Green click synthesis of β-hydroxy-1,2,3-triazoles in water in the presence of a Cu(ii)-azide catalyst: a new function for Cu(ii)-azide complexes

Article abstract of DOI:10.1039/c6nj03865d

A new Cu(ii)-azide complex, [Cu(H₂L)(N₃)]·CH₃OH (1), was synthesized by the reaction of Cu(NO₃)₂ 3H₂O with 2-{[(1E)-(2-hydroxyphenyl)methylene]amino}-2-methylpropane-1,3-diol (H₃

Full text of DOI:10.1039/c6nj03865d

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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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ARTICLE TYPE
Green click synthesis of βꢀhydroxyꢀ1,2,3ꢀtriazoles in water in the
presence of Cu(II)ꢀAzide catalyst: A new function for Cu(II)ꢀAzide
complexes
Nader Noshiranzadeh,a,* Marzieh Emami,a Rahman Bikas,a Anna Kozakiewiczb
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
A new Cu(II)ꢀazide complex, [Cu(H2L)(N3)]·CH3OH (1), was synthesized by the reaction of Cu(NO3)2
3H2O with 2ꢀ{[(1E)ꢀ(2ꢀhydroxyphenyl)methylene]amino}ꢀ2ꢀmethylpropaneꢀ1,3ꢀdiol (H3L) in the
10 presence of azide anion and methanol solvent. The complex was characterized by elemental analysis,
spectroscopic methods (FTꢀIR and UVꢀVis) and its structure was determined by single crystal Xꢀray
analysis. Xꢀray studies showed that the asymmetric unit of this compound is a mononuclear complex of
Cu(II) which converts to a dinuclear one by endꢀtoꢀend (EE)ꢀazide bridges. Complex 1 was used as
catalyst for threeꢀcomponent azideꢀepoxideꢀalkyne cycloaddition reaction in water as green solvent. The
15 effect of the amount of catalyst, temperature and also the coordinated azide in the cycloaddition reaction
was studied and the products were characterized by FTꢀIR, NMR and single crystal Xꢀray analyses. At
temperatures below than 50 °C just one product formed while in higher temperatures two compounds
formed by the azide attack to the epoxide ring. The structural studies indicated that complex 1 converts to
a tetranuclear Cu(II) complex, [Cu4(HL)4], after catalytic reaction in the absence of sodium azide. The
20 results showed that complex 1 is an active catalyst for preparing 1,2,3ꢀtriazole based compounds
containing primary and secondary alcoholic functionalities. Based on the obtained results, a mechanism
was proposed for this catalytic reaction.
highly useful and premier reactions in ‘click chemistry’.
Recently, the catalytic preparation of 1,2,3ꢀtriazoles in the
presence of transition metal ions such as Zn,13 Cu,14,15 Ru,16 Pd,17
Ce18 etc., have been developed. Among these, the Cuꢀcatalyzed
45 Azide–Alkyne Cycloaddition (CuAAC) reaction has attracted
much attention due to exclusive regioselectivity, wide substrate
scope, mild reaction conditions and very high yields.19 CuAAC
reaction is the most reliable ‘click reaction’ for practical and
efficient preparation of 1,4ꢀdisubstitutedꢀ1,2,3ꢀtriazoles from a
50 wide range of substrates which cannot be prepared via traditional
Huisgen uncatalyzed thermal approaches. In recent years, a
variety of Cu(I) salts or coordination complexes have been
employed as homogeneous and heterogeneous catalysts for the
azideꢀalkyne cycloaddition.20 Nevertheless, the Cu(I) species in
55 these catalysts are unstable and can be easily oxidized to Cu(II)
or disproportionate to Cu(0) and Cu(II), which limited their
utilization.21
Introduction
25 1,2,3ꢀtriazoles are an important class of fiveꢀmembered nitrogenꢀ
containing aromatic compounds with high chemical stability to
oxidation, reduction and hydrolysis.1 1,2,3ꢀtriazoles are
commonly employed as a powerful tool in many fields. They are
target materials for drug discovery since they show wide range of
30 biological properties such as antibacterial,2 antiviral,3 anticancer,4
and antiꢀallergic5 behavior. In addition, they have found
applications in optical brighteners,6 agrochemicals,7 dyes,8 antiꢀ
HIV therapy,9 fluorescence chemosensors,10 etc. and also are
interesting materials in organic synthesis, coordination chemistry
35 and Nꢀheterocyclic chemistry.11 Consequently, the development
of simple, efficient and practical methods for their synthesis in a
singleꢀstep operation has attracted much attention in recent years.
Huisgen’s 1,3ꢀdipolar cycloaddition of terminal alkynes with
organic azides is the most popular method for the construction of
40 1,2,3ꢀtriazoles.12 This reaction also is one of the wellꢀknown,
Although organic azides are generally stable, preparation,
isolation or purification of some organic azides can be
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problematic processes. Thus, a procedure that avoids the isolation
of organic azides like in situ generation of organic azides is
of complex the shifts of the bands relative to the H3L bands
indicate the coordination of the ligand to the Cu(II) ion. The UV–
desirable. In situ preparing of organic azides minimizes hazards 60 Vis spectrum of complex 1 shows intense bands in the highꢀ
derived from their isolation or handling and avoids the timeꢀ
consuming and waste generation of additional synthetic steps. In
recent years, the copperꢀcatalyzed multicomponent syntheses of
1,2,3ꢀtriazoles from the reaction of terminal alkynes with in situ
generated organic azides (by the reaction of sodium azide with
organic halides22 or by the reaction of sodium azide with
energy region at 215 nm and 240, 269 nm are due to intraligand
transitions. The band at 369 nm is assigned to the intraligand and
ligand to metal charge transfer (LMCT) transitions. The band for
the dꢀd transition appears as a broad weak peak near 650 nm.27
5
65
10 epoxides23) have been reported in the literature. Azidolysis of
epoxides forms azidoalcohols which further cycloaddition with
alkynes results in hydroxyethylꢀ1,2,3ꢀtriazoles founds in peptide
surrogates of HIVꢀ1 protease inhibitors.24 Therefore, it is not
surprising that the development of newer catalysts, methods and
15 strategies for synthesis of 1,2,3ꢀtriazoles has remained a highly
attractive proposition.
