CONTENTS

Transitions
Norrish-I cleavage
Norrish-II cleavage
Paterno-buchi reaction
Photoreduction
Calculation of quantum yield
Photochemistry of enones
Rearrangement of ,-unsaturated ketones
Photo fries rearrangement
Barton reaction



Transitions

Norrish type-1 cleavage(- cleavage)

Norrish type-1 process is given by three types of ketones

Saturated acyalic ketones
Saturated cyclic ketones
,- unsaturated ketones
Norrish type 1 process given by acyclic saturated
ketones:
Norish type-1 clevage
R
1
R
O
R
2
hv
R
C
O
+
R
1
CH
R
2
acyl radical alkyl radical
Primary process:
Norish type-1 clevage
R C
O
Decarbonylation
+
CO
2(a)
acyl radical
alkyl radical
R CH
2
CH
2
R CH
2
+ R CH
2
R
R
(Recombination)
R CH
2
+
R
1
C H
R
2
R CH
3
R
1
R
2
+
intermolecular hydrogen abstraction
scheme 2(a)
:Secondary process
Norish type-1 clevage
O
R
C
+
R
CH
R
2
o
|
O
R
+
R
1
R
2
scheme 2(c)
R
1
CH
R
2
R
1
R
2
O
R
C
+
+
O
R
H
o
|
scheme 2(b)
Norish type-1 clevage
O
n
hv
S
1
ISC
T
1
O
CH
2
C
n
Acyl
-
alkyl biradical
CH
2
CH
2
n
Radical recombination
Intermolecular
hy drogen bonding
n
CH
3
CH
2
n
Cy cloalkane Alkene
Scheme 4(a)
Decarbonylation
(2) Norrish type-1 reaction of saturated cyclic ketones:
O
C
CH
2
n
o
O
CH
3
ketene
Scheme 4(c)
Norish type-1 clevage
(2) Norrish type-1 reaction of saturated cyclic ketones:
n
O
C
CH
2
o
|
O
CH
2
n
unsaturated aldehyde
Scheme 4 (c)
3) Norrish type-1 process given by cyclopentanones:
Norish type-1 clevage
O
O
CH
2
C
CH
2
CH
2
hv
gas phase
-CO
C H
2
CH
2
C H
2
CH
2
+
Scheme 7
-cleavage given by cyclobutanones:
Norish type-1 clevage
O
O
C
CH
2
S
1
-CO
CH
2
CH
2
CH
3
CH
2
1,4
-
acyl
-
al kyl di radi cal
2) By a subsequent -cleavage and formation of ethylene and ketene.
Loss of CO and formation of 1,3-diradical
O
C
CH
2
C H
2
O
C H
2
CH
2
+
I2 2I cycloaddition
+
O
C
CH
2
O O H
R
ROH ring
expansion
Oxacarbene
Acetal
3) Rebonding to oxygen
Norish type-1 clevage
-cleavage reaction:
O
CH
3
hv
breaking of
C
o

C
|
bond
O
H
C H
2
CH
CH
3
(b) (a)
(a)
(b)
1,2-Hydrogen shift
O
C H
3
CH
3
O
C H
2
CH
3
(Major)
(Minor)
3-penten-2-one
4-penten-2-one
Norrish type-II cleavage i.e. -Hydrogen abstraction:
(intramolecular hydrogen abstraction)
H
O
R
H
O
C
R
CH
2
OH
C
R
o
|

hv
n->
t
*
S
1
or T
1
.
cyclic transition state 1,4-diradical
CH
2
OH
C
C H
3
R
OH
H
H
1
2
3
4
CH
3
O H
R
C H
3
H
H
.
.
sp orbitals
cleavage of
|
-bond
cyclisation
OH
R
C H
2
CH
2
OH
R
CH
2
O
R
C H
3
ketoform
alkenol
alkene
+
.
.
PATTERNO-BUCHI REACTIONS
H
5
C
6
C
6
H
5
O
+
C H
2
CH
3
CH
3 hv
O
H
5
C
6
H
5
C
6
CH
3
CH
3
(90% yield)
Addition to Election-rich alkenes
Addition to electron-deficient alkenes
Photoreduction
O
H
5
C
6
H
5
C
6
2
+
C H
3
C H
3
OH
hv
H
5
C
6
C
6
H
5
OH
C
6
H
5
O H
C
6
H
5
+
C H
3
CH
3
O
Benzophenone 2-propanol
Benzpinacol
acetone
1)
S
1
(n ->
t
-
)
ISC
T
1
(n ->
t
-
)
H
5
C
6
C
H
5
C
6
O
Ph
2
CH O
(H
3
C)
2 OH
+
CH Ph
2
OH
(H
3
C)
2
CH
OH
+
(H
3
C)
2
CH OH
(H
5
C
6
)
2
O
(H
5
C
6
)
2
CH
OH
(H
3
C)
2
O
(H
5
C
6
)
2
O
+
+
H
5
C
6
C
OH
C
6
H
5
OH
C C
6
H
5
C
6
H
5
H
5
C
6
OH
H
5
C
6
OH
C
6
H
5
C
6
H
5
+
Calculation of quantum yield

The efficiency of photochemical process is often expressed in terms of quantum yield () which is
defined as the number of molecules reacting per quantum of light absorbed

Mathematically
The energy E absorbed per mole of the reacting substance is called one Einstein

The quantum yield of the product formation
If the law is correct then the quantum yield should be unity. This however is very rare.
Photochemistry of enones

O
hv
O O
ISC
1
3
n
, t
-
t, t
*
Rearrangement of ,-unsaturated ketones
O
R
R
O
C
C
R
R
O
CH
C
R
R
O
R
R
O
R
R
OR
n ->t
-
S
1
ISC
recombination
ROH
Photo-Fries rearrangement
Barton reaction
Barton reaction involves the photolysis of a nitrite to form a -nitroso alcohol.
It is nammed for the british chemist Sir Derek Harold Richard-Barton. The
mechanism is belived to involve a homolytic cleavage of N-O bond followed
by -hydrogen abstraction and free radical recombination.

PHOTOCEHMISTRY AND PERICYCLIC
REACTIONS BY
JAGDAMBA SINGH &JAYA SINGH
NEW AGE INTERNATIONAL PUBLISHERS
SECOND EDITION

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