Design, synthesis and metal sensing studies of ether-linked bis-triazole derivatives

Article abstract of DOI:10.1039/c4nj02035a

Ether-linked-bis-triazole derivatives have been synthesized by (CuAAC) "Click" reaction and well characterized by NMR spectroscopy, mass spectrometry, and elemental analysis. Application of these materials in the field of sensors has also been demonstrated using various spectroscopic techniques. The interaction of the compound with Hg²⁺ was further confirmed by computational studies.

Full text of DOI:10.1039/c4nj02035a

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Graphical Abstract
Ether-linked-bis-triazole derivatives have been synthesized by (CuAAC) “Click” reaction and
well characterized by NMR technique, mass and elemental analysis. Application of these
materials in the field of sensor has also been demonstrated using various spectroscopic
techniques. Interaction of the compound with Hg2+ was further confirmed from computational
studies.

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DOI: 10.1039/C4NJ02035A
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ARTICLE TYPE
Design, synthesis and metal sensing studies of ether-linked bis-triazole derivatives
Arasappan Hemamalinia, Sathish Kumar Mudedlab, Venkatesan Subramanianb and Thangamuthu
Mohan Dasa,c*
aDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai – 600 025, INDIA.
b Chemical Laboratory, CSIRꢀCentral Leather Research Institute, Adyar, Chennai ꢀ 600 020.
cDepartment of Chemistry, School of Basic and Applied Sciences, Central University of Tamil Nadu, Thiruvarur ꢀ610 004; Ph. No. +919489054264; Fax
04366 – 225312; Eꢀmail: tmohandas@cutn.ac.in
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
response with Hg2+ ion is a challenging target. Recently, there
10 Ether-linked-bis-triazole derivatives have been synthesized by
(CuAAC) “Click” reaction and well characterized by NMR
technique, mass and elemental analysis. Application of these
materials in the field of sensor has also been demonstrated
using various spectroscopic techniques. Interaction of the
15 compound with Hg2+ was further confirmed from
computational studies.
are many reports14ꢀ19 on the sensor materials. In this report,
50 the etherꢀlinked chalconeꢀbasedꢀbisꢀsugarꢀtriazole derivatives
were synthesized and their application in the field of sensor
were also realized from the spectroscopic experiments. The
designed chemosensor, 17 exhibits a “turnꢀon” type response
and highly selective fluorescence behaviour for Hg2+ ions.
55 Results and discussion
Introduction
Synthesis and characterisation of sugar chalcone derivatives
Mercury is one of the most significant environmental
pollutants and its contamination is widespread by various
20 natural sources.1 The introduction of mercury in to the food
chain causes serious hazards to the man kind as well as to the
marine lives.2,3 The accumulation of mercury in the liver,
kidney and spleen leads to DNA and nervous system damage.
Although a number of chemosensors such as calix[4]arenes
25 and azaꢀcrown ethers has been developed for selective sensor
for Hg2+ ion, most of them exhibit poor solubility which limits
their application as sensor. Moreover, the use of sugar moiety
increases the solubility of the reaction.
Molecular recognition of anions and cations is an important
30 subfield within supramolecular chemistry due to the major
role that ions play in diverse domains, such as biotechnology,
medicine and environmental research.4ꢀ6 Selfꢀassembled
monolayers (SAMs) that possess molecular recognition motifs
can be used to design chemical sensors,7 nonꢀlinear optical
35 materials,8 and molecular switches.9 Incorporation of crownꢀ
ether groups into selfꢀassembled monolayers and their use as
metal ion sensors were published simultaneously by Moore et
al.10 and Flink et al.11
(4,6ꢀOꢀButylideneꢀβꢀDꢀglucopyranosyl)propanꢀ2ꢀone,
1
and
2,3,4,6ꢀtetraꢀOꢀacetylꢀβꢀDꢀglucopyranosylꢀpropanꢀ2ꢀone,
2
were synthesized by following the literature procedure.20 The
60 reaction of sugarꢀOꢀprotectedꢀpropaneꢀ2ꢀone derivatives, 1 &
2 with different aromatic aldehydes using pyrrolidine as
catalyst resulted in 65ꢀ85% of the corresponding αꢀ,βꢀ
unsaturated compounds, 3-8. The sugarꢀchalcone derivatives
which possess the free hydroxyl group was propargylated with
65 propargylbromide using potassiumcarbonate as base resulted
in the corresponding propargylated derivatives, 9-14. Etherꢀ
linked diazide, 15 was synthesized by adopting the literature
procedure.21 All the synthesized compounds were well
characterized using different spectral techniques.
70 Ether-linked sugar-triazole derivatives
A series of novel symmetrical etherꢀlinked sugarꢀchalconeꢀ
basedꢀbisꢀtriazole derivatives, 16-20 [Scheme 1] were
regioselectively synthesized by the copper(I) catalyzed azide
alkyne cycloaddion (CuAAC) “Click” reaction of sugarꢀ
75 chalconeꢀbasedꢀpropargylated derivatives, 9-14 with etherꢀ
linked diazide, 15. The cycloaddition reaction of
Fluorescent quenching by heavy metal ions may occur due to
40 spin orbit coupling, energy and electron transfer.12,13 A facile
approach for monitoring Hg2+ ions arises due to its propensity
to quench fluorescence emission. Among the fluorescent
triethyleneglycoldiazide
with
sugarꢀchalcone
based
propagylated derivatives was promoted by CuSO4 as catalyst
and sodium ascorbate as reducing agent in 1:1 ratio of THFꢀ
quenching (“turnꢀoff”) and enhancement (“turnꢀon”), the latter 80 H2O mixture. The yield obtained in the reaction was found to
is more preferable because it lessens the chance of false
45 positives. Moreover, there are very few literature reports12
available for the turnꢀon type fluorescent sensors. Hence
designing the fluorescent sensor that provides the turnꢀon
be 50ꢀ83%. Structures of the synthesized sugarꢀtriazole
derivatives were determined by (1H 13C) NMR
spectroscopy, mass spectroscopy and elemental analysis.
