Photochemistry

313 C
 Assistant Prof. Abdelreheem A. Saddik
Doctor of Materials Science
Dep. Chem., Fac. of Sc., Assiut University

Office: Chemistry Building (B), 1st Floor,

Room No.104
 [3]- Photoisomerizaion of
benzenoid compounds
◼ The irradiation of benzene itself brings about a
low conversion into fulvene and benzvalene; the
latter slowly reverts to benzene. Prefulvene is
thought to be an intermediate:
 [4] Photooxidation

◼ Molecular oxygen plays an important role

in organic photochemistry.

◼ It is a reactive compound and combines

readily with radical species that are
intermediates in many photochemical
reactions, which may result in the
appearance of unwanted by products.
 (A)- Formation of peroxy-
compounds
◼The peroxy-compound can be formed by
irradiation the parent organic compound in
the presence of oxygen and a sensitizer.
◼ Reaction occurs by the excitation of the
sensitizer to its triplet state in one of two
ways:
◼Either the triplet abstracts a hydrogen atom
from the substrate to form a radical which
then reacts with oxygen, or it interacts with
the oxygen molecule so as to activate it.
◼ The first type :The best-known example of is the
oxidation of a secondary alcohol to give a hydroxy-
hydroperoxide, with benzophenone as the
sensitizer. The triplet benzophenone reacts with the
alcohol to give a carbon radical which adds oxygen:

1. .1 . .
ph 2 C = O + R 2 CH - OH ph 2 C - O H + R 2 C - OH

Triplet
O
O
R 2 C - OH + O 2
R 2C
OH
 A chain reaction is now propagated:
.
O OH
O O .
+ R 2CH - OH R 2C + R 2C - OH
R 2C
OH
OH

The usefulness of the reaction lies in the fact that

hydroxy-hydroperoxides readily eliminate hydrogen
peroxide to form carbonyl compound:
O 2H

R 2C H R 2 CO + H 2O 2
O
◼ In the second type, the sensitizer in its
triplet state interacts with the triplet oxygen
molecule, i.e. the ground state of oxygen*,
to give singlet oxygen, 1O2, i.e. an excited
oxygen molecule, while the sensitizer
returns to its ground state, S0.

◼Singlet oxygen then interacts directly with

the organic substrate.

◼The common sensitizers are dyes such as

fluorescein & Rose Bengal ( a
halogenated fluorescein).
◼ Three types of oxidation can be brought
about in this way.

First, conjugated dienes yield cyclic

peroxides in a reaction of Diels-Alder type.
Example is:

O
O
1
O2
Second, alkenes with an allylic hydrogen
atom form hydroperoxides, probably as
follows:

H O R O 2H
O
R
R R'
R R'

The products can be reduced to allyl alcohols.

 Third, alkenes with no allylic hydrogen
form dioxetans which, on warming, yield
carbonyl compounds:

O2 heat
R 2 C = CR 2 R 2 C - CR 2 2 R 2 CO
sens.
O -O
(B) - Oxidative coupling of
aromatic compounds
Although the irradiation of cis- or trans-
stilbene in the absence of O2 gives simply
a mixture of the two isomers, in the
presence of O2 phenanthrene is formed.

It has been inferred that cis-stilbene

photocyclizes reversibly to give a small
amount of dihydrophenanthrene which, in
the presence of O2, forms phenanthrene.
Dihydrophenanthrene is oxidized irreversibly
to Phenanthrene :

Ph Ph
h h
Ph
Ph

O2
H
Compounds related to stilbene react
analogously, providing a useful method for
obtaining polycyclic systems, e.g.

h - O 2
 Singlet oxygen reacts with alkenes
in a number of different ways
Continuation to the aforementioned reactions:

1. Simple alkenes containing allylic hydrogen

may react to form allylic hydroperoxides (5).

The process does not go through discrete

radical intermediates formed by hydrogen
abstraction, since a shift of the double bond
occurs invariably (6); it can be represented as
a concerted process as shown.
2. Alkenes without allylic hydrogen(7), or
those with electron-rich double bonds
(8), undergo a cycloaddition with singlet
oxygen to form a .1,2- dioxetane.

