Documente Academic
Documente Profesional
Documente Cultură
Thorat
Assit. Professor of Chemistry
Govt. of Maharashtra, I. Y. College,
Jogeshwari (E),
Maharashtra 400060
04/12/2016
Molecules absorb the photon of appropriate energy so that one of its electrons gets
excited into an orbital of higher energy. The energy of the radiation is nearly equal to
or greater than the energy difference between ground state and excited state i.e. in
ultraviolet
region
or
visible
region.
The resulting molecule in its excited state or alternative excited may take part in the
chemical
reaction.
The reaction may be intramolecular (rearrangement, dissociation, etc.) or
intermolecular (addition reaction). In some cases the excited molecule may transfer
its energy to another molecule which in terns undergoes reaction.
The use of uv-radiations below 200nm wavelength is inconvenient because these are
absorbed by air (excitation of air). Also normal solvents absorbed in the range upto
230nm
hence
use
vacuum.
At room temperature, initially almost all molecules are present in the ground state
(vibrational) So. The excited states are denoted as S1 and T1. It is denoted as S1
(excited single state- the state in which the excited electron and its original partner
have opposite spin) and T1 (excited electron and its original partner have same
spin).
04/12/2016
This energy is rapidly dissipated through molecular collision (vibrational cascade) and
then one of the five process take placei) Molecule returns to its ground state either by giving its energy as heat followed by
vibrational cascade or by emitting the radiations (fluorescence) of low energy than
that of absorbed light.
ii) A chemical reaction occurs (reactions).
iii) A energy of excitation is transferred to another molecule by collision so that
original molecule comes to ground state with excitation of another molecule
(sensitizer).
iv) One of unpaired electron of the excited molecule undergoes an inversion of its
spin and get transferred to its lower energy state as a triplet T1 in which both
electrons (ground state and excited state) has parallel spin. This is called as intersystem
conversion (ISC).
v) In special cases excitation leads dissociation of the excited molecule because S1
state is more energetic than its dissociation energy level.
04/12/2016
The triplet state may be return to the ground state with a further spin inversion
either by emitting the radiations (phosphorescence) or giving up energy in the form
of heat; it may carried out the reaction; it may transfer its energy to another
molecule which is excited to triplet state; it may undergoes association.
flurescence or
internal conversion
S0
phosphorescence or
intersystem crossing
chemical
reaction
So hv
+Y
S1
singlet
ISC
So +Y(S1)
So
chemical
reaction
+Y
S0 + Y(T1)
T1
fragmentation
two
species
fragmentatio
Two
species
The life time of excited singlets are very short (10-6 to 10-9) so that chemical
reactions occurs via these species is very uncommon due to their high energy. Therefore
it is converted to its triplet state which is more stable having life time (> 10-4) so that
the probability of the triplet state taking part in the reaction is much higher than
for a singlet state.
04/12/2016
Reactions:*** Photoreduction of carbonyl compounds:Carbonyl compounds are converted into 1,2-diols and alcohols by irradiation in
presence of a hydrogen donating compounds such as isopropyl alcohol. The reaction
occurs in good state only when the triplet is of the (n, *) type. e.g. Reduction of
benzophenone and acetone. The triplet state abstracts hydrogen atom from hydrogen
donor/second reactant molecule.
R2C=O
hv
R2 C=O
(S1)
R'H
R2 C=O
(T1)
R2C*-OH + R*'.
R2CH(OH)-CH(OH)R2
2R2C*-OH
R2C*-OH + R'H
The alcohol formation is effective when R radical is stable (tertiary) and the
coupling reaction is dominant when R is the radical stabilizing group. (e.g.-aryl).
The coupling reaction is more effective when the reduced alcohol of the starting
carbonyl compound is less stable.
Photoreduction of benzophenone to benzpinacole is carried out by irradiation of a
solution benzophenone and isopropyl alcohol with wavelength 345 nm. The
benzophenone forms n * triplet state at these wavelength but isopropyl alcohol
does not shows absorption. In addition with isopropyl alcohol, toluene; cyclohexane;
OH Ph
hv,
340
nm
Ph
methanol
are used as solvent.Ph C=O + H CCH(OH)CH
04/12/2016
+ H CCOCH 5
2
Ph
Ph
OH
The quantum yield of the benzpinacol formation is one therefore the formation of a second
(A) is not occurred but generated by the reaction between benzophenone and (B).
