Sulphonic acid functionalized porphyrin anchored with a: Meso -substituted triazolium ionic liquid moiety: A heterogeneous photo-catalyst for metal/base free C-C cross-coupling and C-N/C-H activation using aryl chloride under visible light irradiation

Article abstract of DOI:10.1039/d0nj03637d

We report an easy process to synthesize sulphonic acid functionalized porphyrin, anchored with a meso-substituted triazolium ionic liquid moiety (SAFPTILM) for metal/base free C-C cross-coupling and C-N/C-H activation using aryl chloride under visible light irradiation. The acid strength has been measured based on the Hammett indicator. The SAFPTILM photocatalyst comprising 18 π-conjugated electronic systems with the chromophore substituents in the meso-position can provide rapid electronic conducting channels during photocatalysis under the irradiation of visible light. It was found that SAFPTILM is an efficient photocatalyst for the Heck, Sonogashira, Buchwald, Ullmann/Fittig coupling and C-H activation of phenols with different aryl chlorides in the absence of a base/noble metal, using 5 W LED (yellow) light under ambient conditions. The photocatalyst with low band gap (1.55 eV) comprising conjugation, favors coupling reaction of unactivated aryl chlorides, by easy excitation of electrons and transfer to the conjugated benzimidazolium based phenylenediamine support delaying the recombination of photoinduced electron-hole pairs.

Full text of DOI:10.1039/d0nj03637d

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Sulphonic Acid Functionalized Porphyrin Anchored with meso-
Substituted Triazolium Ionic Liquid Moiety: Heterogeneous Photo-
Catalyst for Metal/Base Free C-C Cross-Coupling and C-N/C-H
activation using Aryl Chloride under visible light irradiations
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Karan Bhansali, Subodh Raut, Shital Barange and Pundlik Bhagat*
We report an easy process to synthesize sulphonic acid functionalized porphyrin, anchored with meso-substituted triazolium
ionic liquid moiety (SAFPTILM) for metal/base free C-C cross-coupling and C-N/C-H activation using aryl chloride under visible
light irradiations. The acid strength has been measured by Hammett indicator. The SAFPTILM photocatalyst comprising 18
π-conjugated electronic systems, with the chromophore substituents on the meso-position can provide rapid electronic
conducting channels during photocatalysis by irradiation of visible light. It was found that the SAFPTILM is an efficient
photocatalyst for the Heck, Sonogashira, Buchwald, Ullmann/Fittig coupling and C-H activation of phenols with different aryl
chlorides in absence of base/noble metal, using 5 W LED (yellow) light at ambient conditions. The low band gap (1.55 eV)
of SAFPTILM with conjugation assists photocatalytic reaction using inactivated aryl chlorides, by easy excitation of electrons
and transfer to the conjugated benzimidazlium based phenylene di-imine support delaying the recombination of
photoinduced electron–hole pairs.
/phthalocyanine4,5 also have attracted tremendous
interests pointing to constantly refine their
performance in the production of reactive oxygen
species (ROS), especially singlet oxygen6
photodynamic cancer therapies, artificial light
harvesting, optoelectronic devices, various sensor
technologies7 and light energy conversion.8 Hasobe
et al. have reported that porphyrin-based
nanoarchitectures applicable for light energy
conversion.9 Moreover, they have revealed CTAB-
1. Introduction
Photosynthesis is the only important solar energy
harnessing process, promoting animal and plant life
on the Earth. It is the source of all of our food and
most of the energy resources acquired by absorbing
light energy by chlorophyll. Chlorophyll is one of the
key biological molecules for all phototrophic
organisms which contain tetra-pyrrolic porphyrin
units containing magnesium atom at its center.1
Taking motivation from these, various technologies
have been emerged making use of synthetic
chlorins or porphyrins to imitate photosynthesis
artificially, needing molecules with good absorption
in visible range and other photophysical and redox
characteristics.2,3 Besides, with the rapid
development of different photocatalytic processes
over the past few decades, bio-inspired
assisted TiO2
doped
zinc
meso-tetra(4-
pyridyl)porphyrin hexagonal nanocylinders which
afford effective under visible light for the
generation of hydrogen.10 McHale and his co-
workers have described that self-assembled
structures of porphyrin have prospective role in
solar cell and light harvesting devices.11
Additionally, surfactant aided nanospheres and
nanorods of zinc meso-tetra(4-pyridyl) porphyrins
have also been testified recently, for photocatalytic
porphyrin
photosensitizers
containing
applications.12
Accordingly,
porphyrins,
a*Department of Chemistry, School of Advanced Science,
Vellore Institute of Technology, Vellore-632014, Tamil Nadu, India.
E-mail: drprbhagat111@gmail.com
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
porphyrinoids and their metal complexes have
been widely used in the process of photocatalysis
and environmental remediation, playing the key
role of tentacles for light-sensing probes. The
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spectacular performance perceived due to their was revealed with a great prospective forVi
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slight singlet–triplet splitting, the high quantum range synthetic utility with (E)-selectivity of
yield for the intersystem channel, and the extensive corresponding products from aryl iodides.20 Javier
triplet-state life span. Consequently, they are F. Guastavino and co-workers reported metal free,
magnificent
chemical
stabilizers
and t-BuOK base catalysed process for the synthesis of
photosensitizers under visible light irradiation.13 E-stilbene by direct C-H arylation of alkenes with a
Porphyrin molecules are identified to form wide range of aryl halides, including ArCl using 400
aggregates even in homogeneous solution.14 W lamps.21 The UV light induced reaction applied
Among different aggregates described on porphyrin for the construction of C-C, C-N bonds using aryl
moieties, two types of aggregates are reflected to chlorides and inert arenes in absence of catalyst.22
be very significant one is the H-aggregates, where The metal/base free, mild reaction protocol also
hypsochromic shift is observed due to face-to-face afforded the trifluoromethylation products under
arrangement of molecules and the other J- the optimized conditions tolerating electron
aggregates, in which bathochromic shift is donating and withdrawing groups. Louis Onuigbo’s
dominated due to side-by-side arrangement of group recently described a metal-free Heck
molecules.15 Mandal et al. have fabricated 1- coupling technique, efficiently applied to a wide-
hexadecyl-3-methylimidazolium bromide-assisted ranging substrates including heteroaromatics, with
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zinc octaethylporphyrin (ZnOEP) nanoaggregates strong
electron-donating
substituents
on
and confirm the H-aggregation of porphyrin during diarylethylenes under mild conditions, under
the formation. It was confirmed that IL-supported simulated or natural sunlight.23 Recently, a
ZnOEP indicated high efficiency in transfer of recyclable Pd-rGO/CNT/CaFe2O4 nanocomposite
energy from porphyrin to phthalocyanine compare with high multifunctional photocatalytic activity
to analogous protocol in organic solvent.16 Thus under visible light irradiation established towards
literature study identified the crucial role of IL in the Heck reaction involving aryl iodides to achieve
porphyrin aggregation and enhancement of energy the product in good to excellent yields.24 Recently,
transfer. Taking inspiration from these, our we have synthesized polymer supported Fe-
research group engaged with the design and phthalocyanine
knotted
with
carboxyl
fabrication of porphyrin and phthalocyanine functionalized benzimidazolium moiety for efficient
photosensitizers to imitate artificial photosynthesis visible-light-driven degradation of organic dyes
for harvesting of visible light with good extinction from aqueous solutions. The photocatalyst
coefficient.
