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Moses Gomberg
the founder of radical
chemistry (1866-1947)
Free radicals
Radicals are atoms, molecules, or ions with
reactive.
formed.
In normal circumstances, the body provides
endogenous substances (free-radical scavengers) to
combine with the free radicals. If these scavengers
arent available or if overproduction of free radicals, the
radicals donate to or steal an electron from another
molecule, leading to a chain reaction that triggers
formation of more free radicals. The chain reaction
results in damage to the cell membrane and
deoxyribonucleic acid (DNA), altered enzyme reactions,
and damage to collagen and connective tissues.
regulate
many
biological
processes
including controlling vascular tone.
Cl
water
H
0 electrons
Cl
8 electrons in outer shell
H 2O
H 3O
Cl
Important points
Free radical reactions occur widely in gaseous
Stable radicals
Persistent radicals
Persistent radical compounds are those whose
Diradicals
Diradicals are molecules containing two radical
highly reactive
Their stability will be in the order:
R3C* > R2CH * > RCH2* > CH3*
The sequence shows that stability increases due
to increase in hyper-conjugation and decrease due
to relief of steric strain as the series traversed
Radical forms having allylic or benzylic are more
stable through delocalization of pi electrons e.g
CH2=CH-*CH2
*CH2-CH=CH2
Methods of preparation
Photochemical reactions
Thermal fission
Oxidation reduction
reactions
HEAT
Pb
4 CH3
CH3
Mg
Ph
Mg Br
Ph MgBr
Oxidation reduction
(Electron
Transfer Processes)
SET
R
M +n
M +n+1
Fentons reaction
Tertiary butylhydroperoxide
1- Thermodynamic stability
2-Kinetic stability
Q?
In which case do you think the product is
more stable?
AB-
Answer
The radicals formed from a bond which needs
Conjugated system
It is a system of connected p-orbitals with
1. Conjugation or Mesomerism
This is the primary reason for the existence of stable
radicals
allylic radical
benzylic radical
CH2
CH2
CH2
CH2
Hybridization
Geometry of alkyl radical is considered between
Hybridisation
Radical is more stable than Radical.
As the - character of a radical increases, its thermodynamic stabilisation increases
Hyper-conjugation
Unstable charges on molecules are dispersed
3. Hyperconjugation
H
H
H
C
H
C
thermodynamic stability
H
H
C
H
CH3
C
>
CH3
C
H
H
C
>
C
H
CH3
H
C
>
9 Hyperconjugatable H s
6 Hyperconjugatable H s
3 Hyperconjugatable H s
C
H
b/ Kinetic Stability
This is generally due to steric effects
Steric effects arise from the fact that each atom within a molecule
occupies a certain amount of space. If atoms are brought too close
together, there is an associated cost in energy due to overlapping
electron clouds, and this may affect the molecule's preferred shape
and reactivity
H
*C
H
Methods of detection
Lead-mirror- is deposited on the inside wall of a
1- Addition
2- Displacement
3- Rearrangement
1- Addition
Cl2
hv
*CCl2-CCl3
Cl2
CCl3-CCl3
2-Displacement
Cl2
hv
R-H
+ Cl*
*R + HCl
Cl2
R-Cl
3-Rearrangement
-CO
Ph2MeC - CH2C* =O
Ph2MeC - *CH2
PhMeC* - CH2Ph