O

Ex. 3 I : CH3  C  CH3 CH2  C  CH3

|| |
O OH

II : CH3  C  C  CH3 CH2  C  C  CH3

|| || | ||
O O OH O

III : CH3  C  CH2  C  CH3 CH3  C  CH  C  CH3

|| || | ||
O O OH O
Sol. III > > II > I
76% 1.2% 0.01% (enol content)
Ex. 4 >

Ex. 5

Properties of Keto and enol forms

1. Boiling point : >

Reason : The keto form is more polar and the enol form has intramolecular H-bonding

2. Solubility : In polar solvents (like H2O). The more polar keto forms is more soluble in water, than the less
polar enol form. The enol form has intramolecular H-bonding

3. Polarity Keto form > enol form

4. Optical properties
The carbonyl compounds which have alpha asymmetric carbon (C*) atom and have  – H hydrogen atom,
racemise due to tautomerisation on keeping in aqueous solution.

5. Chemical properties
The -dicarbonyl compounds in aqueous solution show chemical properties of both the forms. The lab tests
of following functional groups are positive.
(i) (ii) C = C (iii) – OH

Keto-enol tautomesion in phenols and its derivatives

1. In phenol (enol form is much more stable due to aromaticity)

2. In catechol
3. In Resorcinol :

4. In Quinol (Hydroquinol)

5. Trihydroxy benzene

(a)

(b) (1, 2, 4)

(c) (1, 3, 5)

(% enol < % keto)

Q.1 Which of the following compounds will racemise on keeping in aqueous solution
CH3 Me
| |
(A*) CH3  CH  CHO (B*) Ph  C  C  CH3 (C) Ph  C  C  CH3 (D) Ph  CH  CH2  C  CH3
| | || | || | ||
D H O Et O D O

Q.2 Which of the following will show tautomerism

O O
|| ||
(A) Me3C – CHO (B*) Me2CD – CHO (C*) Ph  C  CD 3 (D*) Me 3 C  C  CH3

Q.3 Which of the following will show tautomerism

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

Q.4 Write the tautomer of
OH
OH OH OH HO OH
OH
(A) (B) (C) (D) (E)
HO OH
OH HO OH OH

Q.5 ‘X’ is the smallest dicarbonyl compound which has significant enol content. Predict S.F. of ‘X’.
Sol. X = H  C  CH2  C  H
|| ||
O O

Q.6 A (C6H10O2) is an optically active dicarbonyl compound which significantly exists in optically inactive enol
form. Identify A.
Sol. A = CH3  C  CH  C  H or CH3  CH2  C  CH  C  H
|| | || || | ||
O C 2H5 O O CH3 O

Q.7 An aromatic compound X of molecular formula C9H8O2 exists in keto form and predominantly in enolic form
Y. Write all the possible structure of X and Y.

Sol.

(X) (Y)

Ph Ph
| |
X = OHC  CH  CHO Y = HO  HC  C  CH  O

Q.8 Which of the following pairs are tautomers.

(A*) & (B*) and

 Carbocation
Carbocation
A carbon intermediate which contain three bond pair & a positive charge on it is called carbocation.

, Methyl carbocation

CH3 – etc. Ethyl carbocation

Characteristic
(i) sp2 or sp
(ii) Classical & non classical
(iii) Bond angle 120°
(iv) Diamagnetic (6e¯ )

Hybridisation : Carbocation may be sp2 & sp hybridised

Hybridisation Example

sp2

sp H2 C = , HC 
Structure of following carbocations
(i)

(ii)
(iii)

(iv) (Allyl)

(v) (Benzyl)

(vi) (Phenyl carbocation)

Draw their orbital diagram and mention the nature of hybridisation in each case.
Stability of carbocations
Factors affecting stability of carbocation
(i) + I effect
(ii) Hyperconjugation
(iii) Resonance stabilization
(iv) + m effect of substituent groups with lone pair (O, N)
General stability order :-
> > > > > >

> > >

The carbocation is not possible at following bridge head positions I and II

, (Non classical carbocation)

Exceptionally stable carbocations are

and aromatic
 + + +
CH2 CH2 CH2

–
OMe

–
(A) Stability order : 1 > 3 > 2

–
OMe

–
OMe
1 2 3

+ + +
CH2 CH2 CH2
–

–
CH
– 3
(B) Stability order : 3 > 1 > 2

–
CH3
–

CH3
1 2 3

+ + + + +
OMe CH
– – 3
(C) Stability order : 5 > 1 > 2 > 4 > 3
–

–
CH3 CN
1 2 3 4 5

+ +
CH2 CH2
–

+
– CH2 Stability order :
(D) 6  5  1 2  4  3
– CH3
–

CH3
–

CH3
1 2 3
+ + +
CH2 CH2 CH2
–

–
–
–

CH2D NHCOCH3 OMe

4 5 6

    ..
(E) CH3 CH3 – CH – CH3 CH3 – CH – NH2 CH3 – C  O
.. Stability order : 3 > 4 > 2 > 1
1 2 3 4