presented excellent activity towards the
degradation of dyes, without any additives such as
ZnO/TiO2 in the presence of 5 W LED lamp as a
source of light.25 More recently, our group reported
perylene supported metal free brønsted acid-
One of the ways of energy sustainability is to make
viable utilization of light energy to drive chemical
transformations. Our research group has
successfully reported a polymer-supported salen-
palladium complex as a heterogeneous catalyst for
the Mizoroki-Heck cross-coupling reaction and the
Suzuki-Miyaura cross coupling in neat water.17
Waghmode et al. have developed a reusable
PdCl2/TiO2 for C-C coupling reaction for different
substituted aryl iodides with olefins under UV-
functionalized porphyrin
benzimidazolium moiety
intertwined with
for sustainable
etherification of furfuryl alcohol with various
alcohols under irradiation of yellow visible (5 W
LED) light.26
Yet, to influence a high and competent conversion
visible light which affords good yield for the of simulated light energy into chemical energy is
corresponding products at ambient reaction still a great exciting task. As the reports on the
conditions.18 Further visible light-mediated metal vinylation or arylation of olefins by C-Cl bond
free19 Pd-Ru-catalyzed ligand free Heck reaction activation are restricted, finding a highly dynamic
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and recyclable heterogeneous metal/base free (99.5%) and Methanol (99.9%) were
photo-catalyst would be highly desirable. from Fisher Scientific. Formaldehyde solution (37-
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Furthermore special devotion should be paid to the 41% w/v AR), Sodium Hydride (60% dispersion in
design of photocatalytic materials for metal/base Paraffin Oil) and Sodium hydroxide, Chloroform-d
free C-C/C-N coupling in presence of visible light (99.8 atom % D for NMR Spectroscopy), Pyrrole and
irradiation.27 To the best of our knowledge, there is Salicylaldehyde were acquired from S D Fine-Chem.
no article on porphyrin based photocatalyst which Ltd. Acetic acid was received from Sigma Aldrich.
could be convenient for C-C coupling in absence of Triazole (99% Spectrochem), Dimethyl Sulfoxide-d6
base or precious metal. Accordingly, our research (deuteration degree min. 99.8% for NMR
group committed making use of light energy for Spectroscopy), Chloroform and Ethyl Acetate (99%)
organic transformations at ambient conditions. To and Tetrahydrofuran were provided by Sisco
explore the concept, we describe synthesis of Research Laboratories Pvt. Ltd. All of these reagents
Brønsted acid functionalized porphyrin, tangled were used as received without any further
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purification unless otherwise recommended.
with triazolium moiety, offering photocatalytic
applications in metal/base free C-C cross-coupling
(Heck/Sonogashira), C-H/C-N (Buchwald-Hartwig)
activation and Fittig/Ullmann type coupling using
unactivated aryl chloride under 5 W light
irradiations.
2.2. Characterization techniques
1H NMR and 13C spectra of intermediates were
analysed with Bruker spectrometer operating at
400 MHz at ambient temperature; using DMSO-d6
We establish that visible light can stimulate these C-
C/C-N coupling and C-H activation reactions with
the SAFPTILM photocatalyst at ambient
temperature, in home-made photo-reactor and the
rate of photocatalysis influence on the intensity and
wavelength of the light irradiation. The mechanism
of light excited cross coupling reaction and
recyclability heterogeneous photocatalyst were
also illustrated. It is sensible to assume that the
SAFPTILM photocatalyst is prospective for driving a
variety of metal/base free cross-coupling and C-N/
C-H activation reactions with visible light. It may be
noted that the activation of various aryl chlorides
for different reactions may not be the same, but the
affording of several cross-coupling reactions can
offer perception into the mechanism of the
photocatalytic cross-coupling progressions in
general.
1
and CDCl3 as solvent; and TMS (δ = 0.00) for H
calibration. FT-IR spectra were found from IR
affinity 1 Shimadzu FT-IR spectrophotometer using
KBr pellet method. Surface morphology and the
elemental composition of the complex were
examined by scanning electron microscope (SEM)
along with energy dispersive X-ray (EDAX)
spectroscopy (Carl Zeiss EVO/18SH, UK). An
accelerating voltage of 10 kV was applied to obtain
SEM images. Thermal stability of SAFPTILM was
studied using TGA thermoanalyser SII, 7200 (Seiko,
Japan). UV-Vis-NIR Spectrophotometer (Jasco ISN-
723, Sr. no. B 072061154, Made in Japan) was used
to assess DRS-Spectra of solid SAFPTILM
photocatalyst. BET (Autosorb IQ Surface Area Gas
Sorption Analyzer from Quantachrome, made in
Japan) elemental analysis was supported to know
pore diameter and total surface of area of
photocatalyst.
2. Experimental
2.1. Materials
p-Phenylenediamine (PPD) was delivered by Avra.
Hydrochloric acid (35.8-38.0%), Sodium Sulphate
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Scheme 1 Synthesis of 1a
947.05, 902.69, 846.75, 767.67, 717.52, 686.66,
659.66, 572.86, 497.63, 449.41.
2.3. Synthesis of SAFPTILM
2.3.2 Synthesis
of
3-((2H-1,2,3-triazole-2-
2.3.1
Synthesis
of
3-(chloromethyl)-2-
yl)methyl)-2-hydroxybenzaldehyde (1b)
hydroxybenzaldehyde (1a)
To a 100 mL RBF sodium hydride was placed and
mixed with 30 mL n-hexane. The reaction mixture
was stirred at room temperature for 40 min., after
which time the excess solvent was decanted under
vacuum to remove paraffin oil.29 The flask
containing NaH (1.32 g, 55 mmol) was charged with
15 mL tetrahydrofuran (THF), cooled in ice bath to
maintain 2 to 3 C temperature, and solution of
triazole (3.45 g, 50 mmol) in THF was added
dropwise and stirred for 2 h at cold condition. The
The synthesis of 1a was achieved by adapting
procedure from the known literature.28 In a 50 mL
round bottom flask (RBF), the mixture of Conc. HCl
(30 mL) and formaldehyde (3 mL, 100 mmol) was
°
cooled at 0 C and allowed constant stirring for 30
min. To this mixture, salicylaldehyde (2.92 mL, 24
mmol) was charged gradually and reaction mixture
was kept on magnetic stirring for 44 - 48 h at room
temperature (RT). The precipitated desired 1a solid
(white) was separated and washed with 3 x 10 mL
distilled water, followed by acetone and
recrystallized from n-hexane. The resulting
compound (1a) was dried in hot air oven for 12 h
and used for next step. (3.5 g, Yield: 87 %)
°
reaction
mixture
was
loaded
with
chloromethylated salicylaldehyde (1a) (8.50 g, 50
mmol) in THF very slowly at the same temperature.
The reaction mixture was then reflux for 44 - 48 h
°
(60 C). After cooling, the salt was removed by
1H NMR (400MHz, DMSO) δ = 10.92 (s, 1H), 10.27
(s, 1H), 7.72 (d, 1H), 7.58 (q, 1H), 7.02 (d, 1H), 4.75
(s, 2H). 13C NMR (100MHz, DMSO) δ = 191.19,
161.20, 137.43, 129.59, 129.27, 122.44, 118.22,
44.16. FT-IR – 3213.41, 2875.86, 1649.14, 1620.21,
1577.77, 1475.54, 1436.97, 1379.10, 1280.73,
1255.66, 1186.22, 1145.72, 1114.86, 1008.77,
filtration and the solvent was evaporated under
vacuum by rotavapour to get sticky yellowish liquid.
