Anion functionalized ionic liquid from artificial sugar: A sustainable pathway for diverse bis-enol derivatives

Article abstract of DOI:10.1039/c9nj01899a

An artificial sugar saccharine based anion-functionalized ionic liquid [Bmim]Sac was synthesized and used for new and straightforward strategies for the construction of a diverse range of bis-enols. The advantage of this methodology is the use of a non-to

Full text of DOI:10.1039/c9nj01899a

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Anion Functionalized Ionic liquid From Artificial Sugar: A
Sustainable Pathway for Diverse Bis-enol Derivatives
Himani Sharma,a Suman Srivastava*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
An Artificial Sugar Saccharine based anion-functionalized ionic liquid [Bmim]Sac was synthesized and used for new and
straightforward strategies for the construction of diverse range of bis-enol. The advantage of this methodology is use of
non-toxic, inexpensive and reusable catalyst, and high atom economy, and easy purification makes this an efficient
process. Besides, a probable mechanism describing dual activation of ionic liquid as well as dual hydrogen bonding of
saccharinate anion has been proposed.
antiviral agent respectively (Figure 1).10 On the basis of above
said importance of bisenols, development of mild, efficient,
and ecofriendly synthetic methodology is essential.
Introduction,
Diversity-oriented synthesis offers a unique approach for
the synthesis of structurally diverse bioactive skeletons by
varying substrate functionalities and molecular building
blocks.1 Recently green chemistry approach has profoundly
influenced the Diversity-oriented synthesis by considering its
environmental compatibility. Hence, diversity-oriented
synthesis carried out with readily available environmentally
benign solvents and reagents is attractive. In this context,
functionalized ionic liquids have appeared as an important and
essential replacement for toxic, hazardous, flammable, and
highly volatile organic solvents as well as catalyst.2
Functionalized ionic liquid is an effort to take advantage of the
potential “design” capacity of Functionalized ionic liquids and
allowing them as working systems rather than just reaction
media.3 ILs can be functionalized by designing different cations
and anions on the basis of requirement.4 Since anion plays an
important role in ionic liquid catalysis, recently several anion
functional ionic liquids, were synthesized and used for the gas
capture5 and basic catalytic reaction.6
Biscoumarin have been synthesized through the catalyzed
domino reaction with a variety of catalysts including I2,11
RuCl3.nH2O,12 n-dodecylbenzenesulfonic acid,13 Nano silica
chloride,14 Sodium dodecyl sulfate (SDS),15 heteropoly acids,16
cellulose
sulfuric
acid,17
Zn(proline)2,18
CuO-CeO2
nanocomposite catalyst19 Propane-1,2,3-triyltris(hydrogen
sulfate).20 A variety of catalyst have been also used for the
synthesis of Aryl/alkylbispyranylmethane such as organic
bases,21
Fe3O4@SiO2/(CH2)3-[Imidazolium-SO3H]Cl.23
nano
magnetic
core-shell
catalysts,22
Biscoumarin and Aryl/alkylbispyranylmethane
are
renowned as significant organic natural products with
excellent potent of therapeutic applications in the field of
medicinal and biological chemistry.7 Biscoumarin derivatives
such as Acenocoumarol, Phenprocoumon, Warfarin, and
Dicoumarol are anticoagulant agents that act as vitamin K
antagonists (Figure1).8-9 Aryl/alkylbispyranylmethane bearing
4-hydroxy pyran-2-one structural moieties such as
Phaeolschidins and 5-substituted pyrimidine nucleoside with
arylbispyranylmethane moiety can act as anti-oxidant and
Figure1. Bioactive agents bearing Biscoumarin and Aryl
/
alkylbispyranylmethane structural scaffolds
A variety of ionic liquids24-30 has also been used for the synthesis
of biscoumarin and Aryl/alkylbispyranylmethane. Recalling the
previously developed methods and their shortcomings, some of
which have included the application of hazardous organic solvents,
low yield, strongly acidic conditions, expensive moisture-sensitive
catalysts, extended reaction times, high reaction temperatures, and
also tedious work-up conditions, it is still necessary to develop a
non-toxic, green, reusable catalytic system for the synthesis of
Bisenol scaffolds. From previously published work for synthesis of
Bisenol, it is also evident that there is yet a scope of common
aDepartment of Applied Sciences, National Institute of Technology, Delhi. NILERD
campus, Sec A-7, Narela, Delhi, India, 110040, Email: sumanbhu08@gmail.com
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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methodology for various bisenol scaffolds.27, In continuation to In order to show the merit of our procedure, we have performed
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DOI: 10.1039/C9NJ01899A
developing
diversity
oriented
synthesis32
and
green synthesis of Biscoumarin using other ionic liquid (Table 1, entry 1, 2,
multicomponent methodology,33 we herein report synthesis of a 3, 4, and 5). The results were summarized in Table 1.