These can be remarkably stable

compounds, bearing in mind that they
are strained peroxides, although in some
cases they cannot be isolated but break
down to give two carbonyl compounds
(8).
 hv OOH
(5)
O 2 , sensitizer

OH
O=O
H O
(6)

M eO OM e
M eO OM e hv (R) (S)

O 2 , sensitizer (7)
O O
O
hv O O
(8)
O 2 , sensitizer
O
 Ph

Ph
hv O
Ph (9)
O2, sensitizer O

Ph
100%
hv
O (10)
O2, sensitizer O
O O
O O
30%
 [5] Photochemical aromatic
substitution
◼ The distribution of charge in a species in an
excited state can be wholly different from
that in the ground state and especial use
has been made of this difference in
controlling the positional selectivity in
nucleophilic aromatic substitution.
◼For example, when 3,4-dimethoxynitro-
benzene is heated with hydroxide ion.
◼The 4-methoxy substituents is replaced,
whereas when the reaction is carried out
at room temperature under ultraviolet
irradiation it is the 3-methoxy substituents
which is replaced:

O- OMe OMe
-
OMe - OMe O
OH -
OH
heat h

NO 2 NO 2 NO 2
 [6]- Photochemical
fragmentation
◼ In order for light to bring about the fragmentation
of a compound, two conditions must be met :
(1) the wavelength of the light must correspond
both to an energy greater than that of the bond to
be cleaved, (2) and to an electronic excitation of
the molecule concerned.
 (a)- Photolysis of carbonyl
compounds
• • •
h
C H 3 C O C H 3 ⎯⎯ → C H 3 + C H 3 C O → C O + C H 3

The most thoroughly studied example is the photochemical

cleavage of acetone to methyl and acetyl radicals in the vapor
phase.

At room temperature products derived from acetyl radicals are

obtained. 100C loss of CO becomes so rapid and acetone
nearly decomposes to two methyl radicals, (See Norrish Type
I and Norrish Type II).
◼ The n π* excitation of aldehydes and ketones
can bring about two types of fragmentation.
◼ First, fragmentation can occur of the C – C bond
adjacent to carbonyl:

R R' h R .
+ R'
O O
This is termed the Norrish Type I process, and
is followed by one or more of three reactions:
disproportionation to give a ketene,
 R R
R' h . R
R R + R'
O O R C + R'H
O
decarbonylation and then dimerization and/or
disproportionation, e.g.
R R R
h . . R
+
O O

R
. R
. + CO
O
R

R
2 R .
R R
+
or intermolecular hydrogen-atom abstraction
by the acyl radical,

R R'
h . R'
R . +
O O

. R' H R'
R . R
+ +
O
 Second, if the carbonyl compound contains a γ-CH
group, interamolecular hydrogen-atom abstraction
can occur:
O H H R'
R' OH R' O H
R h
R R
This - Norrish Type II process – is followed by
fragmentation,
H H
H O
O . R'
H R'
.
R R +
or by ring closure,
OH
H H R' R'
R
O

Which of the two types of product is formed

by the Type II process depends markedly on
substitution at the carbon adjacent to
carbonyl. For example, in the following case,
 O
O R
ph H2C = CH2
+
h R
ph
RR
OH
ph
R
R
The extent of cyclization relative to fragmentation is
10 % when R = H and 89 % when R = CH3.

The photochemistry of the smaller cyclic ketones is

dominated by the Type I process.
 (b)- Photolysis of compounds
containing the = N+ = N- group

Generation of Carbenes & Nitrenes:

(i) Diazoalkanes.
The irradiation of diazomethane in ether
gives singlet methylene ( CARBENE).

C H 2N 2 h :C H 2 + N2
(ii)- Alkyl azides.
The photolysis of an azide gives a Nitrene,
RN = N = N h RN + N2

which can undergo a variety of intra- and

intermolecular reactions:

intermolecular hydrogen-atom abstraction,

RN + R' RNH + R '.
RNH + R' H RNH2 + R '.
 Photochromism
◼Photochromism [Photo = light, chrom =
colour, ism = Phenomena] means literally the
phenomenon of coloration by light.

◼It has received considerable attention since

its discovery at the end of the nineteenth
century both for organic and inorganic
substrates.
◼Photochromism can be defined also as
reversible transformation of a single
chemical species between two states of
different absorption spectra.

A (  ) h 
B (  )
or h  
 Classification of Photochromic
system
1. Photochrmism based on cis-trans
isomerization:
O
h S S
S C
or h 
C C
C S
O O
O
(1) (2)
Purple Red Yellow

Indigo Dye
2. Photochromism based on Tautomerisation:
Photocheromic tautomerism includes mainly
hydrogen transfer tautomerism and valence
tautomerism (phototropic).

