Organic Free Radical

Dr. Bijan Mohon Chaki

Associate Professor
Department of Chemistry
Begum Rokeya University, Rangpur
 3. Organic Free Radical:

Definitions, generation and detection of free radicals. Long and short lived free
radicals, configuration of free radicals, types of free radical reactions, examples
& mechanism. Autoxidation, radical initiators and radical scavengers.

 Book References:
1. Advanced Organic Chemistry (5th Ed., Part A)- Francis A. Carey and
Richard J Sundberg.

2. Organic Chemistry- I. L. Finar-vol 1

 Free Radical
 A radical is a reactive intermediate with a single unpaired electron, formed
by homolysis of a covalent bond. These species are generally short lived,
extremely short lived in solution, but can have longerlife time in crystal
lattices of other molecules. Examples of some free radicals are: H•, Cl•,
HO•, O2•, O2•-, H3C•
 Free radical are the atoms or group of atoms having an odd or single
unpaired electron.
 A radical contains an atom that does not have an octet of electrons, making
it reactive and unstable.

 Radical processes involve single electrons, so half-headed arrows are used

to show the movement of electrons. One half-headed arrow is used for
each electron.
 Free Radical
 Carbon radicals are classified as primary (1°), secondary (2°), or tertiary (3°) by
the number of R groups bonded to the carbon with the unpaired electron.
 A carbon radical is sp2 hybridized and trigonal planar, like sp2 hybridized
carbocations.
 The unhybridized p orbital contains the unpaired electron and extends above and
below the trigonal planar carbon.

 Radical processes involve single electrons, so half-headed arrows are used to

show the movement of electrons. One half-headed arrow is used for each electron.
 Features of Free Radicals

A free radical has the following characteristic feature:

 Free radicals are electron deficient species.
 They are usually uncharged.
 They contain odd number of electrons.
 The alkyl radical (·CR3) has seven electron around the carbon bearing radical character.
 In methyl radical or other alkyl radicals, the radical centre is trivalent and trigonally
hybridized.
 The carbon is sp2 hybridized.
 It has planar structure.

 The unpaired electron occupies a 2p atomic orbital of carbon. This singly occupied
orbital is often referred as singly occupied molecular orbital (SOMO).
 Features of Free Radicals

 As stated by Pauli, that the two electrons occupying same orbital must have opposite spins
and thus magnetic moment of such species becomes zero. However, free radicals have a net
magnetic moment (paramagnetic) due to the presence of one or more unpaired electrons and
thus can be detected by ESR.
 These species are highly reactive due to the presence of unpaired electron which gets paired
easily with another electron to fill their outer shell.
 The alkyl radical have shallow pyramid geometry i.e., between sp 2 and sp3 hybridization.
 But the energy required to invert the pyramid is very small. Practically speaking alkyl
radicals are considered sp2 hybridized.
 Stability of Free Radical
 Since bond dissociation energies give us an idea of the ease with which radicals can
form, they can also give us an idea of the stability of those radicals once they have
formed. The lower the bond dissociation energy, the higher will be the stability.
Alkyl radicals are stabilized by adjacent lone-pair-bearing heteroatoms and by the π
bonds. The various factors responsible for the stability of free radicals are:
1. Inductive effect
2. Hyperconjugative effect
3. Resonance effect

1. Inductive effect
 Greater the number of alkyl groups attached to the free radical carbon centre more
will be the stability of the radical. This is due to the electron donating inductive
effect of the alkyl groups which decrease the electron deficiency of the radical.
 The bond dissociation energies, of the C-H bonds for the formation of a free radical
of methane, ethane, and other alkanes, clearly shows that radical centres are
stabilized by the replacement of one, two, or three of the hydrogens of the methyl
radical by alkyl groups.
 For example the bond dissociation energy of ethane (98 kcal/mol) is less than
methane (105 KCal/mol).
 Thus, the order of stability is 3o>2o>1o
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 Stability of Free Radical
2. Hyperconjugative effect
 The stability order of alkyl free radicals is tertiary >secondary > primary > CH 3.
This stability order can be explained by hyperconjugation.
 The odd electron in the alkyl radical is delocalized onto the β-hydrogens, through
hyperconjugation, which confers stability to the radical. Thus, tert-butyl radical is
more stable than sec-butyl radical which in turn more stable than n-butyl radical.
 As tert-butyl radical has three methyl groups or nine beta hydrogens which give it
nine hyperconjugative structures. sec-butyl radical has six and n-butyl radical has
three hyperconjugative structures.
 Greater the number of hyperconjugative structures more will be the stability of the
radical.
 Stability of Free Radical
3. Resonance Effect
 In the free radicals where the carbon centre is in conjugation to a double bond, the
resonance effect leads to stabilisation of these molecules. The stabilising effects of
vinyl groups (in allyl radicals) and phenyl groups (in benzyl radicals) are very
significant and can be satisfactorily explained by resonance.
 Allyl and benzyl free radicals are more stable than alkyl free radicals but still have
only a transient existence under ordinary conditions.

