A co-operative effect of visible light photo-catalysis and CoFe2O4 nanoparticles for green synthesis of furans in water

Article abstract of DOI:10.1039/c6nj04091h

A novel approach to poly-functionalized furan synthesis is disclosed via oxidative decarboxylative [3+2] cycloaddition using co-operative catalysis by visible light and CoFe₂O₄ nanoparticles under ambient reaction conditions with water as a solvent. Although the reported method is efficient without catalyst in the presence of visible light (70% yield in 4 h at rt), the use of catalyst not only increases the yield (91%) but also accelerates the conversion rate (2 h at rt).

Full text of DOI:10.1039/c6nj04091h

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PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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A co-operative effect of visible light photo-catalysis and CoFe2O4
nanoparticles for green synthesis of furans in water
Fooleswar Verma,a Puneet K. Singh,b Smita R. Bhardiya,a Manorama Singh,a Ankita Rai,b and
Vijai K. Raia*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A novel approach to poly-functionalized furan synthesis is disclosed via oxidative decarboxylative [3+2] cycloaddition using
co-operative catalysis by visible light and CoFe2O4 nanoparticles at ambient reaction condition in water as solvent. Though,
the reported method is efficient without catalyst in presence of visible light (70% yield in 4h at rt), the use of catalyst not
only increases the yield (91%) but also accelerates the conversion rate (2h, rt).
www.rsc.org/
One of the areas of green chemistry is the use of renewable
energy source and to design a chemical process which reduces
the use of hazardous chemicals in multi-step reactions. Photo-
catalysis using LED light as visible light source has attracted
much attention of synthetic chemists as a renewable energy
source to promote chemical reactions involving electron
transfers.1 Selectivity in homogeneous catalysis is better but
the difficulty of catalyst separation from the final product
creates economic and environmental barriers. Alternatively,
organic synthesis via magnetic attraction is more promising as
they offer an added advantage of being magnetically
separable, thereby eliminating the requirement of catalyst
filtration after completion of the reaction. The preface of
nanoparticles (NPs) could be a gorgeous to overcome the more
than mentioned boundaries due to their exclusive properties
of larger and highly reactive surface areas.2-3 Very recently,
metal ferrite NPs have been extensively applied as catalyst
because of their Lewis acid and Lewis base nature and also
redox properties on the surface.4
O
MeO2C
OH
O
O
N
O
O
O2N
O
N
HO
Me
O
N
O
R= H, Tournefolin C
R= Me, Tournefolin B
H
Angelone
Dantrolene
Figure 1. Some drugs and natural products with Furan motif.
Benary8 methods, a good number of synthetic protocols have
been developed for furan synthesis.9-14 In most of the cases,
construction of the furan ring is based on 3+2 (I),9,10 2+2+1
(II),11 4+1O (IV),13 4+1C (V)14 intermolecular cycloaddition or
intramolecular cycloaddition (III)12 as represented in figure 2.
The [3+2] two component coupling strategy reported for furan
synthesis mainly involves acyclic ketones9,10 and their
derivatives, viz., cyclopropenyl ketones,12c β-acyloxy acetylenic
ketones,15a allenyl ketones,15b o-alkoxyketones,15c,d α-
aryloxyketones15e and α-diazocarbonyl as substrate.10a
Furthermore, use of carboxylic acid has several advantages
such as its ready availability, easy handling, environmentally
benign properties and production of nontoxic CO2 as the by
product.16 As a consequence, the development of new catalytic
route for furan synthesis is still in demand and therefore,
decarboxylative annulation using carboxylic acid is its atom
economical alternative with reduced waste material.
Polyfunctionalized furans represent an important class of
five membered o-heterocycles ubiquitous in natural products,
pharmaceuticals, agrochemicals and have been used in
commercially important pharmaceuticals, drugs and natural
products (Fig.1).5 From chemical viewpoint, they served as
building blocks as well as useful intermediates in organic
synthesis; especially for preparation of aromatic, alicyclic and
acyclic molecules.6 These unique properties have triggered
renewed interest to develop new synthetic methods which
enable rapid access to furans.