(B)
Ph2C=O
(A)
H3CCOCH3
OH Ph
Ph
2(A)
Ph
Ph
OH
There are certain evidences that explain reduction reaction proceeds through triplet state of
benzophenone isi) The rate of reaction does not decrease appreciably when the reaction is carried out with less
amount of benzhydral in benzene. This explains that the excited state of benzophenone is long
lived and waiting for benzhydral molecule.
ii) The presence of small amount of naphthalene in irradiating mixture is reduces the
quantum yield in appreciable manner. The naphthalene does not absorbed the light required
for the n * transition but causes energy transformation so that excited benzophenone
molecules returns to ground state with simultaneously excitation of naphthalene. The
naphthalene is benznes like quenchers.
o-Alkyl substituted aromatic ketones does not under goes photoreduction reaction even
through giving n * triplet because of intramoleculer hydrogen abstraction. The
intermediate enol-tautomer can be trapped by the Diels Alder reaction asR
R
O
hv
CH3
H-transfer
spininversion
OH
COOMe
OH
COOMe
+
[enol-tautomer]
COOMe
COOMe
04/12/2016
-H2O
COOMe
COOMe
Photoaddition Reactions:-
04/12/2016
a)
Ph-CHO
hv
[Ph-CHO]1
ISC
O
. .
[Ph-CHO]3
Ph
H
O
hv
H
Ph
Ph
(oxetane)
04/12/2016
O
Ph
H
(oxetane)
Ph
hv
Ph
Ph
Ph
Ph
Ph
(1-part)
(9-part)
(oxetane)
The ring is formed in two stages. The excited carbonyl triplet state first adds through its
oxygen atom to alkene forming mainly more stable biradical species. The biradical
species under goes spin inversion forming second bond.
Ph2-CO
Ph
hv
[ Ph2-CO ]1
ISC
Ph1
1 O
Ph
spin
O
[Ph2-CO ]3
inversion
Ph (b)
1
Ph
Ph
O
stable
Ph
Ph
(a)
When carbonyl compound reacts with unsymmetrical alkene forming more stable
biradical species which forming major product (a). It is not stereospecific reaction
because the rotation about the single bond occurs faster than the spin inversion of
electrons. e.g. When benzophenone is irradiated with cis- or trans-2-butene gives same
mixture of both isomeric oxetane product.
Ph
Ph
O
CH3CH=CHCH3
hv
Ph 1 1
Ph
C-C
bond rot. Ph
Ph
04/12/2016
Ph
Ph
When alkene containing electron withdrawing group, it react with carbonyl compound
without loss of its stereochemistry. E.g.CN
H3C
CH3
+
CH3
hv
H3C 1 1
H3C
CN
CN
CH3
H3C
H3C
CH3
(cis)
The conjugated diene is also added across the carbonyl compound but yield of the
product is less because of competitive triplet sensitized dimerisation of diene.
H
H
AcO
hv
O
H
OAc
(cis)
The carbonyl compounds is also added to allenes in high regeoselective manner asPh
Ph
hv
O
Ph
Ph
The biacetyl is also reacting with unsaturated ether regeosectively and stereoselectively
to give cis-2-alkoxyoxetane ring.
O
+
O
COCH3
O
O
(cis)
The ,-unsaturated
carbonyl compound under goes intramoleculer Peterno-Buchi10
04/12/2016
reaction.
Drawback:i) The excited energy of ketone is higher than the olefin causes energy transformation
from ketone to alkene. The excited alkene undergoes dimerisation. In such cases
ketones are called as sensitizer.
[CH3COCH3 ]3
CH3COCH3
CH3COCH3
+[
dimer
Therefore to overcome this drawback, the ketone having low triplet state than the
alkene is used. E.g. benzophenone.