The product was charged with the mixture of ethyl
acetate and saturated brine solution to remove
remaining salt. The organic layer was separated and
dried using anhydrous sodium sulphate for
overnight. The ethyl acetate layer was
concentrated using rotavapour to get sticky
yellowish solid. The resulting solid was rinsed by
diethyl ether (3 X 10 mL) and dried in hot air oven
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Scheme 2 Synthesis of 1b
to afford yellowish fine powder 1b. Yield- 84%, 8.5
gram.
1H NMR (400MHz, DMSO) δ = 10.21 (s, 1H), 9.42 (s,
1H), 9.19 (s, 1H), 8.63 (s, 4H), 7.68 (s, 1H), 7.55 (d,
1H NMR (400MHz, DMSO) δ = 10.26 (s, 1H), 8.64 (s, 1H), 7.02 (d, 1H), 5.47 (s, 2H), 3.36 (t, 4H), 2.05 (t,
1H), 7.97 (s, 2H), 7.59 (s, 1H), 7.47 (d, 1H), 6.99 (d, 2H), 1.72 (t, 2H), 1.62 (t, 4H), 1.45 (t, 4H). 13C NMR
1H), 5.35 (s, 2H). 13C NMR (100MHz, DMSO) δ = (100MHz, DMSO) δ = 191.32, 161.35, 142.99,
191.20, 161.44, 152.21, 144.48, 136.61, 128.60, 142.87, 137.19, 129.58, 122.64, 118.25, 74.97,
127.43, 122.68, 118.29, 51.71
70.10, 60.89, 51.66, 48.27, 31.87, 23.30, 22.90,
22.10, 21.81.
2.3.3 Synthesis of
2-(3-formyl-2-
hydroxybenzyl)1,3-bis(4-sulfobutyl)-2H-1,2,3-
triazole1,3-diium hydrogen sulfate (1c)
2.3.4
Synthesis
of
phenylene
bis
1, 4-Butylsultone (6.80 g, 50 mmol) was added (azanylylidene))bis(methanylylidene))bis(2-
(chloromethyl)phenol) (2a)
slowly to
a
30 mL solution of triazole
salicylaldehyde (5.08 g, 25 mmol) (1b) in
acetonitrile into a flask and the mixture was
refluxed with constant stirring for 44 - 48 h. The
solvent was evaporated to dryness by rotavapor
and the resulting zwitter ion intermediate was
quenched with 10% (1ml of H2SO4 in 10 ml of H2O)
aq. H2SO4 solution.30 The reaction mixture was
refluxed for 12 h, after which time the excess
sulfuric acid was evaporated under vacuum. The
solid sticky product was washed with diethyl ether
(3 x 10 mL), to achieve pure sticky product (1c)
confirm by by 1H NMR and 13C NMR. Yield=89%, 15
g.
p-Phenylenediamine (2.16 g, 20 mmol) and
chloromethylated salicylaldehyde (1a, 6.80 g, 40
mmol) were weighed and mixed into a 100 mL RBF
containing 30 mL methanol and the mixture was
refluxed with a magnetic stirring for 3 h.31 The
reaction mixture was cooled to RT affording the
product as a red colour solid product in quantitative
yield. The resulting product was washed with
methanol to acquire red colour solid, obtained by
°
filtering and dried in hot air oven at 80 C. Yield =
92%, 14.5 g.
1H NMR (400MHz, DMSO) δ = 8.65 (d, 2H), 8.63 (d,
2H), 8.54 (s, 4H), 8.45 (s, 2H), 8.18 (d, 2H), 6.55 (s,
2H), 5.01 (s, 4H). 13C NMR (100MHz, DMSO) δ =
166.048, 152.10, 136.61, 133.40, 130.38, 125.37,
118.71, 61.16
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Scheme 3 Synthesis of 1c
Scheme 4 Synthesis of 2a
Scheme 5 Synthesis of 2b
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2.3.6 Synthesis of 1,1’-((((((1E, 1’E)-1,4-
2.3.5 Synthesis of 3-((1H-benzo[d]imidazole-1- phenylenebis(methanylylidene))bis(methylene))b
yl)methyl)-2-hydroxybenzaldehyde(2b)
To a 100 mL RBF sodium hydride was placed and 30
mL n-hexane was added and the reaction mixture
was stirred at RT for 40 min., after which time the
excess solvent was decanted under vacuum to
remove paraffin oil. The flask containing NaH
is(2-hydroxy-3,1-
phenylene))bis(methylene))bis(3-(3-formyl-2-
hydroxybenzyl)-1H-benzo[d]imidazole-3-ium)
chloride (2c)
In a 50 mL RBF, the mixture of phenylene bis
(azanylylidene))bis(methanylylidene))bis(2-
(0.96g, 40 mmol) was charged with 15 mL (chloromethyl)phenol) 2a (0.412 g 1 mmol) and
benzamidazole salicylaldehyde 2b (0.504 g, 2
mmol) was suspended in 30 mL chloroform. The
mixture was set aside on constant stirring for 44 -
48 h.33 After the completion of reaction, the
precipitated NaCl salt was separated by filtration
and rinsed with chloroform twice. The resulting
filtrate was concentrated under vacuum to acquire
precipitate, dried in hot air oven to give 2c.Yield: 74
%, 14.2 g.
tetrahydrofuran (THF), cooled in ice bath to
о
maintain 2 to 3 C temperature, and solution of
benzimidazole (2.36 g, 20 mmol) in THF was added
gradually and stirred for 2 h at cold condition. The
reaction
mixture
was
charged
with
chloromethylated salicylaldehyde (1a) (3.41 g, 20
mmol) in THF steadily at the same temperature. The
reaction mixture was then refluxed for 44 - 48 h (60
оC). After cooling, the salt was discarded by
filtration and the solvent was concentrated under
vacuum by rotavapour to get sticky yellowish liquid.
To the product the mixture of ethyl acetate and
saturated brine solution was added to remove
remaining salt. The organic layer was separated and
dried using anhydrous sodium sulphate for 12 h.
The ethyl acetate layer was evaporated using
rotavapour to get sticky yellowish solid.32 The
resulting solid was washed by diethyl ether (3 X 10
mL) and dried in hot air oven to obtain yellowish
fine powder 2b. Yield- 82 %, 8.2 gram.
1H NMR (400MHz, CdCl3-d6) δ 11.03 (s, 1H),
9.81 (s, 1H), 7.97 (s, 1H), 7.83 (d, 2H), 7.39 (d, 1H),
7.26-7.27 (m, 3H), 6.99 (d, 1H), 5.20 (s, 2H).
13C NMR (100MHz, CdCl3-d6) δ 196.13, 161.54,
143.97, 142.95, 135.62, 133.63, 131.86, 127.07,
123.40, 122.60, 120.60, 120.55, 118.72, 109.86,
47.89
1H NMR (400MHz, DMSO) δ = 10.88 (s, 2H), 10.22
(s, 2H), 8.60 (s, 2H), 8.88 (s, 2H), 7.55-7.57 (m, 6H),
7.51 (d, 5H), 0.00-7.01 (m, 4H), 6.99 (s, 5H), 5.46 (s,
4H), 4.64 (s, 4H), 3.92 (s, 2H), 3.36 (s, 4H). FT-IR.