Resonance in Allyl free radicals

Resonance in Benzyl free radicals

 Stable and Persistent Free Radical
 Most organic free radicals have very short lifetimes but certain structural features
enhance stability.
 Radical without special stabilization rapidly dimerize or disproportionate

 The usual disproportionate process for alkyl radicals involves transfer of a H-atom
from carbon beta to the radical site leading to formation of alkane and alkene.
 Radical also rapidly abstract H-atoms from many types of solvent, and most
radicals are highly reactive toward oxygen.

 Stable and Persistent Free Radical
 A few radicals are infinitely stable under ordinary conditions due to extensive
delocalization of the unpaired electron into aromatic rings.
 These highly stable radicals show no tendency to dimerization or
disproportionation
 Some examples of stable free radicals are shown below where the shape and the
steric hindrance prevents dimerization. The stability may also be increased due to
resonance stabilisation or delocalisation.(1,2 and 4)
 Stable and Persistent Free Radical
 The term inert free radical is known which are unreactive under ordinary
conditions and is thermally stable even at 300 °C (example: 4)
 Stable and Persistent Free Radical
 Persistent free radicals have a long lifetime and they are resistant to dimerization,
disproportionation and other routes to self-annihilation, though they may not be
very stable
 The triphenylmethyl radical was the first radical to be observed by Gomberg in
1900, although it took 30 more years to know what he had made.It can be
generated by the treatment of triphenylmethyl chloride (trityl chloride) with silver.
The presence of the trityl radical in solution can be detected by electron spin
resonance

 Other examples are 2,2,6,6-tetramethylpiperidinoxyl (TEMPO) radical,

phenalenyl radical, 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical

TEMPO Phenylalenyl DPPH

 Detection of Free Radicals
 Species with an unpaired electron are said to be paramagnetic
 The most useful method for detecting and characterizing unstable free radicals is
electron paramagnetic resonance (EPR) spectroscopy or Electron Spin Resonance
(ESR) spectroscopy.
 EPR spectroscopy detects the transition of an electron between the energy levels
associated with the two possible orientations of electron spin in a magnetic field.
 An EPR spectrometer records the absorption of energy when an electron is excited
from the lower to the higher state.
 The energy separation is very small on an absolute scale and corresponds to the
energy of microwaves.
 EPR spectroscopy is a highly specific tool for detecting radical species because
only molecules with unpaired electron give rise to EPR spectra.
 This method can be used to detect the presence of radicals and to determine their
concentration. Furthermore, information concerning the electron distribution and
hence the structure of free radicals can be obtained from the splitting pattern of the
ESR spectrum.
 Detection of Free Radicals
 Electrons have a magnetic moment. When electrons are paired they have opposite spins
which leads to cancelling of their magnetic moments. Such species with paired electron
cannot be detected by ESR. But, species with unpaired electrons have a net magnetic
moment and can be detected by ESR.
 Certain nuclei have a magnetic moment, such as 1H, 13C, 14N, 19F, and 31P. Interaction of the
electron with one or more of these nuclei splits the signal arising from the unpaired
electron. The number of lines is given by (2nI+1), where I is the nuclear spin quantum
number and n is the number of equivalent interacting nuclei.
 Hyperfine splitting of peaks is observed if the carbon bearing radical is attached to proton,
due to the interaction of the equivalent hydrogen atoms present with the unpaired electron.
. .
For example, the signal for CH radical splits into a doublet. The CH3 radical has four
.
signals in its spectrum. Benzene radical ( C6H6) has seven peaks in ESR spectrum.
 Detection of Free Radicals
 Failure to observe ESR spectrum does not prove that radicals are not involved, since the
concentration may be too low for direct observation.