Literature records only few reports on furan synthesis
through a decarboxylative cyclization between ketones and
α,β-unsaturated carboxylic acids.10f,l However, all of these
reactions undergo from one or more disadvantage such as
stoichiometric amount of catalyst, expensive reagents, harsh
reaction conditions, high temperature, long reaction time,
involved oxidant, lower isolated yields and also sometimes no
reusability of catalyst. Due to our interest in developing green
chemistry protocols,17 and new C-C bond forming reaction for
Since the discovery of conventional Paal–Knorr7 and Feist–
a.Department of Chemistry, School of Physical Sciences, Guru Ghasidas
Vishwavidyalaya, Bilaspur-495 009, INDIA. Email: vijaikrai@hotmail.com; Phone.:
+91-7587178627
b.School of Physical Sciences, Jawaharlal Nehru University, New Delhi, 110 029,
INDIA.
† Electronic supplementary information (ESI) available: Method for preparation of
catalyst and compounds and their characterization details are given.
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Table 1 Optimization reaction conditions for synthesis of furan 3a.a
O
Cu-salt
COOH
O
Ref. 10n
Ref. 11
(I)
Ph
Ph
Ph
Addative, solvent
120 oC, 7 h, Air
CO2H
O
Ph
LED light
NPs catalyst
O
N
+
R1
R1
R4
1a
R2
H2O, r.t.
2a
3a
O
Ti(O-i-Pr)4/2 i-PrMgCl
R3
OR
(II)
Entry
Catalyst (NPs)
CoFe2O4
CuO
Mole (%) Time (h)
Yield (%) b, c
R3
R4
H
O
R2
R1
1
20
20
20
20
20
̶
02
03
03
03
03
20
04
28
02
02
91
72
75
77
71
RO
2
(III)
R3
R2
Ts
R1
R3I
3
GO/Fe3O4
CuFe2O4
NiFe2O4
̶
R2
Ref. 12o
Ref. 13
4
Pd(PPh3)4
Ts
O
OAr
Ts
5
d
6
̶
Ts
1.4 equiv H2O
(PPh3)AuNTf2
(IV)
(V)
N
N
I
O
e
N
N
7
̶
̶
70
75 f
R1
R1
R1
R1
THF, 60 o
C
8
CoFe2O4
CoFe2O4
CoFe2O4
20
15
25
9
82
Ph
O
PMPN
Ar
O
Pd(OAc)2
Toluene, rt, 24 h
Ph
10
91
O
a Reaction conditions: 1a (0.5 mmol), 2a (0.5 mmol), water: 5 mL, rt, in air. b Yield of
isolated and purified products. c All compounds gave C and H analyses within ±0.37%,
and spectral (1H NMR, 13C NMR and EIMS: Electron Ionization Mass Spectroscopy data).
Ref. 14
I
Ar
R
O
CoFe2O4
LED light
d
e
f
CO2H
R
In absence of catalyst and LED light. Only in LED light without catalyst. In the
Ar2
Ar1
+
Present work
Ar2
Ar1
H2O
presence of catalyst only without LED light.
O
Figure 2. Different synthetic routes reported for synthesis of Furans 3.
shows the surface features of prepared CoFe2O4. Investigated
particles are cubic in shape with a narrow size distribution and
their particle sizes are 28 nm (calculated from XRD). It can also
be seen that the particle agglomeration which indicates a good
association between the particles together and further
agglomeration was reduced. The increased surface area of
CoFe2O4 is likely to be utilized for further catalysis application
(Figure 3b). The EDX analysis showed that the presence of Co,
Fe, and O elements (Figure 3d). The formation of cubic
CoFe2O4 NPs was also supported from TEM image (Figure 3c).
