AKNOWLEDGEMENT

In the accomplishment of this project

successfully, many people have best
owned upon me their heart pledged
support. I would like to thank all the people
who have been concerned with the
project. First and foremost I would like to
express my gratitude to our Head of
Department, Dr. DEVENDRA NATH
THAKUR, who gave me golden opportunity
to do this wonderful project on
“Photochemistry of Carbonyl
compounds” which helped me to gain
more knowledge about plantation.
Last but not least I would also like to thank
my friends who helped me in finishing this
project within the limited time.
Introduction
Photochemistry has provided a revolutionary advantage in various biological
and chemical processes. It helps to explain the phenomenon of photosynthesis,
Phototaxis, mutagenic effects of light radiations, vision and photodynamic
Action. Many chemicals, which can not be synthesized by dark reactions, are
produced by photochemical methods. These photosynthesized chemical have
great advantage due to higher efficiency and selectivity. Photochemistry
provides a phenomenon of fluorescence and phosphorescence, which is
collectively known as photo physical phenomenon. For basic researches in
photochemical field, the understanding of photo physical, photo biological and
photo chemical process is essential.

Photochemistry of Carbonyl Compound

Carbonyl compound especially ketones, undergo many interesting and versatile

reaction on irradiation. Ketones exhibit mainly four band in their UV absorption
spectra. The most important band is at 280 nm for the photochemistry of
carbonyl compounds. The reaction is initiated by n→π* transition. Promotion
of an electron will lead to either a singlet state or a triplet State. Photochemical
reaction given by carbonyl group takes place either by singlet state or by triplet
or by both states.

Carbonyl compounds give four type of reaction.

These are:-

(1) Norrish type I process or α-cleavage.

(2) Norrish type II process or β-cleavage
(3) Intramolecular and Intermolecular hydrogen abstraction by carbonyl
Oxygen.
(4) Photocyclo addition reaction and oxetane formation.
 • Norrish type I process or α-cleavage

The bond dissociation energy of carbon-carbon bond adjacent to a carbonyl is

comparatively small and consequently photo chemical excitation of ketones
usually results in the homolytic fission of the α-cleavage or Norrish type 1
reaction. It occurs more readily in vapour phase. In the initial primary process, a
diradical is formed by photolysis of cyclohexanone and their it is followed by
secondary process, which result in formation of a mixture of carbon monoxide,
cyclopentane and 5-hexenal.
 • Norrish type II process or β-cleavage
Norrish type II reaction is possible If bond between α and β - carbon is weak. If
reaction occurs in open chain compounds, the abstraction of hydrogen atom
take place from γ-carbon atom and If system is cyclic the abstraction of
hydrogen is from δ-Carbon .In saturated acyclic compound:

In this reaction bond breaking take place between α and β-carbon due to steric
hindrance and hydrogen is abstracting from γ -carbon to carbonyl oxygen.

In saturated closed compound:

In these compound β-cleavage take place by the hydrogen abstraction from the
γ-carbon.
Intramolecular reaction of Carbonyl compound
❖ by saturated cyclic ketones
Intramolecular reaction in cyclic ketones occurs by α -cleavage. On photolysis,
cyclic ketones give a biradical species. These photo reaction take place in
solution or gas phase. After formation of a biradical, a hydrogen atom is
abstracted from α-carbon, finally it yields hydrocarbons and olefines. In
Monocyclic Ketonic Compounds :
 ❖ by saturated Acylic Ketones:
These types of reaction are carried out by all those compound which have
carbonyl group, but aromatic ketones like Benzophenone and acetophenone do
not give these reactions. α -cleavage reaction should always be carried out in
gaseous forms.

Step (a) Acetone forms an alkyl and acyl free radical :

When two α-bonds are not identical in position, then weaker bond has to be
broken
Step (b) In the secondary process of reaction, decarboxylation from acyl free
radical, disproportionation, and abstraction of hydrogen atom take place.

❖Intramolecular reaction of α-β- Unsaturated

Carbonyl compound
Intramolecular reaction of α ,β - unsaturated carbonyl compound gives oxetene
at 700C. On heating this product, it can be converted into reactant.
 • Intermolecular Cycloaddition reaction
Photocyclodimerization
Intermolecular photodimerization of α, β -unsaturated ketones occur most
readily in cyclic systems. on irradiation, it gives two photo dimers undergoing
across the carbon-carbon double bond by π-π*state. For example Irradiation of
cyclopentenone yields head-to-head (I) and head-to-tail(II) dimers. Head-to-
head dimers are preferred in polar solvent, while non-polar solvent favour had
to tail dimers.