Scheme
[Cu(HL)(N3)]·CH3OH (1).
1 The syntheses of ligand (H3L) and complex
To our knowledge, the Cu(II) complexes with Schiff base ligands
have seldom been used as the catalysts for the azideꢀalkyne
coupling reaction and there is not any report for the use of Cu(II)ꢀ
20 azide complexes as catalyst for such reactions. Therefore, we
reasonably assumed that azide coordinated Cu(II) complexes
might be a class of effective copperꢀcatalysts and also azide
sources for the preparation of 1,2,3ꢀtriazoles. Herein, we wish to
report our results in using of a Cu(II)ꢀAzide complex as a new
25 catalytic system for preparing 1,2,3ꢀtriazoles and also introduce a
new function for Cu(II)ꢀazide complexes. The reported Cu(II)ꢀ
Azide complex in this study is stable in air and moisture and was
synthesized from the cheap starting materials with satisfactory
yield. In addition, considering the requirement of green
30 chemistry, this catalyst has good solubility and catalytic reactivity
in water as a natural, nontoxic, cheap, and readily available
solvent for both academic and industrial settings.
70
Fig. 1. UVꢀVis spectrum of ligand H3L (red) and complex 1
(blue). The inset shows dꢀd transition for complex 1.
Xꢀray structure of [Cu(H2L)(N3)]·CH3OH (1)
Results and discussion
In order to define the coordination sphere conclusively, singleꢀ
35 Syntheses and spectroscopy
75 crystal Xꢀray diffraction study was made. Molecular structure of
complex 1 is shown in Fig. 2 and selected bond lengths and
angles are given in Table 1. Xꢀray studies indicated that the
asymmetric part of unit cell consists of a neutral mononuclear
Cu(II) complex and a methanol solvent molecule is located
The reaction of 2ꢀAminoꢀ2ꢀmethylꢀ1,3ꢀpropanediol with
salicylaldehyde in methanol gave the potentially tetradentate
Schiff base ligand, H3L, in good yield and purity (Scheme 1). The
formation of H3L has been confirmed by elemental analyses, FTꢀ
40 IR and NMR spectroscopic studies (Figs. S1ꢀS3). In 1H NMR 80 beside it (Fig. 2a). Methanol molecule is connected to the
spectrum of H3L the singlet peak at δ 8.49 ppm is due to
azomethine (CH=N) hydrogen, the phenolic hydrogen of O–H is
located at δ 14.42 pmm and the alcoholic OH hydrogen atoms
appear at 4.85 ppm. The reaction of copper(II) nitrate trihydrate,
complex molecule by strong O−H···O hydrogen bonding
interactions (see Fig. 2, Table 2). This mononuclear unit converts
to
a dinuclear complex, [Cu(H2L)(ꢁ1,3ꢀN3)]2·2(CH3OH), by
inversion symmetry (i = ꢀx, 1ꢀy, ꢀz). The azide ligand acts as a
45 sodium azide and H3L in 1:1:1.5 molar ratios in methanol leads to 85 bridging ligand and connects two Cu(II) ions in EndꢀtoꢀEnd (EE)
[Cu(H2L)(N3)]·CH3OH (1). In the FTꢀIR spectrum of complex 1
(Fig. S4) the absorption band at 1626 cmꢀ1, can be assigned to the
imine (C=N) stretching frequency of the coordinated ligand.25
Very strong band at 2066 cm–1 is due to the azide, ν(N3),
bridging mode. The Cu···Cu distance through EE azide bridges is
4.8019(5) Å which is close to other reported EEꢀazide bridged
Cu(II) complexes.28 The copper ion has a distorted squareꢀ
pyramidal geometry (τ = 0.04 where τ = difference between the
50 stretching vibration and indicates that the azide is coordinated to 90 two largest angles/60; s = 1 for ideal trigonal–bipyramidal and s =
the copper(II) ion.26 The broad peak at about 3300 cmꢀ1 is due to
the OꢀH groups involved in hydrogen bonding interactions. The
electronic spectra of complex 1 and H3L in methanol are shown
in Fig. 1. The Schiff base ligand displays strong bands at 218,
0 for ideal squareꢀpyramidal) and its coordination environment is
filled by one nitrogen and two oxygen atoms provided by the
Schiff base ligand and two nitrogen atoms from two azide
bridging ligands. Three donor atoms of the Schiff base ligand
55 251, 278, 315 and 401 nm. Based on their extinction coefficients, 95 (O1, N7, O10) and the nitrogen atom of azide group (N10) create
these bands are assigned to intraligand πꢀπ* (218, 251, 278 nm)
and nꢀπ* (315 and 401 nm) transitions. In the UVꢀVis spectrum
equatorial plane of squareꢀpyramidal geometry. The axial
position is occupied by the nitrogen atom of second azide ligand
2
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(N12i). The axial Cu–N12i bond length is considerably elongated
molecules in the crystals package of complex 1, strong and
directed hydrogen bonding interactions is a common feature for
this compound. Complex 1 contains two major functionalities
which can participate in intermolecular hydrogen bond
with respect to the other four, which is consistent with the Zꢀout
Jahn–Teller effect, found in most Cu2+ complexes with d9
electronic configuration.29 H3L has four donor atoms, an
5
azomethine nitrogen, a phenolic oxygen and two alcoholic 25 interactions. These are the OH groups of coordinated and
oxygen atoms. In complex
1
one CH2OH group is not
uncoordinated CH2OH moieties of Schiff base ligand and OH
part of methanol molecule. As shown in Fig. 2b, there is a strong
hydrogen bonding interaction between the hydrogen atom of
coordinated CH2OH group and the oxygen atom of methanol
coordinated to the metal and the remaining CH2OH group is
coordinated to the copper(II) ion without deprotonation. The
hydrogen of phenolic oxygen atom is eliminated during the
10 complexation. As a result the Schiff base ligand is coordinated to 30 molecule. Also, the hydrogen atom of methanol connects to the
the Cu(II) ion as a tridentate monoꢀnegative ligand, (H2L־).
coordinated phenolic oxygen. These hydrogen bonding
interactions cooperate to stabilizing the dinucleat unit. The
hydrogen atom of uncoordinated CH2OH group involved in
intermolecular O–H···N(azide) hydrogen bonding interaction which
35 the nitrogen atom of azide ligand (N10) acts as hydrogen bonding
acceptor (see Fig. 3). 1D polymeric chain forms by this
intermolecular hydrogen bond. Parameters of hydrogen bonding
geometry are given in Table 2.