3. Photochromism based on Photo-Redox

Reactions:
[Electron transfer Reaction]
The photochromic mechanisms based on
redox- photochromis are usually difficult to
determine as they are multi component
systems.
4. Photochromism Based on Dissociation:

Homolytic and heterolytic dissociation

processes play a dominant role in the field
of reactions responsible for the
photochromic properties of chemical
individuals.
5. Photochromism Based on Triplet-
Triplet Absorption:

Photochromic comp's
based on triplet-triplet
HO O
absorption is the OH
easiest photochromic
system which consists
of molecules stable in COOH
ground state and
metastable in excited
state.
6. Photochromism based on pericyclic
Reactions (Valence isomerization &
Electrocyclic Reactions) :

Pericyclic are among the most

important processes that allow for the
design and construction of
photochromic system.
 Microwaves in Organic
Synthesis
Introduction:
The first papers on the use of microwaves for
synthesis reactions appeared in the literature in
1986.

Since that time, over a thousand articles have

been published, numerous conferences have
focused on the advance of microwave
techniques, and the use of microwave
processing is now the hot topic for combinatorial
and parallel strategies.
◼Microwaves are a form of electromagnetic
energy. Microwaves, like all electromagnetic
radiation, have an electrical component as
well as a magnetic component.

◼The microwave portion of the

electromagnetic spectrum is characterized
by wavelengths between 1mm to 30 cm,
and corresponds' to frequencies between
1000 MHz to 300 GHz.
◼Milestone microwave labstations use a
specific, fixed frequency of 2,450 MHz (2.45
GHz).
◼It is useful to consider the quantum energy
of microwaves in relation to other forms of
electromagnetic energy.

◼It is important to recognize that the energy

delivered by microwaves is insufficient for
breaking covalent chemical bonds.

◼This information can help to narrow

speculation on the mechanisms for
enhancement in specific reactions.
 Microwave Oven:
◼Every microwave oven contains a
magnetron, a tube in which electrons are
affected by magnetic and electric fields in
such a way as to produce micro wavelength
radiation at about 2450 Mega Hertz (MHz)
or 2.45 Giga Hertz (GHz).

◼This microwave radiation interacts with the

molecules in food.
◼ As these microwaves generated from the
magnetron bombard the food, they cause the
polar molecules to rotate at the same frequency
millions of times a second. This molecular
agitation creates friction, which heats up the
food.

◼ The friction rips the surrounding molecules apart

causing substantial damage and ultimately
deforming them.

◼ The scientific name for this deformation is

"structural isomerism.
 Microwave Heating:
◼ Microwave heating occurs somewhat differently
from conventional heating.
First, the reaction vessel must be substantially
transparent to the passage of microwaves.

◼ The selection of vessel materials is limited to

fluoropolymers and only a few other engineering
plastics such as polypropylene, or glass fiber filled
PEEK (poly ether-ether-ketone).
◼Heating of the reaction mixture does not
proceed from the surface of the vessel; the
vessel wall is almost always at a lower
temperature than the reaction mixture.

Second, for microwave heating to occur,

there must be some component of the
reaction mixture that absorbs the
penetrating microwaves.
◼Microwaves will penetrate the reaction
mixture, and if they are absorbed, the
energy will be converted into heat.

◼Just as with conventional heating, mixing

of the reaction mixture may occur through
convection, or mechanical means (stirring)
can be employed to homogeneously
distribute the reactants and temperature
throughout the reaction vessel.
 APPLICATIONS OF MICROWAVES
IN ANALYTICAL CHEMISTRY
◼Microwave energy has a number of different
applications in analytical chemistry:

• In electron spin resonance spectroscopy

(ESR). This technique, uses microwave
energy as the irradiation source and is widely
used for structural analysis and in the
elucidation of a variety of problems.
◼In a microwave plasma (MP). These have
been used as sources for atomic emission
spectroscopy (AES) since the 1970s.

◼In microwave-assisted sample preparation

techniques .
 Microwave-Assisted Organic
Chemistry (MAOS)
1. In 1986 Richard Gedye and coworkers published
a short communication in, entitled "The Use Of
Microwave Ovens for Rapid Organic Synthesis"
which for the first time described the utilization
and advantages of microwave irradiation for
organic synthesis.

Original publication for different types of reactions

were studied, including the hydrolysis of
benzamide to benzoic acid under acidic
conditions.
◼Considerable rate increases (5 - 1000 fold)
were observed for all investigated
transformations when compared to classical
thermal reflux conditions.

