ISSN: 2694-1708 DOI: 10.33552/ICBC.2021.01.
000520
Insights in
Chemistry and Biochemistry
Review Article Copyright © All rights are reserved by Shraddha Upadhyay
Photochemical Reaction and Applications in
Organic Synthesis
Shraddha Upadhyay1* and Jitendra Kumar2
1
Department of Applied Chemistry, SITE, SVSU, Meerut, India
2
Department of Mathematics, Keral Verma Subharti College od Science, India
*Corresponding author: Shraddha Upadhyay, Department of Applied Chemistry, Received Date: May 25, 2021
SITE, SVSU, Meerut, U.P., India.
Published Date: June 22, 2021
Abstract
Chemical as well as physical property that may occur under the influence of light is called Photochemistry. Photochemical transformations have
been governed by two fundamental principles. These principals are First law: This law is also called as Grotthuss-Draper law; it states that for a
photochemical reaction to take place it should be essential that light must be absorbed by a compound. Second law: The second law or Stark-Einstein
law gives a photo equivalence law which is states that for each photon of light absorbed by a compound only one molecule of compound is activated
for corresponding reaction. The efficiency of each photochemical process is calculated by Quantum Yield (Φ). Many photochemical reactions are
complex, thus the quantum yield is specified for a particular event. It is defined as “ratios of the number of moles of a reactant disappearing, or the
number of moles of a product obtained, per one mole of light absorbed by compound.” After that many of secondary reactions proceeded (shown in
the gray box). Absorption of light (uv/vis) induces energy sufficient in molecule to break covalent bonds. Since, E = hc / λ, hence, longer wavelength
have less energy and vice-versa. Consequently, ultraviolet light is most effect photochemical reactions. In this review we discuss about amongst all
some of photochemical reactions collectively which are initiated by ultraviolet light specifically.
Keywords: Electromagnetic radiations; Singlet state; Triplet state; Excited state; Photochemical transformations
Introduction
wavelengths less than 200 nm is sufficient to excite a electron to
In the early 1900’s Giacomo Ciamician from University of
a higher energy orbital. A pictorial diagram showing the various
Bologna used sunlight for his research hence he is the father
kinds of possible electronic excitation in organic molecules is
of photochemistry. Before that era, many sources used for a
shown below (Figure 1).
photochemical reaction these are bright incandescent lamps
(chiefly infrared and visible light), low, medium and high pressure All the six transitions outlined are achieved by the energies
mercury lamps (185 - 255 nm, 255 -1000 nm & 220 -1400 nm available in the 200 to 800 nm spectrum. Energetically favored
respectively), high intensity flash sources and lasers. In careful electron excitation will be from the highest occupied molecular
studies of specific chromophore, sources of monochromatic light orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO),
may be desired. In this review we focus on electronic excited states and the resulting state is called an excited state. Electronic transition
which are formed when a photon is absorbed by a chromophoric in the molecule is occurring only after; sufficient light energy will
functional group present in molecule. Ultraviolet radiation having be absorbed. On excitation electron promoted to a higher energy
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Insights in Chemistry and Biochemistry Volume 1-Issue 4
orbital. The spectrum is drawn as a graph of absorbance (A) versus Types of electromagnetic radiation
wavelength. Absorbance usually ranges from 0 (no absorption)
Electromagnetic wave is only wave which is able to travel
to 2 (99% absorption), and is precisely defined in context with
in empty space. Energy which is related with electromagnetic
spectrometer operation. Franck-Condon Principle state that this
wave is called as electromagnetic energy and this is energy in
electronic transition so faster than nuclei can respond. Bonding in
the form of waves. Einstein and Max Plank said in his theory that
an excited state is usually lower than in the ground state. Thus, bond
Electromagnetic radiation exists in form of small packet of energy
length is increased in the excited state. Finely, electron in excited
which is called photons. This energy behaves as waves and energy
state may return to the ground state by emitting a photon (light
packets. Thus we can say that Electromagnetic energy is type of
blue line). This radiative decay is called fluorescence if it takes place
energy which originated from electromagnetic waves. This can
rapidly from the initial excited state. It is termed phosphorescence
also be defined as energy that transmits information (in the form
if it occurs slowly by way of other excited states.