+
+
(F) Stability order : 1 > 3 > 2
.. .. .. +
O
.. O
.. O
..
1 2 3

+ + CH3
– –

(G) – CH – –C –C+ Stability order : 3 > 1 > 2

CH 3

1 2 3

+
+ +
(H) Stability order : 3 > 2 > 1

1 2 3
 + +
(I) CH3 – CH2 – CH2 – CH2 CH 3 – CH – CH 2 – CH 3 Stability order : d > c > b > a
a b
+ +
(CH3)2C – CHCH3 (CH3)3C

–
CH3
c d
+
(J) Draw all isomeric form of C5H11 carbocation, which one is the most stable.
C
+ + +

–
+
C–C–C–C–C C–C–C–C–C C–C–C–C–C C–C–C–C
(a) (b) (c) (d)

– –
C C C – C – C+
+
–

–
C–C–C–C C–C–C–C C
(e) + (f)
(g)
+
(f) C5H11 is most stable.
.. + .. +
(K) CH3 – CH2 – NH – CH – CH2 – CH3 CH3 – CH2 – NH – CH2 – CH – CH3
(a) (b)
CH3 – CH2 – .NH
. – CH2 – CH2 – CH2
(c) + Stability order : a > b > c

+ +
+ +
(L) Stability order : d > c > b > a

a b c d

+ +
+ CH2 CH2
+
–
–

CH2 CH2
–
–

(M) Stability order : a > d > c > b

a b c d
+
+
(N) Stability order : b > a > c
+
(a) (b) (c)

  
(O) > > CH3 – CH – CH3 > CH3 – CH – CH2Cl > CH3 – CH – CH2NO 2

(P)
Rearrangement : Whenever an Intermediate carbocation is formed in reaction it rearranges to a
more stable one.
Not all carbocations rearrange but only those which can produce more stable species can only
rearrange.
(i) The driving force responsible for carbocation rearrangement is formation of more stable carbocation.
(ii) Shifting of H, alkyl, aryl, bond (1, 2)
(iii) Ring expansion (more strained ring to less strain ring)
(iv) Ring contraction
Shifting of H, alkyl, aryl, bond (1, 2)







CH2 = CH – CH2 –  CH2 = CH – – CH3



Carbocation rearrangement involving ring expansion.

  

One very stable carbocation reported is cyclopropylmethyl carbocation. This unique stabilisation is seen in
this case of three member ring only.

(more stable than Benzyl)

cyclopropyl methyl carbocation




Ring contraction : -

+
 ;  ;  +

Complete octet : -



CH3
+ ..
– –

..
(i) CH3 – C – C = O
.. (lI) CH3 – CH2 – O
. . – CH – CH – CH3
+

–
CH3 CH3

CH3 CH3
(III) (IV) CH 3 – CH – CH – N – CH 3
+ +
O

+ .. + ..
(V) CH 3 – CH 2 – CH = O (VI) CH3 – CH – CH – Cl

..
.. ..
CH3

Rearrange (if applicable) these carbocation into more stable form :-

+ CH3 CH3

––
–

+
(a) CH3 – CH2 – CH2 (b) (c) CH3 – C – CH – CH3 (d) CH3
+ +
CH3

+
CH3 CH2
–

+ –
(e) (f) – CH2 (g) (h)
+ + –
CH3

+
+ – CH –
(i) CH2 – CH – CH – CH3 (j)
–

CH3
 Free radicals

Free radical
Ionic reactions are those in which covalent bonds break heterolytically and in which ions are involved as
reactants, intermediates, or products.
Another broad category of reaction mechanisms that involve homolysis of covalent bonds with the production
of intermediates possessing unpaired electrons called radicals (or free radicals):

Free radicals
(i) Homolytic cleavage
(ii) Condition for its generation
Sun light, peroxide, High temperature
(iii) Neutral species with odd e¯
(iv) Gaseous phase or non polar solvent
(v) Paramagnetic

(vi) No rearrangement (generally)

(vii) Hybridisation state – sp2 (generally)

Inhibitors : like oxygen (decreases rate or reaction)

Stability of free radical
(i) Hyperconjugation
(ii) + I, + M

(iii) Decreasing order of stability is ...... > 3° > 2° > 1° >

Stability of radicals

1. CH3 – CH – CH – CH3 CH 3 – CH – CH 2 – CH 2 CH3 – C – CH2 – CH3 c>a>b

–
–

CH3 CH3 CH3

a b c

2. d>b>a>c>e

a b c d e
3. CH2 = CH c>b>d>a

a b c d

CH3 H H H

–
–
–
–

4. c>d>a>b

–
a b c d

• •
5. CH3 – CH2 – CH2 – CH2 CH 3 – CH – CH 2 – CH 3
a b

CH3 •
–

•
(CH3)2CCHCH3 (CH3)3C d>c>b>a

c d

6. Match the following :

Ans. 1 – a, q, y
2 – a, q, x
3 – b, p, z