 In such cases, the spin trapping technique can be used. In this technique, a compound is
added that is able to combine with the very reactive radicals to produce more persistent
radicals that can be observed by ESR.

 The most important spin trapping compounds are nitroso compounds, which react with
radicals to give fairly stable nitroxide radicals.
 Sources of Free Radicals

 A free radical is formed during a homolytic bond cleavage such that each generated
fragment has one electron with it.
Cl Cl Cl + Cl

 The various ways by which free radicals may be generated are:

 Thermal cleavage
 Photochemical cleavage
 Decomposition reaction

 Thermal cleavage

 Free radicals may be generated by thermal cleavage. In the gaseous phase some molecules
break down at high temperature. When the molecule contains bonds with 20 to 40 kcal/mol
of energy, cleavage can be caused in the liquid phase. For example, the thermal cleavage of
peroxides compounds yields free radical. 80 C
C2H5OOC2H5 2C2H5O

O O O
80-100 C
CH3COOCCH3 2CH3CO 2CH3 + 2CO2
 Sources of Free Radicals

 Peroxide are the common source of radical intermediates. An advantage of the generation of
radicals from peroxide is that reaction generally occurs at lower temperature as O-O bond is
weak ( (30 Kcal/mol) and the activation energy for the radical formation is low.

 Perestars are also source of free radicals.free radicals may be generated are:

 Photochemical cleavage

 The energy of light of 600 to 300 nm is 48 to 96 kcal/mol, which is of the order of

magnitude of covalent bond energies. Certain molecules undergo homolytic fission in the
presence of light of that particular wavelength. For example, the photochemical cleavage of
chlorine molecule results into the formation of chlorine free radicals.
 Sources of Free Radicals

 Alkylhydroperoxide give alkoxy radical in conjunction with metal salt.

 Another quite general source of free radicals are decomposition of azo compounds. The
products are molecular nitrogen and the radicals derived from substituents.

AIBN: 2,2’-azobisisobutyronitrile which is frequently used as radical initiator in radical

polymerization.
 Sources of Free Radicals

 Decomposition reaction
 At times a radical molecule may undergo decomposition to form another free radical. For
example, decomposition of benzoxy radical gives phenyl radical and carbondioxide.
 Reactions of Free Radicals

 Radicals undergo two main types of reactions: they react with σ-bonds, and they add to π-
bonds, in both cases achieving an octet of electrons.
 [1] Reaction of a Radical X• with a C–H Bond
A radical X• abstracts a hydrogen atom from a C – H r bond to form H – X and a carbon
radical.

[2] Reaction of a Radical X• with a C––C

A radical X• also adds to the o bond of a carbon–carbon double bond.
 Selective Bromination at Allylic C–H Bonds

Initiation Propagation
Step [1] Cleavage of the N – Br bond Steps [2] and [3] One radical reacts and a new
forms two radicals. radical is formed in each step
 Treatment of cyclohexene with Br2 (in an organic solvent like CCl4) leads to addition via
ionic intermediates.
 Treatment of cyclohexene with NBS (∆, hν or ROOR) leads to allylic substitution, via
radical intermediates.
Product Mixtures in Allylic Halogenation
 Halogenation at an allylic carbon often results in a mixture of products. For example,
bromination of 1-butene under radical conditions forms a mixture of 3-bromo-1-butene
and 1-bromo-2-butene.

 A mixture is obtained because the reaction proceeds by way of a resonance-stabilized

radical. Abstraction of an allylic hydrogen from 1-butene with a Br• radical (from NBS)
forms an allylic radical for which two different Lewis structures can be drawn.

 Whenever two different resonance structures can be drawn for an allylic radical, two
different allylic halides are formed by radical substitution
Allylic Bromination:
Alkenes can be brominated in the allylic position using NBS, the reaction is known as
Wohl-Ziegler reaction. A mechanism for allylic bromination by NBS is shown below. The
Br2 in this process is formed in a side reaction between HBr and NBS. The function of NBS
is to provide a low, constant concentration of bromine and to use up the HBr formed during
the propagation step.
O O Br
Br
H H
N Br N Br + HBr

O O
Br

Br +
 Reactions of Free Radicals
 Abstraction of another atom or group
For example, halogenation of alkanes proceeds via free radical mechanism. The
chlorination of methane is shown below:
It involves three main steps (i) Initiation (ii) Propagation and (ii) Termination.
 (i) Initiation: In this step, free radicals required for the reaction are generated in situ by
irradiation or heating of the reagent or by carrying out the reaction in the presence of an
initiation like peroxides. The process is always endothermic. The first step is initiation
which involves bond.

