LECTURE NOTES

Session - 2012-13

ORGANIC CHEMISTRY
TOPIC : GOC - II
CONTENTS :
1 Inductive Effect
2. Resonance Effect (mesomeric effect)
3. Hyperconjugation
4. Electromeric effect
5. Aromaticity
6. Directive Influence
7. Reaction Intermediates (Free radical, Carbocation, Carbanion )
8. Tautomerism
9. Acid & Base

Proposed ISEET/IIT-JEE Syllabus

CONCEPTS :
Inductive, Resonance and Hyperconjugation Effect, Applications of Electronic
Effects, Aromaticity and Directive Influence, Reaction Intermediates,
Tautomerism, Acid & Base
 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.

RESONANCE page # 2
 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  H2C  H2 C  CH  COOH (II) CH 3  CH 2  CH  CH 2  COOH

| |
Cl Cl

(III) CH 3  CH  CH2  CH 2  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).

RESONANCE page # 3
 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.

RESONANCE page # 4
 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 – C H2 (Conjugation between odd electron and C = C)
–
5. CH2 = CH – CH = CH – CH2 (Conjugation between negative charge and C = C)

RESONANCE page # 5
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
RESONANCE page # 6
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.

RESONANCE page # 7
(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

RESONANCE page # 8
 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.

RESONANCE page # 9
2. +M group increases electron density in benzene ring while –M group decreases electron density in the
benzene ring.

(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 CH2 = CH2
Hyperconjugation in toluene

RESONANCE page # 10
 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)

RESONANCE page # 11
(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 +

RESONANCE page # 12
 Lecture -33 (Aromatic - 1)

1. Aromatic Character : [The Huckel 4n + 2 rule]

The following three rules are useful in predicting whether a particular compound is aromatic or non–aromatic.

1. Aromatic compounds are cyclic and planar.

2. Each atom in an aromatic ring is sp2 hybridised.

3. The cyclic  molecular orbital (formed by overlap of p-orbitals) must contain (4n + 2)  electrons,
i.e., 2, 6, 10, 14 ........  electrons. Where n = an integer 0, 1, 2, 3,..............

Comparision between Aromatic, Antiaromatic and Non-Aromatic :

RESONANCE page # 13
 Examples of Aromatic Compounds : (Table )
 -electrons Aromatic
n Salts Examples of salts
= (4n + 2) compound / ions

H Ph

+ +

+
OH Br
0 2
Ph
Hydroxydiphenyl
H H Cyclopropenyl bromide
Cyclopropenyl
cation
-
+ SbCl6

Cyclopropenyl
hexachloroantimonate

+ Ph Ph
++ ++ 2BF4
0 2 + Ph Ph
Cyclobutenyl Cyclobutenium salt tetraphenylcylo-
di-cation butenyl fluoroborate

- +
K
-
1 6 - Potassium
Cyclopentadienyl Cyclopentadienide cyclopentadienide
anion salts

+
-
+ Br
+
1 6
Tropylium cation Troplyium
(Cycloheptatrienyl Tropylium salt Bromide
cation)

,
2 10
Napthalene , azulene

3 14 Anthracene

Phenanthrene

H
H H
4 18 H H
H

[18] Annulene

RESONANCE page # 14
3. Directive Influence of Substituents In Benzene
The first substituent may occupy any position in benzene ring i.e. one and only one monosubstituted ben-
zene is obtained. The next group may go to ortho, meta or para position, it is the group already present in the
benzene nucleus that determines how readily the attack occurs and at which position, of the ring it occurs.
In other words, the group attached to the ring not only affects the reactivity but also determines the orienta-
tion of substitution. This is called directive influence of substituents in bezene nucleus. The substituent
group is able to activate or deactivate the ring due to a number of factors like inductive effect, electromeric
effect, resonance effect and hyperconjugative effect.

Classification of Substituent Groups:-

E.E. F.G. Act./Deact. of o/p-directing m-directing
Benzene Ring
(1) +m, +I O– Strongly activating  

(2) +m > –I NH2 > NHR > NR2 > OH activating  
> OR > –NHAC > –OAC
(3) +I, H.C. R (alkyl) moderately activating  
C C
–
– –

Me > Et > – C > – C – C

–
C C
(4) –I, +m X = F, Cl, Br, I Deactivating  

–N = O, –N C
 
(5) –I only NR 3 , NH3 , CX3 Strongly deactivating  
 
–

(6) –m, –I –NO2, CO , –CN, –COOH, Strongly deactivating

–

–COOR, –SO3H, COCl

(1)

(2)

RESONANCE page # 15
 (3)

ORTHO-PARA RATIO :
Factors:-
(1) EE:- In case of +m, –I groups +m is same at o/p positions but –I is more at ortho position. So
para position is more e– rich. % para is more than % ortho.
(2) In case of alkyl group ortho position is more e– rich than para position.
(3) – I > + m, halogen : In halobenzenes para position is more e¯ rich than ortho.
(4) Steric factor : If size of substituent G increases or size of E+ increases than para products is formed as
a major product.
DIRECTIVE INFLUENCE IN DISUBSTITUTED RING :
(1) If both groups shows +M effect then electrophile attack in the influence of more +M group.
(2) If one group is + M effect and another is –M effect then electrophile attack in the influence of more +M
group.
(3) If both groups shows –M effect then electrophile attack in the influence of more –M group.

1. Br / Fe
2

2.

+
(CH3)2C = CH2 / H
3.

CH3 CH3
NO2
HNO  H SO
4.  3 2 
4


Cl Cl

CHO CHO
Br
5. Br2 / FeBr3
   

OH OH

RESONANCE page # 16
 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

RESONANCE page # 17
 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 •
–

d>c>b>a
•
(CH3)2CCHCH3 (CH3)3 C

c d

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

RESONANCE page # 18
 sp H2C = , 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

Practice problem :
+ + +
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

RESONANCE page # 19
 1 2 3

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

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)

RESONANCE page # 20
 C

– –
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) Stability order : a > c >b

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)



RESONANCE page # 21
 



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 : -

 

RESONANCE page # 22
 

+
 +

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 CH
+ – 2
+
(e) (f) – CH2 (g) (h) CH2 – CH – CH – CH3
+
–

CH3

+
– CH –
(i)

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

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

RESONANCE page # 23
 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 H2C = , 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

RESONANCE page # 24
 .. .. ..

(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 – NO2 (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

RESONANCE page # 25
(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

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*) +  +

TAUTOMERISM

RESONANCE page # 26
(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) r

(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

RESONANCE page # 27
(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
–OH
O O 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

RESONANCE page # 28
 CH3
|
Ex. 2 CH3  C  CH3 < CH3  CH2  C  CH3 < CH3  CH  C  CH3 ..... (% enol)
|| || ||
O O O

Ex. 3 I : CH3  C  CH3 CH 2  C  CH3

|| |
O OH

II : CH3  C  C  CH3 CH 2  C  C  CH3

|| || | ||
O O OH O

III : CH 3  C  CH 2  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.

RESONANCE page # 29
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)

RESONANCE page # 30
 (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*) Me3 C  C  CH3

Q.3 Which of the following will show tautomerism

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

Q.4 Write the tautomer of

OH
HO OH

(A) (B)
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)

RESONANCE page # 31
 Ph Ph
| |
X = OHC  CH  CHO Y = HO  HC  C  CH  O

Q.8 Which of the following pairs are tautomers.

(A) & (B*) and

RESONANCE page # 32