Intermolecular cycloaddition Reaction:

(Formation of oxetane)
Carbonyl compounds yield oxetane on irradiation in the presence of olefin. This
photocycloaddition reaction of carbonyl compound is known as paterno-Buchi
reaction.

The addition is usually performed by irradiation with the light and it involve the
excited state of carbonyl compounds rather than that of the olefin. The light
energy required for the n-π* transition initiated the reaction in simple carbonyl
compounds.
In this reaction oxygen atom of the ketone 3(n-π*) add to an unsaturated
compound and form a stable diradical Intermediate followed by a final product,
called oxetane, on irradiation.

Other example of patern Buchi reaction in which reaction of Benzophenone with

Cis and trans 2-butene, yields the same mixture of both isomeric
oxetone.Drawback of the paterno-Buchi reaction is the competing energy
transfer process from the excited ketone to the olefine, in cases where the
triplet energy of the former exceed that of the latter. For example irradiation of
acetone with norbornene, yields dimers of norbornene rather than oxetanes.
Photochemistry of unsaturated system

The absorption of a radiation by an organic molecule takes it from its ground

State into an excited state accompanied by change in electronic distribution,
Geometry and uncoupling of electron spin. Although electronically excited
Molecules are normally very short lived, their high reactivity is frequently
sufficient for photochemical reaction occur.

Electronic structure of alkenes can be described in term of π and σ bonding

orbitals, with corresponding of π* and σ* anti-bonding orbitals. There are
generally two type of transitions occur given as

❖ π - π* transition (π, π* excited state) is the more intense absorption with

λmax of around 180nm (ε ~ 104 Mol-1dm 3 cm-1)
❖ π - σ* transition (π, σ* excited state) is weak.

However, gas phase spectra show an evidence of Rydberg absorption leading to

a Rydberg state (π, 3s).Simplest alkenes absorb UV light with λmax of around
180nm, but conjugated Systems such as diene and polyenes or aryl-substituted
alkenes absorb at λmax > 200nm with increment of around 35 nm per successive
double bond. So that for Simple alkene, direct irradiation must be carried out
with vacuum UV sources.

However, a medium-pressure mercury lamp with a quartz filter can be applied

For highly substituted alkenes, possessing wavelength over 200 nm. A feature of
alkenes photochemistry is that singlet and triplet state reactions are more
distinct. There is a large energy difference between singlet (π, π*) and
corresponding triplet state for alkenes, so intersystem crossing is very inefficient
and a triplet sensitizer is needed to populate the triplet state. Thus, the large
energy difference between singlet and triplet state, and different spin
Characteristics lead to different reaction from singlet (direct irradiation) and
triplet state (sensitizer irradiation) in many alkenes. The reactions of alkenes and
dienes are grouped into geometrical isomerization About carbon-carbon double
bond, concerted reaction like electrocyclic, shifts (usually hydrogen) along π-
system, di-π-methane reaction and photoaddition reactions.
Intramolecular reactions of the olefinic bond
In this heading, intramolecular reaction like geometrical isomerization, di-π-
methane reaction and cyclisation reaction of alkenes are discussed in details .

Geometrical isomerism
Alkenes with suitably substitute display geometrical isomerism due to
restriction rotation about carbon-carbon double bond, which exist in two
isomeric forms are called cis and trans form.

Usually, the trans isomer is thermodynamically more stable because of the less
steric hindrance. Interconversion of geometrical isomer of alkenes can be
carried out by thermally, catalytically or photochemically. When thermally and
catalytic methods are used, we get a thermodynamically more stable isomer,
i.e., trans isomer in large proportion. But photochemical can establish a mixture
that is richer in the cis isomer. Irradiation therefore provides a means of
converting a trans alkene to the cis isomer. Photoisomerization in alkenes can
be occurred through direct radiation, photosensitizer and catalysis process.