3535.52, 3109.25, 3055.24, 1774.51, 1707,
1618.28, 1533.41, 1458.18, 1413.82, 1340.53,
1313.52, 1168.86, 1145.72, 1109.07, 1060.85,
985.62, 937.40, 867.97, 823.60, 765.74, 715.59,
661.94, 623.01, 603.72, 567.07, 516.92, 465.20
2.3.7 Synthesis of 2-(3-((15,20-bis(3-((1,3-bis(4-
sulfobutyl)-2H-1,2,3-triazole-1,3diium2yl)methyl)-
2-hydroxybenzyl)-10-(2-hydroxy-3-((1-(2-hydroxy-
3-((((E)-4-(E)-((2-hydroxy-3-((3-(2hydroxy3((10,15,
20-tris(3-((1,3-bis(4-sulfobutyl)-2H-1,2,3-triazole-
1,3-diium-2-yl)methyl)2hydroxybenzyl)porphyrin-
5-yl)methyl)benzyl)-1H-benzo[d]imidazole-3-ium-
1yl)methyl)benzyl)imino)benzylidene)amino)met
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hyl)benzyl)1Hbenzo[d]imidazole3ium1yl)methyl)
benzyl)imino)methyl)benzylidene)amino)methyl)
benzyl)1Hbenzo[d]imidazol3ium3yl)methyl)benzy
l)Porphyrin-5-yl)methyl)2hydroxybenzyl)1,3bis(4-
sulfobutyl)-2H-1,2,3-triazole-1,3-diium dichloride
dodecakis (hydrogen sulphate)
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DOI: 10.1039/D0NJ03637D
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Scheme 6 Synthesis of 2c
Scheme 7 Synthesis of Photocatalyst (SAFPTILM)
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Fig.1 1H NMR Spectrum of Synthesis of SAFPTILM (Photocatalyst)
In a 100 mL RBF, the precursors (1c) (4.03 g, 6 furnish the SAFPTILM photocatalyst.34 Yield: 90 %,
mmol) and (2c) (0.875 g, 1 mmol) were weighed, 4.52 g.
mixed with 25 mL acetic acid and stirred for 10 min.
To this, pyrrole (0.536 g, 8 mmol) was added and 1H NMR (400MHz, DMSO) δ = 9.63 (s, 10H), 8.94 (s,
the reaction mixture continued for stirring at room 12H), 7.34 (s, 6H), 7.29 (s, 4H), 7.19 (s, 2H), 7.03 (s,
temperature for 1 h. The desired dark brown solid 5H), 6.69 (s, 5H), 6.66 (s, 2H), 6.33 (s, 13H), 6.19 (d,
SAFPTILM was separated by vacuum filtration, 20H), 5.71 (d, 29H), 5.45 (d, 3H), 4.06 (s, 16H), 3.17
rinsed with water (5 x 15 mL) to remove traces of (t, 26H), 1.97 (t, 24H), 1.57 (s, 8H), 1.43 (s, 8H), 1.21
acetic acid. Finally the product was frequently (s, 13H), 0.76 (d, 16H), 0.45 (t, 22H), -0.099 (s, 4H).
washed with acetone and dried in oven at 80оC to
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Combine process for the synthesis of photocatalyst (SAFPTILM)
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at 1707 cm-1 that originated due to stretching of
aromatic aldehyde groups of 2c. Moreover, the
appearance of peak at 3055.24 cm-1, more intense
peak at 1533.41 cm-1, 1340.53 cm-1 and 1145.72
cm-1 attributed to C-H, C=N, C=C and C-N stretching
respectively.39 It was reported that there was no
intense stretching band due to SO3 in 2c.
3. Results and discussion
-OH
OH
NH
C-C
SO3
C-N
SAFPTILM
C=N
The spectrum of photocatalyst displays a broad
absorption peaks at 3200 to 3500 cm-1 attributed
to amino ((N-H), and hydroxyl (–OH) groups, but it
less intense in 1c and 2c. Also, an additional band
emerges near 1589.34 cm-1 was the characteristic
of C-C vibration of the phenyl substituents at meso-
position of porphyrin rings, indicating the
formation of SAFPTILM and do not reflected in the
IR spectra of substrates. The absorption bands in
the region of 3000-2800 cm-1 are designated to
aromatic C-H stretching.40 The formation of
photocatalyst was further supported by the
appearance of intense band of symmetric
stretching of SO3 at 1103.28 cm−1 and very weak
intense band at 605.65 cm-1 due to wagging of the
CH and NH bonds. All the compounds 1c, 2c and
photocatalyst SAFPTILM were further confirmed by
2C
C-N
C=C
C=N
C=N
C=O
C=O
C-N
SO3
-OH
1c
3500 3000 2500 2000 1500 1000
Wavenumber / cm-1
500
Fig.
2
Comparative
FT-IR
spectra
of
chloroacetylated product (1c), (2c) and photo-
catalyst
A series of Infrared spectra were recorded to
confirm the formation of SAFPTILM photocatalyst FT-NMR studies.41
from pyrrole, 1c and 2c. In the spectrum 1c (Fig. 2)
the band near 3346.50 cm-1 was attributed to the
hydroxyl group.35 The appearance of intense peaks
at 1598.99 cm-1 was interpreted as an aromatic
aldehyde.36 In addition, relatively intense IR peaks
at 1180.44 cm−1 was exhibited due to SO3 groups37
while the bands appeared at 1516.05 cm−1 and
1180.44 cm−1 are the distinctive bands of C=N and
C-N respectively, evidenced the formation of 1c.38
A very intense peak at 3535.52 cm-1 is assigned to
hydroxyl groups in 2c. Another strong one is found
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DOI: 10.1039/D0NJ03637D
photocatalyst needs the use of diffuse reflectance
spectroscopy (DRS) to know the optical bandgap of
SAFPTILM from a Tauc plot44 (Fig. 4) showed the
UV–vis DRS spectra, indicating band gap of
SAFPTILM photocatalyst by the intercept of
tangents to the plots of (ahv)1/2 versus photo
energy is 1.55 eV.45 This is associated with the
strong absorption characteristics of SAFPTILM in
the visible region accelerating photocatalytic
activity at normal temperature under visible light
irradiations.