&
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Fluorescence studies
35 Fluorescence experiment gives an information about the
binding ability of the synthesized bisꢀtriazole derivatives with
metal ions. Titration experiment was carried out with
perchlorate salts of various metal ions including alkali,
transition and heavy metal ions using acetonitrile as solvent.
40 The triazole compound, 17 was excited at 330 nm wavelength
and the emission was observed around 460 nm. Minimum
response was observed with Na+ and Ni2+ which clearly
depicts that the compound has less affinity towards them
whereas excellent response was observed with heavy metal
45 ions such as Pb2+, Zn2+ and Hg2+. The interaction of the
compound 17 with all the metal ions except Ni2+ ion showed
fluorescent enhancement whereas the compound, 17 with Pb2+
showed better enhancement along with a slight bathochromic
shift. However, the interaction of the compound, 17 with Hg2+
50 gave the highest enhancement with hypsochromic shift of all
the metal ions studied. Thus, the result obtained reveals that
among the three heavy metal ions studied, Hg2+ ions found to
have a unique response with the ligand [Figure 1]. Similar
trend in enhancement of fluorescence was observed upon
55 addition of the metal ion to the receptor.23 Moreover, upon
binding of the target analyte, fluorescent enhancement or
quenching can occur by several mechanisms including photoꢀ
induced electron transfer and eximer formation.24 The
excellent binding ability of bisꢀtriazole derivatives with Hg2+
60 ion has also been reported in the literature.25 Similar results
was observed with the synthesized compound and it has a
unique binding nature with Hg2+ ions compared to the other
heavy metal ions tested.
Scheme 1 Synthesis of ether linked bis-triazole derivatives, 16-20.
The triazole proton of compound, 16 appeared as a singlet at
7.8 ppm. The appearance of two doublets at 7.79 and 6.64
ppm with J value of ~17 Hz respectively corresponds to the
transꢀalkene protons [Table 1]. It also notably exhibited a
large coupling constant for the Hꢀ1 signal (3JH1,H2 ~ 9.6 Hz),
indicating a transꢀdiaxial orientation of Hꢀ1 and Hꢀ2 as
expected for a βꢀDꢀconfigured glucopyranose moiety. The
δ
δ
5
10 formation of the product, 16 was further confirmed from 13C
NMR spectroscopy where the triazole carbon resonated at
144 and 124 ppm and the ꢀ, ꢀunsaturated carbonyl signal
appeared at 197 ppm. DEPTꢀ135 experiment gave a clear
δ
α
β
δ
idea for the formation of the sugarꢀcoupled bisꢀtriazole
15 product, 16 where eight peaks corresponding to the methylene
groups were observed. Formation of the regioisomer of the
triazole product was achieved from the Rodius calculation. It
is reported in the literature22 that if the difference between the
chemical shift value of C4 and C5 value is greater than 20, it
20 is said to be 1,4ꢀregioisomer and much less value is expected
for 1,5ꢀregioisomer. In this case,
δ (C4ꢀC5) of the triazole
cabon for compound, 16 is found to be 20. Thus, it is very
clear from the calculated result that the product is 1,4ꢀ
regioisomer. Reaction between the compounds, 14 and 15
25 under Click condition failed to produce the corresponding bisꢀ
triazole product and it may be due to the insoluble nature of
compound, 14.
Table 1 Etherꢀlinkedꢀbisꢀtriazole derivatives, 16-20
Compound R’ Time Yield
NMR data
TrzꢀH AlkꢀH
(ppm) (ppm)
No.
(h)
(%)
Alk J (
δ
AnoꢀH
(ppm)
δ
δ
H1,
H2) Hz
16.5,
16.5
16
17
18
ꢀOCH3 24
(m)
83
81
50
5.26ꢀ5.14a 7.75
7.79,
6.64
65 Figure 1 Fluorescence spectra of compound, 17 (1x10-5 M) in CH3CN with
different metal ions (1x10-4 M).
ꢀH
24
4.01ꢀ3.97 7.76 7.81,6.69 16.5,
16.5
NMR titration experiment
ꢀCl (p) 24
4.56
5.20
5.31
7.87ꢀ 7.87ꢀ
7.83b 7.83b,
6.76
7.76ꢀ 7.76ꢀ
7.60b 7.60b,
6.87
16.5
15.6
16.2
1H NMR titration experiment was carried out to confirm the
existence of nature of the interaction of the etherꢀlinked bisꢀ
19
20
ꢀH
ꢀH
48
48
71
76
1
70 triazole compound, 17 with Hg2+ ion. Figure 2 shows the H
NMR spectrum of the ligand, 17 in CDCl3 solvent with
different concentration of Hg2+ ions in DMSOꢀd6 solvent.
From the titration experiment it has been observed that the
triazole protons (Htrz) were modestly downfield shifted and
75 the peak shapes were significantly broadened and decreased in
intensity until almost disappearance upon addition of 1.2
equiv. of Hg2+ ions. In addition, the two quartets of
ethyleneglycol moiety linked triazole experienced a downfield
shift, thereby they join together to form a multiplet. Thus, the
80 downfield shift of the triazole and triethyleneglycol protons
8.00
7.63ꢀ
7.59b,
6.76
aPeaks overlapped with –OCH2 protons, bPeaks overlapped with aromatic
30 protons.
2
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40
45
50
5
10
15
Figure 2 1H NMR titration spectrum of compound, 17 in CDCl3 upon
addition of Hg2+: (a), 17 alone; (b), 0.2 equiv.; (c), 0.4 equiv.; (d), 0.6
Fluorescence titration experiment
20 equiv.; (e), 0.8 equiv. and (f), 1.2 equiv.
To investigate the interaction between sensor, 17 and Hg2+ ion
further, fluorescence titration experiment was performed.