Cyclisation reactions
An electrocyclic ring closure, i.e. cyclisation reaction is an intramolecular
reaction that forms a cyclic product containing one more σ bond and one
fewer π bond than the reactant. These reactions occur through the concerted
pericyclic reaction in which bond making and bond breaking occur in a single
step. Such reactions occur thermally or photochemically. In thermal reaction,
thermodynamically stable compound is favored, but in photochemical
reactions, the molecule absorbs a radiation with suitable wavelength and the
direction change will be toward a photostationary state that favors the
compound with lower absorption coefficient at the wavelength of radiation,
for example:-
In these reactions involve a change of the π- and σ-bond positions within a
conjugated system in a cyclic transition state. According to the Woodward–
Hoffmann orbital symmetry rules, the 4n electron systems in the excited state
react through a disrotatory mode in which rotations occur in the same direction
(clockwise or anticlockwise) about the axes of double bonds. Whereas those
reactions with 4n+2 electrons react through a conrotatory pathway in which
rotations occur in the opposite direction (one clockwise and the other
anticlockwise) about these axes.

Example,
Electrocyclic reactions of conjugated dienes take place through the vertical
singlet state. The triplet state is generally not involved in this process. There are
two important factors that affect electro cyclization, (i) reaction efficiency is
usually lowered by a simultaneous geometrical isomerization along the double
bond and (ii) cis-diene conformation must be achieved before cyclization
proceeds. Direct irradiation of dienes may result in wavelength-dependent
photoproduct formation, which is related to different absorption properties
ofthe diene conformers. For example, trans-penta-1,3-diene, irradiated at 254
nm, gives cyclic product in low quantum yield with two other products; however,
when it is irradiated at 229 nm, where the trans-conformation absorbs
predominantly, mostly trans–cis isomerization is observed.

The conjugated triene, e.g., 2,5-dimethylhexa-1,3,5-trine undergoes efficient

Cis-trans isomerization at 254nm, but it cyclizes to a cyclohexadiene using 313
Nm radiation.
Rearrangement of 1,4- and 1,5-dienes

Irradiation of 1,4-diene or 3-phenyl alkenes often lead to vinylcyclo propane or

phenyl cyclo propanes through of an 1,2-shift of vinyl or phenyl group
accompanied by ring closure lead to an photoproduct that is usually not
obtainable by another route. These reactions are termed the di-π-methane
rearrangement, also known as the Zimmerman reaction.

According to the proposed stepwise biradical mechanism, 1,3- and 1,4-biradical

intermediates and also the second π-bond may be involved. The mechanism
starts with formation a bonding between atom 2 and 4 of 1,4-diene unit, then
cleavage of 2,3-bond and formation of a 3,5-bond.

The di-π-methane reaction generally occurs through the excited singlet state
obtained by direct irradiation, whereas the triplet pathway is accessible only
using triplet sensitizers due to the poor intersystem crossing efficiencies of
alkenes. The di-π-methane rearrangements often show a high degree of
diastereoselectivity and/or regioselectivity, for example,
In contrast, cyclic di-π-methane systems rearrange from the triplet state. For
example, triplet sensitization of bicyclo[2.2.2]octa-2,5,7-triene provides
semibullvalene.
Photochemistry of aromatic compounds
The usual chemical reaction shown by benzene and its derivatives has been
studied in detail for a long time. Later is observed by experiments that benzene
is prove to photochemical reactions also. It is known that the electronic
transition in benzene occurs at 230-270nm which corresponds to a energy value
of approximately 448.0kJmol-1and since this value exceeds the resonance
energy of benzene (36kcals or 151.2kJ mol-1). it appears that when benzene is
irradiated with electromagnetic radiations of above mentioned wavelength, a
photo chemical reaction will result with the formation of products that shall not
be aromatic in nature. In fact aromatic compounds undergo transformations of
various derivatives of benzene shows surprising results which are in contrast to
the thermal stability of aromatic compounds. In addition to this the
photochemical rearrangements of benzene derivatives provide direct routes
several highly strained molecules.

Benzene and its various excited states

To have a better look let us consider the exited states of benzene.

❖ When liquid benzene is irradiated with electromagnetic radiation of

wavelength lower than 205 x 10-9 meter, the state T2 is produced. This is
then converted to a different vibrationally excited state singlet state T1
This state produces bicyclo hexenyl biradical (A) digramatically it is shown
below.