40 Fig. 3. 1D polymeric chain obtained by hydrogen bonding
interactions.
Table 2. Hydrogen bonds [Å and °] for 1.
D−H···A
d(D−H)
d(H···A)
d(D···A)
<(DHA)
O10−H10D···O20
O11−H11C···N10i
O11−H11C···N11i
O20−H20D···O1ii
O20−H20D···N10ii
0.820
0.820
0.820
0.820
0.820
1.777
2.152
2.615
2.013
2.691
2.582
2.858
3.333
2.824
3.206
166.93
144.38
146.99
169.63
122.34
Fig. 2. Molecular structure of complex 1 a) asymmetric unit; b)
15 dinuclear complex obtained by EEꢀazide bridges (i = ꢀx, 1ꢀy, ꢀz).
Dashed green line shows hydrogen bonding interactions.
Table 1. Selected bond lengths [Å] and angles [°] for 1.
Symmetry code: i = ꢀx+1, ꢀy+1, ꢀz; ii = ꢀx, 1ꢀy, ꢀz
Bond
Angle [°]
175.18(9)
94.92(9)
86.91(9)
87.71(9)
82.78(9)
95.87(8)
87.97(9)
172.98(10)
88.05(9)
98.81(9)
Bond
Angle [°]
45
Cu1−O1
1.8920(19)
O1−Cu1−O10
O1−Cu1−N7
O1−Cu1−N10
O1−Cu1−N12i
O10−Cu1−N7
O10−Cu1−N10
O10−Cu1−N12i
N7−Cu1−N10
Thermal Gravimetric Analysis (TGA) of complex 1
Cu1−O10
Cu1−N7
1.9782(19)
1.935(2)
1.951(2)
2.793(3)
Thermal behaviour of crystalline samples of complex 1 is
determined in air (Fig. S5) and nitrogen gas (Fig. S6) conditions
with a heating rate of 10 °C/min in the temperature range of 30–
Cu1−N10
Cu1−N12i
50 1000 °C. The thermal decomposition patterns for complex 1 in air
and nitrogen gas conditions are almost the same. In both
atmospheres the complex is stable up to 100 °C, where the
uncoordinated methanol molecule together with the azide ligand
are removed in the range of 100–230 °C [Air: starting mass =
55 6.014 mg, loosed mass at first step = 1.286 mg (21.38%), calcd.
for azide + methanol = 1.287 mg (21.39%). N2: starting mass =
4.946 mg, loosed mass at first step = 1.008 mg (20.38%), calcd.
for azide + methanol = 1.058 mg (21.39%)]. In both conditions,
the organic ligand is removed in two steps (250ꢀ900 °C) to give
60 the final product which is estimated to be copper(II) oxide [Air:
remained mass = 1.363 mg (22.66%), expected calcd. mass for
N7−Cu1−N12i
N10−Cu1−N12i
Symmetry code: i = ꢀx, 1ꢀy, ꢀz
20 Due to presence of several alcoholic groups and methanol
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CuO = 1.383 mg (22.99%). N2: remained mass 1.283 mg
(25.94%), expected calcd. mass for CuO = 1.138 mg (22.99%)].
Catalytic activity
5
Considering the applications of triazoleꢀbased compounds, we
were interested to employ complex 1 as catalyst in alkyne–azideꢀ
epoxide cycloaddition reaction. For this purpose, threeꢀ
component reaction between epoxystyrene, sodium azide and
phenylacetylene was selected as a model reaction to investigate
10 the catalytic activity of complex 1 in preparing 1,2,3ꢀtriazole
compounds. In a preliminary step, styrene oxide was treated with
sodium azide and phenylacetylene in the presence of complex 1.
The reaction was done at room temperature in water as a green
solvent. The progress of reaction was monitored by TLC until
15 one of the primary materials (phenylacetylene or styrene oxide)
was consumed. Control experiments in the absence of catalyst
revealed that the presence of catalyst is essential for this reaction.
When complex 1 was added to the reaction flask, the color of
reaction mixture was changed to light green. In the beginning,
20 there was no considerable change in the reaction mixture but after
about 4 hours some oily blobs were formed in the flask and the
green color of reaction mixture decreased. The amount of oily
droplets was increased continuously and after a while they
aggregated to form an oily layer. By increasing the amount of
25 oily product, their solubility was decreased and near to the end of
reaction, large amount of whiteꢀoily solid appeared. Formation of
this whiteꢀoily solid demonstrated that the reaction was
completed. Checking the reaction mixture by TLC in this stage
showed that the raw materials used in cycloaddition reaction were
30 finished. After this observation the obtained product was
extracted by ethyl acetate. The best isolated yield in this stage
was 92% which indicates this catalytic reaction has high yield.
Obtained products were further purified by plate chromatography
and recrystallization. Elemental analysis together with FTꢀIR
Fig. 4. Molecular structure of product obtained by threeꢀ
component catalytic reaction at T < 50 °C (2Phꢀtriazole).
60 Fig. 5. 1D polymeric chain obtained by intermolecular hydrogen
bonding interactions in the crystal package of 2Phꢀtriazole.
1
35 (Fig. S7), H NMR (Fig. S8) and 13C NMR (Fig. S9) spectra of
In order to get the effect of catalyst in this reaction, the amount of
catalyst in the cycloaddition reaction was investigated. The
65 results (see Table 3) showed that the amount of catalyst had a
significant effect on the time of reaction. Complex 1 with 10
mol% loading, showed high catalytic activities since the isolated
yield of product was 91% after 8 hours. When the amount of the
catalyst was reduced from 10 mol% to 5 mol%, the same yield of
70 triazole was also obtained but in this case the reaction time was
longer (11 hours). The same results were observed when the
catalyst loading decreased to 2.5 mol%. Further decreasing the
amount of catalyst to 1.0 mol% resulted in lower amount of
product (82%). Therefore, 2.5 mol% of catalyst is the optimal
75 amount of catalyst for this cycloaddition reaction.
