A polymer supported ascorbate functionalized task specific ionic liquid: An efficient reusable catalyst for 1,3-dipolar cycloaddition

Article abstract of DOI:10.1039/c4ra16481d

A novel polymer supported ascorbate functionalized task specific ionic liquid was designed and synthesized. It has been demonstrated that the synthesized polymer supported ionic liquid acts as an efficient catalyst for regioselective Huisgen 1,3-dipolar c

Full text of DOI:10.1039/c4ra16481d

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A polymer supported ascorbate functionalized task
specific ionic liquid: an efficient reusable catalyst
for 1,3-dipolar cycloaddition†
Cite this: RSC Adv., 2015, 5, 21396
a
b
a
Received 16th December 2014
Accepted 17th February 2015
*
Jayavant D. Patil, Supriya A. Patil and Dattaprasad M. Pore
DOI: 10.1039/c4ra16481d
www.rsc.org/advances
A novel polymer supported ascorbate functionalized task specific ionic technology and the usage of signicantly reduced amounts of
liquid was designed and synthesized. It has been demonstrated that the ionic liquid. It involve immobilization of ILs onto a surface
the synthesized polymer supported ionic liquid acts as an efficient of a porous high area support material.6 A number of benets
catalyst for regioselective Huisgen 1,3-dipolar cycloaddition of aryl- arise from the use of SILP catalysts, some of which are the ease of
diazonium tetrafluoroborate, sodium azide and terminal alkyne, which separation of catalyst, simply by ltration, recycling and repro-
provide a series of 1,4-disubstituted-1,2,3-triazoles in high yields at ducibility as well as facilitating signicant advances in selec-
room temperature as well as showing an aptitude for in situ incor- tivity. Due to these reasons, in last few years SILP catalysts have
poration of copper.
attracted attention of scientists and due to its inuence several
organic transformations have been successfully accomplished.7
1,2,3-Triazoles are an important class of heterocyclic
compounds, the interest in their synthesis stems from their
wide range of applications in pharmaceuticals, agro chemicals,
dyes, photographic materials, corrosion inhibition,8 etc. and
biological activities such as antiviral, antiepileptic, antiallergic,9
anticancer,10 anti-HIV,11 antimicrobial activities against gram
positive bacteria and b3-adrenergic receptor agonist.12 Due to
such multifarious applications different methods have been
exploited for their synthesis13 and amongst them Huisgen
1,3-dipolar cycloaddition of azides with alkynes is the most
popular method for the construction of 1,2,3-triazole
framework.14
However, the early Huisgen 1,3-dipolar cycloaddition15a–c
process required a strong electron-withdrawing substituent
either on azide or on alkyne, and were oen conducted at high
temperature for a prolonged period of time, and usually led to
the isolation of a mixture of 1,4-disubstituted- and 1,5-disub-
stituted-1,2,3-triazoles.15d,e
Sharpless et al. used Cu(I) salts to promote the reaction of
azide with terminal alkynes to afford 1,4-disubstituted prod-
ucts.16 Fokin and co-workers have developed the method
employing microwave irradiations.17 Moreover in recent years,
several methods have been reported for the synthesis of tri-
azoles18 generally through the coupling reaction between
alkynes and azides at high temperatures19 and by using solid
supported catalysts20 or nanocatalysts.21 Many of the literature
methods are plagued by disadvantages such as use of organic
solvent, no reusability of catalytic system, long reux time,
inuence of microwave irradiation, organic azide as reagent
Introduction
The increasing environmental consciousness of the chemical
community has led to the search for more efficient methods for
organic synthesis acquiring the principles of Green chemistry.1
This goal was achieved by employing green catalysts/solvents
(e.g., water, ionic liquids) as well as efficient and cleanly reus-
able catalytic materials.2 Ionic liquids have emerged as eco-
friendly catalysts as well as multi-use reaction media and green
solvent for a variety of applications due to the fact that they
possess negligibly small vapor pressure, high thermal, chemical
as well as electrochemical stability with widely tunable proper-
ties with regard to polarity, hydrophobicity, solvent miscibility,
etc.3 Despite these advantages, a series of drawbacks such as
their high cost as compared to traditional catalysts and solvents,
low biodegradability and (eco)toxicological properties still
exists,4 their recovery requires tedious process viz. distillation.5
To circumvent the limitations raised with ILs, the use of sup-
ported ionic liquid phase (SILP) catalysts has been devised
which possess advantages of ionic liquid media with solid
support materials, enables the application of xed-bed
aDepartment of Chemistry, Shivaji University, Kolhapur 416 004, India. E-mail:
p_dattaprasad@rediffmail.com; Fax: +91 231 2692333; Tel: +91 231 2690571
bDepartment of Chemistry, Hanyang University, Sungdong-Ku, Haengdang-dong 17,
Seoul, 133-791, Republic of Korea
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c4ra16481d
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Scheme 1 Polymer supported ascorbate functionalized task specific ionic liquid (MR-IMZ-As) catalyzed Huisgen 1,3-dipolar cycloaddition.