When the compound, 17 was excited at 330 nm, a broad
55 emission band is observed at 440 nm. As shown in Figure 3
on addition of Hg2+ ions to the sensor, 17 the intensity of the
peak increased with significant hypsochromic shift. However,
upon continuous addition of Hg2+, the intensity of the peak
gradually increased with increase in concentration of Hg2+
60 ion. This clearly depicts the binding of Hg2+ ion with the
compound, 17.
confirmed the coꢀordination site of Hg2+ ion with the two
oxygen atoms of the etherꢀlinked moiety and the nitrogen
atom of the triazole system. Since negligible shift only has
been observed with benzyl ether moieties, it is well clear that
25 the ligand is found to have only one coꢀordination site. It
implies the existence of only one binding mode and it is
confirmed from the titration experiment that even after the
addition of more than one equivalent of Hg(ClO4), there is no
prominent shift in the triazole protons. In addition, out of the
30 three nitrogens of the 1,2,3ꢀtriazole moiety, though the Hg2+
can bind through either the Nꢀ2 or Nꢀ3, due to the chelation
effect only the Nꢀ2 of the triazole moieties is capable of coꢀ
ordinating with Hg2+ ion.26 It is also revealed that the two
triazoles should be faced each other inwards for the greater
35 coꢀordinating ability with the metal ion. The possible
representation for the binding nature of the ether linked bisꢀ
triazole with Hg2+ ion is shown in Figure 2.
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The relativistic effects for mercury ion were added with the
help of Stuttgart Dresden effective core potentials. The
geometry optimization was carried out without any
35 geometrical constraints. To ensure that the optimized
geometries correspond to true minima on the potential energy
surface, vibrational frequencies were computed using DFT
(B3LYP/6ꢀ31+G**. All these calculations were carried out
using Gaussian 09 package.30 The optimized geometry is
40 shown in figure 5. From the figure, it can be seen that the
mercury ion coordinated to the four groups (two Nꢀ2 nitrogens
of the five member rings and two oxygens from ethers). The
four coordinated bond lengths are 2.105Å (HgꢀN), 2.105Å
(HgꢀN), 2.478Å (HgꢀO) and 2.478Å (HgꢀO), respectively.
45 Square planar complex has not been observed for four
coꢀordinated Hg metal. The calculated bond angles are
measured as NꢀHgꢀN (153.40˚), NꢀHgꢀO (79.42˚), OꢀHgꢀO
(68.04˚) and OꢀHgꢀN (79.42˚). Two coordinated nitrogens are
not exactly linear and two triazole rings are not in same plane.
50 The dihedral angle between the two planes of triazole rings is
107.3˚. From these results, it is confirmed that the proposed
geometry in the experimental part was correct. The Cartesian
coordinates of the optimized geometry is given in supporting
information.
Figure 3 Fluorescence titration spectra of compound, 17 [5 x 10-2 M]
upon titration with Hg(ClO)4 in acetonitrile+water mixture at 25°C [1X10-5
M], (a), 0 equiv. Hg2+; (b), 0.2 equiv. Hg2+; (c), 0.4 equiv. Hg2+; (d), 0.6
equiv. Hg2+; (e), 0.8 equiv. Hg2+; (f), 1 equiv. Hg2+; (g), 1.2 equiv. Hg2+; (h),
1.4 equiv. Hg2+; The arrow mark shows the change in the intensity upon
addition of Hg2+ ion.
5
Absorption studies
Absorption studies were carried out with different equiv. of
10 Hg2+ in actetonitrile solvent in order to find the ligandꢀmetal
binding ratio. The variation in the absorption peak of the
chemosensor, 17 was monitored upon addition of Hg2+ ion
using UVꢀvis spectroscopy. The absorbance for the compound
was observed around 284 and 330 nm. Upon addition of 0.5
15 equiv. of Hg2+ ion, a new peak was observed around 230 nm.
On further addition of 0.5 equiv. results in the decrease in the
absorbance band around 284 and 330 nm with an increase in
the absorption band around 230 nm. This clearly confirms the
interaction of Hg2+ ion with the chemosensor. Furthermore,
20 due to the presence of one isobestic point, it clearly confirmed
the ratio of binding of the ligand with metal as 1:1.
55
Figure 5 Optimized geometry of ether-linked-bis-triazole derivative, 17
with Hg2+ion.
Conclusion
Several
symmetrical
etherꢀlinkedꢀbisꢀsugarꢀtriazole
60 derivatives, 16-20 have been synthesized and characterized
using various spectral techniques. In acetonitrile solution, of
the
5 metal ions screened, chemosensor, 17 responded
selectively to Hg2+ ion. It showed selective fluorescence
enhancement with hypsochromic shift only towards Hg2+. The
Figure 4 Absorption spectra of compound, 17 [5 x 10-4 M] with Hg2+ ion
[1 x 10-2 M] in acetonitrile+water mixture at 25°C (a), 0.5 equiv. Hg2+; (b),
25 1 equiv. Hg2+. The arrow mark shows the change in the absorbance
intensity upon addition of Hg2+ ion.
1
65 shift of the triazole protons towards downfield in the H NMR
titration in the etherꢀlinked bisꢀtriazole derivatives reveals the
interaction of compound with Hg2+ ion. Also, the metal to
ligand ratio was found to be 1:1 from the proton NMR
titration experiment and absorption studies. Hence, the
70 synthesized etherꢀlinked bisꢀtriazole compounds may act as a
potential sensor for the environmental or biological detection
of Hg2+.
Computational Studies
The geometry of complex was optimized using density
functional theory (DFT) with Becke’s three parameter hybrid
30 exchange functional and the Leee Yange Parr correlation
functional (B3LYP)27ꢀ29 and 6ꢀ31+G** basis set was used.
4
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H), 7.21 (d, J = 7.8 Hz, 1H, ArꢀH), 7.11 (t, J = 8.0 Hz, 1H, Arꢀ
H), 6.98 (d, J = 8.1 Hz, 1H, ArꢀH), 6.73 (d, J = 16.5 Hz, 1H,
60 AlkꢀH), 5.24 (t, J = 9.5 Hz, 1H, SacꢀH), 5.08 (t, J = 9.6 Hz,
1H, SacꢀH), 5.00 (t, J = 9.6 Hz, 1H, SacꢀH), 4.78 (d, J = 2.1
Hz, 2H, ꢀOCH2), 4.27 (dd, J = 4.8 Hz, J = 12.5 Hz, 1H, Sacꢀ
H), 4.21ꢀ4.13 (m, 1H, SacꢀH), 4.10 (t, J = 7.2 Hz, 1H, SacꢀH),
4.01 (d, J = 11.7 Hz, 1H, SacꢀH), 3.88 (s, 3H, ꢀOCH3), 3.76ꢀ
65 3.71 (m, 1H, SacꢀH), 3.11 (dd, J = 8.4 Hz, J = 16.5 Hz, 1H, ꢀ
CH2), 2.73 (dd, J = 3.0 Hz, J = 16.4 Hz, 1H, ꢀCH2), 2.62 (t, J
= 2.3 Hz, 1H, ꢀC≡CH), 2.03ꢀ2.01 (m, 12H, ꢀCOCH3); 13C
Experimental section
General methods
DꢀGlucose,
triethyleneglycol,
sodiumazide
and
propargylbromide, were purchased from SigmaꢀAldrich
Chemicals Pvt. Ltd., USA and were of high purity.