◼The same year, an independent study by

the groups of Giguere and Majetich
describing similar rate-enhancements in
microwave-promoted Diels-Alder, Claisen,
and ene reactions was published in the
same journal (10).
 O O

20% H 2SO 4
NH 2 OH
conventional heating: 1h 90%
microwave heating: 10 min 99%

High-speed microwave synthesis has attracted a

considerable amount of attention in recent years.
Since the first reports on the use of microwave
heating to accelerate organic chemical
transformations by the groups of Gedye and
Giguere/Majetich in 1986, more than 2000 articles
have been published in the area of microwave-
assisted organic synthesis (MAOS).
 II- Advantages of Microwave-
assisted organic chemistry
1. Reaction rate enhancement varies from 15x to
2000x compared with that of conventionally
heated samples.

2. Cleaner products, and reduced side reactions.

3. Minimum energy losses, minimum solvent

requirements formicrowave-assisted synthesis
performed on solid inorganicsupport.
4. less floor space and good reproducibility

5. Reduced reaction times.

6. Increased yields.

7. Improved reproducibility
 Synthetic applications of MW-
assisted organic reactions in
opened vessels
1. The Diels-Alder reaction:
O O

+ xylene (Z)

MW (95oC, 7h): 92%

Oil Bath (95oC, 7h): 47% COOEt
EtOOC
EtOOC
+
(E)

COOEt

MW (120W, 1 min, grafite): 92%

Oil Bath (reflux, 60h): 90-96%
 2. Esterification:
MW
Z COOH + R-X Z COOR + K +X -
KOH, Aliquat 10%
-H 2 O
95-99 %

Fischer Esterification

COOH
CO 2 CH 3
H 2 SO 4

Temperature reflux (65 o C) 120 o C (50 psi)

3. Ether Synthesis:

PhC H 2 N + M e 3 C l -
RO H + R'X R-O -R ' + HX
MW
78-85 % , 5-10 m in.

4. Isomerization Reactions
Numerous isomerization reactions have
been investigated using MW irradiation.
For example, eugenol undergoes MW-
assisted isomerization to isoeugenol under
solvent-free conditions using potassium
tert-butoxide .
OH
OH
OCH3
OCH3

t-BuOK

MW (45W, 192oC, 18 min): 94%

o
Oil Bath (200 C, 90 min): 73 %
(E)
5. Polymer Chemistry:

CH 3 CH3
H
OH + H2N C6H13 N
C6H13
O O
MW (140W, 30 min): 96%

CH3
MW
OH + H 2N C6H13
AIBN n m
HO O HN O
O
C6H13
6. Enzyme-Catalyzed Transformation:

OH
OH OH
Lipase
CH3 + RCOOR' CH3 CH3
+

Mw (90 w, 90oC, 10 min): 43%, 100% isomer

Oil Bath (90oC, 90oC, 10 min): 40%, 50%
isommer E
 1. Applications of Microwaves in
Heterocyclic Ring Formation
1.1. Five-Membered Heterocyclic Rings
1.1.a. Pyrroles
The classical Paal-Knorr cyclization
of 1,4-diketones to give pyrroles is
dramatically speeded- up under
microwave irradiation and high yields
are obtained as shown in Scheme 1.
O
RNH 2 R= CH 2C 6H 5,
4-MeOC 6H 4,
N 2-ClC 6H 4 etc.
O
H
R
75-90 %
 ◼1.1.b. Imidazoles

O O R3 R2
+ Al2O 3
R3
R H R2 Mw/NH 4OAc
1
N NH
O
MW, 130W, 10 min., solvent -free R1
75-85 %
1.1.c. Indoles
The classical Fischer-indole synthesis
from an aryl hydrazine and a ketone is
speeded-up by several 100-fold as
documented in Scheme 10.

H O
N
NH 2 30 Sec.
+
N
H
 1.2. Six-Membered Rings:
1.2.a. Dihydropyridines:
The Hantzsch dihydropyridine synthesis remains
one of the most important routes to pyridine ring
systems. Under conventional conditions long
periods of heating are required and yields are poor
to-moderate. Microwaves

Ar
O O O 25% aq NH 4OH EtO 2C CO 2Et
+
(Z) (Z)
Me OEt Ar H
Me N Me
(5 equiv) H
 I.3. Polycyclic Six-Membered Rings
1.3.a. Quinolines
The Skraup synthesis has a bad reputation
as it involves very messy conditions and
gives only low yields of quinolines when
carried out conventionally.
R3
O
(E) R2
R + 1 3 lnCl3/SiO2
R R R
NH2
R2 N R1
MW, 600W, 5-12 min., solvent-free R = H, o-CH3, m-CH3, p-CH 3,
o-OMe, p-OMe, m-OH, m-Cl etc.
R1 = H, CH3, n-C3H7; R2 = H, C2H5;
R3 = CH 3, p-MeOC6H4