Ph2CO
hv
[ Ph2CO]3 +
hv
Ph
Ph
ii) The reaction between the ketone and conjugated diene (whose triplet excited state
energy is less than the ketone) is not occurs.
iii) The acetylenes also participating in Peterno-Buchi reaction forming unstable
oxetene which undergoes ring opening reaction forming unsaturated carbonyl
compounds.
O
Ph2CO + H C
3
04/12/2016
CH3
hv
O
Ph
Ph
..
O
Ph
Ph
Ph
Ph
11
b) Photoaddition of alkene and alkynes to aromatic compounds:Both alkenes and alkynes undergoes photochemical cycloaddition (1,2 or 1,3 or less
commonly 1,4-addition) to benzene gives adduct.
i) 1,2-Addition:- It is 2+2 cycloaddition reaction forming cyclobutane/cyclobutene
ring which is unstable in some cases and undergoes further reaction.
H
CN
hv
(2+2)
H
H
COOMe
COOMe
COOMe
hv
(2+2)
COOMe
H
COOMe
COOMe
NR
H H
O
O
(4+2)
H H
NR
NR
NR
hv
(2+2)
NR
O
ii) 1,3-addition:.
hv
olefine
prefulvene
1,3-addition
The benzene on irradiation gets converted to key intermediate prefulvene which is also
obtained by the photo isomerism of benzene. The prefulvene is formed from a high
vibrational level of the first excited singlet state of benzene. The olefinic
compounds reacts with prefulvene forming 1,3-substituted product. During such
addition the stereochemistry of olefin is maintained. The reaction is used to for the
synthesis of complex structural molecules. It is [3,2]-cycloaddition reaction.
H
hv
hv
H
hv
ISC
R2NH
T1
04/12/2016
13
c) Photodimerisation of alkenes, conjugated dienes and aromatic compounds:It is reaction of the excited state (singlet or triplet) of one molecule of a reactant with
another molecule of same reactant in ground state forming dimeric product. It forming
1:1 adducts. Photodimerisation reactions occur in both alkenes and aromatic
compounds.
Depending on the structure of the reactant and reaction conditions of the excitation, the
excited state is either singlet or triplet. The isolated olefins absorbs below 200 nm
therefore their unsensitized photodimerization are comparatively little used. The
photochemical dimerisation reaction is of the 2+2 type explains with the help of
following orbital diagram.
R R
R
2
hv
(2+2)
R R
R R
R R
Due to these experimental difficulty, the photoaddition reaction of alkene is carried out
through triplet state of alkene by using photo sensitizer e.g. acetophenone. The max of
acetophenone is 270 nm. It first excited to S1 state and then undergoes inter system
crossing (ISC) to T1 state. In T1 acetophenone, collide with alkene gives ground state
sensitizer and triplet alkene. The triplet state alkene adds through one carbon atom to a
carbon atom of a second molecule of alkene and then undergoes spin inversion
followed by coupling gives cyclic product (mechanism).
04/12/2016
hv
acetone
14
Cyclic olefins are also known to undergo addition reactions instead of dimerisation on
irradiating in methanol. The following reaction has been sensitized by xylene.
H3C
hv
xylene
+ CH3OH
OMe
MeO
ISC
S1
T1
energy
exchange
on
collision
S0 (PhCOMe)
04/12/2016
CH3
T1
S0 (alkene)
15
hv
[ Ph2CO]3
Ph2CO
+
H
First two products are formed by [4+2] addition and third by the [2+2] addition
reaction. Three products are formed have nearly equal proportions.
Benzene does not undergo photodimerization but polycyclic aromatic compounds can
undergoes these reactions. e.g. Anthracene dimerises via its excited singlet state [, *]
state.
hv
S-cis
04/12/2016
S-trans
hv
sensitizer
+
cis-
trans-
+
16
Photo-Rearrangement reaction
Some compounds undergo rearrangement reaction in presence of light
forming structural isomers (where groups or atoms in same molecule
occupied different positions) or to valence bond isomers (where groups
or atoms have same positions but having different bonding framework).
a) Cis-Trans isomerism:When olefins are irradiated by ultra-violet light, they under goes cis-trans
isomerism. This transformation has been carried out by direct irradiation
of olefins or irradiation in presence of sensitizer. The isomerism has been
occurs through singlet or triplet excited state species. The triplet state has
lower barrier to rotation around carbon-carbon bond.