Butyraldehyde, pyrrolidine and pꢀtoluenesulphonylchloride
were purchased from SRL, India. Other reagents, such as
hydrochloricacid, sodiumhydrogencarbonate and solvents (AR
grade) were obtained from Sdꢀfine, India, in high purity and
5
10 were used without any purification. Acetylacetone,
coppersulphate and sodiumascorbate were obtained from
LobaꢀChemie, India. Aceticanhydride was purchased from
Fischer Chemicals Pvt. Ltd., India. The solvents were purified
according to standard methods. Column chromatography was
15 performed on silica gel (100 – 200 mesh). NMR spectra were
recorded on a Bruker DRX 300 MHz instrument in either
CDCl3 or DMSOꢀd6. Chemical shifts were referenced to
internal TMS. Absorption studies were recorded on 1800
Shimadzu UV spectrophotometer in the range 190ꢀ800 nm.
20 Fluorescence titration studies were carried out using a Perkin
Elmer LS 45 fluorescence spectrometer. Electrospray
ionization (ESI) mass spectra were recorded on a WATERSꢀ
QꢀTOF PremierꢀHAB213 instrument. Elemental analysis was
performed using PerkinꢀElmer 2400 series CHNS/O analyzer.
25
NMR (75 MHz, CDCl3):
δ 196.5, 170.5, 170.1, 169.8, 169.4,
162.5, 152.9, 146.2, 139.1, 129.3, 127.4, 124.8, 118.7, 114.2,
70 79.0, 76.4, 75.6, 74.2, 74.1, 71.7, 68.5, 62.0, 60.6, 55.8, 41.8,
36.4, 20.6, 20.5 (2C), 14.1.
Spectral
data
of
(E)-1-(4,6-O-butylidene-β-D-
glucopyranosyl)-4-(2-prop-2-ynyloxyphenyl)-but-3-en-2-
75 one (10):
Oꢀpropargylation of compound, 4 (0.38 g, 1 mmol) with
propargylbromide (0.09 ml, 1.2 mmol) using K2CO3 (0.69 g, 5
mmol) as base resulted in compound, 10 as a colourless solid.
Mp: 107ꢀ108 oC; Yield: 0.29 g (69%); 1H NMR (300 MHz,
80 CDCl3): δ 7.95 (d, J = 16.5 Hz, 1H, AlkꢀH), 7.57 (d, J = 7.5
Hz, 1H, ArꢀH), 7.39 (t, J = 8.0 Hz, 1H, ArꢀH), 7.07ꢀ7.00 (m,
2H, ArꢀH), 6.82 (d, J = 16.5 Hz, 1H, AlkꢀH), 4.79 (d, J = 2.4
Hz, 2H, ꢀOCH2), 4.53 (t, J = 5.1 Hz, 1H, SacꢀH), 4.14 (dd, J =
4.2 Hz, J = 9.6 Hz, 1H, SacꢀH), 3.98ꢀ3.91 (m, 1H, SacꢀH),
85 3.73 (t, J = 8.9 Hz, 1H, SacꢀH), 3.46ꢀ3.31 (m, 3H, SacꢀH),
3.25 (t, J = 8.9 Hz, 1H, SacꢀH), 3.25 (t, J = 8.9 Hz, 1H, Sacꢀ
H), 3.14 (dd, J = 4.2 Hz, J = 16.4 Hz, 1H, ꢀCH2), 3.00 (dd, J =
7.2 Hz, J = 16.1 Hz, 1H, ꢀCH2), 2.55 (t, J = 2.4 Hz, 1H, ꢀ
C≡CH), 1.62ꢀ1.60 (m, 2H,ꢀCH2), 1.42 (q, J = 7.8 Hz, 2H, ꢀ
90 CH2), 0.92 (t, J = 7.4 Hz, 3H, ꢀCH3); 13C NMR (75 MHz,
CDCl3): δ 198.7, 156.4, 138.8, 131.8, 128.7, 127.3, 124.0,
121.8, 112.8, 102.5, 80.5, 78.1, 76.2, 75.4, 74.6, 70.6, 68.3,
56.2, 43.2, 36.2, 17.5, 13.9; Elemental analysisAnal. Calc. for
C23H28O7: C, 66.33; H, 6.78%. Found: C, 66.36; H, 6.81.
General
procedure
for
the
synthesis
of
triethyleneglycoldiazide (15):
Triethyleneglycolditosylate (1 equiv.) was treated with
sodium azide (2.5 equiv.) under stirring and then heated for 3
30 hours. After completion of the reaction, work up was done
using ethylacetate followed by the evaporation of the solvent
resulted in the product, 15.
Spectral data of triethyleneglycoldiazide (15)16:
35 Azidation of the compound triethyleneglycolditosylate with
NaN3 gave 15 as a yellow liquid.
1
Nature:Liquid; H NMR (300 MHz, CDCl3):
δ 3.71ꢀ3.68 (m,
95 Spectral
data
of
(E)-1-(4,6-O-butylidene-β-D-
8H, ꢀCH2), 3.39 (t, J = 5.0 Hz, 4H, ꢀCH2); 13C NMR (75 MHz,
CDCl3): 70.7, 70.1, 50.7.
glucopyranosyl)-4-(5-chloro-2-prop-2-ynyloxyphenyl)-but-
3-en-2-one (11):
δ
40
OꢀPropargylation of compound, 5 (0.41 g, 1 mmol) with
propargylbromide (0.09 ml, 1.2 mmol) using K2CO3 (0.69 g, 5
100 mmol) as a base furnished compound 11 as a colourless solid.