/hv
Cl Cl 2Cl
Cl
H3C H CH3 + H Cl
(ii) Chain propagation: Second step is chain propagation. In this step the highly reactive chlorine
radicals with unpaired electron reacts further.

CH3
Cl Cl H3C Cl + Cl
 Reactions of Free Radicals

(iii) Chain termination: The final step is chain termination in which two reactive radicals
combine together.

Home Work: Addition of HX to alkene: Mechanism, How Markovnikov Rule (Ionic

Mechanism) is followed and Kharash Peroxide Effect (Free radical addition)
Radical Reduction:
In a radical reduction reaction, hydrogen is added to a π bond.
For example, the radical reduction of alkyne to alkene with sodium-ammonia is a trans
addition of hydrogen to an alkyne.
Another example of radical reduction is the Birch reduction, as shown here benzene is
reduced to 1,4-Cyclohexadiene in presence of sodium-EtOH in ammonia.

Another example of radical reduction is the Birch reduction, as shown here benzene is
reduced to 1,4-Cyclohexadiene in presence of sodium-EtOH in ammonia.

Mechanism of Birch reduction: From the mechanism it is clear that sodium radical is
involved in the reduction, which also forms some other carbon radicals as intermediate in
the whole process.
Mechanism of Birch reduction: From the mechanism it is clear that sodium radical is
involved in the reduction, which also forms some other carbon radicals as intermediate in
the whole process.
Free-Radical Polymerization of Alkenes
Polymerisation may also occur via generation of free radicals. The most important free
radical chain reaction is the free radical polymerization of ethylene to polyethylene.
(t-BuO)2 H2 H2
n H2C CH2 C C
n

Industrially (t-BuO)2 is used as a initiator. The t-BuO● ·radical adds to ethylene to give the
beginning of a polymer chain.

Initiation: t-Bu-O-O-Bu-t 2 t-Bu-O

t-BuO H H
t-Bu-O H 2C CH2 C C
H H H P H

Propagation: The propagation part has only one step, the addition of an alkyl radical at the
end of a growing polymer to ethylene to give a new alkyl radical at the end of a longer
polymer.
 H H

H2C CH2
P H P H

H H

n H2C CH2 Pm
P H P n H

Termination:
The termination steps are the usual radical–radical coupling (combination) and
disproportionation and chain transfer reactions.
P m + Pn Pm Pn (Coupling)

Pm + Pn Pm + Pn (Disproportionation)

Pm + H-B Pm H + B (Proton transfer)

Autooxidation
The spontaneous oxidation of organic molecules in the presence of oxygen is called
autooxidation.
Ether solvents undergo autooxidation so readily that if stored for a long time oxidize to form
some amount of hydroperoxide products. Hydroperoxide products are unstable and
decompose violently when heated.

Mechanism: The mechanism for the

autooxidation involves abstraction a
hydrogen from the carbon bearing
the ether oxygen by an oxygen
molecule.It leads to formation of a
radical and a hydroperoxide radical.
These two radicals then react with
each other to form the ether
hydroperoxide.
 Autooxidation
Similarly furan also undergoes autooxidation to form explosive peroxide

Synthetic antioxidants such as BHT are added to packaged and prepared food to prevent
oxidation and spoilage. Vitamin E and BHT are radical inhibitors soOH
they terminate radical
mechanism by reacting with radical. (H C) C C(CH )
3 3 3 3

The main causes of food spoilage are

microorganisms and autooxidation.
Antioxidants such as Butylated Hydroxy
Anisole (BHA) and Butylated Hydroxy CH3
Toluene (BHT) are added to the food or BHT
packaging materials, to prevent their (butylated hydroxy toluene)
autooxidation
Summary
Summary
 Free radical have unpaired electron, have a planar trigonal sp2 geometry.

 N-Bromosuccinimide is an excellent source of bromine in low concentrations for allylic

bromination.

 Benzylic and allylic radicals readily form because both are resonance-stabilized.

 The halogenation of an alkane is a radical chain reaction. The anti-Markovnikov addition

of HBr proceeds via a radical intermediate.