of waves) from one place (material) to another or wave which is
Excited states are of two types, singlet and triplet. This produced when charged particles that are placed in magnetic
difference is just because of electron spin angular momentum. Most and electric field which are right angle to each other undergoes
ground states are singlet, hence excited states initially formed by acceleration. The oscillation of the particles in the wave emits
absorption of light is singlet. With loss of heat energy (relaxation), energy called electromagnetic wave energy. This information can
Internal conversion of excited states to lower energy states takes be in the form of light, heat, or in any other form. Let us understand
place. Also, an excited state may return back to the ground state via step by step what electromagnetic energy is. This energy radiation
emitting a photon. The conversion of a singlet state to triplet state, have same speed as speed of light and it contains radio waves, TV
or vice versa, is termed intersystem crossing. This process is slower waves, radar waves, heat, light, X-rays, visible waves, etc. The Sun,
than internal conversion. Radiative decay from a triplet state is the earth and the ionosphere are main sources of electromagnetic
called phosphorescence and is generally quite slow. energy in nature (Table 1).
Table 1: Approximate Boundaries of Electromagnetic Radiations.
Region Name Energy, J Wavelength Frequency, Hz
X-ray 5 x 10 -19
10 nm 3 x 1019
Vacuum ultraviolet 2.5x 10-19 10-200nm 3 x 1016
Near ultraviolet 6.6x10-20 200-400nm 1.5 x 1015
Visible 5 x 10-19 400-800nm 7.5 x 1014
Near Infrared 2.5x 10 -19
0.8-2.5 um 3.8 x 1014
Fundamental infrared 6.6x10-20 2.5-50 um 1x1014
Far Infrared 4x10-21 50-300 um 6 x 1012
Microwave 6.6x10-22 0.3 mm-0.5 m 1 x 1012
Radio wave 4x10 -25
0.5-300 x 10 6
6 x 103
Some facts about electromagnetic energy which causes change in their electric and magnetic fields, which
leads to generate electromagnetic wave. Heat and vibration
1. According to formulae E = hc / λ the higher the energy
generated via this mode depends on the wavelength and energy
of the particles of electromagnetic wave, shorter is their
of the electromagnetic wave (Figure 2).
wavelength.
2. It can travel through any material as well as through Photochemical Reaction
vacuum. Chemical reactions initiated by light are called as photochemical
reactions. Energy in form of photon is absorbed or emitted by
3. Their speed in vacuum is same as that of light, i.e.
matter.
approximately 1, 86,000 miles per second or 3, 00,000
kilometers per second. After absorption of light an electronic excitation from ground
state to excited state takes place. This leads to promote an electron.
4. Most important thing is when it enter into matter, they
The types of excitation are like n→π∗ or π→π∗ etc. Most of
get slow down i.e. their energy decreases, hence wavelength
photochemical reactions take place during excitation from S1 and
increases.
T1 excited states.
5. When this hits an object, it generates heat at the surface,
If a molecule absorbs energy, it can undergo photochemical
this heat in turn causes the particles of that object to vibrate
reactions or there is possibility of they loss of energy via two
while in reverse when object is heated, particles get accelerated
Citation: Shraddha Upadhyay, Jitendra Kumar. Photochemical Reaction and Applications in Organic Synthesis. 1(4): 2021. ICBC. Page 2 of 9
MS.ID.000520. DOI: 10.33552/ICBC.2021.01.000520.
