Basic principles of photochemical reactions

• The study of chemical reactions, isomerization and physical behavior

that may occur under the influence of visible and/or ultraviolet light
is called Photochemistry. Two fundamental principles are the
foundation for understanding photochemical transformations.

• The first law of photochemistry, the Grotthuss-Draper law, states that

light must be absorbed by a compound in order for a photochemical
reaction to take place.

• The second law of photochemistry, the Stark-Einstein law, states that

for each photon of light absorbed by a chemical system, only one
molecule is activated for subsequent reaction. This "photoequivalence
law" was derived by Albert Einstein during his development of the
quantum (photon) theory of light
 Requirements:

• The first requirement, then, is that the reactant should absorb light at a
wavelength which is experimentally accessible.
• below 200 nm is inconvenient because the radiation is absorbed by air and
vacuum techniques are required.
• normal solvents absorb in the range up to 220nm. The useful spectrum
therefore begins at 220nm.
• For the ultraviolet region, a low-pressure mercury arc lamp has its
strongest emission line at 254 nm which is a wavelength at which aromatic
molecules absorb.
• For the visible region, a tungsten lamp or the more powerful xenon arc are
suitable.
• Saturated organic compounds absorb only at wavelengths well below
200nm, but many unsaturated ones absorb above 230nm, so that
photochemical reactions are essentially limited to those in which at least
one of the reactants is unsaturated or aromatic.
compound containing a C =C group. Light of the appropriate
wavelength - in the region 180-200 nm, causes a π-electron to be
excited to the lowest antibonding π orbital (i.e. a π * orbital): the
transition is described as π → π *. The new state of the molecule
is described as the first excited singlet, S1, (since the promoted
electron and its original partner still have opposite spins); this
particular excited singlet is of (π, π*) type.
• For compounds containing a carbonyl group, two types of excitation are commonly
effected:
• one, which requires the more energy and therefore corresponds to shorter
wavelengths (e.g. λmax. 187 nm for acetone), is a π —> π* transition.
• The other, which corresponds to longer wavelengths (e.g. A^ax. 270 nm for acetone),
is an excitation of one of the non-bonding electrons on the oxygen atom into an
antibonding π orbital; it is described as an n→ π* transition and the excited state is of
(n, π *) type.
• Figure shows a typical situation.
• Initially, almost all molecules are
in the lowest vibrational level of
the ground state, S0. The
excitation occurs so rapidly that
the nuclei do not have time to
alter their relative positions; it is
therefore represented by a vertical
line.
• Consequently, the S1 state can be
reached at a point which
corresponds to an excess of
vibrational energy.
• However, this energy is rapidly
dissipated through molecular
collisions (vibrational cascade)
and thereafter one of five
processes takes place:
The triplet state may return to the ground state, with a further spin
inversion, either by emitting radiation {phosphorescence) or by giving up
energy as heat; it may take part in a chemical reaction; it may transfer its
energy to another molecule which is thereby raised to the triplet state; or
it may dissociate.

These processes are summarized as follows:

Types of Photochemical reactions:

• The reactions of excited states, including both

singlets and triplets, can be classified under the
following headings:
1. Photoreduction,
2. Photoaddition,
3. Photorearrangement,
4. Photooxidation,
5. Photoaromatic substitution, and
6. Photofragmentation.
Photoaddition
 Photoaddition
• Photoaddition is the formation of a 1:1 adduct by
reaction of an excited state of one molecule with the
ground state of another.

• The molecule in the ground state is commonly an

alkene; the reactant which is excited can be a carbonyl
compound, quinone, aromatic compound, or another
molecule of the same alkene.