Mp: 124ꢀ125 oC; Yield: 0.34 g (76%); 1H NMR (300 MHz,
CDCl3): δ 7.82 (d, J = 16.2 Hz, 1H, AlkꢀH), 7.51 (s, 1H, Arꢀ
H), 7.31 (dd, J = 2.4 Hz, J = 8.9 Hz, 1H, ArꢀH), 6.98 (d, J =
9.0 Hz, 1H, ArꢀH), 6.77 (d, J = 16.5 Hz, 1H, AlkꢀH), 4.76 (d,
105 J = 2.1 Hz, 2H, ꢀOCH2), 4.53 (t, J = 5.0 Hz, 1H, SacꢀH), 4.15ꢀ
4.10 (m, 1H, SacꢀH), 3.97ꢀ3.90 (m, 1H, SacꢀH), 3.73 (t, J =
8.9 Hz, 1H, SacꢀH), 3.44ꢀ3.22 (m, 4H, SacꢀH, ꢀCH2), 3.14
(dd, J = 3.6 Hz, J = 16.1 Hz, 1H, ꢀCH2), 2.58 (t, J = 2.4 Hz,
1H, ꢀC≡CH), 1.64ꢀ1.60 (m, 2H, ꢀCH2), 1.43 (q, J = 7.2 Hz,
110 2H, ꢀCH2), 0.91 (t, J = 7.4 Hz, 3H, ꢀCH3); 13C NMR (75 MHz,
CDCl3): δ 198.3, 154.8, 137.0, 131.1, 128.1, 128.0, 127.0,
125.6, 114.3, 102.5, 80.5, 77.7, 76.2, 75.3, 74.5, 70.6, 68.3,
56.6, 43.4, 36.2, 17.5, 13.9; Elemental analysisAnal. Calc. for
C23H27ClO7: C, 61.26; H, 6.04%. Found: C, 61.29; H, 6.08.
General procedure for the synthesis of O-propargylated
sugar-chalcone derivatives (9-14):
The hydroxy sugarꢀchalcone derivative (1 equiv.) in DMF was
added the K2CO3 (5 equiv.) and stirred for 10 minutes. To the
45 solution was added propargyl bromide (1.2 equiv.) and then
the mixture was allowed stir for 24 hrs. Once after the
completion of the reaction, work up was done using
chloroform and the product was isolated by the evaporation of
the organic layer.
50
Spectral
data
of
(E)-1-(2,3,4,6-tetra-O-acetyl-β-D-
glucopyranosyl)-4-(3-methoxy-4-prop-2-ynyloxyphenyl)-
but-3-en-2-one (9):
OꢀPropargylation of compound, 3 (0.52 g, 1 mmol) with
55 propargyl bromide (0.09 ml, 1.2 mmol) using K2CO3 (0.69 g,
5 mmol) as base gave 9 as a yellow liquid.
1H NMR (300 MHz, CDCl3):
δ 8.05 (d, J = 16.8 Hz, 1H, Alkꢀ
115 Spectral
data
of
(E)-1-(4,6-O-butylidene-β-D-
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DOI: 10.1039/C4NJ02035A
glucopyranosyl)-4-(3-prop-2-ynyloxyphenyl)-but-3-en-2-
one (12):
137.0, 134.1, 130.9, 128.0, 114.6, 102.5, 80.4, 76.0, 75.4,
60 74.5, 74.0, 70.6, 68.3, 56.4, 43.4, 36.2, 17.5, 13.9.
General procedure for the synthesis of ether-linked-bis-
triazole derivatives (16-20):
To a solution of acetylenic compound, 9-14 (2 equiv.) in a 1:1
(V/V) mixture of THF:H2O were added etherꢀlinkedꢀdiazide,
OꢀPropargylation of compound, 6 (0.38 g, 1 mmol) with
propargyl bromide (0.09 ml, 1.2 mmol) using K2CO3 (0.69 g,
5 mmol) as base gave 12 as a colourless solid.
5
1H NMR (300 MHz, CDCl3):
δ 7.55 (d, J = 16.2 Hz, 1H, Alkꢀ
H), 7.34 (t, J = 8.0 Hz, 1H, ArꢀH), 7.20ꢀ7.15 (m, 2H, ArꢀH), 65 15 (1 equiv.), CuSO4.5H2O (0.2 equiv.), sodiumascorbate (0.4
7.03 (d, J = 8.1 Hz, 1H, ArꢀH), 6.75 (d, J = 16.2 Hz, 1H, Alkꢀ
H), 4.73 (d, J = 2.4 Hz, 2H, ꢀOCH2), 4.53 (t, J = 5.1 Hz, 1H,
10 SacꢀH), 4.13 (dd, J = 4.2 Hz, J = 9.6 Hz, 1H, SacꢀH), 3.96ꢀ
3.91 (m, 1H, SacꢀH), 3.11 (t, J = 8.7 Hz, 1H,. SacꢀH), 3.46ꢀ
equiv.). The mixture was stirred at room temperature for 24
hrs. The reaction mixture was extracted with chloroform and
washed with saturated NH4Cl, water & brine solution. Organic
layer was collected, dried over anhydrous Na2SO4 and
3.30 (m, 3H, SacꢀH), 3.24 (t, J = 8.9 Hz, 1H, SacꢀH), 3.13 (dd, 70 concentrated to dryness under vaccum. The crude mixture was
J = 3.9 Hz, J = 16.1 Hz, 1H, SacꢀH), 2.95 (dd, J = 7.5 Hz, J =
16.2 Hz, 1H, SacꢀH), 2.55 (t, J = 2.3 Hz, 1H, ꢀC≡CH), 1.65ꢀ
15 1.56 (m, 2H, ꢀCH2), 1.42 (q, J = 7.8 Hz, 2H, ꢀCH2), 0.92 (t, J
further purified by column chromatographic technique.