Since temperature has considerable effects in the reactivity and
selectivity of catalytic reactions, the effect of temperature was
studied. For this matter, the cycloaddition reaction was studied at
25 (room temperature), 40, 50, 60, 70, 80 and 100 °C which the
80 results are shown in Table 3. Increasing the reaction temperature
from 25 to 40 and 50 °C increased the catalytic reactivity of
complex 1 since the reaction was completed after 8 and 7 hours,
respectively. Future increasing the temperature to 60, 70, 80 and
100 °C also decreased the reaction time but in these temperatures
85 one other product was also obtained. The amount of this product
at 60 °C was quite low (trace) but by increasing the temperature
to 70 and 80 °C the amount of this product increased up to 20 and
the reaction products confirmed their proposed structures.
Scheme 2. Catalytic azideꢀalkyneꢀepoxide cycloaddition reaction
in the presence of complex 1 (T < 50 ºC).
40
At room temperature just one compound was obtained from the
cycloaddition reaction which is
a 1,2,3ꢀtriazole containing
primary alcoholic functionality. The ꢀCH2OH group is formed
from the epoxide ringꢀopening reaction by nucleophilic attack of
45 azide to the phenyl substituted carbon of epoxide ring. The
structure of 2Phꢀtriazole determined by single crystal Xꢀray
analysis is shown in Fig. 4 and selected bond lengths and angles
are given in Table S2. Xꢀray analysis showed that the 1,2,3ꢀ
triazole ring was successfully synthesized from the threeꢀ
50 component reaction. The bond lengths and angles are in the
normal range reported for 1,2,3ꢀtriazoles. There are two strong
intermolecular O–H···O and C–H···N hydrogen bonding
interactions (see Table S2) which stabilize the crystal package of
2Phꢀtriazole. 1D polymeric chain formed by intermolecular
55 hydrogen bonding interaction is shown in Fig. 5.
4
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33% respectively. At 100 °C, the ratio of two products was
approximately equal (50:50). As a result, increasing the reaction
absence of azide in the reaction media. FTꢀIR spectrum of
complex 1 after this reaction is shown in Fig. S13 which indicates
temperature increases the catalytic reactivity but the selectivity of 45 the coordinated azide is removed from the structure of complex 1.
reaction decreases at temperatures higher than 50 °C. At 50 °C
the selectivity towards 2Phꢀtriazole is 100%.
The new product was isolated by plate chromatography and
characterized by spectroscopic methods (Figs. S10ꢀS12) and
single crystal Xꢀray analysis (Table S3). Although the quality of
the obtained crystals was very low, we could obtain a model for
In order to know the exact structure of complex after catalytic
reaction in the absence of azide, the single crystals of final green
complex were obtained by slow solvent evaporating method. The
crystals were analyzed by single crystals Xꢀray analysis which
50 the primary experiments indicated the unit cell parameters (a =
5
18.322 Å, b = 10.245 Å, c = 23.683 Å,
α = γ = 90 and β =
10 the structure of the new product. The molecular structure of this
product is shown in Fig. 6 and selected bond lengths and angles
are given in Table S2. Single crystal Xꢀray analysis indicated that
the new product is another 1,2,3ꢀtriazole (1Phꢀtriazole)
containing a secondary alcoholic functionality. Analysis of the
15 crystal packing reveals the intermolecular O–H···O and O–H···N
interactions (see Table S1). This product was obtained when
azide attacks to the least substituted carbon atom of epoxide ring
(CH2 moiety). According to the underlying mechanistic scenario
(scheme 3), the regioselective ring opening predominantly occurs
20 from the attack of the azide anion at the more substituted Cꢀatom
(benzylic Cꢀatom) of the epoxide ring12a,22a,30 furnishing the
corresponding product (2Phꢀtriazole) at low temperatures. At
temperatures higher than 50 °C, the azide can also attack to the
CH2 group of epoxide ring to form the second product (1Phꢀ
91.642° with space group P21/c) are the same with a tetranuclear
Cu(II) complex with same ligand.31 Since the structure was
repetitive, full data collection was not preformed but the
55 schematic structure is shown in Scheme S1. Therefore, it is
obvious that the azide ligand from complex 1 transfers to the
structure of 1,2,3ꢀtriazole and four complex molecules aggregate
to form a tetranuclear complex. Although mentioned limitation is
seen for removing sodium azide from the cycloaddition reaction,
60 this method expresses a new function for Cu(II)ꢀazide complexes
together with a new route for preparing 1,2,3ꢀtriazoles in the
absence of NaN3 by using Cu(II)ꢀazide complexes.
Table 3. Complex
1
catalyzed cycloaddition reaction:
25 triazole). By increasing the temperature the selectivity of azide 65 optimization of the catalytic conditions for preparing 2Phꢀ
triazole a
attack decreases; therefore, at 100 °C the amount of two products
is approximately near to each other.
Entry Catalyst
(mmol)
Temperature Time(h)
Yield
(%)b
Selectivity
(%)
1
2
3
4
0
0.1
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
40
50
60
70
80
20
8
0
ꢀ
91
92
91
82
20
91
92
91
91
92
92
100
100
100
100
100
100
100
95>
80
0.05
0.025
0.01
0.2
0.025
0.025
0.025
0.025
0.025
0.025
11
11
11
12
8
7
4
3.5
2
1
5
6c
7
Fig. 6. Molecular structure of second product (1Phꢀtriazole)
30 obtained by threeꢀcomponent catalytic reaction at 50 °C < T.
Dashed lines show disordered (ꢀCHOHꢀ) part of molecule.