large collection of bisenol derivatives such as biscoumarin,
arylbispyranylmethane and tetraketones using green anion Table 1 Reaction condition optimization in presence of different
functionalized ionic liquid synthesized from simple, bio-renewable ionic liquids for the synthesis of Biscoumarin
starting such as Saccharine.34
Saccharine is one of the most widely explored, cheapest, readily
available substrates and due to its non toxic properties,35a it can be
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used for synthesis of anion functionalized ionic liquid. Since anion
play an essential structural element in altering the technical
properties of ionic liquid. Therefore, the selection of saccharine
based anion with non toxic potential proved to be far superior than
S. No
Ionic liquid , Temp and amount of
catalysta
Time
Yield(%)b
-
the anions such as BF4 , (CF3SO2)2N- which have high toxic
potentials.35b,35c In addition, 1-butyl-3-methyl-imidazolium cation
with a short alkyl side chain (C = 4) was chosen because ionic liquids
with longer alkyl side chains (C>6) proved to cause high toxicities.35d
Owing to the wide application of bis-enol derivatives, we were
interested in exploring saccharine based ionic liquid for the
synthesis of bisenol as a novel and green methodology. Present
report focuses on the bisenol synthesis through domino
1
2
[Bmim]Br, 80°C, 20 mol%
[Bmim]OH 80°C, 20 mol%
[Bmim]BF4 80°C, 20 mol%
[Bmim] SO3H, 80°C, 20 mol%
[Bmim]PF6, 80°C, 20 mol%
-, 100°C,
5h
5h
30
65
3
5h
70
4
5h
72
Knoevenagel-Michael
hydroxycoumarin/4-hydroxy-6-methyl-2
reaction
of
aldehyde,
pyrone
and
/Dimidone
4-
5
5h
75
6
24h
5h
trace
60
/Cyclohexanone 1,3- dione in the presence of [Bmim]Sac as a
catalyst in water (scheme 1).
7
[Bmim]Sac, RT, 40 mol%
[Bmim]Sac, 50˚C, 40 mol%
[Bmim]Sac, 60˚C, 40 mol%
8
12h
12h
12h
45min
45min
45min
10 min
62
9
65
10
11
12
13
14
70
[Bmim]Sac, 70˚C, 40 mol%
[Bmim]Sac, 80˚C, 40 mol%
85
Scheme 1. Synthesis of Bisenol scaffolds under mild and eco-friendly
[Bmim]Sac, 80˚C, 30 mol%
[Bmim]Sac, 100˚C, 30 mol%
85
conditions
85
Results and discussion,
[Bmim]Sac, 80˚C, 10 mol%, water
96
[Bmim]Sac was synthesized via reaction of sodium saccharinate
with [Bmim]Br in dry acetone at room temperature. To optimise the
reaction condition, the reaction of 4-Cl-benzaldehyde and 4-
hydroxycoumarin as a model reaction in the presence of different
amount of [Bmim]Sac was studied. In absence of [Bmim]Sac, only a
trace amount of 4b was obtained even at 100 °C (Table 1, entry 6).
The amount of catalyst and reaction temperature was optimized
using same model reaction. Initially, model reaction was performed
in neat ionic liquid at room temperature and it was found that 40
mol% of catalyst (Table 1, entry 7) is sufficient to achieve the target
compound in 60% yield at room temperature. On increasing the
temperature from 50 ˚C to 80˚C, yield increases progressively (Table
1, entry 8-11), and we found that the reaction accomplished in
short duration in presence of only 30 mol% of catalyst at 80˚C
(Table 1, entry 12). Further increase in the temp up to 100 °C
doesn’t have any effect on yield (Table 1, entry 13). But in presence
of water, 10 mol% of ionic liquid is sufficient to complete the
reaction in 10 min (Table 1, entry 14). The presence of water gave
the most excellent result with respect to both time and yield (Table
1, entry 14). This may be due to structural and dynamical changes in
IL-water solution.36 Therefore, 10 mol% [Bmim]Sac in the presence
of water and 80˚C was selected as the optimal reaction condition.
