ORGANIC LECTURE NOTES

GOC-II
PART-II
BASIC STRENGTH, INTERMEDIATE, TAUTOMERISM

Lecture 1

1. Aliphatic amines
2. Aromatic amines
(Ph N H2) or
Anilines

1. BASIC STRENGTH
2. DEFINITION

Lecture 2

3. BASICITY
4. SCALE OF BASICITY
BASIC STRENGTH:-

5. PERIODICITY IN Kb
(BASIC STRENGTH):

3. Amides

Lecture 3

Lecture 4

1. TAUTOMERISM
1. Carbanion
structure,stability 2. Keto-enol
tautomerism
2. Examples
3. Comparison of stability of Keto-enol
tautomers
4.

4. Amidines
5. Hetero Cyclic

6. CARBANION BASES

(:C - )
7. NITROGENOUS

BASES N: :-

Lecture 5
1. Properties of Keto
and enol forms

2. Examples

Lecture 6
1. Carbocation
structure,stability

2. Examples

Lecture 7
1. Carbocation
rearrangement
2. ring expansion.
3. Ring contraction
4. Examples

Lecture 8
1. Free radical
2. Stability of
radicals

Page # 2

BASIC STRENGTH
(I) DEFINITION:

Ex:

(a) Arrhenius base: Those compound which furinishes OH - ions in aquous solutions are known as arrhenius
base.
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.

NH4

R O R + H+

+
R O R
H

NH 3 + 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 NH 2 + H2O
Base

Kb =

+
R NH3 + OH Conjugate Acid (C.A.)

[RNH3 ][OH - ]
[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

Page # 3

(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

CH2

(better resonance due to ve charge on O)

(iv)

<

(Resonance
Stabilisation)

(localised
ve charge)

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)

CH3 CH2 CH2 N H2 > CH2 = CH CH2 N H2 > CH C CH2 N H2

Ex.

(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

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

Page # 4

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 3 amines and more steric hinderance to H ion.
(2) All alkyl amines (1, 2, 3) are stronger bases than ammonia (due to + effect of R group).
(3) In gaseous phase, the basic strength order is 3 > 2 > 1 > NH3 (+ effect of R group).

CH2 NH2 >

(1)

CH2 NH2

N H3 > R O R > R O H > H O H

(+ )
(+ )

N:

>

(4)

(3)

: NH3
> NH2 NH2 >
NH2 O H
Ammonia
Hydrazine Hydroxylamine

(2)

N:

(More compact)

Cyclic Amine is more basic than acyclic amine (if degree of N is same).

:NH2

(5)

Ex.

:NH2

(ii) > (iii) > (i) > (iv)

Page # 5

(6)
Kb order : I > II > III

(7)
I
Sulphonamide

II
Amide

III
Ar. Amine

IV
Aliphatic amine

Kb order : IV > III > II > I

(8)

CH2 CH2 NH2

|
Ph
I

CH3 CH NH2
|
Ph

CH3 CH2 NH
|
Ph

II

III

Kb order : I > II > III

(9)

PhNH2
I

Ph2NH
II

Ph3N
III

Kb order : I > II > III

(10)

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.

Page # 6

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) :

H2N:

H
+
HNH
G

(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.
(1) G = (m, ); NO2

NH2

(a)

(b)

(c)

(d)

Kb :
dbc a

(2) G = (); CCl3

NH2

CCl3

NH2

NH2

NH2

(Aniline > p > m > o).

CCl3

CCl3
(3) G = ( > +m); Cl

NH2

NH2

NH2

Cl

NH2

aniline > p > m > o

Cl

Ex.

Cl

Only () decides the order.

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

Page # 7

NH2

NH2

CH3

NH2

NH2

+m

CH3

O effect,
+
HC

CH3
w
+
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 :

Hybridisation of N : sp3 > sp2 > sp

(a)

(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
H2N C = NH

R
x
y
NH2 C = NH

(1) sp
sp
2
(2) lone pair in sp 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

NH2
:NH
Heterocyclic Compounds (Nitrogenous base) :

+
NH2 = C NH2
NH2

+
:NH2 C = NH2
NH2

H
NH2 C NH2 :NH2 C NH2

Page # 8

H
N:

S.F.:- H
H

6 e
Aromatic
Stronger base

A.O. Diagram:-

(1) Pyridine (C5H5N:)

sp hybrid orbital
(lone pair)
localised

(2) Pyrrole (C4H5N:):-

:N H (sp )
2

A.O. Diagram:-

1.