A UV-Visible spectrum of CoFe2O4 was taken and no
absorption maximum was appeared (Figure 3f).20b
R
O
CoFe2O4
LED light
CO2H
R
Ar2
Ar1
+
Ar1
Ar2
H2O
O
1
3
2
decarboxylative
[3+2] cycloaddition
R= H, Me, Et, Ph
Scheme 1. Photo-catalytic decarboxylative [3+2] cycloaddition route to Furans 3.
heterocyclic synthesis,18 we herein, report an unprecedented
green synthesis of polyfunctionalized furans via [3+2]
cycloaddition between α,β-unsaturated carboxylic acid and
ketone. The synthesis of target compound was affected by co-
operative catalysis using CoFe2O4 and LED light as visible light
source in the envisaged method (Scheme 1).
In our model experiment, cinnamic acid 1a (0.5 mmol) and
acetophenone 2a (0.5 mmol) were taken as substrate and
different NPs such as CoFe2O4, CuO, GO/Fe3O4, CuFe2O4 and
NiFe2O4 as catalyst. The reaction mixture was stirred in water
under the white LED light (7 W domestic white LED was used
as the visible light source) for 2 h and the results are
summarized in Table 1. Out of the tested catalysts, 20 mole %
of CoFe2O4 gave the best yield of furan 3a in 2 h (Table 1,
entries 1-5). When the amount of the catalyst decreased from
20% to 15%, the yield of product 3a reduced (Table 1, entries 1
and 9), but increasing the catalyst loading from 20% to 25% did
not increase the yield of product 3a (Table 1, entries 1 and 10).
Next, we turned out attention to check the catalyst-free
version of the envisaged reaction. Accordingly, an equimolar
mixture of cinnamic acid 1a and acetophenone 2a was stirred
in water (i) in absence of both i.e. the catalyst as well as LED
light (Table 1, entry 6), (ii) only in presence of LED light without
catalyst (Table 1, entry 7) and (iii) in the absence of LED light
with catalyst only (Table 1, entry 8).
Very recently, we have reported the ferrite decorated
graphene oxide as peroxide sensing probe.19 In continuation,
we anticipated exploiting the prepared GO/Fe3O4 as catalyst
for synthesis of target molecule in the present investigation.
To our surprise, it afforded the target furan, though the yield
was not satisfactory (Table 1, entry 3). Then, we turned our
attention to search the most efficient catalyst system for the
present reaction and different NPs viz., CoFe2O4, CuO, CuFe2O4
and NiFe2O4 were screened in addition to GO/Fe3O4. However,
CoFe2O4 has been found the most efficient catalyst system for
the present investigation and was prepared by its reported
method.20
The formation of CoFe2O4 NPs was confirmed by UV, XRD,
SEM, EDX and TEM screening studies (Figure 3). The powder
XRD pattern indicates CoFe2O4 NPs are single phases and have
the cubic spinel structures with reflection planes at (220),
(311), (222), (400), (422), (511), (440) (card JCPDS 22-1086)
(Figure 3a). The average particle size of CoFe2O4 NPs was
determined to be 28 nm, calculated from full width at half
maxima (FWHM) at reflection (311) plane using Debye
Scherrer formula. The average particle size was also confirmed
by plotting size histogram (Figure 3e). SEM micrograph clearly
We found that the catalyst as well as LED light individually
afforded the desired product, but the reaction required
relatively more time with lower yield of final product (Table 1,
entries 7 and 8). However, as anticipated, we found the best
result when the catalyst was used in conjunction with the LED
light in terms of excellent yield of 3a and reducing the reaction
2 | New J. Chem., 2016, 00, 1-3
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.
Figure 3. (a) Powder XRD of freshly prepared and after used CoFe2O4 NPs. (b) SEM image of CoFe2O4 NPs. (c) HR-TEM image shows cubic structure of CoFe2O4 NPs. (d) EDX analysis
shows elemental compositions of CoFe2O4 NPs. (e) Particle size histogram. (f) UV-vis spectra of CoFe2O4 NPs (inset: showing magnetic behaviour).
time as well (Table 1, entry 1). We also performed the synthesized compounds were characterized by their 1H and 13
envisaged reaction in the dark condition to check the role of NMR spectra.