capacity to stabilize copper and cost effective for Huisgen
1,3-dipolar cycloaddition (Fig. 1).
In this context, we designed MR-IMZ-As Merrield resin
(polymer) supported ascorbate functionalized task specic ionic
liquid. Initially, polymer supported ionic liquid 3 was prepared
by treating Merrield resin with 1-methyl imidazole in toluene
employing reux conditions for 24 h. This on anion exchange
using potassium hydroxide in water for 12 h at room tempera-
ture furnished 4. Formation of 3 and 4 was characterized by
infrared spectroscopy. Finally, reacting suspension of 4 with a
solution of ascorbic acid in water at room temperature for 12 h
led polymer supported ascorbate functionalized task specic
ionic liquid 6 (Scheme 2), which was characterized using IR,
SEM and EDX analysis.
Fig. 1 Polymer supported ascorbate functionalized task specific ionic
IR spectrum (Fig. 2) of MR-IMZ-As (C) shows, absorption
liquid (MR-IMZ-As).
band at 1720 cmÀ1 corresponding to C]O stretching of lactone
and at 1626, 1602, 1562 and 1158 cmÀ1 corresponding to C]C,
and limited substrate scope. Thus, the development of an effi-
cient, eco-friendly, regioselective protocol for Huisgen 1,3-
dipolar cycloaddition having wide substrate scope operable at
ambient temperature is highly warranted. To achieve this goal,
we described synthesis of novel polymer supported ascorbate
functionalized task specic ionic liquid [MR-IMZ-As] for
synthesis of 1,4-disubstituted 1,2,3-triazoles employing click
approach (Scheme 1).
C]N, C–N and C–O stretching, respectively. The SEM images of
MR-IMZ-As before and aer use for present transformation
exhibit the morphological differences (Fig. 3).
Next, we focused our attention to explore this novel polymer
supported ascorbate functionalized task specic ionic liquid
(MR-IMZ-As) in the 1,3-dipolar cycloaddition. Aromatic azides
are generally used as one of the precursor in Huisgen 1,3-
dipolar cycloaddition, they are also versatile intermediates in
several organic reactions22 viz. Ugi, Griess, Staudinger, Curtius
and Schmidt, etc. Although, these organic azides are stable
against most reaction conditions, low molecular weight azides
are explosive, high temperatures lead to decomposition of the
organic azides.23 To overcome the drawbacks raised due to
organic azides as direct precursors, scientic community
Result and discussion
Initial attempts were focused on synthesis of novel polymer
supported ionic liquid, which is ecofriendly, recyclable, having
Scheme 2 Preparation of polymer supported ascorbate functionalized task specific ionic liquid (MR-IMZ-As).
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Fig. 2 IR spectra of MS-IM-Cl (A), MS-IM-OH (B), MS-IM-As (C) and
MS-IM-As-Cu (D).
preferred in situ generation of organic azides to achieve a
desired transformation.