1.0
0.8
0.6
0.4
0.2
0.0
5
6
7
8
SAFPTILM
9
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0
10
20
30
40
50
60
Relative Pressure (P/Po)
Fig.3 N2 isotherm of SAFPTILM
The pore size and pore volume of SAFPTILM
photcatalyst were measured from the N2
adsorption/desorption isotherms, using an
Autosorb IQ Surface Area Gas Sorption Analyzer. It
can be seen from the N2 adsorption-desorption
isotherm that synthesized photo-catalyst can be
recognized to type II (or type IV), which suggests a
microporous pore texture.42 (Fig. 3) Furthermore,
from the isotherms of photo-catalyst, it is apparent
that the total surface area of photo-catalyst and
pore width is found to be 125 m2/g and 8.440 Å
respectively, which is comparatively larger than the
reported photo-catalyst. Moreover the surface area
of the photo-catalyst will be more vital for effective
catalysis.43
Photocatalyst
100
90
80
70
60
50
40
10.40%
at 31-209
41.09%
at 209-517
5.85%
at 517-790
0
100 200 300 400 500 600 700 800
Temperature (°C)
Cat-2
Fig.5 TG thermogram of SAFPTILM
The thermal stability of the SAFPTILM was studied
by thermo gravimetric analysis (TGA), as illustrated
in (Fig. 5) The TGA disclosed that the catalyst
follows three-step degradation patterns.46 The first
weight loss 10.40 % below 209 °C may be due to
physisorbed water. The second weight loss 41.09 %
in the range 209–517 °C due to collapse of the
meso-phenyl group by decomposition of –OH/
benzimidazoles groups. Furthermore, the weight
loss above 517 °C may be due to decomposition of
0
1
2
3
4
5
6
7
hv (ev)
Fig.4 DRS Spectrum of SAFPTILM
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porphyrin scaffold. The TGA results confirmed that Acidity is important aspect to assess re
the catalyst is stable up to 517 °C and applicable for
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acidity function (H0) as an indicator for ranking the
solid acid catalysts49. The strength of acidic catalyst
can determine by (H0) Hammett function. pKa
values obtained for SAFPTILM (photocatalyst) using
Hammett indicators. Visual or spectrophotometric
observation of the colour change of an adsorbed
indicator supports in the assessment of the basic or
acid strength of the surface. Hammett indicators
are uncharged bases that can give up the proton
and transformed to conjugate acids. As per
literature, acidity of photo-catalyst was determined
using UV–visible spectrophotometer with a basic
indicator by adapting the concept reported in
literature.50 In the present work, H0 values of
SAFPTILM photo-catalyst was determined using 10
PPM of 4-nitroaniline (50 mL) as the indicator, with
100 mg photo-catalyst. The maximum absorbance
of the unprotonated form of the basic indicator in
water was observed at 370 nm, attests increase in
acidity of the photo-catalyst, whereas the
protonated form of the indicator could not be
observed because of its small molar absorptivity
and its location. Thus, the ratio [I]/[IH+] was
determined from the differences of measured
absorbance after the addition of photo-catalyst and
the relative acidity was calculated by using Eq. (1)
as a Hammett function
high-temperature reaction.47
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Fig.6 SEM/EDX image of SAFPTILM
The SAFPTILM photocatalyst was analysed by SEM-
EDX to investigate surface morphology and
elemental composition (Fig. 6). The SEM image
displays active surfaces, which would be favourable
for photocatalytic properties to absorb light.
Moreover elemental analysis showed all the
expected elements in the photocatalyst with their
composition as 71.12% measured as C, while the
next is 18.89% of O, 4.42% of N, 2.90% of Cl and
2.65% of S by weight.48
1.2
4-nitroaniline
Cat - 2
0.9
0.6
0.3
0.0
(H0) = pK(I)aq + log(I/IH+)………...(1)
Hammett values (H0) of the SAFPTILM photo-
catalyst was found to be H0 = 0.72 and correlated
with their catalytic activity (Fig. 7). The catalytic
activity was enhanced with the acidity of the photo-
catalyst which reveals the formation of hydrogen
bonding of photo-catalyst to the substrate and this
could play a crucial role to facilitate the product
formation.
300
350
400
450
500
Wavelength (nm)
Fig.7 Hammett acidity spectra of photo-catalyst
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4. Heck Coupling
the amount of catalyst used from 5 mgVi
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DOI: 10.1039/D0NJ03637D
(Figure S8 supporting Information) However, the
yield of the product did not alter using 25 mg
photocatalyst, may be due to accumulation of
photocatalyst.52 (Entry 2-6, Table 1). Thus, 20 mg
quantity was evidenced as the optimum loading of
SAFPTILM photocatalyst.
Likewise, the yield of Heck product firmly depends
on the duration of reaction. This was examined by
analysing the model reaction at different intervals
of time. The rate of product formation was
enhanced till the completion at 18 h, beyond which
amount of conversion remained nearly
insignificant. (Entries 7-10, Table 1). This steered to
select optimal reaction time for C-C coupling as 18
h.
Next we explored the impact of light intensity and
wavelength in the Mizoroki-Heck reaction. As
shown in Table 1 comparable yield of the product
was obtained in lesser duration (Entries 11-12)
showing better performance of the catalytic
system, when the intensity of light was increased by
using 9 W (Yield 87 %, 15 h) and 12 W (Yield 90 %,
13 h) LED light with other reaction conditions
unchanged. Thus, there is a progressive relationship
between the reaction rate and the light
intensity.53,54 Similar results were also perceived
when wavelength of visible light changed to green
(Table 1, entry 13) (480 nm) and Solar radiations
using optimized reaction conditions (Table 1, entry
14). It was also confirmed that reaction does not
proceed in the dark using optimized reaction
parameters (Table 1, entries 15). Thus, 20 mg of
photocatalyst for 4-chloroaniline (30 mmol, 3.82
gm) and acrylonitrile (32 mmol, 1.59 gm) under 5 W
LED in home-made photoreactor was established as
optimized reaction parameters for model Heck
coupling reaction.
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Scheme 8
Synthesisof(E)3(4aminophenyl)acrylonitrile
4-chloroaniline (30 mmol, 3.82 gm), acrylonitrile
(32 mmol, 1.59 gm), photocatalyst SAFPTILM (20
mg), 5W yellow light, 18 h
Subsequently, catalytic performance of SAFPTILM
was explored in the valuable carbon-carbon bond
formation via coupling reactions. We have verified
our research by considering Mizoroki-Heck coupling
reaction, a reaction of 4-chloroaniline (30 mmol,
3.82 gm) and acrylonitrile (32 mmol, 1.59 gm) as a
model reaction, using 20 mg photocatalyst for 18 h
in home-made photoreactor at an ambient
temperature.51 The reaction mixture was extracted
with ethyl acetate, the catalyst was separated by
filtration. The desired product was obtained by
evaporation of the solvent with rotavapour and
purified by recrystallization using suitable solvent.
(Entry 1, Table 1) The formation of product was
observed in absence of any solvent/base and
confirmed from spectral analysis (Figure S12 to
Figure S33, supporting file). Then, we have
scrutinized the reaction conditions by changing the
different reaction factors and the results are
summarized in Table 1.
As catalyst quantity in a reaction primarily decides
the catalytic efficiency, the catalyst loading
required for effective transformation was the first
parameter selected and studied. The yield of C-C
product was found to increase with the increase in
Using these optimized reaction conditions, we
explored the general applicability of BAFPBM
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Table 1 Optimization of Heck Coupling
Entry Reagent
photocatalyst with different aryl chlorides and vinyl
View Article Online
Catalyst DOTIi:m10e.1039/D0YNiJe0l3d637D
substituents containing electron withdrawing or
donating groups (Table 2). The BAFPBM catalysed
Mizoroki-Heck reaction tolerated an extensive
range of functional groups such as NO2, Cl, OH and
NH2. The unactivated aryl chlorides and substituted
vinyl compounds demonstrated excellent reactivity
without using any noble metal and base and afford
expected products in high yields under optimized
reactions conditions. (Table 2, entries 1-11).