The isomerism has been occurs because bond lost its character in the
excited state, here the two sets of the substitutions tend to occupied
mutually perpendicular planes so as to minimize the repulsive forces
between them.
Ph
hv
04/12/2016
Ph
Ph
Ph
hv
Ph
Ph
17
Ph2CO
cis-stilbene
trans-stilbene
[Ph CO]1
2
[Ph2CO]3
[ Ph2CO]+ [PhCH=CHPh]3
+[ Ph2CO]3
cis- + trans93%
7%
There are some photochemical cis-trans isomerism has been carried out by
using halogens. Halogen undergoes photochemical decomposition to halogen
atom which adds to olefinic double bond to form radical. Elimination of halogen
atom from radical gives raise to constant ratio of cis and trans isomers.
hv
Br2
R
+
H
04/12/2016
2 Br
R H
Br
Br
- Br
+
H
18
b) Intramolecular Photocyclisation:Many dienes and polyenes are converted photochemically into cyclic isomers. The
reactions are stereospecific and electrocyclic type when proceeds through singlet
excited state. In some examples the given organic compounds has been converted into
highly strained ring compounds proceeds via triplet sensitized state.
e.g Irradiation of trans, trans-1,4-dimethyl-1,3-buadiene gives cis-3,4-dimethyl
cyclobutene by dis-rotatory ring closer. It explains by orbital symmetry principle.
hv
H
H
In some examples ring opening reactions are also occurs such asC9H17
C9H17
hv
H
HO
HO
04/12/2016
ergosterol
precalciferol
19
.
.
OH
OH
Ph
Ph
Ph
O
Ph
hv
Ph
spin
inversion
Ph
Ph
Ph
+
Ph
Ph
Ph
Ph
20
Examples
H
H
hv
OH
H
OH
OH
O
hv
. .
H
H
Ph
Ph
Ph
H Ph
O
O
O
mechanismhv
Ph
04/12/2016
[
Ph
S1
spin
inversion
O
hv
Ph
.
1
]
Ph
ISC
[
Ph
T1
]
Ph
.
Ph
Ph
O Ph
Ph
O
Ph
Ph
.
Ph
Ph
21
. .
.
O
.
There are some reactions which forming cage compounds e.g. cyclopentadiene
adds readily to para-benzoquinone thermally (4+2) manner. The product
formed under goes ring closer by irradiation.
O
O
heat
O
O
+
04/12/2016
hv
22
Photoisomerism of benzoneoid compounds:The absorption spectra of benzene shows weak absorption at 250 nm and strong band at
200 nm due to * transition. Irradiation of benzene by these wavelength radiations
shows interesting photochemical transformation to fulvene, benzvalene and Dewar
benzene ring compound. This transformation proceeds through perfulvene.
.
.
[fulvene]
{prefulvene}
[benzvalene]
If benzene is irradiated at 253.7 nm, then it gives (a) and (b) only whereas if it irradiated
at 160-200 nm then gives mixture of all these products. The benzvalene intermediate
is trapped by using methanol asOMe
hv
OMe
Substituted benzene gives other strained products than (a) and (b) like Dewar benzene.
hv
isohexane
04/12/2016
23
hv
hv
or
O
hv
hv
Pb(OAc)4
hv
O
O
prismane
hv
04/12/2016
hv
hv
24
O
O
.
O
.
O
. }solvent cage
O
O
OH
OH O
.
O
O
04/12/2016
25
Reactions of ,-unsaturated ketone:The conjugated carbonyl group in ,-unsaturated ketone increases the energy of
highest -orbital and decrease the energy of * orbital and hence ( *) transition
become less energetic. The energy of n-orbital does not decreases but that of *
decreases, therefore (n *) transition also become less energetic. After irradiation of
,-unsaturated ketone, the excited state of ketone possess more ( *) than (n *)
triplet character even though there may occur an initial (n *) transition.
O
]+
.
O
+MeO
.