• The majority of the reactions lead to the formation of a

ring.
 (a) Photoaddition of alkenes to carbonyl
compounds
• This photoaddition - the Patemo-Biichi reaction - normally occurs by
reaction of the triplet state of the carbonyl compound with the
ground state of the alkene.
• As in photoreduction, it is more efficient when the triplet is of (n,π*)
rather than ( π, π *) type.
• Typical examples, which also show the marked variations in the
yields of products, are the addition of benzophenone to propylene
and isobutylene:
 (a) Photoaddition of alkenes to carbonyl
compounds
• The ring is formed in two stages. The excited carbonyl compound
(triplet) first adds through its oxygen atom to the alkene so as to give
mainly the more stable of the two possible diradicals. A spin-
inversion then occurs and the second bond is formed.
 (a) Photoaddition of alkenes to carbonyl
compounds
• The reaction is not stereospecific, because the time-lag before the
final spin inversion is more than enough for rotation to occur about
single bonds; for
• example, cis- and trans-2-butene give the same mixture of cis- and
trans-oxetanes with benzophenone:
(a) Photoaddition of alkenes to carbonyl
compounds
• There is one general circumstance in which photoaddition of alkenes to
carbonyl compounds fails: namely, when the energy difference
between the triplet and ground state of the carbonyl compound is
greater than that between the corresponding states of the alkene. In
that event, the excited carbonyl compound can transfer its energy to
the alkene so returning to its ground state and giving triplet-state
alkene. This is then followed by alkene dimerization. For example, the
energy of the triplet from benzophenone is less than that from
norbornene, so that photoaddition occurs:

In contrast, the energy of the triplet from acetophenone is greater than that from
norbornene, so that irradiation of acetophenone in the presence of norbornene
yields mainly norbornene dimers. Acetophenone is here described as a sensitizer
(a) Photoaddition of alkenes to carbonyl
compounds
• There is one general circumstance in which photoaddition of alkenes to
carbonyl compounds fails: namely, when the energy difference
between the triplet and ground state of the carbonyl compound is
greater than that between the corresponding states of the alkene. In
that event, the excited carbonyl compound can transfer its energy to
the alkene so returning to its ground state and giving triplet-state
alkene. This is then followed by alkene dimerization. For example, the
energy of the triplet from benzophenone is less than that from
norbornene, so that photoaddition occurs:

In contrast, the energy of the triplet from acetophenone is greater than that from
norbornene, so that irradiation of acetophenone in the presence of norbornene
yields mainly norbornene dimers. Acetophenone is here described as a sensitizer
(b) Photoaddition of alkenes and alkynes to
aromatic compounds
• Both alkenes and alkynes undergo photochemical addition to
benzene. Cycloaddition occurs to give 1,2-, 1,3-, or (less commonly)
1,4-adducts. Examples of 1,2-addition are:

In the second example, the very

strained electrocyclic ring-
opening reaction.
In the last, photochemical 1,2-
addition to the benzene ring,
which is initiated by n π*
excitation of the maleimide , is
followed by a spontaneous 1,4-
addition of Diels Alder type to
the resultig
1,3-diene.
(c) Photodimerization of alkenes, conjugated
dienes, and aromatic compounds
• A special case of photoaddition is the formation of a 1:1 adduct by
reaction of an excited state of one molecule of a reactant with
another molecule of the same reactant in its ground state. This
process - photodimerization - occurs with both alkenes and aromatic
compounds. Depending on the structure of the reactant and the
conditions of excitation, the excited state may be a singlet or a triplet.
• Since non-conjugated alkenes absorb only in the difficultly accessible
region below 200 nm, their unsensitized photodimerizations are
comparatively little used. Reaction in this case occurs through the
excited singlet S1 and is concerted
(c) Photodimerization of alkenes, conjugated
dienes, and aromatic compounds
• Conjugated dienes do not undergo photodimerization through the
excited singlet but instead undergo photocyclization (p. 506).
However, photodimerization can be effected through triplet
sensitization. Mixtures of products are often formed, as in the
dimerization of cyclopentadiene in the presence of benzophenone;

Here, the first two products represent [π4 + π2] addition and the third represents
a [π4 + π2] addition. The three are formed in approximately equal proportions,
whereas the concerted thermal dimerization of cyclopentadiene gives entirely
endo-dicyclopentadiene
(c) Photodimerization of alkenes, conjugated
dienes, and aromatic compounds
• Benzene does not form a photodimer, but polycyclic aromatic
compounds can do so. For example, anthracene dimerizes through its
excited singlet (π, π*) state:
Photo-oxidation
(a) Formation of peroxy-compounds

• Certain types of peroxy-compound can be formed by irradiating the

parent organic compound in the presence of oxygen and a sensitizer.
Reaction occurs by the excitation of the sensitizer to its triplet state,
and thereafter in one of two ways:

1. the triplet abstracts a hydrogen atom from the substrate to form a

radical which then reacts with oxygen,

2. triplet interacts with the oxygen molecule so as to activate it.