8
9
10
11
12
Removing sodium azide (NaN3) from cycloaddition reaction
For the study of the effect of coordinated azide in the
35 cycloaddition reaction, the reaction was carried out in the absence
of NaN3. This reaction showed that the 2Phꢀtriazole produces in
the absence of NaN3. So, complex 1 can act as catalyst together
with the source of azide in the cycloaddition reaction. By using
complex 1 as catalyst, we can remove one reagent in the azideꢀ
40 alkyneꢀepoxide threeꢀcomponent reaction. However, this reaction
is dependent on the amount of complex 1 and as soon as the
complex finished, the reaction also stopped. This is due to the
67
50
100
a Reaction conditions: epoxystyrene (1 mmol), phenylacetylene (1
mmol), NaN3(1 mmol), catalyst, water (2 mL)
b Isolated yield
70 c Reaction without NaN3
75
90
80
95
85 Scheme 3. The structures of two compounds obtained by
catalytic reaction at T < 50 °C (blue) and T > 50 °C (red).
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Mechanism
reaction was proposed based on the spectroscopic properties of
In general the total mechanism of the reaction is not fully clear. 60 various reagents involved in the reaction. The triazole ring was
However, on the basis of the obtained results in the absence of
azide, the crystal structure of complex and also the FTꢀIR
spectrum of complex 1 after reaction, it is obvious that the
coordinated azide to the copper(II) ion is involved in the
cycloaddition reaction. Moreover, according to the reported
mechanisms for the synthesis of triazoles catalyzed by copper
complexes,21a,32 it is clear that the key step in this reaction is the
obtained in the absence of NaN3 which shows that this complex
can act as a catalyst and the initial source of azide in preparing
1,2,3ꢀtriazoles.
5
10 cyclization reaction between an alkylꢀazide with the arylꢀ
acetylene which is coordinated to the Cu center (copperꢀ
acetylide). In this reaction, the alkylꢀazide can be easily produce
by the reaction of epoxystyrene with the coordinated azide to the
Cu(II) ion. In order to have an evidence for this suggestion, the
15 reaction of epoxystyrene with complex 1 was studied in the
absence of sodium azide and phenylacetylene. Epoxystyrene was
added to the complex 1 in water at room temperature and after 10
hours the solvent was removed. Comparing the FTꢀIR spectrum
of new product with complex 1 (Fig. S14) shows that the position
20 of azide vibration is changed and also some new vibrations are
seen in the FTꢀIR spectrum of product. UVꢀVis spectrum of
complex also shows some changes which can be due to the
reaction of coordinated azide with epoxystyrene. These analyses
confirm the suggested reaction. By considering these notes, the
25 proposed catalytic pathway is shown in Scheme 4. In the
proposed mechanism for the formation of 1,2,3ꢀtriazoles, the
copper complex has three roles, (i) it provides the azide for
nocleophilic attack to the epoxystyrene, (ii) it acts as
epoxystyrene activator for nucleophile attack by coordinated
30 azide anion and (iii) it can activate the terminal alkyne by
interaction with the phenylacetylene to form copper(II) acetylide.
Cycloaddition reaction take place between coordinated acetylide
to the Cu(II) ion and alkylꢀazide moiety which is formed by the
reaction of epoxystyrene with complex 1. After cycloaddition,
35 protonolysis of the Cu–C bond by aqueous media afforded the
corresponding triazole. In the presence of sodium azide, this
catalytic cycle repeats by regenerating of complex 1 through the
coordination of new azide provided by the excess amount of
azide. In the absence of sodium azide, this cycle can not take
40 place once again. In this condition, the hydrogen atom of
coordinated CH2OH group (H10) eliminates to form a dinegative
ligand (ligand coordinates as HL2ꢀ) which also balances the
positive and negative charges. Finally, tetranuclear Cu(II)
complex, [Cu4(HL)4], forms by aggregation of four Cu(HL) units.
45
65
Scheme 4. Proposed mechanism for catalytic cycloaddition
reaction by using complex 1 in the presence and in the absence of
NaN3.
70 Experimental
Materials and instrumentations
Copper(II) nitrate trihydrate, salicylaldehyde, 2ꢀAminoꢀ2ꢀmethylꢀ
1,3ꢀpropanediol, sodium azide, epoxystyrene and phenylacetylene
were purchased from Merck and used as received. Solvents of the
75 highest grade commercially available (Merck) were used without
further purification. IR spectra were recorded as KBr disks with a
Bruker FT–IR spectrophotometer. UV–Vis spectra of solutions
were recorded on
a
thermoꢀspectronic Helios Alpha
spectrophotometer. 1H and 13C NMR spectra in DMSOꢀd6
80 solution were measured on a Bruker 250 MHz spectrometer and
chemical shifts are indicated in ppm relative to tetramethylsilane
(TMS). Thermal gravimetric analysis (TGA) curves of complex 1
were recorded with a SETSYS Evolution TGA instrument in air
and N2 atmospheres.
Conclusions
A new Cu(II)ꢀazide complex was synthesized and characterized
by spectroscopic methods and single crystal Xꢀray analysis. The
catalytic ability of this complex was investigated in the threeꢀ
50 component azideꢀepoxideꢀalkyne cycloaddition reaction. The
effects of various parameters, including the amount of complex,
temperature and NaN3 have been studied. The structure of Cu(II)ꢀ
azide complex after catalytic reaction and the structures of two
possible products for threeꢀcomponent cycloaddition reaction
55 were determined by spectroscopic and single crystal Xꢀray
analyses. The results showed that this complex is an active
catalyst for preparing 1,2,3ꢀtriazoles from azideꢀepoxideꢀalkyne
cycloaddition reaction. The possible mechanism of this catalytic
85
Synthesis
of
ligand
2ꢀ{[(1E)ꢀ(2ꢀ
hydroxyphenyl)methylene]amino}ꢀ2ꢀmethylpropaneꢀ1,3ꢀdiol
(H3L)
A
methanol (10 mL) solution of 2ꢀAminoꢀ2ꢀmethylꢀ1,3ꢀ
90 propanediol (0.315 g, 3.0 mmol) was added dropwise to a
methanol solution (10 mL) of salicylaldehyde (0.319 mL, 3.0
mmol) and the mixture was refluxed for 4 h. The solution was
evaporated on a steam bath to 5 mL and cooled to room
temperature. The resulting light yellow precipitate was separated
95 and filtered off, washed with 5 mL of cooled methanol. Yield:
6
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DOI: 10.1039/C6NJ03865D
94% (0.84 g). M.p. 127ꢀ130 ˚C. Anal. Calc. for C11H15NO3 (MW
2ꢀ(4ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)ethanol (1Phꢀtriazole) were
= 209.25): C, 63.14; H, 7.23; N, 6.69 %. Found: C, 63.19; H, 60 obtained from ethanol.