O
OMe
OMe
OMe
OMe
OMe
When acyclic ,-unsaturated ketones having a -hydrogen are irradiated causes migration
of double bond. The -hydrogen abstraction and transfer to the oxygen atom cause via six
membered cyclic transition state. Therefore, the substrate changes from conjugated to nonconjugated carbonyl compound. The radiation used for such transitions does not carries
decomposition of the compound and excitation of non-conjugated system.
O
04/12/2016
OH
26
Norrish Type-I and Norrish Type-II Reaction:The bond dissociation energy of a carbon-carbon bond adjacent to a carbonyl group
is small and photo-chemically undergoes hemolytic fission is called Norrish type-I
reaction or -cleavage.
The CO-C bond under goes fission forming alkyl and acyl radical. The acyl radical
under goes decarboxylation followed by recombination of two radicals or abstract
of hydrogen atom or secondary fission to get hydrocarbon and olefin. The carbonyl
compound undergoes fission in gaseous or liquid state through (n *) singlet or
triplet state.
CH2
CH2
CO
n
CH2
.
CH
hv
CH2
.CO
-CO
CH2
(a)
n
CH2
(c)
(b)
CH2
CH2
CH2
CH2=CH2 + CH3(CH2)n-3CH=CH2
CH2
CH2
CH3(CH2)n-1CH=CH2
27
During decomposition more stable radical is formed (alkyl radical). The stability
of the alkyl radicals are- 30 > 20 > 10 > methyl >H. The stability of alkyl radical
can be important in the unsymmetrical ketones.
CH3-CO-CH(CH3)2 hv (A)
.CH(CH ) +
hv (B)
3 2
CH3CO
(CH3)2CHCO
CH3
In above example, the route (a) is currect because of stability of the radical.
O
hv
04/12/2016
..
hydrogen
transfer
28
A ketone having -hydrogen atom is under goes Norrish type-II reaction forming
an olefin and enol of a smaller ketone. It is characterized by the transfer of hydrogen atom to a carbonyl group. This transformation has been occurred through
six membered transition state forming methyl carbonyl compound and olefin.
Both (n *) singlet and (n *) triplet are participate in the intramoleculer hydrogen
abstraction reaction will the ketone having low lying ( *) state does not under
goes these reaction.
H
O
R1
R2
H
O
hv
O H
R1
R2
R1
R2
R
R1
CH3
R2
OH
hv
OD
CH3OD
H3C
H3C
D H
H H
OH
COOCH3
Ph hv
Type-II
04/12/2016
Ph
COOCH3
acid
COOCH3
Ph
+
COOCH3
Ph
OH
COOCH3
COOCH3
29
hv
OH
R
or R
H O
R R
OH
H
e.g.
OH
OH
OH
OH
HO
OH
OH
+
O
04/12/2016
30
Photolysis of compounds containing the N2+ group:Irradiation of diazomethane either gives methylene radical in singlet or triplet
state.
..
hv
CH2N2
CH2
N2
N
O
..
MeO
O
MeO
-O
e.g. In 2,3-dimethyl butane, methylene is inserted into both primary and tertiary
C-H bonds whereas carbomethoxymethylene reacts almost all tertiary positions.
CH3
H3C
04/12/2016
..
CHCOOMe
COOMe
31
MeOOC
COOMe
COOMe
H3C
H
MeOOC
H
CH3
spin
inversion
H3C
MeOOC
COOMe
H
CH3
COOMe
Ph
PhCO
hv
N2
04/12/2016
..
Ph
Ph
Ph
Ph
carbene
O
Ph
ketene
Ph
trapping
Ph
Ph
32
Alkenyl and allyl azides gives nitrene which undergoes intramoleculer addition
gives highly strained compounds. e.g.R
R
hv
N3
..
.N.
..
.N.
hv
N3
RN=C=CH2
The nitrene abstract -hydrogen atom and forming cyclic product is the
synthetically useful reaction. The -hydrogen atom must be stereochemically
placed at suitable position. It is called Hoffmann-Loffler-Fretag like reaction.
R
04/12/2016
N3
hv
...
N.
NH
H
N
33
N
mechanism:Cl
N
H
Cl H
+N
hv
acid
.