C
light but low yield (62%) of product 3a was obtained. Next, the We have also examined the recyclability and reusability of
same reaction was undertaken in presence of TEMPO (a stable catalyst CoFe2O4 for the synthesis of 2,5-diphenylfuran 3a
.
free radical) for confirmation of radical generation, but no After completion of reaction, the CoFe2O4 was separated by
product in catalyst-free condition was obtained which led to solvent EtOAc (5 mL) was added to the reaction mixture and
conclude that visible light is not effective in the presence of flask was stirred to completely dissolve the product. The
TEMPO for formation of 3a. Thus, we relied upon the CoFe2O4 NPs was recovered by attaching the external magnet
combined catalytic effect of CoFe2O4 and LED light and the to the walls of reaction flask, providing the clear solution
present optimized synthesis is proficient by an equimolar which was decant to another flask. Then the recovered
mixture of cinnamic acid
1 and acetophenone 2 with CoFe2O4 catalyst was washed carefully with water (2×2 mL) and ethanol
(20 mole %) in water, in presence of white LED light for 2-3 h (2×1 mL) and reused for subsequent reactions up to seven
(Table 2). The present optimized synthesis is accomplished by times without significant loss of catalytic activity (Figure 3a).
taking different α,β unsaturated carboxylic
afforded functionalized furan 3a-q (Table 2). Total 17 analysis which showed in morphology and size was not much
products were synthesized in good to excellent yields with the change (the particles sizes increased from 28 to 35 nm as
best yield of as 96% (Table 2, entry 5). The aryl alkyl ketones, calculated from FWHM using Debye Scherrer formula), which
such as substituted acetophenone, propiophenone, may presumably be the reason for slightly decrease in yield of
butyrophenone and 2-phenyl acetophenone reacted smoothly the products 3a
with α,β unsaturated carboxylic acids. However, we have The formation of furan
1 acids and ketones The cubic morphology of reused catalyst was checked by XRD
2
3
.
3
is explained by tentative
found that substrates tolerated both EWG group (F, Cl, and Br) mechanism for the photocatalytic role of visible light shown in
as well as EDG groups (Me, SMe and OMe) for the formation of Scheme 2. Presumably, Co2+ is irradiated to excited state of
3
within 2-3 h with CoFe2O4 in mild reaction condition. All the Co2+* using white LED light and this excited state is reductively
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White LED
Co 2+
2+
*
Co
SET
H2O
O2, H+
Co +
O
COOH
H
Ph
O
Ph
O
Ph
Me
Ph
4
2
5
1
-H+
Ph
Ph
O
COOH
Ph
Ph
O
2+
3
SET *
Co
9
Co +
Ph
O
Ph
White LED
Co 2+
O2, H+
H2O
-CO2
COOH
Ph
Ph
Co 2+
COOH
-H+
O
COO
Ph
6
Figure 4. Recyclability of CoFe2O4 for the synthesis of 2, 5-Diphenylfuran 3a.
White LED
-H+
SET
Ph
Ph
Ph
SET
O
7
O
2+
*
Co
Co +
reductive quenching resulting the target molecule
catalytic cycle, SET mechanism involves oxidation of Co+ into
Co2+ by molecular O2. However, the formation of product
in
3. In the
8
Co +
White LED
Co 2+
H2O
3
O2, H+
Co 2+
O2, H+
absence of catalyst may presumably be explained by
photocatalytic path as acetophenone has high triplet energy.21
In summary, we have documented an original and efficient
route for the synthesis of polyfunctionalized furans using
readily available α,β-unsaturated carboxylic acids and ketones
and via oxidative decarboxylative [3+2] cycloaddition in
presence of visible light. Thus, the envisaged green method
has its several advantages, viz., higher yields of products,
simple operation, and ambient reaction conditions over the
existing procedures for the synthesis of furan and would be a
better practical alternative to cater the needs of academia as
well as industries.
