1

( I) (II)

10

11

12

13

14

15

16

17

18

19

(C)

20

21

22

Ex:

23

24

6.

25

26

27

28

In the simplest cases an atom in the compound has only seven electrons in its valence shell and
the unpaired electron is localised on either a carbon atom or on a heteroatom. Note the
characteristic 'yl' termination of the systematic names for free radicals and the representation of
the unpaired electron by a dot at the appropriate atom:
Methane
CH4
CH3

CH3CH2CH3
(CH3)3CH
(CH3)3C
CH3

n-Propane
t-Butane

OH t-Butanol
SH Methanethiol

CH3CH2CH2

Methyl
n-Propyl
t-Butyl

(CH3)3C
(CH3)3C

t-Butoxyl

CH3

Methanethiy
l

Optimum geometry - planar - sp2 hybridised:

The norbornyl radical has considerably
increased reactivity because ring-strain
prevents the bridge-head carbon attaining
the optimum planar geometry:

29

Preparation of Free Radicals:

1. Homolytic cleavage of weak single covalent bonds.

R E E R

or h

R E + E R

E = N, O, S, Halogen, etc.
Note the use of 'fish-hook' single-headed curved arrows, i.e.
a single electron.

to indicate the movement of

Thermal cleavage:
N-N, O-O, S-S, Cl-Cl, Br-Br, C-N, N-Cl, O-Cl, O-Br
ca. 130

O O

Di-t-Butyl peroxide
Half-life at 150 ca. 1 h

t-Butoxyl radical

Ph

O
2 Ph

O
Benzoyl radical

O O

Ph

60-100

O
O
Di-Benzoyl peroxide
Half-life at 100 ca. 30 min

NC

N N

CN

60-100

Azobis(isobutyronitrile)
'AIBN'
Half-life at 100 ca. 5 min

2 NC

30

Phenyl
radical

+ N N

2-Cyanoprop-2-yl
radical

Photolytic cleavage
compounds with low-energy electronic absorptions
only:

Ph + CO2

Cl-Cl
Ph

Ph

O O

CH3

O
O
C

h
CH3

R O N O

R O Cl

2 Cl
O

2 Ph

O
C

CH3

Ph + CO2

CH3

R O

NO

R O

Cl

2. Redox reactions of non-radical precursors:

Reduction.

_
+ Na

CH3

O
C

CH3

Na

Na+

Naphthalide
radical anion

_
O
Ketyl radical
C
Na+
anion
CH3
CH3

Oxidation:

Ar3N:

AgPF6

0
[Ar3N] + [PF6]- + Ag
Amminium
radical cation

31

Stability of Free Radicals:

allylic benzylic > 3 alkyl > 2 alkyl > 1 alkyl

1.Substitution effect - radical centres are electron-deficient, hence stabilised by attached

electron releasing alkyl groups and electron with drawing
2.Resonance effect:

The combination of electronic and steric effects can result in very stable - and, in suitable
circumstances, even isolable - free radicals:

32

2,4,6-Tri-t-butylphenoxyl

Galvinoxyl

Detection of Free Radicals:

1. Electron Spin Resonance (ESR) Spectroscopy.
The degeneracy of spin of an unpaired electron is lifted in a strong magnetic field. E
corresponds to microwave radiation. Hyperfine splitting due to electron-proton spin coupling
aids structural interpretation.
Quartet resonance

CH3

Septet resonance

etc. Octet resonance

2. Matrix Isolation:
Free radicals generated and trapped in a radiation-transparent solid argon matrix at very low
temperature may be studied spectroscopically:

33

CH3
O

O O

CH3
O

h
Solid Argon

H3C

5-10 K

Reaction of Free Radicals:

34

O
O

+ CH3

+ CO2

35

Despite what we might expect, simple free radicals do not normally undergo rearrangement:
H
+
CH3 C CH
2
CH3
1

Very rapid
-

H migration

CH3
CH3

CH2
H migration

CH3
CH3

2e in migration
system

H
C

+
C

CH2H

CH3 C CH H
2
CH3
3

3e in migration
system

The transition states for both rearrangements are very similar:

H
CH3
CH3

CH2

= + or

Consider the orbitals involved in the transition state: H 1s and 2 C 2p.

36

1s

2p

2p

Combination of the H 1s and 2 C 2p atomic orbitals gives three molecular orbitals:

(A)

(B)

(C)

(A) is bonding for the hydrogen atom and both carbon atoms.
(B) is bonding for the two C atoms but antibonding for the C2-H interaction.
(C) is antibonding for the two C atoms. In addition there is no net interaction between the
hydrogen atom and the two carbon atoms.
(A) is the lowest energy orbital while (B) and (C) are approximately equivalent in energy.
(B)

(C)
(A)

Carbocation - 2e
Favourable T.S.
Rapid rearrangement

(B)

(C)
(A)

Radical - 3e
Unfavourable T.S.
No rearrangement

-Unsaturated free radicals will undergo rearrangement with migration of the unsaturated
group:

37

 HC
C

CH3
CH3

CH2

CH2
CH

CH2

CH3 C
CH3

CH2

CH3
CH3

CH2
CH
CH2

Stable intermediate

4. Dimerization:

R R

Leads to non-radical products - termination steps in radical chain-reactions.

5. Disproportionation - one radical is oxidised by another:

2 CH3CH2CH2

H 3C

H2
C

CH2

+ H

CH3CH2CH3 + CH3CH=CH2

CH

CH2
H3C

CH3

H2
C

CH3

+
H

CH2
CH3

Hydrogen abstraction from one n-propyl radical by the other results in the radical accepting
hydrogen being reduced to an alkane. The radical losing hydrogen is simultaneously oxidised to
an alkene.
This leads to non-radical products - i.e. is a termination step in radical chain-reactions.
6. Fragmentation:

38

O
Ar

Ar

CO2

4. Dimerization:

R R

Leads to non-radical products - termination steps in radical chain-reactions.

FREE RADICALS IN ORGANIC SYNTHESIS

Free Radical Substitution of Hydrogen by Other Atoms.
(a) Photochemical halogenation of saturated hydrocarbons

Cl2

Initiation

2 Cl

CH3CH2CH3 + Cl

CH3CHCH3 + HCl

CH3CHCH3 + Cl2

CH3CHClCH 3 + Cl

CH3CHCH3 + Cl

Propagation by
chain transfer
Termination

(Fig.

4.1a)

(Fig.4.1c)

39

(Fig.4.1b)

40

41

42

43

Reaction of Carbenes:

44

o Addition Reaction

45

46

47

o Insertion Reaction

48

Exp:

Exp:

49

o Dimerization reaction

o Rearrangement Reaction

50

o Abstraction Reaction

51

52

53

o Rearrangement:

54

Benzyne

55

56

Ex:

57

58

3.
59

60

61

62

63