N+
hv
-Cl
N+
H
base
Cl
-HCl
base
H
N+
Cl or
R2NHCl
Cl
The protonated amine on photolysis gives nitrogen cation radical which abstract the
hydrogen atom form the -carbon via six membered transition state. The resulting
alkyl radical abstract chlorine atom from more of chloramines. The amino group is
released with base which displaced the halogen intramoleculeraly. This reaction
introduced the functionality on the unreactive aliphatic carbon atom. It is used in
steroids series to modified angular methyl groups.
NHMe
H
1. N-Chlosuccinic acid
Me N
04/12/2016 2
2. H2SO4
3. HO Me2N
34
Barton reaction:Irradiation of organic nitrile introduced functionality on the unreactive aliphatic carbon atom carries atleast two hydrogen atoms. The organic nitriles on irradiation
forming oxy-radical which abstract hydrogen atom from -carbon atom forming alkyl
radical. The resulting radical combine with nitric oxide librated in photolysis to give a
nitroso compound and is under goes tautomerism to oxime.
H O N O
hv
-NO
organic nitrile
H O.
Hshift
oxy-radical
OH
NO
O
OAc
HO
HON
OAc
ONO
OH2
HNO2
O
OAc
HO
O
O
HO O
HNO2
HO
OAc
O OH
OH
N OH
hv
NOCl
O
R
OH tautomer
ism
alkyl radical
04/12/2016
NO
O
O
OAc
35
The photolysis of tertiary hypochlorites gives alkoxy radicals which can abstract
the hydrogen atom form -CH group forming intermediate alkyl radical. The alkyl
radical abstract chlorine from second molecule of hypochlorite gives -chloro
alcohol which is cyclised by using base.
example:1)
Cl2O
OH
.O
HO
-RO
Cl HO
HO
2)
OCl
.
-Cl
ROCl
hv
OH
OCl
Cl
O
Cl2O
-O
2.-OH
04/12/2016
36
Hunsdiecker reaction
The Hunsdiecker reaction (also called the Borodin reaction after Alexander
Borodin) is the organic reaction (reflux) of dry silver salts of carboxylic acids with
bromine in carbon tetrachloride to give organic bromide with evolution of carbon
dioxide.
Mercuric oxide will also affect this transformation.
04/12/2016
37
Phenolic Oxidative coupling:Phenolic oxidative coupling reaction is a radical process by which two phenolic moieties are
joined to each other. Two phenolic moieties are reactive via an acid catalyzed Michael reaction
to give dimer which cyclized via the phenol hydroxyl group to give coupled product. e.g.Ac
Ac
OH
HO
K3[Fe(CN)6]
Me
HO
OH
O
Me
OH
Me
Me
OH
HO
O
Ac
OH
HO
O
Ac
Me
OH
Me
Ac
Ac
HO
OH
OH
K3[Fe(CN)6]
Me
Me
HO
.
OH
Ac
Ac
Ac
HO
Me
HO
HO
Me
OH
Ac
Ac
.
O
HO
O
OH
Me
OH
O
Ac
HO
O
Me
Me
Me
OH
HO
.
-OH
.
OH
HO
O
Ac
OH
HO
O
Ac
In this reaction electron transfer from a metal salt to phenol forming quinone radical
(aryl radical) which react with second phenolic ring to give another radical. It further
lose hydroxyl radical/hydrogen atom to give quinone product.
In most of coupling reactions K3[Fe(CN)6] is used instead of metal salt.
04/12/2016
38
Examples:1.
CH3
CH3
hv
2.
O
3.
hv
hv
O
CH3
4.
hv
CO2
CH3
04/12/2016
39
CH3
hv
1.
hv
HC CH
*
*
(2+2)
1,2-H shift
CH3
hv
2.
O
hv
O
04/12/2016
*
*
*O
40
Ph
H
4.
OH
Ph
hv
O
*
O
Ph
Ph
Ph
Ph
OH
triplate state
H
OH
O
HO
COOH
COOH
COOH
OH
COOH
COOH
1.
hv
OH2
04/12/2016
41
NH2
NH2
+
H3COC
H3COC
O
ONO
hv
2.
NOH
O
hv
3. CH3(CH2)4CHO
04/12/2016
sens.
CH3(CH2)4
CH3(CH2)4
42