H2O
Scheme 2. Plausible mechanism for the photo-catalytic construction of Furan 3.
Table 2 Optimization reaction conditions for synthesis of furan 3a.a
R
O
CoFe2O4
visible light
CO2H
R
Ar2
Ar1
+
Ar1
Ar2
Time
H2O
rt, 2-3 h
O
1
3
2
Product
3a
Ar1
Ar2
R
H
Yieldb,c
91
89
84
85
96
85
93
86
88
91
92
92
91
89
88
82
89
Ph
Ph
Ph
2
3b
3c
4-MeC6H4
Ph
H
2.5
3.0
2.5
2.0
2.5
2.0
3.0
2.5
2.0
2.0
3.0
3.0
2.0
2.5
3.0
2.5
4-MeS-C6H4
H
3d
3e
3f
4-MeC6H4
Ph
2-MeC6H4
H
Ph
Me
Me
Me
Me
Me
Me
Me
Me
Et
Preparation of CoFe2O4:
Ph
4-MeC6H4
3g
4-MeC6H4
4-MeOC6H4
4-FC6H4
4-ClC6H4
4-BrC6H4
4-MeC6H4
Ph
Ph
The preparation of CoFe2O4 nanoparticles were carried out
following reported procedure. Solution of Co(OAc)2.7H2O (4.2
g) and anhydrous FeCl3 (4.8 g) was dissolved in distilled water
and vigorously mixed under sonication for 3h at 70 0C.
Subsequently, 0.3 M NaOH was added drop by drop into the
solutions till the pH is reached up to 11 and black precipitate is
formed. Then reaction mixture was centrifuged and rinsed
with ethanol and distilled water and was dried in electric oven.
The resulting powder is then calcinated at 550 °C in an oven
for 4 hours. The magnetic nature of the prepared CoFe2O4
spinel was checked by using external magnet (inset; Figure 3f).
3h
3i
Ph
Ph
3j
Ph
3k
Ph
3l
4-MeC6H4
Ph
3m
3n
3o
3p
3q
4-ClC6H4
4-MeC6H4
4-MeC6H4
4-ClC6H4
Ph
Et
Ph
Et
Ph
Ph
Ph
Ph
a
b
For detail, please see the experimental section. Yield of isolated and purified
c
products. All compounds gave C, H and O analyses within ±0.37%, and satisfactory
spectral (1H NMR, 13C NMR and EIMS) data.
quenched by enol form of acetophenone
simultaneous generation of vinyloxy radical
with substrate affording a cyclic radical . Presumably, the
sequential reduction to and to
by Co2+ followed by
decarboxylation results the formation of radical . Then the
radical
further resumes its aromaticity by Co2+ induced
4
with the
Synthesis Furan 3:
5
, which reacts
1
6
General
6
7
7
8
All chemicals were purchased from Aldrich, Sd-fine and HI-
MEDIA (India) and used as received, except all solvents which
were used after distillation. All reactions were carried out with
9
9
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2
(a) D. Astruc, Nanoparticles and Catalysis, Wiley-VCH Verlag
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Ed., 2004, 43, 1628-1637.
oven-dried glassware under air. Distilled n-hexane and ethyl
acetate were used for column chromatography. Analytical TLC
(Thin Layer Chromatography) was performed on Merck 60F254
silica gel plates (0.25 mm thickness). Column chromatography
was performed on silica gel (60-120 mesh size, HI-MEDIA,
India).
3
(a) V. Polshettiwar and R. S. Varma, Green Chem., 2010, 12
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743-754; (b) M. Gawande, P. Branco and R. S. Varma, Chem.
Soc. Rev., 2013, 42, 3371-3393.
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General method for the preparation of furan 3
4
5
151.