Additionally, heterocyclic aryl chlorides like 2-
chloro thiophene and 2-chloro-pyrimidine and
substituted vinyl compounds also confirmed
admirable reactivity in absence of any noble metal
and base with moderate to excellent yields under
optimized reactions conditions. (Table 2, entries 12-
14). Similarly, heterocyclic vinyl pyrimidine and
thiophene also delivered Heck products with
substituted aryl chlorides. (Table 2, entries 15-16).
Finally both the heterocyclic substrates were also
investigated in our present system rendering 83 %
of coupling product. (Table 2, entry 17).
(*)
(mg)
20
5
(h)
24
24
24
24
(%)
89
54
68
76
1
2
3
4
R1 +R2
R1 +R2
R1 +R2
R1 +R2
10
11
12
13
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45
46
47
48
49
50
51
52
53
54
55
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57
58
59
60
10
15
5
6
R1 +R2
R1 +R2
R1 +R2
R1 +R2
R1 +R2
R1 +R2
R1 +R2
R1 +R2
R1 +R2
R1 +R2
R1 +R2
20
25
20
20
20
20
20
20
20
20
20
24
24
6
89
90
7
61
8
12
18
24
15
13
18
18
18
70
9
88
10
11
12
13
14
15
89
87a
90b
89c
92d
5e
Model reaction of Heck Coupling
*= 5W yellow light; (0.004 w/cm2)
a=9W light ; b= 12 W light ; c= 5W Green light;
d= Solar light;
e= reaction performed in dark
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DOI: 10.1039/D0NJ03637D
Table 2 Heck coupling between various Aryl Halides and Activated Alkene under Photocatalytic
Condition
6
7
8
9
Sr.
No.
1
Alkene
Aryl Halide
Product
Time h
Yield %
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2
18
86
3
4
5
18
18
18
86
82
84
6
7
8
18
18
18
84
81
88
9
18
18
85
87
10
11
12
18
18
81
85
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84
86
17
18
83
Reaction conditions: aryl halide (30 mmol, 3.82 gm), activated alkene (32 mmol, 1.59 gm), photocatalyst
SAFPTILM (20 mg), 5W yellow light, 18 h (Table 2).
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Table 3 H and 13C value for Heck coupling between various Aryl Halides and Activated Alkene under
1
Photocatalytic Conditions.
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Heck Coupling product
Conformation Data (NMR data)
1H NMR (400 MHz, CDCl3) δ : δ 8.20 (d, 2H), 8.18 (d, 2H), 7.53 (d, 1H), 7.51
(d, 1H), 1.55 (s, 3H)
13C NMR (100 MHz, CDCl3) δ: 170.1, 150.3, 142.2, 135.2, 132.0, 125.2,
113.0, 25.1
GC-MS: 207.19
1H NMR (400 MHz, DMSO-d6): δ 7.95 (d, 2H), 6.71 (s, 1H), 6.61 (s, 2H),
6.58 (s, 1H), 5.75 (s, 2H)
13C NMR (100 MHz, DMSO-d6): δ 99.7, 112.84, 126.86, 136.08, 156.16
GC-MS: 144.18
1H NMR (400 MHz, DMSO-d6): δ 10.01 (s, 1H), 7.95 (t, 2H), 7.70 (d, 2H),
7.57 (d, 2H), 2.86 (s, 2H)
13C NMR (100 MHz, DMSO-d6): δ 166.92, 138.25, 131.65, 131.61, 130.12,
129.85, 129.21, 40.2
GC-MS: 225.09
1H NMR (400 MHz, DMSO-d6): δ 10.01 (s, 1H), 7.93 (t, 2H), 7.69 (d, 2H),
7.57 (d, 2H), 4.07 (q, 2H), 36.36 (t, 3H).
13C NMR (100 MHz, DMSO-d6): δ 192.62, 139.40, 135.31, 131.65, 129.84,
129.21, 70.4, 20.2
GC-MS: 204.23
1H NMR (400 MHz, DMSO-d6): δ 8.47 (d, 2H), 8.25 (d, 2H), 7.76 (s, 1H),
7.74 (s, 1H), 4.38 (t, 2H), 1.22 (s, 2H)
13C NMR (100 MHz, DMSO-d6): δ 146.87, 140.64, 130.33, 125.80, 50.2
GC-MS: 178.19
1H NMR (400 MHz, CDCl3) δ : δ 8.66 (d, 2H), 7.53 (d, 1H), 7.31 (t, 1H), 7.11
(d, 1H)
13C NMR (100 MHz, CDCl3) δ: 161.69, 159.86, 159.60, 120.01, 119.7, 105.2
GC-MS: 130.15
1H NMR (400 MHz, CDCl3) δ :δ 8.19 (d, 2H), 8.18 (d, 2H), 7.53 (d, 1H), 7.51
(t, 1H), 1.59 (s, 1H)
13C NMR (100 MHz, CDCl3) δ: 146.55, 141.38, 129.58, 125.18, 124.93, 25.2
GC-MS: 242.07
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1H NMR (400 MHz, DMSO-d6): δ 8.77 (d, 2DHO)I,: 180..150239/(Ds0,N2JH03)6,37D
7.56 (t, 1H), 7.46 (s, 1H), 6.74 (t, 1H), 6.12 (d, 1H), 5.54 (d,
1H)
13C NMR (100 MHz, DMSO-d6): δ 171, 160.698, 160.65,
149.99, 134.92, 121.33, 120.22
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1H NMR (400 MHz, DMSO-d6): δ 10.26 (s, 1H), 7.76 (q, 2H),
7.61 (t, 3H), 7.50 (d, 1H), 7.45 (t, 1H).
13C NMR (100 MHz, DMSO-d6): δ 190.12, 136.75, 136.07,
132.39, 131.03, 129.98, 128.16
1H NMR (400 MHz, DMSO-d6): δ 9.97 (s, 1H), 7.91 (d, 2H),
7.65 (d, 2H), 5.91 (d, 2H), 5.56 (s, 1H), 5.26 (d, 1H), 5.13 (d,
1H).
13C NMR (100 MHz, DMSO-d6): δ 192.67, 139.90, 135.23,
131.63, 129.80, 129.14, 128.82, 128.68, 117, 66.74
1H NMR (400 MHz, DMSO-d6): δ 8.23 (s, 4H), 7.47 (d, 2H),
7.39 (d, 3H), 5.84 (d, 1H), 5.29 (d, 1H), 4.72 (s, 2H).
13C NMR (100 MHz, DMSO-d6): δ 139.67, 138, 125.22,
125.24, 125.21, 125.20, 125.18, 45.2
1H NMR (400 MHz, CDCl3) : δ 10.49 (s, 1H), 8.49 (q, 2H),
7.51 (q, 1H), 7.30 (t, 3H), 7.00 (s, 1H), 6.11 (s, 1H), 5.69 (s,
1H), 5.49 (d, 1H).
13C NMR (100 MHz, CDCl3) : δ 206.97, 149.95, 149.71,
147.10, 138.83, 133.12, 130.62, 129.63, 129.27, 128.37,
127.18, 121.41, 120.80, 118.78, 117.59
1H NMR (400 MHz, CDCl3) : δ 9.98 (s, 1H), 7.83 (d, 3H), 7.82
(d, 2H), 7.52 (t, 2H), 7.51 (d, 2H), 7.42 (s, 2H).