Spectral data of 1,8-bis-(4-hydroxy-methylene-triazolo-4-
(E)-1-2,3,4,6-tetra-O-acetyl-
but-3-en-2-one)-3,6-dioxadecane (16):
157.9, 143.4, 135.8, 130.0, 126.8, 122.0, 117.4, 114.4, 102.5, 75 Compound, 16 was obtained by the (CuAAC) “Click” reaction
β-D-glucopyranosyl-4-phenyl-
= 7.4 Hz, 3H, ꢀCH3); 13C NMR (75 MHz, CDCl3):
δ 198.0,
80.4, 78.2, 75.4, 74.5, 70.6, 68.3, 55.9, 43.5, 36.2, 17.5, 13.9.
Spectral data of (E)-1-(4,6-O-butylidene- -D-
20 glucopyranosyl)-4-(4-prop-2-ynyloxyphenyl)-but-3-en-2-
of sugarꢀpropargyl derivative, 9 (0.56 g, 2 mmol) and
triethyleneglycoldiazide, 15 (0.1 g, 1 mmol) as a yellow solid.
Mp 78ꢀ80 °C; Yield:1.10 g (83%); 1H NMR (300 MHz,
CDCl3): δ 7.79 (d, J = 16.5 Hz, 2H, AlkꢀH), 7.75 (s, 2H, Trzꢀ
β
one (13):
OꢀPropargylation of compound, 7 (0.38 g, 1 mmol) with 80 H), 7.13 (d, J = 7.8 Hz, 2H, ArꢀH), 7.08 (t, J = 8.0 Hz, 2H, Arꢀ
propargylbromide (0.09 ml, 1.2 mmol) using K2CO3 (0.69 g, 5
mmol) as a base resulted in compound, 13 as a colourless
H), 6.98 (d, J = 7.7 Hz, 2H, ArꢀH), 6.64 (d, J = 16.5 Hz, 2H,
AlkꢀH), 5.26ꢀ5.14 (m, 6H, ꢀOCH2, SacꢀH), 5.08 (t, J = 9.6 Hz,
2H, SacꢀH), 4.99 (t, J = 9.6 Hz, 2H, SacꢀH), 4.53 (t, J = 5.1
Hz, 4H, ꢀOCH2), 4.24 (dd, J = 4.8 Hz, J = 12.3 Hz, 2H, Sacꢀ
25 solid.
Mp: 178ꢀ180 C; Yield : 0.26 g (62%); H NMR (300 MHz,
o
1
CDCl3): δ 8.44ꢀ8.39 (m, 3H, ArꢀH, AlkꢀH), 7.88 (d, J = 8.7 85 H), 4.16ꢀ4.09 (m, 2H, SacꢀH), 4.02 (d, J = 12.3 Hz, 2H, Sacꢀ
Hz, 2H, ArꢀH), 7.56 (d, J = 16.2 Hz, 2H, AlkꢀH), 5.63 (d, J =
2.4 Hz, 2H, ꢀOCH2), 5.43 (t, J = 5.0 Hz, 1H, SacꢀH), 5.35 (d, J
30 = 3.6 Hz, 1H, SacꢀOH), 5.06 (s, 1H, SacꢀOH), 4.99 (dd, J =
3.6 Hz, J = 9.6 Hz, 1H, SacꢀH), 4.80 (t, J = 8.4 Hz, 1H, Sacꢀ
H), 3.88 (s, 6H, ꢀOCH3), 3.83 (t, J = 5.1 Hz, 4H, ꢀOCH2),
3.76ꢀ3.70 (m, 2H, SacꢀH), 3.56 (s, 4H, ꢀOCH2), 2.98 (dd, J =
8.1 Hz, J = 16.5 Hz, 2H, ꢀCH2), 2.73 (dd, J = 3.3 Hz, J = 16.5
Hz, 2H, ꢀCH2), 2.03 (s, 12H, ꢀCOCH3), 2.01 (s, 12H, ꢀ
H), 4.56 (t, J = 8.4 Hz, 1H, SacꢀH), 4.30 (t, J = 9.8 Hz, 1H, 90 COCH3); 13C NMR (75 MHz, CDCl3): δ 196.5, 170.7, 170.3,
SacꢀH), 4.24ꢀ4.11 (m, 3H, SacꢀH), 4.03 (dd, J = 2.4 Hz, J =
14.4 Hz, 1H, ꢀCH2), 3.73 (dd, J = 8.7 Hz, J = 15.9 Hz, 1H, ꢀ
35 CH2), 3.49 (t, J = 2.3 Hz, 1H, ꢀC≡CH), 2.55ꢀ2.49 (m, 2H, ꢀ
CH2), 2.32 (q, J = 7.5 Hz, 2H, ꢀCH2), 1.80 (t, J = 7.4 Hz, 3H, ꢀ
169.9, 169.6, 153.1, 146.8, 143.7, 138.6, 129.0, 127.3, 124.7,
124.2, 118.8, 114.3, 75.7, 74.4, 74.1, 71.7, 70.4, 69.4, 68.5,
66.6, 62.1, 60.4, 55.9, 50.1, 42.2, 29.7, 20.7 (2C), 20.6 (2C);
ESIꢀMS: Calc. for C62H76N6O26, 1320.48; m/z found, 1343.47
CH3); 13C NMR (75 MHz, CDCl3): δ 192.5, 154.2, 137.3, 95 [M+Na]+; Elemental analysis Anal. Calc. for C62H76N6O26: C,
124.7, 122.7, 119.5, 110.1, 97.1, 75.3, 72.7, 72.1, 71.3, 70.8,
69.9, 69.6, 65.3, 63.1, 50.6, 38.1, 31.0, 12.1, 8.6; Elemental
40 analysis Anal. Calc. for C20H26O7: C, 63.48; H, 6.93%. Found:
C, 66.53; H, 6.97.
56.36; H, 5.80; N, 6.36%. Found: C, 56.39; H, 5.83; N, 6.39.