❖ If the liquid benzene is irradiated with radiations having λ=254×10-9 m It

transits directly into the excited state T1*Intersystem crossing (ISC)
process converts T1 state to another state T** which produces 1,4-
biradical (B) and [2,2,0] hexenyl biradical (c) which is a bicyclic system.
This is shown below:
 The biradical produces benzvalene and fulvene viz-

Fulvene is obtained from prefulvene C-C bond cleavage and 1,2-hydrogen shift
viz-

Similarly several highly strained molecules (Dewar benzene, prismane etc.) Have
been obtained by when substituted benzenes are irradiated. The Strained
systems are reaction intermediates of photochemical isomerisation of
substituted benzene. The nature of these intermediates depends upon the State
of the aromatic starting material and also upon the wavelength of the light used
in photochemical processes.

Thus it is seen that the above photochemical rearrangements of benzene

molecule provides routes to many highly strained molecules which are in
contrast to thermal stability of aromatic compounds.
Photochemical dimerisation reactions of
aromatic hydrocarbons
It has been observed that under the conditions of high concentration of
aromatic compound, some typical photochemical dimerisation reactions take
place.Napthalene and Anthracene undergo photodimerisation consider the
following reaction of Anthracene.

Here, two molecules of anthracene undergo addition at 9, 10-positions. If a

substituent is present at 9-position of Anthracene than a head to tail dimer is
obtained. This dimerisation has been found to be dependent upon the
wavelength of the light used in the photochemical process. In general irradiation
with longer wavelength results in dimerisation whereas shorter wavelengths
cause other processes to occur because shorter wavelength radiation are
associated with high energy and so cause the photochemical cleavage of the
dimer formed.

For example when 9-nitroanthracene is irradiated with long wavelength Light

produces the dimer on the other hand when the same process is carried out by
irradiation with shorter wavelength the products formed are nitric oxide (NO),
anthraquinone, anthraquinone monoxime, and 10,10/-bianthrone. It is
supposed that these products are produced through 9-anthryl nitrile
intermediate. The reaction is shown below
 • Photo Fries rearrangements

This reaction involves migration of a group across a double bond (1,3 migration)
in structure of the following type: Such rearrangements in aromatic systems lead
to 1,3 and 1,5 migration of an R group.

Photofries rearrangement is an intramolecular rearrangement, where Acyl and

alkyl groups migrate to ortho- and para- positions on irradiation. In this
rearrangement , the substrate dissociates into Phenoxy and acyl radicals, which
recombine within the solvent cage to give intermediates on aromatization to the
product. When photofries rearrangement is carried out in gaseous phase, only
Phenol is obtained, which confirms the formation of solvent cage.
 • Photo Fries reaction of anilides
The corresponding reaction for anilides is as follows

These rearrangements occurs through intermediate formation of free radicals.

• Barton reaction
Photolytic conversion of organic nitrites into nitroso alcohols is known as Barton
reaction. When a compound consists of the C-O-NO group and a C-H Bond is
brought into close proximity (generally 1,5-position), the alkoxyl Radicals are
formed by photolysis of nitrites, in the solution phase , which have Suffficient
energy to bring about selective intramolecular abstraction of Hydrogen atom
and produce a carbon radical.
The produced carbon radical reacts with nitrogen monoxide (NO) and gives
nitroso alcohol. The nitroso alcohol can be isolated from the solution by process
of dimerisation.

Some examples of Barton reaction are given below:

One of the prerequisites for the Barton reaction is the availability of a six
membered cyclic transition state.

As the Barton reaction consists of great selectivity in the hydrogen abstraction

step , it has found application mainly in the field of steroids.
 CONTENT

Introduction
Photochemistry of carbonyl compound
❖ Norrish type I
❖ Norrish type II
❖ Intermolecular and intermolecular hydrogen abstraction
❖ Intermolecular Cycloaddition reaction
Photochemistry of unsaturated system
Intramolecular reactions of the olefinic bond
❖ Geometrical isomerism
❖ Cyclisation reaction
Rearrangement of 1,4- and 1,5-dienes
Photochemistry of aromatic compounds
Benzene and its various excited states
Photochemical dimerisation reactions of aromatic
hydrocarbons
Photo Fries rearrangements
Photo Fries reaction of anilides
Barton reaction
 Project work on

“Organic Chemistry ”

Topic :
“PHOTOCHEMISTRY OF CARBONYL
COMPOUND “

(paper code : CC-08)