7.21; N, 6.74%. FTꢀIR (KBr, cmꢀ1): 3332 (brꢀm), 2957 (w), 2925
(w), 2874 (w), 1630 (v), 1609 (m), 1523 (m), 1498 (m), 1474 (w),
1462 (w), 1411 (w), 1385 (m), 1376 (w), 1354 (w), 1297 (s),
1262 (w), 1237 (w), 1214 (m), 1153 (s), 1132 (m), 1108 (w),
2Phꢀtriazole: M.p. 130ꢀ133 °C. Anal. Calc. for C16H15N3O (MW
= 265.32): C, 72.43; H, 5.70; N, 15.84 %. Found: C, 72.48; H,
5.73; N, 15.88%. FTꢀIR (KBr, cmꢀ1): 3393 (brꢀm), 3088 (w),
5
1061 (vs), 1038 (vs), 998 (s), 979 (m), 943 (w), 913 (s), 887 (m), 65 2925 (m), 2853 (w), 1604 (w), 1584 (w), 1482 (m), 1459 (s),
861 (w), 835 (m), 798 (m), 765 (vs), 737 (s), 683 (w), 648 (w),
579 (w), 567 (w), 551 (w), 532 (m), 487 (w), 473 (w), 458 (w),
1382 (m), 1349 (w), 1306 (w), 1227 (w), 1223 (m), 1208 (m),
1187 (m), 1169 (w), 1152 (w), 1074 (s), 1050 (s), 1025 (s), 1000
(w), 976 (m), 959 (w), 910 (m), 850 (w), 826 (m), 761 (vs), 726
10 443 (m), 406 (W). 1H NMR (250.13 MHz, DMSOꢀd6, 25 °C,
TMS): δ = 14.42 (s, 1H, OH), 8.49 (s, 1H, CH=N), 7.42 (d, 1H, J
(s), 715 (w), 690 (vs), 663 (w), 550 (m), 512 (w), 493 (w), 479
1
=7.00 Hz), 7.26 (t, 1H, J =7.00 Hz), 6.76ꢀ6.82 (m, 2H), 4.85 (s, 70 (w). H NMR (250.13 MHz, CDCl3, 25 °C, TMS): δ = 7.75 (s,
2H, OH), 3.39 (s, 4H, CH2), 1.17 (s, 3H, CH3). 13C NMR (62.90
MHz, DMSOꢀd6): δ = 163.79 (CH=N), 163.04 (ArCꢀOH),
15 132.66, 132.46, 119.01, 117.87, 117.50, 65.81, 64.69, 18.45 ppm.
UVꢀVis (in CH3OH, c = 2.5×10ꢀ5 M, λmax [nm] with ε [Mꢀ1 cmꢀ
1H, NCH=C), 7.71 (d, J = 6 Hz, 2H, ArꢀH), 7.25ꢀ7.40 (m, 8H,
ArꢀH), 5.68 (dd, J = 8.13 Hz, J = 3.75, 1H, CH), 4.63 (t, 1H, J =
9.00 Hz, 1H of CH2), 4.22 (m, 1H, , 1H of CH2), 3.80 (s, 1H,
OH). 13C NMR (62.90 MHz, CDCl3): δ = 147.66 (NC=CH),
1]): 218 (54800), 251 (24000), 278 (17400), 315 (5900), 401 nm 75 136.06, 130.19 (2× ArC), 129.14, 128.97, 128.81, 128.26, 127.15,
(8000).
125.66 (10× ArCH), 120.57 (NC=CH), 67.32, 65.08 ppm. UVꢀ
Vis (in CH3OH, c = 2.5×10ꢀ5 M, λmax [nm] with ε [Mꢀ1 cmꢀ1]): 206
(46800), 245 nm (24400).
20 Synthesis of complex [Cu(H2L)(N3)]·CH3OH (1)
Complex 1 was synthesized by the reaction of the ligand H3L
1Phꢀtriazole: M.p. 153ꢀ155 °C. Anal. Calc. for C16H15N3O (MW
(0.209 g, 1.00 mmol), Cu(NO3)2·3H2O (0.242 g, 1.0 mmol) and 80 = 265.32): C, 72.43; H, 5.70; N, 15.84 %. Found: C, 72.46; H,
sodium azide (0.10 g, 1.54 mmol) in methanol using the thermal
gradient method in a branched tube. The above mentioned
25 amounts of the materials were placed in the main arm of a
branched tube. Methanol was carefully added to fill the arms, the
5.74; N, 15.82%. %. FTꢀIR (KBr, cmꢀ1): 3300 (br, m), 3133 (m),
2923 (m), 2853 (w), 1732 (m), 1602 (w), 1584 (w), 1484 (m),
1466 (s), 1453 (s), 1444 (s), 1362 (w), 1349 (w), 1287 (m), 1264
(m), 1226 (m), 1198 (m), 1085 (vs), 1067 (vs), 1027 (m), 981
tube was sealed and the reagents containing arm was immersed in 85 (m), 917 (m), 892 (m), 827 (m), 763 (vs), 741 (vs), 702 (s), 692
an oil bath at 65˚C, while the other arm was kept at ambient
temperature. After a day, green crystals were deposited in the
30 cooler arm. Yield 78% (0.27 g). Anal. Calc. for C12H21CuN4O4
(MW = 345.85): C, 41.68; H, 5.25; N, 16.20; Cu, 18.37. Found:
(vs), 611 (m), 538 (s), 506 (m), 487 (w), 418 (w). 1H NMR
(250.13 MHz, CDCl3, 25 °C, TMS): δ = 7.80 (s, 1H,NCH=C),
7.77 (d, J = 7.00 Hz, 2H, ArꢀH), 7.26ꢀ7.41 (m, 8H, ArꢀH), 5.24
(d, J= 8.50 Hz, 1H, CH), 4.67 (dd, J=13.87 Hz, J =3.25, 1H),
C, 41.63; H, 5.22; N, 16.29; Cu, 18.43%. FTꢀIR (KBr, cmꢀ1): 90 4.48 (q, J= 8.75 Hz, 1H), 3.18 (s, 1H, OH). 13C NMR (62.90
3306 (br,m), 2930 (w), 2881 (w), 2066 (vs), 1626 (s), 1597 (m),
1541 (w), 1461 (m), 1442 (m), 1398 (w), 1383 (m), 1362 (w),
35 1336 (w), 1306 (m), 1251 (w), 1215 (w), 1189 (w), 1152 (w),
1144 (m), 1223 (w), 1074(m), 1032 (m), 1019 (s), 1002(m), 981
MHz, CDCl3): δ = 142.23 (NC=CH), 140.07, 130.44 (2× ArC),
128.86, 128.81, 128.59, 128.13, 125.87, 125.68 (10× ArCH),
121.11(NC=CH), 73.06, 57.40 ppm. UVꢀVis (in CH3OH, c =
2.5×10ꢀ5 M, λmax [nm] with ε [Mꢀ1 cmꢀ1]): 206 (47100), 245 nm
(w), 940 (w), 610 (w), 888 (w), 861 (w), 818 (w), 775 (s), 652 95 (24700).