Spectral data of 1,8-bis-(4-hydroxy-methylene-triazolo-2-
(E)-1-4,6-O-butylidene-
β-D-glucopyranosyl-4-phenyl-but-
3-en-2-one)-3,6-dioxadecane (17):
Spectral
data
of
(E)-1-(4,6-O-butylidene-
β
-D- 100 Compound, 17 was obtained by the (CuAAC) “Click” reaction
of sugarꢀpropargyl derivative, 10 (0.42 g, 2 mmol) and
triethyleneglycoldiazide, 15 (0.10 g, 1 mmol) as a yellow
glucopyranosyl)-4-(3-bromo-2-prop-2-ynyloxyphenyl)-but-
3-en-2-one (14):
45 OꢀPropargylation of compound, 8 (0.46 g, 1 mmol) with
propargyl bromide (0.09 ml, 1.2 mmol) using K2CO3 (0.69 g,
5 mmol) as a base gave a colourless solid, 14.
liquid.
Mp:92ꢀ94 oC; Yield :0.83 g (81%); 1H NMR (300 MHz,
105 CDCl3): δ 7.81 (d, J = 16.5 Hz, 2H, AlkꢀH), 7.76 (s, 2H, Trzꢀ
H), 7.42 (d, J = 6.6 Hz, 2H, ArꢀH), 7.25 (t, J = 7.7 Hz, 2H, Arꢀ
H), 6.98 (d, J = 8.1 Hz, 2H, ArꢀH), 6.88 (t, J = 7.4 Hz, 2H, Arꢀ
H), 6.69 (d, J = 16.5 Hz, 2H, AlkꢀH), 5.14 (s, 4H, ꢀOCH2),
4.43 (bs, 6H, SacꢀH), 4.01ꢀ3.97 (m, 2H, SacꢀH), 3.83ꢀ3.77 (m,
1H NMR (300 MHz, CDCl3):
δ 7.83 (d, J = 16.2 Hz, 1H, Alkꢀ
H), 7.67 (s, 1H, ArꢀH), 7.46 (dd, J = 2.4 Hz, J = 8.7 Hz, 1H,
50 ArꢀH), 6.95 (d, J = 9.0 Hz, 1H, ArꢀH), 6.77 (d, J = 16.5 Hz,
1H, AlkꢀH), 4.77 (d, J = 2.4Hz, 2H, ꢀOCH2), 4.53 (t, J = 5.1
Hz, 1H, AceꢀH), 4.14 (dd, J = 4.2 Hz, J = 9.6 Hz, 1H, SacꢀH), 110 2H, SacꢀH), 3.73 (t, J = 4.7 Hz, 4H, ꢀOCH2), 3.64 (t, J = 8.6
3.97ꢀ3.90 (m, 1H, SacꢀH), 3.72 (t, J = 8.9 Hz, 1H, SacꢀH),
3.46ꢀ3.30 (m, 3H, SacꢀH), 3.24 (t, J = 9.0 Hz, 1H, SacꢀH),
55 3.13 (dd, J = 3.9 Hz, J = 16.2 Hz, 1H, ꢀCH2), 2.96 (dd, J = 7.2
Hz, J = 16.2 Hz, 1H, ꢀCH2), 2.56 (t, J = 2.4 Hz, 1H, ꢀC≡CH),
Hz, 2H, SacꢀH), 3.44 (bs, 4H, SacꢀH), 3.30 (t, J = 8.7 Hz, 4H,
ꢀOCH2), 3.20ꢀ3.07 (m, 6H, ꢀOCH2, ꢀCH2), 2.78 (dd, J = 8.1
Hz, J = 15.8 Hz, 2H, ꢀCH2), 1.53ꢀ1.49 (m, 4H, ꢀCH2), 1.32 (q,
J = 6.0 Hz, 4H, ꢀCH2), 0.80 (t, J = 7.2 Hz, 6H, ꢀCH3); 13C
1.65ꢀ1.60 (m, 2H, ꢀCH2), 1.42 (q, J = 7.8 Hz, 2H, ꢀCH2), 0.92 115 NMR (75 MHz, CDCl3): δ 198.7, 157.1, 143.4, 138.4, 132.0,
(t, J = 7.4 Hz, 3H, ꢀCH3); 13C NMR(75 MHz, CDCl3):
δ
195.0,
128.6, 126.8, 124.2, 123.8, 121.7, 113.2, 102.4, 80.5, 76.8,
6
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DOI: 10.1039/C4NJ02035A
75.0, 74.7, 70.6, 70.4, 69.3, 68.3, 62.6, 50.4, 43.6, 36.2, 29.7,
OCH2, SacꢀH), 3.71ꢀ3.65 (m, 4H, SacꢀH), 3.64 (bs, 4H, ꢀ
17.5, 13.9; ESIꢀMS: Calc. for C52H68N6O16, 1032.47; m/z 60 OCH2), 3.25ꢀ3.20 (m, 6H, ꢀOCH2, SacꢀH), 2.96ꢀ2.88 (m, 4H, ꢀ
found, 1033.48 [M+H]+; Elemental analysisAnal. Calc. for
C52H68N6O16: C, 60.45; H, 6.63; N, 8.13%. Found: C, 60.48;
H, 6.66; N, 8.16.
Spectral data of 1,8-bis-(4-hydroxy-methylene-triazolo-5-
chloro-2-(E)-1-4,6-O-butylidene-β-D-glucopyranosyl-4-
CH2), 1.72ꢀ1.71 (m, 4H, ꢀCH2), 1.52 (q, J = 6.9 Hz, 4H, ꢀ
CH2), 1.01 (t, J = 7.2 Hz, 6H, ꢀCH3); 13C NMR (75 MHz,
CDCl3): δ 202.6, 165.0, 147.3, 134.8, 134.7, 132.3, 129.4,
120.1, 106.9, 85.4, 81.6, 79.6, 79.4, 75.4, 74.9, 73.9, 73.1,
65 66.5, 54.9, 48.1, 41.0, 22.1, 18.7; Elemental analysis Anal.
Calc. for C52H68N6O16: C, 60.45; H, 6.63; N, 8.13%. Found:
C, 60.47; H, 6.68; N, 8.17.
5
phenyl-but-3-en-2-one)-3,6-dioxadecane (18):
Compound, 18 was obtained by the (CuAAC) “Click” reaction
10 of sugarꢀpropargyl derivative, 11 (0.45 g, 2 mmol) and
triethyleneglycoldiazide, 15 (0.10 g, 1 mmol) as a yellow
liquid.