A mixture of α,β-unsaturated carboxylic acid (0.5 mmol),
ketone (0.5 mmol) and CoFe2O4 nanoparticles (23 mg) in water
(5 mL) was stirred in presence of LED light for 2-3 h. After
completion of the reaction (TLC monitored), and an external
magnet was used for the separation of the catalyst from the
resulting crude reaction mixture. The reaction mixture was
extracted with ethyl acetate (20 mL), washed with brine
solution (2×5 mL) and distilled water (1×10 mL) and dried over
anhydrous sodium sulphate. Solvent was removed under
reduced pressure and left the crude solid product which was
purified by column chromatography on silica gel (ethyl
acetate/n-hexane = 1/9) to provide pure 2,3,5- substituted
functionalized product. The product was confirmed by their
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the Synthesis of Heterocyclic Compounds. In Advances in
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6
1
satisfactory H NMR and 13C NMR spectral analysis. However,
the spectroscopic data of the representative compound is
given. Compound 3a Colourless solid, (91%, 100 mg), mp 85–86 °C;
1H NMR (400 MHz, CDCl3) δ 7.74 (4H, d, J = 7.9 Hz), 7.49 (4H, t, J =
6.7 Hz), 7.34 (2H, t, J = 5.4 Hz), 6.41 (2H, s); 13C NMR (100 MHz,
CDCl3) δ 153.3, 130.7, 128.7, 127.3, 123.7, 107.2; IR (CHCl3) ν 3061,
3020, 1615, 1593 cm-1. Anal. Calcd for C16H12O: C, 87.25; H, 5.49.
Found: C, 87.30; H, 5.58. Compound 3f Colourless solid (85%, 106
7
1
mg), mp 95−96 °C; H NMR (400 MHz, CDCl3) δ 7.79 (d, J = 8.4 Hz,
2H), 7.69 (d, J = 8.4 Hz, 2H), 7.46−7.43 (m, 2H), 7.32−7.29 (m, 3H),
6.65 (s, 1H), 2.45 (s, 3H), 2.37 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
151.4, 148.5, 136.5, 131.0, 129.3, 129.1, 128.7, 127.1, 125.3, 123.7,
123.7, 118.0, 110.8, 21.3, 12.1. Anal. Calcd for C18H16O: C, 87.06; H,
6.49%. Found: C, 87.43; H, 6.50%. Compound 3p Colourless solid
(82%, 127 mg), mp 97−99 °C (lit. mp 99−100 °C); 1H NMR (400 MHz,
CDCl3) δ 7.56 (d, J = 8.0 Hz, 2H), 7.52 (d, J = 8.4 Hz, 2H), 7.40–7.37
(m, 2H), 7.32–7.28 (m, 2H), 7.26–7.20 (m, 3H), 7.17–7.13 (m, 3H),
6.68 (s, 1H), 2.30 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 152.9, 147.6,
137.5, 134.5, 131.3, 129.5, 128.8, 128.7, 128.5, 127.9, 127.5, 127.3,
126.2, 124.6, 123.9, 108.9, 21.4. Anal. Calcd for C23H18O: C, 89.00; H,
5.85%; Found: C, 89.32; H, 5.97%.
8
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Acknowledgements
We sincerely thank the DST, New Delhi (File No. SR/FT/CS-
99/2010) for partial financial support. We are also thankful to
JNU, New Delhi and SAIF, Punjab University, Chandigarh, for
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TABLE OF CONTENT
A co-operative effect of visible light photo-catalysis and CoFe2O4
nanoparticles for green synthesis of furans in water
Fooleswar Verma, Puneet K. Singh, Smita R. Bhardiya, Manorama Singh, Ankita Rai, and Vijai K. Rai*
A novel approach to poly-functionalized furan synthesis is disclosed via oxidative decarboxylative [3+2]
cycloaddition using co-operative catalysis by visible light and CoFe2O4 nanoparticles.