Aryl diazonium salts are best ecofriendly alternative to
organic azides as it easily generates aryl azide by reaction with
sodium azide thus reduces the hazards derived from the
isolation and handling of the azides. A scanty literature is
available for Huisgen 1,3-dipolar cycloaddition involving in
situ generation of aryl azides.24 In these circumstances,
initially a model reaction for Huisgen 1,3-dipolar cycloaddi-
tion of phenyldiazonium tetrauoroborate, sodium azide and
phenyl acetylene in water was carried out in presence of
CuSO4$5H2O and catalytic amount of polymer supported
ionic liquid (MR-IMZ-As) (Scheme 1). Pleasingly, corre-
sponding 1,2,3-triazole was obtained in good yield within
short time duration. By comparing the 1H NMR data, with the
literature reports, the product was conrmed as 1,4-disub-
stituted 1,2,3-triazole instead of 1,5-disubstituted 1,2,3-tri-
azole.25 Thus, the developed method act as a regioselective
method.
For optimization of reaction conditions in terms of catalyst
loading, model reaction was carried out with varied quantities
of the catalyst. Best result was obtained using 25 mg
(0.16 mmol) of catalyst in water at room temperature. We
decided to employ these optimized conditions to probe the
generality of the method. There was no difference in yield and
reaction time when catalyst loading was increased to 30 mg
(0.19 mmol). However, it took longer time for completion of the
reaction when catalyst loading was reduced to 15 mg (0.09
mmol), 10 mg (0.064 mmol) or 5 mg (0.032 mmol). To check the
effect of the catalyst and copper sulphate, a click reaction were
performed without SILP and without copper sulphate, in both
cases no product was obtained.
Fig. 3 SEM analysis of polymer supported ionic liquid (MR-IMZ-As)
before use (a), after use (b).
donating substituents like methyl, methoxy (entries 1, 2, 14;
Table 1), and electron withdrawing substituents such as
chloro, nitro groups and cyano at para position of aryldiazo-
nium tetrauoroborate (entries 3, 4, 5, 13; Table 1) are found
to be equally effective towards the nucleophilic substitution
of in situ generated aryl azide, followed by 1,3-dipolar cyclo-
addition. It is noteworthy that when alicyclic acetylene, 4-
methyl and 4-chloro phenylacetylene are selected as repre-
sentative of terminated alkyne also undergo clean reaction to
produce the corresponding 1,4-disubstituted 1,2,3-triazoles
employing optimized reaction conditions (entries 6–12, 15,
16; Table 1).
The reusability of the catalyst is an important aspect from
economical point of view. So recovery and reusability study of
the catalyst was performed for the reaction of 2-methoxy-
phenyldiazonium tetrauoroborate, sodium azide and phe-
nylacetylene. Aer the completion of the rst reaction, catalyst
was recovered by simple ltration and washed with ethanol
and acetone, dried at 80 ꢀC for 1 h. TEM-EDS analysis (Fig. 4) of
the catalyst aer rst cycle indicated the presence of copper.
This clearly indicates in situ incorporation of copper with
polymer supported ascorbate functionalized task specic ionic
liquid during the progress of reaction. From the XPS spectrum
of catalyst, the values of binding energy at 932.3 and 954.7 eV
corresponding to the Cu 2p3/2 and Cu 2p1/2 and peak centered
at 531.3, 284.5 eV represent O 1s and C 1s, respectively. This
data of binding energy is in agreement with the literature and
revealed presence of CuO26a–c while existence of copper as Cu2+
is also conrmed by presence of the shake-up satellite peak26d,e
with binding energy 940–950 eV (Fig. 5). Thus copper
Aer optimization of the reaction conditions, to delineate
this approach, particularly in regards to library construction,
this methodology was evaluated by using
a diversely
substituted aryldiazonium tetrauoroborate reacted with
sodium azide and terminal alkyne to provide corresponding
1,4-disubstituted 1,2,3-triazoles under optimized reaction
conditions. The results are summarized in Table 1. Electron
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Table 1 Synthesis of 1,2,3-triazoles by click reaction of terminated alkynes, arenediazonium salts and sodium azidea
Entry
1
Diazonium salt
Alkyne
Product
Time (h)
Yieldb (%)
2
2
94
2
3
4
92
82
79
2
2
5
6
7
8
9
2
2
2
2
2
80
90
92
90
96
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Table 1 (Contd.)