Insights in Chemistry and Biochemistry Volume 1-Issue 4
methods: radiative processes which involve emission of a photon. emission of photon. In this case the internal conversion occure
Example of radiative phenomenon is phosphorescence which occur which not involves spin change, such as S1→S0. The intersystem
when electron relaxation to a lower state with different multiplicity, crossing-involves change in spin multiplicity. Excitation by energy
such as T1→S0 (spin forbidden). Other example is fluorescence in transfer is Sensitization (deactivation is Quenching). There are lots
which relaxation occur to lower state of same multiplicity, such of photochemical reactions. Some of these are discuss in this review.
as S1→S0 (spin allowed). The non-radiative processes lead to no
Figure 1: Pictorial diagram showing the various kinds of possible electronic excitation.
Figure 2: Graphical representation of electromagnetic diagram.
1. Geometrical Isomerism: photochemical cis/trans (E/Z) interactions hence it typically absorbs at a lower λ [1] (Image
isomerism in mostly leads to thermodynamically less stable 1).
cis-isomer -cis-isomer have less conjugation b/c of non-bonded
Image 1:
Citation: Shraddha Upadhyay, Jitendra Kumar. Photochemical Reaction and Applications in Organic Synthesis. 1(4): 2021. ICBC. Page 3 of 9
MS.ID.000520. DOI: 10.33552/ICBC.2021.01.000520.
Insights in Chemistry and Biochemistry Volume 1-Issue 4
2. Electrocyclizations: Photochemical electrocyclization 4. Paterno-Büchi Reaction: Paterno and Chieffi observed
occur via LUMO 4n - disrotatory 4n+2- conrotatory. In this the first example of a [2 + 2] cycloaddition between a carbonyl
case a new σ-bond form between the termini of the conjugated and an olefin to make an oxetane [4] (Image 4).
π-system. Both bond breaking and bond formation process take
5. Arene-Olefin Cycloadditions: A photocatalyzed cycload-
place at the same time [2] (Image 2).
ditions reaction between arenes and an olefin takes place all
3. DeMayoReaction: In this reaction [2 + 2] cycloaddition three positions available in arenes. On this basis these are sum-
takes place involving double bond of an enol and another olefin marized as ortho cycloadditions-[2 + 2], para cycloadditions-[4
and the retro-aldol reaction [3] (Image 3). + 2] and meta cycloadditions-[3 + 2] [5] (Image 5).
Image 2:
Image 3:
Image 4:
Image 5:
Citation: Shraddha Upadhyay, Jitendra Kumar. Photochemical Reaction and Applications in Organic Synthesis. 1(4): 2021. ICBC. Page 4 of 9
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Insights in Chemistry and Biochemistry Volume 1-Issue 4
6. Photo induced Electron Transfer (WitkopCyclization): 9. Paterno buchi reaction: when carbonyl compound react
polar solvents facilitate the generation of radical ions and with alkene in presence of light resulted in trimethylene oxide
subsequent chemical reactions [6] (Image 6 & 7). [9] (Image 10).
7. Photolysis of 3-hydroxy-3-methyl-2-butanone: photol- 10. Photoinduced isomerization of azobenzene: the sim-
ysis of 3-hydroxy-3-methyl-2-butanone in presence of UV radi- plest photoinduced isomerisation is seen in azobenzene [10]
ation leads to five major reaction products acetone, acetic acid, (Image 11).
formaldehyde, CO and methanol [7] (Image 8).
11. Norrish type II reaction: when photo-excited ketone
8. Di-pi methane rearrangement: reaction involves the abstract their H-radical from γ-position leads to corresponding
photolysis of molecule having two pi-bonds bonded to single biradicals, which is further resulted into cyclobutane is called
sp3 hybridized C atom resulted into synthesis of cyclopropane Norrish type II reaction [11] (Image 12).
[8] (Image 9).
Image 6:
Image 7:
Image 8:
Image 9:
Citation: Shraddha Upadhyay, Jitendra Kumar. Photochemical Reaction and Applications in Organic Synthesis. 1(4): 2021. ICBC. Page 5 of 9
MS.ID.000520. DOI: 10.33552/ICBC.2021.01.000520.