13C NMR (100 MHz, CDCl3) : δ 190.86, 140.98, 134.73,
131.52, 130.91, 129.47, 128.83, 128.05.
GC-MS: 208.26
1H NMR (400 MHz, DMSO-d6): δ 10.16 (s, 1H), 9.98 (s, 1H),
7.30 (d, 1H), 7.12 (t, 4H), 6.98 (d, 1H), 6.77 (q, 3H).
13C NMR (100 MHz, DMSO-d6): δ 192.42, 170.79, 153.54,
130.28, 129.99, 129.76, 128.99, 128.83, 128.67, 128.40,
128.11, 120.66, 120.41, 120.14, 117.42
GC-MS: 225.25
1H NMR (400 MHz, DMSO-d6): δ 9.98 (s, 1H), 8.00 (d, 2H),
7.42 (t, 4H), 7.31 (q, 2H), 7.10 (d, 1H), 6.76 (s, 1H).
13C NMR (100 MHz, DMSO-d6): δ 192.10, 164.95, 135.27,
135.01, 133.52, 133.49, 132.87, 132.77, 132.50, 132.32,
132.23, 132.04, 131.94, 131.61, 116.91
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filtration, washed with ethyl acetate
V
(
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mL),
On
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finally with acetone and drieDdOIi:n10h.10o3t9/Da0irNJo03v6e3n7D.
The recovered SAFPTILM photocatalyst was use
again for the next cycle by charging substrates.
The catalyst demonstrated excellent stability
and reusability with slight reduction of yield of
the product for six cycles (reduced yield from 88
to 82%) (Fig. 9). The Fourier Transform Infrared
spectroscopy (FT-IR) measurements were
carried out for the Photocatalyst, recovered
after sixth cycle. It was found that FT-IR bands
were in good agreement with original spectra of
the fresh Photocatalyst (Fig. 8 FT-IR). Therefore,
the SAFPTILM is found to be more appropriate
as heterogeneous photocatalyst for C-C
coupling reactions under visible light irradiation
at ambient conditions.
After Sixth Run
After First Run
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4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
Fig.8 FT-IR for Confirmation of Recyclability and
Stability of Photocatalyst
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Number of Run
Fig.9 Recyclability and Stability of
Photocatalyst
Recyclability and Stability of Photocatalyst
In order to know practical utility and efficiency
of heterogeneous SAFPTILM photocatalyst,
reusability of photocatalyst has been evaluated
by performing Heck coupling using 4-
chloroaniline and acrylonitrile as the substrate
under optimized conditions. After the
completion of photocatalytic reaction, the
reaction mixture was allowed to settle for 10
min, and the catalyst was separated by simple
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Scheme 9 Proposed mechanism to explain the role of scavenger (p-BQ and EDTA) in Heck Coupling
reaction.
88
80
60
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0
p-BQ
EDTA
Without Scavenger
desired product of Heck coupling found with 88 %
yield, while the percentage of yield decreased
intensely after adding benzoquinone and EDTA.
These results verified that the electrons and the
holes were dynamic species, for the C-C coupling by
the formation of alkoxy radicals and phenyl radicals
reepectively as shown in the mechanism.
Fig.10 Photocatalytic Heck coupling of Aryl chloride
with acrylonitrile in presence of p-benzoquinone
(electron scavenger) and EDTA (hole scavenger)
It is identified that the electrons and holes are the
important active species generated during the
photocatalytic reaction. Benzoquinone and EDTA,
the scavengers of electrons and holes, respectively,
can be added to investigate the photocatalytic
pathway. As shown in Fig. 10, the formation of
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Scheme 10. Plausible mechanism of C-C Heck coupling using SAFPTILM Photocatalyst
A wide-range of cross coupling reactions have
been developed, involving transition metal
catalysts between prefunctionalized reactants
and an arene or C-H arylation through
functionalization in one coupling substrate.
However, there is aggravation among the
researchers that such coupling reactions always
need high temperature and excessive
equivalent of bases/additives than the
substrates. Hence, photoredox catalysis that
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harness light energy under mild conditions to
Studies have shown that, photostab
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nline
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accelerate arylation by single electron transfer,
has becoming popular over the past decade. A
wide range of aryl radical precursors, have been
reported, that lead to formation of aryl radical
during photocatalysis to enable C-C, C-N, C-S
cross coupling reactions. For example, aryl
diazonium salts for C-H arylation of
heteroarenes55,56 diaryliodonium salts for
arylation of heteroarenes and olefins57,58 and
triaryl sulfonium salts reported for the
generation aryl radicals under visible light
irradiations to afford allylation products.59
Recently, Fazhi et al. have successfully
demonstrated a novel and reliable approach for
the conversion of aryl halides to aryl radical
using a super electron donor, rongalite in
absence of transition metal.60 Among the
reported aryl radical precursors, aryl halides
have attracted global attention for the
generation of aryl radicals, due to easy
availability, inexpensive and stability at normal
conditions. But the access of aryl halides as
precursors for the generation of aryl radical is
often restricted due to high reduction potential
(> -2.0 V) and high bond dissociation energy
(>97 kcal/mol) and resistant to single electron
reductions. To surpass this obstacle, the
research group of de Alaniz61 has demonstrated
generation of aryl radical by using 10-
phenylphenothiazine (PTH) as photocatalyst
under UV light irradiation (380 nm). The
negative reduction potential of excited PTH
afforded aryl radicals from aryl halides with
electron donating groups. Further, aryl radicals
have generated using the excited doublet states
of stable radical anions, by in situ formation
through photoinduced electron transfer
processes.62
dye, perylene bisimides fDoOrIm: 10.10s3t9a/Db0lNeJ03a63n7dD
coloured radical anions under nitrogen
atmosphere.63,64 Similar to this, the
photocatalytic performance of SAFPTILM
photocatalyst was excellent with all cross
coupling and C-H activation under visible light
irradiation at ambient conditions in absence of
noble metal and base (Scheme 9). This may be
due to presence of ionic liquid based triazolium
moiety to acquire basic character and sulfonic
acid groups on the periphery provide strong
electron donor centres in SAFPTILM
photocatalyst. The probable mechanism for C-
C, C-N coupling and C-H activation involve
following steps upon visible light irradiation:
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[A] Excitation of photocatalyst SAFPTILM by
absorption of visible light to form SAFPTILM*.
[B] Photoexcited SAFPTILM* extracts an
electron from electron donor group (-SO3H)
lead to radical anion (SAFPTILM•-) in the
ground state.
[C] The transfer of an electron from a stable
SAFPTILM•- by sequential photoexcitation to
aryl chlorides, creating the aryl radical
precursor ArCl•- and regeneration of neutral
SAFPTILM.
[D] The formation of an active intermediate,
aryl radical (Ar•) by breakup of ArCl•-
[E] The photogenerated holes on the SAFPTILM
photocatalyst could oxidize vinyl cyanide to
vinyl cyanide
radical and protons.65,66
The aryl radical and vinyl cyanide radical
coupled quickly to attain C-C coupled product
while the proton and chloride ion lead to form
HCl byproduct (Scheme 9).
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5. Sonogashira Coupling
Scheme 11 Synthesis of 4-(phenylethynyl)aniline
4-chloroaniline (30 mmol, 3.82 gm), phenyl excellent yields of biaryl compounds (Table 4
entries 1-5). The details of optimization protocols
were tabulated in (Table 3 Supporting Information).