Entry
10
Diazonium salt
Alkyne
Product
Time (h)
Yieldb (%)
2
2
95
11
12
92
90
2
13
14
2
2
94
92
15
2
2
90
92
16
a
Reaction conditions: aryldiazonium tetrauoroborate (1 mmol), sodium azide (1 mmol), terminal alkyne (1 mmol), CuSO4$5H2O (10 mg, 0.04
mmol) and MR-IMZ-As (25 mg, 0.16 mmol) in water (5 mL). b Isolated yield.
incorporated in the catalyst in the form of CuO. Hence reus- supported ascorbate functionalized task specic ionic liquid
ability study was carried out in absence of CuSO4$5H2O. Aer binds copper to minimize deterioration and metal leaching
1st run copper content of the ltrate was determined using and facilitates efficient catalyst recycling. We observed that
atomic absorption spectroscopy (AAS). No copper metal was catalyst was reused at least for ve times resulted 94, 94, 92, 90,
detected in ltrate, which conrms the fact that polymer 89 and 85% yield, respectively (Fig. 6). Metal leaching was also
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Fig. 4 TEM-EDS analysis of used polymer supported ionic liquid (MR-
IMZ-As).
studied by TEM-EDS analysis of the catalyst before and aer
the 5th cycle. Aer 1st and 5th cycle the concentration of in situ
incorporated Cu was found to be 3.33 wt% and 3.09 wt%,
respectively.
Fig. 5 XPS data of used polymer supported ionic liquid (MR-IMZ-As).
Conclusion
Mumbai) were used as received. All reactions were carried out
in air atmosphere in predried glassware. Infrared spectra were
measured with an Agilent Cary (IR-630) spectrophotometer. 1H
NMR and 13C NMR spectra were recorded on a Brucker AC
We have described an efficient, regioselective and green
procedure for the one-pot synthesis of 1,4-disubstituted
1,2,3-triazoles catalyzed by in situ incorporated copper with
polymer supported ascorbate functionalized task specic ionic
liquid in water at room temperature. This protocol provides
advantages such as operational simplicity, general applicability,
one-pot synthesis of triazoles from diazonium salts, high yields,
involving room temperature and recyclability of the catalyst up
to the h run without any appreciable loss of activity. High
purity and yields of the product, excellent regioselectivity and
circumventing the problems encountered with the isolation of
organic azides, enable one to adhere to greener and cost effec-
tive approach for Huisgen cycloaddition.
Experimental
General information
Alkynes (Aldrich/Alfa Aesar), sodium azide (Spectrochem,
Fig.
6 Reusability of used polymer supported ionic liquid
Mumbai) and copper sulphate pentahydrate (Spectrochem, (MR-IMZ-As).
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spectrometer (300 MHz for 1H NMR and 75 MHz for 13C NMR),
using CDCl3 as solvent and tetramethylsilane (TMS) as an
internal standard. Chemical shis (d) are expressed in parts
per million (ppm) and coupling constants are expressed
in hertz (Hz). Mass spectra were recorded on a Shimadzu
QP2010 GCMS. FESEM was performed using a HITACHI
S-4800. TEM-EDS were determined using energy dispersive
X-ray analyser EM912 coupled to transmission electron
microscopy (TEM) JEOL-2100F transmission electron micro-
scope. X-ray photoelectron (XPS) was recorded on VG Multilab
ESCA 2000 system.
Acknowledgements
We gratefully acknowledge the DST New Delhi for nancial
assistance under Fast Track Scheme [no. SB/FT/CS-154/2012].
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´
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