NH

Complete delocalisation of e

>

N
H
H

:NH2
H

Aromatic

N
H
(c)
sp3/2 ()

(a)
(b)
sp3/2
sp2 localised

NH2 C NH2 ; R C NH2

:NH
(1)

:NH
(2)
2
sp

N
H
(d)
sp2

a>c>b>d

N
H

NH3

3
N sp (4e )
H
H
Non-aromatic

+
N
H
Aromatic

3.

(lp. in 2p A.O.)

>

2.

S.F.:-

RCR ;
NH
(3)
2
sp

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

:NH2(x)

4.

(y)

N(z)
H

Basicity order:- y > x > z

Ex:-

6e
Aromatic
Very weak base
Non aromatic after it donates lone pair

Page # 9

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
, CH3

sp3
sp2

H2 C =

sp

HC

, CH2 = CH

Structure of following carbanions

(a)

(b)

(e)

(f)

(c)

(d) CH2 = CH

[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.

Page # 10

Example of stability order :

(A)

CH C ..
1

(Stability order) : 1 > 2 > 3

..
CH2

..
CH C

(B)
1

..

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

..

..

CH3

..

(C)
2
..

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

..
CH3

..
3

..

..

(D)

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

Br

NO2

Cl

(E)

(Stability order) : 1 > 2 > 3

(F)

..
CCl3
1

..
CF3
2

(G)

..
Cl CH2 CH2
1

..
F CH2 CH2 CH2
2

..
CH3 CH
CH3
3

..
CH3 CH2 CH2
4

(Stability order) : 1 > 2

..
CH2 NO 2
1

CH C ..
3

..
CH

(Stability order) :

CHO

NO2

2
..
CH

+
SMe2

..
CH

+
NMe3

4>2>6>3>5>1

..
CH

(I)

..
CH

..
CH
2

(Stability order) : 1 > 2 > 3

(H)

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

CN

6
Page # 11

(J)

..
CH3 CH CH2CH3
b
..
(CH 3)3C
d

..
CH3 CH2 CH2 CH2
a
..
(CH 3)2C CH 2CH 3
c

(k)

O
..
CH2 C CH3
a

O
..
CH2 C H
b

a>b>d>c

O
..
..
CH2 C OCH
.. 3
c

e>b>a>c>d

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

(c) R

(Lot of carbanion like character in 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
|
CH3

(dereasing order of decarboxylation)

Page # 12

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

NO

(i)

(ii)

(iii)

(iv)

(3) Keto-enol tautomerism

General Expression:-

C = C OH
enol form

CC=O
H
Keto form

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

Draw enol forms of following carbonyl compounds

CH3 C = CH CH3 and CH2 = C CH2 CH3

OH
OH

(iii) CH3 C CH2 CH3

CH3
CH2 = C OH

CH3
(ii) CH3 C = O

CH2 = CH OH

(i) CH3 CH = O

Ex.-1

Page # 13

(4) Comparison of stability of Keto-enol tautomers

Keto form

Enol form

|
CC
| ||
H O

|
C C
|
OH

The

group is more resonance stabilized

An alkene is less resonance stabilized

(Positive charge at C and negative

charge at O atoms)

(Positive charge at O and negative

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 stabilization of enol form
H3C C CH2 C CH3

O
keto form (

H3C C = CH C CH3
OH
O
enol form ( 75%)

O
25%)

Compare % enol contents

Ex. 1

Keto form

Enol form

I : CH3CH = O

CH2 = CH OH

II : CH3 CH2 CH = O

Sol.

Ex. 2

Ex. 3

III :
III > II > I

CH3 C CH3 < CH3 CH2 C CH3

||
||
O
O

I :

II :

III :

Sol.

CH3 CH = CH OH

CH3 C CH3
||
O

..... (% enol)

CH2 C CH3
|
OH

CH3 C C CH3
|| ||
O O

CH2 C C CH3
| ||
OH O

CH3 C CH2 C CH3

||
||
O
O

III > > II > I

76%
1.2%
0.01%

CH3
|
< CH3 CH C CH3
||
O

CH3 C CH C CH3
|
||
OH
O

(enol content)
Page # 14

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

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)

Keto form > enol form

(iii) OH

(ii) C = C

Keto-enol tautomesion in phenols and its derivatives

1.

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

2.

In catechol

Page # 15

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

(A*) CH3 CH CHO
|
D

Q.2

Me
|
Ph
C

C CH3
(C)
| ||
Et O

(D) Ph CH CH2 C CH3

|
||
D
O

O
||
(C*) Ph C CD 3

O
||
(D*) Me 3 C C CH3

(C*)

(D)

Which of the following will show tautomerism

(A) Me3C CHO

Q.3

CH3
|

C CH3
Ph
C
(B*)
| ||
H O

(B*) Me2CD CHO

Which of the following will show tautomerism

(A*)

(B)

Page # 16

Q.4

Write the tautomer of

OH

OH

OH

OH

HO

OH

HO

OH

OH
(A)

(B)

(C)
OH

Q.5
Sol.