(w), 603 (w), 590 (w), 531 (w), 471 (w), 460 (w). UVꢀVis (in
CH3OH, c = 2.5×10ꢀ5 M, λmax [nm] with ε [Mꢀ1 cmꢀ1]): 215
40 (29400), 240 (47800), 269 (27100), 369 (10400), 650 nm (184).
Xꢀray crystallography
The green crystals of 1 crystallized in triclinic space group Pꢀ1,
but the colorless crystals of 2Phꢀtriazole and colorless crystals of
General procedure for [3
catalyzed by complex 1
+
2]ꢀcycloaddition reaction 100 1Phꢀtriazole crystallized in monoclinic space group P21/c and
C2/c, respectively. The Xꢀray data were collected at 293(2) K
A 25 mL round bottom flask was charged with Cu(II)ꢀcomplex
45 (0.01 mmol), epoxystyrene (0.144 mL, 1 mmol), NaN3 (0.065 g,
1 mmol), phenylacetylene (0.109 mL, 1 mmol) and water (2 mL).
with an Oxford Sapphire CCD diffractometer using MoKα
radiation λ = 0.71073 Å and ωꢀ2θ method. The analytical
absorption correction was applied with the maximum and
The mixture was stirred at desired temperature and reaction 105 minimum transmissions of 0.8718 and 0.6048 1, 0.9924 and
progress was monitored by TLC until the primary materials were
consumed. The reaction mixture was then extracted with ethyl
50 acetate (3 × 10 mL). The combined organic phase was washed
with water. At higher temperatures two products were obtained
0.9804 2Phꢀtriazole or 0.9659 and 0.9974 1Phꢀtriazole,
respectively.33 The structures were solved by direct methods and
refined with the fullꢀmatrix leastꢀsquares method on F2 with the
use of SHELXꢀ97 program package.34 The Cꢀbonded hydrogen
which were separated by plate chromatography after solvent 110 atoms were calculated form geometry, the Oꢀ hydrogen atoms
extracting. The structures of both products were confirmed by
were located from the difference electron density maps and all
hydrogen atoms were constrained during refinement. The data
collection and refinement processes are summarized in Table 4.
The structure plots were prepared with DIAMOND.35
1
spectroscopic methods (FTꢀIR, H NMR, 13C NMR and UVꢀVis)
55 and single crystal Xꢀray analysis. The crystals of 2ꢀphenylꢀ2ꢀ(4ꢀ
phenylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)ethanol
(2Phꢀtriazole)
were
obtained from ethanol/dichloromethane (50/50) by slow solvent 115
evaporating method over two days while the crystals of 1ꢀphenylꢀ
This journal is © The Royal Society of Chemistry [year]
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New Journal of Chemistry
Page 8 of 10
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DOI: 10.1039/C6NJ03865D
Table 4. Crystal data and structure refinement parameters for 1
1
2
and 2Phꢀtriazole.
Compound
Net formula
Formula weight, g molꢀ1
Wavelength, Å
T, K
(a) Z. Benkhellat, M. Allali, M. Beley, E. Wenger, M. Bernard,
N. Parizel, K. Selmeczi and J.ꢀP. Joly, New J. Chem., 2014,
38, 419–429; (b) B. Schulze and U. S. Schubert, Chem. Soc.
Rev., 2014, 43, 2522–2571; (c) Kelly J. Kilpin, Stéphanie
Crot, Tina Riedel, Jonathan A. Kitchen and Paul J. Dyson,
Dalton Trans., 2014, 43, 1443–1448.
(a) M. H. Shaikh, D. D. Subhedar, L. Nawale, D. Sarkar, F. A.
K. Khan, J. N. Sangshetti and B. B. Shingate, Med. Chem.
Commun., 2015, 6, 1104–1116; (b) J. Genin, D. A. Allwine,
D. J. Anderson, M. R. Barbachyn, D. E. Emmert, S. A.
Garmon, D. R. Graber, K. C. Grega, J. B. Hester, D. K.
Hutchinson, J. Morris, R. J. Reischer, C. W. Ford, G. E.
Zurenko, J. C. Hamel, R. D. Schaadt, D. Stapert and B. H.
Yagi, J. Med. Chem. 2000, 43, 953–970.
Complex 1
C12H18CuN4O4
345.84
0.71073
293(2)
2Phꢀtriazole
C16H15N3O
265.31
0.71073
293(2)
Crystal size, mm
Crystal shape, color
Crystal system
Space group
a, Å
b, Å
c, Å
α, deg
β, deg
0.36 × 0.12 × 0.090.24 × 0.19 × 0.09
needle, green
Triclinic
Pꢀ1
plate, colourless
Monoclinic
P21/c
7.7557(4)
10.0442(5)
10.1321(5)
78.380(4)
78.554(5)
68.519(5)
712.65(7)
2
14.685(3)
5.5450(10)
16.850(3)
90
100.38(3)
90
3
4
(a) H. Cheng, J. Wan, M. Lin, Y. Liu, X. Lu, J. Liu, Y. Xu, J.