Insights in Chemistry and Biochemistry Volume 1-Issue 4
Image 10:
Image 11:
Image 12:
12. Novel photochemical rearrangement: 2-formyl pheny- photochemical reaction afford acyl azirines, which resulted into
lalkeno-derivatives in presence of UV light in benzene solution the corresponding oxazoles [16] (Image 17).
afforded thepolysubstituted isochromanones through Novel
17. 4,4-Diphenylcyclohexenone rearrangement: in such
photochemical rearrangement [12] (Image 13).
type of photo catalytic rearrangement one double bond and one
13. Photo-Fries rearrangement: this photochemical reac- of the phenyl groups, C-4, migrated to C-3 [17] (Image 18).
tion involves the homolytic cleavage of C–O, C–S and C–N, of
18. Photochemical rearrangements of Natural Product:
esters, amides, thioesters etc [13] (Image 14).
the best result of such rearrangement is found in santonin
14. Nitro-nitrite rearrangement: in this type of rearrange- which in presence of light converted into lumisantonin [18].
ment nitro aromatic species undergoes photochemical initiated
19. Photochemical Curtius rearrangement: in curtius re-
rearrangement [14] (Image 15).
arrangement migration takes place along with full retention of
15. Photochemical reaction of ethyl diazotrifluoropro- configuration at R-group [19] (Image 19).
panoate: photolysis of ethyl diazotrifluoropropanoate rear-
20. Photochemical Harger rearrangement: in Harger re-
ranges and resulted into efficient insertion reaction with the
arrangement the phosphinic azide forms a metaphosphonim-
O–H bond [15] (Image 16).
idate in presence of light followed by methanol. This is actually
16. Photochemical rearrangements of isoxazoles: this R-groups which migrate [20] (Image 20).
Citation: Shraddha Upadhyay, Jitendra Kumar. Photochemical Reaction and Applications in Organic Synthesis. 1(4): 2021. ICBC. Page 6 of 9
MS.ID.000520. DOI: 10.33552/ICBC.2021.01.000520.
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Image 13:
Image 14:
Image 15:
Image 16:
Image 17:
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Insights in Chemistry and Biochemistry Volume 1-Issue 4
Image 18:
Image 19:
Image 20:
Conclusion 2. Woodward RB, Hoffmann R (1965) Stereochemistry of Electrocyclic
Reaction. J Am Chem Soc 87: 395.
Photochemistry itself is a mature science in this review, we have 3. Challand BD, Hikino H, Kornis G, Lange G, de Mayo P (1969) de Mayo P
discussed about the unique features of photochemical reactions. A reaction. J Org Chem 34: 794-806.
variety of photochemical reactions is described above. Overview 4. Mihailovic M, Lorenc L, Pauolvic V, Kalvoda J (1977) vitamin D3 analogs.
Tetrahedron 33: 441.
of photochemical reaction also discusses significance of such
5. Wilzbach KE, Kaplan LA (1966) Photochemical 1,3 Cycloaddition of
reactions and is mainly focused on implications for main product.
Olefins to Benzene. J Am Chem Soc 88: 2066–2067.
Ubiquity of photochemical reactions implies the importance of
6. Yonemitsu O, Cerutti P, Witkop B (1966) Photoreductions and
understanding the underlying processes and mechanisms on a photocyclizations of tryptophan. J Am Chem Soc 88: 3941.
molecular level. Now there is more need for new and exciting 7. Bouzidi H, Laversin H, Tomas A, P Coddeville, C Fittschen, et al. (2014)
theory in this explored field. This is expected to be discovered in Reactivity of 3-hydroxy-3-methyl-2-butanone: Photolysis and OH
Reaction kinetics. Atmospheric Environment 98: 540-548.
the future. It seems a promising field for future research.
8. Hixson SS, Mariano SS, Zimmerman EH (1973) Di-.pi.-methane and oxa-
Conflict of Interests di-.pi.-methane rearrangements Chem Rev 73: 531-551.
9. Büchi G, harles Inman GC, Lipinsky ES, Light-catalyzed Organic Reactions
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the Presence of Ultraviolet Light. J Am Chem Soc 76: 4327-4331.
Acknowledgement
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