The SAFPTILM photocatalyst was capable to
delivered Sonogashira products in methanol under
visible light irradiation at ambient conditions in
home-made photocatalytic reactor. Differently
substituted aryl chlorides electron donating and
withdrawing, including heterocyclic ring were also
contributed in this C-C coupling reaction without
any effort. The catalyst was separated, filtered and
reused up to 4 times following the procedure as
illustrated previously and results were incorporated
in the supportive information (Fig. S42 Supporting
Information).
acetylene (30 mmol, 3.06 g), photocatalyst
SAFPTILM (20 mg), 5W yellow light, 24 h
Encouraged by the catalytic performance and
stability of SAFPTILM in Mizoroki-Heck coupling
reactions, we have established its efficacy in one
more significant C-C bond involving reaction by
Sonogashira coupling. It is primarily used in the
synthesis of biaryl compounds, by coupling of a
terminal alkyne and an aryl halide in presence of a
palladium catalyst along with copper co-catalyst.
Here, we have optimized Sonogashira coupling
between 4-chloroaniline and phenyl acetylene
using SAFPTILM photocatalyst. It was found that
only 20 mg of SAFPTILM was necessary to catalyse
Sonogashira coupling of 4-chloroaniline (30 mmol,
3.82 g) and phenyl acetylene (30 mmol, 3.06 g)
under visible light irradiation (5 W LED) in absence
of noble metal in 15 ml of methanol in 24 h with
96% of the biphenyl (Scheme 10). The coupling of
aryl chlorides with deactivating and activating
groups carried out with phenyl acetylene under
optimized reaction conditions to achieve good to
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Table 4 Sonogashira coupling between various Ethynylbenzene and Aryl halide under Photocatalytic
Conditions.
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Sr. No Activated Alkyne
1
Aryl Halide
Product
Time Yield
h
%
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62
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Reaction conditions: aryl halide (30 mmol, 3.82 gm), phenyl acetylene (30 mmol, 3.06 g), photocatalyst
SAFPTILM (20 mg), 5W yellow light, 24 h.
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6. Buchwald-Hartwig Cross Coupling Reaction
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Scheme 12 Synthesis of 4-(1H-pyrrol-1-yl)benzaldehyde
4-chloroaniline (30 mmol, 3.82 gm), 1H-pyrrole (30 condition in absence of any solvent/base/noble
metal, appreciable yield (87%) of N-substituted
mmol, 2.01 gm), photocatalyst SAFPTILM (20 mg),
5W yellow light, 18 h
pyrrole was obtained (Scheme 11). Like other
Next, we have tested prospective of SAFPTILM protocols, the rate of reaction was significantly
photocatalyst in industrially important Buchwald C- enhanced with change of light intensity and
N cross coupling reaction. The Buchwald-Hartwig wavelength (Fig. S10 & Fig. S11 Supporting file) with
amination is a C-N the cross coupling reaction of excellent yield of desired products. A variety of aryl
amines and aryl or heteroaryl-halides in presence of chlorides coupled with pyrrole to attain N-
Pd and base to achieve aryl amines or heteroaryl substituted heterocyclic compounds in good yields
amines. The reaction has acquired extensive under optimized reactions conditions. (Table T5
applications in synthetic organic chemistry, Supporting file). The results were summarized in
particularly pharmaceuticals67 and other industrial Table 5 Aryl chlorides comprising both electron
applications involving α-arylation of carbonyl donating groups (-NH2, OCH3) and electron
compounds and nitriles.68 However, in addition to withdrawing groups (–NO2, CHO) were contributed
argon protected atmosphere, Buchwald C-N in the Buchwald coupling reactions. The results
coupling shows, incompatibility of some groups like indicated that many electronically varied aryl
nitro, ester of substrate with strong bases of the halides tolerated using the current protocol (Table
5)
reaction medium and poisoning/leaching of Pd
catalyst are the major restrictions. To address these
drawbacks of existing catalysts, the scope of
current protocol has been investigated, to justify
the requirement of industries. When a mixture of 4-
chloroaniline (30 mmol), pyrrole (30 mmol), and
20 mg photocatalyst was irradiated under visible
light in home-made photoreactor at ambient
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Table 5 Formation of C-N bond between various Aryl halide, Pyrrole and Morpholine under Photocatalytic
Conditions.
Sr. No Aryl Halide
1
Substrates with NH
Product
Time h
18
Yield %
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Reaction conditions: aryl halide (30 mmol, 4.21 gm), Substrates with NH (30 mmol, 2.01 gm),
photocatalyst SAFPTILM (20 mg), 5W yellow light, 18 h
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7. Ullmann Coupling.
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Scheme 13 Synthesis of benzidine
4-chloroaniline (30 mmol, 3.82 gm), photocatalyst catalysts,
photocatalytic,
microwave-
and
SAFPTILM (20 mg), 5W yellow light, 16 h
ultrasound assisted synthesis, etc. have attracted to
afford biaryl compounds.69,70. Thus, different of aryl
halides including unactivated and activated aryl
chlorides were coupled themselves to produce
corresponding substituted diaryl compounds in
good yields using optimized parameters under
visible light irradiations (See SI Table S9). The results
are indicated in Table 6. Aryl chlorides with
deactivating groups (-NH2) and activating groups
(such as –NO2, CHO ) were involved in the formation
of respective Ullmann/Fittig biaryl products. The
yields of the product found better in the substrate
containing activating groups like NH2 compare to
deactivating group like CHO, NO2 in the coupling
reactions. It is remarkable that Ullmann type biaryl
formation reactions required copper as co-catalyst
and amine/Na or K t-butoxide as base in which are
poisonous in nature. But, in this approach the C-C
coupling reactions were afforded in visible light
One more rationally and industrially essential
reaction is the coupling of sp2-sp2 C-C coupling to
form biaryl compounds either by like Ullmann or
Fittig type reactions. The synthesis of biaryl in
presence of copper catalyst is well-known to attain
C-C bond in organic compounds. The formation of
symmetrical and unsymmetrical aryl–aryl bond is
one of the most important goals to synthesize
precursors and intermediates required in
agrochemical, pharmaceutical and fine chemical
industries. In spite of the impressive achievement
in the copper catalysed biaryl formation, there still
exists a need for new approaches that eliminate use
of strong bases, high temperature; long duration
and adapting cheap and environmentally benign
catalysts operating at normal conditionsThus,
synthetic approaches like metal-, ligand-, and
additive free conditions, reusable heterogenous
28 | J. Name., 2012, 00, 1-3
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New Journal of Chemistry
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radiation under copper and amine-free at ambient acetone, dried in hot air oven and recy
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DOI: 10.1039/D0NJ03637D
times.
conditions with appreciable yields. Moreover
SAFPTILM photocatalyst was separated after
completion of reaction by filtration, washed with
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Table 6 Ullmann coupling product under Photocatalytic Conditions.
Aryl Halide Aryl Halide Product Time h Yield %
Sr. No
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91
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82
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74
Reaction conditions: aryl halide (30 mmol, 3.37 gm), photocatalyst SAFPTILM (20 mg), 5W yellow light,
16 h
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J. Name., 2013, 00, 1-3 | 29
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