Chen, Y. E. Cheng and K. Ding, J. Med. Chem., 2012, 55,
2144–2153; b) C. Nájera and J. M. Sansano, Org. Biomol.
Chem., 2009, 7, 4567–4581.
γ, deg
Volume, Å3
Z
1349.6(4)
4
Density (calc.), g cm−3
1.612
1.306
Absorption coefficient, mm−1 1.554
0.084
(a) K. Easwaramoorthi, A. Jeya Rajendran, K. Chennakesava
Rao, Y. Arun, C. Balachandran, P.T. Perumal, N. Emi, S. M.
Mahalingam, V. Duraipandiyan, N. A. AlꢀDhabi, RSC Adv.,
2015, 5, 105266–105278; (b) N. R. Penthala, L. Madhukuri,
S. Thakkar, N. R. Madadi, G. Lamture, R. L. Eoff and P. A.
Crooks, Med. Chem. Commun., 2015, 6, 1535–1543; (c) H.
Bakhshi, H. Yeganeh, S. MehdipourꢀAtaei, A. Solouk and S.
Irani, Macromolecules, 2013, 46, 7777–7788.
F(000)
Θ range, deg
Independent reflections
Measured reflections
Reflections with I > 2σ(I)
358
2.85 to 28.28
3131
4609
3134
ꢀ10≤h≤8,
ꢀ13≤k≤10,
ꢀ12≤l≤11
0.0205
0/191
1.118
560
2.46 to 28.49
3089
8243
3089
ꢀ18≤h≤18,
ꢀ6≤k≤7,
ꢀ22≤l≤21
0.1386
0/181
0.990
R1 = 0.0984,
wR2 = 0.2496
R1 = 0.2969,
wR2 = 0.3598
0.328
Index ranges hkl
5 (a) D. R. Buckle, C. J. M. Rockell, H. Smith and B. A. Spicer, J.
Med. Chem. 1986, 29, 2269–2267; (b) D. R.Buckle, D. J.
Outred, C. J. M. Rockell, H. Smith and B. A. Spicer, J. Med.
Chem. 1983, 26, 251–254.
Rint
restraints/parameters
Goodness of fit on F2
6 N. Gouault, J. F. Cupif, A. Sauleau and M. David, Tetrahedron
Lett. 2000, 41, 7293–7297.
M. Z. Griffiths and P. L. A. Popelier, J. Chem. Inf. Model.,
2013, 53, 1714–1725.
H. Chai, R. Guo, W. Yin, L. Cheng, R. Liu and C. Chu, ACS
R1 = 0.0354,
wR2 = 0.1026
R1 = 0.0444,
wR2 = 0.1056
Final R indices [I > 2σ(I)]
R indices (all data)
Max electron density/e·Å–3 0.417
Min electron density/e·Å–3 ꢀ0.367
7
8
ꢀ0.240
Comb. Sci., 2015, 17, 147–151.
(a) M. Whiting, J. Muldoon, Y. C. Lin, S. M. Silverman, W.
9
a Largest difference peak and hole. – bR1 = [Σ(║Fo│–│Fc║)/Σ│Fo│]; wR2
Lindstrom, A. J. Olson, H. C. Kolb, M. G. Finn, K. B.
Sharpless, J. H. Elder and V. V. Fokin, Angew. Chem. Int. Ed.
2006, 45, 1435–1439; (b) M. J. Giffin, H. Heaslet, A. Brik, Y.
C. Lin, G. Cauvi, C. H. Wong, D. E. McRee, J. H. Elder, C.
D. Stout and B. E. Torbett, J. Med. Chem. 2008, 51, 6263–
6270.
= [Σ [w(Fo –Fc2)2]/Σ[w(Fo )2]]1/2. – c Goodnessꢀofꢀfit = [Σ [w(Fo –Fc2)2]
2
2
2
5
/(n–p)]1/2
.
Acknowledgments
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J. Phys. Chem. A, 2011, 115 , 8234–8241; (b) S. A. Ingale
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Xu, RSC Adv., 2014, 4, 54256–54262
The authors are thankful to the University of Zanjan and Nicolaus
Copernicus University for support of this study. We also thank to
Prof. Dr. Tadeusz Lis from the University of Wroclaw for his
10 helps in a part of this work.
11 a) A.ꢀS. Felten, N. Petry, B. Henry, N. PellegriniꢀMoïse and K.
Selmeczi, New J. Chem., 2016, 40, 1507–1520; b) M.
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Appendix
CCDC 1449773 and 1449774 contain the supplementary crystallographic
data for 1 and 2Phꢀtriazole, respectively, which can be obtained free of
15 charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html. Electronic
Supplementary Information (ESI) available: Crystallographic information
of 1Phꢀtriazole and 2ꢀphtriazole, TGA curve, UVꢀVis and FTꢀIR spectra
of the complex 1 together with the NMR spectrum of organic products.
Supplementary data to this article can be found online at DOI:...
12 (a) F Alonso, Y. Moglie, G. Radivo and M. Yus, J. Org. Chem.
2011, 76, 8394–8405; (b) R. Huisgen, G. Szeimies and L.
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20
Notes and references
a
Department of Chemistry, Faculty of Sciences, University of Zanjan
13
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45195ꢀ313, Zanjan, I. R. Iran.
Sharma and A. G. Coutsolelos, Dalton Trans., 2015, 44,
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*Corresponding author: Tel.: +98 243 3052583; Fax: +98 243 3083203.
25 Eꢀmail address: nadernoshiranzadeh@yahoo.com (N. Noshiranzadeh).
b Faculty of Chemistry, Nicolaus Copernicus University in Toruń, 87ꢀ100
Toruń, Poland
14
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Journal Name, [year], [vol], 00–00 | 9

New Journal of Chemistry
Page 10 of 10
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DOI: 10.1039/C6NJ03865D
Graphical Abstract
Highlight
• A new method for preparing 1,2,3-triazols via [3+2]-cycloaddition reaction is
introduced. The effect of reaction temperature on the epoxide ring opening
reactions is also investigated.