Dr D.Y.

Patil Arts, Commerce & Science College

Mrs. Tanmayee Vaidya

Chemistry Department
M Sc I CHO 250
Section I
Photochemistry
 Principles of Photochemistry
• Photochemistry is the study of the interaction of light and chemicals.
• Organic photochemistry is a branch of organic chemistry that studies
light-induced chemical reactions of organic compounds.
• Photochemical reactions occur by absorption of electromagnetic
radiation to produce electronically excited states.
• Electronically excited molecules gives products of the reactions.
• The process at raising molecules from ground state of minimum
energy to an excited state of higher energy is called excitation.
• Excitation in the rotational, vibrational or electronic energy levels of
molecules result from absorption in microwave, infrared & ultraviolet
region of the electromagnetic spectrum.
 Principles of Photochemistry
• Electronic excitation :
Principles of Photochemistry
 Principles of Photochemistry
• According to Pauli’s Exclusion principle, when two electrons are accomodated in same the same
orbital, their spins must be opposite.e they are paired. A molecule is said to be in singlet state (S).
• According to Hind’s rule when two electrons are assigned to different orbitals, the lowest energy state
will be the one in which these two electrons have parallel spins & are unpaired. A molecule in which two
electrons are unpaired is in a triplet state (T).
• In organic molecules , there are even nos of e-ns, which are usually paired in ground state (S0). When
an organic molecule absorbs light of appropriate energy there is no spin inversion & so spin remains
paired in excited state. This excited state where there is no spin inversion is called excited singlet state
(S1).
• When e- excitation is followed by spin-inversion give rise to a excited triplet state (T1).
 Principles of Photochemistry
• Molecular orbital diagram showing n-Π* & Π-Π* transitions.
Principles of Photochemistry
 Principles of Photochemistry
• Chemistry of excited molecules
Principles of Photochemistry
Principles of Photochemistry
 Principles of Photochemistry
• Jablonskii diagram : Several paths by which molecule in excited
state dissipate its energy are best shown diagramatically & the
diagram is known as Jablonskii diagram.
 Principles of Photochemistry
1. Prior to excitation the the electronic configuration of molecule is described
as being in ground-state.
2. The excited state molecule may transfer energy to solvent when reaction
proceeds faster than vibrational relaxation.
3. The excited state undergoes intersystem crossing. This process involves
inversion of spin of an electron in half filled orbital & gives triplet state in
which both electrons are having same spin.
4. The designation S & T are used to designate singlet & triplet state.
5. Molecule absorbs energy in ground state & goes to excited state i.e from
S0 to S1. In this state molecule undergoes many changes it emits light &
comes into any one of the vibrational level by vibrational relaxation called
fluorescence.It is spin allowed transition.
6. Molecule in S1 state may cross over to any vibrational level of triplet state
T1, ( of same energy level as S1 i.e S1 to T1 ) . This is called as
“Intersystem system crossing”.
7. Molecule in triplet state emits energy & comes to exited state of singlet the
emission takes place called as ‘ phosphorescence ‘. It is a spin-forbidden
transition.
8. In intersystem crossing ( ISC ) inversion of spin takes place example S2 to
T2 or from S1 to T1.
 Photochemistry of carbonyl compounds
• Norrish Type-I :
• 1. In Norish type – I fragmentation of C-C bond α to carbonyl group
takes place.
• 2. The process originates from carbonyl n-Π* state & proceeds
through the homolytic cleavage of one of the carbonyl alkyl group, as
primary photochemical reaction.
• When reaction is carried out in gas-phase above 100⁰ C primary
photochemical process is followed by secondary decarbonylation. The
products are principally carbon-monoxide ( CO ) & an alkene.
 Photochemistry of carbonyl compounds
• Norrish Type -II Reaction
• This is a typical photochemical reaction of ketone
pocessising gamma C-atom is . The photoexcited carbonyl
group ( n-∏*) state abstracts gamma-hydrogen via six-
membered cyclic pathway to give a diradical which leads to
fission to an alkene & an enol ( which tautomerises to
ketone ).
• The reaction originates through excited state of ketone &
undergoes intramolecular hydrogen transfer ( of gamma
proton ). α-β bond undergoes fission.
 Di-Pi-Methane Rearrangement
• In Di-∏ methane rearrangement 1,4 diene system in
which two ∏ bonds are separated by sp3 C-atom
gives a cyclopropane derivative photochemically.
• It can proceed through either singlet or triplet
excited state .
• This reaction is followed in acyclic – dienes.
• Cyclisations occurs at diene terminals ( best
stabilised radical ). Cyclopropane is the cyclised
product.
 Barton reaction
• Barton reaction are useful for conversion of nitrite esters to
Ƴ-hydroxy oximes
• Barton reaction is a method for achieving remote
functionalization on an unreactive aliphatic site of a nitrite
ester under thermal or photolytic conditions via oxygen-
centered radicals.
• Thermolysis or photolysis of nitrite, hypochlorite generates
an oxygen centered radical.
• In Barton reaction a methyl group in ɗ-position to an OH
group is converted into an oxime group.
 Barton reaction
• Mechanism :
• The alcohol on reaction with nitrosyl-chloride
(NOCl) is converted to nitrite, which on photolysis
undergoes homolytic cleavage to give alkoxy
radical.Abstraction of hydrogen from C-aton in delta
position produces nitroso alcohol, which
tautomerizes to oxime. Transfer of hydrogen to
alkoxy free radical takes place via a six-membered
transition state.
 Barton reaction
• Mechanism :
 Rearrangement of 4,4-diphenyl cyclohexane dinone
• Reaction

• The reaction proceeds through triplet reactive species. The zwitter ion
is a initial photoproduct & this is rearranged to observed product.
 Paterno-Buchi Reaction
• This is an excellent method for the synthesis of four
membered ring – oxetanes. The process involves a
cycloaddition of electronically excited carbonyl compounds
( through triplet state of carbonyl ) with ground state of
olefins.
• Most of the Paterno-Buchi reaction involves ( n-∏*) state of
ketone. The major mode of addition is predicted by
assuming that the radical like oxygen atom of ( n-∏*)
ketone adds to olefins to give preferentially the most stable
biradical intermediate.
 Paterno-Buchi Reaction
• -
 Photoisomerisation of Benzene & Substituted Benzene
• Benzene & substituted benzene undergoes valence isomerisation by
irradiation .
• Excitation into S1 gives meta & ortho products, while excitation into
S2 gives para bonded products by valence isomerisation.
• Irradiation of liquid benzene under nitrogen at 254 nm causes
excitation to S1 state & the products are benzvalene, & fulvene via
1,3 – biradical.
• Dewar benzene is formed via S2 state. Dewar benzene is converted to
prismane by formation of biradical.
• All these strained intermediates are thermally labile & isomerises into
stable benzenoid compounds.
 Photoisomerisation of Benzene & Substituted Benzene

• -
 Photoisomerisation of Benzene & Substituted Benzene

• -