Acknowledgement
Authors acknowledge SERCꢀDST, New Delhi for financial
70 support. T. M. thank DST, New Delhi for use of NMR facility
underDSTꢀFIST programme to the Department of Organic
Chemistry, University of Madras, Guindy Campus, Chennai,
India. A. H. thank CSIR, New Delhi for SRF.
1
Yield :0.55 g (50%); H NMR (300 MHz, CDCl3): δ 7.87ꢀ7.83
(m, 4H, TrzꢀH, AlkꢀH), 7.50 (s, 2H, ArꢀH), 7.32 (d, J = 8.7
15 Hz, 2H, ArꢀH), 7.07 (d, J = 9.0 Hz, 2H, ArꢀH), 6.76 (d, J =
16.5 Hz, 2H, AlkꢀH), 5.26 (d, J = 1.5 Hz, 4H, ꢀOCH2), 4.56 (t,
J = 5.0 Hz, 2H, SacꢀH), 4.53 (t, J = 5.0 Hz, 2H, SacꢀH), 4.12
(t, J = 6.8 Hz, 2H, SacꢀH), 3.90 (t, J = 5.0 Hz, 2H, SacꢀH),
3.65ꢀ3.61 (m, 8H, ꢀOCH2, SacꢀH), 3.38ꢀ3.35 (m, 6H, ꢀOCH2,
20 SacꢀH), 3.29ꢀ3.22 (m, 6H, ꢀOCH2, SacꢀH), 2.91ꢀ2.77 (m, 4H,ꢀ
CH2), 1.63ꢀ1.61 (m, 4H, ꢀCH2), 1.46ꢀ1.38 (m, 4H, ꢀCH2), 0.88
(t, J= 7.2 Hz, 6H, ꢀCH3); 13C NMR(75 MHz, CDCl3): δ 196.4,
168.6, 135.4, 129.5, 126.2, 124.7, 123.9, 100.6, 78.6, 73.5,
68.8, 68.2, 67.6, 66.5, 64.0, 48.8, 46.9, 15.6, 12.1; Elemental
25 analysis Anal. Calc. for C52H66N6O16: C, 56.67; H, 6.04; N,
7.63%. Found: C, 56.71; H, 7.66; N, 7.67.
Notes and references
75 a Department of Organic Chemistry, University of Madras, Guindy
Campus, Chennaiꢀ600 025, INDIA. Fax: (+) 91ꢀ44ꢀ22352494; Tel: +91
44 22202814; Eꢀmail: tmdas_72@yahoo.com
†
1
2
Electronic Supplementary Information (ESI) available: [Experimental
details]. See DOI: 10.1039/b000000x/
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Spectral data of 1,8-bis-(4-hydroxy-methylene-triazolo-3-
(E)-1-4,6-O-butylidene-β-D-glucopyranosyl-4-phenyl-but-
3-en-2-one)-3,6-dioxadecane (19):
85
30 Compound, 19 was obtained by the (CuAAC) “Click” reaction
of sugarꢀpropargyl derivative, 12 (0.42 g, 2 mmol) and
triethyleneglycoldiazide, 15 (0.10 g, 1 mmol) as a yellow
liquid.
5
6
D. Pokhrela and T. Viraraghavan, Chem. Eng. J., 2008, 140, 165ꢀ172.
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90
7
8
9
1
Yield :0.73 g (71%); H NMR (300 MHz, CDCl3): δ 7.76ꢀ7.60
35 (m, 4H, TrzꢀH, AlkꢀH), 7.36ꢀ7.02 (m, 8H, ArꢀH), 6.87 (d, J =
15.6 Hz, 2H, AlkꢀH), 5.20 (bs, 2H, AceꢀH), 4.73 (bs, 6H, ꢀ
SacꢀH), 4.49 (t, J = 5.4 Hz, 4H, ꢀOCH2), 4.15ꢀ4.08 (m, 2H,
SacꢀH), 3.76ꢀ3.67 (m, 6H, ꢀOCH2, SacꢀH), 3.49ꢀ3.44 (m, 6H, ꢀ
OCH2, SacꢀH), 3.26ꢀ3.16 (m, 6H, ꢀOCH2, SacꢀH), 2.71ꢀ2.55
40 (m, 4H, ꢀCH2), 1.61ꢀ1.59 (m, 4H, ꢀCH2), 1.43ꢀ1.37 (m, 4H, ꢀ
CH2), 0.90 (t, J = 6.9 Hz, 6H, ꢀCH3); 13C NMR(75 MHz,
CDCl3): δ 198.4, 157.9, 143.4, 135.9, 130.0, 125.5, 122.0,
117.3, 114.6, 102.5, 82.7, 80.3, 78.8, 78.2, 75.9, 75.1, 72.9,
70.8, 69.7, 68.2, 55.9, 50.8, 36.2, 29.6, 17.4, 13.9; Elemental
45 analysis Anal. Calc. for C52H68N6O16: C, 60.45; H, 6.63; N,
8.13%. Found: C, 60.48; H, 6.67; N, 8.17.
Spectral data of 1,8-bis-(4-hydroxy-methylene-triazolo-4-
(E)-1-4,6-O-butylidene-β-D-glucopyranosyl-4-phenyl-but-
3-en-2-one)-3,6-dioxadecane (20):
50 Compound, 20 was obtained by the (CuAAC) “Click” reaction
of sugarꢀpropargyl derivative, 13 (0.42 g, 2 mmol) and
triethyleneglycoldiazide, 15 (0.10 g, 1 mmol) as a yellow
liquid.
95
10 A. J. Moore, L. Goldenberg, M. R. Bryce, M. C. Petty, A. P.
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Mp :152ꢀ154 oC; Yield :0.78 g (76%); 1H NMR (300 MHz,
55 CDCl3): δ 8.00 (s, 2H, TrzꢀH), 7.63ꢀ7.59 (m, 6H, ArꢀH, Alkꢀ
H), 7.11 (d, J = 8.4 Hz, 4H, ArꢀH), 6.76 (d, J = 16.2 Hz, 2H,
AlkꢀH), 5.31 (bs, 4H, ꢀOCH2), 4.87 (bs, 2H, AceꢀH), 4.64 (bs,
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