Ministry of Higher Education

and Scientific Research

University of Babylon
College of Science

Free Radicals

Wisam Abdul Jaleel Jawad

Faculty of Science, Department of Chemistry

PhD Student

0202-0202
 Free Radicals
Atoms are surrounded by electrons that orbit the atom in layers
called shells. Each shell needs to be filled by a set number of
electrons. When a shell is full; electrons begin filling the next
shell.
If an atom has an outer shell that is not full, it may bond with
another atom, using the electrons to complete its outer shell.
These types of atoms are known as free radicals.
Atoms with a full outer shell are stable, but free radicals are
unstable and in an effort to make up the number of electrons in
their outer shell, they react quickly with other substances.
Causes
Free radical theories of aging and disease may help explain why
some people age more slowly than others.
Although free radicals are produced naturally in the body,
lifestyle factors can accelerate their production, those include:

 Exposure to toxic chemicals, such as pesticides and air

pollution.
 Smoking .
 Alchhol .
 Fried foods.
Free radicals may be defined as the species that contain one or
more unpaired electrons. They are generally less stable and react
in fraction of seconds with another species.
Formation of free radicals:
Thermal Generation : two types of compounds dissociate to give
free-radicals at moderate temperature compounds that have an
intrinsically weak bond such as dialkyl peroixides (DO-O= 155
KJ mol-1), and (ii) compounds that, on fragmentation, form
strongly bonded products, such as AIBN which releases N2 .

Photochemical Generation
Light can bring the fragmentation of a compound if the
wavelength of the light is correspond both to an energy greater
than that of the bond to be cleaved, and to an electronic
excitation of the molecule concerned. This procedure is suitable
for the formation of alkoxy radicals from alkyl nitrite or
hypochlorites.

Redox Generation
Covalent bonds may be broken by electron transfer process
either by accepting an electron from a donor or donating an
electron to an acceptor.
Reactions of Free Radicals
Abstraction
Free radicals proceed reactions with saturated organic molecules
by abstracting an atom from carbon. The selectivity of the free
radicals towards C-H bonds of different types is determined by
bond dissociation energy and polar effects. The rate of the
abstraction process increases as bond dissociation energy
decreases. For examples:
Allylic and benzylic C-H bonds are weaker than those of
saturated systems and exhibit greater reactivity and selectivity
with free radicals.

Addition
Free radicals undergo addition to carbon-carbon double bonds.
The reaction is generally selective. For example, addition to
CH2=CHX takes place exclusively at the methyl group,
irrespective of the nature of X.
Alkynes also exhibit similar reactivity with free radicals.
Rearrangement
Free radicals are known to rearrange in certain circumstances.
For example, the addition of free radical leads to rearrangement
due to relief of strain in the cyclic system.

Substitution in Saturated Carbons

Energetics
Radical catalyzed chlorination and bromination can be
performed both in gas and liquid phases. The energetic
comparison of chlorination, bromination and iodination of
methane follows:
Formation of Carbon-Carbon Bonds
Addition to Carbon-Carbon Double bonds

The following are some examples for radical addition to carbon-

carbon double bond with a variety of types of starting material.
The Coupling of Alkynes
Copper(II) complex catalyzes the coupling of acetylene and
monosubstituted acetylenes to yield diynes in the presence of
base such as pyridine. The reaction probably takes place via
one-electron oxidation of the acetylide anion by copper(II) ion
followed by dimerization of the resulting acetylide radicals:
References:
1- IUPAC Gold Book http://iupac.org/goldbook/R05066.pdf
2- Hayyan, M.; Hashim, M.A.; AlNashef, I.M.
(2016). "Superoxide Ion: Generation and Chemical
Implications". Chem. Rev. 116 (5): 3029–85.
3- Broderick, J.B.; Duffus, B.R.; Duschene, K.S.; Shepard,
E.M. (2014). "Radical S-Adenosylmethionine
Enzymes". Chemical Reviews. 114 (8): 4229–317.
4- Yan, M; Lo, JC; Edwards, JT; Baran, PS
(2016). "Radicals: Reactive Intermediates with
Translational Potential". J Am Chem Soc. 138: 12692–
12714.