1. the triplet abstracts a hydrogen atom from the substrate
to form a radical which then reacts with oxygen,
• The best-known example of the 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 (cf. photoreduction, p. 499) which adds oxygen:

The usefulness of the reaction lies in the fact that hydroxy-hydroperoxides

readily eliminate hydrogen peroxide to form carbonyl compounds:
2. triplet interacts with the oxygen molecule so as to activate it.
• 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 and 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. Examples are:

The usefulness of the reaction lies in the reducibility of the peroxides to diols:
(b) Oxidative coupling of aromatic compounds
• Although the irradiation of cis- or –trans stilbene gives simply a
mixture of the two (p. 505), in the presence of oxygen phenanthrene
is formed. It has been inferred that cis-stilbene photocyclizes
reversibly to give a small proportion of dihydrophenanthrene which,
in the presence of oxygen, is oxidized irreversibly to phenanthrene:

Compounds related to stilbene react analogously, providing a useful method for

obtaining polycyclic systems, e.g.
Photo-fragmentation
 Photo-fragmentation
• In order for light to bring about the fragmentation of a compound, two
conditions must be met: the wavelength of the light must correspond both to
an energy greater than that of the bond to be cleaved, and to an electronic
excitation of the molecule concerned.
• This effectively eliminates saturated organic compounds since, although they
have weaker bonds than correspond to typical, accessible ultraviolet
wavelengths, they do not absorb in this region. For example, methyl iodide is
essentially unaffected by light whereas iodobenzene, having an aromatic
chromophore, dissociates into phenyl radicals and iodine atoms.
• In general, then, fragmentation is characteristic of certain unsaturated organic
compounds together with inorganic compounds such as the halogens. Eg:

fragmentation of peroxides

fragmentation of nitrites
(a) Photolysis o f carbonyl compounds

• The n to π* excitation of aldehydes and ketones can bring about two

types of fragmentation:

1. First, fragmentation can occur of the C—C bond adjacent to

carbonyl:

2. Second, if the carbonyl compound contains a y-CH group,

intramolecularhydrogen-atom abstraction can occur:
 fragmentation can occur of the C—C bond
adjacent to carbonyl:

This is termed the Norrish Type I process, and is followed by one

or more of three reactions: disproportionation to give a ketene.
fragmentation can occur of the C—C bond
adjacent to carbonyl:
decarbonylation and then dimerization or intermolecular hydrogen-
and/or disproportionation, e.g. atom abstraction by the acyl
radical,
if the carbonyl compound contains a y-CH group,
intramolecular hydrogen-atom abstraction can
occur:

Which of the two types of product is formed by the Type II process depends markedly
on the substitution at the carbon atom adjacent to carbonyl.
 Forexample, in the following case,

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, followed by intramolecular reactions;
However, in larger rings, cyclization related to the Type II process
can occur, e.g,
(b) Photolysis of compounds containing the
group
(1) Diazoalkanes. The irradiation of diazomethane in ether gives
methylene in its singlet state:
• The most useful reaction of carbenes is with alkenes to form cyclopropane
derivatives. When the carbene is generated in its singlet state, by direct
photolysis, its insertion into the double bond is essentially stereospecific. For
example, cis-2-butene and dicarbomethoxymethylene give almost entirely
the cis-dimethylcyclopropane:
• However, when the carbene is generated by photolysis in the presence of a
triplet sensitizer, it is formed in its triplet state and the stereospecificity is lost;
for example, cis-2-butene gives largely rra/w-dimethylcyclopropane. This is
because there is a time lag between formation of the two C—C bonds during
which spininversion occurs and this allows rotation about the original C—C
bond:
The carbenes from α-diazoketones have the special property that they undergo
rearrangement faster than they are trapped by, for example, alkenes.
Rearrangement gives a ketene which can be trapped by an alkene and this forms
the basis of a method for synthesizing four-membered rings, e.g.
Alkenyl and allyl azides give nitrenes which undergo
intramolecular addition to give highly strained
compounds, e.g.