Q.6
Sol.

Q.7

(D)

HO

OH

(E)

OH

X is the smallest dicarbonyl compound which has significant enol content. Predict S.F. of X.
X = H C CH2 C H
||
||
O
O

A (C6H10O2) is an optically active dicarbonyl compound which significantly exists in optically inactive enol
form. Identify A.
A = CH3 C CH C H
|| |
||
O C 2H 5 O

or

CH3 CH2 C CH C H
|| |
||
O CH3 O

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
|
X = OHC CH CHO

Q.8

Ph
|
Y = HO HC C CH O

Which of the following pairs are tautomers.

(A*)

&

(B*)

and

Page # 17

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

Page # 18

Practice problem :

+
CH2

+
CH2

+
CH2

OMe
Stability order : 1 > 3 > 2

(A)

OMe

OMe
2

+
CH2

+
CH2

+
CH2

(B)

CH
3

Stability order : 3 > 1 > 2

CH3

CH3
1

OMe

(C)

Stability order : 5 > 1 > 2 > 4 > 3

CN

CH3

+
CH2

Stability order :
6 5 1 2 4 3

CH3

+
CH2

+
CH2

(D)

CH
3

CH3

CH3
3

+
CH2

+
CH2

+
CH2

(E)

CH2D

NHCOCH3

OMe

CH3 CH CH3 CH3 CH NH2

2
3

CH3
1

..
CH3 C O
..
4

Stability order : 3 > 4 > 2 > 1

(G)

+
..
.O.
2

..
.O.
1

+ CH3
C
CH 3

+
CH
1

C+

+
(H)

Stability order : 1 > 3 > 2

.. +
O
..
3

(F)

+
2

Stability order : 3 > 1 > 2

Stability order : 3 > 2 > 1

3
Page # 19

+
+
CH3 CH2 CH2 CH2 CH 3 CH CH 2 CH 3
a
b

+
(CH3)2C CHCH3
CH3
c

+
(CH3)3C
d

+
Draw all isomeric form of C5H11 carbocation, which one is the most stable.
+
CCCCC
(b)

+
CCCCC
(c)

C
+
CCCC
(e)

C
CCCC
+ (f)

C
C C C+
C
(g)

C
+
CCCC
(d)

+
CCCCC
(a)

(J)

Stability order : d > c > b > a

(I)

+
(f) C5H11 is most stable.
(K)

+
..
CH3 CH2 NH CH2 CH CH3
(b)

..
+
CH3 CH2 NH CH CH2 CH3
(a)

CH3 CH2 .NH

. CH2 CH2 CH2
+
(c)
+

Stability order : a > b > c

(L)

Stability order : d > c > b > a

b

+
CH2

+
CH2

+
CH2

+
CH2

(M)

Stability order : a > d > c > b

a

+
+

(N)

Stability order : b > a > c

+
(a)

(O)

(b)

>

(c)

>

CH3 CH CH3 > CH3 CH CH2Cl > CH3 CH CH2NO 2

(P)

Page # 20

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

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Ring contraction : -

Complete octet :

CH3
+ ..
(i) CH3 C C = O
..

CH3
CH3
(IV) CH 3 CH CH N CH 3
+

(III)

CH3

..
(lI) CH3 CH2 O
. . CH CH CH3
+
CH3

+
..
(VI) CH3 CH CH Cl
..

..

+
..
(V) CH 3 CH 2 CH = O
..

CH3

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

(b)

CH3

(e)

(f)

+
(i) CH2 CH CH CH3
CH3

(j)

(c) CH3 C CH CH3

+
CH3

(d)

CH3
CH3
+

+
CH
2

(g)

(h)

+
CH2

CH3

+
(a) CH3 CH2 CH2

CH3

+
CH

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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

CH 3 CH CH 2 CH 2 CH3 C CH2 CH3

CH3
CH3

CH3 CH CH CH3
CH3

1.

2.

c>a>b

d>b>a>c>e
a

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CH2 = CH

c>b>d>a

CH3

3.

c>d>a>b

4.

CH3 CH2 CH2 CH2

5.

d
CH 3 CH CH 2 CH 3

6.

Match the following :

Ans.

1 a, q, y

CH3
(CH3)2CCHCH3

b
(CH3)3C

d>c>b>a

2 a, q, x

3 b, p, z

Page # 24