aReaction Conditions: 4-Cl benzaldehyde (1.0 mmol), 4-hydroxycoumarin
(2a, 2.0 mmol), bIsolated yield
Next, the substrate tolerance of this catalyst for synthesis of Bisenol
was investigated using different veriety of aldehydes and cyclic
active methylene compounds under optimized conditions. Results
displayed in scheme 3 shows that various aromatic aldehydes either
with electron donating or electron withdrawing substituent groups
reacts smoothly with cyclic active methylene compounds to give the
target compounds in good to excellent yields. Heteroaromatic
aldehydes such as thiophene-2-carbaldehyde and furan-2-
carbaldehyde were competent to undergo condensation with 4-
hydroxy coumarin and isolating the corresponding biscoumarin in
quantitative yield (scheme 3, 4j, 4k, 4u). To further evaluate the
scope of substrate, we investigated the catalytic activity of
[Bmim]Sac for synthesis of aryl/alkyl bispyranylmethane as well as
tetraketones derivatives (scheme 2). For this, we replaced 4-
hydroxy coumarin with 4-hydroxy-6-methyl-2-pyrone/ dimedone/
1,3-cyclohexanedione in condensation reaction with substituted
aldehyde and the results are summarized in (scheme 2 and 3).
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Scheme 2. Domino Knoevenagel-Michael reaction of substituted aldehydes 1a-o with 4-hydroxycoumarin/4-hydroxy-6-methyl-2-pyrone/
dimedone/ 1,3-cyclohexanedione 2a-d, catalyzed by [Bmim]Saca
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Scheme 3. Synthesis of biscoumarin, bispyranylmethane and tetraketones via optimized reaction conditions.
aReaction Conditions: Substituted
aldehyde
(1.0 mmol),
4-hydroxycoumarin/4-hydroxy-6-methyl-2-pyrone/dimedone/1,3-
cyclohexanedione(2.0 mmol), [Bmim]Sac (0.1 mmol).; bIsolated yield.
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Aliphatic aldehyde such as n-Butyraldehyde afforded target product
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The reusability of the [Bmim]Sac was also invesVtiiegwaAtretidcleuOsnilninge
DOI: 10.1039/C9NJ01899A
in excellent yield with very short reaction time (scheme 2, 4l and reaction between 4-Cl benzaldehyde and 4-hydroxycoumarin
4v). In most of the cases, the solid products obtained were just as a model system. After the completion of reaction as
filtered off the reaction mixture or in some cases extracted with monitored by TLC, water was added to the reaction mixture.
ethyl acetate and water and later recrystallized from ethanol to The solid precipitate was filtered and the filtrate containing
obtain the pure product. The plausible reaction for [Bmim]Sac water and the ionic liquid catalyst was dried and subsequently
catalyzed one-pot Knoevenagel-Michael reaction mechanism was used for the next run. It was shown that after five cycles the
proposed and is illustrated in Figure. 2. The process represents a catalytic activity had a low decrease (Figure 3), suggesting the
typical domino reaction by dual activation by ionic liquid. The good recyclability of this ionic liquid for Bisenol synthesis. Also
carbonyl group of aldehyde was activated by formation of hydrogen after five cycles of reusability, IR and NMR characterization of
bonds with C-2 hydrogen of [Bmim] cation of ionic liquid, and ionic liquid was performed which is similar to fresh IL
saccharinate anion of IL activated OH of 4-hydroxy-coumarin as a indicating purity and activity of Ionic liquid (See supporting
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hydrogen bond acceptor.
information, Fig 3-6).
Conclusions
Artificial sweetener saccharine based ionic liquid was found
to be an efficient catalyst for the synthesis of Bis-enol
derivatives. The attractive features of this method include
milder and cleaner reaction conditions, higher yields and
purity of the product and an easier work-up and isolation of
products. In addition, this ionic liquid catalyst is easy to
prepare, and its raw materials such as saccharine are highly
biocompatible biodegradable and non toxic, which make the
preparation and utilization procedures more safe and green.
Conflicts of interest
Figure 2: Plausible mechanism via dual activation of [Bmim]Sac
and dual hydrogen bonding of saccharinate anion
“There are no conflicts to declare”.
Acknowledgements
This dual activation led to addition of one molecule of 4-
hydroxycoumarin to one aldehyde molecule. Then,
intermediate which was also activated by the [Bmim] cation of
ionic liquid and then reacted with another molecule of 4-
hydroxycoumarin activated by anion of ionic liquid, leading to
target compound with high efficiency. In this catalytic
procedure, [Bmim] cation and the anion have a synergetic
effect on substrates, and also dual hydrogen bonding ability of
saccharinate anion35a is a possible reason why this catalytic
system could reduce reaction duration significantly.
SS acknowledge Department of Science and Technology
(DST) for financial support through Inspire Faculty Award No
IFA-13-CH-123.
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